Studies in solvolysis. Part VIII. An entropy correlation related to the reaction of various nucleophiles with malachite green

Abstract

The entropies of activation related to the reactions of aqueous malachite green with the nucleophiles water, hydroxide, hydrazine, ammonia, hypochlorite, and sulphite have been calculated from the temperature dependence of the rate constants appropriate to these reactions. The entropies of the transition states for these reactions have been characterized and the transition states shown to be 'reactant like'. A similar correlation, based on data for a series of nucleophiles attacking methyl iodide, suggests that the transition states for the SN2 displacement reactions are also 'reactant like' with respect to the attacking nucleophile. A relationship between two distinct parameters each of which is related to the position of transition states along the reaction coordinate is considered.