Abstract
Knowledge of the halogen cations has expanded rapidly since the discovery of the l2+ cation in 1966. The homopolyatomic cations l2+, Br2+, l3+ and Br3+ have all been obtained as stable salts both in the solid state and in solutions. The structures of l2+ Sb2F11 and Br2+Sb3F16− have been determined by X-ray crystallography and in each case the length of the bond in the cation has been found to be less than that in the neutral molecules l2 and Br2. The triatomic species have been shown by Raman spectroscopy to have angular structures. The mixed cations ICl2+, l2Cl+, IBr2+ and l2Br+ have been prepared as well as a number of fluorocations such as ClF2+ and Cl2F+. In each case the least electronegative halogen occupies the central position and all these triatomic ions appear to have angular structures. All the possible fluorocations HalF4+ and HalF6+ are known, ClF6+ and BrF6+ having been prepared very recently. These latter two cations are of particular interest as the parent fluorides ClF7 and BrF7 are at present unknown.
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