Dinukleare Titankomplexe des Thiacalix[4]arens

Dinuclear Titanium Complexes of Thiacalix[4]arene The reaction of [TiCl4(THF)2] with thiacalix[4]arene (H4TCA) affords almost insoluble [TCA{TiCl2(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 [Ti2(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(OC9H5N)}2(μ–O)] (3).