Ionic cleavage of Ti–Co and Zr–Co bonds: the role of the nucleophilicity of the late transition metal in the reactive behaviour of early–late heterobimetallics

(Note: The full text of this document is currently only available in the PDF Version )

Martin Schubart, Gemma Mitchell, Thomas Kottke, Lutz H. Gade, Ian J. Scowen and Mary McPartlin


Abstract

The ionic cleavage of Ti–Co and Zr–Co bonds occurs upon reaction with ButNC and the products [MeSi{SiMe2N(p-Tol)}3Ti(CNBut)2][Co(CO)4] 3 and[MeSi{SiMe2N(p-Tol)}3Zr(CNBut)3][Co(CO)4] 4 were characterized by single crystal X-ray diffraction; the importance of the nucleophilicity of the late transition metal fragment in reactions of the unsupported early–late heterobimetallics is demonstrated.


References

  1. M. Herberhold and G.-X. Jin, Angew. Chem., Int. Ed. Engl., 1994, 33, 964 CrossRef; C. P. Casey, J. Organomet. Chem., 1990, 400, 205 CrossRef CAS; G. S. Ferguson, P. T. Wolczanski, L. Parkanyi and M. Zonnevylle, Organometallics, 1988, 7, 1967 CrossRef CAS; T. A. Hanna, A. M. Baranger and R. G. Bergman, J. Am. Chem. Soc., 1995, 117, 665.
  2. S. Friedrich, H. Memmler, L. H. Gade, W.-S. Li and M. McPartlin, Angew. Chem., Int. Ed. Engl., 1994, 33, 676 CrossRef; S. Friedrich, H. Memmler, L. H. Gade, W.-S. Li, I. J. Scowen, M. McPartlin and C. E. Housecroft, Inorg. Chem., 1996, 35, 2433 CrossRef CAS; S. Friedrich, L. H. Gade, I. J. Scowen and M. McPartlin, Angew. Chem., Int. Ed. Engl., 1996, 35, 1338 CrossRef CAS; S. Friedrich, L. H. Gade, I. J. Scowen and M. McPartlin, Organometallics, 1995, 14, 5344 CrossRef CAS.
  3. B. Findeis, M. Schubart, C. Platzek, L. H. Gade, I. J. Scowen and M. McPartlin, Chem. Commun., 1996, 219 RSC.
  4. H. Memmler, U. Kauper, L. H. Gade, I. J. Scowen and M. McPartlin, Chem. Commun., 1996, 1751 RSC.
  5. A. Schneider, L. H. Gade, M. Breuning, G. Bringmann, I. J. Scowen and M. McPartlin, Organometallics, 1998, 17, 1643 CrossRef CAS.
  6. R. G. Pearson, H. Sobel and J. Songstad, J. Am. Chem. Soc., 1968, 90, 316.
  7. Examples of ionic dissociation of polar metal–metal bonds which have been studied carefully in solution. D. A. Roberts, W. C. Mercer, S. M. Zahurak, G. L. Geoffroy, C. W. DeBrosse, M. E. Cass and C. G. Pierpont, J. Am. Chem. Soc., 1982, 104, 910 Search PubMed; P. S. Bearman, A. K. Smith, N. C. Tong and R. Whyman, Chem. Commun., 1996, 2061 CrossRef CAS.
  8. G. Fachinetti, G. Fochi, T. Funaioli and P. F. Zanazzi, Angew. Chem., Int. Ed. Engl., 1987, 26, 680 CrossRef and references therein.
  9. G. Jansen, M. Schubart, B. Findeis, L. H. Gade, I. J. Scowen and M. McPartlin, J. Am. Chem. Soc., 1998, 120, 7239 CrossRef CAS.
  10. A. R. Manning, J. Chem. Soc. A, 1968, 1135 RSC.
  11. P. Berno, C. Floriani, A. Chiesi-Villa and C. Rizzoli, J. Chem. Soc., Dalton Trans., 1991, 3085 RSC; B. Temme, G. Erker, R. Fröhlich and M. Grehl, Angew. Chem., Int. Ed. Engl., 1994, 33, 1480 CrossRef; T. Brackemeyer, G. Erker and R. Fröhlich, Organometallics, 1997, 16, 531 CrossRef CAS; W. Ahlers, B. Temme, G. Erker, R. Fröhlich and T. Fox, J. Organomet. Chem., 1997, 527, 191 CrossRef.