Reaction of 1,3,5‐Triazacyclohexanes with TiCl₄: Formation of Cationic Complexes

Abstract

Abstract N ‐substituted 1,3,5‐triazacyclohexanes [R 3 TAC; R = cyclohexyl, p ‐fluorobenzyl or Ph(CH 2 ) n ( n = 1, 2, 3)] react with excess TiCl 4 to give the corresponding cationic κ 3 complexes [(R 3 TAC)TiCl 3 ][Ti 2 Cl 9 ]. Attempts to prepare complexes with titanium‐free anions at lower Ti:R 3 TAC ratio or with added Me 3 SiOTf lead to the same cations with [Ti 2 Cl 10 ] 2– and [Ti 2 Cl 8 (OTf)] – anions. Five complexes as well as ( p ‐fluorobenzyl) 3 TAC 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 1 H NMR signals are detected in solution. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)