[TiSCl 4 ] 2⊖ and [Ti 3 O(S 2 ) 3 Cl 6 ] 2⊖ , a Multinuclear Complex with a Structure Typical for Clusters

In the presence of traces of oxygen , the title reaction of TiCl 4 with S(SiMe 3 ) 2 affords [Ti 3 O(S 2 ) 3 Cl 4 ] in addition to TiSCl 2 . Both compounds can be converted into salts by reaction with Cl ⊖ ions. The X‐ray structural analyses of these salts revealed that [TiSCl 4 ] 2⊖ is square‐pyramidal and [Ti 3 O(S 2 ) 3 Cl 6 ] 2⊖ has the clusterlike structure shown despite the predicted absence of metal–metal bonds.