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Issue 15, 2011
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On the mechanism of water oxidation by a bimetallic manganese catalyst: A density functional study

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Abstract

Density functional theory is used to explore possible mechanisms that lead to water oxidation by a bimetallic manganese catalyst developed by McKenzie and co-workers. On the basis of our calculations we propose that the key active intermediate is a mixed valent Mn(III)(μ-O)Mn(IV)-O˙ oxyl radical species, the oxyl centre being the site of nucleophilic attack by water. The mixed-valent species is in equilibrium with an isomeric diamond-core Mn(IV)(μ-O)2Mn(IV) structure, which acts as reservoir for the active species. The chemistry appears to be unique to pentadentate ligands because these shift the position of the equilibrium between the Mn(III)(μ-O)Mn(IV)-O˙ and Mn(IV)(μ-O)2Mn(IV) isomers, such that significant concentrations of the former are present in solution.

Graphical abstract: On the mechanism of water oxidation by a bimetallic manganese catalyst: A density functional study

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Publication details

The article was received on 08 Oct 2010, accepted on 07 Feb 2011 and first published on 11 Mar 2011


Article type: Paper
DOI: 10.1039/C0DT01362E
Citation: Dalton Trans., 2011,40, 3859-3870
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    On the mechanism of water oxidation by a bimetallic manganese catalyst: A density functional study

    W. M. C. Sameera, C. J. McKenzie and J. E. McGrady, Dalton Trans., 2011, 40, 3859
    DOI: 10.1039/C0DT01362E

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