Synthetic Studies and Structural Aspects of Dinuclear Sulfur Titanium Compounds

Abstract A series of dinuclear sulfur‐bridged titanium derivatives Ti (η 5 ‐C 5 Me 5) R (μ‐S) 2 (R=NMe 2 (1), Ph (2), CH 2 Ph (3), CH 2 SiMe 3 (4) ) has been synthesized from the reaction of Ti (η 5 ‐C 5 Me 5) Cl (μ‐S) 2 with the corresponding lithium salt or Grignard reagent. Formulation of 1 – 4 as symmetric dimers has been confirmed by crystallographic studies. The analogous reaction with Mg (C 3 H 5) Cl afforded the paramagnetic mixed‐valence Ti (III) /Ti (IV) compound Ti (η 5 ‐C 5 Me 5) (μ‐S) 2 (μ‐C 3 H 5) (5). Contrasting with complexes 1 – 4, compound 5 exhibits a bridging μ‐CH 2 CHCH 2 fragment between the titanium atoms, which prevents the formation of a planar Ti 2 S 2 core in the solid‐state structure. Complex 1 reacts with SiH 3 Ph to give Ti (η 5 ‐C 5 Me 5) (μ‐S) 2 (μ‐NMe 2) (6), a paramagnetic mixed‐valence Ti (III) /Ti (IV) compound, structurally and electronically similar to 5. Under mild conditions, treatment of compounds 3 and 4 with H 2 (1 atm) generates quantitatively the Ti (III) tetrametallic sulfide cluster Ti (η 5 ‐C 5 Me 5) (μ 3 ‐S) 4, along with the corresponding alkane.