The efficient functionalization of planar chiral ruthenium naphthalene—and ruthenium indenyl—scaffolds is reported. Mild reaction conditions employing microwave heating have been developed for the derivatization of sensitive cationic naphthalene ruthenium complexes. In particular, a series of novel planar chiral monodentate phosphines and their gold(I) complexes have been synthesized and fully characterized by NMR spectroscopy and X-ray crystallography. Furthermore, the electronic properties of these phosphines (L) have been evaluated via the infrared CO stretching frequencies of the corresponding Ni(CO)3(L) complexes, providing valuable insight for the design and application of these chiral ligands in asymmetric catalysis.