Supporting Information - Wiley-VCH · 2006. 11. 27. · ppm (f1) 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0...
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Supporting Information © Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006
Transcript of Supporting Information - Wiley-VCH · 2006. 11. 27. · ppm (f1) 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0...
Supporting Information
© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006
SUPPORTING INFORMATION
Asymmetric Catalysis in the [2+2+2] Cycloaddition of Arynes and Alkynes: Enantioselective
Synthesis of a Pentahelicene. Caeiro, J.; Peña, D.; Cobas, A.; Pérez, D.; Guitián, E.
I. NMR SPECTRA
ppm (f1)
0.01.02.03.04.05.06.07.08.09.010.0
ppm (f1)
0102030405060708090100110120130140150160170180190200210
ppm (f1)
0102030405060708090100110120130140150160170180190200210
Br
OHMeO
6
NOESY spectrum of 6
ppm (t1)
0.01.02.03.04.05.06.07.08.09.010.0
Br
OTMSMeO
ppm (f1)
0.01.02.03.04.05.06.07.08.09.010.0
ppm (f1)
0102030405060708090100110120130140150160170180190200210
ppm (f1)
0102030405060708090100110120130140150160170180190200210
TMS
OTfMeO
4
ppm (t1)
0.01.02.03.04.05.06.07.08.09.010.0
ppm (t1)
0102030405060708090100110120130140150160170180190200210
ppm (f1)
0102030405060708090100110120130140150160170180190200210
MeO
1
CO2Me
CO2Me
MeO
NOESY spectrum of 1
COSY spectrum of 1
.
min0 2 4 6 8 10 12 14
mAU
0
100
200
300
400
500
DAD1 B, Sig=243,16 Ref=380,100 (GR\JCNA0004.D)
Area: 15074.3
9.2
45
Area: 15195.2 10
.29
5
nm200 225 250 275 300 325 350 375
mAU
0
100
200
300
400
500
600
DAD1, 9.242 (704 mAU,Apx) of JCNA0004.D DAD1, 10.302 (643 mAU,Apx) of JCNA0004.D
HPLC chromatogram of racemic 1 and UV spectra of both enantiomers. Column OL-86;
CH2Cl2/hexanes (25:75); ë = 243 nm.
min0 2 4 6 8 10
mAU
0
200
400
600
800
1000
DAD1 B, Sig=243,16 Ref=380,100 (GR\JC241001.D)
Area: 25684.6
7.5
45
Area: 1450.72 8.3
22
nm200 225 250 275 300 325 350 375
mAU
0
200
400
600
800
1000
1200
1400
DAD1, 7.549 (1448 mAU,Apx) of JC241001.D DAD1, 8.295 (188 mAU,Apx) of JC241001.D
HPLC chromatogram of a sample of (M)-1 (> 90% ee;experiment in Table 2, entry 4) and UV
spectra of both enantiomers. Column OL-86; CH2Cl2/hexanes (35:65); ë = 243 nm.
CD spectrum of a sample of 1, enriched in enantiomer (M) (61% ee), in CH2Cl2.
ppm (t1)
0.01.02.03.04.05.06.07.08.09.010.0
ppm (t1)
0102030405060708090100110120130140150160170180190200210
ppm (t1)
0102030405060708090100110120130140150160170180190200210
MeO
OMe
CO2Me
CO2Me
7
ppm (f1)
0.01.02.03.04.05.06.07.08.09.010.0
ppm (f1)
0102030405060708090100110120130140150160170180190200210
ppm (f1)
0102030405060708090100110120130140150160170180190200210
OMe
OMe
CO2Me
CO2Me
8
NOESY spectrum of 8
COSY spectrum of 8
ppm (f1)
0.01.02.03.04.05.06.07.08.09.010.0
ppm (t1)
-40-30-20-100102030405060708090
P
P
Pd
CO2Me
CO2Me
10
Ph2
Ph2
II. GEOMETRY AND ENERGY INFORMATION
Calculated geometry for transition state TS-1 – BLYP/6-31G(d,p)
6 0.062367 -3.285866 -1.456828 6 1.206825 -2.712910 -0.969528 6 1.175340 -1.408338 -0.357161 6 -0.065446 -0.675674 -0.192553 6 -1.282348 -1.526024 -0.307868 6 -1.211706 -2.742191 -1.100132 6 2.430136 -0.786694 -0.005251 6 0.017990 0.800163 -0.148364 6 1.340327 1.380244 -0.282387 6 2.513460 0.598907 0.017395 6 1.530651 2.690796 -0.843988 1 2.546055 3.061030 -0.976971 6 0.464902 3.419233 -1.301126 6 -0.863513 3.020534 -0.954752 1 0.101756 -4.210320 -2.039552 1 2.178534 -3.171821 -1.138653 1 0.613657 4.360054 -1.837849 6 -1.945672 3.915198 -1.201411 6 -3.189252 3.733405 -0.623450 6 -3.359137 2.659116 0.287456 6 -2.335139 1.718290 0.475688 6 -1.087848 1.797958 -0.209495 1 -1.754339 4.796916 -1.819404 1 -4.013192 4.431565 -0.781620 6 -2.393766 -3.477000 -1.382057 6 -3.623018 -3.154687 -0.813438 1 -2.311262 -4.356828 -2.026254 1 -4.508068 -3.748716 -1.040343 6 -3.653677 -2.097889 0.125362 6 -2.510327 -1.319891 0.363566 8 -4.562855 2.662884 0.957323 8 -4.760569 -1.759431 0.888720 6 -4.805891 1.647779 1.950167 1 -4.821896 0.637710 1.508905
1 -4.055451 1.686903 2.760216 1 -5.794163 1.881648 2.368412 6 -5.953488 -2.547394 0.733423 1 -6.360594 -2.475357 -0.290672 1 -5.773618 -3.608766 0.979384 1 -6.680479 -2.127989 1.441028 6 3.816628 1.316170 0.270872 8 3.950852 2.312355 0.971978 8 4.854852 0.737670 -0.422375 6 3.626018 -1.644757 0.338074 8 4.093878 -2.567903 -0.320200 8 4.113669 -1.283469 1.571586 1 -2.461150 0.980173 1.251542 1 -2.583657 -0.613824 1.176025 6 6.153948 1.353548 -0.192210 1 6.434889 1.280510 0.868809 1 6.854679 0.792471 -0.821970 1 6.133548 2.414727 -0.479913 6 5.281715 -2.036631 2.006042 1 6.119397 -1.886817 1.309067 1 5.525373 -1.642009 2.999709 1 5.050895 -3.110483 2.057582
Calculated geometry for ground state GS-1 – BLYP/6-31G(d,p)
6 0.028045 -3.481873 0.846311 6 -1.130455 -2.742105 0.864793 6 -1.142990 -1.369794 0.426164 6 0.093373 -0.724358 0.078917 6 1.255159 -1.583051 -0.178144 6 1.224986 -2.954156 0.264688 6 -2.385092 -0.646352 0.261753 6 0.093358 0.724327 -0.078949 6 -1.143017 1.369734 -0.426206 6 -2.385103 0.646264 -0.261807 6 -1.130512 2.742049 -0.864828 1 -2.056384 3.183556 -1.229242 6 0.027969 3.481847 -0.846328 6 1.224915 2.954155 -0.264692 1 0.028577 -4.514421 1.207062 1 -2.056321 -3.183632 1.229197 1 0.028481 4.514396 -1.207073 6 2.362972 3.786595 -0.038211 6 3.463993 3.330351 0.664298 6 3.455745 2.006701 1.194617 6 2.375880 1.154093 0.954404 6 1.255118 1.583048 0.178131 1 2.337423 4.816564 -0.405020 1 4.329564 3.966615 0.858904 6 2.363067 -3.786568 0.038226 6 3.464085 -3.330301 -0.664272 1 2.337539 -4.816536 0.405041 1 4.329675 -3.966544 -0.858863 6 3.455810 -2.006655 -1.194600 6 2.375919 -1.154073 -0.954407 8 4.567256 1.682357 1.943191 8 4.567320 -1.682287 -1.943163 6 4.630465 0.364944 2.520345 1 5.591005 0.320431 3.049928 1 3.807926 0.197270 3.237866 1 4.599331 -0.419636 1.744538 6 4.630502 -0.364876 -2.520326 1 3.807967 -0.197229 -3.237857 1 4.599338 0.419708 -1.744524 1 5.591047 -0.320341 -3.049897 1 2.370533 0.152980 1.375080 1 2.370552 -0.152964 -1.375092 6 -3.680741 -1.358001 0.572262 8 -3.955757 -1.902593 1.635578 8 -4.512276 -1.370937 -0.520653 6 -3.680766 1.357901 -0.572297 8 -3.955783 1.902520 -1.635599 8 -4.512230 1.370934 0.520669 6 -5.796526 -2.022165 -0.298869 1 -6.358539 -1.507622 0.494192 1 -6.322968 -1.955130 -1.258341 1 -5.649989 -3.071886 -0.006034 6 -5.796450 2.022243 0.298943 1 -5.649859 3.071945 0.006068 1 -6.358548 1.507715 -0.494067 1 -6.322838 1.955273 1.258450
III. CRYSTALOGRAPHIC INFORMATION
IIIa. X-Ray difracction study of pentahelicene 1 - This structure has been deposited at
the Cambridge Crystallographic Database with deposition number CCDC 605852
Mercury view of the packing of (M,P)-1 (unit cell)
Mercury view of the packing of (M,P)-1 along three axis
1
Table 1. Crystal data and structure refinement for.1
Empirical formula C28 H22 O6
Formula weight 454.46
Temperature 293(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group P 2/c
Unit cell dimensions a = 15.679(4) Å α= 90°
b = 13.123(3) Å β= 109.821(5)°
c = 11.376(3) Å γ = 90°
Volume 2201.8(10) Å3
Z 4
Density (calculated) 1.371 Mg/m3
Absorption coefficient 0.096 mm-1
F(000) 952
Crystal size 0.31 x 0.16 x 0.05 mm3
Theta range for data collection 1.55 to 22.05°.
Index ranges -16<=h<=15, 0<=k<=13, 0<=l<=11
Reflections collected 34321
Independent reflections 2707 [R(int) = 0.0882]
Completeness to theta = 22.05° 99.5 %
Absorption correction SADABS Bruker
Max. and min. transmission 1.0000 and 0.8782
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 2707 / 0 / 312
Goodness-of-fit on F2 1.072
Final R indices [I>2sigma(I)] R1 = 0.0415, wR2 = 0.0958
R indices (all data) R1 = 0.1228, wR2 = 0.1355
Extinction coefficient 0.0061(9)
Largest diff. peak and hole 0.177 and -0.161 e.Å-3
Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 1.
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
________________________________________________________________________________
x y z U(eq)
________________________________________________________________________________
C(101) 5455(3) 2085(3) 2593(4) 50(1)
C(102) 5913(3) 3015(3) 2560(4) 47(1)
C(103) 6819(3) 3023(4) 2557(4) 55(1)
C(104) 7185(3) 3862(4) 2258(4) 61(1)
C(105) 6664(3) 4753(3) 1860(4) 48(1)
C(106) 6987(3) 5575(4) 1333(4) 65(1)
C(107) 6476(3) 6415(4) 891(4) 63(1)
C(108) 5596(3) 6461(4) 925(4) 51(1)
C(109) 5244(3) 5661(3) 1384(3) 44(1)
C(110) 5779(3) 4806(3) 1903(3) 41(1)
C(111) 5428(2) 3935(3) 2389(3) 42(1)
C(112) 5972(3) 1108(3) 2746(5) 60(1)
O(113) 6598(3) 882(2) 3654(3) 90(1)
O(114) 5657(2) 533(2) 1731(3) 67(1)
C(115) 6113(4) -430(4) 1754(5) 97(2)
O(116) 5137(2) 7340(2) 458(3) 66(1)
C(117) 4272(3) 7484(3) 578(4) 71(1)
C(201) 9723(3) 5705(3) 1892(3) 45(1)
C(202) 9380(3) 4773(3) 1260(4) 45(1)
C(203) 8770(3) 4756(3) 8(4) 57(1)
C(204) 8378(3) 3890(4) -531(4) 64(1)
C(205) 8484(3) 2982(3) 168(4) 50(1)
C(206) 7961(3) 2100(4) -321(5) 67(1)
C(207) 7969(3) 1273(4) 392(5) 66(1)
C(208) 8503(3) 1294(3) 1660(5) 56(1)
C(209) 9034(3) 2126(3) 2162(4) 47(1)
C(210) 9073(3) 2961(3) 1419(4) 42(1)
C(211) 9626(2) 3845(3) 1924(3) 38(1)
C(212) 9394(3) 6681(3) 1227(5) 56(1)
O(213) 9465(2) 6958(2) 273(3) 83(1)
O(214) 8971(2) 7219(2) 1854(3) 70(1)
C(215) 8606(4) 8195(3) 1314(5) 100(2)
O(216) 8437(2) 445(2) 2325(4) 76(1)
C(217) 9019(4) 380(4) 3574(5) 99(2)
________________________________________________________________________________
Table 3. Bond lengths [Å] and angles [°] for 1.
_____________________________________________________
C(101)-C(101)#1 1.370(8)
C(101)-C(102) 1.424(5)
C(101)-C(112) 1.494(6)
C(102)-C(111) 1.404(5)
C(102)-C(103) 1.420(6)
C(103)-C(104) 1.337(5)
C(103)-H(103) 0.9300
C(104)-C(105) 1.410(6)
C(104)-H(104) 0.9300
C(105)-C(110) 1.406(5)
C(105)-C(106) 1.410(6)
C(106)-C(107) 1.354(6)
C(106)-H(106) 0.9300
C(107)-C(108) 1.395(6)
C(107)-H(107) 0.9300
C(108)-C(109) 1.369(5)
C(108)-O(116) 1.369(5)
C(109)-C(110) 1.405(5)
C(109)-H(109) 0.9300
C(110)-C(111) 1.457(5)
C(111)-C(111)#1 1.449(7)
C(112)-O(113) 1.196(5)
C(112)-O(114) 1.327(5)
O(114)-C(115) 1.448(5)
C(115)-H(11A) 0.9600
C(115)-H(11B) 0.9600
C(115)-H(11C) 0.9600
O(116)-C(117) 1.420(5)
C(117)-H(11D) 0.9600
C(117)-H(11E) 0.9600
C(117)-H(11F) 0.9600
C(201)-C(201)#2 1.362(7)
C(201)-C(202) 1.428(5)
C(201)-C(212) 1.488(5)
C(202)-C(211) 1.417(5)
C(202)-C(203) 1.421(5)
C(203)-C(204) 1.338(5)
C(203)-H(203) 0.9300
C(204)-C(205) 1.411(6)
C(204)-H(204) 0.9300
C(205)-C(210) 1.410(5)
C(205)-C(206) 1.418(6)
C(206)-C(207) 1.352(6)
C(206)-H(206) 0.9300
C(207)-C(208) 1.401(6)
C(207)-H(207) 0.9300
C(208)-O(216) 1.369(5)
C(208)-C(209) 1.375(5)
C(209)-C(210) 1.398(5)
C(209)-H(209) 0.9300
C(210)-C(211) 1.446(5)
C(211)-C(211)#2 1.432(7)
C(212)-O(213) 1.186(5)
C(212)-O(214) 1.329(5)
O(214)-C(215) 1.451(5)
C(215)-H(21A) 0.9600
C(215)-H(21B) 0.9600
C(215)-H(21C) 0.9600
O(216)-C(217) 1.407(5)
C(217)-H(21D) 0.9600
C(217)-H(21E) 0.9600
C(217)-H(21F) 0.9600
C(101)#1-C(101)-C(102) 120.3(2)
C(101)#1-C(101)-C(112) 120.9(2)
C(102)-C(101)-C(112) 118.7(4)
C(111)-C(102)-C(103) 119.2(4)
C(111)-C(102)-C(101) 119.1(4)
C(103)-C(102)-C(101) 121.3(4)
C(104)-C(103)-C(102) 121.5(4)
C(104)-C(103)-H(103) 119.3
C(102)-C(103)-H(103) 119.3
C(103)-C(104)-C(105) 120.8(4)
C(103)-C(104)-H(104) 119.6
C(105)-C(104)-H(104) 119.6
C(110)-C(105)-C(106) 118.5(4)
C(110)-C(105)-C(104) 120.1(4)
C(106)-C(105)-C(104) 121.3(4)
C(107)-C(106)-C(105) 121.8(4)
C(107)-C(106)-H(106) 119.1
C(105)-C(106)-H(106) 119.1
C(106)-C(107)-C(108) 119.5(4)
C(106)-C(107)-H(107) 120.3
C(108)-C(107)-H(107) 120.3
C(109)-C(108)-O(116) 124.6(4)
C(109)-C(108)-C(107) 120.5(4)
O(116)-C(108)-C(107) 114.9(4)
C(108)-C(109)-C(110) 120.7(4)
C(108)-C(109)-H(109) 119.6
C(110)-C(109)-H(109) 119.6
C(109)-C(110)-C(105) 118.8(4)
C(109)-C(110)-C(111) 122.5(3)
C(105)-C(110)-C(111) 118.5(4)
C(102)-C(111)-C(111)#1 117.8(2)
C(102)-C(111)-C(110) 118.1(3)
C(111)#1-C(111)-C(110) 123.9(2)
O(113)-C(112)-O(114) 124.4(4)
O(113)-C(112)-C(101) 124.6(5)
O(114)-C(112)-C(101) 111.1(4)
C(112)-O(114)-C(115) 116.4(4)
O(114)-C(115)-H(11A) 109.5
O(114)-C(115)-H(11B) 109.5
H(11A)-C(115)-H(11B) 109.5
O(114)-C(115)-H(11C) 109.5
H(11A)-C(115)-H(11C) 109.5
H(11B)-C(115)-H(11C) 109.5
C(108)-O(116)-C(117) 117.9(3)
O(116)-C(117)-H(11D) 109.5
O(116)-C(117)-H(11E) 109.5
H(11D)-C(117)-H(11E) 109.5
O(116)-C(117)-H(11F) 109.5
H(11D)-C(117)-H(11F) 109.5
H(11E)-C(117)-H(11F) 109.5
C(201)#2-C(201)-C(202) 120.9(2)
C(201)#2-C(201)-C(212) 120.5(2)
C(202)-C(201)-C(212) 118.3(3)
C(211)-C(202)-C(203) 119.3(4)
C(211)-C(202)-C(201) 118.7(3)
C(203)-C(202)-C(201) 121.9(4)
C(204)-C(203)-C(202) 121.4(4)
C(204)-C(203)-H(203) 119.3
C(202)-C(203)-H(203) 119.3
C(203)-C(204)-C(205) 120.8(4)
C(203)-C(204)-H(204) 119.6
C(205)-C(204)-H(204) 119.6
C(210)-C(205)-C(204) 119.8(4)
C(210)-C(205)-C(206) 118.3(4)
C(204)-C(205)-C(206) 121.7(4)
C(207)-C(206)-C(205) 122.2(4)
C(207)-C(206)-H(206) 118.9
C(205)-C(206)-H(206) 118.9
C(206)-C(207)-C(208) 118.9(4)
C(206)-C(207)-H(207) 120.5
C(208)-C(207)-H(207) 120.5
O(216)-C(208)-C(209) 124.4(4)
O(216)-C(208)-C(207) 115.0(4)
C(209)-C(208)-C(207) 120.6(5)
C(208)-C(209)-C(210) 121.0(4)
C(208)-C(209)-H(209) 119.5
C(210)-C(209)-H(209) 119.5
C(209)-C(210)-C(205) 118.6(4)
C(209)-C(210)-C(211) 122.1(4)
C(205)-C(210)-C(211) 119.0(4)
C(202)-C(211)-C(211)#2 118.6(2)
C(202)-C(211)-C(210) 117.4(3)
C(211)#2-C(211)-C(210) 123.9(2)
O(213)-C(212)-O(214) 123.2(4)
O(213)-C(212)-C(201) 127.2(4)
O(214)-C(212)-C(201) 109.5(4)
C(212)-O(214)-C(215) 116.0(4)
O(214)-C(215)-H(21A) 109.5
O(214)-C(215)-H(21B) 109.5
H(21A)-C(215)-H(21B) 109.5
O(214)-C(215)-H(21C) 109.5
H(21A)-C(215)-H(21C) 109.5
H(21B)-C(215)-H(21C) 109.5
C(208)-O(216)-C(217) 117.5(4)
O(216)-C(217)-H(21D) 109.5
O(216)-C(217)-H(21E) 109.5
H(21D)-C(217)-H(21E) 109.5
O(216)-C(217)-H(21F) 109.5
H(21D)-C(217)-H(21F) 109.5
H(21E)-C(217)-H(21F) 109.5
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 -x+1,y,-z+1/2 #2 -x+2,y,-z+1/2
Table 4. Anisotropic displacement parameters (Å2x 103)for gt01jc01. The anisotropic displacement factor
exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ]
______________________________________________________________________________
U11 U22 U33 U23 U13 U12
______________________________________________________________________________
C(101) 55(3) 46(3) 40(3) -1(2) 6(3) 1(2)
C(102) 39(3) 53(3) 44(3) -8(2) 9(2) 0(2)
C(103) 44(3) 61(3) 58(3) -13(2) 15(2) 4(3)
C(104) 37(3) 78(4) 69(3) -24(3) 17(2) -4(3)
C(105) 38(3) 59(3) 51(3) -14(2) 19(2) -12(2)
C(106) 51(3) 86(4) 67(3) -17(3) 30(3) -13(3)
C(107) 60(3) 80(4) 58(3) -9(3) 31(3) -29(3)
C(108) 58(3) 57(3) 38(3) -5(2) 17(2) -12(3)
C(109) 43(3) 53(3) 38(3) -5(2) 17(2) -6(2)
C(110) 36(3) 49(3) 36(3) -9(2) 10(2) -7(2)
C(111) 37(2) 51(3) 38(2) -6(2) 11(2) -1(2)
C(112) 60(3) 56(3) 60(4) 2(3) 16(3) 4(3)
O(113) 92(3) 77(3) 82(3) 5(2) 4(2) 32(2)
O(114) 76(2) 48(2) 74(2) -13(2) 21(2) 4(2)
C(115) 106(4) 49(3) 139(5) -23(3) 48(4) 7(3)
O(116) 77(2) 55(2) 68(2) 10(2) 27(2) -7(2)
C(117) 73(4) 64(3) 69(3) 14(3) 16(3) 3(3)
C(201) 53(3) 36(2) 53(3) 1(2) 28(2) 3(2)
C(202) 46(3) 49(3) 43(3) 1(2) 20(2) 8(2)
C(203) 63(3) 55(3) 51(3) 6(2) 15(3) 18(3)
C(204) 63(3) 68(3) 44(3) -3(3) -1(2) 14(3)
C(205) 42(3) 53(3) 50(3) -11(2) 8(2) 10(2)
C(206) 56(3) 74(4) 61(3) -21(3) 8(3) -2(3)
C(207) 50(3) 60(3) 82(4) -26(3) 13(3) -8(3)
C(208) 48(3) 51(3) 72(4) -9(3) 24(3) -1(3)
C(209) 43(3) 47(3) 53(3) -10(2) 18(2) -6(2)
C(210) 35(2) 43(3) 48(3) -5(2) 15(2) 4(2)
C(211) 35(2) 43(2) 40(3) -3(2) 17(2) 4(2)
C(212) 63(3) 51(3) 63(3) 1(3) 34(3) 3(2)
O(213) 116(3) 67(2) 84(3) 28(2) 59(2) 27(2)
O(214) 90(2) 43(2) 95(2) 10(2) 56(2) 16(2)
C(215) 124(5) 50(3) 142(5) 22(3) 67(4) 36(3)
O(216) 80(2) 52(2) 96(3) -6(2) 31(2) -22(2)
C(217) 136(5) 73(4) 90(5) 9(3) 40(4) -31(4)
______________________________________________________________________________
Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for 1.
________________________________________________________________________________
x y z U(eq)
________________________________________________________________________________
H(103) 7164 2432 2768 66
H(104) 7790 3857 2314 74
H(106) 7567 5540 1287 78
H(107) 6710 6956 569 76
H(109) 4643 5684 1353 53
H(11A) 6739 -308 1862 145
H(11B) 5830 -784 981 145
H(11C) 6072 -837 2434 145
H(11D) 3865 6965 116 106
H(11E) 4040 8142 257 106
H(11F) 4328 7442 1444 106
H(203) 8640 5360 -446 69
H(204) 8032 3886 -1376 76
H(206) 7600 2090 -1161 80
H(207) 7625 701 47 80
H(209) 9373 2134 3010 57
H(21A) 9095 8645 1341 149
H(21B) 8259 8486 1781 149
H(21C) 8223 8098 462 149
H(21D) 9634 483 3610 148
H(21E) 8963 -281 3901 148
H(21F) 8858 894 4061 148
________________________________________________________________________________
Table 6. Torsion angles [°] for 1.
________________________________________________________________
C(101)#1-C(101)-C(102)-C(111) 2.7(7)
C(112)-C(101)-C(102)-C(111) 178.6(4)
C(101)#1-C(101)-C(102)-C(103) -170.2(5)
C(112)-C(101)-C(102)-C(103) 5.7(6)
C(111)-C(102)-C(103)-C(104) -7.5(6)
C(101)-C(102)-C(103)-C(104) 165.4(4)
C(102)-C(103)-C(104)-C(105) -3.9(6)
C(103)-C(104)-C(105)-C(110) 7.0(6)
C(103)-C(104)-C(105)-C(106) -168.5(4)
C(110)-C(105)-C(106)-C(107) 1.2(6)
C(104)-C(105)-C(106)-C(107) 176.8(4)
C(105)-C(106)-C(107)-C(108) -1.8(7)
C(106)-C(107)-C(108)-C(109) -0.9(6)
C(106)-C(107)-C(108)-O(116) 180.0(4)
O(116)-C(108)-C(109)-C(110) -176.9(3)
C(107)-C(108)-C(109)-C(110) 4.0(6)
C(108)-C(109)-C(110)-C(105) -4.6(6)
C(108)-C(109)-C(110)-C(111) -179.3(3)
C(106)-C(105)-C(110)-C(109) 2.0(5)
C(104)-C(105)-C(110)-C(109) -173.7(4)
C(106)-C(105)-C(110)-C(111) 176.9(4)
C(104)-C(105)-C(110)-C(111) 1.3(5)
C(103)-C(102)-C(111)-C(111)#1 -169.5(4)
C(101)-C(102)-C(111)-C(111)#1 17.5(6)
C(103)-C(102)-C(111)-C(110) 15.4(5)
C(101)-C(102)-C(111)-C(110) -157.7(3)
C(109)-C(110)-C(111)-C(102) 162.5(4)
C(105)-C(110)-C(111)-C(102) -12.3(5)
C(109)-C(110)-C(111)-C(111)#1 -12.4(6)
C(105)-C(110)-C(111)-C(111)#1 172.9(4)
C(101)#1-C(101)-C(112)-O(113) -119.7(6)
C(102)-C(101)-C(112)-O(113) 64.5(6)
C(101)#1-C(101)-C(112)-O(114) 61.8(6)
C(102)-C(101)-C(112)-O(114) -114.1(4)
O(113)-C(112)-O(114)-C(115) 0.4(7)
C(101)-C(112)-O(114)-C(115) 179.0(4)
C(109)-C(108)-O(116)-C(117) 7.1(6)
C(107)-C(108)-O(116)-C(117) -173.7(4)
C(201)#2-C(201)-C(202)-C(211) 0.1(7)
C(212)-C(201)-C(202)-C(211) -174.3(4)
C(201)#2-C(201)-C(202)-C(203) 177.2(5)
C(212)-C(201)-C(202)-C(203) 2.8(6)
C(211)-C(202)-C(203)-C(204) 4.3(6)
C(201)-C(202)-C(203)-C(204) -172.8(4)
C(202)-C(203)-C(204)-C(205) 6.7(7)
C(203)-C(204)-C(205)-C(210) -5.7(6)
C(203)-C(204)-C(205)-C(206) 169.4(4)
C(210)-C(205)-C(206)-C(207) 4.2(7)
C(204)-C(205)-C(206)-C(207) -171.0(4)
C(205)-C(206)-C(207)-C(208) 0.8(7)
C(206)-C(207)-C(208)-O(216) 177.0(4)
C(206)-C(207)-C(208)-C(209) -2.2(6)
O(216)-C(208)-C(209)-C(210) 179.3(4)
C(207)-C(208)-C(209)-C(210) -1.6(6)
C(208)-C(209)-C(210)-C(205) 6.6(6)
C(208)-C(209)-C(210)-C(211) 180.0(4)
C(204)-C(205)-C(210)-C(209) 167.6(4)
C(206)-C(205)-C(210)-C(209) -7.7(6)
C(204)-C(205)-C(210)-C(211) -6.1(6)
C(206)-C(205)-C(210)-C(211) 178.7(3)
C(203)-C(202)-C(211)-C(211)#2 167.3(4)
C(201)-C(202)-C(211)-C(211)#2 -15.5(6)
C(203)-C(202)-C(211)-C(210) -15.5(5)
C(201)-C(202)-C(211)-C(210) 161.6(3)
C(209)-C(210)-C(211)-C(202) -157.0(3)
C(205)-C(210)-C(211)-C(202) 16.4(5)
C(209)-C(210)-C(211)-C(211)#2 20.0(6)
C(205)-C(210)-C(211)-C(211)#2 -166.6(4)
C(201)#2-C(201)-C(212)-O(213) 125.5(6)
C(202)-C(201)-C(212)-O(213) -60.1(6)
C(201)#2-C(201)-C(212)-O(214) -56.0(6)
C(202)-C(201)-C(212)-O(214) 118.4(4)
O(213)-C(212)-O(214)-C(215) -1.1(7)
C(201)-C(212)-O(214)-C(215) -179.7(4)
C(209)-C(208)-O(216)-C(217) -6.5(6)
C(207)-C(208)-O(216)-C(217) 174.3(4)
________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 -x+1,y,-z+1/2 #2 -x+2,y,-z+1/2
IIIa. X-Ray difracction study of ppalladium complex 10 - This structure has been
deposited at the Cambridge Crystallographic Database with deposition number CCDC
605851
Mercury view of the structure of complex 10
Mercury view of the packing of 10 (unit cell)
Mercury view of the packing mode of 10 along three axis
Table 1. Crystal data and structure refinement for 10.
Empirical formula C50 H38 O4 P2 Pd
Formula weight 871.14
Temperature 293(2) K
Wavelength 0.71073 Å
Crystal system triclinic
Space group P-1
Unit cell dimensions a = 11.147(4) Å α= 103.430(5)°.
b = 13.957(5) Å β= 103.367(5)°.
c = 14.524(5) Å γ = 110.489(5)°.
Volume 1934.1(12) Å3
Z 2
Density (calculated) 1.496 Mg/m3
Absorption coefficient 0.611 mm-1
F(000) 892
Crystal size 0.34x 0.13 x 0.13 mm3
Theta range for data collection 1.53 to 26.42°.
Index ranges -13<=h<=13, -17<=k<=16, 0<=l<=18
Reflections collected 7856
Independent reflections 7856 [R(int) = 0.0609]
Completeness to theta = 26.42° 98.8 %
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 7856 / 0 / 516
Goodness-of-fit on F2 1.031
Final R indices [I>2sigma(I)] R1 = 0.0496, wR2 = 0.1241
R indices (all data) R1 = 0.0791, wR2 = 0.1440
Largest diff. peak and hole 2.579 and -2.641 e.Å-3
Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 10.
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
________________________________________________________________________________
x y z U(eq)
________________________________________________________________________________
Pd(1) 2040(1) 2150(1) 2747(1) 12(1)
P(2) 3669(1) 2802(1) 2038(1) 12(1)
C(3) 2732(4) 2723(4) 780(3) 13(1)
C(4) 2262(4) 3497(4) 630(3) 12(1)
C(5) 2568(4) 4485(4) 1492(3) 12(1)
C(6) 1943(4) 4395(4) 2205(3) 12(1)
P(7) 802(1) 3066(1) 2203(1) 11(1)
C(8) 2286(5) 1744(4) -37(3) 16(1)
C(9) 1470(5) 1567(4) -969(3) 15(1)
C(10) 1057(5) 2369(4) -1167(3) 16(1)
C(11) 1443(4) 3340(4) -364(3) 12(1)
C(12) 3556(4) 5522(4) 1589(3) 13(1)
C(13) 3962(5) 6436(4) 2459(3) 15(1)
C(14) 3330(5) 6309(4) 3199(3) 16(1)
C(15) 2332(5) 5325(4) 3060(3) 15(1)
C(16) 233(5) 2197(4) -2138(3) 21(1)
C(17) -206(5) 2964(4) -2320(3) 20(1)
C(18) 163(5) 3924(4) -1530(3) 19(1)
C(19) 963(5) 4119(4) -574(3) 16(1)
C(20) 4202(5) 5669(4) 860(3) 15(1)
C(21) 5205(5) 6662(4) 1012(4) 18(1)
C(22) 5617(5) 7558(4) 1881(4) 20(1)
C(23) 5014(5) 7447(4) 2593(4) 18(1)
C(24) 4682(4) 2031(4) 1835(3) 14(1)
C(25) 5030(5) 1609(4) 2590(4) 18(1)
C(26) 5849(5) 1054(4) 2540(4) 25(1)
C(27) 6297(5) 890(4) 1738(4) 26(1)
C(28) 5967(5) 1314(4) 994(4) 22(1)
C(29) 5176(5) 1896(4) 1046(3) 19(1)
C(30) 5001(5) 4200(4) 2642(3) 15(1)
C(31) 5875(5) 4661(4) 2164(4) 19(1)
C(32) 6903(5) 5706(4) 2648(4) 23(1)
C(33) 7054(5) 6296(4) 3606(4) 27(1)
C(34) 6195(5) 5832(4) 4094(4) 25(1)
C(35) 5172(5) 4791(4) 3613(3) 19(1)
C(36) 1098(5) 1190(4) 3453(3) 15(1)
C(37) 2225(5) 1150(4) 3564(3) 16(1)
C(38) -202(5) 781(4) 3656(3) 16(1)
O(38) -1299(4) 238(3) 3017(3) 29(1)
O(39) 6(4) 1105(3) 4644(3) 25(1)
C(40) -1227(6) 775(6) 4882(4) 36(1)
C(41) 3136(5) 709(4) 3998(3) 16(1)
O(41) 4103(4) 1189(3) 4770(3) 28(1)
O(42) 2767(3) -319(3) 3424(2) 20(1)
C(43) 3633(5) -826(4) 3770(4) 25(1)
C(44) -492(4) 2412(4) 952(3) 13(1)
C(45) -1115(5) 2966(4) 478(3) 17(1)
C(46) -2082(5) 2448(4) -475(4) 21(1)
C(47) -2420(5) 1363(4) -987(4) 23(1)
C(48) -1789(5) 814(4) -539(4) 22(1)
C(49) -846(5) 1323(4) 429(3) 17(1)
C(50) -75(5) 3395(4) 3074(3) 15(1)
C(51) -1186(5) 3633(4) 2825(4) 20(1)
C(52) -1842(5) 3798(4) 3509(4) 23(1)
C(53) -1407(5) 3722(4) 4449(4) 22(1)
C(54) -284(5) 3512(4) 4719(4) 22(1)
C(55) 377(5) 3343(4) 4036(3) 19(1)
________________________________________________________________________________
Table 3. Bond lengths [Å] and angles [°] for 10.
_____________________________________________________
Pd(1)-C(36) 2.025(4)
Pd(1)-C(37) 2.064(4)
Pd(1)-P(2) 2.3081(13)
Pd(1)-P(7) 2.3167(12)
P(2)-C(30) 1.832(5)
P(2)-C(24) 1.839(5)
P(2)-C(3) 1.839(4)
C(3)-C(4) 1.393(6)
C(3)-C(8) 1.421(6)
C(4)-C(11) 1.439(6)
C(4)-C(5) 1.503(6)
C(5)-C(6) 1.380(6)
C(5)-C(12) 1.430(6)
C(6)-C(15) 1.423(6)
C(6)-P(7) 1.844(4)
P(7)-C(44) 1.819(5)
P(7)-C(50) 1.839(5)
C(8)-C(9) 1.356(6)
C(9)-C(10) 1.414(6)
C(10)-C(16) 1.407(6)
C(10)-C(11) 1.417(6)
C(11)-C(19) 1.430(6)
C(12)-C(13) 1.419(6)
C(12)-C(20) 1.426(6)
C(13)-C(23) 1.419(7)
C(13)-C(14) 1.426(6)
C(14)-C(15) 1.364(7)
C(16)-C(17) 1.375(7)
C(17)-C(18) 1.401(7)
C(18)-C(19) 1.371(6)
C(20)-C(21) 1.371(6)
C(21)-C(22) 1.402(7)
C(22)-C(23) 1.366(7)
C(24)-C(29) 1.384(6)
C(24)-C(25) 1.400(6)
C(25)-C(26) 1.393(7)
C(26)-C(27) 1.372(7)
C(27)-C(28) 1.385(7)
C(28)-C(29) 1.395(7)
C(30)-C(35) 1.389(6)
C(30)-C(31) 1.389(7)
C(31)-C(32) 1.383(7)
C(32)-C(33) 1.381(8)
C(33)-C(34) 1.390(8)
C(34)-C(35) 1.377(7)
C(36)-C(37) 1.251(7)
C(36)-C(38) 1.487(6)
C(37)-C(41) 1.460(6)
C(38)-O(38) 1.196(6)
C(38)-O(39) 1.337(6)
O(39)-C(40) 1.439(6)
C(41)-O(41) 1.206(6)
C(41)-O(42) 1.340(6)
O(42)-C(43) 1.451(5)
C(44)-C(49) 1.396(6)
C(44)-C(45) 1.399(6)
C(45)-C(46) 1.379(7)
C(46)-C(47) 1.392(7)
C(47)-C(48) 1.379(7)
C(48)-C(49) 1.385(7)
C(50)-C(51) 1.383(6)
C(50)-C(55) 1.399(6)
C(51)-C(52) 1.387(7)
C(52)-C(53) 1.380(7)
C(53)-C(54) 1.375(7)
C(54)-C(55) 1.390(7)
C(36)-Pd(1)-C(37) 35.61(19)
C(36)-Pd(1)-P(2) 154.36(13)
C(37)-Pd(1)-P(2) 119.33(14)
C(36)-Pd(1)-P(7) 110.80(14)
C(37)-Pd(1)-P(7) 146.04(14)
P(2)-Pd(1)-P(7) 94.57(5)
C(30)-P(2)-C(24) 101.5(2)
C(30)-P(2)-C(3) 105.7(2)
C(24)-P(2)-C(3) 106.0(2)
C(30)-P(2)-Pd(1) 120.11(15)
C(24)-P(2)-Pd(1) 116.51(15)
C(3)-P(2)-Pd(1) 105.94(14)
C(4)-C(3)-C(8) 119.0(4)
C(4)-C(3)-P(2) 122.5(3)
C(8)-C(3)-P(2) 117.6(3)
C(3)-C(4)-C(11) 119.6(4)
C(3)-C(4)-C(5) 121.3(4)
C(11)-C(4)-C(5) 119.0(4)
C(6)-C(5)-C(12) 120.0(4)
C(6)-C(5)-C(4) 120.8(4)
C(12)-C(5)-C(4) 119.1(4)
C(5)-C(6)-C(15) 119.8(4)
C(5)-C(6)-P(7) 122.3(3)
C(15)-C(6)-P(7) 117.3(3)
C(44)-P(7)-C(50) 105.9(2)
C(44)-P(7)-C(6) 105.1(2)
C(50)-P(7)-C(6) 105.0(2)
C(44)-P(7)-Pd(1) 118.18(15)
C(50)-P(7)-Pd(1) 111.03(15)
C(6)-P(7)-Pd(1) 110.70(14)
C(9)-C(8)-C(3) 121.8(4)
C(8)-C(9)-C(10) 120.7(4)
C(16)-C(10)-C(11) 120.0(4)
C(16)-C(10)-C(9) 120.9(4)
C(11)-C(10)-C(9) 119.0(4)
C(10)-C(11)-C(19) 118.1(4)
C(10)-C(11)-C(4) 119.5(4)
C(19)-C(11)-C(4) 122.4(4)
C(13)-C(12)-C(20) 118.1(4)
C(13)-C(12)-C(5) 119.4(4)
C(20)-C(12)-C(5) 122.4(4)
C(23)-C(13)-C(12) 119.6(4)
C(23)-C(13)-C(14) 121.3(4)
C(12)-C(13)-C(14) 119.1(4)
C(15)-C(14)-C(13) 120.3(4)
C(14)-C(15)-C(6) 121.2(4)
C(17)-C(16)-C(10) 120.7(4)
C(16)-C(17)-C(18) 119.7(4)
C(19)-C(18)-C(17) 121.2(4)
C(18)-C(19)-C(11) 120.3(4)
C(21)-C(20)-C(12) 120.5(4)
C(20)-C(21)-C(22) 121.2(4)
C(23)-C(22)-C(21) 119.9(4)
C(22)-C(23)-C(13) 120.8(4)
C(29)-C(24)-C(25) 118.9(4)
C(29)-C(24)-P(2) 125.6(4)
C(25)-C(24)-P(2) 115.4(3)
C(26)-C(25)-C(24) 120.4(4)
C(27)-C(26)-C(25) 120.4(5)
C(26)-C(27)-C(28) 119.5(5)
C(27)-C(28)-C(29) 120.8(5)
C(24)-C(29)-C(28) 119.9(5)
C(35)-C(30)-C(31) 119.5(4)
C(35)-C(30)-P(2) 119.2(4)
C(31)-C(30)-P(2) 121.2(4)
C(32)-C(31)-C(30) 120.2(4)
C(33)-C(32)-C(31) 120.0(5)
C(32)-C(33)-C(34) 120.0(5)
C(35)-C(34)-C(33) 120.0(5)
C(34)-C(35)-C(30) 120.3(5)
C(37)-C(36)-C(38) 145.0(4)
C(37)-C(36)-Pd(1) 73.9(3)
C(38)-C(36)-Pd(1) 141.1(3)
C(36)-C(37)-C(41) 145.9(5)
C(36)-C(37)-Pd(1) 70.5(3)
C(41)-C(37)-Pd(1) 143.5(3)
O(38)-C(38)-O(39) 124.2(4)
O(38)-C(38)-C(36) 124.3(4)
O(39)-C(38)-C(36) 111.5(4)
C(38)-O(39)-C(40) 113.8(4)
O(41)-C(41)-O(42) 123.2(4)
O(41)-C(41)-C(37) 125.6(4)
O(42)-C(41)-C(37) 111.2(4)
C(41)-O(42)-C(43) 115.8(4)
C(49)-C(44)-C(45) 118.5(4)
C(49)-C(44)-P(7) 118.8(3)
C(45)-C(44)-P(7) 122.7(4)
C(46)-C(45)-C(44) 121.2(5)
C(45)-C(46)-C(47) 119.5(5)
C(48)-C(47)-C(46) 119.9(4)
C(47)-C(48)-C(49) 120.7(5)
C(48)-C(49)-C(44) 120.2(4)
C(51)-C(50)-C(55) 118.2(4)
C(51)-C(50)-P(7) 124.5(4)
C(55)-C(50)-P(7) 117.3(3)
C(50)-C(51)-C(52) 120.6(4)
C(53)-C(52)-C(51) 120.8(4)
C(54)-C(53)-C(52) 119.5(4)
C(53)-C(54)-C(55) 120.0(5)
C(54)-C(55)-C(50) 120.9(4)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
Table 4. Anisotropic displacement parameters (Å2x 103)for 10. The anisotropic displacement factor
exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ]
______________________________________________________________________________
U11 U22 U33 U23 U13 U12
______________________________________________________________________________
Pd(1) 12(1) 14(1) 17(1) 9(1) 7(1) 10(1)
P(2) 12(1) 13(1) 16(1) 7(1) 6(1) 9(1)
C(3) 10(2) 17(2) 18(2) 9(2) 8(2) 10(2)
C(4) 11(2) 13(2) 17(2) 6(2) 8(2) 8(2)
C(5) 15(2) 13(2) 14(2) 5(2) 5(2) 12(2)
C(6) 10(2) 13(2) 18(2) 9(2) 6(2) 7(2)
P(7) 11(1) 13(1) 15(1) 7(1) 6(1) 9(1)
C(8) 16(2) 14(2) 22(2) 8(2) 10(2) 8(2)
C(9) 16(2) 8(2) 19(2) 2(2) 7(2) 3(2)
C(10) 13(2) 17(2) 21(2) 8(2) 10(2) 8(2)
C(11) 11(2) 14(2) 15(2) 8(2) 7(2) 7(2)
C(12) 11(2) 14(2) 18(2) 9(2) 4(2) 10(2)
C(13) 13(2) 18(2) 19(2) 7(2) 6(2) 12(2)
C(14) 18(2) 17(2) 18(2) 5(2) 7(2) 12(2)
C(15) 16(2) 19(2) 15(2) 7(2) 9(2) 11(2)
C(16) 21(3) 22(3) 16(2) 4(2) 5(2) 8(2)
C(17) 18(2) 23(3) 16(2) 10(2) 3(2) 8(2)
C(18) 18(2) 22(3) 23(2) 13(2) 7(2) 12(2)
C(19) 16(2) 15(2) 19(2) 7(2) 5(2) 7(2)
C(20) 18(2) 13(2) 16(2) 6(2) 7(2) 8(2)
C(21) 16(2) 20(2) 25(2) 15(2) 11(2) 9(2)
C(22) 14(2) 14(2) 29(3) 10(2) 6(2) 3(2)
C(23) 17(2) 14(2) 22(2) 3(2) 4(2) 9(2)
C(24) 13(2) 12(2) 20(2) 6(2) 7(2) 8(2)
C(25) 17(2) 24(3) 25(2) 13(2) 13(2) 14(2)
C(26) 19(3) 31(3) 40(3) 22(3) 14(2) 18(2)
C(27) 18(3) 23(3) 47(3) 14(2) 14(2) 16(2)
C(28) 16(2) 23(3) 30(3) 4(2) 12(2) 10(2)
C(29) 16(2) 23(3) 19(2) 6(2) 7(2) 11(2)
C(30) 16(2) 16(2) 19(2) 11(2) 6(2) 10(2)
C(31) 18(2) 24(3) 18(2) 7(2) 4(2) 14(2)
C(32) 13(2) 30(3) 27(3) 16(2) 4(2) 9(2)
C(33) 19(3) 21(3) 38(3) 12(2) 0(2) 10(2)
C(34) 23(3) 23(3) 24(3) 5(2) 2(2) 10(2)
C(35) 20(2) 23(3) 18(2) 11(2) 7(2) 13(2)
C(36) 23(2) 13(2) 18(2) 11(2) 12(2) 12(2)
C(37) 23(3) 18(2) 14(2) 10(2) 8(2) 13(2)
C(38) 18(2) 15(2) 23(2) 9(2) 12(2) 12(2)
O(38) 19(2) 33(2) 27(2) 2(2) 9(2) 8(2)
O(39) 21(2) 37(2) 22(2) 12(2) 12(2) 13(2)
C(40) 28(3) 58(4) 31(3) 20(3) 21(3) 21(3)
C(41) 18(2) 17(2) 23(2) 15(2) 13(2) 13(2)
O(41) 29(2) 28(2) 24(2) 6(2) 0(2) 17(2)
O(42) 20(2) 17(2) 27(2) 9(2) 4(2) 16(1)
C(43) 26(3) 23(3) 36(3) 16(2) 9(2) 18(2)
C(44) 12(2) 14(2) 17(2) 9(2) 8(2) 6(2)
C(45) 18(2) 19(2) 21(2) 11(2) 9(2) 11(2)
C(46) 17(2) 29(3) 22(2) 14(2) 8(2) 11(2)
C(47) 15(2) 27(3) 16(2) 7(2) 1(2) 1(2)
C(48) 25(3) 14(2) 22(2) 2(2) 9(2) 4(2)
C(49) 18(2) 16(2) 23(2) 11(2) 11(2) 9(2)
C(50) 16(2) 13(2) 19(2) 6(2) 8(2) 8(2)
C(51) 15(2) 28(3) 20(2) 9(2) 7(2) 14(2)
C(52) 13(2) 28(3) 30(3) 5(2) 8(2) 15(2)
C(53) 25(3) 23(3) 23(2) 4(2) 16(2) 13(2)
C(54) 32(3) 22(3) 19(2) 9(2) 11(2) 19(2)
C(55) 21(2) 20(2) 21(2) 7(2) 8(2) 15(2)
______________________________________________________________________________
Table 5. Torsion angles [°] for 10.
________________________________________________________________
C(36)-Pd(1)-P(2)-C(30) -111.6(3)
C(37)-Pd(1)-P(2)-C(30) -101.4(2)
P(7)-Pd(1)-P(2)-C(30) 76.61(17)
C(36)-Pd(1)-P(2)-C(24) 11.5(4)
C(37)-Pd(1)-P(2)-C(24) 21.7(2)
P(7)-Pd(1)-P(2)-C(24) -160.30(17)
C(36)-Pd(1)-P(2)-C(3) 129.0(3)
C(37)-Pd(1)-P(2)-C(3) 139.2(2)
P(7)-Pd(1)-P(2)-C(3) -42.76(16)
C(30)-P(2)-C(3)-C(4) -48.8(4)
C(24)-P(2)-C(3)-C(4) -155.9(4)
Pd(1)-P(2)-C(3)-C(4) 79.7(4)
C(30)-P(2)-C(3)-C(8) 141.8(3)
C(24)-P(2)-C(3)-C(8) 34.6(4)
Pd(1)-P(2)-C(3)-C(8) -89.7(3)
C(8)-C(3)-C(4)-C(11) -5.8(6)
P(2)-C(3)-C(4)-C(11) -175.1(3)
C(8)-C(3)-C(4)-C(5) 172.9(4)
P(2)-C(3)-C(4)-C(5) 3.6(6)
C(3)-C(4)-C(5)-C(6) -71.7(6)
C(11)-C(4)-C(5)-C(6) 107.0(5)
C(3)-C(4)-C(5)-C(12) 106.0(5)
C(11)-C(4)-C(5)-C(12) -75.3(5)
C(12)-C(5)-C(6)-C(15) -2.9(6)
C(4)-C(5)-C(6)-C(15) 174.7(4)
C(12)-C(5)-C(6)-P(7) -173.3(3)
C(4)-C(5)-C(6)-P(7) 4.4(6)
C(5)-C(6)-P(7)-C(44) -54.9(4)
C(15)-C(6)-P(7)-C(44) 134.5(3)
C(5)-C(6)-P(7)-C(50) -166.4(4)
C(15)-C(6)-P(7)-C(50) 23.0(4)
C(5)-C(6)-P(7)-Pd(1) 73.7(4)
C(15)-C(6)-P(7)-Pd(1) -96.9(3)
C(36)-Pd(1)-P(7)-C(44) -89.4(2)
C(37)-Pd(1)-P(7)-C(44) -96.3(3)
P(2)-Pd(1)-P(7)-C(44) 86.84(16)
C(36)-Pd(1)-P(7)-C(50) 33.2(2)
C(37)-Pd(1)-P(7)-C(50) 26.3(3)
P(2)-Pd(1)-P(7)-C(50) -150.57(16)
C(36)-Pd(1)-P(7)-C(6) 149.4(2)
C(37)-Pd(1)-P(7)-C(6) 142.5(3)
P(2)-Pd(1)-P(7)-C(6) -34.36(16)
C(4)-C(3)-C(8)-C(9) 3.2(7)
P(2)-C(3)-C(8)-C(9) 173.1(4)
C(3)-C(8)-C(9)-C(10) 1.6(7)
C(8)-C(9)-C(10)-C(16) 178.7(4)
C(8)-C(9)-C(10)-C(11) -3.6(7)
C(16)-C(10)-C(11)-C(19) 0.5(6)
C(9)-C(10)-C(11)-C(19) -177.3(4)
C(16)-C(10)-C(11)-C(4) 178.7(4)
C(9)-C(10)-C(11)-C(4) 1.0(6)
C(3)-C(4)-C(11)-C(10) 3.7(6)
C(5)-C(4)-C(11)-C(10) -175.0(4)
C(3)-C(4)-C(11)-C(19) -178.1(4)
C(5)-C(4)-C(11)-C(19) 3.2(6)
C(6)-C(5)-C(12)-C(13) 4.6(6)
C(4)-C(5)-C(12)-C(13) -173.0(4)
C(6)-C(5)-C(12)-C(20) -178.1(4)
C(4)-C(5)-C(12)-C(20) 4.3(6)
C(20)-C(12)-C(13)-C(23) -2.0(6)
C(5)-C(12)-C(13)-C(23) 175.4(4)
C(20)-C(12)-C(13)-C(14) -180.0(4)
C(5)-C(12)-C(13)-C(14) -2.6(6)
C(23)-C(13)-C(14)-C(15) -179.1(4)
C(12)-C(13)-C(14)-C(15) -1.2(7)
C(13)-C(14)-C(15)-C(6) 3.0(7)
C(5)-C(6)-C(15)-C(14) -1.0(7)
P(7)-C(6)-C(15)-C(14) 169.9(4)
C(11)-C(10)-C(16)-C(17) 0.0(7)
C(9)-C(10)-C(16)-C(17) 177.7(5)
C(10)-C(16)-C(17)-C(18) -0.4(7)
C(16)-C(17)-C(18)-C(19) 0.3(7)
C(17)-C(18)-C(19)-C(11) 0.2(7)
C(10)-C(11)-C(19)-C(18) -0.5(7)
C(4)-C(11)-C(19)-C(18) -178.7(4)
C(13)-C(12)-C(20)-C(21) 1.3(6)
C(5)-C(12)-C(20)-C(21) -176.0(4)
C(12)-C(20)-C(21)-C(22) -0.2(7)
C(20)-C(21)-C(22)-C(23) -0.1(7)
C(21)-C(22)-C(23)-C(13) -0.7(7)
C(12)-C(13)-C(23)-C(22) 1.8(7)
C(14)-C(13)-C(23)-C(22) 179.7(4)
C(30)-P(2)-C(24)-C(29) -81.5(4)
C(3)-P(2)-C(24)-C(29) 28.7(5)
Pd(1)-P(2)-C(24)-C(29) 146.2(4)
C(30)-P(2)-C(24)-C(25) 94.6(4)
C(3)-P(2)-C(24)-C(25) -155.3(4)
Pd(1)-P(2)-C(24)-C(25) -37.7(4)
C(29)-C(24)-C(25)-C(26) -0.7(7)
P(2)-C(24)-C(25)-C(26) -177.0(4)
C(24)-C(25)-C(26)-C(27) -1.6(8)
C(25)-C(26)-C(27)-C(28) 2.2(8)
C(26)-C(27)-C(28)-C(29) -0.6(8)
C(25)-C(24)-C(29)-C(28) 2.2(7)
P(2)-C(24)-C(29)-C(28) 178.2(4)
C(27)-C(28)-C(29)-C(24) -1.6(7)
C(24)-P(2)-C(30)-C(35) -118.5(4)
C(3)-P(2)-C(30)-C(35) 131.1(4)
Pd(1)-P(2)-C(30)-C(35) 11.6(4)
C(24)-P(2)-C(30)-C(31) 58.9(4)
C(3)-P(2)-C(30)-C(31) -51.5(4)
Pd(1)-P(2)-C(30)-C(31) -171.0(3)
C(35)-C(30)-C(31)-C(32) -0.5(7)
P(2)-C(30)-C(31)-C(32) -177.9(4)
C(30)-C(31)-C(32)-C(33) -0.5(7)
C(31)-C(32)-C(33)-C(34) 1.5(7)
C(32)-C(33)-C(34)-C(35) -1.5(8)
C(33)-C(34)-C(35)-C(30) 0.5(7)
C(31)-C(30)-C(35)-C(34) 0.5(7)
P(2)-C(30)-C(35)-C(34) 178.0(4)
P(2)-Pd(1)-C(36)-C(37) 15.4(5)
P(7)-Pd(1)-C(36)-C(37) -173.4(3)
C(37)-Pd(1)-C(36)-C(38) -178.1(7)
P(2)-Pd(1)-C(36)-C(38) -162.7(4)
P(7)-Pd(1)-C(36)-C(38) 8.5(6)
C(38)-C(36)-C(37)-C(41) -3.0(14)
Pd(1)-C(36)-C(37)-C(41) 179.1(8)
C(38)-C(36)-C(37)-Pd(1) 177.9(8)
P(2)-Pd(1)-C(37)-C(36) -172.4(2)
P(7)-Pd(1)-C(37)-C(36) 11.1(4)
C(36)-Pd(1)-C(37)-C(41) -179.1(8)
P(2)-Pd(1)-C(37)-C(41) 8.4(6)
P(7)-Pd(1)-C(37)-C(41) -168.0(4)
C(37)-C(36)-C(38)-O(38) -116.0(8)
Pd(1)-C(36)-C(38)-O(38) 60.8(8)
C(37)-C(36)-C(38)-O(39) 64.6(9)
Pd(1)-C(36)-C(38)-O(39) -118.6(5)
O(38)-C(38)-O(39)-C(40) -2.2(7)
C(36)-C(38)-O(39)-C(40) 177.2(4)
C(36)-C(37)-C(41)-O(41) -100.0(9)
Pd(1)-C(37)-C(41)-O(41) 78.5(7)
C(36)-C(37)-C(41)-O(42) 80.1(9)
Pd(1)-C(37)-C(41)-O(42) -101.4(6)
O(41)-C(41)-O(42)-C(43) -1.7(7)
C(37)-C(41)-O(42)-C(43) 178.1(4)
C(50)-P(7)-C(44)-C(49) -115.2(4)
C(6)-P(7)-C(44)-C(49) 134.0(4)
Pd(1)-P(7)-C(44)-C(49) 10.0(4)
C(50)-P(7)-C(44)-C(45) 67.1(4)
C(6)-P(7)-C(44)-C(45) -43.7(4)
Pd(1)-P(7)-C(44)-C(45) -167.7(3)
C(49)-C(44)-C(45)-C(46) 1.6(7)
P(7)-C(44)-C(45)-C(46) 179.3(4)
C(44)-C(45)-C(46)-C(47) -1.8(7)
C(45)-C(46)-C(47)-C(48) 0.1(7)
C(46)-C(47)-C(48)-C(49) 1.7(7)
C(47)-C(48)-C(49)-C(44) -1.9(7)
C(45)-C(44)-C(49)-C(48) 0.2(7)
P(7)-C(44)-C(49)-C(48) -177.5(4)
C(44)-P(7)-C(50)-C(51) -30.2(5)
C(6)-P(7)-C(50)-C(51) 80.6(4)
Pd(1)-P(7)-C(50)-C(51) -159.7(4)
C(44)-P(7)-C(50)-C(55) 146.3(4)
C(6)-P(7)-C(50)-C(55) -102.8(4)
Pd(1)-P(7)-C(50)-C(55) 16.9(4)
C(55)-C(50)-C(51)-C(52) -1.0(7)
P(7)-C(50)-C(51)-C(52) 175.6(4)
C(50)-C(51)-C(52)-C(53) -0.4(8)
C(51)-C(52)-C(53)-C(54) 2.0(8)
C(52)-C(53)-C(54)-C(55) -2.1(8)
C(53)-C(54)-C(55)-C(50) 0.7(8)
C(51)-C(50)-C(55)-C(54) 0.9(7)
P(7)-C(50)-C(55)-C(54) -175.9(4)
________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
IV. KINETICS OF THE RACEMIZATION PROCESS
A sample of non-racemic 1 dissolved in 1:3 CH2Cl2/hexane (1 mL) was prepared andheated to 45 ºC by immersion in a thermostatic bath. Once the constant temperature was reached, an aliquot was taken, cooled to room temperature, and quickly analyzed byHPLC [OL-86 (CH2Cl2/hexane 35:65)] to determine the initial enantiomeric excess.This process was repeated at four different intervals of time. Representation ofln(ee0/eet) against time resulted in a first order plot, from which the enantiomerizationreaction rate k was determined, from the kinetic ecuation: ln(ee0/eet) = 2k x t]. The same procedure was repeated at constant temperatures 60, 65 and 75 ºC.
45 ºC
t (min) ee (%) ln(eeo/eet)
0 68
61 61 0,10863
123 57 0,17646
175 54 0,23052
240 51 0,28768
300 47 0,36936
60 ºC
t (min) ee (%) ln(eeo/eet)
0 68
30 57 0,17646
62 47 0,36936
90 40 0,53063
120 36 0,63599
150 30 0,81831
65 ºC
t (min) ee (%) ln(eeo/eet)
0 73
31 55 0,28313
59 43 0,52926
91 32 0,82472
120 24 1,11241
153 17 1,45725
75 ºC
t (min) ee (%) ln(eeo/eet)
0 65
16 53 0,2041
30 39 0,51083
46 29 0,80709
60 24 0,99633
70 15 1,46634
0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
0 50 100 150 200 250 300 350
t/min
ln(e
eo
/ee
t) 45
60
65
75
T = 45 ºC y = 1,063E-03x + 4,333E-02 k = 8,858E-06 s-1
T = 60 ºC y = 5,205E-03x + 3,563E-02 k = 43,375E-06 s-1
T = 65 ºC y = 9,617E-03x - 3,191E-02 k = 80,142E-06 s-1
T = 75 ºC y = 2,152E-02x - 1,587E-01 k = 179,33E-06 s-1
Eyring Plot
T (K) k (s-1
) ln (k/T) 1/T (K-1
)
318,15 0,000008858 -17,3967 0,003143
333,15 0,000043375 -15,8542 0,003002
338,15 0,000080142 -15,2552 0,002957
348,15 0,00017933 -14,4785 0,002872
-18
-17
-16
-15
-14
-13
-12
2,8E-03 2,9E-03 3,0E-03 3,1E-03 3,2E-03
1/T
ln (
k/T
)
y = -10894x + 16,866
ΔΔH� = 21.65 kcal/mol
ΔΔS� = -13.70 cal/mol K
ΔΔG� (298K) = 25.73 kcal/mol
