SOLUTION AND VAPOR-PHASE COMPLEX-FORMATION IN THE ZIRCONIUM TETRACHLORIDE ALUMINUM CHLORIDE SYSTEM

Raman spectroscopy provides the first direct evidence that zirconium(IV) chloride forms complexes with aluminum chloride in both the liquid and vapor phases. The spectra are consistent with a structure in which the zirconium is in a 6-coordinate site with two bidentate AlCl4 moieties. The spectra indicate that the complex begins to dissociate above 300°C yielding tetrahedral zirconium chloride molecules and aluminum chloride dimers. The zirconium tetrabromide-aluminum bromide system behaves similarly and in mixed zirconium tetrachloride-aluminum bromide systems halogen exchange occurs rapidly. © 1979.