The Synthesis And Characterization Of Transition Metal Carbonyl Clusters Containing Phosphine And Sulfur Ligands

In recently decades,transition metal carbonyl cluster complexes have aroused general concern in Cluster chemistry,because of theircharacteristic for being metal clusters compounds.Other ligands that contain N, P, S are great substitute for the carbonyl ligand of transition metal carbonyl clusters,and the deverse coordination of transition metal atom is a plus for transition metal carbonyl cluster complexes to being precursors to conduct other new metal cluster complexes and organometallic compounds.Based on the characteristics of transition metal and ligand core atom, two transition metal carbonyl cluster complexes were choosen to obtain some new mixed-metal clusters.The reaction of Co(CO)4SnPh3 and the ligand containing organo aurum was designed to prepare some new materies with higher catalytic activity by inserting atom Au into bimetallic Co-Sn. Result showed that the bond of Co-Sn was broken in reaction,and bond Co-Au was forming. There weren't formation trimetallic carbonyl clusters containing Co,Au,Sn though, a new route to afford heterogeneous bimetallic Co-Au was investigated.To explore the bimetallic reactions, we have prepared the Fe4(CO)16(?4-Sn), and investigated its reaction with group VA donor ligands (SbPh3?PPh3). The reactions of PPh3 with Fe(CO)5, SbPh3 with Fe(CO)5, PPh3 with Fe2(CO)9, SbPh3 with Fe2(CO)9 were designed as control experiments. Results suggested that there is a bimetallic cooperation between atom Fe and atom Sn in the reaction process of Fe4(CO)16(?4-Sn) with group VA donor ligands. Because of the exsit of atom Sn, the CO ligand was divorced from Fe(CO)4, and then bond Fe-VA(P or Sb) was forming. A bimetallic phosphine derivative and a trimetallic Fe-Sn-Sb cluster complex were synthesized under mild condition. Both cluster were characterized by single crystal XRD, and ORTEM diagramssuggest that the phosphine group is in a trans-position to the tin atom about Fe(2), while the antimony group is in a cis-position to the tin atom about Fe(1).