Reactions of Bromine Fluoride Dioxide, BrO2F, for the Generation of the Mixed-Valent Bromine Oxygen Cations Br3O4+ and Br3O6+

Abstract

A reliable synthesis of unstable and highly reactive BrO2F is reported. This compound can be converted into BrO2+SbF6−, BrO2+AsF6−, and BrO2+AsF6−⋅2 BrO2F. The latter decomposes into mixed-valent Br3O4⋅Br2+AsF6− with five-, three-, one-, and zero-valent bromine. BrO2+ H(SO3CF3)2− is formed with HSO3CF3. Excess BrO2F yields mixed-valent Br3O6+OSO3CF3− with five- and three-valent bromine. Reactions of BrO2F and MoF5 in SO2ClF or CH2ClF result in Cl2BrO6+Mo3O3F13−. The reaction of BrO2F with (CF3CO)2O and NO2 produces O2Br-O-CO-CF3 and the known NO2+Br(ONO2)2−. All of these compounds are thermodynamically unstable.