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Cp* – ‐Ruthenium–Nickel‐Based H 2 ‐Evolving Electrocatalysts as Bio‐inspired Models of NiFe Hydrogenases
Author(s) -
Canaguier Sigolène,
Fontecave Marc,
Artero Vincent
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000944
Subject(s) - chemistry , ruthenium , nickel , steric effects , catalysis , hydrogenase , cyclopentadienyl complex , overpotential , hydride , ligand (biochemistry) , medicinal chemistry , crystallography , metal , inorganic chemistry , stereochemistry , electrochemistry , organic chemistry , biochemistry , receptor , electrode
Three dinuclear nickel–ruthenium complexes [Ni(xbsms)RuCp*(L)](PF 6 ) [H 2 xbsms = 1,2‐bis(4‐mercapto‐3,3‐dimethyl‐2‐thiabutyl)benzene; Cp* = pentamethylcyclopentadienyl; L = CH 3 CN, CO and O 2 ] are reported that act as bio‐inspired mimics of NiFe hydrogenases. Because of an increased electron density at the metal centres in comparison with the previously described [Ni(xbsms)RuCp(L)](PF 6 ) (Cp = cyclopentadienyl) analogues, these compounds catalyze the evolution of hydrogen from Et 3 NH + in DMF with an overpotential reduced by around 50 mV, thereby corroborating a previously established structure–function relationship [ Eur. J. Inorg. Chem. 2007 , 18 , 2613–2626; Chem. Eur. J. 2009 , 1 5, 9350–9364]. In addition, the steric protection provided by the bulky Cp* – ligand results in an increased catalytic rate and stability upon cycling.