金属有机化学第十三章

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1、Chapter13LanthanideComplexesandTheirApplications一.TypicalLanthanideComplexesLanthanideCarbeneJ.Am.Chem.Soc.,2007,129(17),5360-5361.Organometallics,2007,26(13),3167-3172,Organometallics,2008,ASAPArticle,LanthanidePhosphinideneComplexJ.AM.CHEM.SOC.2008,130,2408-2409二.Reactivity1.C

2、atalyticHydrogenation2.LanthanideComplexesCatalyzedHydroamination/CyclizationReactionsMarks,T.J.etal,Organometallics1999,18,2568Marks,T.J.;etal,J.Am.Chem.Soc.1999,121,3633.Livinghouse,T.etal,Adv.Synth.Catal.2006,348,701-704.LanthanideComplexesCatalyzedHydroamination/CyclizationR

3、eactionsofaminoalkynes3.LanthanideComplexesCatalyzedHydrophosphination/CyclizationReactionsMarks,T.J.etal,J.Am.Chem.Soc.2000,122,1824.Marks,T.J.etal,Organometallics2003,22,46304.CatalyticHydrosilylation催化剂产率（%，分离）选择性Cp*2LuMeTHF98100:0Cp*2YbCH(TMS)291100:0Cp*2YMeTHF84100:0Cp*2S

4、mCH(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,Organometallics2004,23,12-14.5.CatalyticHydroborationReaction6.Guanylation(胍化反应)ofAromaticAminesBuildingBlockexistsinmanybioactive

5、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

6、./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)b232Cy

7、110/242685CatalyticAdditionoftheAminestotheCarbodiimidesCatalyticActivityoftheCp-FreeLanthanideAmidesontheAdditionofAminestoCarbodiimidesentryCat.Loading(mol%)solventtemp.(C)time(h)Yieldb(%)15THFr.t.249223THFr.t.249531THFr.t.249540.5THFr.t.246650THF0or6024061toluener.t.249771Et

8、2Or.t.249681hexaner.t.249691CH2Cl2r.t.2499entry