Bidentate NHC-Cobalt Catalysts for the Hydrogenation of Hindered Alkenes - Wei et al. - Unknown - Unknown

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SupportingInformationBidentateNHC-CobaltCatalystsfortheHydrogenationofHinderedAlkenes§a§abc,aZeyuanWei,YujieWang,YibiaoLi*,RaffaellaFerraccioli,QiangLiu*aCenterofBasicMolecularScience(CBMS),DepartmentofChemistry,TsinghuaUniversity,Beijing100084,ChinabSchoolofBiotechnologyandHealth,WuyiUniversity,Jiangmen,Guangdong529090,ChinacCNR,IstitutodiScienzeeTecnologieMolecolari(ISTM)ViaC.Golgi19,20133Milan,ItalyE-mail：*qiang_liu@mail.tsinghua.edu.cn*leeyib268@126.comContents1.GeneralConsiderations.....................................................................................................S22.SynthesisofNHCPrecursorsandCobaltComplexes....................................................S22.1SynthesisofNHCPrecursors.....................................................................................S22.2SynthesisofCobaltComplexes...................................................................................S33.GeneralProcedureforHydrogenationofAlkenes.........................................................S34.CharacterizationDataofHydrogenatedProducts.........................................................S45.CrystallographicData.....................................................................................................S105.1MolecularstructureofCo-1.....................................................................................S115.2MolecularstructureofCo-4.....................................................................................S11NMRSpectra.......................................................................................................................S12References:...........................................................................................................................S35S1

11.GeneralConsiderationsAllreactionsandmanipulationsinvolvingair-sensitivecompoundswereconductedinagloveboxorbyusingstandardSchlenktechniques.Solvents,suchasTHF,hexane,DCM,Et2OandCH3CNweredriedoversolventpurificationsystem(InnovativeTechnologyPS-MD-5)andalcoholsolventsweredriedovermagnesiumandiodine.DeuteratedsolventswerepurchasedfromCambridgeIsotopeLaboratories.Otherregularchemicalswerepurchasedfromcommercialsourceswithpurityover95%andusedwithoutfurtherpurification.Thesubstitutedimidazolesweresynthesizedaccordingtoliteratureprocedures.1NMRspectrawererecordedonaBrukerAVANCEIII400MHzspectrometer.Chemicalshiftswerereportedinppmrelativetothedeuteratedsolvents.Abbreviationsareasfollows:s(singlet),d(doublet),t(triplet),q(quartet),m(multiplet),br(broad).GCanalysiswerecarriedoutonaSHIMADAZUGC2010PLUSsystemequippedwithaSH-Rxi-5SilMS(30mx250μmx25μm)column.GC/MSanalyseswerecarriedoutonaSHIMADAZUGC-MS-QP2010SEWsystemequippedwithaSH-Rxi-5SilMS(30meter,0.25mmID,0.25umdf.)column.Electrosprayionizationhighresolutionexactmassmeasurements(ESI-HRMS)wereperformedonaThermoSCIENTIFICQEXACTIVEinstrument.X-RaycrystalstructureanalysiswereperformedwithaMM007HFSaturn724+system.StructuresolutionandrefinementwereaccomplishedwithSheldrick,2014.MagneticsusceptibilitydatawerecollectedwithaQuantumDesignSQUID-VSMmagnetometerunderanappliedfieldof0.1Tover50–300Kinthesweepandthesettlemode.Allsampleswereplacedingelatinecapsulesheldwithinplasticstraws.Thedatawerecorrectedforthediamagneticmagnetizationoftheligands,whichwereestimatedusingPascal’sconstants,andforthesampleholder.ElementalanalysiswasperformedbyPERKINELMERCE-440.Infrared(IR)spectrawererecordedonaBrukerFT–IRalpha(ATRmode)spectrophotometer.2.SynthesisofNHCPrecursorsandCobaltComplexes2.1SynthesisofNHCPrecursorsR-substitutedimidazoles(1.5mmol)wereaddedtothesuspensionofN-substituted-2-chloroethylaminehydrochloride(1.0mmol)in3mLofdryacetonitrile.Thesolutionwasheatedinasealedpressuretubeat100oCfor2-3days.Thesolventwasthenremovedundervacuumtoaffordagraybrownishsolid,whichwasthenwashedbyEt2OorEAtoremovetheunreactedR-substitutedimidazole.TheresultedsolidoroilcompoundwasthendissolvedinMeOHfollowedbytheadditionofexcessamountofNaHCO3andstirredfor2-4hoursatroomtemperature.Thenthereactionsolutionwasfiltratedtoremovethesodiumsalt,andtheremainingsolventwasevaporatedtoeventuallyaffordtherawproduct,whichcouldbefurtherpurifiedbyrecrystallization(MeOH/Et2O)orflashcolumnchromatographyonsilicagel(DCM/MeOH).TheligandsL1-L4wereobtainedasgrayorbrownishpowderin38-49%yields.2ThecharacterizationofligandsL1andL2wasreportedinourpreviouswork.3L3:1HNMR(400MHz,CDCl3):δ=10.39(s,1H),7.61(s,1H),7.43(s,1H),4.45(t,J=5.5Hz,2H),4.09(s,3H),2.75(t,J=5.5Hz,2H),2.28(s,6H)ppm.13CNMR(101MHz,CDCl3):δ=S2

2138.6,122.6,122.4,58.4,47.3,45.2,36.5ppm.L4:1HNMR(400MHz,CDCl3):δ=10.25(s,1H),8.04(s,1H),7.10(s,1H),7.01(s,2H),4.84(t,J=5.5Hz,2H),2.82(t,J=5.5Hz,2H),2.35(s,3H),2.31(s,6H),2.07(s,6H)ppm.13CNMR(101MHz,CDCl3):δ=141.1,138.4,134.3,130.9,129.8,58.6,47.8,45.3,21.1,17.4ppm.FollowingthesimilarprocedureasthoseofL1-L4,L5-L7wereobtainedin40-67%yieldbyusingbis(2-chloroethyl)aminehydrochlorideand2.2equivalentsofR-substitutedimidazolesasthestartingmaterials.3-4N-Meimidazoles(2.2mmol)wereaddedtothesolutionof2,6-di(bromomethyl)pyridine(1mmol)in2mLofdryacetonitrile.Thesolutionwasheatedinasealedpressuretubeat80oCfor24h.Thesolventwasthenremovedundervacuumtoaffordagraybrownishsolid,whichwasthenwashedbyEt2Otoremovetheunreactedimidazole.Theresultedsolidwasfurtherdriedundervacuumtoyieldthedesiredproduct.52.2SynthesisofCo-1andCo-4.6NHCPrecursorsL1/L4(0.2mmol)andAg2O(0.5mmol)wereaddedto5mLofdryDCM.Thereactionwasstirredfor24h,avoidinglightundertheprotectionofsilverpaper.Thesolventwasthenremovedundervacuumtoaffordatansolid.AmixedsolventofTHFandDCM(5mL,1:1)andthenCoCl2(0.2mmol)wereadded.AgClwasfiltratedoffafter12h.TheNHC-Cocomplexeswaspurifiedthroughrecrystallizationfromamixedsolventofdichloromethaneandhexane.SinglecrystalssuitableforX-raydiffractionofCo-1andCo-4wereobtainedbyslowdiffusionofhexaneintoaDCMsolutionatambienttemperature.Co-1:Elementalanalysiscalcd(%)forC,31.25;H,4.87;N,15.62;found:C,31.00;H,5.14;N,14.76.HRESIMS(positiveion):233.0128([M-Cl-]+,calcdfor233.0125)m/z.Magneticsusceptibility:4.3μB.Co-4:Elementalanalysiscalcd(%)forC,49.63;H,5.99;N,10.85;found:C,47.20;H,5.85;N,10.00.HRESIMS(positiveion):351.0909([M-Cl-]+,calcdfor351.0907)m/z.Magneticsusceptibility:3.7μB.3.GeneralProcedureforHydrogenationofAlkenesInanargonfilledglovebox,thecobaltcatalystandadditiveswereweightedintoa4mLvialS3

3equippedwithamagneticstirbar,followedbytheadditionofthesolvent.After30seconds,thealkenesubstratewasthenadded.ThevialwasplacedintoaParrInstrumentsautoclave,whichwasthensealed,movedoutofthegloveboxandpurgedwithhydrogengas.Theautoclavewasheatedtocertaintemperature.Afterreactionfor16hours,theautoclavewascooleddownto0oCbeforereleasingthehydrogengas.ForquantitativeGCanalysis,biphenyl(1.0mmol)astheinternalstandardwasadded.Mostofthedesiredhydrogenationproductswerefurtherisolatedbyflashcolumnchromatography.3.1TableS1.OptimizationofConditionsandControlExperimentsfortheCo-CatalyzedHydrogenationof3,3-dimethylacrylicacidethylester1aaaReactionconditions:1a(1mmol),L1(1mol%),CoClo2(1mol%),THF(0.5mL),additives(2−100mol%),25C,H2(10bar),16h.bYieldsdeterminedbyGCusingbiphenylasaninternalstandard.c2barofH2.TableS1showedtheoptimizationofreactionconditionsusingL1astheligand.TheuseofKOMeinsteadofNaHBEt3astheadditiveforprecatalystactivationresultedinmuchloweryields(entries1and6).TherewasnoreactionwhenK2CO3,KOAc,K3PO4,andKOHwereusedasthebases(entries2−5).THFwasidentifiedastheoptimumsolvent(entries1and7-10).TheminimumamountofNaHBEt3neededtoensureahighreactionefficiencywas3mol%(entries11-12).Thereactionproceededsmoothlyevenunder2barpressureofH2withtheassistanceofahigheramountofNaHBEt3(entry13).Noproductwasobservedusing3mol%NaHBEt3intheabsenceofthemetalcatalyst(entry14),suggestingthatNaHBEt3isnotaneffectivecatalystinthisreaction.Thisreactioncannottakeplacewhen2mol%NaHBEt3and3mol%BEt3wasusedastheadditives(entry15).Mercurypoisoningexperimentindicatedthehomogeneousnatureofthisreaction(entry16).Whenthewell-definedcomplexCo-1wasusedasthecatalyst,quantitativeyieldofthestandardreactioncouldbeobtainedwiththeuseoftwoequiv.ofNaHBEt3(entries17-18)4.CharacterizationDataofHydrogenatedProductsS4

4Ethylisovalerate(2a)71HNMR(400MHz,CDCl3):δ=4.16(q,J=7.2Hz,2H),2.18-2.17(m,2H),2.13-2.07(m,1H),1.27(t,J=7.2Hz,3H),0.97(d,J=6.4Hz,6H)ppm.13CNMR(101MHz,CDCl3):δ=173.1,60.0,43.5,25.7,22.4,14.3ppm.Reactionconditions:L1(1mol%),CoCl2(1mol%),NaHBEt3(3mol%),THF(0.5mL),25oC,H2(10bar),16h.1-Cyclohexylpiperidine(2b)81HNMR(400MHz,CDCl3):δ=2.83(s,4H),2.71(t,J=11.2Hz,1H),2.14-2.11(m,2H),1.88(m,5H),1.69(d,J=13.2Hz,1H),1.55(m,2H),1.42-1.24(m,5H),1.17-1.11(m,1H)ppm.13CNMR(101MHz,CDCl3):δ=65.3,49.8,27.6,25.7,25.6,24.3,23.6ppm.Reactionconditions:L1(5mol%),CoCl2(5mol%),NaHBEt3(15mol%),THF(0.5mL),100oC,H2(50bar),16h.1-Phenylindane(2c)91HNMR(400MHz,CDCl3):δ=7.32-7.28(m,3H),7.23-7.10(m,5H),6.95(d,J=7.4Hz,1H),4.33(t,J=8.3Hz,1H),3.08-2.91(m,2H),2.62-2.54(m,1H),2.11-2.01(m,1H)ppm.13CNMR(101MHz,CDCl3):δ=148.6,145.4,144.3,128.5,128.1,126.5,126.4,126.3,124.9,124.3,51.7,36.6,31.9ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.1-(4’-Methoxyphenyl)indane(2d)91HNMR(400MHz,CDCl3):δ=7.28(d,J=7.2Hz,1H),7.19-7.09(m,4H),6.94(d,J=7.2Hz,1H),6.84(d,J=8.5Hz,2H),4.28(t,J=8.3Hz,1H),3.79(s,3H),3.06-2.88(m,2H),2.58-2.51(m,1H),2.06-1.96(m,1H)ppm.13CNMR(101MHz,CDCl3):δ=158.1,147.2,144.3,137.5,129.0,126.5,126.3,124.9,124.3,113.9,55.3,50.9,36.7,31.8ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2S5

5(50bar),16h.1-Methyl-2,3-dihydro-1H-indene(2e)1HNMR(400MHz,CDCl3):δ=7.21-7.12(m,4H),3.09-3.04(m,2H),3.09-2.52(m,3H),1.6(d,J=5.3Hz,3H)ppm.13CNMR(101MHz,CDCl3):143.8,126.0,124.5,41.2,34.5,20.7ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.2-Benzylindan-1-one(2f)101HNMR(400MHz,CDCl3):δ=7.78(d,J=7.6Hz,1H),7.57(t,J=7.6Hz,1H),7.41-7.40(m,7H),3.40(dd,J=4.2,14.0Hz,1H),3.17(q,J=7.8Hz,1H),3.03-2.97(m,1H),2.89-2.83(m,1H),2.67(dd,J=10.4,14.0Hz,1H)ppm.13CNMR(101MHz,CDCl3):δ=207.8,153.6,139.7,136.6,134.8,128.9,128.5,127.4,126.6,126.4,124.0,49.0,37.0,32.2ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.2-(2’Pyridyl)-indan-1-one(2g)1HNMR(400MHz,CDCl3):δ=7.78(d,J=7.6Hz,1H),7.57(t,J=7.6Hz,1H),7.42-7.35(m,2H),7.27-7.18(m,2H),7.09-7.01(m,2H),3.40(dd,J=4.2,14.0Hz,1H),3.19(q,J=7.8Hz,1H),3.07-3.00(m,1H),2.87(dd,J=4.1,17.0Hz,1H),2.75(dd,J=10.4,14.0Hz,1H)ppm.13CNMR(101MHz,CDCl3):δ=207.4,162.5,160.1,153.5,136.5,134.8,131.2,128.2,127.5,126.6,124.1,115.3,48.0,32.2,30.1ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.2-(4’-Chlorobenzyl)-indan-1-one(2h)10S6

61HNMR(400MHz,CDCl3):δ=7.80(d,J=7.6Hz,1H),7.60(t,J=7.6Hz,1H),7.43-7.18(m,6H),3.35(dd,J=4.2,14.0Hz,1H),3.20(q,J=7.8Hz,1H),3.02-2.96(m,1H),2.87-2.81(m,1H),2.71(dd,J=10.4,14.0Hz,1H)ppm.13CNMR(101MHz,CDCl3):δ=207.4,153.4,138.0,136.5,134.9,132.2,130.3,128.6,127.5,126.6,124.1,48.7,36.2,32.0ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.2-(4’-Bromobenzyl)-indan-1-one(2i)1HNMR(400MHz,CDCl3):δ=7.77(d,J=7.6Hz,1H),7.57(t,J=7.6Hz,1H),7.42-7.11(m,6H),3.32(dd,J=4.2,14.0Hz,1H),3.17(q,J=7.8Hz,1H),3.00-2.93(m,1H),2.84-2.79(m,1H),2.68(dd,J=10.4,14.0Hz,1H)ppm.13CNMR(101MHz,CDCl3):δ=207.4,153.4,138.6,136.5,134.9,131.6,130.7,127.5,126.6,124.1,120.2,48.6,36.3,32.0ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.2-(3’,5’-Dimethoxybenzyl)-indan-1-one(2j)1HNMR(400MHz,CDCl3):δ=7.78(d,J=7.6Hz,1H),7.57(t,J=7.6Hz,1H),7.42-7.35(m,2H),6.40(m,2H),6.33(m,1H),3.07(s,6H),3.34(dd,J=4.2,14.0Hz,1H),3.22-3.16(m,1H),3.02-2.95(m,1H),2.90-2.85(m,1H),2.60(dd,J=10.4,14.0Hz,1H)ppm.13CNMR(101MHz,CDCl3):δ=207.8,160.9,153.7,142.1,136.5,134.8,127.4,126.6,124.0,107.0,98.3,55.3,48.8,37.3,32.3ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.2-(2-Naphthyl)-indan-1-one(2k)1HNMR(400MHz,CDCl3):δ=7.81-7.77(m,4H),7.67(m,1H),7.56(t,J=7.6Hz,1H),7.48-S7

77.35(m,5H),3.56(dd,J=4.2,14.0Hz,1H),3.20-3.07(m,2H),2.93-2.81(m,2H)ppm.13CNMR(101MHz,CDCl3):δ=207.8,153.6,137.2,136.6,134.8,133.6,132.2,128.2,127.7,127.5,127.4,127.3,126.6,126.1,125.5,124.1,48.9,37.2,32.2ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.2,3-diphenyl-1-indanone(2l)111HNMR(400MHz,CDCl3):δ=7.90(d,J=7.6Hz,1H),7.65(t,J=7.6Hz,1H),7.50(t,J=7.6Hz,1H),7.33-7.27(m,7H),7.11(t,J=6.4Hz,4H),4.58(d,J=4.8Hz,1H),3.82(d,J=4.8Hz,1H)ppm.13CNMR(101MHz,CDCl3):δ=205.2,156.1,142.5,138.6,136.2,135.4,128.9128.8,128.4,128.3,127.9,127.2,126.7,124.1,64.6,54.9ppm.Reactioncondition:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.1,1,2-triphenylpropane(2m)121HNMR(400MHz,CDCl3):δ=7.39(d,J=7.6Hz,2H),7.31(t,J=7.6Hz,2H),7.18-7.09(m,7H),7.05-7.02(m,3H),6.95(d,J=7.6Hz,1H),4.06(d,J=11.2Hz,1H),3.61-3.54(m,1H),1.20(d,J=6.8Hz,3H)ppm.13CNMR(101MHz,CDCl3):δ=145.9,144.2,143.9,128.6,128.4,128.3,128.1,128.0,127.7,126.3,125.8,125.7,55.5,44.4,22.2ppm.Reactioncondition:L1(20mol%),CoCl2(20mol%),NaHBEt3(60mol%),THF(0.5mL),120oC,H2(50bar),16h.1,1,2,2-tetraphenylethane(2n)91HNMR(400MHz,CDCl3):δ=7.17(d,J=7.6Hz,8H),7.11(t,J=7.6Hz,8H),7.01(q,J=6.8Hz,4H),4.77(s,2H)ppm.13CNMR(101MHz,CDCl3):δ=143.5,128.6,128.1,125.9,56.4ppm.Reactioncondition:L1(20mol%),CoCl2(20mol%),NaHBEt3(60mol%),THF(0.5mL),120oC,H2(50bar),16h.2-Ethylpyridine(2q)S8

81HNMR(400MHz,CDCl3):δ=8.53(d,1H),7.58(td,J=7.6Hz,1.6Hz,1H),7.16(d,J=7.6Hz,1H),7.10(t,J=4.8Hz,1H),2.82(q,J=7.6Hz,2H),1.33(t,J=7.6Hz,3H)ppm.13CNMR(101MHz,CDCl3):δ=163.5,149.2,136.3,122.0,120.8,31.4,13.9ppm.Reactionconditions:L1(1mol%),CoCl2(1mol%),NaHBEt3(3mol%),THF(0.5mL),25oC,H2(10bar),16h.p-Bromoethylbenzene(2r)131HNMR(400MHz,CDCl3):δ=7.40(d,J=8.4Hz,2H),7.07(d,J=8.0Hz,2H),2.62(q,J=7.6Hz,2H),1.23(t,J=7.6Hz,3H)ppm.13CNMR(101MHz,CDCl3):δ=143.2,131.3,129.6,119.3,28.3,15.5ppm.Reactionconditions:L1(1mol%),CoCl2(1mol%),NaHBEt3(3mol%),THF(0.5mL),25oC,H2(10bar),16h.1-Ethyl-2-pyrrolidinone(2s)141HNMR(400MHz,CDCl3):δ=3.41-3.30(m,4H),2.41-2.35(m,2H),2.06-1.97(m,2H),1.15-1.09(m,3H)ppm.13CNMR(101MHz,CDCl3):δ=174.5,46.5,37.1,31.2,17.8,12.5ppm.Reactionconditions:L1(1mol%),CoCl2(1mol%),NaHBEt3(3mol%),THF(0.5mL),25oC,H2(10bar),16h.Phenylpropylether(2u)1HNMR(400MHz,CDCl3):δ=7.29(t,J=7.6Hz,2H),6.94-6.89(m,3H),3.93(t,J=6.4Hz,2H),1.85-1.76(m,2H),1.03(t,J=7.2Hz,3H)ppm.13CNMR(101MHz,CDCl3):δ=159.1,129.4,120.5,114.5,69.4,22.6,10.6ppm.Reactionconditions:L1(1mol%),CoCl2(1mol%),NaHBEt3(3mol%),THF(0.5mL),25oC,H2(10bar),16h.EthylCyclohexanecarboxylate(2x)15S9

91HNMR(400MHz,CDCl3):δ=3.66(s,3H),2.34(tt,J=3.6,11.2Hz,1H),1.91-1.88(m,2H),1.76-1.73(m,2H),1.66-1.64(m,1H),1.48-1.39(m,2H),1.32-1.17(m,3H)ppm.13CNMR(101MHz,CDCl3):δ=176.6,51.4,43.1,29.0,25.8,25.4ppm.Reactionconditions:L1(1mol%),CoCl2(1mol%),NaHBEt3(3mol%),THF(0.5mL),25oC,H2(10bar),16h.Isopropylbenzene(2z)71HNMR(400MHz,CDCl3):δ=7.31(t,J=7.6Hz,2H),7.24(d,J=7.6Hz,2H),7.19(d,J=7.2Hz,1H),2.95-2.85(m,1H),1.26(d,J=6.8Hz,6H)ppm.13CNMR(101MHz,CDCl3):δ=148.9,128.3,126.4,15.8,34.1,24.0ppm.Reactionconditions:L1(1mol%),CoCl2(1mol%),NaHBEt3(3mol%),THF(0.5mL),25oC,H2(10bar),16h.1,1-Diphenylethane(2aa)71HNMR(400MHz,CDCl3):δ=7.29-7.25(m,4H),7.22-7.20(m,4H),7.18-7.15(m,2H),4.17(q,J=7.2Hz,1H),1.64(d,J=7.2Hz,3H)ppm.13CNMR(101MHz,CDCl3):δ=146.4,128.4,127.7,126.0,44.8,21.9ppm.Reactionconditions:L1(2mol%),CoCl2(2mol%),NaHBEt3(6mol%),THF(0.5mL),60oC,H2(50bar),16h.5.CrystallographicDataCompoundCo-1Co-4CCDCNo.20184382018441formulaC7H13Cl2CoN3C17H25Cl4CoN3Temperature/K173K173KCrystalsystemmonoclinicorthorhombicSpacegroupP21/cPbcaa/Å12.8079(3)17.0639(3)b/Å6.6077(2)14.8204(3)c/Å13.6315(3)17.4588(3)α/o9090β/o103.320(2)90γ/o90903Volume/Å1122.61(10)4415.22(14)S10

10Z48ρcalg/cm31.5921.421μ/mm-116.04710.586F(000)548.01944.0Crystalsize/mm30.350*0.250*0.050RadiationCuKα(λ=1.54184)CuKα(λ=1.54184)2θrangefordata7.092to149.2029.388to149.744collection/oReflectionscollected382112005Independentreflections2110[Rint=0.0359,Rsigma=4417[Rint=0.0475,Rsigma=0.0498]0.0482]Data/restraints/parameters2210/0/1204417/0/231Goodness-offitonF21.0371.025FinalRindexes[I>=2σ(I)]R1=0.0532,wR2=0.1347R1=0.0404,wR2=0.0996FinalRindexes[alldata]R1=0.0597,wR2=0.1404R1=0.0508,wR2=0.1065Largestdiff.peak/hole/eÅ-30.734/-0.9870.372/-0.521FigureS1.MolecularstructureofCo-1.FigureS2.MolecularstructureofCo-4.S11

11NMRSpectraFigureS3.1H-NMRofL3FigureS4.13C-NMRofL3S12

12FigureS5.1H-NMRofL4FigureS6.13C-NMRofL4S13

13FigureS7.1H-NMRof2aFigureS8.13C-NMRof2aS14

14FigureS9.1H-NMRof2bFigureS10.13C-NMRof2bS15

15FigureS11.1H-NMRof2cFigureS12.13C-NMRof2cS16

16FigureS13.1H-NMRof2dFigureS14.13C-NMRof2dS17

17FigureS15.1H-NMRof2eFigureS16.13C-NMRof2eS18

18FigureS17.1H-NMRof2fFigureS18.13C-NMRof2fS19

19FigureS19.1H-NMRof2gFigureS20.13C-NMRof2gS20

20FigureS21.1H-NMRof2hFigureS22.13C-NMRof2hS21

21FigureS23.1H-NMRof2iFigureS24.13C-NMRof2iS22

22FigureS25.1H-NMRof2jFigureS26.13C-NMRof2jS23

23FigureS27.1H-NMRof2kFigureS28.13C-NMRof2kS24

24FigureS29.1H-NMRof2lFigureS30.13C-NMRof2lS25

25FigureS31.1H-NMRof2mFigureS32.13C-NMRof2mS26

26FigureS33.1H-NMRof2nFigureS34.13C-NMRof2nS27

27FigureS35.1H-NMRof2qFigureS36.13C-NMRof2qS28

28FigureS37.1H-NMRof2rFigureS38.13C-NMRof2rS29

29FigureS39.1H-NMRof2sFigureS40.13C-NMRof2sS30

30FigureS41.1H-NMRof2uFigureS42.13C-NMRof2uS31

31FigureS43.1H-NMRof2xFigureS44.13C-NMRof2xS32

32FigureS45.1H-NMRof2zFigureS46.13C-NMRof2zS33

33FigureS47.1H-NMRof2aaFigureS48.13C-NMRof2aaS34

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