REACTIONS OF 1,4,7-TRITHIACYCLONANE, [9]ANES3, WITH EARLY TRANSITION-METAL HALIDES - SYNTHESIS AND X-RAY STRUCTURE OF (FE([9]ANES3)2)[SB2CL8]

The reactions of titanium(III) and (IV) chlorides with the crown thioe ther [9]aneS3 were investigated. [TiCl3(MeCN)3] gives a purple 1:1 add uct with a proposed octahedral structure involving tridentate fac-atta chment of the ligand. With [TiCl4(MeCN)2] the identity of the yellow 1 :1 adduct obtained is discussed in terms of a six-coordinate species w ith bidentate ligand chelation. The title compound was isolated from t he reactions of [9]aneS3 with [TiCl3(MeCN)3][SbCl6] (by accident) and iron filings/SbCl5 in MeCN solution and characterised crystallographic ally. The cation has two macrocyclic ligands coordinated facially to a six-coordinate Fe2+ ion; the anion comprises dimeric [(SbCl4)2] units linked together into a polymeric chain by weak halogen bridging.