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Synthesis, structure and reactivity of binuclear metal-metal bonded molybdenum(V) and tungsten(V) thioselenohalides: Molecular structure of Mo2(μ-S2)2Cl6(SeCl2)2 and W2(μ-S2)2Cl6(SeCl2)2

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Abstract

Thioselenohalide complexes Mo2(μ-S2)2Cl6(SeCl2)2 (I), Mo2(μ-S2)2Br6(SeBr2)2 (II), and W2(μ-S2)2Br6(SeBr2)2 (III) were synthesized by the reactions of corresponding metal halides or carbonyls or molybdenum metal with excesses of S2 X 2+Se2 X 2 mixtures. The complex W2(μ-S2)2Cl6(SeCl2)2 (IV) was obtained by an exchange reaction between (III) and excess of Se2Cl2. Coordination of the neutral SeX 2 ligands to thiohalidesM 2(μ-S2)2 X 6 results in higher thermal stability, and suggests the possibility to synthesize SeX 2 complexes of the unstable parent tungsten thiohalides. An unusual oxidative addition reaction of (I) was detected: {fx27-1} Both (I) and (IV) were characterized by X-ray crystal structure analysis. They are isostructural and form discrete molecules. Bridging S 2−2 ligands are coordinated perpendicularly to the metal-metal bond;d(M−M)=2.8066 Å and 2.793 Å for I and IV, respectively. Nonequivalence of chlorine atoms which are bound to the metal atom, relate to nonequivalence of halogen atoms in the complexesM 2(μ−S2)2 X 2−8 . Chlorine atomstrans to SeCl2 ligands form short bonds with the metal; the corresponding35Cl NQR frequency is increased. The selenium dichloride ligand is ambidentate. The selenium atom binds as a donor to the metal and as an acceptor to two chlorine atoms which are also bound covalently to the same metal atom.

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References

  1. T. Saito,in M. H. Chisholm (ed.),Early Transition Metal Clusters with π-Donor Ligands (VCH Publishers, New York, 1995), pp. 63–164.

    Google Scholar 

  2. J.-C. Gabriel, K. Boubekeur, and P. Batail (1993).Inorg. Chem. 32, 2894.

    Article  CAS  Google Scholar 

  3. A. Müller, E. Krickemeyer, H. Bögge, H. Ratajczak, and A. Armatage (1994).Angew. Chem. Int. Ed. Engl. 33(7), 770.

    Article  Google Scholar 

  4. N. I. Timoshchenko, V. L. Kolesnichenko, S. V. Volkov, Yu. L. Slovokhotov, and Yu. T. Struchkov (1990).Russ. J. Coord. Chem. 16(8), 567.

    Google Scholar 

  5. L. A. Aslanov, S. V. Volkov, V. L. Kolesnichenko, T. B. Mischanchuk, V. B. Rybakov, and N. I. Timoshchenko (1991).Soviet Progress in Chemistry (Ukr. Khim. Zh.).57(7), 1.

    Google Scholar 

  6. N. S. Fortunatov and N. I. Timoshchenko (1965).Ukr. Khim. Zh. 31(10), 1078.

    CAS  Google Scholar 

  7. S. V. Volkov, V. L. Kolesnichenko, and N. I. Timoshchenko (1988).Russ. J. Inorg. Chem. 33(4), 459.

    Google Scholar 

  8. J. Marcoll, A. Rabenau, D. Mootz, and H. Wunderlich (1974).Rev. Chim. Miner. 11(5), 607.

    CAS  Google Scholar 

  9. D. Fenske, B. Czeska, C. Schumacher, R. E. Schmidt, and K. Dehnicke (1985).Z. Anorg. Allg. Chem. 520(1), 7.

    Article  CAS  Google Scholar 

  10. C. D. Borman, V. P. Fedin, M. C. Hong, G. J. Lamprecht, C. H. Kwak, C. A. Routledge, D. M. Saysell, and A. G. Sykes (1995).Pure Appl. Chem. 67(2), 305.

    Article  CAS  Google Scholar 

  11. N. S. Fortunatov and N. I. Timoshchenko (1969).Ukr. Khim. Zh. 35(11), 1207.

    CAS  Google Scholar 

  12. F. A. Cotton, P. A. Kibala, M. Matusz, C. S. McCaleb, and R. B. W. Sandor (1989).Inorg. Chem. 28, 2623.

    Article  CAS  Google Scholar 

  13. V. P. Fedin, M. N. Sokolov, O. A. Geras’ko, B. A. Kolesov, V. Ye. Fedorov, A. V. Mironov, D. S. Yufit, Yu. L. Slovokhotov, and Yu. T. Struchkov (1990).Inorg Chim. Acta. 175, 217.

    Article  CAS  Google Scholar 

  14. T. Saito, A. Yoshikawa, T. Yamagata, H. Imoto, and K. Unora (1989).Inorg. Chem. 28, 3588.

    Article  CAS  Google Scholar 

  15. A. V. Virovets, Yu. L. Slovokhotov, Yu. T. Struchkov, V. E. Fedorov, Yu. V. Mironov, and V. P. Fedin (1990).Koord. Khim. 16(2), 198.

    CAS  Google Scholar 

  16. V. L. Kolesnichenko, S. P. Sharavskaya, O. G. Yanko, and S. V. Volkov (1993).Russ. J. Inorg. Chem. 38(7), 1011.

    Google Scholar 

  17. V. M. Belousov, T. A. Pal’chevskaya, S. V. Volkov, V. L. Kolesnichenko, L. V. Bogutskaya, and S. P. Sharavskaya (1992).Theoret. Exp. Chem. 28(3), 194.

    Article  Google Scholar 

  18. S. V. Volkov, Yu. N. Mikhailov, V. L. Kolesnichenko, A. S. Kanishcheva, and N. I. Timoshchenko (1988).Koord. Khim. 14(3), 363.

    CAS  Google Scholar 

  19. S. V. Volkov, V. L. Kolesnichenko, and N. I. Timoshchenko (1988).J. Coord. Chem. 17, 367.

    Article  CAS  Google Scholar 

  20. H. Stammreich and R. Forneris (1956).Spectrochim. Acta. 8, 46.

    Article  CAS  Google Scholar 

  21. G. Brauer (ed.),Handbuch der Präparativen Anorganischen Chemie (Ferdinand Enke Verlag, Stuttgart, 1981).

    Google Scholar 

  22. S. V. Volkov, Z. A. Fokina, V. F. Lapko, V. E. Pogorelov, and G. I. Salivon (1982).Ukr. Khim. Zh. 48, 899.

    CAS  Google Scholar 

  23. H. G. Stammler and J. Weiss (1989).Z. Naturforsch. 44b, 1483.

    Google Scholar 

  24. B. Krebs, E. Lührs, R. Willmer, and F.-P. Ahlers (1991).Z. Anorg. Allg. Chem. 592, 17.

    Article  CAS  Google Scholar 

  25. F. A. Cotton, P. A. Kibala, and R. B. W. Sandor (1989).Acta Cryst. C45, 1287.

    CAS  Google Scholar 

  26. K. Nakamoto,Infrared and Raman Spectra of Inorganic and Coordination Compounds (John Wiley & Sons, New York, 1986), p. 128.

    Google Scholar 

  27. J. Q. Lee, M. L. Sampson, J. F. Richardson, and M. E. Noble (1995).Inorg. Chem. 34, 5055.

    Article  CAS  Google Scholar 

  28. S. V. Volkov and V. I. Pekhn’o (1993).Russ. J. Coord. Chem. 19(6), 524.

    Google Scholar 

  29. B. Krebs, A. Schäffer, and S. Pohl (1984).Z. Naturforsch. 39b, 1633.

    CAS  Google Scholar 

Download references

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Authors and Affiliations

  1. Institute of General and Inorganic Chemistry, Ukrainian Academy of Sciences, 252680, Kiev, Ukraine

    Vladimir L. Kolesnichenko & Sergei V. Volkov

  2. Department of Chemistry, Moscow State University, B-234, Moscow, Russia

    Victor B. Rybakov & Leonid A. Aslanov

Authors
  1. Vladimir L. Kolesnichenko
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  2. Victor B. Rybakov
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  3. Leonid A. Aslanov
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  4. Sergei V. Volkov
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Kolesnichenko, V.L., Rybakov, V.B., Aslanov, L.A. et al. Synthesis, structure and reactivity of binuclear metal-metal bonded molybdenum(V) and tungsten(V) thioselenohalides: Molecular structure of Mo2(μ-S2)2Cl6(SeCl2)2 and W2(μ-S2)2Cl6(SeCl2)2 . J Clust Sci 8, 27–45 (1997). https://doi.org/10.1007/BF02764127

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