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Matrix Isolation and Spectroscopic Characterization of the Phenylperoxy Radical and Its Rearranged Products
Author(s) -
Mardyukov Artur,
Sander Wolfram
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200801546
Subject(s) - isotopomers , matrix isolation , radical , chemistry , photochemistry , conformational isomerism , argon , infrared spectroscopy , irradiation , spectroscopy , ring (chemistry) , matrix (chemical analysis) , medicinal chemistry , organic chemistry , molecule , chromatography , quantum mechanics , physics , nuclear physics
Abstract The phenylperoxy radical 1 has been synthesized by the reaction of the phenyl radical 2 with 3 O 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 16 O 2 and with 18 O 2 , respectively, the four isotopomers [H 5 ]‐ 16 O 2 ‐ 1 , [D 5 ]‐ 16 O 2 ‐ 1 , [H 5 ]‐ 18 O 2 ‐ 1 , and [D 5 ]‐ 18 O 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.