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 language | English |
|---|---|
| Pages (from-to) | 187-195 |
| Number of pages | 9 |
| Journal | Coordination Chemistry Reviews |
| Volume | 257 |
| Issue number | 1 |
| DOIs | |
| State | Published - 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