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Theoretical studies of the gas-phase pyrolysis kinetics of ω-bromonitriles, ZCH2CH2Br [Z = NC, NCCH2, NCCH2CH2]

✍ Scribed by Jose R. Rojas; Marcos Loroño; Jose R. Mora; Rosa M. Dominguez; Tania Cordova; Gabriel Chuchani

Publisher: John Wiley and Sons
Year: 2009
Tongue: English
Weight: 143 KB
Volume: 41
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.20392

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✦ Synopsis

Abstract

The gas‐phase elimination of several ω‐bromonitriles (ZCH~2~CH~2~Br, Z = NC, NCCH~2~, NCCH~2~CH~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. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 168–175, 2009

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