Computational Study on the Vinyl Azide Decomposition

• Type: Article in International Scientific Journal
• Date: 2014

Authors

Dario J R Duarte (Author) Other; Margarida S Miranda (Author) Other; Joaquim C G E Esteves da Silva (Author) FCUP

Journal

Title: Journal of Physical Chemistry A

Vol. 118

Pages: 5038-5045

ISSN: 1089-5639

Publisher: American Chemical Society

Indexing

ISI Web of Knowledge - 11 Citations

Scopus - 12 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-009-MTN

DOI: 10.1021/jp500140j

Abstract (EN): 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 + N-2, while the conversion of the s-trans conformer to acetonitrile occurs in two steps, s-trans-CH2CHN3 -> cyc-CH2NCH + N-2 -> CH3CN + N-2. 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.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 8