Abstract
STERIC effects may be either thermodynamic or kinetic, that is, they may influence either reaction equilibria or reaction rates: this note is concerned with kinetic steric effects. Such effects depend on mechanism, and even the sign of a kinetic steric effect can be altered by a change of mechanism. ‘Steric hindrance’, obviously an inadequate title under which to summarize thermodynamic steric effects, thus becomes inadequate even to cover all kinetic steric effects.
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References
Dostrovsky, Hughes and Ingold, J. Chem. Soc., 173 (1946).
(a) Hughes, J. Chem. Soc., 255 (1935). Cooper, Hughes, Ingold and MacNulty, ibid., 1183, 1280, 1283 (1937).(b) Hughes, Ingold, Martin and Meigh, Nature, 166, 679 (1950), and unpublished results. (c) Shorter and Hinshelwood, J. Chem. Soc., 2412 (1949). (d) Brown and Fletcher, J. Amer. Chem. Soc., 71, 1845 (1949).
(a) Results of present authors. (b) Prof. P. D. Bartlett and co-workers reported similarly large factors at an International Colloquium in Montpellier, France (April 1950), where our results and conclusions were also communicated.
Dostrovsky and Hughes, J. Chem. Soc., 171 (1946).
Hughes and Ingold, J. Chem. Soc., 2038, et seq. (1948). cf. Whitmore and Stahly, J. Amer. Chem. Soc., 55, 4153 (1933).
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BROWN, F., DAVIES, T., DOSTROVSKY, I. et al. Steric Retardation and Steric Acceleration. Nature 167, 987–988 (1951). https://doi.org/10.1038/167987a0
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DOI: https://doi.org/10.1038/167987a0
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