: Metal-porphyrins are studied intensively due their potential applications, deriving from the variety of electronic and chemical properties, tunable by selecting metal centers and functional groups. Metalation, de- and trans-metalation processes are fundamental in this sense to investigate both the synthesis and the stability of these molecular building blocks. More specifically, Pd coordination in tetrapyrroles revealed to be potentially interesting in the fields of cancer therapy, drug delivery and light harvesting. Thus, we focused on the stability of palladium tetraphenyl porphyrins (PdTPPs) on a copper surface by means of combined spectroscopy and microscopy approaches. We find that PdTPPs undergo coverage-dependent trans-metalation accompanied by steric rearrangements already at room temperature, and fully trans-metalate to CuTPPs upon mild annealing. Side reactions such as (cyclo)-dehydrogenation and structural reorganization affect the molecular layer, with Pd-Cu alloying and segregation occurring at higher temperature. Instead, oxygen passivation of the Cu support prevents the metal-involving reactions, thus preserving the layer and increasing the chemical and temperature stability of the Pd porphyrins.
