Experimental and computational study of the thermal decomposition of 3-buten-1-ol in m-xylene solution

López, Víctor H; Quíjano, Jairo; Luna, Sofía; Ruíz, Pablo; Rios, Diego; Parra, Wilson; Zapata, Edilma; Gaviria, Jaír; Notario, Rafael

doi:10.1007/s11224-013-0234-0

Cited by 10 publications

(18 citation statements)

References 16 publications

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“…1 Scheme 1. Our main goal is the characterization of the electronic patterns governing cyclic transition states, [19][20][21][22][23][24][25][26][27][28] , therefore we will focus on the nature of bonding of the thermal decomposition of 1chlorohexane reaction mechanism as a benchmark of this type of reactivity in gas phase. The nature of bonding at the catalytic reaction center for the electronic rearrangement (i.e., Cl-C α -C β -H β ) remains unknown.…”

Section: Introductionmentioning

confidence: 99%

Understanding the thermal dehydrochlorination reaction of 1-chlorohexane. Revealing the driving bonding pattern at the planar catalytic reaction center

et al. 2015

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The nature of bonding along the gas-phase thermal decomposition of 1-chlorohexane to produce 1-hexene and hydrogen chloride has been examined at the DFT M05-2X/6-311+G(d,p) level of theory. Based on results both from energetical and topological analysis of the electron localization function (ELF), we propose to rationalize the experimental available results not in terms of a decomposition via a four-membered cyclic transition structure (TS), but properly as a two stage one step reaction mechanism featuring a slightly asynchronous process associated to the catalytic planar reaction center at the TS. In this context, the first electronic stage corresponds to the ‫ܥ‬ ఋା ••• ‫݈ܥ‬ ఋି bond cleavage, which take place on the activation path earlier the transition structure be reached. There is no evidence of a Cl-C bond at the TS configuration. The second stage, associated to the top of the energy barrier, includes the TS and extends beyond on the deactivation pathway towards the products. The existence of both bonding and nonbonding non covalent interactions (NCI) are also revealed for the first time for the TS configuration. 17 47 to point -9 along the IRC reaction pathway. Arbitrarily the second stage concerning main electronic changes will be associated to points -9 to +9. Both stages refer to regions where key electronic changes driving the transformation take place. Note that from point -34 to point -5, the population associated to the disynaptic basin V(C α ,C β ) increases from 1.99e to 2.20e, whereas the population integrated in the disynaptic protonated basin V(H β ,C β ) decreases from 1.98e to 1.72e. The attractor corresponding to the forming double bond localizes out of the line connecting the carbon center cores. This topology for the C  -C  region remains unchanged until point 12 in region g. At the top of the energy barrier, within the entire interval IRC=(-0.97962,+0.97971), i.e., point -9 to point 9, we observe an isolated electron localization region integrating to 7.64e which is associated to the migrating chlorine center. This picture, on the top of the barrier, corresponds to a lonely chlorine atom bearing an electronic charge of -0.64 while evolving to the encounter of the H β center.Thereafter, within the tiny region d four valence monosynaptic basins V(Cl) associated to the negatively charged chlorine center adopt a tetrahedral conformation, with an increasing in the population from 7.64e to 7.70e. In this region the valence basins populations for V(C α ,C β ) and V(H β ,C β ) varies from 2.41e to 2.34e, and from 1.81e to 1.51e, respectively. The migrating chlorine center develops thus a maximum charge of -0.71 at the transition structure (point 0). ELF picture of bonding reveals that activation events are mainly associated to conformational changes in preparation of the reaction center (region a), followed by the breaking of the Cl-C α bond (regions b and c), and the start of the migration of H  atom with the associated bonding changes at C α -C β -H β moiety (regions c and d). Regarding t...

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Section: Introductionmentioning

confidence: 99%

Understanding the thermal dehydrochlorination reaction of 1-chlorohexane. Revealing the driving bonding pattern at the planar catalytic reaction center

et al. 2015

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“…The temperature-dependent rate constant [k(T)] for the decomposition reaction of compounds 1-3 have been Table 1 B3LYP/6-311?G**, CBS-QB3 and MP2/6-311?G**//B3LYP/6-311?G** calculated thermodynamic parameters [DH, DG (in kcal mol -1 ), DS (in cal mol -1 K -1 )] at 300 and 550 K for the ground and transition state structures of the thermal decomposition reactions of compounds 1-3 [13] calculated at two different temperatures (i.e., 300 and 550 K). Finding from all three methods show that the temperature-dependent rate constant [k(T)] for the decomposition reaction at 300 and 550 K decreases from compound 1 to compound 3 (see Table 2).…”

Section: Resultsmentioning

confidence: 99%

“…Although there are some published experimental and theoretical data about the kinetics of the thermal decomposition of 3-buten-1-ol (1), 3-methoxy-1-propene (2), and ethoxyethene (3) [11][12][13][14][15][16][17], the impacts of the determinant factors (e.g., electrostatic interactions, hardness and aromaticity) on the thermal decomposition of compounds 1-3 have not been investigated (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

Correlations between hardness, electrostatic interactions, and thermodynamic parameters in the decomposition reactions of 3-buten-1-ol, 3-methoxy-1-propene, and ethoxyethene

et al. 2014

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Decomposition of the three isomeric compounds, 3-buten-1-ol (1), 3-methoxy-1-propene (2), and ethoxyethene (3), at two different (300 and 550 K) temperatures has been investigated by means of ab initio molecular orbital theory (MP2/6-311?G**//B3LYP/6-311?G**), hybrid-density functional theory (B3LYP/6-311?G**), the complete basis set, nuclear magnetic resonance analysis, and the electrostatic model associated with the dipole-dipole interactions. All three levels of theory showed that the calculated Gibbs free energy differences between the transition and ground state structures (DG = ) increase from compound 1 to compound 3. The variations of the calculated DG = values can not be justified by the decrease of the calculated global hardness (g) differences between the ground and transition states structures (i.e., D[g(GS)-g(TS)]). Based on the synchronicity indices, the transition state structures of compounds 1-3 involve synchronous aromatic transition structures, but there is no significant difference between their calculated synchronicity indices. The optimized geometries for the transition state structures of the decomposition reactions of compounds 1-3 consist in chair-like six-membered rings. The variation of the calculated activation entropy (DS = ) values can not be justified by the decrease of D[g(GS)-g(TS)] parameter from compound 1 to compound 3. On the other hand, dipole moment differences between the ground and transition state structures [D(l TS -l GS )] decrease from compound 1 to compound 3. Therefore, the electrostatic model associated with the dipole-dipole interactions justifies the increase of the calculated DG = values from compound 1 to compound 3. The correlations between DG = , D[g(GS)-g(TS)], (DS = ), k(T), electrostatic model, and structural parameters have been investigated.

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“…In the following article, López et al [121] reported on the thermal decomposition of 3-buten-1-ol in m-xylene solution. A one-step process proceeding through a sixmembered cyclic transition state was proposed, and reasonable agreement between experimentally determined and MP2-calculated reaction parameters was revealed.…”

Section: Issuementioning

confidence: 99%

Interplay of thermochemistry and structural chemistry, the journal (volume 24, 2013, issues 5–6) and the discipline

2014

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Experimental and computational study of the thermal decomposition of 3-buten-1-ol in m-xylene solution

Cited by 10 publications

References 16 publications

Understanding the thermal dehydrochlorination reaction of 1-chlorohexane. Revealing the driving bonding pattern at the planar catalytic reaction center

Understanding the thermal dehydrochlorination reaction of 1-chlorohexane. Revealing the driving bonding pattern at the planar catalytic reaction center

Correlations between hardness, electrostatic interactions, and thermodynamic parameters in the decomposition reactions of 3-buten-1-ol, 3-methoxy-1-propene, and ethoxyethene

Interplay of thermochemistry and structural chemistry, the journal (volume 24, 2013, issues 5–6) and the discipline

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