Theoretical calculations on the mechanisms of the gas phase elimination kinetics of chlorocyclohexane, 3-chlorocyclohexene and 4-chlorocyclohexene

Jesús Lezama; Edgar Márquez; José R. Mora; Tania Córdova; Gabriel Chuchani

doi:10.1016/j.theochem.2009.08.029

Theoretical calculations on the mechanisms of the gas phase elimination kinetics of chlorocyclohexane, 3-chlorocyclohexene and 4-chlorocyclohexene

Jesús Lezama
, Edgar Márquez
, José R. Mora
, Tania Córdova
, 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

16 Scopus citations

Abstract

The kinetics of the thermal decomposition of the title compounds in the gas phase have been studied at the B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), MPW91PW91/6-31G(d,p), MPW91PW91/6-31++G(d,p), PBEPBE/6-31G(d,p), and PBEPBE/6-31++G(d,p) levels of theory. These halide substrates produce the corresponding cyclohexadiene and hydrogen chloride. The DFT calculations suggest a non-synchronous four-membered cyclic transition state type of mechanism. The elongation and subsequent polarization of the C-Cl bond, in the direction of C^δ+...Cl^δ-, is rate determining step in these elimination reactions. Differences in reactivity in these substrates are discussed in terms of the transition state structure and electron distribution.

Original language	English
Pages (from-to)	17-22
Number of pages	6
Journal	Journal of Molecular Structure: THEOCHEM
Volume	916
Issue number	1-3
DOIs	https://doi.org/10.1016/j.theochem.2009.08.029
State	Published - 30 Dec 2009
Externally published	Yes

Keywords

3-Chlorocyclohexene
4-Chlorocyclohexene
DFT calculations
Gas-phase elimination

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10.1016/j.theochem.2009.08.029

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@article{54ecbad626314adb8815a7b4a0332493,

title = "Theoretical calculations on the mechanisms of the gas phase elimination kinetics of chlorocyclohexane, 3-chlorocyclohexene and 4-chlorocyclohexene",

abstract = "The kinetics of the thermal decomposition of the title compounds in the gas phase have been studied at the B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), MPW91PW91/6-31G(d,p), MPW91PW91/6-31++G(d,p), PBEPBE/6-31G(d,p), and PBEPBE/6-31++G(d,p) levels of theory. These halide substrates produce the corresponding cyclohexadiene and hydrogen chloride. The DFT calculations suggest a non-synchronous four-membered cyclic transition state type of mechanism. The elongation and subsequent polarization of the C-Cl bond, in the direction of Cδ+...Clδ-, is rate determining step in these elimination reactions. Differences in reactivity in these substrates are discussed in terms of the transition state structure and electron distribution.",

keywords = "3-Chlorocyclohexene, 4-Chlorocyclohexene, DFT calculations, Gas-phase elimination",

author = "Jes{\'u}s Lezama and Edgar M{\'a}rquez and Mora, \{Jos{\'e} R.\} and Tania C{\'o}rdova and Gabriel Chuchani",

note = "Funding Information: T.C. is grateful to Consejo de Desarrollo Cient{\'i}fico y Human{\'i}stico (C.D.C.H.) for Grant No. PG-03-00-6499-2006 . ",

year = "2009",

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doi = "10.1016/j.theochem.2009.08.029",

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TY - JOUR

T1 - Theoretical calculations on the mechanisms of the gas phase elimination kinetics of chlorocyclohexane, 3-chlorocyclohexene and 4-chlorocyclohexene

AU - Lezama, Jesús

AU - Márquez, Edgar

AU - Mora, José R.

AU - Córdova, Tania

AU - Chuchani, Gabriel

N1 - Funding Information: T.C. is grateful to Consejo de Desarrollo Científico y Humanístico (C.D.C.H.) for Grant No. PG-03-00-6499-2006 .

PY - 2009/12/30

Y1 - 2009/12/30

N2 - The kinetics of the thermal decomposition of the title compounds in the gas phase have been studied at the B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), MPW91PW91/6-31G(d,p), MPW91PW91/6-31++G(d,p), PBEPBE/6-31G(d,p), and PBEPBE/6-31++G(d,p) levels of theory. These halide substrates produce the corresponding cyclohexadiene and hydrogen chloride. The DFT calculations suggest a non-synchronous four-membered cyclic transition state type of mechanism. The elongation and subsequent polarization of the C-Cl bond, in the direction of Cδ+...Clδ-, is rate determining step in these elimination reactions. Differences in reactivity in these substrates are discussed in terms of the transition state structure and electron distribution.

AB - The kinetics of the thermal decomposition of the title compounds in the gas phase have been studied at the B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), MPW91PW91/6-31G(d,p), MPW91PW91/6-31++G(d,p), PBEPBE/6-31G(d,p), and PBEPBE/6-31++G(d,p) levels of theory. These halide substrates produce the corresponding cyclohexadiene and hydrogen chloride. The DFT calculations suggest a non-synchronous four-membered cyclic transition state type of mechanism. The elongation and subsequent polarization of the C-Cl bond, in the direction of Cδ+...Clδ-, is rate determining step in these elimination reactions. Differences in reactivity in these substrates are discussed in terms of the transition state structure and electron distribution.

KW - 3-Chlorocyclohexene

KW - 4-Chlorocyclohexene

KW - DFT calculations

KW - Gas-phase elimination

UR - https://www.scopus.com/pages/publications/70350707582

U2 - 10.1016/j.theochem.2009.08.029

DO - 10.1016/j.theochem.2009.08.029

M3 - Artículo

AN - SCOPUS:70350707582

SN - 0166-1280

VL - 916

SP - 17

EP - 22

JO - Journal of Molecular Structure: THEOCHEM

JF - Journal of Molecular Structure: THEOCHEM

IS - 1-3

ER -

Theoretical calculations on the mechanisms of the gas phase elimination kinetics of chlorocyclohexane, 3-chlorocyclohexene and 4-chlorocyclohexene

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Keywords

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