Science of Synthesis

Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 459.

The diamagnetic [Ti(AlX4)2(η6-arene)] (‌1‌, X = Cl) complexes can be prepared from the reaction between titanium(IV) chloride, aluminum powder, and aluminum trichloride in refluxing arene (Fischer–Hafner method) (‌Scheme 1‌).[‌41‌] Treatment of a titanium(IV) halide (TiX4, X = Br, I) with aluminum powder and aluminum trichloride in an arene solvent also gives the well-known [Ti(AlX4)2(η6-arene)] (‌1‌, X = Br, I; arene = benzene, toluene, p-xylene, 1,2,4,5-Me4C6H2, C6Me6, mesitylene) complexes. The structures of complexes ‌1‌ have been determined by X-ray crystallography.[‌42‌,‌43‌] All the arene–titanium(II) complexes possess square-pyramidal coordination around the central titanium atom. The aromatic hydrocarbon molecule is π-bonded to the titanium atom, while the aluminum moiety is chloride-bridged to the titanium chloride. The reaction of ‌1‌ (arene = toluene) with disubstituted alkynes gives cyclobutadienyl–titanium complexes (see Section ‌2.10.8‌).

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References