Synthesis, molecular and electronic structure of Ru3 isomeric clusters carrying C8 rings bonded in allenylic and acetylenic modes

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

Dario Braga, Fabrizia Grepioni, David B. Brown, Brian F. G. Johnson, Maria J. Calhorda and Luis F. Veiros


Abstract

The two new cluster complexes [Ru3H2(CO)9(C8H10 )] 1 and [Ru3H(CO)9(C8H11)] 2 have been isolated as the products of thermolysis of [Ru3(CO)12] in octane containing cycloocta-1,3-diene. The two species are structural isomers ideally differing only in the transfer of one hydrogen atom from the organic ligand to the metal core. The organic ligand in 2 is bonded in an allenyl µ33 fashion, the first allenylic bonded ring system to have been reported, whereas in 1 the ligand is, more conventionally, bound in µ32 fashion with the second unsaturated C[double bond, length as m-dash]C bond not involved in bonding to the cluster. The solid-state structures of 1 and 2 have been studied by single-crystal X-ray diffraction. The bonding of the organic ligands in the clusters has been investigated by molecular orbital calculations of the extended-Hückel type.


References

  1. (a) G. H. Young, A. Wojcicki, M. Galligaris, G. Nardin and N. Bresciani-Pahor, J. Am. Chem. Soc., 1989, 111, 6890 CrossRef CAS; (b) G. H. Young, M. V. Parhael, A. Wojcicki, M. Galligaris, G. Nardin and N. Bresciani-Pahor, Organometallics, 1991, 10, 1934 CrossRef CAS.
  2. D. Nucciarone, N. J. Taylor and A. J. Carty, Organometallics, 1984, 3, 177 CrossRef CAS; D. Nucciarone, S. A. MacLaughlin, N. J. Taylor and A. J. Carty, Organometallics, 1988, 7, 106 CrossRef; J. Suades, F. Dahan and A. Mathieu, Organometallics, 1988, 7, 47 CrossRef; C. E. Schuchart, A. Wojcicki, M. Calligaris, P. Faleschini and G. Nardin, Organometallics, 1994, 13, 1999 CrossRef CAS.
  3. G. Gervasio, D. Osella and M. Valle, Inorg. Chem., 1976, 15, 1221 CrossRef CAS.
  4. M. I. Bruce, J. M. Guss, R. Mason, B. W. Skelton and A. H. White, J. Organomet. Chem., 1983, 251, 261 CrossRef CAS; R. J. Goudsmit, B. F. G. Johnson, J. Lewis, P. R. Raithby and M. J. Rosales, J. Chem. Soc., Dalton Trans., 1983, 2257 RSC; R. D. Adams, X. Qu and W. Wu, Organometallics, 1993, 12, 4117 CrossRef CAS; H. Chen, B. F. G. Johnson, J. Lewis and P. R. Raithby, J. Organomet. Chem., 1989, C7, 376; R. D. Adams, G. Chen, X. Qu, W. Wu and J. H. Yamamoto, J. Am. Chem. Soc., 1992, 114, 10977 CrossRef CAS.
  5. A. G. Orpen, XHYDEX, A Program for Locating Hydrides, Bristol University, 1980; J. Chem. Soc., Dalton Trans., 1980, 2509 Search PubMed.
  6. R. Hoffmann, J. Chem. Phys., 1963, 39, 1397 CrossRef CAS; R. Hoffmann and W. N. Lipscomb, J. Chem. Phys., 1962, 36, 2179, 3489.
  7. R. Hoffmann, B. E. R. Schilling, R. Bau, H. D. Kaesz and D. M. P. Mingos, J. Am. Chem. Soc., 1978, 100, 6088 CrossRef CAS.
  8. M. J. Calhorda and D. M. P. Mingos, J. Organomet. Chem., 1982, 229, 229 CrossRef CAS.
  9. H. Mayr and R. Schneider, Chem. Ber., 1982, 115, 3470 CAS.
  10. G. Granozzi, E. Tondello, R. Bertoncello, S. Aime and D. Osella, Inorg. Chem., 1985, 24, 570 CrossRef CAS.
  11. (a) G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467 CrossRef; (b) G. M. Sheldrick, SHELXL 93, Program for Crystal Structure Determination, University of Göttingen, 1993; (c) E. Keller, SCHAKAL 93, University of Freiburg, 1993.
  12. J. H. Ammeter, H.-B. Bürgi, J. C. Thibeault and R. Hoffmann, J. Am. Chem. Soc., 1978, 100, 3686 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.