Mononuclear Manganese(III) Superoxo Complexes: Synthesis, Characterization, and Reactivity.

Metal-superoxo species are typically proposed as key intermediates in the catalytic cycle of dioxygen activation by metalloenzymes involving different transition metal cofactors. In this regard, while a series of Fe-, Co-, and Ni-superoxo complexes have been reported to date, well-defined Mn-superoxo complexes remain rather rare. Herein, we report two mononuclear Mn-superoxo species, Mn(BDPP)(O) (, HBDPP = 2,6-bis((2-()-diphenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) and Mn(BDPP)(O) (, HBDPP = 2,6-bis((2-()-di(4-bromo)phenylhydroxyl-methyl-1-pyrrolidinyl)methyl)pyridine), synthesized by bubbling O into solutions of their Mn precursors, Mn(BDPP) () and Mn(BDPP) (), at -80 °C.