Some Complex Sulphur Compounds of Titanium and Vanadium
The reactions between TiCl4, TiBr4, TiCl3, VCl4, VCl3, and VBr3 with a range of monodentate sulphur ligands, have been investigated. The ligands used include the aliphatic thioethers, R2S, for R = Me, Et, Prn, and Bun, and tetr a h ydrot h iop hen and pen tamet hylenesulphide. Notable differences have been observed in the reactions of the halides of the two elements. Thus, whereas the tetrahalides of titanium form simple adducts with all ligands tried, vanadium(IV) chloride is reduced rapidly and quantitatively to the tervalent state. Furthermore, tervalent vanadium forms a series of welldefined complexes with sulphur ligands, but the complexes formed by tervalent titanium are very much less stable and readily break down with the formation of complexes of quadrivalent titanium.