Homogeneous Catalysis A Wedding of Theory and Expe

PLEASESCROLLDOWNFORARTICLEThisarticlewasdownloadedby:On:26January2011Accessdetails:AccessDetails:FreeAccessPublisherTaylor&FrancisInformaLtdRegisteredinEnglandandWalesRegisteredNumber:1072954Registeredoffice:MortimerHouse,37-41MortimerStreet,LondonW1T3JH,UKCatalysisReviewsPublicationdetails,includinginstructionsforauthorsandsubscriptioninformation:~content=t713597232HomogeneousCatalysis:AWeddingofTheoryandExperiment.TheEugeneJ.HoudryAwardAddressMiltonOrchinaaDepartmentofChemistry,UniversityofCincinnati,Cincinnati,OhioTocitethisArticleOrchin,Milton(1984)'HomogeneousCatalysis:AWeddingofTheoryandExperiment.TheEugeneJ.HoudryAwardAddress',CatalysisReviews,26:1,59—79TolinktothisArticle:DOI:10.1080/01614948408078060URL::(I),59-79(1984)HomogeneousCatalysis:AWeddingofTheoryandExperiment.TheEugeneJ.HoudryAwardAddressMILTONORCHINDepartmentofChemistryUniversityofCincinnatiCincinnati,Ohio45221I.THEHISTORICALIMPACTOFHOMOGENEOUSCATALYSIS.........................................6011.THEPROPHETICPOWEROFCATALYSTS*-*****--***-61I11SOMEQUALITATIVEBONDINGPRINCIPLES-.-*-****62A.TheImportanceofAntibondingOrbitals......62B.The18Electron(ClosedShell)Rule..*---...--.66THECHEMISTRYOFSOMEPLATINUMCOMPLEXES.........................................67v.HYDROFORMYLATION...............................68IV.VI.STOICHIOMETRICHYDROFORMYLATIONOF1-ALKENES.........................................69VII.THESTOICHIOMETRICREACTIONOFHCo(CO),WITHARYL-SUBSTITUTEDETHYLENES-*----*.*-69*PresentedattheEighthNorthAmericanMeetingoftheCataly-sisSociety,Philadelphia,Pennsylvania,May3,1983.59Copyright01984byMarcelDekker,Inc.01614940/84/260141059$3SO/ODownloadedAt:01:3926January201160ORCHINVIII.PARTITIONINGBETWEENALDEHYDESANDHYDROCARBONS..................................75REFERENCES......................................78I.THEHISTORICALIMPACTOFHOMOGENEOUSCATALYSISGreatBritaindominatedthechemicalindustry,particularlythedyestuffindustry,duringthelasthalfofthenineteenthcentury.WilliamHenryPerkin,whohadapostattheRoyalCollegeofChem-istryinLondonwhenhewas17,butwhowasworkingatthetimeinhishomelaboratory,oxidizedanilinesulfatewithK,Cr,O,andobtainedthedyeanilinepurpleormauve.Recognizingitspoten-tial,heresignedhisacademicpositionandtogetherwithhisfatherbegancommercialmanufactureofthedyewhenhewas19yearsold.Perkinretiredin1874attheageof36todevotefulltimetoresearch.Theotherimportantdyestuffatthetimewasin-digo.UnderImperialBritain,Indiain1890produced5millionpoundsofindigofromthewoadplant;itssellingpricewas$3/lb.ChemistsatBadischeAnilinandSodaFabrikhadbeentryingtosynthesizeindigoformanyyearsandin1897,after18yearsofresearch,thecompanyachievedthefirstcommercialsynthesis.Themajorstumblingblockintheprocesshadbeentheoxidationofnaphthalenetophthalicanhydride,andthesuccessfulsolutionoftheproblemresultedfromanaccident.AchemistbythenameofSapperaccidentallybrokeathermometerwhilehewastryingtooxidizenaphthalenewithsulfuricacid.HgSO,turnedouttobeahomogeneouscatalystforthereaction,althoughuntilthisday,tothebestofmyknowledge,theexactmechanismofthecatalysisisnotunderstood.ThisachievementchangedforevertherelativepositionofthechemicalindustryinGreatBritainvis-a-visGermany,toGermany'sadvantage.ThetremendouseconomicimpactandpotentialofcatalysiswasappreciatedbytheGermanchemists.In1901Ostwald[l]wrote:Thescientificknowledgeandcontrolofcatalyticphe-nomenamustleadtoimmeasurableresultsinatechni-caldirection.ThelastgreattriumphofGermantech-nicalchemistry,thesynthesisofindigo,whichre-versestheeconomicrelationshipsofnations,containsasanessentialfactoranewcatalyticreaction.TheoxidationofnaphthalenebysulfuricacidcanonlybeDownloadedAt:01:3926January2011HOMOGENEOUSCATALYSIS61carriedoutsatisfactorilyinthepresenceofmercury.Ifoneconsidersthattheaccelerationofreactionbycatalyticmeansoccurswithoutexpenditureofenergyormaterial,andisinthissensegratis,itisevidentthatthesystematicuseofcatalystsmayleadtothemostfar-reachingadvancesintechnology.11.THEPROPHETICPOWEROFCATALYSTSAlthoughIhavebeenworkingonvariousaspectsofcatalysisformorethan38years,letmetellyouaboutanincidentthathelpedmetoappreciateitspower.Inabout1957Iwasteach-ingabeginningcourseinorganicchemistrytograduatestudentsinphysicsaspartofthecurriculumintheAppli