Are anion/pi interactions actually a case of simple charge-dipole interactions?

ABSTRACT: Substituent effects in Cl(-)...C(6)H(6-n)X(n) complexes, models for anion/pi interactions, have been examined using density functional theory and robust ab initio methods paired with large basis sets. Predicted interaction energies for 83 model Cl(-)...C(6)H(6-n)X(n) complexes span almost 40 kcal mol(-1) and show an excellent correlation (r = 0.99) with computed electrostatic potentials. In contrast to prevailing models of anion/pi interactions, which rely on substituent-induced changes in the aryl pi-system, it is shown that substituent effects in these systems are due mostly to direct interactions between the anion and the substituents. Specifically, interaction energies for Cl(-)...C(6)H(6-n)X(n) complexes are recovered using a model system in which the substituents are isolated from th

SUBMITTER: Wheeler SE 

PROVIDER: S-EPMC3049731 | biostudies-literature | 2010 Aug

REPOSITORIES: biostudies-literature