The quinones of bicyclo[3.1.0]hexatriene: A computational study of their chemistry and thermochemistry

Kayembe, Aimé; Lewars, Errol G.; Liebman, Joel F.

doi:10.1016/j.jct.2012.03.007

Cited by 3 publications

(2 citation statements)

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“…The possible pathways are as follows: One is along with the singlet-state pathway following the formation of M6 (Singlet) ; the other is along with the triplet-state pathway following the formation of m -benzoquinone M6 . Kayembe et al theoretically determined the most stable bicyclo[3.1.0]quinone generated from singlet-ground state m -benzoquinone M6 (Singlet) ; while using the B3LYP/6-311+G(2d,p) method, Roithová et al considered the reaction pathways for the decarbonylation of m -benzoquinone that lead to CO release. By applying these theoretical approaches in identifying the thermal decomposition routes for CO release, we proposed the singlet-state pathway (pathways 4, Scheme ) leading to CO formation.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Study on Reaction Pathways Leading to CO and CO₂ in the Pyrolysis of Resorcinol

et al. 2017

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Possible pathways for the pyrolysis of resorcinol with the formation of CO and CO as final products were proposed and evaluated using ab initio calculations. Our experimental study revealed that large quantities of CO are generated in the pyrolysis of 1,3-dihydroxybenzene (resorcinol), while the pyrolysis of the dihydroxybenzene isomers 1,2-dihydroxybenzene (catechol) and 1,4-dihydroxybenzene (hydroquinone) produces little CO. The fate of oxygen atoms in catechol and hydroquinone was essentially the formation of CO. In the proposed pathways, the triplet ground state m-benzoquinone was generated initially from simultaneous cleavage of the two O-H bonds in resorcinol. Subsequently, the direct cleavage of a C-C bond of the m-benzoquinone diradical yields 2-oxidanylcyclopenta-2,4-dien-1-yl-methanone, which can be converted via two channels: release of CO from the aldehyde radical group and combination of the ketone radical and carbon atom in the aldehyde radical group to form the 6-oxabicyclo[3.2.0]hepta-2,4-dien-7-one, resulting in the release of CO. Potential energy surfaces along the proposed reaction pathways were calculated employing the CBS-QB3 method, and the rate constants at the high-pressure limit were also evaluated based on transition-state theory to assess the feasibility of the proposed reaction pathways.

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Section: Resultsmentioning

confidence: 99%

Theoretical Study on Reaction Pathways Leading to CO and CO₂ in the Pyrolysis of Resorcinol

et al. 2017

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“…BLYP/6-31G* was checked because of its useful performance with the potentially diradical 1,3-benzyne 4 and this benzyne's quinones. 19 PBE0/cc-pVTZ was examined because with the calculationally demanding oxirene system, it gave results very close to those from "expensive" high-level ab initio calculations 20 (in Gaussian 09, this functional is specified as PBE1PBE). 21 B3LYP is probably still the most popular functional, not without reason, 22 and was thus deemed worthy of a try.…”

Section: Methodsmentioning

confidence: 99%

The chemistry of bowtiene (tricyclo[5.3.0.0^2,6]decapentaene): a computational study

LewarsErrol

2014

Can. J. Chem.

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Reactions of bowtiene (tricyclo[5.3.0.0 2,6 ]decapentaene, cyclobuta [1,2:3,4]dicyclopentene, bicyclopentadienylene, a tricyclic analogue of [10]annulene), in the sphere of unimolecular decomposition and dimerization were studied computationally to gauge its stability and reactivity, which are relevant to its feasability as a synthetic goal. The intuitively likeliest rearrangement mode to give species of lower energy begins with rearrangement to the 1,5-dehydronaphthalene diradical; this was calculated to have a barrier of approximately 220 kJ mol −1 , too high for reaction at room temperature. Nevertheless, the energetics of rearrangement of the 1,5-diradical to the monocyclic 1,6-didehydro[10]annulene, a species of interest regarding its relationship to bowtiene and the diradical, were studied. The energy of bowtiene was compared with that of several other tricyclic 10 C 10 H 6 cyclic polyenes. Résumé :Réactions du bowtiene (tricyclo[5.3.0.0 2,6 ]décapentaene, cyclobuta[1,2:3,4]dicyclopentène, bicyclopentadienylène, analogue tricyclique du [10]annulène), dans le cadre d'une décomposition unimoléculaire et d'une dimérisation, ont été étudiées par des calculs afin de mesurer la stabilité et la réactivité de ce composé, qui sont liés à l'objectif visé de la faisabilité d'une synthèse. Le mode de réarrangement instinctivement le plus susceptible de générer des espèces de plus basse énergie commence est d'abord le réarrangement sous forme du diradical 1,5-déhydronaphthalène; les calculs ont montré que la barrière de ce réarrangement était d'environ 220 kJ mol −1 , une valeur trop élevée pour permettre une réaction à la température ambiante. Cependant, le profil énergétique du réarrangement du 1,5-diradical sous forme de 1,6-didéhydro[10]annulène monocyclique, une espèce intéressante du point de vue de son lien avec le bowtiene et le diradical, a été étudié. L'énergie du bowtiene a été comparée avec celle des plusieurs autres polyènes 10 C 10 H 6 tricycliques. [Traduit par la Rédaction] Mots-clés : bowtiene, tricyclo[5.3.0.0 2,6 ]décapentaene, calculs de théorie de la fonctionnelle de la densité (DFT), stabilité, rearrangement.

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Thermal stability of phenolic resin: new insights based on bond dissociation energy and reactivity of functional groups

et al. 2016

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The quinones of bicyclo[3.1.0]hexatriene: A computational study of their chemistry and thermochemistry

Cited by 3 publications

References 68 publications

Theoretical Study on Reaction Pathways Leading to CO and CO₂ in the Pyrolysis of Resorcinol

Theoretical Study on Reaction Pathways Leading to CO and CO₂ in the Pyrolysis of Resorcinol

The chemistry of bowtiene (tricyclo[5.3.0.0^2,6]decapentaene): a computational study

Thermal stability of phenolic resin: new insights based on bond dissociation energy and reactivity of functional groups

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The quinones of bicyclo[3.1.0]hexatriene: A computational study of their chemistry and thermochemistry

Cited by 3 publications

References 68 publications

Theoretical Study on Reaction Pathways Leading to CO and CO2 in the Pyrolysis of Resorcinol

Theoretical Study on Reaction Pathways Leading to CO and CO2 in the Pyrolysis of Resorcinol

The chemistry of bowtiene (tricyclo[5.3.0.02,6]decapentaene): a computational study

Thermal stability of phenolic resin: new insights based on bond dissociation energy and reactivity of functional groups

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Theoretical Study on Reaction Pathways Leading to CO and CO₂ in the Pyrolysis of Resorcinol

Theoretical Study on Reaction Pathways Leading to CO and CO₂ in the Pyrolysis of Resorcinol

The chemistry of bowtiene (tricyclo[5.3.0.0^2,6]decapentaene): a computational study