First carbon ring closures started by the combustive radical addition of propargyl to butadiyne. A theoretical study

Maranzana, Andrea; Indarto, Antonius; Ghigo, Giovanni; Tonachini, Glauco

doi:10.1016/j.combustflame.2013.05.024

Cited by 16 publications

(1 citation statement)

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“…Another example of resonance-stabilized radicals involving a five-membered ring is the fulvenallenyl (C 7 H 5 ) radicals. , The fulvenallenyl radicals are produced from the C 7 H 6 species, fulvenallene and ethynylcyclopentadienes, which can be generated from multiple reaction pathways including the decomposition of benzyl radicals and their isomers, − the reaction of cyclopentadienyl radicals with acetylene, ,, the reaction of propargyl radicals with diacetylene, − and other C 5 + C 2 and C 4 + C 3 reactions. ,,, Although there have been only a few studies reporting the detection of C 7 H 5 species in flame environment or pyrolysis experiments, ,,, the parent C 7 H 6 molecules including fulvenallene have been more widely observed. ,,,− Since the fulvenallenyl radicals can be readily formed from fulvenallene by the hydrogen atom abstraction or thermal decomposition reactions at high temperatures, their potential roles in combustion and molecular growth chemistry warrant detailed investigation.…”

Section: Introductionmentioning

confidence: 99%

Ring Growth Mechanism in the Reaction between Fulvenallenyl and Cyclopentadienyl Radicals

Matsugi,

Suzuki

2024

J. Phys. Chem. A

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Recombination between resonance-stabilized hydrocarbon radicals is an important class of reactions that contribute to molecular growth chemistry in combustion. In the present study, the ring growth mechanism in the reaction between fulvenallenyl (C 7 H 5 ) and cyclopentadienyl (C 5 H 5 ) radicals is investigated computationally. The reaction pathways are explored by quantum chemical calculations, and the phenomenological and steady-state rate constants are determined by solving the multiplewell master equations. The primary reaction routes following the recombination between the two radicals are found to be as follows: formation of the adducts, isomerization by hydrogen shift reactions, cyclization to form tricyclic compounds, and their isomerization and dissociation reactions, leading to the formation of acenaphthylene. The overall process can be approximately represented as C 7 H 5 + C 5 H 5 → acenaphthylene + 2H with the bimolecular rate constant of about 4 × 10 −12 cm 3 molecule −1 s −1 . A reaction mechanism consisting of 20 reactions, including the formation, isomerization, and dissociation processes of major intermediate species, is proposed for use in kinetic modeling.

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