Enantiopure biphenyl-bridged titanocene and zirconocene complexes were obtained by an asymmetric thermal transformation of the binaphthol complexes formed from the metallocene racemates and subsequent transformation to the corresponding dichlorides, in practically quantitative yields. Increased rates of this transformation in the presence of O-2 gas or TEMPO indicate a radical reaction mechanism. The biphenyl-bridged titanocene enantiomers give rise to an efficient asymmetric catalysis for the hydrogenation of cyclic and noncyclic imines.