Behavior of BrO3F and ClO3F toward strong Lewis acids and the characterization of [XO2][SbF6] (X = Cl, Br) by single crystal X-ray diffraction, Raman spectroscopy, and computational methods.

The interactions of BrO3F and ClO3F with the strong Lewis acids AsF5 and SbF5 were investigated. Although ClO3F is unreactive toward AsF5 and SbF5, BrO3F undergoes fluoride ion abstraction and O2 elimination, accompanied by central halogen reduction, to form [BrO2][Sb(n)F(5n+1)] (n > or = 1), rather than simple fluoride ion abstraction to form BrO3(+) salts. The geometric parameters of the BrO2(+) cation have been obtained in the solid state for the first time by a single-crystal X-ray diffraction study of [BrO2][SbF6] at -173 degrees C and are compared with those of ClO2(+) salts. Quantum-chemical calculations have been used to arrive at the geometries and vibrational frequencies of XO2(+) and XO3(+) (X = Cl, Br) and have been compared with the experimental values for XO2(+). The calculations have also been used to account for the contrasting behaviors of ClO3F and BrO3F toward central halogen reduction in the presence of liquid SbF5. The thermochemical stabilities of ClO3(+) and BrO3(+) salts of the AsF6(-), SbF6(-), Sb2F11(-), and Sb3F16(-) were also investigated, which provided the fluoride ion affinities of AsF5, SbF5, Sb2F10, and Sb3F15 up to and including the CCSD(T) level of theory. These values are compared with the current literature values. Thermochemical studies indicate that XO3(+) formation by fluoride ion abstraction from XO3F is not spontaneous under standard conditions whereas a concerted fluoride abstraction and O2 elimination to give the XO2(+) cations is spontaneous to near thermally neutral. Failure to observe reactivity between ClO3F and any of the aforementioned Lewis acid fluoride ion acceptors is attributed to a significant kinetic barrier to fluoride ion abstraction.