Work

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

Year: 2009

Type: article

Abstract: Substituent effects in cation/pi interactions have been examined using the M05-2X DFT functional and CCSD(T) paired with triple-zeta-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 pi polarization, the trend in substituent effects in cation/pi 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; pi polarization is not the dominant underlying cause.

Source: Journal of the American Chemical Society

DOI: 10.1021/ja809097r

Authors: Steven E. Wheeler, K. N. Houk

Institution: University of California, Los Angeles

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funder: National Institute of General Medical Sciences

Award: Towards the ab Initio Prediction of Catalytic Proficiencies of Enzymes