Using Kamlet-Taft solvent descriptors to explain the reactivity of anionic nucleophiles in ionic liquids

In this paper, we report the effect of ionic liquids on substitution reactions using a variety of anionic nucleophiles. We have combined new studies of the reactivity of polyatomic anions, acetate, trifuoroacetate, cyanide, and thiocyanide, with our previous studies of the halides in [C(4)C(1)py][Tf2N], [C(4)C(1)py][TfO], and [C(4)C(1)im][Tf2N] (where [C(4)C(1)im](+) is 1-butyl-3-methylimidazolium and [C(4)C(1)py](+) is 1-butyl-1-methylpyrrolidinium) and compared their reactivities, k(2), to the same reactions in the molecular solvents dichloromethane, dimethylsulfoxide, and methanol. The Kamlet-Taft solvent descriptors (alpha, beta, pi*) have been used to analyze the rates of the reactions, which were found to have a strong inverse dependency on the alpha value of the solvent. This result is attributed to the ability of the solvent to hydrogen bond to the nucleophile, so reducing its reactivity. The Eyring activation parameters (Delta H-double dagger and Delta S-double dagger), while confirming the reaction mechanism, do not offer obvious correlations with the Kamlet-Taft solvent descriptors.