View PDF Version
 
DOI: 10.1039/A707089F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 271-278

Generation of (η2-benzyne)bis(triphenylphosphine)platinum(>0>): orthometallation of the Pt(PPh3)2 complexes of benzyne (C6H4[hair space]) and cyclohexyne (C6H8)

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

Martin A. Bennett, Thomas Dirnberger, David C. R. Hockless, Eric Wenger and Anthony C. Willis

Abstract

The benzyne–platinum(>0>) complex [Pt(PPh3)2(η2-C6H4)] has been generated by treatment of a mixture of [Pt(PPh3)2(η2-C2H4)] and chlorobenzene with 2,2,6,6-tetramethylpiperid-1-yllithium at 0 °C and identified by comparison of its 31P NMR parameters with those of the cyclohexyne analogue, [Pt(PPh3)2(η2-C6H8)]. The compounds isolated from the reaction and identified by NMR spectroscopy and X-ray crystallography are the (2,2′-biphenyldiyl)platinum(II) complex [Pt(η1∶η1-C6H4C6H4)(PPh3)2], formed by reaction of [Pt(PPh3)2(η2-C6H4)] with free benzyne, and the orthometallated (η1-phenyl)platinum(II) complex [[upper bond 1 start]Pt{C6H4(P[upper bond 1 end]Ph2)-2}(C6H5)(PPh3)], formed by internal hydrogen-atom migration in [Pt(PPh3)2(η2-C6H4)]. The complex [Pt(PPh3)2(η2-C6H8)] undergoes a similar isomerization on heating in benzene to give the (η1-cyclohexen-1-yl)platinum(II) complex [[upper bond 1 start]Pt{C6H4(P[upper bond 1 end]Ph2)-2}(C6H9)(PPh3)], whose structure has also been determined by X-ray crystallography.

References

  1. M. A. Bennett and H. P. Schwemlein, Angew. Chem., 1989, 101, 1349 CrossRef CAS; Angew. Chem., Int. Ed. Engl., 1989, 28, 1296 Search PubMed.
  2. S. L. Buchwald and R. B. Nielsen, Chem. Rev., 1988, 88, 1047 CrossRef.
  3. M. A. Bennett and E. Wenger, Chem. Ber., 1997, 130, 1029 CrossRef CAS.
  4. M. A. Bennett, G. B. Robertson, P. O. Whimp and T. Yoshida, J. Am. Chem. Soc., 1971, 93, 3797 CrossRef CAS.
  5. M. A. Bennett and T. Yoshida, J. Am. Chem. Soc., 1978, 100, 1750 CrossRef CAS.
  6. M. A. Bennett, Pure Appl. Chem., 1989, 61, 1695 CAS.
  7. Z. Lu, K. A. Abboud and W. M. Jones, Organometallics, 1993, 12, 1471 CrossRef CAS.
  8. Z. Lu, K. A. Abboud and W. M. Jones, J. Am. Chem. Soc., 1992, 114, 10 991 CrossRef CAS.
  9. J. Klosin, K. A. Abboud and W. M. Jones, Organometallics, 1995, 14, 2892 CrossRef CAS.
  10. M. A. Bennett, J. S. Drage, T. Okano, N. K. Roberts and H.-P. Schwemlein, unpublished work, cited in ref. 1.
  11. M. A. Bennett, T. W. Hambley, N. K. Roberts and G. B. Robertson, Organometallics, 1985, 4, 1992 CrossRef CAS.
  12. M. A. Bennett and E. Wenger, Organometallics, 1995, 14, 1267 CrossRef CAS.
  13. M. A. Bennett, D. C. R. Hockless and E. Wenger, Organometallics, 1995, 14, 2091 CrossRef CAS.
  14. H. J. S. Winkler and G. Wittig, J. Org. Chem., 1963, 28, 1733 CAS.
  15. T. L. Gilchrist, F. J. Graveling and C. W. Rees, Chem. Commun., 1968, 821 RSC; J. Chem. Soc. C, 1971, 977 Search PubMed.
  16. C. D. Cook and G. S. Jauhal, J. Am. Chem. Soc., 1968, 90, 1464 CrossRef CAS.
  17. K. L. Shepard, Tetrahedron Lett., 1975, 3371 CrossRef CAS.
  18. M. A. Bennett, J. S. Drage, K. D. Griffiths, N. K. Roberts, G. B. Robertson and W. A. Wickramasinghe, Angew. Chem., 1988, 100, 1002 CAS; Angew. Chem., Int. Ed. Engl., 1988, 27, 941 Search PubMed.
  19. M. A. Bennett and A. Rokicki, Aust. J. Chem., 1985, 38, 1307 CAS.
  20. C. Eaborn, K. J. Odell and A. Pidcock, J. Chem. Soc., Dalton Trans., 1978, 357 RSC.
  21. V. V. Grushin, I. S. Akhrem and M. E. Vol'pin, J. Organomet. Chem., 1989, 371, 403 CrossRef CAS.
  22. P. S. Pregosin and R. W. Kunz, 31P- and 13C-NMR of Transition Metal Phosphine Complexes, Springer Verlag, Berlin, 1979, p. 92 Search PubMed.
  23. P. E. Garrou, Chem. Rev., 1981, 81, 229 CrossRef CAS.
  24. M. A. Bennett, D. E. Berry, S. K. Bhargava, E. J. Ditzel, G. B. Robertson and A. C. Willis, J. Chem. Soc., Chem. Commun., 1987, 1613 RSC.
  25. C. Scheffknecht, A. Rhomberg, E. P. Müller and P. Peringer, J. Organomet. Chem., 1993, 463, 245 CrossRef CAS.
  26. H. C. Clark and K. E. Hine, J. Organomet. Chem., 1976, 105, C32 CrossRef CAS.
  27. T. G. Appleton and M. A. Bennett, Inorg. Chem., 1978, 17, 738 CrossRef CAS.
  28. C. K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
  29. T. Debaerdemaeker, R. Hohenadel and H.-A. Brune, J. Organomet. Chem., 1991, 410, 265 CrossRef CAS.
  30. T. Debaerdemaeker, R. Hohenadel and H.-A. Brune, J. Organomet. Chem., 1988, 350, 109 CrossRef CAS.
  31. N. C. Rice and J. D. Oliver, J. Organomet. Chem., 1978, 145, 121 CrossRef CAS.
  32. M. A. Bennett and E. Wenger, Organometallics, 1996, 15, 5536 CrossRef CAS.
  33. J. A. Johnson, Ph.D. Thesis, Australian National University, 1991.
  34. J. Cámpora, A. Llebaria, J. M. Moretó, M. L. Poveda and E. Carmona, Organometallics, 1993, 12, 4032 CrossRef CAS.
  35. R. G. Miller and D. P. Kuhlman, J. Organomet. Chem., 1971, 26, 401 CrossRef CAS.
  36. S. Sostero, O. Traverso, M. Lenarda and M. Graziani, J. Organomet. Chem., 1977, 134, 259 CrossRef CAS.
  37. D. M. Blake and C. J. Nyman, Chem. Commun., 1969, 483 Search PubMed.
  38. R. Ugo, G. La Monica, F. Cariati, S. Cenini and F. Conti, Inorg. Chim. Acta, 1970, 4, 390 CrossRef CAS.
  39. R. Ugo, S. Cenini, M. F. Pilbrow, B. Deibl and G. Schneider, Inorg. Chim. Acta, 1976, 18, 113 CrossRef CAS.
  40. S. Sostero, O. Traverso, R. Ros and R. A. Michelin, J. Organomet. Chem., 1983, 246, 325 CrossRef CAS.
  41. N. A. Grabowski, R. P. Hughes, B. S. Jaynes and A. L. Rheingold, J. Chem. Soc., Chem. Commun., 1986, 1694 RSC.
  42. U. Nagel, Chem. Ber., 1982, 115, 1998 CAS.
  43. TEXSAN, Single Crystal Structure Analysis Software, version 1.6c, Molecular Structure Corporation, The Woodlands, TX, 1993.
  44. D. T. Cromer and J. T. Waber, International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4, p. 72 Search PubMed.
  45. D. C. Creagh and W. J. McAuley, International Tables for X-Ray Crystallography, Kluwer Academic, Boston, MA, 1992, vol. C, p. 219 Search PubMed.
  46. D. C. Creagh and J. H. Hubbell, International Tables for X-Ray Crystallography, Kluwer Academic, Boston, MA, 1992, vol. C, p. 200 Search PubMed.
  47. J. A. Ibers and W. C. Hamilton, Acta Crystallogr., 1964, 17, 781 CrossRef.
  48. G. M. Sheldrick, in Crystallographic Computing 3, eds. G. M. Sheldrick, C. Krüger and R. Goddard, Oxford University Press, 1985, p. 175 Search PubMed.
  49. P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, R. de Gelder, R. Israel and J. M. M. Smits, The DIRDIF 94 Program System, Technical Report of the Crystallographic Laboratory, University of Nijmegen, Nijmegen, 1994.
  50. TEXSAN, Single Crystal Structure Analysis Software, version 1.7, Molecular Structure Corporation, The Woodlands, TX, 1995.
  51. XTAL 3.4 Reference Manual, eds. S. R. Hall, G. S. D. King and J. M. Steward, University of Western Australia, 1995 Search PubMed.
  52. International Tables for X-ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4, pp. 99–101 and 149–150 Search PubMed.
  53. A. Altomare, M. Cascarano, C. Giacovazzo and A. Guagliardi, J. Appl. Crystallogr., 1993, 26, 343 CrossRef.
  54. XTAL 3.0 Reference Manual, eds. S. R. Hall and J. M. Steward, Universities of Western Australia and Maryland, 1990 Search PubMed.
  55. J. Waser, Acta Crystallogr., 1963, 16, 1091 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.