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 [l angle]100[r angle] 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)[sub n]L (n = 2, 3), where L, = -(CH[sub 2])[sub 3]CN, and multinuclear species M[sub 3](CO)[sub 10]([mu]-CO)L were observed on the surface of the covalently bound, self-assembled ligand monolayers when the coated substrates were treated with M[sub 3](CO)[sub 12], where M = Ru and Os. Ruthenium porphyrin macrocycle RuTPP(CO). THF which has a [open quotes]disklike[close quotes] structure was bound to a CPTS axial ligand and then formed a covalently bound, self-assembled monolayer of [open quotes]porphyrin-disk[close quotes] stacking on the quartz surface. This monolayer was analyzed by UV-vis spectroscopy and secondary ion mass spectrometry (SIMS). 30 refs., 9 figs.