Quantum chemical characterization of the mechanism of a supported cobalt-based water oxidation catalyst.

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.