Identifying absolute configurations of PCB atropisomers by comparison of their experimental specific rotations with their DFT calculated values

Abstract

Nineteen enantiomer pairs of polychlorinated biphenyls (PCBs) with three or four chloro substituents about the central carbon–carbon bond form a stable subclass of compounds whose biological effects vary with their chirality. Optical rotations for this group of PCBs were determined from density functional calculations employing extended atomic orbital gauge invariant basis sets. A comparison of these results with the experimental ones found from the literature for 10 of the pairs enabled the identification of their absolute configurations as analytes in gas chromatography studies.