1.Synthesis And Characterization Of Iron, Cobalt And Nickel Complexes Supported By Fulvene Ligands2. Application Of Electron-rich Cobalt And Nickel Complexes Supported By Phosphine Ligands In C-H Bond Activation

Fulvene which has the same formula with benzene is a common ligand in organometallic chemistry. Most fulvenes are synthesized via reactions starting from cyclopentadiene and aldehydes or ketones. Fulvene can react with metal directly, or form metallocene complexes with metal halide by forming cyclopentadiene anion first. The direct reaction between fulvene with metal will produce the compounds with the coordination of η2, η3, η4,η5or η6.The reaction between fulvene and organometallic reagents (organolithium reagents, organic sodiumreagent format reagent, grignard reagent), which forms cyclopentadiene anion, makes the synthesis metallocene complex of the more convenient. Novel metal complexes which have potential applications can be prepared directly by the reaction between fulvene and metal ligands, such as Mo(CO)6Co2(CO)8、Fe2(CO)9. Furthermore, Diels-Aider reaction of fulvene exhibit new approaches to synthesis polycyclic compounds.Because of the versatile applications and scientific importance of fulvene, part of the research during my post graduate studying is focused on the reactions between fulvene derivates and low valent metal, which is supported by trimethylphosphine.Novel metal complexes have been synthesized by the anchoring effect of the cyclopentadienyl ring and heteroatoms, and characterized by IR,1H NMR and31P NMR. Structures of some compounds have been confirmed by X-ray diffraction techniques. Carbon-hydrogen bond activation is of great importance not only in the research on fundamental theories but also in industrial applications. Many of these studies have involved C-H bond activation mediated by transitionemetal complexes. Pd, Ru, Rh based catalysts have attracted much more attention in C-H activation and catalysis. Fe, Co and Ni complexes are relatively underdeveloped, although they have potentially lower cost and environmental impact. Trimethylphosphine is a kind of good ligand with the advantages of strong ability of coordination, convenient preparation and simple spectrometry. Cobalt, Nickel complexes supported by trimethylphosphine are so activated that they can cut C-H bonds.Main contents of this dissertation are shown as below:1. The C-H bond activations in2-[(Diphenylphosphino)methyl]pyridine were investigated using Cobalt, Nickel complexes supported by trimethylphosphine. Unexpectedly, C-H activation with a P-donor group did not occur, instead a series of novel complexes were formed.2-[(Diphenylphosphino)methyl]pyridine in the reaction with CoMe(PMe3)4afforded (PMe3)3Co{CNC4H3CH3P(C6H5)2} complex.The synthesized complexes were fully characterized by NMR spectroscopy techniques and complexes4crystal structures were determined by single-crystal X-ray crystallography.2.The C-H bond activations in1,5-Bis(diphenylphosphino)pentane were investigated using Cobalt, Nickel complexes supported by trimethylphosphine.