期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 15, 期 6, 页码 1462-1467出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200801546
关键词
IR spectroscopy; matrix isolation; phenoxyl radical; phenyl radical; radicals
资金
- Deutsche Forschungsgemeinschaft
- Fond der Chernischen Industrie
The phenylperoxy radical 1 has been synthesized by the reaction of the phenyl radical 2 with O-3(2). Radical 1 could be either generated in the gas phase and subsequently trapped in solid argon at 10 K, or directly synthesized in argon matrices. By reacting 2 as well as its perdeuterated isotopomer [D-5]-2 with O-16(2) and with O-18(2), respectively, the four isotopomers [H-5]-O-16(2)-1, [D-5]-O-16(2)-1 [H-5]-O-18(2)-1, and [D-5]-O-18(2)-1 were matrix-isolated and characterized by IR spectroscopy. The experimental IR spectra are in excellent agreement with results from DFT calculations. Irradiation of 1. with visible light produces the 2-oxepinoxy radical 5 in a clean reaction. Subsequent irradiation results in ring-opening and formation of several conformers of ketoketene 6. The radicals 1, 5, and 6 play an important role in the combustion of aromatic hydrocarbons and could now be isolated and spectroscopically characterized for the first time.
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