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

A high-valent manganese(IV)-hydroxo porphyrin pi-cation radical complex, [Mn(IV)(OH)(Porp+center dot)(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 pi cation radical ligand with a high reactivity in oxidation reactions, including water oxidation.

Automated summary

A high-valent manganese(IV)-hydroxo porphyrin pi-cation radical complex, [Mn(IV)(OH)(Porp+center dot)(X)]+, was synthesized and characterized spectroscopically. The Mn porphyrin intermediate showed high reactivity in alkane hydroxylation, oxygen atom transfer, and water oxidation reactions. This study provides the first example of a manganese Cpd I model compound with a porphyrin pi cation radical ligand that exhibits high reactivity in oxidation reactions, including water oxidation.