ruⅱpnn催化酯转化为醇及ruⅱpnp与醇反应理论分析-theoretical analysis of ru ⅱ pnn catalytic conversion of ester to alcohol and reaction between ru ⅱ pnp and alcohol.docxVIP

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ruⅱpnn催化酯转化为醇及ruⅱpnp与醇反应理论分析-theoretical analysis of ru ⅱ pnn catalytic conversion of ester to alcohol and reaction between ru ⅱ pnp and alcohol.docx

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ruⅱpnn催化酯转化为醇及ruⅱpnp与醇反应理论分析-theoretical analysis of ru ⅱ pnn catalytic conversion of ester to alcohol and reaction between ru ⅱ pnp and alcohol

AbstractInthisthesis,thedensityfunctionaltheory(DFT)calculationsattheB3LYPleveloftheoryarecarriedouttostudythefollowingtwoprojects.Ourmajorpurposeistoinvestigatethemolecularstructures,chemicalbonding,andmechanismsofthetitlereactions,throughwhichfurtherunderstandingfortheessenceofsuchreactionswouldbegivenandhelpfulinformationtoexperimentswouldbepresented.Inrecentyears,globaldemandforenergyisincreasingrapidlyasaresultofCO2emissionsintensifiedandthemaingreenhousegasCO2wasconcernedextensively.In2011,cascadecatalysisforthehomogeneoushydrogenationofCO2tomethanolwasreportedbySanford’sgroup.Suchatransformationconsistsofthreeprocesses：(a)hydrogenationofCO2toformicacid,(b)esterificationtogenerateaformateester,and(c)hydrogenationoftheestertoreleasemethanol.ThelastprocessinvolvestheRu(II)-PNN-catalyzedconversionofmethylformateintoalcohol.Inthepastfewdecades,Ru(II)-PNNandRu(II)-PNPcompoundsascatalystshavebeenwidelyusedinhydrogenationanddehydrogenationreactions.TheRu(II)-PNNcomplexesareregardedaspromisingcatalyststothereductionofestertogeneratemethanol,andshowsomeadvantagesinmanynew-typereactions.Basedonourknowledgeofthecascadereaction,steps(a)and(b)havebeenwidelystudiedboththeoreticallyandexperimentally.But,instep(c),thereactionofhydrogenationoftheestertogeneratemethanolisrarelystudiedtheoretically,whicharousedourstronginteresttoperformatheoreticalinvestigation.Inthisthesis,detailsonthepathsandmechanismsofthisreactionhavebeeninvestigatedonthebasisoftheexperimentalfacts.Baseonthecalculationresults,discussionandanalysishavebeendoneinordertogivefurtherunderstandingforsuchreactions.Inthiswork,thecatalyticreactionmechanismswerestudiedbyusingthedensityfunctionaltheorycalculations.ThereasonablepathwayobtainedfromourtheoreticalstudyisshownintheSchemebelow.(a)HydrogenationofcatalystRu(II)-PNNwiththeassistanceofwater(1+H2to3).(b)ReactionofmethylformatewiththedihydrideRu(II)-PNN,givingmethynolandaldehydeandregeneratingthecatalystRu(II)-PNN(3to1+MeOH+CH2O).(c)ReactionoftheresultingCH2Owith3