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.

Reactions of ClF3 with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates

“…The Mo−O bond lengths lie in the range of 1.6435(17) to 1.6457(17) Å and the Mo−F bond lengths for terminally bound F atoms in the range of 1.8196(13) to 1.9288(13) Å and 2.1071(13) to 2.3161(13) Å for the μ−F atoms. They agree with the previously reported bond lengths for [Cl 2 BrO 6 ][Mo 3 O 3 F 13 ], which are 1.652(2)–1.662(2) Å (Mo−O), 1.819(2)–1.949(2) Å (Mo−F), and 2.102(2)–2.249(2) Å (Mo−μ−F) at 100 K [45] …”

“…The crystal structure can then be described with the Niggli formula . The homologous [BrO 2 ][AsF 6 ] salt, in contrast, forms a layer structure [45] …”

“…salt, in contrast, forms a layer structure. [45] An analysis of the packing motif shows that a consideration of Cl • • • Cl distances of circa 4.56 to 5.49 Å leads to a distorted octahedron as the coordination polyhedron for the Cl atom. When As • • • As distances of approximately 4.83 to 6.77 Å are taken into account, a bicapped cube (BCCU-10) is obtained as the coordination polyhedron for the As atom.…”

“…Crystal structures of [ClO 2 ] + salts with the following anions have been reported: [BF 4 ] − , [GeF 2/2 F 4/1 ] − , [RuF 6 ] − , [SbF 6 ] − , [Sb 2 F 11 ] − , [ClO 4 ] − , [Au(ClO 4 ) 4 ] − and [Sn(ClO 4 ) 6 ] 2− [34,37–44] . Recently, compounds were published containing the complex [Cl 2 BrO 6 ] + cation that might be considered as a central [BrO 2 ] − anion coordinating to two [ClO 2 ] + cations [45] …”

“…[35][36][37][38][39][40] [34,[37][38][39][40][41][42][43][44] Recently, compounds were published containing the complex [Cl 2 BrO 6 ] + cation that might be considered as a central [BrO 2 ] À anion coordinating to two [ClO 2 ] + cations. [45] Salts containing disphenoidal (seesaw) C 2v [XO 2 F 2 ] À anions are also known but they are usually not formed by the direct reaction of XO 2 F with a fluoride ion donor. [46][47][48][49] Thus far, only salts with [IO 2 F 2 ] À anions have been structurally characterized by single-crystal X-ray diffraction.…”