The Open‐Chain Trioxide CF₃OC(O)OOOC(O)OCF₃

Abstract

The open-chain trioxide CF(3)OC(O)OOOC(O)OCF(3) is synthesised by a photochemical reaction of CF(3)C(O)OC(O)CF(3), CO and O(2) under a low-pressure mercury lamp at -40 degrees C. The isolated trioxide is a colourless solid at -40 degrees C and is characterised by IR, Raman, UV and NMR spectroscopy. The compound is thermally stable up to -30 degrees C and decomposes with a half-life of 1 min at room temperature. Between -15 and +14 degrees 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.