Advertisement

Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Synthesis and characterization of dinuclear niobium(IV), niobium(III) and tantalum(III) chloride complexes with strongly basic phosphanes: PCy3 and P(Bu-t)3

Summary

The reactions between niobium and tantalum pentachlorides and tri-t-butylphosphane and tricyclohexylphosphane under various reducing conditions (magnesium turnings, amalgamated magnesium or sodium naphthalenide) were investigated. The products are highly dependent on the experimental conditions. Niobium(IV) adducts: Nb2Cl8[P(Bu-t)3]2 and Nb2Cl8(PCy3)4 were obtained with magnesium turnings, while reduction to Ta2Cl6(PCy3)3 occurred under similar conditions with tantalum. Ligand exchanges from NbCl4(THF)2 also yielded niobium(IV) adducts Nb2Cl8(PR3)3. The formation of the first soluble diamagnetic niobium(IV) adducts appears to be favored by the strong basicity of PCy3 and P(Bu-t)3. However, these crowded niobium(IV) complexes are unstable both in the solid and in solution with respect to niobium(III). Derivatives in oxidation state 3: M2Cl6(PCy3)3 (M=Nb or Ta), Ta2Cl6[P(Bu-t)3]3 and Nb2Cl6[P(Bu-t)3]2 were formed more efficiently with amalgamated magnesium or with sodium naphthalenide. Activation of dinitrogen under mild conditions (normal pressure, room temperature) was observed during the reduction process with magnesium, for both tantalum and niobium; an unstable adduct, Nb2Cl6[P(Bu-t)3]3N2, could be isolated. All products were characterized by elemental analysis, magnetic susceptibility measurements and i.r. spectroscopy; their molecular structure is discussed in terms of the1H and31P n.m.r. data.

This is a preview of subscription content, log in to check access.

References

  1. (1)

    C. A. McAuliffe and W. Levason,Phosphine, Arsine and Stilbine Complexes of the Transition Elements. Elsevier, New York, 1979; C. A. Tolman.Chem. Revs., 77, 313 (1977).

  2. (2)

    J. Chatt, J. R. Dilworth and R. L. Richards,Chem. Revs., 78, 589 (1978); J. A. Ibers,Chem. Soc. Revs., 11, 57 (1982).

  3. (3)

    R. A. Walton,Progr. Inorg. Chem. 22, 105 (1974); J. R. Ebner, D. R. Tyler and R. A. Walton,Inorg. Chem., 15, 833 (1976); G. W. A. Fowles and R. A. Walton,J. Less Comm. Mets., 5, 510 (1963).

  4. (4)

    G. Jamieson and W. E. Lindsell,Inorg. Chim. Acta., 28, 113 (1978).

  5. (5)

    L. G. Hubert-Pfalzgraf and J. G. Riess,Inorg. Chim. Acta, 29, L251 (1978); L. G. Hubert-Pfalzgraf, M. Tsunoda and J. G. Riess,Inorg. Chim. Acta, 52, 231 (1981).

  6. (6)

    A. P. Sattelberger, R. B. Wilson, Jr. and J. C. Huffman,J. Am. Chem. Soc., 102, 7113 (1980); J. R. Wilson, A. P. Sattelberger and J. C. Huffman,J. Am. Chem. Soc., 104, 858 (1982); M. L. Luetkens, Jr., J. C. Huffman and S. P. Sattelberger,J. Am. Chem. Soc., 105, 4474 (1983).

  7. (7)

    S. Datta and S. S. Wreford,Inorg. Chem., 16, 1134 (1977).

  8. (8)

    S. M. Rocklage, H. W. Turner, J. D. Fellmann and R. R. Schrock,Organometallics, 1, 703 (1982).

  9. (9)

    R. Gut and W. Perron,J. Less Comm. Mets., 26, 369 (1972).

  10. (10)

    L. E. Manzer,Inorg. Chem., 16, 525 (1977).

  11. (11)

    E. Samuel, G. Labauze and J. Livage,Nouv. J. Chimie, 1, 93 (1977); G. Labauze, E. Samuel and J. Livage,Inorg. Chem., 19, 1384 (1980).

  12. (12)

    G. Labauze,Ph. D. Thesis, Paris, 1978.

  13. (13)

    G. J. Kubas,J. Chem. Soc. Chem. Commun.,61 (1980); G. Valentini, G. Braco, S. S. Brana and A. Colliglioni,Inorg. Chim. Acta,69, 215 (1983).

  14. (14)

    G. K. Anderson, H. C. Clark and J. A. Davis,Inorg. Chem., 20, 944 (1981); T. Yoshida, T. Okama and S. Otsuka,J. Chem. Soc. Chem. Commun., 855 (1978).

  15. (15)

    J. Emsley and D. Hall,The Chemistry of Phosphorus, Harper & Row, London, 1976.

  16. (16)

    L. G. Hubert-Pfalzgraf, M. Tsunoda and J. G. Riess,Inorg. Chim. Acta, 41, 283 (1980).

  17. (17)

    C. G. Dewey, J. E. Ellis, K. L. Fjare, K. M. Pfohl and C. F. P. Warnock,Organometallics, 2, 388 (1983).

  18. (18)

    R. J. Burt, G. J. Leigh and D. L. Hughes,J. Chem. Soc. Dalton Trans., 793 (1981).

  19. (19)

    M. R. Churchill and J. H. Wasserman,Inorg. Chem., 21, 218 (1982).

  20. (20)

    D. J. Machin and J. F. Sullivan,J. Less Common Mets., 19, 405 (1969).

  21. (21)

    C. A. Tolman,J. Am. Chem. Soc., 92, 2956 (1970);ibid., 96, 7589 (1974).

  22. (22)

    I. R. Beattie, T. R. Gilson and G. A. Ozin,J. Chem. Soc. A, 2765 (1968).

  23. (23)

    T. T. Derencsenyi,Inorg. Chem.,20, 665 (191).

  24. (24)

    F. A. Cotton and W. T. Hall,J. Am. Chem. Soc., 101, 5094 (1979).

  25. (25)

    S. R. Trade, G. R. Willey,J. Inorg. Nucl. Chem., 42, 1133 (1980); M. J. Anker, J. Chatt, G. J. Leigh and A. G. Wedd,J. Chem. Soc. Dalton Trans., 639 (1975); S. H. Summerville and R. Hoffmann,J. Am. Chem. Soc., 101, 3821 (1979).

  26. (26)

    A. Broll, H. G. von Schnering and H. Schafer,J. Less Comm. Mets., 22, 243 (1970); G. J. Wessel and J. W. Ijdo,Acta Crystallogr., 104, 466 (1957).

  27. (27)

    F. Calderazzo, G. Pampaloni and P. F. Zanazzi,J. Chem. Soc. Chem. Commun., 1304 (1982).

  28. (28)

    D. G. Bligh and D. L. Kepert,Inorg. Chem., 11, 1556 (1972); J. J. Howe and T. J. Pinnavaia,J. Am. Chem. Soc., 92, 7342 (1970).

  29. (29)

    L. G. Hubert-Pfalzgraf,Inorg. Chim. Acta, 76, L233 (1983).

  30. (30)

    R. B. Jackson and W. E. Streib,Inorg. Chem., 10, 1760 (1971); P. Sharp and R. R. Schrock,J. Am. Chem. Soc., 102, 1430 (1980).

  31. (31)

    R. G. Goël, W. P. Henry and N. K. Jha,Inorg. Chem., 21, 2551 (1982).

Download references

Author information

Correspondence to Liliane G. Hubert-Pfalzgraf.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Morancais, J.-., Hubert-Pfalzgraf, L.G. Synthesis and characterization of dinuclear niobium(IV), niobium(III) and tantalum(III) chloride complexes with strongly basic phosphanes: PCy3 and P(Bu-t)3 . Transition Met Chem 9, 130–134 (1984). https://doi.org/10.1007/BF00935927

Download citation

Keywords

  • Magnesium
  • Adduct
  • Magnetic Susceptibility
  • Niobium
  • Tantalum