TY - JOUR
T1 - Kinetics and thermodynamics of formation and electron-transfer reactions of Cu-O 2 and Cu 2-O 2 complexes
AU - Fukuzumi, Shunichi
AU - Karlin, Kenneth D.
N1 - 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.).
PY - 2013/1/1
Y1 - 2013/1/1
N2 - 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.
AB - 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.
KW - Copper-dioxygen complexes
KW - Inner-sphere electron transfer
KW - Marcus theory of electron transfer
KW - Metal ion-coupled electron transfer
KW - Outer-sphere electron transfer
UR - http://www.scopus.com/inward/record.url?scp=84870392949&partnerID=8YFLogxK
U2 - 10.1016/j.ccr.2012.05.031
DO - 10.1016/j.ccr.2012.05.031
M3 - Review article
AN - SCOPUS:84870392949
SN - 0010-8545
VL - 257
SP - 187
EP - 195
JO - Coordination Chemistry Reviews
JF - Coordination Chemistry Reviews
IS - 1
ER -