Ab initio and DFT calculations of benzaldoxime elimination kinetics in the gas phase

Jose R. Mora; Tania Cordova; Gabriel Chuchani

doi:10.1002/qua.21715

Ab initio and DFT calculations of benzaldoxime elimination kinetics in the gas phase

Jose R. Mora
, Tania Cordova
, Gabriel Chuchani^*

^*Corresponding author for this work

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

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

5 Scopus citations

Abstract

The mechanism for the gas-phase molecular elimination kinetics of benzaldoxime was examined at MP2/6-31G, MP2/6-31G(d,p), B3LYP/6-31G, B3LYP/6-31G(d,p), MPW1PW91/6-31G, and MPW1PW91/6-31G(d,p) levels of theory. The products of elimination of this oxime are benzonitrile and water. Calculated thermodynamic and kinetic parameters estimated from B3LYP/6-31G was found to be in better agreement with the experimental values. Transition state structure is best described as a four-membered cyclic structure with good approximation to planarity. NBO charges analysis revealed a little greater polarization of the benzylic C^δ - H^δ+ rather than N ^δ - OH^δ-. Bond indexes and synchronicity parameters are in agreement with a concerted semi-polar type of mechanism with benzylic C - H bond breaking as determining step of the reaction.

Original language	English
Pages (from-to)	1735-1741
Number of pages	7
Journal	International Journal of Quantum Chemistry
Volume	108
Issue number	10
DOIs	https://doi.org/10.1002/qua.21715
State	Published - 2008
Externally published	Yes

Keywords

Ab initio
Bezaldoxime
DFT calculations
Gas phase elimination
Kinetics

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10.1002/qua.21715

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@article{8bf8482f871c46ecbf26628fc2bcea8f,

title = "Ab initio and DFT calculations of benzaldoxime elimination kinetics in the gas phase",

abstract = "The mechanism for the gas-phase molecular elimination kinetics of benzaldoxime was examined at MP2/6-31G, MP2/6-31G(d,p), B3LYP/6-31G, B3LYP/6-31G(d,p), MPW1PW91/6-31G, and MPW1PW91/6-31G(d,p) levels of theory. The products of elimination of this oxime are benzonitrile and water. Calculated thermodynamic and kinetic parameters estimated from B3LYP/6-31G was found to be in better agreement with the experimental values. Transition state structure is best described as a four-membered cyclic structure with good approximation to planarity. NBO charges analysis revealed a little greater polarization of the benzylic Cδ - Hδ+ rather than N δ - OHδ-. Bond indexes and synchronicity parameters are in agreement with a concerted semi-polar type of mechanism with benzylic C - H bond breaking as determining step of the reaction.",

keywords = "Ab initio, Bezaldoxime, DFT calculations, Gas phase elimination, Kinetics",

author = "Mora, \{Jose R.\} and Tania Cordova and Gabriel Chuchani",

year = "2008",

doi = "10.1002/qua.21715",

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

volume = "108",

pages = "1735--1741",

journal = "International Journal of Quantum Chemistry",

issn = "0020-7608",

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

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}

TY - JOUR

T1 - Ab initio and DFT calculations of benzaldoxime elimination kinetics in the gas phase

AU - Mora, Jose R.

AU - Cordova, Tania

AU - Chuchani, Gabriel

PY - 2008

Y1 - 2008

N2 - The mechanism for the gas-phase molecular elimination kinetics of benzaldoxime was examined at MP2/6-31G, MP2/6-31G(d,p), B3LYP/6-31G, B3LYP/6-31G(d,p), MPW1PW91/6-31G, and MPW1PW91/6-31G(d,p) levels of theory. The products of elimination of this oxime are benzonitrile and water. Calculated thermodynamic and kinetic parameters estimated from B3LYP/6-31G was found to be in better agreement with the experimental values. Transition state structure is best described as a four-membered cyclic structure with good approximation to planarity. NBO charges analysis revealed a little greater polarization of the benzylic Cδ - Hδ+ rather than N δ - OHδ-. Bond indexes and synchronicity parameters are in agreement with a concerted semi-polar type of mechanism with benzylic C - H bond breaking as determining step of the reaction.

AB - The mechanism for the gas-phase molecular elimination kinetics of benzaldoxime was examined at MP2/6-31G, MP2/6-31G(d,p), B3LYP/6-31G, B3LYP/6-31G(d,p), MPW1PW91/6-31G, and MPW1PW91/6-31G(d,p) levels of theory. The products of elimination of this oxime are benzonitrile and water. Calculated thermodynamic and kinetic parameters estimated from B3LYP/6-31G was found to be in better agreement with the experimental values. Transition state structure is best described as a four-membered cyclic structure with good approximation to planarity. NBO charges analysis revealed a little greater polarization of the benzylic Cδ - Hδ+ rather than N δ - OHδ-. Bond indexes and synchronicity parameters are in agreement with a concerted semi-polar type of mechanism with benzylic C - H bond breaking as determining step of the reaction.

KW - Ab initio

KW - Bezaldoxime

KW - DFT calculations

KW - Gas phase elimination

KW - Kinetics

UR - https://www.scopus.com/pages/publications/45749136480

U2 - 10.1002/qua.21715

DO - 10.1002/qua.21715

M3 - Artículo

AN - SCOPUS:45749136480

SN - 0020-7608

VL - 108

SP - 1735

EP - 1741

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

IS - 10

ER -

Ab initio and DFT calculations of benzaldoxime elimination kinetics in the gas phase

Abstract

Keywords

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