Issue 12, 2010
From the journal:

Dalton Transactions

Mechanism of hydrogen evolution catalyzed by NiFe hydrogenases: insights from a Ni–Ru model compound†

Loredana Vaccaro,a   Vincent Artero,*b   Sigolène Canaguier,b   Marc Fontecavebc  and  Martin J. Field*a  

* Corresponding authors

a Laboratoire de Dynamique Moléculaire, Institut de Biologie Structurale «Jean-Pierre Ebel», UMR CNRS/UJF/CEA 5075, 41 rue Jules Horowitz F-38027, Grenoble cedex 1, France
E-mail: martin.field@ibs.fr
Fax: 0033 438785122
Tel: 0033 438785904

b Laboratoire de Chimie et Biologie des Métaux; Université Joseph Fourier, Grenoble, France; CNRS, UMR 5249, France; CEA, DSV/iRTSV, 17 rue des Martyrs F-38054, Grenoble cedex 9, France
E-mail: vincent.artero@cea.fr
Fax: 0033 438789124
Tel: 0033 438789106

c Collège de France, 11 place Marcellin-Berthelot, Paris

Abstract

DFT modeling has been used to investigate a previously proposed mechanism of proton reduction catalyzed by [Ni(xbsms)Ru(CO)2Cl2] (H2xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene), a bio-inspired mimic of NiFe hydrogenases based on a Ni–Ru framework. Protonation of the 2e−-reduced compound, from which a chloride anion has been eliminated, results in the formation of a semi-bridging hydride derivative with structural features comparable to those of the Ni–C state catalytic intermediate of native hydrogenases. The present study thus provides structural and functional insights into the enzymatic mechanism including the possible involvement of a bridging hydride derivative and heterolytic formation of a dihydrogen molecule on a {Ni(μ-S)2M} framework.

Graphical abstract: Mechanism of hydrogen evolution catalyzed by NiFe hydrogenases: insights from a Ni–Ru model compound

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Article information

DOI
https://doi.org/10.1039/B912690B
Article type
Paper
Submitted
29 Jun 2009
Accepted
23 Oct 2009
First published
14 Dec 2009

Dalton Trans., 2010,39, 3043-3049

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Mechanism of hydrogen evolution catalyzed by NiFe hydrogenases: insights from a Ni–Ru model compound

L. Vaccaro, V. Artero, S. Canaguier, M. Fontecave and M. J. Field, Dalton Trans., 2010, 39, 3043 DOI: 10.1039/B912690B

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