title: DFT modeling of reactivity in an ionic liquid: How many ion pairs?
abstract: The modeling of reactivity in an ionic liquid is examined with DFT and DFT/MM calculations on the S(N)2 intramolecular rearrangement of the Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole into 4-benzoylamino-2,5-diphenyl-1,2,3-triazole induced by amines. Experimental research has shown that the reaction occurs in 1-butyl-3-methylimidazolium tetrafluoroborate, and in conventional organic solvents such as acetonitrile with comparable rates. The structure for the reactants, transition states and products for the rate-determining step are optimized, and the energy barrier is computed in three different environments: gas phase, water solvent, and ionic liquid. The results are encouraging in describing the energy barrier in the ionic liquid. A simple model is formulated to explain the effect of the solvent in this particular process, and a procedure to study theoretically the reactivity in an ionic liquid is proposed.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Catalonia, Spain.
authors.forename: Fabienne
authors.initials: F
authors.lastname: Bessac
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras