DFT modeling of reactivity in an ionic liquid: How many ion pairs?

✍ Scribed by Fabienne Bessac; Feliu Maseras

• Book ID: 102303973
• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 219 KB
• Volume: 29
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20846

✦ Synopsis

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. © 2007 Wiley Periodicals, Inc. J Comput Chem 2008