Dinukleare Titankomplexe des Thiacalix[4]arens

Dinuclear Titanium Complexes of Thiacalix[4]arene The reaction of [TiCl 4 (THF) 2 ] with thiacalix[4]arene (H 4 TCA) affords almost insoluble [TCA{TiCl 2 (THF)} 2 ] ( 1 ). Single crystal X‐ray analysis reveals that the thiacalix[4]arene ligand coordinates at least in a part of the reaction product in an 1,2‐alternate cone conformation and that the metal atoms are therefore arranged in opposite directions with respect to a plane through the sulfur atoms of the ligand ( anti ‐configuration). The use of [Ti 2 (acac) 4 (μ‐O) 2 ] as starting material causes the formation of the soluble homodinuclear complex [TCA{Ti(acac)} 2 (μ–O)] ( 2 ) in good yields, in which the thiacalix[4]arene ligand adopts a cone conformation and the metal atoms are thus arranged in syn ‐configuration. Reaction of 2 with 8‐hydroxyquinoline leads to substitution of the acetylacetonato ligands of 2 under formation of crystallographically characterized [TCA{Ti(OC 9 H 5 N)} 2 (μ–O)] ( 3 ).