Sulfur Compounds, Part 186 . The Synthesis of Cyclic Organosulfur Compounds from (C 5 H 5 ) 4 Ti 2 C 2 S 4 by Ligand Transfer Reactions

The tetrathiaoxalate complex Cp 4 Ti 2 C 2 S 4 ( 1 ) reacts with an equimolar amount of COCl 2 to give the blue‐green mononuclear complex Cp 2 TiC 2 S 4 CO ( 4 ). This reaction is analogous to the known reactions of 1 with SCl 2 or S 2 Cl 2 . However, when 1 was treated with equimolar amounts of the bifunctional sulfenyl chlorides 1,2‐C 2 H 4 (SCl) 2 ( 5 ), 1,3‐C 3 H 6 (SCl) 2 ( 6 ) or 1,2‐C 6 H 4 (SCl) 2 ( 7 ), the bi‐ or monocyclic tetrakisdisulfanes C 6 H 8 S 8 ( 9b ), C 8 H 12 S 8 ( 10 ), and C 14 H 8 S 8 ( 11 ), respectively, were obtained. The X‐ray crystal structure analysis of 11 · CS 2 showed that 11 possesses C i symmetry with a central exocyclic CC double bond similar to tetrathiafulvalenes: C 6 H 4 (μ‐S 2 ) 2 CC(μ‐S 2 ) 2 C 6 H 4 .