Advertisement

Site of Protonation in Gaseous Five-Membered Ring Systems C4H4X(X=NH,O,S,CH2)

  • Raymond Houriet
  • Helmut Schwarz
Chapter
Part of the Lecture Notes in Chemistry book series (LNC, volume 31)

Abstract

The study of acid-base properties of isolated systems have resulted in a fast growing output of data obtained in high pressure mass spectrometers and in low pressure ion cyclotron resonance spectrometers (ICR), (see Ref. 1 for recent reviews). These studies provide the basis for evaluating intrinsic substituent effects and Taft et al. [2] have recently stressed the predominance of polarization effects over polar (inductive) effects in stabilizing charged species. Subsequent comparison of gas phase and condensed phase data have the potentiality of disclosing solvent effects operating in the condensed phase [3]. While the understanding of the basic properties of monofunctional compounds is a relatively unambiguous matter, the situation becomes evidently more complex in multifunctional systems. Recent examples of the latter are provided by the ketene molecule in which it was found that the carbonyl group is less basic than the methylene group by 18 ± 8 kcal/mol [4], and also by enamine systems where the N-site was found to be less basic than the p-C-site by approximately 9 kcal/mol [5].

Keywords

Proton Affinity Double Resonance Proton Affinity Proton Affinity Deuterated Sample Double Resonance Experiment 
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.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    “Gas-Phase Ion Chemistry”, M.T. Bowers, Ed., Chapters 9–11, Academic Press, New York (1979).Google Scholar
  2. 2.
    R.W. Taft, M. Taagepera, J.L.M. Abboud, J.F. Wolf, D.J. DeFrees, W.J. Hehre, J.E. Bartmess and R.T. Mclver Jr., J. Am. Chem. Soc. 100 (1978) 7767.CrossRefGoogle Scholar
  3. 3.
    E.M. Arnett, Acc. Chem. Res. 6 (1973) 404Google Scholar
  4. 2b).
    P. Kebarle, W.R. Davidson, J. Sunner and S. Meza-Höjer, Pure Appl. Chem. 51 (1979) 63.CrossRefGoogle Scholar
  5. 4.
    J. Vogt, A.D. Williamson and J.L. Beauchamp, J. Am. Chem. Soc, 97 (1975) 6682.CrossRefGoogle Scholar
  6. 5.
    R. Houriet, J. Vogt and E. Haselbach, Chimia 34 (1980) 277.Google Scholar
  7. 6.
    J.F. Wolf, R.H. Staley, I. Koppel, M. Taagepera, R.T. Mclver Jr., J.L. Beauchamp and R.W. Taft, J. Am. Chem. Soc. 99 (1977) 5417.CrossRefGoogle Scholar
  8. 7.
    R. Houriet, H. Schwarz, W. Zummack, J. G. Andrade and P.v.R. Schleyer, Nouv. J. Chim., in press.Google Scholar
  9. 8.
    T.B. McMahon and J.L. Beauchamp, Rev. Sci. Instr., 43 (1972) 509.CrossRefGoogle Scholar
  10. 9.
    R. Houriet, H. Schwarz and W. Zuramack, Angew. Chem. 92 (1980) 934CrossRefGoogle Scholar
  11. 9a.
    R. Houriet, H. Schwarz and W. Zuramack, Angew. Chem. Int. Ed. Engl. 19 (1980) 905.CrossRefGoogle Scholar
  12. 10.
    P. Politzer and H. Weinstein, Tetrahedron, 31 (1975) 915.CrossRefGoogle Scholar
  13. 11.
    See for example, T.A. Lehman and M.M. Bursey, “Ion Cyclotron Resonance Spectrometry”, Wiley-Interscience, New York (1976).Google Scholar
  14. 12.
    See for example D.K. Bohme, G.I. Mackay and H.I. Schiff, J. Chem. Phys. 73 (1980) 4976.CrossRefGoogle Scholar
  15. 13.
    For leading articles on “homoconjugation” see P.R. Story and B.C. Clark Jr., in “Carbonium Ions”, p. 1007, G.A. Olah and P.V.R. Schleyer, eds., Wiley-Interscience, New York (1972) and references cited therein.Google Scholar
  16. 14.
    F.P. Lossing and J.C. Traeger, J. Am. Chem. Soc. 97 (1975) 1579.Google Scholar
  17. 15.
    J.D. Cox and G. Pilcher, “Thermochemistry of Organic and Organometallic Compounds”, Academic Press, New York (1970).Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1982

Authors and Affiliations

  • Raymond Houriet
    • 1
  • Helmut Schwarz
    • 2
  1. 1.Institut de Chimie Physique EPF-LausanneSwitzerland
  2. 2.Institut für Organische ChemieTechnischen Universität BerlinBerlinWest Germany

Personalised recommendations