Synthesis and crystal structure of the tris(amide) cations [M{N(SiMe₃)₂}₃]⁺ (M = Zr or Hf ): evidence for M–Si–C interactions

Abstract

Reaction of the strong Lewis acid B(C₆F₅)₃ with [M{N(SiMe₃)₂}₃Me] (M = Zr or Hf ) gave the compounds [M{N(SiMe₃)₂}₃][MeB(C₆F₅)₃]. Crystallographic analyses of these compounds revealed the formation of multicentre bonds between the SiCH₃ units of the amide ligands and the otherwise electron-deficient metal centre. The new tris(amide) complexes [M{N(Ph)SiMe₃}₃Cl] and [M{N(Ph)SiMe₃}₃Me] (M = Zr or Hf ) have also been synthesized.

References

1. X. Yang, C. L. Stern and T. J. Marks, J. Am. Chem. Soc., 1991, 113, 3623.
2. M. Bochmann and S. J. Lancaster, Organometallics, 1994, 13, 2235.
3. D. J. Gillis, M.-J. Tuboret and M. C. Baird, J. Am. Chem. Soc., 1993, 115, 2543.
4. M. Müller, V. C. Williams, L. H. Doerrer, M. A. Leech, S. A. Mason, M. L. H. Green and K. Prout, Inorg. Chem., in the press.
5. H. van der Hejden, C. J. Schaverien and A. G. Orpen, Organometallics, 1989, 8, 255.
6. R. Anderson, Inorg. Chem., 1979, 18, 1724.
7. A. D. Horton and J. de With, Chem Commun., 1996, 1375.
8. A. D. Horton, J. de With, A. J. van der Linden and H. van de Weg, Organometallics, 1996, 15, 2672.
9. J. R. Galsworthy, M. L. H. Green, M. Müller and K. Prout, J. Chem. Soc., Dalton Trans., 1997, 1309.
10. D. C. Bradley, H. Chudzynska, J. D. J. Backer-Dirks, M. B. Hursthouse, A. A. Ibrahim, M. Motevalli and A. C. Sullivan, Polyhedron, 1990, 9, 1423.
11. A. G. Massey and A. J. Park, J. Organomet. Chem., 1964, 2, 245.
12. D. Gewirth, The HKL Manual, written with the co-operation of the program authors, Z. Otwinowski and W. Minor, Yale University, 1995.
13. E. Prince, Mathematical Techniques in Crystallography and Material Sciences, Springer, New York, 1982.
14. International Tables for Crystallography, Kluwer, Dordrecht, 1992, vol. C.
15. D. J. Watkin, C. K. Prout, J. R. Carruthers and P. W. Betteridge, CRYSTALS Issue 10, Chemical Crystallography Laboratory, University of Oxford, 1996.