Cyclopentadienyl ruthenium-nickel catalysts for biomimetic hydrogen evolution: electrocatalytic properties and mechanistic DFT studies.
The new 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(-) = cyclopentadienyl; L = DMSO, CO, PPh(3), and PCy(3)) are reported and are bioinspired mimics of NiFe hydrogenases. These compounds were characterized by X-ray diffraction techniques and display novel structural motifs. Interestingly, [Ni(xbsms)RuCpCO][PF(6)] is stereochemically nonrigid in solution and an isomerization mechanism was derived with the help of density functional theory (DFT) calculations. Because of an increased electron density on the metal centers [Eur. J. Inorg. Chem. 2007, 18, 2613-2626] with respect to the previously described [Ni(xbsms)Ru(CO)(2)Cl(2)] and [Ni(xbsms)Ru(p-cymene)Cl](+) complexes, [Ni(xbsms)RuCp(dmso)][PF(6)] catalyzes hydrogen evolution from Et(3)NH(+) in DMF with an overpotential reduced by 180 mV and thus represents the most efficient NiFe hydrogenase functional mimic. DFT calculations were carried out with several methods to investigate the catalytic cycle and, coupled with electrochemical measurements, allowed a mechanism to be proposed. A terminal or bridging hydride derivative was identified as the active intermediate, with the structure of the bridging form similar to that of the Ni-C active state of NiFe hydrogenases.
Canaguier
Sigolène
S
Laboratoire de Chimie et Biologie des Métaux, Université Joseph Fourier, Grenoble, France.
Vaccaro
Loredana
L
Artero
Vincent
V
Ostermann
Rainer
R
Pécaut
Jacques
J
Field
Martin J
MJ
Fontecave
Marc
M
D002384:Catalysis; D020134:Catalytic Domain; D018360:Crystallography, X-Ray; D003517:Cyclopentanes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry / Q000378:metabolism; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*
D003517:Cyclopentanes; D009532:Nickel; D012428:Ruthenium; D006859:Hydrogen; C043296:nickel-iron hydrogenase; D006864:Hydrogenase