Crossed Beam Reactions of the Phenyl (C6H5; X2A1) and Phenyl-d5 Radical (C6D5; X2A1) with 1,2-Butadiene (H2CCCHCH3; X1A′)
| Autor: | Beni B. Dangi, Alexander M. Mebel, Tao Yang, Dorian S. N. Parker, Vadim V. Kislov, Ralf I. Kaiser |
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| Rok vydání: | 2014 |
| Předmět: | |
| Zdroj: | The Journal of Physical Chemistry A. 118:4372-4381 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp411642w |
| Popis: | We explored 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 finding 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 energi... |
| Databáze: | OpenAIRE |
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