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

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish
Pages (from-to)168-175
Number of pages8
JournalInternational Journal of Chemical Kinetics
Volume41
Issue number3
DOIs
StatePublished - Mar 2009

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