A two-step surface functionalization approach has been used to encase Au nanoparticles in monolayer organometallic Ru-complex shells by the reaction of an intermediate surface-bound mercaptopropanoic acid capping species with Ru dodecacarbonyl (Ru-3(CO)(12)) clusters. Vibrational ( infrared and Raman) spectroscopy shows that insertion of carboxylate groups into the Ru clusters results in their fragmentation and the formation of a shell of Ru dicarbonyl carboxylate oligomers that remain attached to the Au nanoparticles through the original Au-alkanethiolate bonds. The structural integrity of the metallic nanoparticulate Au cores has been verified by X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy. The organometallic Ru-complex shell may be decomposed thermally to eliminate the mercaptopropanoate and carbonyl groups and leave a mixed phase of Au and RuO2.