Trifluormethylnitrat,CF3ONO2

Trifluoromethyl Nitrate, CF₃ONO₂ From different routes to CF₃ONO₂, the reaction of CF₃OF with NO₂ at room temperature under high pressure is the most favorable to synthesize CF₃ONO₂ in preparative scale. The pure product is isolated for the first time after repeated trap‐to‐trap condensation in vacuo. CF₃ONO₂ is a colourless gas with a boiling point of –18 ± 3 °C (extrapol.) and a melting point of –163 °C. Trifluoromethyl nitrate decays slowly into CF₂O and FNO₂ at room temperature in the gas phase as well as in the liquid state at lower temperatures. Furthermore, CF₃ONO₂ is characterized spectroscopically by NMR, IR, Raman, and UV, and structurally by gas electron diffraction and quantum chemical calculations (B3LYP, MP2). The CF₃–O bond is in the plane of the NO₃ moiety, the central CF₃O–NO₂ bond of 1.493(6) Å is very long. The B3LYP/6‐31G* calculation reproduces best the experimental data.