Dinuclear Nickel–Ruthenium Complexes as Functional Bio-Inspired Models of [NiFe] Hydrogenases

✍ Scribed by Yohan Oudart; Vincent Artero; Jacques Pécaut; Colette Lebrun; Marc Fontecave

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 345 KB
• Volume: 2007
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200700067

✦ Synopsis

Abstract

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‐mercapto‐3,3‐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(μ‐SR)~2~Ru bridge. These complexes catalyze hydrogen evolution by electroreduction of the weakly acidic Et~3~NH^+^ 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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)