A Manganese Compound I Model with a High Reactivity in the Oxidation of Organic Substrates and Water.

Abstract

A high-valent manganese(IV)-hydroxo porphyrin π-cation radical complex, [Mn(IV)(OH)(Porp+•)(X)]+, was synthesized and characterized spectroscopically. The Mn porphyrin intermediate was highly reactive in alkane hydroxylation and oxygen atom transfer reactions. More importantly, the Mn porphyrin intermediate reacted with water at a fast rate, resulting in the dioxygen evolution. To the best of our knowledge, we report the first manganese Cpd I model compound bearing a porphyrin π-cation radical ligand with a high reactivity in oxidation reactions, including water oxidation.