Kinetics and thermodynamics of formation and electron-transfer reactions of Cu-O 2 and Cu 2-O 2 complexes

Shunichi Fukuzumi, Kenneth D. Karlin

Research output: Contribution to journalReview articlepeer-review

72 Scopus citations

Abstract

The kinetics and thermodynamics of formation of Cu(II)-superoxo (Cu-O 2) complexes by the reaction of Cu(I) complexes with dioxygen (O 2) and the reduction of Cu(II)-superoxo complexes to dinuclear Cu-peroxo complexes are discussed. In the former case, electron transfer from a Cu(I) complex to O 2 occurs concomitantly with binding of O 2 -to the corresponding Cu(II) species. This is defined as an inner-sphere Cu(II) ion-coupled electron transfer process. Electron transfer from another Cu(I) complex to preformed Cu(II)-superoxo complexes also occurs concomitantly with binding of the Cu(II)-peroxo species with the Cu(II) species to produce the dinuclear Cu-peroxo (Cu 2-O 2) complexes. The kinetics and thermodynamics of outer-sphere electron-transfer reduction of Cu 2-O 2 complexes are also been discussed in light of the Marcus theory of outer-sphere electron transfer.

Original languageEnglish
Pages (from-to)187-195
Number of pages9
JournalCoordination Chemistry Reviews
Volume257
Issue number1
DOIs
StatePublished - 1 Jan 2013

Bibliographical note

Funding Information:
The authors gratefully acknowledge the contributions of their collaborators and coworkers mentioned in the references. The authors also acknowledge continuous support of their study by Grants-in-Aid from the Ministry of Education, Culture, Sports, Science and Technology, Japan (S.F.), the KOSEF/MEST through WCU project (R31-2008-000-10010-0) in Korea (S.F. and K.D.K.) and the USA National Institutes of Health (GM 28962) (K.D.K.).

Keywords

  • Copper-dioxygen complexes
  • Inner-sphere electron transfer
  • Marcus theory of electron transfer
  • Metal ion-coupled electron transfer
  • Outer-sphere electron transfer

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