We report the first surface-selective depositions of Pd and Ag films from metal-organic precursors. We also describe mechanistic studies of this process by in situ kinetic and spectroscopic studies conducted in ultrahigh vacuum. We have studied three precursors containing the hexafluoroacetylacetonato (hfac) ligand: Pd(hfac)[sub 2] (1), Ag(hfac)(PMe[sub 3]) (2), and AF(hfac)(PMe[sub 3])[sub 2] (3). These compounds (especially 1) are reasonably volatile and sublime readily in vacuo at temperatures of 20-50[degree]C. Chemical vapor depositions from these precursors have been conducted at 200-245[degree]C both under vacuum (10[sup [minus]4] Torr) and in the presence of H[sub 2]. In the presence of H[sub 2], Pd(hfac)[sub 2] readily gives micron-thick films of pure palladium metal on glass, silicon, copper, tungsten, aluminum, and nickel at temperatures as low as 200[degrees]C. Mass spectrometic analysis of the byproducts suggests that deposition of Pd involves the reaction of Pd(hfac)[sub 2] with H[sub 2] to form hexafluoroacetylacetone (hfacH). Similar surface-independent depositions of Ag films are observed for the silver precursors under an H[sub 2] atmosphere. This redox transmetalation route may be generally applicable provided that the redox potentials are favorable and that the surface atoms can be carried away as a volatile hfac complex. 33 refs., 1 fig.