Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
REACTIONS OF OCTACYANOMOLYBDATE(V) AND OCTACYANOTUNGSTATE(V)
WITH s2 METAL-ION REDUCING CENTERS
Zhiyong Yang and Edwin S. Gould
SUPPLEMENTARY MATERIALS
Tables S-1 to S-4. Detailed kinetic data for redox reactions.
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Sl
Table S-1. Reduction of Mo(CN)83- by Sn(II). Kinetic dataa
[Sn(II)], mM
[H+], M
[Cl-], M
10-3k2, M-1s-1 b
1.0
1.0
0.10
0.15 (0.12)
1.0
1.0
0.20
0.46 (0.50)
1.0
1.0
0.40
1.47 (1.60)
1.0
1.0
0.60
2.6 (2.8)
1.0
1.0
0.80
3.7 (3.9)
1.0
1.0
0.90
4.3 (4.4)
1.0
0.10
1.00
4.1 (4.2)
1.0
0.20
1.00
4.3 (4.3)
1.0
0.40
1.00
4.4 (4.4)
1.0
0.60
1.00
4.8 (4.6)
1.0
0.90
1.00
4.9 (4.9)
1.0
1.0
1.00
5.1 (4.9)
2.0
1.0
1.00
5.3 (4.9)
3.0
1.0
1.00
5.3 (4.9)
4.0
1.0
1.00
5.3 (4.9)
a
Reactions were carried out at 22.0  0.5 oC;  = 1.0 M (HCl/NaCl or HClO4/NaCl/NaClO4);
 = 389 nm; [Mo(V)] = 2.0 x 10-4 M throughout. bParenthetical values were calculated using
eq. (14) and parameters in Table 2.
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
S2
Table S-2. Reduction of W(CN)83- by Sn(II). Kinetic data.a
[H+], M
[Cl-], M
k2, M-1s-1 b
20.0
0.20
1.00
1.37 (1.36)
20.0
0.40
1.00
1.57 (1.58)
20.0
0.60
1.00
1.79 (1.79)
20.0
0.90
1.00
2.0 (2.1)
20.0
1.00
0.25
0.38 (0.34)
20.0
1.00
0.35
0.61 (0.59)
20.0
1.00
0.45
0.85 (0.85)
20.0
1.00
0.55
1.25 (1.12)
20.0
1.00
0.65
1.40 (1.39)
20.0
1.00
0.80
1.77 (1.76)
20.0
1.00
0.90
1.96 (1.99)
20.0
1.00
1.00
2.2 (2.2)
15.0
1.00
1.00
2.0 (2.2)
10.0
1.00
1.00
2.0 (2.2)
5.0
1.00
1.00
2.1 (2.2)
[Sn(II)], mM
a
Reactions were carried out at 22.0  0.5 oC;  = 1.0 M (HClO4/NaClO4/NaCl/HCl);  = 357 nm;
[W(V)] = 0.30 mM.
Table 2.
b
Parenthetical values were calculated using eq. (14) and parameters in
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
S3
Table S-3. Reduction of Mo(CN)83- by Ge(II). Kinetic dataa
10-2k2, M-1s-1 b
[Ge(II)], mM
[H+], M
[Cl-], M
0.90
1.0
1.0
3.9 (4.1)
1.35
1.0
1.0
3.9 (4.1)
1.80
1.0
1.0
4.1 (4.1)
3.60
1.0
1.0
4.2 (4.1)
1.80
0.20
1.0
2.6 (2.2)
1.80
0.30
1.0
2.8 (2.4)
1.80
0.40
1.0
3.0 (2.7)
1.80
0.60
1.0
3.4 (3.2)
1.80
0.90
1.0
3.9 (3.9)
1.80
1.0
0.20
2.1 (2.5)
1.80
1.0
0.30
2.5 (2.7)
1.80
1.0
0.40
2.9 (3.0)
1.80
1.0
0.60
3.4 (3.4)
1.80
1.0
0.80
3.8 (3.7)
1.80
1.0
0.90
3.9 (4.0)
0.10c
1.0
1.0
4.0 (4.1)
0.10d
1.0
1.0
4.1 (4.1)
a
Reactions were carried out at 22.0  0.5 oC;  = 1.0 M (HClO4/LiCl/HCl);  = 405 nm;
[Mo(V)] = 2.0 x 10-4 M unless otherwise indicated. bParenthetical values were calculated using
eq. (15) and parameters in Table 2. c[Mo(V)] = 0.60 mM. d[Mo(V)] = 0.80 mM.
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
S4
Table S-4. Reduction of W(CN)83- with In(I). Kinetic dataa
[H+], M
10-5k2, M-1s-1 b
0.025
0.010c
1.34  0.05
0.040
0.010c
1.26  0.04
0.060
0.010c
1.35  0.04
0.080
0.010c
1.36  0.04
0.060
0.010c
1.20  0.03
0.060
0.010
2.07  0.08
0.060
0.020
2.09  0.06
0.060
0.040
2.01  0.05
0.060
0.10
2.14  0.06
0.060
0.20
2.16  0.06
0.060
0.40
1.91  0.07
0.060
0.50
2.04  0.08
[In(I)], mM
a
Reactions were carried out at 22.0  0.5 oC;  = 0.50 M (NaClO4/HClO4) unless otherwise
indicated;  = 357 nm; [W(V)] = 0.100 mM throughout. Solutions were 0.4-0.8 M in CH3CN,
present in solution during the generation of InI (ref. 2). Rates were independent of [CH3CN] in
this range. bRate constants were obtained under second order conditions as described by
Espenson (ref. 13). c = 0.010 M HClO4 – 0.10 M NaClO4.