Electrocatalytic reduction of ROOH by iron porphyrins
| Autor: | James P. Collman, Christopher J. Sunderland, Roman Boulatov, Marina Kaplun |
|---|---|
| Rok vydání: | 2004 |
| Předmět: |
inorganic chemicals
Reaction mechanism Aqueous solution Chemistry Metalloporphyrins Inorganic chemistry Carboxylic Acids Disproportionation General Chemistry Biochemistry Ferric Compounds Catalysis Ferrous Peroxides Electron transfer Kinetics Colloid and Surface Chemistry medicine Electrochemistry Ferric Ferrous Compounds Cyclic voltammetry Oxidation-Reduction medicine.drug |
| Zdroj: | Journal of the American Chemical Society. 126(36) |
| ISSN: | 0002-7863 |
| Popis: | Electrocatalytic reduction of a series of chemical oxidants of different power (tert-butyl hydroperoxide, potassium peroxomonosulfate, peracetic acid, and m-chloroperbenzoic acid) at iron-porphyrin-modified graphite electrodes is studied in buffered aqueous solutions by rotating disk and ring-disk voltammetry. Both ferric and ferrous porphyrins are catalytically active. Turnover of ferric catalysts is slower than that of the ferrous analogues and involves competing catalytic reduction and disproportionation. The kinetic data are consistent with reactant binding being the rate-determining step in catalysis by Fe(III). In catalysis by Fe(II), the turnover is controlled by the first electron transfer. The covalently linked proximal imidazole ligand is found to be crucial for achieving the Fe(III) catalysis. |
| Databáze: | OpenAIRE |
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