Russian Chemical Bulletin

, Volume 52, Issue 8, pp 1702–1708

New class of neutral paramagnetic binuclear sulfur-containing iron nitrosyl complexes

  • S. M. Aldosh
  • N. A. Sanina
  • O. A. Rakova
  • G. V. Shilov
  • A. V. Kulikov
  • Yu. M. Shulga
  • N. S. Ovanesyan


Neutral paramagnetic binuclear iron nitrosyl complexes, whose structures and properties differ from those of the known Roussin"s red salt esters, were synthesized for the first time. The iron nitrosyl complexes [Fe22-SR)2(NO)4nH2O (η1-S, η1-N; n = 1 or 2; R is 5-amino-1,2,4-triazol-3-yl (1), 1,2,4-triazol-3-yl (2), 1-methyltetrazol-5-yl (3), or benzothiazol-2-yl (4)) were prepared by the exchange reactions of Na2Fe2(S2O3)2(NO)4 with heterocyclic thiols. According to the results of X-ray diffraction analysis, complex 1 has a centrosymmetrical dimeric structure in which the iron atoms are linked through the μ-N—C—S structural fragment. Each Fe atom is bound to the N atom of one ligand and the S atom of another ligand. The isomer shifts of complexes 1—4 have virtually equal values (δFe = 0.291(1)—0.304(1) mm s–1 at T = 85 K), which are twice as large as δFe for Roussin"s red salt esters. The iron atoms in complexes 1—4 have the low-spin configuration d7 (Fe+). The ESR spectra of polycrystalline powders of complexes 1—4 consist of a single Lorentzian line with g = 2.032 and a width of 6—10 mT. The temperature dependence of the magnetic susceptibility of complex 1 in the temperature range of 80—300 K is adequately described by the Curie—Weiss law with θ ≈ 8 K; the effective magnetic moment per iron atom is 1.85 μB.

synthesis sulfur-containing iron nitrosyl complexes heterocyclic thiols complexes of the g ∼2.03 family X-ray diffraction analysis ESR Mössbauer spectroscopy 


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  1. 1.
    T. Ueno, Y. Suzuki, S. Fujii, and T. Yoshimura, Biochem. Pharmacol., 2002, 63, 485.Google Scholar
  2. 2.
    S. Costanzo, S. Menage, R. Purrello, R. P. Bonomo, and M. Fontecave, Inorg. Chim. Acta., 2001, 318, 1.Google Scholar
  3. 3.
    A. R. Butler and I. L. Megson, Chem. Rev., 2002, 102, 1155.Google Scholar
  4. 4.
    P. G. Wang, M. Xian, X. P. Tang, X. J. Wu, Z. Wen, T. W. Cai, and A. J. Janczuk, Chem. Rev., 2002, 102, 1091.Google Scholar
  5. 5.
    N. Reginato, C. T. C. McCrory, D. Pervitsky, and L. J. Li, J. Am. Chem. Soc., 1999, 121, 43, 10217.Google Scholar
  6. 6.
    R. Basosi, E. Gaggelli, E. Tiezzi, and G. Valensin, J. Chem. Soc., Perkin Trans. 2, 1975, 423.Google Scholar
  7. 7.
    A. F. Vanin, Biokhimiya, 1998, 63, 782 [Biochemistry (Moscow), 1998, 63 (Engl. Transl.)].Google Scholar
  8. 8.
    A. F. Vanin, R. A. Stukan, and E. B. Manukhina, Biophysics, 1997, 42, 7.Google Scholar
  9. 9.
    A. R. Butler, C. Glidewell, and M. H. Li, Adv. Inorg. Chem., 1988, 32. 335.Google Scholar
  10. 10.
    C. Glidewell, R. J. Lambert, M. E. Harman, and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1990, 2685.Google Scholar
  11. 11.
    O. A. Rakova, N. A. Sanina, G. V. Shilov, Yu. M. Shul´ga, V. M. Martynenko, N. S. Ovanesyan, and S. M. Aldoshin, Koord. Khim. 2002, 28, 364 [Russ. J. Coord. Chem., 2002, 28 (Engl. Transl.)].Google Scholar
  12. 12.
    O. A. Rakova, N. A. Sanina, S. M. Aldoshin, and Y. M. Shulga, J. Inorg. Biochem., 2001, 8, 309.Google Scholar
  13. 13.
    E. S. Raper, Coord. Chem. Rev., 1997, 165, 475.Google Scholar
  14. 14.
    E. S. Raper, Coord. Chem. Rev., 1985, 61, 115.Google Scholar
  15. 15.
    P. D. Akrivos, Coord. Chem. Rev., 2001, 213, 181.Google Scholar
  16. 16.
    C. Glidewell, M. E. Harman, M. B. Hursthouse, I. L. Johnson, and M. Motevalli, J. Chem. Res. (S), 1988, 212.Google Scholar
  17. 17.
    J. T. Thomas, J. H. Robertson, and E. G. Cox, Acta Crystallogr., 1958, 11, 599.Google Scholar
  18. 18.
    C. Glidewell, D. Baty, R. G. Willis, M. G. Burdon, A. R. Butler, I. L. Johnson, and R. Massey, Inorg. Chim. Acta, 1987, 138, 15.Google Scholar
  19. 19.
    O. A. Rakova, N. A. Sanina, G. V. Shilov, V. V. Strelets, I. B. Borzova, A. V. Kulikov, and S. M. Aldoshin, Koord. Khim. 2001, 27, 698 [Russ. J. Coord. Chem., 2002, 27 (Engl. Transl.)].Google Scholar
  20. 20.
    A. K. Sen, R. N. Singh, R. N. Handa, S. N. Dubey, and P. J. Squattrito, J. Molecular. Struct., 1998, 470, 61.Google Scholar
  21. 21.
    J. Jolley, W. I. Cross, R. G. Pritchard, C. A. McAuliffe, and K. B. Nolan Inorg. Chim. Acta, 2001, 315, 36.Google Scholar
  22. 22.
    D. H. Templeton, A. Zalkin, and T. Ueki, Acta Crystallogr., Sect. A., 1966, 21, 154.Google Scholar
  23. 23.
    I. A. Latham, G. J. Leigh, and C. J. Pickett, J. Chem. Soc. Dalton Trans., 1986, 1986.Google Scholar
  24. 24.
    E. Konig and K. J. Watson, Chem. Phys. Lett., 1970, 6, 457.Google Scholar
  25. 25.
    M. Gerloch, R. F. McMeeking, and A. M. White, J. Chem. Soc. Dalton Trans., 1975, 2452.Google Scholar
  26. 26.
    S. M. Aldoshin and N. A. Sanina, Tez. dokl., III Natsional'naya kristallokhimicheskaya konf. [Abstrs. of Papers, III All-Russian Crystal-Chemcial Conf.] (Chernogolovka, May 19-23, 2003), Chernogolovka, 2003, 36 (in Russian).Google Scholar
  27. 27.
    M. Fontecave and J. L. Pierre, Bull. Soc. Chim. Fr., 1994, 131, 620.Google Scholar
  28. 28.
    N. A. Sanina, O. A. Rakova, S. M. Aldoshin, I. I. Chuev, E. G. Atovmyan, and N. S. Ovanesyan, Koord. Khim. 2001, 27, 198 [Russ. J. Coord. Chem., 2002, 27 (Engl. Transl.)].Google Scholar
  29. 29.
    J. Lewis, R. J. Irving, and G. Wilkinson, J. Inorg. Nucl. Chem., 1958, 7, 32.Google Scholar
  30. 30.
    O. A. Rakova, N. A. Sanina, Yu. M. Shul´ga, V. M. Martynenko, N. S. Ovanesyan, and S. M. Aldoshin, Dokl. Akad. Nauk 2002, 383, 350 [Dokl. Chem., 2002 (Engl. Transl.)].Google Scholar
  31. 31.
    L. D. Pettit and M. Bezer, Coord. Chem. Rev., 1985, 61, 97.Google Scholar
  32. 32.
    K. A. Mitchell and C. M. Jensen, Inorg. Chim. Acta, 1997, 265, 103.Google Scholar
  33. 33.
    V. A. Klimova, Osnovnye mikrometody analiza organicheskikh soedinenii [Main Micromethods for Analysis of Organic Compounds], Khimiya, Moscow, 1975, 21 (in Russian).Google Scholar
  34. 34.
    G. M. Sheldrick, SHELX-97, Release 97-2, Program for Crystal Structure Refinement University of Göttingen, Göttingen (Germany), 1997.Google Scholar

Copyright information

© Plenum Publishing Corporation 2003

Authors and Affiliations

  • S. M. Aldosh
    • 1
  • N. A. Sanina
    • 1
  • O. A. Rakova
    • 1
  • G. V. Shilov
    • 1
  • A. V. Kulikov
    • 1
  • Yu. M. Shulga
    • 1
  • N. S. Ovanesyan
    • 1
  1. 1.Institute of Problems of Chemical PhysicsRussian Academy of SciencesChernogolovkaRussian Federation

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