A Nickel-Doped Dehydrobenzoannulene-Based Two-Dimensional Covalent Organic Framework for the Reductive Cleavage of Inert Aryl C-S Bonds

Article abstract of DOI:10.1021/jacs.0c01026

The development of metalated covalent organic frameworks (COFs) is useful for generating recyclable catalytic systems for practical applications. Herein, we report the synthesis, characterization, and catalytic properties of an azine-linked two-dimensional (2D) COF containing nickel-doped dehydrobenzoannulene (DBA) units. We demonstrate that Ni-DBA-2D-COF can be used to reductively cleave the aryl C-S bonds of several organosulfur compounds utilizing dimethylethylsilane as the reducing agent. The Ni-DBA-2D-COF catalytic system displays excellent recyclability and good yields. This work highlights a rare example of utilizing metalated DBA complexes to perform catalytic transformations.

Full text of DOI:10.1021/jacs.0c01026

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Communication
A Nickel-Doped Dehydrobenzoannulene-Based Two-Dimensional Covalent
Organic Framework for the Reductive Cleavage of Inert Aryl C-S Bonds
W. Karl Haug, Eric R. Wolfson, Blake T. Morman, Christine M. Thomas, and Psaras L. McGrier
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c01026 • Publication Date (Web): 12 Mar 2020
Downloaded from pubs.acs.org on March 12, 2020
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A Nickel-Doped Dehydrobenzoannulene-Based Two-Dimensional
Covalent Organic Framework for the Reductive Cleavage of Inert
Aryl C-S Bonds
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W.ꢀKarlꢀHaug,ꢀEricꢀR.ꢀWolfson,ꢀBlakeꢀT.ꢀMorman,ꢀChristineꢀM.ꢀThomas,ꢀPsarasꢀL.ꢀMcGrier*ꢀ
DepartmentꢀofꢀChemistryꢀandꢀBiochemistry,ꢀTheꢀOhioꢀStateꢀUniversity,ꢀColumbus,ꢀOhio,ꢀ43210,ꢀUnitedꢀStatesꢀꢀ
ꢀ
ꢀ
SupportingꢀInformationꢀPlaceholder
ABSTRACTꢀ Theꢀ developmentꢀ ofꢀ metalatedꢀ covalentꢀ organicꢀ
frameworksꢀ(COFs)ꢀisꢀusefulꢀforꢀgeneratingꢀrecyclableꢀcatalyt-
icꢀ systemsꢀ forꢀ practicalꢀ applications.ꢀ Herein,ꢀ weꢀ reportꢀ theꢀ
synthesis,ꢀ characterization,ꢀ andꢀ catalyticꢀ propertiesꢀ ofꢀ anꢀ
azine-linkedꢀ two-dimensionalꢀ (2D)ꢀ COFꢀ containingꢀ nickel-
dopedꢀdehydrobenzoannuleneꢀ(DBA)ꢀunits.ꢀꢀWeꢀdemonstrateꢀ
thatꢀNi-DBA-2D-COFꢀcanꢀbeꢀusedꢀtoꢀreductivelyꢀcleaveꢀtheꢀarylꢀ
C-Sꢀ bondsꢀ ofꢀ severalꢀ organosulfurꢀ compoundsꢀ utilizingꢀ di-
methylethylsilaneꢀasꢀtheꢀreducingꢀagent.ꢀTheꢀNi-DBA-2D-COFꢀ
catalyticꢀ systemꢀ displaysꢀ excellentꢀ recyclabilityꢀ andꢀ goodꢀ
yields.ꢀThisꢀworkꢀhighlightsꢀaꢀrareꢀexampleꢀofꢀutilizingꢀmeta-
latedꢀDBAꢀcomplexesꢀtoꢀperformꢀcatalyticꢀtransformations.ꢀꢀꢀꢀ
Schemeꢀ1.ꢀSynthesisꢀofꢀDBA-COF-5ꢀusingꢀDBA[12]-CHOꢀandꢀ
Hydrazineꢀ Monomerꢀ Unitsꢀ Followedꢀ byꢀ Metalationꢀ withꢀ
Ni(COD)
2
ꢀtoꢀProduceꢀNi-DBA-2D-COF.ꢀ
O
N
N
N
N
O
O
DBA[12]-CHO
N
N
o-DCB / n-BuOH / 6M AcOH
120 ˚C / 72 h
+
DBA-COF 5
N
N
2 2
H N NH
Hydrazine
N
N
N
N
N
N
Theꢀ reductiveꢀ cleavageꢀ ofꢀ C-Sꢀ bondsꢀ (i.e.,ꢀ hydrodesulfuriza-
tionꢀ(HDS))ꢀplaysꢀaꢀpivotalꢀroleꢀinꢀremovingꢀsulfurꢀimpuritiesꢀ
fromꢀpetroleumꢀfeedstocksꢀtoꢀproduceꢀcleanꢀchemicalꢀfuels. ꢀ
N
N
1
N
N
TheꢀC-Sꢀbondsꢀofꢀorganosulfurꢀcompoundsꢀcanꢀalsoꢀbeꢀutilizedꢀ
asꢀcleavableꢀdirectingꢀgroupsꢀtoꢀhelpꢀproduceꢀsyntheticꢀpre-
Ni-DBA-2D-COF
N
Ni(COD)
Toluene
2
N
2
cursors. ꢀWhileꢀbothꢀchemicalꢀtransformationsꢀareꢀoftenꢀac-
3
4
N
N
complishedꢀusingꢀexpensiveꢀtransitionꢀmetalsꢀ(i.e.,ꢀPd, ꢀꢀRh, ꢀ
etc.),ꢀitꢀisꢀmuchꢀmoreꢀdesirableꢀtoꢀuseꢀcheapꢀearthꢀabundantꢀ
metalsꢀlikeꢀNi,ꢀwhichꢀareꢀlessꢀtoxicꢀandꢀmoreꢀenvironmentallyꢀ
N N
=
Ni(0)
5
friendly.ꢀInterestingly,ꢀVicicꢀandꢀJonesꢀhaveꢀshown ꢀthatꢀtheꢀ
__________________________________________________ꢀ
2
HDSꢀofꢀthiopheneꢀcanꢀbeꢀachievedꢀbyꢀusingꢀaꢀ[(dippe)NiH)] ꢀ
ofꢀcrystallineꢀporousꢀpolymers,ꢀhaveꢀemergedꢀasꢀanꢀexcellentꢀ
platformꢀtoꢀaddressꢀtheseꢀissuesꢀdueꢀtoꢀtheirꢀhighꢀchemicalꢀ
stability,ꢀtunableꢀporeꢀsizes,ꢀandꢀhighꢀinternalꢀsurfaceꢀareas.ꢀ
TheseꢀꢀꢀcharacteristicsꢀꢀꢀmakeꢀꢀꢀCOFsꢀꢀꢀusefulꢀꢀꢀforꢀꢀꢀapplicationsꢀ
nickelꢀhydrideꢀdimerꢀandꢀhydrogenꢀgasꢀasꢀtheꢀreducingꢀagent.ꢀ
6
Alternatively,ꢀMartinꢀandꢀcoworkersꢀhaveꢀdemonstrated ꢀthatꢀ
unactivatedꢀarylꢀC-Sꢀbondsꢀcanꢀbeꢀreductivelyꢀcleavedꢀusingꢀaꢀ
bis(1,5-cyclooctadiene)nickel(0)ꢀ (Ni(COD)
2
)ꢀ complexꢀ andꢀ hy-
12,13ꢀ
14,15
relatedꢀ toꢀ gasꢀ storage,
protonꢀ conduction, ꢀ cataly-
drosilanesꢀ asꢀ theꢀ reducingꢀ agents.ꢀ Whileꢀ bothꢀ reactionsꢀ areꢀ
effectiveꢀunderꢀhomogenousꢀconditions,ꢀcomplicationsꢀasso-
ciatedꢀwithꢀcatalystꢀstability,ꢀrecyclability,ꢀandꢀcatalystꢀsepa-
rationꢀ areꢀ stillꢀ aꢀ challenge.ꢀ Althoughꢀ Raneyꢀ nickelꢀ hasꢀ beenꢀ
utilizedꢀforꢀmanyꢀdecadesꢀasꢀanꢀeffectiveꢀheterogeneousꢀcata-
16,17
18,19
20-22
sis, ꢀoptoelectronics, ꢀandꢀenergyꢀstorage. ꢀTheꢀmod-
ularꢀnatureꢀofꢀCOFsꢀpermitsꢀtheꢀintegrationꢀofꢀsuitableꢀmon-
omerꢀ unitsꢀ thatꢀ canꢀ beꢀ metalatedꢀ andꢀ utilizedꢀ toꢀ completeꢀ
anyꢀdesirableꢀcatalyticꢀtransformation.ꢀForꢀinstance,ꢀLiu,ꢀCui,ꢀ
23
andꢀ coworkersꢀ haveꢀ shown ꢀ thatꢀ salen-basedꢀ two-
7,8ꢀ
lystꢀforꢀtheꢀreductiveꢀcleavageꢀofꢀC-Sꢀbonds, ꢀtheꢀefficiencyꢀꢀꢀꢀꢀꢀꢀ
ofꢀtheꢀcatalystꢀsignificantlyꢀdecreasesꢀafterꢀtheꢀfirstꢀreduction.ꢀꢀꢀ
Thus,ꢀ itꢀ isꢀ advantageousꢀ toꢀ developꢀ novelꢀ heterogeneousꢀ
catalyticꢀsystemsꢀtoꢀhelpꢀimproveꢀtheꢀefficiencyꢀandꢀrecycla-
bilityꢀofꢀtheꢀcatalysts.ꢀꢀꢀ
dimensionalꢀ(2D)ꢀchiralꢀCOFꢀꢀsystemsꢀꢀmetalatedꢀꢀwithꢀꢀFeꢀꢀorꢀꢀ
Mnꢀ ꢀ areꢀ ꢀ effectiveꢀ atꢀ catalyzingꢀ theꢀ epoxidationꢀ ofꢀ alkenes.ꢀ
Fangꢀ andꢀ coworkersꢀ haveꢀ alsoꢀ demonstrated ꢀ thatꢀ three-
dimensionalꢀ (3D)ꢀ salphen-basedꢀ COFꢀ systemsꢀ metalatedꢀꢀꢀꢀ
withꢀCu(II)ꢀareꢀusefulꢀꢀforꢀremovingꢀꢀsuperoxideꢀꢀradicalsꢀꢀfromꢀ
24
9
-11ꢀ
ꢀ
ꢀꢀCovalentꢀorganicꢀframeworksꢀꢀ(COFs), ꢀanꢀꢀadvancedꢀꢀclassꢀ
antioxidants.ꢀWhileꢀbothꢀofꢀtheꢀsystemsꢀhighlightꢀtheꢀutilityꢀofꢀ
ACS Paragon Plus Environment

Journal of the American Chemical Society
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Figureꢀ2.ꢀIndexedꢀexperimentalꢀ(red)ꢀandꢀPawleyꢀrefinedꢀ(blue)ꢀ
PXRDꢀpatternsꢀofꢀDBA-COFꢀ5ꢀcomparedꢀtoꢀtheꢀsimulatedꢀhexago-
nalꢀunitꢀcellꢀ(green)ꢀwithꢀanꢀoffsetꢀofꢀ9ꢀÅ,ꢀandꢀviewsꢀalongꢀtheꢀxꢀ
andꢀyꢀdirections.ꢀ
1.5ꢀ
1ꢀ
0.5ꢀ
0ꢀ
ꢀ
1ꢀ
2ꢀ
3ꢀ
4ꢀ
gloveboxꢀforꢀ16ꢀhꢀtoꢀproduceꢀNi-DBA-2D-COFꢀasꢀaꢀdarkꢀgreenꢀ
crystallineꢀpowder.ꢀNi-DBA-2D-COFꢀwasꢀobtainedꢀbyꢀfiltrationꢀ
andꢀ washedꢀ withꢀ dryꢀ hexanesꢀ toꢀ removeꢀ excessꢀ Ni(COD)
Inductivelyꢀ coupledꢀ plasma-atomicꢀ emissionꢀ spectroscopyꢀ
ICP-AES)ꢀanalysisꢀrevealedꢀthatꢀ~ꢀ8.56ꢀwtꢀ%ꢀofꢀNiꢀwasꢀincor-
PoreꢀWidthꢀ(nm)ꢀ
ꢀ
Figureꢀ 1.ꢀ Nitrogenꢀ adsorption/desorptionꢀ isothermsꢀ (top)ꢀ andꢀ
NLDFTꢀporeꢀsizeꢀdistributionsꢀ(bottom)ꢀforꢀDBA-COFꢀ5ꢀ(red)ꢀandꢀ
Ni-DBA-2D-COFꢀ(blue)ꢀmeasuredꢀatꢀ77ꢀK.ꢀ
2
.ꢀ
(
poratedꢀintoꢀNi-DBA-2D-COF,ꢀwhichꢀcorrespondsꢀtoꢀ~ꢀ64%ꢀofꢀ
DBA[12]ꢀunitsꢀbeingꢀmetalated.ꢀꢀꢀ
ꢀ
COFsꢀ asꢀ heterogeneousꢀ catalysts,ꢀ examplesꢀ ofꢀ usingꢀ COF-
basedꢀsystemsꢀtoꢀreductivelyꢀcleaveꢀC-Sꢀbondsꢀhaveꢀnotꢀbeenꢀ
reported.ꢀ
ꢀ
ꢀꢀTheꢀ porosityꢀ ofꢀ DBA-COFꢀ 5ꢀ andꢀ Ni-DBA-2D-COFꢀ wereꢀ de-
terminedꢀbyꢀnitrogenꢀgasꢀadsorptionꢀmeasurementsꢀatꢀ77ꢀK.ꢀ
DBA-COFꢀ 5ꢀ exhibitedꢀ aꢀ type-Iꢀ isothermꢀ displayingꢀ aꢀ sharpꢀ
uptakeꢀatꢀlowꢀpressureꢀ(P/P
microporousꢀmaterialꢀ(Figureꢀ1).ꢀTheꢀBrunauer-Emmett-Tellerꢀ
BET)ꢀmodelꢀwasꢀappliedꢀoverꢀtheꢀlow-pressureꢀregionꢀ(0.03ꢀ<ꢀ
P/P ꢀ<ꢀ0.07)ꢀofꢀtheꢀisothermꢀtoꢀaffordꢀaꢀsurfaceꢀareaꢀofꢀ1643ꢀ
ꢀ
ꢀꢀHerein,ꢀweꢀreportꢀtheꢀsynthesis,ꢀcharacterization,ꢀandꢀcata-
lyticꢀpropertiesꢀofꢀanꢀazine-linkedꢀ2DꢀCOFꢀcontainingꢀnickel-
0
ꢀ<ꢀ0.1),ꢀwhichꢀisꢀindicativeꢀofꢀaꢀ
2
5
dopedꢀdehydrobenzoannuleneꢀ(DBA) ꢀunits.ꢀDBAsꢀareꢀplanarꢀ
triangular-shapedꢀꢀꢀmacrocyclesꢀꢀꢀꢀthatꢀꢀꢀꢀhaveꢀꢀꢀꢀtheꢀꢀꢀabilityꢀꢀꢀ
toꢀꢀꢀuseꢀꢀꢀtheirꢀꢀꢀsoftꢀalkynylꢀligandsꢀtoꢀformꢀcomplexesꢀwithꢀ
lowꢀ oxidationꢀ stateꢀ transitionꢀ metals. ꢀ However,ꢀ toꢀ theꢀ
bestꢀofꢀourꢀknowledge,ꢀtheꢀcatalyticꢀactivityꢀofꢀmetalatedꢀDBAꢀ
complexesꢀhasꢀnotꢀbeenꢀreported.ꢀWeꢀdemonstrateꢀthatꢀtheꢀ
DBA[12]ꢀmonomerꢀunitsꢀofꢀDBA-COFꢀ5ꢀcanꢀbeꢀmetalatedꢀwithꢀ
(
0
2
-1
2
6,27
0
m ꢀg .ꢀTheꢀtotalꢀporeꢀvolumeꢀcalculatedꢀatꢀP/P ꢀ=ꢀ0.899ꢀpro-
3
-1
videdꢀ aꢀ valueꢀ ofꢀ 0.70ꢀ cm ꢀ g .ꢀ Theꢀ poreꢀ sizeꢀ distributionꢀ ofꢀ
DBA-COFꢀ 5ꢀ wasꢀ estimatedꢀ usingꢀ theꢀ nonlocalꢀ densityꢀ func-
tionalꢀtheoryꢀmethodꢀ(NLDFT)ꢀyieldingꢀanꢀaverageꢀporeꢀsizeꢀofꢀ
1.9ꢀnm.ꢀTheꢀexperimentalꢀporeꢀsizeꢀisꢀlowerꢀthanꢀtheꢀtheoret-
icalꢀvalueꢀofꢀ2.8ꢀnm,ꢀwhichꢀsuggestsꢀthatꢀtheꢀadjacentꢀlayersꢀ
areꢀsignificantlyꢀoffset.ꢀInꢀcontrast,ꢀNi-DBA-2D-COFꢀalsoꢀexhib-
itedꢀaꢀtype-Iꢀisotherm.ꢀApplicationꢀofꢀtheꢀBETꢀmodelꢀoverꢀtheꢀ
2
Ni(COD) ꢀtoꢀgenerateꢀNi-DBA-2D-COF,ꢀandꢀusedꢀtoꢀreductivelyꢀ
cleaveꢀtheꢀinertꢀarylꢀC-Sꢀbondsꢀofꢀseveralꢀorganosulfurꢀcom-
poundsꢀusingꢀdimethylethylsilaneꢀasꢀtheꢀreducingꢀagent.ꢀ Ni-
DBA-2D-COFꢀ exhibitsꢀ greatꢀ recyclabilityꢀ withꢀ yieldsꢀ thatꢀ areꢀ
comparableꢀ toꢀ otherꢀ Ni-basedꢀ homogeneousꢀ catalyticꢀ sys-
tems.ꢀ
0
low-pressureꢀ regionꢀ (0.03ꢀ <ꢀ P/P ꢀ <ꢀ 0.07)ꢀ providedꢀ aꢀ surfaceꢀ
2
-1
areaꢀofꢀ1565ꢀm ꢀg .ꢀTheꢀNLDFTꢀporeꢀsizeꢀofꢀNi-DBA-2D-COFꢀ
revealedꢀaꢀslightꢀreductionꢀtoꢀ1.8ꢀnm,ꢀwhichꢀisꢀveryꢀcloseꢀtoꢀ
theꢀexperimentalꢀporeꢀsizeꢀofꢀtheꢀDBA-COFꢀ5.ꢀTheꢀtotalꢀporeꢀ
volumeꢀ calculatedꢀ atꢀ P/P ꢀ =ꢀ 0.899ꢀ providedꢀ aꢀ valueꢀ ofꢀ 0.68ꢀ
0
cm ꢀg .ꢀ
ꢀꢀTheꢀ crystallinityꢀ ofꢀ DBA-COFꢀ 5ꢀ andꢀ Ni-DBA-2D-COFꢀ wereꢀ
evaluatedꢀusingꢀpowderꢀX-rayꢀdiffractionꢀ(PXRD).ꢀConsideringꢀ
theꢀ differencesꢀ betweenꢀ theꢀ experimentalꢀ andꢀ theoreticalꢀ
poreꢀsizes,ꢀDBA-COFꢀ5ꢀwasꢀmodeledꢀusingꢀaꢀP6ꢀhexagonalꢀunitꢀ
cellꢀinꢀwhichꢀtheꢀadjacentꢀlayersꢀwereꢀoffsetꢀbyꢀ9ꢀÅ (Figureꢀ2).ꢀꢀ
DBA-COFꢀ 5ꢀ exhibitsꢀ anꢀ intenseꢀ peakꢀ atꢀ 3.89°ꢀ followedꢀ byꢀ
smallerꢀ peaksꢀ atꢀ 6.73°ꢀ andꢀ 26.5°,ꢀ whichꢀ correspondꢀ toꢀ theꢀ
ꢀ
ꢀꢀDBA-COFꢀ5ꢀwasꢀsynthesizedꢀbyꢀreactingꢀDBA[12]-CHOꢀwithꢀ
hydrazineꢀinꢀo-dichlorobenzeneꢀ(o-DCB),ꢀn-butanolꢀ(n-BuOH),ꢀ
andꢀ6Mꢀaceticꢀacidꢀ(AcOH)ꢀinꢀaꢀflame-sealedꢀampuleꢀatꢀ120ꢀ°Cꢀ
forꢀ 72ꢀ hꢀ (Schemeꢀ 1).ꢀ DBA-COFꢀ 5ꢀ wasꢀ obtainedꢀ byꢀ filtrationꢀ
andꢀwashedꢀwithꢀmethanolꢀtoꢀproduceꢀaꢀbrightꢀyellowꢀcrystal-
lineꢀpowder.ꢀThermogravimetricꢀanalysisꢀrevealedꢀthatꢀDBA-
COFꢀ5ꢀmaintainsꢀ~ꢀ95%ꢀofꢀit’sꢀweightꢀupꢀtoꢀ430ꢀ°Cꢀ(FigureꢀS10,ꢀ
SI).ꢀ Scanningꢀ electronꢀ microscopyꢀ (SEM)ꢀ imagesꢀ ꢀ revealedꢀꢀꢀ
theꢀꢀformationꢀꢀofꢀfluffy-likeꢀcrystallitesꢀ(FigureꢀS11,ꢀSI).ꢀMeta-
lationꢀwasꢀachievedꢀbyꢀcombiningꢀ67ꢀmgꢀofꢀDBA-COFꢀ5ꢀwithꢀ
3
-1
ꢀ
49ꢀ mgꢀ ofꢀ Ni(COD)
wasꢀꢀthenꢀꢀstirredꢀꢀatꢀꢀroomꢀꢀtemperatureꢀꢀinꢀꢀanꢀargon-purgedꢀ
2
ꢀ inꢀ 6.5ꢀ mlꢀ ofꢀ dryꢀ toluene.ꢀ Theꢀ mixtureꢀꢀꢀꢀꢀꢀꢀ
(
100),ꢀ (110),ꢀ andꢀ (001)ꢀ planes,ꢀ respectively.ꢀ Pawleyꢀ refine-
mentꢀꢀofꢀꢀtheꢀexperimentalꢀdataꢀprovidedꢀunitꢀcellꢀparametersꢀ
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Journal of the American Chemical Society
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00ꢀ
7ꢀ
6ꢀ
5ꢀ
4ꢀ
3ꢀ
1
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9
0ꢀ
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70ꢀ
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40ꢀ
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1
0ꢀ
0ꢀ
0ꢀ
2ꢀ
1ꢀ
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0
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0
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9
0
1
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9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
0ꢀ
0ꢀ
200ꢀ
1
ꢀ
2ꢀ
3ꢀ
4ꢀ
5ꢀ
300ꢀ
400ꢀ
500ꢀ
600ꢀ
700ꢀ
800ꢀ
NumberꢀofꢀCyclesꢀ
ꢀ
Wavelengthꢀ(nm)ꢀ
ꢀ
Figureꢀ4.ꢀRecyclabilityꢀofꢀNi-DBA-2D-COFꢀafterꢀreductivelyꢀcleav-
ingꢀ 2-(methylthio)naphthaleneꢀ (1c)ꢀ atꢀ 130ꢀ °Cꢀ usingꢀ di-
methylethylsilaneꢀasꢀtheꢀreducingꢀagent.ꢀꢀ
Figureꢀ 3.ꢀ Kubelka-Munkꢀ diffuseꢀ reflectanceꢀ spectraꢀ andꢀ photo-
graphsꢀofꢀDBA-COFꢀ5ꢀ(orange)ꢀandꢀNi-DBA-2D-COFꢀ(green).ꢀ
ꢀ
ꢀ
ofꢀaꢀ=ꢀbꢀ=ꢀ26.222ꢀÅꢀandꢀcꢀ=ꢀ3.4ꢀÅꢀ(residualsꢀRpꢀ=ꢀ3.81%,ꢀRwpꢀ=ꢀ
5.12%)ꢀ Theꢀ simulatedꢀ patternsꢀ wereꢀ almostꢀ identicalꢀ toꢀ theꢀ
experimentalꢀplot.ꢀItꢀshouldꢀbeꢀnotedꢀthatꢀtheꢀcrystallinityꢀofꢀ
DBA-COFꢀ5ꢀisꢀmaintainedꢀafterꢀsoakingꢀtheꢀmaterialꢀinꢀaque-
ous,ꢀ acidic,ꢀ andꢀ basicꢀ solutionsꢀ forꢀ 24ꢀ hꢀ (Figureꢀ S5,ꢀ SI).ꢀ Theꢀ
PXRDꢀ profileꢀ ofꢀ Ni-DBA-2D-COFꢀ alsoꢀ revealedꢀ retentionꢀ ofꢀ
crystallinityꢀfollowingꢀmetalationꢀwithꢀNi(COD)2ꢀ(FigureꢀS4,ꢀSI).ꢀꢀ
Surprisingly,ꢀ Fourierꢀ transformꢀ infraredꢀ (FT-IR)ꢀ spectraꢀ ofꢀ
DBA-COFꢀ 5ꢀ andꢀ Ni-DBA-2D-COFꢀ bothꢀ exhibitedꢀ identicalꢀ –
C=N-ꢀ andꢀ –N-N-ꢀ stretchingꢀ modesꢀ atꢀ 1620ꢀ andꢀ 1081ꢀ cm ,ꢀ
respectively,ꢀwhichꢀsuggestsꢀthatꢀtheꢀmetalꢀisꢀpredominantlyꢀꢀꢀ
boundꢀ withinꢀ theꢀ cavityꢀ ofꢀ DBA[12]ꢀ ꢀ toꢀ produceꢀ aꢀ Ni(0)ꢀ 16ꢀ
electronꢀ complex withꢀ virtuallyꢀ noꢀ interactionꢀ atꢀ theꢀ azineꢀ
linkageꢀ(FigureꢀS1,ꢀSI).ꢀꢀꢀꢀ
distinctꢀ resonanceꢀ atꢀ ~ꢀ 93ꢀ ppmꢀ (Figureꢀ S6,ꢀ SI).ꢀ Afterꢀ meta-
lation,ꢀtheꢀalkynylꢀpeakꢀofꢀDBA-COFꢀ5ꢀshiftsꢀdownfieldꢀtoꢀ~109ꢀ
ppm,ꢀ whichꢀ isꢀ indicativeꢀ ofꢀ formingꢀ theꢀ DBA-Ni(0)ꢀ complexꢀ
2
7,28
(FigureꢀS7,ꢀSI). ꢀTheꢀUV-Visꢀdiffuseꢀreflectanceꢀspectrumꢀofꢀ
DBA-COFꢀ 5ꢀ exhibitsꢀ broadꢀ absorbanceꢀ bandsꢀ rangingꢀ fromꢀ
200ꢀ toꢀ 500ꢀ nmꢀ (Figureꢀ 3).ꢀ Afterꢀ metalation,ꢀ aꢀ noticeableꢀ
chargeꢀ transferꢀ bandꢀ surfacesꢀ atꢀ ~ꢀ 690ꢀ nmꢀ forꢀ Ni-DBA-2D-
COF,ꢀwhichꢀfurtherꢀsuggestsꢀtheꢀformationꢀofꢀtheꢀDBA-Ni(0)ꢀ
complex.ꢀ Lastly,ꢀ theꢀ X-rayꢀ photoelectronꢀ spectroscopyꢀ (XPS)ꢀ
spectrumꢀ ofꢀ Ni-DBA-2D-COFꢀ revealedꢀ theꢀ presenceꢀ ofꢀ twoꢀ
broadꢀ peaksꢀ atꢀ 855.89ꢀ andꢀ 852.89ꢀ eV,ꢀ whichꢀ correspondꢀ toꢀ
theꢀcoreꢀenergyꢀlevelsꢀofꢀNi(II)2p3/2ꢀandꢀNi(0)2p3/2ꢀ(FigureꢀS14,ꢀ
SI).ꢀTheꢀpeakꢀatꢀ855.89ꢀeVꢀresultsꢀfromꢀresidualꢀNi(II)ꢀthatꢀisꢀ
-1
2
8ꢀ
2
8
carriedꢀoverꢀafterꢀmetalationꢀwithꢀNi(COD) . ꢀXPSꢀalsoꢀcon-
2
firmedꢀtheꢀpresenceꢀofꢀtheꢀcarbon,ꢀnitrogen,ꢀandꢀoxygenꢀat-
omsꢀofꢀNi-DBA-2D-COFꢀ(FigureꢀS13,ꢀSI).ꢀ
ꢀ
ꢀꢀTheꢀpresenceꢀofꢀtheꢀDBA-Ni(0)ꢀcomplexꢀwasꢀconfirmedꢀbyꢀ
1
3
characterizingꢀDBA-COFꢀ5ꢀandꢀNi-DBA-2D-COFꢀusingꢀ Cꢀcross-ꢀ
polarizationꢀmagicꢀangleꢀspinningꢀ(CP-MAS)ꢀNMRꢀandꢀUV-Visꢀ
diffuseꢀ reflectanceꢀ spectroscopies.ꢀ Theꢀ alkynylꢀ unitsꢀ forꢀꢀꢀꢀ
ꢀꢀꢀSinceꢀtheꢀcatalyticꢀactivityꢀofꢀmetalatedꢀDBAꢀcomplexesꢀhasꢀ
notꢀ beenꢀ experimentallyꢀ evaluatedꢀ orꢀ reported,ꢀ weꢀ firstꢀ as-
sessedꢀ theꢀ reactivityꢀ ofꢀ variousꢀ arylꢀ thioetherꢀ substratesꢀ inꢀ
theꢀpresenceꢀofꢀdimethylethylsilaneꢀatꢀtemperaturesꢀrangingꢀ
fromꢀ90-130ꢀ°Cꢀusingꢀ10ꢀmol%ꢀNi-DBA[12]ꢀ(SchemeꢀS1,ꢀSI)ꢀasꢀ
aꢀ homogeneousꢀ catalystꢀ (Tableꢀ 1).ꢀ Interestingly,ꢀ theꢀ Ni-
DBA[12]ꢀcatalystꢀdemonstratedꢀgreatꢀfunctionalꢀgroupꢀtoler-
anceꢀandꢀproducedꢀyieldsꢀrangingꢀfromꢀ26-99ꢀ%ꢀforꢀsubstratesꢀ
2a-2f.ꢀꢀSubstrateꢀ2gꢀproducedꢀtheꢀlowestꢀyieldꢀ(5ꢀ%),ꢀwhichꢀ
indicatesꢀthatꢀthisꢀsystemꢀmightꢀnotꢀbeꢀcapableꢀofꢀefficientlyꢀ
cleavingꢀarylꢀsubstratesꢀcontainingꢀtwoꢀthioetherꢀfunctionali-
ties.ꢀInꢀcontrast,ꢀNi-DBA-2D-COFꢀalsoꢀexhibitedꢀaꢀlowꢀyieldꢀforꢀ
13
DBA-COFꢀ5ꢀwereꢀconfirmedꢀꢀbyꢀꢀ CꢀCP-MASꢀꢀNMRꢀdisplayingꢀaꢀꢀ
_
_________________________________________________ꢀ
a
Tableꢀ1.ꢀCatalyticꢀperformanceꢀofꢀNi-DBA[12] ꢀandꢀNi-DBA-
2D-COF ꢀforꢀtheꢀreductiveꢀcleavageꢀofꢀarylꢀC-Sꢀbonds.ꢀ
b
Ni-DBA-2D-COF (10 mol%)
or
SMe
Ni-DBA[12] (10 mol%)
H
R
R
EtMe Si-H (5.0 equiv.)
Toluene / 130 ˚C / 14 h
2
1a-h
2a-h
H
H
O
H
H
2
g,ꢀbutꢀmuchꢀhigherꢀyieldsꢀforꢀ2a-2fꢀ(22-87%)ꢀandꢀ2hꢀ(18%).ꢀItꢀ
MeO
Br
O
shouldꢀbeꢀnotedꢀthatꢀtheseꢀyieldsꢀareꢀhigherꢀthanꢀorꢀcompa-
rableꢀ toꢀ otherꢀ homogeneousꢀ Ni-basedꢀ catalystsꢀ thatꢀ haveꢀ
beenꢀ utilizedꢀ forꢀ theꢀ desulfurizationꢀ ofꢀ organosulfurꢀ com-
2a, 26%d
2b, 45%
2c, 99%
2d, 38%
d
Ni-DBA[12]
a, 22%c,d
2b, 76%c
2c,87%c
2
d, 45%c,d
Ni-DBA-2D-COF
2
H
H
6,29
H
H
pounds. ꢀ Surprisingly,ꢀ Ni-DBA-2D-COFꢀ exhibitedꢀ excellentꢀ
recyclabilityꢀ upꢀ toꢀ fiveꢀ cyclesꢀ andꢀ noꢀ reductionꢀ inꢀ catalyticꢀ
activityꢀprovidingꢀyieldsꢀrangingꢀfromꢀ75-89%ꢀafterꢀreductivelyꢀ
cleavingꢀꢀ2-(methylthio)naphthaleneꢀ(1c)ꢀtoꢀproduceꢀ2cꢀ(Fig-
ureꢀ 4).ꢀ XPSꢀ andꢀ PXRDꢀ dataꢀ takenꢀ afterꢀ catalysisꢀ revealedꢀ
preservationꢀofꢀtheꢀDBA-Ni(0)ꢀcomplexꢀandꢀretentionꢀofꢀcrys-
tallinity,ꢀrespectivelyꢀ(FiguresꢀS15ꢀ&ꢀS16,ꢀSI).ꢀTheꢀlackꢀofꢀaddi-
tionalꢀpeaksꢀinꢀtheꢀPXRDꢀalsoꢀsuggestsꢀthatꢀnoꢀNi-basedꢀna-
noparticlesꢀ areꢀ formedꢀ afterꢀ catalysis.ꢀ However,ꢀ aꢀ nitrogenꢀ
adsorptionꢀ isothermꢀ ofꢀ Ni-DBA-2D-COFꢀ takenꢀ afterꢀ catalysisꢀ
Cl
F
H
Ni-DBA[12]
2e, 79%
2
e, 46%c
2f, 72%
2g, 5%
2g, 2%
2h, 9%
2h,18%c
Ni-DBA-2D-COF
2f, 44%c
ꢀ
a
ꢀ
Reactionꢀ conditions:ꢀ 4.6ꢀ mgꢀ (0.011ꢀ mmol)ꢀ ofꢀ Ni-DBA[12]ꢀ wasꢀ
addedꢀtoꢀ2.0ꢀmLꢀofꢀtolueneꢀcontainingꢀEtMe SiHꢀ(5ꢀequiv.,ꢀ0.55ꢀ
mmol)ꢀandꢀtheꢀarylꢀthioethersꢀ(0.11ꢀmmol). ꢀPerformedꢀwithꢀ5.0ꢀ
mgꢀ (0.011ꢀ mmol)ꢀ ofꢀ Ni-DBA-2D-COF.ꢀ ꢀ Yieldsꢀ areꢀ basedꢀ onꢀ anꢀ
2
ꢀ
b
c
dꢀ
averageꢀofꢀthreeꢀtrials.ꢀ Reactionꢀwasꢀperformedꢀatꢀ90ꢀ°C.ꢀꢀ
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Journal of the American Chemical Society
Page 4 of 5
revealedꢀaꢀslightꢀreductionꢀinꢀtheꢀsurfaceꢀareaꢀofꢀtheꢀmaterialꢀ
FigureꢀS17ꢀ&ꢀS18,ꢀSI).ꢀThisꢀreductionꢀcouldꢀbeꢀattributedꢀtoꢀ
Universityꢀ(OSU)ꢀCampusꢀChemicalꢀInstrumentꢀCenterꢀ(CCIC)ꢀ
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(
andꢀ Tanyaꢀ Whitmerꢀ forꢀ assistanceꢀ withꢀ theꢀ CP-MASꢀ NMRꢀ
measurementsꢀ andꢀ accessꢀ toꢀ theꢀ instrumentation.ꢀ Electronꢀ
microscopyꢀwasꢀperformedꢀatꢀtheꢀCenterꢀforꢀElectronꢀMicros-
copyꢀandꢀAnalysisꢀ(CEMAS)ꢀatꢀOSU.ꢀWeꢀalsoꢀthankꢀDr.ꢀYehiaꢀ
minorꢀ amountsꢀ ofꢀ desulfurizedꢀ productꢀ trappedꢀ withinꢀ theꢀ
poresꢀ ofꢀ Ni-DBA-2D-COF.ꢀ Inꢀ addition,ꢀ aꢀ mercuryꢀ poisoningꢀ
experimentꢀandꢀleachingꢀtestꢀhasꢀconfirmedꢀthatꢀtheꢀhetero-
geneityꢀofꢀNi-DBA-2D-COFꢀremainsꢀintactꢀ(seeꢀSectionꢀNꢀinꢀtheꢀ
SI).ꢀICP-MSꢀanalysisꢀofꢀtheꢀfiltrateꢀafterꢀcatalysisꢀalsoꢀrevealedꢀ
minimalꢀleachingꢀofꢀNiꢀionsꢀ(~ꢀ0.02%).ꢀꢀꢀ
KhalifaꢀforꢀassistanceꢀwithꢀXPSꢀmeasurements.ꢀ
ꢀ
REFERENCES
ꢀ
ꢀꢀMechanistically,ꢀ weꢀ believeꢀ thatꢀ theꢀ DBA-Ni(0)ꢀ catalyticꢀ
(
1) Brunet, S.; Mey, D.; Pérot, G.; Bouchy, C.; Diehl, F. On the
systemꢀ proceedsꢀ throughꢀ aꢀ classicalꢀ Ni(0)/Ni(II)ꢀ catalyticꢀ
hydrodesulfurization of FCC gasoline: a review. App. Catalyst A:
Gen. 2005, 278, 143-172.
(2) Rentner, J. Kljajic, M.; Offner, L.; Breinbauer, R. Recent ad-
vances and applications of desulfurization in organic synthesis. Tetra-
hedron 2014, 70, 8983-9027.
30
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
pathway. ꢀ However,ꢀ DFTꢀ calculationsꢀ revealꢀ thatꢀ theꢀ arylꢀ
thioetherꢀ substratesꢀ doꢀ notꢀ bindꢀ toꢀ theꢀ centerꢀ ofꢀ theꢀ DBA-
Ni(0)ꢀcomplexꢀdueꢀtoꢀtheꢀNiꢀcenterꢀbeingꢀcoordinatelyꢀsatu-
ratedꢀwithꢀallꢀthreeꢀalkynylꢀunitsꢀ(FigureꢀS20,ꢀSI).ꢀAsꢀaꢀconse-
quenceꢀ theꢀDFTꢀcalculationsꢀ suggestꢀ thatꢀ theꢀNiꢀ hasꢀ toꢀ popꢀ
outꢀofꢀtheꢀDBA[12]ꢀcavityꢀandꢀbindꢀwithꢀonlyꢀoneꢀalkynylꢀunitꢀ
toꢀformꢀaꢀthree-coordinateꢀcomplexꢀbeforeꢀitꢀcanꢀoxidativelyꢀ
addꢀtheꢀC(aryl)-SMeꢀbond.ꢀThisꢀinitialꢀoxidativeꢀadditionꢀstepꢀ
isꢀ estimatedꢀ toꢀ beꢀ thermodynamicallyꢀ ~ꢀ 30ꢀ kcal/molꢀ uphill,ꢀ
butꢀ accessibleꢀ sinceꢀ theꢀ reactionꢀ isꢀ performedꢀ atꢀ highꢀ tem-
perature.ꢀ Afterwards,ꢀ σ-bondꢀ metathesisꢀ withꢀ di-
methylethylsilane,ꢀ followedꢀ byꢀ reductiveꢀ eliminationꢀ regen-
eratesꢀ theꢀ DBA-Ni(0)ꢀ complexꢀ (Figureꢀ S23,ꢀ SI).ꢀ Theꢀ σ-bondꢀ
metathesisꢀstepꢀisꢀsupportedꢀꢀꢀꢀꢀbyꢀtheꢀisolationꢀandꢀcharac-
terizationꢀ ofꢀ dimethylethyl(methylthio)silane,ꢀ whichꢀ isꢀ aꢀ
commonꢀ byproductꢀ fromꢀ thisꢀ particularꢀ σ-bondꢀ metathesisꢀ
reactionꢀ(FigureꢀS22,ꢀSI).ꢀꢀꢀ
(
3) Huang, H.; Li, J.; Lescop, C.; Duan, Z. Palladium-Catalyzed
Regioselective C-S Bond Cleavage of Thiophenes. Org. Lett. 2011,
1
3, 5252-5255.
(4) Shibue, M.; Hirotsu, M.; Nishioka, T.; Kinoshita, I. Ruthenium
and Rhodium Complexes with thiolate-Containing Pincer Ligands
Produced by C-S Bond Cleavage of Pyridyl-Substituted Dibenzothio-
phenes. Organometallics 2008, 27, 4475-4483.
(
5) Vicic, D. A.; Jones, W. D. Modeling the Hydrodesulfurzation
Reaction at Nickel. Unusual Reactivity of Dibenzothiophenes Rela-
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7606-7617.
(
6) Barbero, N.; Martin, R. Ligand-Free Ni-Catalyzed Reductive
Cleavage of Inert Carbon-Sulfur Bonds. Org. Lett. 2012, 14, 796-799.
7) Mozingo, R.; Wolf, D. E.; Harris, S. A.; Folkers, K. Hydrogen-
(
olysis of Sulfur Compounds by Raney Nickel Catalyst. J. Am. Chem.
Soc. 1943, 65, 1013-1016.
(
8) Hendsbee, J. A.; Thring, R. W.; Dick, D. G. Raney Nickel for
ꢀ
ꢀꢀInꢀconclusion,ꢀweꢀhaveꢀdemonstratedꢀthatꢀaꢀDBA-COFꢀmeta-
the Desulphurization of FCC Gasoline. J. Can. Petrol. Technol. 2006,
latedꢀwithꢀNiꢀcanꢀbeꢀusedꢀtoꢀreductivelyꢀcleaveꢀinertꢀarylꢀC-Sꢀ
bonds.ꢀ Theꢀ Ni-DBA-2D-COFꢀ catalyticꢀ systemꢀ exhibitedꢀ greatꢀ
recyclabilityꢀandꢀprovidedꢀgoodꢀyields.ꢀThisꢀworkꢀhighlightsꢀaꢀ
rareꢀexampleꢀofꢀutilizingꢀaꢀNi-dopedꢀDBA-COFꢀasꢀaꢀplatformꢀ
forꢀ theꢀ desulfurizationꢀ ofꢀ organosulfurꢀ compounds.ꢀ Sinceꢀ
DBAsꢀcanꢀbeꢀdopedꢀwithꢀotherꢀearthꢀabundantꢀmetalsꢀ(i.e.ꢀFe,ꢀ
4
5, 47-50.
(9) Côté, A.P.; Benin, A.I; Ockwig, N.W; O’Keeffe, M.; Matzger,
A.J.; Yaghi, O. M. Science 2005, 310, 1166-1170.
(10) Huang, N.; Wang, P.; Jiang, D. Covalent organic frameworks:
a materials platform for structural and functional designs. Nat. Rev.
Mater. 2016, 1, 16068.
(11) Bisbey, R.P.; Dichtel, W. R. Covalent Organic Frameworks as
a Platform for Multidimensional Polymerization. ACS Cent. Sci.
31
Co,ꢀ etc.), ꢀ theꢀ proof-of-principleꢀ isꢀ importantꢀ asꢀ metalatedꢀ
DBA-COFsꢀcouldꢀalsoꢀbeꢀutilizedꢀtoꢀperformꢀmanyꢀotherꢀꢀsus-
tainableꢀcatalyticꢀtransformations.ꢀꢀꢀꢀꢀꢀꢀ
2
017, 3, 533-543.
12) Furukawa, H.; Yaghi, O. M. Storage of Hydrogen, Methane,
(
and Carbon Dioxide in Highly porous Covalent Organic Frameworks
for Clean Energy Applications. J. Am. Chem. Soc. 2009, 131, 8875-
ꢀ
ASSOCIATEDꢀCONTENTꢀꢀ
8
883.
(13) Zeng, Y.; Zou, R.; Zhao, Y. Covalent Organic Frameworks for
CO Capture. Adv. Mater. 2016, 28, 2855-2873.
14) Chandra, S.; Kundu, T.; Kandambeth, S.; BabaRao, Y.;
Supporting Information
2
(
13
Syntheticꢀ procedures,ꢀ FT-IR,ꢀ solid-stateꢀ Cꢀ NMR,ꢀ XPS,ꢀ TGAꢀ
PXRD,ꢀandꢀSEM.ꢀThisꢀmaterialꢀisꢀavailableꢀfreeꢀofꢀchargeꢀviaꢀ
theꢀinternetꢀatꢀhttp://pubs.acs.org.ꢀꢀ
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(
C.-Y.; Wang, W. Construction of Covalent Organic Framework for
Catalysis: Pd/COF-LZU1 in Suzuki-Miyaura Coupling Reaction.
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AUTHOR INFORMATION
Corresponding Author
(
17) Fang, Q.; Gu, S.; Zheng, J.; Zhuang, Z.; Qiu, S; Yan, Y. 3D
Microporous Base-Functionalized Covalent Organic Frameworks for
Size-Selective Catalysis. Angew. Chem., Int. Ed. 2014, 53, 2878-
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fer Towards Included Fullerene. Angew. Chem., Int. Ed. 2013, 52,
*
mcgrier.1@osu.eduꢀ
Notes
Theꢀauthorsꢀdeclareꢀnoꢀcompetingꢀfinancialꢀinterests.ꢀ
ACKNOWLEDGMENTS
2
920-2924.
P.L.MꢀacknowledgesꢀfinancialꢀsupportꢀfromꢀtheꢀNationalꢀSci-
enceꢀ Foundationꢀ (CHE-1856442).ꢀ Weꢀ thankꢀ Theꢀ Ohioꢀ Stateꢀ
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