Dioxygen Activation by a Non-Heme Iron(II) Complex: Formation of an Iron(IV)-Oxo Complex via C-H Activation by a Putative Iron(III)-Superoxo Species

Iron(III)-superoxo intermediates are believed to play key roles in oxygenation reactions by non-heme iron enzymes. We now report that a non-heme iron(II) complex activates O-2 and generates its corresponding iron(IV)-oxo complex in the presence of substrates with weak C-H bonds (e.g., olefins and alkylaromatic compounds). We propose that a putative iron(III)-superoxo intermediate initiates the O-2-activation chemistry by abstracting a H atom from the substrate, with subsequent generation of a high-valent iron(IV)-oxo intermediate from the resulting iron(III)-hydroperoxo species.