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

Yang, Tao; Parker, Dorian S.  N.; Dangi, Beni B.; Kaiser, Ralf I.; Kislov, Vadim V.; Mebel, Alexander M.

doi:10.1021/jp411642w

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

Journal Article · Mon Jun 02 00:00:00 EDT 2014 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/jp411642w· OSTI ID:1602786

Yang, Tao ^[1]; Parker, Dorian S. N. ^[2]; Dangi, Beni B. ^[2]; Kaiser, Ralf I. ^[2]; Kislov, Vadim V. ^[3]; Mebel, Alexander M. ^[3]

Univ. of Hawaii at Manoa, Honolulu, HI (United States); University of Hawaii at Manoa
Univ. of Hawaii at Manoa, Honolulu, HI (United States)
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 (Δ_RG = -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 (Δ_RG = -33 ± 10 kJ mol^–1) and 1-phenyl-2-butyne (Δ_RG = -24 ± 10 kJ mol^–1) to be the dominant products.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Hawaii, Honolulu, HI (United States); Florida International Univ., Miami, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-03ER15411; FG02-04ER15570

OSTI ID:: 1602786

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 25 Vol. 118; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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