Reactions of Bromine Fluoride Dioxide, BrO2 F, for the Generation of the Mixed-Valent Bromine Oxygen Cations Br3 O4 + and Br3 O6.

A reliable synthesis of unstable and highly reactive BrO2 F is reported. This compound can be converted into BrO2 + SbF6 - , BrO2 + AsF6 - , and BrO2 + AsF6 - ⋅2 BrO2 F. The latter decomposes into mixed-valent Br3 O4 ⋅Br2 + AsF6 - with five-, three-, one-, and zero-valent bromine. BrO2 + H(SO3 CF3 )2 - is formed with HSO3 CF3 . Excess BrO2 F yields mixed-valent Br3 O6 + OSO3 CF3 - with five- and three-valent bromine. Reactions of BrO2 F and MoF5 in SO2 ClF or CH2 ClF result in Cl2 BrO6 + Mo3 O3 F13 - . The reaction of BrO2 F with (CF3 CO)2 O and NO2 produces O2 Br-O-CO-CF3 and the known NO2 + Br(ONO2 )2 - . All of these compounds are thermodynamically unstable.