View PDF Version
 
DOI: 10.1039/A904866I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3515-3521

Chelating versus bridging behaviour and NMR fluxionality of dppf in the nido clusters [M3Se2(CO)7(dppf[hair space])] [M = Fe or Ru, dppf = Fe(η5-C5H4PPh2)2]. Crystal structure of the chelated ruthenium derivative[hair space]†

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

Daniele Cauzzi, Claudia Graiff, Chiara Massera, Giovanni Predieri, Antonio Tiripicchio and Domenico Acquotti

Abstract

The reactions of [M3(CO)12] (M = Fe or Ru) with the diphosphine diselenide dppf[hair space]Se2 [dppf[hair space]Se2 = Fe(η5-C5H4P(Ph2)Se)2], in the presence of Me3NO afforded the disubstituted square pyramidal selenido clusters [Fe3Se2(CO)7(µ-dppf[hair space])] 1 and [Ru3Se2(CO)7(dppf[hair space])] 2. In the previously reported structure of 1 the dppf ligand bridges the two non-bonded iron atoms, whereas in 2 the same ligand chelates to one ruthenium atom of the basal plane of the square pyramidal cluster. Compound 2 represents the first reported example of chelating dppf to a carbonyl cluster. Both compounds exhibit fluxional behaviour in solution, consisting in the rocking motion of the bidentate bridging ligand below the square basal plane of the iron clusters in 1 and in the exchange of the axial and equatorial positions between the two chelating P atoms in 2. The dynamic behaviour of both compounds was studied by variable temperature 1-D and 2-D COSY and EXSY 1H NMR. The solid state structures correspond to the static structures in solution below 258 K for 1 and 213 K for 2. The cluster [Ru3Se2(CO)7(µ-dppe)] 3 [dppe = (CH2PPh2)2] has also been synthesized from dppeSe2, and its structure determined for comparison.

References

  1. L. C. Roof and J. W. Kolis, Chem. Rev., 1993, 93, 1037 CrossRef CAS.
  2. G. Hogarth, N. J. Taylor, A. J. Carty and A. Meyer, J. Chem. Soc., Chem. Commun., 1988, 834 RSC.
  3. S. M. Stuczynski, Y.-U. Kwon and M. L. Steigerwald, J. Organomet. Chem., 1993, 449, 167 CrossRef CAS.
  4. W. Imhof and G. Huttner, J. Organomet. Chem., 1993, 448, 247 CrossRef CAS.
  5. P. Baistrocchi, D. Cauzzi, M. Lanfranchi, G. Predieri, A. Tiripicchio and M. Tiripicchio Camellini, Inorg. Chim. Acta, 1995, 235, 173 CrossRef CAS.
  6. A. M. Z. Slawin, M. B. Smith and J. D. Woollins, J. Chem. Soc., Dalton Trans., 1997, 1877 RSC.
  7. D. Cauzzi, C. Graiff, M. Lanfranchi, G. Predieri and A. Tiripicchio, J. Organomet. Chem., 1997, 536–537, 497 CrossRef.
  8. Z.-G. Fang, Y.-S. Wen, R. K. L. Wong, S.-C. Ng, L.-K. Liu and T. S. A. Hor, J. Cluster Sci., 1994, 5, 327 CAS.
  9. B. F. G. Johnson, T. M. Layer, J. Lewis, A. Martin and P. R. Raithby, J. Organomet. Chem., 1992, 429, C41 CrossRef CAS.
  10. (a) D. Cauzzi, C. Graiff, M. Lanfranchi, G. Predieri and A. Tiripicchio, J. Chem. Soc., Dalton Trans., 1995, 2321 RSC; (b) D. Cauzzi, C. Graiff, G. Predieri, A. Tiripicchio and C. Vignali, J. Chem. Soc., Dalton Trans., 1999, 237 RSC.
  11. (a) K.-S. Gan and T. S. A. Hor, in Ferrocenes, eds. A. Togni and T. Hayashi, VCH, Weinheim, 1995, ch. 1 Search PubMed; (b) P. Zanello, ibid., ch. 7 Search PubMed.
  12. F. H. Allen and O. Kennard, Chem. Des. Autom. News, 1993, 8, 31 Search PubMed.
  13. N. Walker and D. Stuart, Acta Crystallogr., Sect. A, 1983, 39, 158 CrossRef; F. Ugozzoli, Comput. Chem., 1987, 11, 109 CrossRef.
  14. G. M. Sheldrick, SHELXS 86, Program for the Solution of Crystal Structures, Universität Göttingen, 1986.
  15. G. M. Sheldrick, SHELX 97, Program for the refinement of crystal structures, University of Göttingen, 1997.
  16. G. M. Sheldrick, SHELXL 93, Program for the refinement of crystal structures, University of Göttingen, 1993.
  17. S. T. Chacon, W. R. Cullen, M. J. Bruce, O. B. Shawkataly, F. W. B. Einstein, R. H. Jones and A. C. Willis, Can. J. Chem., 1990, 68, 2001 CAS.
  18. W. R. Cullen, S. J. Rettig and T. Zheng, Organometallics, 1992, 11, 853 CrossRef CAS.
  19. A. J. Blake, A. Harrison, B. F. G. Johnson, E. J. L. McInnes, S. Parsons, D. S. Shephard and L. J. Yellowlees, Organometallics, 1995, 14, 3160 CrossRef CAS.
  20. G. Rheinwald, H. Stoeckli-Evans and G. Süss-Fink, J. Organomet. Chem., 1996, 512, 27 CrossRef CAS.
  21. L. Pauling, The Nature of the Chemical Bond, Cornell University Press, Ithaca, NY, 1959 Search PubMed.
  22. M. I. Bruce, I. R. Butler, W. R. Cullen, G. A. Koutsantonis, M. R. Snow and E. R. T. Tiekink, Aust. J. Chem., 1988, 41, 963 CAS; A. Santos, J. Lopez, J. Montoya, P. Noheda, A. Romero and A. M. Echavarren, Organometallics, 1994, 13, 3605 CrossRef CAS; R. T. Hembre, J. S. McQueen and V. W. Day, J. Am. Chem. Soc., 1996, 118, 798 CrossRef CAS; M. Sato and M. Asai, J. Organomet. Chem., 1996, 508, 121 CrossRef CAS.
  23. S. B. Jensen, S. J. Rodger and M. D. Spicer, J. Organomet. Chem., 1998, 556, 151 CrossRef CAS.
  24. H. Günther, NMR Spectroscopy. An Introduction, Wiley, Chichester, 1980, p. 380 Search PubMed.
  25. S. M. Draper, C. E. Housecroft and A. L. Rheingold, J. Organomet. Chem., 1992, 435, 9 CrossRef CAS.
  26. (a) I. D. Salter, V. Sik, S. A. Williams and T. Adatia, Polyhedron, 1995, 14, 2803 CrossRef CAS; (b) I. D. Salter, S. A. Williams and T. Adatia, J. Chem. Soc., Dalton Trans., 1996, 643 RSC.
  27. S.-L. Lam, Y.-X. Cui, S. C. F. Au-Yeung, Y.-K. Yan and T. S. A. Hor, Inorg. Chem., 1994, 33, 2407 CrossRef CAS.
  28. C. Housecroft, S. M. Owen, P. R. Raithby and B. A. M. Shaykh, Organometallics, 1990, 9, 1617 CrossRef CAS.
  29. H. Shen, S. G. Bott and M. G. Richmond, Inorg. Chim. Acta, 1996, 241, 71 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.