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The Interhalogen Cations [Br2 F5 ]+ and [Br3 F8 ].

The synthesis and characterization of unique polyhalogen cations containing μ-bridging fluorine atoms are reported. The [Br2 F5 ]+ cation features a symmetric [F2 Br-μ-F-BrF2 ] bridge, whereas the [Br3 F8 ]+ contains asymmetric μ-F bridges. These fluoronium ions, obtained as [SbF6 ]- salts, were investigated using Raman and 19 F NMR spectroscopy, as well as single-crystal X-ray diffraction. Quantum chemical calculations were carried out for the gas-phase cations as well as for the solid-state compounds. Population analyses show the μ-F atoms to possess the most negative partial charge within the cations.