Trifluoromethoxycarbonyl Peroxynitrate, CF₃OC(O)OONO₂

Abstract

The trioxide, CF(3)OC(O)OOOC(O)OCF(3), reacts with NO(2) at 0 degrees C to yield the new peroxynitrate, CF(3)OC(O)OONO(2), which is stable for hours at room temperature. It is spectroscopically characterized and some thermal properties are reported. From the vapor pressure, ln(p/p(0)) = 14.06 - 4565/T, of the liquid above the melting point of -89 degrees C, the extrapolated boiling point is 52 degrees C. CF(3)OC(O)OONO(2) dissociates at higher temperatures and low pressures into the radicals CF(3)OC(O)OO and NO(2) as demonstrated by matrix isolation experiments. The matrix-isolated peroxy radicals consist in a rotameric mixture of trans,trans,trans-CF(3)OC(O)OO and trans,trans,cis-CF(3)OC(O)OO, where trans and cis denote dihedral angles of ca. 180 degrees and 0 degree, respectively, around beta F-C-O-C, beta C-O-C-O, and beta O-C-O-O, with an equilibrium composition dependent on the thermolysis temperature. The radical trans,trans,cis-CF(3)OC(O)OO is found to be ca. 3 kJ mol(-1) higher in enthalpy than trans,trans,trans-CF(3)OC(O)OO. DFT calculations are performed to support the vibrational assignments and to provide structural information about CF(3)OC(O)OONO(2).

Fluorocarbon oxy and peroxy radicals

“…CF 3 OCðOÞOOðþMÞ (40) CF 3 OCðOÞOO þ NO 2 ðþMÞ ! CF 3 OCðOÞOONO 2 ðþMÞ (41) From CF 3 OC(O)OOOC(O)OCF 3[53] as starting material pure CF 3 OC(O)OONO 2 has recently been isolated and is a subject of further studies[128]. Bis(trifluoromethyl)trioxide was mentioned for the first time in 1963…”

Synthesis and solution studies on azaphthalocyanines with quaternary aminoethyl substituents

“…Because of the intense absorption of AzaPcs in the visible range, the aim of the present work has been to prepare new water-soluble derivatives with quaternised ammonium groups as substituents that are especially useful for providing solubility within a wide pH range, which is important for the number of applications [e.g. as infrared (IR) absorbers and photosensitisers] [13][14][15]. Dimethylaminoethylsulphanyl substituents enhance the solubility of AzaPc in common organic solvents, whereas trimethylaminosulphanyl residues enhance their solubility in water [15][16][17].…”

Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF3OC(O)O2NO2

“…Industrial fluorinated compounds such as chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, and hydrofluoroethers (CFCs, HCFCs, HFCs, and HFEs, respectively) lead to the formation of various fluorinated peroxy acyl nitrates in the atmosphere, for example, fluorocarbonyl (FC(O)O 2 NO 2 ), trifluoroacetyl (FPAN; CF 3 C(O)O 2 NO 2 ), and trifluoromethoxicarbonyl (CF 3 OC(O)O 2 NO 2 ) peroxy nitrates [7].…”

“…von Ahsen et al [7] synthesized the pure peroxy nitrate in bulk quantities and characterized the molecule (vapor pressure, boiling, and melting points, UV cross sections, IR and Raman spectra, NMR, etc.). In this paper, we present the study of the thermal decomposition of CF 3 OC(O)O 2 NO 2 :…”