The use of chlorine kinetic isotope effects for evaluating ion pairing in nucleophilic displacements at saturated carbon

Use of the Winstein scheme to describe ion pairing leads to the conclusion that chlorine kinetic isotope effects (KIE) are primarily responsive to processes involving the covalently bound chlorine and less indicative of reactions which occur after the formation of the initial ion pair. This conclusion has been tested by showing that the calculated equilibrium isotope effect (1.0057) and observed (1.0059/sub 6/ +- 0.0001/sub 1/) KIE are nearly identical when the solvolysis of p-methylbenzyl chloride is forced toward a limiting case with 97% trifluoroethanol as solvent. The reaction of p-phenoxybenzyl chloride showed similar behavior with an equilibrium KIE value of 1.0058/sub 4/ +- 0.0001/sub 1/. These results suggest that competing ion-pair and S/sub N/2 processes may be one factor contributing to Hammett plot curvature for these nucleophilic displacement reactions. Chloride KIE values for the reaction of n-butyl chloride with thiophenoxide anion, where ion pairing does not occur, show little variation with a wide variety of solvents. 3 tables.