Fe配合物催化的乙醛氢化反应机制的理论研究

:2009-12-24:(1979),,,,,Fe(,250014):Gaussian03Fe:,:1FeH2,2FeH2,Gaussian03NBONPA2,Fe,:,,,Fe:O64:A:1008-021X(2010)04-0016-06TheoreticalStudyonReactionMechanismofHydrogenationofAldehydeCatalyzedbyIronComplexSUNNan(CollegeofChemistry,ChemicalEngineeringandMaterialScience,ShandongNormalUniversity,Jinan250014,China)Abstract:ThereactionmechanismofhydrogenationofaldehydecatalyzedbyironcomplexwasstudiedwiththeGaussian03programpackage.Thehydrogenationreactionincludestwoprocesses:hydrogentransferprocessanddihydrogenactivationprocess.Thedihydrogenactivationprocessmayproceedviatwopathswithout(path1)orwith(path2)theassistanceofalcohol.Geometricstructuresofallthereactants,transitionstatesandproductsinvolvedinthereactionprocesswereoptimizedwiththedensityfunctionaltheory.ThenaturalpopulationanalysiswasperformedwithNBOversion3.1incorporatedintheGaussian03package.Throughtheanalysisontheenergybarrier,wecometotheconclusionthatpath2isfavorableandthehydrogentransferprocessistherate-determiningstepinthewholecatalyticcycle.Keywords:catalytichydrogenation;DFT;aldehyde;ironcomplex80,Shvo1(1),Casey,,13[1],(Rh)(Ru)(Ir)3[2],Fe,Fe,FeCaseyFe,Shvo,23,,2,Fe,Fe,(DFT)Fe,,,Fe,61SHANDONGCHEMICALINDUSTRY201039©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[3],(DFT),B3LYP[4-5],,FeLANL2DZ[6],CHO6-31G(d,p)[7-8]()(),,IRC,HFeTMS,,Gaussian03NBO[9]NPA(Naturalpopulationanalysis)42Fe,,3():Fe1TS1,1FeO24(),:1FeH2;2FeH22.14,1EHG,581SHANDONGCHEMICALINDUSTRY201039©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.ÜA,Fe-1.09812,1.754ÜA,2111.18kcal/mol;2TS1,13.37kcal/molTS1Fe-H210.105ÜA,O1-H110.152ÜA,C1-O110.047ÜA,O2-H11.300ÜA,Fe-0.913,1FeO,33O1H11.724ÜA,3H2Fe1.724ÜA,C21.169ÜA,H2C2,15.97kcal/molCasey6,6FeO2[10],FeO22.072ÜA,O1H,1.665ÜA6320.15kcal/mol,,636,,6,2.22.2.1161()6,21EHG,7Fe4C-O1.247ÜA4H25,4H215.14kcal/molH1-H20.816ÜA0.100ÜA,Fe-H2Fe-H11.656ÜA,O91:Fe©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.ÜA,Fe-H150.047ÜA,O-H11.425ÜA,H10.340,H2-0.062,Fe,O,TS241.20kcal/mol711KJ/molEHG1+0002-11.18-8.860.16TS12.191.7615.053-5.97-2.059.764+9.0812.3911.186-20.15-15.27-3.1821EHG4+H20005-15.14-12.43-3.09TS210.6610.7120.591-30.54-26.06-16.792.2.22828,32EHG,93H24’,3H29.21kcal/mol,4’O1H11.838ÜA,H2-H30.812ÜA,0.096ÜA,Fe-H21.717ÜA,Fe-H302SHANDONGCHEMICALINDUSTRY201039©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.’TS3,3.94kcal/mol,122.10kcal/mol,21TS3H2-H34’0.102ÜA,Fe-H34’0.054ÜA,O2-H14’0.187ÜA,O1-H11.528ÜA,H20.318,H3-0.034Fe,O,5’5’O2H11.747ÜA5’1,,32E(kcal/mol)H(kcal/mol)G(kcal/mol)3+H20004’-9.21-5.5416.86TS3-5.27-3.514.435’-27.86-22.33-15.821+-15.48-11.62-15.3692,:349.08kcal/mol,4’3H29.21kcal/mol,H2,34’,23Fe:,:1FeH2,2FeH2125.80kcal/mol,23.94kcal/mol,1221.86kcal/mol,:21,Fe1+2TS13,3+H24’TS35’1+13.37kcal/mol,3.94kcal/mol,:Fe,[1],,,.[J].,2005(6):16-19.[2]CaseyCP,GuanH.CyclopentadienoneIronAlcoholComplexes:Synthesis,Reactivity,andImplicationsfortheMechanismofIron-CatalyzedHydrogenationofAldehydes[J].JAmChemSoc,2009,131:2499.[3]FrischMJ,TrucksGW,SchlegelHBW,etal.Gaussian03,RevisionD.01,Gaussian,Inc.,WallingfordCT,2004.[4]BeckeAD.Density-functionalexchange-energyapproximationwithcorrectasymptoticbehavior[J].Phys.Rev.A1988,38:3098.[5]BeckeAD.Density-functionalthermochemistry.III.Theroleofexactexchange[J].JChemPhys,1993,98:5648.[6]HayJP,WadtWR.Abinitioeffectivecorepotentialsformolecularcalculations.PotentialsforthetransitionmetalatomsSctoHg[J].J.Chem.Phys.1985,82:270.[7]HohenbergP,KohnW.InhomogeneousElectronGas[J].PhysRev,1964,136:B864.[8]KohnW,ShamLJ.Self-ConsistentEquationsIncludingExchangeandCorrelationEffects[J].PhysRev,1965,140:A1133.[9]ReedAE,CurtissLA,WeinholdF.Intermolecularinteractionsfromanaturalbondorbital,donor-acceptorviewpoint[J].ChemRev,1988,88:899.[10]CaseyCP.GuanH.AnEfficientandChemoselectiveIronCatalystfortheHydrogenationofKetones[J].JAmChemSoc,2007,129(18):5816-5817.(:.Fe[J].,2010,39(4):16-21.)12:Fe©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.