- The Open-Chain Trioxide CF3OC(O)OOOC(O)OCF3
-
The open-chain trioxide CF3OC(O)OOOC(O)OCF3 is synthesised by a photochemical reaction of CF3C(O)OC(O)CF 3, CO and O2 under a low-pressure mercury lamp at -40°C. The isolated trioxide is a colourless solid at -40°C and is characterised by IR, Raman, UV and NMR spectroscopy. The compound is thermally stable up to -30°C and decomposes with a half-life of 1 min at room temperature. Between -15 and +14°C the activation energy for the dissociation is 86.5 kJ mol-1 (20.7 kcal mol-1). Quantum chemical calculations have been performed to support the vibrational assignment and to discuss the existence of rotamers.
- Von Ahsen, Stefan,Garcia, Placido,Willner, Helge,Paci, Maximiliano Burgos,Argueello, Gustavo A.
-
-
Read Online
- The reaction of photochemically generated CF3O radicals with CO
-
CF3O2CF3 was photolyzed at 254 nm in the presence of CO in 760 torr N2 or air at 296 K in a static reactor. In N2, the products CF3OC(O)C(O)OCF3 and CF3OC(O)O2C(O)OCF3 were detected by FTIR spectroscopy. In air, the only observed products were CF2O and CO2 and a chain process, initiated by CF3O, was invoked for the conversion of CO to CO2. From both product studies, a mechanism for the CF3O initiated oxidation of CO was derived, involving the addition reaction CF3O2 + CO → CF3OC(O). The rate constant for the reaction CF3O + CO at 296 K at a total pressure of 760 torr air was determined to be k(CF3O + CO) = (5.0 ± 0.9) ± 10-14 cm3 molecule-1 s-1.
- Meller, Richard,Moortgat, Geert K.
-
p. 579 - 587
(2007/10/03)
-