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Electron Transfer to Dioxygen by Keggin Heteropolytungstate Cluster Anions

  • Ophir Snir
  • Ira A. Weinstock
Conference paper
Part of the NATO Science for Peace and Security Series B: Physics and Biophysics book series (NAPSB)

Abstract

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).

Keywords

Reorganization Energy Superoxide Radical Anion Reaction Distance Keggin Anion Organic Electron Donor 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Springer Science+Business Media Dordrecht 2012

Authors and Affiliations

  1. 1.Department of ChemistryBen Gurion University of the NegevBeer ShevaIsrael

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