| Autor: |
Duarte DJ; Laboratorio de Estructura Molecular y Propiedades, Área de Quı́mica Fı́sica-Departamento de Quı́mica, Facultad de Ciencias Exactas y Naturales y Agrimensura, Universidad Nacional del Nordeste , Avenida Libertad 5460, 3400 Corrientes, Argentina., Miranda MS, Esteves da Silva JC |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. A [J Phys Chem A] 2014 Jul 10; Vol. 118 (27), pp. 5038-45. Date of Electronic Publication: 2014 Jul 01. |
| DOI: |
10.1021/jp500140j |
| Abstrakt: |
The decomposition mechanism 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 Quantum Theory of Atoms in Molecules (QTAIM), has been carried out with the aim of comprehending the electron redistribution mechanisms that take place in the formation of vinyl nitrenes. The electronic structure calculations reveal that the decomposition of the s-cis conformer of vinyl azide leads to the formation of ketenimine through a single-step conversion, s-cis-CH2CHN3 → CH2CNH + N2, while the conversion of the s-trans conformer to acetonitrile occurs in two steps, s-trans-CH2CHN3 → cyc-CH2NCH + N2 → CH3CN + N2. 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 and thus could act as a monodentate Lewis base, while singlet vinyl nitrene has two lone pairs on the VSCC of nitrogen and thus could act as a bidentate Lewis base. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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