Titanium Nitrogen Halides

Ruff and Eisner found that when TiCl₄.6NH₃ is extracted with liquid ammonia a complex chloramide is formed, which when carefully heated in a vacuum at 270° C. leaves impure titanium nitrogen chloride, TiNCl, as a dirty green residue. This substance reacts vigorously with water, forming ammonium chloride, nitrogen, and titanium dioxide. On being strongly heated it decomposes thus:

8TiNCl = 6TiN + 2TiCl₄ + N₂.Titanium nitrogen bromide, TiNBr, was obtained in a pure state in a similar way, the residue from the ammonia extraction being heated at 200° C. under 4 mm. pressure. It reacts with water similarly to the chloride.

The contrast between the behaviour of silicon and titanium halides towards ammonia is noteworthy. Silicon easily loses all its halogen; titanium, in accordance with its more electropositive character, retains one halogen atom in the compounds TiNCl and TiNBr, to which silicon presents no analogy.