title: Developing principles for predicting ionic liquid effects on reaction outcome. The importance of the anion in controlling microscopic interactions.
abstract: A series of ionic liquids containing anions of differing coordination strength were investigated as solvents for the condensation reaction of an alkyl amine and an aromatic aldehyde. As predicted, the rate constant of the process was found to increase with the proportion of the ionic liquid in the reaction mixture. Temperature-dependent kinetic analyses demonstrated that by varying the ability of the anion to interact with the cation the magnitude of both the enthalpy and entropy of activation could be controlled in a predictable manner, with the activation parameters being linearly dependent on the ionic liquid basicity. Interestingly, the unexpected trend in the rate constants observed when altering the anion of the ionic liquid highlighted the presence of more subtle secondary microscopic interactions involving the anion, further emphasizing the fragility of the enthalpy - entropy balance.
authors.affiliation: School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia. j.harper@unsw.edu.au.
authors.forename: Sinead T
authors.initials: ST
authors.lastname: Keaveney
authors.forename: Ronald S
authors.initials: RS
authors.lastname: Haines
authors.forename: Jason B
authors.initials: JB
authors.lastname: Harper