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A Computational Study of Azine, Azoethene, and Diimine Linkages in the Poly/oligoazine System

Brian K. Schmitz, William B. Euler, Journal of Computational Chemistry, 1994, 15, 1163 – 1175

Abstract

Hartree-Fock (HF) and molecular mechanics calculations were performed on linear azine oligomers and model compounds. The rotational energy curves for the model compounds formaldazine, H2C=N–N=CH2, ethenyl diazene, H2C=CH–N=NH, and ethanediimine, HN=CH–CH=NH, were calculated for a variety of basis sets at the HF and MP2 level. In all cases the rotational energy barriers are quite different from butadienes or aza-substituted butadienes because of the lone pair – lone pair interaction of the adjacent nitrogen atoms. The results on the model compounds were used to generate a set of molecular mechanics (MM) parameters that are appropriate for linear oligo- and polyazines. Comparisons of the geometries of the HF results and the MM results for the oligoazines showed that the two methods gave comparable results.

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