Synthesis,Characterization And Properties Of Half-Sandwich Iridium And Ruthenium Complexes With Acylhydrazone

One of the most important methods for synthesizing C-N bonds in organic synthesis is the N-alkylation of amines.The method mainly applies the hydrogen borrowing strategy.It mainly uses transition metal catalysts to activate alcohols as reagents for alkylation reaction.Half-sandwich metal complexes boast high thermal stability,good catalytic properties and rich reactivity,therefore attracting much attention from researchers in recent years.Starting from the[Cp*IrCl₂]₂（Cp*=pentamethylcyclopentadienyl）structure,a series of iridium（Ⅲ）complexes containing half-sandwich structures are synthesized.On top of that,the application of these complexes in N-alkylation of amine compounds is studied.The main research work is as follows:1.A series of acylhydrazone ligands are prepared by reacting benzoylhydrazine with acetophenone of different electronic substituent effect.Later,by reacting the acylhydrazone ligands with[Cp*IrCl₂]₂,the half-sandwich iridium complexes that support N,O-coordination with acylhydrazone ligands are successfully prepared.Then,the synthesized iridium complexes are characterized by NMR,EA,FI-IR,etc.The single crystals of the complexes are also cultured by means of solvent diffusion to confirm their fine structures by X-ray diffraction.Moreover,with the complexes as catalysts,the optimal conditions for the N-alkylation reaction of alcohols and amines are topped out.According to the results,the iridium complexes have high catalytic efficiency and good substrate universality.2.By reacting benzoylhydrazine with acetophenone with different electronic substituent effect under acidic conditions and then reacting the four synthesized ligands with different electronic effect with[（p-cymene）RuCl₂]₂,a series of N,O-coordinated half-sandwich ruthenium complexes are produced.The obtained complexes are characterized by NMR,FI-IR,etc.