Abstract
THE mechanism of free radical chain transfer reactions has been discussed recently by Kenner1 and Russell2 with regard to the question of the importance of electron transfer in a free radical abstraction process. Kenner1 advocates a two-step treatment1: 
in which a proton transfer step (b) follows an initial electron transfer (a). That electron transfer would precede atom transfer is not unreasonable in view of the general acceptability of the Born–Oppenheimer approximation. An alternative approach by Russell is to consider the reaction as proceeding via a transition state which encompasses both factors2,3. 
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References
Kenner, J., Tetrahedron, 3, 78 (1958); 8, 350 (1960).
Russell, G. A., Tetrahedron, 5, 101 (1959); 8, 101 (1959).
(a) Russell, G. A., J. Org. Chem., 23, 1407 (1958). (b) Howard, J. A., and Ingold, K. U., Canad. J. Chem., 41, 1741 (1963).
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Russell, G. A., J. Amer. Chem. Soc., 78, 1047 (1956).
(a) Walling, C., Free Radicals in Solution (J. Wiley and Sons, Inc., New York, 1957). (b) Bartlett, P. D., and Ruchardt, C., J. Amer. Chem. Soc., 82, 1756 (1960). (c) Martin, M. M., and Gleicher, G. I., ibid., 86, 242 (1964).
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Kochi, J. K., Davis, D. D., and Buchanan, D. B. (to be published).
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Taube, H., Advances in Inorganic and Radiochemistry, 1, 1 (Academic Press, New York, 1959).
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KOCHI, J., DAVIS, D. Electron Transference in Free Radical Chain Transfer Reactions. Nature 202, 690–691 (1964). https://doi.org/10.1038/202690a0
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DOI: https://doi.org/10.1038/202690a0
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