Unimolecular decomposition of chemically activated methylallylether

Ibuki, Toshio; Takezaki, Yoshimasa

doi:10.1002/kin.550090205

Cited by 4 publications

(1 citation statement)

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“…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: 98%

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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