Substituent effects on the gas phase reactivity of alkyl allyl sulfides, a theoretical study
Year
: 2005
Abstract: The potential energy surface of the reaction C3H5SCH2X/C3H6CXCHZS was studied for the various X substitutions (XZCH3, H, Cl, F) at the high level of the theory (G3MP2 method) using the 6-31G(d) basis set. It was demonstrated that CH3, H, Cl and F substitution, respectively, accelerates the reaction (This order for the substitutions will be called XZCH3-to-F throughout this paper). Barrier height changes from DEsZ 167.76 to 148.63 kJ molK1, because of the electronic effects introduced upon the substitution. It was shown that the XZCH3-to-F substitution in the C6-position posses two types of contribution to the calculated energy barriers and bond lengths at the transition state (TS). First, it facilitates the TS complex formation, consequently reduces the barrier height. Second, it reduces the H1–C2 bond length, the major component of the reaction coordinate at the TS, and increases the rate of the reaction. Charge analysis shows that the acceptor substituent (F) induces more positive character on C6 atom at the Transition state (TS), while donor substituent (CH3) induces the less positive one, therefore, the reactivity decreases.
HOMO–LUMO energy differences confirmed the activation energy and reactivity order. The G3MP2 results show the capability of this level of calculation to predict the reactivity of the intramolecular retro-ene reaction correctly.
HOMO–LUMO energy differences confirmed the activation energy and reactivity order. The G3MP2 results show the capability of this level of calculation to predict the reactivity of the intramolecular retro-ene reaction correctly.
Keyword(s): Alkyl allyl sulfides,Retro-ene reaction,Pyrolysis,Concerted mechanism,Gas-phase kinetics,G3MP2
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Substituent effects on the gas phase reactivity of alkyl allyl sulfides, a theoretical study
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contributor author | محمد ایزدیار | en |
contributor author | M.R. Gholami | en |
contributor author | Mohammad Izadyar | fa |
date accessioned | 2020-06-06T14:32:48Z | |
date available | 2020-06-06T14:32:48Z | |
date issued | 2005 | |
identifier uri | http://libsearch.um.ac.ir:80/fum/handle/fum/3401301?locale-attribute=en | |
description abstract | The potential energy surface of the reaction C3H5SCH2X/C3H6CXCHZS was studied for the various X substitutions (XZCH3, H, Cl, F) at the high level of the theory (G3MP2 method) using the 6-31G(d) basis set. It was demonstrated that CH3, H, Cl and F substitution, respectively, accelerates the reaction (This order for the substitutions will be called XZCH3-to-F throughout this paper). Barrier height changes from DEsZ 167.76 to 148.63 kJ molK1, because of the electronic effects introduced upon the substitution. It was shown that the XZCH3-to-F substitution in the C6-position posses two types of contribution to the calculated energy barriers and bond lengths at the transition state (TS). First, it facilitates the TS complex formation, consequently reduces the barrier height. Second, it reduces the H1–C2 bond length, the major component of the reaction coordinate at the TS, and increases the rate of the reaction. Charge analysis shows that the acceptor substituent (F) induces more positive character on C6 atom at the Transition state (TS), while donor substituent (CH3) induces the less positive one, therefore, the reactivity decreases. HOMO–LUMO energy differences confirmed the activation energy and reactivity order. The G3MP2 results show the capability of this level of calculation to predict the reactivity of the intramolecular retro-ene reaction correctly. | en |
language | English | |
title | Substituent effects on the gas phase reactivity of alkyl allyl sulfides, a theoretical study | en |
type | Journal Paper | |
contenttype | External Fulltext | |
subject keywords | Alkyl allyl sulfides | en |
subject keywords | Retro-ene reaction | en |
subject keywords | Pyrolysis | en |
subject keywords | Concerted mechanism | en |
subject keywords | Gas-phase kinetics | en |
subject keywords | G3MP2 | en |
journal title | Journal of Molecular Structure | fa |
pages | 15-Nov | |
journal volume | 759 | |
journal issue | 1 | |
identifier link | https://profdoc.um.ac.ir/paper-abstract-1017503.html | |
identifier articleid | 1017503 |