title: Quantum chemical characterization of the mechanism of a supported cobalt-based water oxidation catalyst.
abstract: Quantum chemical modeling is employed to elucidate the catalytic cycle of a recently described supported cobalt compound that catalyzes water oxidation. Key features of the catalytic cycle include a supporting corrole that is rendered non-innocent early in the oxidation process and a pendant carboxylate moiety that functions as a general base to further activate a water molecule that nucleophilically attacks a reactive metal oxo functionality. Fluorination of the supporting corrole appears both to modulate the electrophilicity of the metal-oxo fragment and to mitigate decomposition reactions that might otherwise be expected for a corrole radical cation.
authors.affiliation: Department of Chemistry and Supercomputer Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, USA.
authors.forename: Mehmed Z
authors.initials: MZ
authors.lastname: Ertem
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer