Supporting Information

Table S1. Kinetic data for reactions of 4-nitrobenzofurazan 1 with 4-methoxyphenoxide anion 2a in
aqueous solution at 20 C.
Correlatio
[4- kobsd (s-1)
k1 k-1 n
methoxyphenoxide]
(M-1 s-1) (s-1) coefficien
(mol L-1) pH = 9.97a pH = 9.67b
t
1 x 10-3 8.04 x 10-3 9.14 x 10-3

2 x 10-3 1.03 x 10-2 1.33 x 10-2

3 x 10-3 - 1.45 x 10-2

4 x 10-3 1.84 x 10-2 - 2.82 6.00 x 10-3 0.9944

6 x 10-3 2.22 x 10-2 2.30 x 10-2

8 x 10-3 2.98 x 10-2 -

1 x 10-2 - 3.47 x 10-2

b
1 : 2 Buffer. c 1 : 4 Buffer.

Table S2. Kinetic data for reactions of 4-nitrobenzofurazan 1 with 4-methylphenoxide anion 2b in
aqueous solution at 20 C.
kobsd (s-1)
[4-methylphenoxide] k1 k-1 Correlation
(mol L-1) (M-1 s-1) (s-1) coefficient
pH = 9.89a pH = 9.59b

1 x 10-3 - 5.50 x 10-3

2 x 10-3 7.80 x 10-3 7.64 x 10-3

4 x 10-3 1.02 x 10-2 1.04 x 10-2

5 x 10-3 1.34 x 10-2 -

1.66 4.50 x 10-3 0.9866
-3 -2
6 x 10 - 1.59 x 10

7 x 10-3 1.61 x 10-2 -

8 x 10-3 - 1.73 x 10-2

9 x 10-3 1.89 x 10-2 -

b
1 : 2 Buffer. c 1 : 4 Buffer.
Table S3. Kinetic data for reactions of 4-nitrobenzofurazan 1 with phenoxide anion 2c in aqueous
solution at 20 C.
Correlatio
kobsd (s-1)
[phenoxide] k1 k-1 n
(mol L-1) (M-1 s-1) (s-1) coefficien
pH = 9.58a pH = 9.28b
t
1 x 10-3 2.26 x 10-3 -

2 x 10-3 3.56 x 10-3 3.26 x 10-3

4 x 10-3 4.10 x 10-3 5.10 x 10-3

5 x 10-3 - 5.61 x 10-3

5.74 x 10-1 2.20 x 10-3 0.9760
6 x 10-3 - -

7 x 10-3 - 6.30 x 10-3

8 x 10-3 6.80 x 10-3 -

1 x 10-2 7.32 x 10-3 8.23 x 10-3

b
1 : 2 Buffer. c 1 : 4 Buffer.

Table S4. Kinetic data for reactions of 4-nitrobenzofurazan 1 with 4-chlorophenoxide anion 2d in
aqueous solution at 20 C.
Correlatio
kobsd (s-1)
[4-chlorophenoxide] k1 k-1 n
(mol L-1) (M-1 s-1) (s-1) coefficien
pH = 9.05a pH = 8.75b
t
1 x 10-3 9.20 x 10-4 1.03 x 10-3

2 x 10-3 1.21 x 10-3 -

4 x 10-3 - 1.66 x 10-3

6 x 10-3 2.10 x 10-3 2.31 x 10-3

2.38 x 10-1 7.45 x 10-4 0.9940
-3 -3
7 x 10 - 2.46 x 10

8 x 10-3 2.53 x 10-3 -

9 x 10-3 - 2.98 x 10-3

1 x 10-2 3.03 x 10-3 -

b
1 : 2 Buffer. c 1 : 4 Buffer
Table S5. The kobsd and k values for the reactions of the 4-nitrobenzofurazan 1 with OH- in 50% H2O-
50% MeCN at 20 C.
Correlation
[OH-] (mol L-1) kobsd (s-1) k1 (M-1 s-1)
coefficient
1 x 10-3 1.33 x 10-2

2 x 10-3 2.72 x 10-2

3 x 10-3 4.13 x 10-2 1.29 x 101 0.9958

4 x 10-3 5.55 x 10-2

5 x 10-3 6.36 x 10-2

Table S6. 1H and 13C nuclear magnetic resonance parameters of 4-nitrobenzofurazan 1 and hydroxy-
adduct in 50:50 (v/v) (DMSO-d6/ D2O).
Compound δH7 δH6 δH5 Coupling constants b δC7 δC6 δC5

1 8.40 7.76 8.58 J5-6 = 7.0; J6-7 = 9.0 130.95 129.10 130.47

1-OH 4.43 6.63 6.87 J5-6 = 9.6; J6-7 = 5.0 39.03 143.97 114.99

a
δ in ppm relative to internal TMS.
b
Coupling constants in Hz.

H OH
7
N 7
N
6 6
O O
5 4 5 4
N N
NO2 NO2
1 1-OH
 0,025
pH = 9.89
pH = 9.59
0,02 pH = 9.05 2b
X = CH
3
pH = 8.75

0,015
-1
/s
obsd
k

0,01

0,005
2d
X = Cl

0
0 0,002 0,004 0,006 0,008 0,01 0,012
-1 -1
[4-X-phenoxide anion] / M L

Figure S1. Effect of the phenoxide anions 2b and 2d concentration and pH on the observed first-order
rate constants, kobsd, for formation of adducts 3b and 3d in aqueous solutions at 20 °C.