Intramolecular [3 + 2] Cycloaddition Reactions of Unsaturated Nitrile Oxides. A Study from the Perspective of Bond Evolution Theory (BET)

Abel Idrice Adjieufack, Vincent Liégeois, Ibrahim Mbouombouo Ndassa, Joseph Ketcha Mbadcam, Benoît Champagne

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

The reaction mechanism of the [3 + 2] intramolecular cycloaddition of 3,3-dimethyl-2-(prop-2-en-1-yloxy) and (prop-2-en-1-ylsulfanyl) nitrile oxides is analyzed using different DFT functionals with the 6-311++G(d,p) basis set. The activation and the reaction energies for the cis and trans pathways are evaluated at the DFT, MP2, and CCSD(T) levels of theory as well as their Gibbs free energy counterparts. It is shown that the trans regioisomers are both thermodynamic and kinetic compounds, in agreement with experimental outcomes. For a deeper understanding of the reaction mechanism, a BET analysis along the reaction channel (trans and cis) has been carried out. This analysis reveals that the lone pair on the nitrogen atom is formed first, then the C-C bond, and finally the O-C one. The global mechanism is similar for the two compounds and for the two pathways even if some small differences are observed, for instance, in the values of the reaction coordinates of appeareance of the different basins.

langue originaleAnglais
Pages (de - à)7472-7481
Nombre de pages10
journalJournal of physical chemistry A
Volume122
Numéro de publication37
Les DOIs
étatPublié - 20 sept. 2018

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Nitriles
Cycloaddition
nitriles
cycloaddition
Discrete Fourier transforms
Oxides
oxides
Gibbs free energy
Nitrogen
Chemical activation
Thermodynamics
Atoms
Kinetics
functionals
nitrogen atoms
activation
thermodynamics
kinetics

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abstract = "The reaction mechanism of the [3 + 2] intramolecular cycloaddition of 3,3-dimethyl-2-(prop-2-en-1-yloxy) and (prop-2-en-1-ylsulfanyl) nitrile oxides is analyzed using different DFT functionals with the 6-311++G(d,p) basis set. The activation and the reaction energies for the cis and trans pathways are evaluated at the DFT, MP2, and CCSD(T) levels of theory as well as their Gibbs free energy counterparts. It is shown that the trans regioisomers are both thermodynamic and kinetic compounds, in agreement with experimental outcomes. For a deeper understanding of the reaction mechanism, a BET analysis along the reaction channel (trans and cis) has been carried out. This analysis reveals that the lone pair on the nitrogen atom is formed first, then the C-C bond, and finally the O-C one. The global mechanism is similar for the two compounds and for the two pathways even if some small differences are observed, for instance, in the values of the reaction coordinates of appeareance of the different basins.",
author = "Adjieufack, {Abel Idrice} and Vincent Li{\'e}geois and {Mbouombouo Ndassa}, Ibrahim and {Ketcha Mbadcam}, Joseph and Beno{\^i}t Champagne",
year = "2018",
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Intramolecular [3 + 2] Cycloaddition Reactions of Unsaturated Nitrile Oxides. A Study from the Perspective of Bond Evolution Theory (BET). / Adjieufack, Abel Idrice; Liégeois, Vincent; Mbouombouo Ndassa, Ibrahim; Ketcha Mbadcam, Joseph; Champagne, Benoît.

Dans: Journal of physical chemistry A, Vol 122, Numéro 37, 20.09.2018, p. 7472-7481.

Résultats de recherche: Contribution à un journal/une revueArticle

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T1 - Intramolecular [3 + 2] Cycloaddition Reactions of Unsaturated Nitrile Oxides. A Study from the Perspective of Bond Evolution Theory (BET)

AU - Adjieufack, Abel Idrice

AU - Liégeois, Vincent

AU - Mbouombouo Ndassa, Ibrahim

AU - Ketcha Mbadcam, Joseph

AU - Champagne, Benoît

PY - 2018/9/20

Y1 - 2018/9/20

N2 - The reaction mechanism of the [3 + 2] intramolecular cycloaddition of 3,3-dimethyl-2-(prop-2-en-1-yloxy) and (prop-2-en-1-ylsulfanyl) nitrile oxides is analyzed using different DFT functionals with the 6-311++G(d,p) basis set. The activation and the reaction energies for the cis and trans pathways are evaluated at the DFT, MP2, and CCSD(T) levels of theory as well as their Gibbs free energy counterparts. It is shown that the trans regioisomers are both thermodynamic and kinetic compounds, in agreement with experimental outcomes. For a deeper understanding of the reaction mechanism, a BET analysis along the reaction channel (trans and cis) has been carried out. This analysis reveals that the lone pair on the nitrogen atom is formed first, then the C-C bond, and finally the O-C one. The global mechanism is similar for the two compounds and for the two pathways even if some small differences are observed, for instance, in the values of the reaction coordinates of appeareance of the different basins.

AB - The reaction mechanism of the [3 + 2] intramolecular cycloaddition of 3,3-dimethyl-2-(prop-2-en-1-yloxy) and (prop-2-en-1-ylsulfanyl) nitrile oxides is analyzed using different DFT functionals with the 6-311++G(d,p) basis set. The activation and the reaction energies for the cis and trans pathways are evaluated at the DFT, MP2, and CCSD(T) levels of theory as well as their Gibbs free energy counterparts. It is shown that the trans regioisomers are both thermodynamic and kinetic compounds, in agreement with experimental outcomes. For a deeper understanding of the reaction mechanism, a BET analysis along the reaction channel (trans and cis) has been carried out. This analysis reveals that the lone pair on the nitrogen atom is formed first, then the C-C bond, and finally the O-C one. The global mechanism is similar for the two compounds and for the two pathways even if some small differences are observed, for instance, in the values of the reaction coordinates of appeareance of the different basins.

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