1、Chapter 13 Lanthanide Complexes and Their ApplicationsLnLnClClLn1Typical Lanthanide Complexes and Synthetic MethodologiesLnSSNa or KCpNa +LnI2MM=Na,or K,2+LnI2LnII(THF)nTHF(C10H8)YbI(DME)22+2YbIOOOO2LnCl(THF)Orac/mesoNaDMEOLnIIOO mesoO1)K,THF/r.t.2)LnI23)DMED2+(Me3Si)2N3Ln(-Cl)Li(THF)3nTolueneDnDnLn
2、IIn=1,D=OOONn=2,D=Me2N-;MeO-;Nn=3,D=Me2N-Ln=Yb,EuRHRRR=H,or Me,or Me3Si,or tBuNHSiMe2NSiMeMeLnClClLnLnHHLnNaHLnRRLnLiCH2SiMe3H2LiNR1R2LnNNLnR1R2R1R2LnCl(THF)n+LiCH(SiMe3)2LnCH(SiMe3)2H2LnHHLnSiLnN(SiHMe2)2+3 AlHiBu2hexane,r.t.SiLnSiHHLnLn=Y,4 days,72%Ln=Ho,10 days,46%SiLnN(SiHMe2)2Si+LnN(SiHMe2)23(T
3、HF)2SiLnN(SiHMe2)2+2 AlR13,r.t.hexane-R2AlN(SiHMe2)2SiLnR1R1AlR1R1+THF+2 AlR13-AlR13(THF)SiLnR1THFLanthanide 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.2008,130,2408-2409LnI2(THF)x
4、Ln=Yb,Eu,SmLnI2(THF)x and related complexesLn=Tm,Dy,Nd(C9H7)2Sm(THF)x +N2OTHF,15 min(C9H7)2Sm(THF)2(-O)+(C9H7)3Sm(THF)二二.ReactivityStoichiometric Reactions(C9H7)2Sm(THF)x +C8H8THF,15 min(C9H7)Sm(C8H8)(THF)x+(C9H7)3Sm(THF)2,2-bipyridine(C9H7)Sm(C8H8)(biPy)(C9H7)2YbII(THF)2 +HCNCHNtButBu(C9H7)2YbIIICH
5、NCHNtButButolueneTHFYbIITHFTHF+HCNCHNButtButolueneYbIIICHNCHNtButBuTHF(C9H7)2YbII(THF)2 +HCNCHN(C9H7)2YbIIICHNCHNtolueneTHF(C9H7)2YbII(THF)2 +MeCNCMeNtolueneNMePhNMePhPhYbYbNPhYbNYb2(C9H7)2YbII(THF)2 +MeCNCMeNtoluene-2 THFMeMeYbPhNPhNYb+C9H8(C9H7)2YbII(THF)2 +HCNNtolueneCHNNHNNYbSi+SmI2THFSi(8-46)C2
6、B10H11NaSmIII=CTHFTHFSiCCLiLiGLiClLi(THF)4G=NMe2,OMe+SmI2(8-58)SmSiSmClGGSiCatalytic Reactions1.Catalytic Hydrogenation5%Cp*2YMe(THF)1 atm H2,benzene rt,1h,72%H0.7%Me2Si(Cp)(C5H3R*)SmCH(TMS)21 atm.H2,heptane,rt,1 h,95%,71%eeR*=Cp=C5Me4,Cp*2LnRH2-RHCp*2LnHRRLnCp*2HH2RHHRHHCp*2LnR +H2Cp*2LnCp*2LnH +RH
7、(1)Cp*2LnRH2-RHCp*2LnHHRnHRnLnCp*2HRnLnCp*2-Cp*2LnH 脱氢H2HRnCH3HRn氢化环化的催化循环2.Lanthanide Complexes Catalyzed Hydroamination/Cyclization ReactionsH2NHNCat.Cat.SiNN(SiMe3)2Ln=Sm,NdLnMarks,T.J.et al,Organometallics 1999,18,2568n-C5H11HNH2Nn-C5H11HHCH3HCat.SiNN(SiMe3)2SmCat.=Marks,T.J.;et al,J.Am.Chem.Soc
8、.1999,121,3633.NH2Rcat.LY-N(TMS)2NnRL=NNEtEtEtEtNNPriPriorn=1,2Livinghouse,T.et al,Adv.Synth.Catal.2006,348,701-704.Lanthanide Complexes Catalyzed Hydroamination/Cyclization Reactions of aminoalkynesCp*2LnEE=H,CH(TMS)2,N(TMS)2H2NnHECp*2LnNHCp*2LnNHCp*2LnNH*H2NnNH*Catalytic Cycle for Hydroamination3.
9、Lanthanide Complexes Catalyzed Hydrophosphination/Cyclization ReactionsH2PHPCat.Cat.SiNN(SiMe3)2PhSmPhOr(Me3Si)2N3Lnnnn=1,2Marks,T.J.et al,J.Am.Chem.Soc.2000,122,1824.Marks,T.J.et al,Organometallics 2003,22,4630Cp*2LnCH(TMS)2E=CH(TMS)2Cp*2LnPHCp*2LnPHCp*2LnPH*H2PnPH*H2Pn+CH2(TMS)24.Catalytic Hydrosi
10、lylationn-C8H17n-C8H17PhH2Sin-C8H17SiH2Ph5%catalystPhSiH3,rt,1-24h,75%,28:1+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)2891:23%Cp*2YCH(TMS)2PhSiH
11、3,benzene,rt 92 h,91%SiH2Ph3%Cp*2YCH(TMS)2PhSiH3,toluene,rt 18 h,97%SiH2Ph3%Cp*2YCH(TMS)2PhSiH3,benzene,rt 96 h,61%,2:1dsSiH2Phn-C6H135%(C5Me4i-Pr)2YCH(TMS)2 PhSiH3,50 0C 12 h,78%,4:1PhH2SiHHSiH2Ph+n-C6H13n-C6H13OOn-C5H11 PhSiH3,50 0C 24 h,85%Cp*2YMe(THF)HSiH2Phn-C5H11OOLaN(TMS)233 mol%cat.PhSiH3600
12、C,9hSiH2PhLivinghouse,T.;et al,Organometallics 2004,23,12-14.Cp*2LnRR3SiH-RSiR3Cp*2LnHRRLnCp*2HRHSiR3R3SiHCatalytic Cycle for Hydrosilylation reactionCp*2LnCH(TMS)2OBOHOBOCH(TMS)2Cp*2LnHRCp*2LnROBOHOBORH5.Catalytic Hydroboration Reaction6.Guanylation of Aromatic AminesNHNHNRRRBuilding Block exists i
13、n many bioactive compoundsArNH2+CRNNRCat.NHNHNArRR?ArNH2+CRNNRCat.(1 mol%)80 C,benzeneNHNHNArRRSiNLnRCH2SiMe3(thf)nCat.=Zhang,W.;Nishiura,M.;Hou,Z.Chem.Eur.J.2007,13,4037.+(Me3Si)2N3Ln(-Cl)Li(THF)3LnNMe3SiSiMe3Ln=Y(1),Sm(2),Yb(3)toluenerefluxRNC NRR1R2NHNHNNR1R2RR2 mol%Cat.toluene,r.t.or 110 CNHNHNR
14、1RRR2=H1,3-H shiftCatalyst=5-(CH2)2(C9H6)2LnN(SiMe3)2(Ln=Y(1);Sm(2);Yb(3)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./1214921
15、22Cyr.t./121591H2NH2NH2NNH2H2NOCH3H2NOCH3H3COCatalytic 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,c202Pri110/122395212Cy110/122497222Pri110/24258
16、1(84)b232Cy110/242685NH2NH2H2NClH2NBrH2NNO2H2NNO2H2NO2NCatalytic Addition of the Amines to the CarbodiimidesCatalytic Activity of the Cp-Free Lanthanide Amides on the Addition of Amines to CarbodiimidesR3NH2NCNR1R1cat.HNR2R2cat.?(Me3Si)2N3Ln(-Cl)Li(THF)3H2NNHCyNHCy+Cy=cyclohexylcat.CyNC NCyNsolventC
17、at.=(Me3Si)2N3Yb(-Cl)Li(THF)3entry 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.2499H2NNHCyNHCy+Cy=cyclohexylcat.CyNC NCyNsolventCat.=(Me3Si)2N3Ln(-Cl)Li(THF)31%entry c
18、atalyst ArNH2 yield 1Ln=YbPhNH2962Ln=YPhNH2973Ln=EuPhNH2964Ln=SmPhNH2985Ln=LaPhNH2996(Me3Si)2N3Yb PhNH2967(Me3Si)2N3Yb 4-O2NPhNH2938(Me3Si)2N3Y4-O2NPhNH292050100150200250020406080100Yield(%)Time(min)(Me3Si)2N3La(-Cl)Li(THF)3(Me3Si)2N3Y(-Cl)Li(THF)3(Me3Si)2N3Yb(-Cl)Li(THF)3(Me3Si)2N3YbPlot of Yields
19、of Guanidine versus Reaction Time.The Reaction was performed by treating 1 equiv.of aniline with 1 equiv.of N,N-dicyclohexylcarbodiimide.NR1+HNHNNArR1R11 mol%cat.solvent,40 C,or 60 CCR1NR1NCR1HNNR2R3R2=H,R3=ArHNR2R31,3-H shiftentryR1R2R3NHproductyield1i-Pr4-Cl-phenylNH21932Cy4-Cl-phenylNH22983t-Bu4-
20、Cl-phenylNH23954i-Pr4-Br-phenylNH2489(88)5Cy4-Br-phenylNH2593(98)6i-Pr2-O2N-PhenylNH2662(85)7Cy2-O2N-PhenylNH2776(90)8i-Pr4-O2N-PhenylNH28909Cy4-O2N-PhenylNH2994RNC NRArNHNRRArH2 mol%Cat.THF,80 CCatalytic Addition of the C-H Bond to the CarbodiimideentryCata.RArTp(oC)/time(h)ProductYield(%)a11PriPh8
21、0/3359222PriPh80/3359033PriPh80/3359041CyPh80/3368952CyPh80/3368563CyPh80/3368671Pri4-MeOC6H480/3378581Cy4-MeOC6H480/3388393Cy4-MeOC6H480/33881101Pri4-FC6H480/33994111Pri4-ClC6H480/34095121Cy4-ClC6H480/34193Catalytic Addition of the alkynes to the CarbodiimidesLn-N(TMS)2R1R2NHLn-NR1R2HN(TMS)2NRCNRNN
22、NR1R2RRLnR1R2NHNHNNR1R2RRNHNHNR1RRR2=HAB1,3-shiftLn=EBILnZhou,S.;Wang,S.*et al,Organometallics 2007,26,3755.Li,Q.;Wang,S.*et al,J.Org.Chem.2007,72,6763.Ln-C CArArC CHHN(TMS)2ArC CHArNHNRRNNC CArRRLnAB7.Lanthanide Complexes Catalyzed Olefin PolymerizationLnROMeO1,4 additioninitiationORMeOLnconjugatea
23、dditionpropagationLnOOOMeRMeOR=N(SiMe3)2Cat.=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 Di
24、sproportionationCOHCONH2+YCl3LiN(SiMe3)2+CH2OH(5 mol%)2NObioactive importanceThe methodology for the preparation of amide from aldehydeRCOHRCONH2RCOOHwet-Al2O3,MeSO2Cl 100oCH2NOH.HClRCOHRCONH2COH+NHORh+NoOBeckmann RearrangementIndirect methodCatalytic reactionOptimization of the reaction conditionsr
25、atioaT(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.toluene5388CO2NONH
26、2CH2OHO2N+3g4gCO2NOH2+LiN(SiMe3)2YCl32-10%Ar CHO2CAr2.H2O+ArCH2OHLiN(SiMe3)21.YCl3(5 mol%)+134ONH2Reaction 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
27、-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 show
28、n in parentheses.LiN(SiMe3)2+CHOO2NCO2NONH2+CH2OHO2N22.H2O1.LnCl3(5 mol%)3g4gThe effects of lanthanide metal on the reactionLnnoneYPrNdSmEuDyHoYbYield of 3(%)478560827870758085The mechanism of the catalytic reactionLiN(SiMe3)2CHOO2N+CO2NONH22 YCl3+CH2OHO2N 5 mol%85%85%CHOO2N+CO2NONH2LiN(SiMe3)22+CH2
29、OHO2N47%49%YN(SiMe3)23CHOO2N+CO2NONH26+CH2OHO2N82%79%33CHOO2N+CO2NONH26(Me3Si)2N3Y(-Cl)Li(THF)3+CH2OHO2N88%80%33LnCl3+3LiN(SiMe3)2(Me3Si)2N3Ln62.H2O+3a-m4a-m1.1equiv.of(Me3Si)2N3Y(-Cl)Li(THF)3OHRONH2RCH2OHR33Ar-solventTime(d)Product of 3Yield of 3(%)bProduct of 4Yield of 4(%)b4-O2NC6H4-CH2Cl223g934g
30、884-O2NC6H4-C6H623g884g804-O2NC6H4-toluene23g884g804-O2NC6H4-Et2O23g704g724-O2NC6H4-THF23g474g50C6H5-CH2Cl233a584a624-CH3C6H4-CH2Cl233b684b704-CH3OC6H4-CH2Cl233c584c552-CH3OC6H4-CH2Cl233d574d594-ClC6H4-CH2Cl223e784e764-BrC6H4-CH2Cl223f824f782-Furyl-CH2Cl223h774h70C6H5CH=CH-CH2Cl233i524i584-F3CC6H4-C
31、H2Cl223j904j854-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-MSOCHOCH2Cl2(Me3Si)2N3Y(-Cl)Li(THF)3+6H2OOCONHSiMe3+OCH2OSiMe333OCONH2OCH2OH+3h4h33C
32、OD+(Me3Si)2N3Y(-Cl)Li(THF)3CH2Cl2CONHSiMe3CD2OSiMe3+H2OCONH2CD2OH+63333The process of the hydride transfer in the reactionAr COOCH2ArH2OAr CONH2+Ar CH2OHArCHOAr CONHSiMe3Ar CH2OSiMe3(Me3Si)2N3Ln(-Cl)Li(THF)3?+Tischchenko reaction(Me3Si)2N3Ln(-Cl)Li(THF)3COOCH2(Me3Si)2N3Y(-Cl)Li(THF)3no reactionCOOC2
33、H5(Me3Si)2N3Y(-Cl)Li(THF)3no reactionThe proposed mechanism for the Cannizarro-type reactionZhang,L.;Wang,S.et al.J.Org.Chem.2006,71,3149-3153.3 LiN(SiMe3)2LnCl3LnN(SiMe3)23ArCHOArHOLnN(SiMe3)2AArCHOArOLnCArN(SiMe3)2OBHHArCH2OSiMe3ArNOLnSiMe3ArN(SiMe3)2OCDEFArNSiMe3OLiLiN(SiMe3)2ArCH2OHH2OArNH2OH2ON
34、HSiMe3OArH2O9.Catalytic Cyclotrimerization of Aromatic IsocyanatesLn=Yb,YX=O,SLnNPh2+PhN=C=XLnXCNNPh2PhShen,Q.;et al,Organometallics 2002,21,2529.Shen,Q.;et al,Organometallics 1997,16,3711.Can Lanthanide Amides Selectively Catalyze Cyclotrimerization of Aromatic Isocyanates?ArN=C=ONNNOOOArArAr(1)?NN
35、OOArArCatCat.NNOOArArnSiNNRRRRR1R1LnN(SiMe3)2OR,R1=different substituentsLn=rare earth metalsIf the lanthanide amides have different Metal-Nitrogen bonds,Whats the selectivity?Synthesis of the lanthanide amides of Incorporating a diamido ligand with a CH2SiMe2 linkNHSiNH+(Me3Si)2N3Ln(-Cl)Li(THF)3tol
36、ueneNSiNLnN(SiMe3)2THFLn=Yb(2),Y(3),Dy(4),Sm(5),Nd(6)Dy ComplexSm complexYb complexY complexNCOcatalystsolvent3NNNOOO?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(
37、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(%)b
38、12(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%)to
39、luener.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-Iso
40、propylphenylr.t./124650/12817a34-Isopropylphenylr.t./125480/1299Conditions,solvent:THF;a solvent:tolueneWu,Y.;Wang,S.;et al,Inorg.Chem.2008,in press.NHNHSi(Me3Si)2N3Ln(-Cl)Li(THF)3NNSi+tolueneLnN(SiMe3)2THFSynthesis of the lanthanide amides incorporating a diamido ligang with a Me2Si Bridge Ln=Yb(7)
41、,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
42、%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)9
43、82(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
44、 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-Isopropy
45、lphenyl40/12h986104-Isopropylphenyl40/12h97784-Nitrophenyl40/12h088Cyclohexyl40/12h9099Cyclohexyl40/12h491010Cyclohexyl40/12h47Crystal Structures of cyclotrimerization productsSelective Reaction of Different Metal-Nitrogen Bonds with GreaseSiNNLnN(SiMe3)2OC4H8(Me2SiO)3SiNNLnN(SiMe3)2SiOSiNNLn(Me3Si)
46、2NSiOLn=Yb(12),Sm(13)selective insertion to this bondnot insertion to this bondYtterbium complexSamarium complexSiNNRRRRR1R1LnN(SiMe3)2ONCO+SiNNRRRRR1R1LnN(SiMe3)2NCOSiNNRRRRR1R1LnN(SiMe3)2NCONCONNNLnNSiRRR1RR1RCOCONCOProposed Catalytic CycleHeterolysis of the Ln-N BondCan the Ln-N Bond be Homolytic
47、 Cleavage?(L)2LnIIINR2(L)2LnIII +-NR2(L)2LnIIINR2(L)2LnII +NR210.Homolysis of Lanthanide Metal-Nitrogen BondSynthesis and Characterization of Tetracoordinated Lanthanide AmidesLnCl3 +3(Me3Si)2NLi(Me3Si)2N3Ln(Cl)Li(THF)3Ln=Sm,Eu,Dy,Tm,YbN(1)-Yb-N(2)114.83(18)N(1)-Yb-N(3)117.88(18)N(3)-Yb-N(2)117.2(2)
48、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.NRRNRNYbIIH+(Me3Si2N)3YbIII(-Cl)Li(THF)3toluene/reflux2+(Me3Si)2N2R=t-BuNHSiMe2(7),Me3Si(9),H(10)Homolysis of the Yb-N Bond+(Me3Si2N)3YbIII(-Cl)Li(THF)3YbIIIN(SiMe3)2Toluene/refluxtoluene/reflux
49、 3d.YbIIIN(SiMe3)2Heteroatom Substituted Group Effect(Me3Si)2N3LnIII(-Cl)Li(THF)3 (Ln=Yb,Eu,Sm)(Me3Si)2N3LnIIISublimationtoluenereflux2+(Me3Si2N)3YbIII(-Cl)Li(THF)3YbIIIN(SiMe3)2DDDDYbIID-2HN(SiMe2)2+1/2N(SiMe3)22Ln=Yb,D=NMe2RRRRRHSheng,E.;Wang,S.Organometallics 2003,22,684.Proposed MechanismSiN2+(M
50、e3Si)2N3EuIII(-Cl)Li(THF)3toluenerefluxSiNSiNSiNSiNEuEuClSiNSiNClEuEuWang,S.;Zhou,S.;et al Organometallics 2003,22,3546NMe3SiHNNLnClRR+(Me3Si)2N3Ln(-Cl)Li(THF)3toluene/reflux+1/2(Me3Si)2N2 2 HN(SiMe3)2 +3THF2R=Me3Si-Ln=Yb,EuWang,S.;Tang,X.;Vega,A.;Saillard,J.-Y.;et al.Organometallics 2006,25,2399-24
