Crossed beam reaction of phenyl radicals with unsaturated hydrocarbon molecules. I. Chemical dynamics of phenylmethylacetylene (C6H5CCCH3;X 1A′) formation from reaction of C6H5(X 2A1) with methylacetylene, CH3CCH(X 1A1)
| Autor: | P. v. R. Schleyer, Henry F. Schaefer, Y. T. Lee, Holger F. Bettinger, Oskar Asvany, Ralf I. Kaiser |
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| Rok vydání: | 2000 |
| Předmět: | |
| Zdroj: | Scopus-Elsevier |
| ISSN: | 1089-7690 0021-9606 |
| Popis: | The chemical reaction dynamics to form phenylmethylacetylene, C6H5CCCH3(X 1A′), via reactive collisions of the phenyl radical C6H5(X 2A1) with methylacetylene, CH3CCH(X 1A1), are unraveled under single collision conditions in a crossed molecular beam experiment at a collision energy of 140 kJ mol−1. The laboratory angular distribution and time-of-flight spectra of C9H8+ at m/e=116 indicate the existence of a phenyl radical versus hydrogen replacement pathway. Partially deuterated methylacetylene, CH3CCD(X 1A1), was used to identify the site of the carbon–hydrogen bond cleavage. Only the loss of the acetylenic hydrogen atom was observed; the methyl group is conserved in the reaction. Electronic structure calculations reveal that the reaction has an entrance barrier of about 17 kJ mol−1. Forward-convolution fitting of our data shows that the chemical reaction dynamics are on the boundary between an osculating complex and a direct reaction and are governed by an initial attack of the C6H5 radical to the π el... |
| Databáze: | OpenAIRE |
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