Vanadium(III) complexes incorporating the silylamino(disilylamido) ligand [(Me3Si)N{CH2CH2N(SiMe3)}2]2– [N{N″}2]2–. Synthesis and crystal structure of the dimeric, non-metallocene vanadium(III) hydride [{V(N{N″}2)}2(µ-H)2]

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Gerald P. Clancy, Howard C. S. Clark, Guy K. B. Clentsmith, F. Geoffrey N. Cloke and Peter B. Hitchcock


Abstract

Three vanadium(III) complexes incorporating the chelating silylamino(disilylamido) ligand [(Me3Si)N{CH2CH2N(SiMe3)}2]2– ([N{N″}2]2–) have been reported. Addition of Li2[N{N″}2] to VCl3·3THF cleanly yielded the vanadium(III) chloride [{V(N{N″}2)Cl}2] 1, from which the vanadium(III) hydrocarbyl [V(N{N″}2){CH(SiMe3)2}] 2 could be generated by means of salt metathesis. Hydrogenolysis of 2 under dihydrogen produced the thermally stable, dimeric vanadium(III) hydride [{V(N{N″}2)}2(µ-H)2] 3. The solid state structure of 3 was determined.


References

  1. C. C. Cummins, Prog. Inorg. Chem., 1998, 47, 685 CAS and refs. therein.
  2. R. Ferguson, E. Solari, C. Floriani, D. Osella, M. Ravera, N. Re, N. Chiesi-Villa and C. Rizzoli, J. Am. Chem. Soc., 1997, 119, 10104 CrossRef CAS.
  3. J.-I. Song and S. Gambarotta, New J. Chem., 1996, 2, 1258 Search PubMed.
  4. A. L. Odom, C. C. Cummins and J. D. Protasiewicz, J. Am. Chem. Soc., 1995, 117, 6613 CrossRef CAS.
  5. K. B. P. Ruppa, N. Desmangles, S. Gambarotta, G. Yap and A. L. Rheingold, Inorg. Chem., 1997, 36, 1194 CrossRef CAS.
  6. C. P. Gerlach and J. Arnold, Inorg. Chem., 1996, 35, 5770 CrossRef CAS.
  7. M. G. Fickes, W. M. Davis and C. C. Cummins, J. Am. Chem. Soc., 1995, 117, 6384 CrossRef CAS.
  8. N. Desmangles, S. Gambarotta, C. Bensimon, S. Davis and H. Zahalka, J. Organomet. Chem., 1998, 562, 53 CrossRef CAS.
  9. P. Berno, M. Moore, R. Minhas and S. Gambarotta, Can. J. Chem., 1996, 74, 1930 CAS.
  10. G. J. Leigh, Science, 1995, 268, 827 CAS and refs. therein.
  11. See R. R. Schrock, Acc. Chem. Res., 1997, 30, 9 Search PubMed; W. A. Herrmann, M. Denk, R. W. Albach, J. Behm and E. Herdtweck, Chem. Ber., 1991, 124, 683 CrossRef CAS.
  12. A. D. Horton, J. De With, A. J. Van de Linden and H. Van de Weg, Organometallics, 1996, 15, 2672 CrossRef CAS.
  13. F. G. N. Cloke, J. B. Love and P. B. Hitchcock, J. Chem. Soc., Dalton Trans., 1995, 25 RSC.
  14. H. C. S. Clark, F. G. N. Cloke, P. B. Hitchcock, J. B. Love and A. P. Wainwright, J. Organomet. Chem., 1995, 503, 333 CrossRef CAS.
  15. H. C. S. Clark, F. G. N. Cloke, J. C. Green, P. B. Hitchcock and J. B. Love, J. Am. Chem. Soc., 1999, 121, 6843 CrossRef CAS.
  16. N. Emig, F. P. Gabbai, H. Krautscheid, R. Réau and G. Bertrand, Angew. Chem., Int. Ed. Engl., 1998, 37, 989 CrossRef CAS.
  17. N. Emig, R. Réau, H. Krautscheid, D. Fenske and G. Bertrand, J. Am. Chem. Soc., 1996, 118, 5822 CrossRef CAS.
  18. J. H. Teuben, in Fundamental and Technological Aspects of Organo-f-Element Chemistry, ed. T. J. Marks and I. L. Fragalà, D. Reidel, Dordrecht, 1985, p. 195 and refs. therein Search PubMed.
  19. C. K. Johnson, ORTEPII, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
  20. C. C. Cummins, J. Lee, R. R. Schrock and W. D. Davies, Angew. Chem., Int. Ed. Engl., 1992, 31, 1501 CrossRef.
  21. C. P. Gerlach and J. Arnold, Organometallics, 1996, 15, 5260 CrossRef CAS.
  22. P. Berno and S. Gambarotta, J. Chem. Soc., Chem. Commun., 1994, 2419 RSC.
  23. P. Berno and S. Gambarotta, Organometallics, 1994, 13, 2569 CrossRef CAS.
  24. P. Berno, R. Minhas, S. Hao and S. Gambarotta, Organometallics, 1994, 13, 1052 CrossRef CAS.
  25. P. Berno and S. Gambarotta, Angew. Chem., Int. Ed. Engl., 1995, 34, 822 CrossRef CAS.
  26. L. E. Manzer, Inorg. Synth., 1982, 21, 135 CAS.
  27. M. A. Schwindt, T. Lejon and L. S. Hegedus, Organometallics, 1990, 9, 2814 CrossRef CAS.
  28. D. J. Davidson, D. H. Harris and M. F. Lappert, J. Chem. Soc., Dalton Trans., 1976, 2268 RSC.
  29. D. H. Grant, J. Chem. Educ., 1995, 72, 39 CrossRef CAS.
  30. D. F. Evans, J. Chem. Soc., 1959, 2003 RSC.
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