Synthesis,Characterization And Properties Of Iron,Titanium,Zirconium,Hafnium Complexes Supported By N-aryl-phenanthren(Acenphthen)-iminoquinone Ligands

In recent years,the conception of non-innocent ligand has been used more and more widely.A large quantity of novel ligands,with conjudged framework and redox-activity,have been designed and synthesized.Imino ligands reacting with transitional metals can synthesize various of organometallic complexs,whose structures are stable and catalysis properties are excellent.Therefore,exploring the chemical changes between imino ligands and central metals in the process of forming coordination complexes is of great importance.In this paper,we have successfully designed and synthesized kinds of novel Fe,Ti,Zr,Hf complexes supported by N-aryl-phenanthren(acenphthen)-iminoquinone ligands.In order to research the reaction process about how the ligand deliver its redox-activity,we characterize the structures and magnetic property of these complexes by NMR,X-ray diffraction analysis,Mossbauer spectroscopy and SQUID temperature-dependent magnetization.DFT calculation of these compounds also plays an vital role in analyzing the redox-activity in the reaction.In the third chapter,five kinds of different Iron complexes supported by N-aryl-phenanthren-iminoquinone have been synthesized successfully.It is found that the redox-reaction occurs in the formation of the coordination complexes through the combination of structural and magnetic property characterization.The ligands can contain one or two electrons to form radical anionic or dianionic amino-phenolato under the coordination circumstance,which like electronic sponge that can absorb and release electrons from central metals.In the fourth chapter,series of novel Ti,Zr,Hf complexes supported by N-aryl-phenanthren(acenphthen)-iminoquinone have been synthesized successfully.Six stable complexes were prepared by Mg complexes of these ligands reacting with the fourth subgroup metals.The ligands in these complxes were found to have a dianionic amino-phenolato nature.We have made it clear that whether the ligands change their oxide-state when they coordinate with central metal.