C – C coupling of ethyne to the carbido ligand in products from reactions with Ru5(μ5C)(CO)15

The reaction of Ru5(μ5-C)(CO)15, 1 with C2H2 at 48 °C for 60 h yielded four new pentaruthenium carbonyl cluster compounds: Ru5[μ5-η5-CC(H)C(H)C(H)C(H)](CO)13(μ4-η2-HCCH), 2; Ru5[μ4-η5-CC(H)C(H)C(H)C(H)](CO)12(μ4-η2-HCCH), 3; Ru5(CO)13[μ4-η7-C(H)C(H)CC(H)C(H)C(H)C(H)], 4 and Ru4(CO)11(μ4-η2-HCCH)Ru(CO)3(μ-η1-η5-C5H4), 5. Compounds 2 3 were formed by opening the Ru5 1, addition three equivalents C2H2, two which became coupled to each other carbido ligand form bridging CC(H)C(H)C(H)C(H), pentadienyl ligands. also contain a quadruply-bridging η2-HCCH ligand. Compound contains an open cluster, in heptadienyl η7-C(H)C(H)CC(H)C(H)C(H)C(H) 5 butterfly-tetrahedral Ru4 Ru(CO)3(μ-η1-η5-C5H4) grouping containing metalated-cyclopentadienyl that is linked one wing-tip Ru atoms cluster. believed have been cyclization bridging, compound 2. All compounds characterized single-crystal X-ray diffraction analyses.