SULFUR-COMPOUNDS .176. THE UTILIZATION OF TITANOCENE POLYSULFIDE COMPLEXES FOR THE SYNTHESIS OF ORGANIC POLYSULFANES

Titanocene pentasulfide reacts with Ph(3)CCl and CCl3S5 to give (Ph(3) C)(2)S-5, and (CCl3)(2)S-7, respectively, the molecular structures of which show helical CSnC backbones. (Ph(3)C)(2)S-6 and (CN)(2)S-9 posse ss non-helical structures. C2H4(SCl)(2), C6H4(SCl)(2), C6H4(SSCl)(2) a nd CH3C6H3(SCl)(2) react with Cp(2)TiS(5) to give the corresponding su lfur-rich heterocycles with up to nine sulfur atoms. Dicyclopentadiene trisulfane is used to prepare the dicyclopentadiene tetra-, penta-, h exa- and octasulfanes by (a) derivatization to SCl or SH compounds fol lowed by sulfur transfer reactions using Cp(2)TiS(5), (Cp'2ClTi)(2)S-3 or S2Cl2 as reagents. Several cyclic, bicyclic and tricyclic organosu lfur heterocycles are obtained from Cp(4)Ti(2)C(2)S(4) or from Cp(2)Ti S(2)C(3)H(6) by reactions with SCl2, S2Cl2, C2H4(SCl)(2), COCl2 or C6H 4(SCl)(2).