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.
| Original language | English |
|---|---|
| Pages (from-to) | 7472-7481 |
| Number of pages | 10 |
| Journal | Journal of physical chemistry A |
| Volume | 122 |
| Issue number | 37 |
| DOIs | |
| Publication status | Published - 20 Sep 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.
In: Journal of physical chemistry A, Vol. 122, No. 37, 20.09.2018, p. 7472-7481.Research output: Contribution to journal › Article
TY - JOUR
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.
UR - http://www.scopus.com/inward/record.url?scp=85053190968&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.8b06711
DO - 10.1021/acs.jpca.8b06711
M3 - Article
AN - SCOPUS:85053190968
VL - 122
SP - 7472
EP - 7481
JO - The journal of physical chemistry. A
JF - The journal of physical chemistry. A
SN - 1089-5639
IS - 37
ER -