The compound Rh(CO)(4)GePh3, 3, was obtained in a high yield (95%) from the reaction of [Rh(CO)(2)Cl](2) with LiGePh3 under a CO atmosphere. Reaction of 3 with HGePh3 yielded the new dirhodium compound Rh-2(CO)(6)(GePh3)(2)(mu-GePh2), 4 (55% yield), by a loss of CO and the combination of one equivalent of HGePh3 with two equivalents of 3. Compound 4 contains contains a Rh-Rh bond and a bridging GePh2 ligand formed by cleavage of a phenyl group from a GePh3 ligand. Compound 4 reacts with Pt(PBu3t)(2) to add a Pt(PBu3t) to the Rh-Rh bond to form the compound PtRh2(CO)(6)(GePh3)(2)(PBu3t)(mu-GePh2), 5 (42% yield). Fenske-Hall molecular orbitals were calculated for compounds 4 and 5 to explain the nature of the metal-metal bonding in these compounds. Compounds 3-5 were fully characterized by IR, NMR, and single-crystal X-ray diffraction analyses.