Nickel, Iron, And Rare-earth Complexes Supported By Non-innocent Ligand: Synthesis, Characterization And Catalytic Properties

In this thesis, some nickel, iron, and rare-earth complexes supported bynon-innocent BIAN ligands were designed and synthesized. All these new compoundshave been characterized by1H NMR,13C NMR, and the molecular structure of somenickel, and yttrium complexes were well established by single crystal X-raydiffraction analysis.In the second chapter, three kinds of Ni complexes have been synthesized by thereactions of sodium of the ligand BIAN with different Ni chloride and structurallycharacterized. The complexes show moderate activities in ethylene polymerizationwith aluminum alkyl as the cocatalyst. In order to investigate the mechanism, thereactions of the neutral nickel complexes with alkylaluminum were studied in detail,from which the Ni-Al dinuclear complex bearing the monoaninic ligand was obtained.Further treatment of the dinuclear complex with borate affords the cationic bisligantednickel complex, which shows no catalytic activity in ethylene polymerization. Thepolymerization data and the reaction of the nickel complexes with differentcocatalysts reveal that in the polymerization system involving the Brookhart catalyst(neutral ccomplexes) and MAO, the quasi neutral mechanism was more reasonable.In the third chapter, a series of different substituents BIAN ligands have beensynthesized via several different methods. And the reaction of these BIAN ligandswith FeCl2affords corresponding BIAN iron complexes. All the iron complexes havebeen employed to catalyze the polymerization of isoprene. The polymerization resultshow that these catalysts are active in isoprene polymerization.The selectivity of thepolymers were sensitive to the substituents in the ligands and varied in the rangeform1,4-selective (88%), to3,4-selective(84%).In the last part, two methods were used to synthesize the rare-earth complexesbased on BIAN. The one was the reaction of ligand sodium and the rare-earthchlorides, and the other was the direct reaction of alkyl rare-earth complexes with theBIAN ligand. All the complex was characterized by NMR, and one molecular structure was confirmed X-ray crystallography.