The functionalization of highly enantiomerically enriched planar chiral cyclopentadienyl(4-bromoindenyl)ruthenium complexes is detailed. Lithium/bromine exchange followed by an electrophilic quench using N,N-dimethylformamide (DMF), trimethylsilyl chloride, benzaldehyde, acetone, or 1,2-diiodoethane afforded the corresponding enantiomerically enriched planar chiral complexes. Suzuki–Miyaura cross-coupling led to cyclopentadienyl(indenyl)ruthenium complexes bearing aryl and alkenyl groups in high yields. Similarly, in situ generation of the boronate intermediate using 9-MeO-9-BBN and a metalated species in the Suzuki–Miyaura reaction gave heteroaryl, alkynyl, and alkyl cyclopentadienyl(indenyl)ruthenium complexes with retention of configuration and enantiomeric excess.