A New Synthetic Method and Solution Equilibria for the Chlorotitanate(IV) Anions− Evidence for the Existence of a New Species: [Ti2Cl11]3−

Emmanuel Robé (1) , Jean-Claude Daran (2) , Sandrine Vincendeau (2) , Rinaldo Poli (1)

1 LSEO - Laboratoire de Synthèse et Electrosynthèse Organométalliques
2 LCC - Laboratoire de chimie de coordination

TiCl3 is oxidized by SOCl2 in the presence of the appropriate amount of [NEt3Bz]Cl or [PPN]Cl [Bz = benzyl; PPN = bis(triphenylphosphanyl)iminium] to afford the corresponding salts of [Ti2Cl9]−, [Ti2Cl10]2− or [TiCl6]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 [Ti2Cl10]2− on one side and a mixture of [Ti2Cl9]− and a previously unreported [Ti2Cl11]3− species on the other side. In the solid state, however, a compound with the [PPN]3[Ti2Cl11] stoichiometry exists as a mixture of [PPN]2[Ti2Cl10] and [PPN]2[TiCl6]. The PPN salt of [Ti2Cl9]− has been structurally characterized by X-ray diffractometry. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Mots clés: Titanium; Thionyl chloride; Electrochemistry; Low-frequency infrared spectroscopy; Undecachloroditatanate(IV)

Domaines: Chimie de coordination

Emmanuel Robé, Jean-Claude Daran, Sandrine Vincendeau, Rinaldo Poli. A New Synthetic Method and Solution Equilibria for the Chlorotitanate(IV) Anions− Evidence for the Existence of a New Species: [Ti2Cl11]3−. European Journal of Inorganic Chemistry, 2004, 2004 (20), pp.4108-4114. ⟨10.1002/ejic.200400293⟩. ⟨hal-03278488⟩