4.8 Article

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

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 145, Issue 15, Pages 8319-8325

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.3c01818

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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.
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.

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