On the formation of phenyldiacetylene (C6H5CCCCH) and D5-phenyldiacetylene (C6D5CCCCH) studied under single collision conditions
Literature Information
D. S. N. Parker, F. Zhang, Y. S. Kim, R. I. Kaiser, A. Landera, A. M. Mebel
The crossed molecular beam reactions of the phenyl and D5-phenyl radical with diacetylene (C4H2) was studied under single collision conditions at a collision energy of 46 kJ mol−1. The chemical dynamics were found to be indirect and initiated by an addition of the phenyl/D5-phenyl radical with its radical center to the C1-carbon atom of the diacetylene reactant. This process involved an entrance barrier of 4 kJ mol−1 and lead to a long lived, bound doublet radical intermediate. The latter emitted a hydrogen atom directly or after a few isomerization steps via tight exit transition states placed 20–21 kJ mol−1 above the separated phenyldiacetylene (C6H5CCCCH) plus atomic hydrogen products. The overall reaction was determined to be exoergic by about 49 ± 26 kJ mol−1 and 44 ± 10 kJ mol−1 as determined experimentally and computationally, thus representing a feasible pathway to the formation of the phenyldiacetylene molecule in combustion flames of hydrocarbon fuel.
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Physical Chemistry Chemical Physics

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