Influence of Molecular Structure on the CN Bond Strength in the Nitroalkane Series:

AbstractThe equilibrium geometric parameters, enthalpies of formation of molecular and radical species, and dissociation energies of the CN bond at 0 and 298 K were determined by the B3LYP density functional method for nitroethane, fluoronitroethanes, chloronitroethanes, and mixed fluorochloronitroethanes. Trends in variation of the geometric and electronic parameters of the molecules, enthalpies of formation, and dissocia-tion energies were discussed. Independent theoretical estimation of the dissocia-tion energy of the CN bond is important for under-standing of the general relationships in the reactivity of nitroalkanes, especially for elucidating the mechan-ism of their gas-phase monomolecular decomposition. The B3LYP calculations of the dissociation energies of nitromethane and a series of its halo derivatives were made in [1]. Here we report on the dissociation energies of the CN bond and on the main trends in variation of the geometric and electronic parameter