A Static and Dynamic Density Functional Theory Study of ：一个静态的和动态的密度泛函理论研究.ppt

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1、AStaticandDynamicDensityFunctionalTheoryStudyofMethanolCarbonylationMinserkCheong,aRochusSchmid,bandTomZieglercaDepartmentofChemistry,KyungHeeUniversity,Seoul130-701,KoreabTechnischeUniversitatMunchen,Anorganisch-ChemischesInstitut,D-85747Garching,GermanycDepartmentofChemistry,Universit

2、yofCalgary,Alberta,CanadaT2N1N4AbstractQuantummechanicalcalculationsbasedondensityfunctionaltheory(DFT)werecarriedoutinordertoinvestigatethereactionmechanismforthecarbonylationofmethanoltoaceticacidby[M(CO)2I2]-(M=Rh,Ir).ThestudyincludedtheinitialoxidativeadditionofCH3Ito[M(CO)2I2]-:(1)

3、[M(CO)2I2]-+CH3I[M(CO)2I3(CH3)]-,aswellasthemigratoryinsertionofCOintotheM-CH3bond:(2)[M(CO)2I3(CH3)]-[M(CO)I3(COCH3)]-.ConsiderationswerealsogiventomigratoryinsertionprocesseswheretheI--ligandtranstomethylwasreplacedbyanotherligandL(whereL=MeOH,MeC(O)OH,CO,P(OMe)3orSnI3-)oranemptycoo

4、rdinationsite.Thecalculatedfreeenergiesofactivationandheatofreactionsareingoodagreementwiththeexperimentaldata.Afullanalysisisprovidedofhowligandstranstothemigratingmethylgroupinfluencethebarrierofmigratoryinsertion.2MOCIOCIMIIOCICCH3OMOCIOCIICH3MOCIOCIHIH2OCMeICH3OMeCOIMeOHIMeCO2HCO123

5、4CatalyticCycleforAceticAcidSynthesisM=Rh+,Ir+3ThermodynamicsofoxidativeadditionreactionsMetalDH298(g)DS298(g)DG298(g)DEsolvDG298(solv)Rh29.5-13.633.6-22.013.6Ir22.4-15.126.9-22.54.4kcal/molMetalDH298(g)DS298(g)DG298(g)DEsolvDG298(solv)Rh-38.9-28.4-30.418.6-11.8Ir-41.4-27.7-33.114.0-19.

6、14IRhOCICOICr(Rh-H)r(C-I)r(Rh-C)RC=3DGORC=r(M-C)-r(I-C)TransitionStateRegionOCOCRhCIIIr(C-I)r(Rh-C)RC=-1.05Comparisonofstatic(ADF)calculationsanddynamic(PAW)calculationMetalDH‡DS‡DG‡RhPAWADF19.213.8-21.1-43.925.526.9Expt12.0-39.423.7IrPAW12.1-23.419.1ADF6.0-44.619.3Expt12.9-26.820.9kcal

7、/mol6IOICRhCICO2.772.391.91OOICCRhCIIOICRhOCCOIC0kcal/molDH‡=18kcal/molDS‡=1.1cal/mol•KDG‡=17kcal/molDH=-5.6kcal/molDS=2.3cal/mol•KDG=-6.2kcal/molMigratoryInsertionof[MeRh(CO)2I3]-TransitionStateReactantProductDH‡expt=15kcal/molDS‡expt=-14cal/mol•KDG‡expt=19kcal/molDHexpt=-8.8k