A di-iron dithiolate possessing structural elements of the carbonyl/cyanide sub-site of the H-centre of Fe-only hydrogenase

Abstract

The synthesis and characterisation of the first {2Fe2S}-cluster bearing both CO and CN ligands is described; the iron atoms are linked by the bridging 1,3-propanedithiolate unit that has been identified in the crystallographic structure of the {2Fe2S} sub-unit of the H-centre of the all-iron hydrogenase from Desulfovibrio desulfuricans.

References

1. Y. Nicolet, C. Piras, P. Legrand, C. E. Hatchikian and J. C. Fontecilla-Camps, Structure, 1999, 7, 13.
2. J. W. Peters, W. N. Lanzilotta, B. J. Lemon and L. C. Seefeldt, Science, 1998, 282, 1853.
3. A. J. Peirik, M. Hulstein, W. R. Hagen and S. P. J. Albracht, Eur. J. Biochem., 1998, 258, 572.
4. A. Winter, L. Zsolnai and G. Huttner, Z. Naturforsch., Teil B, 1982, 37, 1430.
5. D. Seyferth, G. B. Womack, M. K. Galagher, M. Cowie, B. W. Hames, J. P. Fackler and A. M. Mazany, Organometallics, 1987, 6, 283 and references therein.
6. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Wiley, New York, 5th edn., 1988, p. 1036.
7. NCA calculations were performed using the program suite QCMP067 (General Vibrational Analysis System, D. F. McIntosh and M. R. Peterson), Quantum Chemical Program Exchange, Indiana University. Initial values of the CO stretching and interaction force constants were obtained from a previous study of Fe₂(CO)₆(µ-Y)₂ complexes (G. Bor, J. Organomet. Chem., 1975, 94, 181).