Theoretical estimation of kinetic parameters for nucleophilic substitution reactions in solution: an application of a solution translational entropy model

Abstract

The kinetic parameters, such as activation entropy, activation enthalpy, activation free-energy, and reaction rate constant, for a series of nucleophilic substitution (SN) reactions in solution, are investigated using both a solution-phase translational entropy model and an ideal gas-phase translational entropy model. The results obtained from the solution translational entropy model are in excellent agreement with the experimental values, while the overestimation of activation free-energy from the ideal gas-phase translational entropy model is as large as 6.9 kcal mol⁻¹. For some of the reactions studied, such as 1b+2b and 1c+2b in methanol, and 1d+2d and 1d+2e in aqueous solution, the explicit + implicit model, namely, a cluster-continuum type model, should be employed to account for the strong solvent–solute interactions. In addition, the explicit + implicit models have also been applied to the DMSO–H₂O mixtures, which would open up a door to investigate the reactions in a mixed solvent using density functional theory (DFT) methods.