Reaction of CF3 Radicals with CO and O2. Isolation of Bis(trifluoromethyl)peroxydicarbonate, CF3OC(O)OOC(O)OCF3, and Identification of Bis(trifluoromethyl)trioxydicarbonate, CF3OC(O)OOOC(O)OCF3

GUSTAVO A. ARGÜELLO; HELGE WILLNER; FABIO E. MALANCA

INORGANIC CHEMISTRY

American Chemical Society

Año: 2000 vol. 39 p. 1195 - 1199

0020-1669

The synthesis of CF3OC(O)OOCF3, CF3 OC(O)OOC(O)OCF3, and CF3OC(O)OOOC(O)OCF3 is accomplished by the photolysis of a mixture of (CF3CO)2O, CO, and O2. Pure CF3OC(O)OOCF3 and CF3OC(O)OOC(O)OCF3 are isolated after thermal decomposition of CF3OC(O)OOOC(O)OCF3 and repeated trap-to-trap  condensation. Additional spectroscopic data of known CF3OC(O)OOCF3 are obtained by recording NMR, IR, Raman, and UV spectra. At room temperature CF3OC(O)OOC(O)OCF3 is stable for days in the liquid or gaseous state. The melting point is -38 °C, and the boiling point is extrapolated to 73 °C from the vapor pressure curve log p ) 8.657 - 1958/T (p/mbar, T/K). The new compound is characterized by molecular mass determination and by NMR, vibrational, and UV spectroscopy. The new trioxide CF3OC(O)OOOC(O)OCF3 cannot be separated from CF3-OC(O)OOC(O)OCF3 by distillation due to their similar boiling points. CF3OC(O)OOOC(O)OCF3 decomposes at room temperature within hours into a mixture of CF3OC(O)OOC(O)OCF3, CF3OC(O)OOCF3, CO2, and O2. Its characterization is discussed along with a possible mechanism for formation and decomposition reactions.