Driving force effects in proton coupled electron transfer

Mauro C.M. Laranjeira, Rosemary A. Marusak, A. Graham Lappin

Research output: Contribution to journalArticlepeer-review

Abstract

The rates of reduction of the nickel(III) oxime-imine complexes, [Ni(III)(Me2L)]+ and [Ni(III)(Me2LH)]2+ by the corresponding iron(II) species are determined. Comparisons with rates calculated with the use of Marcus theory reveal that reactions of [Fe(III)(Me2LH)]+, where the electron transfer product is the highly acidic [Fe(III)(Me2LH)]2+, show rate enhancements of several orders of magnitude. These are ascribed to a strong coupling of the electron transfer with the concomitant, thermodynamically favorable proton transfer. A free energy correlation supports this conclusion.

Original languageEnglish (US)
Pages (from-to)186-190
Number of pages5
JournalInorganica Chimica Acta
Volume300-302
DOIs
StatePublished - Apr 30 2000
Externally publishedYes

Bibliographical note

Funding Information:
The authors thank CAPES (Brazil) for a maintenance grant to M.C.M.L.

Keywords

  • Electron transfer
  • Iron complexes
  • Nickel complexes
  • Oxime-imine complexes
  • Proton transfer

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