Secondary Kinetic Isotope Effects in Bimolecular Nucleophilic Substitutions. IV. The Temperature Dependence of the Deuterium Effect for the Reaction of N,N-Dimethyl-d6-aniline and Methyl p-toluenesulfonate. Correlation of Isotope Effects on Activation Parameters
- 1 February 1971
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 49 (3) , 439-446
- https://doi.org/10.1139/v71-069
Abstract
The temperature dependence of the isotope effect for the reaction of dimethylaniline and dimethyl-d6-aniline with methyl p-toluenesulfonate in nitrobenzene solvent has been measured, yielding the result, (ΔHD* − ΔHH*) = −134 ± 30 cal mole−1, (ΔSD* − ΔSH*) = −0.15 ± 0.09 cal mol–1 degree−1.This result has been compared with 15 other temperature dependence studies by plotting ΔΔH* per D atom vs. TΔΔS* per D atom. The points fall on two clearly separated straight lines. A similar correlation is found for a plot of ΔΔG* per D atom vs. ΔΔH* per D atom.The significance of the correlation is discussed and a possible rationalization, in terms of mechanism and particularly the role of the solvent is given.Keywords
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