[Ni(xbsms)Ru(CO)₂Cl₂]: A Bioinspired Nickel−Ruthenium Functional Model of [NiFe] Hydrogenase

As a model of the active site of [NiFe] hydrogenases, a dinuclear nickel−ruthenium complex [Ni(xbsms)Ru(CO)2Cl2] was synthesized and fully characterized. The three-dimensional structure reveals a nickel center in a square-planar dithioether−dithiolate environment connected to a ruthenium moiety via a Ni(μ-SR)2Ru bridge. This complex catalyzes hydrogen evolution by electroreduction of the weakly acidic Et3NH+ ions in N,N-dimethylformamide and is therefore the first functional bioinspired model of [NiFe] hydrogenases.