The modeling of reactivity in an ionic liquid is examined with DFT and DFT/MM calculations on the SN2 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. © 2007 Wiley Periodicals, Inc.
|Journal||Journal of Computational Chemistry|
|Publication status||Published - 30 Apr 2008|
- Ion pairs
- Ionic liquids
- S 2 substitution N
- Solvation effects