engleski

Reactions in crystalline molecular solids: activation parameters and the nature of transition state

Using the dimerization-dissociation of aromatic C-nitroso compounds as a molecular model (Scheme) we have developed the method for studying the reaction mechanisms in the molecular crystals. By detailed studies of the thermodynamics and kinetics of these thermally induced reactions we have found that the most important parameter, which modify the chemical reactivity is activation entropy. Variation in activation entropy could be explained by softening of the reactive zone around the transition state within the crystal. Since the analogous entropic effect of the variable rigidity has been found also for the transition state encapsulated in the enzyme cavity, our investigations of the solid-state reaction mechanisms by using convenient models could be of more general importance in physical organic chemistry.

solid-state reaction mechanism ; nitroso compounds ; activation parameters

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