稀土金属有机化学课件

Chapter13LanthanideComplexesandTheirApplicationsTypicalLanthanideComplexesandSyntheticMethodologiesLanthanideCarbeneJ.Am.Chem.Soc.,2007,129(17),5360-5361.Organometallics,2008,ASAPArticle,LanthanidePhosphinideneComplexJ.Am.Chem.Soc.2008,130,2408-2409CatalyticReactions1.CatalyticHydrogenation2.LanthanideComplexesCatalyzedHydroamination/CyclizationReactionsMarks,T.J.etal,Organometallics

1999,18,2568Marks,T.J.;etal,

J.Am.Chem.Soc.

1999,121,3633.3.LanthanideComplexesCatalyzedHydrophosphination/CyclizationReactionsMarks,T.J.

etal,J.Am.Chem.Soc.2000,122,1824.Marks,T.J.

etal,Organometallics

2003,22,

46304.CatalyticHydrosilylation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.;etal,

Organometallics

2004,23,12-14.5.CatalyticHydroborationReaction6.GuanylationofAromaticAminesBuildingBlockexistsinmanybioactivecompoundsZhang,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./121591CatalyticAdditionoftheAminetotheCarbodiimides132Prir.t./121693142Cyr.t./121792152Prir.t./121892(88)c162Cyr.t./121993(95)b172Cy110/362080(82)b182Pri110/3620Noreactiona,b,c192Cy110/3620Noreactiona,b,c202Pri110/122395212Cy110/122497222Pri110/242581(84)b232Cy110/242685CatalyticAdditionoftheAminestotheCarbodiimidesCatalyticActivityoftheCp-FreeLanthanideAmidesontheAdditionofAminestoCarbodiimidesentry

Cat.Loading(mol%)

solvent

temp.(C)

time(h)

Yieldb

(%)

15THFr.t.249223THFr.t.249531THFr.t.249540.5THFr.t.246650THF0or6024061toluener.t.249771Et2Or.t.249681hexaner.t.249691CH2Cl2r.t.2499entry

catalyst

ArNH2

yield

1Ln=YbPhNH2962Ln=YPhNH2973Ln=EuPhNH2964Ln=SmPhNH2985Ln=LaPhNH2996[(Me3Si)2N]3Yb

PhNH2967[(Me3Si)2N]3Yb

4-O2NPhNH2938[(Me3Si)2N]3Y4-O2NPhNH292PlotofYieldsofGuanidineversusReactionTime.TheReactionwasperformedbytreating1equiv.ofanilinewith1equiv.ofN,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-PhenylNH2994CatalyticAdditionoftheC-HBondtotheCarbodiimideentryCata.RArTp(oC)/time(h)ProductYield(%)a11PriPh80/3359222PriPh80/3359033PriPh80/3359041CyPh80/3368952CyPh80/3368563CyPh80/3368671Pri4-MeOC6H480/3378581Cy4-MeOC6H480/3388393Cy4-MeOC6H480/33881101Pri4-FC6H480/33994111Pri4-ClC6H480/34095121Cy4-ClC6H480/34193CatalyticAdditionofthealkynestotheCarbodiimidesZhou,S.;Wang,S.*etal,Organometallics

2007,26,3755.Li,Q.;Wang,S.*etal,J.Org.Chem.

2007,72,6763.7.LanthanideComplexesCatalyzedOlefinPolymerizationCat.=Me2Si(Me4C5)(C5H3R*)LnN(SiMe3)2[O(CH2H2C9H6)2]LnN(SiMe3)2Qian,C.T.;etal,

Organometallics

2001,20,3106.Yamamoto,Y.;Marks,T.J.etal,

J.Am.Chem.Soc.1995,117,3276.Anwander,R.;etal,Organometallics

2003,22,1212.8.LanthanideComplexesInitiatedCannizzaroTypeDisproportionationThemethodologyforthepreparationofamidefromaldehydeBeckmannRearrangementIndirectmethodCatalyticreactionOptimizationofthereactionconditionsratioaT(C)solventCat.()T(d)Yieldof3g(%)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.toluene5388Reactionconditions:tolueneassolvent;roomtemperature;2-3d

Ar-T(d)Productof3Yieldof3(%)bProductof4Yieldof4(%)bC6H5-33a56(18)c4a62(21)c4-CH3C6H4-33b624b654-CH3OC6H4-33c584c604-ClC6H4-23e764e784-BrC6H4-23f824f784-O2NC6H4-23g854g854-F3CC6H4-23j834j814-Me2NC6H4-33k524k50TheresultsofthereactionofaldehydeswithlithiumamidecatalyzedbyYCl3aReactionconditions:tolueneassolvent;roomtemperature;

bIsolatedyieldbasedonthelithiumamide;cIsolatedyieldsintheabsenceofYCl3areshowninparentheses.TheeffectsoflanthanidemetalonthereactionLnnoneYPrNdSmEuDyHoYbYieldof3(%)478560827870758085ThemechanismofthecatalyticreactionAr-solventTime(d)Productof3Yieldof3(%)bProductof4Yieldof4(%)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-CH2Cl33m654m60Theresultsofreactionofaldehydeswithyttriumamide[(Me3Si)2N]3Y(-Cl)Li(THF)3TheresultsofthereactionprobedbyGC-MSTheprocessofthehydridetransferinthereactionTheproposedmechanismfortheCannizarro-typereactionZhang,L.;Wang,S.etal.J.Org.Chem.2006,71,3149-3153.9.CatalyticCyclotrimerizationofAromaticIsocyanatesShen,Q.;etal,Organometallics

2002,21,2529.Shen,Q.;etal,Organometallics

1997,16,3711.CanLanthanideAmidesSelectivelyCatalyzeCyclotrimerizationofAromaticIsocyanates?IfthelanthanideamideshavedifferentMetal-Nitrogenbonds,What’stheselectivity?SynthesisofthelanthanideamidesofIncorporatingadiamidoligandwithaCH2SiMe2linkDyComplexSmcomplexYbcomplexYcomplex?OptimizedconditionsonthecyclotrimerizationofphenylisocyanateEntryCat.(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.TheinfluenceofdifferentrareearthmetalamidesonthecyclotrimerizationofphenylisocyanateEntryCat.(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./1299continuedDatafortheCyclotrimerizationofDifferentIsocyanatesentryCatR-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;asolvent:tolueneWu,Y.;Wang,S.;etal,Inorg.Chem.2008,inpress.SynthesisofthelanthanideamidesincorporatingadiamidoligangwithaMe2SiBridgeLn=Yb(7),Y(8),Eu(9),Sm(11),Nd(11)YbComplexSmcomplexNdComplexYComplexCatalyticActivityoftheComplexesonCyclotrimerizationofPhenylIsocyanateEntryCat.(mol%)aSolventTemp(°C)Time(h)Yield(%)b11%THFroomtemp129721%tolueneroomtemp122731%Et2Oroomtemp124441%n-hexaneroomtemp124052%CH2Cl2roomtemp122461%THF4069371%THF40129780.5%THF40129790.25%THF401298100.25%toluene401221110.25%n-hexane401229Catalyst:{(Me2Si)[(2,6-iPr2C6H3)N]2}SmN(SiMe3)2(THF)(9)

Influenceofdifferentrareearthmetalamidesonthecyclotrimerizationofphenylisocyanate

EntryCatalystaYield(%)b1{(Me2Si)[(2,6-iPr2C6H3)N]2}YbN(SiMe3)2(THF)982{(Me2Si)[(2,6-iPr2C6H3)N]2}YN(SiMe3)2(THF)973{(Me2Si)[(2,6-iPr2C6H3)N]2}EuN(SiMe3)2(THF)964{(Me2Si)[(2,6-iPr2C6H3)N]2}SmN(SiMe3)2(THF)985{(Me2Si)[(2,6-iPr2C6H3)N]2}NdN(SiMe3)2(THF)926c{(Me2Si)[(C6H5)N]2}YbN(SiMe3)2(THF)95d7c{(Me2Si)[(C6H5)N]2}SmN(SiMe3)2(THF)98daCatalystloading:0.25mol%;bIsolatedyieldbyrunningthereactioninTHFat40Cfor12h.ccatalystloading:1mol%;dIsolatedyieldbyrunningthereactioninTHFat60Cfor24hDataforthecyclotrimerizationofdifferentisocyanatesEntryCatalystR-T(C)/t(h)Yield(%)18Benzyl40/12h9429Benzyl40/12h95310Benzyl40/12h98484-Isopropylphenyl40/12h98594-Isopropylphenyl40/12h986104-Isopropylphenyl40/12h97784-Nitrophenyl40/12h088Cyclohexyl40/12h9099Cyclohexyl40/12h491010Cyclohexyl40/12h47Crystal