title: A cobalt-dithiolene complex for the photocatalytic and electrocatalytic reduction of protons.
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.
authors.affiliation: Department of Chemistry, University of Rochester, Rochester, New York 14627, United States.
authors.forename: William R
authors.initials: WR
authors.lastname: McNamara
authors.forename: Zhiji
authors.initials: Z
authors.lastname: Han
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Alperin
authors.forename: William W
authors.initials: WW
authors.lastname: Brennessel
authors.forename: Patrick L
authors.initials: PL
authors.lastname: Holland
authors.forename: Richard
authors.initials: R
authors.lastname: Eisenberg