Research Article
Ruthenium(III) Catalysis in Perborate Oxidation of 5-Oxoacids
Table 6
Influence of dielectric constant of the medium on ruthenium(III) catalysisa.
| | AcOH—H2O % (v/v)
|
102 [H+] (mol dm−3) |
103 (s−1) |
103() (s−1) | p-OCH3 | p-CH3 | p-C6H5 | –H | p-Cl | p-Br | m-NO2 | p-OCH3 | p-CH3 | p-C6H5 | –H | p-Cl | p-Br | m-NO2 |
| 53.18 | 30–70 | 0.88 | 7.26 (4.81) | 3.62 (2.40) | 2.64 (1.75) | 2.38 (1.58) | 0.73 (0.49) | 0.37 (0.25) | 0.17 (0.12) | 2.45 | 1.22 | 0.88 | 0.80 | 0.24 | 0.12 | 0.05 | 46.48 | 40–60 | 0.88 | 12.95 (4.47) | 6.47 (2.24) | 4.72 (1.63) | 4.25 (1.47) | 1.30 (0.45) | 0.66 (0.23) | 0.32 (0.12) | 8.48 | 4.23 | 3.08 | 2.78 | 0.85 | 0.43 | 0.21 | 39.78 | 50–50 | 0.88 | 18.27 (4.11) | 9.13 (2.05) | 6.66 (1.49) | 6.00 (1.35) | 1.85 (0.42) | 0.94 (0.21) | 0.46 (0.11) | 14.16 | 7.08 | 5.16 | 4.65 | 1.43 | 0.72 | 0.36 | 33.08 | 60–40 | 0.88 | 24.66 (3.86) | 12.32 (1.93) | 8.99 (1.41) | 8.10 (1.27) | 2.49 (0.39) | 1.27 (0.19) | 0.63 (0.09) | 20.79 | 10.39 | 7.58 | 6.83 | 2.10 | 1.07 | 0.53 | 26.08 | 70–30 | 0.88 | 30.34 (3.68) | 15.17 (1.84) | 11.07 (1.34) | 9.97 (1.21) | 3.07 (0.37) | 1.56 (0.19) | 0.77 (0.09) | 26.66 | 13.33 | 9.72 | 8.76 | 2.70 | 1.37 | 0.68 | 53.18 | 30–70 | 14.9 | 24.63 (11.77) | 12.31 (5.89) | 8.98 (4.29) | 8.09 (3.87) | 2.49 (1.19) | 1.27 (0.61) | 0.63 (0.30) | 12.86 | 6.42 | 4.68 | 4.22 | 1.30 | 0.66 | 0.32 | 46.48 | 40–60 | 14.9 | 24.99 (11.10) | 12.49 (5.55) | 9.11 (4.05) | 8.21 (3.65) | 2.53 (1.13) | 1.28 (0.57) | 0.63 (0.29) | 13.88 | 6.94 | 5.06 | 4.56 | 1.40 | 0.71 | 0.35 | 39.78 | 50-50 | 14.9 | 27.33 (11.56) | 13.66 (5.78) | 9.97 (4.22) | 8.98 (3.80) | 2.77 (1.17) | 1.28 (0.57) | 0.63 (0.29) | 15.78 | 7.88 | 5.75 | 5.18 | 1.59 | 0.81 | 0.40 | 33.08 | 60–40 | 14.9 | 30.37 (10.83) | 15.18 (5.41) | 11.08 (3.95) | 9.98 (3.56) | 3.07 (1.09) | 1.56 (0.56) | 0.77 (0.28) | 19.55 | 9.77 | 7.13 | 6.42 | 1.98 | 1.00 | 0.49 | 26.08 | 70–30 | 14.9 | 36.79 (10.34) | 18.39 (5.17) | 13.42 (3.77) | 12.09 (3.40) | 3.72 (1.05) | 1.90 (0.54) | 0.94 (0.27) | 26.33 | 13.16 | 9.60 | 8.65 | 2.66 | 1.35 | 0.67 |
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a103[Perborate]0 = 1.0 mol dm−3; 102[5-oxoacid]0 = 4.0 mol dm−3; *104[Ru(III)] = 1.0 mol dm−3; HOAc—H2O = 1 : 1 % (v/v); temp. = 308 K. Parentheses values indicate the rate constant (, s−1) of uncatalyzed reactions.
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