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Kinetics and mechanism of the reactions of ozone with superoxo, hydroperoxo, and hydrido complexes of rhodium(III)

TitleKinetics and mechanism of the reactions of ozone with superoxo, hydroperoxo, and hydrido complexes of rhodium(III)
Publication TypeJournal Article
Year of Publication2008
AuthorsVasbinder MJ, Bakac A
Journal TitleInorganica Chimica Acta
Volume361
Pages3193-3198
Date Published07
Type of ArticleArticle
ISBN Number0020-1693
Accession NumberISI:000257475300028
Keywordsaqueous-solutions, DECOMPOSITION, derivatives, EXCHANGE, hydrido, hydrogen-atom transfer, hydroperoxo, kinetics, oxidation, ozone, PEROXIDE, PRODUCT, reactivity, rhodium, superoxo, water
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) x 10(5) M-1 s(-1) and an isotope effect k(H)/k(D) = 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) x 10(3) 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). (C) 2007 Elsevier B.V. All rights reserved.
DOI10.1016/j.ica.2007.11.022
Alternate JournalInorg. Chim. Acta