1,1'-DISUBSTITUTED TITANOCENE DITHIOLENE CHELATES OF TYPE (ETA-5-ME3EC5H4)2TI(S2C2R2) (E=C, SI, GE)

Reaction of the titanocene dichlorides (eta5-Me3EC5H4)2TiCl2 (E = C, 1 a; E = Si, 1b; E = Ge, 1c) with the 1,2-dithiolates (NaS)2C2H2, (NaS)2 C2(CN)2 or (LiS)2C6H3Me-4 gave the new titanocene dithiolene chelates (eta5-Me3EC5H4)2Ti(S2C2H2) (2a - c), (eta5-Me3EC5H4)2Ti[S2C2(CN)2] (3a - c) and (eta5-Me3EC5H4)2Ti(S2C6H3Me-4) (4a - c). These have been cha racterized by H-1 NMR, IR, and mass spectroscopy, and have been compar ed with the unsubstituted eta5-C5H5 analogues 2d, 3d and 4d. Activatio n energies for the chelate ring inversion in solution of 2a - c, 3a - d and 4a - c have been estimated by temperature-dependent H-1 NMR spec troscopy.