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

doi:10.1002/kin.20392

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^*

^*Corresponding author for this work

Universidad de Oriente - Venezuela
Instituto Venezolano de Investigaciones Científicas (I.V.I.C.)
Universidad Central de Venezuela, Facultad de Ciencias

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

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 language	English
Pages (from-to)	168-175
Number of pages	8
Journal	International Journal of Chemical Kinetics
Volume	41
Issue number	3
DOIs	https://doi.org/10.1002/kin.20392
State	Published - Mar 2009
Externally published	Yes

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@article{019a40d790204d18b68b62ee6813a2ac,

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

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.",

author = "Rojas, \{Jose R.\} and Marcos Loro{\~n}o and Mora, \{Jose R.\} and Dominguez, \{Rosa M.\} and Tania Cordova and Gabriel Chuchani",

year = "2009",

month = mar,

doi = "10.1002/kin.20392",

language = "Ingl{\'e}s",

volume = "41",

pages = "168--175",

journal = "International Journal of Chemical Kinetics",

issn = "0538-8066",

publisher = "John Wiley \& Sons Inc.",

number = "3",

}

TY - JOUR

T1 - Theoretical studies of the gas-phase pyrolysis kinetics of ω-bromonitriles, ZCH2CH2Br [Z = NC, NCCH 2, NCCH2CH2]

AU - Rojas, Jose R.

AU - Loroño, Marcos

AU - Mora, Jose R.

AU - Dominguez, Rosa M.

AU - Cordova, Tania

AU - Chuchani, Gabriel

PY - 2009/3

Y1 - 2009/3

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/61649118985

U2 - 10.1002/kin.20392

DO - 10.1002/kin.20392

M3 - Artículo

AN - SCOPUS:61649118985

SN - 0538-8066

VL - 41

SP - 168

EP - 175

JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

IS - 3

ER -

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

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