《稀土金属有机化学》PPT课件.ppt

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Chapter13LanthanideComplexesandTheirApplications,TypicalLanthanideComplexesandSyntheticMethodologies,LanthanideCarbene,J.Am.Chem.Soc.,2007,129(17),5360-5361.,Organometallics,2007,26(13),3167-3172,Organometallics,2008,ASAPArticle,LanthanidePhosphinideneComplex,J.Am.Chem.Soc.2008,130,2408-2409,二.ReactivityStoichiometricReactions,CatalyticReactions1.CatalyticHydrogenation,2.LanthanideComplexesCatalyzedHydroamination/CyclizationReactions,Marks,T.J.etal,Organometallics1999,18,2568,Marks,T.J.;etal,J.Am.Chem.Soc.1999,121,3633.,Livinghouse,T.etal,Adv.Synth.Catal.2006,348,701-704.,LanthanideComplexesCatalyzedHydroamination/CyclizationReactionsofaminoalkynes,3.LanthanideComplexesCatalyzedHydrophosphination/CyclizationReactions,Marks,T.J.etal,J.Am.Chem.Soc.2000,122,1824.Marks,T.J.etal,Organometallics2003,22,4630,4.CatalyticHydrosilylation,Livinghouse,T.;etal,Organometallics2004,23,12-14.,5.CatalyticHydroborationReaction,6.GuanylationofAromaticAmines,BuildingBlockexistsinmanybioactivecompounds,Zhang,W.;Nishiura,M.;Hou,Z.Chem.Eur.J.2007,13,4037.,CatalyticAdditionoftheAminetotheCarbodiimides,CatalyticAdditionoftheAminestotheCarbodiimides,CatalyticActivityoftheCp-FreeLanthanideAmidesontheAdditionofAminestoCarbodiimides,PlotofYieldsofGuanidineversusReactionTime.TheReactionwasperformedbytreating1equiv.ofanilinewith1equiv.ofN,N-dicyclohexylcarbodiimide.,CatalyticAdditionoftheC-HBondtotheCarbodiimide,CatalyticAdditionofthealkynestotheCarbodiimides,Zhou,S.;Wang,S.*etal,Organometallics2007,26,3755.Li,Q.;Wang,S.*etal,J.Org.Chem.2007,72,6763.,7.LanthanideComplexesCatalyzedOlefinPolymerization,Cat.=Me2Si(Me4C5)(C5H3R*)LnN(SiMe3)2O(CH2H2C9H6)2LnN(SiMe3)2,Qian,C.T.;etal,Organometallics2001,20,3106.Yamamoto,Y.;Marks,T.J.etal,J.Am.Chem.Soc.1995,117,3276.Anwander,R.;etal,Organometallics2003,22,1212.,8.LanthanideComplexesInitiatedCannizzaroTypeDisproportionation,Themethodologyforthepreparationofamidefromaldehyde,BeckmannRearrangement,Indirectmethod,Catalyticreaction,Optimizationofthereactionconditions,Reactionconditions:tolueneassolvent;roomtemperature;2-3d,TheresultsofthereactionofaldehydeswithlithiumamidecatalyzedbyYCl3,aReactionconditions:tolueneassolvent;roomtemperature;bIsolatedyieldbasedonthelithiumamide;cIsolatedyieldsintheabsenceofYCl3areshowninparentheses.,Theeffectsoflanthanidemetalonthereaction,Themechanismofthecatalyticreaction,Theresultsofreactionofaldehydeswithyttriumamide(Me3Si)2N3Y(-Cl)Li(THF)3,TheresultsofthereactionprobedbyGC-MS,Theprocessofthehydridetransferinthereaction,TheproposedmechanismfortheCannizarro-typereaction,Zhang,L.;Wang,S.etal.J.Org.Chem.2006,71,3149-3153.,9.CatalyticCyclotrimerizationofAromaticIsocyanates,Shen,Q.;etal,Organometallics2002,21,2529.Shen,Q.;etal,Organometallics1997,16,3711.,CanLanthanideAmidesSelectivelyCatalyzeCyclotrimerizationofAromaticIsocyanates?,IfthelanthanideamideshavedifferentMetal-Nitrogenbonds,Whatstheselectivity?,SynthesisofthelanthanideamidesofIncorporatingadiamidoligandwithaCH2SiMe2link,DyComplex,Smcomplex,Ybcomplex,Ycomplex,?,Optimizedconditionsonthecyclotrimerizationofphenylisocyanate,Table.Theinfluenceofdifferentrareearthmetalamidesonthecyclotrimerizationofphenylisocyanate,continued,DatafortheCyclotrimerizationofDifferentIsocyanates,Conditions,solvent:THF;asolvent:toluene,Wu,Y.;Wang,S.;etal,Inorg.Chem.2008,inpress.,SynthesisofthelanthanideamidesincorporatingadiamidoligangwithaMe2SiBridge,Ln=Yb(7),Y(8),Eu(9),Sm(11),Nd(11),YbComplex,Smcomplex,NdComplex,YComplex,CatalyticActivityoftheComplexesonCyclotrimerizationofPhenylIsocyanate,Catalyst:(Me2Si)(2,6-iPr2C6H3)N2SmN(SiMe3)2(THF)(9),Influenceofdifferentrareearthmetalamidesonthecyclotrimerizationofphenylisocyanate,aCatalystloading:0.25mol%;bIsolatedyieldbyrunningthereactioninTHFat40Cfor12h.ccatalystloading:1mol%;dIsolatedyieldbyrunningthereactioninTHFat60Cfor24h,Dataforthecyclotrimerizationofdifferentisocyanates,CrystalStructuresofcyclotrimerizationproducts,SelectiveReactionofDifferentMetal-NitrogenBondswithGrease,Ytterbiumcomplex,Samariumcomplex,ProposedCatalyticCycle,HeterolysisoftheLn-NBond,CantheLn-NBondbeHomolyticCleavage?,10.HomolysisofLanthanideMetal-NitrogenBond,SynthesisandCharacterizationofTetracoordinatedLanthanideAmides,N(1)-Yb-N(2)114.83(18)N(1)-Yb-N(3)117.88(18)N(3)-Yb-N(2)117.2(2)Cl-Yb-N(1)100.77(13)Cl-Yb-N(2)100.71(14)Cl-Yb-N(3)100.59(13),Zhou,S.;Wang,S*.etal,Polyhedron2003,22,1019.,HomolysisoftheYb-NBond,HeteroatomSubstitutedGroupEffect,(Me3Si)2N3LnIII(-Cl)Li(THF)3(Ln=Yb,Eu,Sm),Sheng,E.;Wang,S.Organometallics2003,22,684.,ProposedMechanism,Wang,S.;Zhou,S.;etalOrganometallics2003,22,3546,Wang,S.;Tang,X.;Vega,A.;Saillard,J.-Y.;etal.Organometallics2006,25,2399-2401.Organometallics,2007,26,1512-1522.,ControlledSynthesisofrac-OganometallicCompounds,Rac-Lanthanide(II)andLanthanide(III)complexes,Rac-Divalentandtrivalentlanthanidecomplexes,europiumcomplex,Ytterbiumcomplex,
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