Theoretical studies of the gas‐phase pyrolysis kinetics of ω‐bromonitriles, ZCH 2 CH 2 Br [Z = NC, NCCH 2 , NCCH 2 CH 2 ] | Zendy

Rojas Jose R. | Zendy; Loroño Marcos | Zendy; Mora Jose R. | Zendy; Dominguez Rosa M. | Zendy; Cordova Tania | Zendy; Chuchani Gabriel | Zendy

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Theoretical studies of the gas‐phase pyrolysis kinetics of ω‐bromonitriles, ZCH 2 CH 2 Br [Z = NC, NCCH 2 , NCCH 2 CH 2 ]

Author(s) -

Rojas Jose R.,

Loroño Marcos,

Mora Jose R.,

Dominguez Rosa M.,

Cordova Tania,

Chuchani Gabriel

Publication year - 2009

Publication title -

international journal of chemical kinetics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.341

H-Index - 68

eISSN - 1097-4601

pISSN - 0538-8066

DOI - 10.1002/kin.20392

Subject(s) - chemistry , gas phase , substituent , yield (engineering) , kinetic energy , kinetics , thermodynamics , stereochemistry , physics , quantum mechanics

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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