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Title: Crossed Beam Reactions of the Phenyl (C6H5; X2A1) and Phenyl-d5 Radical (C6D5; X2A1) with 1,2-Butadiene (H2CCCHCH3; X1A')

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
DOI: https://doi.org/10.1021/jp411642w · OSTI ID:1602786
 [1];  [1];  [1];  [1];  [2];  [2]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  2. Florida International Univ., Miami, FL (United States)

We investigated the reactions on the phenyl (C6H5; X2A1) and phenyl-d5 (C6D5; X2A1) radical with 1,2-butadiene (C4H6; X1A') at a collision energy of about 52 ± 3 kJ mol–1 in a crossed molecular beam apparatus. The reaction of phenyl with 1,2-butadiene is initiated by adding the phenyl radical with its radical center to the π electron density at the C1/C3 carbon atom of 1,2-butadiene. Later, the initial collision complexes isomerize via phenyl group migration from the C1/C3 carbon atoms to the C2 carbon atom of the allene moiety of 1,2-butadiene. The resulting intermediate undergoes unimolecular decomposition through hydrogen atom emission from the methyl group of the 1,2-butadiene moiety via a rather loose exit transition state leading to 2-phenyl-1,3-butadiene in an overall exoergic reaction (ΔRG = -72 ± 10 kJ mol–1). This result reveals the strong collision-energy dependence of this system when the data are compared with those of the phenyl radical with 1,2-butadiene previously recorded at collision energies up to 160 kJ mol–1, with the previous study exhibiting the thermodynamically less stable 1-phenyl-3-methylallene (ΔRG = -33 ± 10 kJ mol–1) and 1-phenyl-2-butyne (ΔRG = -24 ± 10 kJ mol–1) to be the dominant products.

Research Organization:
Univ. of Hawaii, Honolulu, HI (United States); Florida International Univ. (FIU), Miami, FL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-03ER15411; FG02-04ER15570
OSTI ID:
1602786
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 118, Issue 25; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

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