Sulfur Compounds, 199 . Novel Titanocene Thiolato Complexes and Their Application in Preparing New Sulfur‐Containing Heterocycles

Treatment of Cp 2 Ti(CO) 2 ( 3 ) with the di‐ and polysulfanes 1,2,4‐(CH 2 ) 2 S 3 , C 4 S 6 ( 9 ), C, 7 H 10 S 3 ( 11 ), 1,2,4,6‐(CH 2 ) 3 S 4 ( 16 ), C 6 H 10 S 6 ( 19 ), and S 6 affords the titanocene chelate complexes Cp 2 TiS 3 (CH 2 ) 2 ( 8 ), (Cp 2 Ti) 2 C 4 S 6 ( 10 ), Cp 2 TiS 3 C 7 H 10 ( 13 ), Cp 2 TiS 2 C 7 H 10 ( 14 ), Cp 2 TiS 4 (CH 2 ) 3 ( 17 ), Cp, 2 TiS 6 C 6 H 6 H 10 ( 20 ), and Cp 2 TiS 8 ( 23 ). 14 is also obtained from Cp 2 TiCl 2 ( 1 ) and the geminal dithiol of norbornene. The analogous reaction with the dithiol of dicyclopentadiene yields Cp 2 TiS 2 C 10 H 12 ( 15 ). In ligand transfer reactions, 8 reacts with SCl 2 to give 1,2,3,5‐tetrathiane ( 25 ), 10 provides 9 on reaction with Cl 2 , 13 when treated with S 2 Cl 2 affords C 7 H 10 S 5 ( 12 ), 15 reacts with S 2 Cl 2 Cl 2 to give C 10 H 12 S 4 . 17 and SCl 2 yield 1,2,3,5,7‐pentathiepane ( 18 ), 20 is converted to C 6 H 10 S 7 ( 22 ) on reaction with SCl 2 , and 23 yields S 10 and 1,2,‐C 6 H 4 (SCl) 2 , respectively. With phosgene, thiophosgene, and thionyl chloride, compound 15 yields the corresponding dithiocarbonate 26 , the trithiocarbonate 27 and the trisulfane 2‐oxide 28 . The structure of 27 was determined by X‐ray crystallography.