2916

Organometallics2010,29,2916–2925DOI:

10.1021/om1001155

Synthesis,Characterization,andElectrochemicalPropertiesof

BisosmabenzenesBridgedbyDiisocyanides

JinboHuang,RanLin,LiqiongWu,QianyiZhao,CongqingZhu,TingBinWen,*and

HaipingXia*

StateKeyLaboratoryforPhysicalChemistryofSolidSurfaces,andDepartmentofChemistry,CollegeofChemistryandChemicalEngineering,XiamenUniversity,Xiamen,361005,People’sRepublicofChina

ReceivedFebruary12,2010

Treatmentofosmabenzene[Os(CHC(PPh3)CHC(PPh3)CH)Cl2(PPh3)2]OH(3)withvariousdiiso-cyanidesinthepresenceofNH4PF6affordedaseriesofdiisocyanide-bridgedbisosmabenzenes[(μ-CN-R-NC){Os(CHC(PPh3)CHC(PPh3)CH)Cl2(PPh3)}2][PF6]2(R=4,40-C6H4-C6H4(5a),4,40-C6H4CH2C6H4(5b),4,40-C6H4OC6H4(5c),1,4-C6H4(5d))ingoodyieldsthroughligandsubstitutionreactions.Similarly,reactionofosmafuran[Os(CHC(PPh3)C(OEt)O)Cl2(PPh3)2](6)with1,4-pheny-lenediisocyanideproducedthediisocynide-bridgedbisosmafuran[μ-(1,4-phenylenediisocyanide){Os-(CHC(PPh3)C(OEt)O)Cl(PPh3)2}2]Cl2(7).Bisosmabenzenescontainingachloroandaphosphoniumsubstituentoneachmetallacycle[(μ-CN-R-NC){Os(CHC(PPh3)CHCClCH)Cl(PPh3)2}2]Cl2(R=4,40-C6H4-C6H4(9a),4,40-C6H4CH2C6H4(9b),4,40-C6H4OC6H4(9c),1,4-C6H4(9d))couldbeobtainedinmodestyieldsfromthereactionsoftheosmacycle[Os(CHdC(PPh3)CH(OH)-η2-CtCH)Cl2-(PPh3)2](8)withcorrespondingdiisocyanidesinthepresenceofNH4PF6andNaClvianucleophilicadditionreactions.Allofthesecomplexeshavebeenfullycharacterizedby1H,31P{1H},and13C{1H}NMRspectrometry,IRspectrometry,andelementalanalyses.Moreover,thestructureof9dhasbeenestablishedbyX-raycrystallography.Theelectrochemicalpropertiesofstablebisosmabenzenes9a-dhavebeeninvestigated,whichrevealedthatthetwometalcentersin9cand9dcaninteractwitheachotherthroughadiisocyanidebridge.

Introduction

Sincethefirststabletransitionmetal-containingmetalla-benzenewasreportedin1982byRoperetal.,1impressiveprogresshasbeenmadeinthechemistryofthisinterestingclassofaromaticcompoundsbothexperimentally2and

*Towhomcorrespondenceshouldbeaddressed.(T.B.W.)Fax:(þ86)592-218-6085.E-mail:chwtb@.(H.P.X.)Fax:(þ86)592-218-6628.E-mail:hpxia@.

(1)Elliott,G.P.;Roper,W.R.;Waters,J.M.J.Chem.Soc.,mun.1982,811.

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PublishedonWeb06/15/2010

theoretically.3Anumberofstablemetallabenzenes,includ-ingruthenabenzenes,4osmabenzenes,5iridabenzenes,6platinabenzenes,7andothermetallabenzenes,8havebeensuccessfullyisolatedandcharacterizedinthepastdecades.However,studiesoftheirphysicalpropertiesarestillrather

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