Synthesis And Reactivities Properties Of New Tridentate NNP Ligands Based Rare Earth Metal Complexes

The dissertation presents the synthesis and reactivity of rare-earth metal complexes supported by new tridentate NNP mutidentate ?-diketiminato and amidine-type ligands.In addition,we attempted to synthesis the main group metal hydrides based on new tridentate mutidentate NNP amidine ligands1.Synthesis of cationic scandium aryloxy complexes.New ligands HL1-HL14 supported by a new type of tridentate NNP mutidentate ligands were synthesized.And then scandium dialkyl complexes[LScR2][R=CH2SiMe3,L=L1(7);L4(11);L5(8);L6(9);L7(10);L8(35);L14(36)]and[LScR'2][R'=o-CH2C6H4NMe2,L=L8(37);L9(38)]were synthesized.Treatment of the resulting scandium dialkyl complexes with equimolar 2,6-ditert-butylphenol afforded the mixed alkyl/aryloxide species[LScR(OAr)][R=(CH2SiMe3)2,L=L1(12):L5(13):L6(14);L7(15):L14(39),Ar=2,6-'Bu2-C6H3]?[LScR'(OAr)][R'=o-CH2C6H4NMe2,L8(40);L9(41),Ar=2,6-'Bu2-C6H3].Finally,the desired complexes[LSc(OAr)][B(C6F5)4][L=L1(16);L5(17);L6(18);L7(19);L13(42);L8(43);L9(44),Ar=2,6-'Bu2-C6H3]were successfully synthesized through protonolysis of 21-23 by using the Br(?)nsted acid[PhNMe2H][B(C6F5)4].Complexes 13,15,37 and 38 were characterized by X-ray single crystal diffraction.2.Based on the cationic scandium aryloxyl complexes obtained,their reaction performance in the activation of small molecules was studied(1)In the reaction of complex 16 with phenyl isocyanate,4-isopropyl phenyl isocyanate,phenyl isocyanate and benzaldehyde,Sc/?-C[4+2]cycloaddition product 20-23 were obtained.Complexes 21 and 22 were characterized by X-ray single crystal diffraction(2)Complex 17 reacted with phenyl isocyanate and 4-tert-butyl phenyl isocyanate,and the Sc/y-C[4+2]cycloaddition products 24 and 25 were also obtained(3)Complex 18 reacted with isopropyl benzaldehyde to obtain Sc/P FLP type reaction product 26(4)Complex 19 reacted with phenyl isocyanate,methyl methacrylate(MMA)and y-methyl-a-methylene-?-butylactone(MMBL)to obtain Sc/P FLP type reaction product 27-29.Complex 29 was characterized by X-ray single crystal diffraction.Complex 19 exhibited high polymerization activity and initiation efficiency in catalytic polymerization of monomer MMBL(5)The activation of complexes 42-44 on unconjugated small molecule substrates also showed FLP-type reactivity.