This paper describes interactions between metal complexes and self-assemblies of covalently bound ligand monolayers on surfaces. Covalently bound molecular self-assemblies of (3-cyanopropyl) trichlorosilane (CPTS) were anchored on the surfaces of fused quartz and the native oxide of the [100] crystallographic orientation of p-doped Si wafers. The formations of a number of ruthenium and osmium metal carbonyl complexes on both the substrates and substrates coated with ligand monolayers have been examined with polarized variable-angle internal attenuated total reflection infrared spectroscopy (PVAI-ATR-IR). Both mononuclear species M(CO)(n)L (n = 2,3), where L = -(CH2)3CN, ana multinuclear species M3(CO)10(mu-CO)L were observed on the surface of the covalently bound, self-assembled ligand monolayers when the coated substrates were treated with M3(CO)12, where M = Ru and Os. Ruthenium porphyrin macrocycle RuTPP(CO).THF which has a "disklike" structure was bound to a CPTS axial ligand and then formed a covalently bound, self-assembled monolayer of "porphyrin-disk" stacking on the quartz surface. This monolayer was analyzed by UV-vis spectroscopy and secondary ion mass spectrometry (SIMS).