Oriented External Electric Fields: Tweezers and Catalysts for Reactivity in Halogen-Bond Complexes.

Abstract

This theoretical study establishes ways of controlling and enabling an uncommon chemical reaction, the displacement reaction, B:---(X-Y) → (B-X)+ + :Y-, which is nascent from a B:---(X-Y) halogen bond (XB) by nucleophilic attack of the base, B:, on the halogen, X. In most of the 14 cases examined, these reactions possess high barriers either in the gas phase (where the X-Y bond dissociates to radicals) or in solvents such as CH2Cl2 and CH3CN (which lead to endothermic processes). Thus, generally, the XB species are trapped in deep minima, and their reactions are not allowed without catalysis. However, when an oriented-external electric field (OEEF) is directed along the B---X---Y reaction axis, the field acts as electric tweezers that orient the XB along the field's axis, and intensely catalyze the process, by tens of kcal/mol, thus rendering the reaction allowed. Flipping the OEEF along the reaction axis inhibits the reaction and weakens the interaction of the XB. Furthermore, at a critical OEEF, each XB undergoes spontaneous and barrier-free reaction. As such, OEEF achieves quite tight control of the structure and reactivity of XB species. Valence bond modeling is used to elucidate the means whereby OEEFs exert their control.