Gas–Phase Synthesis of 3–Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X2Π) with 1,3–Butadiene (CH2CHCHCH2; X1Ag)
Abstract
The crossed molecular beam reactions of the methylidyne radical (CH; X2Π) with 1,3-butadiene (CH2CHCHCH2; X1Ag) along with their (partially) deuterated counterparts were performed at collision energies of 20.8 kJ mol-1 under single collision conditions. Combining our laboratory data with ab initio calculations, we reveal that the methylidyne radical may add barrierlessly to the terminal carbon atom and/or carbon-carbon double bond of 1,3-butadiene, leading to doublet C5H7 intermediates with life times longer than the rotation periods. Furthermore, these collision complexes undergo non-statistical unimolecular decomposition through hydrogen atom emission yielding the cyclic cis- and trans-3-vinyl-cyclopropene products with reaction exoergicities of 119±42 kJ mol-1. Since this reaction is barrierless, exoergic, and all transition states are located below the energy of the separated reactants, these cyclic C5H6 products are predicted to be accessed even in low-temperature environments, such as in hydrocarbon-rich atmospheres of planets and cold molecular clouds such as TMC-1.
- Authors:
-
[1];
[5];
[1]
- University of Hawai'i at Manoa, Honolulu, HI (United States)
- Samara National Research University (Russia)
- Samara National Research University (Russia); Florida International University, Miami, FL (United States)
- Samara National Research University (Russia); Lebedev Physical Institute, Samara (Russia)
- Florida International University, Miami, FL (United States)
- Publication Date:
- Research Org.:
- University of Hawai'i at Manoa, Honolulu, HI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Science and Higher Education of the Russian Federation
- OSTI Identifier:
- 1657228
- Alternate Identifier(s):
- OSTI ID: 1630685
- Grant/Contract Number:
- FG02-03ER15411; FG02‐04ER15570; 14.Y26.31.0020; FG02-04ER15570
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemPhysChem
- Additional Journal Information:
- Journal Volume: 21; Journal Issue: 12; Journal ID: ISSN 1439-4235
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; gas-phase chemistry; reaction dynamics; reaction intermediates; single-collision conditions; 3-vinylcyclopropene
Citation Formats
He, Chao, Zhao, Long, Doddipatla, Srinivas, Thomas, Aaron M., Nikolayev, Anatoliy A., Galimova, Galiya R., Azyazov, Valeriy N., Mebel, Alexander M., and Kaiser, Ralf I. Gas–Phase Synthesis of 3–Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X2Π) with 1,3–Butadiene (CH2CHCHCH2; X1Ag). United States: N. p., 2020.
Web. doi:10.1002/cphc.202000183.
He, Chao, Zhao, Long, Doddipatla, Srinivas, Thomas, Aaron M., Nikolayev, Anatoliy A., Galimova, Galiya R., Azyazov, Valeriy N., Mebel, Alexander M., & Kaiser, Ralf I. Gas–Phase Synthesis of 3–Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X2Π) with 1,3–Butadiene (CH2CHCHCH2; X1Ag). United States. https://doi.org/10.1002/cphc.202000183
He, Chao, Zhao, Long, Doddipatla, Srinivas, Thomas, Aaron M., Nikolayev, Anatoliy A., Galimova, Galiya R., Azyazov, Valeriy N., Mebel, Alexander M., and Kaiser, Ralf I. Tue .
"Gas–Phase Synthesis of 3–Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X2Π) with 1,3–Butadiene (CH2CHCHCH2; X1Ag)". United States. https://doi.org/10.1002/cphc.202000183. https://www.osti.gov/servlets/purl/1657228.
@article{osti_1657228,
title = {Gas–Phase Synthesis of 3–Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X2Π) with 1,3–Butadiene (CH2CHCHCH2; X1Ag)},
author = {He, Chao and Zhao, Long and Doddipatla, Srinivas and Thomas, Aaron M. and Nikolayev, Anatoliy A. and Galimova, Galiya R. and Azyazov, Valeriy N. and Mebel, Alexander M. and Kaiser, Ralf I.},
abstractNote = {The crossed molecular beam reactions of the methylidyne radical (CH; X2Π) with 1,3-butadiene (CH2CHCHCH2; X1Ag) along with their (partially) deuterated counterparts were performed at collision energies of 20.8 kJ mol-1 under single collision conditions. Combining our laboratory data with ab initio calculations, we reveal that the methylidyne radical may add barrierlessly to the terminal carbon atom and/or carbon-carbon double bond of 1,3-butadiene, leading to doublet C5H7 intermediates with life times longer than the rotation periods. Furthermore, these collision complexes undergo non-statistical unimolecular decomposition through hydrogen atom emission yielding the cyclic cis- and trans-3-vinyl-cyclopropene products with reaction exoergicities of 119±42 kJ mol-1. Since this reaction is barrierless, exoergic, and all transition states are located below the energy of the separated reactants, these cyclic C5H6 products are predicted to be accessed even in low-temperature environments, such as in hydrocarbon-rich atmospheres of planets and cold molecular clouds such as TMC-1.},
doi = {10.1002/cphc.202000183},
journal = {ChemPhysChem},
number = 12,
volume = 21,
place = {United States},
year = {Tue Apr 14 00:00:00 EDT 2020},
month = {Tue Apr 14 00:00:00 EDT 2020}
}
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