On the chemical consequences of long-range interactions in chiral systems

Abstract

The chemical manifestations of discrimination in long-range (non- contact) interactions of chiral molecules are analysed in three stages. A simple thermodynamic model is used to establish a method of presenting experimental data (such as differences in racemization rates, solubilities and redox potentials of pure enantiomers in non- associating chiral media) in terms of well defined thermodynamic discriminations. The thermodynamic quantities are then related directly to discriminations in intermolecular interactions through a statistical thermodynamic treatment. Estimates of the discrimination in intermolecular forces from experimental thermodynamic data suggest that only electrostatic interactions are sufficiently large to account for the experimentally observed values of the discrimination.