Gas‐Phase Synthesis of 3‐Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X2Π) with 1,3‐Butadiene (CH2CHCHCH2; X1Ag)

He, Chao; Zhao, Long; Doddipatla, Srinivas; Thomas, Aaron M.; Nikolayev, Anatoliy A.; Galimova, Galiya R.; Azyazov, Valeriy N.; Mebel, Alexander M.; Kaiser, Ralf I.

doi:10.1002/cphc.202000183

Cited by 7 publications

(1 citation statement)

References 59 publications

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“…Initial recombination of the methylidyne with the propionitrile is barrierless due to high reactivity of the CH radical. [26][27][28][29][30][31][32] It may result in the formation of several initial adducts including w1-w5 and w12. Addition of the methylidyne to the propionitrile's nitrogen atom leads to the formation of w1 (À37.9 kcal/mol relative to the initial reactants).…”

Section: Pesmentioning

confidence: 99%

Reaction of propionitrile with methylidyne: A theoretical study

Krikunova

Nikolayev

Porfiriev

et al. 2022

J Chinese Chemical Soc

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The results of a CCSD(T)‐F12/cc‐pVTZ‐f12//ωB97XD/cc‐pVTZ quantum‐chemical study of the potential energy surface (PES) for the reaction of propionitrile with methylidyne are combined with Rice‐Ramsperger‐Kassel‐Marcus (RRKM) calculations of the reaction rate constants and product branching ratios in the deep space conditions corresponding to the zero‐pressure limit at various collision energies. The most energetically favorable reaction pathways have been identified. The reaction outcome has been shown to strongly depend on the branching in the entrance reaction channel, between CH additions and insertions into various C‐H and C‐C bonds. For instance, CH addition to the N atom predominantly leads to 3H‐pyrrole + H (p9), with CH2NC + C2H4 (p2) also being a significant product. CH addition to the triple C≡N bond mostly results in 2‐methylene‐2H‐azirine + CH3 (p13), whereas CH insertions into C‐H bonds in the CH3 and CH2 groups of propionitrile form CH2CN + C2H4 (p1) and CH2CHCN + CH3 (p7) respectively. Less likely CH insertions into single C‐C bonds yield CH3CHCHCN + H (p5) and CH2CHCH2CN + H (p8). The results indicate that the methylidyne + propionitrile reaction may represent a critical step toward the formation of heterocyclic N‐containing molecules in the interstellar medium and in planetary atmospheres.

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Section: Pesmentioning

confidence: 99%

Reaction of propionitrile with methylidyne: A theoretical study

Krikunova

Nikolayev

Porfiriev

et al. 2022

J Chinese Chemical Soc

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Gas-Phase Formation of C₅H₆ Isomers via the Crossed Molecular Beam Reaction of the Methylidyne Radical (CH; X²Π) with 1,2-Butadiene (CH₃CHCCH₂; X¹A′)

Nikolayev

Zhao

et al. 2021

J. Phys. Chem. A

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The bimolecular gas-phase reaction of the methylidyne radical (CH; X 2 Π) with 1,2-butadiene (CH 2 CCHCH 3 ; X 1 A′) was investigated at a collision energy of 20.6 kJ mol −1 under single collision conditions. Combining our laboratory data with high-level electronic structure calculations, we reveal that this bimolecular reaction proceeds through the barrierless addition of the methylidyne radical to the carbon−carbon double bonds of 1,2-butadiene leading to doublet C 5 H 7 intermediates. These collision adducts undergo a nonstatistical unimolecular decomposition through atomic hydrogen elimination to at least the cyclic 1-vinyl-cyclopropene (p5/p26), 1-methyl-3-methylenecyclopropene (p28), and 1,2-bis(methylene)cyclopropane (p29) in overall exoergic reactions. The barrierless nature of this bimolecular reaction suggests that these cyclic C 5 H 6 isomers might be viable targets to be searched for in cold molecular clouds like TMC-1.

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Aromatic Formation Promoted by Ion-Driven Radical Pathways in EUV Photochemical Experiments Simulating Titan’s Atmospheric Chemistry

et al. 2021

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In the atmosphere of Titan, Saturn's main satellite, molecular growth is initiated by 85.6 nm-Extreme UltraViolet (EUV) photons triggering a chemistry with charged and free-radical species. However, the respective contribution of these species to the complexification of matter is far from being known. This work presents a chemical analysis in order to contribute to a better understanding of aromatic formation pathways. A gas mixture N 2 /CH 4 (90/10 %) within the closed SURFACAT reactor was irradiated at relatively low pressure (0.1 mbar) and room temperature for six hours by EUV photons (∼ 85.6 nm). The neutral molecules formed at the end of the irradiation were condensed in a cryogenic trap and analyzed by electron ionization mass spectrometry. An analysis of the dominant chemical pathways highlights the identification of benzene and toluene and underlies the importance of small ion and radical reactions. On the basis of the experimental results, a speculative mechanism based on sequential Helimination/CH 3 -addition reactions is proposed for the growth of aromatics in Titan's atmosphere. Elementary reactions to be studied are given to instill future updates of photochemical models of Titan's atmosphere.

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Gas‐Phase Synthesis of 3‐Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X²Π) with 1,3‐Butadiene (CH₂CHCHCH₂; X¹A_g)

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 7 publications

References 59 publications

Reaction of propionitrile with methylidyne: A theoretical study

Reaction of propionitrile with methylidyne: A theoretical study

Gas-Phase Formation of C₅H₆ Isomers via the Crossed Molecular Beam Reaction of the Methylidyne Radical (CH; X²Π) with 1,2-Butadiene (CH₃CHCCH₂; X¹A′)

Aromatic Formation Promoted by Ion-Driven Radical Pathways in EUV Photochemical Experiments Simulating Titan’s Atmospheric Chemistry

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Gas‐Phase Synthesis of 3‐Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X2Π) with 1,3‐Butadiene (CH2CHCHCH2; X1Ag)

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 7 publications

References 59 publications

Reaction of propionitrile with methylidyne: A theoretical study

Reaction of propionitrile with methylidyne: A theoretical study

Gas-Phase Formation of C5H6 Isomers via the Crossed Molecular Beam Reaction of the Methylidyne Radical (CH; X2Π) with 1,2-Butadiene (CH3CHCCH2; X1A′)

Aromatic Formation Promoted by Ion-Driven Radical Pathways in EUV Photochemical Experiments Simulating Titan’s Atmospheric Chemistry

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Gas‐Phase Synthesis of 3‐Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X²Π) with 1,3‐Butadiene (CH₂CHCHCH₂; X¹A_g)

Gas-Phase Formation of C₅H₆ Isomers via the Crossed Molecular Beam Reaction of the Methylidyne Radical (CH; X²Π) with 1,2-Butadiene (CH₃CHCCH₂; X¹A′)