Publication 646

Che. Rev. 109, 2245-2274, 2009. DOI: 10.1021/cr800542q
Structural and Functional Analogues of the Active Sites of the [Fe]-, [NiFe]-, and [FeFe]-Hydrogenases

*Laboratoire d’Electrochimie Moléculaire, Université Paris Diderot, UMRCNRS 7591, 15 rue Jean-Antoine de Baïf, 75205 Paris Cedex 13, France, and †Energy Materials Laboratory, School of Chemistry, University of East Anglia, Norwich NR4 7TJ, United Kingdom

Introduction ( Beginning)

This article sets out to review the chemistry relating to the synthesis of structural and functional analogues of the three classes of hydrogenases. This chemistry has grown explosively over the last 10 or so years since the first X-ray structures of [NiFe]- and [FeFe]-hydrogenase systems were published. There are now some 400 papers covering structural and functional aspects, with the majority of these associated with the di-iron system.
As much emphasized in earlier papers and reviews, there are two principal drivers to research on active site analogues. The first is to provide metric, spectroscopic, and reactivity precedents for the biological systems; the second is the prospect of producing technological materials for a “hydrogen economy” guided by the chemistry of the enzymatic systems. ......