Hydrogenase active site

Fig. 5.4(a). Structures of iron-sulfur clusters found in proteins, (b) An hydrogenase active site. Note the presence of CO and CN ligands, which could have been present in the primitive anaerobic environment. 

Volbeda A, Garcin E, Piras C, et al. 1996. Structure of the [NiFe] hydrogenase active site evidence for biologically uncommon Fe ligands. J Am Chem Soc 118 12989-96. 

Ma Y, Balbuena PB (2007) Density functional theory approach for improving the catalytic activity of a biomimetic model based on the Fe-only hydrogenase active site. J Electroanal Chem (in press)... 

Sun L, Akermark B, Ott S. Iron hydrogenase active site mimics in supramolecular systems aiming for light-driven hydrogen production. Coord Chem Rev 2005 249 1653-63. 

Bruschi M, De Gioia L, Zampella G, Reiher M, Fantucci P, Stein M,(2004). A theoretical study of spin states in Ni-S4 complexes and models of the [NiFe] hydrogenase active site. J. Biol. Inorg. Chem. 9 873-884... 

Dawson J, Ghiotto F, McMaster J, Schroder M. Metal complex of hydrogenase active sites. In Wydrzynski TJ, Hillier W, editors. Molecular solar fuels. Cambridge, UK The Royal Society of Chemistry 2012. p. 326-86. 

Barton BE, Whaley CM, Rauchfuss TB, Gray DF. Nickel-iron dithiolato hydrides relevant to the [NiFe]-hydrogenase active site. J Am Chem Soc. 2009 131(20) 6942-3. 

Kaur-Ghumaan S, Schwartz L, Lomoth R, Stein M, Ott S. Catalytic hydrogen evolution from mononuclear iron(II) carbonyl complexes as minimal functional models of the [FeFe] hydrogenase active site. Angew Chem Int Ed. 2010 49(43) 8033-6. 

Liu, T. and M. Darensbourg. 2007. A Mixed-Valent, Fe(II)Fe(I), Diiron Complex Reproduces the Unique Rotated State of the [FeFe] Hydrogenase Active Site. Journal of the American Chemical Society 129(22) 7008-7009. 

Darensbourg, Tom Rauchfuss, and Chris Picket saw a simple diiron organometallic molecule as an obvious mimic of the iron hydrogenase active site. Darensbourg said that this comparison was a good starting point for modeling... 

FIGURE 3.2 Examples of two of the main iron-sulfur cluster containing hydrogenase active sites. 

This structure mimics the resting state of the [FeFe]hydrogenase active site. The enzyme holds this conformation in position throughout proton/electron coupling/ decoupling reactions. 

Mixed Valent, Fe(II)Fe(I), Diiron Complexes Reproduce the Unique Rotated State of the [FeFe]Hydrogenase Active Site... 

The synthesis and stndy of low molecular weight model complexes that mimic the electronic structure and coordination chemistry of the hydrogenase active site is a timely area of research and has been reviewed. Typical examples of mixed Ni-Fe complexes that have been prepared include complexes (113)/ (114)/ (115)/ and (116).i i... 

Schwartz L (2009) Synthetic [FeFe] hydrogenase active site model complexes. Ph.D. thesis, Uppsala University Schwartz AW, Voet AB (1984) Recent progress in the prebiotic chemistry of HCN. Oiig Life Evol Biosph 14 91-98 Schwitzguebel JP, Porta A (2003) Outlook and expected developments. In Vanek T, Schwitzguebel JP (Hrg.) (eds) Phytoremediation Inventory. COST Action 837 View. Hlavacek. pp 79-84... 

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