Synthesis and Characterisation of [XeF 5 ] 3 [Ti 4 F 19 ] Containing a Discrete [Ti 4 F 19 ] 3– Anion

The complex [XeF 5 ] 3 [Ti 4 F 19 ] was prepared by reaction of XeF 2 , TiF 4 and UV‐irradiated elemental fluorine in anhydrous hydrogen fluoride as the solvent. The crystal structure of [XeF 5 ] 3 [Ti 4 F 19 ] consists of [XeF 5 ] + cations and discrete [Ti 4 F 19 ] 3– anions. The [XeF 5 ] units have usual slightly distorted pseudo‐octahedral symmetry. Contrary to the previously reported [Ti 4 F 18 ] 2– anion, where each TiF 6 octahedron shares three apexes with three other octahedra, in [Ti 4 F 19 ] 3– , only two μ 3 ‐[TiF 6 ] octahedra share three apexes with three other [TiF 6 ] units. Each of the remaining two μ 2 ‐[TiF 6 ] octahedra shares only two vertices with two of the above‐mentioned μ 3 ‐[TiF 6 ] moieties. The Raman spectrum of [XeF 5 ] 3 [Ti 4 F 19 ] is in agreement with the presence of [XeF 5 ] + cations and [Ti 4 F 19 ] 3– anions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)