Reactions of Bromine Fluoride Dioxide, BrO(2)F, for the Generation of the Mixed‐Valent Bromine Oxygen Cations Br(3)O(4) (+) and Br(3)O(6) (+)

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.