Charge and Spin Delocalization to the Trifluoromethyl Group

  • Leon M. Stock
  • Michael R. Wasielewski


Herbert Brown has a long-standing interest in the concepts of hyperconjugation and non-classical behavior as influences in carbonium ion chemistry. It seems appropriate to consider at this symposium the analogous problem of delocalization to saturated substituents such as the trifluoromethyl group in negatively charged ions and in radicals.


Fluorine Atom Trifluoromethyl Group Group Orbital Ortho Hydrogen Fluorine Substitution 
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  1. 1.
    J. D. Roberts, R. L. Webb, and E. A. McElhill, J. Am. Chem. Soc., 22, 408 (1950).CrossRefGoogle Scholar
  2. 2.
    R. S. Mulliken, C. A. Rieke, and W. G. Brown, J. Am. Chem. Soc., 41 (1941),Google Scholar
  3. 3.
    C. A. Coulson, Valence, Oxford, Clarendon Press, 1952, pp 310–314.Google Scholar
  4. 4.
    R. Hoffmann, L. Radom, J. A. Pople, P. von R. Schleyer, W. J. Hehre, and L. Salem, J. Am. Chem. Soc., 94, 6221 (1972).CrossRefGoogle Scholar
  5. 5.
    A. R. Rossi and D. E. Wood, J. Am. Chem. Soc., 98, 3452 (1976).CrossRefGoogle Scholar
  6. 6.
    K. Morokuma, J. Am. Chem. Soc., 91, 5412 (1969).CrossRefGoogle Scholar
  7. 7.
    L. C. Snyder and H. Basch, Molecular Wave Functions and Properties, Wiley, 1972, pp 346–350.Google Scholar
  8. 8.
    C. L. Liotta, D. F. Smith, Jr., H. P. Hopkins, Jr., and K. A. Rhodes, J. Phys. Chem., 76, 1909 (1972).CrossRefGoogle Scholar
  9. 9.
    D. Holtz, Prog. Phys. Org. Chem., 8, 1 (1971).CrossRefGoogle Scholar
  10. 10.
    W. A. Sheppard, J. Am. Chem. Soc., 87, 2410 (1965).CrossRefGoogle Scholar
  11. 11.
    D. D. Perrin. Dissociation Constants of Organic Bases in Aqueous Solution, Butterworths, London, 1965.Google Scholar
  12. 12.
    A. I. Biggs and R. A. Robinson, J. Chem. Soc., 388 (1961).Google Scholar
  13. 13.
    A. Streitwieser, Jr., and H. F. Koch, J. Am. Chem. Soc., 86, 404 (1964).CrossRefGoogle Scholar
  14. 14.
    K. J. Klabunde and D. J. Burton, J. Am. Chem. Soc., 94, 820 (1972).CrossRefGoogle Scholar
  15. 15.
    A. M. Porto, L. Altieri, A. J. Castro, and J. A. Brieux, J. Chem. Soc., B, 963 (1966).Google Scholar
  16. 16.
    a) J. Miller, Aust. J. Chem., 9, 61 (1956);CrossRefGoogle Scholar
  17. 16.
    b) J. Miller and W. Kai-Yan, J. Chem. Soc., 3492 (1963);Google Scholar
  18. 16.
    c) K. C. Ho and J. Miller, Aust. J. Chem., 19, 423 (1966).CrossRefGoogle Scholar
  19. 17.
    W. Greizerstein, R. A, Bonelli, and J. A. Brieux, J. Am. Chem. Soc., 84, 1026 (1962).CrossRefGoogle Scholar
  20. 18.
    S. Andreades, J. Am. Chem. Soc., 86, 2003 (1964).CrossRefGoogle Scholar
  21. 19.
    A. Streitwieser, Jr., and D. Holtz, J. Am. Chem. Soc., 89, 692 (1967).CrossRefGoogle Scholar
  22. 20.
    D. J. Burton, R. D. Howells, and P. D. Vander Valk, J. Am. Chem. Soc., 99, 4830 (1977).CrossRefGoogle Scholar
  23. 21.
    W. A. Sheppard and C. M. Sharts, Organic Fluorine Chemistry, Benjamin, New York (1969), Chapter 2.Google Scholar
  24. 22.
    J. D. Hepworth, J. A. Hudson, D. A, Ibbitson, and G. Hallas, J. Chem. Soc. Perkin II, 1905 (1972).Google Scholar
  25. 23.
    The data are reviewed by L. M. Stock and M. R. Wasielewski, Prog. Phys. Org. Chem., 14, 000 (1978).Google Scholar
  26. 24.
    L. M. Stock and J. Suzuki, J. Am. Chem. Soc., 87, 3909 (1965).CrossRefGoogle Scholar
  27. 25.
    D. Kosman and L. M. Stock, J. Am. Chem. Soc., 92, 409 (1970).CrossRefGoogle Scholar
  28. 26.
    R. O. C. Norman and B. C. Gilbert, J. Phys. Chem., 11, 14 (1967).CrossRefGoogle Scholar
  29. 27.
    F. B. Mallory, J. Am. Chem. Soc., 95, 7747 (1973).CrossRefGoogle Scholar
  30. 28.
    Please consult M. R. Wasielewski, Thesis, University of Chicago Library, for a full account of the results discussed in this article.Google Scholar
  31. 29.
    M. Broze, Z. Luz, and B. L. Silver, J. Chem. Phys., 46, 4891 (1967 ).CrossRefGoogle Scholar
  32. 30.
    L. M. Stock and P. E. Young, J. Am. Chem. Soc., 94, 7686 (1972).CrossRefGoogle Scholar
  33. 31.
    L. M. Stock and M. R. Wasielewski, J. Am. Chem. Soc., 97, 5620 (1975). —CrossRefGoogle Scholar
  34. 32.
    P. L. Kölker and W. A. Waters, J. Chem. Soc., 1136 (1964).Google Scholar
  35. 33.
    E. A. Polenov, B. I. Shapiro, and L. M. Yagupol’skii, Zhur. Strukt. Khim., 12, 163 (1971).Google Scholar
  36. 34.
    E. G. Janzen and J. L. Gerlock, J. Am. Chem. Soc., 89, 4902 (1967).CrossRefGoogle Scholar
  37. 35.
    Under the reasonable assumptions that BH is negligible and that is the same for the nitrobenzene anion radicals, aHCH2X/aHCH3 is given by (cos20H + (cos20H + 120°)). The minimum 2 value is 0.5.Google Scholar
  38. 36.
    K. S. Chen, P. J. Krusic, P. Meakin, and J. K. Kochi, J. Phys. Chem., 78, 2014 (1974).CrossRefGoogle Scholar
  39. 37.
    I. Biddies, J. Cooper, A. Hudson, R. A. Jackson, and J. T. Wiffen, Mol. Phys., 25, 225 (1973).CrossRefGoogle Scholar
  40. 38.
    D. R. Eaton, A. D. Josey, and W. A. Sheppard, J. Am. Chem. Soc., 85, 2689 (1963).CrossRefGoogle Scholar
  41. 39.
    P. J. Scheidler and J. R. Bolton, J. Am. Chem. Soc., 88, 371 (1966).CrossRefGoogle Scholar
  42. 40.
    E. G. Janzen and J. L. Gerlock, J. Phys. Chem., 71, 4577 (1967).CrossRefGoogle Scholar
  43. 41.
    W. R. Knolle and J. R. Bolton, J. Am. Chem. Soc., 91, 5411 (1969).CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1978

Authors and Affiliations

  • Leon M. Stock
    • 1
  • Michael R. Wasielewski
    • 1
  1. 1.Department of ChemistryThe University of ChicagoChicagoUSA

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