摘要：

DFT computations were performed on the SN1 and SN2 solvolyses of substituted cumyl chlorides and benzyl chlorides in ethanol and water, by increasing stepwise the CCl distance and by optimization. The total energy increases with the increase in the ClC distance in SN1 reactions, while free energy of activation pass through maximum. To validate the results, the calculated free energies of activation were compared with data obtained by kinetic measurements. The structural parameters of the transition states were correlated with the Hammett substituent constants and compared with the data of hydrolyses of tert-butyl chloride and methyl chloride, which proceed with known mechanisms. Conclusions on the mechanisms of the reactions were driven from the effect of sub

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