Ionic Liquids as Solvents for S N 2 Processes. Demonstration of the Complex Interplay of Interactions Resulting in the Observed Solvent Effects

: Bimolecular nucleophilic substitution reactions between triphenylphosphine and benzylic electrophiles have been examined in an ionic liquid to probe interactions with species along the reaction coordinate. Trends in the rate constant were found on both varying the leaving group and the electronic nature of the aromatic ring. In all the cases considered, interactions between the components of the ionic liquid and the transition state were shown to be more significant in determining reaction outcome than previously observed for this class of reaction. This demonstrates the importance of considering interactions of the ionic liquid components with all species along the reaction coordinate when investigating the origin of ionic liquid solvent effects, along with how such effects might be exploited.