The internal barriers of rotation for the 209 polychlorinated biphenyls

Andersson, Patrik L.; Haglund, Peter; Tysklind, Mats

The internal barriers of rotation for the 209 polychlorinated biphenyls

1997

Andersson, Patrik L. | Haglund, Peter | Tysklind, Mats

The internal barrier of rotation (Erot) was calculated for all 209 polychlorinated biphenyls (PCBs) by using a semi-empirical method, viz. the Austin Model 1 (AMI) Hamiltonian. The difference in total energy between a forced planar state and an optimised twisted structure was defined as Erot. The Erot values were in the range of 8.33 to 483 kj/mol, and were significantly influenced by the number of chlorine atoms inortho position. An additional structural characteristic of the PCBs influencing Erot ofortho substituted congeners was substitution by chlorine atoms in vicinalmeta positions, which is assumed to prevent outward bending ofortho substituents. This so-called buttressing effect contributed with 4 to 31 kj/mol per added chlorine atom. In conclusion, the internal barrier of rotation, calculated for all 209 PCBs, provides an important structure dependent physico-chemical parameter for multivariate modelling of future quantitative structure-activity and structure-property relationships (QSARs/QSPRs).

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