A cobalt-dithiolene complex for the photocatalytic and electrocatalytic reduction of protons |
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Authors: | McNamara William R Han Zhiji Alperin Paul J Brennessel William W Holland Patrick L Eisenberg Richard |
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Institution: | Department of Chemistry, University of Rochester, Rochester, New York 14627, United States. |
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Abstract: | The complex Co(bdt)(2)](-) (where bdt = 1,2-benzenedithiolate) is an active catalyst for the visible light driven reduction of protons from water when employed with Ru(bpy)(3)(2+) as the photosensitizer and ascorbic acid as the sacrificial electron donor. At pH 4.0, the system exhibits very high activity, achieving >2700 turnovers with respect to catalyst and an initial turnover rate of 880 mol H(2)/mol catalyst/h. The same complex is also an active electrocatalyst for proton reduction in 1:1 CH(3)CN/H(2)O in the presence of weak acids, with the onset of a catalytic wave at the reversible redox couple of -1.01 V vs Fc(+)/Fc. The cobalt-dithiolene complex Co(bdt)(2)](-) thus represents a highly active catalyst for both the electrocatalytic and photocatalytic reduction of protons in aqueous solutions. |
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