Kinetics and mechanism of the reactions of ozone with superoxo, hydroperoxo, and hydrido complexes of rhodium(III) |
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Authors: | Michael J. Vasbinder |
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Affiliation: | Ames Laboratory, Iowa State University, Ames, IA 50011, United States |
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Abstract: | Oxidation of the title complexes with ozone takes place by hydrogen atom, hydride, and electron transfer mechanisms. The reaction with (NH3)4(H2O)RhH2+ is a two electron process, believed to involve hydride transfer with a rate constant k = (2.2 ± 0.2) × 105 M−1 s−1 and an isotope effect kH/kD = 2. The oxidation of (NH3)4(H2O)RhOOH2+ to (NH3)4(H2O)RhOO2+ by an apparent hydrogen atom transfer is quantitative and fast, k = (6.9 ± 0.3) × 103 M−1 s−1, and constitutes a useful route for the preparation of the superoxo complex. The latter is also oxidized by ozone, but more slowly, k = 480 ± 50 M−1 s−1. |
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Keywords: | Ozone Hydroperoxo Superoxo Hydrido Rhodium Kinetics |
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