The Cr(II) reduction of [Co(bpy)3]3+. Observation of a dimeric Cr(III) reduction product

Ghazala Ali, Nita A. Lewis

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3 Scopus citations

Abstract

The Cr(II) reduction of [Co(bpy)3]3+ proceeds by a series of steps which are accounted for by a complex and highly unusual mechanism. The chromium(III) product of the reaction is a dimer formulated as [Cr2(bpy)(OH)2(OH2)6]4+. The cobalt products include [Co(OH2)6]2+ and [Co(bpy)(OH2)4]3+. Intact free 2,2′-bipyridine and a reduced bipyridine species are also recovered. Four consecutive reactions are observed on the stopped-flow traces. The first one is independent of the [Cr(II)] concentration indicating that reduction has already occurred. The rate constant for this reaction is 46.3 ± 0.2 s-1. The second reaction is auto-catalyzed and has a rate constant of approximately (1.38 ± 0.2) × 102 s-1 assuming first order behavior. The thrid reaction is dependent on [Cr(II)] and has a rate constant kobs = k′3 + k″3[H+] where k′3 = 53 ± 3 M-1 s-1 and k″3 = (4.6 ± 0.2) × 102 M-2 s-1. The fourth reaction is independent of [Cr(II)] and has a rate constant kobs = k′4 + k″4[H+] where k′4 = 0.39 ± 0.02 s-1 and k″4 = 2.16 ± 0.06 M-1 s-1. A mechanism consistent with these observations is proposed.

Original languageEnglish (US)
Pages (from-to)5-13
Number of pages9
JournalInorganica Chimica Acta
Volume167
Issue number1
DOIs
StatePublished - Jan 2 1990

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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