873303-49-2

N-substituted 1,3,5-triazacyclohexanes [R3TAC; R = cyclohexyl, p-fluorobenzyl or Ph(CH2)n (n = 1, 2, 3)] react with excess TiCl4 to give the corresponding cationic κ3 complexes [(R3TAC)TiCl3][Ti2Cl9]. Attempts to prepare complexes with titanium-free anions at lower Ti:R 3TAC ratio or with added Me3SiOTf lead to the same cations with [Ti2Cl10]2- and [Ti2Cl 8(OTf)]- anions. Five complexes as well as (p-fluorobenzyl)3TAC have been characterised by X-ray crystallography. The ring C-H bonds engage in hydrogen bonding interactions in the crystals and strongly solvent and anion dependent 1H NMR signals are detected in solution. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.