The Synthesis And Catalytic Properties Of Main Group-,Transition-and Rare Earth-Organometallic Compounds Based On ?-Diketiminate Ligands

In this paper,the synthesis and catalytic properties of main group-,transition-and rare earth-metal complexes based on ?-diketiminate ligands were studied.It includes the following four parts.Firstly,the ?-diketiminate ligand HL1(HL1=N-{-4-[(2,6-diisopropyl-phenylamino)pent-3-en-2-ylidene]-6-methyl}pyridin-2-amine)was designed and synthesized.Three aluminum complexes of formulae[Al(L1)Me2](1),[Al(L1)Et2](2)and[AI(L1)EtCl](3)were prepared.Complexes 1-3 were characterized by NMR and elemental analysis,and their structures were determined by X-ray single crystal diffraction analyses.Compounds 1-3 are mononuclear.It was found that complexes 1-3 could catalyze the ring-opening polymerization of ?-caprolactone in the presence of benzyl alcohol.Secondly,the reactions of ligands HL1 and HL2(HL2=N-{4-[(2,6-diisopropyl-phenyl)imino]pent-2-en-2-yl}pyridin-2amine)with nBuLi and(nBu)2Mg,respectively,gave complexes of compositions[(LiL1)2](4),[(LiL2)2](5),[Mg(L1)2](6)and[Mg(L1)2(THF)](7).Complexes 4-7 were characterized by NMR and elemental analysis.The structures of 5 and 6 were determined by X-ray single crystal diffraction.It was found that complexes 4-7 could effectively catalyze the hydroboration of aldehydes/ketones.They all showed good activity.Thirdly,the reactions of the ligands HL1 and HL2 with FeBrZ,CoCl2 and CoBr2,respectively,generated compounds of formulae[Fe(HL1)Br2](8),[Fe(L2)Br2Li(THF)2](9),[Co2(L1)2Br2].Tol(10)and[Co2(L2)2Cl2](11).The structures of complexes 8-11 were determined by X-ray single crystal diffraction.Complex 9 is a Fe-Li bimetallic compound.Complex 8 could effectively catalyze the hydroboration of aldehydes.Fourthly,the 1:1:1 reaction of HL2/nBuLi/ScCl3 leads to the formation of compound[Sc(L2)Cl2(THF)]·Tol(12).The l:1:1:1 reaction of HL1/nBuLi/Y[N(SiMe3)2]3/AlMe3 results in the production of complex[Y(L1)3Al2Me3](13).The structures of 12 and 13 were determined by X-ray single crystal diffraction.Complex 13 was a Y-Al bimetallic compound.It was found that complex 12 could effectively catalyze the hydroboration of aldehydes/ketones.Very high yields are attained at very short time.