Dinuclear nickel-ruthenium complexes as functional bio-inspired models of [NiFe] hydrogenases

作者：Oudart Yohan; Artero Vincent^*; Pecaut Jacques; Lebrun Colette; Fontecave Marc

来源：European Journal of Inorganic Chemistry, 2007, 2007(18): 2613-2626.

DOI：10.1002/ejic.200700067

• nickel
• ruthenium
• hydrogen
• electrocatalysis
• biomimetic chemistry
• hydrogenases

Three new dinuclear nickel ruthenium complexes, namely [Ni(xbsms)Ru(p-cymene)Cl](+), [Ni(emi)Ru(CO)(2)Cl-2](2-) and [Ni(emi)Ru(p-cymene)Cl](-) [H(2)xbsms = 1,2-bis(4-mercapto3,3-dimethyl-2-thiabutyl)benzene, H(2)emi = N,N'-ethylenebis(2-mercaptoisobutyramide], have been synthesized and fully characterized as models of the active site of [NiFe] hydrogenases. The three-dimensional structure of [Ni(xbsms)Ru(p-cymene)Cl](+) reveals a nickel center in a square-planar dithioether-dithiolate environment that is connected to a ruthenium moiety via a Ni(mu-SR)(2)Ru bridge. These complexes catalyze hydrogen evolution by electroreduction of the weakly acidic Et3NH+ ions in dimethylformamide and are therefore among the first bio-inspired functional models of [NiFe] hydrogenases. The catalytic activity of these new complexes is explained by the existence of a cooperative effect between the metal centers and is further related to their electronic properties.

• 出版日期2007-6
• 单位中国地震局