Electronic effect on the rotational barriers of PN bond in aminophosphanes. A theoretical approach

Rotational barriers of PN bonds were studied under density functional theory using the B3LYP functional and two different basis sets to establish the electronic effect in them. These calculations were performed with toluene solvent interaction using the Polarizable Continuum Model to simulate the experimental conditions. The anomeric effect was established as an electronic effect that drives the PN rotational barriers. This effect is characterized by the highest chlorine substitution over the phosphorous atom using the NBO analysis, and the bond energy was calculated using a modified version of the bond energy change. The stabilization criterion was established by the normalized value of the bond energy. Additionally, intercross molecular orbital energies in rotational barriers were established as another criterion of conformation stabilization.