稀土金属有机化学.pptx

Chapter 13 Lanthanide Complexes and Their Applications一一.Typical Lanthanide Complexes and Synthetic MethodologiesLanthanide CarbeneJ.Am.Chem.Soc.,2007,129(17),5360-5361.Organometallics,2007,26(13),3167-3172,Organometallics,2008,ASAP Article,Lanthanide Phosphinidene ComplexJ.Am.Chem.Soc.2008,130,2408-2409二二.ReactivityStoichiometric ReactionsCatalytic Reactions1.Catalytic Hydrogenation2.Lanthanide Complexes Catalyzed Hydroamination/Cyclization ReactionsMarks,T.J.et al,Organometallics 1999,18,2568Marks,T.J.;et al,J.Am.Chem.Soc.1999,121,3633.Livinghouse,T.et al,Adv.Synth.Catal.2006,348,701-704.Lanthanide Complexes Catalyzed Hydroamination/Cyclization Reactions of aminoalkynes3.Lanthanide Complexes Catalyzed Hydrophosphination/Cyclization ReactionsMarks,T.J.et al,J.Am.Chem.Soc.2000,122,1824.Marks,T.J.et al,Organometallics 2003,22,46304.Catalytic Hydrosilylation催化剂产率（%，分离）选择性Cp*2LuMeTHF98100:0Cp*2YbCH(TMS)291100:0Cp*2YMeTHF84100:0Cp*2SmCH(TMS)29011:1Cp*2NdCH(TMS)2853.2:1Cp*2LaCH(TMS)2901.9:1Me2SiCp”2YCH(TMS)28431:1Me2SiCp”2SmCH(TMS)2981:2Me2SiCp”2NdCH(TMS)2891:2Livinghouse,T.;et al,Organometallics 2004,23,12-14.5.Catalytic Hydroboration Reaction6.Guanylation of Aromatic AminesBuilding Block exists in many bioactive compoundsZhang,W.;Nishiura,M.;Hou,Z.Chem.Eur.J.2007,13,4037.entryCat.RAmineTp(C)/time(h)ProductYield(%)a12Prir.t./1249322Cyr.t./12595(95)b(92)c32Prir.t./1269342Cyr.t./1279552Prir.t./1289262Cyr.t./1299472Prir.t./12109582Cyr.t./12119692Prir.t./121296(92)c102Cyr.t./121395112Prir.t./121492122Cyr.t./121591Catalytic Addition of the Amine to the Carbodiimides132Prir.t./121693142Cyr.t./121792152Prir.t./121892(88)c162Cyr.t./121993(95)b172Cy110/362080(82)b182Pri110/3620No reaction a,b,c192Cy110/3620No reaction a,b,c202Pri110/122395212Cy110/122497222Pri110/242581(84)b232Cy110/242685Catalytic Addition of the Amines to the CarbodiimidesCatalytic Activity of the Cp-Free Lanthanide Amides on the Addition of Amines to Carbodiimidesentry Cat.Loading(mol%)solvent temp.(C)time(h)Yieldb(%)15THFr.t.249223THFr.t.249531THFr.t.249540.5THFr.t.246650THF0 or 6024061toluener.t.249771Et2Or.t.249681hexaner.t.249691CH2Cl2r.t.2499entry catalyst ArNH2 yield 1Ln=YbPhNH2962Ln=YPhNH2973Ln=EuPhNH2964Ln=SmPhNH2985Ln=LaPhNH2996(Me3Si)2N3Yb PhNH2967(Me3Si)2N3Yb 4-O2NPhNH2938(Me3Si)2N3Y4-O2NPhNH292Plot of Yields of Guanidine versus Reaction Time.The Reaction was performed by treating 1 equiv.of aniline with 1 equiv.of N,N-dicyclohexylcarbodiimide.entryR1R2R3NHproductyield1i-Pr4-Cl-phenylNH21932Cy4-Cl-phenylNH22983t-Bu4-Cl-phenylNH23954i-Pr4-Br-phenylNH2489(88)5Cy4-Br-phenylNH2593(98)6i-Pr2-O2N-PhenylNH2662(85)7Cy2-O2N-PhenylNH2776(90)8i-Pr4-O2N-PhenylNH28909Cy4-O2N-PhenylNH2994Catalytic Addition of the C-H Bond to the CarbodiimideentryCata.RArTp(oC)/time(h)ProductYield(%)a11PriPh80/3359222PriPh80/3359033PriPh80/3359041CyPh80/3368952CyPh80/3368563CyPh80/3368671Pri4-MeOC6H480/3378581Cy4-MeOC6H480/3388393Cy4-MeOC6H480/33881101Pri4-FC6H480/33994111Pri4-ClC6H480/34095121Cy4-ClC6H480/34193Catalytic Addition of the alkynes to the CarbodiimidesZhou,S.;Wang,S.*et al,Organometallics 2007,26,3755.Li,Q.;Wang,S.*et al,J.Org.Chem.2007,72,6763.7.Lanthanide Complexes Catalyzed Olefin PolymerizationCat.=Me2Si(Me4C5)(C5H3R*)LnN(SiMe3)2 O(CH2H2C9H6)2LnN(SiMe3)2Qian,C.T.;et al,Organometallics 2001,20,3106.Yamamoto,Y.;Marks,T.J.et al,J.Am.Chem.Soc.1995,117,3276.Anwander,R.;et al,Organometallics 2003,22,1212.8.Lanthanide Complexes Initiated Cannizzaro Type DisproportionationThe methodology for the preparation of amide from aldehydeBeckmann RearrangementIndirect methodCatalytic reactionOptimization of the reaction conditionsratioaT(C)solventCat.()T(d)Yield of 3g(%)b1:1r.ttoluene52402:1r.t.toluene52853:1r.t.toluene52852:1r.t.C6H652852:1r.t.Et2O52652:1r.t.THF52402:1r.t.CH2Cl25202:1r.t.hexane52322:1r.t.toluene02472:1r.t.toluene22782:1r.t.toluene102802:10toluene52482:170toluene52402:1r.t.toluene51752:1r.t.toluene5388Reaction conditions:toluene as solvent;room temperature;2-3d Ar-T(d)Product of 3Yield of 3(%)bProduct of 4Yield of 4(%)bC6H5-33a56(18)c4a62(21)c4-CH3C6H4-33b624b654-CH3OC6H4-33c584c604-ClC6H4-23e764e784-BrC6H4-23f824f784-O2NC6H4-23g854g854-F3CC6H4-23j834j814-Me2NC6H4-33k524k50The results of the reaction of aldehydes with lithium amide catalyzed by YCl3aReaction conditions:toluene as solvent;room temperature;bIsolated yield based on the lithium amide;cIsolated yields in the absence of YCl3 are shown in parentheses.The effects of lanthanide metal on the reactionLnnoneYPrNdSmEuDyHoYbYield of 3(%)478560827870758085The mechanism of the catalytic reactionAr-solventTime(d)Product of 3Yield of 3(%)bProduct of 4Yield of 4(%)b4-O2NC6H4-CH2Cl223g934g884-O2NC6H4-C6H623g884g804-O2NC6H4-toluene23g884g804-O2NC6H4-Et2O23g704g724-O2NC6H4-THF23g474g50C6H5-CH2Cl233a584a624-CH3C6H4-CH2Cl233b684b704-CH3OC6H4-CH2Cl233c584c552-CH3OC6H4-CH2Cl233d574d594-ClC6H4-CH2Cl223e784e764-BrC6H4-CH2Cl223f824f782-Furyl-CH2Cl223h774h70C6H5CH=CH-CH2Cl233i524i584-F3CC6H4-CH2Cl223j904j854-Me2NC6H4-CH2Cl233k564k502,4-Cl2C6H3-CH2Cl223l914l802,4-(MeO)2C6H3-CH2Cl33m654m60The results of reaction of aldehydes with yttrium amide(Me3Si)2N3Y(-Cl)Li(THF)3The results of the reaction probed by GC-MSThe process of the hydride transfer in the reactionThe proposed mechanism for the Cannizarro-type reactionZhang,L.;Wang,S.et al.J.Org.Chem.2006,71,3149-3153.9.Catalytic Cyclotrimerization of Aromatic IsocyanatesShen,Q.;et al,Organometallics 2002,21,2529.Shen,Q.;et al,Organometallics 1997,16,3711.Can Lanthanide Amides Selectively Catalyze Cyclotrimerization of Aromatic Isocyanates?If the lanthanide amides have different Metal-Nitrogen bonds,Whats the selectivity?Synthesis of the lanthanide amides of Incorporating a diamido ligand with a CH2SiMe2 linkDy ComplexSm complexYb complexY complex?Optimized conditions on the cyclotrimerization of phenyl isocyanateEntryCat.(mol%)asolventTemp()/time(h)Yield(%)b13(3%)toluener.t./129923(2%)toluener.t./128333(1%)toluener.t./126643(1%)toluene80/129953(2%)THFr.t./129963(1%)THFr.t./129273(1%)THF50/129983(3%)CH2Cl2r.t./127193(3%)CH2Cl240/1299103(2%)CH2Cl240/1274113(1%)CH2Cl240/1262Table.The influence of different rare earth metal amides on the cyclotrimerization of phenyl isocyanateEntryCat.(mol%)a solventTemp(C)/time(h)Yield(%)b12(1%)toluener.t./126222(1%)toluene80/129932(1%)THFr.t./129943(1%)toluener.t./126653(1%)toluene80/129963(1%)THFr.t./129274(1%)toluener.t./126284(1%)toluene80/129994(1%)THFr.t./1299EntryCat.(mol%)a solventTemp(C)/time(h)Yield(%)b105(1%)toluener.t./1261115(1%)toluene80/1299125(1%)THFr.t./1299136(1%)toluener.t./1256146(1%)toluene80/1299156(1%)THFr.t./1299continuedData for the Cyclotrimerization of Different IsocyanatesentryCatR-t(C)/T(h)Yield(%)t(C)/time(h)Yield(%)12Phenylr.t./129950/12/23Phenylr.t./129250/129932Benzylr.t./129950/12/43Benzylr.t./129950/12/524-Isopropylphenylr.t./129950/12/634-Isopropylphenylr.t./124650/12817a34-Isopropylphenylr.t./125480/1299Conditions,solvent:THF;a solvent:tolueneWu,Y.;Wang,S.;et al,Inorg.Chem.2008,in press.Synthesis of the lanthanide amides incorporating a diamido ligang with a Me2Si Bridge Ln=Yb(7),Y(8),Eu(9),Sm(11),Nd(11)Yb ComplexSm complex Nd ComplexY ComplexCatalytic Activity of the Complexes on Cyclotrimerization of Phenyl IsocyanateEntryCat.(mol%)aSolventTemp(C)Time(h)Yield(%)b11%THFroom temp 129721%tolueneroom temp122731%Et2Oroom temp124441%n-hexaneroom temp124052%CH2Cl2room temp122461%THF4069371%THF40129780.5%THF40129790.25%THF401298100.25%toluene401221110.25%n-hexane401229Catalyst:(Me2Si)(2,6-iPr2C6H3)N2SmN(SiMe3)2(THF)(9)Influence of different rare earth metal amides on the cyclotrimerization of phenyl isocyanate EntryCatalystaYield(%)b1(Me2Si)(2,6-iPr2C6H3)N2YbN(SiMe3)2(THF)982(Me2Si)(2,6-iPr2C6H3)N2YN(SiMe3)2(THF)973(Me2Si)(2,6-iPr2C6H3)N2EuN(SiMe3)2(THF)964(Me2Si)(2,6-iPr2C6H3)N2SmN(SiMe3)2(THF)985(Me2Si)(2,6-iPr2C6H3)N2NdN(SiMe3)2(THF)926c(Me2Si)(C6H5)N2YbN(SiMe3)2(THF)95d7c(Me2Si)(C6H5)N2SmN(SiMe3)2(THF)98da Catalyst loading:0.25 mol%;b Isolated yield by running the reaction in THF at 40 C for 12h.c catalyst loading:1 mol%;d Isolated yield by running the reaction in THF at 60 C for 24h Data for the cyclotrimerization of different isocyanatesEntry CatalystR-T(C)/t(h)Yield(%)18Benzyl40/12h9429Benzyl40/12h95310Benzyl40/12h98484-Isopropylphenyl40/12h98594-Isopropylphenyl40/12h986104-Isopropylphenyl40/12h97784-Nitrophenyl40/12h088Cyclohexyl40/12h9099Cyclohexyl40/12h491010Cyclohexyl40/12h47Crystal Structures of cyclotrimerization productsSelective Reaction of Different Metal-Nitrogen Bonds with GreaseYtterbium complexSamarium complexProposed Catalytic CycleHeterolysis of the Ln-N BondCan the Ln-N Bond be Homolytic Cleavage?10.Homolysis of Lanthanide Metal-Nitrogen BondSynthesis and Characterization of Tetracoordinated Lanthanide AmidesN(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*.et al,Polyhedron 2003,22,1019.Homolysis of the Yb-N BondHeteroatom Substituted Group Effect(Me3Si)2N3LnIII(-Cl)Li(THF)3 (Ln=Yb,Eu,Sm)Sheng,E.;Wang,S.Organometallics 2003,22,684.Proposed MechanismWang,S.;Zhou,S.;et al Organometallics 2003,22,3546Wang,S.;Tang,X.;Vega,A.;Saillard,J.-Y.;et al.Organometallics 2006,25,2399-2401.Organometallics,2007,26,1512-1522.Controlled Synthesis of rac-Oganometallic CompoundsRac-Lanthanide(II)and Lanthanide(III)complexesRac-Divalent and trivalent lanthanide complexeseuropium complexYtterbium complex