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.
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.
Gao
Yan
Y
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 10691 Stockholm, Sweden.
Akermark
Torbjörn
T
Liu
Jianhui
J
Sun
Licheng
L
Akermark
Björn
B
D006878:Hydroxides / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D008954:Models, Biological; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D045332:Photosystem II Protein Complex / Q000737:chemistry; D011166:Porphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D014867:Water / Q000737:chemistry*; D020122:tert-Butylhydroperoxide / Q000737:chemistry
D006878:Hydroxides; D045332:Photosystem II Protein Complex; D011166:Porphyrins; C431863:corrole; D014867:Water; D008345:Manganese; C031356:hydroxide ion; D020122:tert-Butylhydroperoxide; D010100:Oxygen