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

Articlelimitedtoafewreports.DuringthecourseofoursystematicinvestigationonthechemistryofmetallabenzenesbasedonourfacileapproachestoconstructaromaticmetallacyclesthroughcycloadditionofunsaturatedC5buildingblockswithsimpletransition-metalcomplexesbearingphosphineligands,4d,5k,nwehavereportedrecentlytheelectrochemicalproperties5n,9,10ofaseriesofruthenabenzenesandosmabenzenes.Impor-tantly,itwasfoundthatthereiselectroniccommunicationbetweenthetwo9metalcentersinthetrichloro-bridgedbisru-thenabenzenesandbisosmanaphalenes.10Bismetallabenzenesandtheiranalogues,althoughinteresting,areextemelyrare.Tothebestofourknowledge,thetrichloro-bridgedbisruthena-benzenesandbisosmanaphthalenesreportedbyourgrouprepresenttheonlyexamplesuptonow,9,10whiletherutheniumcomplexeswithtwoπ-coordinatedruthenabenzeneligandsreportedbySalzerarebis(metallabenzene)π-complexes,whichbelongtometallabenzenesandwichcompounds.11Thelackofconvenientmethodstoconstructbismetallabenzenesmaypartlypreventthephysicalpropertystudiesofthesecom-pounds.Thus,itwouldbeofinteresttodevelopnewap-proachesforthepreparationofbismetallabenzenesandinvestigatetheirelectrochemicalproperties.

Isocyanideshavebeenwellknowntostabilizecomplexesbyparticipatingasnotonlystrongσ-donorsbutalsoπ-acceptorligands.12,13Especiallythemetal-carbonπ-interactionsplay

(6)Recentexamplesforthesynthesisofiridabenzenes:(a)Hughes,R.P.;Trujillo,H.A.;Egan,J.W.,Jr.;Rheingold,A.L.J.Am.Chem.Soc.2000,122,2261.(b)Gilbertson,R.D.;Weakley,T.J.R.;Haley,M.M.Chem.-Eur.J.2000,6,437.(c)Bleeke,J.R.;Hinkle,P.V.;Rath,anometallics2001,20,1939.(d)Bleeke,J.R.;Blanchard,J.M.B.;Donnay,anometallics2001,20,324.(e)Wu,H.-P.;Lanza,S.;Weakley,T.J.R.;Haley,anometallics2002,21,2824.(f)Gilbertson,R.D.;Lau,T.L.S.;Lanza,S.;Wu,H.-P.;Weakley,T.J.R.;Haley,anometallics2003,22,3279.(g)Paneque,M.;Posadas,C.M.;Poveda,M.L.;Rend on,N.;Salazar,V.;O~nate,E.;Mereiter,K.J.Am.Chem.Soc.2003,125,9898.(h)Bleeke,J.R.;Hinkle,P.V.;Shokeen,M.;Rath,anometallics2004,23,4139.(i)Chin,C.S.;Lee,H.Chem.-Eur.J.2004,10,4518.(j)Wu,H.-P.;Weakley,T.J.R.;Haley,M.M.Chem.-Eur.J.2005,11,1191.(k)Chin,C.S.;Lee,H.;Eum,anometallics2005,24,4849.(l)Ilg,K.;Paneque,M.;Poveda,M.L.;Rend on,N.;Santos,L.L.;Carmona,E.;Mereiter,anometallics2006,

25,2230.(m)Alvarez, E.;Paneque,M.;Poveda,M.L.;Rend on,N.Angew.

Chem.,Int.Ed.2006,45,474.(n)Clark,G.R.;Lu,G.-L.;Roper,W.R.;Wright,anometallics2007,26,2167.(o)Paneque,M.;C.M.;Poveda,M.L.;Rendo

n,N.;Santos,L.L.;Alvarez, Posadas,

E.;Salazar,V.;Mereiter,K.;O~nate,anometallics2007,26,3403.(p)Wu,H.-P.;Ess,D.H.;Lanza,S.;Weakley,T.J.R.;Houk,K.N.;Baldridge,K.K.;Haley,anometallics2007,26,3957.(q)Paneque,M.;Poveda,M.L.;

Rend on,N.;Alvarez, E.;Carmona,E.Eur.J.Inorg.Chem.2007,2711.(r)

Clark,G.R.;Johns,P.M.;Roper,W.R.;Wright,anometallics2008,27,451.(s)Dalebrook,A.F.;Wright,anometallics2009,28,5536.(7)Recentexamplesforthesynthesisofplatinabenzenes:(a)Jacob,V.;Weakley,T.J.R.;Haley,M.M.Angew.Chem.,Int.Ed.2002,41,3470.(b)Jacob,V.;Weakley,T.J.R.;Haley,anometallics2002,21,5394.(c)Landorf,C.W.;Jacob,V.;Weakley,T.J.R.;Haley,anometallics2004,23,1174.(d)Jacob,V.;Landorf,C.W.;Zakharov,L.N.;Weakley,T.J.R.;Haley,anometallics2009,28,5183.(8)(a)Wu,H.-P.;Weakley,T.J.R.;Haley,anometallics2002,21,4320.(b)Ferede,R.;Allison,anometallics1983,2,463.(c)Riley,P.N.;Profilet,R.D.;Salberg,M.M.;Fanwick,P.E.;Rothwell,I.P.Polyhedron1998,17,773.

(9)Zhang,H.;Feng,L.;Gong,L.;Wu.,L.;He,G.;Wen,T.;Yang,F.;Xia.,anometallics2007,26,2705.

(10)Liu,B.;Xie,H.;Wang,H.;Wu,L.;Zhao,Q.;Chen,J.;Wen,T.B.;Cao,Z.;Xia.,H.Angew.Chem.,Int.Ed.2009,48,5461.

(11)(a)Englert,U.;Podewils,F.;Schiffers,I.;Salzer,A.Angew.Chem.,Int.Ed.1998,37(15),2134.(b)Effertz,U.;Englert,U.;Podewils,F.;Salzer,A.;Wagner,T.;Kaupp,anometallics2003,22,264.(12)Grubisha,D.S.;Rommel,J.S.;Lane,T.M.;Tysoe,W.T.;Bennett,D.W.Inorg.Chem.1992,31,5022.

(13)(a)Guy,M.P.;Guy,J.T.,Jr.;Bennett,anometallics1986,5,1696.(b)Guy,M.P.;Coffer,J.L.;Rommel,J.S.;Bennett,D.W.Inorg.Chem.1988,27,2942.(c)Johnston,R.F.J.Coord.Chem.1994,31,57.

Organometallics,Vol.29,No.13,20102917

keyrolesinthestabilityofmetal-isocyanidesandelectronicinteractionsbetweenthemetalcenterandisocyanideligands.Thustransition-metalcomplexesoforganicisocyanidesarewidelyusedinorganicandorganometallicsynthesis,14a-ccatalysis,14doptoelectronicmaterials,14e-ibuildingblocksfororganometallicpolymers,15andmolecularself-assembly12e,16fields.Inparticular,multiisocyanideshavebeensuggestedaspossible“alligatorclips”formolecularwiresandtheelectronictransportbetweenmetalcontacts.15dTherefore,themultiisocya-nide-bridgedmetalcomplexeshavealsogainedimportancefortheirversatilestructuralandphysicochemicalpropertiesinfieldsincludingluminescence17,18andelectronictransmission.19,20Forexample,thediisocyanideligands,suchas1,4-diisocyanoben-zene,arecapableofformingstructureandelectronicbridgesbetweentwometalcenters,facilitatingelectronpolarizationandtransferthroughthemetal-ligand-metalsystem.12,20

Inourinvestigationonthereactivityofmetallabenzenes,wehavereportedthatruthenabenzene[Ru(CHC(PPhCHC(PPh)CH)Cl)3)-32(PPh32]Cl(1)canreadilyundergoli-gandsubstitutionreactionwithtBuNCtoproducestable

(14)(a)Robinson,R.E.;Holovics,T.C.;Deplazes,S.F.;Lushing-ton,G.H.;Powell,D.R.;Barybin,M.V.J.Am.Chem.Soc.2003,125,4432.(b)Weber,L.Angew.Chem.,Int.Ed.1998,37,1515.(c)Farrell,J.R.;Eisenberg,A.H.;Mirkin,C.A.;Guzei,I.A.;Liable-Sands,L.M.;Incarvito,C.D.;Rheingold,A.L.;Stern,anometallics1999,18,4856.(d)Song,L.-C.;Yang,Z.-Y.;Bian,H.-Z.;Liu,Y.;Wang,H.-T.;Liu,X.-F.;Hu,anometallics2005,24,6126.(e)Bay on,R.;Coco,S.;Espinet,P.Chem.-Eur.J.2005,11,1079.(f)Bay on,R.;Coco,S.;Espinet,P.;Fern andez-Mayordomo,C.;Martín-Alvarez,J.M.Inorg.Chem.1997,36,2329.(g)Fournier,E.;Sicard,S.;Decken,A.;Harvey,P.D.Inorg.Chem.2004,43,1491.(h)Sharma,V.;Piwnica-Worms,D.Chem.Rev.1999,99,2545.(i)Carnahan,E.M.;Protasiewicz,J.D.;Lippard,S.J.Acc.Chem.Res.1993,26,90.

(15)(a)Fortin,D.;Drouin,M.;Harvey,P.D.Inorg.Chem.2000,39,2758.(b)Fortin,D.;Drouin,M.;Turcotte,M.;Harvey,P.D.J.Am.Chem.Soc.1997,119,531.(c)Turcotte,M.;Harvey,P.D.Inorg.Chem.2002,41,2971.(d)Murphy,K.L.;Tysoe,W.T.;Bennett,ngmuir2004,20,1732.

(16)(a)Philp,D.;Stoddart,J.F.Angew.Chem.,Int.Ed.1996,35,1154.(b)Mayr,A.;Guo,J.Inorg.Chem.1999,38,921.

(17)(a)White-Morris,R.L.;Olmstead,M.M.;Balch,A.L.J.Am.Chem.Soc.2003,125,1033.(b)Coppens,P.;Gerlits,O.;Vorontsov,I.I.;Kovalevsky,A.Y.;Chen,Y.-S.;Graber,T.;Gembicky,M.;Novozhilova,mun.2004,2144.(c)Villegas,J.M.;Stoyanov,S.R.;Huang,W.;Lockyear,L.L.;Reibenspies,J.H.;Rillema,D.P.Inorg.Chem.2004,43,6383.(d)Rios,D.;Olmstead,M.M.;Balch,A.L.DaltonTrans.2008,4157.(e)A.; Arias,J.;Bardají,M.;Espinet,P.Inorg.Chem.2008,47,3559.(f)Díez,Forni es,J.;Fuertes,S.;Lalinde,E.;Larraz,C.;L opez,J.A.;Martín,A.;Moreno,M.T.;Sicilia,anometallics2009,28,1705.(g)Leung,C.-F.;Ng,S.-M.;Xiang,J.;Wong,W.-Y.;Lam,M.H.-W.;Ko,C.-C.;Lau,anometallics2009,28,5709.(h)Elbjeirami,O.;Gonser,M.W.A.;Stewart,B.N.;Bruce,A.E.;Bruce,M.R.M.;Cundari,T.R.;Omary,M.A.DaltonTrans.2009,1522.

(18)Paek,J.H.;Song,K.H.;Jung,I.;Kang,S.O.;Ko,J.Inorg.Chem.2007,46,2787.

(19)(a)Shapiro,P.J.;Zehnder,R.;Foo,D.M.;Perrotin,P.;Budzelaar,P.H.M.;Leitch,S.;Twamley,anometallics2006,25,719.(b)Tian,Y.;Kamata,K.;Yoshida,H.;Iyoda,T.Chem.-Eur.J.2006,12,584.(c)Lee,J.-O.;Lientschnig,G.;Wiertz,F.;Struijk,M.;Janssen,R.A.J.;Egberink,R.;Reinhoudt,D.N.;Hadley,P.;Dekker,C.NanoLett.2003,3,113.(d)Chen,J.;Calvet,L.C.;Reed,M.A.;Carr,D.W.;Grubisha,D.S.;Bennett,D.W.Chem.Phys.Lett.1999,313,741.(e)Dupraz,C.J.-F.;Beierlein,U.;Kotthaus,J.P.ChemPhysChem2003,4,1247.(f)Seminario,J.M.;Zacarias,A.G.;Tour,J.M.J.Am.Chem.Soc.1999,121,411.(g)Hsu,S.C.N.;Chen,H.H.Z.;Lin,I.-J.;Liu,J.-J.;Chen,anomet.Chem.2007,692,3676.(h)Yu,M.P.Y.;Yam,V.W.-W.;Cheung,K.-K.;

Mayr,anomet.Chem.2006,691,4514.(i)Cle

ment,S.;Aly,S.M.;Fortin,D.;Guyard,L.;Knorr,M.;Abd-El-Aziz,A.S.;Harvey,P.D.Inorg.Chem.2008,47,10816.

(20)(a)Rommel,J.S.;Weinrach,J.B.;Grubisha,D.S.;Bennett,D.W.Inorg.Chem.1988,27,2945.(b)Kim,H.S.;Lee,S.J.;Kim,N.H.;Yoon,J.K.;Park,H.K.;Kim,ngmuir2003,19,6701.(c)Ryu,H.;Knecht,S.;Subramanian,L.R.;Hanack,M.Synth.Met.1995,72,289.(d)Wagner,N.L.;Laib,F.E.;Bennett,mun.2000,3,87.

2918Organometallics,Vol.29,No.13,2010

Scheme1.SyntheticPathwaysfortheBismetallabenzenes5a-dBridgedbyDiisocyanide

Ligands

Huangetal.

isocyanide-coordinatedruthenabenzene2(eq1).9Giventheimportantroleofdiisocyanidesinmolecularelectronicsandrecentprogressinoptoelectronicmaterialsmentionedabove,wearemotivatedtodesignanewbismetallabenzenesystemwithdiisocyanideasthebridgingligands.Ofparticularinter-estisthediisocyanide-bridgedbismetallabenzenesconstitut-inglargeconjugatedsystem,whichmightexhibitspecialelectrochemicalandotherphysicochemical

properties.

Inthiswork,wehavesuccessfullyconstructedaseriesofbisosmabenzenesusingdiisocyanideswithdifferentlinkingspacersasthebridgingligands.Asacomparativestudy,abisosmafuranbridgedby1,4-phenylenediidocyanidehasalsobeensynthesized.Theelectrochemicalpropertiesofseveralcomplexeshavebeenstudiedbycyclicvoltammetry.

ResultsandDiscussion

SynthesisandCharacterizationofDiisocyanide-BridgedBisosmabenzenesfromLigandSubtitutionReactions.Asal-readystated,inourstudiesonthereactivityofruthenaben-zeneswiththeisocyanides,9wehavefoundthatoneoftheClligandsin1canbereadilyreplacedbytBuNCtoproducestableisocyanide-coordinatedruthenabenzene2(eq1).Weenvisionedthatanalogousosmambenzenecomplex[Os-(CHC(PPh3)CHC(PPh3)CH)Cl2(PPh3)2]OH(3)21mayalsoundergosimilarligandsubstitutionreactionwithdiisocya-nide.Thus,wehavecarriedoutthereactionof3withaseriesofdiisocyanideligands,withthehopetoobtainbismetalla-benzenecomplexes.Asexpected,anumberofbisosmaben-zeneshavebeensuccessfullysynthesizedandfullycharac-terized.ThegeneralsyntheticrouteforthepreparationofbismetallabenzenesisoutlinedinScheme1.

Treatmentofosmabenzene[Os(CHC(PPh3)CHC(PPh3)-CH)Cl2(PPh3)2]OH(3)with0.5equivofdiisocyanideligandCN-Ln-NC(4a-d,Lnisthelinkingspacer)inthepresenceofNH4PF6atroomtemperaturefor0.5-1.0hledtotheformationofbisosmabenzenes5a-d,whichwereisolatedasgreenishsolidsinyieldsrangingfrom58%to78%.Itwasfoundthatthereactionproceededveryslowlyintheabsence

(21)Xia,H.;He,G.;Zhang,H.;Wen,T.B.;Sung,H.H.Y.;Williams,I.D.;Jia,G.J.Am.Chem.Soc.2004,126,6862.

ofNH4PF6,whileadditionofNH4PF6couldspeedupthereaction.ProbablyNH4PF6wasaddedtoabstractonechlor-ideligandfirst,sothattheligandsubstitutionreactioncanbeaccelerated.Inthesolidstateandunderaninertatmosphere,thesecomplexesareallstableatroomtemperatureforatleastonemonthandcanbestoredat0οCforatleastseveralmonthswithoutappreciabledecomposition.However,itisimportanttonotethatcomplexes5a-dcanslowlydecomposeinsolutionatambienttemperature,resultingintheformationofamixtureofunidentifiedproducts.

Allofthecompoundshavebeencharacterizedbyelemen-talanalysis,IR,and1H,13C{1H},and31P{1H}NMRspec-trometry.Althoughthemolecularstructuresof5a-dhavenotbeencharacterizedsofarbyX-raydiffraction,duetothelackofX-rayqualitysinglecrystals,itisbelievedthateachmoleculehastwosymmetricallyrelatedunits,asinferredfromtheNMRdata.SelectedNMRandIRdataforthebisosmabenzenes5a-daregiveninTable1.Onthewhole,theNMRdataof5a-daresimilartoeachotherwithrespecttochemicalshiftsandsignalpatterns.Inthe31P{1H}NMRspectrum,eachoftheosmiumcomplexes5a-dshowsonesingletintheregionδ=-1.20to-1.83attributedtoOsPPh3andanothertwosingletsforCPPh3intheregionsδ=19.74-20.65and24.88-25.58ppm,respectively.Inthe1

HNMRspectrumthecharacteristicsignalsforOsCHofthemetallacycleareobservedatδ=14.54-15.74ppmwithaH-Pcouplingconstantofapproximately25Hzandδ=16.36-17.45ppmwithaH-Pcouplingconstantofapproxi-mately19Hz.TheprotonresonancesonthecarbonsparatotheOscentersappearatδ=7.95-9.09ppmaccordingto1

H-13CHSQC.Incomparisonto3,the1HNMRsignalsoftheringprotonsfor5a-dareshiftedconsiderablyupfielded.5n,21Asimilartrendwasobservedforthemeta-carbonsinthe13CNMRspectrum,inwhichthesignalsofγ-CHareobservedintherangeδ=152.76-158.91ppm,whereasthesignalsofortho-andpara-carbonstotheOscentersareshifteddownfield,whichappearintherangesδ=238.03-259.75and114.32-120.41ppm.Additionally,theisocyano-carbonsignalsaregenerallyoflowintensity,22whichappearasasingletatδ=143.15-145.15ppm.Inparticular,onlyoneν(CtN)absorptionisobservedforeachcomplexat2081-2109cm-1intheFTIRspectra,indicatingthepresenceofonetypeofisocyanogroupineachcomplex.

(22)Efraty,A.;Feinstein,I.;Wackerle,L.;Goldman,.Chem.1980,45,4059.

ArticleOrganometallics,Vol.29,No.13,2010

Table1.Selected1H,13C{1H},and31P{1H}NMRandIRDataforComplexes5a-dand9a-d

31

2919

P{1H}(ppm)

H1

1

H(ppm)H39.098.337.987.957.797.827.567.83

H517.4017.4516.3616.4516.6216.6816.6216.52

C1254.70253.76259.75253.67233.40232.45233.16233.01

C2114.40115.46119.72114.32115.48115.36115.35116.04

13

C{1H}(ppm)

C4115.36116.86120.41116.11136.53136.38136.42136.34

C5240.35238.03245.35240.12251.94265.09251.70251.89

NtC143.15143.34145.15144.06153.18141.78156.22156.21

IR(cm-1)NtC20952109208120882084208620752064

compd5a5b5c5d9a9b9c9d

a

C3153.74152.76158.91152.89139.47139.69139.28139.58

20.64,25.58,-1.4819.74,24.88,-1.2020.59,25.48,-1.8320.65,25.36,-1.4718.68,-3.3418.57,-3.0117.00,-5.1818.67,-2.1215.6915.7414.6214.5413.7313.7713.6713.63

Numberingschemesforthehydrogenandcarbonatomsin5a,band9a,b

are

SynthesisandCharacterizationof1,4-Phenylenediisocya-nide-BridgedBisosmafuran.Metallafurans,aclassoffive-memberedmetallacycles,arealsoacommonrepresentativeofmetalla-heteroaromaticcompounds.Asacomparativestudy,wehavealsopreparedadiisocynide-bridgedbisosma-furanvialigandsubstitutionreaction.Inamannersimilartothatfor5a-d,treatmentatroomtemperatureofosmafuran[Os(CHC(PPh3)C(OEt)O)Cl2(PPh3)2](6)23with0.5equivof1,4-phenylenediisocyanideinthepresenceofNH4PF6over10hresultedintheformationof1,4-phenylenediisocyanide-bridgedbisosmafurancomplex7,whichwasisolatedasalightyellowsolidaftercolumnchromatographyin78%yield(Scheme2).Althoughstableinthesolidstate,asolutionofcomplex7inCH2Cl2canalsoslowlydecomposeatroomtemperatureunderaninertatmosphere.

Complex7hasbeencharacterizedby1H,31P{1H},and13

C{1H}NMR.Thespectroscopicdataareconsistentwithourproposedstructuralformulation.AsinferredfromtheNMRdata,italsocontainstwosymmetricallyrelatedunits.The31P{1H}NMRspectrumshowstheCPPh3signalatδ=14.83ppmandtheOsPPh3signalatδ=10.23ppm,respec-tively,indicatingthetransdispositionofthetwophosphineligands.The1HNMRspectrumshowsthecharacteristicOsCHsignalasadoubletatδ=12.73ppmwithaH-Pcouplingconstantof12.4Hz.Again,incomparisontothatin5,complex7displaysanappreciablyupfieldshiftinreso-nancesfortheortho-protonstoOsontheosmafuranrings,consistentwithincreasedπ-back-bondingbetweenthemetalsandtheisocyanogroupsin6.Inthe13C{1H}NMRspectrum,thesignalsforthemetallacyclecarbonsareobservedat239.51,181.50,and98.81ppm,respectively.Thesignalsoftheethylgroupsappearatδ=64.41and13.50ppm.The13CNMR

(23)Lin,Y.;Gong,L.;Xu,H.;He,X.;Wen,T.B.;Xia,anometallics2009,28,1524.

resonancesoftheisocyanogroupsappearasasingletatδ=145.73ppm.

SynthesisandCharacterizationofDiisocyanide-BridgedBisosmabenzenesfromNucleophilicAdditionReactions.InourpreviousstudyonthereactionofOsCl2(PPh3)3withterminalalkyneHCtCCH(OH)CtCH,whichresultedintheformationoftheosmabenzene[Os(CHC(PPh3)CHC-(PPh3)CH)Cl2(PPh3)2]OH(3),wehavesucceededinisolat-ingakeyintermediate,theosmacycle-containingcoordi-natedalkynealcohol[Os(CHdC(PPh3)CH(OH)-η2-CtCH)Cl2(PPh3)2](8).5n,21Ithasbeenfoundthattheisolatedcomplex8cannotonlyreadilyreactwithPPh3toproducethediphosphoniumosmabenzene3butalsoreactwithothernucleophilessuchasI-andSCN-togivemonophospho-nium-substitutediodo-aswellasthiocyanato-osmabenzenesvianucleophilicattackatthecoordinatedalkyne.5nThere-fore,wewerepromptedtoattemptconstructionofbisosma-benzenesdirectlyfromthereactionsof8withdiisocyanidesinthepresenceofnucleophile.Withthisstrategy,asshowninScheme3,bisosmabenzenes9a-dcouldbeproducedfromthereactionsof8withasolutionofdiisocyanideligands4a-dinthepresenceofNH4PF6andNaCl.Aftercolumnchromatography,9a-dwereisolatedasgreenishsolidsinmodestyieldsrangingfrom47%to67%.Again,NH4PF6wasaddedtoabstractoneofthechlorideligandsin8toacceleratethereaction,whiletheaddedNaClcanprovidesufficientnucleophilesinthereactionmedia,whichcanimprovetheyields.Additionofexcessisocyanideligandledtotheformationofunidentifiedinsolubleproduct,prob-ablysomepolymericspecies.Itshouldbenotedthatcom-plexes9a-dshowexcellentthermalstabilityunderN2atmosphereinsolidstate,inviewofthefactthatthesolidsampleremainsalmostunchangedwhenheatedat120οCunderaninertatmosphereover10h.Unlikebisosmaben-zenes5a-d,thesecomplexesarestableinCH2Cl2solution

2920Organometallics,Vol.29,No.13,2010

Scheme3.SyntheticPathwaysfortheBisosmabenzenes9a-dBridgedbyDiisocyanide

Ligands

Huangetal.

evenunderrefluxovernightandcanbestoredatroomtemperatureforatleastamonthwithoutdecompositioninaninertatmosphere.

Complexes9a-dhavealsobeencharacterizedbyelemen-talanalysis,IR,andmultinuclearNMRspectroscopy.Alldataarefoundtobeconsistentwithexpectations.SelectedNMRandIRdataareshowninTable1.

AsshowninTable1,9a-dexhibitNMRsignalswithsimilarchemicalshiftsandcouplingconstants,whichisconsistentwiththeirnearlyidenticalligandenvironmentsaroundtheOsmetalcenters.The31P{1H}NMRspectrashowtwosingletsintherangesδ=17.00-18.68ppm(CPPh3)and-2.12to-5.18ppm(OsPPh3),respectively.Inthe1HNMRspectrum,eachofthecomplexes9a-dshowsasingletintherangeδ=16.52-16.68ppmandadoubletatδ=13.63-13.77ppmwithaH-Pcouplingconstantofapproximately29.0HzforOsCHCClandOsCHCPPh3,respectively.Thepara-protonstothemetalcentersontheringgiveadoubletatδ=7.56-7.83ppmwithaH-Pcoupl-ingconstantofapproximately13.3Hz.Theprotonsontheringsoppositethephosphoniumgroupsaremoredownfieldcomparedwiththoseattheortho-positioninthecomplexes9a-d.Thiseffectwasalsoobservedforourpreviouslyreportedmetallabenzeneswithonephosphoniumgrouponthecarbonatomofthemetallacycles.5k,l,n,21The13CNMRspectrademonstratesimilartrends,thatthesignalsforcarbonatomsontheosmabenzeneringsresonateintherangeδ=232.45-233.40(OsCHCPPh3),251.70-265.09(OsCHCCl),136.34-136.42(CCl),115.35-116.04(CPPh3),and139.28-139.58(CClCH)ppm,respectively.Overall,complexes9a-ddisplayaconsiderablyupfieldshiftinresonancesincompari-sonto5a,bduetothepresenceofonlyonephosphoniumgrouponthemetallacycle,whichdecreasestheelectroniceffect.

Inaddition,theisocyano-carbonsignalsappearintherangeδ=141.78-156.22ppm.TheFTIRspectraof9a-dexhibitastrongIRabsorptionintherangeν=2064-2086cm-1fortheCtNtriplebond,whichundergoesanabout30cm-1shifttolowerfrequencycomparedwiththoseofthefreeligandsprobablyduetotheM-Cπ-bondinginteraction.20b,24

Repeatedeffortstogrowcrystalsof5a-dand7wereunsuccessful.However,wedidobtaingood-qualitycrystalsfor9d.Thestructureofcomplex9dhasbeenunambiguously

(24)Swanson,S.A.;McClain,R.;Lovejoy,K.S.;Alamdari,N.B.;Hamilton,J.S.;Scott,ngmuir2005,21,5034.

establishedbysingle-crystalX-raydiffraction.ApreliminarythermalellipsoiddrawingofthedicationisshowninFigure1.Itconfirmsthatcomplex9dindeedcontainstwosix-mem-beredmetallacyclesconnectedbya1,4-phenylenediisocyanidebridge.Thismoleculeiscentrosymmetric,andthustheasym-metricalunitofthisstructurecontainshalfamolecule.Eachmetallacyclecontainsaphosphoniumandachlorosubstitu-entatC2andC4,respectively.ThemetallabenzeneringconsistingofOs1/C1/C2/C3/C4/C5isalmostcoplanar,which

)fromthermsplanesofisreflectedbythedeviation(0.0471A

thebestfit,andthemetallacycleisalmostperpendiculartothebenzeneringof1,4-phenylenediisocyanidewiththedihe-dralanglebetweenthemetallabenzeneringandthebridgingbenzeneringof98.1°.ThebonddistancesforOs1-C1

),C1-C2(1.383(7)A),C2-C3(1.424(7)A),(2.046(5)A

),C4-C5(1.401(8)A),andOs1-C5C3-C4(1.366(7)A

),togetherwiththoseforOs1-P1(2.4013(12)A)(1.952(5)A

),areconsistentwiththoseofourandOs1-Cl1(2.5048(13)A

previouslyreportedosmabenzenesderivatives.5nAsexpected,

)bondisshorterthantypicalOs-CtheOs1-C01(1.979(5)A

)islongerthanthesinglebonds,whereasC01tN1(1.159(6)A

freeCtNtriplebond,showingsubstantialπ-back-bondingcontributionfromthemetalcentertotheisocyanideligand.19a,25TheOs-CtNbondangleof168.7°isclosetolinearity.Thesolid-statestructureof9disconsistentwithitsspectroscopicdatasummarizedinTable1.Asmentionedabove,the31P{1H}NMRspectrumshowstheCPPh3signalatδ=18.67ppmandtheOsPPh3signalatδ=-2.12ppm,respectively.The1HNMRspectrumshowsasingletatδ=16.52ppmfortheOsCHCClandadoubletatδ=13.63ppmfortheOsCHC-(PPh3),whereasinthe13C{1H}NMRspectrumthemetalla-cyclecarbonsignalsareobservedat233.01(C1),116.04(C2),139.58(C3),136.34(C4),and251.89(C5)ppm,respectively.Additionally,theCtNstretchforthebismetallabenzene9doccursatν=2064cm-1,somewhatlowerinenergythanthatofthefree1,4-phenylenediisocyanideligand(ν=2118cm-1).24

Mechanistically,formationofthediisocyanide-bridgedosmabenzenes9a-dfromthereactionsshowninScheme3issimilartotheformationofthemonophosphonium-sub-stitutediodo-aswellasthiocyanato-osmabenzenes,which

(25)(a)Rickard,C.E.F.;Roper,W.R.;Williamson,A.;Wright,anometallics1998,17,4869.(b)Clark,G.R.;Waters,J.M.;Whittle,K.R.J.Chem.Soc.,DaltonTrans.1976,2029.(c)Johnson,T.W.;Tetrick,S.M.;Fanwick,P.E.;Walton,R.A.Inorg.Chem.1991,30,4146.(d)Cheung,W.-M.;Zhang,Q.-F.;William,I.D.;Leung,W.-H.Inorg.Chem.2007,46,5754.

ArticleOrganometallics,Vol.29,No.13,20102921

wereportedpreviously.5n,21AsdescribedinScheme4,com-plex8caninitiallyreactwithdiisocyanideinthepresenceofNH4PF6togivethediisocyanide-bridgedintermediateA,whichundergoesnucleophilicattackoftheCl-attheco-ordinatedalkyne,followedbyeliminationofanOH-fromtheγ-carbonatomtogivecomplexes9a-d.Infact,inourpreviousinvestigationontherelatedreactionofcomplex8withNaCl,wecouldalsodetecttheformationofmonopho-sphonium-substitutedchloro-osmabenzene,yetthereactionisnotclean,andourattempttoobtainpuresamplefromthecrudeproductsfailedprobablyduetotherelativelyweaknucleophilicityofchlorideionandthereadydecompositionofcomplex8andtheformedchloro-osmabenzeneinsolu-tion.5nItiswellknownthatisocyanideisagoodπ-acidicligand;thusreplacementofachlorideligandin8willdecreasetheelectrondensityofthemetalcenterandthecoordinatedalkyne,whichfacilitatesthenucleophilicattackatthecoordinatedalkynebythechlorideion.

ElectrochemicalStudies.Whilemanytheoreticalstudiesandvarioussyntheticmethodsofmetallabenzeneshavebeenreported,theelectrochemicalstudiesofmetallabenzenesarestillratherlimited.Tothebestofourknowledge,ourrecent

studiesontheelectrochemicalpropertiesofaseriesofruthe-nabenzenesandosmabenzenesandtheiranaloguesaretheonlyreportedexamples.5n,9,10Ofparticularinterestistheelectroniccommunicationbetweenthetwometalcentersobservedinthetrichloro-bridgedbisruthenabenzenes9andbisosmanaphalenes.10

Onthebasisofourfacilepreparationstrategyofthediisocyanide-bridgedbismetallabenzenesmentionedabove,wealsointendedtostudytheirelectrochemicalproperties.However,complexes5a-dand7couldslowlydecomposeinsolutiontogiveamixtureofundentifiedproducts.Wethushaveinvestigatedtheredoxbehaviorsofthestablebisme-tallabenzenes9a-d(1mMinCH2Cl2)bycyclicvoltammetry(CV)anddifferentialpulsevoltammogramtechniques(DPV)with0.1Mn-Bu4NClO4asthesupportingelectrolyte.ThevaluesofthepotentialsforthesecomplexesarepresentedinTable2,andtypicalCVsofcomplexes9a-daredisplayedinFigures2-5.

AsshowninFigures2and3,theCVandDPVofcomplex9aexhibitonequasi-reversibleoxidationwaveatEp,a=þ1.22Vpresumablyattributedtotheoxidationoftheosmiumcenter.Thisresultindicatesthatthereislittle

if

2922Organometallics,Vol.29,No.13,2010Table2.CyclicVoltammetryDataforComplexes9a-din

CH2Cl2Containing0.1Mn-Bu4NClO4a

potentialdata/V

Ep,a,1

Ep,c,1ΔEp,1Ep,a,2Ep,c,2ΔEp,29a1.221.070.159b1.221.080.149c0.580.380.200.770.590.199d

0.160.010.15

0.81

0.65

0.16

a

PotentialversusAg/AgCl,scanrate=0.10Vs-1

.

anyelectronicinteractionbetweenthemetalcentersincomplex9a.Itislikelyascribedtorotationoftwoconjoiningbenzeneringsincomplex9a26,whichbreakstheπ-conjugatedelectroniccommunication.Additionally,anadsorptionprewave(AI)canbeseenintheCVofcomplex9a,indicatingthatreactant9acanbestronglyadsorbedontheglassycarbonelectrode.27Similaradsorptionpeaksfortheoxida-tionof9bcanbealsoobservedinFigures2and3.Theredox

(26)(a)Ghazala,S.I.;Paul,F.;Toupet,L.;Roisnel,T.;Hapiot,P.;Lapinte,C.J.Am.Chem.Soc.2006,128,2463.(b)Xia,J.-L.;Wu,X.;Lu,Y.;Chen,G.;Jin,S.;Yu,G.;Liu,anometallics2009,28,2701.(27)Wopschall,R.H.;Shain,I.Anal.Chem.1967,39,1514.

Huangetal.

Figure4.Cyclic(a)anddifferentialpulse(b)voltammogramsofcomplex-9c1inCH2Cl2with0.1Mn-Bu4NClO4atascanrateof0.10Vs.

performanceof9bissimilartothatof9a.Again,noelectro-nicinteractionbetweenthetwoosmiumcentersforcomplex9bwasobserved,whichmightbeduetothelackofconjuga-tionin9b.

Interestingly,forcomplex9c,withanoxygenatomin-sertedbetweentwo1,4-phenylenegroupsofcomplex9a,aweakbutappreciableelectronicinteractionbetweenthemetalcenterscanbeobserved(Figure4).ThetwooxidationwavesatEp,a=þ0.58VandEp,a=þ0.77VarepartlyoverlappedandtheΔEforcomplex9cisfoundtobe0.19V,indicatingthepresenceofastrongerinteractionbetweenthetwometalcentersin9cthanthatin9a.Undoubtedly,animportantcontributoristhepresenceofalonepairofelectronsontheoxygenatom,28whichprovidesarelativelysoftsetofdelocalizedformsthroughwhichtheincreaseinthepositivechargeuponoxidationmaybefeltbyoneOsunitfromtheother,thereforegivingrisetoaconsiderableincreaseininternuclearcommunicationbetweenthetwoOsunits.

Asexpected,amoderatemetal-metalinteractionisclearlyobservedinbismetallabenzene9dthroughthe1,4-phenylene-diisocyanidebridge.AsshowninFigure5,9dundergoestwoconsecutive,chemicallyandelectrochemically,

one-electron

(28)Rigaut,S.;Olivier,C.;Costuas,K.;Choua,S.;Fadhel,O.;Massue,J.;Turek,P.;Saillard,J.-Y.;Dixneuf,P.H.;Touchard,D.J.Am.Chem.Soc.2006,128,5859.

ArticleFigure5.Cyclic(a)anddifferentialpulse(b)voltammogramsofcomplex-9d1inCH2Cl2with0.1Mn-Bu4NClO4atascanrateof0.10Vs.

oxidationprocesses,givingrisetoredoxwavesatEþ0.16VandEp,a=p,a=þ0.81V,respectively.Thelargesepara-tionoftheprocess(ΔE=0.65V)for9destablishesthattheoxidizedspeciesarestableinsolutionandshouldcorres-pondtotheformationof[μ-(1,4-phenylenediisocyanide){Os-(CHC(PPh3)CHCClCH)Cl(PPh3)2}2]3þand[μ-(1,4-phenyl-enediisocyanide){Os(CHC(PPh3)CHCClCH)Cl(PPh3)2}2]4þ,respectively.5nInthiscontext,itisworthytonotethatthecommunicationsbetweenthearomaticosmabenzeneringsys-temsin9dmaybeprecludedduetotheperpendicularorienta-tionbetweenthebridgingphenylringandtheosmabezenerings,whichhasalreadybeenconfirmedbyX-raycrystal-lographicstudy.

Conclusion

Thoughtherehavebeenmanymetallabenzenecomplexessynthesizedsofar,bismetallabenzenesandtheiranaloguesarerareandthestudiesoftheirphysicalpropertiesarestillratherlimited.Inthiswork,wehavesuccessfullyconstructedaseriesofdiisocyanide-bridgedbisosmabenzeneseithervialigandsubstitutionreactionsofosmabenzenes[Os(CHC-(PPh3)CHC(PPh3)CH)Cl2(PPh3)2]OHwithvariousdiisocya-nidesorthroughsimilarligandsubstitutionreactionsoftheosmacycle[Os(CHdC(PPhfollowedbynucleophilicattack3)CH(OH)-η2-CtCH)Clatthecoordinated2(PPhalkyne.3)2]Electrochemicalstudieshaveshownthatbisosmabenzenes

Organometallics,Vol.29,No.13,20102923

[(μ-CN-R-NC){Os(CHC(PPh4,40-oxybisphenyl;9d3)CHCClCH)Cl(PPhR=1,4-phenylene)3)exhibit2}2]Cl(9cR=2metal-metalinteractionthroughtheconjugateddiisocya-nidebridgeandundergotwoconsecutive,chemicallyandelectrochemically,one-electronredoxprocesses.

ExperimentalSection

GeneralConsiderations.AllmanipulationswerecarriedoutatroomtemperatureunderanitrogenatmosphereusingstandardSchlenktechniques,unlessotherwisestated.Solventsweredistilledundernitrogenfromsodiumbenzophenone(diethylether,tetra-hydrofuran)orcalciumhydride(dichloromethane).Thestartingmaterials[Os(CHC(PPh3)CHC(PPh3)CH)Cl2(PPh3)2]OH(3),5n,21[Os(CHC(PPh23)C(OEt)O)Cl2(PPh3)2](6),230[Os(CHdC(PPh23,29CH)Cl-biphenyldiisocya-3)-CH(OH)-η-Ctnide(4a),4,40-diisocyanodiphenylmethane2(PPh3)2](8),5n,214,4(4b),30bis(4-iso-cyanophenyl)ether(4c),31and1,4-phenylenediisocyanide(4d)22,32were0synthesizedbyliteratureprocedures.4,40-Biphenylamine,4,4-diaminobiphenylmethane,and4,40-diaminobiphenyletherwerepurchasedfromSigma-AldrichandAlfaAesar.Columnchromatographywasperformedonneutralalumina(200-300mesh).AlltheNMRspectrawererecordedwithaBrukerAV300(1H300.11MHz;13C75.5MHz;31P121.5MHz)oraBrukerAV400(H400.1MHz;13C100.6MHz;31P162.0MHz)spectro-meter.131

Hand13CNMRchemicalshiftsarerelativetoTMS,andPNMRchemicalshiftsarerelativeto85%HanalysesdatawereobtainedonaThermoQuest3POItalia4.ElementalSPAEA1110instrument.Samplesforinfraredspectroscopywerepreparedaspellets(KBr),withspectraacquiredonNicoletAvatar370spectrometers,ThermoElectronCorporation,U.S.A.

Cyclicvoltammetrywasperformedatroomtemperature(25οC)underNNClO2atmosphereinfreshlydistilledCH2Cl2containing0.1MBu44(TBAP),usingaCHI660Avoltammetricanalyzer.Athree-electrodesysteminasingle-compartmentcellwithresistancecompensationwasusedthroughout.Theworkingelectrodewasaglassycarbondisk(diameter=3mm).Thiselectrodewascarefullypolishedwith1mm,0.3mm,and0.05mmaluminapowderandultrasonicallyrinsedwithdistilledwaterandethanolbeforeeachrun.Theauxiliaryelectrodewasaplatinumsheet,andthereferenceelectrodewasAg/AgClinCH2Cl2with0.1MTBAP.Theferro-cene/ferroceniumredoxcouplewaslocatedat0.39Vunderourexperimentalconditions.

CAUTION!Theaminobiphenylsareverycarcinogenicmateri-alsandmustbehandledwithextremecare.Additionally,allisocyanidepreparationsshouldbeconductedinafumehoodowingtothetoxicgas.

[μ-(4,40-Biphenyldiisocyanide){Os(CHC(PPh3)CHC(PPhCH)ClToasolutionofcomplex3(0.323)-2(PPh3)}2][PF6]2(5a).g,0.23mmol)indrydichloromethane(30mL)wereadded4,40-biphenyldiisocyanide(4a)(23mg,0.12mmol)andNH(38mg,0.23mmol).Thesolutionwasstirredfor0.5hatroom4PF6temperature.Afterfiltration,thesolutionwasconcentratedtoca.5mL.Diethyletherwasaddedslowlytogiveagreenprecipitate,whichwascollectedbyfiltration.Recrystallizationofthecrudeproductfromdichloromethane/diethylethergave5aasadeepgreensolid.Yield:0.18g,371%.1HNMR((CD300.1MHz):δ(ppm)17.40(d,J(PH)=18.6Hz,23)H,2-CO,OsCH),15.69(d,3J(PH)=25.2Hz,2H,OsCH),9.09(t,3J(PH)=12.7Hz,2H,OsCHC(PPh3)CH),6.54-8.12(m,98H,PPh

3

(29)Henderson,J.I.;Feng,S.;Ferrence,G.M.;Bein,T.;Kubiak,C.P.Inorg.Chim.Acta1996,242,115.

(30)(a)Morel,G.;Marchand,E.;Sinbandhit,S.;Carlier,.Chem.2001,655.(b)Ugi,I.;Fetzer,U.;Eholzer,U.;Knupfer,H.;Offermann,K.Angew.Chem.,Int.Ed.Engl.1965,4,472.

(31)(a)Michalik,D.;Schaks,A.;Wessjohann,.Chem.2007,149.(b)Rivera,D.G.;Wessjohann,L.A.J.Am.Chem.Soc.2006,128,7122.

(32)Henderson,J.I.;Feng,S.;Bein,T.;Kubiak,ngmuir2000,16,6183.

2924Organometallics,Vol.29,No.13,2010andphenylene).31P{1H}NMR((CD3)2CO,121.5MHz):δ(ppm)-144.7825.58(septet,(s,CPPPh3),20.64(s,CPPh3),-1.482JF(s,OsPPh3),(PC)6).13C{1H}NMR((CD=15.1Hz,OsCH),3)240.352CO,75.5MHz):δ(ppm)254.70(d,(d,2J(PC)=15.1Hz,OsCH),153.74(t,2J(PC)=21.9Hz,OsCHC(PPhCH),143.15(s,CtN),118.47-135.47(m,PPh3)-J(PC)=71.9Hz,OsCHC(PPh3andphenylene),115.36(d,1(PPh3)),114.40(d,1J(PC)=70.1Hz,OsCHCforC3)).IR(cm-1):νCtN=2095cm-1.Anal.Calcd132H104Cl4F12N2P8Os2:C,58.37;H,3.86;N,1.03.Found:C,58.25;H,4.23;N,1.13.

[μ-(4,40-Diisocyanodiphenylmethane){Os(CHC(PPh)CH)Cl][PF3)CHC-(PPh32(PPh3)}2,complex6]2(5b).Bythesamemethodasthatforthepreparationof5a5bwasobtainedasagreensolidfromthereactionof3(0.31g,0.22mmol)with4,40-diisocyano-diphenylmethane(4b)(24mg,0.11mmol)indichloromethane(30mL)inthepresenceofNH4PF6(37mg,0.22mmol).Yield:0.213

g,68%.1HNMR(CD2Cl2,300.1MHz):δ(ppm)17.45(d,J(PH)=18.9Hz,2H,OsCH),15.74(d,3J(PH)=24.9Hz,2H,OsCH),8.33(t,3J(PH)=14.4Hz,2H,OsCHC(PPh3)CH),6.39-7.99(m,98H,PPh3andphenylene),3.81(s,CH2).31P{1H}NMR(CD2Cl2,121.5MHz):δ(ppm)24.88(s,CPPh3),19.74(s,CPPh3),-1.20(s,OsPPh3),-144.75(septet,PF6).13C{1H}NMR(CD2Cl2,75.5MHz):δ(ppm)253.76(d,2J(PC)=15.2Hz,OsCH),238.03(d,2J(PC)=15.5Hz,OsCH),152.76(t,2J(PC)=21.8Hz,OsCHC(PPh3)CH),143.341(s,CtN),117.46-136.78(m,PPh3andphenylene),116.86(d,J(PC)=75.6Hz,OsCHC-(PPh3)),115.46(d,1J(PC)=70.6Hz,OsCH(CPPh3)),41.36(s,CH2).IR(cm-1):νCtN=2109cm-1.Anal.CalcdforC133H106-Cl4F12N2P8Os2:C,58.51;H,3.91;N,1.03.Found:C,58.32;H,3.61;N,1.09.

[μ-(Bis(4-isocyanophenyl)ether){Os(CHC(PPhCl)}3)CHC(PPh3)-CH)2(PPhof35a2][PF,complex6]2(5c).Bythesamemethodasthatforthepreparation5cwasobtainedasagreensolidfromthereactionof3(0.36g,0.26mmol)withbis(4-isocyanophenyl)ether(4c)(28mg,0.13mmol)indichloromethane(35mL)inthe1

presenceofNH4PF6(44mg,0.27mmol),Yield:0.21g,58%.HNMR((CD3)2CO,400.1MHz):δ(ppm)16.36(d,3J(PH)=19.6Hz,2H,OsCH),14.62(d,3J(PH)=25.2Hz,2H,OsCH),7.98(t,3J(PH)=13.2Hz,2H,OsCHC(PPhH,PPh3)CH),6.81-7.98(m,983andphenylene).31P{1H}NMR((CD25.48(s,CPPhPPh3)2CO,162.0MHz):δ(ppm)3),20.59(s,CC{1H}NMR((CD3),-1.83(s,OsPPhMHz):3),-144.22(septet,PFδ(ppm)259.75(d,6).132J(PC)=15.4Hz,Os3)2CO,100.6CH),245.35(d,2J(PC)=15.9Hz,OsCH),158.91(t,2J(PC)=21.9Hz,OsCHC(PPhandphenylene),3)CH),145.15(s,CtN),120.21-140.61(m,PPh120.41(d,1J(PC)=70.9Hz,OsCHC(PPh3119.72(d,1J(PC)=70.5Hz,OsCHC(PPh3)),cm-1.Anal.CalcdforC3)).IR(cm-1):νCtN=2081H,3.84;N,1.03.Found:C,58.24;132H104ClH,4.04;4F12NN,2OP1.05.

8Os2:C,58.02;[μ-(1,4-Phenylenediisocyanide){Os(CHC(PPhPPh3)CHC(PPhCH)Cl3)-2(3)}2][PF6]2(5d).Bythesamemethodasthatforthepreparationof5a,complex5dwasobtainedasagreensolidfromthereactionof3(0.25g,0.18mmol)with1,4-phenylene-diisocyanide(4d)(12mg,0.09mmol)indichloromethane(25mL)inthepresenceofNH4PF6(30mg,0.18mmol).Yield:0.18g,78%.13

HNMR((CD3)2CO,300.1MHz):δ(ppm)16.45(d,J(PH)=18.9Hz,2H,OsCH),14.54(d,3J(PH)=23.7Hz,2H,OsCH),7.95(t,3J(PH)=12.6Hz,2H,OsCHC(PPh7.82(m,94H,PPh1H}3)CH),6.14-3andphenylene).31P{NMR((CD3)2CO,121.5MHz):δ(ppm)25.36(s,CPPh3),20.65(s,CPPh3),-1.47(s,OsPPh3),-144.56(septet,PF6).13C{1H}NMR((CD3)2CO,75.5MHz):δ(ppm)253.67(d,2J(PC)=215.3Hz,OsCH),240.12(d,2J(PC)=15.4Hz,OsCH),152.89(t,J(PC)=21.9Hz,OsCHC(PPhPPh3)CH),144.06(s,CtN),118.65-135.45(m,3andphenylene),1116.11(d,1J(PC)=70.8Hz,OsCHC-(PPhν3)),114.32(d,J(PC)=70.8Hz,OsCHC(PPh=2088cm-1.Anal.CalcdforC3)).IR(cm-1):CtN126H100Cl4F12N2P1.06.Found:C,57.43;H,4.16;N,0.85.

8Os2:C,57.32;H,3.82;N,[μ-(1,4-Phenylenediisocyanide){Os(CHC(PPh3)C(OEt)O)Cl-(PPh3)2}2Cl2(7).Amixtureofcomplex6(0.20g,0.18mmol),

Huangetal.

1,4-phenylenediisocyanide(4d)(11mg,0.09mmol),andNHmg,0.35mmol)inCH4PF(586htogivea2Clbrown2(30mL)wasstirredatroomtemperaturefor10suspension.Evaporationofthesolventgaveasolid,whichwaspurifiedbycolumnchromato-graphy(neutralalumina,solvent:dichloromethane,eluent:dichloromethane/methanol,20:0.3).Theyellowbandwascollected,evaporatedtodryness,andrecrystallizedfromdichloromethaneanddiethyl1ethertogiveabrightyellowpowderof7.Yield:0.17g,78%.HNMR(CDCl3,400.1MHz):δ(ppm)12.73(d,3J(PH))=12.4Hz,2H,OsCH),6.81-7.70(m,94H,PPh31(m,4H,OCHHz,3andphenylene),3.982),0.50(t,3J(HH))=7.26H,OCH162.0MHz):δ(ppm)14.83(s,C2CHPPh3).P{1

H}NMR(CDCl(s,OsPPh).13C{3,1H}NMR(CDCl3),10.23H),3181.50(d,2J(PC)=16.43,100.6MHz):δ(ppm)239.51(m,OsCHz,C(OCHCtN),98.81(d,1J(PC)=73.4Hz,CPPh2CH3)),145.73(s,135.00(m,PPh3),114.88-CH3andphenylene),64.41(s,OCH2),13.50(s,OCH23).Anal.CalcdforC126H106O2N2P6ClN,1.16.Found:C,62.74;H,4.66;N,1.05.

4Os2:C,62.53;H,4.41;[μ-(4,40-Biphenyldiisocyanide){Os(CHC(PPhflaskwascharged3)CHCClCH)Cl-(PPh3)2}2]Cl2(9a).ASchlenkwithcomplex8(0.43g,0.38mmol),4,40-biphenyldiisocyanide(4a)(39mg,0.19mmol),NH4PF6(63mg,0.38mmol),NaCl(0.11g,1.91mmol),anddegassedCH2Cl2(30mL).Themixturewasheatedunderrefluxfor3handthenallowedtocoolbeforebeingfilteredthroughCelite.Evaporationofthesolutiongaveasolid,whichwaspurifiedbycolumnchromatography(neutralalumina,sol-vent:dichloromethane,eluent:dichloromethane/acetone,3:1).Thegreenbandwascollected,evaporatedtodryness,andrecrys-tallizedfromdichloromethaneanddiethylethertogiveagreenishpowderδofH,(ppm)OsCH16.629a.Yield:CPPh(s,2H,0.32OsCg,H65%.1CCl),H13.73NMR(d,(CD32Cl2,300.1MHz):J(PH)=27.9Hz,23),7.79(d,3J(PH)=13.1Hz,2H,OsCHCClCH),6.30-7.57(m,98H,PPh3andphenylene).31P{1H}NMR(CD2Cl2,121.5MHz):δ(ppm)18.68(s,CPPh3),-3.34(s,OsPPh3).13C{1H}NMR(CD2Cl2,75.5MHz):δ(ppm)251.94(s,OsCHCCl),233.40(br,OsCHCPPh3),153.18(s,CtN),139.47(d,2J(PC)=22.4Hz,OsCHCClCH),136.53(d,3J(PC)=15.5Hz,OsCH1CCl),126.22-135.05(m,PPh3andphenylene),115.48(d,J(PC)=72.5Hz,OsCHC(PPh3)).IR(cm-1):νCtN=2084cm-1.Anal.CalcdforC132H104Cl6N2P6Os2:C,63.49;H,4.20;N,1.12.Found:C,63.74;H,4.26;N,1.05.

[μ-(4,40-Diisocyanodiphenylmethane){Os(CHC(PPh)Cl(PPh9b).Bythesamemethodasthat3)CHC-ClCH3)2}2]Cl2(forthepreparationof9a,complex9bwasobtainedasagreensolidfromthereactionof8(0.34g,0.28mmol)with4,40-diisocyanodiphe-nylmethane(4b)(32mg,0.15mmol)indichloromethane(35mL)inthepresenceofNaCl(87mg,1.49mmol)andNH4PF0.28δ(ppm)mmol).16.68Yield:(s,20.21H,7.82OsCg,54%.16(45mg,(d,HCCl),HNMR3J(PH)13.77=13.4(d,(CD3J2Cl(PH)2,400.1MHz):=27.9Hz,2H,OsCHCPPh3),Hz,2H,OsCHC-ClC31

H),6.38-7.59(m,98H,PPh3andphenylene),3.98(s,CH2).-P{13.01H}(s,NMROsPPh(CD2Cl2,162.0MHz):δ(ppm)18.57(s,CPPh100.6MHz):3),3).13C{1H}NMR(CD2Cl2,δ(ppm)265.09(s,OsCHCCl),232.45(br,OsCHCPPh(s,C3tN),139.69(d,2J(PC)=22.1Hz,OsCHCClCH),3),141.78136.38(d,J(PC)=13.1Hz,OsCHCCl),125.88-134.89(m,PPhandphenylene),115.36(d,1J(PC)=72.7Hz,OsCHC(PPh33)),42.12(s,CH2).IR(cm-1):ν63.61;CtN=2086cm-1.Anal.CalcdforC133H106Cl6N2P6Os2:C,H,4.25;N,1.12.Found:C,63.73;H,4.72;N,1.03.

[μ-(Bis(4-isocyanophenyl)ether){Os(CHC(PPh3)CHCClCH)-Cl(PPh3)2}2]Cl2(9c).Bythesamemethodasthatforthepre-parationof9a,complex9cwasobtainedasagreensolidfromthereactionof8(0.35g,0.31mmol)withbis(4-isocyanophe-nyl)ether(4c)(34mg,0.15mmol)indichloromethane(35mL)inthepresenceofNaCl(0.12g,1.98mmol)andNH4PFδ(ppm)mmol).16.62Yield:(s,2H,0.18OsCg,47%.1HCCl),H13.67NMR(d,(CDCl6(52mg,0.323J(PH)3,400.1MHz):=30.4Hz,2H,OsCHCPPh3),7.56(d,3J(PH)=13.2Hz,2H,OsCHCClCH),6.23-7.36(m,98H,PPh3andphenylene).31P{1H}NMR

Article

Table3.CrystalDataandStructureRefinementfor9d

9d32CH2Cl234H2O

empiricalformulaC126H100Cl8N2Os2P6fw

2733.8232CH2Cl234H2Otemperature,K

173(2)radiation(MoKR),A

0.71073crystsysttriclinicspacePa,Agroup13.2136(4)b,A13.7646(4)c,A18.1729(6)Rβ,deg103.599(3)γ,deg99.835(3)V,,deg

A395.375(2)3134.34(17)Z

1dcalcd,gcm-31.448F(000)

1372

crystsize,mm30.2Â0.2Â0.05θreflnsrange,collecteddeg2.3527768-25.00indepreflns

10764obsdreflns(I>2σ(I))8964

data/restraints/params10764/60/704goodness-of-fitonF21.000

finalR(I>2σ(I))R1=0.0368,wR2=0.0927Rindices(alldata)

R1=0.0487,wR2=0.0955

(CDCl3,162.0MHz):δ(ppm)17.00(s,CPPh).13C{1H}NMR(CDCl3),-5.18(s,OsPPh33,100.6MHz):δ(ppm)251.70(s,Os2

CHCCl),233.16(br,OsCHCPPhH),3),156.22(s,CtN),139.28(d,J(PC)=22.1Hz,OsCHCClC136.42(d,3J(PC)=11.5Hz,OsCH1CCl),126.20-135.01(m,PPh3andphenylene),115.35(d,J(PC)-1=72.6Hz,OsCHC(PPh.Anal.CalcdforC3)).IR(cm-1):νCtN=2075cm132H104Cl6N2OP6Os2:C,63.08;H,4.17;N,1.11.Found:C,63.34;H,4.38;N,1.08.

[μ-(1,4-Phenylenediisocyanide){Os(CHC(PPh9d).Bythesamemethodasthat3)CHCClCH)-Cl(PPh3)2}2]Cl2(forthepre-parationof9a,complex9dwasobtainedasagreensolidfromthereactionof8(0.32g,0.28mmol)with1,4-phenylenediisocyanide(4d)(18mg,0.14mmol)indichloromethane(30mL)inthepresenceofNaCl(82mg,1.40mmol)andNH0.23g,67%.1HNMR(CD4PF6(45mg,0.28mmol).Yield:2Cl2,300.1MHz):δ

Organometallics,Vol.29,No.13,20102925

(ppm)16.52(s,2H,OsCHCCl),13.63(d,3J(PH)=28.5Hz,2H,OsCHCPPh3),7.83(d,3J(PH)=13.6Hz,2H,OsCHCClCH),6.01-7.63(m,94H,PPh3andphenylene).31P{1H}NMR(CD13

,121.51MHz):δ(ppm)18.67(s,CPPh2.12(s,OsPPh2-Cl23),-3).C{H}NMR(CDHCCl),2Cl2,75.5MHz):δ(ppm)251.89(s,OsC-2

233.01(br,OsCHCPPh3),156.21(s,CtN),139.58(d,J(PC)=22.7Hz,OsCHCClCH),136.34(d,3J(PC)=12.8Hz,OsCHCCl),126.32-135.17(m,PPh(d,1J(PC)=74.8Hz,OsCHC(PPh3andphenylene),116.04cm-1.Anal.CalcdforCN3)).IR(cm-1):νCtN=2064Found:C,62.39;H,126H4.22;100ClN,61.13.

2P6Os2:C,62.50;H,4.16;N,1.16.X-rayCrystalStructuresDeterminationof9d.Datacollec-tionswereperformedonanOxfordGeminiSUltraCCDareadetectorusing(λ=0.71073A

graphite-monochromatedMoKRradiation

)at173K.Multiscanorempiricalabsorptioncorrections(SADABS)wereapplied.Allstructuresweresolvedbydirectmethods,expandedbydifferenceFouriersyntheses,DC-745238(9d)dc.cam.ac.uk/data_request/cif.Detailsoncrystaldata,datacollection,andrefinementsaresummarizedinTable3.

Acknowledgment.ThisworkwasfinanciallysupportedbytheNationalScienceFoundationofChina(Nos.20925208,20872123,and20772100),theProgramforNewCenturyExcellentTalentsinUniversityofChina(NCET-08-0471),theProgramforNewCenturyExcellentTalentsinFujianProvinceUniversity,andtheYoungTalentProjectoftheDepartmentofScience&TechnologyofFujianProvince(2007F3095).

SupportingInformationAvailable:X-raycrystallographicfiles(CIF).ThesematerialsareavailablefreeofchargeviatheInternetat.

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