Abstract
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).
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsPreview
Unable to display preview. Download preview PDF.
References
Pross, A.: Acc. Chem. Res. 18, 212 (1985); Shaik, S. S.: Progr. Phys. Org. Chem. 15, 197 (1985).
Pedersen, E. B., Petersen, T. E., Torssell, K., Lawesson, S.-O.: Tetrahedron 29, 579 (1973).
Fukuzumi, S., Kochi, J. K.: J. Am. Chem. Soc. 103, 7240 (1981).
Fukuzumi, S., Kochi, J. K.: J. Am. Chem. Soc. 104, 7599 (1981).
Eberson, L.: Unpublished work.
Eberson, L., Radner, F.: Acta Chem. Scand. B39, 357 (1985).
Eberson, L., Radner, F.: Acta Chem. Scand. B34, 739 (1980).
Eberson, L., Radner, F.: Acta Chem. Scand. B40, 71 (1986); Acc. Chem. Res. 20, 53 (1987).
Eberson, L., Radner, F.: Acta Chem. Scand. B38, 861 (1984).
Ingold, C. K.: Quart. Rev. 11, 1 (1957).
Edwards, J. O.: J. Am. Chem. Soc.: 76, 1540 (1954).
Dessy, R. E., Pohl, R. L., King, R. B.: J. Am. Chem. Soc. 88, 5121 (1966).
Ritchie, C. D.: J. Am. Chem. Soc. 105, 7313 (1983).
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).
See Tables 1 and 2, Chapt. IV and Table 4, Chapt. VIII.
Lund, T., Lund, H.: Acta Chem. Scand. B40, 412 (1986).
Bilevitch, K. A., Pubnov, N. N., Okhlobystin, O. Yu.; Tetrahedron Lett. 1968, 3465.
Eberson, L.: Acta Chem. Scand. B38, 439 (1984).
Ashby, E. C., Goel, A. B., DePriest, R. N.: J. Org. Chem. 48, 2429 (1981).
Huszthy, P., Lempert, K., Simig, G.: J. Chem. Soc. Perkin Trans. 2 1985, 1323.
Ashby, E. C., Park, W. S., Goel, A. B., Su, W.-Y.: J. Org. Chem. 50, 5184 (1985).
Huszthy, P., Lempert, K., Simig, G., Vekey, K.: J. Chem. Soc. Perkin Trans. 1 1982, 3012.
Prousek, J.: Coll. Czech. Chem. Comm. 45, 3347 (1980).
Beadle, C. D., Bowman, W. R., Prousek, J.: Tetrahedron Lett. 25, 4979 (1984).
Zefirov, N. S., Makhonkov, D. I.: Chem. Rev. 82, 615 (1982).
Buncel, E., Menon, B. G.: J. Am. Chem. Soc. 102, 3499 (1980).
Beadle, C. D., Bowman, W. R.: J. Chem. Res. (S) 1985, 150; (M) 1985, 1814.
Author information
Authors and Affiliations
Rights and permissions
Copyright information
© 1987 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Eberson, L. (1987). ET and Polar Mechanisms; How Are They Connected?. In: Electron Transfer Reactions in Organic Chemistry. Reactivity and Structure Concepts in Organic Chemistry, vol 25. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-72544-9_11
Download citation
DOI: https://doi.org/10.1007/978-3-642-72544-9_11
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-72546-3
Online ISBN: 978-3-642-72544-9
eBook Packages: Springer Book Archive