Argon matrix infrared spectra of CF3OOF and CF3OOOCF3 and their photolysis products. Spectroscopic evidence for the CF3OO radical

Abstract

Ultraviolet photolysis of fluoroperoxytrifluoromethane, CF₃OOF, in argon matrices at 8 °K produced CF₄ and a new species, tentatively identified as the CF₃OO radical, with infrared absorptions at 1173.7 and 1094.1 cm⁻¹. This species was also produced, along with CF₄, CF₃OCF₃, and COF₂, by photolysis of bistrifluoromethyl trioxide, CF₃OOOCF₃, at wavelengths below 300 nm. In the latter case, extensive isotopic labeling experiments with CF₃ ¹⁶O¹⁶O¹⁶OCF₃, CF₃ ¹⁶O¹⁸O¹⁶OCF₃, CF₃ ¹⁸O¹⁶O¹⁸OCF₃, and CF₃ ¹⁸O¹⁸O¹⁸OCF₃ led to the observation of four distinct isotopic absorptions for the O–O stretching vibration (1094.1 cm), thus confirming the nonequivalent oxygen atom structure of CF₃OO.