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Leaving-Group Effects on Volumes of Activation for Dissociative Substitution Processes.

A simple model is proposed to explain the common observation that the activation volume for a dissociative substitution process is independent of the molar volume of the leaving group. The model is applied to substitutions of FeII(CN)5(Y) and CrIII(TPP)(Cl)(Y) and the base hydrolyses of CoIII(NH3)5(Y) and CrIII(NH3)5(Y) systems. The implications for the aquation reactions of the latter also are explored.