Abstract
A combination of matrix isolation and FTIR spectroscopy was applied to investigate 1,1,1-trifluoro-2-chloroethyl ( 1) and 1,1,1-trifluoro-2-chloroethylperoxyl ( 2) radicals. Radical 2 was obtained by vacuum pyrolysis of 1,1,1-trifluoro-2-bromo-2-chloroethane ( 3). Corresponding peroxyl radicals was generated by co-condensation of pyrolysis products and molecular oxygen in an argon matrix. To assign the experimental bands DFT calculations (B3LYP/6–311G**) were carried out. The fundamental bands of O–O and C–O stretching vibrations of peroxyl radical CF 3CHClOO (1102.1, 972.7, cm −1) were identified by their red shifts to 1044.7 and 954.1 cm −1 in the spectra of 18O substituted derivatives. UV photolysis of the radical 2 in the low-temperature matrix produced difluoroformaldehyde CF 2O, radicals ClCO, CF 3, as well as CO and HCl as the primary photoproducts.
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