Formation of fulvene in the reaction of C2H with 1,3-butadiene - Archive ouverte HAL Access content directly
Journal Articles International Journal of Mass Spectrometry Year : 2015

Formation of fulvene in the reaction of C2H with 1,3-butadiene

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Abstract

Products formed in the reaction of C2H radicals with 1,3-butadiene at 4 Torr and 298 K are probed using photoionization time-of-flight mass spectrometry. The reaction takes place in a slow-flow reactor, and products are ionized by tunable vacuum-UV light from the Advanced Light Source. The principal reaction channel involves addn. of the radical to one of the unsatd. sites of 1,3-butadiene, followed by H-loss to give isomers of C6H6. The photoionization spectrum of the C6H6 product indicates that fulvene is formed with a branching fraction of (57 ± 30)%. At least one more isomer is formed, which is likely to be one or more of 3,4-dimethylenecyclobut-1-ene, 3-methylene-1-penten-4-yne or 3-methyl-1,2-pentadien-4-yne. An exptl. photoionization spectrum of 3,4-dimethylenecyclobut-1-ene and simulated photoionization spectra of 3-methylene-1-penten-4-yne and 3-methyl-1,2-pentadien-4-yne are used to fit the measured data and obtain max. branching fractions of 74%, 24% and 31%, resp., for these isomers. An upper limit of 45% is placed on the branching fraction for the sum of benzene and 1,3-hexadien-5-yne. The reactive potential energy surface is also investigated computationally. Min. and first-order saddle-points on several possible reaction pathways to fulvene + H and 3,4-dimethylenecyclobut-1-ene + H products are calcd. [on SciFinder(R)]

Dates and versions

hal-01069616 , version 1 (29-09-2014)

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Jessica F. Lockyear, Martin Fournier, Ian R. Sims, Jean-Claude Guillemin, Craig A. Taatjes, et al.. Formation of fulvene in the reaction of C2H with 1,3-butadiene. International Journal of Mass Spectrometry, 2015, 378, pp.232-245. ⟨10.1016/j.ijms.2014.08.025⟩. ⟨hal-01069616⟩
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