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) …… 此处隐藏：6023字，全部文档内容请下载后查看。喜欢就下载吧 ……