Photochemistry of perfluoroacyl halides in the presence of O2 and CO

FABIO E. MALANCA; MAXIMILIANO A. BURGOS PACI; GUSTAVO A. ARGÜELLO

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY

Elsevier Science

Lugar: Holanda; Año: 2002 vol. 150 p. 1 - 6

1010-6030

Photolyses of CF3C(O)X and C2F5C(O)X (X = Cl, F) at 254 nm in the presence of O2 yield the perfluorinated radicals C2F5O (C2) and CF3O (C1), respectively. The C2 radicals decompose to give CF3 radicals: C2F5O -> CF3 + CF2O which, in turn, react with O2 leading to the formation of C1 radicals. When in addition to O2, CO is present, the C1 radicals react with it leading to its catalytic oxidation to CO2. The trioxide CF3OC(O)O3C(O)OCF3 was observed following the photolysis of all four halides in the presence of O2 and CO. The other radical partners coming from the initial step in the photolysis (XC(O)) as well as the products of their reaction with O2 (XC(O)Oy , y = 1, 2) do not react with CO but when X = F they lead to the formation of a new stable peroxy molecule with the formula CF3OC(O)O2C(O)F. Some of the properties of this newmolecule, its stability and its IR features are presented in this work.