Properties of Fluorocarbonyl Peroxynitrate

Abstract

The synthesis of FC(O)OONO2 is accomplished by the photolysis of a mixture of (FCO)2, NO2, and O2. The pure product is isolated after trap-to-trap condensation and the removal of byproducts by treatment of the crude product with O3 and AsF5. The colorless liquid freezes at −105 °C; its boiling point is 32 °C. At 20 °C and a few millibars, FC(O)OONO2 decomposes in the gas phase with a half-life of 20 h. FC(O)OONO2 is characterized by vapor pressure measurements, vibrational, 19F NMR, 13C NMR and UV spectroscopies as well as by mass spectrometry. According to the vibrational and NMR spectra, the compound exists at room temperature only as a syn conformer. The molecular structure of FC(O)OONO2 is determined by gas electron diffraction. The molecule possesses a skew structure with a dihedral angle of φ(COON) = 86.2(14)°. The short O−O bond (1.420(6) Å) and the long N−O bond (1.514(6) Å) are consistent with the chemical properties of this compound. The experimental geometry is reproduced reasonably well by quantum chemical.

IR and UV Spectra of the Matrix‐Isolated Peroxy Radicals CF3OO,trans‐FC(O)OO, andcis‐FC(O)OO

“…With HO 2 the corresponding hydroperoxides are formed, and the reaction with NO according to Equation (1) is likely to be the major fate of the CF 3 OO and FC(O)OO radicals in the atmosphere. [2±5] In the presence of NO 2 , peroxynitrates [6,7] are formed [Eq. (2)]; these may serve as reservoir species for either ROO or NO 2 radicals.…”

“…Recent examples are FCO 2 [31] and ClO 3 , [32] formed by dissociation of the precursors FC(O)OOC(O)F and ClOClO 3 , respectively. Suitable thermally labile precursors for the syntheses of the peroxy radicals XOO (X CF 3 , CFO) are the peroxy nitrates XOONO 2 (X CF 3 , [7] FCO [6] ) and the trioxides XOOOX (X CF 3 , [16] FC(O)). [33] This last species, FC(O)OOOC(O)F, was prepared in pure state very recently.…”

Bis(fluoroformyl)trioxide, FC(O)OOOC(O)F

“…[16] Pure trioxide reacts with equimolar amounts of NO 2 at low temperature (slow thawing) to form the known FC(O)OONO 2 . [17] For further characterization of the trioxide, NMR, UV, and mass spectra were recorded, and an X-ray diffraction study was performed. The NMR spectroscopic data fit very well with the data of the related compounds On storage of the trioxide in evacuated glass ampoules on dry ice, over several months single crystals of mm size were formed.…”

Gas Phase Structures of Peroxides: Experiments and Computational Problems

“…[72,74,75] The most remarkable structural feature of these peroxides is the extremely long NÀO bond. Gas-phase structures of covalent nitrates XONO 2 demonstrate that the NÀO single bond length depends strongly on the electronegativity of the substituent X.…”