Substituent Effects in Cation/π Interactions and Electrostatic Potentials above the Centers of Substituted Benzenes Are Due Primarily to Through-Space Effects of the Substituents

Abstract

Substituent effects in cation/π interactions have been examined using the M05-2X DFT functional and CCSD(T) paired with triple-ζ-quality basis sets. In contrast to popular, intuitive models, trends in substituent effects are explained primarily in terms of direct through-space interactions with the substituents. While there is some scatter in the data, which is attributed to π polarization, the trend in substituent effects in cation/π interactions is captured by an additive model in which the substituent is isolated from the aryl ring. Similarly, changes in the electrostatic potential at a point above the center of a substituted benzene arise largely from through-space effects of the substituents; π polarization is not the dominant underlying cause.