PROFESSOR RAZVAN LIVIU NISTOR ASSOCIATE PROFESSOR IRIMIE EMIL POPA PROFESSOR ADRIANA TIRON TUDOR
Supplementary Information - Royal Society of Chemistry · Supplementary Information Relative...
Transcript of Supplementary Information - Royal Society of Chemistry · Supplementary Information Relative...
1
Supplementary Information Relative kinetic reactivity of boronic acid to boronate ion toward Tiron,
2,2-biphenol, and propyleneglycol
Eisuke Watanabe,a Chiaki Miyamoto,a Asumi Tanaka,a Kenzo Iizuka,a Satoshi Iwatsuki,b
Masahiko Inamo,c Hideo D. Takagi,d and Koji Ishiharaa*
Figs S1 – S8 Tables S1 – S4
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Fig. S1 Change in UV-Vis spectra of 3-Pyridylboronicacid with pH in aqueous solution at 25 ºC
and I = 1.0 M. CB = 1.0 × 10–4 M. pH 2.69–10.14
Fig. S2 Change in UV-Vis spectra of Tiron with pH in aqueous solution at 25 ºC and I =
1.0 M. CL = 1.47 × 10–4 M. pH 2.25–12.42
1.0
0.8
0.6
0.4
0.2
0
abso
rban
ce
300280260240220200
wavelength / nm
2.5
2.0
1.5
1.0
0.5
0
abso
rban
ce
340320300280260240220
wavelength / nm
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Fig. S3 (a)
and I = 1.
measureme
25.0 ºC an
spectra of
3.00 x 10–3
reaction of
3.0 x 10–3 M
) Change in
.0 M. CB =
ents (at 309
nd I = 1.0 M
3-PyB(OH3 M, CL = 1
f 2,2’-biphe
M, CL = 6.0
n UV-Vis sp
1.0 x 10–3
9 nm) for th
M. CB = 6.0
)2 with 2,2’
.45 x 10–4 M
enol with 3-
0 x 10–5 M, a
(a)
Red: Tir
Black: T
+ 3-PyB
(c)
Red
+ 3-
Blue
pectra of 3-P3 M, CL = 5
he reaction
x 10–4 M, C
’-biphenol i
M, and pH =
PyB(OH)2
and pH = 4.
ron
Tiron
B(OH)2
: 2,2’-biphenol
PyB(OH)2
e: 2,2’-biphenol
3
PyB(OH)2 w
5.0 x 10–5 M
of Tiron w
CL = 5.00 x
in acidic aq
= 4.40; (d)
in acidic aq
.80.
0
0
0
0
0
Abs
orba
nce
with Tiron i
M, and [H+
with 3-PyB(O
10–5 M, and
queous solu
time course
queous solu
0.25
0.20
0.15
0.10
0.05
000
in acidic aq
] = 1.0 x 1
OH)2 in aci
d pH = 6.07
ution at 25 º
e measurem
tion at 15.0
0.4.2Time
queous solu
10–4 M; (b)
idic aqueou
7; (c) Chang
ºC and I =
ments (at 294
0 ºC and I =
0.6e / s
(d)
ution at 25 º
time cours
us solution
ge in UV-V
1.0 M. CB
4 nm) for th
= 1.0 M. CB
(b)
0.8
ºC
se
at
Vis
=
he
=
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Fig. S4 1
3-PyB(OH
x 10–2 M, C
1.0
0.8
0.6
0.4
0.2
0
Abs
orba
nce
2
(i)
(ii)
11B NMR sp
H)2 at pD = 6
CL = 4.8 x 1
0
8
6
4
2
02240230
Wav
(a)
(b)
pectra of (a
6.0, and (d)
10–2 M; (c)
260250
velength / n
(a
a) 3-PyB(OH
3-PyB(OH
CB = 6.9 x 1
280270
nm
a)
(c)
4
Abs
orba
nce
H)2 at pD =
H)2 + Tiron a
10–2 M; (d)
0.18
0.16
0.14
0.12
0.10
0.080
= 2.6, (b) 3-
at pD = 6.0.
CB = 6.9 x
(c)
(d)
0.20.1
Time
PyB(OH)2 +
(a) CB = 7.
10–2 M, CL
00.3
/ s
+ Tiron at p
1 x 10–2 M;
L = 4.6 x 10–
(b)
0.4
pD = 2.6, (c
; (b) CB = 1–2 M.
c)
.0
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
Fig. S5 (
(PG) (blue
with PG at
in D2O. (
= 1.00 M,
CPG = 2.6 x
Fig. S6 (
glycol (blu
3-FPhB(OH
3-FPhB(OH
(b) CB = 2
11.0, (ii) C
0.5
0.4
0.3
0.2
0.1
Abs
orba
nce
2
(i)
(ii)
(a) UV-Vis
) at 25 ºC a
t 270 nm; (c
(a) CB = 3.5
CCAPS = 0.1
x 10–2
M, pD
(a) UV-Vis
ue) at 25 º
H)2 with P
H)2 and PG
.4 mM, CPG
CB = 1.7 x 10
2524030
Wave
(a)
spectra of P
and I = 0.10
c) 11B NMR
5 x 10–3 M,
10 M, pH =
D = 11.6.
spectra of 3
ºC and I =
PG at 268 n
G (ii) in D2O
G = 2.50 x 1
0–2 M, CPG
2726050
elength / nm
PhB(OH)2 (
M; (b) chan
R spectra of
CL = 9.9 x1
= 10.40; (c)
3-FPhB(OH
0.10 M; (
nm; (c) 11B
O. (a) CB =
0–1 M, CCA
= 3.3 x 10–
28070
m
(c)
5
(red) and th
nge in abso
f PhB(OH)2
10–1 M, CCA
(i) CB = 1.
H)2 (red) an
(b) change
B NMR spe
= 6.1 x 10–
APS = 0.10 M1 M, pD = 1
0.4
0.3
0.3
0.3
Abs
orba
nce
)
he mixture o
rbance with
2 (i) and the
APS = 0.10 M
0 x 10–2 M
nd the mixtu
in absorba
ectra of 3-F4 M, CL = 1
M, pH = 10.
11.0.
40
38
36
34
0.0
of PhB(OH
h time for th
e mixture of
M, pH = 11.0
, pD = 11.6
ure of 3-FPh
nce with ti
FPhB(OH)2
1.1 M, CCAP
30; (c) (i) C
1.0.5
Time / s
H)2 and prop
he reaction o
f PhB(OH)
0; (b) CB =
6, (ii) CB =1
hB(OH)2 an
ime for the
(i) and the
PS = 0.10 M
CB = 3.4 x 1
1.5
s
(b)
pylene glyco
of PhB(OH
2 and PG (i
3.3 mM, CP
1.0 x 10–2 M
nd propylen
e reaction o
e mixture o
M, pH = 10.4
10–2 M, pD
ol
H)2
ii)
PG
M,
ne
of
of
4;
=
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Fig. S7 D
25 ºC and I
Fig. S8 D
3-FPhB(OH
Table S1
propyleneg
k slop
eK*
25x
k slop
eK*
Dependence
I = 0.10 M.
Dependence
H)2 with PG
Rate con
glycol in alk
2500
2000
1500
1000
500
0100
103
20
15
10
5
02100
(a)
e of (a) kslope
e of (a) kslope
G at 25 ºC a
nstants (25
kaline soluti
403020
10-9[H+]-1 /
40300
10-9[H]-1 / M-1
e on [H+]–1
,
e on [H+]–1
,
and I = 0.10
ºC, I = 0
ion. CB = 3.
706050
M-1
706050
1
6
(b) kint vs [
(b) kint vs [
M.
0.10 M) fo
.3 x 10–3 M
0
kk in
t
H+] for the
H+] for the
or the reac
, CAPS buf
5
4
3
2
1
0
k int
0
3.0
2.5
2.0
1.5
1.0
0.5
0
int
0
reactions of
ction of ph
ffer (0.10 M
32010
1012[H+
2010
1012[H
(b)
(b)
f PhB(OH)2
re
henylboroni
M) was used
504030
+] / M
504030
H+] / M
2 with PG a
actions of
ic acid wit
0
0
at
th
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Table S2 Rate constants (25 ºC, I = 0.10 M) for the reaction of 3-F-phenylboronic acid with
propyleneglycol in alkaline solution. CB = 2.4 x 10–3 M, CAPS buffer (0.10 M) was used.
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Table S3 Rate constants (25 ºC, I = 1.0 M) for the reaction of 3-pyridylboronic acid with Tiron in
acidic aqueous solution. CL = 5.0 x 10–5 M.
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Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
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Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
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Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
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Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
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Table S4 Rate constants (15 ºC, I = 1.0 M) for the reaction of 3-pyridylboronic acid with
2,2’-biphenol in acidic aqueous solution (CB >> CL). CL = 6.0 x 10–5 M.
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Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013