Reaction of CF3 radicals with CO and O-2. Isolation of bis(trifluoromethyl)peroxydicarbonate, CF3OC(O)OOC(O)OCF3, and identification of bis(trifluoromethyl)trioxydicarbonate, CF3OC(O)OOO(O)OCF3
Ga. Arguello et al., Reaction of CF3 radicals with CO and O-2. Isolation of bis(trifluoromethyl)peroxydicarbonate, CF3OC(O)OOC(O)OCF3, and identification of bis(trifluoromethyl)trioxydicarbonate, CF3OC(O)OOO(O)OCF3, INORG CHEM, 39(6), 2000, pp. 1195-1199
The synthesis of CF3OC(O)OOCF3, CF3OC(O)OOC(O)OCF3, and CF3OC(O)OOOC(O)OCF3
is accomplished by the photolysis of a mixture of (CF3CO)(2)O, CO, and O-2
. Pure CF3OC(O)OOCF3 and CF3OC(O)OOC(O)OCF3 are isolated after thermal deco
mposition of CF3OC(O)OOOC(O)OCF3 and repeated trap-to-trap condensation. Ad
ditional spectroscopic data of known CF3OC(O)OOCF3 are obtained by recordin
g 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 d
egrees C, and the boiling point is extrapolated to 73 degrees C from the va
por pressure curve log p = 8.657 - 1958/T (p/mbar, T/K). The new compound i
s characterized by molecular mass determination and by NMR, vibrational, an
d UV spectroscopy. The new trioxide CF3OC(O)OOOC(O)OCF3 cannot-be separated
from CF3OC(O)OOC(O)OCF3 by distillation due to their similar boiling point
s. CF3OC(O)OOOC(O)OCF3 decomposes at room temperature within hours into a m
ixture of CF3OC(O)OOC(O)OCF3, CF3OC(O)OOCF3, CO2, and O-2. Its characteriza
tion is discussed along with a possible mechanism for formation and decompo
sition reactions.