A Pd-metalated porous organic polymer as a highly efficient heterogeneous catalyst for C-C couplings

Article abstract of DOI:10.1016/S1872-2067(15)60952-4

An efficient catalyst system based on a Pd-metalated porous organic polymer bearing phenanthroline ligands was designed and synthesized. This catalyst was applied to various C-C bond-forming reactions, including the Suzuki, Heck and Sonogashira couplings, and afforded the corresponding products while exhibiting excellent activities and selectivities. More importantly, this catalyst can be readily recycled. These features show that such catalysts have significant potential applications in the future.

Full text of DOI:10.1016/S1872-2067(15)60952-4

ChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ54–60
ꢀ
ꢀ ꢀ ꢀ
ꢀ ꢀ ꢀ ꢀ
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
ꢀ
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
ꢀ
ꢀ
Article (Special Column on New Porous Catalytic Materials)
AꢀPd‐metalatedꢀporousꢀorganicꢀpolymerꢀasꢀaꢀhighlyꢀefficientꢀ ꢀ
heterogeneousꢀcatalystꢀforꢀC–Cꢀcouplingsꢀ
ZhifengꢀDai,ꢀFangꢀChen,ꢀQiꢀSun,ꢀYanyanꢀJi,ꢀLiangꢀWang,ꢀXiangjuꢀMengꢀ*,ꢀFeng‐ShouꢀXiao
ꢀ
KeyꢀLaboratoryꢀofꢀAppliedꢀChemistryꢀofꢀZhejiangꢀProvinceꢀandꢀDepartmentꢀofꢀChemistry,ꢀZhejiangꢀUniversity,ꢀHangzhouꢀ310028,ꢀZhejiang,ꢀChinaꢀ
A R T I C L E ꢀ I N F O ꢀ
A B S T R A C T ꢀ
Articleꢀhistory:ꢀ
AnꢀefficientꢀcatalystꢀsystemꢀbasedꢀonꢀaꢀPd‐metalatedꢀporousꢀorganicꢀpolymerꢀbearingꢀphenanthro‐
lineꢀligandsꢀwasꢀdesignedꢀandꢀsynthesized.ꢀThisꢀcatalystꢀwasꢀappliedꢀtoꢀvariousꢀC–Cꢀbond‐formingꢀ
reactions,ꢀincludingꢀtheꢀSuzuki,ꢀHeckꢀandꢀSonogashiraꢀcouplings,ꢀandꢀaffordedꢀtheꢀcorrespondingꢀ
productsꢀwhileꢀexhibitingꢀexcellentꢀactivitiesꢀandꢀselectivities.ꢀMoreꢀimportantly,ꢀthisꢀcatalystꢀcanꢀbeꢀ
readilyꢀrecycled.ꢀTheseꢀfeaturesꢀshowꢀthatꢀsuchꢀcatalystsꢀhaveꢀsignificantꢀpotentialꢀapplicationsꢀinꢀ
theꢀfuture.ꢀ
Receivedꢀ20ꢀMayꢀ2015ꢀ
Acceptedꢀ28ꢀJuneꢀ2015ꢀ
Publishedꢀ5ꢀJanuaryꢀ2016ꢀ
Keywords:ꢀ
©ꢀ2016,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences.
Porousꢀorganicꢀpolymerꢀ
Phenanthrolineꢀligandꢀ
Carbon–carbonꢀcouplingsꢀ
Pd‐basedꢀheterogeneousꢀcatalyst
PublishedꢀbyꢀElsevierꢀB.V.ꢀAllꢀrightsꢀreserved.
1
.ꢀ ꢀ Introductionꢀ
supportsꢀareꢀrelativelyꢀdifficultꢀtoꢀmodifyꢀowingꢀtoꢀtheirꢀinertꢀ
structuresꢀ[13,14]ꢀandꢀsilicaꢀsupportsꢀreadilyꢀdissolveꢀinꢀalka‐
lineꢀmediaꢀ[15–17].ꢀTherefore,ꢀitꢀwouldꢀbeꢀgreatlyꢀbeneficialꢀtoꢀ
designꢀ highlyꢀ stable,ꢀ easilyꢀ modifiedꢀ supportsꢀ forꢀ theꢀ hetero‐
genizationꢀofꢀhomogeneousꢀcatalysts.ꢀ
Recently,ꢀ porousꢀ organicꢀ polymersꢀ (POPs)ꢀ exhibitingꢀ rela‐
tivelyꢀ goodꢀ stabilityꢀ andꢀ capableꢀ ofꢀ uniqueꢀ functionalizationꢀ
haveꢀemergedꢀasꢀanꢀinterestingꢀclassꢀofꢀmaterialsꢀwithꢀsignifi‐
cantꢀpotentialꢀinꢀtheꢀfieldsꢀofꢀgasꢀstorage,ꢀseparationꢀandꢀcatal‐
ysisꢀ [18–21].ꢀ Inꢀ particular,ꢀ POPsꢀ mayꢀ actꢀ asꢀ highlyꢀ tunableꢀ
platforms,ꢀ throughꢀ theꢀ introductionꢀ ofꢀ specificꢀ activeꢀ species,ꢀ
forꢀtheꢀdevelopmentꢀofꢀextremelyꢀefficientꢀheterogeneousꢀcata‐
lystsꢀ withꢀ applicationsꢀ toꢀ variousꢀ organicꢀ transformationsꢀ
[22–25].ꢀ ꢀ
Carbon–carbonꢀ bondꢀ formingꢀ reactionsꢀ catalyzedꢀ byꢀ Pdꢀ
species,ꢀ suchꢀ asꢀ theꢀ Suzuki,ꢀ Heckꢀ andꢀ Sonogashiraꢀ couplings,ꢀ
haveꢀbeenꢀextremelyꢀimportantꢀinꢀtheꢀsynthesisꢀofꢀpharmaceu‐
ticalsꢀandꢀfunctionalizedꢀmaterialsꢀforꢀsomeꢀtimeꢀnowꢀ[1–8].ꢀToꢀ
promoteꢀtheseꢀcouplings,ꢀaꢀwideꢀrangeꢀofꢀhomogeneousꢀcata‐
lyticꢀ systemsꢀ haveꢀ beenꢀ developed,ꢀ someꢀ ofꢀ whichꢀ haveꢀ
achievedꢀwidespreadꢀacceptanceꢀdueꢀtoꢀtheirꢀsuperiorꢀselectiv‐
ityꢀandꢀactivity,ꢀsuchꢀthatꢀseveralꢀhaveꢀfoundꢀindustrialꢀapplica‐
tions.ꢀDespiteꢀtheseꢀachievements,ꢀtheꢀcommonꢀusageꢀofꢀsuchꢀ
couplingꢀreactionsꢀinꢀindustrialꢀprocessesꢀhasꢀoftenꢀbeenꢀhin‐
deredꢀbyꢀtheꢀcomplicatedꢀnatureꢀofꢀtheꢀsyntheticꢀprocessesꢀandꢀ
theꢀ difficultlyꢀ inꢀ recyclingꢀ theꢀ catalystꢀ [9,10].ꢀ Toꢀ overcomeꢀ
theseꢀissues,ꢀaꢀseriesꢀofꢀPd‐basedꢀheterogeneousꢀcatalystsꢀhaveꢀ
beenꢀdeveloped,ꢀusingꢀaꢀvarietyꢀofꢀinsolubleꢀsupports,ꢀsuchꢀasꢀ
thoseꢀ basedꢀ onꢀ carbonꢀ andꢀ silicaꢀ [11,12].ꢀ However,ꢀ carbonꢀ
Moreꢀrecently,ꢀweꢀhaveꢀshownꢀthatꢀtheꢀstable,ꢀporousꢀPOPꢀ
polydivinylbenzeneꢀ(PDVB)ꢀcanꢀfunctionꢀasꢀaꢀpowerful,ꢀinsolu‐
bleꢀsupportꢀforꢀtheꢀfunctionalizationꢀofꢀcatalyticallyꢀactiveꢀspe‐
*ꢀCorrespondingꢀauthor.ꢀTel/Fax:ꢀ+86‐571‐88273698;ꢀE‐mail:ꢀmengxj@zju.edu.cnꢀ
ThisꢀworkꢀwasꢀsupportedꢀbyꢀtheꢀNationalꢀNaturalꢀFoundationꢀofꢀChinaꢀ(21422306,ꢀ21203165,ꢀ21403193)ꢀandꢀtheꢀFundamentalꢀResearchꢀFundsꢀforꢀ
theꢀCentralꢀUniversitiesꢀ(2015XZZX004‐04).ꢀ
DOI:ꢀ10.1016/S1872‐2067(15)60952‐4ꢀ|ꢀhttp://www.sciencedirect.com/science/journal/18722067ꢀ|ꢀChin.ꢀJ.ꢀCatal.,ꢀVol.ꢀ37,ꢀNo.ꢀ1,ꢀJanuaryꢀ2016ꢀ ꢀ ꢀ

ꢀ
ZhifengꢀDaiꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ54–60ꢀ
55ꢀ
ciesꢀasꢀheterogeneousꢀcatalystsꢀ[26].ꢀInꢀtheꢀpresentꢀwork,ꢀtheꢀ
rationalꢀsynthesisꢀofꢀaꢀPOPꢀcontainingꢀphenanthrolineꢀligandsꢀ
wasꢀ attempted,ꢀ throughꢀ theꢀ copolymerizationꢀ ofꢀ divinylben‐
zeneꢀandꢀvinyl‐functionalizedꢀphenanthrolineꢀmonomersꢀunderꢀ
solvothermalꢀ conditions.ꢀ Theꢀ phenanthrolineꢀ ligandꢀ wasꢀ se‐
lectedꢀowingꢀtoꢀitsꢀstrongꢀmetalꢀcoordinationꢀabilityꢀandꢀrela‐
tivelyꢀ highꢀ chemicalꢀ stabilityꢀ [27–31].ꢀ Afterꢀ metalationꢀ withꢀ
Scanningꢀ electronꢀ microscopyꢀ (SEM)ꢀ wasꢀ performedꢀ usingꢀ aꢀ
Hitachiꢀ SU1510ꢀ andꢀ SU4800ꢀ andꢀ transmissionꢀ electronꢀ mi‐
croscopyꢀ(TEM)ꢀwasꢀcarriedꢀoutꢀwithꢀaꢀHitachiꢀHT‐7700.ꢀX‐rayꢀ
photoelectronꢀspectroscopyꢀ(XPS)ꢀspectraꢀwereꢀacquiredꢀonꢀaꢀ
ThermoꢀESCALABꢀ250ꢀwithꢀAlꢀKꢀirradiationꢀatꢀθꢀ=ꢀ90°ꢀandꢀtheꢀ
bindingꢀenergiesꢀwereꢀcalibratedꢀusingꢀtheꢀC1sꢀpeakꢀatꢀ284.9ꢀ
eV.ꢀICP‐OESꢀanalysisꢀwasꢀperformedꢀwithꢀaꢀPerkinElmerꢀplas‐
1
2
Pd(OAc) ,ꢀtheꢀresultingꢀheterogeneousꢀcatalystꢀexhibitedꢀexcel‐
maꢀ 40ꢀ emissionꢀspectrometerꢀandꢀ HꢀNMRꢀspectraꢀwereꢀrec‐
lentꢀactivityꢀandꢀrecyclabilityꢀduringꢀtheꢀSuzuki,ꢀHeckꢀandꢀSo‐
nogashiraꢀcouplingꢀreactions.ꢀ
ordedꢀonꢀaꢀBrukerꢀAvance‐400ꢀ(400ꢀMHz)ꢀspectrometer,ꢀwithꢀ
chemicalꢀshiftsꢀexpressedꢀinꢀppmꢀdownfieldꢀfromꢀTMSꢀatꢀδꢀ=ꢀ0ꢀ
13
ppm.ꢀ Cꢀ(100.5ꢀMHz)ꢀmagicꢀangleꢀspinningꢀ(MAS)ꢀNMRꢀspectraꢀ
wereꢀ recordedꢀ onꢀ aꢀ Varianꢀ infinityꢀ plusꢀ 400ꢀ spectrometerꢀ
2.ꢀ ꢀ Experimentalꢀ ꢀ
equippedꢀwithꢀaꢀmagicꢀangleꢀspinꢀprobeꢀandꢀaꢀ4‐mmꢀZrO
2
ꢀrotor.ꢀ
2.1.ꢀ ꢀ Sampleꢀsynthesisꢀ ꢀ
2.3.ꢀ ꢀ Catalyticꢀtestsꢀ ꢀ
Solventsꢀ wereꢀ purifiedꢀ accordingꢀ toꢀ standardꢀ laboratoryꢀ
methods;ꢀTHFꢀwasꢀdistilledꢀoverꢀsodium/benzophenone,ꢀDMFꢀ
wasꢀdistilledꢀoverꢀcalciumꢀhydride,ꢀandꢀCHCl ꢀwasꢀdistilledꢀoverꢀ
anhydrousꢀCaCl .ꢀDivinylbenzeneꢀ(DVB),ꢀazobisisobutyronitrileꢀ
AIBN)ꢀandꢀethylbenzeneꢀwereꢀobtainedꢀfromꢀTianjinꢀGuangfuꢀ
Chemicalꢀ Reagents,ꢀ whereasꢀ 1,10‐phenanthrolineꢀ monohy‐
drate,ꢀ Pd(OAc) ,ꢀ bromobenzene,ꢀ phenylboronicꢀ acid,ꢀ phenyla‐
InꢀaꢀtypicalꢀSuzukiꢀcoupling,ꢀ1ꢀmmolꢀhalide,ꢀ1.2ꢀmmolꢀphe‐
nylboronicꢀ acid,ꢀ 1.5ꢀ mmolꢀ K PO ·3H O,ꢀ 0.01ꢀ gꢀ catalyst,ꢀ 3ꢀ mLꢀ
waterꢀandꢀ2ꢀmLꢀethanolꢀwereꢀreactedꢀatꢀ80–120ꢀ°Cꢀwithꢀcon‐
stantꢀstirring.ꢀAꢀtypicalꢀHeckꢀcouplingꢀusedꢀ1ꢀmmolꢀhalide,ꢀ1.2ꢀ
3
3
4
2
2
(
mmolꢀvinylicꢀsubstrate,ꢀ1.5ꢀmmolꢀK
3
PO
4
·3H O,ꢀ0.01ꢀgꢀcatalystꢀ
2
2
andꢀ5ꢀmLꢀNMPꢀ(1‐methy‐2‐pyrrolidinone)ꢀatꢀ130–140ꢀ°C.ꢀInꢀaꢀ
typicalꢀ Sonogashiraꢀ coupling,ꢀ 1ꢀ mmolꢀ halide,ꢀ 1.2ꢀ mmolꢀ ben‐
cetyleneꢀandꢀethylꢀacrylateꢀwereꢀpurchasedꢀfromꢀtheꢀAladdinꢀ
Company,ꢀLtd.ꢀ ꢀ
zyne,ꢀ1.5ꢀmmolꢀK
3
PO
4
·3H O,ꢀ0.01ꢀgꢀcatalystꢀandꢀ5ꢀmLꢀsolventꢀ
2
AsꢀshownꢀinꢀSchemeꢀ1,ꢀaꢀPOPꢀcontainingꢀphenanthrolineꢀ
ligandsꢀ(POP‐Phen)ꢀwasꢀsynthesizedꢀbyꢀtheꢀcopolymerizationꢀ
ofꢀDVBꢀwithꢀvinyl‐functionalizedꢀphenanthrolineꢀmonomers.ꢀ
Inꢀaꢀtypicalꢀreaction,ꢀ2.0ꢀgꢀDVBꢀandꢀ0.5ꢀgꢀvinyl‐functionalizedꢀ
wereꢀusedꢀatꢀ120–140ꢀ°C.ꢀAfterꢀeachꢀreaction,ꢀtheꢀcatalystꢀwasꢀ
removedꢀ byꢀ centrifugationꢀ andꢀ analyzedꢀ byꢀ gasꢀ chromatog‐
raphyꢀ(GC‐1690,ꢀKexiaoꢀCo.)ꢀusingꢀaꢀflameꢀionizationꢀdetectorꢀ
andꢀaꢀDB‐1ꢀcapillaryꢀcolumn.ꢀ
1
,10‐phenanthrolineꢀ(V‐Phen)ꢀwereꢀdissolvedꢀinꢀ20ꢀmLꢀDMF,ꢀ
followedꢀ byꢀ theꢀ additionꢀ ofꢀ 0.05ꢀ gꢀ AIBN.ꢀ Theꢀ mixtureꢀ wasꢀ
subsequentlyꢀtransferredꢀtoꢀanꢀautoclaveꢀandꢀheldꢀforꢀ24ꢀhꢀatꢀ
3.ꢀ ꢀ Resultsꢀandꢀdiscussionꢀ ꢀ
3.1.ꢀ ꢀ Characterizationꢀ ꢀ
100ꢀ°C.ꢀAfterꢀwashingꢀwithꢀethanol,ꢀaꢀsolidꢀorangeꢀproductꢀwasꢀ
obtained,ꢀdenotedꢀasꢀPOP‐Phenꢀhereinꢀ[32].ꢀ
Theꢀ Pd‐metalatedꢀ POPꢀ (Pd/POP‐Phen)ꢀ catalystꢀ wasꢀ pre‐
paredꢀbyꢀtreatingꢀtheꢀPOP‐PhenꢀwithꢀPd(OAc)
ꢀinꢀtoluene.ꢀTheꢀ
mixtureꢀ wasꢀ initiallyꢀ stirredꢀ overnightꢀ atꢀ roomꢀ temperature,ꢀ
followedꢀbyꢀfiltrationꢀofꢀtheꢀsolidꢀproductꢀandꢀwashingꢀwithꢀaꢀ
significantꢀ quantityꢀ ofꢀ toluene.ꢀ Afterꢀ dryingꢀ underꢀ vacuumꢀ atꢀ
roomꢀ temperature,ꢀ theꢀ brownꢀ Pd‐supportedꢀ catalystꢀ wasꢀ ob‐
tained.ꢀ Inductivelyꢀ coupledꢀ plasmaꢀ opticalꢀ emissionꢀ spectros‐
copyꢀ(ICP‐OES)ꢀdeterminedꢀthatꢀtheꢀPdꢀloadingꢀinꢀtheꢀpolymerꢀ
wasꢀapproximatelyꢀ5.0%ꢀbyꢀweight.ꢀ
1
3
Figureꢀ1ꢀshowsꢀtheꢀ CꢀMASꢀNMRꢀandꢀIRꢀspectraꢀofꢀtheꢀPDVBꢀ
andꢀ POP‐Phenꢀ samples.ꢀ Inꢀ theꢀ 13Cꢀ MASꢀ NMRꢀ spectraꢀ ofꢀ theꢀ
POP‐Phen,ꢀ twoꢀ peaksꢀ areꢀ seenꢀ atꢀ 163ꢀ andꢀ 175ꢀ ppm,ꢀ bothꢀ ofꢀ
whichꢀareꢀassociatedꢀwithꢀC=OꢀandꢀC=NꢀbondsꢀinꢀtheꢀV‐Phenꢀ
componentꢀ[33–36].ꢀTheꢀIRꢀspectrumꢀofꢀPOP‐Phenꢀdisplaysꢀaꢀ
2
−1
strongꢀbandꢀatꢀ1698ꢀcm ꢀthatꢀisꢀassignedꢀtoꢀtheꢀV‐PhenꢀC=Oꢀ
bondꢀ [32].ꢀ Theseꢀ resultsꢀ indicateꢀ successfulꢀ incorporationꢀ ofꢀ
theꢀ1,10‐phenanthrolineꢀligandꢀintoꢀtheꢀsample.ꢀFurthermore,ꢀ
TGꢀanalysisꢀfoundꢀthatꢀtheꢀmassꢀlossꢀofꢀtheꢀPOP‐Phenꢀoccuredꢀ
aboveꢀ 360ꢀ °C,ꢀ associatedꢀ withꢀ decompositionꢀ ofꢀ theꢀ polymerꢀ
2.2.ꢀ ꢀ Characterizationꢀ ꢀ
skeleton,ꢀ indicatingꢀ itsꢀ superiorꢀ thermalꢀ stability.ꢀ N ꢀsorptionꢀ
2
isothermsꢀrevealedꢀthatꢀbothꢀPOP‐PhenꢀandꢀPd/POP‐Phenꢀ(Fig.ꢀ
2(a))ꢀ generatedꢀ aꢀ hysteresisꢀ loopꢀ overꢀ theꢀ relativeꢀ pressureꢀ
rangeꢀofꢀ0.45ꢀtoꢀ0.95,ꢀdemonstratingꢀtheꢀpresenceꢀofꢀmesoporesꢀ
inꢀtheꢀsamples.ꢀTheꢀsampleꢀporeꢀsizesꢀwereꢀprimarilyꢀdistrib‐
Nitrogenꢀsorptionꢀisothermsꢀatꢀ−196ꢀ°Cꢀwereꢀacquiredꢀusingꢀ
MicromeriticsꢀASAPꢀ2020MꢀandꢀTristarꢀsystems.ꢀTheꢀsamplesꢀ
wereꢀoutgassedꢀforꢀ10ꢀhꢀatꢀ100ꢀ°Cꢀpriorꢀtoꢀtheseꢀmeasurements.ꢀ
Schemeꢀ1.ꢀStructureꢀandꢀsyntheticꢀproceduresꢀforꢀtheꢀpreparationꢀofꢀPd/PCP‐Phen.ꢀ

56ꢀ
ZhifengꢀDaiꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ54–60ꢀ
(a)
(b)
(2)
163
175
1698
(
2) *
*
*
(1)
(
1)
*
1500
1600
1700
1800
0
50
100
150
200
250

1

Wavenumber (cm )
13
Fig.ꢀ1.ꢀ CꢀMASꢀNMRꢀ(a)ꢀandꢀIRꢀspectraꢀ(b)ꢀofꢀPDVBꢀ(1)ꢀandꢀPOP‐Phenꢀsamplesꢀ(2).ꢀ
(
a)
600
500
400
300
200
100
0
(b)
(2)
(
2)
(1)
(1)
0
.0
0.2
Relative pressure (p/p
ꢀsorptionꢀisothermsꢀ(a)ꢀandꢀporeꢀsizeꢀdistributionsꢀ(b)ꢀofꢀPOP‐Phenꢀ(1)ꢀandꢀPd/POP‐Phenꢀ(2)ꢀsamples.ꢀTheꢀPd/POP‐Phenꢀisothermꢀandꢀporeꢀ
0.4
0.6
0.8
1.0
0
50
100
150
0
)
Pore diamiter (nm)
Fig.ꢀ2.ꢀN
sizeꢀdistributionꢀhaveꢀbeenꢀoffsetꢀbyꢀ300ꢀcm /gꢀandꢀ0.70ꢀcm /gꢀalongꢀtheꢀverticalꢀaxis,ꢀrespectively,ꢀforꢀclarity.ꢀ
2
3
3
utedꢀ aroundꢀ meansꢀ ofꢀ 11.2ꢀ andꢀ 7.3ꢀ nmꢀ inꢀ theꢀ POP‐Phenꢀ andꢀ
Pd/POP‐Phen,ꢀ respectivelyꢀ (Fig.ꢀ 2(b)),ꢀ asꢀ calculatedꢀ byꢀ theꢀ
Barrett–Joyner–Halendaꢀ(BJH)ꢀmethod.ꢀTheꢀBETꢀsurfaceꢀareasꢀ
viously,ꢀtheꢀpresenceꢀofꢀmesoporousꢀstructuresꢀinꢀtheꢀsamplesꢀ
isꢀbeneficialꢀwithꢀregardꢀtoꢀmassꢀtransferꢀduringꢀreaction.ꢀ
Figureꢀ4ꢀpresentsꢀXPSꢀdata,ꢀinꢀwhichꢀtheꢀPd/POP‐Phenꢀsam‐
pleꢀisꢀseenꢀtoꢀgenerateꢀPdꢀ3d5/2ꢀandꢀPdꢀ3d3/2ꢀpeaksꢀatꢀ337.6ꢀandꢀ
2
ofꢀtheꢀspecimensꢀwereꢀestimatedꢀtoꢀbeꢀ574ꢀandꢀ462ꢀm /g.ꢀSEMꢀ
(Figs.ꢀ3(a,ꢀb))ꢀandꢀTEMꢀimagesꢀ(Figs.ꢀ3(c,ꢀd))ꢀofꢀtheꢀPOP‐Phenꢀ
343.1ꢀeꢀV,ꢀvaluesꢀthatꢀareꢀlowerꢀthanꢀthoseꢀofꢀPd(OAc) ꢀ(338.6ꢀ
2
andꢀPd/POP‐Phenꢀgiveꢀdirectꢀevidenceꢀofꢀtheꢀabundantꢀmeso‐
andꢀ 343.8ꢀ eV,ꢀ Fig.ꢀ 4(a)).ꢀ Atꢀ theꢀ sameꢀ time,ꢀ theꢀ Pd/POP‐Phenꢀ
sampleꢀexhibitsꢀanꢀNꢀ1sꢀpeakꢀatꢀ400.0ꢀeVꢀthatꢀisꢀobviouslyꢀlo‐
catedꢀ higherꢀ thanꢀ thatꢀ ofꢀ theꢀ POP‐Phenꢀ (399.3ꢀ eV,ꢀ Fig.ꢀ 4(b)).ꢀ
Theseꢀ resultsꢀ stronglyꢀ supportꢀ coordinationꢀ betweenꢀ
porosity,ꢀinꢀgoodꢀagreementꢀwithꢀtheꢀN
2
ꢀsorptionꢀresults.ꢀOb‐
(a)
(b)
1,10‐phenanthrolineꢀmoietiesꢀinꢀtheꢀPOP‐PhenꢀandꢀPdꢀspeciesꢀ
[29].ꢀ ꢀ
3.2.ꢀ ꢀ Evaluationꢀofꢀcatalyticꢀperformanceꢀ ꢀ
Tableꢀ1ꢀpresentsꢀtheꢀSuzuki,ꢀSonogashiraꢀandꢀHeckꢀcouplingꢀ
reactionꢀ resultsꢀ overꢀ theꢀ Pd/POP‐Phenꢀ catalyst.ꢀ Duringꢀ theꢀ
Suzukiꢀcoupling,ꢀwhenꢀbromobenzeneꢀandꢀphenylboronicꢀacidꢀ
wereꢀusedꢀasꢀtheꢀreactantsꢀandꢀaꢀmixtureꢀofꢀethanolꢀandꢀwaterꢀ
wasꢀemployedꢀasꢀtheꢀsolvent,ꢀaꢀveryꢀhighꢀyieldꢀofꢀbiphenylꢀ(>ꢀ
(c)
(d)
99%)ꢀwasꢀobtainedꢀinꢀaꢀshortꢀreactionꢀtimeꢀ(30ꢀmin,ꢀentryꢀ1).ꢀ
Inꢀcontrast,ꢀtheꢀcorrespondingꢀPd‐basedꢀhomogeneousꢀcatalystꢀ
showedꢀ aꢀ veryꢀ lowꢀ yieldꢀ (1.7%)ꢀ underꢀ theꢀ sameꢀ conditionsꢀ
(entryꢀ2).ꢀTheseꢀresultsꢀindicateꢀthatꢀtheꢀPd/POP‐Phenꢀcatalystꢀ
Fig.ꢀ 3.ꢀ SEMꢀ (a,ꢀ b)ꢀ andꢀ TEMꢀ (c,ꢀ d)ꢀ imagesꢀ ofꢀ POP‐Phenꢀ (a,ꢀ c)ꢀ andꢀ
Pd/POP‐Phenꢀ(b,ꢀd)ꢀsamples.ꢀ
isꢀ veryꢀ activeꢀ forꢀ Suzukiꢀ coupling.ꢀ Moreꢀ importantly,ꢀ theꢀ
Pd/POP‐Phenꢀ catalystꢀ exhibitedꢀ excellentꢀ recyclability.ꢀ Afterꢀ

ꢀ
ZhifengꢀDaiꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ54–60ꢀ
57ꢀ
(b)
(a)
338.6
400
343.8
(2)
399.3
(3)
337.6
343.1
(1)
(2)
332
336
340
344
348
390
395
400
405
410
Binding energy (eV)
Binding energy (eV)
Fig.ꢀ4.ꢀPdꢀ3dꢀ(a)ꢀandꢀNꢀ1sꢀ(b)ꢀspectraꢀofꢀPOP‐Phenꢀ(1),ꢀPd/POP‐Phenꢀ(2)ꢀandꢀPd(OAc) ꢀ(3).ꢀ
2
fiveꢀrecyclingꢀtrials,ꢀnoꢀsignificantꢀlossꢀofꢀtheꢀcatalyticꢀactivityꢀ
wasꢀ observedꢀ (entryꢀ 3).ꢀ Inꢀ addition,ꢀ noꢀ residualꢀ Pdꢀ speciesꢀ
wereꢀ detectedꢀ inꢀ theꢀ filteredꢀ reactionꢀ mixtureꢀ (resultsꢀ belowꢀ
theꢀ limitꢀ ofꢀ detectionꢀ ofꢀ theꢀ ICP‐OESꢀ analysis,ꢀ <10ꢀ ppb),ꢀ sug‐
gestingꢀthatꢀthereꢀwasꢀnoꢀleachingꢀofꢀPdꢀfromꢀtheꢀcatalyst.ꢀThisꢀ
resultꢀmayꢀbeꢀreasonablyꢀattributedꢀtoꢀtheꢀstrongꢀcoordinationꢀ
betweenꢀ theꢀ Pdꢀ speciesꢀ andꢀ theꢀ phenanthrolineꢀ moieties,ꢀ asꢀ
observedꢀinꢀFig.ꢀ4.ꢀ
Tableꢀ1ꢀ
ꢀa
ResultsꢀofꢀSuzuki,ꢀSonogashiraꢀandꢀHeckꢀcouplingsꢀoverꢀtheꢀPd/POP‐Phenꢀcatalyst .ꢀ
ꢀ
ꢀ
b
ꢀb
Reactionꢀ
Entryꢀ
1ꢀ
Arylꢀhalideꢀ
ꢀ
Couplingꢀsubstrate Yield ꢀ(%) Reaction Entryꢀ
Arylꢀhalideꢀ
Couplingꢀsubstrate Yield ꢀ(%)
ꢀ
d
Suzukiꢀ
99ꢀ
ꢀ ꢀ ꢀ 1.7ꢀ
97ꢀ
ꢀ
16 ꢀ
17ꢀ
95ꢀ
99ꢀ
99ꢀ
98ꢀ
96ꢀ
99ꢀ
99ꢀ
99ꢀ
99ꢀ
43ꢀ
99ꢀ
99ꢀ
99ꢀ
97ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
c
Br
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
2 ꢀ
ꢀ
ꢀ
ꢀ
d
3 ꢀ
4ꢀ
ꢀ
18ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
g
95ꢀ
ꢀ
19 ꢀ
ꢀg
5ꢀ
96ꢀ
ꢀ
20 ꢀ
21ꢀ
22ꢀ
23ꢀ
24ꢀ
25cꢀ
6ꢀ
99ꢀ
Heckꢀ
7ꢀ
99ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
e
8 ꢀ
98ꢀ
ꢀ
ꢀ
ꢀ
e
9 ꢀ
94ꢀ
ꢀ
e
ꢀ
ꢀ
ꢀ
ꢀ
10 ꢀ
99ꢀ
ꢀ
ꢀ
ꢀ
f
ꢀd
11 ꢀ
24ꢀ
26 ꢀ
ꢀ
f
ꢀg
12 ꢀ
32ꢀ
27 ꢀ
ꢀ
ꢀ
ꢀ
f
ꢀg
13 ꢀ
34ꢀ
28 ꢀ
ꢀ
ꢀ
ꢀ
ꢀg
Sonogashiraꢀ 14ꢀ
99ꢀ
29 ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
c
ꢀ
15 ꢀ
93ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
aꢀ
Suzukiꢀconditions:ꢀhalide1ꢀmmol,ꢀphenylboronicꢀacidꢀ1.2ꢀmmol,ꢀK
3 4 2
PO ·3H Oꢀ2ꢀmmol,ꢀcatalystꢀ0.01ꢀg,ꢀwaterꢀ3ꢀmL,ꢀethanolꢀ2ꢀmL,ꢀ80ꢀ°C,ꢀ30ꢀmin;ꢀSo‐
3 4 2
nogashiraꢀconditions:ꢀhalideꢀ1ꢀmmol,ꢀbenzyneꢀ1.2ꢀmmol,ꢀK PO ·3H Oꢀ1.5ꢀmmol,ꢀcatalystꢀ0.01ꢀg,ꢀbutanolꢀ5ꢀmL,ꢀ120ꢀ°C,ꢀ30ꢀmin;ꢀHeckꢀconditions:ꢀhalideꢀ
1
ꢀmmol,ꢀvinylicꢀsubstrateꢀ1.2ꢀmmol,ꢀK
3
PO
4
·3H Oꢀ1.5ꢀmmol,ꢀcatalystꢀ0.01ꢀg,ꢀNMPꢀ(1‐methy‐2‐pyrrolidinone)ꢀ5ꢀmL,ꢀ130ꢀ°C,ꢀ20ꢀmin.ꢀ
2
bꢀ
GCꢀyield.ꢀ
1
cꢀ
2
ꢀmgꢀPd(OAc) ꢀandꢀ0.9ꢀmgꢀ1,10‐phenanthrolineꢀasꢀaꢀhomogeneousꢀcatalyst.ꢀ
dꢀ
eꢀ
Recycledꢀfiveꢀtimes.ꢀ
Reactionꢀtimeꢀ20ꢀmin.ꢀ
fꢀ
Reactionꢀconditions:ꢀhalideꢀ1ꢀmmol,ꢀphenylboronicꢀacidꢀ1.2ꢀmmol,ꢀKOHꢀ2ꢀmmol,ꢀcatalystꢀ0.05ꢀg,ꢀwaterꢀ5ꢀmL,ꢀ120ꢀ°C,ꢀ2ꢀh.ꢀ
gꢀ140ꢀ°C,ꢀ30ꢀmin.ꢀ

58ꢀ
ZhifengꢀDaiꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ54–60ꢀ
Aꢀ seriesꢀ ofꢀ substratesꢀ wasꢀ appliedꢀ toꢀ theꢀ Suzukiꢀ couplingꢀ
theꢀcorrespondingꢀhomogeneousꢀcatalystꢀ(entryꢀ25).ꢀWhenꢀarylꢀ
bromidesꢀwereꢀemployed,ꢀtheꢀyieldsꢀwereꢀstillꢀinꢀtheꢀrangeꢀofꢀ
97%–99%ꢀafterꢀ30ꢀminꢀ(entriesꢀ28ꢀandꢀ29).ꢀTheꢀcatalystꢀwasꢀ
alsoꢀfound,ꢀonceꢀagain,ꢀtoꢀbeꢀrecyclableꢀandꢀproducedꢀaꢀyieldꢀofꢀ
99%ꢀfollowingꢀfiveꢀrecyclingꢀtrialsꢀ(entryꢀ26).ꢀ
reactionꢀoverꢀtheꢀPd/POP‐Phenꢀcatalystꢀ(Tableꢀ1,ꢀentriesꢀ4‐13).ꢀ
Notably,ꢀ theꢀ useꢀ ofꢀ arylꢀ bromidesꢀ generatedꢀ excellentꢀ yieldsꢀ
fromꢀ bothꢀ electron‐poorꢀ andꢀ electron‐richꢀ reagentsꢀ
(
94%–99%,ꢀentriesꢀ4–10).ꢀHowever,ꢀinꢀtheꢀcaseꢀofꢀtheꢀlessꢀre‐
activeꢀarylꢀchlorides,ꢀtheꢀcatalyticꢀactivityꢀofꢀtheꢀPd/POP‐Phenꢀ
wasꢀ insufficient,ꢀ affordingꢀ relativelyꢀ lowꢀ yieldsꢀ (24%–34%)ꢀ
evenꢀwhenꢀtheꢀreactionsꢀwereꢀcarriedꢀoutꢀatꢀaꢀhigherꢀtempera‐
tureꢀ (120ꢀ °C),ꢀ overꢀ aꢀ longerꢀ reactionꢀ timeꢀ (2ꢀ h)ꢀ andꢀ withꢀ aꢀ
higherꢀcatalystꢀloadingꢀ(0.05ꢀg,ꢀentriesꢀ11–13).ꢀTherefore,ꢀsomeꢀ
limitationsꢀstillꢀremainꢀregardingꢀtheꢀSuzukiꢀreactionꢀcatalyzedꢀ
byꢀtheꢀPd/POP‐Phenꢀcatalyst.ꢀ
InꢀSonogashiraꢀcoupling,ꢀtheꢀPd/POP‐Phenꢀcatalystꢀwasꢀalsoꢀ
foundꢀtoꢀbeꢀveryꢀactive.ꢀUsingꢀiodobenzeneꢀasꢀtheꢀsubstrate,ꢀaꢀ
yieldꢀofꢀ99%ꢀwasꢀobtainedꢀ(entryꢀ14).ꢀThisꢀvalueꢀisꢀsomewhatꢀ
higherꢀthanꢀtheꢀyieldꢀofꢀ93%ꢀobtainedꢀfromꢀtheꢀcorrespondingꢀ
homogeneousꢀcatalystꢀ(entryꢀ15).ꢀInꢀaddition,ꢀiodotolueneꢀandꢀ
iodoanisoleꢀbothꢀgaveꢀyieldsꢀofꢀ99%ꢀ(entriesꢀ17ꢀandꢀ18)ꢀand,ꢀ
whenꢀ arylꢀ bromidesꢀ wereꢀ employedꢀ asꢀ substrates,ꢀ theꢀ yieldsꢀ
wereꢀ asꢀ highꢀ asꢀ 96%–99%ꢀ evenꢀ inꢀ theꢀ absenceꢀ ofꢀ theꢀ CuIꢀ
co‐catalystꢀ (entriesꢀ 19ꢀ andꢀ 20).ꢀ Theꢀ absenceꢀ ofꢀ theꢀ CuIꢀ com‐
pletelyꢀ avoidsꢀ theꢀ formationꢀ ofꢀ theꢀ diyneꢀ by‐productꢀ thatꢀ isꢀ
usuallyꢀformedꢀfromꢀanꢀacetyleneꢀhomocouplingꢀsideꢀreactionꢀ
ItꢀisꢀworthꢀnotingꢀthatꢀtheꢀPd/POP‐Phenꢀheterogeneousꢀcat‐
alystꢀ exhibitedꢀ higherꢀ activitiesꢀ thanꢀ theꢀ homogeneousꢀ
Pd/Phenꢀcatalystꢀinꢀtheseꢀreactions,ꢀwhichꢀmayꢀbeꢀattributedꢀtoꢀ
theꢀdifferencesꢀinꢀtheꢀreactantꢀconcentrationsꢀbetweenꢀtheꢀcat‐
alysts.ꢀInꢀtheꢀcaseꢀofꢀtheꢀheterogeneousꢀcatalyst,ꢀtheꢀcatalyticꢀ
materialꢀisꢀhighlyꢀporous,ꢀresultingꢀinꢀaꢀmuchꢀhigherꢀreactantꢀ
concentrationꢀinꢀtheꢀcatalystꢀporesꢀcomparedꢀwithꢀthatꢀonꢀtheꢀ
homogeneousꢀ catalyst.ꢀ Duringꢀ theꢀ Suzukiꢀ coupling,ꢀ forꢀ exam‐
ple,ꢀ theꢀ bromobenzeneꢀ concentrationꢀ inꢀ theꢀ poresꢀ ofꢀ theꢀ
Pd/POP‐Phenꢀcatalystꢀwasꢀalmostꢀ14ꢀtimesꢀtheꢀconcentrationꢀ
inꢀtheꢀPd/Phenꢀsystem.ꢀ Accordingꢀtoꢀtheꢀ Arrheniusꢀequation,ꢀ
higherꢀreactantꢀconcentrationsꢀshouldꢀgiveꢀriseꢀtoꢀhigherꢀcata‐
lyticꢀactivity,ꢀwhichꢀisꢀconsistentꢀwithꢀpreviouslyꢀreportedꢀre‐
sultsꢀ[40].ꢀ
4.ꢀ ꢀ Conclusionsꢀ ꢀ
Inꢀsummary,ꢀaꢀnovelꢀstrategyꢀforꢀtheꢀpreparationꢀofꢀhighlyꢀ
efficientꢀ Pd‐basedꢀ heterogeneousꢀ catalystsꢀ usingꢀ porousꢀ or‐
ganicꢀ polymersꢀ containingꢀ phenanthrolineꢀ moietiesꢀ hasꢀ beenꢀ
demonstrated.ꢀThisꢀcatalystꢀnotꢀonlyꢀexhibitsꢀexcellentꢀcatalyticꢀ
activityꢀbutꢀalsoꢀoutstandingꢀstabilityꢀasꢀwellꢀasꢀsuperiorꢀrecy‐
clabilityꢀ inꢀ Suzuki,ꢀ Sonogashiraꢀ andꢀ Heckꢀ couplings.ꢀ Theseꢀ
characteristicsꢀareꢀimportantꢀwithꢀregardꢀtoꢀdevelopingꢀpracti‐
calꢀsynthesesꢀofꢀfineꢀchemicalsꢀinꢀtheꢀfuture.ꢀ
[37–39].ꢀAfterꢀfiveꢀrecyclingꢀtrials,ꢀaꢀyieldꢀofꢀ95%ꢀcouldꢀstillꢀbeꢀ
obtainedꢀfromꢀtheꢀcatalystꢀ(entryꢀ16).ꢀ
InꢀtheꢀcaseꢀofꢀHeckꢀcoupling,ꢀtheꢀPd/POP‐Phenꢀcatalystꢀonceꢀ
againꢀexhibitedꢀveryꢀhighꢀactivityꢀandꢀselectivity.ꢀAsꢀanꢀexam‐
ple,ꢀarylꢀiodidesꢀcouldꢀbeꢀfullyꢀconvertedꢀoverꢀshortꢀtimeꢀinter‐
valsꢀofꢀ20ꢀtoꢀ30ꢀmin,ꢀgivingꢀyieldsꢀupꢀtoꢀ99%ꢀ(entriesꢀ21–24ꢀandꢀ
27).ꢀTheseꢀvaluesꢀareꢀobviouslyꢀhigherꢀthanꢀthatꢀobtainedꢀfromꢀ
GraphicalꢀAbstractꢀ
Chin.ꢀJ.ꢀCatal.,ꢀ2016,ꢀ37:ꢀ54–60ꢀ ꢀ ꢀ doi:ꢀ10.1016/S1872‐2067(15)60952‐4
AꢀPd‐metalatedꢀporousꢀorganicꢀpolymerꢀasꢀaꢀhighlyꢀefficientꢀheterogeneousꢀcatalystꢀforꢀC–Cꢀcouplingsꢀ
ꢀ
ZhifengꢀDai,ꢀFangꢀChen,ꢀQiꢀSun,ꢀYanyanꢀJi,ꢀLiangꢀWang,ꢀXiangjuꢀMeng*,ꢀFeng‐ShouꢀXiaoꢀ
ZhejiangꢀUniversityꢀ
R
X +
B(OH)2
R
*
*
*
O
*
HN
N
*
N
R
X
+
Pd
R
H3CCOO
OOCCH3
R2
R1
X
+
R2
R1
ꢀ
AꢀPd‐metalatedꢀporousꢀpolymerꢀbearingꢀphenanthrolineꢀmoietiesꢀ(Pd/POP‐Phen)ꢀexhibitsꢀhighꢀactivities,ꢀexcellentꢀselectivitiesꢀandꢀsupe‐
riorꢀrecyclabilitiesꢀinꢀSuzuki,ꢀSonogashiraꢀandꢀHeckꢀcouplings.ꢀ

ꢀ
ZhifengꢀDaiꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ54–60ꢀ
59ꢀ
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