Krishnankutty, K.

Thankarajan, N.

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erR ~ erRN~"'~ - ro' NIN,~o /0:Y''' yro "I",II I (JI IR=3-methyl, ~-methyl,2- methoxY,3-mtthoxyor4.- methoxyionic in benzeneandhencemay be representedas[Fe(LhCI3J.Any deprotonation,of the ligandsduringcom-plex formationis ruled out since no hydrogenchloridecouldbe detectedin the effluentvapoursfromthereactionflask. It is thusevidentthatthephenylazonaphtholsactasneutralligands.Additionof aqueouscausticsodaor mineralacid resultsinthe decompositionof the complexesgiving theligandsin almostquantitativeyield.Hydroxyazo compoundsexhibit azo-hydrazonetautomerism2.In the caseof o-hydroxyazocom-pounds,the tautomersexist as stronglyhydrogenbondedstructures!(I) and (II), the latter predo-minating3• In accordancewith structure(II), theinfrared spectraof I-phenylazo-2-naphtholsshowa bandat 1610+10em-I,whichmaybe attributedto the hydrogen bonded carbonyl group4. Inkeeping with the hydrogen bonded N-H ...Ostructure,theX-H (X=N or 0) bandaround2400cm-1is broadenedalmostout of recognition.TheX-H bandremainsunalteredin themetalcomplexesalso,showingthat the hydrogenbond persistsinthe compIexed state. This is furthercorroboratedby the fact that like the free ligands,the metalcomplexesalso do not form any ammoniumsaltwith dry ammoniain benzene. In view of thehydrogenbonded structure of the coordinatedligands,theymaybeexpectedto actonlyasmono-dentateligands. SincetheC=O stretchingfrequencyof theligandsremainsundepressedinthe complexes,it is evident that the oxygen atom does notcoordinates.It appears,therefore,that it is one of thenitrogenatomsof the ligandthat is bondedto theReceived20 September1976;aCCtpted8 October1976N. THANKARAJAN& K. KRISHNANKUTTYDepartmentof Chemistry,University of Calicut, CalicutNOT ES[Found:C, 62·74;H, 4·20;Ti, 6·71. [(C6H4(0)CHOJ2Ti[(C6HshPOrJ2requiresC, 62'99; H, 4·14; Ti.6·63%J.Other compoundswerepreparedsimilarly.References1. SCHUMANN,H., JUTZ!, P., ROTH, A. & SCHAUER, E.,]. organometal.Chem.,10 (1967),71.2. 1SSLEIB,K. & WALTHER, B., ]. organometal.Chem.,10(1967),177.3. RIDENOUR,R. E. & FLAGG,E. E., J. organometal.Chem.,16 (1969),393.4. FELD, R., The organic chemistryof titanium (Butter-worths, London), 1965,140.5. PANDIT, S. K., NERLEKAR,P. G. & GUPTA,J., Indian J.Chem.,5 (1967),121.6. GREENWOOD,N. N., ]. chem.Soc.• (1960),1130.AdductsofI-Phenylazo-2-naphtholswithFe(III)ChlorideI-Phenylazo-2-naphtholsform adductsof thetypeFeCI3.L2with iron(III) chloride.Infrared spectralstudiesshowthattheligandsactasmonodentate,co-ordinatingthroughtheira-nitrogenatoms. Thecom-plexesarenon-ionicin benzene.METAL complexesof azocompoundshavereceiv-ed considerableattentionin the past in viewof theirapplicationasstabledye-stuffs'. However,attentionwasdevotedmostlyto stablemetalcom-plexes,havinggreatlyenhancedfastnessproperties.Thus, whereasthe literatureis extensiveon 0,0'-dihydroxyazocompoundsand their metalchelates,very few reportsexist on labile complexesof 0-monohydroxyazocompounds1•Hencethis investi-gationon complexesof I-phenylazo-2-naphthols(I)with iron(III) chloridewas undertaken.Six o-hydroxyazoligands used by us formedlustrousblack crystals with anhydrousiron(III)chloridein boilingdry benzene.Thesecomplexesare non-hygroscopicand could be recrystallizedseveraltimesfrom benzene.The complexeshavethecompositionFeCI3.L2(Table1). Thesearenon----NFeCILigand8·1715·9074·50(8·48)(16'11)(75·68)8·578·0056(8,16)8'1 )5·456 3· 235 8- 8·04 27·7 4 727-451 27 77·80 8·004 678C H--59·584·39(59·51)(4·08)60·0-46-6 7526'823 0Ligand (I) m.p. (OC*)(R=)H2103-Methyl042-Methoxy195oxy4-Methoxy 185*Melt with decomposition;yield about 80%.tCalculatedvalues are given in parentheses.Calculatedvalues for isomericcompoundsare not mentioned.TABLE 1- ANALYTICALDATA OF THE COMPLEXESFound (%)t465H OHI I(0) OHC6H4-C =NCH2CH-R(R =Hand CH3)(I)H HI I(0) OHC6H4-C =N-(CH2)u-N =C-C6H40H(n =2 and 3)(II)The reactionswerecarriedout underanhydrousconditionsas the resultingSchiff base complexesof U(V) are moisture-sensitive.Uranium penta-ethoxidewas preparedas describedby Gilmanct al.2, and distilled beforeuse [Found: U, 51,31;OC2H5,48·42.Calc.for U(OC2H5)5:U,51·40;OC2H5,48·60%].Schiff bases of the type OHC6H4CH=NXOH[X= -CH2-CH2- or -CH2CH(CH3)J were prepared3by refluxingthe stoichiometricamountsof salicyl-aldehydeand 2-hydroxy-ethylamineor 2-hydroxy-1-propylaminefor severalhoursand thendistillingthe productsbeforeuse. Schiffbasesof the typeOHC6H4CH=N(CH2)nN=CHC6H40H(where n=2or 3) werepreparedby heatingthe stoichiometricamountsof salicylaldehydeand ethylenediamineor 1,3-propylenediaminein absoluteethanolandthe productswererecrystallized.Preparation of the comPlexes- To a solutionofuraniumpenta-ethoxidein anhydrousbenzene(,.....,60ml) was addedthe requisiteamountof the Schiffbase. After refluxingthereactionmixture,ethanol-benzeneazeotropeand the excessof the solventwere fractionatedoff. The resulting brown orbrownish-redsolids were separatedand analysed(Table I).Exchange reactionsof Schiff basecomPlexeswitht-butanol- The Schiffbasecomplexesandt-butanolweremixedin anhydrousbenzene.After refluxingthereactionmixture,ethanol-benzeneazeotropewasremovedand the excessbenzenedistilledat a highreflux ratio. The resultingbrownish-orangesolidswere separatedand analysed(Table 2). The re-actionswere successfulin the caseof complexescontaining terminal ethoxy groups. Complexeshavingonlybridgingethoxygroupsdidnotundergoexchangereactionsevenin the presenceof excesst-butanol.The dibasictridentateSchiffbases(SBH2)reactwith uranium penta-ethoxidein the ratios 1:1,1:2and2:3to giveproductsof thetypesU(OC2Hs)3(SB), U(OC2H5)(SB)2and U2(OC2Hs)4(SB)3respec-tively with the liberationof 2, 4 and 6 molesofethanol. The dibasic tetradentateSchiff bases(SlBlH2)alsoreactwith uraniumpenta-ethoxideinthe ratios I: 1, 1:2 and 2:3 to give productsU(OC2H5)3(SlBl),U(OC2H5)(SlBl)2 and U2(OC2Hs)4(S3Bl)3with the liberationof 2, 4 and 6 molesofethanolrespectively.INDIAN J. CHEM., VOL. lSA, MAY 1977having the donor systemHO-N-OH and dibasic1:etradentateligandsof the type SlB1H2(II) havingthe donor systemHO-N-N-OH.Sch basecomplexesof uranium(V)of the typesU(OCH5).(SB), U(OC.H5)(SB)., U.(OC.H5).(SBbU(OC.H5).(SlB1), U(OC.H5)(SlB1handU.(OC.H5).(SlB1)"have eensynthesizedbythereactionsof uranium(V)ethox'ewiththedibasictridentate(SBH.)anddibasictetradntate(SlBIH.) Schiffbasesin 1:1, 1:2 and2:3 olar ratios (metal:ligand). On the basis ofelemetal analysis,molecularweightandIR spectraldata,probablestructuresfor the compoundshavebeen indicated.The exchangereactionsof U(V)comp xescontainingterminalethoxygroupsin thepresece of excesst-butanolhavealso beencarriedout a d the resultsshowthat the terminalethoxygroup are labile in natureand undergoexchangereactins.R. G. VlJAY & J. P. TANDONDepartment of Chemistry, University of RajasthanJ aipur 302004R~ceived10 May 1976;accepted23 December19761. PRicE. R., The chemistryof syntheticdyes, edited by. Venkataraman, Vol. 3 (Academic Press, Newark), 1970.2. WI EY, R. H. & JARBDE (Jr), C. H., j. Am. chem.Soc.,7 (1955),403.3. VE KATARAMAN, K., The chemistryof syntheticdyes,1. I (Academic Press, New York), 1952,446.4. BA SIGNANA, P. & COGROSSI, C., Tetrahedron,20 (1964),2 61.5. LA PERT, M. F., j. chem.Soc., (1961),817.6. SA MA, B. D., RAY, K. R., SIEVERS, R. E. & BAILAR( r), J. C., ]. Am. chem.Soc.,86 (1964),14.7. SA MA, B. D. & BAILAR (Jr), ]. C., ]. Am. chem.Soc.,7 (1955),5476.8. BE LAMY, L. ]., The infraredspectraof complexmolecules( ethuen & Co., London), 1964,268, 271.Uranlum(V)Complexesof DibasicTridentate& TetradentateSchiffBasesIN n earlier communicationlwe have reportedur nium(V) complexesof monobasicbidentateSchi basesderivedfromsalicylaldehydeandalkyl-amins. However,reactionsof dibasictridentateor te radentateSchiffbaseswith uranium(V)etho-xide have not been investigatedearlier. Werepor here the reactionsof uranium(V) ethoxidewith ibasictridentateligandsof the typeSBH2(1)Referencesmetal. The spectrumof each complexresemblesclosel that of the correspondingligand, exceptthat mediumintensityband of the ligandsat1595 5 cm-l (attributablepartly to aromaticskeletI vibrationsand partly to vC=N6 becomesmore tensein thespectraof the complexes,prob-ably eto coordinationby theazomethinenitrogenatom of the ligand. Unlike vC=O, vC=N isgener ly unaffectedon coordination7, althoughvariatonin theintensityof absorptionof thelatteris obsrved8•The authorsthank the CSIR, New Delhi, forsuppoting the investigation.466j !'Ilil

Adducts of 1-Phenylazo-2-naphthols with Fe(III) Chloride

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Adducts of 1-Phenylazo-2-naphthols with Fe(III) Chloride

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