Thermal reactions of Ru₃(CO)₁₂ with hexa-2,4-diyne-1,6-diol and 1,4-diphenyl-1,3-butadiyne were studied. Reaction of the triruthenium cluster with HOCH₂C₂C₂CH₂OH results in substitution of two CO groups and coordination of the diyne ligand to a ruthenium triangle in parallel μ₃,η²-mode via one of the conjugated triple bonds, The structure of the final product Ru₃(CO)₁₀(μ₃,η²-HOCH₂C₂C₂CH₂OH) was determined by a single-crystal X-ray study. The analogous reaction with PhC₂C₂Ph affords the binuclear ruthenium complex Ru₂(CO)₆, (μ₃,η₄-C(Ph)C(C₂Ph)C(C₂Ph)C(Ph)). The starting diyne ligand in this complex is dimerized forming a ruthenacyclopentadiene ring Ru-C(Ph)=C(R)C(R)=C(Ph). As a whole, the structural unit obtained can be rationalized as a cluster skeleton containing two d-and four p-elements arranged into nido pentagonal bipyramid with eight skeletal electron pairs; this cluster pattern is very typical for the iron subgroup alkyne polynuclear complexes.