Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 15, 2011
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

Article information


Submitted
08 Oct 2010
Accepted
07 Feb 2011
First published
11 Mar 2011

Dalton Trans., 2011,40, 3859-3870
Article type
Paper

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

Social activity

Search articles by author

Spotlight

Advertisements