Organometallics 2010, 29, 2916–2925电化学(2)

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.

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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

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