Enantiomerically pure planar chiral complexes are of interest for both asymmetric synthesis and catalysis. In this thesis, we report on an easy access to highly enantioenriched neutral [Cr(CO)3(naphthalene)], [RuCp(indenyl)], [FeCp*(indenyl)] and cationic [RuCp*(naphthalene)] complexes via desymmetrization of prochiral dihalide complexes using a bulky chiral palladium catalyst. Ligand optimization and mechanistic analyses result in a clear picture of the reaction and the asymmetric induction. The potential utility of this reaction is illustrated in the synthesis of a ide range of highly enantioenriched planar chiral complexes. Particularly, the access to peri-palladacycles is of high interest in view of their evaluation in asymmetric catalysis.