Ordered Solvents and Ionic Liquids Can Be Harnessed for Electrostatic Catalysis

Longkun Xu, Ekaterina I. Izgorodina, Michelle L. Coote

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2 Citations (Scopus)

Abstract

Herein, we employ classical molecular dynamics simulations using the Drude oscillator-based polarizable force field, quantum chemical calculations, and ONIOM multiscale calculations to study (a) how an external field orders the solvent environment in a chemical reaction and then (b) whether in the absence of this same applied field the ordered solvent environment alone can electrostatically catalyze a chemical reaction when compared with the corresponding disordered solvent. Our results show that a 0.2 V/Å external electric field, which is below the threshold for bond breaking of solvent molecules, leads to significant ordering of bulk methanol solvent and the ionic liquid [EMIM][BF4]. Importantly, in the absence of this same field, the ordered solvent lowers the activation energy of the hydrogen-transfer reaction of o-alkylphenyl ketones in excess of 20 kcal/mol when the solvent is methanol and by over 30 kcal/mol for [EMIM][BF4]. Even a 0.1 V/Å external field has effects of ca. 10 and 20 kcal/mol, respectively. This work suggests a possible strategy for scaling electrostatic catalysis by applying a pulsed external field to the reaction medium to maintain solvent ordering while allowing the reaction to proceed largely in the absence of an external field.

Original languageEnglish
Pages (from-to)12826-12833
Number of pages8
JournalJournal of the American Chemical Society
Volume142
Issue number29
DOIs
Publication statusPublished - 22 Jul 2020

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