Volume, enthalpy and entropy of activation of the Diels-Alder reaction of dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate with 1-hexene

Kiselev, V. D.; Kashaeva, E. A.; Iskhakova, G. G.; Shihab, Mahdi S.; Коновалов, А. И.

doi:10.1016/s0040-4020(99)00697-3

Cited by 11 publications

(9 citation statements)

References 21 publications

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“…In Table 3, the calculated activation volumes ( V # ) of pathway A and pathway B show that the transition states TSBa-1 to TSBa-4 of pathway B are more compact than the respective transition states (TSAa-1 to TSAa-4). The experimental data confirms the relationship for pathway B [36]. Therefore, pathway B is favored for this type of Diels-Alder reaction.…”

Section: Cycloaddition Via Pathway Asupporting

confidence: 84%

“…6. Optimized geometries were calculated using DFT (B3LYP/6-31G*) energies for the rate determining-step of pathway B between diene 1 and 1-hexene using AM1, PM3, HF/3-21G//AM1 and HF/3-21G, were 24.5, 37.9, 23.6 and 23.5 kcal mol −1 respectively (Tables 4, 5 , 6, 9), and are overestimated compared to the experimental value for the activation energy of 8.6 kcal mol −1 (Dioxane) of the same reaction [36]. In contrast, at B3LYP/6-31G*//AM1, B3LYP/6-31G* and MP2//B3LYP/6-31G* levels of theory, the calculated values of the activation energies of the rate determining-step of pathway B between diene (1) and 1-hexene are 13.1, 12.2 and 6.3 kcal mol −1 ( Table 7, 8,10), which are closer to experimental data [17].…”

Section: Cycloaddition Of Pathway Bmentioning

confidence: 77%

“…This was done from the viewpoint of energy by comparing with the experimental data [36,37]. Therefore, the total energy of the structures in pathway B were recalculated by using PM3 (Table 5), and then single point energy calculations were performed using HF/3-21G and DFT (B3LYP/6-31G*) on the optimized geometries obtained from the semiempirical AM1 method (Tables 6 and 7).…”

Section: Cycloaddition Of Pathway Bmentioning

confidence: 99%

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Theoretical Study of the Mechanism of an Inverse-Demand Diels–Alder Reaction

Shihab

2011

Arab J Sci Eng

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Quantum mechanical calculations (AM1, PM3, ab initio HF/3-21G, DFT(B3LYP/6-31G*) and MP2 //(B3LYP/6-31G*) have been used to study the inverse-demand synchronous concerted Diels-Alder reactions between dimethyl-1,2,4,5-tetrazine-3,6-dicarboxylate (diene) and a variety of dienophiles (ethylene, cyclopentadiene, 1-hexene, cyclohexene). All the molecular structures (reactants, transition states, intermediates and adducts) were optimized using the semi-empirical AM1 method. The calculated energies and volumes showed that the cycloaddition reaction followed a mechanism involving the formation of an intermediate, elimination of N 2 , and a 1,3-hydrogen shift adduct. The reaction energies of the systems were obtained by using semi-empirical AM1 calculations and showed good agreement with the experimental data. In contrast, calcula

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Section: Cycloaddition Via Pathway Asupporting

confidence: 84%

Section: Cycloaddition Of Pathway Bmentioning

confidence: 77%

Section: Cycloaddition Of Pathway Bmentioning

confidence: 99%

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Theoretical Study of the Mechanism of an Inverse-Demand Diels–Alder Reaction

Shihab

2011

Arab J Sci Eng

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“…The energy barriers (∆G ‡ b→TS1, kcal/mol), free energy changes between 1 and b (∆G, kcal/mol), and the entropy (kcal mol −1 K −1 ) for each component in the absence of OEEFs. References (46)(47)(48)(49)(50)(51)(52)(53)(54)(55)(56)(57)(58)(59)…”

Section: Dft Calculationmentioning

confidence: 99%

Electric field–induced selective catalysis of single-molecule reaction

et al. 2019

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Oriented external electric fields (OEEFs) offer a unique chance to tune catalytic selectivity by orienting the alignment of the electric field along the axis of the activated bond for a specific chemical reaction; however, they remain a key experimental challenge. Here, we experimentally and theoretically investigated the OEEF-induced selective catalysis in a two-step cascade reaction of the Diels-Alder addition followed by an aromatization process. Characterized by the mechanically controllable break junction (MCBJ) technique in the nanogap and confirmed by nuclear magnetic resonance (NMR) in bottles, OEEFs are found to selectively catalyze the aromatization reaction by one order of magnitude owing to the alignment of the electric field on the reaction axis. Meanwhile, the Diels-Alder reaction remained unchanged since its reaction axis is orthogonal to the electric fields. This orientation-selective catalytic effect of OEEFs reveals that chemical reactions can be selectively manipulated through the elegant alignment between the electric fields and the reaction axis.

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“…At present, there exist a lot of papers on the activation volume and the DAR volume. [16,22,[28][29][30][31][32][33][34][35]119] The reliability of the quantitative data on the rate and equilibrium of this non-polar process, excluding electrostriction, allows one to note that for the non-polar and isopolar processes the contribution of the intermolecular package sufficiently exceeds the change in the van der Waals volume. [16,30,120] In other words, these volume parameters are formed not only by the changes of the own volume of reagents (the change in the van der Waals volume) during the transition to the activated complex or to the adduct, but also due to the change of the volume of the intermolecular package during the reaction in solution.…”

Section: Dars Under Elevated Pressurementioning

confidence: 99%

Internal and external factors influencing the Diels–Alder reaction

Kiselev

Коновалов

2009

J of Physical Organic Chem

Self Cite

112

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The internal and external key factors influencing the reaction rates were considered for the Diels-Alder reaction (DAR) with normal electron demand. A simple dependence lgk 2 ¼ S28.81 R316.3/(IP D SE A )S69.9 R 1-4 /(IP D SE A )S0.054DH r-n for the reaction rate as a function of the ionization potential of p-donor dienes, electron affinity of p-acceptor dienophiles, heat of reaction and diene structure (R 1-4 ) was obtained. This relation allows one to explain the origin of the conventional and 'anomalous' relations between activity and selectivity, and the variety of relationships between the kinetic activity and thermodynamic stability. It helps one to choose the conditions for the directed synthesis of desired products, to explain the acceleration effects in the presence of Lewis acids and to predict the rates of the DAR between the different reagents with C --C bonds not explored earlier.The values of the rate constants were taken from References [13,14,23,24,36,[58][59][60][61][62][63][64][65]; data on IP, E A were taken from References [13,18,56,57,59,62,[66][67][68][69]; data on the enthalpies of reactions were taken from References [24,67,[69][70][71][72]. The values of enthalpies of reactions 81, 82 93 were calculated (Reference [67]) from the data of the heat of formation of reagents and adducts.

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Volume, enthalpy and entropy of activation of the Diels-Alder reaction of dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate with 1-hexene

Cited by 11 publications

References 21 publications

Theoretical Study of the Mechanism of an Inverse-Demand Diels–Alder Reaction

Theoretical Study of the Mechanism of an Inverse-Demand Diels–Alder Reaction

Electric field–induced selective catalysis of single-molecule reaction

Internal and external factors influencing the Diels–Alder reaction

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