The rotational barrier of an enaminonitrile. Charge and energy redistribution during rotation about the C-N bond

Abstract

Ab initio quantum mechanical techniques were used together with PROAIM electron density partitioning and CHELPG electrostatic potential analysis to examine the charge density distribution of model enaminonitrile1 in its planar ground state and in its two rotational transition states. The barrier to rotation about the C-N bond was calculated to be 15.4 and 15.6 kcal/mole for the two rotational transition states at the HF/6-31G** level of theory, and was found to originate from a redistribution of electronic kinetic energy between the amino group and the rest of the molecule in a manner similar to that found for formamide and sulfonamide. Similarly, the C-N bond length and amino group electron population were found to depend upon the C-N torsional angle. Electrostatically derived atomic point charges were also examined at each stationary point using the CHELPG program. CHELPG electrostatic potential results were found to represent the traditional “external” viewpoint of the charge density consistent with a resonance model, while the results from PROAIM calculations were found to describe the underlying charge density and kinetic energy density redistribution responsible for the rotational barrier.