32的合成及其不对称催化氢化性能研究

广西师范大学硕士学位论文含NH官能团Ni(Ⅱ)配合物的合成及其不对称催化氢化性能研究姓名：张玉贞申请学位级别：硕士专业：无机化学指导教师：陈自卢;梁福沛200705012007NHNi()200490RhRuIrNHNoyori2001NHRhRuIr3dNHNi()NH61NiCl2enopdaN,N,N’,N’-tmen[Ni(en)(2,2′-bipy)(H2O)2]Cl21,[Ni(en)(H2O)2(tmen)]Cl2·2H2O2,[Ni(opda)(Phen)Cl2]·CH3OH31P21/ca=14.132(5)Å,b=8.371(3)Å,c=15.454(6)Å,β=115.734(5)°2Pbcna=15.005(4)Å,b=9.591(3)Å,c=12.505(3)Å3C2/ca=13.898(4)Å,b=18.246(5)Å,c=10.015(3)Å,β=126.313(3)°2NiCl2dachR,R-12-[(R,R)-dpen][Ni(dach)(tmen)(H2O)2]Cl2·2H2O5[Ni(dach)(2,2′-bipy)2(Cl)2]·2H2O6[Ni2((R,R)-dpen)4(H2O)2Cl2]Cl2·CH3CH2OCH38[Ni((R,R)-dpen)(phen)(CH3OH)2]Cl29[Ni2(dach)2(phen)2(Cl)2(H2O)2]Cl210,[Ni((R,R)-dpen)(tmen)(H2O)2]Cl2115Iba2a=14.160(2)Å,b=9.8435(14)Å,c=15.221(2)Å6C2/ca=15.270(15)Å,b=17.732(17)Å,c=10.244(10)Å,β=127.535(10)°8P1a=19.738(7)Å,b=10.439(8)Å,c=16.418(12)Å,α=105.044(11)°β=98.591(10)°γ=90.003(11)°9C2/ca=15.270(15)Å,b=17.732(17)Å,c=10.244(10)Å,β=127.535(10)°10P21/na=12.378(3)Å,b=13.836(3)Å,c=21.279(5)Å,β=101.273(3)°11P1a=9.017(3)Å,b=11.690(4)Å,c=13.095(5)Å,α=77.431(4)°β=89.984(4)°γ=69.298(5)°II20073NiCl218-(dant)[Ni2(dant)4(DMF)2Cl2]Cl2·3H2O12N,N,N’,N’-(datm)[Ni(datm)2]14MnCl213[phen2(en)]n1214P21/c12a=15.0758(10)Å,b=22.7726(15)Å,c=16.3817(11)Å,β=113.3880(10)°14a=8.822(2)Å,b=11.832(3)Å,c=15.635(3)Å,β=119.190(3)°13P1a=7.6518(8)Å,b=9.8985(10)Å,c=10.6525(11)Å,α=69.492(2)°,β=70.416(2)°,γ=80.602(2)°43489121515-12KOH72.1%-NiNHIII2007SynthesisofNickelComplexesContainingNHFunctionalityandtheirAppicationinAsymmetricCatalysisAbstractPostgraduate:Yu-ZhenZhangSupervisors:Dr.Zi-LuChenProf.Fu-PeiLiangInrecentdecades,asymmetriccatalysisofunsaturatedcompoundscontainingcarbonylgrouphasattractedmuchattention.Especiallysince1990s,thestudyonasymmetriccatalysisusinglatetransitionmetal(Rh,Ru,Ir)complexescontainingNHfunctionalityhasmadearapidprogress.NoyoriwontheNobelPrizein2001forhisexcellentstudyonasymmetriccatalysis.InthereportedstudiesaboutasymmetriccatalysisusingtransitionmetalcomplexescontainingNHfunctionalityascatalystsaremainlyconcentratedonexpensivemetals,suchasRhRuIr.Muchlessstudiesweremadeon3dtransitionmetals.OuraiminthisworkistousethemuchcheapermetalNiasthemetalcentertosynthesizethesimilarcatalystscontaningNHfunctionalitiesandtoinvestigatetheircatalytichydrogenationofketones.Inthisthesis,wehavemanagedtosynthesizeaseriesofnickelcomplexes,andsixamongofthemwereselectedtostudythecatalysisofhydrogenationofketones.1.ThereactionsofNiCl2withethylenediamine(en),o-phenylenediamine(opda),orN,N,N’,N’-tetramethylethylenediamine(tmen)gave[Ni(en)(2,2′-bipy)(H2O)2]Cl2(1),[Ni(en)(H2O)2(tmen)]Cl2·2H2O(2)and[Ni(opda)(Phen)Cl2]CH3OH(3),respectively.Complex1crystallizesinthemonoclinicspacegroupP21/cwitha=14.132(5)Å,b=8.371(3)Å,c=15.454(6)Å,β=115.734(5)°.Complex2crystallizesintheOrthorhombicspacegroupPbcnwitha=15.005(4)Å,b=9.591(3)Å,c=12.505(3)Å.Complex3crystallizesinthemonoclinicspacegroupC2/cwitha=13.898(4)Å,b=18.246(5)Å,c=10.015(3)Å,β=126.313(3)°.2.ThereactionsusingNiCl2anddiaminocyclohexane(dach)or(R,R)-(+)-1,2-diphenylenediamine((R,R)-dpen)asthemainstartingmaterialsprovided[Ni(dach)(tmen)(H2O)2]Cl2·2H2O(5),[Ni(dach)(2,2′-bipy)2(Cl)2]·2H2O(6),[Ni2((R,R)-dpen)4(H2O)2Cl2]Cl2·CH3CH2OCH3(8),[Ni((R,R)-dpen)(phen)(CH3OH)2]Cl2(9),[Ni2((R,R)-dpen)2(phen)2(Cl)2(H2O)2]Cl2(10)and[Ni((R,R)-dpen)(tmen)(H2O)2]Cl2(11).Complex5crystallizesintheOrthorhombicspacegroupIbamwitha=14.160(2)Å,b=9.8435(14)Å,c=15.221(2)Å.Complex6crystallizesinthemonoclinicspacegroupC2/cwitha=15.270(15)Å,b=17.732(17)Å,c=10.244(10)Å,β=127.535(10)°.Complex8crystallizesintheTriclinicspacegroupP1witha=9.738(7)Å,b=10.439(8)Å,c=16.418(12)Å,α=105.044(11)°β=98.591(10)°,γ=90.003(11)°.Complex9crystallizesinthemonoclinicspacegroupC2/cwithaIV2007=15.270(15)Å,b=17.732(17)Å,c=10.244(10)Å,β=127.535(10)°.Complex10crystallizesinthemonoclinicspacegroupP21/nwitha=12.378(3)Å,b=13.836(3)Å,c=21.279(5)Å,β=1101.273(3)°.Complex11crystallizesintheTriclinicspacegroupPīwitha=9.017(3)Å,b=11.690(4)Å,c=13.095(5)Å,α=77.431(4)°,β=89.984(4)°,γ=69.298(5)°.3.Anotherthreecompounds[Ni2(dant)4(DMF)2Cl2]Cl2·3H2O(12),[en(phen)24H2O]Cl2(14)and[Ni(datm)2](13)wereisolatedfromthereactionsofNiCl2with1,8-diaminonaphthalene(dant)ordiacetamide(datm):12and14crystallizeinthemonoclinicspacegroupP21/cwitha=15.0758(10)Å,b=22.7726(15)Å,c=16.3817(11)Å,β=113.3880(10)°for12anda=8.822(2)Å,b=11.832(3)Å,c=15.635(3)Å,β=119.190(3)°for14.13crystallizesinthetriclinicspacegroupP1witha=7.6518(8)Å,b=9.8985(10)Å,c=10.6525(11)Å,α=69.492(2)°,β=70.416(2)°,γ=80.602(2)°.4.Complexes3,4,8,9,12and15wereselectedtoperformtheasymmetriccatalytichydrogenationofketones.Threekindsofasymmetriccatalytichydrogenationwerecarriedout:(a)catalyticionichydrogenationsusingH2ashydrogensource,(b)transferhydrogenationusingisopropanolashydrogensource,(c)transferhydrogenationusingformicacid-triethylamineashydrogensource.TheproductsarecheckedbyGC.Theresultsrevealedthatthesecomplexesshownicecatalyticeffectsincatalyticionichydrogenations.Amongofthema72.1%conversionofacetophenoneintothecorrespondingalcoholwasfoundinthecatalytichydrogenationofketoneusingcom