Copper complexes with dissymmetrically substituted bis(thiosemicarbazone) ligands as a basis for PET radiopharmaceuticals: Control of redox potential and lipophilicity

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Dalton Transactions

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Copperꢀcomplexesꢀwithꢀdissymmetricallyꢀsubstitutedꢀbis(thiosemicarbazone)ꢀligandsꢀasꢀaꢀbasisꢀforꢀ

PETꢀradiopharmaceuticals:ꢀcontrolꢀofꢀredoxꢀpotentialꢀandꢀlipophilicityꢀ

1

2

3

2*

*,1ꢀ

§

OliverꢀCꢀBrown, ꢀJuliaꢀBaguñaꢀTorres, ꢀKatherineꢀBꢀHolt, ꢀPhilipꢀJꢀBlower ꢀandꢀMichaelꢀJꢀWent

1

UniversityꢀofꢀKent,ꢀSchoolꢀofꢀPhysicalꢀSciences,ꢀCanterburyꢀCT2ꢀ7NH,ꢀUKꢀ

2

th

King’sꢀCollegeꢀLondon,ꢀDivisionꢀofꢀImagingꢀSciencesꢀandꢀBiomedicalꢀEngineering,ꢀ4 ꢀFloorꢀLambethꢀ

Wing,ꢀStꢀThomas’ꢀHospital,ꢀLondonꢀSE1ꢀ7EH,ꢀUKꢀ

3

UniversityꢀCollegeꢀLondon,ꢀDepartmentꢀofꢀChemistry,ꢀ20ꢀGordonꢀSt,ꢀLondon,ꢀWC1Hꢀ0AJ,ꢀUKꢀ

*

Jointꢀcorrespondingꢀauthorsꢀꢀ

^§Theseꢀauthorsꢀcontributedꢀequallyꢀ

Keyꢀwords:ꢀBis(thiosemicarbazone),ꢀCopper,ꢀDissymmetric,ꢀZinc,ꢀHypoxia,ꢀPET,ꢀTransmetallationꢀ

ꢀ

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Abstractꢀ

Copperꢀ(II)ꢀbis(thiosemicarbazone)ꢀderivativesꢀhaveꢀbeenꢀusedꢀextensivelyꢀinꢀpositronꢀemissionꢀ

tomographyꢀ(PET)ꢀtoꢀimageꢀhypoxiaꢀandꢀbloodꢀflowꢀandꢀtoꢀradiolabelꢀcellsꢀforꢀcellꢀtracking.ꢀTheseꢀ

applicationsꢀdependꢀonꢀcontrolꢀofꢀredoxꢀpotentialsꢀandꢀlipophilicityꢀofꢀtheꢀbis(thiosemicarbazone)ꢀ

complexes,ꢀwhichꢀcanꢀbeꢀadjustedꢀbyꢀalteringꢀperipheralꢀligandꢀsubstituents.ꢀThisꢀpaperꢀreportsꢀtheꢀ

synthesisꢀofꢀaꢀlibraryꢀofꢀnewꢀdissymmetricallyꢀsubstitutedꢀbis(thiosemicarbazone)ꢀligandsꢀbyꢀ

controllingꢀtheꢀcondensationꢀreactionsꢀbetweenꢀdicarbonylꢀcompoundsꢀandꢀ4-substituted-3-

thiosemicarbazidesꢀorꢀusingꢀacetalꢀprotection.ꢀCopperꢀcomplexesꢀofꢀtheꢀnewꢀligandsꢀhaveꢀbeenꢀ

preparedꢀbyꢀreactionꢀwithꢀcopperꢀacetateꢀorꢀviaꢀtransmetallationꢀofꢀtheꢀcorrespondingꢀzincꢀ

complexes,ꢀwhichꢀareꢀconvenientꢀprecursorsꢀforꢀtheꢀrapidꢀsynthesisꢀofꢀradio-copperꢀcomplexes.ꢀ

Well-definedꢀstructure-activityꢀrelationshipsꢀlinkingꢀligandꢀalkylationꢀpatternsꢀwithꢀredoxꢀpotentialꢀ

andꢀlipophilicityꢀofꢀtheꢀcomplexesꢀareꢀreported.ꢀ

ꢀ

2

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Introductionꢀ

6

4

62

Cuꢀorꢀ Cuꢀcomplexesꢀwithꢀbis(thiosemicarbazonate)ꢀligandsꢀcanꢀbeꢀusedꢀasꢀtracersꢀforꢀPETꢀ

1

-4

5

6-9

(

positronꢀemissionꢀtomography)ꢀforꢀimagingꢀhypoxicꢀtissues, ꢀcerebral ꢀandꢀmyocardialꢀperfusion, ꢀ

1

0,11

changesꢀinꢀbrainꢀtraffickingꢀofꢀcopperꢀassociatedꢀwithꢀneurologicalꢀdisease, ꢀandꢀforꢀcellꢀ

1

2

labelling. ꢀForꢀimagingꢀhypoxia,ꢀCu-diacetyl-bis(N4-methylthiosemicarbazonate)ꢀ(Cu-ATSM,ꢀlabelledꢀ

6

4

62

13

64

withꢀ Cuꢀorꢀ Cu),ꢀhasꢀbeenꢀwidelyꢀevaluatedꢀclinically. ꢀTheꢀ12.7-hꢀhalf-lifeꢀofꢀ Cuꢀallowsꢀitꢀtoꢀbeꢀ

1

4

usedꢀinꢀcentresꢀdistantꢀfromꢀsiteꢀofꢀradionuclideꢀproduction. ꢀTheꢀmechanismꢀofꢀtrappingꢀwithinꢀ

cells,ꢀwhetherꢀhypoxia-selectiveꢀorꢀnon-selective,ꢀreliesꢀonꢀtheꢀcomplexesꢀbeingꢀneutralꢀandꢀ

membraneꢀpermeable,ꢀallowingꢀthemꢀtoꢀfreelyꢀdiffuseꢀintoꢀandꢀoutꢀofꢀcells.ꢀWhenꢀinꢀcellsꢀtheꢀ

complexesꢀareꢀconvertedꢀbyꢀintracellularꢀreducingꢀagentsꢀtoꢀputativeꢀCu(I)-BTSCꢀintermediatesꢀthatꢀ

canꢀrapidlyꢀdissociate,ꢀleadingꢀtoꢀintracellularꢀtrappingꢀofꢀtheꢀreleasedꢀcopper.ꢀInꢀnormoxicꢀcellsꢀ

Cu(I)-ATSMꢀisꢀcapableꢀofꢀresistingꢀCu(I)ꢀdissociationꢀlongꢀenoughꢀtoꢀbeꢀre-oxidisedꢀbyꢀmolecularꢀ

oxygenꢀtoꢀCu(II)-ATSM,ꢀwhichꢀisꢀfreeꢀtoꢀdiffuseꢀbackꢀoutꢀofꢀtheꢀcells.ꢀHowever,ꢀinꢀhypoxicꢀcellsꢀthisꢀre-

1

,7,13,15-19

oxidationꢀisꢀslow,ꢀallowingꢀdissociationꢀandꢀhenceꢀhypoxia-selectiveꢀtrappingꢀwithinꢀtheꢀcells.

ꢀ

Onꢀaꢀslowerꢀtime-scale,ꢀnativeꢀCu-traffickingꢀmechanismsꢀcanꢀwashꢀtheꢀtrappedꢀcopperꢀoutꢀofꢀtheꢀ

2

0

cells,ꢀpreventingꢀprolongedꢀcopperꢀretentionꢀdespiteꢀtheꢀpresenceꢀofꢀhypoxia. ꢀꢀ

Theꢀbiologicalꢀbehaviourꢀandꢀselectivityꢀofꢀcopperꢀbis(thiosemicarbazone)ꢀcomplexesꢀdependsꢀonꢀ

2

1,22

manyꢀfactorsꢀincludingꢀlipophilicity,ꢀplanarity,ꢀmolecularꢀweight,ꢀpK

Investigationsꢀintoꢀtheꢀstructure-activityꢀrelationshipsꢀofꢀcopperꢀbis(thiosemicarbazone)ꢀcomplexesꢀ

haveꢀshownꢀthatꢀtheꢀsubstituentsꢀatꢀtheꢀdiimineꢀbackboneꢀ(Fig.ꢀ1,ꢀQ ꢀandꢀQ ꢀpositions)ꢀareꢀtheꢀ

ꢀReplacingꢀhydrogenꢀatꢀQ ꢀandꢀQ

progressivelyꢀlowersꢀtheꢀCu(I/II)ꢀredoxꢀpotentialꢀbyꢀaboutꢀ60ꢀmVꢀperꢀalkylꢀgroup.ꢀAlkylꢀsubstitutionsꢀ

onꢀtheꢀterminalꢀaminoꢀgroupsꢀ(R ,ꢀR ,ꢀR ꢀandꢀR )ꢀhaveꢀlessꢀeffectꢀonꢀtheꢀCu(I/II)ꢀredoxꢀpotential,ꢀbutꢀ

doꢀcontrolꢀlipophilicity. ꢀLowꢀredoxꢀpotentialsꢀ(i.e.ꢀbelowꢀ-0.5ꢀVꢀvs.ꢀAg/AgClꢀreferenceꢀelectrode)ꢀ

a

ꢀandꢀredoxꢀpotential.

ꢀ

1

2

1-24

primaryꢀdeterminantsꢀofꢀtheꢀredoxꢀpotentialꢀofꢀtheꢀcomplex.

1

2

ꢀ

1

2

3

4

2

wereꢀfoundꢀtoꢀbeꢀessentialꢀforꢀhypoxicꢀselectivity. ꢀThereꢀisꢀfurtherꢀscopeꢀforꢀtuningꢀofꢀpropertiesꢀtoꢀ

2

5,26

obtainꢀoptimalꢀcomplexesꢀforꢀtheꢀvariousꢀapplications. ꢀTheꢀvalueꢀofꢀsubtleꢀchangesꢀtoꢀtheꢀalkylꢀ

2

substitutionꢀpatterns ꢀinꢀimprovingꢀbiologicalꢀpropertiesꢀforꢀspecificꢀapplicationsꢀisꢀillustratedꢀbyꢀ

3

,27

recentꢀreportsꢀofꢀimprovedꢀhypoxiaꢀimagingꢀpropertiesꢀforꢀcardiologicalꢀapplications. ꢀInꢀthisꢀwork,ꢀ

therefore,ꢀweꢀaimedꢀtoꢀextendꢀtheꢀrangeꢀofꢀalkylꢀsubstitutionꢀpatternsꢀwithinꢀtheꢀligandꢀfromꢀwhichꢀ

toꢀchooseꢀcomplexesꢀwithꢀoptimisedꢀpropertiesꢀtailoredꢀtoꢀdifferentꢀuses,ꢀbyꢀintroducingꢀ

dissymmetricꢀligandsꢀwithꢀtwoꢀdifferentꢀthiosemicarbazoneꢀarms.ꢀ

Q₁

N

Q₂

N

Q₁

Q₂

N

HN

NH

N

Cu

R₁

R₃

R₁

R₃

N

S

N

S

N

R₂

R₄

R₂

R₄

ꢀ

Fig.ꢀ1ꢀStructureꢀofꢀbis(thiosemicarbazone)ꢀandꢀitsꢀcopperꢀcomplex,ꢀwithꢀsubstituentꢀnomenclature;ꢀ

,ꢀR ,ꢀR ,ꢀandꢀR ꢀareꢀalkyl,ꢀarylꢀorꢀhydrogen;ꢀQ ꢀandꢀQ ꢀareꢀalkylꢀorꢀhydrogen.ꢀ

R

1

2

3

4

1

2

Bis(thiosemicarbazone)ꢀpro-ligandsꢀareꢀdescribedꢀhereꢀasꢀsymmetricꢀwhenꢀtheꢀsubstituentsꢀonꢀtheꢀ

twoꢀterminalꢀnitrogensꢀareꢀtheꢀsame,ꢀandꢀdissymmetricꢀwhenꢀtheꢀsubstituentsꢀonꢀtheꢀterminalꢀ

nitrogensꢀareꢀdissimilarꢀ(NR

1 2 3 4

R ≠NR R ).ꢀAlmostꢀallꢀligandsꢀevaluatedꢀinꢀPETꢀimagingꢀtoꢀdateꢀareꢀ

ꢀ

3

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symmetricꢀinꢀthisꢀrespect.ꢀDissymmetricꢀligandsꢀcanꢀbeꢀfurtherꢀclassifiedꢀasꢀsinglyꢀdissymmetricꢀorꢀ

doublyꢀdissymmetricꢀwithꢀrespectꢀtoꢀtheꢀbackboneꢀsubstituentsꢀQ

theꢀbackboneꢀareꢀidenticalꢀ(Q =Q )ꢀtheyꢀcanꢀbeꢀclassedꢀasꢀsinglyꢀdissymmetricꢀandꢀifꢀtheyꢀareꢀ

dissimilarꢀ(Q ≠Q )ꢀtheyꢀareꢀdoublyꢀdissymmetric.ꢀ

1 2

ꢀandꢀQ .ꢀWhenꢀtheꢀsubstituentsꢀonꢀ

1

2

1

2

7

,22,26,28-34

Symmetricꢀpro-ligands

ꢀareꢀtypicallyꢀsynthesisedꢀbyꢀadditionꢀofꢀatꢀleastꢀtwoꢀequivalentsꢀofꢀaꢀ

4

-substituted-thiosemicarbazideꢀtoꢀaꢀvicinalꢀdiketoneꢀunderꢀacidꢀcatalysis.ꢀTheꢀsynthesisꢀofꢀ

3

5

dissymmetricꢀbis(thiosemicarbazone)ꢀpro-ligands,ꢀfirstꢀreportedꢀbyꢀGreenꢀandꢀco-workers, ꢀhasꢀ

3

6

beenꢀreviewed. ꢀTheꢀmostꢀgenerallyꢀapplicableꢀapproachꢀinvolvesꢀprotectionꢀofꢀoneꢀofꢀtheꢀcarbonylꢀ

groups,ꢀforꢀexampleꢀreactingꢀisonitroacetoneꢀwithꢀaꢀchosenꢀthiosemicarbazideꢀ(Fig.ꢀ2)ꢀgivingꢀanꢀ

intermediateꢀwhichꢀisꢀthenꢀdeprotectedꢀandꢀreactedꢀwithꢀaꢀsecondꢀ(dissimilar)ꢀthiosemicarbazide.ꢀ

3

5

Limꢀetꢀal.ꢀreported ꢀthatꢀthisꢀmethodꢀgaveꢀaꢀmixtureꢀofꢀsymmetricꢀandꢀdissymmetricꢀ

bis(thiosemicarbazones).ꢀSimilarly,ꢀuseꢀofꢀacetalꢀprotectionꢀtoꢀcontrolꢀreactionꢀwithꢀtheꢀfirstꢀ

3

5,37,38

thiosemicarbazide,

beenꢀreportedꢀforꢀQ

stepꢀcanꢀbeꢀavoidedꢀbyꢀusingꢀtheꢀmildꢀLewisꢀacidꢀlithiumꢀtetrafluoroborateꢀ(LiBF

ꢀfollowedꢀbyꢀhydrolysisꢀofꢀtheꢀacetalꢀbeforeꢀtreatingꢀwithꢀtheꢀsecond,ꢀhasꢀ

ꢀ=ꢀCH ꢀandꢀQ ꢀ=ꢀHꢀ(Fig.ꢀ2).ꢀHydrolysisꢀofꢀtheꢀimineꢀgroupꢀduringꢀtheꢀdeprotectionꢀ

)ꢀasꢀtheꢀcatalystꢀ(Fig.ꢀ

). ꢀStepwiseꢀadditionꢀofꢀtwoꢀthiosemicarbazidesꢀtoꢀanꢀunprotectedꢀdiketoneꢀ(Fig.ꢀ2)ꢀhasꢀalsoꢀbeenꢀ

used.ꢀTheꢀmono(thiosemicarbazone)ꢀformedꢀinitiallyꢀprecipitatesꢀandꢀcanꢀbeꢀisolatedꢀandꢀreactedꢀ

1

3

2

4

3

5

2

3

9,40

withꢀaꢀsecondꢀthiosemicarbazideꢀunderꢀmoreꢀforcingꢀconditions. ꢀThisꢀmethodꢀhasꢀbeenꢀusedꢀtoꢀ

3

0,39-44

makeꢀdissymmetricꢀbis(thiosemicarbazone)ꢀpro-ligandsꢀwithꢀQ1ꢀ=ꢀQ

2

ꢀ=ꢀMe,

2

ꢀandꢀQ1ꢀ=ꢀMe,ꢀQ ꢀ=ꢀ

3

6,39

45

H

ꢀbutꢀyieldsꢀmixedꢀbis(thiosemicarbazone)ꢀproligandsꢀandꢀcyclicꢀby-productsꢀinꢀsomeꢀcases. ꢀ

2

5,26,46,47ꢀ

Cyclisation

ofꢀtheꢀintermediateꢀmayꢀalsoꢀoccur.ꢀDissymmetricꢀbis(thiosemicarbazone)ꢀ

proligandsꢀhaveꢀbeenꢀreportedꢀinꢀwhichꢀoneꢀsideꢀarmꢀisꢀmodifiedꢀtoꢀimproveꢀwaterꢀsolubilityꢀ(usingꢀaꢀ

4

8

39

49

50

carbohydrate ꢀorꢀsulfonate ),ꢀintroduceꢀfluorescence ꢀorꢀradiolabelꢀwithꢀfluorine-18. ꢀTheseꢀpro-

ligandsꢀwereꢀderivedꢀfromꢀaꢀdissymmetricꢀbis(thiosemicarbazone)ꢀinꢀwhichꢀoneꢀthiosemicarbazideꢀ

4

0,42-44,51

armꢀisꢀaꢀthiocarbohydrazide

ꢀ(Fig.ꢀ2).ꢀꢀ

TheꢀaimsꢀofꢀtheꢀpresentꢀworkꢀwereꢀtoꢀexpandꢀtheꢀavailableꢀlibraryꢀofꢀBTSCꢀcomplexesꢀtoꢀincludeꢀ

moreꢀdissymmetricꢀonesꢀfromꢀwhichꢀtoꢀchooseꢀfine-tunedꢀpropertiesꢀforꢀPETꢀapplications,ꢀevaluateꢀ

transmetallationꢀasꢀaꢀmethodꢀtoꢀsynthesiseꢀtheꢀcopperꢀcomplexesꢀfromꢀtheꢀzincꢀ(II)ꢀcomplexes,ꢀandꢀ

measureꢀtheꢀeffectsꢀofꢀtheꢀresultingꢀdifferentꢀalkylationꢀpatternsꢀonꢀredoxꢀpotentialꢀandꢀlipophilicity.ꢀ

ꢀ

4

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Q₁

View Article Online

DOI: 10.1039/C7DT02008B

H

N

H

Q₁

O

N

H⁺^/H O

+

N

S

N

O

H

2

S

HN

N

O

R₁

H

N

R₁

R₂

R R NC(S)NHNH

3

4

2

DMF, heat

Q₁

N

S

HN

NH

H

N

H

Q₁

O

OCH₃

N

R₁

N

R₃

S

N

+

S

N

^R2

^R4

R₁

R₂

DMF

R R NC(S)NHNH

3 4

2

DMF

Q₁

N

Q₁

OCH₃

O

N

S

HN

R₁

N

S

^Lⁱ^B^F4

% aq MeCN

N

2

R₂

Q₁

N

Q₂

O

H

N

H

^Q1

^Q2

+

H /H O

2

+

S

N

HN

O

R₁

N

S

R₁

R₂

R R NC(S)NHNH

2

3

4

DMF

Q₁

N

Q₂

N

HN

NH

R₁

R₃

N

S

N

R₂

R₄

H

O

N

S

N

HN

NH

HN

NH

Z

R₁

NH₂

R₁

N

H

S

N

H

S

N

H

Z

ꢀ

Fig.ꢀ2.ꢀLiteratureꢀroutesꢀforꢀsynthesisꢀofꢀdissymmetricꢀbis(thiosemicarbazone)ꢀpro-ligandsꢀusingꢀ

isonitroneꢀorꢀacetalꢀprotectionꢀandꢀusingꢀunprotectedꢀdiketones,ꢀandꢀdissymmetricꢀfunctionalisationꢀ

viaꢀaꢀthiocarbohydrazideꢀsideꢀarm.ꢀ

ꢀ

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ResultsꢀandꢀDiscussionꢀ

BTSCꢀligandsꢀwithꢀtwoꢀdifferentꢀthiosemicarbazoneꢀarmsꢀwereꢀsynthesisedꢀviaꢀaꢀrangeꢀofꢀstrategiesꢀ

asꢀdescribedꢀbelow,ꢀwithꢀlessꢀthanꢀ5%ꢀcontaminationꢀbyꢀscrambledꢀorꢀsymmetricꢀproligandsꢀunlessꢀ

otherwiseꢀnoted.ꢀMono(thiosemicarbazone)ꢀintermediates,ꢀlistedꢀinꢀTableꢀ1,ꢀareꢀreferredꢀtoꢀbyꢀaꢀ

letterꢀdesignationꢀAꢀ–ꢀM,ꢀwhileꢀbis(thiosemicarbazone)ꢀpro-ligandsꢀ(Tableꢀ2)ꢀareꢀreferredꢀtoꢀbyꢀaꢀ

numericꢀdesignationꢀ1ꢀ–ꢀ36.ꢀWhenꢀusedꢀtoꢀdefineꢀtheirꢀCu(II)ꢀandꢀZn(II)ꢀcomplexes,ꢀtheꢀnumericꢀ

designationꢀimpliesꢀcoordinationꢀinꢀtheꢀformꢀofꢀtheꢀdoubly-deprotonatedꢀdianion.ꢀBTSCꢀligandsꢀwithꢀ

twoꢀidenticalꢀthiosemicarbazoneꢀarmsꢀ(1,ꢀ2,ꢀ5,ꢀ6,ꢀ7,ꢀ8,ꢀ20,ꢀ21,ꢀ25)ꢀwereꢀpreparedꢀfollowingꢀaꢀ

2

previouslyꢀreportedꢀprocedure ꢀandꢀobtainedꢀinꢀhighꢀyieldꢀandꢀpurity.ꢀꢀ

SynthesisꢀofꢀPro-ligandsꢀviaꢀProtectedꢀDicarbonylsꢀ

3

5

UsingꢀtheꢀmethodꢀofꢀGreen ꢀ(Fig.ꢀ3),ꢀ4-methyl-3-thiosemicarbazideꢀwasꢀreactedꢀwithꢀmethylglyoxal-

,1-dimethylacetalꢀinꢀDMFꢀtoꢀgiveꢀA,ꢀwhichꢀwasꢀdeprotectedꢀtoꢀgiveꢀBꢀ(andꢀDꢀwasꢀpreparedꢀ

1

analogouslyꢀfromꢀC).ꢀHowever,ꢀBꢀwasꢀmoreꢀconvenientlyꢀpreparedꢀdirectlyꢀbyꢀꢀaqueousꢀreactionꢀofꢀ4-

methyl-3-thiosemicarbazideꢀwithꢀmethylglyoxal-1,1-dimethylacetal;ꢀHꢀandꢀIꢀwereꢀdirectlyꢀpreparedꢀ

analogouslyꢀfromꢀmethylglyoxal-1,1-dimethylacetal.ꢀBꢀwasꢀreactedꢀwithꢀthiosemicarbazideꢀtoꢀaffordꢀ

3

5

theꢀknownꢀdissymmetricꢀpro-ligandꢀ3 ꢀinꢀ6%ꢀoverallꢀyield.ꢀAgainꢀinꢀaꢀsimilarꢀmannerꢀtoꢀGreen,ꢀ

3

5

reversingꢀtheꢀorderꢀofꢀthiosemicarbazideꢀadditionꢀgaveꢀintermediatesꢀCꢀandꢀDꢀandꢀpro-ligandꢀ4 ꢀinꢀ

%ꢀoverallꢀyield.ꢀApplyingꢀthisꢀstrategyꢀtoꢀ3,3-dimethoxy-2-butanoneꢀtoꢀprepareꢀEꢀrequiredꢀuseꢀofꢀ

4

ethanolꢀasꢀtheꢀreactionꢀsolventꢀfollowedꢀbyꢀextractionꢀwithꢀdiethylꢀether.ꢀIntermediateꢀEꢀisꢀaꢀ

precursorꢀtoꢀF,ꢀwhichꢀhasꢀbeenꢀmoreꢀconvenientlyꢀpreparedꢀbyꢀHollandꢀetꢀal.ꢀusingꢀtheꢀdiketoneꢀ

4

0

routeꢀ(Fig.ꢀ2). ꢀ

ꢀ

6

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ꢀ

1 2 1 2

Tableꢀ1. ꢀM ono(thiosemicarbazone)ꢀintermediates.ꢀR ,ꢀR ,ꢀQ ꢀandꢀQ ꢀreferꢀtoꢀsubstituentsꢀasꢀdefinedꢀ

inꢀFigs.ꢀ1ꢀandꢀ2;ꢀXꢀdesignatesꢀwhetherꢀtheꢀnon-reactingꢀcarbonylꢀgroupꢀisꢀprotectedꢀasꢀtheꢀ

dimethylketalꢀorꢀnot.ꢀ

Compoundꢀ

R

1

ꢀ

R

2

ꢀ

Q

1

ꢀ

Q

2

ꢀ

Xꢀ

(OMe)

=Oꢀ

Aꢀ

Bꢀ

Cꢀ

Dꢀ

Eꢀ

Fꢀ

Meꢀ

Hꢀ

Meꢀ

Hꢀ

2

ꢀ

Hꢀ

(OMe)

=Oꢀ

Hꢀ

Meꢀ

Hꢀ

Meꢀ

Hꢀ

(OMe)

=Oꢀ

Hꢀ

Gꢀ

Hꢀ

Iꢀ

Hꢀ

=Oꢀ

Etꢀ

Phꢀ

Meꢀ

Hꢀ

=Oꢀ

Hꢀ

=Oꢀ

Jꢀ

Meꢀ

Hꢀ

Meꢀ

Etꢀ

=Oꢀ

Kꢀ

Lꢀ

=Oꢀ

Meꢀ

Etꢀ

Hꢀ

=Oꢀ

Mꢀ

Hꢀ

=Oꢀ

ꢀ

7

Dalton Transactions

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Tableꢀ2.ꢀRedoxꢀandꢀlipophilicityꢀpropertiesꢀofꢀcopper(II)ꢀcomplexes.ꢀ*derivedꢀfromꢀliteratureꢀvalues.ꢀ

I/II

II/III

Pro-ꢀ

R

1

ꢀ

R

2

ꢀ

Q

1

ꢀ

Q

2

ꢀ

R

3

ꢀ

R

4

ꢀ

E(DE )ꢀCu ꢀ E(DE )ꢀCu

ꢀ

logPꢀ

referenceꢀ

p

ligandꢀ

(mV)ꢀ

1

2

3

4

5

6

7

8

9

ꢀ

Meꢀ Hꢀ

Etꢀ Hꢀ

Hꢀ

Hꢀ Meꢀ

-960(65)ꢀ

220(170)ꢀ

1.28ꢀ 22,ꢀ11,ꢀ33,ꢀ56,ꢀ57ꢀ

Hꢀ

Etꢀ

Hꢀ

-1060(63)ꢀ

130(131)ꢀ

1.58ꢀ

33ꢀ

35ꢀ

Meꢀ Hꢀ Meꢀ Hꢀ

Hꢀ Hꢀ Meꢀ Hꢀ

Meꢀ Hꢀ Meꢀ Hꢀ

ꢀ

Hꢀ Meꢀ

ꢀ

35ꢀ

-1040*ꢀ

-1060*ꢀ

-1050*ꢀ

ꢀ

1.52*ꢀ

ꢀ

22,ꢀ56,ꢀ60ꢀ

22ꢀ

Meꢀ Meꢀ Meꢀ Hꢀ Meꢀ Meꢀ

ꢀ

Etꢀ

Hꢀ Meꢀ Hꢀ

Hꢀ

Etꢀ

ꢀ

1.74*ꢀ

ꢀ

22,ꢀ60ꢀ

22ꢀ

Phꢀ

Hꢀ Phꢀ

ꢀ

Meꢀ Hꢀ Meꢀ Hꢀ Meꢀ Meꢀ -1010(73)ꢀ

Meꢀ Hꢀ Meꢀ Hꢀ Hꢀ Etꢀ

Etꢀ Hꢀ Meꢀ Hꢀ Hꢀ Meꢀꢀ -1080(72)ꢀ

Meꢀ Hꢀ Meꢀ Hꢀ

240(97)ꢀ

ꢀ

1.70ꢀ

ꢀ

35ꢀ

1

2

3

0ꢀ

1ꢀ

2ꢀ

3ꢀ

4ꢀ

5ꢀ

6ꢀ

7ꢀ

8ꢀ

9ꢀ

0ꢀ

1ꢀ

2ꢀ

3ꢀ

4ꢀ

5ꢀ

6ꢀ

7ꢀ

8ꢀ

9ꢀ

0ꢀ

1ꢀ

2ꢀ

3ꢀ

4ꢀ

5ꢀ

6ꢀ

ꢀ

newꢀ

180(90)ꢀ

ꢀ

1.64ꢀ

1.91ꢀ

ꢀ

newꢀ

Hꢀ Phꢀ

Hꢀ Hꢀ

-930(69)ꢀ

ꢀ

newꢀ

Etꢀ

Hꢀ Meꢀ Hꢀ

ꢀ

newꢀ

Hꢀ Meꢀ Hꢀ Meꢀ Meꢀ -1050(68)ꢀ

200(95)ꢀ

ꢀ

1.81ꢀ

1.98ꢀ

ꢀ

newꢀ

Etꢀ

Hꢀ Meꢀ Hꢀ

Hꢀ Phꢀ -1060(60)ꢀ

Hꢀ Hꢀ

Hꢀ Meꢀꢀ -1040(93)ꢀ

newꢀ

Phꢀ

ꢀ

newꢀ

ꢀ

1.87ꢀ

ꢀ

newꢀ

Hꢀ Meꢀ Hꢀ Meꢀ Meꢀ

Hꢀ Meꢀ Hꢀ Hꢀ Etꢀꢀ

ꢀ

newꢀ

-970(61)ꢀ

ꢀ

1.97ꢀ

1.69*ꢀ

1.86*ꢀ

1.87ꢀ

1.49ꢀ

1.68ꢀ

1.40ꢀ

1.63ꢀ

1.81ꢀ

1.73ꢀ

1.61ꢀ

1.72ꢀ

ꢀ

newꢀ

Meꢀ Hꢀ Meꢀ Meꢀ Hꢀ Meꢀ -1120(90)ꢀ

Etꢀ Hꢀ Meꢀ Meꢀ Hꢀ Etꢀ -1130(88)ꢀ

Meꢀ Hꢀ Meꢀ Meꢀ Meꢀ Meꢀ -1050(65)ꢀ

190(81)ꢀ

180(84)ꢀ

260(87)ꢀ

180(83)ꢀ

190(82)ꢀ

140(66)ꢀ

140(84)ꢀ

180(80)ꢀ

170(79)ꢀ

150(81)ꢀ

210(66)ꢀ

ꢀ

22,ꢀ56,ꢀ57,ꢀ60ꢀ

58,ꢀ60ꢀ

30ꢀ

Hꢀ

Hꢀ Meꢀ Meꢀ Hꢀ Meꢀꢀ -1120(75)ꢀ

Hꢀ Meꢀ Meꢀ Meꢀ Meꢀ -1130(79)ꢀ

newꢀ

Hꢀ Meꢀ Etꢀ

Hꢀ

-1160(51)ꢀ

22,ꢀ56,ꢀ60,ꢀ3,ꢀ27ꢀ

newꢀ

Hꢀ Meꢀꢀ -1130(74)ꢀ

Hꢀ Meꢀ Etꢀ Meꢀ Meꢀ -1100(72)ꢀ

newꢀ

Hꢀ Meꢀ Etꢀ

Hꢀ

Etꢀꢀ -1110(72)ꢀ

newꢀ

Meꢀ Hꢀ Meꢀ Etꢀ

Etꢀ Hꢀ Meꢀ Etꢀ

Meꢀ Hꢀ Hꢀ Hꢀ

Hꢀ Meꢀ Hꢀ

Hꢀ Meꢀ Meꢀ Hꢀ

Hꢀ

-1130(73)ꢀ

-1140(53)ꢀ

-960*ꢀ

newꢀ

Hꢀ Meꢀ

22,ꢀ56,ꢀ10,ꢀ11ꢀ

22,ꢀ56ꢀ

22,ꢀ56,ꢀ3,ꢀ27ꢀ

22,ꢀ56ꢀ

22,ꢀ56,ꢀ3ꢀ

22,ꢀ56ꢀ

Hꢀ

-1030*ꢀ

-1120*ꢀ

-1110*ꢀ

-1120*ꢀ

-1110*ꢀ

220*ꢀ

170*ꢀ

190*ꢀ

160*ꢀ

180*ꢀ

ꢀ

Meꢀ Hꢀ Meꢀ Etꢀ

Hꢀ Meꢀ

ꢀ

Hꢀ

Etꢀ

Hꢀ

ꢀ

Meꢀ Hꢀ

Hꢀ Meꢀ

2.01*ꢀ

ꢀ

8

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Reactionꢀofꢀthiosemicarbazideꢀwithꢀ3,3-dimethoxy-2-butanoneꢀinꢀDMFꢀinꢀtheꢀpresenceꢀofꢀmolecularꢀ

sievesꢀunexpectedlyꢀledꢀdirectlyꢀtoꢀketoneꢀGꢀwithoutꢀisolationꢀofꢀtheꢀdiacetal.ꢀReactionꢀofꢀGꢀwithꢀ4-

methyl-3-thiosemicarbazideꢀgivesꢀtheꢀnewꢀdissymmetricꢀpro-ligandꢀ23ꢀinꢀgoodꢀyield.ꢀThisꢀoutcomeꢀ

promptedꢀevaluationꢀofꢀmethylglyoxal-1,1-dimethylacetalꢀasꢀaꢀcommerciallyꢀavailableꢀprecursorꢀthatꢀ

isꢀcheaperꢀandꢀmoreꢀconvenientꢀthanꢀpyruvicꢀaldehyde.ꢀThus,ꢀknownꢀsymmetricꢀpro-ligandsꢀ5,ꢀ6ꢀandꢀ

5

2

7

ꢀwereꢀpreparedꢀbyꢀreactionꢀwithꢀtwoꢀequivalentsꢀofꢀtheꢀappropriateꢀthiosemicarbazideꢀwithꢀ

methylglyoxal-1,1-dimethylacetal.ꢀTheꢀnewꢀpro-ligandꢀ8ꢀwasꢀalsoꢀpreparedꢀbyꢀthisꢀmethod.ꢀꢀ

Usingꢀtheꢀsameꢀapproachꢀdissymmetricꢀpro-ligandsꢀcanꢀbeꢀobtainedꢀviaꢀtheꢀintermediateꢀaldehydesꢀ

derivedꢀfromꢀtheꢀcorrespondingꢀdimethylacetal.ꢀReactionꢀofꢀBꢀwithꢀtheꢀappropriateꢀ

3

5

53

37

1

thiosemicarbazideꢀaffordsꢀtheꢀknownꢀcompoundsꢀ3, ꢀ9, ꢀ10 ꢀandꢀtheꢀnewꢀcompoundꢀ12.ꢀ HꢀNMRꢀ

spectroscopyꢀindicatesꢀthatꢀsomeꢀscramblingꢀoccursꢀduringꢀtheseꢀreactions,ꢀthusꢀforꢀexampleꢀ12ꢀ

containsꢀ3%ꢀofꢀbothꢀsymmetricꢀligandsꢀwithꢀmethylꢀorꢀphenylꢀgroupsꢀatꢀtheꢀterminalꢀpositionsꢀ(seeꢀ

supplementaryꢀinformationꢀforꢀspectroscopicꢀevidenceꢀofꢀcontamination,ꢀorꢀlackꢀofꢀit,ꢀofꢀpro-ligandsꢀ

3

8

byꢀisomersꢀandꢀscrambledꢀproducts).ꢀTheꢀintermediateꢀHꢀhasꢀbeenꢀpreviouslyꢀreported ꢀandꢀwasꢀ

usedꢀhereꢀtoꢀsynthesiseꢀtheꢀnewꢀdissymmetricꢀpro-ligandsꢀ13ꢀandꢀ14ꢀefficiently,ꢀasꢀwellꢀasꢀtheꢀ

3

8

previouslyꢀreportedꢀ11. ꢀTheꢀnewꢀintermediateꢀIꢀwasꢀusedꢀtoꢀprepareꢀnewꢀdissymmetricꢀpro-ligandsꢀ

6,ꢀ17,ꢀ18ꢀandꢀ19.ꢀReactionꢀofꢀHꢀwithꢀ4-phenyl-3-thiosemicarbazideꢀsimilarlyꢀgaveꢀtheꢀdesiredꢀ15ꢀbutꢀ

1

significantlyꢀcontaminatedꢀ(10%)ꢀwithꢀtheꢀsymmetricꢀproligandꢀ8.ꢀSimilarly,ꢀreactionꢀofꢀIꢀwithꢀ4,4-

dimethyl-3-thiosemicarbazideꢀproducedꢀtheꢀdesiredꢀ18ꢀcontaminatedꢀwithꢀ25%ꢀofꢀtheꢀknownꢀ

proligandꢀ6.ꢀ

SynthesisꢀofꢀPro-ligandsꢀviaꢀUnprotectedꢀDiketonesꢀ

Dissymmetricꢀpro-ligandsꢀcanꢀbeꢀpreparedꢀfromꢀ2,3-butanedioneꢀviaꢀmono-substituted-3-

thiosemicarbazoneꢀintermediatesꢀ(Fig.ꢀ2).ꢀReactionꢀofꢀ2,3-butanedioneꢀwithꢀoneꢀequivalentꢀofꢀ

4

0

thiosemicarbazide,ꢀ4-methyl-3-thiosemicarbazideꢀorꢀ4,4-dimethyl-3-thiosemicarbazideꢀaffordsꢀG,ꢀF ꢀ

andꢀJ,ꢀrespectively.ꢀReactionꢀofꢀFꢀwithꢀthiosemicarbazide,ꢀandꢀGꢀwithꢀ4,4-dimethyl-3-

thiosemicarbazide,ꢀaffordsꢀtheꢀnewꢀpro-ligandsꢀ23ꢀandꢀ24ꢀrespectivelyꢀinꢀgoodꢀyieldꢀandꢀpurity.ꢀ23ꢀ

couldꢀalsoꢀbeꢀpreparedꢀbyꢀadditionꢀofꢀtheꢀthiosemicarbazideꢀarmsꢀinꢀtheꢀreverseꢀorder,ꢀi.e.ꢀreactionꢀ

ofꢀFꢀwithꢀthiosemicarbazide;ꢀsimilarly,ꢀ22ꢀwasꢀpreparedꢀbyꢀreactionꢀofꢀFꢀwithꢀ4,4-dimethyl-3-

thiosemicarbazide.ꢀ

Doublyꢀdissymmetricꢀpro-ligandsꢀcouldꢀbeꢀsynthesisedꢀbyꢀexploitingꢀtheꢀreactivityꢀdifferenceꢀ

betweenꢀtheꢀethylꢀandꢀmethylꢀketoneꢀfunctionalitiesꢀofꢀ2,3-pentanedione:ꢀreactionꢀwithꢀ

thiosemicarbazideꢀaffordsꢀKꢀ(inꢀwhichꢀtheꢀreactionꢀhasꢀoccurredꢀatꢀtheꢀmethylꢀketone)ꢀinꢀ66%ꢀyieldꢀ

withꢀaꢀ9%ꢀimpurityꢀinꢀwhichꢀtheꢀthiosemicarbazideꢀreactedꢀwithꢀtheꢀethylꢀketone.ꢀSimilarly,ꢀreactionsꢀ

withꢀ4-methyl-3-thiosemicarbazideꢀandꢀ4-ethyl-3-thiosemicarbazideꢀaffordꢀLꢀandꢀMꢀwithꢀ4%ꢀandꢀ

1

0%ꢀimpuritiesꢀrespectively.ꢀGivenꢀthisꢀhighꢀdegreeꢀofꢀselectivity,ꢀtheꢀethylꢀketoneꢀintermediatesꢀ

wereꢀreactedꢀwithꢀfurtherꢀthiosemicarbazidesꢀtoꢀaffordꢀnewꢀdoublyꢀasymmetricꢀpro-ligandsꢀ26,ꢀ27,ꢀ

8,ꢀ29ꢀandꢀ30,ꢀwithꢀlessꢀthanꢀ5%ꢀofꢀtheꢀminorꢀisomersꢀwithꢀtheꢀpositionꢀofꢀtheꢀarmsꢀreversedꢀ(seeꢀ

2

supplementaryꢀinformation).ꢀ

SynthesisꢀofꢀComplexesꢀ

KnownꢀCu-BTSCꢀcomplexesꢀwereꢀsynthesisedꢀandꢀpurifiedꢀꢀfollowingꢀaꢀpreviouslyꢀreportedꢀ

2

protocol. ꢀSimilarlyꢀreactionsꢀofꢀtheꢀdissymmetricꢀpro-ligandsꢀ12,ꢀ14,ꢀ16,ꢀ17,ꢀ23,ꢀ24,ꢀ26,ꢀ27,ꢀ28,ꢀ29ꢀ

ꢀ

9

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DOI: 10.1039/C7DT02008B

andꢀ30ꢀwithꢀcopperꢀ(II)ꢀacetateꢀinꢀwaterꢀaffordedꢀaꢀrangeꢀofꢀnewꢀbis(thiosemicarbazone)ꢀcopperꢀ

complexesꢀwhichꢀwereꢀcharacterisedꢀbyꢀIRꢀandꢀRamanꢀspectroscopy,ꢀelementalꢀanalysis,ꢀUV-visꢀ

spectroscopy,ꢀandꢀmassꢀspectroscopy;ꢀtheꢀcolour,ꢀsolubilityꢀandꢀallꢀanalyticalꢀandꢀspectroscopicꢀdataꢀ

includingꢀvibrationalꢀandꢀelectronicꢀspectraꢀwereꢀconsistentꢀwithꢀ1:1ꢀCu(II)ꢀcomplexesꢀwithꢀtheꢀ

expectedꢀplanar,ꢀfourꢀcoordinateꢀstructureꢀdescribedꢀforꢀpreviouslyꢀreportedꢀmembersꢀofꢀtheꢀ

2

2,57

series. ꢀꢀDespiteꢀsomeꢀproligandsꢀhavingꢀminorꢀcontaminationꢀwithꢀisomersꢀorꢀ“scrambled”ꢀ

proligands,ꢀHPLCꢀindicatedꢀthatꢀcomplexesꢀwereꢀlargelyꢀfreeꢀofꢀcontaminationꢀbyꢀisomericꢀorꢀ

scrambledꢀcomplexesꢀunlessꢀotherwiseꢀindicated.ꢀ

Zincꢀbis(thiosemicarbazone)ꢀcomplexesꢀcanꢀbeꢀusedꢀasꢀprecursorsꢀforꢀcopperꢀbis(thiosemicarbazone)ꢀ

4

0

complexesꢀbyꢀtransmetallationꢀwithꢀcopperꢀacetateꢀinꢀwater. ꢀThisꢀisꢀaꢀquickꢀandꢀconvenientꢀ

approachꢀforꢀradiolabellingꢀBTSCꢀligandsꢀwithꢀradiocopper,ꢀdemonstratedꢀbyꢀtheꢀattachmentꢀofꢀaꢀ

zincꢀbis(thiosemicarbazone)ꢀcomplexꢀtoꢀaꢀsolidꢀsupportꢀviaꢀanꢀaxialꢀpyridylꢀligand,ꢀandꢀelutingꢀwithꢀaꢀ

6

4

54,55

[

Cu]Cu-acetateꢀsolution. ꢀAsꢀwellꢀasꢀprovidingꢀaꢀsimpleꢀradiolabellingꢀmethodology,ꢀtheꢀsolidꢀ

support-basedꢀtransmetallationꢀapproachꢀoffersꢀtheꢀadvantageꢀthatꢀtheꢀconcentrationꢀofꢀfreeꢀligandꢀ

5

4

inꢀtheꢀfinalꢀproductꢀisꢀlowꢀbecauseꢀunusedꢀligandꢀisꢀretainedꢀonꢀtheꢀcolumn. ꢀTreatmentꢀofꢀzincꢀ

acetateꢀwithꢀbis(thiosemicarbazone)ꢀproligandsꢀinꢀrefluxingꢀethanolꢀgaveꢀtheꢀzincꢀcomplexesꢀasꢀ

yellowꢀorꢀorangeꢀprecipitates.ꢀSpectroscopicꢀpropertiesꢀwereꢀconsistentꢀwithꢀ1:1ꢀcomplexesꢀwithoutꢀ

additionalꢀligands.ꢀReactionꢀofꢀtheꢀZn(II)ꢀcomplexesꢀZn(14),ꢀZn(17)ꢀorꢀZn(29)ꢀwithꢀcopperꢀacetateꢀ

monohydrateꢀaffordedꢀtheꢀcorrespondingꢀCu(II)ꢀcomplexes,ꢀasꢀconfirmedꢀbyꢀIR,ꢀRamanꢀandꢀmassꢀ

spectroscopy,ꢀinꢀgoodꢀyield.ꢀTheꢀzincꢀcomplexesꢀareꢀaꢀconvenientꢀandꢀstableꢀformꢀinꢀwhichꢀtoꢀstoreꢀ

theꢀligandsꢀforꢀfutureꢀsynthesisꢀofꢀtheꢀcopperꢀcomplexesꢀorꢀforꢀradiolabelling,ꢀandꢀtheirꢀsimpleꢀ

isolationꢀprovidesꢀaꢀusefulꢀmeansꢀtoꢀobtainꢀthemꢀfreeꢀofꢀtheirꢀprecursorsꢀandꢀby-products.ꢀꢀ

Electrochemistryꢀ

CyclicꢀvoltammetryꢀwasꢀperformedꢀonꢀallꢀcomplexesꢀwhoseꢀHPLCꢀindicatedꢀsufficientꢀpurityꢀ(i.e.ꢀ<5%ꢀ

contaminationꢀwithꢀpossibleꢀscrambledꢀorꢀisomericꢀcomplexes)ꢀusingꢀaꢀglassyꢀcarbonꢀworkingꢀ

electrodeꢀwithꢀferroceneꢀasꢀanꢀinternalꢀstandard.ꢀTableꢀ2ꢀshowsꢀtheꢀelectrochemicalꢀreductionꢀandꢀ

oxidationꢀpotentials,ꢀalongꢀwithꢀpeakꢀseparationsꢀofꢀtheꢀreductiveꢀandꢀoxidativeꢀwaves,ꢀofꢀcomplexesꢀ

determinedꢀinꢀthisꢀworkꢀ(Cu(1),ꢀCu(2),ꢀCu(9),ꢀCu(11),ꢀCu(12),ꢀCu(14),ꢀCu(15),ꢀCu(17),ꢀCu(19),ꢀCu(20),ꢀ

Cu(21),ꢀCu(22),ꢀCu(23),ꢀCu(24),ꢀCu(25),ꢀCu(26),ꢀCu(27),ꢀCu(28),ꢀCu(29),ꢀCu(30)).ꢀAllꢀcomplexesꢀ

measuredꢀshowedꢀaꢀquasi-reversibleꢀone-electronꢀreductionꢀ(e.g.,ꢀFig.ꢀ3).ꢀInꢀaddition,ꢀquasi-

reversibleꢀCu(II/III)ꢀprocessesꢀwereꢀobservedꢀwhoseꢀpotentialsꢀcouldꢀbeꢀsimilarlyꢀdeterminedꢀinꢀsomeꢀ

cases.ꢀMeasurementꢀofꢀtheꢀCu(I/II)ꢀelectrodeꢀpotentialsꢀofꢀCu(1),ꢀCu(20)ꢀandꢀCu(25),ꢀwhoseꢀ

2

2,56,57,58

electrochemistryꢀhasꢀbeenꢀreportedꢀpreviously,

newꢀdataꢀwithꢀpreviouslyꢀpublishedꢀdata,ꢀbyꢀcorrectingꢀtheꢀdifferenceꢀinꢀreferenceꢀelectrodeꢀ

subtractingꢀ530ꢀmVꢀfromꢀvaluesꢀinꢀref.ꢀ22).ꢀTheseꢀpreviouslyꢀpublishedꢀdataꢀareꢀalsoꢀincluded,ꢀafterꢀ

adjustmentꢀinꢀthisꢀway,ꢀinꢀTableꢀ2ꢀ(denotedꢀwithꢀasterisk).ꢀTheꢀstructure-activityꢀrelationshipsꢀwereꢀ

ꢀenabledꢀcombinationꢀandꢀcomparisonꢀofꢀtheꢀ

(

2

2,56,57,58

inꢀaccordꢀwithꢀpreviousꢀobservations

ꢀ(Fig.ꢀ4),ꢀshowingꢀthatꢀtheꢀdissymmetricꢀcomplexꢀCu(I/II)ꢀ

2

redoxꢀpotentials,ꢀlikeꢀthoseꢀofꢀtheꢀpreviouslyꢀreportedꢀsymmetricꢀones,ꢀcorrelatedꢀ(R ꢀ=ꢀ0.74)ꢀwithꢀ

1 2

theꢀnumberꢀofꢀalkylꢀgroupsꢀatꢀQ ꢀandꢀQ ꢀ(withꢀCu(I/II)ꢀredoxꢀpotentialsꢀloweredꢀbyꢀ66ꢀmVꢀperꢀalkylꢀ

2

group,ꢀasꢀdeterminedꢀfromꢀtheꢀregressionꢀlineꢀinꢀFig.ꢀ4).ꢀAsꢀobservedꢀpreviously, ꢀcompoundsꢀwithꢀ

phenylꢀgroupsꢀinsteadꢀofꢀalkylꢀgroupsꢀatꢀtheꢀterminalꢀpositionsꢀprovedꢀtoꢀincludeꢀoutliersꢀandꢀwereꢀ

excludedꢀfromꢀtheꢀcorrelationꢀinꢀFig.ꢀ4.ꢀThoseꢀcompoundsꢀwithꢀtwoꢀalkylꢀgroupsꢀatꢀtheꢀQ

1 2

ꢀandꢀQ ꢀ

positionsꢀshowedꢀlowꢀandꢀtightly-groupedꢀCu(I/II)ꢀredoxꢀpotentialsꢀ(Fig.ꢀ4).ꢀInꢀcontrast,ꢀtheꢀspreadꢀofꢀ

ꢀ

10

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1

Cu(II/III)ꢀredoxꢀpotentialsꢀwasꢀmuchꢀlessꢀandꢀthereꢀwasꢀnoꢀclearꢀcorrelationꢀwithꢀalkylationꢀatꢀQ ꢀandꢀ

2

Q

2

1

ꢀ(R ꢀ=ꢀ0.02)ꢀorꢀR

1 4

ꢀ–ꢀR .ꢀEvenꢀwithinꢀgroupsꢀofꢀcompoundsꢀwithꢀtheꢀsameꢀnumberꢀofꢀalkylꢀgroupsꢀatꢀ

ꢀandꢀQ ,ꢀtheꢀeffectꢀofꢀtheꢀnumberꢀofꢀterminalꢀalkylꢀgroupsꢀonꢀCu(I/II)ꢀredoxꢀpotentialsꢀwasꢀsmallꢀ

2

(

13ꢀmVꢀperꢀalkylꢀgroupꢀforꢀcompoundsꢀwithꢀalkylꢀgroupsꢀatꢀbothꢀQ

1 2

ꢀandꢀQ )ꢀandꢀpoorlyꢀcorrelatedꢀ(R ꢀ

=

ꢀ0.35)ꢀ(supplementaryꢀdata,ꢀFig.ꢀS22).ꢀToꢀensureꢀthatꢀtheꢀconformityꢀofꢀtheꢀredoxꢀbehaviourꢀofꢀtheꢀ

2

2,56

newꢀcompoundsꢀtoꢀtheꢀtrendsꢀpreviouslyꢀobserved ꢀwasꢀnotꢀundulyꢀinfluencedꢀ(andꢀhenceꢀ

invalidated)ꢀbyꢀincludingꢀtheꢀpublishedꢀdata,ꢀweꢀalsoꢀplottedꢀtheꢀnewꢀCu(I/II)ꢀredoxꢀpotentialsꢀalone;ꢀ

theꢀcorrelationꢀwasꢀsimilarꢀtoꢀthatꢀderivedꢀfromꢀtheꢀcombinedꢀdataꢀset,ꢀwithꢀaꢀ59ꢀmVꢀloweringꢀofꢀtheꢀ

2

potentialꢀperꢀalkylꢀgroupꢀatꢀQ

1

/Q

2

ꢀ(R ꢀ=ꢀ0.64)ꢀ(seeꢀsupplementaryꢀdata,ꢀFig.ꢀS23),ꢀsimilarꢀtoꢀtheꢀ

2

2ꢀ

averageꢀshiftꢀofꢀaroundꢀ60ꢀmVꢀperꢀalkylꢀgroupꢀobservedꢀpreviously.

Cu(III/II)

Cu(II/I)

+

E/Vꢀvs.ꢀFc /Fcꢀ

ꢀ

Fig.ꢀ3.ꢀExemplarꢀcyclicꢀvoltammogramꢀofꢀCu(30)ꢀinꢀdeoxygenatedꢀanhydrousꢀDMSO/0.1ꢀMꢀ

[Bu N][BF ]ꢀatꢀ0.1ꢀV/sꢀscanꢀrate.ꢀꢀ

4

ꢀ

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Cu(II/I)

DOI: 10.1039/C7DT02008B

-

0.90

0.95

1.00

1.05

1.10

1.15

1.20

yꢀ=ꢀ-0.066xꢀ- 0.9853

R²ꢀ=ꢀ0.74035

Cu(II/III)

0.30

0.25

0.20

0.15

0.10

0.05

0.00

yꢀ=ꢀ-0.0071xꢀ+ꢀ0.1963

R²ꢀ=ꢀ0.02094

0

1

2

NumberꢀofꢀalkylꢀgroupsꢀatꢀQ ,ꢀQ

1

2

ꢀ

Fig.ꢀ4.ꢀCorrelation,ꢀwithꢀregressionꢀlines,ꢀofꢀCu(I/II)ꢀ(top)ꢀandꢀCu(II/III)ꢀ(bottom)ꢀredoxꢀpotentialsꢀwithꢀ

alkylationꢀatꢀQ ꢀandꢀQ .ꢀSomeꢀpointsꢀhaveꢀbeenꢀoffsetꢀslightlyꢀhorizontallyꢀforꢀvisualꢀclarity.ꢀAllꢀ

1

2

availableꢀdataꢀareꢀincluded,ꢀfromꢀthisꢀworkꢀandꢀliteratureꢀdataꢀ(correctedꢀforꢀdifferentꢀreferencing),ꢀ

withꢀtheꢀexceptionꢀofꢀcompoundsꢀcontainingꢀphenylꢀgroups.ꢀ

LogPꢀmeasurementꢀ

Reversed-phaseꢀHPLCꢀwasꢀusedꢀtoꢀestimateꢀtheꢀlipophilicityꢀofꢀtheꢀnewlyꢀsynthesisedꢀCu-BTSCꢀ

complexesꢀasꢀanꢀalternativeꢀtoꢀoctanol-waterꢀpartitioning.ꢀLipophilicityꢀassessmentꢀbyꢀreversed-

phaseꢀHPLCꢀassumesꢀaꢀlinearꢀrelationshipꢀbetweenꢀtheꢀlogarithmꢀofꢀtheꢀretentionꢀfactorꢀofꢀtheꢀ

5

9

compoundꢀ(logK) ꢀandꢀitsꢀlogP.ꢀThus,ꢀreferenceꢀCu-BTSCꢀcomplexesꢀ(Cu(20),ꢀCu(21),ꢀCu(5),ꢀCu(7)ꢀandꢀ

6

0

Cu(36) )ꢀwereꢀchromatographedꢀandꢀtheirꢀexperimentalꢀlogKꢀvaluesꢀcorrelatedꢀdirectlyꢀwithꢀtheirꢀ

6

0

knownꢀexperimentalꢀlogPꢀvaluesꢀ(fromꢀoctanolꢀwaterꢀextractionꢀexperiments )ꢀtoꢀcreateꢀaꢀ

calibrationꢀcurveꢀ(seeꢀFigureꢀ5),ꢀwhichꢀwasꢀindeedꢀlinearꢀandꢀwasꢀusedꢀtoꢀcalculateꢀtheꢀlogPꢀvaluesꢀofꢀ

theꢀnewꢀCu-BTSCꢀcomplexes,ꢀwhichꢀareꢀsummarisedꢀinꢀTableꢀ2ꢀ(withꢀthoseꢀusedꢀforꢀtheꢀcalibrationꢀ

markedꢀwithꢀanꢀasterisk).ꢀAsꢀexpected,ꢀhigherꢀlogPꢀvaluesꢀcorrelatedꢀwithꢀgreaterꢀmolecularꢀweight,ꢀ

withꢀcomplexesꢀhavingꢀphenylꢀgroupsꢀinꢀtheirꢀstructureꢀbeingꢀtheꢀmostꢀlipophilic.ꢀAlthoughꢀtheꢀeffectꢀ

ofꢀalkylationꢀonꢀlogPꢀisꢀexpectedꢀtoꢀvaryꢀwithꢀlocationꢀandꢀidentityꢀofꢀtheꢀalkyl/arylꢀgroup,ꢀitꢀisꢀclearꢀ

thatꢀalkylationꢀofꢀbothꢀtheꢀdiimineꢀbackboneꢀandꢀpendantꢀaminoꢀarmsꢀcontributedꢀtoꢀenhancingꢀtheꢀ

ꢀ

12

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lipophilicityꢀofꢀCu-BTSCsꢀ(byꢀ0.16ꢀperꢀalkylꢀgroupꢀonꢀaverage,ꢀfromꢀlinearꢀleastꢀsquaresꢀregressionꢀofꢀ

logPꢀandꢀtotalꢀnumberꢀofꢀalkylꢀgroupsꢀatꢀR

S24).ꢀꢀ

1 4 1 2

ꢀ–ꢀR ꢀandꢀQ ꢀ–ꢀQ ;ꢀseeꢀsupplementaryꢀinformation,ꢀFig.ꢀ

2

.1

2

1

.9

.8

.7

.6

.5

.4

y = 0.386x + 1.5448

R² = 0.98256

-0.1

0.1

0.3

0.5

0.7

0.9

1.1

LogK

ꢀ

6

0

Fig.ꢀ5ꢀCorrelationꢀbetweenꢀtheꢀliteratureꢀlogPꢀvalues ꢀofꢀCu(20),ꢀCu(21),ꢀCu(5),ꢀCu(7)ꢀandꢀCu(36)ꢀandꢀ

theirꢀexperimentalꢀlogKꢀvaluesꢀmeasuredꢀbyꢀHPLC.ꢀAꢀC18ꢀcolumnꢀwasꢀusedꢀasꢀtheꢀstationaryꢀphaseꢀ

andꢀaꢀwaterꢀ+ꢀ0.1ꢀ%ꢀTFAꢀ(60%)/acetonitrileꢀ+ꢀ0.1ꢀ%ꢀTFAꢀ(40%)ꢀisocraticꢀmobileꢀphase.ꢀ

Recentꢀmechanisticꢀstudiesꢀwithꢀhypoxia-targetingꢀcopper(II)ꢀbis(thiosemicarbazone)ꢀcomplexes,ꢀ

combinedꢀwithꢀinꢀvivoꢀstudiesꢀinꢀrodentꢀtumourꢀmodels,ꢀsuggestꢀthatꢀtheꢀcombinationꢀofꢀredoxꢀ

potentialꢀandꢀlipophilicityꢀofferedꢀbyꢀCuATSMꢀ(Cu(20))ꢀmayꢀnotꢀbeꢀidealꢀforꢀhypoxiaꢀimagingꢀandꢀthatꢀ

lessꢀlipophilicꢀcomplexesꢀmayꢀgiveꢀimprovedꢀpharmacokinetics.ꢀInꢀparticular,ꢀCuATSꢀ(Cu(33))andꢀ

CuCTSꢀ(Cu(25))ꢀshowedꢀimprovedꢀclearanceꢀfromꢀnon-hypoxicꢀtissueꢀandꢀsuperiorꢀhypoxic-to-

normoxicꢀtissueꢀuptakeꢀratio,ꢀasꢀwellꢀasꢀaꢀmoreꢀfavourableꢀpO

2

ꢀthresholdꢀofꢀselectivity,ꢀwarrantingꢀinꢀ

vivoꢀevaluationꢀforꢀcardiacꢀhypoxiaꢀimaging,ꢀbasedꢀonꢀexperimentsꢀinꢀtheꢀLangendorffꢀisolatedꢀ

3

,27

perfusedꢀratꢀheartꢀmodel. ꢀBothꢀhaveꢀaꢀsimilarꢀredoxꢀpotentialꢀbutꢀreducedꢀlipophilicityꢀcomparedꢀ

toꢀCuATSM.ꢀByꢀincludingꢀcomplexesꢀwithꢀdissymmetricꢀligands,ꢀwhichꢀareꢀnowꢀaccessibleꢀbyꢀtheꢀ

methodsꢀdescribedꢀhere,ꢀtheꢀlibraryꢀofꢀcompoundsꢀforꢀbiologicalꢀevaluationꢀwithꢀlipophilicityꢀandꢀ

redoxꢀpotentialꢀsimilarꢀtoꢀCuATSꢀandꢀCuCTSꢀcanꢀbeꢀextendedꢀtoꢀallowꢀselectionꢀofꢀoptimalꢀcomplexesꢀ

forꢀhypoxiaꢀimagingꢀinꢀdifferentꢀclinicalꢀcontexts.ꢀInꢀparticular,ꢀCu(23),ꢀCu(24),ꢀCu(26)ꢀandꢀCu(29),ꢀ

amongꢀtheseꢀcompounds,ꢀshouldꢀbeꢀevaluatedꢀbiologicallyꢀasꢀtheyꢀhaveꢀlogPꢀvaluesꢀcomparableꢀtoꢀ

thoseꢀofꢀCuATSꢀandꢀCuCTSꢀandꢀslightlyꢀlowerꢀthanꢀthatꢀofꢀCuATSM,ꢀandꢀCu(I/II)ꢀredoxꢀpotentialsꢀinꢀ

theꢀappropriateꢀrange.ꢀ

Conclusionsꢀ

Thisꢀpaperꢀreportsꢀtheꢀsynthesisꢀofꢀnewꢀdissymmetricallyꢀsubstitutedꢀbis(thiosemicarbazone)ꢀligandsꢀ

inꢀhighꢀpurityꢀbyꢀcontrollingꢀtheꢀcondensationꢀreactionsꢀbetweenꢀdicarbonylꢀcompoundsꢀandꢀ4-

substituted-3-thiosemicarbazidesꢀorꢀusingꢀacetalꢀprotection.ꢀReadyꢀaccessꢀtoꢀdissymmetricꢀpro-

ligandsꢀextendsꢀtheꢀlibraryꢀofꢀcomplexesꢀthatꢀhaveꢀsuitableꢀpropertiesꢀforꢀhypoxiaꢀimagingꢀandꢀfromꢀ

whichꢀoptimalꢀimagingꢀagentsꢀcanꢀbeꢀselected.ꢀCopperꢀcomplexesꢀofꢀtheꢀnewꢀligandsꢀhaveꢀbeenꢀ

preparedꢀbyꢀreactionꢀwithꢀcopperꢀacetateꢀorꢀviaꢀtransmetallationꢀofꢀtheꢀcorrespondingꢀzincꢀ

complexes,ꢀwhichꢀareꢀconvenientꢀprecursorsꢀforꢀtheꢀrapidꢀsynthesisꢀofꢀtheꢀcopperꢀ(andꢀradiocopper)ꢀ

complexes.ꢀTheꢀnewꢀdissymmetricꢀcomplexesꢀdisplayꢀreductionꢀpotentialsꢀthatꢀcorrelateꢀwithꢀtheꢀ

ꢀ

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numberꢀofꢀbackboneꢀ(Q

1

,ꢀQ

2

)ꢀalkylꢀgroups,ꢀasꢀseenꢀpreviouslyꢀforꢀtheꢀsymmetricꢀcomplexes,ꢀandꢀ

extendꢀtheꢀrangeꢀofꢀlipophilicityꢀvaluesꢀavailable.ꢀ

Experimentalꢀ

AllꢀreagentsꢀwereꢀpurchasedꢀfromꢀSigma-Aldrich,ꢀAlfaꢀAesar,ꢀInterlinkꢀScientificꢀServicesꢀandꢀVWRꢀ

InternationalꢀLtd.ꢀandꢀusedꢀwithoutꢀfurtherꢀpurification,ꢀunlessꢀotherwiseꢀstated.ꢀNMRꢀanalysisꢀwasꢀ

6

undertakenꢀinꢀd -DMSOꢀusingꢀaꢀJEOLꢀNMRꢀECS-400ꢀandꢀJEOLꢀDeltaꢀv5.02ꢀsoftwareꢀoperatingꢀatꢀ400ꢀ

1

13

1

MHzꢀforꢀ Hꢀspectraꢀandꢀ100ꢀMHzꢀforꢀ Cꢀ{ H}ꢀspectra.ꢀSpectraꢀwereꢀreferenceꢀtoꢀresidualꢀsolventꢀandꢀ

JꢀvaluesꢀareꢀgivenꢀinꢀHz.ꢀFTIRꢀspectraꢀwereꢀobtainedꢀusingꢀaꢀShimadzuꢀIRꢀAffinity-1ꢀFourierꢀTransformꢀ

InfraredꢀSpectrometerꢀwithꢀaꢀGoldenꢀGateꢀDiamondꢀAttenuatedꢀTotalꢀReflectanceꢀ(ATR)ꢀattachment.ꢀ

CHNꢀanalysesꢀwereꢀobtainedꢀatꢀtheꢀScienceꢀCentre,ꢀLondonꢀMetropolitanꢀUniversityꢀutilisingꢀaꢀCarloꢀ

ErbaꢀFlashꢀ2000ꢀelementalꢀanalyser.ꢀRamanꢀspectraꢀwereꢀobtainedꢀusingꢀaꢀHoribaꢀLabRAM-HRꢀ

Ramanꢀspectrometerꢀutilisingꢀlasersꢀoperatingꢀatꢀ532.00,ꢀ632.81ꢀorꢀ784.15ꢀnm.ꢀAꢀ×50ꢀobjectiveꢀlensꢀ

wasꢀusedꢀgivingꢀaꢀbeamꢀdiameterꢀofꢀapproximatelyꢀ2ꢀµmꢀonꢀtheꢀsample.ꢀTheꢀspectrometerꢀwasꢀ

-

1

calibratedꢀagainstꢀtheꢀsiliconꢀlineꢀatꢀ520.6ꢀcm .ꢀUV-visibleꢀspectraꢀwereꢀobtainedꢀwithꢀaꢀShimadzuꢀ

UV-1800ꢀspectrometer.ꢀAꢀBrukerꢀmicrOTOF-Qꢀmassꢀspectrometerꢀwasꢀusedꢀtoꢀrecordꢀpositiveꢀmodeꢀ

ESIꢀmassꢀspectra.ꢀSamplesꢀwereꢀdissolvedꢀinꢀDMSOꢀatꢀaꢀconcentrationꢀofꢀ1ꢀmg/mlꢀbeforeꢀbeingꢀ

dilutedꢀ1ꢀinꢀ100ꢀinꢀmethanol.ꢀꢀ10ꢀµLꢀofꢀsampleꢀsolutionꢀwasꢀinjectedꢀintoꢀaꢀflowingꢀstreamꢀofꢀ10ꢀmMꢀ

ammoniumꢀacetateꢀinꢀ95%ꢀmethanolꢀinꢀwaterꢀ(flowꢀrate:ꢀ0.02ꢀmL/min)ꢀandꢀtheꢀflowꢀdirectedꢀintoꢀ

theꢀelectrosprayꢀsourceꢀofꢀtheꢀspectrometer.ꢀDataꢀwereꢀprocessedꢀinꢀBruker’sꢀCompassꢀDataꢀ

Analysisꢀsoftwareꢀutilisingꢀaꢀlockꢀmass.ꢀꢀ

CyclicꢀvoltammogramsꢀwereꢀrecordedꢀusingꢀaꢀμAUTOLABꢀpotentiostatꢀ(MetrohmꢀAutolabꢀB.ꢀV.,ꢀ

Netherlands)ꢀandꢀGeneralꢀPurposeꢀElectrochemicalꢀSystemꢀ(GPES)ꢀacquisitionꢀandꢀanalysisꢀsoftware,ꢀ

withꢀaꢀscanꢀrateꢀofꢀ0.1ꢀV/sꢀunderꢀargonꢀusingꢀaꢀglassyꢀcarbonꢀworkingꢀelectrode,ꢀaꢀsilverꢀwireꢀ

pseudo-referenceꢀelectrodeꢀandꢀaꢀplatinumꢀauxiliaryꢀelectrode,ꢀinꢀDMSOꢀ(5ꢀmL)ꢀwithꢀ

tetrabutylammoniumꢀhexafluorophosphateꢀ(0.1ꢀM,ꢀSigmaꢀAldrich)ꢀasꢀaꢀsupportꢀelectrolyteꢀandꢀaꢀCu-

complexꢀconcentrationꢀofꢀ0.5ꢀmM.ꢀAllꢀpotentialsꢀwereꢀreferencedꢀtoꢀtheꢀinternalꢀstandardꢀ

ferrocene/ferroceniumꢀcouple.ꢀTheꢀredoxꢀpotentialsꢀwereꢀcalculatedꢀasꢀtheꢀmidpointꢀbetweenꢀtheꢀ

reductionꢀandꢀoxidationꢀpeaks.ꢀ

ReversedꢀphaseꢀHPLCꢀwasꢀusedꢀbothꢀtoꢀdetermineꢀpurityꢀandꢀlipophilicityꢀ(logP)ꢀofꢀnewꢀcopperꢀ

complexes,ꢀusingꢀanꢀEclipseꢀXDB-C18ꢀcolumnꢀ(4.6ꢀxꢀ150ꢀmm,ꢀ5ꢀμm)ꢀasꢀtheꢀstationaryꢀphaseꢀandꢀanꢀ

isocraticꢀmobileꢀphaseꢀconsistingꢀofꢀwaterꢀ+ꢀ0.1ꢀ%ꢀTFAꢀ(60ꢀ%)ꢀandꢀacetonitrileꢀ+ꢀ0.1ꢀ%ꢀTFAꢀ(40ꢀ%).ꢀCu-

BTSCꢀcomplexesꢀofꢀknownꢀlogPꢀvaluesꢀ(Cu(10),ꢀCu(11),ꢀCu(21),ꢀCu(22)ꢀandꢀCu(23)),ꢀdeterminedꢀbyꢀ

6

0

octanol-waterꢀextraction )ꢀwereꢀchromatographedꢀandꢀtheꢀlogarithmsꢀofꢀtheirꢀretentionꢀfactorsꢀ

5

9

(

logK )ꢀplottedꢀagainstꢀtheirꢀliteratureꢀlogPꢀvaluesꢀtoꢀconstructꢀaꢀcalibrationꢀcurve.ꢀLogKꢀvaluesꢀwereꢀ

calculatedꢀusingꢀlogKꢀ=ꢀlog[(t -t )/t )],ꢀwhereꢀt ꢀisꢀtheꢀretentionꢀtimeꢀofꢀtheꢀcomplexꢀandꢀt ꢀisꢀtheꢀ

r

o

r

o

retentionꢀtimeꢀofꢀtheꢀsolventꢀ(DMSO).ꢀTheꢀresultingꢀlinearꢀleast-squaresꢀregressionꢀequationꢀwasꢀ

usedꢀtoꢀcalculateꢀlogPꢀvalues.ꢀThinꢀlayerꢀchromatographyꢀ(TLC)ꢀwasꢀperformedꢀusingꢀMerckꢀ60ꢀF254ꢀ

silicaꢀgelꢀTLCꢀplatesꢀasꢀtheꢀstationaryꢀphaseꢀandꢀethylꢀacetateꢀasꢀtheꢀmobileꢀphase.ꢀ

ProligandꢀprecursorsꢀA-Mꢀ

SynthesisꢀofꢀA:ꢀ4-methyl-3-thiosemicarbazideꢀ(1.315ꢀg,ꢀ0.013ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(40ꢀmL),ꢀ

followedꢀbyꢀtheꢀadditionꢀofꢀmethylglyoxal-1,1-dimethylacetalꢀ(1.5ꢀmL,ꢀ0.012ꢀmol,ꢀ1.5ꢀg).ꢀTheꢀ

ꢀ

14

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resultingꢀsolutionꢀwasꢀleftꢀtoꢀstirꢀ(3ꢀdays).ꢀꢀTheꢀvolumeꢀwasꢀreducedꢀunderꢀvacuumꢀandꢀdiethylꢀetherꢀ

wasꢀaddedꢀtoꢀtheꢀresultingꢀviscousꢀoilꢀandꢀcooledꢀonꢀiceꢀovernight.ꢀTheꢀprecipitateꢀwasꢀisolated,ꢀ

washedꢀwithꢀdiethylꢀetherꢀ(4ꢀxꢀ1ꢀmL)ꢀandꢀdried.ꢀAꢀclearꢀcrystallineꢀsolidꢀ(0.585ꢀg)ꢀwasꢀrecoveredꢀ(24%ꢀ

1

yield).ꢀ HꢀNMRꢀ(DMSO-d

6

,ꢀ400ꢀMHz):ꢀδꢀ=ꢀ10.19ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ8.94ꢀ(q,ꢀ1ꢀH,ꢀH

),ꢀ2.93ꢀ(d,ꢀ3ꢀH,ꢀHN-CH ,ꢀJ=ꢀ4.4ꢀHz),ꢀ1.78ꢀ(s,ꢀ3ꢀH,ꢀN=C-CH

,ꢀ100ꢀMHz):ꢀδ=ꢀ179.57ꢀ(C=S),ꢀ148.60ꢀ(C=N),ꢀ106.87ꢀ(HC-O),ꢀ55.16ꢀ(O-CH ),ꢀ31.39ꢀ(HN-CH

).ꢀIRꢀ(neat):ꢀνmax/cm 3279ꢀ(m),ꢀ3227ꢀ(w),ꢀ2936ꢀ(w),ꢀ1537ꢀ(m),ꢀ1504ꢀ(m),ꢀ1435ꢀ(m),ꢀ

3

C-NH,ꢀJ=ꢀ4.4ꢀHz),ꢀ4.49ꢀ(s,ꢀ

1

3

1

ꢀH,ꢀO-CH),ꢀ3.25ꢀ(s,ꢀ6ꢀH,ꢀO-CH

3

).ꢀ Cꢀ{ H}ꢀNMRꢀ

),ꢀ

(

DMSO-d

6

3

-

1ꢀ

1

9

1

9

1.17ꢀ(N=C-CH

3

410ꢀ(m),ꢀ1366ꢀ(m),ꢀ1325ꢀ(m),ꢀ1271ꢀ(m),ꢀ1213ꢀ(m),ꢀ1192ꢀ(m),ꢀ1115ꢀ(m),ꢀ1072ꢀ(s),ꢀ1057ꢀ(s),ꢀ986ꢀ(s),ꢀ

-

1ꢀ

49ꢀ(s),ꢀ860ꢀ(m),ꢀ660ꢀ(m),ꢀ559ꢀ(s),ꢀ494ꢀ(m).ꢀRamanꢀ(neat),ꢀνmax/cm 784.15ꢀnm:ꢀ1642ꢀ(s),ꢀ1539ꢀ(w),ꢀ

499ꢀ(w),ꢀ1450ꢀ(w),ꢀ1437ꢀ(w),ꢀ1324ꢀ(w),ꢀ1277ꢀ(w),ꢀ1224ꢀ(w),ꢀ1156ꢀ(w),ꢀ1062ꢀ(w),ꢀ1044ꢀ(w),ꢀ1022ꢀ(w),ꢀ

85ꢀ(m),ꢀ963ꢀ(w),ꢀ860ꢀ(s),ꢀ799ꢀ(s),ꢀ660ꢀ(w),ꢀ632ꢀ(w),ꢀ582ꢀ(m),ꢀ573ꢀ(s),ꢀ495ꢀ(w),ꢀ435ꢀ(w),ꢀ354ꢀ(w),ꢀ308ꢀ

o

(

m),ꢀ272ꢀ(m).ꢀMp:ꢀ>84-88ꢀ C.ꢀ

SynthesisꢀofꢀB:ꢀ4-methyl-3-thiosemicarbazideꢀ(2.500ꢀg,ꢀ24.0ꢀmmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀwaterꢀ

o

(

100ꢀmL,ꢀ50ꢀ C)ꢀandꢀHClꢀ(32%,ꢀ5ꢀdrops)ꢀwasꢀadded.ꢀMethylgloxal-1,1-dimethylacetalꢀ(8.70ꢀmL,ꢀ72ꢀ

o

mmol,ꢀ8.49ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀvigorouslyꢀstirredꢀ(50ꢀ C,ꢀ5ꢀminutes).ꢀTheꢀprecipitateꢀwasꢀ

recoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(10ꢀxꢀ50ꢀmL)ꢀandꢀdried.ꢀAꢀyellowꢀsolidꢀ(2.473ꢀ

g)ꢀwasꢀrecoveredꢀ(65%ꢀyield).ꢀδ

H

ꢀ11.16ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ9.32ꢀ(1ꢀH,ꢀs,ꢀO=CH),ꢀ8.98ꢀ(1ꢀH,ꢀm,ꢀJ=ꢀ4.4,ꢀH

),ꢀ1.90ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ).ꢀδCꢀ192.10ꢀ(C=O),ꢀ179.45ꢀ(C=S),ꢀ145.94ꢀ(C=N),ꢀ

).ꢀꢀIR:ꢀνmax/cm ꢀ3350ꢀ(m),ꢀ3171ꢀ(m),ꢀ2845ꢀ(w),ꢀ1692ꢀ(m),ꢀ1593ꢀ(m),ꢀ

537ꢀ(m),ꢀ1504ꢀ(s),ꢀ1410ꢀ(m),ꢀ1369ꢀ(m),ꢀ1200ꢀ(s),ꢀ1146ꢀ(m),ꢀ1113ꢀ(m),ꢀ1047ꢀ(s),ꢀ1001ꢀ(s),ꢀ856ꢀ(s),ꢀ789ꢀ

3

C-

NH),ꢀ2.98ꢀ(3ꢀH,ꢀd,ꢀJ=ꢀ4.4,ꢀHN-CH

3

-

1

3

1

3 3

1.67ꢀ(HN-CH ),ꢀ9.66ꢀ(N=C-CH

-

1ꢀ

(

m),ꢀ665ꢀ(s),ꢀ592ꢀ(s),ꢀ569ꢀ(s),ꢀ534ꢀ(s).ꢀꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm 3354ꢀ(w),ꢀ3179ꢀ(w),ꢀ2921ꢀ(w),ꢀ

2

7

848ꢀ(w),ꢀ1696ꢀ(m),ꢀ1577ꢀ(s),ꢀ1433ꢀ(w),ꢀ1278ꢀ(w),ꢀ1227ꢀ(w),ꢀ1192ꢀ(w),ꢀ1116ꢀ(w),ꢀ1045ꢀ(w),ꢀ856ꢀ(w),ꢀ

o

83ꢀ(w),ꢀ567ꢀ(w),ꢀ357ꢀ(w),ꢀ296ꢀ(w),ꢀ237ꢀ(w).ꢀMp:ꢀ>156ꢀ Cꢀ(dec.).ꢀ

o

SynthesisꢀofꢀC:ꢀFreshlyꢀactivatedꢀmolecularꢀsievesꢀ(3ꢀÅ,ꢀ0.801ꢀg)ꢀwasꢀaddedꢀtoꢀDMFꢀ(15ꢀmL,ꢀ60ꢀ C),ꢀ

followedꢀbyꢀtheꢀadditionꢀofꢀthiosemicarbazideꢀ(0.770ꢀg,ꢀ0.0084ꢀmol).ꢀThisꢀwasꢀfollowedꢀbyꢀtheꢀ

additionꢀofꢀmethylglyoxal-1,1-dimethylacetalꢀ(1ꢀmL,ꢀ0.0083ꢀmol,ꢀ1ꢀg).ꢀTheꢀresultingꢀsolutionꢀwasꢀleftꢀ

toꢀstirꢀ(roomꢀtemperature,ꢀ3ꢀdays).ꢀTheꢀmolecularꢀsievesꢀwereꢀfilteredꢀoffꢀandꢀtheꢀDMFꢀwasꢀremovedꢀ

underꢀvacuum.ꢀTheꢀcrudeꢀproductꢀwasꢀwashedꢀwithꢀaꢀlittleꢀdiethylꢀetherꢀandꢀdried.ꢀAnꢀoffꢀwhiteꢀsolidꢀ

(

0.769ꢀg)ꢀwasꢀrecoveredꢀ(48%ꢀyield).ꢀδ

.48ꢀ(s,ꢀ1ꢀH,ꢀO-CH),ꢀ3.24ꢀ(s,ꢀ6ꢀH,ꢀO-CH ),ꢀ1.78ꢀ(s,ꢀ3ꢀH,ꢀN=C-CH

HC-O),ꢀ55.16ꢀ(O-CH ),ꢀ11.21ꢀ(N=C-CH ).ꢀ

H

ꢀ10.21ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ8.23ꢀ(s,ꢀ1ꢀH,ꢀC-NH),ꢀ7.72ꢀ(s,ꢀ1ꢀH,ꢀC-NH),ꢀ

4

3

).ꢀδCꢀ179.90ꢀ(C=S),ꢀ149.02ꢀ(C=N),ꢀ106.78ꢀ

(

3

SynthesisꢀofꢀD:ꢀCompoundꢀCꢀ(0.754ꢀg,ꢀ0.004ꢀmol)ꢀwasꢀdissolvedꢀinꢀanꢀacetonitrileꢀsolutionꢀ(15ꢀmL,ꢀ

o

9

8%ꢀacetonitrile,ꢀ2%ꢀde-ionisedꢀwater,ꢀ60ꢀ C).ꢀLiBF

4

ꢀ(0.720ꢀg,ꢀ0.008ꢀmol)ꢀwasꢀaddedꢀandꢀtheꢀresultingꢀ

solutionꢀwasꢀleftꢀtoꢀstirꢀ(60ꢀ C,ꢀ1ꢀhour).ꢀAꢀsaturatedꢀsolutionꢀofꢀNa CO ꢀ(30ꢀmL)ꢀwasꢀaddedꢀrapidlyꢀ

resultingꢀinꢀtheꢀformationꢀofꢀaꢀbrown/orangeꢀsolution.ꢀTheꢀproductꢀwasꢀextractedꢀwithꢀdiethylꢀetherꢀ

1ꢀxꢀ50ꢀmL,ꢀ2ꢀxꢀ25ꢀmL)ꢀandꢀtheꢀorganicꢀsolutionꢀwasꢀdriedꢀoverꢀmagnesiumꢀsulfateandꢀevaporatedꢀtoꢀ

dryness.ꢀAꢀbrownꢀsolidꢀ(0.137ꢀg)ꢀwasꢀrecoveredꢀ(24%ꢀyield).ꢀδ ꢀ11.18ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ9.32ꢀ(s,ꢀ1ꢀH,ꢀ

,ꢀJ=ꢀ4.8ꢀHz),ꢀ1.90ꢀ(s,ꢀ3ꢀH,ꢀN=C-CH ).ꢀδ ꢀ192.16ꢀ

).ꢀIR:ꢀνmax/cm ꢀ3352ꢀ(w),ꢀ3173ꢀ(m),ꢀ

o

2

3

(

H

O=CH),ꢀ9.01ꢀ(m,ꢀ1ꢀH,ꢀH

3

C-NH),ꢀ2.99ꢀ(d,ꢀ3ꢀH,ꢀHN-CH

3

C

-

1

(

C=O),ꢀ179.46ꢀ(C=S),ꢀ145.93ꢀ(C=N),ꢀ31.69ꢀ(HN-CH

3

),ꢀ9.68ꢀ(N=C-CH

3

2

1

963ꢀ(w),ꢀ2843ꢀ(w),ꢀ1694ꢀ(m),ꢀ1593ꢀ(m),ꢀ1537ꢀ(m),ꢀ1504ꢀ(m),ꢀ1410ꢀ(m),ꢀ1369ꢀ(m),ꢀ1200ꢀ(s),ꢀ1146ꢀ(m),ꢀ

111ꢀ(m),ꢀ1047ꢀ(s),ꢀ1001ꢀ(s),ꢀ856ꢀ(m),ꢀ789ꢀ(m),ꢀ665ꢀ(s),ꢀ594ꢀ(s),ꢀ569ꢀ(s),ꢀ534ꢀ(s),ꢀ503ꢀ(m).ꢀꢀ

ꢀ

15

Dalton Transactions

Page 16 of 38

View Article Online

DOI: 10.1039/C7DT02008B

SynthesisꢀofꢀE:ꢀ4-methyl-3-thiosemicarbazideꢀ(0.890ꢀg,ꢀ8.5ꢀmmol)ꢀwasꢀdissolvedꢀinꢀethanolꢀ(30ꢀmL,ꢀ

o

6

0ꢀ Cꢀ),ꢀfollowedꢀbyꢀtheꢀadditionꢀofꢀ3,3-dimethoxy-2-butanoneꢀ(1.25ꢀmL,ꢀ9.3ꢀmmol,ꢀ1.23ꢀg).ꢀTheꢀ

o

resultingꢀsolutionꢀwasꢀleftꢀtoꢀstirꢀatꢀ60ꢀ Cꢀforꢀ36ꢀh.ꢀTheꢀprecipitateꢀwasꢀfilteredꢀoffꢀandꢀdiscarded.ꢀTheꢀ

solventꢀwasꢀremovedꢀandꢀtheꢀresultingꢀsolidꢀwasꢀextractedꢀwithꢀdiethylꢀetherꢀ(1ꢀxꢀ50ꢀmL,ꢀ2ꢀxꢀ25ꢀmL).ꢀ

Theꢀdiethylꢀetherꢀwasꢀremovedꢀandꢀtheꢀremainingꢀsolidꢀwasꢀdried.ꢀAꢀwhiteꢀsolidꢀ(0.308ꢀg)ꢀwasꢀ

recoveredꢀ(17%ꢀyield).ꢀδHꢀ9.98ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.01ꢀ(1ꢀH,ꢀm,ꢀH

3 3

C-NH),ꢀ3.06ꢀ(6ꢀH,ꢀs,ꢀO-CH ),ꢀ2.96ꢀ(3ꢀH,ꢀd,ꢀ

Jꢀ=ꢀ4.8,ꢀHN-CH ),ꢀ1.86ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ1.37ꢀ(3ꢀH,ꢀs,ꢀO-C-CH ).ꢀ

3

SynthesisꢀofꢀF:ꢀ4-methyl-3-thiosemicarbazideꢀ(0.89ꢀg,ꢀ8.5ꢀmmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀwaterꢀ

o

(

100ꢀmL).ꢀTheꢀsolutionꢀwasꢀcooledꢀ(4ꢀ C)ꢀoverꢀice,ꢀfollowedꢀbyꢀtheꢀadditionꢀofꢀHClꢀ(32%,ꢀ2ꢀdrops).ꢀ2,3-ꢀ

o

butanedioneꢀ(7.15ꢀmL,ꢀ81.5ꢀmmol,ꢀ7.01ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀvigorouslyꢀstirredꢀatꢀ4ꢀ Cꢀforꢀ1ꢀh.ꢀ

Theꢀprecipitateꢀwasꢀrecoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(3ꢀxꢀ30ꢀmL),ꢀethanolꢀ(20ꢀ

mL,ꢀcold),ꢀdiethylꢀetherꢀ(25ꢀmL,ꢀcold)ꢀandꢀdried.ꢀTheꢀcrudeꢀwasꢀrecrystallizedꢀfromꢀethanolꢀinꢀaꢀ

freezer.ꢀAꢀwhiteꢀcrystallineꢀsolidꢀ(0.684ꢀg)ꢀwasꢀrecoveredꢀ(60%ꢀyield).ꢀδHꢀ10.61ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.59ꢀ(1ꢀ

H,ꢀq,ꢀJꢀ=ꢀ4.4,ꢀH

3

C-NH),ꢀ3.01ꢀ(3ꢀH,ꢀd,ꢀJꢀ=ꢀ4.4,ꢀHN-CH

3

),ꢀ2.38ꢀ(3ꢀH,ꢀs,ꢀO=C-CH

),ꢀ25.31ꢀ(O=C-CH

max/cm ꢀ3285ꢀ(m),ꢀ1670ꢀ(s),ꢀ1593ꢀ(w),ꢀ1537ꢀ(m),ꢀ1495ꢀ(s),ꢀ1427ꢀ(m),ꢀ1410ꢀ(s),ꢀ1360ꢀ(m),ꢀ1207ꢀ(s),ꢀ

152ꢀ(s),ꢀ1126ꢀ(s),ꢀ1105ꢀ(s),ꢀ1047ꢀ(s),ꢀ999ꢀ(m),ꢀ835ꢀ(m),ꢀ725ꢀ(w),ꢀ667ꢀ(m),ꢀ629ꢀ(m),ꢀ606ꢀ(s),ꢀ577ꢀ(s).ꢀ

3

),ꢀ1.91ꢀ(3ꢀH,ꢀs,ꢀN=C-CH

3

).ꢀδCꢀ

1

98.04ꢀ(C=O),ꢀ179.49ꢀ(C=S),ꢀ146.49ꢀ(C=N),ꢀ31.94ꢀ(HN-CH

3

),ꢀ10.57ꢀ(N=C-CH ).ꢀIR:ꢀ

3

-

1

ν

1

-

1

Ramanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ3289ꢀ(w),ꢀ2919ꢀ(w),ꢀ1671ꢀ(m),ꢀ1591ꢀ(s),ꢀ1409ꢀ(w),ꢀ1367ꢀ(w),ꢀ1304ꢀ(w),ꢀ

1

>

213ꢀ(w),ꢀ1128ꢀ(w),ꢀ1106ꢀ(w),ꢀ1000ꢀ(w),ꢀ947ꢀ(w),ꢀ836ꢀ(w),ꢀ725ꢀ(w),ꢀ609ꢀ(w),ꢀ578ꢀ(w),ꢀ318ꢀ(w).ꢀMp:ꢀ

o

149ꢀ Cꢀ(dec.).ꢀ

SynthesisꢀofꢀG:ꢀMethodꢀ1:ꢀFreshlyꢀactivatedꢀmolecularꢀsievesꢀ(3ꢀÅ,ꢀ0.808ꢀg)ꢀwasꢀaddedꢀtoꢀDMFꢀ(15ꢀ

o

mL,ꢀ60ꢀ C),ꢀfollowedꢀbyꢀtheꢀadditionꢀofꢀthiosemicarbazideꢀ(0.773ꢀg,ꢀ8.5ꢀmmol)ꢀandꢀ3,3-dimethoxy-2-

o

butanoneꢀ(1.5ꢀmL,ꢀ11ꢀmmol,ꢀ1.48ꢀg).ꢀTheꢀresultingꢀsolutionꢀwasꢀleftꢀtoꢀstirꢀatꢀ60ꢀ Cꢀforꢀ3ꢀd.ꢀTheꢀ

molecularꢀsievesꢀandꢀsolidꢀby-productsꢀwereꢀfilteredꢀoff,ꢀtheꢀDMFꢀwasꢀremovedꢀunderꢀvacuumꢀandꢀ

theꢀsampleꢀdried.ꢀAꢀbrownꢀsolidꢀ(0.342ꢀg)ꢀwasꢀrecoveredꢀ(20%ꢀyield).ꢀMethodꢀ2:ꢀThiosemicarbazideꢀ

(

1.55ꢀg,ꢀ17.0ꢀmmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀwaterꢀ(100ꢀmL,ꢀwarm).ꢀTheꢀsolutionꢀwasꢀcooledꢀ(5ꢀ

o

C)ꢀonꢀice,ꢀfollowedꢀbyꢀtheꢀadditionꢀofꢀHClꢀ(32%,ꢀ20ꢀdrops).ꢀ2,3-butanedioneꢀ(5.97ꢀmL,ꢀ68.0ꢀmmol,ꢀ

o

5

.86ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀvigorouslyꢀstirredꢀatꢀ5ꢀ Cꢀforꢀ10ꢀm.ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀviaꢀ

filtration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(6ꢀxꢀ50ꢀmL)ꢀandꢀdried.ꢀAnꢀoffꢀwhiteꢀsolidꢀ(1.687ꢀg)ꢀwasꢀ

recoveredꢀ(62%ꢀyield).ꢀδ ꢀ10.54ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.67ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ8.05ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ2.33ꢀ(3ꢀH,ꢀs,ꢀ

O=C-CH ),ꢀ1.90ꢀ(ꢀ3ꢀH,ꢀs,ꢀN=C-CH ).ꢀδ ꢀ198.15ꢀ(C=O),ꢀ180.27ꢀ(C=S),ꢀ146.39ꢀ(C=N),ꢀ25.28ꢀ(O=C-CH ),ꢀ

).ꢀIR:ꢀνmax/cm ꢀꢀ3443ꢀ(m),ꢀ3323ꢀ(m),ꢀ3165ꢀ(m),ꢀ1682ꢀ(s),ꢀ1587ꢀ(s),ꢀ1504ꢀ(s),ꢀ1452ꢀ(m),ꢀ

418ꢀ(m),ꢀ1364ꢀ(m),ꢀ1290ꢀ(m),ꢀ1107ꢀ(s),ꢀ1045ꢀ(m),ꢀ993ꢀ(m),ꢀ949ꢀ(m),ꢀ853ꢀ(s),ꢀ712ꢀ(m),ꢀ621ꢀ(s),ꢀ608ꢀ(s),ꢀ

H

3

C

3

-

1

5

1

9

0.59ꢀ(N=C-CH

3

-

1

56ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀꢀ3445ꢀ(w),ꢀ3323ꢀ(w),ꢀ3175ꢀ(w),ꢀ3000ꢀ(w),ꢀ2956ꢀ(w),ꢀ2905ꢀ(w),ꢀ

675ꢀ(s),ꢀ1605ꢀ(s),ꢀ1462ꢀ(w),ꢀ1426ꢀ(w),ꢀ1371ꢀ(w),ꢀ1307ꢀ(w),ꢀ1284ꢀ(w),ꢀ1107ꢀ(s),ꢀ1045ꢀ(w),ꢀ1008ꢀ(w),ꢀ

o

46ꢀ(w),ꢀ846ꢀ(w),ꢀ741ꢀ(w),ꢀ608ꢀ(w),ꢀ464ꢀ(w),ꢀ315ꢀ(w),ꢀ143ꢀ(w).ꢀMp:ꢀ>173ꢀ Cꢀ(dec.).ꢀ

SynthesisꢀofꢀH:ꢀ4-ethyl-3-thiosemicarbazideꢀ(2.288ꢀg,ꢀ19.2ꢀmmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀwaterꢀ

200ꢀmL,ꢀwarm),ꢀtheꢀinsolubleꢀparticulatesꢀwereꢀfilteredꢀoffꢀandꢀthenꢀtheꢀsolutionꢀwasꢀcooledꢀtoꢀ

roomꢀtemperature.ꢀHClꢀwasꢀaddedꢀ(32%,ꢀ8ꢀdrops)ꢀfollowedꢀbyꢀtheꢀrapidꢀadditionꢀofꢀmethylglyoxal-

(

o

1

,1-dimethylacetalꢀ(6.96ꢀmL,ꢀ58.0ꢀmmol,ꢀ6.79ꢀg).ꢀTheꢀsolutionꢀwasꢀvigorouslyꢀstirredꢀ(50ꢀ C,ꢀ1ꢀhour).ꢀ

Theꢀprecipitateꢀwasꢀrecoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(8ꢀxꢀ50ꢀmL)ꢀandꢀdried.ꢀAꢀ

paleꢀyellowꢀsolidꢀ(2.047ꢀg)ꢀwasꢀrecoveredꢀ(62%ꢀyield).ꢀδ ꢀ11.08ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ9.34ꢀ(1ꢀH,ꢀs,ꢀO=CH),ꢀ

C-NH),ꢀ1.90ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ1.03ꢀ(6ꢀH,ꢀt,ꢀJꢀ

H

9

.01ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ5.6,ꢀH

2

C-NH),ꢀ3.56ꢀ(2ꢀH,ꢀqd,ꢀJꢀ=ꢀ7.2,ꢀ5.6,ꢀH

2

3

ꢀ

16

Page 17 of 38

Dalton Transactions

View Article Online

=

9

1

8

ꢀ7.2,ꢀH

2

C-CH

3

,ꢀJ=ꢀ7.2).ꢀδCꢀ191.18ꢀ(C=O),ꢀ178.41ꢀ(C=S),ꢀ146.00ꢀ(C=N),ꢀ39.19ꢀ(N-CH ),ꢀ14.54ꢀ(H C-CH ),ꢀ

2 2 3

DOI: 10.1039/C7DT02008B

-

1

.68ꢀ(N=C-CH

3

).ꢀIR:ꢀνmax/cm ꢀ3319ꢀ(w),ꢀ3142ꢀ(m),ꢀ2976ꢀ(w),ꢀ2835ꢀ(w),ꢀ1688ꢀ(s),ꢀ1587ꢀ(m),ꢀ1541ꢀ(s),ꢀ

489ꢀ(m),ꢀ1422ꢀ(m),ꢀ1368ꢀ(m),ꢀ1279ꢀ(m),ꢀ1188ꢀ(s),ꢀ1126ꢀ(s),ꢀ1086ꢀ(m),ꢀ1059ꢀ(m),ꢀ1007ꢀ(m),ꢀ939ꢀ(m),ꢀ

-

1

49ꢀ(m),ꢀ710ꢀ(m),ꢀ660ꢀ(s),ꢀ538ꢀ(w).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀꢀ3325ꢀ(w),ꢀ3146ꢀ(w),ꢀ2910ꢀ(w),ꢀ2835ꢀ

(

w),ꢀ1686ꢀ(m),ꢀ1586ꢀ(s),ꢀ1437ꢀ(w),ꢀ1367ꢀ(w),ꢀ1331ꢀ(w),ꢀ1272ꢀ(w),ꢀ1183ꢀ(w),ꢀ1145ꢀ(w),ꢀ1121ꢀ(w),ꢀ1060ꢀ

w),ꢀ1008ꢀ(w),ꢀ938ꢀ(w),ꢀ811ꢀ(w),ꢀ776ꢀ(w),ꢀ668ꢀ(w),ꢀ626ꢀ(w),ꢀ578ꢀ(w),ꢀ540ꢀ(w),ꢀ374ꢀ(w).ꢀMp:ꢀ>132-

o

1

34 C.ꢀ

SynthesisꢀofꢀI:ꢀ4-phenyl-3-thiosemicarbazideꢀ(0.803ꢀg,ꢀ4.8ꢀmmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀ

o

water/ethanolꢀsolutionꢀ(50ꢀmLꢀwater,ꢀ25ꢀmLꢀethanol,ꢀ50ꢀ C).ꢀInsolubleꢀparticulatesꢀwereꢀfilteredꢀoffꢀ

andꢀHClꢀ(32%,ꢀ3ꢀdrops)ꢀwasꢀadded.ꢀMethylglyoxal-1,1-dimethylacetalꢀ(1.74ꢀmL,ꢀ14.4ꢀmmol,ꢀ1.698ꢀg)ꢀ

o

wasꢀaddedꢀrapidlyꢀandꢀtheꢀsolutionꢀwasꢀvigorouslyꢀstirredꢀatꢀ50ꢀ Cꢀforꢀ5ꢀmin.ꢀTheꢀprecipitateꢀwasꢀ

recoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(2ꢀxꢀ50ꢀmL)ꢀandꢀdried.ꢀAꢀyellowꢀsolidꢀ(0.821ꢀg)ꢀ

wasꢀrecoveredꢀ(77%ꢀyield).ꢀδ

),ꢀ7.36ꢀ(2ꢀH,ꢀm,ꢀꢀ

C=O),ꢀ178.24ꢀ(C=S),ꢀ146.53ꢀ(C=N),ꢀ139.48ꢀ(C(1)ꢀaryl),ꢀ139.11ꢀ(C(1)ꢀaryl),ꢀ128.33ꢀ(C(3,5)ꢀaryl),ꢀ126.40ꢀ(C(4)ꢀ

H

ꢀ11.49ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.57ꢀ(1ꢀH,ꢀs,ꢀPh-NH),ꢀ9.45ꢀ(1ꢀH,ꢀs,ꢀO=CH),ꢀ7.53ꢀ(2ꢀ

H,ꢀm,ꢀH(2,6)ꢀaryl

ꢀ

H

(3,5)ꢀꢀaryl),ꢀ7.20ꢀ(1ꢀH,ꢀm,ꢀH(4)ꢀaryl ),ꢀ1.97ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ).ꢀδ ꢀ192.57ꢀ

ꢀ

3

C

(

-

1

3

aryl),ꢀ126.24ꢀ(C(2,6)ꢀaryl),ꢀ9.88ꢀ(N=C-CH ).ꢀIR:ꢀνmax/cm ꢀ3277ꢀ(w),ꢀ3150ꢀ(m),ꢀ2968ꢀ(w),ꢀ2851ꢀ(w),ꢀ1697ꢀ

(

m),ꢀ1593ꢀ(m),ꢀ1520ꢀ(s),ꢀ1495ꢀ(s),ꢀ1447ꢀ(m),ꢀ1425ꢀ(m),ꢀ1366ꢀ(m),ꢀ1229ꢀ(m),ꢀ1167ꢀ(s),ꢀ1157ꢀ(s),ꢀ1119ꢀ

-

1

m),ꢀ1016ꢀ(m),ꢀ935ꢀ(m),ꢀ831ꢀ(m),ꢀ748ꢀ(m),ꢀ698ꢀ(s),ꢀ615ꢀ(s),ꢀ590ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ3283ꢀ

w),ꢀ3068ꢀ(w),ꢀ2918ꢀ(w),ꢀ2860ꢀ(w),ꢀ1695ꢀ(s),ꢀ1590ꢀ(s),ꢀ1518ꢀ(m),ꢀ1448ꢀ(w),ꢀ1346ꢀ(w),ꢀ1292ꢀ(m),ꢀ1227ꢀ

m),ꢀ1146ꢀ(m),ꢀ1117ꢀ(m),ꢀ1030ꢀ(w),ꢀ1005ꢀ(s),ꢀ933ꢀ(w),ꢀ834ꢀ(w),ꢀ770ꢀ(w),ꢀ752ꢀ(m),ꢀ680ꢀ(w),ꢀ617ꢀ(m),ꢀ607ꢀ

o

m),ꢀ448ꢀ(w),ꢀ411ꢀ(w),ꢀ269ꢀ(w).ꢀMp:ꢀ>151ꢀ Cꢀ(dec.).ꢀ

SynthesisꢀofꢀJ:ꢀ4,4-dimethyl-3-thiosemicarbazideꢀ(0.500ꢀg,ꢀ4.2ꢀmmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀ

o

waterꢀ(60ꢀmL).ꢀSolutionꢀcooledꢀ(4ꢀ C)ꢀoverꢀice,ꢀfollowedꢀbyꢀtheꢀadditionꢀofꢀHClꢀ(32%,ꢀ2ꢀdrops).ꢀ2,3-

o

butanedioneꢀ(0.36ꢀmL,ꢀ41.0ꢀmmol,ꢀ0.35ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀvigorouslyꢀstirredꢀatꢀ5ꢀ Cꢀforꢀ1ꢀh.ꢀ

Theꢀprecipitateꢀwasꢀrecoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(2ꢀxꢀ30ꢀmL).ꢀTheꢀcrudeꢀ

wasꢀrecrystallizedꢀfromꢀethanolꢀinꢀaꢀfreezer.ꢀTheꢀcrystallineꢀsolidꢀwasꢀfilteredꢀoff,ꢀwashedꢀwithꢀ

petroleumꢀetherꢀ(2ꢀxꢀ10ꢀmL)ꢀandꢀleftꢀtoꢀdry.ꢀAꢀbrightꢀyellowꢀcrystallineꢀsolidꢀ(0.191ꢀg)ꢀwasꢀrecoveredꢀ

(

25%ꢀyield).ꢀδ

H

ꢀ9.85ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ3.27ꢀ(6ꢀH,ꢀs,ꢀN-(CH

3

)

2

),ꢀ2.28ꢀ(3ꢀH,ꢀs,ꢀO=C-CH

),ꢀ24.83ꢀ(O=C-CH

).ꢀIR:ꢀνmax/cm ꢀꢀ3362ꢀ(w),ꢀ2920ꢀ(w),ꢀ1670ꢀ(s),ꢀ1578ꢀ(m),ꢀ1537ꢀ(m),ꢀ1429ꢀ(m),ꢀ1354ꢀ(s),ꢀ1290ꢀ(s),ꢀ

3

),ꢀ1.91ꢀ(3ꢀH,ꢀs,ꢀN=C-

CH

3

).ꢀδ

C

ꢀ197.81ꢀ(C=O),ꢀ182.39ꢀ(C=S),ꢀ147.05ꢀ(C=N),ꢀ43.16ꢀ(N-(CH

3

)

2

3

),ꢀ10.07ꢀ(N=C-

-

1

CH

1

198ꢀ(s),ꢀ1150ꢀ(s),ꢀ1107ꢀ(s),ꢀ1063ꢀ(s),ꢀ1005ꢀ(m),ꢀ901ꢀ(m),ꢀ804ꢀ(s),ꢀ702ꢀ(m),ꢀ611ꢀ(m),ꢀ602ꢀ(m),ꢀ527ꢀ(s).ꢀ

-

1

Ramanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀꢀ3364ꢀ(w),ꢀ2923ꢀ(w),ꢀ1669ꢀ(s),ꢀ1580ꢀ(s),ꢀ1364ꢀ(m),ꢀ1342ꢀ(m),ꢀ1289ꢀ(w),ꢀ

1

3

194ꢀ(m),ꢀ1150ꢀ(w),ꢀ1009ꢀ(m),ꢀ946ꢀ(w),ꢀ903ꢀ(w),ꢀ805ꢀ(w),ꢀ701ꢀ(w),ꢀ633ꢀ(w),ꢀ603ꢀ(w),ꢀ525ꢀ(w),ꢀ457ꢀ(w),ꢀ

o

70ꢀ(w),ꢀ217ꢀ(w).ꢀMp:ꢀ>129 Cꢀ(dec.).ꢀ

SynthesisꢀofꢀK:ꢀThiosemicarbazideꢀ(1.55ꢀg,ꢀ17.0ꢀmmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀwaterꢀ(200ꢀmL,ꢀ

o

warm).ꢀSolutionꢀcooledꢀ(10 C)ꢀoverꢀice,ꢀfollowedꢀbyꢀtheꢀadditionꢀofꢀHClꢀ(32%,ꢀ20ꢀdrops).ꢀ2,3-

o

pentanedioneꢀ(7.12ꢀmL,ꢀ68ꢀmmol,ꢀ6.81ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀvigorouslyꢀstirredꢀatꢀ10 Cꢀforꢀ10ꢀ

min.ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(2ꢀxꢀ50ꢀmL)ꢀandꢀ

dried.ꢀAnꢀoffꢀwhiteꢀsolidꢀ(1.957g)ꢀwasꢀrecoveredꢀ(66%ꢀyield).ꢀδHꢀ10.55ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.66ꢀ(1ꢀH,ꢀs,ꢀC-

NH),ꢀ8.04ꢀ(1ꢀH,ꢀs,ꢀC-NH),2.90ꢀ(2H,ꢀq,ꢀJꢀ=ꢀ7.2,ꢀCH

2

),ꢀ1.92ꢀ(3ꢀH,ꢀs,ꢀN=C-CH

3

),ꢀ0.90ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀC-CH

2

-

CH ).ꢀδCꢀ200.71ꢀ(C=O),ꢀ180.25ꢀ(C=S),ꢀ145.90ꢀ(C=N),ꢀ29.64ꢀ(C-CH

3

2

),ꢀ10.88ꢀ(N=C-CH

3

),ꢀ8.68ꢀ(C-CH -CH

2

3

).ꢀ

-

1

IR:ꢀνmax/cm ꢀ3412ꢀ(w),ꢀ3302ꢀ(m),ꢀ3177ꢀ(m),ꢀ2984ꢀ(w),ꢀ1688ꢀ(s),ꢀ1593ꢀ(s),ꢀ1491ꢀ(m),ꢀ1422ꢀ(m),ꢀ1362ꢀ

(

m),ꢀ1233ꢀ(s),ꢀ1090ꢀ(s),ꢀ1043ꢀ(s),ꢀ932ꢀ(m),ꢀ843ꢀ(m),ꢀ797ꢀ(m),ꢀ700ꢀ(m),ꢀ590ꢀ(s),ꢀ552ꢀ(s).ꢀRamanꢀ(632.81ꢀ

ꢀ

17

Dalton Transactions

Page 18 of 38

-

1

View Article Online

DOI: 10.1039/C7DT02008B

nm):ꢀνmax/cm ꢀ3302ꢀ(w),ꢀ3192ꢀ(w),ꢀ2986ꢀ(w),ꢀ2945ꢀ(w),ꢀ2919ꢀ(w),ꢀ2898ꢀ(w),ꢀ1683ꢀ(m),ꢀ1614ꢀ(s),ꢀ1464ꢀ

(

w),ꢀ1364ꢀ(w),ꢀ1258ꢀ(w),ꢀ1103ꢀ(m),ꢀ1091ꢀ(m),ꢀ1045ꢀ(m),ꢀ930ꢀ(w),ꢀ838ꢀ(w),ꢀ602ꢀ(w),ꢀ487ꢀ(w),ꢀ461ꢀ(w),ꢀ

o

4

10ꢀ(w),ꢀ313ꢀ(w).ꢀMp:ꢀ>165ꢀ Cꢀ(dec.).ꢀ

SynthesisꢀofꢀL:ꢀ4-methyl-3-thiosemicarbazideꢀ(1.788ꢀg,ꢀ17.0ꢀmmol)ꢀwasꢀdissolvedꢀinꢀaꢀsolutionꢀofꢀde-

o

ionisedꢀwaterꢀ(200ꢀmL)ꢀandꢀethanolꢀ(80ꢀmL).ꢀTheꢀsolutionꢀwasꢀcooledꢀ(-10 C)ꢀinꢀaꢀsalt/iceꢀbathꢀ(300ꢀgꢀ

ice,ꢀ100ꢀgꢀtableꢀsalt),ꢀfollowedꢀbyꢀtheꢀadditionꢀofꢀHClꢀ(32%,ꢀ6ꢀdrops).ꢀ2,3-pentanedioneꢀ(3.56ꢀmL,ꢀ34ꢀ

o

mmol,ꢀ3.41ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀvigorouslyꢀstirredꢀatꢀca.ꢀ-10 Cꢀforꢀ5ꢀm.ꢀTheꢀprecipitateꢀwasꢀ

recoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(4ꢀxꢀ50ꢀmL)ꢀandꢀdried.ꢀAnꢀoffꢀwhiteꢀsolidꢀ

(

1.572g)ꢀwasꢀrecoveredꢀ(49%ꢀyield).ꢀδHꢀ10.58ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.55ꢀ(1ꢀH,ꢀq,ꢀJꢀ=4.8,ꢀH

Jꢀ=ꢀ4.8,ꢀHN-CH ),ꢀ2.93ꢀ(2H,ꢀq,ꢀJꢀ=ꢀ7.2,ꢀC-CH ),ꢀ1.93ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ0.93ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀCH

00.54ꢀ(C=O),ꢀ179.48ꢀ(C=S),ꢀ145.60ꢀ(C=N),ꢀ31.91ꢀ(HN-CH ),ꢀ29.59ꢀ(C-CH ),ꢀ10.84ꢀ(N=C-CH ),ꢀ8.62ꢀ(CH

).ꢀIR:ꢀνmax/cm ꢀ3379ꢀ(w),ꢀ3210ꢀ(w),ꢀ2982ꢀ(w),ꢀ1682ꢀ(s),ꢀ1541ꢀ(s),ꢀ1499ꢀ(s),ꢀ1429ꢀ(m),ꢀ1406ꢀ(m),ꢀ

3

C-NH),ꢀ3.00ꢀ(3ꢀH,ꢀd,ꢀ

3

2

3

2

-CH

3

).ꢀδCꢀ

2

3

2

3

2

-

1

CH

3

1

375ꢀ(m),ꢀ1360ꢀ(m),ꢀ1207ꢀ(s),ꢀ1146ꢀ(s),ꢀ1107ꢀ(s),ꢀ1088ꢀ(s),ꢀ1055ꢀ(m),ꢀ1034ꢀ(s),ꢀ932ꢀ(m),ꢀ835ꢀ(m),ꢀ797ꢀ

-

1

(

m),ꢀ652ꢀ(m),ꢀ559ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀꢀ3322ꢀ(w),ꢀ2940ꢀ(w),ꢀ1684ꢀ(m),ꢀ1677ꢀ(m),ꢀ1600ꢀ

s),ꢀ1367ꢀ(w),ꢀ1203ꢀ(m),ꢀ1143ꢀ(w),ꢀ1115ꢀ(w),ꢀ1090ꢀ(w),ꢀ1047ꢀ(m),ꢀ831ꢀ(m),ꢀ649ꢀ(w),ꢀ561ꢀ(w),ꢀ415ꢀ(w),ꢀ

o

3

15ꢀ(w).ꢀMp:ꢀ>136-141ꢀ C.ꢀ

SynthesisꢀofꢀM:ꢀ4-ethyl-3-thiosemicarbazideꢀ(1.013ꢀg,ꢀ85.0ꢀmmol)ꢀdissolvedꢀinꢀaꢀsolutionꢀofꢀde-

o

ionisedꢀwaterꢀ(100ꢀmL)ꢀandꢀethanolꢀ(60ꢀmL).ꢀTheꢀsolutionꢀwasꢀcooledꢀ(-12 C)ꢀinꢀaꢀsalt/iceꢀbathꢀ(300ꢀgꢀ

ice,ꢀ100ꢀgꢀtableꢀsalt),ꢀfollowedꢀbyꢀtheꢀadditionꢀofꢀHClꢀ(32%,ꢀ3ꢀdrops).ꢀ2,3-pentanedioneꢀ(1.78ꢀmL,ꢀ17ꢀ

o

mmol,ꢀ1.70ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀvigorouslyꢀstirredꢀatꢀca.ꢀ-11 Cꢀforꢀ4ꢀm.ꢀTheꢀprecipitateꢀwasꢀ

recoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(3ꢀxꢀ50ꢀmL)ꢀandꢀdried.ꢀAnꢀoffꢀwhiteꢀsolidꢀ

(

0.862g)ꢀwasꢀrecoveredꢀ(50%ꢀyield).ꢀδ

dq,ꢀJꢀ=ꢀ7.6,ꢀ6.0,ꢀHN-CH ),ꢀ2.93ꢀ(2H,ꢀq,ꢀJꢀ=ꢀ7.2,ꢀC-CH

),ꢀ0.93ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀC-CH -CH ).ꢀδ ꢀ200.53ꢀ(C=O),ꢀ178.47ꢀ(C=S),ꢀ145.65ꢀ(C=N),ꢀ39.27ꢀ(HN-

),ꢀ29.59ꢀ(C-CH ),ꢀ14.66ꢀ(N-CH -CH ),ꢀ10.86ꢀ(N=C-CH

H

ꢀ10.51ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.60ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ6.0,ꢀH

2

C-NH),ꢀ3.58ꢀ(2ꢀH,ꢀ

2

),ꢀ1.93ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ1.11ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.6,ꢀN-

3

CH

2

-CH

3

2

3

C

-

1

2

3

3 2 3

),ꢀ8.60ꢀ(C-CH -CH ).ꢀIR:ꢀνmax/cm ꢀ3345ꢀ(w),ꢀ

3

1

188ꢀ(w),ꢀ2974ꢀ(w),ꢀ1686ꢀ(s),ꢀ1612ꢀ(w),ꢀ1537ꢀ(s),ꢀ1499ꢀ(s),ꢀ1427ꢀ(m),ꢀ1364ꢀ(m),ꢀ1190ꢀ(s),ꢀ1155ꢀ(m),ꢀ

117ꢀ(m),ꢀ1092ꢀ(m),ꢀ1038ꢀ(s),ꢀ949ꢀ(m),ꢀ824ꢀ(m),ꢀ800ꢀ(m),ꢀ600ꢀ(s),ꢀ563ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀ

-

1

ν

max/cm ꢀꢀ3346ꢀ(w),ꢀ2913ꢀ(w),ꢀ1683ꢀ(w),ꢀ1611ꢀ(w),ꢀ1448ꢀ(w),ꢀ1366ꢀ(w),ꢀ1265ꢀ(w),ꢀ1189ꢀ(w),ꢀ1153ꢀ(w),ꢀ

o

1

115ꢀ(w),ꢀ1039ꢀ(w),ꢀ819ꢀ(w),ꢀ654ꢀ(w),ꢀ560ꢀ(w),ꢀ304ꢀ(w).ꢀMp:ꢀ>103-104ꢀ C.ꢀ

Proligandsꢀ1ꢀ-ꢀ30ꢀ

2

33

22

58

30

22

Knownꢀproligandsꢀ1, ꢀ2, ꢀ5, ꢀ20, ꢀ21, ꢀ22 ꢀandꢀ25 ꢀwereꢀsynthesisedꢀasꢀdescribedꢀpreviously.ꢀ

Previouslyꢀreportedꢀproligandsꢀ6,ꢀ7,ꢀandꢀ8ꢀwereꢀsynthesisedꢀbyꢀnewꢀmethodsꢀdescribedꢀbelow.ꢀOtherꢀ

previouslyꢀreportedꢀproligandsꢀlistedꢀinꢀTableꢀ2ꢀwereꢀnotꢀsynthesisedꢀinꢀthisꢀworkꢀandꢀtheirꢀdataꢀ

reportedꢀinꢀTableꢀ2ꢀareꢀliteratureꢀvalues.ꢀ

Synthesisꢀofꢀ3:ꢀCompoundꢀBꢀ(0.510ꢀg,ꢀ0.0032ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(3ꢀmL)ꢀandꢀfiltered.ꢀ

Thiosemicarbazideꢀ(0.292ꢀg,ꢀ0.0032ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(10ꢀmL),ꢀHClꢀ(10%,ꢀ2ꢀdrops)ꢀwasꢀ

addedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀ(roomꢀtemperature,ꢀ5ꢀhours).ꢀ

De-ionisedꢀwaterꢀ(26ꢀmL)ꢀwasꢀadded,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀoffꢀandꢀwashedꢀwithꢀde-ionisedꢀ

o

waterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(10ꢀ

mL)ꢀtheꢀresultingꢀsolutionꢀwasꢀfilteredꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(20ꢀmL).ꢀTheꢀ

precipitateꢀwasꢀrecoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀ

o

andꢀ50ꢀmL,ꢀ80ꢀ C)ꢀandꢀdried.ꢀAꢀwhiteꢀsolidꢀ(0.456ꢀg)ꢀwasꢀrecoveredꢀ(61%ꢀyield).ꢀδ

H

ꢀ11.66ꢀ(s,ꢀ1ꢀH,ꢀN-

ꢀ

18

Page 19 of 38

Dalton Transactions

View Article Online

NH),ꢀ10.35ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ8.50ꢀ(q,ꢀ1ꢀH,ꢀH

s,ꢀ1ꢀH,ꢀN=CH),ꢀ2.94ꢀ(ꢀd,ꢀ3ꢀH,ꢀHN-CH ,ꢀJ=ꢀ4.8ꢀHz),ꢀ2.09ꢀ(s,ꢀ3ꢀH,ꢀN=C-CH

47.54ꢀ(C=N),ꢀ142.95ꢀ(C=N),ꢀ31.58ꢀ(HN-CH ),ꢀ11.52ꢀ(N=C-CH ).ꢀIR:ꢀνmax/cm ꢀ3414ꢀ(w),ꢀ3148ꢀ(m),ꢀ1988ꢀ

w),ꢀ1607ꢀ(m),ꢀ1531ꢀ(s),ꢀ1497ꢀ(s),ꢀ1458ꢀ(m),ꢀ1364ꢀ(m),ꢀ1335ꢀ(m),ꢀ1269ꢀ(m),ꢀ1217ꢀ(s),ꢀ1155ꢀ(m),ꢀ1070ꢀ

3

C-NH,ꢀJ=ꢀ4.8ꢀHz),ꢀ8.28ꢀ(s,ꢀ1ꢀHꢀC-NH),ꢀ7.87ꢀ(s,ꢀ1ꢀHꢀC-NH),ꢀ7.61ꢀ

DOI: 10.1039/C7DT02008B

(

3

).ꢀδCꢀ178.76ꢀ(C=S),ꢀ178.59ꢀ(C=S),ꢀ

-

1

3

(

-

1

s),ꢀ924ꢀ(m),ꢀ833ꢀ(s),ꢀ656ꢀ(m),ꢀ565ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀꢀꢀ2915ꢀ(w),ꢀ1672ꢀ(w),ꢀ1600ꢀ(m),ꢀ

585ꢀ(s),ꢀ1374ꢀ(w),ꢀ1336ꢀ(w),ꢀ1268ꢀ(w),ꢀ1223ꢀ(w),ꢀ1126ꢀ(w),ꢀ1013ꢀ(w),ꢀ878ꢀ(w),ꢀ792ꢀ(w),ꢀ481ꢀ(w),ꢀ307ꢀ

1

(

o

w),ꢀ219ꢀ(w).ꢀFound:ꢀC,ꢀ31.1;ꢀH,ꢀ5.1;ꢀN,ꢀ36.1.ꢀCalc.ꢀforꢀC

6

H

12

N

6

S

2

:ꢀC,ꢀ31.0;ꢀH,ꢀ5.1;ꢀN,ꢀ36.2%.ꢀMp:ꢀ>217ꢀ

Cꢀ(dec.).ꢀ

o

Synthesisꢀofꢀ4:ꢀFreshlyꢀactivatedꢀmolecularꢀsievesꢀ(3ꢀÅ,ꢀ0.075ꢀg)ꢀwasꢀaddedꢀtoꢀDMFꢀ(17ꢀmL,ꢀ60ꢀ C),ꢀ

followedꢀbyꢀtheꢀadditionꢀofꢀcompoundꢀDꢀ(0.131ꢀg,ꢀ0.0009ꢀmol)ꢀandꢀ4-methyl-3-thiosemicarbazideꢀ

(

0.101ꢀg,ꢀ0.0010ꢀmol).ꢀTheꢀheatꢀwasꢀturnedꢀoffꢀandꢀtheꢀsolutionꢀwasꢀleftꢀtoꢀstirꢀ(3ꢀdays,ꢀcoolingꢀdownꢀ

toꢀroomꢀtemperature).ꢀTheꢀmolecularꢀsievesꢀwereꢀfilteredꢀoffꢀandꢀtheꢀDMFꢀwasꢀremovedꢀunderꢀ

vacuum.ꢀTheꢀcrudeꢀproductꢀwasꢀwashedꢀwithꢀaꢀlittleꢀethylꢀacetateꢀandꢀdiethylꢀetherꢀ(1ꢀxꢀ25ꢀmL)ꢀandꢀ

dried.ꢀAꢀsawdustꢀcolouredꢀsolidꢀ(0.130ꢀg)ꢀwasꢀrecoveredꢀ(62%ꢀyield).ꢀδ

ꢀH,ꢀN-NH),ꢀ8.38ꢀ(quartetꢀoverlappingꢀaꢀsinglet,ꢀ1ꢀH,ꢀH C-NH,ꢀJ=ꢀ4.4ꢀHz),ꢀ8.35ꢀ(singletꢀoverlappingꢀaꢀ

quartet,ꢀ1ꢀHꢀC-NH),ꢀ7.60ꢀ(s,ꢀ1ꢀHꢀC-NH),ꢀ7.61ꢀ(s,ꢀ1ꢀH,ꢀN=CH),ꢀ2.95ꢀ(ꢀd,ꢀ3ꢀH,ꢀHN-CH ,ꢀJ=ꢀ4.4ꢀHz),ꢀ2.04ꢀ(s,ꢀ3ꢀ

H,ꢀN=C-CH ).ꢀδCꢀ179.27ꢀ(C=S),ꢀ178.24ꢀ(C=S),ꢀ148.02ꢀ(C=N),ꢀ142.55ꢀ(C=N),ꢀ31.47ꢀ(HN-CH ),ꢀ11.62ꢀ(N=C-

CH ).ꢀ

H

ꢀ11.69ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ10.33ꢀ(s,ꢀ

1

3

Synthesisꢀofꢀ5:ꢀ4-methyl-3-thiosemicarbazideꢀ(1.100ꢀg,ꢀ0.0105ꢀmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀ

o

waterꢀ(40ꢀmL,ꢀ50ꢀ C)ꢀandꢀHClꢀ(32%,ꢀ2ꢀdrops)ꢀwasꢀadded.ꢀMethylglyoxal-1,1-dimethylacetalꢀ(0.58ꢀmL,ꢀ

o

0

.0048ꢀmol,ꢀ0.566ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀleftꢀtoꢀstirꢀ(50ꢀ C,ꢀ5ꢀminutes).ꢀTheꢀprecipitateꢀwasꢀ

removedꢀbyꢀfiltrationꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ

o

C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(17ꢀmL).ꢀTheꢀsolutionꢀwasꢀfiltered,ꢀrecrystallisedꢀwithꢀ

de-ionisedꢀwaterꢀ(34ꢀmL).ꢀTheꢀprecipitateꢀwasꢀremovedꢀviaꢀfiltration,ꢀwashedꢀwithꢀwaterꢀ(50ꢀmL)ꢀandꢀ

leftꢀtoꢀdry.ꢀAꢀcreamꢀsolidꢀ(0.858ꢀg)ꢀwasꢀrecoveredꢀ(73%ꢀyield).ꢀδ

N-NH),ꢀ8.49ꢀ(m,ꢀ1ꢀH,ꢀH C-NH,ꢀJ=ꢀ4.4ꢀHz),ꢀ8.38ꢀ(m,ꢀ1ꢀHꢀH C-NH,ꢀJ=ꢀ4.8ꢀHz),ꢀ7.62ꢀ(s,ꢀ1ꢀH,ꢀN=CH),ꢀ2.94ꢀ(ꢀ

twoꢀoverꢀlappingꢀdoublets,ꢀ6ꢀH,ꢀHN-CH ,ꢀJ=ꢀ4.4ꢀHz),ꢀ2.12ꢀ(s,ꢀ3ꢀH,ꢀN=C-CH ).ꢀδ ꢀ178.76ꢀ(C=S),ꢀ178.22ꢀ

C=S),ꢀ147.63ꢀ(C=N),ꢀ142.40ꢀ(C=N),ꢀ31.58ꢀ(HN-CH ),ꢀ31.47ꢀ(HN-CH ),ꢀ11.62ꢀ(N=C-CH

302ꢀ(w),ꢀ3142ꢀ(w),ꢀ1531ꢀ(s),ꢀ1489ꢀ(s),ꢀ1431ꢀ(m),ꢀ1408ꢀ(m),ꢀ1354ꢀ(w),ꢀ1213ꢀ(s),ꢀ1152ꢀ(m),ꢀ1088ꢀ(s),ꢀ

H

ꢀ11.73ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ10.33ꢀ(s,ꢀ1ꢀH,ꢀ

3

C

-

1

(

3

).ꢀIR:ꢀνmax/cm ꢀ

3

1

-

1

024ꢀ(s),ꢀ914ꢀ(m),ꢀ820ꢀ(m),ꢀ548ꢀ(s),ꢀ517ꢀ(m).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ2909ꢀ(w),ꢀ1785ꢀ(w),ꢀ1657ꢀ

(

w),ꢀ1577ꢀ(s),ꢀ1442ꢀ(w),ꢀ1364ꢀ(w),ꢀ1279ꢀ(w),ꢀ1226ꢀ(w),ꢀ1124ꢀ(w),ꢀ1017ꢀ(w),ꢀ879ꢀ(w),ꢀ775ꢀ(w),ꢀ560ꢀ(w),ꢀ

o

4

05ꢀ(w),ꢀ115ꢀ(w).ꢀMp:ꢀ>214ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ6:ꢀ4,4-dimethyl-3-thiosemicarbazideꢀ(0.321ꢀg,ꢀ0.0027ꢀmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀ

o

waterꢀ(50ꢀmL,ꢀ50ꢀ C)ꢀandꢀHClꢀ(32%,ꢀ2ꢀdrops)ꢀwasꢀadded.ꢀMethylglyoxal-1,1-dimethylacetalꢀ(0.15ꢀmL,ꢀ

o

0

.0012ꢀmol,ꢀ0.15ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀleftꢀtoꢀstirꢀ(50ꢀ C,ꢀ1ꢀhour).ꢀTheꢀprecipitateꢀwasꢀremovedꢀbyꢀ

o

filtrationꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀ

productꢀwasꢀdissolvedꢀinꢀDMSOꢀ(3ꢀmL).ꢀTheꢀsolutionꢀwasꢀfiltered,ꢀandꢀtheꢀproductꢀwasꢀrecrystallisedꢀ

withꢀde-ionisedꢀwaterꢀ(6ꢀmL).ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀwashedꢀwithꢀwaterꢀ(50ꢀmL)ꢀ

andꢀdried.ꢀAꢀyellowꢀsolidꢀ(0.065ꢀg)ꢀwasꢀrecoveredꢀ(20%ꢀyield).ꢀδ

NH),ꢀ7.78ꢀ(s,ꢀ1ꢀH,ꢀN=CH),ꢀ3.23ꢀ(s,ꢀ6ꢀH,ꢀN-(CH ),ꢀ2.05ꢀ(s,ꢀ3ꢀH,ꢀN=C-CH

50.11ꢀ(C=N),ꢀ144.54ꢀ(C=N),ꢀ42.80ꢀ(N-(CH ),ꢀ42.47ꢀ(N-(CH ),ꢀ11.37ꢀ(N=C-CH

w),ꢀ2922ꢀ(w),ꢀ1533ꢀ(s),ꢀ1490ꢀ(m),ꢀ1362ꢀ(m),ꢀ1328ꢀ(s),ꢀ1281ꢀ(m),ꢀ1229ꢀ(s),ꢀ1150ꢀ(s),ꢀ1113ꢀ(m),ꢀ1057ꢀ

H

ꢀ11.07ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ9.59ꢀ(s,ꢀ1ꢀH,ꢀN-

3

)

2

3

).ꢀδ ꢀ181.79ꢀ(C=S),ꢀ180.89ꢀ(C=S),ꢀ

C

-

1

3

)

2

3

)

2

3

).ꢀIR:ꢀνmax/cm ꢀ3404ꢀ

(

-

1

m),ꢀ1022ꢀ(m),ꢀ905ꢀ(s),ꢀ785ꢀ(m),ꢀ542ꢀ(m).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ2917ꢀ(w),ꢀ1581ꢀ(s),ꢀ1436ꢀ(w),ꢀ

ꢀ

19

Dalton Transactions

Page 20 of 38

View Article Online

DOI: 10.1039/C7DT02008B

1

381ꢀ(w),ꢀ1281ꢀ(w),ꢀ1237ꢀ(m),ꢀ1132ꢀ(w),ꢀ1027ꢀ(w),ꢀ864ꢀ(w),ꢀ718ꢀ(w),ꢀ546ꢀ(w),ꢀ438ꢀ(w),ꢀ394ꢀ(w),ꢀ171ꢀ

o

(

w),ꢀ107ꢀ(w).ꢀMp.ꢀ>106ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ7:ꢀ4-ethyl-3-thiosemicarbazideꢀ(1.251ꢀg,ꢀ0.0105ꢀmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀwaterꢀ

o

(

50ꢀmL,ꢀ50ꢀ C).ꢀꢀTheꢀinsolubleꢀparticulatesꢀwereꢀfilteredꢀandꢀHClꢀwasꢀaddedꢀ(32%,ꢀ2ꢀdrops).ꢀ

Methylglyoxal-1,1-dimethylacetalꢀ(0.58ꢀmL,ꢀ0.0048ꢀmol,ꢀ0.57ꢀg)ꢀwasꢀaddedꢀrapidlyꢀandꢀleftꢀtoꢀstirꢀ(50ꢀ

o

C,ꢀ5ꢀminutes).ꢀTheꢀprecipitateꢀwasꢀremovedꢀbyꢀfiltrationꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL).ꢀ

TheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(35ꢀmL).ꢀTheꢀsolutionꢀwasꢀfilteredꢀandꢀtheꢀproductꢀwasꢀ

recrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(70ꢀmL).ꢀTheꢀprecipitateꢀwasꢀisolatedꢀviaꢀfiltration,ꢀwashedꢀwithꢀ

ꢀ

waterꢀ(50ꢀmL)ꢀandꢀdried.ꢀAꢀyellowishꢀwhiteꢀsolidꢀ(0.870ꢀg)ꢀwasꢀrecoveredꢀ(66%ꢀyield).ꢀδ

N-NH),ꢀ10.24ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ8.52ꢀ(t,ꢀ1ꢀH,ꢀH C-NH,ꢀJ=ꢀ6.0ꢀHz),ꢀ8.41ꢀ(t,ꢀ1ꢀHꢀH

H,ꢀN=CH),ꢀ3.52ꢀ(m,ꢀ4ꢀH,ꢀH C-NH),ꢀ2.13ꢀ(s,ꢀ3ꢀH,ꢀN=C-CH ),ꢀ1.07ꢀ(twoꢀoverlappingꢀtriplets,ꢀ6ꢀH,ꢀH

J=ꢀ7.2ꢀHz).ꢀδ ꢀ177.65ꢀ(C=S),ꢀ177.15ꢀ(C=S),ꢀ147.66ꢀ(C=N),ꢀ142.41ꢀ(C=N),ꢀ39.01ꢀ(N-CH ),ꢀ38.87ꢀ(N-CH

5.01ꢀ(H C-CH ).ꢀIR:ꢀνmax/cm ꢀ3289ꢀ(m),ꢀ3161ꢀ(w),ꢀ2967ꢀ(m),ꢀ1526ꢀ

s),ꢀ1476ꢀ(s),ꢀ1427ꢀ(s),ꢀ1315ꢀ(m),ꢀ1229ꢀ(s),ꢀ1198ꢀ(s),ꢀ1096ꢀ(s),ꢀ1043ꢀ(s),ꢀ934ꢀ(s),ꢀ808ꢀ(s),ꢀ664ꢀ(m),ꢀ579ꢀ

H

11.65ꢀ(s,ꢀ1ꢀH,ꢀ

2

C-NH,ꢀJ=ꢀ6.0ꢀHz),ꢀ7.62ꢀ(s,ꢀ1ꢀ

C-CH ,ꢀ

),ꢀ

2

3

2

3

C

2

-

1

2

3 2 3 3

),ꢀ14.87ꢀ(H C-CH ),ꢀ11.38ꢀ(N=C-CH

(

-

1

s),ꢀ550ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ3375ꢀ(w),ꢀ2936ꢀ(w),ꢀ1578ꢀ(s),ꢀ1516ꢀ(w),ꢀ1436ꢀ(w),ꢀ1365ꢀ(m),ꢀ

o

1

284ꢀ(w),ꢀ1236ꢀ(w),ꢀ1202ꢀ(w),ꢀ1132ꢀ(w),ꢀ1020ꢀ(w),ꢀ874ꢀ(w),ꢀ757ꢀ(w),ꢀ541ꢀ(w),ꢀ457ꢀ(w).ꢀMp.ꢀ>220ꢀ Cꢀ

(

dec.).ꢀ

Synthesisꢀofꢀ8:ꢀ4-phenyl-3-thiosemicarbazideꢀ(0.439ꢀg,ꢀ2.63mmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀ

o

water/ethanolꢀsolutionꢀ(25ꢀmLꢀwater,ꢀ13ꢀmLꢀethanol,ꢀ50ꢀ C).ꢀTheꢀinsolubleꢀparticulatesꢀwereꢀfilteredꢀ

andꢀHClꢀ(32%,ꢀ2ꢀdrops)ꢀwasꢀadded.ꢀMethylgloxal-1,1-dimethylacetalꢀ(0.15ꢀmL,ꢀ1.2ꢀmmol,ꢀ0.146ꢀg)ꢀ

o

wasꢀaddedꢀrapidlyꢀandꢀleftꢀtoꢀstirꢀatꢀ50ꢀ Cꢀforꢀ5ꢀmin.ꢀTheꢀprecipitateꢀwasꢀremovedꢀbyꢀfiltrationꢀandꢀ

o

washedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀ

dissolvedꢀinꢀDMSOꢀ(15ꢀmL).ꢀTheꢀsolutionꢀwasꢀfiltered,ꢀtheꢀproductꢀwasꢀrecrystallisedꢀwithꢀde-ionisedꢀ

waterꢀ(30ꢀmL).ꢀTheꢀprecipitateꢀwasꢀfilteredꢀandꢀwashedꢀwithꢀwaterꢀ(50ꢀmL)ꢀandꢀdried.ꢀTheꢀsampleꢀ

o

wasꢀfurtherꢀwashedꢀwithꢀethanolꢀ(2ꢀxꢀ25ꢀmL),ꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀ80ꢀ C)ꢀandꢀdried.ꢀAꢀmustardꢀ

colouredꢀsolidꢀ(0.244ꢀg)ꢀwasꢀrecoveredꢀ(55%ꢀyield).ꢀδ

H

ꢀ12.10ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.75ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ

1

0.19ꢀ(1ꢀH,ꢀs,ꢀPh-NH),ꢀ10.01ꢀ(1ꢀH,ꢀs,ꢀPh-NH),ꢀ7.82ꢀ(1ꢀH,ꢀs,ꢀN=CH),ꢀ7.50ꢀ(4ꢀH,ꢀm,ꢀH(2,6)ꢀaryl

ꢀ

),ꢀ7.32ꢀ(4ꢀH,ꢀm,ꢀꢀ

H

(3,5)ꢀꢀaryl),ꢀ7.17ꢀ(2ꢀH,ꢀm,ꢀH(4)ꢀaryl

ꢀ

),ꢀ2.25ꢀ(3ꢀH,ꢀs,ꢀN=C-CH

3

).ꢀδ

C

ꢀ177.30ꢀ(C=S),ꢀ176.76ꢀ(C=S),ꢀ148.49ꢀ(C=N),ꢀ

1

43.48ꢀ(C=N),ꢀ139.48ꢀ(C(1)ꢀaryl),ꢀ139.45ꢀ(C(1)ꢀaryl),ꢀ128.66ꢀ(C(3,5)ꢀaryl),ꢀ126.55ꢀ(C(4)ꢀaryl),ꢀ126.09ꢀ(C(2,6)ꢀ

-

1

3

aryl),ꢀ11.97ꢀ(N=C-CH ).ꢀIR:ꢀνmax/cm ꢀ3292ꢀ(w),ꢀ3136ꢀ(w),ꢀ2980ꢀ(w),ꢀ1595ꢀ(m),ꢀ1518ꢀ(s),ꢀ1491ꢀ(s),ꢀ1445ꢀ

(

m),ꢀ1350ꢀ(m),ꢀ1256ꢀ(m),ꢀ1173ꢀ(s),ꢀ1070ꢀ(m),ꢀ1026ꢀ(m),ꢀ934ꢀ(m),ꢀ750ꢀ(m),ꢀ689ꢀ(s),ꢀ640ꢀ(m),ꢀ559ꢀ(m).ꢀ

-

1

Ramanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ3061ꢀ(w),ꢀ1579ꢀ(s),ꢀ1433ꢀ(w),ꢀ1370ꢀ(w),ꢀ1285ꢀ(w),ꢀ1254ꢀ(m),ꢀ1178ꢀ(w),ꢀ

o

1

122ꢀ(w),ꢀ1023ꢀ(w),ꢀ942ꢀ(w),ꢀ1864ꢀ(w),ꢀ744ꢀ(w),ꢀ614ꢀ(w),ꢀ257ꢀ(w),ꢀ195ꢀ(w).ꢀMp:ꢀ>177ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ9:ꢀCompoundꢀBꢀ(0.255ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(1.5ꢀmL)ꢀandꢀfiltered.ꢀ4,4-

dimethyl-3-thiosemicarbazideꢀ(0.191ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(3ꢀmL),ꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀ

wasꢀaddedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀ(roomꢀtemperature,ꢀ5ꢀ

hours).ꢀDe-ionisedꢀwaterꢀ(9ꢀmL)ꢀwasꢀadded,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀoffꢀandꢀwashedꢀwithꢀde-

o

ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80 C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀ

DMSOꢀ(9ꢀmL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(18ꢀmL).ꢀTheꢀprecipitateꢀwasꢀ

recoveredꢀbyꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL)ꢀandꢀdried.ꢀAꢀyellowꢀsolidꢀ(0.158ꢀg)ꢀwasꢀ

recoveredꢀ(38%ꢀyield).ꢀδ

H

ꢀ11.19ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ10.41ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ8.45ꢀ(q,ꢀ1ꢀH,ꢀH

.72ꢀ(s,ꢀ1ꢀH,ꢀN=CH),ꢀ3.21ꢀ(ꢀs,ꢀ6ꢀH,ꢀHN-(CH ),ꢀ2.95ꢀ(ꢀd,ꢀ3ꢀH,ꢀHN-CH ,ꢀJ=ꢀ4.4ꢀHz),ꢀ2.05ꢀ(s,ꢀ3ꢀH,ꢀN=C-CH

181.06ꢀ(C=S),ꢀ178.82ꢀ(C=S),ꢀ147.56ꢀ(C=N),ꢀ143.95ꢀ(C=N),ꢀ42.96ꢀ(N-(CH ),ꢀ31.56ꢀ(HN-CH ),ꢀ11.65ꢀ

3

C-NH,ꢀJ=ꢀ4.4ꢀHz),ꢀ

7

δ

3

)

2

3

).ꢀ

ꢀ

C

3

)

2

3

ꢀ

20

Page 21 of 38

Dalton Transactions

-

1

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(

N=C-CH

3

).ꢀIR:ꢀνmax/cm ꢀ3306ꢀ(m),ꢀ3200ꢀ(m),ꢀ2999ꢀ(w),ꢀ1589ꢀ(w),ꢀ1526ꢀ(s),ꢀ1495ꢀ(s),ꢀ1406ꢀ(m),ꢀ1354ꢀ

DOI: 10.1039/C7DT02008B

m),ꢀ1273ꢀ(s),ꢀ1225ꢀ(s),ꢀ1142ꢀ(m),ꢀ1107ꢀ(s),ꢀ1045ꢀ(s),ꢀ966ꢀ(m),ꢀ935ꢀ(s),ꢀ878ꢀ(m),ꢀ812ꢀ(m),ꢀ658ꢀ(m),ꢀ623ꢀ

-

1

s),ꢀ584ꢀ(s),ꢀ565ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ1589ꢀ(m),ꢀ1570ꢀ(s),ꢀ1417ꢀ(m),ꢀ1363ꢀ(m),ꢀ1295ꢀ(m),ꢀ

275ꢀ(m),ꢀ1225ꢀ(m),ꢀ1143ꢀ(m),ꢀ1064ꢀ(m),ꢀ1016ꢀ(m),ꢀ876ꢀ(m),ꢀ744ꢀ(m),ꢀ583ꢀ(w),ꢀ314ꢀ(w),ꢀ131ꢀ(w).ꢀ

1

Elementalꢀanalysis:ꢀFound:ꢀC,ꢀ37.0;ꢀH,ꢀ6.2;ꢀN,ꢀ32.2.ꢀCalc.ꢀforꢀC

8

H

16

N

6

S

2

:ꢀC,ꢀ36.9;ꢀH,ꢀ6.2;ꢀN,ꢀ32.3%.ꢀMp.ꢀ

o

>

205ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ10:ꢀCompoundꢀBꢀ(0.255ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(1ꢀmL)ꢀandꢀfiltered.ꢀ4-

ethyl-3-thiosemicarbazideꢀ(0.191ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(5ꢀmL),ꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀwasꢀ

addedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀ(roomꢀtemperature,ꢀ5ꢀhours).ꢀ

De-ionisedꢀwaterꢀ(12ꢀmL)ꢀwasꢀadded,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ

o

(

50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(6ꢀmL),ꢀ

filteredꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(12ꢀmL).ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀ

washedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL)ꢀandꢀdried.ꢀAꢀcreamꢀsolidꢀ(0.191ꢀg)ꢀwasꢀrecoveredꢀ(46%ꢀyield).ꢀ

δ

H

ꢀ11.68ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ10.33ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ8.50ꢀ(q,ꢀ1ꢀH,ꢀH

.0ꢀHz),ꢀ7.62ꢀ(s,ꢀ1ꢀH,ꢀN=CH),ꢀ3.52ꢀ(dq,ꢀ2ꢀH,ꢀH C-NH,ꢀJ=7.2,ꢀ6.0ꢀHz),2.94ꢀ(d,ꢀ3ꢀH,ꢀN-CH

),ꢀ1.08ꢀ(tꢀ,ꢀ3ꢀH,ꢀH C-CH ,ꢀJ=ꢀ7.2ꢀHz).ꢀδ ꢀ178.75ꢀ(C=S),ꢀ177.17ꢀ(C=S),ꢀ147.64ꢀ(C=N),ꢀ

42.44ꢀ(C=N),ꢀ38.86ꢀ(N-CH ),ꢀ31.58ꢀ(N-CH ),ꢀ15.01ꢀ(H

316ꢀ(w),ꢀ3165ꢀ(w),ꢀ2988ꢀ(w),ꢀ1537ꢀ(s),ꢀ1497ꢀ(s),ꢀ1435ꢀ(m),ꢀ1412ꢀ(m),ꢀ1327ꢀ(m),ꢀ1219ꢀ(s),ꢀ1159ꢀ(m),ꢀ

3

C-NH,ꢀJ=ꢀ4.4ꢀHz),ꢀ8.42ꢀ(t,ꢀ1ꢀHꢀH

2

C-NH,ꢀJ=ꢀ

6

2

3

,ꢀJ=ꢀ4.4ꢀHz),ꢀ2.13ꢀ

(

s,ꢀ3ꢀH,ꢀN=C-CH

3

2

3

C

-

1

3

1

2

3

2 3 3

C-CH ),ꢀ11.68ꢀ(N=C-CH ).ꢀIR:ꢀνmax/cm ꢀ3374ꢀ(w),ꢀ

-

1

084ꢀ(s),ꢀ1042ꢀ(m),ꢀ935ꢀ(m),ꢀ814ꢀ(m),ꢀ664ꢀ(m),ꢀ619ꢀ(m),ꢀ546ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ2902ꢀ

(

w),ꢀ1580ꢀ(s),ꢀ1518ꢀ(w),ꢀ1364ꢀ(w),ꢀ1284ꢀ(w),ꢀ1220ꢀ(w),ꢀ1130ꢀ(w),ꢀ1016ꢀ(w),ꢀ879ꢀ(w),ꢀ773ꢀ(w),ꢀ572ꢀ(w),ꢀ

4

6

61ꢀ(w),ꢀ307ꢀ(w),ꢀ236ꢀ(w),ꢀ180ꢀ(w).ꢀFound:ꢀC,ꢀ37.0;ꢀH,ꢀ6.25;ꢀN,ꢀ32.2.ꢀCalc.ꢀforꢀC

8

H

16

N

6

S

2

:ꢀC,ꢀ36.9;ꢀH,ꢀ

o

.2;ꢀN,ꢀ32.3%.ꢀMp.ꢀ>220ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ11:ꢀCompoundꢀHꢀ(0.554ꢀg,ꢀ0.0032ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2ꢀmL)ꢀandꢀfiltered.ꢀ4-

methyl-3-thiosemicarbazideꢀ(0.337ꢀg,ꢀ0.0032ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(6ꢀmL),ꢀHClꢀ(10%,ꢀ2ꢀdrops)ꢀ

wasꢀaddedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀ(roomꢀtemperature,ꢀ5ꢀ

hours).ꢀDe-ionisedꢀwaterꢀ(50ꢀmL)ꢀwasꢀadded,ꢀaꢀgelatinousꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltrationꢀandꢀ

o

washedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80 C).ꢀTheꢀcrudeꢀproductꢀwasꢀ

leftꢀonꢀtheꢀwaterꢀpumpꢀuntilꢀitsꢀvolumeꢀdecreasedꢀthenꢀdissolvedꢀinꢀDMSOꢀ(6ꢀmL),ꢀfilteredꢀandꢀ

recrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(60ꢀmL).ꢀTheꢀwaxyꢀgelatinousꢀprecipitateꢀwasꢀrecoveredꢀbyꢀ

o

filtration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C),ꢀandꢀdried.ꢀTheꢀ

o

productꢀwasꢀfurtherꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C),ꢀandꢀ

dried.ꢀꢀAꢀyellowishꢀwhiteꢀsolidꢀ(0.118ꢀg)ꢀwasꢀrecoveredꢀ(14%ꢀyield).ꢀδ

ꢀH,ꢀN-NH),ꢀ8.53ꢀ(t,ꢀ1ꢀHꢀH C-NH,ꢀJ=ꢀ6.0ꢀHz),ꢀ8.39ꢀ(q,ꢀ1ꢀH,ꢀH C-NH,ꢀJ=ꢀ4.4ꢀHz),ꢀ7.62ꢀ(s,ꢀ1ꢀH,ꢀN=CH),ꢀ3.52ꢀ

dq,ꢀ2ꢀH,ꢀH C-NH,ꢀJ=7.2,ꢀ6.0ꢀHz),ꢀ2.95ꢀ(d,ꢀ3ꢀH,ꢀN-CH ,ꢀJ=ꢀ4.4ꢀHz),ꢀ2.12ꢀ(s,ꢀ3ꢀH,ꢀN=C-CH ),ꢀ1.07ꢀ(tꢀ,ꢀ3ꢀH,ꢀ

ꢀ178.23ꢀ(C=S),ꢀ177.69ꢀ(C=S),ꢀ147.70ꢀ(C=N),ꢀ142.37ꢀ(C=N),ꢀ39.00ꢀ(N-CH ),ꢀ31.47ꢀ

).ꢀIR:ꢀνmax/cm ꢀ3366ꢀ(w),ꢀ3129ꢀ(w),ꢀ2982ꢀ(w),ꢀ1518ꢀ(s),ꢀ1491ꢀ

H

ꢀ11.71ꢀ(s,ꢀ1ꢀH,ꢀN-NH),ꢀ10.24ꢀ(s,ꢀ

1

2

3

(

2

3

H

2

C-CH

3

,ꢀJ=ꢀ7.2ꢀHz).ꢀδ

C

2

-

1

(

N-CH

3

),ꢀ14.87ꢀ(H

2

3 3

C-CH ),ꢀ11.62ꢀ(N=C-CH

(

s),ꢀ1425ꢀ(m),ꢀ1364ꢀ(m),ꢀ1242ꢀ(m),ꢀ1204ꢀ(s),ꢀ1076ꢀ(s),ꢀ1040ꢀ(m),ꢀ914ꢀ(m),ꢀ812ꢀ(m),ꢀ631ꢀ(m),ꢀ600ꢀ(m),ꢀ

-

1

5

1

6

40ꢀ(s),ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ1581ꢀ(s),ꢀ1434ꢀ(w),ꢀ1362ꢀ(w),ꢀ1328ꢀ(w),ꢀ1275ꢀ(w),ꢀ1204ꢀ(w),ꢀ

125ꢀ(w),ꢀ1023ꢀ(w),ꢀ917ꢀ(w),ꢀ873ꢀ(w),ꢀ774ꢀ(w),ꢀ598ꢀ(w),ꢀ420ꢀ(w),ꢀ298ꢀ(w),ꢀ211ꢀ(w).ꢀFound:ꢀC,ꢀ37.0;ꢀH,ꢀ

o

.3;ꢀN,ꢀ32.2.ꢀCalc.ꢀforꢀC

8

H

16

N

6

S

2

:ꢀC,ꢀ36.9;ꢀH,ꢀ6.2;ꢀN,ꢀ32.3%.ꢀMp.ꢀ>220ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ12:ꢀIntermediateꢀBꢀ(0.255ꢀg,ꢀ1.6ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2ꢀmL)ꢀandꢀfiltered.ꢀ4-

phenyl-3-thiosemicarbazideꢀ(0.268ꢀg,ꢀ1.6ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2.5ꢀmL),ꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀwasꢀ

addedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ(9ꢀmL)ꢀ

ꢀ

21

Dalton Transactions

Page 22 of 38

View Article Online

DOI: 10.1039/C7DT02008B

wasꢀadded,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀ

o

temperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(12ꢀmL),ꢀfilteredꢀandꢀ

recrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(24ꢀmL).ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀwashedꢀ

o

withꢀethanolꢀ(2ꢀxꢀ25mL,ꢀroomꢀtemperature),ꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀ80ꢀ C)ꢀandꢀdried.ꢀAnꢀoffꢀwhiteꢀ

solidꢀ(0.313ꢀg)ꢀwasꢀrecoveredꢀ(63%ꢀyield).ꢀδ

Ph-NH),ꢀ8.55ꢀ(1ꢀH,ꢀq,ꢀJꢀ=ꢀ4.4,ꢀCH -NH),ꢀ7.73ꢀ(1ꢀH,ꢀs,ꢀN=CH),ꢀ7.48ꢀ(2ꢀH,ꢀd,ꢀJꢀ=ꢀ8.0,ꢀH(2,6)ꢀaryl),ꢀ7.33ꢀ(2ꢀH,ꢀ

dd,Jꢀ=ꢀ8.0, (3,5)ꢀꢀaryl),ꢀ7.17ꢀ(1ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.0,ꢀH(4)ꢀaryl),ꢀ2.96ꢀ(3ꢀH,ꢀd,ꢀJꢀ=ꢀ4.4,ꢀN-CH ),ꢀ2.18ꢀ(3ꢀH,ꢀs,ꢀN=C-

CH ).ꢀδ ꢀ178.79ꢀ(C=S),ꢀ176.68ꢀ(C=S),ꢀ147.50ꢀ(C=N),ꢀ143.50ꢀ(C=N),ꢀ139.44ꢀ(C(1)ꢀaryl),ꢀ128.63ꢀ(C(3,5)ꢀaryl),ꢀ

26.53ꢀ(C(4)ꢀaryl),ꢀ126.06ꢀ(C(2,6)ꢀaryl),ꢀ31.61ꢀ(N-CH

136ꢀ(w),ꢀ2988ꢀ(w),ꢀ1589ꢀ(w),ꢀ1541ꢀ(s),ꢀ1499ꢀ(s),ꢀ1449ꢀ(m),ꢀ1400ꢀ(m),ꢀ1356ꢀ(m),ꢀ1315ꢀ(m),ꢀ1263ꢀ(m),ꢀ

H

ꢀ12.06ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.40ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ9.97ꢀ(1ꢀH,ꢀs,ꢀ

3

ꢀ

H

3

C

-

1

3

1

3

3 3

),ꢀ11.71ꢀ(N=C-CH ).ꢀIR:ꢀνmax/cm ꢀꢀ3331ꢀ(w),ꢀ3285ꢀ(w),ꢀ

-

1

200ꢀ(s),ꢀ1072ꢀ(s),ꢀ934ꢀ(m),ꢀ745ꢀ(m),ꢀ691ꢀ(m),ꢀ665ꢀ(m),ꢀ635ꢀ(m),ꢀ569ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ

044ꢀ(w),ꢀ1585ꢀ(s),ꢀ1513ꢀ(w),ꢀ1367ꢀ(w),ꢀ1278ꢀ(w),ꢀ1236ꢀ(w),ꢀ1118ꢀ(w),ꢀ1016ꢀ(w),ꢀ934ꢀ(w),ꢀ873ꢀ(w),ꢀ745ꢀ

(

16 6 2

w),ꢀ638ꢀ(w),ꢀ410ꢀ(w),ꢀ290ꢀ(w),ꢀ224ꢀ(w).ꢀFound:ꢀC,ꢀ46.7;ꢀH,ꢀ5.2;ꢀN,ꢀ27.25.ꢀCalc.ꢀforꢀC12H N S :ꢀC,ꢀ46.7;ꢀ

o

H,ꢀ5.1;ꢀN,ꢀ27.2%.ꢀMp:ꢀ>205ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ13:ꢀCompoundꢀHꢀ(0.554ꢀg,ꢀ0.0032ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2ꢀmL)ꢀandꢀfiltered.ꢀ

Thiosemicarbazideꢀ(0.292ꢀg,ꢀ0.0032ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(10ꢀmL),ꢀHClꢀ(10%,ꢀ2ꢀdrops)ꢀwasꢀ

addedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀ(roomꢀtemperature,ꢀ5ꢀhours).ꢀ

De-ionisedꢀwaterꢀ(24ꢀmL)ꢀwasꢀadded,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀoffꢀandꢀwashedꢀwithꢀde-ionisedꢀ

o

waterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(25ꢀ

mL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL).ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀ

o

filtration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C),ꢀandꢀdried.ꢀAnꢀ

offꢀwhiteꢀsolidꢀ(0.386ꢀg)ꢀwasꢀrecoveredꢀ(49%ꢀyield).ꢀδHꢀ11.65ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.26ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.53ꢀ

(

1ꢀH,ꢀt,ꢀJꢀ=ꢀ6.0,ꢀH

2

C-NH),ꢀ8.28ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ7.88ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ7.62ꢀ(1ꢀH,ꢀs,ꢀN=CH),ꢀ3.52ꢀ(2ꢀH,ꢀdq,ꢀJꢀ=ꢀ

C-NH),ꢀ2.09ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ1.07ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀH C-CH ).ꢀδ ꢀ178.57ꢀ(C=S),ꢀ177.67ꢀ(C=S),ꢀ

47.62ꢀ(C=N),ꢀ142.93ꢀ(C=N),ꢀ38.99ꢀ(N-CH ),ꢀ14.87ꢀ(H C-CH ),ꢀ11.53ꢀ(N=C-CH

148ꢀ(m),ꢀ2982ꢀ(m),ꢀ1593ꢀ(m),ꢀ1530ꢀ(s),ꢀ1493ꢀ(s),ꢀ1456ꢀ(m),ꢀ1352ꢀ(m),ꢀ1310ꢀ(m),ꢀ1269ꢀ(m),ꢀ1202ꢀ(s),ꢀ

7

1

3

1

.2,ꢀ6.0,ꢀH

2

3

2

3

C

-

1

2

3

).ꢀIR:ꢀνmax/cm ꢀ3292ꢀ(w),ꢀ

-

1

090ꢀ(s),ꢀ926ꢀ(m),ꢀ829ꢀ(s),ꢀ662ꢀ(m),ꢀ548ꢀ(s).ꢀRaman(632.81ꢀnm):ꢀνmax/cm ꢀꢀ2978ꢀ(w),ꢀ2908ꢀ(w),ꢀ1583ꢀ

(

s),ꢀ1425ꢀ(w),ꢀ1350ꢀ(w),ꢀ1270ꢀ(w),ꢀ1209ꢀ(w),ꢀ1128ꢀ(w),ꢀ1014ꢀ(w),ꢀ936ꢀ(w),ꢀ874ꢀ(w),ꢀ800ꢀ(w),ꢀ483ꢀ(w),ꢀ

3

>

07ꢀ(w),ꢀ209ꢀ(w).ꢀFound:ꢀC,ꢀ34.0;ꢀH,ꢀ5.8;ꢀN,ꢀ34.0.ꢀCalc.ꢀforꢀC

7

H

14

N

6

S

2

:ꢀC,ꢀ34.1;ꢀH,ꢀ5.7;ꢀN,ꢀ34.1%.ꢀMp:ꢀ

o

207ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ14:ꢀCompoundꢀHꢀ(0.277ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(1.5ꢀmL)ꢀandꢀfiltered.ꢀ4,4-

dimethyl-3-thiosemicarbazideꢀ(0.191ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(3ꢀmL),ꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀ

wasꢀaddedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀ(roomꢀtemperature,ꢀ5ꢀ

hours).ꢀDe-ionisedꢀwaterꢀ(24ꢀmL)ꢀwasꢀadded,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀandꢀwashedꢀwithꢀde-

ionisedꢀwaterꢀ(2ꢀxꢀ50ꢀmL).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(7ꢀmL),ꢀfilteredꢀandꢀ

recrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(14ꢀmL).ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀwashedꢀ

o

withꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀ80ꢀ C)ꢀandꢀdried.ꢀAꢀyellowꢀsolidꢀ(0.117ꢀg)ꢀwasꢀrecoveredꢀ(27%ꢀyield).ꢀδ

H

ꢀ

1

1.18ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.36ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.46ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ6.0,ꢀH

dq,ꢀJꢀ=7.2,ꢀ6.0,ꢀH C-NH),ꢀ3.21ꢀ(6ꢀH,ꢀs,ꢀHN-(CH ),ꢀ2.05ꢀ(3ꢀH,ꢀs,ꢀN=C-CH

ꢀ181.00ꢀ(C=S),ꢀ177.76ꢀ(C=S),ꢀ147.57ꢀ(C=N),ꢀ144.09ꢀ(C=N),ꢀ42.90ꢀ(HN-(CH

2

C-NH),ꢀ7.75ꢀ(1ꢀH,ꢀs,ꢀN=CH),ꢀ3.52ꢀ(2ꢀH,ꢀ

),ꢀ1.08ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀH C-CH ).ꢀ

),ꢀ39.00ꢀ(N-CH ),ꢀ14.87ꢀ

).ꢀIR:ꢀνmax/cm ꢀ3341ꢀ(w),ꢀ3134ꢀ(m),ꢀ2988ꢀ(m),ꢀ1589ꢀ(w),ꢀ1526ꢀ(s),ꢀ1489ꢀ(s),ꢀ

410ꢀ(m),ꢀ1348ꢀ(m),ꢀ1269ꢀ(s),ꢀ1206ꢀ(s),ꢀ1140ꢀ(m),ꢀ1049ꢀ(s),ꢀ920ꢀ(s),ꢀ868ꢀ(m),ꢀ806ꢀ(m),ꢀ783ꢀ(m),ꢀ660ꢀ

2

3

)

2

3

2

3

δ

C

3

)

2

-

1

2 3 3

(H C-CH ),ꢀ11.67ꢀ(N=C-CH

1

-

1

(

ꢀ

m),ꢀ625ꢀ(m),ꢀ581ꢀ(m).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀꢀ2936ꢀ(w),ꢀ1575ꢀ(s),ꢀ1361ꢀ(w),ꢀ1284ꢀ(w),ꢀ1274ꢀ

22

Page 23 of 38

Dalton Transactions

View Article Online

DOI: 10.1039/C7DT02008B

(

w),ꢀ1206ꢀ(w),ꢀ1143ꢀ(w),ꢀ1102ꢀ(w),ꢀ1016ꢀ(w),ꢀ964ꢀ(w),ꢀ934ꢀ(w),ꢀ870ꢀ(w),ꢀ742ꢀ(w),ꢀ626ꢀ(w),ꢀ308ꢀ(w).ꢀ

o

9 18 6 2

Found:ꢀC,ꢀ39.4;ꢀH,ꢀ6.7;ꢀN,ꢀ30.6.ꢀCalc.ꢀforꢀC H N S :ꢀC,ꢀ39.4;ꢀH,ꢀ6.6;ꢀN,ꢀ30.6%.ꢀMp:ꢀ>180ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ15:ꢀCompoundꢀ15ꢀwasꢀpreparedꢀfromꢀcompoundꢀHꢀandꢀ4-phenyl-3-thiosemicarbazideꢀinꢀ

1

aꢀsimilarꢀmannerꢀtoꢀ14ꢀabove.ꢀ HꢀNMRꢀshowedꢀthatꢀtheꢀproductꢀwasꢀcontaminatedꢀwithꢀupꢀtoꢀ10%ꢀofꢀ

2

theꢀ(known )ꢀsymmetricꢀligandꢀ8.ꢀꢀ

Synthesisꢀofꢀ16:ꢀCompoundꢀIꢀ(0.354ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2.5ꢀmL)ꢀandꢀfiltered.ꢀ

Thiosemicarbazideꢀ(0.146ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(5ꢀmL),ꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀwasꢀaddedꢀ

andꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀ(roomꢀtemperature,ꢀ5ꢀhours).ꢀDe-

ionisedꢀwaterꢀ(15ꢀmL)ꢀwasꢀadded,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀ

o

mL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(7ꢀmL),ꢀfilteredꢀ

andꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(14ꢀmL).ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀwashedꢀ

o

withꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C),ꢀandꢀdried.ꢀAꢀyellowishꢀwhiteꢀ

solidꢀ(0.273ꢀg)ꢀwasꢀrecoveredꢀ(58%ꢀyield).ꢀδHꢀ11.70ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.71ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.15ꢀ(1ꢀH,ꢀs,ꢀ

Ph-NH),ꢀ8.32ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ7.92ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ7.71ꢀ(1ꢀH,ꢀs,ꢀN=CH),ꢀ7.50ꢀ(2ꢀH,ꢀd,ꢀJ=ꢀ8.0,ꢀH(2,6)ꢀaryl),ꢀ

7

.31ꢀ(2ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.0,ꢀꢀ

3

H(3,5)ꢀꢀaryl),ꢀ7.15ꢀ(1ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.0,ꢀH(4)ꢀaryl),ꢀ2.16ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ).ꢀδCꢀ178.71ꢀ

(

C=S),ꢀ177.27ꢀ(C=S),ꢀ148.54ꢀ(C=N),ꢀ142.93ꢀ(C=N),ꢀ139.48ꢀ(C(1)ꢀaryl),ꢀ128.64ꢀ(C(3,5)ꢀaryl),ꢀ126.09ꢀ(C(4)ꢀaryl),ꢀ

-

1

25.91ꢀ(C(2,6)ꢀaryl),ꢀ11.77ꢀ(N=C-CH

3

).ꢀIR:ꢀνmax/cm ꢀꢀ3449ꢀ(w),ꢀ3296ꢀ(w),ꢀ3157ꢀ(m),ꢀ2974ꢀ(w),ꢀ1595ꢀ(m),ꢀ

516ꢀ(s),ꢀ1493ꢀ(s),ꢀ1447ꢀ(m),ꢀ1366ꢀ(m),ꢀ1335ꢀ(m),ꢀ1267ꢀ(m),ꢀ1250ꢀ(m),ꢀ1179ꢀ(s),ꢀ1090ꢀ(s),ꢀ1069ꢀ(m),ꢀ

-

1

024ꢀ(m),ꢀ935ꢀ(m),ꢀ824ꢀ(m),ꢀ756ꢀ(m),ꢀ694ꢀ(s),ꢀ588ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀꢀ3054ꢀ(w),ꢀ1580ꢀ

(

w),ꢀ1373ꢀ(w),ꢀ1277ꢀ(w),ꢀ1253ꢀ(w),ꢀ1172ꢀ(w),ꢀ1124ꢀ(w),ꢀ1017ꢀ(w),ꢀ937ꢀ(w),ꢀ870ꢀ(w),ꢀ781ꢀ(w),ꢀ758ꢀ(w),ꢀ

08ꢀ(w),ꢀ423ꢀ(w),ꢀ259ꢀ(w),ꢀ206ꢀ(w).ꢀFound:ꢀC,ꢀ44.7;ꢀH,ꢀ4.8;ꢀN,ꢀ28.5.ꢀCalc.ꢀforꢀC11 :ꢀC,ꢀ44.9;ꢀH,ꢀ4.8;ꢀ

6

14 6 2

H N S

o

N,ꢀ27.2%.ꢀMp:ꢀ>215ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ17:ꢀCompoundꢀIꢀ(0.354ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2.5ꢀmL)ꢀandꢀfiltered.ꢀ4-

methyl-3-thiosemicarbazideꢀ(0.168ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(4ꢀmL),ꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀ

wasꢀaddedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀ(roomꢀtemperature,ꢀ5ꢀ

hours).ꢀDe-ionisedꢀwaterꢀ(13ꢀmL)ꢀwasꢀadded,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀandꢀwashedꢀwithꢀde-

o

ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀ

DMSOꢀ(10ꢀmL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(20ꢀmL).ꢀTheꢀprecipitateꢀwasꢀ

o

recoveredꢀbyꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C),ꢀ

andꢀdried.ꢀAnꢀoff-whiteꢀsolidꢀ(0.319ꢀg)ꢀwasꢀrecoveredꢀ(65%ꢀyield).ꢀδ

s,ꢀN-NH),ꢀ10.14ꢀ(1ꢀH,ꢀs,ꢀPh-NH),ꢀ8.43ꢀ(1ꢀH,ꢀq,ꢀJꢀ=ꢀ4.4,ꢀH C-NH),ꢀ7.71ꢀ(1ꢀH,ꢀs,ꢀN=CH),ꢀ7.50ꢀ(2ꢀH,ꢀd,ꢀJꢀ=ꢀ8.0,ꢀ

(2,6)ꢀaryl),ꢀ7.31ꢀ(2ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.0, (3,5)ꢀꢀaryl),ꢀ7.15ꢀ(1ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.0,ꢀH(4)ꢀaryl),ꢀ2.96ꢀ(3ꢀH,ꢀd,ꢀJꢀ=ꢀ4.4,ꢀN-

CH ),ꢀꢀ2.20ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ).ꢀδ ꢀ178.29ꢀ(C=S),ꢀ177.23ꢀ(C=S),ꢀ148.63ꢀ(C=N),ꢀ142.39ꢀ(C=N),ꢀ139.48ꢀ(C(1)ꢀ

aryl),ꢀ128.64ꢀ(C(3,5)ꢀaryl),ꢀ126.06ꢀ(C(4)ꢀaryl),ꢀ125.89ꢀ(C(2,6)ꢀaryl),ꢀ31.49ꢀ(N-CH ),ꢀ11.87ꢀ(N=C-CH ).ꢀIR:ꢀ

max/cm ꢀ3291ꢀ(w),ꢀ3157ꢀ(w),ꢀ2999ꢀ(w),ꢀ1595ꢀ(w),ꢀ1518ꢀ(s),ꢀ1495ꢀ(s),ꢀ1477ꢀ(s),ꢀ1447ꢀ(m),ꢀ1352ꢀ(m),ꢀ

250ꢀ(m),ꢀ1173ꢀ(s),ꢀ1090ꢀ(m),ꢀ1038ꢀ(m),ꢀ932ꢀ(m),ꢀ797ꢀ(m),ꢀ748ꢀ(m),ꢀ687ꢀ(m),ꢀ559ꢀ(s).ꢀRamanꢀ(632.81ꢀ

H

ꢀ11.77ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.70ꢀ(1ꢀH,ꢀ

3

H

ꢀ

H

3

C

3

-

1

ν

1

-

1

nm):ꢀνmax/cm ꢀꢀ1577ꢀ(s),ꢀ1514ꢀ(w),ꢀ1367ꢀ(w),ꢀ1286ꢀ(w),ꢀ1247ꢀ(w),ꢀ1174ꢀ(w),ꢀ1128ꢀ(w),ꢀ1020ꢀ(w),ꢀ934ꢀ

(

w),ꢀ874ꢀ(w),ꢀ773ꢀ(w),ꢀ602ꢀ(w),ꢀ541ꢀ(w),ꢀ435ꢀ(w),ꢀ194ꢀ(w).ꢀFound:ꢀC,ꢀ46.7;ꢀH,ꢀ5.2;ꢀN,ꢀ27.25.ꢀCalc.ꢀforꢀ

o

12 16 6 2

C H N S :ꢀC,ꢀ46.6;ꢀH,ꢀ5.2;ꢀN,ꢀ27.6%.ꢀMp:ꢀ>210ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ18:ꢀProligandꢀ18ꢀwasꢀsynthesisedꢀfroꢀcompoundꢀHꢀandꢀ4,4-dimethyl-3-

1

thiosemicarbazideꢀinꢀaꢀsimilarꢀmannerꢀtoꢀ14ꢀabove,ꢀbutꢀ HꢀNMRꢀindicatedꢀthatꢀtheꢀproductꢀwasꢀ

2

contaminatedꢀwithꢀupꢀtoꢀ25%ꢀofꢀtheꢀ(known )ꢀpro-ligandꢀ8.ꢀ

ꢀ

23

Dalton Transactions

Page 24 of 38

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DOI: 10.1039/C7DT02008B

Synthesisꢀofꢀ19:ꢀCompoundꢀIꢀ(0.354ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2.5ꢀmL)ꢀandꢀfiltered.ꢀ4-

ethyl-3-thiosemicarbazideꢀ(0.191ꢀg,ꢀ0.0016ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(5ꢀmL),ꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀwasꢀ

addedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀ(roomꢀtemperature,ꢀ5ꢀhours).ꢀ

De-ionisedꢀwaterꢀ(15ꢀmL)ꢀwasꢀadded,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ

o

(

50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(11ꢀmL),ꢀ

filteredꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(22ꢀmL).ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀ

o

washedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C),ꢀandꢀdried.ꢀAꢀyellowishꢀ

creamꢀsolidꢀ(0.309ꢀg)ꢀwasꢀrecoveredꢀ(60%ꢀyield).ꢀδHꢀ11.71ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.69ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.15ꢀ

(

1ꢀH,ꢀs,ꢀPh-NH),ꢀ8.47ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ6.0,ꢀH

2ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.0,ꢀꢀ (3,5)ꢀꢀaryl),ꢀ7.15ꢀ(1ꢀH,ꢀdd,ꢀJꢀ=8.0,ꢀH(4)ꢀaryl),ꢀ3.54ꢀ(2ꢀH,ꢀdq,ꢀJꢀ=ꢀ7.2,ꢀ6.0,ꢀH

),ꢀ1.09ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀH C-CH ).ꢀδ ꢀ177.24ꢀ(C=S),ꢀ148.63ꢀ(C=N),ꢀ142.42ꢀ(C=N),ꢀ139.48ꢀ(C(1)ꢀ

aryl),ꢀ128.64ꢀ(C(3,5)ꢀaryl),ꢀ126.06ꢀ(C(4)ꢀaryl),ꢀ125.90ꢀ(C(2,6)ꢀaryl),ꢀ38.90ꢀ(N-CH ),ꢀ15.00ꢀ(H C-CH ),ꢀ11.93ꢀ

).ꢀIR:ꢀνmax/cm ꢀ3294ꢀ(w),ꢀ3132ꢀ(m),ꢀ2970ꢀ(w),ꢀ1591ꢀ(w),ꢀ1518ꢀ(s),ꢀ1491ꢀ(s),ꢀ1447ꢀ(m),ꢀ1335ꢀ

m),ꢀ1277ꢀ(m),ꢀ1227ꢀ(s),ꢀ1182ꢀ(s),ꢀ1123ꢀ(m),ꢀ1072ꢀ(m),ꢀ937ꢀ(m),ꢀ787ꢀ(m),ꢀ748ꢀ(m),ꢀ696ꢀ(s),ꢀ635ꢀ(m),ꢀ577ꢀ

2

C-NH),ꢀ7.71ꢀ(1ꢀH,ꢀs,ꢀN=CH),ꢀ7.50ꢀ(2ꢀH,ꢀd,ꢀJꢀ=ꢀ8.0,ꢀH(2,6)ꢀaryl),ꢀ7.32ꢀ

(

H

2

C-NH),ꢀ2.21ꢀ(3ꢀ

H,ꢀs,ꢀN=C-CH

3

2

3

C

2

3

-

1

(

N=C-CH

3

-

1

s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ2966ꢀ(w),ꢀ1582ꢀ(s),ꢀ1445ꢀ(w),ꢀ1372ꢀ(w),ꢀ1253ꢀ(w),ꢀ1177ꢀ(m),ꢀ1125ꢀ

w),ꢀ1019ꢀ(w),ꢀ924ꢀ(w),ꢀ865ꢀ(w),ꢀ751ꢀ(w),ꢀ527ꢀ(w),ꢀ419ꢀ(w),ꢀ293ꢀ(w),ꢀ206ꢀ(w).ꢀFound:ꢀC,ꢀ48.3;ꢀH,ꢀ5.6;ꢀN,ꢀ

o

2

6.0.ꢀCalc.ꢀforꢀC13

H

18

N

6

S

2

:ꢀC,ꢀ48.4;ꢀH,ꢀ5.6;ꢀN,ꢀ26.0%.ꢀMp:ꢀ>207ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ23:ꢀMethodꢀ1:ꢀThiosemicarbazideꢀ(0.158ꢀg,ꢀ1.7ꢀmmol)ꢀwasꢀdissolvedꢀinꢀethanolꢀ(50ꢀmL,ꢀ

o

5

0ꢀ C)ꢀandꢀaddedꢀHClꢀ(10%,ꢀ1ꢀdrop).ꢀCompoundꢀFꢀ(0.300ꢀg,ꢀ1.7ꢀmmol)ꢀaddedꢀtoꢀtheꢀsolutionꢀandꢀleftꢀ

o

toꢀstirꢀatꢀ50ꢀ Cꢀforꢀ5ꢀh.ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀdissolvedꢀinꢀDMSOꢀ(5ꢀmL)ꢀandꢀ

recrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(5ꢀmL).ꢀTheꢀprecipitateꢀwasꢀfilteredꢀoff,ꢀwashedꢀwithꢀaꢀlittleꢀ

amountꢀofꢀacetoneꢀandꢀdried.ꢀAꢀwhiteꢀsolidꢀ(0.145ꢀg)ꢀwasꢀrecoveredꢀ(35%ꢀyield).ꢀδHꢀ10.19ꢀ(2ꢀH,ꢀs,ꢀN-

NH),ꢀ8.37ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ8.34ꢀ(1ꢀH,ꢀq,ꢀJꢀ=ꢀ4.4,ꢀH

CH ),ꢀ2.16ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ2.12ꢀ(3ꢀH,ꢀs,ꢀN=C-CH

48.43ꢀ(C=N),ꢀ31.74ꢀ(HN-CH ),ꢀ12.26ꢀ(N=C-CH ),ꢀ12.07ꢀ(N=C-CH

215ꢀ(m),ꢀ3150ꢀ(m),ꢀ1605ꢀ(m),ꢀ1553ꢀ(m),ꢀ1489ꢀ(s),ꢀ1362ꢀ(m),ꢀ1288ꢀ(m),ꢀ1231ꢀ(m),ꢀ1169ꢀ(m),ꢀ1142ꢀ(m),ꢀ

3

C-NH),ꢀ7.82ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ2.97ꢀ(3ꢀH,ꢀd,ꢀJꢀ=ꢀ4.4,ꢀHN-

3

).ꢀδ ꢀ179.32ꢀ(C=S),ꢀ178.97ꢀ(C=S),ꢀ148.92ꢀ(C=N),ꢀ

C

-

1

3

1

3

8

3

).ꢀIR:ꢀνmax/cm ꢀꢀ3414ꢀ(m),ꢀ3352ꢀ(w),ꢀ

-

1

080ꢀ(s),ꢀ953ꢀ(m),ꢀ854ꢀ(m),ꢀ826ꢀ(m),ꢀ716ꢀ(m),ꢀ644ꢀ(m),ꢀ565ꢀ(s),ꢀ544ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ

212ꢀ(w),ꢀ2913ꢀ(w),ꢀ1604ꢀ(s),ꢀ1589ꢀ(m),ꢀ1461ꢀ(w),ꢀ1374ꢀ(m),ꢀ1329ꢀ(w),ꢀ1237ꢀ(w),ꢀ1123ꢀ(w),ꢀ1005ꢀ(w),ꢀ

54ꢀ(w),ꢀ747ꢀ(w),ꢀ461ꢀ(w),ꢀ398ꢀ(w),ꢀ216ꢀ(w).ꢀFound:ꢀC,ꢀ34.2;ꢀH,ꢀ5.8;ꢀN,ꢀ34.0.ꢀCalc.ꢀforꢀC

7

H

14

N

6

S

2

:ꢀC,ꢀ

o

4.1;ꢀH,ꢀ5.7;ꢀN,ꢀ34.1%.ꢀMp:ꢀ>215ꢀ Cꢀ(dec.).ꢀMethodꢀ2:ꢀ2,3-butanedioneꢀ(5.26ꢀmL,ꢀ60ꢀmmols)ꢀwasꢀ

dissolvedꢀinꢀ100ꢀmLꢀofꢀcoldꢀdistilledꢀwaterꢀ(0ꢀ°C)ꢀinꢀaꢀconicalꢀflask.ꢀFiveꢀdropsꢀofꢀconcentratedꢀHClꢀ

97%)ꢀwereꢀaddedꢀtoꢀtheꢀreactionꢀmixture,ꢀfollowedꢀbyꢀ4-methyl-3-thiosemicarbazideꢀ(3.45ꢀg,ꢀ32.8ꢀ

(

mmol).ꢀAfterꢀstirringꢀforꢀ1ꢀhour,ꢀtheꢀresultingꢀsuspensionꢀwasꢀfilteredꢀandꢀtheꢀresidueꢀrinsedꢀwithꢀ

waterꢀ(3ꢀxꢀ100ꢀmL),ꢀethanolꢀ(3ꢀxꢀ50ꢀmL)ꢀandꢀdiethylꢀetherꢀ(3ꢀxꢀ10ꢀmL)ꢀandꢀrecrystallisedꢀfromꢀwarmꢀ

ethanolꢀtoꢀaffordꢀpureꢀmono-substituted-3-thiosemicarbazoneꢀintermediateꢀ(2.4ꢀg,ꢀ43%).ꢀThisꢀ

intermediateꢀ(0.80ꢀg,ꢀ4.62ꢀmmols)ꢀwasꢀaddedꢀoverꢀ2ꢀhꢀinꢀportionsꢀtoꢀaꢀsolutionꢀofꢀthiosemicarbazideꢀ

inꢀmethanolꢀ(0.44ꢀg,ꢀ4.82ꢀmmol)ꢀpreviouslyꢀacidifiedꢀwithꢀconcentratedꢀHCl.ꢀTheꢀreactionꢀmixtureꢀ

wasꢀheatedꢀunderꢀrefluxꢀ(~65ꢀ°C)ꢀforꢀ5ꢀh,ꢀduringꢀwhichꢀaꢀwhitishꢀsuspensionꢀformed.ꢀAfterꢀcoolingꢀ

downꢀtoꢀroomꢀtemperature,ꢀtheꢀsolutionꢀwasꢀfilteredꢀunderꢀvacuumꢀandꢀtheꢀprecipitateꢀwashedꢀ

withꢀethanolꢀ(3ꢀxꢀ50ꢀmL)ꢀandꢀdiethylꢀetherꢀ(3ꢀxꢀ10ꢀmL).ꢀTheꢀresultingꢀsolidꢀwasꢀthenꢀrecrystallisedꢀ

fromꢀwarmꢀDMSO/waterꢀ(50:50)ꢀtoꢀyieldꢀpureꢀ23ꢀ(0.90ꢀg,ꢀ79%).ꢀ

Synthesisꢀofꢀ24:ꢀIntermediateꢀGꢀ(0.255ꢀg,ꢀ1.6ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(1.5ꢀmL)ꢀandꢀfiltered.ꢀ4,4-

dimethyl-3-thiosemicarbazideꢀ(0.191ꢀg,ꢀ1.6ꢀmmol)ꢀdissolvedꢀinꢀDMFꢀ(2.5ꢀmL),ꢀHClꢀ(10%,ꢀ2ꢀdrops)ꢀwasꢀ

addedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ(33ꢀ

ꢀ

24

Page 25 of 38

Dalton Transactions

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DOI: 10.1039/C7DT02008B

mL)ꢀwasꢀadded,ꢀtheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltrationꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀ

o

mL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(3ꢀmL),ꢀfilteredꢀ

andꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(6ꢀmL).ꢀTheꢀprecipitateꢀwasꢀfilteredꢀoff,ꢀwashedꢀwithꢀde-

o

ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C)ꢀandꢀdried.ꢀAꢀyellowꢀsolidꢀ(0.170ꢀg)ꢀwasꢀ

recoveredꢀ(41%ꢀyield).ꢀδHꢀ10.18ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ9.49ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.38ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ7.83ꢀ(1ꢀH,ꢀs,ꢀC-

NH),ꢀ3.22ꢀ(6ꢀH,ꢀs,ꢀN-(CH

3

)

2

),ꢀ2.11ꢀ(3ꢀH,ꢀs,ꢀN=C-CH

3

),ꢀ2.10ꢀ(3ꢀH,ꢀs,ꢀN=C-CH

3 C

).ꢀδ ꢀ182.16ꢀ(C=S),ꢀ179.35ꢀ

-

1

(

C=S),ꢀ150.00ꢀ(C=N),ꢀ148.96ꢀ(C=N),ꢀ42.80ꢀ(N-(CH

3

)

2

),ꢀ11.96ꢀ(N=C-CH ),ꢀ11.70ꢀ(N=C-CH ).ꢀIR:ꢀνmax/cm ꢀ

3

395ꢀ(w),ꢀ3221ꢀ(m),ꢀ3148ꢀ(m),ꢀ1591ꢀ(m),ꢀ1545ꢀ(m),ꢀ1460ꢀ(m),ꢀ1412ꢀ(m),ꢀ1396ꢀ(m),ꢀ1368ꢀ(m),ꢀ1261ꢀ

(

m),ꢀ1221ꢀ(m),ꢀ1134ꢀ(m),ꢀ1103ꢀ(m),ꢀ1055ꢀ(m),ꢀ968ꢀ(m),ꢀ847ꢀ(m),ꢀ708ꢀ(m),ꢀ606ꢀ(m),ꢀ515ꢀ(s).ꢀRamanꢀ

-

1

632.81ꢀnm):ꢀνmax/cm ꢀꢀ2913ꢀ(w),ꢀ1603ꢀ(m),ꢀ1586ꢀ(s),ꢀ1498ꢀ(w),ꢀ1463ꢀ(w),ꢀ1397ꢀ(w),ꢀ1371ꢀ(w),ꢀ1338ꢀ

m),ꢀ1263ꢀ(w),ꢀ1229ꢀ(w),ꢀ1128ꢀ(m),ꢀ1110ꢀ(w),ꢀ1006ꢀ(w),ꢀ850ꢀ(w),ꢀ736ꢀ(w),ꢀ612ꢀ(w),ꢀ461ꢀ(w).Found:ꢀC,ꢀ

o

3

6.9;ꢀH,ꢀ6.2;ꢀN,ꢀ32.3.ꢀCalc.ꢀforꢀC

8

H

16

N

6

S

2

:ꢀC,ꢀ36.9;ꢀH,ꢀ6.2;ꢀN,ꢀ32.2%.ꢀMp:ꢀ>192ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ26:ꢀIntermediateꢀKꢀ(0.277ꢀg,ꢀ1.6ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(3ꢀmL).ꢀ4-methyl-3-

thiosemicarbazideꢀ(0.168ꢀg,ꢀ1.6ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(4ꢀmL)ꢀandꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀwasꢀ

added.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ(14ꢀmL)ꢀwasꢀ

added,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL).ꢀTheꢀcrudeꢀproductꢀ

wasꢀdissolvedꢀinꢀDMSOꢀ(8ꢀmL)ꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(16ꢀmL).ꢀTheꢀprecipitateꢀwasꢀ

filteredꢀoff,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL),ꢀethanolꢀ(5ꢀxꢀ10ꢀmL)ꢀandꢀdried.ꢀAꢀyellow/whiteꢀ

solidꢀ(0.275ꢀg)ꢀwasꢀrecoveredꢀ(66%ꢀyield).ꢀδ

NH),ꢀ8.32ꢀ(1ꢀH,ꢀq,ꢀJꢀ=4.8,ꢀH C-NH),ꢀ7.74ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ2.97ꢀ(3ꢀH,ꢀd,ꢀJꢀ=ꢀ4.8,ꢀHN-CH

),ꢀ2.10ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ0.84ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀCH -CH ).ꢀδCꢀ179.28ꢀ(C=S),ꢀ178.93ꢀ(C=S),ꢀ

52.24ꢀ(C=N),ꢀ147.92ꢀ(C=N),ꢀ31.76ꢀ(HN-CH ),ꢀ17.38ꢀ(C-CH ),ꢀ12.38ꢀ(N=C-CH ),ꢀ11.45ꢀ(CH -CH ).ꢀIR:ꢀ

max/cm ꢀꢀ3424ꢀ(w),ꢀ3223ꢀ(w),ꢀ2982ꢀ(w),ꢀ1603ꢀ(m),ꢀ1551ꢀ(m),ꢀ1491ꢀ(s),ꢀ1437ꢀ(m),ꢀ1366ꢀ(w),ꢀ1290ꢀ(m),ꢀ

231ꢀ(m),ꢀ1144ꢀ(m),ꢀ1082ꢀ(s),ꢀ1063ꢀ(s),ꢀ989ꢀ(w),ꢀ926ꢀ(w),ꢀ841ꢀ(m),ꢀ775ꢀ(w),ꢀ563ꢀ(m).ꢀRamanꢀ(632.81ꢀ

H

10.37ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.19ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.40ꢀ(1ꢀH,ꢀs,ꢀC-

3

),ꢀ2.80ꢀ(2H,ꢀq,ꢀJꢀ=ꢀ

7

1

.6,ꢀC-CH

2

3

2

3

2

3

2

3

-

1

ν

1

-

1

nm):ꢀνmax/cm ꢀ2935ꢀ(w),ꢀ1603ꢀ(s),ꢀ1457ꢀ(w),ꢀ1378ꢀ(w),ꢀ1336ꢀ(w),ꢀ1247ꢀ(w),ꢀ1145ꢀ(w),ꢀ1124ꢀ(w),ꢀ1048ꢀ

(

w),ꢀ992ꢀ(w),ꢀ925ꢀ(w),ꢀ741ꢀ(w),ꢀ484ꢀ(w),ꢀ456ꢀ(w),ꢀ327ꢀ(w),ꢀ226ꢀ(w).ꢀFound:ꢀC,ꢀ36.9;ꢀH,ꢀ6.2;ꢀN,ꢀ32.3.ꢀ

o

Calc.ꢀforꢀC

8

H

16

N

6

S

2

:ꢀC,ꢀ36.8;ꢀH,ꢀ6.1;ꢀN,ꢀ32.2%.ꢀMp:ꢀ>198ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ27:ꢀIntermediateꢀKꢀ(0.452ꢀg,ꢀ2.6ꢀmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2ꢀmL)ꢀandꢀfiltered.ꢀ4,4-

dimethyl-3-thiosemicarbazideꢀ(0.310ꢀg,ꢀ2.6ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(4ꢀmL),ꢀHClꢀ(10%,ꢀ2ꢀdrops)ꢀ

wasꢀaddedꢀandꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ

(

37ꢀmL)ꢀwasꢀaddedꢀandꢀsolutionꢀwasꢀputꢀinꢀtheꢀfreezerꢀ(10ꢀmin).ꢀTheꢀprecipitateꢀwasꢀfilteredꢀoffꢀandꢀ

o

washedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80 C).ꢀTheꢀcrudeꢀproductꢀwasꢀ

dissolvedꢀinꢀDMSOꢀ(3.5ꢀmL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(60ꢀmL).ꢀTheꢀprecipitateꢀ

wasꢀrecoveredꢀbyꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(2ꢀxꢀ50ꢀmL)ꢀandꢀdried.ꢀAꢀyellowꢀsolidꢀ

(

0.171ꢀg)ꢀwasꢀrecoveredꢀ(24%ꢀyield).ꢀδ

.74ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ3.22ꢀ(6ꢀH,ꢀs,ꢀN-(CH

H,ꢀt,ꢀJꢀ=ꢀ7.6,ꢀCH -CH ).ꢀδCꢀ182.39ꢀ(C=S),ꢀ179.32ꢀ(C=S),ꢀ153.32ꢀ(C=N),ꢀ147.88ꢀ(C=N),ꢀ42.95ꢀ(N-(CH

),ꢀ12.01ꢀ(N=C-CH

932ꢀ(w),ꢀ1593ꢀ(m),ꢀ1541ꢀ(m),ꢀ1483ꢀ(s),ꢀ1433ꢀ(s),ꢀ1260ꢀ(m),ꢀ1105ꢀ(s),ꢀ1076ꢀ(m),ꢀ1055ꢀ(s),ꢀ1020ꢀ(m),ꢀ

H

ꢀ10.18ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.53ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.38ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ

),ꢀ2.77ꢀ(2H,ꢀq,ꢀJꢀ=ꢀ7.6,ꢀC-CH ),ꢀ2.08ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ0.88ꢀ(3ꢀ

),ꢀ

3 2 3

),ꢀ10.92ꢀ(CH -CH ).ꢀIR:ꢀνmax/cm ꢀ3410ꢀ(w),ꢀ3229ꢀ(m),ꢀ3148ꢀ(w),ꢀ2974ꢀ(w),ꢀ

7

3

)

2

3

2

3

3 2

)

-

1

2

9

7.04ꢀ(CH

2

-

1

89ꢀ(m),ꢀ926ꢀ(m),ꢀ843ꢀ(m),ꢀ511ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ2934ꢀ(w),ꢀ1600ꢀ(s),ꢀ1583ꢀ(s),ꢀ1495ꢀ

(

w),ꢀ1458ꢀ(w),ꢀ1396ꢀ(w),ꢀ1367ꢀ(w),ꢀ1345ꢀ(w),ꢀ1246ꢀ(w),ꢀ1126ꢀ(m),ꢀ1111ꢀ(w),ꢀ991ꢀ(w),ꢀ732ꢀ(w),ꢀ633ꢀ(w),ꢀ

6

03ꢀ(w),ꢀ461ꢀ(w),ꢀ386ꢀ(w),ꢀ332ꢀ(w).ꢀFound:ꢀC,ꢀ39.3;ꢀH,ꢀ6.2;ꢀN,ꢀ30.6.ꢀCalc.ꢀforꢀC

9

H

18

N

6

S

2

:ꢀC,ꢀ39.4;ꢀH,ꢀ6.2;ꢀ

o

N,ꢀ30.6%.ꢀMp:ꢀ>180ꢀ Cꢀ(dec.).ꢀ

ꢀ

25

Dalton Transactions

Page 26 of 38

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DOI: 10.1039/C7DT02008B

Synthesisꢀofꢀ28:ꢀIntermediateꢀKꢀ(0.277ꢀg,ꢀ1.6ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(3ꢀmL).ꢀ4-ethyl-3-

thiosemicarbazideꢀ(0.191ꢀg,ꢀ1.6ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(5ꢀmL)ꢀandꢀaddedꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀwasꢀ

added.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ(14ꢀmL)ꢀwasꢀ

added,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀoffꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL).ꢀTheꢀcrudeꢀproductꢀ

wasꢀdissolvedꢀinꢀDMSOꢀ(8ꢀmL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(16ꢀmL).ꢀTheꢀ

precipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL),ꢀethanolꢀ(5ꢀxꢀ10ꢀmL)ꢀ

andꢀdried.ꢀAꢀyellowish-whiteꢀsolidꢀ(0.168ꢀg)ꢀwasꢀrecoveredꢀ(38%ꢀyield).ꢀδHꢀ10.29ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.19ꢀ

(

1ꢀH,ꢀs,ꢀN-NH),ꢀ8.40ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ8.60ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ6.0,ꢀH

2

C-NH),ꢀ7.74ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ3.54ꢀ(2ꢀH,ꢀdq,ꢀJꢀ=ꢀ

),ꢀ2.14ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ1.09ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀN-CH -CH ),ꢀ

3

).ꢀδCꢀ179.28ꢀ(C=S),ꢀ177.90ꢀ(C=S),ꢀ152.19ꢀ(C=N),ꢀ147.86ꢀ(C=N),ꢀ39.35ꢀ(HN-

7

0

.2,ꢀ6.0,ꢀHN-CH

.84ꢀ(3ꢀH,ꢀt,ꢀJꢀ=7.2,ꢀC-CH

2 3 3 2 3

),ꢀ17.04ꢀ(C-CH ),ꢀ14.89ꢀ(N-CH -CH ),ꢀ12.39ꢀ(N=C-CH ),ꢀ11.44ꢀ(C-CH -CH ).ꢀIR:ꢀνmax/cm ꢀꢀ3428ꢀ(w),ꢀ

2

),ꢀ2.80ꢀ(2H,ꢀq,ꢀJꢀ=ꢀ7.2,ꢀC-CH

2

3

2

3

2

-CH

-

1

CH

2

3

210ꢀ(w),ꢀ2982ꢀ(w),ꢀ1601ꢀ(m),ꢀ1537ꢀ(m),ꢀ1493ꢀ(s),ꢀ1435ꢀ(m),ꢀ1290ꢀ(m),ꢀ1213ꢀ(m),ꢀ1146ꢀ(m),ꢀ1080ꢀ(s),ꢀ

-

1

059ꢀ(m),ꢀ926ꢀ(w),ꢀ837ꢀ(m),ꢀ777ꢀ(w),ꢀ716ꢀ(w),ꢀ652ꢀ(w),ꢀ565ꢀ(m),ꢀ517ꢀ(m).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm

1

ꢀ

2934ꢀ(w),ꢀ1599ꢀ(s),ꢀ1589ꢀ(m),ꢀ1532ꢀ(w),ꢀ1457ꢀ(w),ꢀ1395ꢀ(w),ꢀ1368ꢀ(w),ꢀ1345ꢀ(w),ꢀ1247ꢀ(w),ꢀ1215ꢀ(w),ꢀ

1

C

120ꢀ(m),ꢀ1049ꢀ(w),ꢀ991ꢀ(w),ꢀ741ꢀ(w),ꢀ463ꢀ(w),ꢀ318ꢀ(w).ꢀFound:ꢀC,ꢀ39.5;ꢀH,ꢀ6.5;ꢀN,ꢀ30.55.ꢀCalc.ꢀforꢀ

o

9 18 6 2

H N S :ꢀC,ꢀ39.4;ꢀH,ꢀ6.6;ꢀN,ꢀ30.6%ꢀꢀMp:ꢀ>218ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ29:ꢀIntermediateꢀLꢀ(0.599ꢀg,ꢀ3.2ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2ꢀmL)ꢀandꢀfiltered.ꢀ

Thiosemicarbazideꢀ(0.292ꢀg,ꢀ3.2ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(10ꢀmL),ꢀHClꢀ(10%,ꢀ2ꢀdrops)ꢀwasꢀaddedꢀ

andꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ(24ꢀmL)ꢀwasꢀ

added,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀoffꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀ

o

andꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(31ꢀmL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀ

de-ionisedꢀwaterꢀ(62ꢀmL).ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ

o

(

50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C)ꢀandꢀdried.ꢀAnꢀoffꢀwhiteꢀsolidꢀ(0.597ꢀg)ꢀwasꢀrecoveredꢀ

72%ꢀyield).ꢀδHꢀ10.29ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.21ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.39ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ8.27ꢀ(1ꢀH,ꢀq,ꢀJꢀ=ꢀ4.8,ꢀH

),ꢀ2.87ꢀ(2H,ꢀq,ꢀJꢀ=ꢀ7.2,ꢀCH ),ꢀ2.10ꢀ(3ꢀH,ꢀs,ꢀN=C-

).ꢀδCꢀ179.35ꢀ(C=S),ꢀ178.96ꢀ(C=S),ꢀ152.89ꢀ(C=N),ꢀ147.48ꢀ(C=N),ꢀ31.80ꢀ

3

C-

NH),ꢀ7.80ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ2.98ꢀ(3ꢀH,ꢀd,ꢀJꢀ=ꢀ4.8,ꢀHN-CH

CH ),ꢀ0.85ꢀ(3ꢀH,ꢀt,ꢀJꢀ=7.2,ꢀCH -CH

HN-CH ),ꢀ17.36ꢀ(CH ),ꢀ12.21ꢀ(N=C-CH

150ꢀ(m),ꢀ2978ꢀ(w),ꢀ2938ꢀ(w),ꢀ1603ꢀ(m),ꢀ1541ꢀ(m),ꢀ1491ꢀ(s),ꢀ1464ꢀ(s),ꢀ1439ꢀ(s),ꢀ1364ꢀ(m),ꢀ1227ꢀ(m),ꢀ

144ꢀ(m),ꢀ1082ꢀ(s),ꢀ1059ꢀ(s),ꢀ860ꢀ(m),ꢀ826ꢀ(m),ꢀ797ꢀ(m),ꢀ640ꢀ(m),ꢀ509ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀ

3

2

3

2

3

-

1

(

3

2

3 2 3

),ꢀ11.53ꢀ(CH -CH ).ꢀIR:ꢀνmax/cm ꢀ3408ꢀ(m),ꢀ3337ꢀ(w),ꢀ3229ꢀ(m),ꢀ

3

1

-

1

ν

max/cm ꢀ2937ꢀ(w),ꢀ1604ꢀ(s),ꢀ1591ꢀ(m),ꢀ1591ꢀ(w),ꢀ1380ꢀ(w),ꢀ1341ꢀ(w),ꢀ1232ꢀ(w),ꢀ1144ꢀ(w),ꢀ1123ꢀ(m),ꢀ

1

024ꢀ(w),ꢀ985ꢀ(w),ꢀ737ꢀ(w),ꢀ675ꢀ(w),ꢀ481ꢀ(w),ꢀ460ꢀ(w).ꢀFound:ꢀC,ꢀ36.8;ꢀH,ꢀ6.2;ꢀN,ꢀ32.2.ꢀCalc.ꢀforꢀ

o

C

8 16 6 2

H N S :ꢀC,ꢀ36.9;ꢀH,ꢀ6.2;ꢀN,ꢀ32.3%.ꢀMp:ꢀ>202ꢀ Cꢀ(dec.).ꢀ

Synthesisꢀofꢀ30:ꢀIntermediateꢀMꢀ(0.322ꢀg,ꢀ1.6ꢀmmol)ꢀdissolvedꢀinꢀDMFꢀ(2.5ꢀmL)ꢀandꢀfiltered.ꢀ

Thiosemicarbazideꢀ(0.146ꢀg,ꢀ1.6ꢀmmol)ꢀdissolvedꢀinꢀDMFꢀ(5.5ꢀmL),ꢀaddedꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀandꢀ

filtered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ(16ꢀmL)ꢀwasꢀ

added,ꢀfilteredꢀoffꢀprecipitateꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀ

o

mL,ꢀ70 C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(14ꢀmL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀde-

ionisedꢀwaterꢀ(28ꢀmL).ꢀFilteredꢀoffꢀprecipitate,ꢀwashedꢀde-ionisedꢀwaterꢀ(50ꢀmL)ꢀandꢀdried.ꢀAꢀwhiteꢀ

solidꢀ(0.237ꢀg)ꢀwasꢀrecoveredꢀ(54%ꢀyield).ꢀδ

C-NH),ꢀ8.28ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ6.0,ꢀH C-NH),ꢀ7.80ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ3.55ꢀ(2ꢀH,ꢀdq,ꢀJꢀ=ꢀ7.2,ꢀ6.0,HN-CH

q,ꢀJꢀ=ꢀ7.2,ꢀC-CH ),ꢀ2.10ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ1.09ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀN-CH -CH ),ꢀ0.86ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀC-CH

CH ).ꢀδCꢀ179.37ꢀ(C=S),ꢀ177.94ꢀ(C=S),ꢀ152.77ꢀ(C=N),ꢀ147.47ꢀ(C=N),ꢀ39.07ꢀ(HN-CH ),ꢀ17.48ꢀ(C-CH ),ꢀ14.89ꢀ

).ꢀIR:ꢀνmax/cm ꢀ3410ꢀ(w),ꢀ3333ꢀ(w),ꢀ3219ꢀ(m),ꢀ3152ꢀ

m),ꢀ2978ꢀ(w),ꢀ1601ꢀ(m),ꢀ1531ꢀ(m),ꢀ1493ꢀ(s),ꢀ1466ꢀ(s),ꢀ1439ꢀ(s),ꢀ1385ꢀ(m),ꢀ1292ꢀ(m),ꢀ1250ꢀ(m),ꢀ1207ꢀ

H

ꢀ10.30ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.15ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.38ꢀ(1ꢀH,ꢀs,ꢀ

2

),ꢀ2.86ꢀ(2H,ꢀ

2

3

2

3

2

-

3

2

-

1

(

2 3 3 2 3

N-CH -CH ),ꢀ12.20ꢀ(N=C-CH ),ꢀ11.50ꢀ(C-CH -CH

ꢀ

26

Page 27 of 38

Dalton Transactions

View Article Online

DOI: 10.1039/C7DT02008B

(

s),ꢀ1167ꢀ(m),ꢀ1146ꢀ(m),ꢀ1080ꢀ(s),ꢀ1059ꢀ(s),ꢀ860ꢀ(m),ꢀ818ꢀ(m),ꢀ797ꢀ(m),ꢀ652ꢀ(m),ꢀ501ꢀ(s).ꢀRamanꢀ

-

1

632.81ꢀnm):ꢀνmax/cm ꢀ2953ꢀ(w),ꢀ1602ꢀ(s),ꢀ1589ꢀ(m),ꢀ1533ꢀ(w),ꢀ1456ꢀ(w),ꢀ1393ꢀ(w),ꢀ1373ꢀ(w),ꢀ1347ꢀ

w),ꢀ1248ꢀ(w),ꢀ1214ꢀ(w),ꢀ1146ꢀ(w),ꢀ1122ꢀ(w),ꢀ1027ꢀ(w),ꢀ990ꢀ(w),ꢀ741ꢀ(w),ꢀ464ꢀ(w),ꢀ306ꢀ(w).ꢀFound:ꢀC,ꢀ

o

3

9.3;ꢀH,ꢀ6.5;ꢀN,ꢀ30.55.ꢀCalc.ꢀforꢀC

9

H

18

N

6

S

2

:ꢀC,ꢀ39.4;ꢀH,ꢀ6.6;ꢀN,ꢀ30.6%.ꢀMp:ꢀ>200ꢀ Cꢀ(dec.).ꢀ

SynthesisꢀofꢀCopperꢀComplexesꢀ

2

33

22

58

22

Cu(1), ꢀCu(2), ꢀCu(5), ꢀCu(6), ꢀCu(7), ꢀCu(8), ꢀCu(20), ꢀCu(21) ꢀandꢀCu(25) ꢀwereꢀsynthesisedꢀasꢀ

describedꢀpreviously.ꢀCopperꢀcomplexesꢀCu(3),ꢀCu(4),ꢀCu(10),ꢀCu(13),ꢀCu(18),ꢀCu(31),ꢀCu(32),ꢀCu(33),ꢀ

Cu(34),ꢀCu(35)ꢀandꢀCu(36)ꢀwereꢀnotꢀsynthesisedꢀinꢀthisꢀwork;ꢀanyꢀdataꢀreportedꢀinꢀTableꢀ2ꢀareꢀ

derivedꢀfromꢀliteratureꢀvalues.ꢀOtherꢀcopperꢀcomplexesꢀwereꢀsynthesisedꢀbyꢀaꢀgenericꢀmethodꢀasꢀ

follows:ꢀBis(thiosemicarbazone)ꢀpro-ligandsꢀ(0.6ꢀmmol)ꢀwereꢀaddedꢀtoꢀaꢀNaOHꢀsolutionꢀ(1M,ꢀ13ꢀmL,ꢀ

o

5

0ꢀ C),ꢀtheꢀminimumꢀamountꢀofꢀDMFꢀwasꢀaddedꢀtoꢀachieveꢀfullꢀdissolution.ꢀCopperꢀ(II)ꢀacetateꢀ

monohydrateꢀ(0.140ꢀg,ꢀ0.7ꢀmmol)ꢀwasꢀdissolvedꢀinꢀde-ionisedꢀwaterꢀ(5ꢀmL).ꢀTheꢀsolutionsꢀwereꢀ

combinedꢀandꢀleftꢀtoꢀstirꢀovernight.ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀviaꢀfiltration,ꢀwashedꢀwithꢀ

methanolꢀ(3ꢀxꢀ10ꢀmL)ꢀandꢀde-ionisedꢀwaterꢀ(1ꢀxꢀ10ꢀmL).ꢀTheꢀproductsꢀwereꢀdriedꢀinꢀair.ꢀ

+

DataꢀforꢀCu(9):ꢀHPLCꢀR

t

ꢀ7.17ꢀmin,ꢀ>95%.ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC

8

H

14

N

6

S

2

ꢀ+ꢀH] ꢀ=ꢀ322.0090ꢀ(calc.),ꢀ

3

22.0093ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ0.38;ꢀ

+

DataꢀforꢀCu(11):ꢀHPLC:ꢀR

22.0098ꢀ(found).ꢀ

t

ꢀ=ꢀ5.49ꢀmin,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC

8

H

14

N

6

S

2

ꢀ+ꢀH] ꢀ=ꢀ322.0090ꢀ(calc.),ꢀ

3

-

1

DataꢀforꢀCu(12):ꢀYield:ꢀ61%.ꢀIR:ꢀνmax/cm ꢀ3294ꢀ(m),ꢀ1597ꢀ(w),ꢀ1547ꢀ(m),ꢀ1524ꢀ(s),ꢀ1497ꢀ(m),ꢀ1458ꢀ(s),ꢀ

1

435ꢀ(s),ꢀ1391ꢀ(s),ꢀ1368ꢀ(m),ꢀ1344ꢀ(m),ꢀ1317ꢀ(m),ꢀ1248ꢀ(m),ꢀ1219ꢀ(s),ꢀ1194ꢀ(s),ꢀ1179ꢀ(s),ꢀ1134ꢀ(m),ꢀ

123ꢀ(m),ꢀ926ꢀ(m),ꢀ897ꢀ(w),ꢀ881ꢀ(w),ꢀ808ꢀ(w),ꢀ758ꢀ(s),ꢀ687ꢀ(s),ꢀ664ꢀ(m),ꢀ631ꢀ(m),ꢀ610ꢀ(m),ꢀ586ꢀ(m),ꢀ507ꢀ

-

1

(

m),ꢀ446ꢀ(m),ꢀ419ꢀ(m).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ1595ꢀ(w),ꢀ1540ꢀ(s),ꢀ1519ꢀ(m),ꢀ1466ꢀ(s),ꢀ1425ꢀ(w),ꢀ

348ꢀ(w),ꢀ1311ꢀ(w),ꢀ1242ꢀ(w),ꢀ1218ꢀ(m),ꢀ1131ꢀ(w),ꢀ993ꢀ(w),ꢀ922ꢀ(w),ꢀ820ꢀ(w),ꢀ664ꢀ(w),ꢀ590ꢀ(m),ꢀ485ꢀ

w),ꢀ358ꢀ(w).ꢀFound:ꢀC,ꢀ38.9;ꢀH,ꢀ3.7;ꢀN,ꢀ22.6.ꢀCalc.ꢀforꢀCu :ꢀC,ꢀ39.0;ꢀH,ꢀ3.8;ꢀN,ꢀ22.7%.ꢀMp:ꢀ

1

(

1

C

12

H

14

-1

N

6

S

2

o

3

-1

>

220ꢀ Cꢀ(decomp.).ꢀUV-Vis:ꢀλmax/nmꢀ(DMSO)ꢀ320ꢀ(ε/dm ꢀmol ꢀcm ꢀ18ꢀ900),ꢀ378ꢀ(13ꢀ100),ꢀ496ꢀ(9ꢀ700)ꢀ

+

andꢀ540ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ(Calc.)ꢀ370.0092ꢀ(370.0096)ꢀ{Mꢀ+ꢀH }.ꢀHPLC:ꢀR

t

ꢀ=ꢀ19.17ꢀmin,ꢀ>95%;ꢀESI ꢀ

+

MS:ꢀm/zꢀforꢀ[CuC12H N S ꢀ+ꢀH] ꢀ=ꢀ370.0090ꢀ(calc.),ꢀ370.0093ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ0.54.ꢀ

14 6 2

-

1

DataꢀforꢀCu(14):ꢀYield:ꢀ63%.ꢀIR:ꢀνmax/cm ꢀ3321ꢀ(m),ꢀ2965ꢀ(w),ꢀ2926ꢀ(w),ꢀ1514ꢀ(s),ꢀ1483ꢀ(m),ꢀ1462ꢀ(s),ꢀ

391ꢀ(m),ꢀ1366ꢀ(s),ꢀ1339ꢀ(s),ꢀ1310ꢀ(s),ꢀ1258ꢀ(m),ꢀ1234ꢀ(s),ꢀ1179ꢀ(s),ꢀ1138ꢀ(s),ꢀ1059ꢀ(m),ꢀ1013ꢀ(m),ꢀ916ꢀ

1

-

1

(

m),ꢀ862ꢀ(m),ꢀ826ꢀ(m),ꢀ800ꢀ(m),ꢀ658ꢀ(m),ꢀ594ꢀ(m),ꢀ525ꢀ(s),ꢀ474ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ1589ꢀ

w),ꢀ1538ꢀ(m),ꢀ1482ꢀ(s),ꢀ1460ꢀ(m),ꢀ1373ꢀ(w),ꢀ1312ꢀ(m),ꢀ1225ꢀ(m),ꢀ1008ꢀ(m),ꢀ931ꢀ(m),ꢀ661ꢀ(w),ꢀ632ꢀ(w),ꢀ

5

1 9 16 6 2

96ꢀ(m),ꢀ351ꢀ(w).ꢀFound:ꢀC,ꢀ32.3;ꢀH,ꢀ4.7;ꢀN,ꢀ25.2.ꢀCalc.ꢀforꢀCu C H N S :ꢀC,ꢀ32.2;ꢀH,ꢀ4.8;ꢀN,ꢀ25.0%.ꢀUV-

3

-1

Vis:ꢀλmax/nmꢀ(DMSO)ꢀ320ꢀ(ε/dm ꢀmol ꢀcm ꢀ21ꢀ500),ꢀ360ꢀ(sh),ꢀ492ꢀ(9ꢀ500)ꢀandꢀ540ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ

+

(

Calc.)ꢀ336.0255ꢀ(336.0252)ꢀ{Mꢀ+ꢀH }.ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC

9

H

16

N

6

S

2

ꢀ+ꢀH] ꢀ=ꢀ336.0247ꢀ(calc.),ꢀ

3

36.0255ꢀ(found);ꢀHPLC:ꢀR ꢀ=ꢀ11.72ꢀmin,ꢀ>ꢀ95%;ꢀTLC:ꢀRfꢀ=ꢀ0.34.ꢀ

t

+

DataꢀforꢀCu(15):ꢀHPLC:ꢀR

t

ꢀ=ꢀ28.9ꢀmin,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC13

H

16

N

6

S

2

ꢀ+ꢀH] ꢀ=ꢀ384.0247ꢀ(calc.),ꢀ

3

84.0247ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ0.59.ꢀ

-

1

DataꢀforꢀCu(16):ꢀYield:ꢀ69%.ꢀIR:ꢀνmax/cm ꢀ3289ꢀ(m),ꢀ3073ꢀ(m),ꢀ1632ꢀ(w),ꢀ1591ꢀ(m),ꢀ1541ꢀ(m),ꢀ1497ꢀ(s),ꢀ

408ꢀ(s),ꢀ1368ꢀ(s),ꢀ1319ꢀ(s),ꢀ1256ꢀ(m),ꢀ1244ꢀ(m),ꢀ1184ꢀ(s),ꢀ1150ꢀ(s),ꢀ928ꢀ(m),ꢀ891ꢀ(m),ꢀ864ꢀ(m),ꢀ847ꢀ

m),ꢀ820ꢀ(m),ꢀ750ꢀ(s),ꢀ735ꢀ(m),ꢀ685ꢀ(s),ꢀ640ꢀ(m),ꢀ617ꢀ(m),ꢀ600ꢀ(m),ꢀ584ꢀ(s),ꢀ505ꢀ(s),ꢀ463ꢀ(s).ꢀRamanꢀ

1

(

ꢀ

27

Dalton Transactions

Page 28 of 38

-

1

View Article Online

DOI: 10.1039/C7DT02008B

(

632.81ꢀnm):ꢀνmax/cm ꢀ1528ꢀ(s),ꢀ1470ꢀ(s),ꢀ1431ꢀ(m),ꢀ1314ꢀ(w),ꢀ1237ꢀ(m),ꢀ1185ꢀ(w),ꢀ996ꢀ(w),ꢀ929ꢀ(w),ꢀ

6

3

6

70ꢀ(w),ꢀ618ꢀ(w),ꢀ599ꢀ(w),ꢀ359ꢀ(w),ꢀ300ꢀ(w).ꢀFound:ꢀC,ꢀ37.2;ꢀH,ꢀ3.3;ꢀN,ꢀ23.4.ꢀCalc.ꢀforꢀCu C H N S :ꢀC,ꢀ

1 11 12 6 2

3

-1

7.1;ꢀH,ꢀ3.4;ꢀN,ꢀ23.6%.ꢀUV-Vis:ꢀλmax/nmꢀ(DMSO)ꢀ314ꢀ(ε/dm ꢀmol ꢀcm ꢀ21ꢀ000),ꢀ372ꢀ(13ꢀ300),ꢀ494ꢀ(9ꢀ

+

00)ꢀandꢀ540ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ(Calc.)ꢀ355.9935ꢀ(355.9939)ꢀ{Mꢀ+ꢀH }.ꢀ

-

1

DataꢀforꢀCu(17):ꢀYield:ꢀ61%.ꢀIR:ꢀνmax/cm ꢀ3279ꢀ(w),ꢀ3213ꢀ(w),ꢀ2932ꢀ(w),ꢀ1597ꢀ(m),ꢀ1582ꢀ(w),ꢀ1545ꢀ(m),ꢀ

493ꢀ(s),ꢀ1433ꢀ(s),ꢀ1346ꢀ(s),ꢀ1321ꢀ(s),ꢀ1279ꢀ(s),ꢀ1244ꢀ(m),ꢀ1196ꢀ(s),ꢀ1148ꢀ(s),ꢀ1043ꢀ(m),ꢀ934ꢀ(m),ꢀ891ꢀ

w),ꢀ847ꢀ(m),ꢀ822ꢀ(m),ꢀ745ꢀ(s),ꢀ685ꢀ(s),ꢀ610ꢀ(m),ꢀ584ꢀ(m),ꢀ503ꢀ(s),ꢀ484ꢀ(m).ꢀRamanꢀ(632.81ꢀnm):ꢀ

1

(

-

1

ν

max/cm ꢀ1576ꢀ(m),ꢀ1507ꢀ(s),ꢀ1470ꢀ(s),ꢀ1429ꢀ(m),ꢀ1383ꢀ(w),ꢀ1351ꢀ(w),ꢀ1312ꢀ(w),1273ꢀ(m),ꢀ1243ꢀ(m),ꢀ

1

3

192ꢀ(w),ꢀ994ꢀ(w),ꢀ932ꢀ(m),ꢀ676ꢀ(w),ꢀ600ꢀ(m),ꢀ542ꢀ(w),ꢀ479ꢀ(w),ꢀ368ꢀ(w),ꢀ130ꢀ(w).ꢀFound:ꢀC,ꢀ38.9;ꢀH,ꢀ

3

.7;ꢀN,ꢀ22.6.ꢀCalc.ꢀforꢀCu

1

C

12

H

14

N

6

S

2

:ꢀC,ꢀ39.0;ꢀH,ꢀ3.8;ꢀN,ꢀ22.7%.ꢀUV-Vis:ꢀλmax/nmꢀ(DMSO)ꢀ318ꢀ(ε/dm ꢀ

-

1

-1

mol ꢀcm ꢀ20ꢀ600),ꢀ380ꢀ(sh),ꢀ492ꢀ(10ꢀ100)ꢀandꢀ540ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ(Calc.)ꢀ370.0092ꢀ(370.0096)ꢀ{Mꢀ

+

ꢀH }.ꢀHPLC:ꢀR

t

ꢀ=ꢀ16.05ꢀmin,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC12

H

14

N

6

S

2

ꢀ+ꢀH] ꢀ=ꢀ370.0090ꢀ(calc.),ꢀ370.0095ꢀ

(

found);ꢀTLC:ꢀRfꢀ=ꢀ0.41.ꢀ

+

DataꢀforꢀCu(19):ꢀHPLC:ꢀR

t

ꢀ=ꢀ27.57ꢀmin,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC13

H

16

N

6

S

2

ꢀ+ꢀH] ꢀ=ꢀ384.0247ꢀ(calc.),ꢀ

3

84.0247ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ0.52.ꢀ

+

DataꢀforꢀCu(22):ꢀHPLC:ꢀR

t

ꢀ=ꢀ16.01ꢀmin,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC

9

H

16

N

6

S

2

ꢀ+ꢀH] ꢀ=ꢀ336.0247ꢀ(calc.),ꢀ

3

36.0249;ꢀTLC:ꢀRfꢀ=ꢀ0.42.ꢀ

-

1

DataꢀforꢀCu(23):ꢀYield:ꢀ59%.ꢀIR:ꢀνmax/cm ꢀ3458ꢀ(w),ꢀ3321ꢀ(m),ꢀ3287ꢀ(w),ꢀ3136ꢀ(w),ꢀ1626ꢀ(m),ꢀ1549ꢀ(m),ꢀ

1

5

504ꢀ(m),ꢀ1443ꢀ(s),ꢀ1396ꢀ(m),ꢀ1364ꢀ(m),ꢀ1344ꢀ(s),ꢀ1287ꢀ(s),ꢀ1221ꢀ(s),ꢀ1188ꢀ(m),ꢀ1150ꢀ(m),ꢀ1099ꢀ(m),ꢀ

057ꢀ(m),ꢀ1038ꢀ(m),ꢀ984ꢀ(m),ꢀ841ꢀ(m),ꢀ756ꢀ(w),ꢀ733ꢀ(m),ꢀ700ꢀ(m),ꢀ629ꢀ(m),ꢀ610ꢀ(m),ꢀ563ꢀ(m),ꢀ527ꢀ(m),ꢀ

-

1

09ꢀ(s),ꢀ419ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ1542ꢀ(m),ꢀ1496ꢀ(s),ꢀ1379ꢀ(w),ꢀ1284ꢀ(s),ꢀ1184ꢀ(w),ꢀ998ꢀ

(

w),ꢀ837ꢀ(w),ꢀ697ꢀ(w),ꢀ609ꢀ(w),ꢀ588ꢀ(w),ꢀ390ꢀ(w),ꢀ346ꢀ(w),ꢀ316ꢀ(w),ꢀ271ꢀ(w),ꢀ253ꢀ(w),ꢀ138ꢀ(w).ꢀMp:ꢀ

o

3

-1

>

5

266ꢀ Cꢀ(decomp.).ꢀUV-Vis:ꢀλmax/nmꢀ(DMSO)ꢀ314ꢀ(ε/dm ꢀmol ꢀcm ꢀ22ꢀ500),ꢀ350ꢀ(sh),ꢀ476ꢀ(6ꢀ900)ꢀandꢀ

+

20ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ(Calc.)ꢀ307.9935ꢀ(307.9939)ꢀ{Mꢀ+ꢀH }.ꢀHPLC:ꢀR

t

ꢀ=ꢀ3.46ꢀmin,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀ

+

forꢀ[CuC

7

H

12

N

6

S

2

ꢀ+ꢀH] ꢀ=ꢀ307.9934ꢀ(calc.),ꢀ307.9935ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ0.39.ꢀ

-

1

DataꢀforꢀCu(24):ꢀYield:ꢀ53%.ꢀIR:ꢀνmax/cm ꢀ3426ꢀ(w),ꢀ3289ꢀ(w),ꢀ3157ꢀ(w),ꢀ2918ꢀ(w),ꢀ1622ꢀ(m),ꢀ1589ꢀ(w),ꢀ

541ꢀ(m),ꢀ1499ꢀ(m),ꢀ1439ꢀ(m),ꢀ1387ꢀ(s),ꢀ1362ꢀ(s),ꢀ1296ꢀ(s),ꢀ1258ꢀ(s),ꢀ1217ꢀ(s),ꢀ1171ꢀ(s),ꢀ1140ꢀ(m),ꢀ1115ꢀ

s),ꢀ1055ꢀ(s),ꢀ999ꢀ(m),ꢀ908ꢀ(s),ꢀ841ꢀ(s),ꢀ762ꢀ(m),ꢀ706ꢀ(m),ꢀ610ꢀ(m),ꢀ596ꢀ(m),ꢀ515ꢀ(m),ꢀ430ꢀ(s).ꢀRamanꢀ

1

(

-

1

(

532.00ꢀnm):ꢀνmax/cm ꢀ2837ꢀ(w),ꢀ2807ꢀ(w),ꢀ2144ꢀ(w),ꢀ1901ꢀ(w),ꢀ1804ꢀ(w),ꢀ1598ꢀ(w),ꢀ1543ꢀ(m),ꢀ1497ꢀ

(

m),ꢀ1298ꢀ(s),ꢀ1263ꢀ(w),ꢀ1204ꢀ(w),ꢀ1003ꢀ(w),ꢀ921ꢀ(w),ꢀ846ꢀ(w),ꢀ602ꢀ(w).ꢀFound:ꢀC,ꢀ29.7;ꢀH,ꢀ4.2;ꢀN,ꢀ25.9.ꢀ

3

-1

1 8 14 6 2

Calc.ꢀforꢀCu C H N S :ꢀC,ꢀ29.85;ꢀH,ꢀ4.4;ꢀN,ꢀ26.1%.ꢀUV-Vis:ꢀλmax/nmꢀ(DMSO)ꢀ313(ε/dm ꢀmol ꢀcm ꢀ17ꢀ

+

9

=

t

00),ꢀ350ꢀ(sh),ꢀ481ꢀ(6ꢀ700)ꢀandꢀ540ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ(Calc.)ꢀ322.0097ꢀ(322.0096)ꢀ{Mꢀ+ꢀH }.ꢀHPLC:ꢀR ꢀ

+

8 14 6 2

ꢀ6.43ꢀmin,ꢀ>ꢀ95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC H N S ꢀ+ꢀH] ꢀ=ꢀ322.0090ꢀ(calc.),ꢀ322.0085ꢀ(found).ꢀ

-

1

DataꢀforꢀCu(26):ꢀYield:15%.ꢀIR:ꢀνmax/cm ꢀ3292ꢀ(w),ꢀ3146ꢀ(w),ꢀ1626ꢀ(w),ꢀ1541ꢀ(m),ꢀ1518ꢀ(w),ꢀ1479ꢀ(m),ꢀ

1

445ꢀ(m),ꢀ1391ꢀ(m),ꢀ1335ꢀ(w),ꢀ1217ꢀ(m),ꢀ1190ꢀ(m),ꢀ1152ꢀ(m),ꢀ1107ꢀ(w),ꢀ1061ꢀ(w),ꢀ951ꢀ(w),ꢀ779ꢀ(w),ꢀ

-

1

7

27ꢀ(w),ꢀ592ꢀ(m).ꢀRamanꢀ(532.00ꢀnm):ꢀνmax/cm ꢀꢀ2127ꢀ(w),ꢀ2075ꢀ(w),ꢀ1537ꢀ(m),ꢀ1515ꢀ(m),ꢀ1480ꢀ(w),ꢀ

1

335ꢀ(m),ꢀ1249ꢀ(m),ꢀ1025ꢀ(w),ꢀ794ꢀ(w),ꢀ604ꢀ(m).ꢀFound:ꢀC,ꢀ29.7;ꢀH,ꢀ4.3;ꢀN,ꢀ26.0.ꢀCalc.ꢀforꢀ

3

-1

1 8 14 6 2

Cu C H N S :ꢀC,ꢀ29.85;ꢀH,ꢀ4.4;ꢀN,ꢀ26.1%.ꢀUV-Vis:ꢀλmax/nmꢀ(DMSO)ꢀ312(ε/dm ꢀmol ꢀcm ꢀ11ꢀ300),ꢀ350ꢀ

+

(

sh),ꢀ480ꢀ(4ꢀ100)ꢀandꢀ530ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ(Calc.)ꢀ322.0135ꢀ(322.0096)ꢀ{Mꢀ+ꢀH }.ꢀHPLC:ꢀR

t

ꢀ=ꢀ5.36ꢀ

+

min,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC H N S ꢀ+ꢀH] ꢀ=ꢀ322.0090ꢀ(calc.),ꢀ322.0080ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ0.53.ꢀ

8 14 6 2

ꢀ

28

Page 29 of 38

Dalton Transactions

-

1

View Article Online

DOI: 10.1039/C7DT02008B

DataꢀforꢀCu(27):ꢀYield:ꢀ43%.ꢀIR:ꢀνmax/cm ꢀ3360ꢀ(w),ꢀ3285ꢀ(w),ꢀ3129ꢀ(w),ꢀ3129ꢀ(w),ꢀ2931ꢀ(w),ꢀ1632ꢀ(m),ꢀ

1

585ꢀ(w),ꢀ1537ꢀ(m),ꢀ1493ꢀ(m),ꢀ1456ꢀ(s),ꢀ1389ꢀ(s),ꢀ1321ꢀ(m),ꢀ1300ꢀ(s),ꢀ1258ꢀ(s),ꢀ1240ꢀ(s),ꢀ1213ꢀ(s),ꢀ1169ꢀ

(

s),ꢀ1115ꢀ(s),ꢀ1061ꢀ(m),ꢀ957ꢀ(m),ꢀ910ꢀ(m),ꢀ847ꢀ(w),ꢀ795ꢀ(m),ꢀ706ꢀ(m),ꢀ631ꢀ(m),ꢀ598ꢀ(m),ꢀ536ꢀ(s),ꢀ517ꢀ(s),ꢀ

-

1

4

96ꢀ(s),ꢀ428ꢀ(s).ꢀRamanꢀ(532.00ꢀnm):ꢀνmax/cm ꢀ1590ꢀ(w),ꢀ1536ꢀ(w),ꢀ1497ꢀ(w),ꢀ1320ꢀ(w),ꢀ1302ꢀ(w),ꢀ

o

1

247ꢀ(w),ꢀ633ꢀ(w),ꢀ598ꢀ(w).ꢀMp:ꢀ>220ꢀ Cꢀ(decomp.).ꢀFound:ꢀC,ꢀ32.4;ꢀH,ꢀ4.8;ꢀN,ꢀ24.9.ꢀCalc.ꢀforꢀ

3

-1

1 9 16 6 2

Cu C H N S :ꢀC,ꢀ32.2;ꢀH,ꢀ4.8;ꢀN,ꢀ25.0%.ꢀUV-Vis:ꢀλmax/nmꢀ(DMSO)ꢀ314ꢀ(ε/dm ꢀmol ꢀcm ꢀ23ꢀ400),ꢀ350ꢀ

+

(

sh),ꢀ484ꢀ(8ꢀ800)ꢀandꢀ530ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ(Calc.)ꢀ336.0247ꢀ(336.00252)ꢀ{Mꢀ+ꢀH }.ꢀHPLC:ꢀR

t

ꢀ=ꢀ11.96ꢀ

+

min,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC H N S ꢀ+ꢀH] ꢀ=ꢀ336.0247ꢀ(calc.),ꢀ336.0247ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ0.57.ꢀ

9 16 6 2

-

1

DataꢀforꢀCu(28):ꢀYield:ꢀ43%.ꢀIR:ꢀνmax/cm ꢀ3347ꢀ(w),ꢀ3157ꢀ(w),ꢀ2963ꢀ(w),ꢀ1628ꢀ(w),ꢀ1587ꢀ(w),ꢀ1537ꢀ(m),ꢀ

1

506ꢀ(m),ꢀ1476ꢀ(m),ꢀ1445ꢀ(m),ꢀ1416ꢀ(s),ꢀ1366ꢀ(m),ꢀ1335ꢀ(m),ꢀ1310ꢀ(m),ꢀ1221ꢀ(s),ꢀ1184ꢀ(m),ꢀ1142ꢀ(m),ꢀ

-

1

061ꢀ(m),ꢀ955ꢀ(w),ꢀ787ꢀ(m),ꢀ689ꢀ(m),ꢀ597ꢀ(m),ꢀ419ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀꢀ3329ꢀ(w),ꢀ1584ꢀ

(

w),ꢀ1533ꢀ(s),ꢀ1504ꢀ(m),ꢀ1479ꢀ(s),ꢀ1371ꢀ(m),ꢀ1352ꢀ(m),ꢀ1330ꢀ(m),ꢀ1248ꢀ(m),ꢀ1230ꢀ(m),ꢀ1172ꢀ(m),ꢀ1030ꢀ

o

w),ꢀ999ꢀ(w),ꢀ957ꢀ(w),ꢀ787ꢀ(w),ꢀ602ꢀ(m),ꢀ338ꢀ(m),ꢀ317ꢀ(w),ꢀ261ꢀ(w),ꢀ221ꢀ(w),ꢀ157ꢀ(m).ꢀMp:ꢀ>210ꢀ Cꢀ

1 9 16 6 2

decomposed).ꢀFound:ꢀC,ꢀ32.3;ꢀH,ꢀ4.8;ꢀN,ꢀ24.85.ꢀCalc.ꢀforꢀCu C H N S :ꢀC,ꢀ32.2;ꢀH,ꢀ4.8;ꢀN,ꢀ25.0%.ꢀUV-

3

-1

Vis:ꢀλmax/nmꢀ(DMSO)ꢀ314ꢀ(ε/dm ꢀmol ꢀcm ꢀ25ꢀ500),ꢀ350ꢀ(sh),ꢀ480ꢀ(8ꢀ200)ꢀandꢀ530ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ

+

(

Calc.)ꢀ336.0287ꢀ(336.0252)ꢀ{Mꢀ+ꢀH }.ꢀHPLC:ꢀR

t

ꢀ=ꢀ8.12ꢀmin,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC

9 16 6 2

H N S ꢀ+ꢀH] ꢀ

=

ꢀ336.0247ꢀ(calc.),ꢀ336.0287ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ0.47.ꢀ

-

1

DataꢀforꢀCu(29):ꢀYield:ꢀ54%.ꢀIR:ꢀνmax/cm ꢀ3281ꢀ(w),ꢀ3119ꢀ(w),ꢀ1643ꢀ(w),ꢀ1622ꢀ(w),ꢀ1541ꢀ(m),ꢀ1504ꢀ(m),ꢀ

1

9

441ꢀ(s),ꢀ1350ꢀ(m),ꢀ1281ꢀ(m),ꢀ1240ꢀ(m),ꢀ1215ꢀ(s),ꢀ1186ꢀ(s),ꢀ1150ꢀ(m),ꢀ1101ꢀ(m),ꢀ1076ꢀ(m),ꢀ1028ꢀ(m),ꢀ

-

1

43ꢀ(m),ꢀ800ꢀ(m),ꢀ719ꢀ(m),ꢀ638ꢀ(m),ꢀ615ꢀ(m)ꢀ471ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ1582ꢀ(w),ꢀ1532ꢀ

(

m),ꢀ1497ꢀ(s),ꢀ1433ꢀ(w),ꢀ1380ꢀ(w),ꢀ1321ꢀ(w),ꢀ1281ꢀ(m),ꢀ1238ꢀ(m),ꢀ1190ꢀ(w),ꢀ1031ꢀ(w),ꢀ987ꢀ(w),ꢀ943ꢀ(w),ꢀ

8

48ꢀ(w),ꢀ801ꢀ(w),ꢀ702ꢀ(w),ꢀ610ꢀ(w),ꢀ395ꢀ(w),ꢀ351ꢀ(w),ꢀ320ꢀ(w),ꢀ139ꢀ(w).ꢀFound:ꢀC,ꢀ29.8;ꢀH,ꢀ4.5;ꢀN,ꢀ26.0.ꢀ

3

-1

1 8 14 6 2

Calc.ꢀforꢀCu C H N S :ꢀC,ꢀ29.85;ꢀH,ꢀ4.4;ꢀN,ꢀ26.1%.ꢀUV-Vis:ꢀλmax/nmꢀ(DMSO)ꢀ314ꢀ(ε/dm ꢀmol ꢀcm ꢀ16ꢀ

+

6

=

0

t

00),ꢀ350ꢀ(sh),ꢀ478ꢀ(5ꢀ200)ꢀandꢀ520ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ(Calc.)ꢀ322.0092ꢀ(322.0096)ꢀ{Mꢀ+ꢀH }.ꢀHPLC:ꢀR ꢀ

+

ꢀ4.96ꢀmin,ꢀ>95%;ꢀESI ꢀMS:ꢀm/zꢀforꢀ[CuC

8

14 6 2

H N S ꢀ+ꢀH] ꢀ=ꢀ322.0090ꢀ(calc.),ꢀ322.0093ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ

.53.ꢀ

-

1

DataꢀforꢀCu(30):ꢀYield:ꢀ34%.ꢀIR:ꢀνmax/cm ꢀ3374ꢀ(w),ꢀ3339ꢀ(m),ꢀ3152ꢀ(w),ꢀ2972ꢀ(w),ꢀ1630ꢀ(m),ꢀ1593ꢀ(w),ꢀ

1

539ꢀ(w),ꢀ1508ꢀ(m),ꢀ1479ꢀ(m),ꢀ1437ꢀ(s),ꢀ1381ꢀ(m),ꢀ1329ꢀ(m),ꢀ1304ꢀ(m),ꢀ1261ꢀ(w),ꢀ1236ꢀ(m),ꢀ1211ꢀ(s),ꢀ

173ꢀ(m),ꢀ1142ꢀ(m),ꢀ1103ꢀ(m),ꢀ1032ꢀ(m),ꢀ951ꢀ(m),ꢀ841ꢀ(w),ꢀ820ꢀ(w),ꢀ802ꢀ(w),ꢀ731ꢀ(m),ꢀ600ꢀ(m),ꢀ540ꢀ

-

1

(

m),ꢀ505ꢀ(s),ꢀ484ꢀ(s),ꢀ415ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm ꢀ1591ꢀ(w),ꢀ1533ꢀ(s),ꢀ1482ꢀ(m),ꢀ1460ꢀ(m),ꢀ

374ꢀ(w),ꢀ1355ꢀ(w),ꢀ1324ꢀ(m),ꢀ1299ꢀ(m),ꢀ1228ꢀ(m),ꢀ1171ꢀ(w),ꢀ1033ꢀ(m),ꢀ951ꢀ(w),ꢀ840ꢀ(w),ꢀ778ꢀ(w),ꢀ602ꢀ

w),ꢀ336ꢀ(w),ꢀ265ꢀ(w),ꢀ165ꢀ(m).ꢀElementalꢀanalysis:ꢀC,ꢀ32.3;ꢀH,ꢀ4.8;ꢀN,ꢀ24.9.ꢀCalc.ꢀforꢀCu :ꢀC,ꢀ

2.2;ꢀH,ꢀ4.8;ꢀN,ꢀ25.0%.ꢀUV-Vis:ꢀλmax/nmꢀ(DMSO)ꢀ314ꢀ(ε/dm ꢀmol ꢀcm ꢀ22ꢀ100),ꢀ350ꢀ(sh),ꢀ480ꢀ(7ꢀ100)ꢀ

1

(

1 9 16 6 2

C H N S

3

-1

3

+

andꢀ530ꢀ(sh).ꢀMSꢀ(ESI):ꢀm/zꢀ(Calc.)ꢀ336.0297ꢀ(336.0252)ꢀ{Mꢀ+ꢀH }.ꢀHPLC:ꢀR

t

ꢀ=ꢀ7.68ꢀmin,ꢀ>95%;ꢀESI ꢀMS:ꢀ

+

m/zꢀforꢀ[CuC

9

H

16

N

6

S

2

ꢀ+ꢀH] ꢀ=ꢀ336.0247ꢀ(calc.),ꢀ336.0248ꢀ(found);ꢀTLC:ꢀRfꢀ=ꢀ0.54ꢀ

SynthesisꢀofꢀZincꢀComplexesꢀ

Exemplarꢀzincꢀbis(thiosemicarbazonate)ꢀcomplexesꢀlistedꢀbelowꢀwereꢀsynthesisedꢀbyꢀaꢀgenericꢀ

methodꢀasꢀfollows:ꢀtheꢀbis(thiosemicarbazone)ꢀpro-ligandꢀ(0.6ꢀmmol)ꢀwasꢀaddedꢀtoꢀethanolꢀ(15ꢀmL).ꢀ

Anhydrousꢀzincꢀ(II)ꢀacetateꢀ(0.128ꢀg,ꢀ0.7ꢀmmol)ꢀwasꢀaddedꢀtoꢀtheꢀsuspension.ꢀTheꢀsuspensionꢀwasꢀ

thenꢀbroughtꢀtoꢀrefluxꢀforꢀ2ꢀh.ꢀTheꢀyellow-orangeꢀprecipitateꢀwasꢀrecoveredꢀviaꢀfiltration,ꢀwashedꢀ

withꢀethanolꢀ(1ꢀxꢀ15ꢀmL)ꢀandꢀdiethylꢀetherꢀ(5ꢀxꢀ15ꢀmL).ꢀTheꢀsolidꢀwasꢀdriedꢀinꢀair.ꢀ

ꢀ

29

Article Doi

Copper complexes with dissymmetrically substituted bis(thiosemicarbazone) ligands as a basis for PET radiopharmaceuticals: Control of redox potential and lipophilicity

DOI: 10.1039/c7dt02008b

Source and publish data:

Authors:

Article abstract of DOI:10.1039/c7dt02008b

Full text of DOI:10.1039/c7dt02008b

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