Structural Chemistry

, Volume 3, Issue 5, pp 301–305 | Cite as

Electron distribution on an intramolecular hydrogen bond: A semiempirical AM1 study

  • Peter Ertl
  • Otto Exner
Article

Abstract

Dipole moments of seven molecules were studied by AM1, each containing an intramolecular hydrogen bond between a hydroxyl group and a carbonyl or nitro group as hydrogen acceptors. The hydrogen bond causes two electron shifts: from H to O within the hydroxyl group and from C to O within the carbonyl group. The latter is accompanied by withdrawal of electrons from even more distant atoms. If the total electron density change is expressed as a vector, its direction is close to the direction of the O-H bond. This electron redistribution is in agreement with the previous, somewhat, puzzling experimental results. However, it differs from the commonly accepted picture according to which electron density changes on the hydrogen acceptor moiety are less important than those on the O-H bond.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Richards, J. H.; Walker, S.Trans. Faraday Soc. 1961,57, 399, 406, 412, and 418.Google Scholar
  2. 2.
    Lutskii, A. E.; Gorokhova, N. I.Teor. Eksp. Khim. 1968,4, 831.Google Scholar
  3. 3.
    Eda, B.; Ito, K.Bull. Chem. Soc. Jpn. 1956,29, 524.Google Scholar
  4. 4.
    Eda, B.; Ito, K.Bull. Chem. Soc. Jpn. 1957,30, 164.Google Scholar
  5. 5.
    Minkin, V. I.; Zhdanov, Yu, A.; Garnovskii, A. D.; Sadekov, I. D.Dokl. Akad. Nauk SSSR 1965,162, 108.Google Scholar
  6. 6.
    Koll, A.; Ratajczak, H.; Sobczyk, L.Rocz. Chem. 1970,44, 825.Google Scholar
  7. 7.
    Plesničar, B.; Smolíková, B.; Jehlička, V.; Exner, O.Collect. Czech. Chem. Commun. 1978,43, 2754.Google Scholar
  8. 8.
    Exner, O.; Plesničar, B.Collect. Czech. Chem. Commun. 1978,43, 3079.Google Scholar
  9. 9.
    Artemenko, A. I.; Tikunova, I. V.; Anufriev, E. K.; Jehlička, V.; Exner, O.Collect. Czech. Chem. Commun. 1981,46, 729.Google Scholar
  10. 10.
    Exner, O.; Smolíková, J.; Jehlička, V.; Shawali, A. S.Collect. Czech. Chem. Commun. 1979,44, 2494.Google Scholar
  11. 11.
    Exner, O.; Koudelka, J.; Vašíčková, S.Collect. Czech. Chem. Commun. 1983,48, 735.Google Scholar
  12. 12.
    Rospenk, M.; Koll, A.Bull. Soc. Chim. Belg. 1983,92, 329.Google Scholar
  13. 13.
    Exner, O.; Pecka, J.J. Chem. Res. (S)1988, 404.Google Scholar
  14. 14.
    Exner, O.Dipole Moments in Organic Chemistry; Georg Thieme: Stuttgart, 1975; ch. 3.3.Google Scholar
  15. 15.
    Exner, O.Collect. Czech. Chem. Commun. 1981,46, 1002.Google Scholar
  16. 16.
    Rospenk, M.J. Mol. Struct. 1990,221, 109.Google Scholar
  17. 17.
    Sobczyk, L.Pure Appl. Chem. 1987,59, 1661.Google Scholar
  18. 18.
    Takasuka, M.; Matsui, Y.J. Chem. Soc., Perkin Trans 2 1979, 1743.Google Scholar
  19. 19.
    Seguin, J. P.; Guillaume-Vilport, F.; Uzan, R.; Doucet, J. P.J. Chem. Soc., Perkin Trans. 2,1986, 773.Google Scholar
  20. 20.
    Hadži, D.; Prevoršek, D.Spectrochim. Acta, Ser. A 1957,10, 38.Google Scholar
  21. 21.
    Kavčič, R.; Plesničar, B.; Hadži, D.Spectrochim. Acta, Part A,1967,23, 2483.Google Scholar
  22. 22.
    Kollman, P. A.; Allen, L. C.Chem. Rev. 1972,72, 283.Google Scholar
  23. 23.
    Rospenk, M.; Zeegers-Huyskens, T.Spectrosc. Lett. 1987,20, 177.Google Scholar
  24. 24.
    Umeyama, H.; Morokuma, K.J. Am. Chem. Soc. 1977,99, 1316.Google Scholar
  25. 25.
    Catalán, J.; Macías, A.J. Mol. Struct. 1977,38, 209.Google Scholar
  26. 26.
    Orttung, W. H.; Scott, G. W.; Vosooghi, D.THEOCHEM 1984,18, 161.Google Scholar
  27. 27.
    Lutskii, A. E.; Korunova, A. F.; Dolzhenko, Yu. I.Zh. Obshch. Khim. 1980,50, 2339.Google Scholar
  28. 28.
    Dietrich, S. W.; Jorgensen, E. C.; Kollman, P. A.; Rothenberg, S.J. Am. Chem. Soc. 1976,98, 8310.Google Scholar
  29. 29.
    George, P.; Bock, C. W.; Trachtman, M.THEOCHEM 1985,26, 11.Google Scholar
  30. 30.
    Newton, M. D.; Jeffrey, G. A.J. Am. Chem. Soc. 1977,99, 2413.Google Scholar
  31. 31.
    Jensen, H. H.; Moellendal, H.; Nilssen, E. W.J. Mol. Struct. 1976,30, 145.Google Scholar
  32. 32.
    Bouma, W. J.; Radom, L.Aust. J. Chem. 1978,31, 1167.Google Scholar
  33. 33.
    Radom, L.; Lathan, W. A.; Hehre, W. J.; Pople, J. A.Aust. J. Chem. 1972,25, 1601.Google Scholar
  34. 34.
    Dewar, M. J. S.; Zoebisch, E. G., Healy, A. F.; Stewart, J. J. P.J. Am. Chem. Soc. 1985,107, 3902.Google Scholar
  35. 35.
    Buemi, G.; Zuccarello, F.; Raudino, A.THEOCHEM 1988,41, 379.Google Scholar
  36. 36.
    Buemi, G.; Gandolfo, C.J. Chem. Soc., Faraday Trans 2 1989,85, 215.Google Scholar
  37. 37.
    Jones, H.; Curl, P. F.J. Mol. Spectrosc. 1972,42, 65.Google Scholar
  38. 38.
    Marstokk, K.-M.; Moellendal, H.J. Mol. Struct. 1973,16, 259.Google Scholar
  39. 39.
    Larsen, I. K.Acta Crystallogr., Sect. B 1988,44, 527.Google Scholar
  40. 40.
    Exner, O.The Chemistry of Peroxides; Patai, S. (Ed.); Wiley: Chichester, 1983; p. 85.Google Scholar
  41. 41.
    Upadhyay, A. P.; Upadhyay, K. N.Indian J. Phys. B 1981,55, 232.Google Scholar
  42. 42.
    Schreiber, V. M.J. Mol. Struct. 1989,197, 73.Google Scholar
  43. 43.
    Ponec, R. Personal communication 1986.Google Scholar
  44. 44.
    Koller, J.; Harb, V.; Hodošček, M.; Hadži, D.J. Mol. Struct. 1985,122, 343.Google Scholar

Copyright information

© Plenum Publishing Corporation 1992

Authors and Affiliations

  • Peter Ertl
    • 1
  • Otto Exner
    • 2
  1. 1.Department of ChemistryComenius UniversityBratislavaCzechoslovakia
  2. 2.Institute of Organic Chemistry and BiochemistryCzechoslovak Academy of SciencesPrague 6Czechoslovakia

Personalised recommendations