Nucleophilic displacement reactions (the SN2 reaction) of ions in the gas phase are a prototypical reaction system that allows a study of dynamics, mechanisms, and structure-energy relations. This article reviews aspects of the kinetics (especially the applicability of statistical reaction rate theory), the relation of structure and reactivity, and the effects of small numbers of solvent molecules on the reaction and compares the behavior of the ionic reaction in the gas phase with that in solution.
Rates of SN2 reactions of chloride ion with methyl- and tert-butyl-substituted chloroacetonitrile were measured by using Fourier transform-ion cyclotron resonance spectrometry to follow the isotopic exchange reaction. Barrier heights for these reactions indicate that steric effects in the gas phase are diminished relative to apparent steric effects in solution. We attribute the increased barrier in solution to a solvation effect. Monte Carlo simulations done using statistical perturbation theory confirm that steric hindrance to solvation contributes to SN2 barriers in solution.
This paper explores the contribution of solvation to the overall steric effects of S(N)2 reactions observed in solution. The reactions of chloride ion with a series of alkyl chloronitriles, RCH(CN)Cl (R = methyl, ethyl, isopropyl, tert-butyl) were investigated both experimentally and theoretically. These reactions serve as a model system for the parent reactions, Cl(-) + RCH(2)Cl, which are too slow to measure. Each additional substitution at the beta-carbon lowers the reactivity, clearly demonstrating a steric hindrance effect. The magnitude of the steric effect, however, is not significantly different in the gas phase and in solution. We conclude that the solvation energies of the corresponding S(N)2 transition states must be similar regardless of size of the substituent. This lack of size dependence in the current system is in sharp contrast with many other ionic systems such as ionization of simple alkyl alcohols, where solvation depends strongly on size. We propose that the weak size dependence results from the compensation between a direct shielding effect of the substituent and an indirect ionic solvation effect, which arises from the geometric perturbations introduced by the substitution. The conclusion is further supported by calculations using polarizable continuum models and QM/MM simulations.
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