Application of reaction field theory to the calculation of solvent effects on the t-butyl chloride solvolysis, and on the Me4N+Cl– ion pair

Abstract

The reaction field theory previously developed to calculate solvent effects on equilibria involving rotational or conformational isomers has been applied to the calculation of solvent effects on values of ΔG‡ for the decomposition of t-butyl chloride in aprotic solvents and the gas phase. Calculations in terms of a transition state of dipole moment µ= 7·40 D lead to good agreement between calculated and observed values over the entire solvent range including the gas phase. Even better agreement is obtained by calculations in terms of a transition state of µ= 8·80 D in polar solvents and a less polar, four-centred, transition state of µ= 7·29 D in less polar solvents and the gas phase. Calculations are also reported of solvent effects on the free energy of the Me₄N⁺Cl^– ion pair, again in good agreement with the observed values in aprotic solvents.