Charge Analyses Involving Nuclear Magnetic Resonance Shifts

  • Sándor Fliszár
Chapter

Abstract

The critical examination of charge analyses derived in the spirit of a generalized Mulliken scheme (Eqs. 1.3–1.5) indicates that the results obtained from different theoretical models are in general agreement. The validity of this unifying conclusion has been established in a detailed fashion only for the saturated hydrocarbons but it is clear that departures from the usual halving of overlap populations are to be considered in any case involving heteronuclear overlap partners. Unfortunately, the practical extension of these views to other classes of compounds is not yet feasible because of the lack of precise guidelines providing a general recipe for the appropriate partitioning of overlap populations. Therefore, it becomes necessary in some cases to use indirect methods for obtaining charge analyses by putting common sense to work as a temporary replacement for mathematical formulations.

Keywords

Nuclear Magnetic Resonance Atomic Charge Mulliken Charge Charge Analysis Charge Result 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
This is a preview of subscription content, log in to check access.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    D.G. Farnum, Adv. Phys. Org. Chem., V. Gold and D. Bethell, Eds., 11, 123 (1975);Google Scholar
  2. 1a.
    G.L. Nelson and E.A. Williams, Prog. Phys. Org. Chem., R.W. Taft, Ed., 12, 229 (1976).Google Scholar
  3. 2.
    G.J. Martin, M.L. Martin, and S. Odiot, Org. Magn. Res., 7, 2 (1975).CrossRefGoogle Scholar
  4. 3.
    W.J. Hehre, R.W. Taft, and R.D. Topsom, Prog. Phys. Org. Chem., R.W. Taft, Ed., 12, 159 (1976).Google Scholar
  5. 4.
    N.F. Ramsey, Phys. Rev., 77, 567 (1950);CrossRefGoogle Scholar
  6. 4a.
    ibid., 83, 540 (1951)CrossRefGoogle Scholar
  7. 4b.
    ibid., 86, 243 (1952)CrossRefGoogle Scholar
  8. 4c.
    See also: W.H. Flygare, “Molecular Structure and Dynamics”, Prentice-Hall Inc., Englewood Cliffs, NY, 1978.Google Scholar
  9. 5.
    R.M. Stevens, R.M. Pitzer, and W.N. Lipscomb, J. Chem. Phys., 38, 550 (1963).CrossRefGoogle Scholar
  10. 6.
    W.N. Lipscomb, Adv. Magn. Res. J.S. Waugh, Ed., 2, 137 (1966).Google Scholar
  11. 7.
    J.A. Pople, J.W. Mclver, and N.S. Ostlund, J. Chem. Phys., 49, 2960 (1968).CrossRefGoogle Scholar
  12. 8.
    J.A. Pople, J. Chem. Phys., 37, 53 (1962).CrossRefGoogle Scholar
  13. 9.
    J. Tillieu, Annales de Physique, Vol. 2, 471, 631 (1957).Google Scholar
  14. 10.
    J.R. Didry and J. Guy, C.R. Acad. Sci., 239, 1203 (1954).Google Scholar
  15. 11.
    W.N. Lipscomb, MTP International Review of Science, Physical Chemistry, Series One, Vol. 1., W. Byers Brown, Ed., Butterworths, London, 1972, p. 167.Google Scholar
  16. 12.
    R. Ditchfield, Mol. Phys., 27, 789 (1974).CrossRefGoogle Scholar
  17. 13.
    K.A.K. Ebraheem and G.A. Webb, Org. Magn. Res., 9, 241 (1977);CrossRefGoogle Scholar
  18. 13a.
    K.A.K. Ebraheem and G.A. Webb, Org. Magn. Res., 10, 70 (1977);CrossRefGoogle Scholar
  19. 13b.
    G.I. Grigor and G.A. Webb, ibid., 9, 477 (1977);Org. Magn. Res. CrossRefGoogle Scholar
  20. 13c.
    M. Jallali and G.A. Webb, ibid., 11, 34 (1978);Org. Magn. Res. CrossRefGoogle Scholar
  21. 13d.
    K.A.K. Ebraheem, G.A. Webb, and M. Wittanwsky, ibid., 11, 27 (1978);Org. Magn. Res. CrossRefGoogle Scholar
  22. 13e.
    K.A.K. Ebraheem and G.A. Webb, J. Magn. Res., 25, 399 (1977).Google Scholar
  23. 14.
    M.J. Stephen, Proc. Roy. Soc., A242, 264 (1957).Google Scholar
  24. 15.
    R.M. Aminova, H.I. Zoroatskaya, and Yu. Yu. Samitov, J. Magn. Res., 33, 497 (1979).Google Scholar
  25. 16.
    E. Vauthier, S. Odiot, and F. Tonnard, Can. J. Chem., 60, 957 (1982).CrossRefGoogle Scholar
  26. 17.
    J.A. Pople and D.L. Beveridge, “Approximate Molecular Orbital Theory”, McGraw-Hill Book Company, New York, NY, 1970.Google Scholar
  27. 18.
    S. Fliszár, G. Cardinal, and M.-T. Béraldin, J. Am. Chem. Soc., 104, 5287 (1982).CrossRefGoogle Scholar
  28. 19.
    A.A. Germer, Theor. Chim. Acta, 34, 245 (1974).CrossRefGoogle Scholar
  29. 20.
    M. Jallah-Heravi and G.A. Webb, Org. Magn. Res., 13, 116 (1980).CrossRefGoogle Scholar
  30. 21.
    E. Vauthier, S. Fliszár, F. Tonnard, and S. Odiot, Can. J. Chem., 61, 1417 (1983).CrossRefGoogle Scholar
  31. 22.
    H. Spiesecke and W.G. Schneider, Tetrahedron Lett., 468 (1961).Google Scholar
  32. 23.
    G.A. Olah and G.D. Mateescu, J. Am. Chem. Soc., 92, 1430 (1970).CrossRefGoogle Scholar
  33. 24.
    G.A. Olah, J.M. Bollinger, and A.M. White, J. Am. Chem. Soc., 91, 3667 (1969).CrossRefGoogle Scholar
  34. 25.
    G.J. Ray, A.K. Colter, and R.J. Kurland, Chem. Phys. Lett., 2, 324 (1968).CrossRefGoogle Scholar
  35. 26.
    E.A. LaLancette and R.E. Benson, J. Am. Chem. Soc., 87, 1941 (1965).CrossRefGoogle Scholar
  36. 27.
    H. Henry and S. Fliszár, J. Am. Chem. Soc., 100, 3312 (1978).CrossRefGoogle Scholar
  37. 28.
    M.-T. Béraldin, E. Vauthier, and S. Fliszár, Can. J. Chem., 60, 106 (1982).CrossRefGoogle Scholar
  38. 29.
    P.C. Lauterbur, J. Am. Chem. Soc., 83, 1838 (1961).CrossRefGoogle Scholar
  39. 30.
    J.M. Sichel and M.A. Whitehead, Theor. Chim. Acta, 5, 35 (1966).CrossRefGoogle Scholar
  40. 31.
    S. Fliszár, A. Goursot, and H. Dugas, J. Am. Chem. Soc., 96, 4358 (1974).CrossRefGoogle Scholar
  41. 32.
    N.C. Baird and M.A. Whitehead, Theor. Chim. Acta, 6, 167 (1966).CrossRefGoogle Scholar
  42. 33.
    G. Kean and S. Fliszár, Can. J. Chem., 52, 2772 (1974).CrossRefGoogle Scholar
  43. 34.
    R. Roberge and S. Fliszár, Can. J. Chem., 53, 2400 (1975).CrossRefGoogle Scholar
  44. 35.
    G. Kean, D. Gravel, and S. Fliszár, J. Am. Chem. Soc., 98, 4749 (1976).CrossRefGoogle Scholar
  45. 36.
    H. Henry and S. Fliszár, Can. J. Chem., 52, 3799 (1974).CrossRefGoogle Scholar
  46. 37.
    S. Fliszár, J. Am. Chem. Soc, 102, 6946 (1980).CrossRefGoogle Scholar
  47. 38.
    H. Henry, S. Fliszár, and A. Julg, Can. J. Chem., 54, 2085 (1976);CrossRefGoogle Scholar
  48. 38a.
    S. Fliszár and J.-L. Cantara, Can. J. Chem., 59, 1381 (1981).CrossRefGoogle Scholar
  49. 39.
    C. Delseth and J.-P. Kintzinger, Helv. Chim. Acta, 61, 1327 (1978).CrossRefGoogle Scholar
  50. 40.
    S. Fliszár and M.-T. Béraldin, Can. J. Chem., 60, 792 (1982).CrossRefGoogle Scholar
  51. 41.
    K. Watanabe, T. Nakayama, and J. Mottl, J. Quant. Spectrosc. Radiat. Transfer, 2, 369 (1962).CrossRefGoogle Scholar
  52. 42.
    C. Delseth and J.-P. Kintzinger, Helv. Chim. Acta, 59, 466 (1976);CrossRefGoogle Scholar
  53. 42a.
    C. Delseth and J.-P. Kintzinger, Helv. Chim. Acta, 59, 1411 (1976).CrossRefGoogle Scholar
  54. 43.
    M.-T. Béraldin, J. Bridet, and S. Fliszár, unpublished results.Google Scholar
  55. 44.
    M. Christi, Chem. Ber., 108, 2781 (1975).CrossRefGoogle Scholar
  56. 45.
    A. Veillard and G. Del Re, Theor. Chim. Acta, 2, 55 (1964);CrossRefGoogle Scholar
  57. 45a.
    G. Del Re, U. Esposito, and M. Carpentieri, Theor. Chim. Acta, 6, 36 (1966).CrossRefGoogle Scholar
  58. 46.
    K.B. Wiberg, Tetrahedron, 24, 1083 (1968).CrossRefGoogle Scholar
  59. 47.
    C. Trindle and O. Sinanoglu, J. Chem. Phys., 49, 65 (1968).CrossRefGoogle Scholar
  60. 48.
    J.E. Lennard-Jones and J.A. Pople, Proc Roy. Soc. (London), A220, 446 (1950);Google Scholar
  61. 48a.
    ibid., A210, 190 (1951).Google Scholar
  62. 49.
    C. Edmiston and K. Ruedenberg, Rev. Mod. Phys., 35, 457 (1963);CrossRefGoogle Scholar
  63. 49a.
    C. Edmiston and K. Ruedenberg, J. Chem. Phys., 43, S97 (1965).CrossRefGoogle Scholar
  64. 50.
    C. Trindle and O. Sinanoglu, J. Am. Chem. Soc, 91, 853 (1969).CrossRefGoogle Scholar
  65. 51.
    C. Juan and H.S. Gutowsky, J. Chem. Phys., 37, 2198 (1962).CrossRefGoogle Scholar
  66. 52.
    O. Sinanoglu, J. Chem. Phys., 33, 1212 (1960);CrossRefGoogle Scholar
  67. 52a.
    ibid., 36, 706 (1962);CrossRefGoogle Scholar
  68. 52b.
    O. Sinanoglu, Advan. Chem. Phys., 6, 315(1964).CrossRefGoogle Scholar
  69. 53.
    O. Sinanoglu and H.Ö. Pamuk, J. Am. Chem. Soc., 95, 5435 (1973), and references cited therein.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag New York Inc. 1983

Authors and Affiliations

  • Sándor Fliszár
    • 1
  1. 1.Département de chimie, Faculté des arts et des sciencesUniversité de MontréalMontréalCanada

Personalised recommendations