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J Am Chem Soc. 2009 Jul 1;131(25):8726-7. doi: 10.1021/ja901139r.

Nucleophilic attack of hydroxide on a Mn(V) oxo complex: a model of the O-O bond formation in the oxygen evolving complex of photosystem II.

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  • 1Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 10691 Stockholm, Sweden.


A manganese(III) corrole complex, 1, has been synthesized and used to study a potential mechanism for oxidation of water to molecular oxygen. Oxidation by t-BuOOH gave the Mn(V)=O complex 2. Addition of hydroxide led to release of oxygen via the Mn(IV) complex 4 and regeneration of complex 1. It could be shown that the oxygen from (18)O-labeled water was incorporated in both the formed molecular oxygen and the peroxy intermediate 4.

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