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INTERNATIONALJOURNALOFAPPLIEDENGINEERINGRESEARCH,DINDIGUL

Volume1,No2,2010
Copyright2010AllrightsreservedIntegratedPublishingAssociation
RESEARCHARTICLE ISSN 09764259
222
Synthesisandstructuralinvestigationsofcoordinationcompoundsof
palladium(II)with5methyluracil
AnshuSrivastava
1
,Gupta.D.C
2
1AppliedscienceandHumanitiesDepartment,KanpurInstituteofTechnology,Kanpur
2Departmentofchemistry,AtarraP.G.CollegeAtarra,Banda
mily13@rediffmail.com
ABSTRACT
A new series of mixed ligand coordination compound of Palladium having square planner
stereochemistry, around the metal ion with the general formula [PdL
2
Cl
2
] where L= 5 methyl
uracilhave been isolated inthesolidstatebythe interactionofwiththeaforesaid ligands.The
synthesized coordination compound has been characterized by elemental analysis, electrical
conductance, magnetic measurements,molecularweightdetermination,electronspinresonance,
infraredspectralmeasurementsandNMRstudies.Asquareplannerstructurehasbeenproposed
for square planner complex. It is observed that:The synthesized compound is light brown in
colour. It is non hygroscopic.It is soluble in DMF, DMSO, slightly soluble in acetonitrile and
sparingly soluble inothersolvents.Itisthermallystableanddoesnotdecomposedupto260
0
C.
Thecompoundhasd8configuration.Thecomplexhasantitumoractivity.
Keywords:Coordinationchemistry,5methyluracil,palladium,Antitumoractivity
Introduction
Considerable attention has focused on 5 methyl uracil palladium complex and their
rearrangementmechanismsbecausetheyarepostulatedintermediatesforcertainhomogeneously
catalyzed reactions. Coordination of a reactive organic moiety to the transition metal often
allows a configuration to be assumed which leads to stereoselectivity in the reaction
products .Presumable, studies of these complexes will lead to a greater understanding of the
factors which influence these stereo selective reactions. Recent investigations have shown that
PMR spectroscopy is a facile diagnostic tool for the elucidation of the mechanisms by which
differentconfigurationsofthiscomplexmayinterconvert.
The substitution reaction of the palladium (II) complex has been reviewed in the past. Some
recentliteraturesconcerningthekinetics,thermodynamicandstructuralfeaturesarepresentedin
chapterIandIIwiththetitles.Ligandsubstitutionreactionsofsquareplanner Palladium(II)
complex occur with the retention of configuration. The kinetics of substitutions reactions of
squareplannercomplex(equation1)followsatwotermratelaw,
MA
3
X+Y

MA
3
Y+X

(M=Pd
II
) 1
Rate={k
1
+k
2
[Y

}}[MA
3
X]
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wherek
1
isthefirstorderrateconstantandk
2
,asecondorderrateconstant,and[Y

]represents
the concentration of the entering ligand. Both routes are thought to involve an associative (A)
mechanism. The kinetics of solvent exchange and displacement by monovented ligands on cis
[Pd (L
2
)(Cl)
2
] L = 5methyl uracil complexes have provided a clear cut example of ligand
dissociation as the dominant step in substitutions reactions of square planner complexes . It is
thereforethoughtworthwhiletosynthesizedandcharacterized
8
complexesarePalladiumwith
5fluorouraciland5methyluracil.
2.Experimental methods
2.1 MaterialsandMethods
Uraciland5methyluracilwereprocuredfromAldrichChemicalCompany,U.S.A.andusedas
such.PdCl
2
5fluoro uracil and 5methyl uracil were obtained from TOKYO KASEI Organic
Chemical,JapanandB.D.HEngland.Distilledwaterusedinalltheoperations.
2.1.1 Preparationoftheligand,Uracil
The classical and primary synthetic route to uracil from Formalaceticacid (made in situ from
malicacid)andureainsulphuricacidisstillimportant(1).Somealternativesynthesesusemalic
acid, urea, and PPA (2) or maleic/ fumaric acid, urea, and poly phosphoric acid (PPA) (2).The
reactionof formyl acetatewiththioureaisconvenientforthesynthesisof2thiouracil. Another
main synthesis involvesthereactionofureaswithketoestersdiketeneoracidanhydride(3).
Orotic acids are synthesized from oxaloacetate and ureas in the presence of hydrogen chloride
via ring transformation of hydantoin into the uracil ring system. Treatment of the easily
obtainable2thiouracilwithchloroaceticacidfollowedbyacidhydrolysisorbyoxidationwith
dimethylsulphoxide(DMSO)inconc.Sulphuricacid(4)arealternativepathways.1,3dimethyl
uracil istransformedwithureainethanolicsodiumethoxideintouracil.Somemorerecenturacil
syntheses start with propanoic acid and urea in PPA (or conc. sulfuric acid and benzene as
solvent. A broad choices of hetrocondensed uracils are easily and generally accessible from
heterocyclic enamino esters and isocyanides.(5).the mixed urea intermediate is smoothly
cyclizedwith5%aq.NaOHthewholeprocedurecabbecarriedoutinaonestepreaction,when
pyridineservesassolventandbasecatalyst fortheringclosure.Thecondensationofureawith
protected keto esters gives 6 or (di)substituted uracils (6) by means of retro Diels Alder
splitting, nonbornene condensed tricyclic dihydrouracils , accessible from aminononbornene
carboxylic acid and 1,1 carbonyl di imidazole ,afford ,upon heating ,uracils (7) in good yield
Substituted uracils are obtained from imido esters, isocyanates, and malononitrile. Similarly N
substitutedNcyanoacetylureascyclizeinanalkalinemedium.Hetrocondenseduracilsareeasily
accessiblefromacyllactones,lactums,andthiolactones(8),andheterocyclicenaminoesters
especially .The later gives a broad range of novel types of condensed systems. With the aid of
the hexamethyldisilazane trimethylchlorosilane (9) (HMDS/TMSCl) technique or the use of
NaOHandhalosugars,respectively,simpleapproacheshavebeendevelopedtoobtainunusual
nucleosides[10].
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2.2Preparationofthecoordinationcompound
2.2.1 Preparationof[Pd(5 methylUracil)
2
Cl
2
]
A mixture of PdCl
2
(500mg) and ligand 5Methyl Uracil (1gm) in water and methanol (50ml)
was refluxed at 80
0
C 67 hours until it become a clear yellowish colour solution .This volume
wasreducedto5mlandtreatedwithmethanol.Theresultinggraywhitecrystalswerecollected
andwashedwellwithethanolandacetone.Theanalyticaldataisgiveninthetable3.4
TheGeneralreactionforthepreparationofcoordinationcompoundofpalladiumisasfollows:
CH
3
OH
[Pd(Cl)
2
]+ 2L[Pd(L
2
)(Cl)
2
]
H
2
O
whereL=5MethylUracil
Carbon, hydrogen, nitrogen and oxygen present in the investigated complex were estimated
micro analytically. For the estimation of Palladium as Palladium 1, 2, 3 benzotriazole, the
synthesizedcompoundsolutionweremixedwith10mlof2M.aceticacidsodiumacetatebuffer
and 5ml of 4% EDTA solution.. Then 2.5 % acetic acid was added with shaking. Digest the
solutionbetween60
0
C90
0
C,are20minutes.Theresultingprecipitatewasfiltered(G3),washed
several times with very dilute HCl (1:100), finally with distilled water and dried to a constant
weightat110
0
C.MolecularweightdeterminationofthesynthesizedcomplexwasmadebyRasts
method.Magnetic susceptibility measurementwas madeatroomtemperaturebyGouy method.
A magnetic field strength of 8500 gauss was employed. The apparatus was calibrated using
cobalt mercurythiocyanateHg[Co(NCS)
4
].Thediamagneticcorrectionswerecomputedusing
Pascals constant. For calculation of effective magnetic moments, following equation has been
used.
Effectivemagneticmoments(eff)=2.84(x
m
corr
.T)
1/2
where T = temperature in absolute scale , and x
m
corr
= corrected molar susceptibility
ConductanceswasmeasuredinanalyticalgradeMethanolusingdiptypecellwiththehelpofa
PhilipsConductivity Bridge. An infraredspectrum(4000600cm1)oftheuncoordinatedligand
and the synthesized complex was recorded in nujol mulls supported between sodium chloride
platex(rocksaltregion)onPerkinElmerSpectrum(RXI)spectrometer.
1
HNMR spectraof the synthesized compound will be recordedon AC 300F spectrometer
(300MHz) using TMS as an internal standard. Electron spin resonance spectra of the complex
wererecordedatroomtemperatureonaVariumE3spectrometerusingpowderedsampleatthe
microwarefrequency9.53GHz.Thegvalueswerecalculatedusingthegivenequation.
G= 714.44X (GHz)
H(G)
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where (GHz) = microwave frequency in GHz at which sample operated, and H(G) = field in
Gauss forthesample. Thecomplexesare non hygroscopicand stableatroomtemperature.The
solubilityofcomplexisgivenintable3.5.TheyaresolubleinDMFandDMSO,slightlysoluble
inacetonitrileandinsolubleinotherorganicsolvent.Theydonotpossesssharpmeltingpoints.
3.ResultandDiscussion
The magnetic values of the synthesized complex measured at room temperature. The magnetic
moment values of the complex are zero. Hence, they are diamagnetic. The square planar
geometry of the complex is evident from their diamagnetic nature. The Analytical and physical
dataoftheligandanditsmetalcomplex aregivenintable1.
Table1:AnalyticalDataoftheComplexes
Compound %Pd
Found
(Calc.)
%C
Found
(Calc.)
%H
Found
(Calc.)
%N
Found
(Calc.)
%Cl
Found
(Calc.)
%F
Found
(Calc.)
[Pd(5
Methyl
Uracil)
2
Cl
2
]
24.34
(24.56)
21.94
(21.46)
1.37
(1.36)
12.80
(12.81)
16.23
(16.26)
8.68
(8.60)
The value of molar conductance are in the range 0.0520.058
1
cm
1
mol
1
suggesting non
electrolyte nature of the synthesized complex. The details of infrared spectral bands of the
synthesizedcomplexcontainingcoordinated5methyluracilpossesses3possibledonorsites
(i)Twocyclicnitrogenand
(ii)oxygenoftheketonicgroupinringrespectively.
Out of these two the cyclic nitrogen of ring system is supposed to be involved in coordination
through the Nitrogen atom. In the IR spectra of the synthesized complex of 5methyl uracil
studied here ,the IR frequency of cyclic nitrogenof ring has been changed, therebysuggesting
that the cyclic nitrogen has been participate in the coordination. In the IR spectra of both the
complexes with 5 methyl uracil the bands at 640cm
1
suffered a lower shift of 640cm
1,
indicating that metal nitrogen coordination present in the synthesized compound. Hambright et
al. confirmed metal nitrogen coordination in the large series of the complex of Zn(II), Cu(II),
Ni(II),Co(II) and Pd(II). Recently, Pennell and coworkers have experimentally confirmed the
metal nitrogencoordinationinthecomplexes.
The electronic spectral bands of the complexes (table II) were assigned according to the
literature.
Table2:ImportantIRspectralbandsandtheirassignments
Sl.No. Compound
MC
(cm
1
)
Me(sym)
(cm
1
)
1 [(PEt
3
)
2
Pd(CH
3
)X]
X=Br
SCN
CN
510
526
502
1162
1180
1161
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2 [(PEt
3
)
2
Pd(CH
3
)
2
] 491,457 1164
3 [(AsEt
3
)
2
Pd(CH
3
)
2
] 498,479 1152,1124
4 [(PPh
3
)
2
Pd(CH
3
)
2
] 529,482 1129
5 [(bipyr)Pd(CH
3
)
2
] 534,522
6 [MeS(CH
2
)
2
(SMe)Pd(CH
3
)
2
] 525,512 1168
Themolecularorbitalapproachwasusedtoexplainthestructureofsquareplanarcomplexesof
the d
8
elements. The metal orbitals involved in bonding in square planer complexes are the
ndz
2
, ndx
2
y
2
, (n+1)P
x
and (n+1)P
y
. Nevertheless, judging from the values of the overlap
integrals,nd
x2y2
(n+1)s,(n+1)P
x
and(n+1)P
y
accountformostofthebonds,andndz
2
makes
onlyaminorcontributionoforbitalsoftheligands.
The correlation of the bands observed in the electronic spectra for the studied complexes with
thoseof[M(CN)
4
]
2
[M=Pd
II
]promptedustoassumethefollowingassignments
1
A
1g
1
A
2g
[b
2g
(*) b
1g
(*) ], (dd):
1
A
1g
1
B
1g
[b
2g
(*) a
1g
(*) ],
(dd)
1
A
1g
1
E
g
[e
g
(*) b
1g
(*)], (dd)
1
A
1g
1
B
1u
[b
2g
(*)
a
2u
(*)],
( C.T)
1
A
1g
1
E
u
[e
g
(*)] a
2u
(*)],(C.T).
The relation between the bands in the present complex and the described for the typical
complexes [M (CN)
4
]
2
leads to the conclusion that all the new complex has the same square
planergeometry.
The analytical data and all the evidences presented above suggest the formulation of this
complex as. The mixed ligand complex [PdL
2
Cl
2
] where (L = 5methyl uracil), have been
prepared by the interaction of parent compound [PdCl
2
] with ligand. The complex is
characterizedbyelementalanalysis,magneticmeasurementelectronspinresonanceandinfrared
spectralstudiescontainingPd(II)d
8
configuration.
4.Conclusion
Thecomplexisdiamagneticsuggestingsquareplannergeometry.Itisobservedthat
(i)Thesynthesizedcompoundislightyellowincolour.
(ii)Itisnonhygroscopic.
(iii)Itissoluble inDMF,DMSO,slightly soluble inacetonitrileandsparingly soluble inother
solvents.
(iv)Itisthermallystableanddonotdecomposedupto260
0
C.
(v)Thecompoundhaved
8
configuration.
(vi)Thecomplexhasantitumoractivity.
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Acknowledgement
Dr.Anshu is grateful tothe Department of chemistry Atarra P.G.Colllege Atarra Banda.
TheauthorswishtothankCDRI,Lucknow,India,forproviding AnalyticaldataandDr.
AvadheshChandraNigamforkindcooperation.
5.References
1. Beyer.H.,andStehwein,D.ArchPharm.,Berl.286(1953) pp13.
2. V.Pechmann.H.(a)Ber.dtschchem...Gees.21(1988)2751(b)28(189)1624
(c)withWedekind,E.28(1895)1693(d)withBurkard,E.33(1900)3590(e)withW.
Bauer,42(1909)659(f)JustusLiebigsAnninChem.262(1891)pp 265.
3. McGee.,M.A.,Newbold,G.T.,Redpth,J.Spring,JF.S.J.Chem.Soc.(1960) pp
2536.
4. Ardnt,F(a)withLoewe,L.AndTarlanAkon,A.Chem.Abstr.42(1948)8190
(b)withLoewe,LandErgener,L.43(1949) pp579.
5. SpanishPat.219,066(1955)[Chem.Abstr.50(1956)pp9449.