View PDF Version
 
DOI: 10.1039/A704879C (Paper) Reference Section for: Chem. Commun., 1997, 1711-1712

Iron complexes with an N/S chromophore relevant to the active site of the hydrolytic metalloenzyme nitrile hydratase

(Note: The full text of this document is currently only available in the PDF Version )

Alexandre L. Nivorozhkin, Ali I. Uraev, Gennadii I. Bondarenko, Alla S. Antsyshkina, Vasilii P. Kurbatov, Alexandre D. Garnovskii, Constantin I. Turta and Nikolai D. Brashoveanu

Abstract

Iron(III) complexes with a 3N/3S chromophore reproduce a mixed N/S heterocyclic ligand environment, metal–ligand bond lengths, and low-spin state (S = 1/2) characteristic of the hydrolytic metalloenzyme nitrile hydratase; FeIIIN2S2Cl species possesses a quantum mechanically admixed S = 3/2, 5/2 state and able to form low-spin solvent adducts, possible analogues of the substrate-bound form of the enzyme.

References

  1. D. H. Flint and R. M. Allen, Chem. Rev., 1996, 96, 2315 CrossRef CAS.
  2. H. Beinert, M. C. Kennedy and C. D. Stout, Chem. Rev., 1996, 96, 2335 CrossRef CAS.
  3. (a) Y. Sugiura, J. Kuwahara, T. Nagasawa and H. Yamada, J. Am. Chem. Soc., 1987, 109, 5848 CrossRef CAS; (b) M. J. Nelson, H. Jin, I. M. Turner, Jr., G. Grove, R. C. Scarrow, B. A. Brennan and L. Que, Jr., J. Am. Chem. Soc., 1991, 113, 7072 CrossRef CAS; (c) H. Jin, I. M. Turner, Jr., M. J. Nelson, R. J. Gurbiel, P. E. Doan and B. M. Hoffman, J. Am. Chem. Soc., 1993, 115, 5290 CrossRef CAS; (d) B. A. Brennan, J. G. Cummings, D. B. Chase, I. M. Turner and M. J. Nelson, Biochemistry, 1996, 35, 10 068 CrossRef CAS; (e) R. C. Scarrow, B. A. Brennan, J. G. Cummings, H. Jim, D. J. Duong, J. T. Kindt and M. J. Nelson, Biochemistry, 1996, 35, 10 078 CrossRef CAS.
  4. (a) G. Fallon and B. M. Gatehouse, J. Chem. Soc., Dalton Trans., 1975, 1344 RSC; (b) P. J. Marini, K. S. Murray and B. O. West, J. Chem. Soc., Dalton Trans., 1983, 143 RSC; (c) T. Beissel, K. S. Bürger, G. Voigt, K. Weighardt, C. Butzlaff and A. X. Trautwein, Inorg. Chem., 1993, 32, 124 CrossRef CAS; (d) S. C. Shoner, D. Barnhart and J. A. Kovacs, Inorg. Chem., 1995, 34, 4517 CrossRef CAS; (e) N. Govindaswamy, D. A. Quarless, Jr. and S. A. Koch, J. Am. Chem. Soc., 1995, 117, 8468 CrossRef CAS.
  5. A. L. Nivorozhkin, G. I. Bondarenko, V. I. Nevodchikov, A. I. Uraev, I. S. Vasilchenko, A. S. Antsyshkina, L. E. Nivorozhkin and A. D. Garnovskii, in Abstracts of the European Inorganic Chemistry Research Seminars, EICS-VI, Biocoordination Chemistry, Inorganic Compounds with Framework Structures, Karrebaeksminde, Denmark, 1996, p. 64 Search PubMed.
  6. Yields 60–70%. Correct microanalyses. The ligands were prepared following literature procedures, A. I. Uraev and A. D. Garnovskii, Russ. J. Koord. Khim. 1997, submitted Search PubMed; A. L. Nivorozhkin, H. Toftlund and M. Nielsen, J. Chem. Soc., Dalton Trans., 1994, 361 Search PubMed.
  7. (a) S. Koch, S. C. Tang, R. H. Holm and R. B. Frankel, J. Am. Chem. Soc., 1975, 97, 914 CrossRef CAS; (b) N. N. Greenwood and T. G. Gibb, Mössbauer Spectroscopy, Chapman & Hall, London, 1971, p. 154 Search PubMed.
  8. M. Gerloch and F. E. Mabbs, J. Chem. Soc. A, 1967, 1900 RSC.
  9. (a) M. M. Maltempo, J. Chem. Phys., 1974, 61, 2540 CrossRef CAS; (b) C. A. Reed, T. Mashiko, S. P. Bentley, M. E. Kastner, W. R. Sheidt, K. Spartalian and G. Lang, J. Am. Chem. Soc., 1979, 101, 2948 CrossRef CAS; (c) W. R. Scheidt and C. A. Reed, Chem. Rev., 1981, 81, 543 CrossRef CAS.
  10. J. P. Fitzgerald, B. S. Haggerty, A. L. Rheingold, L. May and G. A. Brewer, Inorg. Chem., 1992, 31, 2067.
  11. No synthetic iron–sulfur complexes able to hydrolyze nitriles are, as yet, reported. See for example, a recent review: R. A. Michelin, M. Mozzon and R. Bertani, Coord. Chem. Rev., 1996, 147, 299 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.