Catalytic four-electron reduction of O2 via rate-determining proton-coupled electron transfer to a dinuclear cobalt-μ-1,2-peroxo complex.
Four-electron reduction of O(2) by octamethylferrocene (Me(8)Fc) occurs efficiently with a dinuclear cobalt-μ-1,2-peroxo complex, 1, in the presence of trifluoroacetic acid in acetonitrile. Kinetic investigations of the overall catalytic reaction and each step in the catalytic cycle showed that proton-coupled electron transfer from Me(8)Fc to 1 is the rate-determining step in the catalytic cycle.
Department of Material and Life Science, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan. fukuzumi@chem.eng.osaka-u.ac.jp
Shunichi
S
Fukuzumi
Sukanta
S
Mandal
Kentaro
K
Mase
Kei
K
Ohkubo
Hyejin
H
Park
Jordi
J
Benet-Buchholz
Wonwoo
W
Nam
Antoni
A
Llobet
D002384:Catalysis; D003035:Cobalt / Q000737:chemistry*; D004579:Electron Transport; D004583:Electrons; D005296:Ferrous Compounds / Q000737:chemistry; D000075163:Metallocenes; D008958:Models, Molecular; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry*; D011522:Protons
D005296:Ferrous Compounds; D000075163:Metallocenes; D010545:Peroxides; D011522:Protons; D003035:Cobalt; D010100:Oxygen; C004998:ferrocene