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Kinetics and thermodynamics of formation and electron-transfer reactions of Cu-O2 and Cu2-O2 complexes
Shunichi Fukuzumi1, Kenneth D Karlin
1Department 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.
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 O2 occurs 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-O2 complexes are also been discussed in light of the Marcus theory of outer-sphere electron transfer.
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