Computational Study on the Vinyl Azide Decomposition

DARÍO J. R. DUARTE; MARGARIDA S. MIRANDA; JOAQUIM C. G. ESTEVES DA SILVA

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Lugar: Washington; Año: 2014 vol. 118 p. 5038 - 5045

1089-5639

Mechanism decomposition of vinyl azide (CH2CHN3) has been studied by calculations of the electronic structure. In addition, a study based on the topology of the electron charge density distribution and its Laplacian function within the framework of the Quantum Theory of Atoms in Molecules (QTAIM) has been made in order to understand the electron redistribution mechanisms that occur during the formation of the vinyl nitrenes. The electronic structure calculations reveal that the decomposition of cis-vinyl azide leads to the formation of ketenimine through single-step conversion cis-CH2CHN3→CH2CNH. While the conversion of the trans isomer to acetonitrile (CH3CN) occurs in two steps, trans-CH2CHN3→cyc-CH2NCH + N2→CH3CN + N2. Moreover, the topological analysis of the L(r) function reveals that triplet vinyl nitrene has one lone pair on the valence shell charge concentration (VSCC) of nitrogen (could act as a monodentate Lewis base), while that singlet vinylnitrene has two lone pairs on the VSCC of nitrogen (could act as a bidentate Lewis base).