The reaction of Pt2Ru4(CO)18, 1 with 1,8-bis(phenylethynyl)naphthalene, 2 has yielded two metal carbonyl cluster complexes: Ru2(CO)6[μ-η2-C10H6C4Ph2], 3 (60% yield) and Ru2Pt(CO)6[μ-η2-C10H6C4Ph2]2, 4 (8% yield). Both compounds were characterized by a single crystal X-ray diffraction analysis. Both products were formed as a result of fragmentation of the Pt2Ru4 cluster of 1. Compound 3 contains two ruthenium atoms. They are bridged by a tricyclic C10H6C4Ph2 ligand formed by the coupling of the two α-carbon atoms of the alkyne groups. The β-carbon atoms of the alkynes are σ-bonded to one of the ruthenium atoms to form a metallacycle and this entire group is π-bonded to the second ruthenium atom. Compound 4 contains two ruthenium atoms with a platinum atom between them. This molecule contains two tricyclic C10H6C4Ph2 ligands similar to that in 3, and two metallacycles formed by coordination of the β-carbon atoms of both ligands to the platinum atom. One ligand is π-bonded to each of the ruthenium atoms.