A Computational Study on the Configurational Behaviors of Dihalodiazenes and their Analogues Containing P and As Atoms

Abstract

In this research, we report the results of DFT calculations using xc-hybrid functional, B3LYP and employ NBO interpretation to investigate the stereoelectronic effects. Electrostatic and steric impacts on the conformational properties of 1,2-difluorodiazene (1), 1,2-dichlorodiazene (2) and 1,2-dibromodiazene (3) are also studied. Factors determining the thermodynamically stable molecular structure of 1,2-dihalodiazenes and their analogues containing P and As atom are discussed, and the energetic effects of intra-molecular hyperconjugations and steric repulsion in each molecular system are theoretically estimated using NBO theory. The Energy components calculated help us to justify the conformational behaviour of our target compounds. One of the interesting features extracted from NBO analysis is that dissociation energies are controlled by the stabilization energies associated with electron delocalizations in these compounds. The main parameter considered in this study is the Gibbs free energy estimated for <em>cis</em> and <em>trans</em> configurations of compounds and for the <em>cis</em>-to-<em>trans</em> conversion through rotation and inversion mechanisms.