Halide abstraction from TiX(4) by AlX(3) in the presence of some aromatic hydrocarbons afforded the eta(6)-arene complexes of titanium(IV) of formula [TiX(3)(eta(6)-arene)]AlX(4) (arene=1,3,5-Me(3)C(6)H(3), X=Cl, Br; arene=1,2,4,5-Me(4)C(6)H(2), X=Cl; arene=Me,C-6, X=Cl, Br, I). The corresponding chloro complexes of 1,4-Me(2)C(6)H(4), 1,2,3-Me(3)C(6)H(3) and 1,2,4-Me(3)C(6)H(3) were characterized in solution by C-13 NMR spectroscopy. Arene displacement from [TiCl3(eta(6)-arene)][AlCl4] occurs with THF or TlCp (Cp=C5H5-) to afford TiCl4(THF)(2) or CpTiCl(3), respectively. The titanium(IV)-arene complexes efficiently promote the hydrogen-deuterium exchange of the ring protons between C6D6 and C(6)H(6-n)Me(n).