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 - http://www.scopus.com/inward/record.url?scp=61649118985&partnerID=8YFLogxK
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 -