Catalytic four-electron reduction of O 2 via rate-determining proton-coupled electron transfer to a dinuclear cobalt-μ-1,2-peroxo complex

Abstract

Four-electron reduction of O 2 by octamethylferrocene (Me 8Fc) 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 8Fc to 1 is the rate-determining step in the catalytic cycle. © 2012 American Chemical Society.