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DFT modeling of reactivity in an ionic liquid: How many ion pairs?
Author(s) -
Bessac Fabienne,
Maseras Feliu
Publication year - 2007
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20846
Subject(s) - reactivity (psychology) , ionic liquid , ion , computational chemistry , ionic bonding , chemistry , chemical physics , organic chemistry , medicine , alternative medicine , pathology , catalysis
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