At Least 60 Years of Ferrocene：The Discovery and Rediscovery of the Sandwich Complexes

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1、Angewandte.EssaysDOI:10.1002/anie.201201598CoordinationChemistryAtLeast60YearsofFerrocene:TheDiscoveryandRediscoveryoftheSandwichComplexesHelmutWerner*historyofchemistry·NobelPrizes·DedicatedtoPeterL.Pausonpolyphenylchromiumcompounds·sandwichcomplexesInDecember1951andFebru

2、ary1952twopapersappeared—preparecompoundsFeR2containingtwocovalentlybonded[1]acommunicationinNatureandashortarticleintheJournaldialkylordiarylgroupsfromRMgBrandFeCl3.Therefore,[2]oftheChemicalSociety—whichpresumablyonlyaminorityPausonandKealyattributedtheunusualstabilityof

3、[Fe-[3]ofthereadersofthosejournalsnoticed.PeterL.Pauson,(C5H5)2]“tothetendencyofthecyclopentadienylgrouptoayoungassistantprofessorattheDuquesneUniversityinbecomearomaticbyacquisitionofanegativecharge,Pittsburgh,andhisco-workerThomasJ.Kealyhadtriedtoresultinginimportantco

4、ntributionsfromtheresonanceform[1]preparethecompoundC10H8,namedfulvalene,whichthey(II)andintermediateforms”(Scheme2).assumedwouldpossessaromaticproperties,similartotheisomericnaphthalene.TheirideawastoconverttheanioniccyclopentadienylligandoftheGrignardreagent1tothecyclope

5、ntadienylradicalC5H5Cbyoxidation,andconvertthedihydrofulvalene2,formedbythecouplingoftwoC5H5Cradicals,tothedesiredproduct3afterdihydrogenation(Scheme1).PausonassumedthatFeCl3mightbeausefulScheme2.AlmostatthesametimeasPausonandKealy,SamuelA.Miller,inthosedaysDirectorofResea

6、rchwithBritishOxygen,withhisco-workersJohnA.TebbothandJohnF.[2]Scheme1.Tremaineisolated,againunexpectedly,[Fe(C5H5)2].Theyhadattemptedtoprepareaminesfromsaturatedorunsatu-ratedhydrocarbonsandnitrogenbyusingthe“doubly-reagentforthegenerationofthecyclopentadienylradicalpromo

7、tedsyntheticammoniacatalyst”developedinthefromtheGrignardcompoundaswellasfortheabstractionofcontextofHaberspioneeringworkonthesynthesisofH2fromintermediate2togive3,becauseitwasavailableinNH3.WhentheyreactedcyclopentadieneandN2at3008C[4]itsnon-hydratedformandassuchsolublei

8、nether.Afterandatmosphericpressure,theyobtained[Fe(C5H5)2].LikeadditionofFeCl3toasolution