ET and Polar Mechanisms; How Are They Connected?

  • Lennart Eberson
Part of the Reactivity and Structure Concepts in Organic Chemistry book series (REACTIVITY, volume 25)


The problem posed in the heading is a fundamental one and thus difficult to answer definitively. Provided the reader has become convinced that there exists such a thing as an outer-sphere ET mechanism (remember that this depends on a definition of outer-sphere ET as occurring via a transition state with maximally 1 kcal mol-1 (4 kJmol-1) of electronic interaction between the reactants) the problem can be given a distinct formulation: Are our elementary reactions — defined as reactions which so far have been formulated with one transition state only — really elementary, or do we have reason to write them in two steps, the initial one being of outer-sphere ET type? A clearcut case, to be discussed in more detail below (see Sect. XI.2.b) is the reaction between benzene and nitronium ion, the archetype of a polar, single transition state step (Fig. 1).


Radical Cation Alkyl Halide Polar Mechanism Electrophilic Aromatic Substitution Trityl Chloride 
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.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Pross, A.: Acc. Chem. Res. 18, 212 (1985); Shaik, S. S.: Progr. Phys. Org. Chem. 15, 197 (1985).CrossRefGoogle Scholar
  2. 2.
    Pedersen, E. B., Petersen, T. E., Torssell, K., Lawesson, S.-O.: Tetrahedron 29, 579 (1973).CrossRefGoogle Scholar
  3. 3.
    Fukuzumi, S., Kochi, J. K.: J. Am. Chem. Soc. 103, 7240 (1981).CrossRefGoogle Scholar
  4. 4.
    Fukuzumi, S., Kochi, J. K.: J. Am. Chem. Soc. 104, 7599 (1981).CrossRefGoogle Scholar
  5. 5.
    Eberson, L.: Unpublished work.Google Scholar
  6. 6.
    Eberson, L., Radner, F.: Acta Chem. Scand. B39, 357 (1985).CrossRefGoogle Scholar
  7. 7.
    Eberson, L., Radner, F.: Acta Chem. Scand. B34, 739 (1980).CrossRefGoogle Scholar
  8. 8.
    Eberson, L., Radner, F.: Acta Chem. Scand. B40, 71 (1986); Acc. Chem. Res. 20, 53 (1987).CrossRefGoogle Scholar
  9. 9.
    Eberson, L., Radner, F.: Acta Chem. Scand. B38, 861 (1984).CrossRefGoogle Scholar
  10. 10.
    Ingold, C. K.: Quart. Rev. 11, 1 (1957).CrossRefGoogle Scholar
  11. 11.
    Edwards, J. O.: J. Am. Chem. Soc.: 76, 1540 (1954).CrossRefGoogle Scholar
  12. 12.
    Dessy, R. E., Pohl, R. L., King, R. B.: J. Am. Chem. Soc. 88, 5121 (1966).CrossRefGoogle Scholar
  13. 13.
    Ritchie, C. D.: J. Am. Chem. Soc. 105, 7313 (1983).CrossRefGoogle Scholar
  14. 14.
    Lowry, T. H., Richardson, K. S.: Mechanism and Theory in Organic Chemistry, New York, Harper & Row 19812; Schrauzer, G. N., Deutsch, E., Windgassen, R. J.: J. Am. Chem. Soc. 90, 2441 (1968); Schrauzer, N. G.: Angew. Chem. 88, 465 (1976).Google Scholar
  15. 15.
    See Tables 1 and 2, Chapt. IV and Table 4, Chapt. VIII.Google Scholar
  16. 16.
    Lund, T., Lund, H.: Acta Chem. Scand. B40, 412 (1986).Google Scholar
  17. 17.
    Bilevitch, K. A., Pubnov, N. N., Okhlobystin, O. Yu.; Tetrahedron Lett. 1968, 3465.Google Scholar
  18. 18.
    Eberson, L.: Acta Chem. Scand. B38, 439 (1984).CrossRefGoogle Scholar
  19. 19.
    Ashby, E. C., Goel, A. B., DePriest, R. N.: J. Org. Chem. 48, 2429 (1981).CrossRefGoogle Scholar
  20. 20.
    Huszthy, P., Lempert, K., Simig, G.: J. Chem. Soc. Perkin Trans. 2 1985, 1323.Google Scholar
  21. 21.
    Ashby, E. C., Park, W. S., Goel, A. B., Su, W.-Y.: J. Org. Chem. 50, 5184 (1985).CrossRefGoogle Scholar
  22. 22.
    Huszthy, P., Lempert, K., Simig, G., Vekey, K.: J. Chem. Soc. Perkin Trans. 1 1982, 3012.Google Scholar
  23. 23.
    Prousek, J.: Coll. Czech. Chem. Comm. 45, 3347 (1980).Google Scholar
  24. 24.
    Beadle, C. D., Bowman, W. R., Prousek, J.: Tetrahedron Lett. 25, 4979 (1984).CrossRefGoogle Scholar
  25. 25.
    Zefirov, N. S., Makhonkov, D. I.: Chem. Rev. 82, 615 (1982).CrossRefGoogle Scholar
  26. 26.
    Buncel, E., Menon, B. G.: J. Am. Chem. Soc. 102, 3499 (1980).CrossRefGoogle Scholar
  27. 27.
    Beadle, C. D., Bowman, W. R.: J. Chem. Res. (S) 1985, 150; (M) 1985, 1814.Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1987

Authors and Affiliations

  • Lennart Eberson
    • 1
  1. 1.Chemical CenterUniversity of LundLundSweden

Personalised recommendations