Carbazolyl-Substituted [OSSO]-Type Zirconium(IV) Complex as a Precatalyst for the Oligomerization and Polymerization of α-Olefins Norio Nakata.pdf

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Received:9May2019;Accepted:7June2019;Published:13June2019
Abstract:Thedibenzylzirconium(plex(4)incorporatingwithacarbazolyl(Cbz)-substituted[OSSO]-typebis(phenolate)?edmethylaluminoxane(dMMAO),precatalyst4atrelativelylowcatalystloadingswasfoundtopromotethe1,2-regioselectiveoligomerizationof1-oproducethecorrespondingvinylidene-ended?oligomerswithmoderateturnoverfrequencies(TOFs)-enrichedoligo(1-hexene)sin39–62%(dMAO)alsoexhibitedgoodperformanceinthepolymerizationofstyreneyieldingisotacticpolystyrenes([mm]>99%)withquitelargemolecular?1?1?1weights(Mw<508,100gmol)andrelativelyhighcatalyticactivity(upto2810gmmol(4)h).Keywords:zirconium;oligomerization;-Nattacatalystandsingle-sitemetallocenecatalyst,thedevelopmentofpreciseoligomerizationandpolymerizationcatalystsforα-ole?nshasbeenattractiveinbothacademicandindustrial?elds[1–4].Duringthepasttwodecades,considerableattentionhasbeenfocusedparticularlyonthedevelopmentanddesignofearlytransitionmetalcatalystsfeaturingnon-Cp(cyclopentadienyl)ligandswhichdemonstratehighactivityandregio-andstereocontrolsintheα-ole?npolymerization[5–8].Amongthem,dianionic[OSSO]-typetetradentateligands,basedontwophenoxideframeworkswithtwosulfurdonorsattheortho-orbenzyl-positionshavebeenofgreatinterestsofar[9–37].plexeshavinganoriginal[OSSO]-typebis(phenolate)ligandpossessingatrans-1,2-cyclooctanediylplatform[38–45].plexesandactivatorscouldachievethecontrolledisotacticpolymerizationofvariousα-ole?,wehavealsopreliminarilyinvestigatedthepreparationofdibenzylzirconium(plexes(1and2)bearing[OSSO]-typebis(phenolate)ligandssubstitutedwithphenylor2,6-dimethylphenyl(Dmp)groupsonthephenolategroups(Scheme1)[46].UponactivationwithdMAO(driedmethylaluminoxane),plexes1??and2promotehighperformanceinthepolymerizationofstyrene(activity<7700gmmol(cat.)1h1)?1yieldingthecorrespondingisotacticpolymerswithmolecularweightsofMw<181,,thesecatalystsystemscouldcatalyzetheoligomerizationof1-hexeneatlowcatalystloadings(–%)toyieldthecorrespondingvinylidene-endeddimer(74–91%)asthe?mainproductwithrelativelyhighturnoverfrequencies(TOFs)upto11,100h1[47].essfulresultswitharyl-substituted[OSSO]-typezirconium(plexesstimulatedustoexpandfurtherCatalysts2019,9,528;doi:,9,xFORPEERREVIEW2of9catalystsystemscouldcatalyzetheoligomerizationof1-hexeneatlowcatalystloadings(–,%)9,528toyieldthecorrespondingvinylidene-endeddimer(74–91%)asthemainproductwith2of9?1relativelyhighturnoverfrequencies(TOFs)upto11,100h?1[47].essfulresultswitharyl-substituted[OSSO]-typezirconium(plexesstimulatedustoexpandfurtherexploringthesubstitutedexploringthe[OSSO]-typesynthesisandzirconium(plexesofnewstimulated[OSSO]-plexexpandfurtherintheoligomerizationexploringthesynthesisandcatalyticperformanceofnew[OSSO]-plexintheoligomerizationandsynthesisandpolymerizationandcatalyticofα-ole?[OtoSSO]-plexsynthesisinofthedibenzyloligomerizationzirconium(IV)andpolymerizationofα-(IV)plex(4)incorporatingof-(Cbz)-substitutedwewishtopresentthesynthesis[OSSO]-typeofdibenzylpreligandzirconium(IV)(3)anditscomplex(4)incorporatingwithacarbazolyl(Cbz)-substituted[OSSO]-typepreligand(3)anditscomplexperformance(4)incorporatingintheoligomerizationwithacarbazolyl(Cbz)of1-ogether-substitutedwithpolymerization[OSSO]-typeofpreligandstyrene,as(3)aandpartitsofperformanceintheoligomerizationof1-ogetherwithpolymerizationofstyrene,asapartofperformanceourinvestigationintheinoligomerizationthesingle-sitenon-Cpof1-,asapartofourinvestigationinthesingle-sitenon-(plexes1and2having[OSSO]-typebis(phenolate)(plexes1and2having[OSSO]-typebis(phenolate)-substituted[OSSO]-ordingtotoliteratureliteratureprocedureprocedure[48],[48],thatis,bybytreatmenttreatmentofofthethecorrespondingcorresponding2-(bromomethyl)-6-(92-(bromomethyl)-6-(9H-carbazol-9-yl)-4-methylphenol-carbazol-9-yl)-4-methylphenolandtrans-cyclooctane-1,2-(plex4trans-cyclooctane-1,2-dithiol-cyclooctane-1,2-(plex4wasreadilysynthesizedaspaleyellowcrystalsin93%yieldbythereactionof3withZr(CH2Ph)4inwasreadilysynthesizedasaspalepaleyellowyellowcrystalscrystalsinin93%93%yieldyieldbybythethereactionreactionofof3with3withZr(CHZr(CH2Ph)2Ph)4in41tolueneintolueneatroomatroomtemperaturetemperature(Scheme(Scheme2).In2).theIn1HtheNMR1HspectrumNMRspectrumof4,anofAB4pattern,anABforpatterntheS-benzylfortheδgeminalS-(δ??)(δwith?)withconstantacouplingof8Hz,constantduetotheofshielding8Hz,--symmetricindicatestructureitsC2-(CH2Ph)4SOCHPhS24SCH2PhZrStoluene,RTSCH2PhSOHtoluene,RTO2CbzCbzCbzNCbzCbz=MeMeMe34(93%)(IV)(plex44withwithcarbazolyl-substitutedcarbazolyl-substituted[OSSO]-type[OSSO]-typebis(phenolate)(IV)zirconium(plex4,,weweexaminedexaminedthetheoligomerizationofof1-hexene1-..UponactivationactivationwithwithdMMAOdMMAO((),mmol),plex4((,mmol,%)actedmolas%)aactedprecatalystasatooligomerize1-hexene(,)withoutanysolventstogivevinylidene-terminatedoligomers?%in1hat25C(Table1,Run1).ThecorrespondingTOFvalueCatalysts2019,9,xFORPEERREVIEW3of9precatalysttooligomerize1-hexene(,)withoutanysolventstogivevinylidene-%in1hat25°C(Table1,Run1).TheCatalysts2019,9,5283of9correspondingTOFvalueis1130h?1,whichisstillhigherthanthatofMAO-activatedzirconocene(TOF=296h?1)[49],butapproximatelyone-paredtothatofphenyl-substituted??is1130[OSSO]-typeh1,plexisstillhigher1(TOFthan=11,100thathof?1)MAO-activated[47].Thisresultzirconocenewouldbeexplained(TOF=by296sterich1)hindrance[49],butofapproximatelybulkyCbzgroupsone-paredLewisaciditytothatoftheofacphenyl-substitutedtivecenterbytheelectr[OSSO]-?(TOFThe=11,100microstructureh1)[47].,2-;Themicrostructurethevinylideneoftheresultingselectivityoligomerswascalculatedwasestimatedtobe98%by(see,1HandFigure13CS2).{1H}NMRHighspectrum1,2-regioselectivityoftheoligomerswaspresentedcon?rmedtwointhesets1HforNMRtwovinylidenespectrumofcarbontheoligomers;%(see,Figure110andS2).150Theppm13C{as1H}minorNMRsignalsspectrumcorrespondingoftheoligomerstothedimerpresentedandtwoothersetsoligomersfortwo(rimer)carbonofatoms1-hexene,(sppmee,FigureastheS3).majorIncontsignalsrasttoandprecatalystsapproximately1and1102,veryandweak150ppmresonancesasminorforsignalsvinylene-terminatedcorrespondingtogroupsthedimerwereandconfirmedotheroligomersaround130()relativeof1-hexene,integralratiorespectivelyofthesevinylidene(see,FiguresignalsS3).Insuggestedcontrasttoanprecatalystsoligomericdistribution1and2,veryasweakfollow;resonances39%ofdimer,forvinylene-terminated34%oftrimer,and27%?,ratio200,oftheseand250vinylideneequivalentssignalsalsosuggestedresultedaninoligomericthedominantdistributionproductionasfollow;of39%vinylidene-endedofdimer,34%ofoligomerstrimer,andincluding27%?–62%(TableofdMMAO1,Runsto2150,4).200,Theandcorresponding250equivalentsconversionsalsoresultedandinTOFsthedominantwererecordedproductionintheofrangesvinylidene-–%andoligomers1350–1690includingh?1,respectively,dimersofhighincreasingcontentswithin56–62%elevating(Tablethe1,amountRuns2–4).,–%exhibitedthe?andhighest1350–1690TOFhof1,respectively,1690h–1inthisincreasingstudy(Tablewithelevating1,Run4).,urewasraiseditisto?noteworthy40°C,essfullythehighestyieldingTOFvinylidene-terminatedof1690h1inthisoligomersstudy?(Table(Table1,Run1,Run4).When5).ThetheslightlyreactionincreasedtemperatureconversionwasandraisedTOFtovalue40wereC,%and2080proceededh?1,-terminatedoligomersshowedadimeoligomersrdistribution(Tableof1,53%Runsimilar5).ThetothoseslightlyinRuns?increased1–(%–34%)andobtained2080hwith1,%1andsimilar2(8to–11%).thoseOverall,inRunsthe1–?trimerspeculateddistributionsbythe(21–34%)(8–11%).Overall,positionofactivespeciessuchasZr?--(%)dMMAOConditionsnHOligomerDistribution[%][%]VinylideneVinylidene/??1SelectivitySelectivitybDimerDimerTrimerTrimerOthersOthers[C][°C][%][%][h[h]?1][%][%]**********.**********.:4(,%),1-hexene(,),reactiontime:1h;;EstimatedbyC{H}(plexes1and2featuringaryl-substituted[OSSO]-typeligandsaConditions:4(,%),1-hexene(,),reactiontime:1h;bEstimatedhavealreadyservedasusefulprecatalystsfortheisospeci?cpolymerizationofstyrene[46],wenextby1HNMRspectroscopyinCDCl3;cEstimatedby13C{1H}