A Cobalt-Dithiolene Complex for the Photocatalytic and Electrocatalytic Reduction of Protons

作者：McNamara William R; Han Zhiji; Alperin Paul J; Brennessel William W; Holland Patrick L^*; Eisenberg Richard

来源：Journal of the American Chemical Society, 2011, 133(39): 15368-15371.

DOI：10.1021/ja207842r

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 CH3CN/H2O 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.

• 出版日期2011-10-5