Synthesis And Characterization Of (μ₃-CR)Co₃ Tetrahedral Carbonyl Clusters Containing Triphosphine Ligand And Cobalt Carbonyl Clusters Containing Lanthanide

There are two sections in this paper. 1. Reactions of a series of tetrahedral cobalt carbonylclusters with organic triphosphine compound were carried out to construct the multinuclearcarbonyl clusters. 2. Several rare earth complexes coordinated with cobalt carbonyl cluster werealso attempted to prepare in order to obtain the complexes containing lanthanide andtransition-metal.First, five tetrahedral cobalt carbonyl clusters, PhCCo₃(CO)₉, CHCo₃(CO)₉, ClCCo₃(CO)₉,HOOCCCo₃(CO)₉, (CH₃)₃CO₂CCCo₃(CO)₉ were synthesized according to the methods ofliteratures. The reaction of these tetrahedron cobalt clusters with the triphosphine compound[(C₆H₅)₂PCH₂]₃CCH₃ (1,1-Tris(diphenylphosphiomethyl)ethane) (L) afforded eight (μ₃-CR)Co₃tetrahedral carbonyl clusters containing triphosphine ligand. All clusters were characterized by C/Hanalysis, IR and ¹H NMR; several of them were characterized by ³¹P-NMR and MS analysis.Clusterlwas determined by X-ray single crystal diffraction analysis. According to the analysis data,we know that three phosphorus atoms of ligand L bonded to three cobalt atoms of tetrahedral cobaltcarbonyl cluster in cluster 1, respectively, and the structure of cluster 4 is similar to that of cluster1. And in other clusters, the three cobalt atoms not only were coordinated with three phosphorusatoms but also were bonded with one or two Co(CO)₃ unit, respectively.Second, reactions of lanthanide complexes with cobalt carbonyl cluster containing the hydroxylgroup were also carried out in order to obtain the complexes containing lanthanide andtransition-metal for the study of electrochemistry. Unfortunately, we did not obtain the desired products and only got some unknown complexes which were simply characterized by C/H analysis,IR, fluorescent spectroscopy and ICP.