Treatment of the carbido cluster Ru5(μ5-C)(CO)15 with Me3NO followed by addition of the tungsten acetylide complexes LW(CO)3(CCPh) (L = Cp, C5Me5) affords the two heterometallic cluster complexes LWRu5(μ5-C)(CCPh)(CO)15 (1a, L = Cp; 1b, L = C5Me5) and LWRu5(μ5-C)(CCPh)(CO)13 (2a, L = Cp; 2b, L = C5Me5). Thermolysis of 1 results in the irreversible formation of 2. The reactivity of 2 was studied. Thus, hydrogenation of 2b furnishes the two cluster compounds (C5Me5)WRu5(μ6-C)(μ-CCH2Ph)(μ-H)2(CO)13 (3) and (C5Me5)WRu5(μ4-C)(μ3-CCH2Ph)(μ-H)4(CO)12 (4), generated via 1,1-addition of H2 to the ligated acetylide and concurrent formation of two or four bridging hydrides. Treatment of 3 with CO gives the octahedral cluster (C5Me5)WRu5(μ6-C)(μ-CCH2Ph)(CO)14 (5). The spectral and structural properties of all species are presented and discussed.

Treatment of carbido cluster Rus(/zs-C)(CO)~5 with Me3NO in acetonitrile solution followed by addition of dimethyl maleate or dimethyl acetylene dicarboxylate affords new clusters Rus(/zs-C)(CO)~3[C2H2(CO2Me)2] (1) and Rus(/zs-C)(CO)Is[C2(CO2Me)2] (2), respectively. Single crystal X-ray structural studies reveal that both complexes contain a wingtip-bridged butterfly pentametallic skeleton. In complex 1 the maleate fragment is coordinated to one wingtip Ru atom through its carbon-carbon double bond and to the adjacent Ru atom by the formation of two O ~ Ru dative bonding interactions, while the acetylene dicarboxylate fragment in 2 is best considered as a cis-dimetaUated alkene, linking one hinge Ru atom and the nearby Ru atom at the bridged position.