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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

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013

2

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


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

=


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


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;

=


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


7

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.


8


9

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.


10


11


12


13


14

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.


15


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