Synthesis and Characterisation of [XeF5]3[Ti4F19] Containing a Discrete [Ti4F19]3- Anion

The complex [XeF5](3)[Ti4F19] was prepared by reaction of XeF2, TiF4 and UV-irradiated elemental fluorine in anhydrous hydrogen fluoride as the solvent The crystal structure of [XeF5](3)[Ti4F19] consists of [XeF5](+) cations and discrete [Ti4F19](3-) anions. The [XeF5] units have usual slightly distorted pseudo-octahedral symmetry. Contrary to the previously reported [Ti4F18](2-) anion, where each TiF5 octahedron shares three apexes with three other octahedra, in [Ti4F19](3-), only two mu(3)-[TiF6] octahedra share three apexes with three other [TiF6] units Each of the remaining two mu(2)-[TiF6] octahedra shares only two vertices with two of the above-mentioned mu(3)-[TiF6] moieties The Raman spectrum of [XeF5](3)-[Ti4F19] is in agreement with the presence of [XeF5](+) cations and [Ti4F19](3-) anions. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)