Silylamine Modified Metal Imine Compounds: Synthesis Characterization And Their Catalytic Activities

This dissertation focuses on synthesis, characterization and their ethylene polymerization of silylamine modified metal imine compounds. Includingη3-1-azaallyl,η3-1,3-diazaallyl, silyl-linded amidinate-amidine ligands, the four kinds of ligands and their corresponding transition metal complexes were successfully prepared. These compounds were characterized by 1HNMR,13CNMR, elemental analysis and X-ray diffraction. Upon activation with aluminum compounds, their corresponding Zr complexes are active for ethylene (co)polymerization. Four main parts are included in this dissertation:Part 1:The introduction of metal and metalloid amide mainly with definition and classification is summarized. And the synthesis and development ofβ-diketiminate ligands has been briefly discussed.Part 2:A novel silyl-linked amidinate-amidine monoanionic ligand 3 was synthesized by double additions of PhCN starting from silyl-linked bis(amino) monoanion 2, which undergoing an intramolecular Li/H metathesis and twice bulky silyl-group shifts. The related Zr(IV) complex 4 was prepared and confirmed by X-ray diffraction enduring a structural rearrangement from its precursor. The mechanisms for the reaction processes have been proposed. Each of compounds 2,3 and 4 was characterized by NMR spectroscopy, element analysis and X-ray diffraction. The complex 4 exhibited moderate activity for ethylene polymerizationin the presence of methylalumoxane (MAO), copolymerization of ethylene and 1-hexene. Relying on different complexes and reaction conditions, the resultant polyethylenes had the molecular weights with Mw in the range of 220-6580 kg/mol and the broader molecular weight distribution.Part 3:A series ofη-1-azaallyl ligands complexes 3a-3f were synthesized and characterized by NMR spectroscopy, element analysis and X-ray diffraction. Upon treatment with MAO, the Zr compound 3e showed moderate activity for ethylene polymerization in the presence of methylalumoxane (MAO).Part 4:A series ofη3-1,3-diazaallyl metal complexes 4a-4j were synthesized and characterized by elemental and spectroscopic analysis as well as by single-crystal X-ray crystallography.Part 5:A series of silyl-modified toluene metal compounds 5a-4h were synthesized and characterized by single-crystal X-ray crystallography. The interaction between silyl-modified toluene carbon anions and NiCl(CuCl2) will results reductive homo-coupling reaction.