一种嵌有双亚胺基吡啶配体的全共轭有机聚合物材料及其在CC偶联反应中的应用可编辑

《一种嵌有双亚胺基吡啶配体的全共轭有机聚合物材料及其在CC偶联反应中的应用可编辑》由会员分享，可在线阅读，更多相关《一种嵌有双亚胺基吡啶配体的全共轭有机聚合物材料及其在CC偶联反应中的应用可编辑（26页珍藏版）》请在装配图网上搜索。

1、一种嵌有双亚胺基吡啶配体的全共轭有机聚合物材料及其在C-C偶联反应中的应用 ChineseJournal ofCat alysis35 72014540?545 催化学报2014 年第 35 卷第 4 期 | ww w. chx b. cnavailable ?at ?/0.journal ?homepage: ?/./locate/chnjcArticle?Imine ?linked conjugated organic polymer bearingbisiminopyridine ligands and its catalytic applicationin C?C coupling r

2、eactionsa, b a, a a a aGuifuCh en , F e ng W ang *,Y ehong Wang ,Xiao chenZhang ,HongqiangQin ,HanfaZou ,a,#JieXuaDalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, ChinabGraduate University of Chinese Academy of Sciences, Beijing 100049, China?ARTIC L E INFO

3、ABSTRACT?Article history:Covalent organicpolymers are anemerging class ofmaterials withpotentialapplications in areasReceiv ed1Nov ember 2013 i n clu d in g mole cu la r s e pa ra ti on, ga s s o rp ti on, a n d cata l ys isA n ov el full y conju g at ed o r ga n i c p ol y?Accept ed6Jan uary 2014 m

4、er bearing bisiminopyridineCOP?BIPandits catalytic function are reported hereUnlike pre?Pu bl ish e d 20April 2014 viousCO Pma terial s, theimine bonds ofCO P?BI Pact as bothlinkagesandcompl exation sites forth ebinding ofmetal ions.Aclear structureis presented based on ultrav iolet?visibl e, F ou r

5、ier transformi n f r a r e d, an d m a tr ix ?a ss is te d l as er d e s or pt i on/ i on izat i on ti m e? of ?f li gh t ma ss s pe c tr ometr y cha r ac?Keywords:terizationTh eCOP?BI Pmaterial sarethermall yst ableu pto44 0Can dar ei ns olu b le i nconv en t ion?Conjugatedorganicpol ymermateriala

6、l s olv en tsIn addi t i on, COP?BI P comp le xe s Pd i ons on b is i minopyridinesites andforms ahetero?B is im in op yr i di ne l i ga n dg e ne ou s cat al ys t, wh i ch exh i bi tsex c el le ntca ta l y ti ca ct iv it y in the Suzuki ?Miyaura C?C cou pl in gCa ta ly si sreactionSuzuki?M iy au ra

7、C?Ccoupling2014,DalianInstitu teofCh emical Physics,Ch in es eAcademyof S ci ences.P u bl ish e d by E ls ev i erB.VA ll r i ght sr e se rv e d1. Introductioncal us e isd ifficult because of limited synthetic dive rs if icationA l thoug h n uc lea r m ag netic res o na nc e te c h niq u es h a ve be

8、 enCovalentorganicpolymers are anemerging class ofmateri? employed, the precis e chemic al s truc tures of C OP s are mostlyals with p otential applic ations in areas such as molecula r sepa ? unknownFor c atalytic ap p lications, it isd esirablet ha t COPration, gas sorption, and ca ta lysis 1,2The

9、succe ssf ul des ig n materials shouldbe stabletoward heat, air, ands olvents, a ndand synthesis of thesep olymers linkedb y B?O 3 ?5, C?C 6,7,bed es ig nableC ? N 8, a ndCN 9?12 bond s ha veb ee n re p or t ed R ec e nt In organometallic chemis tr y a wider ange of ligand s ha ves t ud i e sha v es

10、 ho w nt ha tc o n j ug a te do r g a n i cp o l y m e r s C O P sbeen used to b ind metals , and bisimino pyridines ligandsarew i t h e x t e n d e d ? c o n j u g a t i o np os s e s sh i g h t he r m a l s t a b i l i t y a ndamong the most c ommon S cheme 1Thisis presumab ly be?s t r uc t ure d

11、i ve rs ity 1 3? 1 5 How e ver , t he s ynthes is of these caus e oft he ir r elatively facile f unctiona lization, stability a ndCOP ma terials us ua lly requires expensive precursors and intri? ability tobind a large numberof transitionmetalions dand fcatetechniques.Furthermodification ofthese COP

12、s for practi? blocks 16?20With a dvantage s ofs eparation, r ecyc ling, and*Correspondin g au th or.Tel/Fa x:+86?411?84379762;E?mail:wangfeng/.#Correspondingau th or.Tel /Fax:+86?411?84379245;E?mail:xuj ie /.This w ork was supported by the Nat ional Natural Science Foundation of Ch ina 21073184, 212

13、73231 and Hundred T al ents Progr am of th e C h i n e s eAcademy ofSci encesDOI:10. 1016/S1872?20671460021?8 |h /. ce direct /sci en ce/j ou rnal/18722067|Chin.J.Catal.,Vol.35,No4,Ap ril2014 Guifu Chen et al/ Chinese Journal of Catalysis 35 2014 540?5455411.5CNo13580 C, 24 hOHC N CHON75acetonitrile

14、N BIP N451.0site30HNNH2 2conjugated organic polymer1510Scheme 1.Synth es is of theCOP? BI Pmaterial50.531reus e, heterog eneous catalys tsa re w id ely used in the prod uc?0 mintionof chemicalsTo datethe useof COPs as catalytic materia lsisrare.We thus investiga te d the incorporation of0.0bisiminop

15、yridineligandsinto COPsto prepare solid catalysts250 300 350 400 450 500up on c oordina tion w ith me tal ions Herein w e rep ort, f or th eWavelength nmfirs ttime, amethodofpreparing bisimino pyridine?c ontainingFig1 Monitoringtheformationof the CN bondduring the synthesisconjugated p olymers C OP

16、?BIP based on Schiff?base chemis?at375nmbyliquid?phaseUV?Viss pectroscopytry.TheCOP?BIPmaterial was highly stable upto 440 Candwas ins oluble in water a nd a protic s olvents T hebisimino pyridine ligands , asbinding s ites , formed c omplexes1with P d ion to g ive a hete rogeneous catalyst, whic h

17、demon?strated excellentcatalyticactivity inaclassic Suzuki?MiyaurareactionWe als o show t ha t ma trix?a ssis ted laser desorp?tion/ionization time?of?flig ht MALD I?TOF mass spectros copyi sa d ir e c ta n dr e l i a b l e m e t h o df o r t h ed e t e r m i n a t i o n of t h e C OP2structure2. Ex

18、perimental343733570.21710The COP?BIP ma terial wasp repared from the r ea ction be ? 1623 tween 2,6?pyridinedicarboxaldehyde a nd 1 ,4?d ia mine b enzene4000 3500 3000 2500 2000 1500 1000at 80 C in acetonitrile via a n imination reaction w ith the elim?1Wavenumber cm ination ofwater, asshown in Sche

19、me1The mixture becameyellow and then turbidA t 24h, a precip itate had formeda nd Fig2F T? IR s pectra of the COP?BIP material1 Freshly synthesizedmaterialdriedat110Cinairfor2h ;2Treatedat250C in H 2 f or2h.was collected bycentrifugation.Asmall amountof aceticacidcan rema rkably a cc elerate the re

20、action, but it w as not u sed information ofiminebondsCNThe aldehydeCO peak atour synthesis so that a puremateria l could be obtaine dS ol?1 ?11710 cma ndthe two b road b ands a t 3437 and 3357 cmvents such as methanol, ethanol, d imethylfor mamide, and di?assignedto unre ac ted ?NHs uggested thec o

21、?existe nce of ter?methyls ulfoxide wereuseda ndgaveid enticalmaterials2minal?CHOg roupsand?NH groupsA Suzuki?M iyaura cross?c oupling reaction w ascarriedout 2The conjug ated p olymer e xhibited h ig h s tability ase vi?as f ollows A b ou t 0.5 mmol 4?bromoanis olein 1 mL e thanoldenc edb y thermal

22、 gravimetric analys isTGA Ass hown in FigHPLC grade, 0.75 mmol phenylboronic acid in 1 mL e thanol,3, an apparentdecompositionweight loss ofapprox.3% oc?1.0 mgP dC l /COP?BIP, and 0.1 mmol K COwere added se?2 2 3curred a t 440 C in Nandat 420 Cin air.Theseresultsindi?quentiallyinto a 5 mLvial and st

23、irred at 50 C for3hThe c on? 2catethat COP?BIP ismore stablethan other covalentorganicvers ion of 4 ?b romoanis ole was dete rmined b y gaschroma tog?polymers s uc h as triaz ine?ba sed framewor ks about 410 C inr ap h y us inga calib r ation cur v eair20, me lamine?bas edp olymer ab out 400 C in N

24、8,2C O F?LZU1 abou t 310 C i n N 2, a nd P OFsabout 400 Cin3. Results and discussion2N 10Bycomparison,apolymerwith a N,O,N unit 21,2which isd if ferent to the N,N,N unit of COP?BIP, is stablea t 300Monitoringthe r eaction by time?dependent liquid u ltravio?C in N The imine ca n ber ed uc ed to the a

25、mine by hydroge na?let?visible UV?Vis spectroscop y show edthat the CN absorp ? 2tion.Atestc onductedinH a t 2 5 0 Cf o u n d n oa p p a r e n t c ha n g etion a t 375 nm c onstantly increased Fig 1, indicating that t he2in s tr ucture as observedb y IR Fig2 The refore, COP?BIP wasreac tion between

26、?CHO and ?NH wasconsistent withthat2very s ta ble under both oxidativea nd reductive c onditionsW ereportedin the literaturewhereinthebright yellow color wasc o n c l ud et ha tth eh ig h s ta b i li tyo f C O P? B I P ar i s e sf r o m t hedue tothe C N chromophore10 bisimino pyridines ites and the

27、fullyconju gateds tructureThe succ essful b uild?up ofaconjugated polymer was con?COP?BIP is ins oluble in conventional s olvents s u ch as hy?firmed b y Four ier trans f or m infrared FT?IR spectroscopy?1drocarbons, alcohols, ke tones, nitriles, a mides, a nd sulfoxidesFig2A strongvibration a t 162

28、3 c m clearlyindicatedtheAbsorbanceTransmittance 542Guifu Chen et al/ Chinese Journal of Catalysis 35 2014 540?545100NaH N N N280MW 207440 N N NH2MWN-n-N60N315 + 207nMW 92MW 22340 n20HNNH2 20100 200 300 400 500 600 700 800MWN-n-OoTemperature C 225 + 207nNCHO100H N Nb 2MW 20780MW 133N N420 N60MW 92n4

29、0MWO-n-O20242 + 207nOHC N CHO0100 200 300 400 500 600 700oTemperature COHC N NCHOFig3T GAcur vesofCOP?BI Pin N a andartifici al a irN :O 4:1b.2 2 2 N NMW 207Experimentconditions:ramp rate 10 C/min, N flow speed302MW 133N NmL/minNMW 209nThisinherent ins olubility r espons iblef or thedes ir able p ro

30、per ?ties of the COP materials makes a detailed s tructural analysisScheme 2.Three types ofconjugated COP?BIP chain and their calcu?difficultMALD I?TOF mass s pectrometry isused to c ha racterizel a te d mol e cul a r we i gh tsNin di cat esth eNH ? te rmin ate dgr oup sM W2oligomersand can provide

31、direct a ndu namb iguouss truc tural 92 or223,a nd O is th e CH O? termin at ed grou ps MW 133 or 209.ni n di cat esth enu mber ofr ep e atu ni ts in s qua rebra cketsM W 207inf or ma tion 22W eha vere p or te dtheus e ofthis te c hniq ueinpeptidesanalysis 23Inthis study,theslow mixingof the twomono

32、mer s olutions generate d oligomers duringt he initial r e? The ma ss spectraof the COP?BIP oligomers indicate d that a taction, and this c ould be analyz edb y MA LDI?TOF mass spec? am/zratioless than3000it had distinctive peaks Fig4atrometryIt is noteworthy that the precise structuresof COP Three

33、series of sing le p olymers were p resent w ith the samematerials are seldom r eporte dIn thiss tudy, the MALD I?TOF repeatunit of207m/z , w h ic hist hem o la rm assoft her ep ea tanalysisconfirmedthemass and thushelped toestablishthe unit see squareb ra ckets in S cheme 2 Figure 4b shows anCOP?BIP

34、 structureBecause of the te ndency of MA LDI?TOF enlargedview ofthem/zratio f rom 600 to 1000Two s ets ofma ss sp ectrometry t o fa vor the i o n iz a t i o n of lo w e r m o le c u la r peaks n 2and3, wherenis the number of the repeat unitw e ight s p ec i es , the spe c tr a of theseoligomersshoul

35、d not be weredifferentiated byan interval of 207m/z These resultsconsid ered to represent the truemolecular weight distribution agree well withthe expected masses fromthethreedifferent24e n d ? g r o u p s S c h e m e2 a nd T a b l e 1 F o r n i nc r e a s e d t o1 a b o v e ,N-3-O a N-2-O b cN-2-O

36、N-2-N O-2-O639+Na 846+NaN-2-N N-3-N729+Na936+NaO-2-O756+NaO-3-O963+Na500 1000 1500 2000 2500 600 650 700 750 800 850 900 950 1000 1050 662 663 664 665 752 753 754 755 779 780 781 782m/z m/z m/zm/z m/zm/z m/z m/zFig4 a MALDI?TOF mass spectraof COP?BIP in therangeofm/z 500?3000; b Enlar ged view of th

37、em/z ratiofrom 600 to1000;cCalculateddas hed li ne an dobservedsoli d curvei sotopi c distributionsf orN?2?O,N?2?N,andO?2?ONormalized intensityMass %Mass %Normalized intensity Guifu Chen et al/ Chinese Journal of Catalysis 35 2014 540?545543Table 1O?3?O oligomer 963m/z has two ?CHOgroups attheendsCa

38、lcul atedmass signalsoftheoligomers withvarying repeatunitsn*After reacting w ith aniline, it s h ould i ncreas e its ma ss by 7 5n1 2 3 4 5 6 7 7m/z , which was present as O?3?O + 75, 1083m/z in Fig5aN?n?O ? 639 846 1053 1260 1467 1674The olig omerO?3?O + 75 reacte d with a niline, and its ma ssN?n

39、?N 522 729 936 1143 1350 1557 1764was increased to O?3?O + 75 + 75, 1158m/z.Thesame calcu?O?n ?O 549 756 963 1170 1377 1584 1791lation r ule was applie d to the N ?n ?Oo l i g o me rs N o i n c r e a s ein* The table data show the imum isotopicmass.Thecalculation wa sma ssca u sed by t he N ?n?Nolig

40、omerswas foundin thebased ontheformu lashowninScheme2MA LD I?TOF analys is The ma sss igna l intens itiesincreased asfollows : O?3?O O?3?O +7 5 O?3?O + 75 +75, indica tingall the ca lculatedmass spec tra weref oundin the experimentalthe end?capping approached comp letion a lthough theMALDI?TOF Table

41、1andFig4a.Oligomersof N?n ?Na n dMALD I?TOF analysis was s emi?quantitative Simila r resultsO?n ?Oc an b e viewed as exclus ive N?n?O 225 + 207n re ac tionswerefoundwhen end?capping with benzaldehyde Fig5bwith1,4?diaminebenzeneto form N?n?N 315 + 207n, a ndThe N?n ?O a ndN ?n ?No lig o mersw er e ca

42、p p e d, a n d the irmassw i t h2 ,6 ?p y r i d in e d ic a r b o x a ld eh y d et o f or m O ?n ?O 342 +increas edby88m/z207n,respectively.Theisotopic distributions obtained ex?Bisiminopyridines, as bind ing sites, have many p otentialperimentallyby this techniqueare in goodagreement with theapplic

43、 ationss uch as ligandsf or metal ions to p roducecatalys tspredic ted values ob tained b y using the freesoftware IsoP roH e re in, w e p rep ar eda Pdc a talys t with b isiminopyr idine as3.1 a f ree 30 da y evalutation ve rs ion w ritten by M Senko , a sthe ligand PdCl /C OP ?BIP It waspr ep ar e

44、db y s oa k ing2demons tratedforN?2 ?O, N?2?N,and O?2 ?OinFig.4cCOP?BIP in aboilingPdCl ?a cetonitrile solutionf or 6 h The2The unreacted end?groupsof ?CHOand?NH can further2catalyst wasthen washedthreetimes with hot acetonitriletoreact withanilineandbenzaldehyde,respectively,to formaremove weakly a

45、dsorbedP dC l Elementa l analysis Ta ble 22benzene?terminated p olymerunderthesameconditions,thesoandTGAgave a c ompara blePdw eightcontent8.5%and8.1%,called“end?cap”10.This reaction canbe usedto gauge therespective ly, s uggesting that a bout 20% of theamountof terminalamine andaldehyde groupsin CO

46、P?BIPbisimino pyridine c oordinated w ith the Pd ionTheEnd?capping ofthe?CHO groupscan be clearly seen in the par?PdCl /C OP ?BIP catalys t showed s imilar the rmal s ta bility to2tially capped oligomers s h own inF i g 5 a Fo re x a mp l e,th eCOP?BIP F i g 6 T heca t a l ystw ase v a l u a tedi n

47、aS uz u k i ?Miyaur a C?C coupling r ea ction, w hich is us edin homogene ous1.5End-cap with aniline:amedia for the facile f ormation of C?C bonds Tab le 3 25Un?RCHO + PhNH RCNPh + H O2 2der reaction c onditions le ss demanding than that reported inMWMW+75the literaturefor MOFandCOPmaterials 2, the

48、conversion of1.0p ?bromoanis ole reac hed confirmedb y MS 99% w ith a se?lectivity forp ?phenylanisoleof 99% overthe0.16% Pd cata?lystThe turnover number TON was calc ulated as 625, ind i?0.5Table 2El e me n t alan al ys isof CO P?BI Pan dPd C l 2 /CO P?B I PC o mp os it i on wt% SampleC H N O PdCl

49、20.0aCOP?BIP 73.44 4.58 19.96 2.0201000 1050 1100 1150 1200 1250 1300 1350 1400baPdCl /CO P?B I P 62.97 4.02 17.02 1.73 14.162m/z aO bt ai ne d by su btr a c ti onbObt ai ned by calcu lation :73.44/ 62.97 2. 02/x,x1.73End-cap with benzaldehyde:b1.5RNH + PhCHORNCPh + H O2 2MWMW+881001.080401600.54020

50、0.0700 800 900 1000 1100 1200 0100 200 300 400 500 600 700 800m/zoTemperature CFig5.aEnd?capping reaction withanilineb End?capping withbenzaldeh ydeNote: N? 2? O + 88 727m/z h a d a si mila r ma ss t o N? 2? NFig6 TG Ac u r v e o fPd C l 2/COP?BIP in artificialairN 2 :O 2 4:1.Ex?729m/z,andthusth eir

51、 is otopicpartl y overlappedperiment alcon ditions:ramprate10 C/min,flowr at e30mL/minNormalized mass intensityNormalized mass intensityO-3-ON-2-OO-3-O + 75N-2-O + 88N-2-NN-4-OO-2-OO-3-O+ 75 +75N-2-N + 88N-4-O + 75N-3-ON-4-NO-4-ON-2-N + 88 + 88N-3-O + 88N-3-NO-3-OO-4-O + 75N-3-N + 88N-5-ON-4-OO-4-O

52、+ 75 +75N-3-N + 88 + 88N-5-O + 75N-4-O + 88N-5-NMass %544Guifu Chen et al/ Chinese Journal of Catalysis 35 2014 540?545Table 3A, N agas e S, Jian gD LAngew Chem Int Ed,2011,50:1289C?CcouplingreactionoverthePdCl / CO P? B I P c at al yst2 4 WanS,GuoJ, KimJ,Ihee H,JiangDLAngew Chem Int Ed,2008,47:OMe 8826OMe 0.16 mo