We prepared the bimetallic hafnium complex 1 by reaction of Hf(CH2Ph)(4) with the alcohol-imine proligand L via deprotonation and subsequent benzyl migration from the hafnium atom to the imine moiety of L. The complex 1 was obtained as a diastereomeric mixture of la (SR, heterochiral) and lb (RR and SS, homochiral); the SR isomer la was readily isolated by simply washing with toluene. Treatment of la with [Ph3C][B(C6F5)(4)] in C6H5Cl afforded the dicationic complex 2a, which was characterized by spectroscopic data and an X-ray diffraction study, revealing the eta(6) coordination of the phenyl group bound to the chelating ligand to the cationic hafnium center. Complex 2a showed catalytic activity for 1-hexene oligomerization at 100 C in combination with 2 equiv of [Ph3C][B(C6F5)(4)], while 4,4'-dimethoxydiphenylacetylene reacted with 2a to quantitatively afford alkene 3 at room temperature after hydrolysis. The addition of PMe2Ph and pyridine to 2a dissociated the eta(6)-arene coordination of the ligand to give the corresponding adducts 5a and 6a, whose structures were fully characterized by X-ray diffraction analysis.