A New Synthetic Method and Solution Equilibria for the Chlorotitanate( IV ) Anions − Evidence for the Existence of a New Species: [Ti 2 Cl 11 ] 3−

TiCl 3 is oxidized by SOCl 2 in the presence of the appropriate amount of [NEt 3 Bz]Cl or [PPN]Cl [Bz = benzyl; PPN = bis(triphenylphosphanyl)iminium] to afford the corresponding salts of [Ti 2 Cl 9 ] − , [Ti 2 Cl 10 ] 2− or [TiCl 6 ] 2− . The results of cyclic voltammetric and solution IR studies in the Ti−Cl stretching region are interpreted in terms of a rapid chloride‐redistribution equilibrium between [Ti 2 Cl 10 ] 2− on one side and a mixture of [Ti 2 Cl 9 ] − and a previously unreported [Ti 2 Cl 11 ] 3− species on the other side. In the solid state, however, a compound with the [PPN] 3 [Ti 2 Cl 11 ] stoichiometry exists as a mixture of [PPN] 2 [Ti 2 Cl 10 ] and [PPN] 2 [TiCl 6 ]. The PPN salt of [Ti 2 Cl 9 ] − has been structurally characterized by X‐ray diffractometry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)