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Catalytic Water Oxidation by a Bio-inspired Nickel Complex with a Redox-Active Ligand
1Department of Chemistry and Biochemistry and Center for Biomolecular Structure and Dynamics, University of Montana , Missoula, Montana 59812, United States.
Abstract:
The oxidation of water (H2O) to dioxygen (O2) is important in natural photosynthesis. One of nature's strategies for managing such multi-electron transfer reactions is to employ redox-active metal-organic cofactor arrays. One prototype example is the copper tyrosinate active site found in galactose oxidase. In this work, we have implemented such a strategy to develop a bio-inspired nickel phenolate complex capable of catalyzing the oxidation of H2O to O2 electrochemically at neutral pH with a modest overpotential. Employment of the redox-active ligand turned out to be a useful strategy to avoid the formation of high-valent nickel intermediates while a reasonable turnover rate (0.15 s-1) is retained.
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