1

Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Non-Autocatalytic

Chemical Model of Prebiotic Chirality Amplification

Evgenii P Talsiab

Anna A Bryliakovab Roman V Ottenbacher

ab Tatyana V Rybalova

ac and

Konstantin P Bryliakov ab

a Novosibirsk State University Pirogova 2 Novosibirsk 630090 Russian Federation b Boreskov Institute of Catalysis Pr Lavrentieva 5 Novosibirsk 630090 Russian Federation c Vorozhtsov Novosibirsk Institute of Organic Chemistry Pr Lavrentieva 9 Novosibirsk 630090

Russian Federation

E-mail bryliakocatalysisru

Supporting Information

Materials and methods 2

Syntheses of Mn complexes 3

Kinetic resolution procedures 4

Schemes S1 and S2 treatment of the kinetic scheme 6

Figure S1 9

Effect of concentration on the nonlinear ee growth (Table S1 Figure S2) 10

Effect of temperature on the nonlinear ee growth (Table S2 Figure S3) 11

Figures S4 Table S3 12

Figure S5 13

Figure S6 14

X-ray crystallography 15

DFT calculations 21

Additional references 23

Copies of NMR spectra 24

HPLC traces 26

DFT optimized Cartesian coordinates of Mn complexes 50

2

Materials

For catalytic epoxidation experiments 30 analytical grade aqueous H2O2 was used Mn

complexes 221 43031 and (S)-1-phenylethanol30 were prepared as described All chemicals and

solvents were either Aldrich Acros Organics or Alfa Aesar commercial reagents (and were used

without additional purification unless noted otherwise) or were prepared according to literature

procedures

Methods 1H and 13C NMR spectra were measured on Bruker Avance 400 at 40013 and 100613 MHz

respectively or on Bruker DPX-250 at 25013 and 62903 MHz respectively Chemical shifts were

internally referenced to tetramethylsilane Specific rotation values (in CH3CN) were measured using

Kruss Optronic polarimeter P8000-T using 100 mm cuvette

Reaction mixtures were analyzed by HPLC (Shimadzu LC-20) with chiral stationary phase

Chiralcel OD-H to obtain the relative concentrations of the 1-phenylethanol and acetophenone and

the enantiomeric excess of the 1-arylalkanol (see table below) Experimental uncertainty of

enantioselectivity measurements did not exceed plusmn05 ee

Mn complexes (RR)-4 (SS)-4 1 2 and 3 were resolved by HPLC (Shimadzu LC-20) with

chiral stationary phase Chiralpak OJ-H (eluent hexaneethanol 9010 01 trifluoroacetic acid) 20

degC 08 mLmin detection at 206 nm

Experimental (kinetic) data were treated using Origin 90 package

HPLC separation details

Analyte Column T degC

Eluent

λ

nm

V

mLmin

tR1 min

(config)

tR2 min

(config)

O

Chiralcel OD-H 20 i-PrOH hexane

397 206 10 64 (minus)

OH

Chiralcel OD-H 20 i-PrOH hexane

397 206 10 120 (R) 144 (S)

3

(SS)-4 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 168

(RR)-4 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 198

1 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 262

2 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 273

3 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 254

a 01 vol trifluoroacetic acid was added

Syntheses of Mn complexes

N1N

2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-

yl)methyl)ethane-12-diamine To 2-(chloromethyl)-3-methyl-4-(222-

trifluoroethoxy)pyridine hydrochloride (3037 mg 11 mmol) and N1N2-

dimethylethane-12-diamine (54 microL 050 mmol) water (10 mL) and CH2Cl2

(15 mL) were added and NaOH (88 mg 22 mmol) was added in one portion

The mixture was stirred overnight at r t diluted with water (2 mL) and

extracted with CH2Cl2 (3times5 mL) Combined organic extracts were washed with aqueous NaCl dried

with CaSO4 and evaporated under reduced pressure The crude product was purified on a short SiO2

column (eluent acetone acetoneMeOH 51) to yield the desired product (173 mg 70 )

1H NMR (CDCl3CCl4 25 degC) δ 826 (d 2H Ar-H 3JHH = 55 Hz) 658 (d 2H Ar-H 3JHH

= 55 Hz) 434 (q 4H OCH2CF3 3JHF = 79 Hz) 363 (s 4H ArCH2N) 261 (s 4H C2H4) 223 (s

6H ArCH3) 220 (s 6H NCH3)

N

N

N

N

OCH2CF3

OCH2CF3

4

13C NMR1H (CDCl3CCl4 25 degC) δ 16158 (2C C) 15855 (2C C) 14729 (2C CH)

12305 (q 2C CF3 1JHF = 278 Hz) 12244 (2C C) 10522 (2C CH) 6541 (q 2C CH2CF3

2JHF =

36 Hz) 6234 (2C ArCH2N) 5548 (2C C2H4) 4266 (2C NCH3) 1038 (2C ArCH3)

Complex 1

To N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-

yl)methyl)ethane-12-diamine (150 mg 030 mmol) in acetonitrile (15 mL)

Mn(OTf)2middotCH3CN (118 mg 030 mmol) was added in one portion and the

mixture was stirred overnight The mixture was filtered and diethyl ether (10

mL) was layered upon to afford in a few days colorless crystals of 1 (1325

mg)

Complex 3

To tris((4-methoxy-35-dimethylpyridin-2-yl)methyl)amine (66 mg

0142 mmol) in acetonitrile (08 mL) Mn(OTf)2middotCH3CN (59 mg 015

mmol) was added in one portion and the mixture was stirred for 1 h

followed by filtering layering with diethyl ether (6 mL) and storing at

+4 degC for several days Second recrystallization from CH3CNEt2O

afforded X-ray quality colorless needle crystals of 3 (71 mg)

Kinetic resolution procedures

Kinetic resolution of scalemic 1-phenylethanol

Scelemic 1-phenylethanol mixtures were prepared by mixing calculated volumes of racemic and

non-racemic 1-phenylethanol (either homemade 92 ee (S)-1-phenylethanol or commercial (R)-1-

N

NMn

N

N OH2

OTf

OCH2CF3

OCH2CF3

+OTf

_

N

N

N

MnN

H3CO

OCH3

H3CO

OTf

OH2

+OTf

_

5

phenylethanol gt990 ee SigmaAldrich) The resulting mixture with total amount of 1-

phenylethanol of 018hellip023 mmol and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL or 08 or 02 mL in the case of experiments presented in Figure 2 red and green curves

respectively) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions The

results were presented in the form of ee vs conversion and [S][R] vs conversion plots

Kinetic resolution of scalemic alkyl mandelates

The solution of the appropriate racemic alkyl mandelate and enantiopure (R)-alkyl mandelate (total

amount of alkyl mandelate 02 mmol) and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions No

increase in the ee was observed over the reaction course

6

Scheme S1 Proposed reaction scheme of 1-phenylethanol oxidation mediated by dynamically racemic Mn catalysts

7

Treatment of the kinetic scheme

R + -cat P + -catk R

S + -cat P + -catk S

K

R + -cat -catmiddotR

K

S + -cat -catmiddotS

kR

R

R + -catmiddotR P + -catmiddotR

kR

S

S + -catmiddotR P + -catmiddotR

kS

R

R + -catmiddotS P + -catmiddotS

kS

S

S + -catmiddotS P + -catmiddotS

reaction mediated

by free catalyst

catalyst-substratecomplexation

reaction mediated by

substrate-complexed

catalyst

R + -cat P + -catk R

S + -cat P + -catk S

Keq-cat -cat fast enantiomerization

of free catalyst Keq = 1

Scheme S2 Model kinetic scheme of kinetic resolution with dynamically racemic catalyst P is

product cat is catalyst R and S stand for the enantiomers of the chiral substrate

In Scheme S2 formation of catalyst-substrate adducts [∆-CatmiddotS] and [Λ-CatmiddotR] has been

neglected assuming that stability constants for such adducts should be ltlt K DFT calculations

(Table S8 SI) provide qualitative support of this assumption

The overall rates of consumption of the (S)- and (R)-alcohol respectively are

]S][Scat[]S][Rcat[]S][cat[]S][cat[]S[

sdotminusΛminussdotminus∆minusminusΛminusminus∆minus= Λ∆S

SS

R kkkkdt

d (S1)

]R][Scat[]R][Rcat[]R][cat[]R][cat[]R[

sdotminusΛminussdotminus∆minusminusΛminusminusminus∆minus= Λ∆R

SR

Rkkkk

dt

d (S2)

8

Assuming that the enantiomerization equilibrium of the free catalyst is the fastest reaction in

Scheme S1 (ie [∆-Cat] = [Λ-Cat] = [X]) and taking into account the catalyst-substrate

complexation equilibria and the mass balance for catalyst Cat0 = [∆-Cat] + [Λ-Cat] + [∆-

CatmiddotR] + [Λ-CatmiddotS] one can calculate the concentrations of all forms of the catalyst

]S[]R[2

cat]cat[ 0

KK ++=

]S[]R[2

]S][cat[cat]Scat[ 0

KK

K

++minusΛ

=sdot ]S[]R[2

]R][cat[cat]Rcat[ 0

KK

K

++minus∆

=sdot (S3)

We notice the following self-evident relationships

]R][X[]R][X[]R][X[]R][cat[]R][cat[ kkkkk RRRR minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S4)

]S][X[]S][X[]S][X[]S][cat[]S][cat[ kkkkk RRSS minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S5)

which in combination with eq (S1) (S2) and (S3) leads to the following equation

]R][R[]R][S[]R[

]S][S[]S][R[]S[

]R[

]S[

RR

RS

SS

SR

KkKkk

KkKkk

d

d

++++

= (S6)

Taking into account that evidently kSR = kR

S and kSS = kR

R multiplying left and right parts

of (S6) by R0S0 (R0 and S0 are the initial concentrations of the (R)- and (S)-enantiomers)

substituting k

Kk SR

=k

Kk RS

= A and k

Kk SS

= k

Kk RR

= B and introducing dimensionless

concentrations s = [S]S0 and r = [R]R0 one obtains

2

0

000

20

0

00

rS

RBSsrASr

sBSsrS

RASs

dr

ds

++

++

= (S5)

R0S0 for each experiment is known (and equal to 0

0

0

0

1

1

ee

ee

S

R

+

minus= where ee0 is expressed as a

decimal fraction) In effect this equation can be solved numerically to yield s = F(A B r)

Parameters A and B can be revealed by fitting the ee vs conversion or better er vs conversion

9

dependencies to the experimental points For this purpose the following obvious relationships have

been used

minus

+==

0

0

1

1

][

][

ee

ee

r

s

R

Ser

2

)1()1(2])[]([ 00

00

00 eeseer

RS

RSRSconversion

+minusminusminus=

+

+minus+=

+

minus+

+

minusminus

=+minus

=

0

0

0

0

1

1

1

1

][][

][][

ee

eers

ee

eers

RS

RSee

Figure S1 Enantiomeric excess (ee) vs conversion (A) plot and [S][R] ratio (er) vs conversion

plot (B) for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

Dots represent experimental data solid lines are theoretical fits with averaged parameters A = 345

M-1 B = 129 M-1 Curves are numbered in accordance with the numbers of entries in Table 1

0 10 20 30 40 50 60 70 80 90 100

10

15

20

25

30

35

40

45

50

55

1

2

3

conversion

ee

0 10 20 30 40 50 60 70 80 90 100 10

12

14

16

18

20

22

24

26

28

30

conversion

er

1

2

3

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

2

Materials

For catalytic epoxidation experiments 30 analytical grade aqueous H2O2 was used Mn

complexes 221 43031 and (S)-1-phenylethanol30 were prepared as described All chemicals and

solvents were either Aldrich Acros Organics or Alfa Aesar commercial reagents (and were used

without additional purification unless noted otherwise) or were prepared according to literature

procedures

Methods 1H and 13C NMR spectra were measured on Bruker Avance 400 at 40013 and 100613 MHz

respectively or on Bruker DPX-250 at 25013 and 62903 MHz respectively Chemical shifts were

internally referenced to tetramethylsilane Specific rotation values (in CH3CN) were measured using

Kruss Optronic polarimeter P8000-T using 100 mm cuvette

Reaction mixtures were analyzed by HPLC (Shimadzu LC-20) with chiral stationary phase

Chiralcel OD-H to obtain the relative concentrations of the 1-phenylethanol and acetophenone and

the enantiomeric excess of the 1-arylalkanol (see table below) Experimental uncertainty of

enantioselectivity measurements did not exceed plusmn05 ee

Mn complexes (RR)-4 (SS)-4 1 2 and 3 were resolved by HPLC (Shimadzu LC-20) with

chiral stationary phase Chiralpak OJ-H (eluent hexaneethanol 9010 01 trifluoroacetic acid) 20

degC 08 mLmin detection at 206 nm

Experimental (kinetic) data were treated using Origin 90 package

HPLC separation details

Analyte Column T degC

Eluent

λ

nm

V

mLmin

tR1 min

(config)

tR2 min

(config)

O

Chiralcel OD-H 20 i-PrOH hexane

397 206 10 64 (minus)

OH

Chiralcel OD-H 20 i-PrOH hexane

397 206 10 120 (R) 144 (S)

3

(SS)-4 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 168

(RR)-4 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 198

1 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 262

2 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 273

3 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 254

a 01 vol trifluoroacetic acid was added

Syntheses of Mn complexes

N1N

2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-

yl)methyl)ethane-12-diamine To 2-(chloromethyl)-3-methyl-4-(222-

trifluoroethoxy)pyridine hydrochloride (3037 mg 11 mmol) and N1N2-

dimethylethane-12-diamine (54 microL 050 mmol) water (10 mL) and CH2Cl2

(15 mL) were added and NaOH (88 mg 22 mmol) was added in one portion

The mixture was stirred overnight at r t diluted with water (2 mL) and

extracted with CH2Cl2 (3times5 mL) Combined organic extracts were washed with aqueous NaCl dried

with CaSO4 and evaporated under reduced pressure The crude product was purified on a short SiO2

column (eluent acetone acetoneMeOH 51) to yield the desired product (173 mg 70 )

1H NMR (CDCl3CCl4 25 degC) δ 826 (d 2H Ar-H 3JHH = 55 Hz) 658 (d 2H Ar-H 3JHH

= 55 Hz) 434 (q 4H OCH2CF3 3JHF = 79 Hz) 363 (s 4H ArCH2N) 261 (s 4H C2H4) 223 (s

6H ArCH3) 220 (s 6H NCH3)

N

N

N

N

OCH2CF3

OCH2CF3

4

13C NMR1H (CDCl3CCl4 25 degC) δ 16158 (2C C) 15855 (2C C) 14729 (2C CH)

12305 (q 2C CF3 1JHF = 278 Hz) 12244 (2C C) 10522 (2C CH) 6541 (q 2C CH2CF3

2JHF =

36 Hz) 6234 (2C ArCH2N) 5548 (2C C2H4) 4266 (2C NCH3) 1038 (2C ArCH3)

Complex 1

To N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-

yl)methyl)ethane-12-diamine (150 mg 030 mmol) in acetonitrile (15 mL)

Mn(OTf)2middotCH3CN (118 mg 030 mmol) was added in one portion and the

mixture was stirred overnight The mixture was filtered and diethyl ether (10

mL) was layered upon to afford in a few days colorless crystals of 1 (1325

mg)

Complex 3

To tris((4-methoxy-35-dimethylpyridin-2-yl)methyl)amine (66 mg

0142 mmol) in acetonitrile (08 mL) Mn(OTf)2middotCH3CN (59 mg 015

mmol) was added in one portion and the mixture was stirred for 1 h

followed by filtering layering with diethyl ether (6 mL) and storing at

+4 degC for several days Second recrystallization from CH3CNEt2O

afforded X-ray quality colorless needle crystals of 3 (71 mg)

Kinetic resolution procedures

Kinetic resolution of scalemic 1-phenylethanol

Scelemic 1-phenylethanol mixtures were prepared by mixing calculated volumes of racemic and

non-racemic 1-phenylethanol (either homemade 92 ee (S)-1-phenylethanol or commercial (R)-1-

N

NMn

N

N OH2

OTf

OCH2CF3

OCH2CF3

+OTf

_

N

N

N

MnN

H3CO

OCH3

H3CO

OTf

OH2

+OTf

_

5

phenylethanol gt990 ee SigmaAldrich) The resulting mixture with total amount of 1-

phenylethanol of 018hellip023 mmol and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL or 08 or 02 mL in the case of experiments presented in Figure 2 red and green curves

respectively) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions The

results were presented in the form of ee vs conversion and [S][R] vs conversion plots

Kinetic resolution of scalemic alkyl mandelates

The solution of the appropriate racemic alkyl mandelate and enantiopure (R)-alkyl mandelate (total

amount of alkyl mandelate 02 mmol) and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions No

increase in the ee was observed over the reaction course

6

Scheme S1 Proposed reaction scheme of 1-phenylethanol oxidation mediated by dynamically racemic Mn catalysts

7

Treatment of the kinetic scheme

R + -cat P + -catk R

S + -cat P + -catk S

K

R + -cat -catmiddotR

K

S + -cat -catmiddotS

kR

R

R + -catmiddotR P + -catmiddotR

kR

S

S + -catmiddotR P + -catmiddotR

kS

R

R + -catmiddotS P + -catmiddotS

kS

S

S + -catmiddotS P + -catmiddotS

reaction mediated

by free catalyst

catalyst-substratecomplexation

reaction mediated by

substrate-complexed

catalyst

R + -cat P + -catk R

S + -cat P + -catk S

Keq-cat -cat fast enantiomerization

of free catalyst Keq = 1

Scheme S2 Model kinetic scheme of kinetic resolution with dynamically racemic catalyst P is

product cat is catalyst R and S stand for the enantiomers of the chiral substrate

In Scheme S2 formation of catalyst-substrate adducts [∆-CatmiddotS] and [Λ-CatmiddotR] has been

neglected assuming that stability constants for such adducts should be ltlt K DFT calculations

(Table S8 SI) provide qualitative support of this assumption

The overall rates of consumption of the (S)- and (R)-alcohol respectively are

]S][Scat[]S][Rcat[]S][cat[]S][cat[]S[

sdotminusΛminussdotminus∆minusminusΛminusminus∆minus= Λ∆S

SS

R kkkkdt

d (S1)

]R][Scat[]R][Rcat[]R][cat[]R][cat[]R[

sdotminusΛminussdotminus∆minusminusΛminusminusminus∆minus= Λ∆R

SR

Rkkkk

dt

d (S2)

8

Assuming that the enantiomerization equilibrium of the free catalyst is the fastest reaction in

Scheme S1 (ie [∆-Cat] = [Λ-Cat] = [X]) and taking into account the catalyst-substrate

complexation equilibria and the mass balance for catalyst Cat0 = [∆-Cat] + [Λ-Cat] + [∆-

CatmiddotR] + [Λ-CatmiddotS] one can calculate the concentrations of all forms of the catalyst

]S[]R[2

cat]cat[ 0

KK ++=

]S[]R[2

]S][cat[cat]Scat[ 0

KK

K

++minusΛ

=sdot ]S[]R[2

]R][cat[cat]Rcat[ 0

KK

K

++minus∆

=sdot (S3)

We notice the following self-evident relationships

]R][X[]R][X[]R][X[]R][cat[]R][cat[ kkkkk RRRR minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S4)

]S][X[]S][X[]S][X[]S][cat[]S][cat[ kkkkk RRSS minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S5)

which in combination with eq (S1) (S2) and (S3) leads to the following equation

]R][R[]R][S[]R[

]S][S[]S][R[]S[

]R[

]S[

RR

RS

SS

SR

KkKkk

KkKkk

d

d

++++

= (S6)

Taking into account that evidently kSR = kR

S and kSS = kR

R multiplying left and right parts

of (S6) by R0S0 (R0 and S0 are the initial concentrations of the (R)- and (S)-enantiomers)

substituting k

Kk SR

=k

Kk RS

= A and k

Kk SS

= k

Kk RR

= B and introducing dimensionless

concentrations s = [S]S0 and r = [R]R0 one obtains

2

0

000

20

0

00

rS

RBSsrASr

sBSsrS

RASs

dr

ds

++

++

= (S5)

R0S0 for each experiment is known (and equal to 0

0

0

0

1

1

ee

ee

S

R

+

minus= where ee0 is expressed as a

decimal fraction) In effect this equation can be solved numerically to yield s = F(A B r)

Parameters A and B can be revealed by fitting the ee vs conversion or better er vs conversion

9

dependencies to the experimental points For this purpose the following obvious relationships have

been used

minus

+==

0

0

1

1

][

][

ee

ee

r

s

R

Ser

2

)1()1(2])[]([ 00

00

00 eeseer

RS

RSRSconversion

+minusminusminus=

+

+minus+=

+

minus+

+

minusminus

=+minus

=

0

0

0

0

1

1

1

1

][][

][][

ee

eers

ee

eers

RS

RSee

Figure S1 Enantiomeric excess (ee) vs conversion (A) plot and [S][R] ratio (er) vs conversion

plot (B) for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

Dots represent experimental data solid lines are theoretical fits with averaged parameters A = 345

M-1 B = 129 M-1 Curves are numbered in accordance with the numbers of entries in Table 1

0 10 20 30 40 50 60 70 80 90 100

10

15

20

25

30

35

40

45

50

55

1

2

3

conversion

ee

0 10 20 30 40 50 60 70 80 90 100 10

12

14

16

18

20

22

24

26

28

30

conversion

er

1

2

3

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

3

(SS)-4 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 168

(RR)-4 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 198

1 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 262

2 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 273

3 Chiralcel OJ-H 20 EtOH

hexane 1090 a

206 08 254

a 01 vol trifluoroacetic acid was added

Syntheses of Mn complexes

N1N

2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-

yl)methyl)ethane-12-diamine To 2-(chloromethyl)-3-methyl-4-(222-

trifluoroethoxy)pyridine hydrochloride (3037 mg 11 mmol) and N1N2-

dimethylethane-12-diamine (54 microL 050 mmol) water (10 mL) and CH2Cl2

(15 mL) were added and NaOH (88 mg 22 mmol) was added in one portion

The mixture was stirred overnight at r t diluted with water (2 mL) and

extracted with CH2Cl2 (3times5 mL) Combined organic extracts were washed with aqueous NaCl dried

with CaSO4 and evaporated under reduced pressure The crude product was purified on a short SiO2

column (eluent acetone acetoneMeOH 51) to yield the desired product (173 mg 70 )

1H NMR (CDCl3CCl4 25 degC) δ 826 (d 2H Ar-H 3JHH = 55 Hz) 658 (d 2H Ar-H 3JHH

= 55 Hz) 434 (q 4H OCH2CF3 3JHF = 79 Hz) 363 (s 4H ArCH2N) 261 (s 4H C2H4) 223 (s

6H ArCH3) 220 (s 6H NCH3)

N

N

N

N

OCH2CF3

OCH2CF3

4

13C NMR1H (CDCl3CCl4 25 degC) δ 16158 (2C C) 15855 (2C C) 14729 (2C CH)

12305 (q 2C CF3 1JHF = 278 Hz) 12244 (2C C) 10522 (2C CH) 6541 (q 2C CH2CF3

2JHF =

36 Hz) 6234 (2C ArCH2N) 5548 (2C C2H4) 4266 (2C NCH3) 1038 (2C ArCH3)

Complex 1

To N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-

yl)methyl)ethane-12-diamine (150 mg 030 mmol) in acetonitrile (15 mL)

Mn(OTf)2middotCH3CN (118 mg 030 mmol) was added in one portion and the

mixture was stirred overnight The mixture was filtered and diethyl ether (10

mL) was layered upon to afford in a few days colorless crystals of 1 (1325

mg)

Complex 3

To tris((4-methoxy-35-dimethylpyridin-2-yl)methyl)amine (66 mg

0142 mmol) in acetonitrile (08 mL) Mn(OTf)2middotCH3CN (59 mg 015

mmol) was added in one portion and the mixture was stirred for 1 h

followed by filtering layering with diethyl ether (6 mL) and storing at

+4 degC for several days Second recrystallization from CH3CNEt2O

afforded X-ray quality colorless needle crystals of 3 (71 mg)

Kinetic resolution procedures

Kinetic resolution of scalemic 1-phenylethanol

Scelemic 1-phenylethanol mixtures were prepared by mixing calculated volumes of racemic and

non-racemic 1-phenylethanol (either homemade 92 ee (S)-1-phenylethanol or commercial (R)-1-

N

NMn

N

N OH2

OTf

OCH2CF3

OCH2CF3

+OTf

_

N

N

N

MnN

H3CO

OCH3

H3CO

OTf

OH2

+OTf

_

5

phenylethanol gt990 ee SigmaAldrich) The resulting mixture with total amount of 1-

phenylethanol of 018hellip023 mmol and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL or 08 or 02 mL in the case of experiments presented in Figure 2 red and green curves

respectively) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions The

results were presented in the form of ee vs conversion and [S][R] vs conversion plots

Kinetic resolution of scalemic alkyl mandelates

The solution of the appropriate racemic alkyl mandelate and enantiopure (R)-alkyl mandelate (total

amount of alkyl mandelate 02 mmol) and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions No

increase in the ee was observed over the reaction course

6

Scheme S1 Proposed reaction scheme of 1-phenylethanol oxidation mediated by dynamically racemic Mn catalysts

7

Treatment of the kinetic scheme

R + -cat P + -catk R

S + -cat P + -catk S

K

R + -cat -catmiddotR

K

S + -cat -catmiddotS

kR

R

R + -catmiddotR P + -catmiddotR

kR

S

S + -catmiddotR P + -catmiddotR

kS

R

R + -catmiddotS P + -catmiddotS

kS

S

S + -catmiddotS P + -catmiddotS

reaction mediated

by free catalyst

catalyst-substratecomplexation

reaction mediated by

substrate-complexed

catalyst

R + -cat P + -catk R

S + -cat P + -catk S

Keq-cat -cat fast enantiomerization

of free catalyst Keq = 1

Scheme S2 Model kinetic scheme of kinetic resolution with dynamically racemic catalyst P is

product cat is catalyst R and S stand for the enantiomers of the chiral substrate

In Scheme S2 formation of catalyst-substrate adducts [∆-CatmiddotS] and [Λ-CatmiddotR] has been

neglected assuming that stability constants for such adducts should be ltlt K DFT calculations

(Table S8 SI) provide qualitative support of this assumption

The overall rates of consumption of the (S)- and (R)-alcohol respectively are

]S][Scat[]S][Rcat[]S][cat[]S][cat[]S[

sdotminusΛminussdotminus∆minusminusΛminusminus∆minus= Λ∆S

SS

R kkkkdt

d (S1)

]R][Scat[]R][Rcat[]R][cat[]R][cat[]R[

sdotminusΛminussdotminus∆minusminusΛminusminusminus∆minus= Λ∆R

SR

Rkkkk

dt

d (S2)

8

Assuming that the enantiomerization equilibrium of the free catalyst is the fastest reaction in

Scheme S1 (ie [∆-Cat] = [Λ-Cat] = [X]) and taking into account the catalyst-substrate

complexation equilibria and the mass balance for catalyst Cat0 = [∆-Cat] + [Λ-Cat] + [∆-

CatmiddotR] + [Λ-CatmiddotS] one can calculate the concentrations of all forms of the catalyst

]S[]R[2

cat]cat[ 0

KK ++=

]S[]R[2

]S][cat[cat]Scat[ 0

KK

K

++minusΛ

=sdot ]S[]R[2

]R][cat[cat]Rcat[ 0

KK

K

++minus∆

=sdot (S3)

We notice the following self-evident relationships

]R][X[]R][X[]R][X[]R][cat[]R][cat[ kkkkk RRRR minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S4)

]S][X[]S][X[]S][X[]S][cat[]S][cat[ kkkkk RRSS minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S5)

which in combination with eq (S1) (S2) and (S3) leads to the following equation

]R][R[]R][S[]R[

]S][S[]S][R[]S[

]R[

]S[

RR

RS

SS

SR

KkKkk

KkKkk

d

d

++++

= (S6)

Taking into account that evidently kSR = kR

S and kSS = kR

R multiplying left and right parts

of (S6) by R0S0 (R0 and S0 are the initial concentrations of the (R)- and (S)-enantiomers)

substituting k

Kk SR

=k

Kk RS

= A and k

Kk SS

= k

Kk RR

= B and introducing dimensionless

concentrations s = [S]S0 and r = [R]R0 one obtains

2

0

000

20

0

00

rS

RBSsrASr

sBSsrS

RASs

dr

ds

++

++

= (S5)

R0S0 for each experiment is known (and equal to 0

0

0

0

1

1

ee

ee

S

R

+

minus= where ee0 is expressed as a

decimal fraction) In effect this equation can be solved numerically to yield s = F(A B r)

Parameters A and B can be revealed by fitting the ee vs conversion or better er vs conversion

9

dependencies to the experimental points For this purpose the following obvious relationships have

been used

minus

+==

0

0

1

1

][

][

ee

ee

r

s

R

Ser

2

)1()1(2])[]([ 00

00

00 eeseer

RS

RSRSconversion

+minusminusminus=

+

+minus+=

+

minus+

+

minusminus

=+minus

=

0

0

0

0

1

1

1

1

][][

][][

ee

eers

ee

eers

RS

RSee

Figure S1 Enantiomeric excess (ee) vs conversion (A) plot and [S][R] ratio (er) vs conversion

plot (B) for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

Dots represent experimental data solid lines are theoretical fits with averaged parameters A = 345

M-1 B = 129 M-1 Curves are numbered in accordance with the numbers of entries in Table 1

0 10 20 30 40 50 60 70 80 90 100

10

15

20

25

30

35

40

45

50

55

1

2

3

conversion

ee

0 10 20 30 40 50 60 70 80 90 100 10

12

14

16

18

20

22

24

26

28

30

conversion

er

1

2

3

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

4

13C NMR1H (CDCl3CCl4 25 degC) δ 16158 (2C C) 15855 (2C C) 14729 (2C CH)

12305 (q 2C CF3 1JHF = 278 Hz) 12244 (2C C) 10522 (2C CH) 6541 (q 2C CH2CF3

2JHF =

36 Hz) 6234 (2C ArCH2N) 5548 (2C C2H4) 4266 (2C NCH3) 1038 (2C ArCH3)

Complex 1

To N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-

yl)methyl)ethane-12-diamine (150 mg 030 mmol) in acetonitrile (15 mL)

Mn(OTf)2middotCH3CN (118 mg 030 mmol) was added in one portion and the

mixture was stirred overnight The mixture was filtered and diethyl ether (10

mL) was layered upon to afford in a few days colorless crystals of 1 (1325

mg)

Complex 3

To tris((4-methoxy-35-dimethylpyridin-2-yl)methyl)amine (66 mg

0142 mmol) in acetonitrile (08 mL) Mn(OTf)2middotCH3CN (59 mg 015

mmol) was added in one portion and the mixture was stirred for 1 h

followed by filtering layering with diethyl ether (6 mL) and storing at

+4 degC for several days Second recrystallization from CH3CNEt2O

afforded X-ray quality colorless needle crystals of 3 (71 mg)

Kinetic resolution procedures

Kinetic resolution of scalemic 1-phenylethanol

Scelemic 1-phenylethanol mixtures were prepared by mixing calculated volumes of racemic and

non-racemic 1-phenylethanol (either homemade 92 ee (S)-1-phenylethanol or commercial (R)-1-

N

NMn

N

N OH2

OTf

OCH2CF3

OCH2CF3

+OTf

_

N

N

N

MnN

H3CO

OCH3

H3CO

OTf

OH2

+OTf

_

5

phenylethanol gt990 ee SigmaAldrich) The resulting mixture with total amount of 1-

phenylethanol of 018hellip023 mmol and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL or 08 or 02 mL in the case of experiments presented in Figure 2 red and green curves

respectively) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions The

results were presented in the form of ee vs conversion and [S][R] vs conversion plots

Kinetic resolution of scalemic alkyl mandelates

The solution of the appropriate racemic alkyl mandelate and enantiopure (R)-alkyl mandelate (total

amount of alkyl mandelate 02 mmol) and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions No

increase in the ee was observed over the reaction course

6

Scheme S1 Proposed reaction scheme of 1-phenylethanol oxidation mediated by dynamically racemic Mn catalysts

7

Treatment of the kinetic scheme

R + -cat P + -catk R

S + -cat P + -catk S

K

R + -cat -catmiddotR

K

S + -cat -catmiddotS

kR

R

R + -catmiddotR P + -catmiddotR

kR

S

S + -catmiddotR P + -catmiddotR

kS

R

R + -catmiddotS P + -catmiddotS

kS

S

S + -catmiddotS P + -catmiddotS

reaction mediated

by free catalyst

catalyst-substratecomplexation

reaction mediated by

substrate-complexed

catalyst

R + -cat P + -catk R

S + -cat P + -catk S

Keq-cat -cat fast enantiomerization

of free catalyst Keq = 1

Scheme S2 Model kinetic scheme of kinetic resolution with dynamically racemic catalyst P is

product cat is catalyst R and S stand for the enantiomers of the chiral substrate

In Scheme S2 formation of catalyst-substrate adducts [∆-CatmiddotS] and [Λ-CatmiddotR] has been

neglected assuming that stability constants for such adducts should be ltlt K DFT calculations

(Table S8 SI) provide qualitative support of this assumption

The overall rates of consumption of the (S)- and (R)-alcohol respectively are

]S][Scat[]S][Rcat[]S][cat[]S][cat[]S[

sdotminusΛminussdotminus∆minusminusΛminusminus∆minus= Λ∆S

SS

R kkkkdt

d (S1)

]R][Scat[]R][Rcat[]R][cat[]R][cat[]R[

sdotminusΛminussdotminus∆minusminusΛminusminusminus∆minus= Λ∆R

SR

Rkkkk

dt

d (S2)

8

Assuming that the enantiomerization equilibrium of the free catalyst is the fastest reaction in

Scheme S1 (ie [∆-Cat] = [Λ-Cat] = [X]) and taking into account the catalyst-substrate

complexation equilibria and the mass balance for catalyst Cat0 = [∆-Cat] + [Λ-Cat] + [∆-

CatmiddotR] + [Λ-CatmiddotS] one can calculate the concentrations of all forms of the catalyst

]S[]R[2

cat]cat[ 0

KK ++=

]S[]R[2

]S][cat[cat]Scat[ 0

KK

K

++minusΛ

=sdot ]S[]R[2

]R][cat[cat]Rcat[ 0

KK

K

++minus∆

=sdot (S3)

We notice the following self-evident relationships

]R][X[]R][X[]R][X[]R][cat[]R][cat[ kkkkk RRRR minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S4)

]S][X[]S][X[]S][X[]S][cat[]S][cat[ kkkkk RRSS minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S5)

which in combination with eq (S1) (S2) and (S3) leads to the following equation

]R][R[]R][S[]R[

]S][S[]S][R[]S[

]R[

]S[

RR

RS

SS

SR

KkKkk

KkKkk

d

d

++++

= (S6)

Taking into account that evidently kSR = kR

S and kSS = kR

R multiplying left and right parts

of (S6) by R0S0 (R0 and S0 are the initial concentrations of the (R)- and (S)-enantiomers)

substituting k

Kk SR

=k

Kk RS

= A and k

Kk SS

= k

Kk RR

= B and introducing dimensionless

concentrations s = [S]S0 and r = [R]R0 one obtains

2

0

000

20

0

00

rS

RBSsrASr

sBSsrS

RASs

dr

ds

++

++

= (S5)

R0S0 for each experiment is known (and equal to 0

0

0

0

1

1

ee

ee

S

R

+

minus= where ee0 is expressed as a

decimal fraction) In effect this equation can be solved numerically to yield s = F(A B r)

Parameters A and B can be revealed by fitting the ee vs conversion or better er vs conversion

9

dependencies to the experimental points For this purpose the following obvious relationships have

been used

minus

+==

0

0

1

1

][

][

ee

ee

r

s

R

Ser

2

)1()1(2])[]([ 00

00

00 eeseer

RS

RSRSconversion

+minusminusminus=

+

+minus+=

+

minus+

+

minusminus

=+minus

=

0

0

0

0

1

1

1

1

][][

][][

ee

eers

ee

eers

RS

RSee

Figure S1 Enantiomeric excess (ee) vs conversion (A) plot and [S][R] ratio (er) vs conversion

plot (B) for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

Dots represent experimental data solid lines are theoretical fits with averaged parameters A = 345

M-1 B = 129 M-1 Curves are numbered in accordance with the numbers of entries in Table 1

0 10 20 30 40 50 60 70 80 90 100

10

15

20

25

30

35

40

45

50

55

1

2

3

conversion

ee

0 10 20 30 40 50 60 70 80 90 100 10

12

14

16

18

20

22

24

26

28

30

conversion

er

1

2

3

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

5

phenylethanol gt990 ee SigmaAldrich) The resulting mixture with total amount of 1-

phenylethanol of 018hellip023 mmol and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL or 08 or 02 mL in the case of experiments presented in Figure 2 red and green curves

respectively) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions The

results were presented in the form of ee vs conversion and [S][R] vs conversion plots

Kinetic resolution of scalemic alkyl mandelates

The solution of the appropriate racemic alkyl mandelate and enantiopure (R)-alkyl mandelate (total

amount of alkyl mandelate 02 mmol) and of appropriate manganese complex (02 micromol) in CH3CN

(040 mL) was prepared and analyzed by chiral HPLC (twice) to obtain the initial enantiomeric

imbalance (ee0) The mixture was thermostated at -10 degC and 30 aqueous H2O2 was added in

appropriate portions (typically 2-5 microL every 05 h At the end of each 05 h period 25 microL aliquot

was taken dissolved in 025 mL of i-propanol and analyzed by chiral HPLC to obtain the relative

concentrations of the alcohol and the ketone and the alcohol ee at several different conversions No

increase in the ee was observed over the reaction course

6

Scheme S1 Proposed reaction scheme of 1-phenylethanol oxidation mediated by dynamically racemic Mn catalysts

7

Treatment of the kinetic scheme

R + -cat P + -catk R

S + -cat P + -catk S

K

R + -cat -catmiddotR

K

S + -cat -catmiddotS

kR

R

R + -catmiddotR P + -catmiddotR

kR

S

S + -catmiddotR P + -catmiddotR

kS

R

R + -catmiddotS P + -catmiddotS

kS

S

S + -catmiddotS P + -catmiddotS

reaction mediated

by free catalyst

catalyst-substratecomplexation

reaction mediated by

substrate-complexed

catalyst

R + -cat P + -catk R

S + -cat P + -catk S

Keq-cat -cat fast enantiomerization

of free catalyst Keq = 1

Scheme S2 Model kinetic scheme of kinetic resolution with dynamically racemic catalyst P is

product cat is catalyst R and S stand for the enantiomers of the chiral substrate

In Scheme S2 formation of catalyst-substrate adducts [∆-CatmiddotS] and [Λ-CatmiddotR] has been

neglected assuming that stability constants for such adducts should be ltlt K DFT calculations

(Table S8 SI) provide qualitative support of this assumption

The overall rates of consumption of the (S)- and (R)-alcohol respectively are

]S][Scat[]S][Rcat[]S][cat[]S][cat[]S[

sdotminusΛminussdotminus∆minusminusΛminusminus∆minus= Λ∆S

SS

R kkkkdt

d (S1)

]R][Scat[]R][Rcat[]R][cat[]R][cat[]R[

sdotminusΛminussdotminus∆minusminusΛminusminusminus∆minus= Λ∆R

SR

Rkkkk

dt

d (S2)

8

Assuming that the enantiomerization equilibrium of the free catalyst is the fastest reaction in

Scheme S1 (ie [∆-Cat] = [Λ-Cat] = [X]) and taking into account the catalyst-substrate

complexation equilibria and the mass balance for catalyst Cat0 = [∆-Cat] + [Λ-Cat] + [∆-

CatmiddotR] + [Λ-CatmiddotS] one can calculate the concentrations of all forms of the catalyst

]S[]R[2

cat]cat[ 0

KK ++=

]S[]R[2

]S][cat[cat]Scat[ 0

KK

K

++minusΛ

=sdot ]S[]R[2

]R][cat[cat]Rcat[ 0

KK

K

++minus∆

=sdot (S3)

We notice the following self-evident relationships

]R][X[]R][X[]R][X[]R][cat[]R][cat[ kkkkk RRRR minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S4)

]S][X[]S][X[]S][X[]S][cat[]S][cat[ kkkkk RRSS minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S5)

which in combination with eq (S1) (S2) and (S3) leads to the following equation

]R][R[]R][S[]R[

]S][S[]S][R[]S[

]R[

]S[

RR

RS

SS

SR

KkKkk

KkKkk

d

d

++++

= (S6)

Taking into account that evidently kSR = kR

S and kSS = kR

R multiplying left and right parts

of (S6) by R0S0 (R0 and S0 are the initial concentrations of the (R)- and (S)-enantiomers)

substituting k

Kk SR

=k

Kk RS

= A and k

Kk SS

= k

Kk RR

= B and introducing dimensionless

concentrations s = [S]S0 and r = [R]R0 one obtains

2

0

000

20

0

00

rS

RBSsrASr

sBSsrS

RASs

dr

ds

++

++

= (S5)

R0S0 for each experiment is known (and equal to 0

0

0

0

1

1

ee

ee

S

R

+

minus= where ee0 is expressed as a

decimal fraction) In effect this equation can be solved numerically to yield s = F(A B r)

Parameters A and B can be revealed by fitting the ee vs conversion or better er vs conversion

9

dependencies to the experimental points For this purpose the following obvious relationships have

been used

minus

+==

0

0

1

1

][

][

ee

ee

r

s

R

Ser

2

)1()1(2])[]([ 00

00

00 eeseer

RS

RSRSconversion

+minusminusminus=

+

+minus+=

+

minus+

+

minusminus

=+minus

=

0

0

0

0

1

1

1

1

][][

][][

ee

eers

ee

eers

RS

RSee

Figure S1 Enantiomeric excess (ee) vs conversion (A) plot and [S][R] ratio (er) vs conversion

plot (B) for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

Dots represent experimental data solid lines are theoretical fits with averaged parameters A = 345

M-1 B = 129 M-1 Curves are numbered in accordance with the numbers of entries in Table 1

0 10 20 30 40 50 60 70 80 90 100

10

15

20

25

30

35

40

45

50

55

1

2

3

conversion

ee

0 10 20 30 40 50 60 70 80 90 100 10

12

14

16

18

20

22

24

26

28

30

conversion

er

1

2

3

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

6

Scheme S1 Proposed reaction scheme of 1-phenylethanol oxidation mediated by dynamically racemic Mn catalysts

7

Treatment of the kinetic scheme

R + -cat P + -catk R

S + -cat P + -catk S

K

R + -cat -catmiddotR

K

S + -cat -catmiddotS

kR

R

R + -catmiddotR P + -catmiddotR

kR

S

S + -catmiddotR P + -catmiddotR

kS

R

R + -catmiddotS P + -catmiddotS

kS

S

S + -catmiddotS P + -catmiddotS

reaction mediated

by free catalyst

catalyst-substratecomplexation

reaction mediated by

substrate-complexed

catalyst

R + -cat P + -catk R

S + -cat P + -catk S

Keq-cat -cat fast enantiomerization

of free catalyst Keq = 1

Scheme S2 Model kinetic scheme of kinetic resolution with dynamically racemic catalyst P is

product cat is catalyst R and S stand for the enantiomers of the chiral substrate

In Scheme S2 formation of catalyst-substrate adducts [∆-CatmiddotS] and [Λ-CatmiddotR] has been

neglected assuming that stability constants for such adducts should be ltlt K DFT calculations

(Table S8 SI) provide qualitative support of this assumption

The overall rates of consumption of the (S)- and (R)-alcohol respectively are

]S][Scat[]S][Rcat[]S][cat[]S][cat[]S[

sdotminusΛminussdotminus∆minusminusΛminusminus∆minus= Λ∆S

SS

R kkkkdt

d (S1)

]R][Scat[]R][Rcat[]R][cat[]R][cat[]R[

sdotminusΛminussdotminus∆minusminusΛminusminusminus∆minus= Λ∆R

SR

Rkkkk

dt

d (S2)

8

Assuming that the enantiomerization equilibrium of the free catalyst is the fastest reaction in

Scheme S1 (ie [∆-Cat] = [Λ-Cat] = [X]) and taking into account the catalyst-substrate

complexation equilibria and the mass balance for catalyst Cat0 = [∆-Cat] + [Λ-Cat] + [∆-

CatmiddotR] + [Λ-CatmiddotS] one can calculate the concentrations of all forms of the catalyst

]S[]R[2

cat]cat[ 0

KK ++=

]S[]R[2

]S][cat[cat]Scat[ 0

KK

K

++minusΛ

=sdot ]S[]R[2

]R][cat[cat]Rcat[ 0

KK

K

++minus∆

=sdot (S3)

We notice the following self-evident relationships

]R][X[]R][X[]R][X[]R][cat[]R][cat[ kkkkk RRRR minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S4)

]S][X[]S][X[]S][X[]S][cat[]S][cat[ kkkkk RRSS minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S5)

which in combination with eq (S1) (S2) and (S3) leads to the following equation

]R][R[]R][S[]R[

]S][S[]S][R[]S[

]R[

]S[

RR

RS

SS

SR

KkKkk

KkKkk

d

d

++++

= (S6)

Taking into account that evidently kSR = kR

S and kSS = kR

R multiplying left and right parts

of (S6) by R0S0 (R0 and S0 are the initial concentrations of the (R)- and (S)-enantiomers)

substituting k

Kk SR

=k

Kk RS

= A and k

Kk SS

= k

Kk RR

= B and introducing dimensionless

concentrations s = [S]S0 and r = [R]R0 one obtains

2

0

000

20

0

00

rS

RBSsrASr

sBSsrS

RASs

dr

ds

++

++

= (S5)

R0S0 for each experiment is known (and equal to 0

0

0

0

1

1

ee

ee

S

R

+

minus= where ee0 is expressed as a

decimal fraction) In effect this equation can be solved numerically to yield s = F(A B r)

Parameters A and B can be revealed by fitting the ee vs conversion or better er vs conversion

9

dependencies to the experimental points For this purpose the following obvious relationships have

been used

minus

+==

0

0

1

1

][

][

ee

ee

r

s

R

Ser

2

)1()1(2])[]([ 00

00

00 eeseer

RS

RSRSconversion

+minusminusminus=

+

+minus+=

+

minus+

+

minusminus

=+minus

=

0

0

0

0

1

1

1

1

][][

][][

ee

eers

ee

eers

RS

RSee

Figure S1 Enantiomeric excess (ee) vs conversion (A) plot and [S][R] ratio (er) vs conversion

plot (B) for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

Dots represent experimental data solid lines are theoretical fits with averaged parameters A = 345

M-1 B = 129 M-1 Curves are numbered in accordance with the numbers of entries in Table 1

0 10 20 30 40 50 60 70 80 90 100

10

15

20

25

30

35

40

45

50

55

1

2

3

conversion

ee

0 10 20 30 40 50 60 70 80 90 100 10

12

14

16

18

20

22

24

26

28

30

conversion

er

1

2

3

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

7

Treatment of the kinetic scheme

R + -cat P + -catk R

S + -cat P + -catk S

K

R + -cat -catmiddotR

K

S + -cat -catmiddotS

kR

R

R + -catmiddotR P + -catmiddotR

kR

S

S + -catmiddotR P + -catmiddotR

kS

R

R + -catmiddotS P + -catmiddotS

kS

S

S + -catmiddotS P + -catmiddotS

reaction mediated

by free catalyst

catalyst-substratecomplexation

reaction mediated by

substrate-complexed

catalyst

R + -cat P + -catk R

S + -cat P + -catk S

Keq-cat -cat fast enantiomerization

of free catalyst Keq = 1

Scheme S2 Model kinetic scheme of kinetic resolution with dynamically racemic catalyst P is

product cat is catalyst R and S stand for the enantiomers of the chiral substrate

In Scheme S2 formation of catalyst-substrate adducts [∆-CatmiddotS] and [Λ-CatmiddotR] has been

neglected assuming that stability constants for such adducts should be ltlt K DFT calculations

(Table S8 SI) provide qualitative support of this assumption

The overall rates of consumption of the (S)- and (R)-alcohol respectively are

]S][Scat[]S][Rcat[]S][cat[]S][cat[]S[

sdotminusΛminussdotminus∆minusminusΛminusminus∆minus= Λ∆S

SS

R kkkkdt

d (S1)

]R][Scat[]R][Rcat[]R][cat[]R][cat[]R[

sdotminusΛminussdotminus∆minusminusΛminusminusminus∆minus= Λ∆R

SR

Rkkkk

dt

d (S2)

8

Assuming that the enantiomerization equilibrium of the free catalyst is the fastest reaction in

Scheme S1 (ie [∆-Cat] = [Λ-Cat] = [X]) and taking into account the catalyst-substrate

complexation equilibria and the mass balance for catalyst Cat0 = [∆-Cat] + [Λ-Cat] + [∆-

CatmiddotR] + [Λ-CatmiddotS] one can calculate the concentrations of all forms of the catalyst

]S[]R[2

cat]cat[ 0

KK ++=

]S[]R[2

]S][cat[cat]Scat[ 0

KK

K

++minusΛ

=sdot ]S[]R[2

]R][cat[cat]Rcat[ 0

KK

K

++minus∆

=sdot (S3)

We notice the following self-evident relationships

]R][X[]R][X[]R][X[]R][cat[]R][cat[ kkkkk RRRR minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S4)

]S][X[]S][X[]S][X[]S][cat[]S][cat[ kkkkk RRSS minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S5)

which in combination with eq (S1) (S2) and (S3) leads to the following equation

]R][R[]R][S[]R[

]S][S[]S][R[]S[

]R[

]S[

RR

RS

SS

SR

KkKkk

KkKkk

d

d

++++

= (S6)

Taking into account that evidently kSR = kR

S and kSS = kR

R multiplying left and right parts

of (S6) by R0S0 (R0 and S0 are the initial concentrations of the (R)- and (S)-enantiomers)

substituting k

Kk SR

=k

Kk RS

= A and k

Kk SS

= k

Kk RR

= B and introducing dimensionless

concentrations s = [S]S0 and r = [R]R0 one obtains

2

0

000

20

0

00

rS

RBSsrASr

sBSsrS

RASs

dr

ds

++

++

= (S5)

R0S0 for each experiment is known (and equal to 0

0

0

0

1

1

ee

ee

S

R

+

minus= where ee0 is expressed as a

decimal fraction) In effect this equation can be solved numerically to yield s = F(A B r)

Parameters A and B can be revealed by fitting the ee vs conversion or better er vs conversion

9

dependencies to the experimental points For this purpose the following obvious relationships have

been used

minus

+==

0

0

1

1

][

][

ee

ee

r

s

R

Ser

2

)1()1(2])[]([ 00

00

00 eeseer

RS

RSRSconversion

+minusminusminus=

+

+minus+=

+

minus+

+

minusminus

=+minus

=

0

0

0

0

1

1

1

1

][][

][][

ee

eers

ee

eers

RS

RSee

Figure S1 Enantiomeric excess (ee) vs conversion (A) plot and [S][R] ratio (er) vs conversion

plot (B) for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

Dots represent experimental data solid lines are theoretical fits with averaged parameters A = 345

M-1 B = 129 M-1 Curves are numbered in accordance with the numbers of entries in Table 1

0 10 20 30 40 50 60 70 80 90 100

10

15

20

25

30

35

40

45

50

55

1

2

3

conversion

ee

0 10 20 30 40 50 60 70 80 90 100 10

12

14

16

18

20

22

24

26

28

30

conversion

er

1

2

3

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

8

Assuming that the enantiomerization equilibrium of the free catalyst is the fastest reaction in

Scheme S1 (ie [∆-Cat] = [Λ-Cat] = [X]) and taking into account the catalyst-substrate

complexation equilibria and the mass balance for catalyst Cat0 = [∆-Cat] + [Λ-Cat] + [∆-

CatmiddotR] + [Λ-CatmiddotS] one can calculate the concentrations of all forms of the catalyst

]S[]R[2

cat]cat[ 0

KK ++=

]S[]R[2

]S][cat[cat]Scat[ 0

KK

K

++minusΛ

=sdot ]S[]R[2

]R][cat[cat]Rcat[ 0

KK

K

++minus∆

=sdot (S3)

We notice the following self-evident relationships

]R][X[]R][X[]R][X[]R][cat[]R][cat[ kkkkk RRRR minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S4)

]S][X[]S][X[]S][X[]S][cat[]S][cat[ kkkkk RRSS minus=minusminus=minusΛminusminus∆minus Λ∆Λ∆ (S5)

which in combination with eq (S1) (S2) and (S3) leads to the following equation

]R][R[]R][S[]R[

]S][S[]S][R[]S[

]R[

]S[

RR

RS

SS

SR

KkKkk

KkKkk

d

d

++++

= (S6)

Taking into account that evidently kSR = kR

S and kSS = kR

R multiplying left and right parts

of (S6) by R0S0 (R0 and S0 are the initial concentrations of the (R)- and (S)-enantiomers)

substituting k

Kk SR

=k

Kk RS

= A and k

Kk SS

= k

Kk RR

= B and introducing dimensionless

concentrations s = [S]S0 and r = [R]R0 one obtains

2

0

000

20

0

00

rS

RBSsrASr

sBSsrS

RASs

dr

ds

++

++

= (S5)

R0S0 for each experiment is known (and equal to 0

0

0

0

1

1

ee

ee

S

R

+

minus= where ee0 is expressed as a

decimal fraction) In effect this equation can be solved numerically to yield s = F(A B r)

Parameters A and B can be revealed by fitting the ee vs conversion or better er vs conversion

9

dependencies to the experimental points For this purpose the following obvious relationships have

been used

minus

+==

0

0

1

1

][

][

ee

ee

r

s

R

Ser

2

)1()1(2])[]([ 00

00

00 eeseer

RS

RSRSconversion

+minusminusminus=

+

+minus+=

+

minus+

+

minusminus

=+minus

=

0

0

0

0

1

1

1

1

][][

][][

ee

eers

ee

eers

RS

RSee

Figure S1 Enantiomeric excess (ee) vs conversion (A) plot and [S][R] ratio (er) vs conversion

plot (B) for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

Dots represent experimental data solid lines are theoretical fits with averaged parameters A = 345

M-1 B = 129 M-1 Curves are numbered in accordance with the numbers of entries in Table 1

0 10 20 30 40 50 60 70 80 90 100

10

15

20

25

30

35

40

45

50

55

1

2

3

conversion

ee

0 10 20 30 40 50 60 70 80 90 100 10

12

14

16

18

20

22

24

26

28

30

conversion

er

1

2

3

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

9

dependencies to the experimental points For this purpose the following obvious relationships have

been used

minus

+==

0

0

1

1

][

][

ee

ee

r

s

R

Ser

2

)1()1(2])[]([ 00

00

00 eeseer

RS

RSRSconversion

+minusminusminus=

+

+minus+=

+

minus+

+

minusminus

=+minus

=

0

0

0

0

1

1

1

1

][][

][][

ee

eers

ee

eers

RS

RSee

Figure S1 Enantiomeric excess (ee) vs conversion (A) plot and [S][R] ratio (er) vs conversion

plot (B) for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

Dots represent experimental data solid lines are theoretical fits with averaged parameters A = 345

M-1 B = 129 M-1 Curves are numbered in accordance with the numbers of entries in Table 1

0 10 20 30 40 50 60 70 80 90 100

10

15

20

25

30

35

40

45

50

55

1

2

3

conversion

ee

0 10 20 30 40 50 60 70 80 90 100 10

12

14

16

18

20

22

24

26

28

30

conversion

er

1

2

3

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

10

Effect of concentration on the nonlinear ee growth

Table S1 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate initial ee ()b

S0 M catalyst сonversion ()b

final ee ()b

A M-1 B M-1

1 1-Ph-ethanol 225 015 1 980 460 330 139

2 1-Ph-ethanol 233 025 1 973 484 330 135

3 1-Ph-ethanol 245 053 1 965 517 330 148

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC (see above)

Figure S2 Enantiomeric excess (A) and enantiomeric ratio (B) vs conversion plots for the kinetic

resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1 at different initial

substrate concentrations Dots represent experimental data solid lines are theoretical curves Red S0

= 053 M-1 ee0 = 245 blue S0 = 025 M ee0 = 233 green S0 = 015 M ee0 = 225

0 10 20 30 40 50 60 70 80 90 100 20

25

35

40

45

50

55

60

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

ee

A B

er

conversion conversion

30

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

11

Effect of temperature on the nonlinear ee growth

Table S2 Kinetic resolution of scalemic 1-phenylethanol in the presence of Mn complexes at

different initial concentrations of the substrate a

Modeling results No substrate T K initial ee ()b

S0 M catalyst

A M-1 B M-1

1 1-Ph-ethanol 250 149 029 1 298 116

2 1-Ph-ethanol 263 157 029 1 345 c 129 c

3 1-Ph-ethanol 275 142 031 1 319 115

a Reaction conditions as reported in page 4 of the SI b Determined by chiral HPLC as reported (refs

2ab) a Average A and B values (A = 345plusmn05 M-1 B = 129plusmn08 M-1 see main text)

The corresponding ee vs conversion and er vs conversion curves are presented in Figure S2

Figure S3 Enantiomeric excess (ee) vs conversion (A) and enantiomeric ratio (er) vs conversion

(B) plots for the kinetic resolution of scalemic 1-phenylethanol in the presence of achiral catalyst 1

at different temperatures Dots represent experimental data solid lines are theoretical fits Blue T =

250 K S0 = 027 M-1 ee0 = 0149 Red T = 263 K S0 = 029 M-1 ee0 = 0157 Wine T = 275 K S0

= 027 M-1 ee0 = 0142

0 10 20 30 40 50 60 70 80 90 100

15

20

25

30

35

40

45

50

conversion

ee

0 10 20 30 40 50 60 70 80 90 100

14

16

18

20

22

24

26

28

30

conversion

er

CH3CN

H2O2

-10 degC

Mn cat (01 mol )

HO OHO

+

small ee larger ee

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

12

Figure S4 Enantiomeric excess (ee) vs conversion plots for the kinetic resolution of

ndash (S)-1-phenylethanol in the presence of achiral catalyst 1 (wine ee0 = 157 entry 3 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 2 (blue ee0 = 194 entry 6 of Table 1)

ndash (S)-1-phenylethanol in the presence of achiral catalyst 3 (orange ee0 = 128 entry 7 of Table 1)

ndash (R)-methyl mandelate in the presence of achiral catalyst 1 (red ee0 = 174 entry 8 of Table 1)

Table S3 Optical rotation values of complexes 1 2 3 4 (values averaged over 7 measurements for

each complex)

Complex C Solvent [α]D20 Comment

1 119 CH3CN +016 deg 2 142 CH3CN +014 deg 3 206 CH3CN +018 deg a fortiori achiral complex 4 154 CH3CN ndash6035 deg (SS)-enantiomer

In the cases of 1 2 3 the specific rotation values fell within the experimental uncertainty

(plusmn02 deg) cf -604 deg for the enantiomerically pure chiral complex 4 This clearly shows that chiral-at-

metal complexes 1 and 2 are not rotating like the achiral complex 3

0 10 20 30 40 50 60 70 80 90 100 10

15

20

25

30

35

40

45

50

conversion

ee

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

13

Figure S5 Theoretically predicted enantiomeric excess vs conversion plots for at different initial

ees ee0 = 10 (A) ee0 = 30 (B) ee0 = 50 (C) S0 = 030 M B = 10 M-1 AB = 1 (black) 2

(grey) 5 (navy) 10 (green) 25 (blue) 104 M-1 (red)

0 10 20 30 40 50 60 70 80 90 100

0 10 20 30 40 50 60 70 80 90 100 0

10

20

30

40

50

60

70

80

90

100 A

B

ee

ee

0

10

20

30

40

50

60

70

80

90

100

conversion

conversion

0 10 20 30 40 50 60 70 80 90 100

conversion

ee

0

10

20

30

40

50

60

70

80

90

100 C

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

14

Figure S6 Proposed model of through-competition chirality amplification in the absence of

exogenous sources of chirality ldquoR-rdquo and ldquoS-rdquo are enantiomeric substrates ldquoCatrdquo stands for catalyst

aacchhiirraall pprreebbiioottiicc ssoouupp

CCaatt CCaatt

SS--

RR--

SS--

SS-- RR-- RR-- RR--

RR-- RR-- RR--

SS--

SS--

SS--

SS-- SS--

SS--

SS--

+

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

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6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

15

X-ray crystallography

X-ray data for complex 1 and 3

Single-crystal diffraction data for 1 and 3 were collected at room temperature on a Bruker Kappa

Apex II CCD diffractometer using φ ω scans of narrow (05deg) frames with Mo Kα radiation (λ =

071073 Aring) and a graphite monochromator The structures were solved by direct methods and

refined by full-matrix least-squares method against all F2 in anisotropic (isotropic for H)

approximation using the SHELX-97 programs setS1 Absorption corrections were applied based on

intensities of equivalent reflections using SADABS programsS2 The hydrogen atoms positions were

calculated geometrically and refined in riding model exept the water hydrogens refined

independently with restriction of O-H bond length of 083 Aring Free solvent accessible volume for

compound 2 derived from PLATONS3S4 routine analysis was found to be 116 (4498 Aring3) This

volume is occupied by highly disordered solvent molecules that could not be modeled as a set of

discrete atomic sites We employed PLATONSQUEEZE procedure to calculate the contribution to

the diffraction from the solvent region and thereby produced a set of solvent-free diffraction

intensities The most probable solvents can be H2O andor acetonitryl Asymmetric unit of 5

contains two independent molecules

The crystallographic data and details of the structure refinements are summarized in Table

S4 Selected bond distances and angles are listed in Table S5 for 1 and Table S6 for 3

In contrast to previously reported bipyrrolidine- and 12-ethylenediamine derived

aminopyridine Mn triflates in 1 and 3 only one of the triflates is coordinated to Mn while the other

Mn cite is occupied by H2O molecule (Figure S7) In both complexes hydrogens of the Mn-

coordinated water molecules form О-НmiddotmiddotmiddotО hydrogen bonds with the outer-sphere triflates forming

associates (supermolecules) consisting of two Mn complexes and two triflate molecules (Figure S8)

The hydrogen bond parameters are collected in Table S7

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

16

Figure S7 X-ray structures of complexes 1 and 3 in a ball-and-stick representation Hydrogen

atoms (and the second molecule for 3) are omitted for clarity

(A) (B)

Figure S8 The H-bonded supermolecules of 1 (A) and 3 (B) Each independent molecule of 3

forms the supermolecule independently (substantively)

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

17

Table S4 Crystal data and structure refinement for 1 and 3

Identification code 1 3

Empirical formula [C23H30F9MnN4O6S]macr[CF3SO3]+ [C28H38F3MnN4O7S]macr[CF3SO3]

+

Formula weight 86558 83569

Crystal system Monoclinic Triclinic

Space group P21c P-1

a Aring 17329(4) 15800(2)

b Aring 14618(3) 16123(2)

c Aring 15853(3) 16406(2)

α 9000 109302(4)

β 104790(6) 100003(4)

γ 9000 105981(4)

V Aring3 3883(2) 36268(6)

Z 4 4

D(calcd) gcm3 1481 1531

Absorption coefficient mmminus1 0553 0568

F(000) 1756 1724

Crystal size mm 100 times 080 times 030 077 times 012 times 006

θ range for data collection deg 122ndash2525 137ndash3111

Index ranges minus20 le h le 20 minus15 le k le 17 minus18 le l le 18

minus22 le h le 22 minus23 le k le 23 minus23 le l le 23

Reflections collected independent

36553 6966 85834 23058

Rint 01214 00747

Tmin Tmax 04602 07452 07414 08018

Reflections with I gt 2σ(I) 3504 12510

Data restraints parameters 6966 32 479 23058 6 967

Goodness-of-fit on F2 1024 1001

Final R1 [I gt 2σ(I)] 01093 00557

wR2 (all data) 03234 01714

Largest diff peak hole eAring3 1119 minus0680 0908 minus0471

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

18

Table S5 Selected bond lengths and angles for 1

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2171(6) Mn(1) ndash O(2) 2167(6)

Mn(1) ndash N(1) 2241(7) Mn(1) ndash N(2) 2273(6)

Mn(1) ndashN(3) 2293(6) Mn(1) ndash N(4) 2223(6)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 979(2) O(2)ndashMn(1)ndashN(1) 907(2)

O(1)ndashMn(1)ndashN(1) 917(2) O(2)ndashMn(1)ndashN(2) 926(2)

O(1)ndashMn(1)ndashN(2) 1627(2) O(2)ndashMn(1)ndashN(3) 1636(2)

O(1)ndashMn(1)ndashN(3) 931(2) O(2)ndashMn(1)ndashN(4) 941(2)

O(1)ndashMn(1)ndashN(4) 942(2) N(1)ndashMn(1)ndashN(2) 743(2)

N(2)ndashMn(1)ndashN(3) 800(2) N(1)ndashMn(1)ndashN(3) 1012(2)

N(2)ndashMn(1)ndashN(4) 989(2) N(1)ndashMn(1)ndashN(4) 1718(2)

N(3)ndashMn(1)ndashN(4) 728(2)

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

19

Table S6 Selected bond lengths and angles for two independent molecules of 3

Bond d Aring Bond d Aring

Mn(1) ndash O(1) 2130(3) Mn(2) - O(3) 2116(3)

Mn(1) ndash O(2) 2152(2) Mn(2) - O(4) 2184(2)

Mn(1) ndash N(1) 2216(2) Mn(2) - N(5) 2199(2)

Mn(1) ndash N(2) 2305(2) Mn(2) - N(6) 2301(2)

Mn(1) ndash N(3) 2263(2) Mn(2) - N(7) 2239(2)

Mn(1) ndash N(4) 2252(2) Mn(2) - N(8) 2259(2)

Angle ω deg Angle ω deg

O(1)ndashMn(1)ndashO(2) 9443(10) O(3)ndashMn(2)ndashO(4) 9511(9)

O(1)ndashMn(1)ndashN(1) 10554(10) O(3)ndashMn(2)ndashN(5) 10344(10)

O(1)ndashMn(1)ndashN(2) 16097(8) O(3)ndashMn(2)ndashN(6) 16191(8)

O(1)ndashMn(1)ndashN(3) 10692(10) O(3)ndashMn(2)ndashN(7) 10965(10)

O(1)ndashMn(1)ndashN(4) 8619(9) O(3)ndashMn(2)ndashN(8) 8768(9)

O(2)ndashMn(1)ndashN(1) 8949(8) O(4)ndashMn(2)ndashN(5) 8657(8)

O(2)ndashMn(1)ndashN(2) 10453(9) O(4)ndashMn(2)ndashN(6) 10296(8)

O(2)ndashMn(1)ndashN(3) 8459(9) O(4)ndashMn(2)ndashN(7) 8369(8)

O(2)ndashMn(1)ndashN(4) 17879(9) O(4)ndashMn(2)ndashN(8) 17662(9)

N(1)ndashMn(1)ndashN(2) 7678(8) N(5)ndashMn(2)ndashN(6) 7703(8)

N(1)ndashMn(1)ndashN(3) 14735(9) N(5)ndashMn(2)ndashN(7) 14616(9)

N(1)ndashMn(1)ndashN(4) 8935(8) N(5)ndashMn(2)ndashN(8) 9093(8)

N(2)ndashMn(1)ndashN(3) 7376(8) N(6)ndashMn(2)ndashN(7) 7377(8)

N(2)ndashMn(1)ndashN(4) 7489(8) N(6)ndashMn(2)ndashN(8) 7423(8)

N(3)ndashMn(1)ndashN(4) 9623(8) N(7)ndashMn(2)ndashN(8) 9718(8)

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

20

Table S7 Parameters of H-bonds of 1 and 3

complex interaction O-H Aring H O Aring O O Aring O‒H O deg

O2‒H1W O3 082(6) 200(6) 2766(9) 155(6)

2 O2‒H2W O5 082(5) 201(8) 2650(14) 135(7)

O2‒H1W O19 082(3) 195(3) 2765(3) 168(4)

O2‒H2W O20 082(2) 195(2) 2768(3) 174(4)

O4‒H3W O16 084(3) 195(3) 2785(3) 172(3)

4

O4‒H4W O15 083(2) 194(2) 2766(3) 176(4)

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

21

DFT calculations computational methods

Calculations on cationic parts of complexes [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-phenylethanol)(CH3CN)] ([Λ-CatmiddotR]

and [Λ-CatmiddotS]) were performed with the hybrid B3-LYPS5S6 density functional theory scheme (DFT) using GAUSSIAN 09 program suite

with the LANL2DZ basis set with associated HayndashWadt nonrelativistic effective core potential for the Mn atomS7 and 6-311G(d)S8 basis set

for other atoms Calculations on 5[Λ-CatmiddotR] in CH3CN and

5[Λ-CatmiddotS] in CH3CN were also done with UB3LYP and PBE0S9 functionals

Geometry optimizations were carried out without symmetry restrictions Solvation effects (with CH3CN or H2O) were incorporated using

polarized continuum model (PCM) method as implemented in GAUSSIAN 09 The results are presented in Table S8 and Figure S9

Table S8 Selected solvation-corrected energies bond lengths and spin densities for Mn complexes

Bond lengths Aring Spin density Entry Complex E au

∆E kcalmol MnndashO MnndashN(equivCCH3) Mn O(R) N(equivCCH3) N4 (Ligand)

1 5[Λ-CatmiddotR] in CH3CN -185064742 2330 181 234 395 006 001 -004

2 5[Λ-CatmiddotS] in CH3CN -185064794 2003 181 234 396 005 001 -004

3 3[Λ-CatmiddotR] in CH3CN -185063793 8284 181 203 198 015 -002 -012

4 3[Λ-CatmiddotS] in CH3CN -185063834 8021 181 203 199 015 -002 -012

5 1[Λ-CatmiddotR] in CH3CN -185059556 34853 176 202 - - - -

6 1[Λ-CatmiddotS] in CH3CN -185059633 34368 176 202 - - - -

7 5[Λ-CatmiddotR] in H2O -185065065 0307 181 234 395 006 001 -004

8 5[Λ-CatmiddotS] in H2O -185065114 0 181 234 396 005 001 -004

9 5[Λ-CatmiddotR] in CH3CN -185064742 0325 181 234 395 006 001 -004

10 5[Λ-CatmiddotS] in CH3CN -185064794 0 181 234 396 005 001 -004

11 5[Λ-CatmiddotR] in CH3CN -184853429 0881 181 231 407 002 000 -008

12 5[Λ-CatmiddotS] in CH3CN -184853569 0 181 231 408 000 000 -008

Calculated at the UB3LYP level Calculated at the PBE0 level

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

22

The calculations provide qualitative evidence that the [Λ-CatmiddotS] structure is energetically

preferable with respect to [Λ-CatmiddotR] either in water or in acetonitrile solutions (cf Table S8 entry 7

vs 8 9 vs 10 and 11 vs 12) On the PBE0 calculations level the difference between [Λ-CatmiddotS] and

[Λ-CatmiddotR] is 0881 kcalmol which at -10 degC should corresponds to a [Λ-CatmiddotS][Λ-CatmiddotR]

equilibrium ratio of 54 as 1st approximation the existence of the less stable coordination

stereoisomer [Λ-CatmiddotR] could be neglected

Similarly [∆-CatmiddotR] should prevail over [∆-CatmiddotS] In both cases more preferable was the

quintet state (overall S = 2) which is archetypical of d4 Mn(III) ionsS10 In the 5[Λ-CatmiddotR] and 5[Λ-

CatmiddotS] structures long MnndashN(equivCCH3) and the opposite MnndashN(ligand) contacts (232 Aring) are indicative

of Jahn-Teller tetragonal elongation of the coordination octahedron typical for high-spin d4 metal

complexesS11

5[Λ-CatmiddotR] in CH3CN 5[Λ-CatmiddotR] in CH3CN

Figure S9 DFT optimized structures of [Λ-Cat((R)-1-phenylethanol)(CH3CN)] and [Λ-Cat((S)-1-

phenylethanol)(CH3CN)] in CH3CN at the B3-LYP level Hydrogen atoms are omitted for clarity

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

23

Additional references

S1 G M Sheldrick Acta Crystallogr Sect A 2008 64 112ndash122

S2 SADABS v 2008-1 Bruker AXS Madison WI USA 2008

S3 A L Spek PLATON A Multipurpose Crystallographic Tool version 10M Utrecht

University The Netherlands 2003

S4 A L Spek J Appl Crystallogr 2003 36 7ndash13

S5 A D Becke J Chem Phys 1993 98 5648-5652

S6 C Lee W Yang R G Parr Phys Rev B 1988 37 785-789

S7 W R Wadt P J Hay J Chem Phys 1985 82 284-98

S8 E R Davidson D Feller Chem Rev 1986 86 681-696

S9 C Adamo V Barone J Chem Phys 1999 110 6158-69

S10 D P Goldberg J Tesler J Krzystek A G Montalban L C Brunel A G M Barrett B

M Hoffman J Am Chem Soc 1997 119 8722-8723

S11 D F Shriver P W Atkins Inorganic Chemistry (3rd ed) Oxford University Press 1999

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

24

1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

25

13C1H NMR spectrum (CDCl3CCl4 25 degC) of N1N2-dimethyl-N1N2-bis((3-methyl-4-(222-trifluoroethoxy)pyridin-2-yl)methyl)ethane-12-diamine

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

26

HPLC traces

Table 1 Entry 2 Figure 2A green trace

Table 1 Entry 2 Figure 2A green trace 0th

point

Time min Area Assignment Amount()

11646 434950 OH

(R)- 14158 565050

(S)-

100 130 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

Notice Artifacts originating from the eluent ldquofrontrdquo are observed at 3-5 min they were not

integrated

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

27

Table 1 Entry 2 Figure 2A green trace 1st point

Time min Area Assignment Amount()

6385 46999

53

11723 414930 OH

(R)- 14206 538071

(S)-

947 129 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

28

Table 1 Entry 2 Figure 2A green trace 2nd

point

Time min Area Assignment Amount()

6412 118520

134

11810 381994 OH

(R)- 14295 499486

(S)-

864 133 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

29

Table 1 Entry 2 Figure 2A green trace 3rd

point

Time min Area Assignment Amount()

6407 195903

219

11779 346235 OH

(R)- 14257 457862

(S)-

781 139 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

30

Table 1 Entry 2 Figure 2A green trace 4th

point

Time min Area Assignment Amount()

6394 327645

359

11798 283928 OH

(R)- 14281 388427

(S)-

641 155 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

31

Table 1 Entry 2 Figure 2A green trace 5th

point

Time min Area Assignment Amount()

6392 445755

480

11802 228856 OH

(R)- 14284 325389

(S)-

520 174 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

32

Table 1 Entry 2 Figure 2A green trace 6th

point

Time min Area Assignment Amount()

6378 665987

696

11717 131040 OH

(R)- 14203 202974

(S)-

304 215 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

33

Table 1 Entry 2 Figure 2A green trace 7th

point

Time min Area Assignment Amount()

6409 788186

801

11846 78703 OH

(R)- 14323 133111

(S)-

199 263 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

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6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

34

Table 1 Entry 2 Figure 2A green trace 8th

point

Time min Area Assignment Amount()

9091 913051

923

16585 29377 OH

(R)- 20059 57573

(S)-

77 324 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 07 mLmin λ 206 nm 20 degC

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

35

Table 1 Entry 2 Figure 2A green trace 9th

point

Time min Area Assignment Amount()

6379 955771

961

11726 12699 OH

(R)- 14213 31531

(S)-

39 426 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

36

Table 1 Entry 2 Figure 2A green trace 10th

point

Time min Area Assignment Amount()

6370 968984

973

11805 08272 OH

(R)- 14296 22744

(S)-

27 467 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 10 mLmin λ 206 nm 20 degC

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

37

Table 1 Entry 8 Figure 3A violet trace

Table 1 Entry 8 Figure 3A violet trace 0th

point

Time min Area Assignment Amount()

10902 597651 OH

(R)- 13105 402349

(S)-

100 195 ee (R)-

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

38

Table 1 Entry 8 Figure 3A violet trace 1st point

Time min Area Assignment Amount()

5526 57076

65

10446 563872 OH

(R)- 12550 379252

(S)-

935 196 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

39

Table 1 Entry 8 Figure 3A violet trace 2nd

point

Time min Area Assignment Amount()

5492 154074

173

10413 508916 OH

(R)- 12508 337010

(S)-

827 203 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

40

Table 1 Entry 8 Figure 3A violet trace 3rd

point

Time min Area Assignment Amount()

5497 301823

332

10397 424358 OH

(R)- 12508 273819

(S)-

668 216 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

41

Table 1 Entry 8 Figure 3A violet trace 4th

point

Time min Area Assignment Amount()

5522 429384

463

10443 351582 OH

(R)- 12549 219034

(S)-

537 232 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

42

Table 1 Entry 8 Figure 3A violet trace 5th

point

Time min Area Assignment Amount()

5492 605203

637

10448 249198 OH

(R)- 12543 145599

(S)-

362 262 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

43

Table 1 Entry 8 Figure 3A violet trace 6th

point

Time min Area Assignment Amount()

5488 688730

717

10452 199986 OH

(R)- 12554 111284

(S)-

283 285 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

44

Table 1 Entry 8 Figure 3A violet trace 7th

point

Time min Area Assignment Amount()

5497 784575

808

10451 141193 OH

(R)- 12559 74232

(S)-

192 311 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

45

Table 1 Entry 8 Figure 3A violet trace 8th

point

Time min Area Assignment Amount()

5493 886603

899

10413 74848 OH

(R)- 12536 38549

(S)-

101 357 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

46

Table 1 Entry 8 Figure 3A violet trace 9th

point

Time min Area Assignment Amount()

5487 929584

938

10408 48557 OH

(R)- 12508 21858

(S)-

62 379 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

47

Table 1 Entry 8 Figure 3A violet trace 10th

point

Time min Area Assignment Amount()

5477 945997

952

10433 37891 OH

(R)- 12532 16112

(S)-

48 403 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

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1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

48

Table 1 Entry 8 Figure 3A violet trace 11th

point

Time min Area Assignment Amount()

5495 960228

965

10444 28344 OH

(R)- 12550 11429

(S)-

35 425 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

49

Table 1 Entry 8 Figure 3A violet trace 12th

point

Time min Area Assignment Amount()

5489 971751

975

10398 20524 OH

(R)- 12493 07725

(S)-

25 453 ee

Conditions Chiralcel OD-H i-PrOH hexane 397 115 mLmin λ 206 nm 20 degC

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

50

DFT optimized Cartesian coordinates

5[Λ-CatmiddotR] in CH3CN

7 021853 06153 217984

25 -013139 -039284 009932

7 -220495 -044218 01829

7 -060932 -167033 -177693

7 -002077 -235169 10338

7 19067 -074106 -008491

8 -632001 -050717 024462

8 589933 -163682 -050221

6 -288697 00941 121426

6 -426802 011342 127892

6 -495845 -046748 020088

6 -426912 -105856 -086788

6 -286822 -101078 -084095

6 -206686 -154039 -201276

6 -499246 070158 245751

6 -700567 056473 -043828

6 -501261 -172161 -199738

6 013557 -125742 -298816

6 -021923 -304289 -137194

6 -062498 -332673 006204

6 -076119 -247041 232508

6 14248 -266854 129981

6 239254 -186505 047365

6 373999 -222297 0365

6 458004 -133935 -033166

6 407526 -017061 -092705

6 27219 007711 -077369

6 427209 -350137 095821

6 677714 -127183 058428

6 495923 075723 -171348

8 -003902 116789 -081181

6 043593 437855 059942

6 137687 540843 065119

6 227322 558786 -040002

6 222008 473553 -150449

6 127572 371305 -155552

6 037306 352131 -0502

6 -067728 24222 -056702

6 -172316 268732 -165373

6 06392 122268 306259

1 -22905 051783 201216

1 -221462 -084643 -284425

1 -248032 -249614 -234921

1 -569393 -002014 288118

1 -429162 100088 323741

1 -557233 158281 217224

1 -677277 055842 -150511

1 -80668 037922 -029115

1 -673602 153157 -000873

1 -607324 -179179 -176769

1 -464564 -273497 -21758

1 -49017 -116694 -293366

1 -00741 -021045 -319703

1 -014373 -186764 -385425

1 120454 -136834 -281529

1 086166 -313118 -148744

1 -067098 -379339 -203124

1 -170699 -326321 017274

1 -033798 -434417 03417

1 -182049 -228998 216273

1 -063651 -3476 273607

1 -037888 -174305 303608

1 158572 -374135 117801

1 162262 -244929 235154

1 224543 094974 -120007

1 431808 -345214 20502

1 527348 -370689 058615

1 364225 -435473 069763

1 649476 -178507 150578

1 777261 -158471 027882

1 676173 -019196 074534

1 572882 120769 -10818

1 547499 022017 -251251

1 437738 15643 -215924

1 -025838 424546 142392

1 140922 60665 151356

1 300738 638593 -03619

1 291277 487101 -232893

1 123979 305994 -242132

1 -118407 238937 040417

1 -220144 365734 -149478

1 -249874 191877 -163986

1 -1259 269171 -264269

6 116396 19878 417503

1 04386 200209 498991

1 136415 301159 385518

1 209157 15357 452957

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

51

5[Λ-CatmiddotS] in CH3CN

25 040435 -028999 019183

7 243301 005722 -006331

7 104617 -230574 -03097

7 002008 -018692 -209387

7 -158747 -087941 010687

8 644483 062477 -077056

8 -552239 -20574 -01721

6 296351 129234 -002197

6 430929 153653 -023557

6 512203 042227 -050966

6 458225 -087126 -058458

6 321192 -100401 -033952

6 254992 -235446 -028835

6 486827 293201 -02025

6 733702 049188 035639

6 5443 -206112 -091863

6 053789 -336786 060814

6 050785 -258706 -168486

6 067317 -140889 -262582

6 057054 101577 -275904

6 -145335 -02077 -224808

6 -221421 -080383 -108233

6 -355385 -118812 -123013

6 -422927 -16351 -00851

6 -357423 -17284 115511

6 -224883 -133509 118907

6 -424683 -113196 -256659

6 -653467 -103716 -003251

6 -426817 -225776 237889

7 071408 -073114 247042

8 006965 146542 048113

6 105066 -071717 357115

6 146843 -070422 49583

6 -201231 270987 056956

1 -129672 132675 202793

1 -081508 359852 290975

6 -012698 311182 221393

6 -175139 35553 -051571

6 -27951 415131 -121961

1 225967 208748 01885

1 143591 -171634 536438

1 285353 -283934 064204

1 406935 367007 -012564

1 544744 314035 -110429

1 553786 307567 06495

1 729941 -052018 076518

1 833319 069761 -002767

1 708539 12131 11365

1 500779 -265276 -172748

1 556242 -272551 -005776

1 643162 -174069 -123963

1 -054863 -337971 059463

1 088067 -317369 162077

1 090377 -434574 028365

1 -054461 -284387 -157306

1 100696 -346878 -20965

1 027143 -167472 -361061

1 173052 -118281 -276819

1 165333 103232 -264955

1 01605 190503 -228611

1 032642 102494 -382717

1 -179125 08273 -234775

1 -172837 -070843 -318079

1 -168219 -138584 211019

1 -436902 -010204 -29139

1 -523094 -159069 -250715

1 -368016 -166845 -33313

1 -645229 -029554 -082964

1 -748825 -155413 -010692

1 -645642 -05435 093811

1 -472714 -322733 217512

1 -356693 -237359 320592

1 -506637 -158807 270873

6 -087227 208246 135711

6 -411914 391495 -084494

6 -334065 247936 093606

6 -438928 307937 023696

1 032528 388149 158398

1 066315 262491 278976

1 -25764 480321 -205931

1 -072503 374758 -080998

1 -541507 289025 053657

1 -493236 437995 -13925

1 -356085 182706 177618

1 248711 -032068 503363

1 080193 -006413 553834

1 290162 -300221 -109396

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

52

3[Λ-CatmiddotR] in CH3CN

7 024078 046828 180311

25 -013891 -041965 002331

7 -215798 -041655 019851

7 -053622 -148114 -173526

7 -004144 -236943 095896

7 187739 -074626 -01361

8 -627778 -055113 027045

8 590673 -156716 -04271

6 -284618 003975 126232

6 -422848 003423 133046

6 -491732 -04844 022087

6 -422436 -0991 -088885

6 -282707 -092143 -085564

6 -199531 -132909 -204176

6 -49564 053609 254642

6 -698976 053466 -036102

6 -495905 -158903 -205974

6 023427 -101986 -292448

6 -017475 -290741 -145415

6 -061558 -330355 -00634

6 -0803 -254424 222881

6 139975 -268012 123949

6 237173 -185551 043784

6 372993 -218849 037261

6 457552 -129069 -029456

6 406638 -012816 -089533

6 27028 009183 -078621

6 426321 -345729 098506

6 674522 -116511 067538

6 49543 082395 -164837

8 -008427 113625 -089018

6 03263 428598 072595

6 12679 53035 089101

6 22467 551193 -007815

6 227413 470175 -121468

6 132921 369153 -137822

6 034521 346843 -040708

6 -070751 238503 -059575

6 -168801 273516 -171992

6 056825 101327 276078

1 -225749 041964 208581

1 -209347 -054952 -280068

1 -237225 -224683 -24982

1 -563916 -022403 293188

1 -425605 080406 333812

1 -555698 141989 231737

1 -674793 059418 -142411

1 -804599 030937 -023542

1 -675401 148422 012366

1 -600947 -173481 -18175

1 -454555 -256155 -233575

1 -48997 -094742 -294387

1 005522 00416 -306824

1 -007694 -157967 -381066

1 12955 -118268 -275892

1 090623 -299637 -15548

1 -062402 -356677 -220167

1 -170075 -326164 002517

1 -031616 -433242 015429

1 -186117 -237205 205386

1 -067203 -356164 260783

1 -044459 -183901 297393

1 157299 -374998 11052

1 158172 -247409 229686

1 222837 096043 -122094

1 426353 -340985 207821

1 528315 -364161 065444

1 366177 -432302 069865

1 645667 -167906 159495

1 775788 -144887 039847

1 669346 -008486 082764

1 569662 128521 -099222

1 550372 030419 -243653

1 436963 1623 -210497

1 -043379 41316 148669

1 123632 592889 177744

1 298203 629978 004831

1 303068 486056 -197653

1 135647 307267 -226919

1 -12722 230182 033896

1 -217174 369537 -152208

1 -246563 197247 -180255

1 -116793 280468 -267831

6 097414 169808 396941

1 010045 191166 4587

1 146851 263551 370954

1 166844 107159 453162

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

53

3[Λ-CatmiddotS] in CH3CN

25 0394 -030516 011772

7 239435 005534 -009857

7 104039 -231991 -034461

7 005917 -013235 -193983

7 -154102 -091652 013751

8 643657 06477 -064763

8 -546794 -213355 -017662

6 292252 128902 -001697

6 427592 154065 -017241

6 5104 04362 -043357

6 457105 -085606 -054035

6 319142 -099587 -034644

6 254206 -235457 -031824

6 482435 293883 -009358

6 728841 050076 050668

6 544618 -20412 -085388

6 053994 -340761 054378

6 050914 -256398 -172446

6 068266 -133283 -258503

6 063189 109292 -256521

6 -14252 -009577 -213417

6 -219035 -078102 -103516

6 -352288 -117272 -120094

6 -41796 -169831 -007813

6 -350919 -18537 114697

6 -218704 -144571 119349

6 -4225 -104601 -252759

6 -649071 -113158 000935

6 -418617 -245929 234503

7 07456 -061562 208976

8 -000494 143815 035957

6 103316 -069718 319977

6 139302 -08021 459774

6 -203856 273229 058344

1 -131 127635 195756

1 -073568 349945 290884

6 -008666 302504 216804

6 -179617 363602 -045852

6 -285028 428091 -110125

1 221191 208154 017565

1 216846 -155979 472158

1 284505 -284773 060804

1 401817 367025 -002824

1 543128 316956 -097149

1 546505 307021 078237

1 724021 -051715 090004

1 829748 071417 01618

1 700859 120964 128876

1 503789 -263204 -167732

1 554469 -270938 000698

1 644228 -171469 -114452

1 -054585 -343621 052065

1 087217 -323325 156374

1 092336 -437314 020272

1 -054297 -282955 -163049

1 10161 -342047 -217786

1 025407 -149493 -357752

1 174037 -111307 -272472

1 171619 106448 -250394

1 026683 196352 -20294

1 033741 114825 -361681

1 -172596 095447 -213734

1 -167753 -049782 -311741

1 -161463 -15458 210531

1 -439518 876E-4 -279478

1 -518802 -155087 -250087

1 -363942 -149654 -333231

1 -641585 -035201 -075151

1 -743911 -165395 -009009

1 -641724 -068397 100249

1 -464014 -341906 20903

1 -347552 -261706 315695

1 -498603 -181613 272066

6 -088607 204512 130281

6 -416733 403512 -070863

6 -33604 249363 096837

6 -441958 314126 032996

1 035886 380967 155166

1 071486 250275 269554

1 -264493 497806 -190735

1 -077586 38375 -076762

1 -543972 294413 064355

1 -498873 453779 -120866

1 -356703 179599 177485

1 177249 015788 495169

1 051874 -108242 518703

1 29067 -298916 -112913

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

54

1[Λ-CatmiddotR] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

55

1[Λ-CatmiddotS] in CH3CN

25 03587 -026358 01448

7 236663 003712 -01099

7 099444 -232789 -023565

7 009693 -01658 -194267

7 -156298 -090481 014461

8 642603 053724 -066589

8 -546285 -218119 -02742

6 291667 126607 -011423

6 427369 148824 -027811

6 508885 03577 -045134

6 453739 -093029 -047199

6 315427 -103764 -027879

6 248819 -238077 -015789

6 484088 288115 -030035

6 726621 044738 050276

6 539829 -214604 -069531

6 045531 -339424 065101

6 05126 -259549 -162871

6 072449 -139307 -252279

6 066926 102754 -262375

6 -138454 -014243 -21536

6 -217216 -08097 -105566

6 -349355 -122484 -125713

6 -418426 -172674 -014437

6 -355553 -184073 110774

6 -224108 -14171 11897

6 -414916 -115222 -261182

6 -650421 -118718 -016412

6 -426811 -242179 229725

7 059716 -055307 212784

8 861E-4 145542 028649

6 085775 -065974 324298

6 117523 -079582 464918

6 -193279 284126 060112

1 -121553 135639 195968

1 -046487 354249 286949

6 011536 304204 209065

6 -16834 375823 -04275

6 -273251 444181 -10372

1 222397 208632 001151

1 129114 -185129 490086

1 27558 -279467 081725

1 404553 36271 -028531

1 544727 30402 -119446

1 54872 306536 056181

1 720321 -05454 095396

1 828059 062965 015561

1 698756 120304 124022

1 498849 -27867 -147972

1 54808 -275509 020994

1 640101 -185372 -099927

1 -062929 -341552 05897

1 074979 -320279 167975

1 084119 -437171 034656

1 -054482 -284962 -156629

1 102524 -346791 -204566

1 032438 -158986 -352172

1 178819 -118961 -263996

1 17536 100259 -256095

1 030405 19251 -213323

1 037792 103614 -367814

1 -169038 090652 -218091

1 -162453 -056267 -313255

1 -170105 -148506 212321

1 -431883 -011813 -292476

1 -510798 -166548 -260036

1 -353204 -162719 -337789

1 -641429 -043844 -095378

1 -744171 -172696 -027347

1 -647028 -069851 08117

1 -469861 -339535 20542

1 -358577 -254554 313886

1 -509062 -178072 262456

6 -07907 21056 128567

6 -404759 422113 -062444

6 -325273 262331 100441

6 -430503 331209 039962

1 055683 380626 144751

1 09213 248073 256794

1 -252427 514911 -183343

1 -06647 3939 -075353

1 -532411 313483 072771

1 -486463 475484 -109861

1 -346198 191338 179901

1 210555 -02705 487064

1 037121 -037082 52521

1 287103 -308717 -08987

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

56

5[Λ-CatmiddotR] in H2O

7 021993 063109 21687

25 -01248 -039353 009842

7 -219818 -045148 018371

7 -059803 -168785 -176752

7 -000582 -234367 104825

7 191478 -073484 -008442

8 -631303 -053333 024737

8 590956 -162193 -050041

6 -288187 009012 121121

6 -426295 010365 127645

6 -495122 -048908 020355

6 -426007 -108634 -08603

6 -285941 -103199 -083462

6 -205668 -156819 -200241

6 -498914 069796 245087

6 -700048 053488 -043941

6 -500049 -176281 -198385

6 014302 -12808 -298312

6 -019967 -305502 -135224

6 -060325 -333034 00839

6 -074762 -245595 233938

6 144102 -264989 131944

6 240493 -185226 048336

6 375323 -220726 037529

6 458921 -132724 -033043

6 408004 -016517 -0935

6 27262 007974 -078161

6 428955 -347918 097855

6 678721 -124244 058126

6 495992 075839 -173103

8 -003848 116205 -082337

6 035983 439426 057852

6 128383 543872 064183

6 220437 561917 -038818

6 219236 475306 -148312

6 126476 37159 -154589

6 033823 352299 -051355

6 -069543 240891 -059204

6 -17273 265806 -169596

6 064188 124768 304437

1 -22869 052271 200543

1 -220958 -088289 -284006

1 -246539 -252933 -232907

1 -568976 -002227 287847

1 -428916 100288 322931

1 -556996 157673 215987

1 -676994 052286 -150672

1 -806131 035014 -028887

1 -672986 150411 -001589

1 -606205 -182869 -175725

1 -463387 -277891 -214726

1 -488514 -12207 -292689

1 -007274 -023686 -320074

1 -01339 -189988 -384369

1 121283 -138435 -281068

1 08816 -313788 -146767

1 -064734 -381305 -200564

1 -168564 -327323 019422

1 -030909 -434347 037154

1 -18076 -228308 217371

1 -061769 -345743 27586

1 -037079 -172075 304518

1 160716 -372339 121222

1 163707 -241504 236814

1 224622 094711 -121469

1 433174 -342258 207029

1 529294 -368268 061079

1 366409 -433687 072144

1 650971 -174964 150754

1 778406 -155176 027654

1 676542 -01614 073352

1 573177 121355 -110553

1 547265 021667 -252894

1 437542 156196 -217966

1 -035311 42599 138674

1 128448 610694 149697

1 292578 642831 -034071

1 290431 48888 -229098

1 126093 305217 -24043

1 -121724 237239 037102

1 -222136 362171 -154662

1 -24925 187903 -169307

1 -124702 266686 -26772

6 116885 202452 414748

1 046984 20007 49848

1 131538 305861 383178

1 21255 160873 446775

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

57

5[Λ-CatmiddotS] in H2O

25 041265 -025909 018901

7 244321 006966 -00722

7 106097 -231011 -01271

7 004912 -036285 -209915

7 -157832 -085543 014293

8 64611 058645 -078432

8 -550566 -207227 -007552

6 297274 130478 -012947

6 432018 15316 -034983

6 513602 039968 -052197

6 459787 -089629 -049515

6 322536 -10099 -025143

6 256451 -235284 -009421

6 488044 292486 -042608

6 734751 050133 035187

6 546202 -210823 -072478

6 05493 -328567 088046

6 053381 -271509 -147461

6 070866 -162542 -251577

6 060433 078078 -285743

6 -142277 -040172 -226327

6 -219298 -088998 -105421

6 -353022 -128989 -117996

6 -421657 -163339 -000618

6 -357569 -160589 124461

6 -225104 -120798 125566

6 -421002 -135314 -252271

6 -65281 -105821 002618

6 -428022 -2019 250679

7 070733 -048623 249703

8 006485 151491 030702

6 105658 -038422 358914

6 14909 -025981 496552

6 -205093 270576 04132

1 -117572 152692 196249

1 -071475 390089 25257

6 -006312 335255 184071

6 -190849 338272 -080395

6 -302398 387143 -148035

1 2267 211403 000717

1 159807 -124997 541097

1 286546 -276189 087256

1 408363 366811 -038656

1 544193 3068 -135167

1 556732 312643 039993

1 731138 -049285 08019

1 834514 069462 -003492

1 70887 125287 110038

1 502196 -277629 -146863

1 559515 -268781 019356

1 644498 -181497 -108671

1 -053695 -330541 085905

1 088201 -299661 187365

1 092299 -42875 06518

1 -051968 -296139 -135019

1 103727 -362939 -180086

1 031685 -197844 -347699

1 17677 -141276 -266713

1 168641 08052 -274346

1 019365 170578 -245912

1 036618 070433 -392421

1 -176317 061818 -246256

1 -168843 -098812 -314743

1 -169357 -117318 218305

1 -430749 -036028 -297075

1 -520415 -17834 -242849

1 -36472 -197337 -322472

1 -644923 -034504 -079711

1 -747651 -158668 -003295

1 -645889 -052946 097865

1 -478805 -297583 2372

1 -357619 -211335 333414

1 -503993 -128911 279847

6 -083216 220604 117363

6 -430157 369553 -09456

6 -333397 253393 093931

6 -445355 302791 02681

1 03113 40514 108883

1 078492 296092 240683

1 -289703 439262 -242384

1 -091855 352845 -122281

1 -544255 288581 069171

1 -517046 407729 -147165

1 -346176 201209 18833

1 245155 025611 500407

1 075541 031104 55343

1 291952 -306224 -08443

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

58

5[Λ-CatmiddotR] in CH3CN

7 021851 061515 217957

25 -013127 -039281 009904

7 -220492 -044198 018281

7 -060946 -167015 -177712

7 -002085 -23517 103356

7 190685 -074116 -008488

8 -631998 -050743 024518

8 589942 -163729 -050191

6 -288685 009404 121439

6 -426789 011317 127925

6 -49584 -046765 02012

6 -426919 -105852 -08677

6 -286828 -101058 -084098

6 -206698 -153998 -201291

6 -499224 07011 245799

6 -700581 05643 -043783

6 -501276 -172157 -199715

6 013543 -125726 -298837

6 -021949 -304276 -137221

6 -062517 -332662 006177

6 -076127 -247038 232486

6 142465 -26687 129964

6 239252 -186526 047361

6 373996 -22233 036503

6 458015 -133969 -033147

6 407553 -017083 -092678

6 272218 007698 -07735

6 427185 -350181 095818

6 677716 -127225 058461

6 495963 075696 -171311

8 -003876 116805 -081184

6 043556 437927 059905

6 137637 540928 065074

6 227314 55883 -040019

6 222054 473545 -150429

6 127631 371284 -155524

6 037326 352149 -050198

6 -067703 242236 -056697

6 -172294 268747 -165364

6 063889 122291 306221

1 -229031 051772 201225

1 -221463 -084583 -284426

1 -248052 -249563 -234959

1 -569329 -002088 288191

1 -429131 100073 32377

1 -557257 158207 217282

1 -677307 055785 -150469

1 -80669 03787 -029051

1 -673618 153121 -000845

1 -607331 -17921 -176722

1 -464555 -273479 -217589

1 -490227 -116666 -293335

1 -007408 -021023 -319711

1 -0144 -186735 -385449

1 12044 -136837 -281556

1 08614 -313115 -148779

1 -067136 -379319 -203154

1 -170718 -326303 017251

1 -033823 -43441 034138

1 -182057 -229004 216251

1 -063652 -347592 27359

1 -037899 -174292 30358

1 158549 -374152 117781

1 162242 -244949 23514

1 224583 094969 -119986

1 431732 -345286 20502

1 527341 -370722 058653

1 364214 -435512 069706

1 649453 -178519 150619

1 777261 -158543 027939

1 676199 -019233 074541

1 572922 120736 -108138

1 54754 021989 -251214

1 437787 156408 -215889

1 -025909 424648 142332

1 140829 606776 151279

1 300722 638645 -036212

1 291358 48706 -23285

1 124074 305935 -242075

1 -118379 238946 040424

1 -220129 365747 -149461

1 -249848 191887 -163981

1 -12588 269197 -264259

6 116319 198857 417449

1 043961 199902 4991

1 135881 301352 385557

1 20933 15395 452638

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

59

5[Λ-CatmiddotS] in CH3CN

25 04043 -029025 019191

7 243296 005716 -006327

7 104638 -230598 -030958

7 002021 -018725 -209379

7 -158758 -087945 010696

8 644467 062523 -077076

8 -552258 -205707 -01722

6 296329 129235 -002209

6 430902 153672 -02358

6 51219 042254 -050981

6 45823 -087108 -058459

6 321199 -100399 -033946

6 255014 -235452 -028831

6 48678 293227 -020293

6 733689 04926 035621

6 544318 -206085 -091861

6 053827 -336817 060828

6 050801 -258743 -168469

6 067315 -140931 -262576

6 05708 101535 -275902

6 -145324 -020783 -224799

6 -221423 -080387 -108228

6 -35539 -118801 -123014

6 -422943 -163486 -008512

6 -357449 -172817 115513

6 -224904 -133498 118914

6 -424679 -113186 -256664

6 -653478 -103672 -00327

6 -426852 -225743 237889

7 0714 -073135 247044

8 006962 146515 048117

6 105055 -071753 357119

6 146838 -070488 495831

6 -20122 270989 056959

1 -129684 132661 20279

1 -08149 359821 290991

6 -012685 311146 221406

6 -175113 355535 -051563

6 -279474 415154 -121951

1 225936 20874 018836

1 143545 -171705 536428

1 285383 -283943 064204

1 406877 367022 -012592

1 544671 314066 -110488

1 553758 307609 06489

1 729939 -051937 076518

1 833303 069837 -002791

1 708519 121395 113618

1 500794 -265269 -172729

1 556285 -272509 -005765

1 643169 -174031 -123981

1 -054825 -338024 059471

1 088093 -31739 162093

1 090436 -434599 028385

1 -054441 -284433 -157279

1 100716 -346915 -209628

1 027122 -167519 -361045

1 173047 -118324 -276837

1 16536 103173 -264959

1 016092 190468 -228608

1 032661 102454 -382713

1 -179099 082721 -234764

1 -172831 -070852 -318072

1 -168246 -138576 21103

1 -436883 -010195 -291404

1 -523097 -159045 -250721

1 -368016 -166849 -333128

1 -64523 -029516 -082988

1 -748841 -155362 -010713

1 -645653 -054301 093788

1 -472744 -322703 217515

1 -356735 -23732 320599

1 -506677 -158776 270862

6 -087226 208228 135715

6 -411882 391536 -084488

6 -334056 247951 093602

6 -43891 307972 023694

1 032553 38811 158418

1 06632 262439 278986

1 -257592 480346 -205917

1 -072473 37475 -080988

1 -541492 289072 053651

1 -493196 438053 -139241

1 -356088 182714 177604

1 248723 -032179 503364

1 080217 -006459 553844

1 290185 -30022 -109397

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

60

5[Λ-CatmiddotR] in CH3CN

7 024013 07682 205869

25 -01252 -039737 010146

7 -217335 -046153 020792

7 -058292 -179525 -165532

7 001464 -224615 116765

7 189238 -071768 -008112

8 -626875 -051729 026934

8 586274 -161469 -050841

6 -285129 015012 11921

6 -422906 017302 125451

6 -491564 -048994 022713

6 -422799 -116125 -078792

6 -283155 -11077 -076368

6 -203466 -172939 -188111

6 -495717 085074 236993

6 -691766 047431 -053307

6 -496231 -191079 -185553

6 013515 -144335 -288732

6 -015094 -311266 -116137

6 -055771 -329776 027993

6 -072804 -227363 244799

6 145139 -250704 146511

6 239603 -178408 055589

6 373847 -214266 04483

6 455276 -131717 -033695

6 402918 -020475 -100999

6 268063 004585 -08478

6 428814 -335773 112955

6 672874 -11668 053885

6 488867 065682 -187833

8 -007176 108106 -093265

6 021186 432274 049054

6 112532 536825 059788

6 211799 552596 -03623

6 218666 463848 -143325

6 126958 360013 -153988

6 027462 342767 -057552

6 -073628 230753 -070228

6 -172967 256246 -182776

6 072499 147486 282656

1 -225339 063576 195586

1 -221523 -112806 -277755

1 -242977 -272547 -211213

1 -566179 016467 2845

1 -426238 121464 312782

1 -55359 170421 200691

1 -667084 03465 -159015

1 -798568 032957 -038591

1 -663416 147937 -021098

1 -602469 -196452 -162446

1 -459285 -293537 -194752

1 -484765 -143541 -283452

1 -01067 -041746 -316179

1 -012973 -211781 -371008

1 120941 -151001 -271601

1 09347 -317205 -126601

1 -057254 -392403 -176785

1 -16438 -324515 037612

1 -025505 -428569 064116

1 -179222 -214347 226264

1 -057502 -323517 294717

1 -037675 -147322 30958

1 163227 -358528 146822

1 164672 -216264 248531

1 21848 087985 -132997

1 434187 -322361 221421

1 528925 -358104 076423

1 36654 -423552 094017

1 645358 -16152 149684

1 773013 -148677 025923

1 670038 -007758 062412

1 56912 112673 -130418

1 536226 006538 -266559

1 430111 144795 -234586

1 -056258 420523 124469

1 106154 605714 143475

1 283416 633751 -027947

1 29562 475844 -218992

1 132579 291698 -23826

1 -129136 225905 02446

1 -223974 351861 -168336

1 -24839 177188 -185982

1 -121419 258937 -27915

6 132979 236287 378699

1 063297 255304 460483

1 158175 33071 330043

1 223846 190934 41864

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351

61

5[Λ-CatmiddotS] in CH3CN

25 042941 -025491 022078

7 243507 008452 -00314

7 105031 -226295 -019765

7 00977 -021179 -204936

7 -15395 -082304 012612

8 6415 061556 -082355

8 -546701 -194814 -01797

6 296298 131503 -004136

6 430247 154747 -028601

6 510455 042522 -053785

6 456437 -086587 -055648

6 320322 -098424 -02808

6 25394 -232049 -015598

6 486847 293105 -030756

6 730098 04875 029237

6 541004 -20622 -086459

6 05233 -327741 074237

6 053412 -258177 -155825

6 074677 -144421 -252658

6 066869 095986 -272577

6 -136021 -022882 -223439

6 -214369 -077257 -106924

6 -348164 -114216 -122768

6 -417668 -154756 -00846

6 -354461 -161277 116506

6 -221807 -12362 12078

6 -414765 -1111 -256836

6 -64368 -090026 -008652

6 -426512 -209203 238353

7 071976 -060552 248661

8 009984 150657 045233

6 105235 -052935 358538

6 146266 -043868 496421

6 -208631 252985 050895

1 -12041 134703 20438

1 -094242 372036 271291

6 -022406 32439 204075

6 -193083 326139 -066997

6 -303911 369586 -138679

1 226009 211787 015315

1 146876 -143307 541342

1 283076 -274426 080944

1 407693 367799 -023648

1 543072 310564 -122742

1 555766 309362 052563

1 725446 -051906 071633

1 830057 067693 -009276

1 705995 122076 106603

1 496114 -267262 -165251

1 553495 -270366 001293

1 639697 -175642 -120745

1 -056445 -328354 071023

1 084964 -304781 175442

1 088766 -427059 046208

1 -052881 -280808 -145905

1 101803 -349139 -192803

1 037435 -173327 -351745

1 181386 -123737 -263979

1 175174 096324 -260552

1 026895 186486 -227157

1 043636 095431 -379722

1 -169362 080424 -237947

1 -162256 -076299 -315436

1 -166363 -126751 213945

1 -422916 -008998 -295335

1 -514788 -15361 -251011

1 -358595 -169308 -33039

1 -629995 -016786 -088632

1 -740813 -137914 -01892

1 -637505 -039743 08818

1 -474546 -305456 21949

1 -357984 -220427 322468

1 -505156 -139401 268291

6 -087399 208283 129723

6 -432318 34107 -092882

6 -337473 225075 095999

6 -448805 269067 02489

1 013518 399481 133191

1 062371 2887 263093

1 -290189 426244 -230285

1 -093135 349374 -102516

1 -548543 246585 061441

1 -518984 375116 -14869

1 -351211 168545 187845

1 246495 -001121 502231

1 076798 019953 551261

1 289875 -302252 -091351