Research Article
Ruthenium(III) Catalysis in Perborate Oxidation of 5-Oxoacids
Table 4
Oxidation rates at different aciditiesa.
| 5-Oxoacid |
103 (s−1) 102[H+] (mol dm−3) |
103() (s−1) | 0.88 | 1.88 | 3.88 | 6.88 | 9.88 | 14.9 | 19.9 | 0.88 | 1.88 | 3.88 | 6.88 | 9.88 | 14.9 | 19.9 |
| p-OCH3 | 20.27 (4.11) | 21.45 (4.41) | 22.86 (5.93) | 23.65 (7.42) | 24.26 (8.64) | 27.33 (11.56) | 28.70 (12.80) | 16.16 | 17.04 | 16.93 | 16.23 | 15.62 | 15.78 | 15.90 | p-CH3 | 9.13 (2.05) | 11.12 (2.21) | 11.43 (2.97) | 11.82 (3.71) | 12.13 (4.32) | 13.66 (5.78) | 14.35 (6.40) | 7.08 | 8.92 | 8.46 | 8.46 | 7.81 | 7.88 | 7.94 | p-C6H5 | 6.66 (1.44) | 8.12 (1.61) | 8.34 (2.17) | 8.63 (2.71) | 8.85 (3.15) | 9.97 (4.22) | 10.47 (4.67) | 5.16 | 6.51 | 6.17 | 6.17 | 5.70 | 5.75 | 5.80 | –H | 6.00 (1.35) | 7.31 (1.45) | 7.51 (1.95) | 7.77 (2.44) | 7.97 (2.84) | 8.98 (3.80) | 9.43 (4.21) | 4.65 | 5.86 | 5.56 | 5.33 | 5.13 | 5.18 | 5.22 | p-Cl | 1.84 (0.42) | 2.25 (0.45) | 2.31 (0.60) | 2.39 (0.75) | 2.45 (0.88) | 2.77 (1.17) | 2.90 (1.29) | 1.43 | 1.80 | 1.71 | 1.64 | 1.58 | 1.59 | 1.60 | p-Br | 0.94 (0.21) | 1.14 (0.23) | 1.83 (0.31) | 1.22 (0.38) | 1.25 (0.45) | 1.41 (0.59) | 1.48 (0.66) | 0.72 | 0.91 | 0.87 | 0.83 | 0.80 | 0.81 | 0.81 | m-NO2 | 0.46 (0.11) | 0.56 (0.11) | 0.58 (0.15) | 0.60 (0.18) | 0.62 (0.22) | 0.69 (0.33) | 0.73 (0.33) | 0.35 | 0.45 | 0.43 | 0.42 | 0.40 | 0.36 | 0.40 |
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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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