Theoretical studies of the gas-phase pyrolysis kinetics of ω-bromonitriles, ZCH2CH2Br [Z = NC, NCCH 2, NCCH2CH2]

Jose R. Rojas, Marcos Loroño, Jose R. Mora, Rosa M. Dominguez, Tania Cordova, Gabriel Chuchani

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

Resumen

The gas-phase elimination of several ω-bromonitriles (ZCH 2CH2Br, Z = NC, NCCH2, NCCH2CH 2) has been examined at the MP2/6-31G(d,p), MP2/6-31G(2d,2p), B3PW91/6-31G(2d,2p), and MPW91PW91/6-31(2p,2d) levels of theory. The bromonitriles yield the corresponding cyano-olefin and HBr gas in a rate-determining step. The MPW91PW91/6-31G(2p,2d) results suggest a concerted mechanism, with a polar, four-membered transition state. The calculated kinetic and thermodynamic parameters were found to be within reasonable agreement with the experimental determinations. Substituent effects are discussed in terms of electronic structure.

Idioma originalInglés
Páginas (desde-hasta)168-175
Número de páginas8
PublicaciónInternational Journal of Chemical Kinetics
Volumen41
N.º3
DOI
EstadoPublicada - mar 2009

Huella

Profundice en los temas de investigación de 'Theoretical studies of the gas-phase pyrolysis kinetics of ω-bromonitriles, ZCH<sub>2</sub>CH<sub>2</sub>Br [Z = NC, NCCH <sub>2</sub>, NCCH<sub>2</sub>CH<sub>2</sub>]'. En conjunto forman una huella única.

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