【word】 取代四甲基环戊二烯基钌羰基化合物的合成及晶体结构（英文）

【word】 取代四甲基环戊二烯基钌羰基化合物的合成及晶体结构（英文） 取代四甲基环戊二烯基钌羰基化合物的合 成及晶体结构(英文) 第26卷第6期 2010年6月 无机化学 CHINESEJOURNALOFINORGANICCHEMISTRY Vol_26No.6 1121.1124 蠕墒 I(研究 廷., 取代四甲基环戊二烯基钌羰基化合物的合成及晶体结构 马志宏1,2赵明霞林丽枝,郑学忠林进 f河北师范大学化学与材料科学学院,石家庄050016) f2河北医科大学基础医学院,石家庄050017) f,华北制药康欣有限公司,石家庄050015) 关键词:羰基钌;二聚物;结构;环戊二烯基 中图分类号:0614.82+1文献标识码:A文章编号:1001—4861(2010)06—1121—04 SynthesisandCrystalStructureofSubstitutedTetramethylcyclopentadienyl DirutheniumMetalCarbonylComplexes MAZhi.Hong1.ZHAOMing.XiaLINLi—ZhiZHENGXue—ZhongLINJi n, (collegeofChemistry&MaterialScience,HebeiNormalUniversity,Shijiazhuang050016) (2CollegeofBasicMedicine,HebeiMedicalUniversity,Sh(iazhuang050017) (3NorthChinaPharmaceuticalKangxinCo.,Ltd,Shijiazhuang050015) Abstract:Theligands(C5Me4R)[R=—Butyl(1),Benzyl(2),PhMe一2(3)】 reactedwithRu3(C0)12inrefluxing xv1enet0givec0rrespondingnewsubstitutedtetrametbylcyclopentadienyldirutheniummetalearbonylcomplexes 【(叼一CsMe4R)Ru(CO)(/x—CO)l2【R=n—Butyl(4),Benzyl(5),PhMe 一2(6)],respectively?Thethreenew..mpleXewe characterizedbyelementalanalysis,IRandHNMRspectra.Thecrystalstructureofcomplex5wasdetemned bvsinglecrysta1X—raydiffraction.TheX.raycrystalstructureofcomplex5confirlnsthestructurewithbridging andterminalCOgroups.CCDC:709601. Keywords:rutheniumcarbonyl;dimer:structure;cyclopentadienyl 0Introduction Cyclopentadienylmetalcomplexeshavebeen extensivelyinvestigatedsinceferrocenehasbeen discovered.Replacementofthehydrogenatomsby 0thersubstituentsaltersboththestericandelectronic innueBeesoftherf-eyclopentadienylring,resultingin diff(ngreactivityandstabilityofthesubstituted cvclopentadienylmetalcomplexes【lJ.Especiallyfor metallocenepolymerizationcatalysts,thesterleand electroniceffectsofcyclopentadienylringsubstituents greatlyinfluencecatalyticactivity嘲.Inthisstudy,the reaeti0nsofsubstitutedtetramethylcycl0pentadiene withRu3fC0)12werereported.Theaimistoobtaina deeperinsightintothestericinfluencesofsubstituents onthemolecularstructuresandreactionsofthe correspondingbiscyclopentadieny1dinuclearmetal carbonylcomplexes. 收稿日期:2010—01一o4.收修改稿日期:2010—02—26. 河北省自然科学基金资助项目(N0.B20O8000150)和河北师范大学 博士启动基金资助项g(No-L2005B18). 通讯联系人.E—mail:tinjin64@126.con 第一作者:马志宏,女,37岁,副教授;研究方向:金属有机化学. l122无机化学第26卷 1Experimental 1.1Generalprocedures Alloperationsinvolvingair--ormoisture—-sensitive compoundswerecarriedoutunderanargonatmosphere usingstandardSchlenktechniques.Diethylether, xylene,andn—hexanewerefreshlydistilledfrom sodium/benzophenoneketylunderargonpriortouse. MethylenechloridewasdistilledoverP205underargon. 2,3,4,5一tetramethylcyclopentenonewaspurchasedfrom Aldrich.Columnchromatographywascarriedouton aluminacolumnusingdichloromethaneandpetroleum etheraseluent. HNMRspectrawasrecordedonaBrukerAV400 instrument,whileIRspectrumwasrecordedasKBr pelletonFTIR.8900spectrometer.Elementalanalysis wasperformedonaVarioELmanalyzer.Theligands (C5Me4R)[R=n-Butyl(1),Benzyl(2),PhMe-2(3)]were synthesizedaccordingtotheliterature[31. 1.2Synthesisofcomplexes 1.2.1Synthesisofcomplex [-C,MedBu)Ru(CO)一CO)]z(4) Asolutionofligand1(0.25g,1.41mmo1)and Ru3(CO)12(0.3g,0.47mmo1)in30mLofxylenewas refluxedfor12h.Afterremovalofsolvent,theresidue waschromatographedonanaluminacolumnusing petroleumether/CH2C12aseluent.Theorangeband affordedcomplexasredcrystals(0.35g,75%yield), m.P.190-191?.Ana1.Calc.forC30H42O,Ru2(%):c, 53.88;H,6.33.Found(%):C,53.82;H,6.35.HNMR (CDC13,400MHz,ppm):2.29(t,4H,J=7.2Hz, CsMe4CH2),1.39brs,8H,(CH/)2),0.94(t,6H,J=6.8 Hz,CH3),1.91(s,12H,C5Men),1.85(s,12H,C5Men).IR co,cm—1):1935(s),l744(s). 1.2.2Synthesisofcomplex [(r/5-CsMe4CH2Cg-I5)Ru(c0)(-c0)]2(5) Usingaproceduresimilartothatdescribedabove, reactionofligand2withRu3(CO)12inrefluxingxylene affordedcomplex5asorange—redcrystalsin70%yield, m.P.193oC.Ana1.Calc.forC36H38Ru204(%):C,58.68; H,5.20.Found(%):C,58.64;H,5.12.HNMR(CDC13, 400MHz,ppm):7.13-7.20(m,10H,Cj-I~),3.67(s, 4H,CH2),1.93(s,12H,C5Men),1.86(s,12H,CsMe4). IR(pco,cm):1931(s),1747(s). 1.2.3Synthesisofcomplex [(ns-CsneaPhMe一2)Ru(CO)(/x-CO)h(6) Usingaproceduresimilartothatdescribedabove, reactionofligand3withRH3(CO)12inrefluxingxylene affordedcomplex6asorange—redcrystalsin46%yield, m.P.165—166?.Ana1.Calc.forC36H38Ru20%):C, 58.68;H,5.20.Found(%):C,58.60;H,5.16.HNMR (CDC13,400MHz,ppm):7.35,7.27(m,8H,C6I-In), 2.35(s,6H,CH3Ph),1.88(s,12H,CH3),1.79(s,12H, CH3);IR(/”CO,cm):l935(s),1744(s). 1.3Crystalstructuredeterminationforcomplex5 Thecrystalstructureofcomplex5wasdetermined bysinglecrystalX?raydiffraction.Asuitableorange— redblockcrystalwithdimensionsofO.12mmx0.10 mmx0.08mmwasmountedonaglassfiberfordata collectionperformedonaBrukerSmart1000CCD diffraetometerequippedwithaMoKaradiation= 0.071073nm).Atotalof4090reflectionswerecollected intherangeof2.06.??25.05.usingSMART program,ofwhich2710wereuniqueim=O.0130)and 2593wereconsideredasobserved(1>20-(,)).Semiem— piriealabsorptioncorrectionswereappliedusingthe SADABSprogram.Thestructurewassolvedbydirect methodandrefinedbyfull—matrixleastsquares.All calculationswereperformedusingtheSHELXTL programsystem.Thefinalfull-matrixleast—squares refinementgaveR=0.0216,wR=0.0572w=1110-(确+ (0.0370n+0.197l,whereP=(Fo2+2Fo~)/3)basedon 2593observedreflectionswith1>2o-(,).S=I.041, (a/0-)m~=0.000,(Ap)~=565and(?p)=一419e?nm. ThecrystaldataandsummaryofX—raydatacollection arepresentedinTable1.Selectedbondlengthsand anglesarelistedinTable2. DC:709601. Table1CrystaldataandstructurerefinementforComplex5 EmpiricalformulaC36}{04Ru2/inm,1.105 Formulaweight736.8F(000)374 Temperature/K273(2)Crystalsize/mm0.12x0.10x0.08 第6期马志宏等:取代四甲基环戊二烯基钌羰基化合物的合成及晶 体结构1123 ContinuedTable1 Wavelength/nmO.0710730rangefordatacollection/f.12.06-25.05 CrystalsystemTriclinicLimitingindices一9?h?9.一10?k?11.一12?l?9 SpacegroupP1Reflectionscollected/unique4090/2710(O.0130) a/nm0.83420(10)Completenessto0=25.02./%99.30 b/nm1.00567(12)AbsorptioncorrectionSemi—empiricalfromequivalents c/nm1.00831(12)Max.andmin.transmission0.9416and0.8879 ot/(.)86.978(2)RefinementmethodFull—matrixleast—squaresonF /(.)79.266(2)Data/restraints/parameters2710/0/194 .y/(.)68.474(2)GoodnessoffitOilF1.04 V/nm3O.77302(16,FinalRindices[,>2?]R1=0.0216,wR2=O.0572 Z2Rindices(alldata)R1=0.0227,wR2=O.0584 D/(g?cm-3)1.583Largestdiff.peakandhole/(e?nn1-3)565and一419 Table2Selectedbonddistances(nm)andangles(.)forcomplex5 Ru1.Ra1A Rn1一C1 Ru1一C2 Rul—C3 Rul—C4 Ru1一C2一Ru1A Cl—Ru1一C2 C1一Rn1-C2A C2一Ru1.C2A 0.27537(4) 0.1860(2) 0.2039(2) 0.2214(2) 0.2270(2) 84.91(9) 92.87(9) 93.67(10) 95.09(9) Ru1-C5 Ru1C6 Ru1.C7 C2一Ru1A C3一C4 C1一Ru1.C3 C2一Ru1一C3 C1一Ru1一C4 C2.Ru1一C4 0.2296f21 0.2310(2) 0.2262(2) 0.204Of21 0.1434(3) 93.82(9) 133.95(9) 114.25(9) 149.99(9) C4一C5 C5一C6 C6一C7 01一C1 O2一C2 C2A—Ru1.C4 C1一Rtl1.Rn1A C2.Ru1Rn1A C2(A)一Rul?RulA 0.1426(3) 0.1429(3) 0.1417(31 0.1146(3) 0.1173(3) 95.69(8) 94.85(7) 47.56(6) 47.53(6) Symmetrycode:A:-x+l,十2,-z+1 2Resultsanddiscussion 2.1Synthesisofcomplexes Whentheligands(C5Me4R)[R=n—Butyl(1),Benzyl (2),PhMe一2(3)]reactedwithRu3(CO)t2underrefluxing xylenefor12h.thecorrespondingRu—Rubonded dinuclearcomplexes4,5and6wereobtained, respectively(Scheme1). R!: xylene,reflux CO Rm/z-Butyl(4),Benzyl(5),PhMe一2(6) Scheme1Synthesisofcomplexes TheIRspectraofdirutheniumcomplexes4,5and 6areverysimilarandallshowtwostrongterminal carbonylabsorptionsat1931,1935cm一andtwo strongbridingcarbonylabsorptionsat1744-1747cm一. Thisindicatesthattheelectroniceffectofthe substituentshasverylessinfluenceonthediruthenium complexes.TheHNMRspectraof4,5and6showtwo groupsofsingletsforthefourmethylsprotons.The HNMRspectraof5and6showonegroupof muhipletsforthephenylprotons,indicatingthe symmetricalstructuresinsolution,consistentwiththe crystalstructure. 2.2Crystalstructureofcomplex5 Thecrystalstructureofthecomplex5(Fig.1) revealsthatthecomplexhasatransconformationwith twobridgingcarbonylligands.Similartothecyclopen— tadienylanaloguetrans一[~/5-CpRu(CO)一co)]2翻(where Cpcycl0pentadienylligand),boththestructuresare transformandhaveCisymmetry.Thetwocyclopen— tadienylringplanesareparalle1.Twocarbonylsare bridgedandtwocarbonylsaretermina1.TheRu—Ru bonddistance(0.27537(4)nm)isslightlylongerthan thatintrans-[V5-CpRu(CO)(/z—C0)]2(0.2735(2)nm)翻 andtrans一[7/5-CpMe2hexRu(co)(g—CO)】2(0.27429(8) l124无机化学第26卷 nm)嘲,isslightlyshorterthanthatin【075-C5Me5)Ru(CO) (一co)h(o.2752(1)rim)and[(rf-CsMe,Et)Ru(CO)(/~一 C0)]2(0.27584(5)nm)阎,Thisdistanceiscomparableto thosefoundinothersubstitutedcycl0pentadienyl rutheniumdi—carbonyldimers. Displacementellipsoidsaredrawnatthe30%probabilitylevel; Symmetrycode:A:-x+1,-y+2,-z+l Fig.1Structureofcomplex5withtheatomicnumbering seheme Inconclusion,threenewrutheniumcarbonyl complexeshavesynthesized,andonecrystalstructure ofthemhasbeenobtained.Comparingtherangeof structuresthathavebeendeterminedforcomplexesof thetypeCp*2Ru2(CO)4whereCp=substitutedcyclopen— tadienylligand),wefindthatthesameoverallstructure withtwobridgingandtwoterminalCOgroupsis presentedinallcompounds.WealsoseethattheCp ligandsaretransinthedimericstructuresinthesolid state.Thechangeofthesubstituentshasonlyasmall effectontheRu—Rubondlength. RefeFences: [1】(a)KingRB.Coord.Chem.Rev.,1976,20:155—169 (b)StalkeD.Angew.Chem.,,nz.Ed.En.,1994,33:2168— 217l fc)JutziP,BurfordN.Chem.Rev.,1999,99:969-990 (d)SitzmannH.Coord.Chem.Rev.,2001,214:287—327 fe)AmdtS.OkudaJ.Chem.Rev.,2002,102:1953—1976 (f)QianYL,HuangJL,BalaMD,eta1.Chem.Rev.,2003, 103:2633—2690 【2](a)MohringPC,CovilleNJ.Organomet.Chem.,1994,479: l一29 (b)M~hringPC,CovilleNJ.Coord.Chem.Rev.,2006,250:18- 35 [3】BensIeyDM,MintzEA,SussangkarnSJ.Org.Chem., 4419 1988,53:4417— 【4]SheldrickGM.SADABSBrukerAFeo,DetectorAbsorption Corrections,BrukerAXSInc.,Madison,WI,1996. [5】MillsOS,NiceJP.Organornet.Chem.,1967,9:339-344 [6】SiyabongaN,MikaelH,SusanJ,eta1.Organomet.Chem., 2008,693:343—348 [7]SteinerA,GornitzkaH,StalkeD,eta1..J=Organomet.Chem., 1992.431:C2l—C25 [8】BaileyNA,RadfordSL,SandersonJA,eta1.J=Organomet. Chem.,1978,154:343—351 [9]SchumannH,StenzS,GirgsdiesF,eta1.Naturforsch,2002, 57b:】O】7.】026