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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')

Abstract

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.

Authors:
 [1];  [1];  [1];  [1];  [2];  [2]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  2. Florida International Univ., Miami, FL (United States)
Publication Date:
Research Org.:
Univ. of Hawaii, Honolulu, HI (United States); Florida International Univ., Miami, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1602786
Grant/Contract Number:  
FG02-03ER15411; FG02-04ER15570
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 118; Journal Issue: 25; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yang, Tao, Parker, Dorian S. N., Dangi, Beni B., Kaiser, Ralf I., Kislov, Vadim V., and Mebel, Alexander M.. Crossed Beam Reactions of the Phenyl (C6H5; X2A1) and Phenyl-d5 Radical (C6D5; X2A1) with 1,2-Butadiene (H2CCCHCH3; X1A'). United States: N. p., 2014. Web. https://doi.org/10.1021/jp411642w.
Yang, Tao, Parker, Dorian S. N., Dangi, Beni B., Kaiser, Ralf I., Kislov, Vadim V., & Mebel, Alexander M.. Crossed Beam Reactions of the Phenyl (C6H5; X2A1) and Phenyl-d5 Radical (C6D5; X2A1) with 1,2-Butadiene (H2CCCHCH3; X1A'). United States. https://doi.org/10.1021/jp411642w
Yang, Tao, Parker, Dorian S. N., Dangi, Beni B., Kaiser, Ralf I., Kislov, Vadim V., and Mebel, Alexander M.. Mon . "Crossed Beam Reactions of the Phenyl (C6H5; X2A1) and Phenyl-d5 Radical (C6D5; X2A1) with 1,2-Butadiene (H2CCCHCH3; X1A')". United States. https://doi.org/10.1021/jp411642w. https://www.osti.gov/servlets/purl/1602786.
@article{osti_1602786,
title = {Crossed Beam Reactions of the Phenyl (C6H5; X2A1) and Phenyl-d5 Radical (C6D5; X2A1) with 1,2-Butadiene (H2CCCHCH3; X1A')},
author = {Yang, Tao and Parker, Dorian S. N. and Dangi, Beni B. and Kaiser, Ralf I. and Kislov, Vadim V. and Mebel, Alexander M.},
abstractNote = {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.},
doi = {10.1021/jp411642w},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 25,
volume = 118,
place = {United States},
year = {2014},
month = {6}
}

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