Organometallics 2010, 29, 2916–2925电化学

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.

(2)Seeforrecentreviews:(a)Bleeke,J.R.Acc.Chem.Res.2007,40,1035.(b)Jia,G.Coord.Chem.Rev.2007,251,2167–2187.(c)Wright,L.J.DaltonTrans.2006,1821.(d)Landorf,C.W.;Haley,M.M.Angew.Chem.2006,118,4018;Angew.Chem.,Int.Ed.2006,45,3914.(e)Jia,G.Acc.Chem.Res.2004,37,479.(f)Bleeke,J.R.Chem.Rev.2001,101,1205.(3)Recentexamplesoftheoreticalwork:(a)Tsipis,A.C.Phys.Chem.Chem.Phys.2009,11,8244.(b)Welch,W.R.W.;Harris,S.Inorg.Chim.Acta2008,361,3012.(c)Periyasamy,G.;Burton,N.A.;Hillier,I.H.;Thomas,J.M.H.J.Phys.Chem.A2008,112,5960.(d)Brzostowska,E.M.;Hoffmann,R.;Parish,C.A.J.Am.Chem.Soc.2007,129,4401.(e)Fern andez,I.;Frenking,G.Chem.;Eur.J.2007,13,5873.(f)Zhu,J.;Jia,G.;Lin,anometallics2007,26,1986.(g)Karton,A.;Iron,M.A.;vanderBoom,M.E.;Martin,J.M.L.J.Phys.Chem.A2005,109,5454.(h)Iron,M.A.;Lucassen,A.C.B.;Cohen,H.;vanderBoom,M.E.;Martin,J.M.L.J.Am.Chem.Soc.2004,126,11699.(i)Iron,M.A.;Martin,J.M.L.;vanderBoom,M.E.J.Am.Chem.Soc.2003,125,13020.(j)Iron,M.A.;Martin,J.M.L.;vanderBoom,M.E.J.Am.Chem.Soc.2003,125,11702.(k)Iron,M.A.;Martin,J.M.L.;vanderBoom,mun.2003,132.(l)Ng,S.M.;Huang,X.;Wen,T.B.;Jia,G.;Lin,anometallics2003,22,3898.(m)Huang,Y.;Yang,S.;Li,X.Chin.J.Chem.Phys.2003,16,/Organometallics

PublishedonWeb06/15/2010

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

(4)Recentexamplesforthesynthesisofruthenabenzenes:(a)Yang,J.;Jones,W.M.;Dixon,J.K.;Allison,N.T.J.Am.Chem.Soc.1995,117,9776.(b)Bruce,M.I.;Zaitseva,N.N.;Skelton,B.W.;White,A.H.J.Chem.Soc.,DaltonTrans.2002,1678.(c)Liu,S.H.;Ng,W.S.;Chu,H.S.;Wen,T.B.;Xia,H.;Zhou,Z.Y.;Lau,C.P.;Jia,G.Angew.Chem.,Int.Ed.2002,41,1589.(d)Zhang,H.;Xia,H.;He,G.;Wen,T.B.;Gong,L.;Jia,G.Angew.Chem.,Int.Ed.2006,45,2920.(e)Clark,G.R.;O'Neale,T.R.;Roper,W.R.;Tonei,D.M.;Wright,anometallics2009,28,567.(5)Recentexamplesforthesynthesisofosmabenzenes:(a)Rickard,C.E.F.;Roper,W.R.;Woodgate,S.D.;Wright,L.J.Angew.Chem.,Int.Ed.2000,39,750.(b)Roper,W.R.Angew.Chem.,Int.Ed.2001,40,2440.(c)Wen,T.B.;Zhou,Z.Y.;Jia,G.Angew.Chem.,Int.Ed.2001,40,1951.(d)Barrio,P.;Esteruelas,M.A.;O nate,E.J.Am.Chem.Soc.2004,126,1946.(e)Wen,T.B.;Hung,W.Y.;Sung,H.H.Y.;Williams,I.D.;Jia,G.J.Am.Chem.Soc.2005,127,2856.(f)Clark,G.R.;Johns,P.M.;Roper,W.R.;Wright,anometallics2006,25,1771.(g)Hung,W.Y.;Zhu,J.;Wen,T.B.;Yu,K.P.;Sung,H.H.Y.;Williams,L.D.;Lin,Z.;Jia,G.J.Am.Chem.Soc.2006,128,13742.(h)He,G.;Zhu,J.;Hung,W.Y.;Wen,T.B.;Sung,H.H.-Y.;Williams,I.D.;Lin,Z.;Jia,G.Angew.Chem.,Int.Ed.2007,46,9065.(i)Esteruelas,M.A.;Masamunt,A.B.;Oliv an,M.;O~nate,E.;Valencia,M.J.Am.Chem.Soc.2008,130,11612.(j)Gong,L.;Lin,Y.;He,G.;Zhang,H.;Wang,H.;Wen,T.B.;Xia,anometallics2008,27,309.(k)Gong,L.;Lin,Y.;Wen,T.B.;Zhang,H.;Zeng,B.;Xia,anometallics2008,27,2584.(l)Gong,L.;Lin,Y.;Wen,T.B.;Xia,anometallics2009,28,1101.(m)Wang,T.;Li,S.;Zhang,H.;Lin,R.;Han,F.;Lin,Y.;Wen.,T.B.;Xia,H.Angew.Chem.,Int.Ed.2009,48,6453.(n)Zhang,H.;Wu,L.;Lin,R.;Zhao,Q.;He,G.;Yang,F.;Wen,T.B.;Xia,H.Chem.-Eur.J.2009,15,3546.

r2010AmericanChemicalSociety