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Review
. 2009 Jan;38(1):100-8.
doi: 10.1039/b801796b. Epub 2008 Oct 31.

Small molecule mimics of hydrogenases: hydrides and redox

Frédéric Gloaguen  1 , Thomas B Rauchfuss
Affiliations
Review

Small molecule mimics of hydrogenases: hydrides and redox

Frédéric Gloaguen et al. Chem Soc Rev. 2009 Jan.

Abstract

This tutorial review is aimed at chemical scientists interested in understanding and exploiting the remarkable catalytic behavior of the hydrogenases. The key structural features are analyzed for the active sites of the two most important hydrogenases. Reactivity is emphasized, focusing on mechanism and catalysis. Through this analysis, gaps are identified in the synthesis of functional replicas of these fascinating and potentially useful enzymes.

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Figures

Fig. 1
Fig. 1
Structure of H-cluster from C. pasteurianum, a line drawing of the same, omitting the water situated near the distal (rightmost) Fe center, and the structure of the prototypical Fe2(pdt)(CO)6.
Fig. 2
Fig. 2
Synthetic models with appended clusters and photosensitizers.,
Fig. 3
Fig. 3
Structure of the active site of the [NiFe]-H2ase and line drawing of the same.
Fig. 4
Fig. 4
Cyclic voltammograms of a solution 2.2 mM Fe2(bdt)(CO)6 in MeCN-Bu4NPF6 upon addition of an increasing amount of toluenesulfonic acid (HOTs) up to 33 mM. Inset: dependence of the catalytic peak current vs. [HOTs] (conditions: glassy carbon electrode 0.071 cm2in surface area; scan rate 0.1 V s−1).
Scheme 1
Scheme 1
N- and Fe-protonation of a diiron azadithiolato complex and its 1e−-reduction.
Scheme 2
Scheme 2
Generation of models for the Hox and Hoxco states.
Scheme 3
Scheme 3
Selected models for the [NiFe]-H2ases active site featuring the Ni(SR)2 core and at least one biomimetic ligand.,,,
Scheme 4
Scheme 4
Scheme 5
Scheme 5
See this image and copyright information in PMC

References

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Publication types