该【Copper(I) azide and copper(I) cyanate π-complexes 2021 Evgeny Goreshnik 】是由【可卿】上传分享，文档一共【11】页，该文档可以免费在线阅读，需要了解更多关于【Copper(I) azide and copper(I) cyanate π-complexes 2021 Evgeny Goreshnik 】的内容，可以使用淘豆网的站内搜索功能，选择自己适合的文档，以下文字是截取该文章内的部分文字，如需要获得完整电子版，请下载此文档到您的设备，方便您编辑和打印。:.
JournalofCoordinationChemistry
ISSN:(Print)(Online)Journalhomepage:
Copper(I)azideandcopper(I)cyanateπ-complexes
EvgenyGoreshnik
Tocitethisarticle:EvgenyGoreshnik(2021)Copper(I)azideandcopper(I)cyanateπ-complexes,
JournalofCoordinationChemistry,74:11,1919-1928,DOI:.1938013
Tolinktothisarticle:/
©2021TheAuthor(s).PublishedbyInforma
UKLimited,tradingasTaylor&Francis
Group
Publishedonline:12Jun2021.
Submityourarticletothisjournal
Articleviews:140
Viewrelatedarticles
ViewCrossmarkdata
FullTerms&Conditionsofaccessandusecanbefoundat
?journalCode=gcoo20:.
JOURNALOFCOORDINATIONCHEMISTRY
2021,,,1919–1928
/
Copper(I)azideandcopper(I)cyanatep-complexes
EvgenyGoreshnik
DepartmentofInorganicChemistryandTechnology,JozefStefanInstitute,Ljubljana,Slovenia
ABSTRACTARTICLEHISTORY
ElectrochemicalalternatingcurrentsynthesisstartingfromanReceived4January2021
ethanolsolutionofCuSO45H2OandallylamineinthepresenceAccepted7May2021
ofsolidsodiumazideresultsinformationofCu[C3H5NH2]
trigonal-pyramidalcoordinationenvironmentofbothcrystallo-KEYWORDS
graphicallyindependentcopperionsconsistsoftheC¼C-bondCopper;coordination
ofoneallylaminemolecule,theNH-groupofanotherligandmoi-chemistry;azide;cyanate;
2p-interaction
etyandtwoN-atomsofthetwoazide-
terminalcoordinationmodeandtheotherisal3-1,1,3-bridge.
Thebridgingfunctionofbothallylamineandazideleadstofor-
mationofacomplicated3--
natedC¼C-bondandastrongshiftofthesmodeintheRaman
spectrumconfirmeffectiveCu–(C¼C)
routestartingfromamethanolsolutionofCu(BF4)26H2Ointhe
presenceofsolidpotassiumcyanateresultsinformationof
Cu[C3H5NH2]-anionisboundtocopperthrough
C¼C-bondfromanotherligandcompletethetrigonal-planar
¼C-
bondandtheshiftofs(C¼C)modeintheRamanspectrumare
similartothoseintheazidederivative.
Cuþwith3d10electronconfigurationinteractswithmultiplecarbon-carbonbonds.
Copper--
atedhydrocarbonsappeartobemoresuitableligandsforstudyofcopper(I)
CONTACTEvgenyGoreshnikevgeny.******@,
JozefStefanInstitute,Jamova39,1000Ljubljana,Slovenia.
ß2021TheAuthor(s).PublishedbyInformaUKLimited,tradingasTaylor&FrancisGroup
ThisisanOpenAccessarticledistributedunderthetermsoftheCreativeCommonsAttribution-NonCommercial-NoDerivatives
License(-nc-nd//),whichpermitsnon-commercialre-use,distribution,andreproductionin
anymedium,providedtheoriginalworkisproperlycited,andisnotaltered,transformed,:.
p-(I)p-complexeswerefocusedoncatalytic
[1,2],biological[3]properties,andcrystalengineeringofmetal-organicframeworks
[4].Allylamineattractsattentionasapotentialligandwithvariouscoordinationabil-
[5]containingCucenterandanallylamineskel-
-raystructurally
exploredcopper(I)cyanoacetate[6]andcopper(I)bromide-sulfate[7]p-complexes
-
niummoiety,whichdiffersmarkedlyinitscoordinationabilitiesfromneutralallyl-
(exceptthecaseofweaklyboundones)
usuallyoccurincopper(I)p-complexesandstronglyinfluencethecopper-olefininter-
–(C¼C)interactionstabilizestheCuþoxidationstateandallowsisola-
tionofcomplexesunknowninfreestatesalts,suchasCuClO4[8],CuBF4[8],CuNO3
[9],Cu(HCOO)[10],CuOOCCF3[10],CuSO3NH2[11,12],Cu(CF3COCHCOCF3)[13],
Cu2SiF6[14],CuPF6[15,16],Cu2SO4[10],CuHSO4[17],andCuSO3CF3[18].Besidewell-
studiedderivativesofcopper(I)chlorideandbromide,p-complexesofcopper(I)iodide
[19],cyanide[20],organicanions–forexample,benzenesulfonate[21]andtrifluoro-
methanesulfonate[22],weaklybondedanionssuchas(CH)B[23],SbF[24],
6546
Al(OC(CF))][25],andsomeotherswerealsoreported.
334
Theazide,despitethepotentialexplosivenessofitsderivatives,wasusedinthe
preparationofenvironmentallyfriendly,high-energymaterialsbasedonnitrogen-rich
andoxygen-freesystems[26,27].Itsabilityforvariouscoordinationmodeswasused
inengineeringcoordinationandsupramolecularcopper-organicnetworks[28],poly-
mericcomplexes[29],andcluster-supportedmetal-organicframeworks[30].Tothe
bestofourknowledgecopper(I)azidep-complexesareunknown(despitethefact
thatCuN3itselfiswellestablished[31]).
CoppercomplexescontainingisoelectronicandgeometricallysimilartoNand
3
cyanatearelessdiscovered[32–34].,
theonlyoneexampleof120entriesfoundinCCDC[5]relatestoCu(I)oxidationstate.
Incontrasttoazide,cyanateinstructurallystudiedcomplexesusuallyisterminalora
1,1-l2-bridgeinbondingwithmetalcenter(s)throughnitrogenonly.
Tofillthisgap,copper(I)azideandcopper(I)cyanatep-complexeswithallylamine
of1:1compositionweresynthesizedandcharacterizedbysingle-crystalX-raydiffrac-
.
Sodiumazide(Acrosorganics,99þ%),potassiumcyanate(Fluka,purum),coppersul-
fatepentahydrate(ZorkaSabac,.),coppertetrafluoroboratehexahydrate(AlfaSabac,.),coppertetrafluoroboratehexahydrate(Alfa
Aesar,98%),allylamine(AlfaAesar,98þ%),andethanol(CarloErba,)wereusedas
-qualitysinglecrystalsofCu[C3H5NH2]N3(1)wereobtainedbyalternat-
ingcurrentelectrochemicalsynthesis[35]
CuSO45H2O(,)andallylamine(,11mmol)wasplacedina
smalltest-tubeandsolidsodiumazide(,)
waswrappedintoaspiralof:.
JOURNALOFCOORDINATIONCHEMISTRY1921
.
12
FormulaCu(C13H5NH2)N3Cu(C3H5NH2)NCO
M(gmol)
T(K)150150
CrystalsystemMonoclinicMonoclinic
SpacegroupP21/nP21/n
a(Å)(3)(6)
b(Å)(6)(3)
c(Å)(5)(7)
b()(4)(7)
V(Å3)(9)(7)
Z84
F(000)6563283
qcalcd(gcm1)
l(mm)
Radiation,wavelengthMoKa,,
hmin/hmax(),,
FinalR1/wR2[I>2r(I)]
wR2(alldata)
Goodness-of-–3
(eÅ),,
,immersedintheabove-men-
,
colorlessprismaticcrystalsofCu[C3H5NH2]
waycrystalsofCu[C3H5NH2]NCO(2)(,
)wasplacedinasmalltest-tubeandadropofwaterwasadded.
Cu(BF4)26H2O(,)andallylamine(,11mmol)weredissolvedin
ethanol,andthedeep-bluesolutionwasdecantedintoatest-
wereinsertedincork,immersedinthesolutionandalternatingcurrentof50Hzvolt-
,andthetest-tubewasplaced
inarefrigeratorandstoredat18
afteroneweek.
Single-crystaldatawerecollectedonaGeminiAdiffractometerequippedwithan
treatedusingtheCrysAlisProsoftwaresuiteprogrampackage[36].Analyticalabsorp-
-space
algorithmbySHELXT[37]implementedinOlexcrystallographicsoftware[38].
StructurerefinementswereperformedwiththeSHELXL-2014[39]
ofhydrogensfromamino-groupswerelocalizedonadifferenceFouriermapandtheir
toallylgroupswereplacedonidealpositionsandrefinedasridingatomswithrelative
[40]and
(1)and2047213(2)containthesupplementarycrystallo-
.
,orbyemailingdata_******@,orby:.
[C3H5NH2]
aredrawnat70%:(i)1=2þx,1=2y,1=2þz,(ii)1x,1y,z,
(iii)x,y,1þz,(iv)1=2þx,1=2y,1=2þz.
contactingtheCambridgeCrystallographicDataCentre,12UnionRoad,Cambridge
CB21EZ,UK;Fax:þ441223336033.
ARamanspectrumwasmeasuredwithaHoribaJobin-YvonLabRAMHRspectrometer
-nmexcitationlineofaHe–
decompositionofthesample,adensityfilterwasappliedtoreducethepowerofthe
long-
,
thespectrometerwascalibratedusingaSipolycrystallineplateasastandardwitha
air,thecrystalusedforXRDexperimentwasdismountedfromthepintothewatch
andtransferredtotheRamanspectrometer.
Therearetwocrystallographicallyindependentcopperionsinthestructureof
Cu[C3H5NH2]-pyramidalenvironmentconsisting
ofNazide,Namine,andtheC¼CgroupinthebasalplaneandanotherNazideatthe
apicalposition(Figure1).TheCu–(2)(17)Å,
andtheCu–(2)(2)Åintheequatorialplane
(2)(2)Å:.
JOURNALOFCOORDINATIONCHEMISTRY1923
TheDewar-Chatt-Duncansonconcept[41,42]indicatesthattheCu–(C¼C)bond
consistsofa(Cuþ–L)r-donorcomponentduetooverlappingoftheoccupiedolefin
p-orbitalandtheunoccupied4s0orbitaloftheCuþ,andaCuþ–(C¼C)p-dativecom-
ponent,arisingfromelectrondensityback-donationfromthe3d10Cuþorbitalstothe
unoccupiedantibondingorbitaloftheC¼-componentcausesashort-
eningoftheCu–mdistance(misthemidpointoftheC¼C-bond),whereasthe
p-dativecomponent,beingstronglydependentonolefinorientationinthemetal
coordinationsphere,causesalengtheningoftheC¼C-,ashorteningof
theCu–mdistanceandalengtheningoftheC¼Cdistance,togetherwithanincreas-
ingoftheC–Cu–Cangle,areusefuldataforanevaluationoftheCu–(C¼C)inter-
–(C¼C)interactionresultsintransformationofthe
Cucoordinationpolyhedronfromtetrahedraltotrigonalpyramidal,withtheolefin
grouplocatedinthebasalplane,andalengtheningofthedistancebetweenthe
metalionandtheaxialligand.
-pyramidalgeometry[43].
Inbothcoordinationpolyhedra,themetalionsdeviateslightlyfromthemeanequa-
torialplanetowardtheapicalside(ÅforCu1andCu2,respectively),and
theC¼
geometryofcopper(I)istypicalforaneffectivep-–mdistan-
ÅÅforCu2andmediumelongationofthecoordinated
o
Copper(I) azide and copper(I) cyanate π-complexes 2021 Evgeny Goreshnik 来自淘豆网www.taodocs.com转载请标明出处.