| In this paper, the reactions of simple transition metal carbonyl clusters with organic multi-phosphine compounds were carried out. Additionally, the syntheses of mixed metal double polyhedral carbonyl clusters containing alkyne-bridging were investigated.During this work, a total of eight clusters were obtained, including seven unreported clusters and one known cluster synthesized by the other method. All clusters were characterized by C/H analysis; IR and 1H NMR; several of them containing P atom were characterized by 31P-NMR. In addition, Cluster 1 was determined by X-ray single crystal diffraction analysis and Cluster 3 and 6 were characterized by MS analysis.Firstly, the reactions of Fe3(CO)12, Ru3(CO)12, Co2(CO)6(C2Ph2), and Co2(CO)6 (HCCCH2OH) with triphosphine ligand [(C6H5)2PCH2]3CCH3 (1,1-Tris(diphenyl phosphiomethyl)ethane) (L1) afforded three bimetallic carbonyl clusters bridged by triphosphine ligand (Cluster 1, Cluster 2 and Cluster 4) and two linked carbonyl clusters containing Co2C2 unit (Cluster 3 and Cluster 5).Secondly, the reaction of Co2(CO)6(C2Ph2) with [(C6H5)2P(CH2)]3P (Tris(2-diphenylphosphino ethyl)phosphine) (L2) afforded a phosphine-linked cluster containing two Co2C2 units (cluster 6).Thirdly, the reaction of cluster (Co2(CO)6)2(CH≡CCH2OCO)2 with Fe3(CO)12 were investigated to give a linked cluster containing a tetrahedral cluster unit and a octahedral cluster unit (cluster 7).Lastly, a known cobalt complex (compound 8) coordinated with six sulfur atoms was obtained by reaction of Co2(CO)6(C2Ph2) with ligand (L3).
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