Ionic liquids through the looking glass: theory mirrors experiment and provides further insight into aromatic substitution processes

Abstract

Aromatic substitution of 1-fluoro-2,4-dinitrobenzene has been shown to proceed more rapidly in an ionic liquid than in ethanol, primarily due to entropic, rather than enthalpic, effects. By using molecular dynamics simulations, an anion–π interaction appears to contribute to strong ordering within the starting material complex that accounts for the relative differences in the S_NAr k.