Group-IVB elements

Very little is known about chalcogenide halides of Group IVB elements. Although the existence of sulfide chlorides (45, 274, 329, 365) and of a selenide chloride (329) of titanium was claimed in early publications, their true composition, and even their existence, remains doubtful. They have usually been obtained by the reaction of titanium chlorides with sulfur and selenium, respectively, or with hydrogen sulfide. The synthesis of a pure compound, TiSClj, was published in 1959 (113). It is an intermediate of the reaction of TiCU with HjS. 

Transition Metal Complexes with Group IVB Elements J. F. Young... 

Transition metal complexes with Group IVB elements 241... 

Lukevits, E. Y., and Voronkov, M. G., Organic Insertion Reactions of Group IVB Elements (transl. M. J. Newlands). Consultants Bureau, New York, 1966. 

In the lower oxidation states the chemistry of titanium has little or no counterpart in the chemistries of the group IVB elements. The only lower oxidation state of these elements is two, for which the stability order is Ge < Sn < Pb. However,, both zirconium(III) and hafnium(III) are similar to if less stable (towards oxidation) than titanium(III) and have comparable although less extensively investigated chemistries. 

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