Chapter5OxidativeadditionandreductiveeliminationOutlineA.IntroductiontooxidativeadditionreactionsB.MechanismofoxidativeadditionreactionsC.ExamplesofadditionofspecificmoleculesD.ReductiveeliminationE.OxidativecouplingReferencesandsuggestedreadings:1.TheOrganometallicChemistryoftheTransitionMetals,RobertH.Crabtree,3rdEdition,2001,Chapter6.2.OrganometallicChemistry,G.O.Spessard,G.L.G.L.Miessler,Prentice-Hall:NewJersey,1997,Chapter7.3.AdvancedInorganicChemistry,F.A.Cotton,G.Wilkinson,JohnWiley&Sons,5thed.1988,Chapter27,1186.4.OrganotransitionMetalChemistry,AkioYamamoto,1986,Chapter6.2.A.Introductiontooxidativeadditionreactions1).Types2).FactorsaffectingO.A.reactions1).TypesXXiLnM+LnMYY16e18e∆O.S.=2C.N.=nC.N.=n+2Example:HClLH2ClLIrIrLCOLHCO++iiLnM+ELnME∆O.S.=2∆C.N.=1Example:++Fe(CO)5+H[HFe(CO)5]IronPentacarbonylXiiiLnM+XYLnMYXLnM+XYLnMYExample:PPh3ClPPh3ClOIr+O=OIrPh3PCOOCOPPh3Note:Fortypesi-iii:Metalcentermusthaveextravalenceelectrons.Question:DothefollowingcomplexesundergoO.A.reactions?TiR4WR6+iiiiLnMMLn+A-BLnMALnMB18e18e18e∆O.S.=1AB+A-BLnMMLnLnMMLn∆O.S.=1Example:OCCOCOCOCOCOCoCo+H22HCoOCCOCOCOCOCOR'O-OR'R'OOR'(RO)3MoMo(OR)3(RO)3MoMo(OR)32)FactorsaffectingO.A.reactionsXXbond+LMLnMnstrengthYYelectronbondstrengthrichnessiMetalsMetalswithmoreback-donationfavorO.A.reaction.Fe(0)Co(I)Ni(II)increasetendencyforO.A.Ru(0)Rh(I)Pd(II)Os(0)Ir(I)Pt(II)increasetendencyforO.A.Question.WhichofthefollowingreactionshasalargerKeq?IClClLLIrIr(a)+CH3ILLCOCOCH3IClClLLRhRh(b)+CH3ILLCOCOCH3transitionseriesiiLigandsLnwithmoreelectrondonationfavorO.A.reaction.Q1:RanktheorderofKeqforthereactionsbelow.HLClKeqYLRh+H-YRhCOLCOLClL=PPh3,PMe3,P(OPh)3Q2.WhichoneofthefollowingismorereactivewithH2?PhP+3PPh3OCPPhPhPRhRh33PPh3OCPPhIrPd3Ph3PClPh3PClPhP3ClPh3PCl(a)(b)(c)(d)IIIX-Y:WeakX-YbondfavorsO.A.reaction.StableM-X,M-Ybondsfa