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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)

Journal Article · · ChemPhysChem
 [1];  [2];  [2];  [2];  [3];  [4];  [5];  [6];  [2]
  1. University of Hawai'i at Manoa, Honolulu, HI (United States); University of Hawaii at Manoa, Department of Chemistry
  2. University of Hawai'i at Manoa, Honolulu, HI (United States)
  3. Samara National Research University (Russia)
  4. Samara National Research University (Russia); Florida International University, Miami, FL (United States)
  5. Samara National Research University (Russia); Lebedev Physical Institute, Samara (Russia)
  6. Florida International University, Miami, FL (United States)
+ Show Author Affiliations

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.

Research Organization:
University of Hawai'i at Manoa, Honolulu, HI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Science and Higher Education of the Russian Federation
Grant/Contract Number:
FG02-03ER15411; FG02-04ER15570
OSTI ID:
1657228
Alternate ID(s):
OSTI ID: 1630685
Journal Information:
ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 12 Vol. 21; ISSN 1439-4235
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

3-vinylcyclopropene
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
gas-phase chemistry
reaction dynamics
reaction intermediates
single-collision conditions