The chloryl cation, ClO2+

Article abstract of DOI:10.1021/ic50081a050

The 1:1 adducts ClO₂F·AsF₅ and ClO₂F·BF₃ have been investigated. Whereas ClO₂F·AsF₅ is stable at ambient temperature, the ClO₂F·BF₃ adduct shows a dissociation pressure of 225 mm at 25°. A pressure-temperature curve gives a heat of reaction of 24.0 kcal mol^-1, for the dissociation process: ClO₂F·BF₃(s) = ClO₂F(g) + BF₃(g). The X-ray powder patterns of ClO₂F·AsF₅ and ClF₃·AsF₅ were recorded and indexed. Infrared and Raman measurements show that ClO₂F·AsF₅ and ClO₂F·BF₃ have the ionic structures ClO₂⁺AsF₆^- and ClO₂⁺BF₄^-, respectively, in the solid state. All fundamental vibrations were observed and a valence force field was calculated for ClO₂⁺.