@inbook{4c08470491f145e7b8199fee07bf0797,
title = "Electron transfer to dioxygen by keggin heteropolytungstate cluster anions",
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).",
author = "Ophir Snir and Weinstock, {Ira A.}",
year = "2012",
month = jan,
day = "1",
doi = "10.1007/978-94-007-5548-2_12",
language = "English",
isbn = "9789400755475",
series = "NATO Science for Peace and Security Series B: Physics and Biophysics",
publisher = "Springer Verlag",
pages = "207--228",
booktitle = "Complexity in Chemistry and Beyond",
address = "Germany",
}