Skip to main content
SpringerLink
Log in

Bimolecular substitution and oxidation reactions of 17-electron pentacoordinate metal carbonyl radicals

  • Full Papers
  • Published:
Transition Metal Chemistry Aims and scope Submit manuscript

Summary

Quantitative and semiquantitative data for reactions of M2(CO)10-2nL2n (M=Mn or Re; L=P-donor ligand; n=0, 1) are analyzed to provide information regarding the mechanisms and relative rates of substitution and oxidation reactions of the [M(CO)5-nLn] radicals. Both associative and dissociative paths for substitution can be inferred, but the dissociative paths are generally much slower and occur only at high temperatures and/or when associative substitution is sterically disfavoured. Quantitative comparison of the reactivities of various radicals is made.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. W. Hieber and W. Freyer,Chem. Ber., 92, 1765 (1959).

    Google Scholar 

  2. W. Hieber, W. Beck, and G. Zeitler,Angew. Chem., 73, 364 (1961); H. Wawersik and F. Basolo,Chem. Comm., 366 (1966); J. R. Miller and D. H. Myers,Inorg. Chim. Acta, 5, 215 (1971).

    Google Scholar 

  3. R. H. Reiman and E. Singleton,J. Organometal. Chem., 38, 113 (1972); E. Singleton, J. T. Moelwyn-Hughes, and A. W. B. Garner,J. Organometal. Chem., 21, 449 (1970); H. Nakayama,Bull. Chem. Soc. Jpn., 43, 2057 (1970); M. Freni, D. Giusto, and P. Romiti,J. Inorg. Nucl. Chem., 29, 761 (1967); F. Nyman,Chem, Ind., 604 (1965); R. S. Nyholm and D. V. Ramana Rao,Proc. Chem. Soc., 130 (1959).

    Google Scholar 

  4. P. K. Baker, N. G. Connelly, J. P. Maher, and K. R. Sommers,J. Chem. Soc. Dalton Trans., 579 (1980).

  5. G. Guttner, D. Newgebauer, and A. Razari,Angew. Chem. Int. Edit., 14, 353 (1975).

    Google Scholar 

  6. D. J. Cox and R. Davis,Inorg. Nucl. Chem. Lett., 13, 301 (1977); D. J. Cox and R. Davis,J. Organometal. Chem., 186, 339 (1980).

    Google Scholar 

  7. D. R. Kidd, C. P. Cheng, and T. L. Brown,J. Am. Chem. Soc., 100, 4103 (1978).

    Google Scholar 

  8. R. A. Jackson and A. J. Poë,Inorg. Chem., 17, 997 (1978).

    Google Scholar 

  9. L. I. B. Haines and A. J. Poë,Nature, 215, 699 (1967);218, 562 (1968).

    Google Scholar 

  10. J. P. Fawcett, A. J. Poë, and M. V. Twigg,J. Organometal. Chem., 51 C17 (1973); J. P. Fawcett, A. J. Poë, and K. R. Sharma,J. Am. Chem. Soc., 98, (1976) 1401.

    Google Scholar 

  11. J. P. Fawcett, A. J. Poë, and K. R. Sharma,J. Chem. Soc. Dalton Trans., 1886 (1979).

  12. J. P. Fawcett, R. A. Jackson, and A. J. Poë,J. Chem. Soc. Dalton Trans., 789 (1978);idem. J. C. S. Chem. Comm., 733 (1975).

  13. D. M. Chowdhury, A. J. Poë, and K. R. Sharma,J. Chem. Soc. Dalton Trans., 2352 (1977).

  14. J. P. Fawcett and A. J. Poë,J. Chem. Soc. Dalton Trans., 1302 (1977).

  15. J. P. Fawcett and A. J. Poë,J. Chem. Soc. Dalton Trans., 2039 (1976).

  16. D. E. DeWit, J. P. Fawcett, and A. J. Poë,J. Chem. Soc. Dalton Trans., 528 (1976).

  17. H. Huber, E. P. Kündig, and G. A. Ozin,J. Am. Chem. Soc., 96, 5585 (1974); H. Huber, E. P. Kündig, G. A. Ozin, and A. J. Poë,ibid., 97, 308 (1975).

    Google Scholar 

  18. J. L. Hughey, C. P. Anderson, and T. J. Meyer,J. Organometal. Chem., 125, C49 (1977).

    Google Scholar 

  19. M. S. Wrighton and D. S. Ginley,J. Am. Chem. Soc., 97, 2065 (1975).

    Google Scholar 

  20. A. Hudson, M. F. Lappert, and B. K. Nicholson,J. Chem. Soc. Dalton, Trans., 551 (1977).

  21. L. S. Benner and A. L. Balch,J. Organometal. Chem., 134, 212 (1977).

    Google Scholar 

  22. A. S. Huffadine, B. M. Peake, B. H. Robinson, J. Simpson, and P. A. Dawson,J. Organometal. Chem., 121, 391 (1976).

    Google Scholar 

  23. W. Hieber and W. Schropp,Z. Naturforsch. Teil B, 15, 271 (1960); See also D. L. Morse and M. S. Wrighton,J. Am. Chem. Soc., 98, 3931 (1976).

    Google Scholar 

  24. H. B. Abrahamson and M. S. Wrighton,J. Am. Chem. Soc., 99, 5510 (1977).

    Google Scholar 

  25. C. L. Reichel and M. S. Wrighton,ibid., 101, 6769 (1979).

    Google Scholar 

  26. R. W. Wegman and T. L. Brown,ibid., 102, 2429 (1980), and ref. therein.

    Google Scholar 

  27. J. L. Hughey, C. R. Bock, and T. J. Meyer,J. Am. Chem. Soc., 97, 4440 (1975).

    Google Scholar 

  28. M. Absi-Halabi, J. D. Atwood, N. P. Forbus, and T. L. Brown,J. Am. Chem. Soc., 102, 6248 (1980).

    Google Scholar 

  29. R. M. Laine and P. C. Ford,Inorg. Chem., 16, 388 (1977).

    Google Scholar 

  30. A. Fox and A. J. Poë,J. Am. Chem. Soc., 102, 2497 (1980).

    Google Scholar 

  31. D. R. Kidd and T. L. Brown,J. Am. Chem. Soc., 100, 4095 (1978).

    Google Scholar 

  32. R. A. Epstein, T. R. Gaffney, G. L. Geoffroy, W. L. Gladfelter, and R. S. Henderson,J. Am. Chem. Soc., 101, 3847 (1979).

    Google Scholar 

  33. D. Sonnenburger and J. D. Atwood,J. Am. Chem. Soc., 102, 3484 (1980).

    Google Scholar 

  34. J. P. Fawcett,Ph. D. Thesis, London University, 1973, p.59.

  35. B. L. Booth, R. N. Haszeldine, and D. M. Reynolds,J. Chem. Soc. Dalton Trans., 407 (1980).

  36. L. I. B. Haines, D. Hopgood, and A. J. Poë,J. Chem. Soc. A, 421 (1968); ref. 30, p.51.

  37. R. A. Jackson,Ph. D. Thesis, University of Toronto, p.142 (1977).

  38. H. Wawersik and F. Basolo,Inorg. Chim. Acta, 3, 113 (1969).

    Google Scholar 

  39. G. Reichenbach, G. Innorta, and A. Foffani,Inorg. Chim. Acta, 3, 139 (1969).

    Google Scholar 

  40. G. Cardaci, S. M. Murgia, and G. Reichenbach,Inorg. Chim. Acta, 4, 118 (1970).

    Google Scholar 

  41. C. J. Picket and D. Pletcher,J. Chem. Soc. Dalton Trans., 749 (1976).

  42. S. A. Fieldhouse, B. W. Fullam, G. W. Neilson, and M. C. R. Symons,J. Chem. Soc. Dalton Trans., 567 (1974).

  43. J. H. Bayston, F. D. Looney, and M. E. Winfield,Aust. J. Chem., 16, 557 (1963).

    Google Scholar 

  44. B. H. Byers and T. L. Brown,J. Am. Chem. Soc., 99, 2527 (1977).

    Google Scholar 

  45. A. Fox, J. Malito, and A. J. Poë,J. Chem. Soc. Chem. Comm., in press.

  46. A. F. Hepp and M. S. Wrighton,J. Chem. Soc., 103, 1258 (1981).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. J. Tuzo Wilson Laboratories, Erindale College, University of Toronto, L5L 1C6, Mississauga, On, Canada

    Anthony Poë

Authors
  1. Anthony Poë
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Poë, A. Bimolecular substitution and oxidation reactions of 17-electron pentacoordinate metal carbonyl radicals. Transition Met Chem 7, 65–69 (1982). https://doi.org/10.1007/BF00618183

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00618183

Keywords

Search

Navigation