Electron transfer to dioxygen by keggin heteropolytungstate cluster anions

Ophir Snir, Ira A. Weinstock

Research output: Chapter in Book/Report/Conference proceedingChapterpeer-review

1 Scopus citations


This chapter describes recent developments in understanding electron transfer to dioxygen (O2) and the outer-sphere oxidation of the superoxide radical anion, O 2 •-, by metal complexes. The following topics, of broad spectrum value in the complex chemistry of polyoxometalate (POM) systems and quantitative electron transfer are addressed: the nature of electron self-exchange between POMs; electron self-exchange between O2 and O 2 •- (including the problem of size differences between O2 or O 2 •- and their typical metal-complex electron donors or acceptors); and reactions of the one-electron-reduced POMs with O2. Electron transfer from Keggin POMs to O2 occurs by an outer-sphere mechanism; the effect of POM charge on rate constants for the reduction of O2 is significant and attributable to anion-anion repulsion within the successor-complex ion pairs formed between the negatively charged POM anions and O 2 •-. These findings were followed by the discovery of a concerted proton-electron (CPET) pathway for electron transfer to O2 at lower pH values (<1).

Original languageEnglish
Title of host publicationComplexity in Chemistry and Beyond
Subtitle of host publicationInterplay Theory and Experiment: New and Old Aspects of Complexity in Modern Research
PublisherSpringer Verlag
Number of pages22
ISBN (Print)9789400755475
StatePublished - 1 Jan 2012

Publication series

NameNATO Science for Peace and Security Series B: Physics and Biophysics
ISSN (Print)1874-6500

ASJC Scopus subject areas

  • Biotechnology
  • Biophysics
  • General Physics and Astronomy
  • Electrical and Electronic Engineering


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