title: Kinetics and thermodynamics of formation and electron-transfer reactions of Cu-O2and Cu2-O2complexes.
abstract: The kinetics and thermodynamics of formation of Cu(II)-superoxo (Cu-O2) complexes by the reaction of Cu(I) complexes with dioxygen (O2) 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 O2occurs concomitantly with binding of O2•-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 the Cu(II)-peroxo species with the Cu(II) species to produce the dinuclear Cu-peroxo (Cu2-O2) complexes. The kinetics and thermodynamics of outer-sphere electron-transfer reduction of Cu2-O2complexes are also been discussed in light of the Marcus theory of outer-sphere electron transfer.
authors.affiliation: Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA (JST), Suita, Osaka 565-0871, Japan ; Department of Bioinspired Science, Ewha Womans University, Seoul 120-750, Korea.
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
keywords: Marcus theory of electron transfer; copper-dioxygen complexes; inner-sphere electron transfer; metal ion-coupled electron transfer; outer-sphere electron transfer