Ab initio and molecular mechanics calculations on imine derivatives: A study of the rotational barriers and the development of MM2 parameters

The application of molecular mechanics methods for the study of structures has become a standard approach to conformational analysis. The MM2 force field has been extended to include imines. In general, a diverse group of aliphatic and aromatic imine structures can now be treated. The rotational energy profiles and barriers to N-substituted imines about the C_sp2? C_sp2 single bonds adjacent to C?N functional group were calculated via ab initio MO theory. Information obtained from the quantum mechanical calculations at the 3-21G, 6-31G*, and MP4/6-31G* //6-31G* levels was used both to study the phenomena involved and to parameterize MM2. The syn-anti isomerization was also studied, and the mechanistic pathways have been evaluated. In cases where the comparison with experimental data can be made, the agreements are good.