Pd-isatin Schiff base complex immobilized on γ-Fe2O3 as a magnetically recyclable catalyst for the Heck and Suzuki cross-coupling reactions

Article abstract of DOI:10.1016/S1872-2067(14)60291-6

A Pd-isatin Schiff base complex immobilized on γ-Fe₂O₃ (Pd-isatin Schiff base-γ-Fe₂O₃) was synthesized and characterized by Fourier transform infrared, scanning electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, thermogravimetric gravimetric analysis, inductively-coupled plasma, X-ray photoelectron spectroscopy, and elemental analysis. It was used as a magnetically reusable Pd catalyst for the Heck and Suzuki cross-coupling reactions.

Full text of DOI:10.1016/S1872-2067(14)60291-6

ChineseꢀJournalꢀofꢀCatalysisꢀ36ꢀ(2015)ꢀ555–563
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ꢀ ꢀ ꢀ
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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
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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
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ꢀ
Article
Pd‐isatinꢀSchiffꢀbaseꢀcomplexꢀimmobilizedꢀonꢀγ‐Fe O3ꢀasꢀaꢀ ꢀ
2
magneticallyꢀrecyclableꢀcatalystꢀforꢀtheꢀHeckꢀandꢀSuzukiꢀ
cross‐couplingꢀreactionsꢀ ꢀ
ꢀ
SaraꢀSobhani*,ꢀFarzanehꢀZarifi
ꢀ
DepartmentꢀofꢀChemistry,ꢀCollegeꢀofꢀSciences,ꢀUniversityꢀofꢀBirjand,ꢀBirjand,ꢀIranꢀ
A R T I C L E ꢀ I N F O ꢀ
A B S T R A C T ꢀ
Articleꢀhistory:ꢀ
AꢀPd‐isatinꢀSchiffꢀbaseꢀcomplexꢀimmobilizedꢀonꢀγ‐Fe
2
O
3ꢀ(Pd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O )ꢀwasꢀsynthe‐
3
Receivedꢀ15ꢀNovemberꢀ2014ꢀ
Acceptedꢀ8ꢀJanuaryꢀ2015ꢀ
Publishedꢀ20ꢀAprilꢀ2015ꢀ
sizedꢀandꢀcharacterizedꢀbyꢀFourierꢀtransformꢀinfrared,ꢀscanningꢀelectronꢀmicroscopy,ꢀhighꢀresolu‐
tionꢀtransmissionꢀelectronꢀmicroscopy,ꢀX‐rayꢀdiffraction,ꢀthermogravimetricꢀgravimetricꢀanalysis,
inductively‐coupledꢀplasma,ꢀX‐rayꢀphotoelectronꢀspectroscopy,ꢀandꢀelementalꢀanalysis.ꢀItꢀwasꢀusedꢀ
asꢀaꢀmagneticallyꢀreusableꢀPdꢀcatalystꢀforꢀtheꢀHeckꢀandꢀSuzukiꢀcross‐couplingꢀreactions.ꢀ
©
ꢀ2015,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences.
Keywords:ꢀ
Heterogeneousꢀcatalystꢀ
Palladiumꢀ
PublishedꢀbyꢀElsevierꢀB.V.ꢀAllꢀrightsꢀreserved.
Ironꢀoxideꢀ
HeckꢀandꢀSuzukiꢀcross‐couplingꢀ
reactions
1.ꢀ ꢀ Introductionꢀ
showꢀhighꢀcatalyticꢀactivity,ꢀpossessꢀhighꢀthermalꢀandꢀmechan‐
icalꢀstabilityꢀandꢀcanꢀbeꢀusedꢀforꢀlargeꢀscaleꢀproductionꢀ[12].ꢀ
Magneticꢀ ironꢀ oxideꢀ nanoparticlesꢀ haveꢀ receivedꢀ aꢀ greatꢀ
Transitionꢀ metal‐catalyzedꢀ carbon‐carbonꢀ andꢀ carbon‐
het‐
ꢀ
dealꢀ ofꢀ attentionꢀ becauseꢀ ofꢀ theirꢀ uniqueꢀ physicochemicalꢀ
characteristicsꢀ [1]ꢀ andꢀ wideꢀ rangeꢀ ofꢀ applicationsꢀ inꢀ proteinꢀ
separationꢀ[2],ꢀmagneticꢀresonanceꢀimagingꢀ(MRI)ꢀ[3,4],ꢀdrugꢀ
deliveryꢀ [5,6],ꢀ andꢀ asꢀ magneticꢀ sensorsꢀ [7]ꢀ andꢀ inꢀ magneticꢀ
refrigerationꢀ[8].ꢀRecentꢀreportsꢀonꢀtheꢀapplicationsꢀofꢀmagnet‐
icꢀnanoparticlesꢀ(MNPs)ꢀhaveꢀfocusedꢀonꢀtheirꢀuseꢀasꢀaꢀpromis‐
ingꢀ supportꢀ forꢀ theꢀ immobilizationꢀ ofꢀ homogeneousꢀ catalystsꢀ
suchꢀ asꢀ metalꢀ complexesꢀ forꢀ organicꢀ transformationꢀ [9].ꢀ Theꢀ
mainꢀinterestꢀinꢀtheꢀsynthesisꢀofꢀsupportedꢀcatalystsꢀonꢀMNPsꢀ
isꢀtoꢀhaveꢀaꢀquickꢀandꢀsimpleꢀprocedureꢀforꢀtheirꢀreuseꢀbyꢀusingꢀ
anꢀexternalꢀmagnetꢀ[10].ꢀThisꢀseparationꢀeliminatesꢀtheꢀneces‐
sityꢀforꢀtediousꢀandꢀtimeꢀconsumingꢀlaboriousꢀseparationꢀstepsꢀ
suchꢀasꢀcentrifugationꢀorꢀfiltrationꢀandꢀallowsꢀpracticalꢀcontin‐
uousꢀ catalysisꢀ [11].ꢀ Moreover,ꢀ catalystsꢀ supportedꢀ onꢀ MNPsꢀ
eroatomꢀ bondꢀ formingꢀ reactionsꢀ [13]ꢀ areꢀ powerfulꢀ toolsꢀ forꢀ
advancedꢀorganicꢀsynthesisꢀinꢀbothꢀacademicꢀ[14]ꢀandꢀindus‐
trialꢀ laboratoriesꢀ [15].ꢀ Inꢀ thisꢀ area,ꢀ Heckꢀ andꢀ Suzukiꢀ
cross‐couplingꢀ reactionsꢀ areꢀ importantꢀ strategiesꢀ forꢀ theꢀ for‐
mationꢀ ofꢀ carbon‐carbonꢀ bonds.ꢀ Theyꢀ areꢀ catalyzedꢀ byꢀ aꢀ ho‐
mogeneousꢀPdꢀcatalystꢀ[16].ꢀTheꢀuseꢀofꢀreadilyꢀavailableꢀstart‐
ingꢀmaterials,ꢀandꢀsimplicityꢀandꢀgeneralityꢀofꢀtheꢀmethodꢀmakeꢀ
theseꢀ cross‐couplingꢀ reactionsꢀ particularlyꢀ attractiveꢀ forꢀ theꢀ
synthesisꢀofꢀaꢀgreatꢀvarietyꢀofꢀcomplexꢀorganicꢀmoleculesꢀsuchꢀ
asꢀ drugs,ꢀ fineꢀ chemicals,ꢀ naturalꢀ products,ꢀ polymers,ꢀ agro‐
chemicals,ꢀandꢀbiologicallyꢀactiveꢀmoleculesꢀ[17,18].ꢀHowever,ꢀ
theseꢀreactionsꢀsufferꢀfromꢀproblemsꢀassociatedꢀwithꢀtheꢀsepa‐
rationꢀandꢀrecoveryꢀofꢀtheꢀhomogeneousꢀcatalystꢀandꢀhighꢀcostꢀ
ofꢀPdꢀwhichꢀmayꢀalsoꢀresultꢀinꢀundesirableꢀmetalꢀcontaminationꢀ
*ꢀCorrespondingꢀauthor.ꢀTel/Fax:ꢀ+98‐56‐32202065;ꢀE‐mail:ꢀssobhani@birjand.ac.ir,ꢀsobhanisara@yahoo.comꢀ
DOI:ꢀ10.1016/S1872‐2067(14)60291‐6ꢀ|ꢀhttp://www.sciencedirect.com/science/journal/18722067ꢀ|ꢀChin.ꢀJ.ꢀCatal.,ꢀVol.ꢀ36,ꢀNo.ꢀ4,ꢀAprilꢀ2015ꢀ ꢀ ꢀ

556ꢀ
SaraꢀSobhaniꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ36ꢀ(2015)ꢀ555–563ꢀ
ofꢀ theꢀ product.ꢀ Therefore,ꢀ toꢀ haveꢀ anꢀ efficientꢀ recoveryꢀ andꢀ
recyclingꢀofꢀtheꢀPdꢀcatalyst,ꢀtheꢀimmobilizationꢀofꢀhomogene‐
ousꢀ Pdꢀ catalyticꢀ systemsꢀ onꢀ differentꢀ supportsꢀ hasꢀ beenꢀ theꢀ
subjectꢀofꢀintenseꢀresearchꢀ[19,20].ꢀOtherꢀchallengeꢀfacingꢀthisꢀ
fieldꢀisꢀtheꢀdesignꢀofꢀcatalystsꢀthatꢀareꢀmoreꢀrobustꢀandꢀefficientꢀ
usingꢀvaluableꢀligandsꢀasꢀstabilizersꢀforꢀPdꢀspeciesꢀ[21].ꢀInꢀtheꢀ
pastꢀ decades,ꢀ theꢀ mostꢀ commonꢀ ligandsꢀ usedꢀ forꢀ theseꢀ
cross‐couplingꢀreactionsꢀhaveꢀbeenꢀtheꢀphosphine‐basedꢀonesꢀ
Theꢀγ‐Fe
30ꢀmin.ꢀ3‐Aminopropyltriethoxysilaneꢀ(3.5ꢀmL,ꢀ13ꢀmmol)ꢀwasꢀ
addedꢀ toꢀ theꢀ dispersedꢀ γ‐Fe 3ꢀ inꢀ tolueneꢀ underꢀ mechanicalꢀ
stirring.ꢀTheꢀmixtureꢀwasꢀslowlyꢀheatedꢀtoꢀ105ꢀ°Cꢀandꢀkeptꢀatꢀ
thisꢀ temperatureꢀ forꢀ 24ꢀ h.ꢀ Theꢀ solidꢀ wasꢀ separatedꢀ byꢀ anꢀ
externalꢀ magnet,ꢀ washedꢀ threeꢀ timesꢀ withꢀ ethanolꢀ andꢀ driedꢀ
2
O3ꢀ(3.5ꢀg)ꢀwasꢀsonicatedꢀinꢀdryꢀtolueneꢀ(50ꢀmL)ꢀforꢀ
2
O
underꢀ vacuum,ꢀ andꢀ thusꢀ amino‐functionalizedꢀ γ‐Fe
2
O ꢀ wasꢀ
3
obtained.ꢀ
[22,23].ꢀ Sinceꢀ mostꢀ ofꢀ theꢀ phosphine‐basedꢀ ligandsꢀ areꢀ airꢀ
Theꢀ amino‐functionalizedꢀ γ‐Fe O3ꢀ (3ꢀ g)ꢀ wasꢀ sonicatedꢀ inꢀ
2
and/orꢀmoisture‐sensitive,ꢀinꢀrecentꢀyears,ꢀseveralꢀgroupsꢀhaveꢀ
triedꢀ toꢀ developꢀ phosphine‐freeꢀ Pdꢀ complexesꢀ forꢀ theꢀ
cross‐couplingꢀreactionsꢀ[24–26].ꢀHowever,ꢀtheꢀreportedꢀcom‐
plexesꢀhaveꢀtheꢀdrawbacksꢀofꢀrequiringꢀanꢀexcessꢀofꢀexpensiveꢀ
ligands,ꢀ multistepꢀ synthesesꢀ andꢀ inertꢀ conditions.ꢀ Moreover,ꢀ
mostꢀ ofꢀ theꢀ reportedꢀ methodsꢀ areꢀ amenableꢀ onlyꢀ forꢀ theꢀ
cross‐couplingꢀreactionsꢀofꢀarylꢀiodidesꢀandꢀbromidesꢀ[27–29].ꢀ
Therefore,ꢀitꢀwouldꢀbeꢀmoreꢀbeneficialꢀifꢀarylꢀchlorides,ꢀwhichꢀ
areꢀfarꢀcheaperꢀandꢀmoreꢀavailableꢀthanꢀotherꢀarylꢀhalides,ꢀcanꢀ
beꢀusedꢀforꢀtheseꢀcross‐couplingꢀreactionsꢀ[30].ꢀ
absoluteꢀethanolꢀ(50ꢀmL)ꢀforꢀ30ꢀmin.ꢀIsatinꢀ(0.19ꢀg,ꢀ13ꢀmmol)ꢀ
wasꢀaddedꢀslowlyꢀtoꢀtheꢀsonicatedꢀmixtureꢀandꢀstirredꢀatꢀ80ꢀ°Cꢀ
forꢀ 24ꢀ h.ꢀ Theꢀ resultingꢀ mixtureꢀ wasꢀ cooledꢀ toꢀ roomꢀ
temperature.ꢀTheꢀsolidꢀwasꢀseparatedꢀbyꢀanꢀexternalꢀmagnet,ꢀ
washedꢀwithꢀethanolꢀandꢀdriedꢀatꢀ50ꢀ°Cꢀinꢀovenꢀunderꢀvacuum.ꢀ
TheꢀpreparedꢀsampleꢀdenotedꢀasꢀisatinꢀSchiffꢀbase‐γ‐Fe
2 3
O .ꢀ
IsatinꢀSchiffꢀbase‐γ‐Fe ꢀ(3.3ꢀg)ꢀwasꢀaddedꢀtoꢀaꢀsolutionꢀofꢀ
2 3
O
palladiumꢀacetateꢀ(0.11ꢀg)ꢀinꢀdryꢀacetoneꢀ(30ꢀmL).ꢀTheꢀreactionꢀ
mixtureꢀ wasꢀ stirredꢀ atꢀ roomꢀ temperatureꢀ forꢀ 24ꢀ h.ꢀ Afterꢀ
stirring,ꢀtheꢀsolidꢀwasꢀseparatedꢀbyꢀanꢀexternalꢀmagnet,ꢀwashedꢀ
withꢀacetone,ꢀethanolꢀandꢀether,ꢀandꢀthenꢀdriedꢀinꢀanꢀovenꢀatꢀ90ꢀ
Isatinꢀ isꢀ aꢀ well‐knownꢀ naturalꢀ productꢀ foundꢀ inꢀ plantsꢀ ofꢀ
genusꢀ Isatisꢀ andꢀ inꢀ Couropitaꢀ guianancisꢀ aublꢀ [31,32].ꢀ Itꢀ hasꢀ
beenꢀisolatedꢀasꢀaꢀmetabolicꢀderivativeꢀofꢀadrenalineꢀinꢀhumansꢀ
°CꢀovernightꢀtoꢀgiveꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
O .ꢀ
2 3
[33,34].ꢀIsatinꢀandꢀitsꢀderivativesꢀareꢀuniqueꢀmembersꢀinꢀtheꢀ
2.2.ꢀ ꢀ Characterizationꢀ
Schiffꢀ baseꢀ familyꢀ dueꢀ toꢀ theirꢀ pharmacologicalꢀ propertiesꢀ
whichꢀincludeꢀantibacterialꢀ[35],ꢀanticonvulsantꢀ[36],ꢀanti‐HIVꢀ
NMRꢀspectraꢀwereꢀrecordedꢀinꢀppmꢀconcentrationsꢀinꢀCDCl ꢀ
3
[
37],ꢀ antifungalꢀ [38]ꢀ andꢀ antiviralꢀ activityꢀ [39].ꢀ Isatinꢀ Schiffꢀ
onꢀaꢀBrukerꢀAvanceꢀDPX‐400ꢀinstrumentꢀusingꢀTMSꢀasꢀinternalꢀ
standard.ꢀTheꢀpurityꢀofꢀtheꢀproductsꢀandꢀprogressꢀofꢀreactionꢀ
wereꢀmeasuredꢀbyꢀTLCꢀusingꢀsilicaꢀgelꢀpolygramꢀSILG/UV254ꢀ
plates.ꢀ Fourierꢀ transformꢀ infraredꢀ (FT‐IR)ꢀ spectraꢀ wereꢀ rec‐
ordedꢀonꢀaꢀJASCOꢀFT‐IRꢀ460ꢀplusꢀspectrophotometer.ꢀHighꢀres‐
olutionꢀ transmissionꢀ electronꢀ microscopyꢀ (HRTEM)ꢀ analysisꢀ
wasꢀperformedꢀusingꢀaꢀHRTEMꢀmicroscopeꢀ(PhilipsꢀCM30).ꢀTheꢀ
morphologyꢀ ofꢀ theꢀ productsꢀ wasꢀ determinedꢀ usingꢀ aꢀ Hitachiꢀ
Modelꢀ S4160ꢀ scanningꢀ electronꢀ microscopeꢀ (SEM)ꢀ atꢀ anꢀ
acceleratingꢀ voltageꢀ ofꢀ 15ꢀ kV.ꢀ Thermogravimetricꢀ analysisꢀ
(TGA)ꢀ wasꢀ performedꢀ usingꢀ aꢀ Shimadzuꢀ thermogravimetricꢀ
analyzerꢀ(TG‐50).ꢀElementalꢀanalysisꢀwasꢀcarriedꢀoutꢀonꢀaꢀCos‐
techꢀ 4010ꢀ CHNSꢀ elementalꢀ analyzer.ꢀ Powerꢀ X‐rayꢀ diffractionꢀ
basesꢀreadilyꢀcoordinateꢀwithꢀaꢀwideꢀrangeꢀofꢀtransitionꢀmetalꢀ
ions,ꢀyieldingꢀstableꢀmetalꢀcomplexesꢀwhichꢀexhibitꢀinterestingꢀ
biological,ꢀ clinical,ꢀ andꢀ pharmacologicalꢀ propertiesꢀ [40].ꢀ Re‐
cently,ꢀweꢀdevelopedꢀtheꢀsynthesisꢀofꢀnewꢀheterogeneousꢀcata‐
lystsꢀ basedꢀ onꢀ magneticꢀ nanoparticlesꢀ [41–50].ꢀ Inꢀ continuingꢀ
thisꢀwork,ꢀweꢀhaveꢀsynthesizedꢀPd‐isatinꢀSchiffꢀbaseꢀcomplexꢀ
immobilizedꢀ onꢀ γ‐Fe
2
O
3ꢀ (Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe
2
O )ꢀ andꢀ
3
usedꢀitꢀasꢀanꢀefficient,ꢀair‐ꢀandꢀmoisture‐stableꢀandꢀmagneticallyꢀ
recoverableꢀ catalystꢀ forꢀ theꢀ Heckꢀ andꢀ Suzukiꢀ cross‐couplingꢀ
reactionsꢀunderꢀsolvent‐freeꢀconditionsꢀ[51].ꢀ
2
.ꢀ ꢀ Experimentalꢀ
(
XRD)ꢀ wasꢀ performedꢀ onꢀ aꢀ Brukerꢀ D8‐advanceꢀ X‐rayꢀ diffrac‐
tometerꢀorꢀonꢀaꢀX’PertꢀProꢀMPDꢀdiffractometerꢀwithꢀCuꢀK
ꢀ(λꢀ=ꢀ
.154ꢀ nm)ꢀ radiation.ꢀ Surfaceꢀ analysisꢀ spectroscopyꢀ ofꢀ theꢀ
2.1.ꢀ ꢀ Synthesisꢀ ꢀ
α
0
TheꢀchemicalsꢀwereꢀpurchasedꢀfromꢀMerckꢀChemicalꢀCom‐
catalystꢀwasꢀperformedꢀonꢀanꢀESCA/AESꢀsystem.ꢀThisꢀsystemꢀ
wasꢀequippedꢀwithꢀaꢀconcentricꢀhemisphericalꢀ(CHA)ꢀelectronꢀ
energyꢀ analyzerꢀ (Specsꢀ modelꢀ EA10ꢀ plus)ꢀ suitableꢀ forꢀ X‐rayꢀ
photoelectronꢀ spectroscopyꢀ (XPS).ꢀ Theꢀ Pdꢀ contentꢀ onꢀ theꢀ
catalystꢀwasꢀdeteminedꢀbyꢀOPTIMAꢀ7300DVꢀICPꢀanalyzer.ꢀ
pany.ꢀγ‐Fe
co‐precipitationꢀtechniqueꢀusingꢀferricꢀandꢀferrousꢀionsꢀinꢀalkaliꢀ
solutionꢀ andꢀ withꢀ minorꢀ modificationsꢀ [52,53].ꢀ FeCl ·4H Oꢀ
1.99ꢀg)ꢀ andꢀFeCl ·6H Oꢀ(3.25ꢀ g)ꢀ wereꢀ dissolvedꢀinꢀ deionizedꢀ
waterꢀ(30ꢀmL)ꢀunderꢀanꢀArꢀatmosphereꢀatꢀroomꢀtemperature.ꢀAꢀ
NH OHꢀ solutionꢀ (0.6ꢀ mol/L,ꢀ 200ꢀ mL)ꢀ wasꢀ addedꢀ dropwiseꢀ
dropꢀ rateꢀ =ꢀ 1ꢀ mL/min)ꢀ toꢀ theꢀ stirredꢀ mixtureꢀ atꢀ roomꢀ
2
O3ꢀMNPsꢀwereꢀsynthesizedꢀbyꢀaꢀreportedꢀchemicalꢀ
2
2
(
3
2
4
2.3.ꢀ ꢀ Reactionꢀ
(
temperatureꢀ toꢀ aꢀ reactionꢀ pHꢀ ofꢀ 11.ꢀ Theꢀ resultingꢀ blackꢀ
dispersionꢀ wasꢀ continuouslyꢀ stirredꢀ forꢀ 1ꢀ hꢀ atꢀ roomꢀ
temperature,ꢀ andꢀ heatedꢀ toꢀ refluxꢀ forꢀ 1ꢀ hꢀ toꢀ yieldꢀ aꢀ brownꢀ
dispersion.ꢀTheꢀMNPsꢀwereꢀsubsequentlyꢀseparatedꢀbyꢀaꢀmag‐
neticꢀ barꢀ andꢀ washedꢀ withꢀ deionizedꢀ waterꢀ untilꢀ theyꢀ wereꢀ
Generalꢀ procedureꢀ forꢀ theꢀ Heckꢀ cross‐couplingꢀ reaction.ꢀ Aꢀ
mixtureꢀ ofꢀ arylꢀ halideꢀ (1ꢀ mmol),ꢀ olefinꢀ (1.1ꢀ mmol),ꢀ Et Nꢀ (2ꢀ
3
mmol)ꢀandꢀcatalystꢀ(0.002ꢀg,ꢀ0.5ꢀmol%)ꢀwasꢀstirredꢀatꢀ100ꢀ°Cꢀ
forꢀanꢀappropriateꢀtimeꢀ(Tableꢀ2).ꢀEtOAcꢀ(5ꢀmL)ꢀwasꢀaddedꢀtoꢀ
theꢀreactionꢀmixture.ꢀTheꢀcatalystꢀwasꢀseparatedꢀbyꢀanꢀexternalꢀ
magnet,ꢀwashedꢀwithꢀEtOAc,ꢀdriedꢀandꢀreusedꢀforꢀaꢀconsecutiveꢀ
runꢀ underꢀ theꢀ sameꢀ reactionꢀ conditions.ꢀ Evaporationꢀ ofꢀ theꢀ
solventꢀofꢀtheꢀfiltrateꢀunderꢀreducedꢀpressureꢀgaveꢀtheꢀcrudeꢀ
ꢀ
neutral.ꢀTheꢀas‐synthesizedꢀsampleꢀwasꢀheatedꢀatꢀ2ꢀ°C/min toꢀ
250ꢀ °Cꢀ andꢀ thenꢀ keptꢀ inꢀ theꢀ furnaceꢀ forꢀ 3ꢀ hꢀ toꢀ giveꢀ aꢀ
reddish‐brownꢀpowder,ꢀi.e.ꢀγ‐Fe ꢀMNPs.ꢀ
2 3
O

ꢀ
SaraꢀSobhaniꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ36ꢀ(2015)ꢀ555–563ꢀ
557ꢀ
3
3
3
products.ꢀTheꢀpureꢀproductsꢀwereꢀisolatedꢀbyꢀchromatographyꢀ
onꢀsilicaꢀgelꢀelutedꢀwithꢀn‐hexane:ꢀEtOAcꢀ(50:1).ꢀ
(d,ꢀ2H,ꢀ Jꢀ=ꢀ8.4ꢀHz),ꢀ7.57ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ15.2ꢀHz),ꢀ7.60ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ8.0ꢀ
Hz);ꢀ13CꢀNMRꢀ(100ꢀMHz,ꢀCDCl
):ꢀδꢀ13.5,ꢀ19.0,ꢀ30.5,ꢀ64.4,ꢀ113.0,ꢀ
3
GeneralꢀprocedureꢀforꢀtheꢀSuzukiꢀcross‐couplingꢀreaction.ꢀAꢀ
mixtureꢀofꢀarylꢀhalidꢀ(1ꢀmmol),ꢀphenylboronicꢀacidꢀ(1.1ꢀmmol),ꢀ
118.1,ꢀ121.6,ꢀ128.3,ꢀ132.4,ꢀ138.4,ꢀ141.8,ꢀ165.7.ꢀ
1
(E)‐1,2‐Diphenylethene.ꢀ Hꢀ NMRꢀ (400ꢀ MHz,ꢀ CDCl
3
):ꢀ ꢀ7.18ꢀ
3
3
3
Et Nꢀ(2ꢀmmol)ꢀandꢀcatalystꢀ(0.002ꢀg,ꢀ0.5ꢀmol%)ꢀwasꢀstirredꢀatꢀ
(s,ꢀ2H),ꢀ7.33ꢀ(t,ꢀ2H,ꢀ Jꢀ=ꢀ6.8ꢀHz),ꢀ7.42ꢀ(t,ꢀ4H,ꢀ Jꢀ=ꢀ7.0ꢀHz),ꢀ7.58ꢀ(d,ꢀ
4H,ꢀ Jꢀ =ꢀ 7.2ꢀ Hz);ꢀ13Cꢀ NMRꢀ (100ꢀ MHz,ꢀ CDCl
3
100ꢀ °Cꢀ forꢀ anꢀ appropriateꢀ timeꢀ (Tableꢀ 3).ꢀ EtOAcꢀ (5ꢀ mL)ꢀ wasꢀ
3
):ꢀ δꢀ 126.7,ꢀ 127.8,ꢀ
addedꢀtoꢀtheꢀreactionꢀmixture.ꢀTheꢀcatalystꢀwasꢀseparatedꢀbyꢀ
anꢀexternalꢀmagnet,ꢀwashedꢀwithꢀEtOAc,ꢀdriedꢀandꢀreusedꢀforꢀaꢀ
consecutiveꢀ runꢀ underꢀ theꢀ sameꢀ reactionꢀ conditions.ꢀ
Evaporationꢀ ofꢀ theꢀ solventꢀ ofꢀ theꢀ filtrateꢀ underꢀ reducedꢀ
pressureꢀ gaveꢀ theꢀ crudeꢀ products.ꢀ Theꢀ pureꢀ productsꢀ wereꢀ
isolatedꢀ byꢀ chromatographyꢀ onꢀ silicaꢀ gelꢀ elutedꢀ withꢀ
n‐hexane:EtOAcꢀ(50:1).ꢀ
128.8,ꢀ137.4.ꢀ
1
(E)‐1‐Methoxy‐4‐styrylbenzene.ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl
3
):ꢀ
3
3
ꢀ3.89ꢀ(s,ꢀ3H),ꢀ6.92ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ8.4ꢀHz),ꢀ6.99ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ16.4ꢀHz),ꢀ
3
3
7.09ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ16.0ꢀHz),ꢀ7.36ꢀ(t,ꢀ2H,ꢀ Jꢀ=ꢀ7.6ꢀHz),ꢀ7.46–7.52ꢀ(m,ꢀ
3H);ꢀ 13Cꢀ NMRꢀ (100ꢀ MHz,ꢀ CDCl
):ꢀ δꢀ 55.3,ꢀ 114.1,ꢀ 126.3,ꢀ 126.6,ꢀ
3
127.2,ꢀ127.8,ꢀ128.2,ꢀ128.7,ꢀ130.1,ꢀ137.7,ꢀ159.3.ꢀ
1
(E)‐1‐Chloro‐4‐styrylbenzene.ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl
3
):ꢀꢀ
7
.07ꢀ(s,ꢀ2H),ꢀ7.28–7.39ꢀ(m,ꢀ5H),ꢀ7.43–7.46ꢀ(m,ꢀ2H),ꢀ7.50–7.52ꢀ
2.4.ꢀ ꢀ Spectralꢀdataꢀofꢀrepresentativeꢀcompoundsꢀ
(m,ꢀ 2H);ꢀ 13Cꢀ NMRꢀ (100ꢀ MHz,ꢀ CDCl
3
):ꢀ δꢀ 127.7,ꢀ 128.5,ꢀ 128.8,ꢀ
1
29.0,ꢀ129.9,ꢀ130.0,ꢀ130.4,ꢀ134.3,ꢀ136.9,ꢀ138.1.ꢀ
1
1
(
E)‐Methylꢀcinnamate.ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl
3
):ꢀꢀ3.74ꢀ(s,ꢀ
(E)‐4‐Styrylbenzonitrile.ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl
3
):ꢀꢀ7.09ꢀ
3
3
3
3
2
5
H),ꢀ6.38ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.4ꢀHz),ꢀ7.31–7.33ꢀ(m,ꢀ3H),ꢀ7.45–7.47ꢀ(m,ꢀ
H),ꢀ7.63ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.4ꢀHz);ꢀ13CꢀNMRꢀ(100ꢀMHz,ꢀCDCl
1.6,ꢀ117.7,ꢀ128.1,ꢀ128.9,ꢀ130.3,ꢀ134.3,ꢀ144.8,ꢀ167.3.ꢀ
E)‐Methylꢀ 2‐methyl‐3‐phenylacrylate.ꢀ Hꢀ NMRꢀ (400ꢀ MHz,ꢀ
):ꢀꢀ2.15ꢀ(s,ꢀ3H),ꢀ3.83ꢀ(s,ꢀ3H),ꢀ7.21–7.41ꢀ(m,ꢀ5H),ꢀ7.92ꢀ(d,ꢀ
H,ꢀ Jꢀ=ꢀ16.0ꢀHz);ꢀ CꢀNMRꢀ(100ꢀMHz,ꢀCDCl
(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.0ꢀHz),ꢀ7.22ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.0ꢀHz),ꢀ7.31–7.34ꢀ(t,ꢀ1H,ꢀ
3
3
3
3
3
):ꢀδꢀ
Jꢀ=ꢀ4.0ꢀHz),ꢀ7.38–7.41ꢀ(t,ꢀ2H,ꢀ Jꢀ=ꢀ4.0ꢀHz),ꢀ7.54ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ7.2ꢀ
3
3
13
Hz),ꢀ7.58ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ8.4ꢀHz),ꢀ7.64ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ8.4ꢀHz);ꢀ CꢀNMRꢀ
(100ꢀ MHz,ꢀ CDCl ):ꢀ δꢀ 111.7,ꢀ 120.2,ꢀ 127.8,ꢀ 128.0,ꢀ 128.1,ꢀ 129.8,ꢀ
130.0,ꢀ133.5,ꢀ133.6,ꢀ137.4,ꢀ142.9.ꢀ
1
(
3
CDCl
3
3
13
1
1
3
):ꢀδꢀ14.1,ꢀ52.0,ꢀ127.9,ꢀ
(E)‐1‐Nitro‐4‐styrylbenzene.ꢀ Hꢀ NMRꢀ (400ꢀ MHz,ꢀ CDCl ):ꢀ ꢀ
3
1
29.6,ꢀ135.8,ꢀ138.9,ꢀ169.1.ꢀ
7.06–7.18ꢀ (m,ꢀ 1H),ꢀ 7.40–7.45ꢀ (m,ꢀ 4H),ꢀ 7.49–766ꢀ (m,ꢀ 4H),ꢀ
1
13
(
E)‐Ethylꢀ cinnamate.ꢀ Hꢀ NMRꢀ (400ꢀ MHz,ꢀ CDCl
3
):ꢀ ꢀ 1.43ꢀ (t,ꢀ
3
8.15–8.26ꢀ(m,ꢀ2H);ꢀ CꢀNMRꢀ(100ꢀMHz,ꢀCDCl ):ꢀδꢀ125.2,ꢀ127.4,ꢀ
3
3
3
3H,ꢀ Jꢀ=ꢀ8.0ꢀHz),ꢀ4.19ꢀ(q,ꢀ2H,ꢀ Jꢀ=ꢀ8.0ꢀHz),ꢀ6.35ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16ꢀHz),ꢀ
128.0,ꢀ128.2,ꢀ130.0,ꢀ134.4,ꢀ137.3,ꢀ145.0,ꢀ147.8.ꢀ
3
1
3
7.27–7.28ꢀ(m,ꢀ3H),ꢀ7.41–7.42ꢀ(m,ꢀ2H),ꢀ7.63ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.0ꢀHz);ꢀ
Biphenyl.ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl
3
):ꢀꢀ7.46ꢀ(t,ꢀ2H,ꢀ Jꢀ=ꢀ7.2ꢀ
13Cꢀ NMRꢀ (100ꢀ MHz,ꢀ CDCl
):ꢀ δꢀ 14.2,ꢀ 60.0,ꢀ 118.2,ꢀ 127.9,ꢀ 128.7,ꢀ
Hz),ꢀ7.56ꢀ(t,ꢀ4H,ꢀ Jꢀ=ꢀ8.0ꢀHz),ꢀ7.72ꢀ(d,ꢀ4H,ꢀ Jꢀ=ꢀ6.8ꢀHz);ꢀ13CꢀNMRꢀ
3
3
3
1
30.1,ꢀ134.3,ꢀ144.3,ꢀ166.6.ꢀ
(100ꢀMHz,ꢀCDCl
3
):ꢀδꢀ127.2,ꢀ127.3,ꢀ128.8,ꢀ141.3.ꢀ
1
1
(
E)‐n‐Butylꢀcinnamate.ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl
3
):ꢀꢀ0.88ꢀ(t,ꢀ
4‐Methoxybiphenyl.ꢀ Hꢀ NMRꢀ (400ꢀ MHz,ꢀ CDCl
3H),ꢀ6.99ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ8.8ꢀHz),ꢀ7.31ꢀ(t,ꢀ1H,ꢀ Jꢀ=ꢀ7.2ꢀHz),ꢀ7.43ꢀ(t,ꢀ2H,ꢀ
3
):ꢀ ꢀ 3.83ꢀ (s,ꢀ
3
3
3
3
2
7
H,ꢀ Jꢀ=ꢀ7.6ꢀHz),ꢀ1.34–1.36ꢀ(m,ꢀ2H),ꢀ1.59–1.62ꢀ(m,ꢀ2H),ꢀ4.13ꢀ(t,ꢀ
H,ꢀ Jꢀ=ꢀ6.8ꢀHz),ꢀ6.36ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.0ꢀHz),ꢀ7.29–7.30ꢀ(m,ꢀ3H),ꢀ
.43–7.45ꢀ (m,ꢀ 2H),ꢀ 7.60ꢀ (d,ꢀ 1H,ꢀ Jꢀ =ꢀ 16.4ꢀ Hz);ꢀ 13Cꢀ NMRꢀ (100ꢀ
3
3
3
3
13
Jꢀ=ꢀ8.0ꢀHz),ꢀ7.55ꢀ(t,ꢀ4H,ꢀ Jꢀ=ꢀ8.8ꢀHz);ꢀ CꢀNMRꢀ(100ꢀMHz,ꢀCDCl ):ꢀ
3
3
δꢀ56.5,ꢀ115.3,ꢀ127.8,ꢀ127.9,ꢀ129.3,ꢀ129.9,ꢀ134.9,ꢀ142.0,ꢀ160.3.ꢀ
4‐Chlorobiphenyl.ꢀ Hꢀ NMRꢀ (400ꢀ MHz,ꢀ CDCl
(m,ꢀ5H),ꢀ7.51–7.57ꢀ(m,ꢀ4H);ꢀ CꢀNMRꢀ(100ꢀMHz,ꢀCDCl ):ꢀδꢀ128.1,ꢀ
1
MHz,ꢀCDCl
3
):ꢀδꢀ13.7,ꢀ19.2,ꢀ30.8,ꢀ64.3,ꢀ118.2,ꢀ128.0,ꢀ128.8,ꢀ130.1,ꢀ
3
):ꢀ ꢀ 7.31–7.49ꢀ
13
134.4,ꢀ144.4,ꢀ166.8.ꢀ
3
(
E)‐n‐Butylꢀ 3‐(4‐methoxyphenyl)acrylate.ꢀ 1Hꢀ NMRꢀ (400ꢀ
128.7,ꢀ129.3,ꢀ129.5,ꢀ130.0,ꢀ130.2,ꢀ140.8,ꢀ141.1.ꢀ
3
1
MHz,ꢀ CDCl
3
):ꢀ ꢀ 0.91ꢀ (t,ꢀ 3H,ꢀ Jꢀ =7.0ꢀ Hz),ꢀ 1.35–1.40ꢀ (m,ꢀ 2H),ꢀ
3
4‐Nitrobiphenyl.ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl ):ꢀꢀ7.43–7.52ꢀ(m,ꢀ
3
1
1
.60–1.62ꢀ(m,ꢀ2H),ꢀ3.72ꢀ(s,ꢀ3H),ꢀ4.13ꢀ(m,ꢀ2H,ꢀ Jꢀ=7.0ꢀHz),ꢀ6.24ꢀ(d,ꢀ
H,ꢀ Jꢀ=ꢀ16.0ꢀHz),ꢀ6.81ꢀ(d,ꢀ3H,ꢀ Jꢀ=ꢀ4.8ꢀHz),ꢀ7.39ꢀ(d,ꢀ3H,ꢀ Jꢀ=ꢀ4.2ꢀ
Hz),ꢀ 7.58ꢀ (d,ꢀ1H,ꢀ Jꢀ =ꢀ 16.0ꢀ Hz);ꢀ 13Cꢀ NMRꢀ (100ꢀ MHz,ꢀ CDCl
3H),ꢀ7.62–7.64ꢀ(m,ꢀ2H),ꢀ7.73–7.76ꢀ(m,ꢀ2H),ꢀ8.29–8.30ꢀ(m,ꢀ2H);ꢀ
3
3
3
13CꢀNMRꢀ(100ꢀMHz,ꢀCDCl
3
):ꢀδꢀ125.2,ꢀ128.5,ꢀ128.9,ꢀ130.0,ꢀ130.3,ꢀ
3
3
):ꢀ δꢀ
139.9,ꢀ148.2,ꢀ148.7.ꢀ
1
):ꢀꢀ7.41–7.51ꢀ(m,ꢀ
1
1
3.6,ꢀ 19.1,ꢀ 30.7,ꢀ 55.0,ꢀ 64.0,ꢀ 114.1,ꢀ 115.5,ꢀ 127.0,ꢀ 129.5,ꢀ 144.0,ꢀ
61.2,ꢀ167.1.ꢀ
E)‐n‐Butylꢀ 3‐(4‐chlorophenyl)acrylate. Hꢀ NMRꢀ (400ꢀ MHz,ꢀ
4‐Cyanobiphenyl.ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl
3
13
3H),ꢀ7.56–7.60ꢀ(m,ꢀ2H),ꢀ7.68–7.74ꢀ(m,ꢀ4H);ꢀ CꢀNMRꢀ(100ꢀMHz,ꢀ
CDCl ):ꢀδꢀ112.0,ꢀ120.1,ꢀ128.3,ꢀ128.8,ꢀ129.8,ꢀ130.2,ꢀ133.7,ꢀ140.3,ꢀ
ꢀ
1
(
3
3
CDCl
3
):ꢀꢀ0.90ꢀ(t,ꢀ3H,ꢀ Jꢀ=ꢀ7.2ꢀHz),ꢀ1.33–1.39ꢀ(m,ꢀ2H),ꢀ1.57–1.64ꢀ
146.8.ꢀ
3
3
(
(
m,ꢀ2H),ꢀ4.13ꢀ(t,ꢀ2H,ꢀ Jꢀ=ꢀ6.8ꢀHz),ꢀ6.64ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.0ꢀHz),ꢀ7.45ꢀ
d,ꢀ2H,ꢀ Jꢀ=ꢀ8.0ꢀHz),ꢀ7.63ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.0ꢀHz),ꢀ7.74ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ8.0ꢀ
Hz);ꢀ CꢀNMRꢀ(100ꢀMHz,ꢀCDCl
29.1,ꢀ129.4,ꢀ132.9,ꢀ136.0,ꢀ143.0,ꢀ166.7.ꢀ
3
3
3
3.ꢀ ꢀ Resultsꢀandꢀdiscussionꢀ
3.1.ꢀ ꢀ SynthesisꢀandꢀcharacterizationꢀofꢀPd‐isatinꢀSchiffꢀ
13
3
):ꢀδꢀ13.7,ꢀ19.2,ꢀ30.7,ꢀ64.4,ꢀ118.8,ꢀ
1
1
(E)‐n‐Butylꢀ 3‐(4‐nitrophenyl)acrylate.ꢀ Hꢀ NMRꢀ (400ꢀ MHz,ꢀ
base‐γ‐Fe O ꢀ
2 3
3
CDCl
3
):ꢀꢀ0.92ꢀ(t,ꢀ3H,ꢀ Jꢀ=ꢀ7.2ꢀHz),ꢀ1.35–1.44ꢀ(m,ꢀ2H),ꢀ1.62–1.69ꢀ
3
(
(
1
1
m,ꢀ2H),ꢀ4.17–4.24ꢀ(m,ꢀ2H),ꢀ6.53ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.0ꢀHz),ꢀ7.63–7.68ꢀ
Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe
shownꢀ inꢀ Schemeꢀ 1.ꢀ First,ꢀ γ‐Fe
3‐aminopropyltriethoxysilaneꢀ toꢀ obtainꢀ amino‐functionalizedꢀ
γ‐Fe .ꢀ Theꢀ reactionꢀ ofꢀ theꢀ amino‐functionalizedꢀ MNPsꢀ withꢀ
isatinꢀproducedꢀisatinꢀSchiffꢀbase‐γ‐Fe Finally,ꢀtheꢀsupport‐
2
O3ꢀwasꢀ synthesizedꢀ byꢀ theꢀ stepsꢀ
m,ꢀ3H),ꢀ8.20ꢀ(d,ꢀ2H,ꢀ Jꢀ=ꢀ8.0ꢀHz);ꢀ13CꢀNMRꢀ(100ꢀMHz,ꢀCDCl
3
):ꢀδꢀ
3.6,ꢀ19.1,ꢀ30.6,ꢀ64.7,ꢀ122.5,ꢀ124.0,ꢀ128.6,ꢀ140.5,ꢀ141.5,ꢀ148.3,ꢀ
66.0.ꢀ
3
2 3
O ꢀ wasꢀ reactedꢀ withꢀ
O
2 3
ꢀ
1
(E)‐n‐Butylꢀ 3‐(4‐cyanophenyl)acrylate. Hꢀ NMRꢀ (400ꢀ MHz,ꢀ
2 3 ꢀ
O .
3
CDCl
3
):ꢀꢀ0.77ꢀ(t,ꢀ3H,ꢀ Jꢀ=ꢀ7.0ꢀHz),ꢀ1.30–1.38ꢀ(m,ꢀ2H),ꢀ1.57–1.64ꢀ
edꢀPdꢀcatalystꢀwasꢀobtainedꢀbyꢀtheꢀreactionꢀofꢀdissolvingꢀpalla‐
diumꢀ(ΙΙ)ꢀacetateꢀinꢀmethanolꢀwithꢀtheꢀaboveꢀsynthesizedꢀisatinꢀ
3
3
(
m,ꢀ2H),ꢀ4.14ꢀ(t,ꢀ2H,ꢀ Jꢀ=ꢀ6.8ꢀHz),ꢀ6.45ꢀ(d,ꢀ1H,ꢀ Jꢀ=ꢀ16.0ꢀHz),ꢀ7.54ꢀ

558ꢀ
SaraꢀSobhaniꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ36ꢀ(2015)ꢀ555–563ꢀ
O
O
O
O
N
(
EtO) Si
NH2
3
H
2
-Fe O
3
Si
O
NH

-Fe
2
O
3
-Fe
2
O
3
Si
NH2
N
O
O
O
NH

-Fe
2
O
3
Si
N
Pd
O
O
OAc
AcO
Schemeꢀ1.ꢀSynthesisꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O .ꢀ
3
2 3
Schiffꢀ base‐γ‐Fe O .ꢀ Theꢀ synthesizedꢀ Pd‐isatinꢀ Schiffꢀ
sphericalꢀshapeꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe O3ꢀwithꢀanꢀaverageꢀ
2
base‐γ‐Fe 3ꢀ wasꢀ characterizedꢀ byꢀ FT‐IR,ꢀ SEM,ꢀ HRTEM,ꢀ XRD,ꢀ
TGA,ꢀICP,ꢀXPSꢀandꢀelementalꢀanalysis.ꢀ
2
O
diameterꢀ ofꢀ 12ꢀ nmꢀ (Fig.ꢀ 3).ꢀ Theꢀ blackꢀ spotsꢀ withꢀ anꢀ averageꢀ
diameterꢀofꢀ2ꢀnmꢀwereꢀattributedꢀtoꢀsupportedꢀPd.ꢀ
Theꢀ FT‐IRꢀ spectraꢀ ofꢀ amino‐functionalizedꢀ γ‐Fe
2
O
3
,ꢀ isatinꢀ
AsꢀshownꢀinꢀFig.ꢀ4,ꢀsixꢀcharacteristicꢀdiffractionꢀpeaksꢀ(2θꢀ=ꢀ
30.4°,ꢀ35.7°,ꢀ43.4°,ꢀ53.8°,ꢀ57.3°,ꢀandꢀ63.0°)ꢀcorrespondingꢀtoꢀtheꢀ
(220),ꢀ(311),ꢀ(400),ꢀ(422),ꢀ(511)ꢀandꢀ(440)ꢀreflections,ꢀrespec‐
Schiffꢀbase‐γ‐Fe
2
O
3
,ꢀandꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe O3ꢀareꢀshownꢀ
2
−1
inꢀ Fig.ꢀ 1.ꢀ Theꢀ bandꢀ atꢀ 550–670ꢀ cm ꢀ wasꢀ assignedꢀ toꢀ theꢀ
stretchingꢀvibrationꢀofꢀtheꢀFe‐Oꢀbondꢀinꢀtheseꢀcompounds.ꢀTheꢀ
peaksꢀ atꢀ 1085,ꢀ 3438,ꢀ 3480,ꢀ andꢀ 2869–2906ꢀ cm ꢀ inꢀ ami‐
no‐functionalizedꢀγ‐Fe ꢀcorrespondedꢀtoꢀC–N,ꢀN–HꢀandꢀC–Hꢀ
stretchingꢀ modesꢀ ofꢀ theꢀ alkylꢀ chain,ꢀ respectively.ꢀ Theꢀ N‐Hꢀ
2 3
tively,ꢀofꢀinverseꢀspinelꢀγ‐Fe O ꢀNPsꢀwereꢀobserved.ꢀThisꢀindi‐
–
1
catedꢀthatꢀtheꢀγ‐Fe 3ꢀNPsꢀmostlyꢀexistedꢀinꢀtheꢀfaceꢀcenteredꢀ
2
O
O
2 3
–1
bendingꢀ modeꢀ appearedꢀ atꢀ 1631ꢀ cm .ꢀ Forꢀ isatinꢀ Schiffꢀ
base‐γ‐Fe ,ꢀ newꢀ bandsꢀ wereꢀ observedꢀ atꢀ 1455,ꢀ 1608,ꢀ andꢀ
718ꢀcm ,ꢀwhichꢀwereꢀdueꢀtoꢀtheꢀC=C,ꢀC=N,ꢀandꢀC=Oꢀstretchingꢀ
vibrations,ꢀ respectively.ꢀ Theseꢀ bandsꢀ provedꢀ thatꢀ isatinꢀ hadꢀ
beenꢀ successfullyꢀ reactedꢀ withꢀ amino‐functionalizedꢀ γ‐Fe .ꢀ
Theꢀ N‐Hꢀ stretchingꢀ bandꢀ ofꢀ theꢀ amideꢀ groupꢀ inꢀ isatinꢀ over‐
2 3
O
–
1
1
O
2 3
–1
lappedꢀ theꢀ broadꢀ O‐Hꢀ band,ꢀ whichꢀ wasꢀ foundꢀ atꢀ 3390ꢀ cm .ꢀ
Overꢀ theꢀ Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe ,ꢀ theꢀ C=Nꢀ andꢀ C=Oꢀ
stretchingꢀfrequenciesꢀwereꢀshiftedꢀtoꢀtheꢀlowerꢀwavenumbersꢀ
O
2 3
–1
Fig.ꢀ2.ꢀSEMꢀimageꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O .ꢀ
3
(
1600,ꢀ1704ꢀcm ),ꢀwhichꢀshowedꢀtheꢀsuccessfulꢀcoordinationꢀ
ofꢀnitrogenꢀandꢀoxygenꢀtoꢀtheꢀmetalꢀcenter.ꢀ ꢀ
TheꢀSEMꢀimageꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O ꢀshowedꢀtheꢀ
3
uniformityꢀandꢀsphericalꢀmorphologyꢀofꢀtheꢀMNPsꢀ(Fig.ꢀ2).ꢀ
TheꢀsizeꢀandꢀstructureꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe 3ꢀwereꢀ
determinedꢀ usingꢀ HRTEM.ꢀ Theꢀ resultsꢀ demonstratedꢀ theꢀ
2
O
(1)
(2)
(3)
3
700 3300 2900 2500 2100 1700 1300 900 500
1
Wavenumber (cm )
Fig.ꢀ1.ꢀFT‐IRꢀspectraꢀofꢀamino‐functionalizedꢀγ‐Fe
base‐γ‐Fe ꢀ(2),ꢀandꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe ꢀ(3).ꢀ
2
O ꢀ(1),ꢀisatinꢀSchiff
3
O
2 3
O
2 3
Fig.ꢀ3.ꢀHRTEMꢀimagesꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O .ꢀ
3

ꢀ
SaraꢀSobhaniꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ36ꢀ(2015)ꢀ555–563ꢀ
559ꢀ
3d5/2 = 337.6
3d3/2 = 342.1
20
30
40
50o
/( )
60
70
80
327 330 333 336 339 342 345 348
Binding energy (eV)
2
Fig.ꢀ4.ꢀXRDꢀpatternꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2 3
O .ꢀ
Fig.ꢀ6.ꢀXPSꢀspectrumꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O .ꢀ
3
cubicꢀ structure.ꢀ Theꢀ XRDꢀ patternꢀ ofꢀ Pd‐isatinꢀ Schiffꢀ
base‐γ‐Fe ꢀshowedꢀaꢀweakꢀpeakꢀatꢀ(2θꢀ=ꢀ39.4°)ꢀwhichꢀcorre‐
spondꢀtoꢀtheꢀ(111)ꢀreflectionꢀofꢀsupportedꢀPd.ꢀ ꢀ
(Tableꢀ 1).ꢀ Theꢀ modelꢀ reactionꢀ wasꢀ examinedꢀ inꢀ differentꢀ sol‐
ventsꢀsuchꢀasꢀDMF,ꢀH Oꢀandꢀtolueneꢀatꢀ100ꢀ°C,ꢀandꢀinꢀrefluxingꢀ
EtOHꢀandꢀCH CNꢀ(Tableꢀ1,ꢀentriesꢀ1–5).ꢀTheꢀbestꢀyieldꢀwasꢀob‐
O
2 3
2
3
Theꢀ thermalꢀ behaviorꢀ ofꢀ Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe
investigatedꢀbyꢀTGA.ꢀAsꢀshownꢀinꢀFig.ꢀ5,ꢀtheꢀweightꢀlossꢀatꢀ180ꢀ
Cꢀwasꢀrelatedꢀtoꢀtheꢀlossꢀofꢀadsorbedꢀwater.ꢀThereꢀwasꢀalsoꢀaꢀ
significantꢀ weightꢀ lossꢀ ofꢀ 13.92%ꢀ fromꢀ 200ꢀ toꢀ 800ꢀ °C,ꢀ whichꢀ
wasꢀrelatedꢀtoꢀtheꢀdecompositionꢀofꢀtheꢀisatinꢀSchiffꢀbaseꢀligandꢀ
andꢀorganicꢀcomponentsꢀlocatedꢀonꢀtheꢀsurfaceꢀofꢀtheꢀMNPs.ꢀ ꢀ
2
O3ꢀ wasꢀ
tainedꢀinꢀDMFꢀ(Tableꢀ1,ꢀentryꢀ1).ꢀToꢀtryꢀtoꢀavoidꢀtheꢀuseꢀofꢀtoxicꢀ
andꢀexpensiveꢀorganicꢀsolvents,ꢀtheꢀreactionꢀwasꢀalsoꢀstudiedꢀ
underꢀ solvent‐freeꢀ conditionsꢀ (Tableꢀ 1,ꢀ entryꢀ 6).ꢀ Itꢀ wasꢀ ob‐
servedꢀthatꢀtheꢀcross‐couplingꢀreactionꢀgaveꢀaꢀhighꢀyieldꢀofꢀtheꢀ
correspondingꢀproductꢀinꢀ0.5ꢀhꢀunderꢀtheꢀsolvent‐freeꢀcondi‐
°
tions.ꢀAmongꢀtheꢀstudiedꢀbases,ꢀEt Nꢀshowedꢀtheꢀbestꢀresultsꢀ
3
TheꢀloadingꢀamountꢀofꢀtheꢀPd‐complexꢀonꢀγ‐Fe
2
O
3ꢀwasꢀalsoꢀ
forꢀthisꢀreactionꢀinꢀtermsꢀofꢀreactionꢀtimeꢀandꢀyieldꢀ(Tableꢀ1,ꢀ
entriesꢀ 6–9).ꢀ Theꢀ effectꢀ ofꢀ theꢀ reactionꢀtemperatureꢀwasꢀalsoꢀ
studied.ꢀItꢀwasꢀfoundꢀthatꢀtheꢀreactionꢀtimeꢀincreasedꢀandꢀyieldꢀ
ofꢀ theꢀ desiredꢀ productꢀ decreasedꢀ whenꢀ theꢀ temperatureꢀ wasꢀ
reducedꢀfromꢀ100ꢀtoꢀ80ꢀ°Cꢀ(Tableꢀ1,ꢀentryꢀ10).ꢀIncreasingꢀtheꢀ
quantifiedꢀbyꢀelementalꢀanalysis,ꢀandꢀitꢀwasꢀ0.31ꢀmmol/gꢀbasedꢀ
onꢀ theꢀ nitrogenꢀ andꢀ carbonꢀ amountsꢀ (0.86%ꢀ andꢀ 3.95%,ꢀ re‐
spectively).ꢀ
Theꢀ Pdꢀ contentꢀ ofꢀ Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe
determinedꢀbyꢀICP.ꢀTheꢀICPꢀanalysisꢀshowedꢀthatꢀ0.28ꢀmmolꢀofꢀ
Pdꢀwasꢀanchoredꢀonꢀ1.0ꢀgꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe .ꢀ
TheꢀXPSꢀspectrumꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe 3ꢀisꢀshownꢀ
inꢀ Fig.ꢀ 6.ꢀ Theꢀ observedꢀ peaksꢀ atꢀ 337.6ꢀ (3d5/2)ꢀ andꢀ 342.1ꢀ eVꢀ
2
O3ꢀ wasꢀ
Tableꢀ1ꢀ
2 3
O
Heckꢀ cross‐couplingꢀ reactionꢀ ofꢀ iodobenzeneꢀ withꢀ n‐butylꢀ acrylateꢀ
underꢀdifferentꢀconditions.ꢀ
2
O
Iodobenzene:ꢀ
n‐Butylꢀacrylateꢀ
Timeꢀ
(h)ꢀ
Yieldꢀaꢀ
(%)ꢀ
95ꢀ
63ꢀ
51ꢀ
84ꢀ
59ꢀ
95ꢀ
73ꢀ
(
3d3/2)ꢀcorrespondedꢀtoꢀPdꢀinꢀtheꢀ+2ꢀoxidationꢀstate.ꢀNoꢀpeaksꢀ
Entryꢀ
Baseꢀ
Solventꢀ
DMFꢀ
0
correspondingꢀtoꢀPd ꢀwasꢀdetected.ꢀ
1
ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
1:1.1ꢀ
3
Et Nꢀ
3
Et Nꢀ
3
Et Nꢀ
3
Et Nꢀ
3
Et Nꢀ
3
Et Nꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
24ꢀ
24ꢀ
24ꢀ
24ꢀ
1ꢀ
2
ꢀ
2
H Oꢀ
3
.2.ꢀ ꢀ CatalyticꢀactivityꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O ꢀforꢀtheꢀ
3
3
ꢀ
Tolueneꢀ
EtOHꢀ
HeckꢀandꢀSuzukiꢀcross‐couplingꢀreactionsꢀ
4
ꢀ
5
ꢀ
3
CH CNꢀ
Theꢀ Heckꢀ cross‐couplingꢀ reactionꢀ ofꢀ iodobenzeneꢀ andꢀ
n‐butylꢀacrylateꢀinꢀtheꢀpresenceꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
0.5ꢀmol%)ꢀwasꢀchosenꢀasꢀaꢀmodelꢀreactionꢀforꢀoptimizingꢀtheꢀ
6ꢀ
7ꢀ
8ꢀ
9ꢀ
—ꢀ
—ꢀ
O
2 3ꢀ
K
2
CO
KOHꢀ
NaOAcꢀ
3
ꢀ
—
ꢀ
ꢀ
42ꢀ
64ꢀ
90ꢀ
95ꢀ
traceꢀ
traceꢀ
traceꢀ
traceꢀ
64ꢀ
(
—
reactionꢀ parametersꢀ suchꢀ asꢀ theꢀ baseꢀ andꢀ solventꢀ atꢀ 100ꢀ °Cꢀ
b
—ꢀ
—ꢀ
—ꢀ
—ꢀ
—ꢀ
—ꢀ
—ꢀ
1
1
0ꢀ ꢀ
1ꢀcꢀ
Et
3
Nꢀ
Nꢀ
Et
3
o
12ꢀ
—ꢀ
1
9
98.92 C
9.56%
100
d
1
1
1
1
3ꢀ ꢀ
4ꢀeꢀ
5ꢀfꢀ
6ꢀgꢀ
Et
3
3
3
3
Nꢀ
Et
Et
Et
Nꢀ
Nꢀ
Nꢀ
95
90
85
Reactionꢀ conditions:ꢀ Et
3
Nꢀ 2ꢀ equivalents,ꢀ Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe
O
2 3
0.5ꢀmol%,ꢀ100ꢀ°C.ꢀ
o
a
7
8
99.95 C
5.60%
ꢀIsolatedꢀyield.ꢀ
Temperature:ꢀ80ꢀ°C.ꢀ
Catalyst:ꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
bꢀ
cꢀ
2
O ꢀ(1ꢀmol%).ꢀ
3
d
ꢀNoꢀcatalyst.ꢀ
1
00 200 300 400 500 o600 700 800 900
eꢀ
fꢀ
Catalyst:ꢀγ‐Fe
2
O
3ꢀ(0.04ꢀg).ꢀ
.ꢀ
/γ‐Fe O3ꢀ(1ꢀmol%).ꢀ
Temperature ( C)
Catalyst:ꢀPd(OAc)
2
gꢀ
Catalyst:ꢀPd(OAc)
2
2
Fig.ꢀ5.ꢀTGAꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O .ꢀ
3

560ꢀ
SaraꢀSobhaniꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ36ꢀ(2015)ꢀ555–563ꢀ
molarꢀratioꢀofꢀtheꢀcatalystꢀtoꢀ1ꢀmol%ꢀdidꢀnotꢀhaveꢀanyꢀsignifi‐
cantꢀeffectsꢀonꢀtheꢀprogressꢀofꢀtheꢀreactionꢀ(Tableꢀ1,ꢀentryꢀ11).ꢀ
Aꢀtraceꢀamountꢀofꢀtheꢀdesiredꢀproductꢀwasꢀformedꢀafterꢀ24ꢀhꢀinꢀ
theꢀabsenceꢀofꢀtheꢀcatalystꢀorꢀtheꢀbaseꢀ(Tableꢀ1,ꢀentriesꢀ12ꢀandꢀ
Tableꢀ3ꢀ
Suzukiꢀcross‐couplingꢀreactionꢀofꢀphenylboronicꢀacidꢀwithꢀarylꢀhalidesꢀ
inꢀtheꢀpresenceꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O
3
ꢀasꢀaꢀcatalystꢀatꢀ100ꢀ°C.ꢀ
HO
Pd-isatin Schiff base--Fe
Et
2
O
3
(0.5mol%)
X
+
B
N, 100 oC, solvent-free
R
3
R
HO
1
3).ꢀTheseꢀresultsꢀshowedꢀtheꢀimportanceꢀofꢀtheꢀcatalystꢀandꢀ
theꢀbaseꢀforꢀthisꢀreaction.ꢀTheꢀcross‐couplingꢀreactionsꢀdidꢀnotꢀ
takeꢀplaceꢀinꢀtheꢀpresenceꢀofꢀγ‐Fe ꢀandꢀPd(OAc) ꢀevenꢀafterꢀ
4ꢀ hꢀ (Tableꢀ 1,ꢀ entriesꢀ 14ꢀ andꢀ 15).ꢀ Theꢀ catalyticꢀ activityꢀ ofꢀ
Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe ꢀ wasꢀ higherꢀ thanꢀ thatꢀ ofꢀ
Pd‐supportedꢀγ‐Fe ꢀ[Pd(OAc) /γ‐Fe ]ꢀasꢀaꢀcatalystꢀ(Tableꢀ
,ꢀentryꢀ16).ꢀ
Then,ꢀtheꢀreactionꢀofꢀaꢀvarietyꢀofꢀarylꢀhalidesꢀwithꢀolefinsꢀinꢀ
theꢀ presenceꢀ ofꢀ Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe ꢀ (0.5ꢀ mol%)ꢀ andꢀ
Et Nꢀatꢀ100ꢀ°Cꢀunderꢀsolvent‐freeꢀconditionsꢀwasꢀinvestigated.ꢀ
Timeꢀ
Isolatedꢀ
yieldꢀ(%)
95ꢀ
93ꢀ
86ꢀ
ꢀ 90ꢀ*ꢀ
ꢀ 70ꢀ*ꢀ
97ꢀ
Entryꢀ ꢀ
Arylꢀhalideꢀ
PhIꢀ
(
min)ꢀ
ꢀ 30ꢀ
180ꢀ
ꢀ 45ꢀ
ꢀ 45ꢀ
ꢀ 45ꢀ
270ꢀ
ꢀ 90ꢀ
270ꢀ
ꢀ 60ꢀ
120ꢀ
O
2 3
2
1
2
ꢀ ꢀ
ꢀ ꢀ
2
4‐MeOC
4‐ClC
PhBrꢀ
4‐MeOC
4‐O NC
4‐NCC
PhClꢀ
NC
4‐NCC
6
H
4
Iꢀ
O
2 3
3ꢀ ꢀ
4ꢀ ꢀ
6
H
4
Iꢀ
O
2 3
2
O
2 3
5ꢀ ꢀ
6ꢀ ꢀ
7ꢀ ꢀ
8ꢀ ꢀ
6
H
4
Brꢀ
Brꢀ
1
2
6
H
H
4
6
4
Brꢀ
60ꢀ
O
2 3
ꢀ 90ꢀ*ꢀ
ꢀ 93ꢀ*ꢀ
ꢀ 76ꢀ*ꢀ
3
9ꢀ ꢀ
10ꢀ ꢀ
4‐O
2
6
H
H
4
Clꢀ
Clꢀ
TheꢀresultsꢀofꢀthisꢀstudyꢀareꢀcollectedꢀinꢀTableꢀ2.ꢀAsꢀexpected,ꢀ
theꢀcatalystꢀdemonstratedꢀexcellentꢀefficiencyꢀinꢀtheꢀreactionꢀofꢀ
arylꢀ iodidesꢀ withꢀ alkylꢀ acrylatesꢀ andꢀ gaveꢀ theꢀ correspondingꢀ
productsꢀ inꢀ highꢀ yieldsꢀ (Tableꢀ 2,ꢀ entriesꢀ 1–6).ꢀ Arylꢀ bromidesꢀ
underwentꢀtheꢀreactionꢀwithꢀn‐butylꢀacrylateꢀtoꢀaffordꢀtheꢀde‐
siredꢀproductsꢀinꢀgoodꢀtoꢀhighꢀyieldsꢀ(Tableꢀ2,ꢀentriesꢀ7–9).ꢀItꢀisꢀ
6
4
Reactionꢀconditions:ꢀarylꢀhalideꢀ1ꢀmmol,ꢀphenylboronicꢀacidꢀ1.1ꢀmmol,ꢀ
Et Nꢀ2ꢀmmol,ꢀcatalystꢀ0.5ꢀmol%ꢀ(*ꢀ1.5ꢀmol%).ꢀProductsꢀwereꢀcharacter‐
izedꢀbyꢀcomparisonꢀofꢀtheirꢀphysicalꢀpropertiesꢀwithꢀreferenceꢀsamplesꢀ
3
[59,60].ꢀ
ꢀ
tron‐donatingꢀ andꢀ electron‐withdrawingꢀ groupsꢀ underwentꢀ
theꢀcross‐couplingꢀreactionꢀwithꢀphenylboronicꢀacidꢀtoꢀproduceꢀ
theꢀcorrespondingꢀproductsꢀinꢀgoodꢀtoꢀhighꢀyields.ꢀ ꢀ
importantꢀ toꢀ noteꢀ thatꢀ Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe
2
O ꢀ wasꢀ
3
successfullyꢀappliedꢀasꢀaꢀcatalystꢀforꢀtheꢀreactionꢀofꢀarylꢀchlo‐
ridesꢀwithꢀn‐butylꢀacrylateꢀ(Tableꢀ2,ꢀentriesꢀ10–12).ꢀTheꢀreac‐
tionꢀofꢀarylꢀiodides,ꢀbromidesꢀandꢀchloridesꢀwithꢀstyreneꢀalsoꢀ
proceededꢀwellꢀ(Tableꢀ2,ꢀentriesꢀ13–20).ꢀ ꢀ
3.3.ꢀ ꢀ Recyclingꢀofꢀtheꢀcatalystꢀ
FollowingꢀthisꢀinitialꢀsuccessꢀinꢀtheꢀHeckꢀcross‐couplingꢀre‐
action,ꢀ weꢀ investigatedꢀ theꢀ applicationꢀ ofꢀ Pd‐isatinꢀ Schiffꢀ
Inꢀ Fig.ꢀ 7,ꢀ theꢀ resultsꢀ ofꢀ theꢀ recyclingꢀ ofꢀ Pd‐isatinꢀ Schiffꢀ
2 3
base‐γ‐Fe O ꢀ forꢀ fiveꢀ consecutiveꢀ runsꢀ ofꢀ theꢀ halobenzenesꢀ
base‐γ‐Fe O3ꢀinꢀtheꢀSuzukiꢀreaction.ꢀAsꢀshownꢀinꢀTableꢀ3,ꢀvari‐
2
(
iodo,ꢀbromoꢀandꢀchloro)ꢀwithꢀn‐butylꢀacrylateꢀ(Heckꢀreaction)ꢀ
ousꢀ arylꢀ iodides,ꢀ bromidesꢀ andꢀ chloridesꢀ containingꢀ elec‐
andꢀphenylboronicꢀacidꢀ(Suzukiꢀreaction)ꢀareꢀpresented.ꢀAfterꢀ
eachꢀ run,ꢀ EtOAcꢀ wasꢀ addedꢀ toꢀ theꢀ reactionꢀ mixtureꢀ andꢀ theꢀ
catalystꢀ wasꢀ separatedꢀ byꢀ anꢀ externalꢀ magnet,ꢀ washedꢀ withꢀ
Tableꢀ2ꢀ
Heckꢀcross‐couplingꢀreactionꢀofꢀolefinsꢀwithꢀarylꢀhalidesꢀinꢀtheꢀpresenceꢀ
ofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O ꢀasꢀaꢀcatalystꢀatꢀ100ꢀ°C.ꢀ
3
(a)
Iodobenzene
Chlorobenzene
Bromobenzene
R'
2 3
Pd-isatin Schiff base--Fe O (0.5mol%)
X +
Et
3
N, 100 oC, solvent-free
100
R
R
R'
Timeꢀ Isolatedꢀ
h)ꢀ yieldꢀ(%)
80
Entryꢀ ꢀ
Arylꢀhalideꢀ
Olefinꢀ
(
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
ꢀ ꢀ
ꢀ ꢀ
ꢀ ꢀ
ꢀ ꢀ
ꢀ ꢀ
ꢀ ꢀ
ꢀ ꢀ
ꢀ ꢀ
PhIꢀ
PhIꢀ
PhIꢀ
PhIꢀ
CH
CH =C(Me)‐CO
CH =CH‐CO Etꢀ
2
=CH
2
‐CO
2
Meꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
0.5ꢀ
4ꢀ
0.75ꢀ
7ꢀ
2ꢀ
95ꢀ
90ꢀ
92ꢀ
95ꢀ
87ꢀ
90ꢀ
63ꢀ
64ꢀ
ꢀ 90ꢀ*ꢀ
ꢀ 82ꢀ*ꢀ
ꢀ 90ꢀ*ꢀ
ꢀ 90ꢀ*ꢀ
93ꢀ
89ꢀ
90ꢀ
ꢀ 77ꢀ*ꢀ
63ꢀ
71ꢀ
60
40
20
0
2
2
Meꢀ
2
2
n
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
=CH‐CO
=CH‐CO
=CH‐CO
=CH‐CO
=CH‐CO
=CH‐CO
=CH‐CO
=CH‐CO
=CH‐CO
2
2
2
2
2
2
2
2
2
Bu ꢀ
n
4‐MeOC
4‐ClC
PhBrꢀ
NC
4‐NCC
PhClꢀ
NC
4‐NCC
PhIꢀ
4‐MeOC
4‐ClC
PhBrꢀ
4‐NC‐C
4‐O N‐C
PhClꢀ
NC
6
H
4
Iꢀ
Bu ꢀ
n
6
H
4
Iꢀ
Bu ꢀ
n
Bu ꢀ
(b)
Iodobenzene
Chlorobenzene
Bromobenzene
n
4‐O
2
6
H
4
Brꢀ
Brꢀ
Bu ꢀ
100
n
ꢀ ꢀ
6
H
4
Bu ꢀ
5ꢀ
n
0ꢀ ꢀ
1ꢀ ꢀ
2ꢀ
3ꢀ
4ꢀ
5ꢀ
6ꢀ
7ꢀ
8ꢀ
9ꢀ
0ꢀ
Bu ꢀ
0.5ꢀ
0.5ꢀ
2ꢀ
1ꢀ
4ꢀ
2ꢀ
4ꢀ
6ꢀ
5ꢀ
80
60
40
20
0
n
4‐O
2
6
H
4
Clꢀ
Clꢀ
Bu ꢀ
n
6
H
4
Bu ꢀ
PhCH=CH
PhCH=CH
PhCH=CH
PhCH=CH
PhCH=CH
PhCH=CH
PhCH=CH
PhCH=CH
2
ꢀ
2
ꢀ
2
ꢀ
2
ꢀ
2
ꢀ
2
ꢀ
2
ꢀ
2
ꢀ
6
H
4
Iꢀ
6
H
4
Iꢀ
6
H
4
‐Brꢀ
Brꢀ
2
6
H
4
4ꢀ
6ꢀ
ꢀ 60ꢀ*ꢀ
ꢀ 70ꢀ*ꢀ
Nꢀ2ꢀmmol,ꢀ
1
2
3
Run
4
5
4‐O
2
6
H
4
Clꢀ
Reactionꢀconditions:ꢀarylꢀhalideꢀ1ꢀmmol,ꢀolefinꢀ1.1ꢀmmol,ꢀEt
catalystꢀ0.5ꢀmol%ꢀ(*ꢀ1.5ꢀmol%).ꢀTheꢀproductsꢀwereꢀcharacterizedꢀbyꢀ
comparisonꢀ ofꢀ theirꢀ physicalꢀ propertiesꢀ withꢀ theꢀ authenticꢀ samplesꢀ
3
Fig.ꢀ 7.ꢀ Reusabilityꢀ ofꢀ Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe
recyclableꢀ heterogeneousꢀ catalystꢀ forꢀ theꢀ Heckꢀ (halobenzenesꢀ withꢀ
n‐butylꢀacrylate)ꢀ(a)ꢀandꢀSuzukiꢀ(halobenzenesꢀwithꢀphenylboronicꢀacid
b)ꢀcross‐couplingꢀreactionsꢀatꢀ100ꢀ°Cꢀinꢀ0.5ꢀh.ꢀ
2 3
O ꢀ asꢀ aꢀ magneticallyꢀ
[54–58].ꢀ
(

ꢀ
SaraꢀSobhaniꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ36ꢀ(2015)ꢀ555–563ꢀ
561ꢀ
Tableꢀ4ꢀ
2
CatalyticꢀactivityꢀofꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe O3ꢀcomparedꢀwithꢀsomeꢀcatalystsꢀreportedꢀforꢀtheꢀHeckꢀ(n‐butylꢀacrylateꢀwithꢀarylꢀhalides)ꢀandꢀSuzukiꢀ
(phenylboronicꢀacidꢀwithꢀarylꢀhalides)ꢀcouplingꢀreactions.ꢀ
a
En‐ꢀ Couplingꢀ
tryꢀ reaction
Catalystꢀ
(mol%)ꢀ
POCOPꢀ ꢀ(0.3)ꢀ
Timeꢀ
(h)ꢀ
1.5,ꢀ6,ꢀ24ꢀ
4ꢀ
24ꢀ
0.5ꢀ
2ꢀ
Yieldꢀ ꢀ ꢀ
Halide
Conditionsꢀ
CO ,ꢀDMF,ꢀ100ꢀ°Cꢀ
Bu N,ꢀDMA,ꢀ100ꢀ°Cꢀ
CO ,ꢀDMF,ꢀ110ꢀ°Cꢀ
N,ꢀn‐Bu NBr,ꢀ120ꢀ°Cꢀ
DABCO,ꢀSolvent‐free,ꢀ140ꢀ°C
[Ref.]ꢀ
(%)ꢀ ꢀ
94,ꢀ85,ꢀ67ꢀc
95ꢀ
b
1
ꢀ
Heckꢀ
Heckꢀ
Heckꢀ
Heckꢀ
I,ꢀBr,ꢀCl
K
2
3
[61]ꢀ
[62]ꢀ
[63]ꢀ
[64]ꢀ
[65]ꢀ
[45]ꢀ
[47]ꢀ
2
ꢀ
Pd/DIAIONꢀHP20ꢀ(0.2)ꢀ
Iꢀ
Brꢀ
Brꢀ
Iꢀ
3
3ꢀ
[Pd(L)Cl
2
]ꢀdꢀ(0.5)ꢀ
K
2
3
75ꢀ
ꢀe
4ꢀ
Bis(oxamato)palladate(II)ꢀcomplex ꢀ(1)ꢀ
Et
3
4
99ꢀ
92ꢀ
ꢀ
f
5ꢀ
Heckꢀ SMNPs‐supportedꢀ4,5‐diazafluroen‐9‐one‐Pd ꢀ(0.2)
6
ꢀ
Heckꢀ
Heckꢀ
Heckꢀ
Suzukiꢀ
Suzukiꢀ
Suzukiꢀ
Pd‐DABCO‐γ‐Fe
γ‐Fe ‐acetamidine‐Pdꢀ(0.12)ꢀ
Pd‐isatinꢀSchiffꢀbase‐γ‐Fe ꢀ(0.5,ꢀ0.5,ꢀ1.5)ꢀ
2
O
3
ꢀ(1,ꢀ3,ꢀ3)ꢀ
I,ꢀBr,ꢀCl Et
I,ꢀBr,ꢀCl
3
N,ꢀSolvent‐free,ꢀ100ꢀ°Cꢀ
Et N,ꢀDMF,ꢀ100ꢀ°Cꢀ
N,ꢀSolvent‐free,ꢀ100ꢀ°Cꢀ
CO ,ꢀDMF,ꢀ70ꢀ°Cꢀ
CO ,ꢀH O,ꢀ100ꢀ°Cꢀ
.3H O,ꢀH
N,ꢀn‐Bu
PO
N,ꢀDMF,ꢀ100ꢀ°Cꢀ
0.5,ꢀ7,ꢀ24ꢀ
1,ꢀ0.5,ꢀ24ꢀ
0.5,ꢀ7,ꢀ0.5ꢀ
6ꢀ
92,ꢀ83,ꢀ43ꢀg
94,ꢀ69,ꢀ0ꢀ
7
ꢀ
2
O
3
3
8
ꢀ
2
O
3
I,ꢀBr,ꢀCl Et
Iꢀ
3
95,ꢀ63,ꢀ82 thisꢀworkꢀ
ꢀhꢀ
7ꢀ
Pd–BOX (2)ꢀ
K
2
3
100ꢀ
[66]ꢀ
[67]ꢀ
[68]ꢀ
[64]ꢀ
[69]ꢀ
[47]ꢀ
ꢀiꢀ
8
ꢀ
SiO
2
‐pA‐Cyan‐Cys‐Pd (0.5)ꢀ
I,ꢀBr,ꢀCl
K
2
3
2
5,ꢀ5.5,ꢀ6ꢀ
5,ꢀ6,ꢀ13ꢀ
2ꢀ
95,ꢀ88,ꢀ52
98,ꢀ90,ꢀ87
78,ꢀ65ꢀlꢀ
ꢀjꢀ
9
1
1
1
ꢀ
NHC‐Pd(II)ꢀcomplex (0.2)ꢀ
I,ꢀBr,ꢀCl K
I,ꢀBrꢀ
3
PO
Et
4
2
2
O,ꢀTBAB,ꢀ40ꢀ°C
0bꢀ Suzukiꢀ
1cꢀ Suzukiꢀ
2ꢀ
3dꢀ Suzukiꢀ
Bis(oxamato)palladate(II)ꢀcomplex ꢀ(5)ꢀ
ꢀk
3
4
NBr,ꢀ120ꢀ°Cꢀ
ꢀm
77.7,ꢀ0.9ꢀl
Pd
3
(dba) ꢀ(1)ꢀ
Br,ꢀCl
I,ꢀBr,ꢀCl
K
3
4
,ꢀTHF,ꢀ80ꢀ°Cꢀ
24ꢀ
Suzukiꢀ
γꢀ‐Fe
O
‐acetamidine‐Pdꢀ(0.12)ꢀ
ꢀ(0.5,ꢀ1.5,ꢀ1.5)ꢀ
Et
3
0.5,ꢀ0.5,ꢀ10ꢀ 96,ꢀ96,ꢀ41
2
3
1
Pd‐isatinꢀSchiffꢀbase‐γ‐Fe
2
O
3
I,ꢀBr,ꢀCl Et N,ꢀSolvent‐free,ꢀ100ꢀ°Cꢀ 0.5,ꢀ0.75,ꢀ4.5ꢀ 95,ꢀ90,ꢀ90 thisꢀworkꢀ
3
aꢀ
Isolatedꢀyield.ꢀ ꢀ
bꢀ
POCOP:ꢀBisphosphiniteꢀPCP‐pincerꢀpalladiumꢀcomplex.ꢀ ꢀ
NBrꢀwasꢀusedꢀasꢀanꢀadditive.ꢀ ꢀ
L:ꢀ1‐benzyl‐4‐phenylthiomethyl.ꢀ ꢀ
cꢀ
n‐Bu
4
dꢀ
eꢀ
O.ꢀ ꢀ
4 2
Bis(oxamato)palladate(II)ꢀcomplex:ꢀ(n‐Bu N) [Pd(2‐Mepma)
2
].4H
2
fꢀ
SMNPs:ꢀSilica‐coatedꢀmagnetiteꢀnanoparticles.ꢀ ꢀ
g
ꢀ
Conversion.ꢀ
hꢀ
Pd–BOX:ꢀPalladium–bis(oxazoline)ꢀcomplex.ꢀ ꢀ
SiO
iꢀ
‐pA‐Cyan‐Cys‐Pd:ꢀPropylamine‐cyanuric‐cysteineꢀpalladiumꢀcomplexꢀimmobilizedꢀontoꢀsilica.ꢀ
2
jꢀ
NHC‐Pdꢀ(II):ꢀ[1,1‐(hexylene‐1,6‐diyl)bis(3‐n‐butylbenzimidazol‐2‐ylidene)][PdCl
2
(CH
3
CN)] .ꢀ ꢀ
2
kꢀ
4 2
Bis(oxamato)palladate(II)ꢀcomplexes:ꢀ(n‐Bu N) [Pd(2‐Mepma)
2
2
].4H O.ꢀ
lꢀ
DeterminedꢀbyꢀGC.ꢀ ꢀ
mꢀPd
)
3 3 3 6 4 6 5 2 5 6 4 6 4
(dba):ꢀN P (O‐C H ‐p‐P(C H ) ) (O‐C H ‐p‐C H ‐p‐O(CH Si(OCH
2
3
3
3
) .ꢀ
EtOAc,ꢀdriedꢀandꢀre‐usedꢀforꢀaꢀconsecutiveꢀrunꢀunderꢀtheꢀsameꢀ
reactionꢀconditions.ꢀAlthoughꢀnoꢀsignificantꢀlossꢀofꢀtheꢀcatalyticꢀ
reactionsꢀ byꢀ usingꢀ Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe
2
O ꢀ asꢀ aꢀ phos‐
3
phine‐freeꢀPdꢀcatalyst.ꢀTheꢀsynthesisꢀofꢀthisꢀmagneticallyꢀreus‐
ableꢀcatalystꢀfromꢀcommerciallyꢀavailableꢀstartingꢀmaterials,ꢀitsꢀ
goodꢀtoꢀhighꢀyieldsꢀofꢀtheꢀproducts,ꢀandꢀsimpleꢀandꢀconvenientꢀ
methodꢀ forꢀ theꢀ separationꢀ andꢀ reuseꢀ ofꢀ theꢀ catalystꢀ areꢀ theꢀ
advantagesꢀofꢀthisꢀcatalyticꢀsystemꢀforꢀC‐Cꢀbondꢀformationꢀbyꢀ
theꢀ reactionꢀofꢀ arylꢀhalidesꢀ(iodides,ꢀ bromidesꢀandꢀ chlorides)ꢀ
withꢀolefinsꢀandꢀphenylboronicꢀacid.ꢀ ꢀ ꢀ
activityꢀwasꢀobservedꢀforꢀPd‐isatinꢀSchiffꢀbase‐γ‐Fe O3ꢀinꢀtheseꢀ
2
reactions,ꢀ theꢀ amountꢀ ofꢀ Pdꢀ leachedꢀ fromꢀ theꢀ heterogeneousꢀ
catalystꢀwasꢀdeterminedꢀbyꢀICP.ꢀItꢀwasꢀfoundꢀthatꢀlessꢀthanꢀ1ꢀ
ppmꢀ ofꢀ theꢀ totalꢀ amountꢀ ofꢀ theꢀ originalꢀ Pdꢀ speciesꢀ wasꢀ lostꢀ
duringꢀtheꢀreaction.ꢀ
Aꢀ comparisonꢀ ofꢀ theꢀ activityꢀ ofꢀ variousꢀ Pdꢀ catalystsꢀ withꢀ
Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe
reactionsꢀ publishedꢀ inꢀ theꢀ literatureꢀ isꢀ listedꢀ inꢀ Tableꢀ 4.ꢀ Itꢀ
showsꢀ thatꢀ Pd‐isatinꢀ Schiffꢀ base‐γ‐Fe 3ꢀdisplayedꢀ goodꢀ cata‐
2
O3ꢀinꢀ theꢀ Heckꢀ andꢀ Suzukiꢀ couplingꢀ
Acknowledgmentsꢀ
2
O
lyticꢀactivityꢀforꢀtheꢀHeckꢀandꢀSuzukiꢀreactions,ꢀbutꢀcomparedꢀ
withꢀ theꢀ otherꢀ catalysts,ꢀ theꢀ advantageꢀ wasꢀ notꢀ remarkable,ꢀ
andꢀ someꢀ ofꢀ theꢀ otherꢀ catalyticꢀ systemsꢀ wereꢀ muchꢀ better.ꢀ
However,ꢀ ourꢀ procedureꢀ providesꢀ significantꢀ advantagesꢀ inꢀ
termsꢀofꢀaꢀcatalystꢀsimplyꢀpreparedꢀfromꢀanꢀinexpensiveꢀligandꢀ
andꢀitꢀwasꢀactiveꢀwithꢀdifferentꢀhalobenzenesꢀ(iodo,ꢀbromoꢀandꢀ
chloro)ꢀ withꢀ desirableꢀ yields.ꢀ Moreꢀ importantly,ꢀ amongꢀ theꢀ
supportedꢀ Pdꢀ catalysts,ꢀ ourꢀ catalystꢀ supportedꢀ onꢀ magneticꢀ
nanoparticlesꢀ canꢀ beꢀ easilyꢀ separatedꢀ fromꢀ theꢀ reactionꢀ mix‐
tureꢀbyꢀanꢀexternalꢀmagnet.ꢀ
FinancialꢀsupportꢀofꢀthisꢀprojectꢀbyꢀtheꢀIranꢀNationalꢀScienceꢀ
Foundationꢀ(INSF)ꢀandꢀUniversityꢀofꢀBirjandꢀResearchꢀCouncilꢀ
isꢀappreciated.ꢀ
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Pd‐isatinꢀSchiffꢀbaseꢀcomplexꢀimmobilizedꢀonꢀγ‐Fe 3ꢀasꢀaꢀ
2
O
magneticallyꢀrecyclableꢀcatalystꢀforꢀtheꢀHeckꢀandꢀSuzukiꢀ
cross‐couplingꢀreactionsꢀ
ꢀ
SaraꢀSobhani*,ꢀFarzanehꢀZarifiꢀ
-Fe2O3
HO
HO
R'
B
UniversityꢀofꢀBirjand,ꢀIranꢀ
O
O
Si O O Si
X
X
ꢀ
ꢀ
R
R
N
HN
N
OAc
NH
Pd
OAc
AcO
O
R
R'
O
R
OAc
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