The complex [(C 6 H 3 Me 3 ) 2 Zr(μ-Cl) 2 AlCl 2 ](Al 2 Cl 7 ) has been prepared by reductive Friedel-Crafts synthesis. Its structure confirms remarkable differences in chemistry of arene complexes of Ti(II) and Zr(II). The crystalline complex TiCl 3 (OPh) was formed by slow oxidation of (C 6 H 6 )TiAl 2 Cl 8 in air, whereas partial oxidation of Zr arene complexes gave the oxohalogenoaluminates containing cationic arene Zr(II) species.