Cp*--Ruthenium-Nickel-Based H2-Evolving Electrocatalysts as Bio-inspired Models of NiFe Hydrogenases

被引：25

作者：

Canaguier, Sigolene ^{[1
]}

Fontecave, Marc ^{[1
,2
]}

Artero, Vincent ^{[1
]}

机构：

[1] Univ Grenoble 1, Lab Chim & Biol Met, CNRS UMR 5249, CEA DSV iRTSV, F-38054 Grenoble 9, France

[2] Coll France, F-75005 Paris, France

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2011年 / 07期

关键词：

Hydrogen; Biomimetic synthesis; Enzyme models; Metalloenzyme models; Electrocatalysis; Nickel; Ruthenium; COMPLEXES; EVOLUTION; CATALYST; ANALOGS; H-2;

D O I：

10.1002/ejic.201000944

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Three dinuclear nickel-ruthenium complexes [Ni(xbsms)RuCp*(L)](PF6) [H(2)xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl) benzene; Cp* = pentamethylcyclopentadienyl; L = CH3CN, 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)](PF6) (Cp = cyclopentadienyl) analogues, these compounds catalyze the evolution of hydrogen from Et3NH+ 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, 15, 9350-9364]. In addition, the steric protection provided by the bulky Cp*-ligand results in an increased catalytic rate and stability upon cycling.

引用

收藏

页码：1094 / 1099

页数：6

相关论文

共 19 条

[1] Nickel-Iron Dithiolato Hydrides Relevant to the [NiFe]-Hydrogenase Active Site [J].

Barton, Bryan E. ;

Whaley, C. Matthew ;

Rauchfuss, Thomas B. ;

Gray, Danielle L. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (20) :6942-+

[2] Modelling NiFe hydrogenases: nickel-based electrocatalysts for hydrogen production [J].

Canaguier, Sigolene ;

Artero, Vincent ;

Fontecave, Marc .

DALTON TRANSACTIONS, 2008, (03) :315-325

[3] A structural and functional mimic of the active site of NiFe hydrogenases [J].

Canaguier, Sigolene ;

Field, Martin ;

Oudart, Yohan ;

Pecaut, Jacques ;

Fontecave, Marc ;

Artero, Vincent .

CHEMICAL COMMUNICATIONS, 2010, 46 (32) :5876-5878

[4] Cyclopentadienyl Ruthenium-Nickel Catalysts for Biomimetic Hydrogen Evolution: Electrocatalytic Properties and Mechanistic DFT Studies [J].

Canaguier, Sigolene ;

Vaccaro, Loredana ;

Artero, Vincent ;

Ostermann, Rainer ;

Pecaut, Jacques ;

Field, Martin J. ;

Fontecave, Marc .

CHEMISTRY-A EUROPEAN JOURNAL, 2009, 15 (37) :9350-9364

[5] Structure/function relationships of [NiFe]- and [FeFe]-hydrogenases [J].

Fontecilla-Camps, Juan C. ;

Volbeda, Anne ;

Cavazza, Christine ;

Nicolet, Yvain .

CHEMICAL REVIEWS, 2007, 107 (10) :4273-4303

[6] Electrocatalytic hydrogen evolution at low overpotentials by cobalt macrocyclic glyoxime and tetraimine complexes [J].

Hu, Xile ;

Brunschwig, Bruce S. ;

Peters, Jonas C. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (29) :8988-8998

[7] Direct comparison of the electrocatalytic oxidation of hydrogen by an enzyme and a platinum catalyst [J].

Jones, AK ;

Sillery, E ;

Albracht, SPJ ;

Armstrong, FA .

CHEMICAL COMMUNICATIONS, 2002, (08) :866-867

[8] COBALT(I) PORPHYRIN CATALYSIS OF HYDROGEN-PRODUCTION FROM WATER [J].

KELLETT, RM ;

SPIRO, TG .

INORGANIC CHEMISTRY, 1985, 24 (15) :2373-2377

[9]

KOEPP HM, 1960, Z ELEKTROCHEM, V64, P483

[10] pH-dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases [J].

Kure, Bunsho ;

Matsumoto, Takahiro ;

Ichikawa, Koji ;

Fukuzumi, Shunichi ;

Higuchi, Yoshiki ;

Yagi, Tatsuhiko ;

Ogo, Seiji .

DALTON TRANSACTIONS, 2008, 35 (35) :4747-4755