Through-Space Effects of Substituents Dominate Molecular Electrostatic Potentials of Substituted Arenes.

ABSTRACT: Model systems have been studied using density functional theory to assess the contributions of π-resonance and through-space effects on electrostatic potentials of substituted arenes. The results contradict the widespread assumption that changes in molecular ESPs reflect only local changes in the electron density. Substituent effects on the ESP above the molecular plane are commonly attributed to changes in the aryl π-system. We show that ESP changes for a collection of substituted benzenes and more complex aromatic systems can be accounted for mostly by through-space effects, with no change in the aryl π-electron density. Only when π-resonance effects are substantial do they influence changes in the ESP above the aromatic ring to any extent. Examples of substituted arenes studied here are

SUBMITTER: Wheeler SE 

PROVIDER: S-EPMC2806064 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature