Journal of the American Chemical Society, Vol.134, No.24, 9906-9909, 2012
Catalytic Four-Electron Reduction of O-2 via Rate-Determining Proton-Coupled Electron Transfer to a Dinuclear Cobalt-mu-1,2-peroxo Complex
Four-electron reduction of O-2 by octamethylferrocene (Me(8)Fc) occurs efficiently with a dinuclear cobalt-mu-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.