Inverse Axial-Ligand Effects in the Activation of H_2O_2 and ROOH by an Mn~(III) Corrolazine**

摘要

The activation of dioxygen and its two-electron-reduced analogues H_2O_2 and ROOH by both heme- and non-hemerelated metal complexes has been the focus of intense efforts because of its relevance to biochemical processes, as well as the potential applications of this chemistry in oxidative catalysis. Heme enzymes such as cytochrome P450, catalases, and peroxidases react with dioxygen and H_2O_2 to give highvalent iron–oxido intermediates such as iron(IV)–oxido pcation radical ((porph+·)Fe~(IV)=O), which is presumed to be the critical oxidizing intermediate in cytochrome P450.