CHLORYL CATION, CLO2+

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· AsF6 were recorded and indexed. Infrared and Raman measurements show that ClO2F·AsF6 and ClO3F · 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+. © 1969, American Chemical Society. All rights reserved.