Aggarwal, R. C.

Narang, K. K.

English

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6. ROSENBLUM, M., SANTER, J. O. & HAVELLS, W. G.,J. Am. chem. Soc., 85 (1963), 1450.7. COTTON,F. A. & \VILKINSON, G. VI'., Advanced inorganicchemistry (Iriterscience, New York), 1968, 564.8. ANDREWS, L. J. & KEEFER, R. M., J. Am. chem. Soc.,73 (1951), 4169.9. SAVITSKIV, A. V. & SVRKIN, YA. K., Chern. Abstr., 55(1961), 27246i.10. GRADDON,D. P., An introduction to coordination chemis-try (Pergamon Press, London), 1968, 132.11. WILKINSON, G. & BIRMINGHAM, J. M., J. Am. chem.Soc., 76 (1954), 4281.12. WOODWARD,R. B., J. Am. chem, Soc., 74 (1952) 2125.Base Adducts of Bis(N-acetyl-N' -benzoyl-hydrazinato )nickel(II)R. C. AGGARWAL& K. K. NARANGChemistry Department, Banaras Hindu UniversityVaranasi 221005Received 1 March 1975; accepted 12 May 1975The complexes Ni(ABHh.2Py, Ni(ABH)2.BH and Ni(ABHh.IBH, where ABH2=N-acetyl-N'-benzoylhydra-zine, Py = pyridine, BH = N-benzoylhydrazine, andIBH = N-isopropylidene,N'-benzoylhydrazine, havebeen prepared and characterized on the basis of ele-mental analyses, conductometric and electronic and IRdata. The complexes are octahedral, and their Iigand-metal charge transfer bands appear in the blue regton,The Ilgand field parameters show an appreciable co-valency in the BH- and Py-complexes. ABH- acts asa bidentate Iigand.POLYMERIC Ni(II) complex, Ni(ABH)2.2H20(C),has been reported- to be formed by the reactionof N-acetyl-N'-benzoylhydrazine (ABH2) with metalions like that of acetyl acetone which exists inketo-enol forms. However, pyridine and otheramines break the polymeric nature of metal acetylacetonates and yield the mixed ligand com-plexes-, the formation of which has been utilizedfor the solvent extraction of metal ions", In thepresent investigation the complexes of C withpyridine (Py), N-benzoylhydra~me (BH) and N-isopropylidene-N'-benzoylhydrazme (IBH) have beenprepared with a view to understanding the behaviourof these bases towards C.The compounds C, BH and IBH were preparedand purified as described earlier--s. Ni(II) in thecomplexes was estimated gravimetrically and thehydrazine content estimated volumetrically by KI03after acid hydrolysis by the standard proceduress.Procedure - Ni (ABH) 2.2Py was prepared by addingPy (BDH grade) slowly to the suspension of C inEtOH till the compound was dissolved. The solventand the unreacted base were removed under reducedpressure. The residue was washed several times withether and the sticky mass dried in vacuo. Thecomplexes Ni(ABH)2.BH and Ni(ABH)2.IBH wereprepared by mixing BH or IBH with C in 2:1molar ratios in EtOH and heated till a clearsolution was obtained. The residue left afterthe removal of EtOH was washed in the case ofBH-complex with hot benzene till free from un-reacted BH. As the IBH -complex was solubleNOTESin benzene its benzene solution was repeatedlyshaken with water to free from unreacted IBH.Benzene was distilled and the residue dried invacuo.Ni(ABH)2.2Py: m.p. 114-16° (Found: Ni, 10·41;N2H4, 11·45. Ni(ABHh2Py requires Ni, 10·32;N2H4• 11·38%). Ni(ABH).BH: m.p, 116-18° (Found:Ni, 10·58; N2H4, 17'60°. Ni(ABHhBH, requires.Ni, 10·50; N2H4, 17·48%), Ni(ABH)2.IBH: m.p.134-36° (Found: Ni, 10·50; N2H4• 15·59. Ni(ABHh.IBH, requires Ni, 10·00; N2H4, 16·32%).For conductometric titrations, C was suspendedin EtOH and dilute solutions of BH and IBH wereslowly added. The contents were stirred and con-ductance of the resulting mixture was measured ona Phillips magic eye conductivity bridge (model4494). The spectrophotometric titrations were j er-formed by mixing the weighed amounts of C andBH in different molar ratios in EtOH at a constantvolume, and the absorbance recorded at 372 nm ona Perkin-Elmer spectrophotometer model 227.Despite the higher molar ratios used for the pre-paration of the complexes, the analysis of theisolated products show 1:2 (C:Py) and 1:1 (C:BHor IBH) compositions, which show the monodentat echaracter of Py and bidentate character of BH andIBH6,7. The complexes are either green or yellowishgreen and do not have sharp rn.ps. They areinsoluble in water but soluble in organic solventslike EtOH, benzene, CHCl3, CCl4 etc. The conduc-tornetric and spectrophotometric plots show a 1:1composition of C: BH and C: IBH complexes.The electronic spectral of Ni(ABH)2.2H20 showthree bands in the visible region, due to d-d transi-tions, at 350, 610 and 875 nm for octahedral Ni(II)complexes. Ni(ABHhBH and Ni(ABHh2Py showbands at 600, 950 and 600, 900 nm respectivelybesides the intense CT-band in the blue region havingEmax228and 240 litre mole? cmr! respectively. Theligand field parameters calculated using two d-dbands'' and three d-d banes? for octahedral Ni(II}complexes show 22·7,25'4 and 41·6% covalency (~o).for Ni(ABH)2.2H20, Ni(ABHhBH and Ni(ABH)2'2Py respectively. The nephelauxetic ratios (~) aregenerally observed between 0·60 and 0·80 forpredominantly covalent complexes-". The ~ valueof Py-cornplex (0·584) is fairly close to the .lowerrange of ~ values showing a high covalency 1ll thecomplex. Solubility behaviour of the three com-plexes also indicate a high covalent character of Py-complex. Ni(ABH)2.2H20 is insoluble in all organicsolvents, Ni(ABHh.BH is soluble in EtOH and veryslightly soluble in CHC13 while Ni(ABHh2Py ishighly soluble in EtOH, CHC13 and benzene.The IR spectra show vNH for Py-cornplex at 3175-and 3070 cm'+, for BH-complex at 3300, 3175 and3065 cm'", and for IBH-complex at 3275, 3150 and3045 em-s. Coordination of )C=O group of ABH-in the complexes is apparent from the appearanceof 1620 crrr? band while that of Pv ring nitrogenfrom 1600 cm-I band--. Coordination of BH6 from'C=O and NH2, and of IBH from )C=O and<C=N-groups can be inferred from the observed IRhands at 1650 (C = 0 stretching) 1120 (NH2 rocking),1005 and 990 (NH2 wagging) in BH-complex, and28:>c 70o:~ 50"0j 50c 73 pomp~ 40.91~ 30Ii;0;520co;310INDIAN J. CHEM., VOL. 14A, APRIL 1976at 1645 (C = 0 stretching) and 1635 crrr+ (C = Nstretching) in IBH-complex.The authors are thankful to the Heads of theChemistry Departments of Lucknow University,Lucknow and Banaras Hindu University, Varanasi,for laboratory facilities.References1. AGGARWAL,R. C. & NARANG,K. K., Inorg. chim, Acta, 7(1973)' 651.2. HASHAGEN, J. T. & FACKLER, J. P., J. Am. chem, Soc.,87 (1965), 2821.3. WALKER, W. R. & LI, N. C., J. inorg. nucl. cu-«, 27(1965), 411; IRVING, H. & EDINGTON, D. N., J. inorg.nucl. Chem., 27 (1965), 1359.4. CURTIUS,T. & STRUVE,C. T., J. prakt. Chem., 50 (1894),285, 30S.5. VOGEL, A. 1., A text book of quantitative inorganic analysis,3rd ed. (Longmans, Green, London), 1962.6. AGGARWAL,R. C. & NARANG, K. K., Indian J. Chem.,(accepted). .7. ISSA, R. M., EL-SHAZLY, M. F. & ISKANDER, M. F., Z.anorg. allg. cu«; 354 (1967), 98.8. LEVER, A. B. P., J. chem, Educ., 45 (1968), 711.9. DRAGO, R. S., Physical methods in inorganic chemistry(Rei-i hold, New York), 1965.10. HARE, C. R., Spectroscopy and structure of metal chelates,edited by K. Nakamoto (John Wiley, New York), 1968,86.11. GILL, N. S., NUTTAL, R. H., SCAIFE, D. E. & SHARP,D. W. A., J. inorg. nucl, cu«; 18 (1961), 79.Polarographic Studies on D- Glucuronic AcidM. BHADURI, F. H. CHOWDHURY*& N. B. FOUZDERtDepartment of Applied Chemistry, Rajshahi UniversityRajshahi, BangladeshReceived 29 March 1975; accepted 17 June 1975The polarographic behaviour of D-~lucuronic acidhas been investigated using tetramethylarrnnoniumiodide as the supporting electrolyte. Three waves areobserved. One of the waves is ascribed to the reductionof hydrogen ion while the succeeding two waves havebeen explained on the basis of the formation ofgtucuronctactone which is reduced in two steps.Glucuronic acid itself is not reduced at the d.m.e,THE polarographic reduction of D-~lucuronic acidwas studied by Ishidate and Shimozawa- whoobserved that the polarographic wave does notappear immediately after dissolution of the ~cidbut it appears after a long interval of time.Thibert et al.2,s obtained reproducible polarographicwaves of n-glucuronolactone in potassium chlorideand lithium chloride solutions. The waves havebeen found to disappear at high PH and decreasein magnitude on heating. The effect of PH andphosphate ion on the reduction of D-glucuronol-act one has also been reported". In the presentnote, the general polarographic behaviour ofn-zlucuronic acid has been described.Pure D-glucuronic acid was obtained from L.Light & Co. (England). It was stored over anhydrous*Member, UGC, Bangladesh.tCorrespondence should be addressed to this author atChemistry Department, Imperial College of Science andTechnology, London SW 7 2AY, UK.284Fig. 1 - Polarogram for the reduction of D-glucuronic acidin tetramethyl ammonium iodide solutionmagnesium sulphate in a vacuum dessicator andused without further purification. Tetramethyl-ammonium iodide (TMAI) and tetramethylammo-nium hydroxide were BDH reagents.A general purpose Cambridge polarograph inconjunction with a Cambridge spot galvanometerwas used for current-potential measurements. Thed.m.e. had the following characteristics: t = 2·97see, m = 1·93 uiglsec in distilled water at a mercurycolumn height of 66 em at 0·0 V open ircuit poten-tial. PH measurements were carried out using aCambridge bench type PH meter. Working solutionswere made up in 0·2.1\:{ tetramethylammoniumiodide (TMAI) solution. Freshly prepared gelatin(0·02%) was used for suppressing the maxima.Solutions were thermostated at 30° and deoxygenat-ed by bubbling a continuous stream of hydrogen gasthrough the solution prior to each measurement.Buffer solutions were prepared by mixing 0·2Mtetramethylammonium hydroxide solution.Three distinct waves were observed for the re-duction of D-glucuronic acid in TMAI solution (Fig.1). The first wave disappears in alkaline mediaand its half-wave potential agrees with the valueobtained for the hydrogen discharge wave for aceticacid and propionic acid determined separately.Contrary to earlier reports-, preliminary observationsshowed that all the waves appear immediately afterthe dissolution of the glucuronic acid. However,magnitude of the first wave decreases with time,while those of the other two increase with time.After 3 hr no further change in wave-heights wasobserved. This behaviour is probably due to theslow conversion of the free acid to the correspondinglactone, the equilibrium between the two formsbeing attained in about 3 hr. Hence, in all thesubsequent experiments sufficient time was allowedfor the establishment of this equilibrium. Thesecond and the third waves are diffusion-controlledas shown by the linear dependence of their limitingcurrents on the square-root of the height of themercury column. Diffusion controlled characterof the waves was further substantiated by theirdependence on temperature and the temperaturecoefficient of the limiting current being about0·87% per degree. Logarithmic analysis- showedthat both the waves are irreversible in nature.

Base Adducts of Bis(N-acetyl-N'–benzoyl-hydrazinato)nickel(II)

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Base Adducts of Bis(N-acetyl-N'–benzoyl-hydrazinato)nickel(II)

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