席夫碱稀土配合物合成及其催化内酯开环聚合性能-synthesis of schiff base rare earth complexes and their catalytic properties for ring-opening polymerization of lactones.docxVIP

席夫碱稀土配合物的合成及其催化内酯开环聚合性能英文摘要SynthesisoflanthanidecomplexessupportedbySchiff-baseligandsandtheircatalyticbehaviorforthering-openingpolymerizationoflactonesAbstractTwelvelanthanidecomplexessupportedbySchiff-baseligandsweresynthesizedandcharacterized.Theircatalyticbehaviorforthering-openingpolymerizationofε-caprolactone、L-lactideandD,L-lactidewasalsostudied.Themainresultsareasfollowing:ReactionsofSchiff-baseligand3,5-But-2-(OH)-CHCH=N-2-Cl-CH(HL1)26264withLn[N(SiMe3)2]2(THF)2affordeddivalentlanthanideSchiff-basecomplex[L12Eu]2(1)forthelessactiveEu,whiletrivalentlanthanideSchiff-basecomplex4wasformedfortheactiveYbviatheligandreductivecoupling.Meanwhilethereactivityofcomplex1withO2wasalsotestedandtheperoxidebridgedlanthanidecomplex[L12Eu(THF)]2(μ-η2:η2-O2)(5)wasalsoachieved.Complexes1,4and5werecharacterizedbyelementanalysis,FT-IRandsinglecrystalX-raydiffraction.ReactionsofSchiff-baseligands,3,5-But-2-(OH)-CHCH=N-2,4-Cl-CH262263(HL2)and3,5-But-2-(OH)-CHCH=N-2-OCH-CH(HL3),with262364Eu[N(SiMe3)2]2(THF)2affordeddivalenteuropiumSchiff-basecomplexes[L22Eu]2(2)and[L32Eu]2(3)respectively.Bothcomplexes2and3werecharacterizedbyelementanalysisandFT-IR.Moreover,Complex3werecharacterizedbysinglecrystalX-raydiffraction.Treatmentsofβ-ketoiminateligand(C6H5)COCHC(CH3)NH-4-Cl-C6H4(HL4)withLn[N(SiMe3)2]3affordedhomolepticcomplexesLnL43(THF)n[n=0,Ln=Yb(6),Y(7);n=1Ln=Nd(8)].Thosethreecomplexescharacterizedbyelementanalysis,FT-IRandsinglecrystalX-raydiffraction.ReactionsofLnCl3with1equivofL5Li2[H2L5=(C6H5)COCHC(CH3)NHCH2CH2NHC(CH3)CH2CO(C6H5)]affordedthemononuclear英文摘要席夫碱稀土配合物的合成及其催化内酯开环聚合性能lanthanidechlorideL5LnCl(THF)2(Ln=Yb(9),Y(10)).Bothcomplexes9and10werecharacterizedbyelementanalysis,FT-IRandsinglecrystalX-raydiffraction.Complex9wasusedasstartingmaterialtoprepareβ-ketoiminate-ytterbiumderivatives.Treatmentofcomplex9withNaN(SiMe3)2producedthedimericytterbiumamide{L5Yb[N(SiMe3)2]}2(11),whilesimilarreactionofcomplex9withNaOAr(ArO=2,6-But-4-MeC6H2O)ledtothemononuclearytterbiumaryloxideL5YbOA