SOME DEUTERIUM ISOTOPE EFFECTS: I. WATER SOLVOLYSIS OF METHYL-d3 ESTERS

Abstract

The α-deuterium isotope effect has been examined for the solvolysis of a series of esters containing a fully deuterated methyl group. The possible sources of the effect have been divided into "thermodynamic" effects which appear to favor more rapid reaction of the protium compound and "zero point" effects where stiffening of out-of-plane vibrations may account for the direction of the observed isotope effects. It appears that the inverse isotope effect may be a measure of the spatial restrictions placed on the hydrogen atoms on the carbon atom in the activated complex.