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.

Fluorinated Peroxides

“…Photolysis of an argon matrix sample of CF 3 OOF at 8 K affords CF 4 and the CF 3 OO radical. The formation of CF 4 is believed to occur by a concerted intramolecular process in which the O−F and C−O bonds are broken along with the simultaneous formation of a C−F bond and molecular oxygen …”

“…Bis(trifluoromethyl) trioxide photodissociates to produce CF 3 OCF 3 , CF 4 , COF 2 , and the CF 3 OO radical as the predominant infrared observable products …”

van der Waals Complexes between Carbonyl Fluoride and Boron Trifluoride Observed in Liquefied Argon, Krypton, and Nitrogen: A FTIR and ab Initio Study

“…In the present paper we report the data on complexation of carbonyl fluoride, COF 2 , with boron trifluoride, BF 3 . Intermolecular interactions involving carbonyl fluoride are of interest since this compound is believed to be one of the intermediates in the photodecomposition of chlorofluorocarbons in the stratosphere. , Another motivation of the study is that COF 2 is often observed in matrix-isolation infrared experiments as a product of photolysis of various fluorine-containing compounds. − Since the formation of COF 2 is sometimes accompanied by its complexation, , knowledge of structures and energies of plausible complexes is important for interpreting the observed spectra. In addition, it may be noted that COF 2 is one of the simplest asymmetric top molecules which has been widely used for testing various theoretical models of vibrational spectroscopy. − It appears interesting to correlate the complexation effect on vibrational spectra with some of the theoretical predictions.…”

“…18,19 Another motivation of the study is that COF 2 is often observed in matrix-isolation infrared experiments as a product of photolysis of various fluorine-containing compounds. [20][21][22][23] Since the formation of COF 2 is sometimes accompanied by its complexation, 21,22 knowledge of structures and energies of plausible complexes is important for interpreting the observed spectra. In addition, it may be noted that COF 2 is one of the simplest asymmetric top molecules which has been widely used for testing various theoretical models of vibrational spectroscopy.…”

Methoxysulfinyl Radical CH3OSO: Gas-Phase Generation, Photochemistry, and Oxidation

“…Nearly 60% of CF 3 S­(O)­OCH 3 decomposes at 1000 K. As a result, CF 3 (b, 1249.8, 1083.7, 700.9 cm –1 ), SO 2 (d, 1351.5, 1152.6 cm –1 ), CH 3 (e, 611.1 cm –1 ), F 2 CO (f, 1940.2, 1912.6 cm –1 ), and H 2 CO (g, 1737.6 cm –1 ) were identified by IR spectroscopy. Additionally, a few new IR bands (c, Figure B) at 2958.7, 1464.0, 1145.9, 985.7, and 713.5 cm –1 were observed.…”