Inorganic Chemistry, Vol.35, No.13, 3725-3726, 1996
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 Fe-II(CN)(5)(Y) and Cr-III(TPP)(CI)(Y) and the base hydrolyses of Co-III(NH3)(5)(Y) and Cr-III(NH3)(5)(Y) systems. The implications for the aquation reactions of the latter also are explored.
Keywords:BASE HYDROLYSIS;MECHANISTIC INFORMATION;PENTAAMMINE COMPLEXES;AQUEOUS-SOLUTION;AMINE COMPLEXES;AQUATION;COBALT(III);CHROMIUM(III);SERIES;PENTACYANOFERRATES(II)