ExperimentX

SynthesisofMetalAcetylacetonates

PreparationofTris(2,4pentanedionato)chromium(III)

AdaptedfromZ.Szafran;R.M.Pike;M.M.Singh;MicroscaleInorganic Chemistry, Wiley:

NewYork,1991.

Introduction
Coordinationcompounds(orcomplexes)consistofacentralatomsurroundedbyvarious
otheratoms,ions,orsmallmolecules(calledligands).Thereisonlyatenuousdistinctionatbest
betweencoordinationcomplexesandmolecularcompounds.Themostcommondividinglineis
thatcomplexeshavemoreligandsthanthecentralatomoxidationnumber.Silicontetrafluoride,
SiF4,wouldnotbeacoordination compound,as therearefourligands ontheSi(IV). But
[SiF6]2wouldbeconsideredacoordinationcompoundastherearesixligandsontheSi(IV).In
this experiment, the coordination compound tris(2,4pentanedionato)chromium(III) is
synthesizedandcharacterized.
Inthe presence ofbase, 2,4pentanedione, acacH, readily loses a protonto form the
acetylacetonateanion,acac,asshown.

CH3 CH3 CH3 CH3

C=O C=O C=O C O-

H
H
C H C : H C H C
H C=O C=O CO C O

CH3 CH3 CH3 CH3

acacH acac

Hydrogenatomsoncarbonatomsthatareadjacenttocarbonyl,C==O,groupsarerelatively
acidic. Thethreedifferentrepresentationsoftheacetylacetonateanionarecalledresonance
forms(theydifferonlyinthelocationoftheelectrons).
 2 CH141Labs:Expt.X

In this experiment, the basic solution needed to remove the proton from the acac is
providedbygeneratingammonia,NH3,viathehydrolysisofurea:
(NH2)2C=O+H2O 2NH3+CO2
Inwater,ammoniaactsasabase:
NH3+H2O +(aq)+OH(aq)
NH4
Acetylacetonateisanexampleofabidentate(bitwo,dentteeth)ligand,sinceitcanbondtoa
metalviabothoxygenatoms.Ligandsofthistypearealsooftencalledchelating(chelosclaw)
ligands.Threeacacligandsarethereforeneededtocompletetheoctahedralcoordinationabout
thecentralmetalion,givingformula[M(acac) 3]n+.Thestructureofthechromium(III)complex
isshownintheFigure. Sincetheouterpartofthecomplexconsistsoforganicgroups,most
metalacetylacetonatesarehydrophobic,andinsolubleinwater.

acac StructureofCr(acac) 3

acac Cr
MW349.3g/mol

acac

PreparationofTris(2,4pentanedionato)chromium(III)
SafetyRecommendations
Chromium(III)chloridehexahydrate. Chromiumcompoundsareconsideredmildly
toxic.Chromium(III)compounds,ingeneral,havelittletoxicity.Certainofthem,however,have
beenlistedascarcinogensbytheEPA.
2,4Pentanedione. (Alsoknownasacetylacetone.)Thecompoundisamildirritantto
theskinandmucousmembranes.Itisaflammableliquid.
Urea.Ureaisnotgenerallyconsidereddangerousandisclassifiedasadiuretic.

ChemicalData
Compound FW Amount mmol bp(oC) mp(oC) Density
CrCl3.6H2O 266.4 130mg 0.49 83 1.760
 3 CH141Labs:Expt.X

Urea 60.06500mg 8.3 133135 1.335

2,4Pentanedione 100.120.4mL 3.84 140 23 0.975

RequiredEquipment
Magneticstirringhotplate,10mLErlenmeyerflask,microwatchglass,magneticstirring
bar,10mLgraduatedcylinder,2mLsyringe,evaporatingdish,Goochfunnel,filterpaper.

TimeRequiredforExperiment:2.5h.

ExperimentalProcedure1
In a 10mL Erlenmeyer flask fitted with a microwatch glass cover and containing a
magneticstirringbar,place2.0mLofdistilledwater(graduatedcylinder)and130mg(0.49
mmol)ofchromium(III)chloridehexahydrate.Whenthechromiumcomplexhasdissolved,add
500mg(8.3mmol)ofureaand0.40mL(3.8mmol)ofacetylacetone.AlargeexcessofacacH
isused,asithelpsthereactiongotocompletion.

NOTE:TheacacHshouldbedispensedintheHOOD.

ClamptheErlenmeyerflaskinanevaporatingdishofboilingwatersetonamagneticstirringhot
plate.Heatthemixture,withstirring,for~1h.Astheureareleasesammoniaandthesolution
becomesbasic,deepmarooncrystalswillbegintoform.Theseformasacrustatthesurfaceof
thereactionmixture.
IsolationofProduct
Coolthereactionflasktoroomtemperature.Collectthecrystallineproductbysuctionfiltration
usingaGoochfunnel.Washthecrystalswiththree0.20mLportionsofdistilledwater.Drythe
productonapieceoffilterpaper,anddeterminethepercentageyield.
CharacterizationofProduct
Takethemeltingpointofthematerial.Iftimeisavailable,theinstructormaysuggestthatyou
obtaintheIR(infrared)spectrumoftheproductandofpure2,4pentanedioneusingthediffuse
reflectanceaccessoryandtheFourierTransformInfraredSpectrometer(FTIR)onthesecond
floor.

References
1.Fernelius,W.C.;Blanch,J.E.Inorg.Syn.1957,5,130.
2.Charles,R.G.Inorg.Syn.1963,7,183.
 4 CH141Labs:Expt.X

3.Fackler,J.P.,Jr.,"MetalKetoenolateComplexes"inProgressinInorganicChemistry,F.A.Cotton,Ed.,Interscience:
NewYork,1966,Vol.7,p.471.