Unimolecular rearrangements of ethylnitrene: An exploratory theoretical study

The products of the rearrangement of ethylnitrene are ethylideneimine via a 1,2 hydrogen shift, N-methyl methyleneimine via a 1,2 methyl shift, and the corresponding aziridine by cyclization. The three reactions have been studied by the semiempirical MNDO method. The charge transfer effects have been investigated. Theoretically calculated vibrational frequencies and kinetic properties have been used in calculating macroscopic thermodynamic and kinetic properties. The entropies of activation, the high pressure rate constants, k_∞, and the high pressure Arrhenius parameters, A_∞ and E_∞, have been computed. The kinetic isotope effects have also been studied.