Outer-sphere oxidation of the superoxide radical anion

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20 Scopus citations


Efforts to use the Marcus model to describe oxidations of the superoxide radical anion (O2-) by transition-metal complexes have failed dramatically, with discrepancies between theory and experiment spanning 13 orders of magnitude. As a result, the prevailing view is that these reactions involve some complex interactions that are not yet understood. We now show that once the familiar form of the Marcus cross relation (MCR) is modified to allow for the relatively small size of O2-, excellent agreement is obtained between theory and experiment. This simple finding dispels the decades of uncertainty surrounding these reactions and provides a reliable method for determining whether oxidations of O2- occur via inner- or outer-sphere pathways. More generally, the modified MCR is applicable to any homogeneous electron-transfer process characterized by significant differences in size between electron donors and acceptors.

Original languageEnglish
Pages (from-to)404-406
Number of pages3
JournalInorganic Chemistry
Issue number2
StatePublished - 21 Jan 2008

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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