SULFUR-COMPOUNDS .186. THE SYNTHESIS OF CYCLIC ORGANOSULFUR COMPOUNDSFROM (C5H5)(4)TI2C2S4 BY LIGAND TRANSFER-REACTIONS

The tetrathiaoxalate complex Cp(4)Ti(2)C(2)S(4) (1) reacts with an equ imolar amount of COCl2 to give the blue-green mononuclear complex Cp(2 )TiC(2)S(4)CO (4). This reaction is analogous to the known reactions o f 1 with SCl2 or S2Cl2. However, when 1 was treated with equimolar amo unts of the bifunctional sulfenyl chlorides 1,2-C2H4(SCl)(2) (5), 1,3- C3H6(SCl)(2) (6) or 1,2-C6H4(SCl)(2) (7), the bi- or monocyclic tetrak isdisulfanes C6H8S8 (9b), C8H12S8 (10), and C14H8S8 (11), respectively , were obtained. The X-ray crystal structure analysis of 11 . CS2 show ed that 11 possesses C-i symmetry with a central exocyclic CC double b ond similar to tetrathiafulvalenes: C6H4(mu-S-2)(2)C=C(mu-S-2)(2)C6H4.