Synthesis of Bis(trichloromethyl)tetra‐ and ‐heptasulfane from Titanocene Polysulfide Complexes and Structure of (CCl 3 ) 2 S 7

CCl 3 SCl reacts with (C 5 H 5 ) 2 TiS 5 to give the heptasulfane (CCl 3 ) 2 S 7 which forms colorless crystals of m.p. 38°C. An X‐ray structural analysis revealed that the C‐S 7 ‐C chain is helical but the CCl 3 groups are slightly tilted. In the triclinic crystals the molecules are arranged parallel to each other. Decomposition of (CCl 3 ) 2 S 7 provides other members of the homologous series with 4–12 sulfur atoms as shown by HPLC analysis. The reaction of CCl 3 SCl with (C 5 H 4 ‐CH 3 ) 4 Ti 2 S 4 yields colorless crystals of (CCl 3 ) 2 S 4 , demonstrating the usefulness also of dinuclear titanocene polysulfide complexes for the synthesis of organic polysulfanes. Infrared, Raman, and 13 C‐NMR spectra of (CCl 3 ) 2 S 7 and (CCl 3 )S 7 are reported.