The hexafluoroacetylacetonate complexes Rh(hfac)(C2H4)(2) and Pt(hfac)(2) are known to serve as chemical vapor deposition precursors to Rh and Pt thin films. In the absence of a reducing carrier gas, the depositions ate surface-selective and occur preferentially on copper, but under these conditions, the metallization processes are unexpectedly inefficient relative to the rapid deposition of Pd on Cu seen for the palladium analogue Pd(hfac)(2). Mechanistic studies of the reactions of Rh(hfac)(C2H4)(2) and Pt(hfac)(2) on copper sui faces under ultrahigh vacuum conditions have now been performed in order to elucidate the factors responsible for the differences among these surface-selective metallization processes. The studies demonstrate that adsorption of the rhodium complex Rh(hfac)(C2H4)(2) on copper surfaces is accompanied by the loss of the coordinated ethylene groups, even at 100 K. At these low temperatures, the adsorbed Rh(hfac) fragments are oriented in several ways with respect to the surface. Healing the substrate above similar to 150 K causes the hfac ligands to realign to a perpendicular orientation relative to the surface. The platinum precursor Pt(hfac)(2) adsorbs molecularly at 100 K with the molecular planes of the hfac ligands oriented parallel to the copper surface. Heating the substrate to temperatures above 150 K again results in a realignment of the hfac ligands to a perpendicular orientation. This reorientation is accompanied by a partial reduction of the Pt centers (as judged from shifts seen in X-ray photoelectron spectroscopy core level data), a result suggesting that the hfac ligands begin to dissociate from the platinum centers near 150 K. At temperatures above 220 K, the transfer uf the hfac ligands from both complexes to the copper surface is complete, as signaled by the reduction of the metal centers to the zero-valent state. The copper-bound hfac ligands are further transformed upon heating, either reacting with copper surface atoms to yield Cu(hfac)(2) (which desorbs at temperatures above 250 K) or decomposing (with fragments desorbing above 350 K). The presence of platinum on the copper surface promotes the former reaction as judged by the appearance of a new reaction-limited desorption process fur Cu(hfac)(2). The presence of rhodium on the copper surface does not promote the formation of Cu(hfac)(2). although autocalalysis is noted in the steady-stale reactive scattering data. The inability of the Rh and Pt precursors to engage in a sustained transmetalation reaction with the copper surface is attributed to the slow interdiffusion of copper through the Rh/Cu and Pt/Cu alloys that are produced in the near-surface region.