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 BrO 2 F is reported. This compound can be converted into BrO 2 + SbF 6 − , BrO 2 + AsF 6 − , and BrO 2 + AsF 6 − ⋅2 BrO 2 F. The latter decomposes into mixed‐valent Br 3 O 4 ⋅Br 2 + AsF 6 − with five‐, three‐, one‐, and zero‐valent bromine. BrO 2 + H(SO 3 CF 3 ) 2 − is formed with HSO 3 CF 3 . Excess BrO 2 F yields mixed‐valent Br 3 O 6 + OSO 3 CF 3 − with five‐ and three‐valent bromine. Reactions of BrO 2 F and MoF 5 in SO 2 ClF or CH 2 ClF result in Cl 2 BrO 6 + Mo 3 O 3 F 13 − . The reaction of BrO 2 F with (CF 3 CO) 2 O and NO 2 produces O 2 Br‐O‐CO‐CF 3 and the known NO 2 + Br(ONO 2 ) 2 − . All of these compounds are thermodynamically unstable.