On-surface metalation provides a tool to vary magnetic and electronic properties of metal–organic complexes and produces clean samples of the desired product. We used this technique to metalate 5,5′-dibromosalophene with the 3d transition metals Co, Fe, and Cr on Co-intercalated graphene grown on Ir(111). The metalation process was investigated by X-ray photoelectron spectroscopy (XPS). The electronic structure of the obtained salophene complexes was investigated using a combination of scanning tunneling microscopy and spectroscopy with density functional theory calculations. XPS data show that deposition of the transition metals at 398 K causes the metal atoms to interact with the molecules, while higher temperatures are needed to complete the reaction. Furthermore, we are able to distinguish the three different metal–organic complexes by their electronic structure.