INDIAN J. CHEM., VOL. HA, FEBRUARY 1976

refiuxed in benzene and product isolated as in (b),yield 3·8 g (80% of theory) [Found: Ti, 10·60; C,64,68; H, 4·40. {[(CloH902hTi(OC8Hu)J20 requiresTi, 10·10; C, 65,05; H, 4·50%}. The compound issoluble in benzene.

(d) Reaction between dicyclohexanoxy dichloro-titanium and benzoylacetone- Dicyclohexanoxydichlorotitanium" (3·17 g; 0·01 mole) and benzoyl-acetone (4'05 g; 0·025 mole) were mixed in benzene(50 ml) and dry ammonia bubbled in the cold forseveral minutes. The precipitated ammoniumchloride was filtered off, the filtrate evaporated underreduced pressure, washed with hexane and driedin vacuo at 60°; yield 3·8 g (80% of theory). Thecompound was found identical with the productobtained in (c). Other compounds were preparedsimilarly and were found to be identical with theproducts obtained from cyclohexyl titanate and theligand.

References1. TANDON, S. G. & BHATTACHARYA,S. C., J. chem, Eugng

Data, 7 (1962), 553.2. TANDON, S. G. & BHURA, D. c.. J. chem. Engng Data, 16

(1971), 106; 14 (1969), 278.3. TANDON, S. G. & coworkers, J. chem . Engng Data, 12

(1967), 143; 16 (1971), 371; 16 (1971),495; 17 (1972),248, 257.

4. TANDON,S. G. & coworkers, J. Indian chem. Soc., 46 (1969),831; 48 (1971), 397, 753.

5. RIEDEL, A., J. radioanalyt . Chem., 13 (1973), 125.6. NESMEYANOV,A. ;S-., Selected works in organic chemistry

(Pergamon Press, Oxford), 1963, 816.7. RAZUVAEV,G. A., BOBINOVA,L. M. & ETLIS, U. S., Tetra-

hedron, 6 (1959), 154.8. GOPINATHAN,C. & GUPTA, J., Indian J. cso«, 5 (1967)'

167.9. FAY, R. C. & LOWRY, R. )/., Lnorg : Chem., 9 (1970), 2048.

4-Aminoantipyrine Complexes of Fe(II)

C. PAvITHRAN & P. T. JOSEPHIndustrial Testing & Research Laboratorv

Tr ivandru m 19 .and

C. P. PRABHAKARANDepartment of Chemistry, University of Ker ala

Tri vaudru m 1

Received 30 November 1974; accepted 31 March 1975

4 - Amino - 2,3 - dimethyl - 1 - phenyl - 5 - pyrazolone(4-aminoantipyrine, L) complexes of Fe(lI) havingthe compositions Fe(CIO')2.6L, FeCI2.2L, FeBr2.2L andFeI2.2L have been prepared and their IR spectra,magnetic susceptibilities and conductance behaviourInvesttgated. IR spectra show the unidentate bondingbehaviour of the li~and through its carbonyl oxygenatom. All the complexes are of the htgh-spln type.The perchlorate complex behaves as a 1 : 2 electrolytein nitrobenzene and methanol. The halo complexesbehave as non-conductors in nitrobenzene but dis-sociate considerably in methanol. The magneticsusceptibilities along with the electronic spectrasuggest a regular octahedral structure for the per-chlorate complex and distorted octahedral structuresfor the halo complexes.

134

THE donor properties of 2,3-dimethyl-l-phenyl-5-pyrazolone (antipyrine) have been extensively

investigated-+. Its 4-amino derivative also hasbeen used as a ligand". Unlike antipyrine, 4-amino-antipyrine has two potential donor sites in aminonitrogen and carbonyl oxygen. We report here thepreparation and physicochemical properties of somenew complexes of 4-aminoantipyrine with Fe (II)perchlorate, chloride, bromide and iodide.

Hydrated Fe(II) halides were prepared by dissolv-ing iron powder in solutions of the respective hydro-gen halides, and crystallizing the salts from theaqueous solution. Fe(II) perchlorate was preparedby dissolving iron powder in perchloric acid.4-Aminoantipyrine was a BDH reagent of LRgrade. All the solvents used were purified bystandard methods". The Fe(II) salt solutions wereshaken with iron powder and filtered in nitrogenatmosphere before using them for the preparationof the complexes.

Fe(LhCI2 was prepared by mixing ethanolicsolutions of FeCI2.6H20 (1·5 g) and the ligand (8·5 g)and evaporating the resulting solution to a syrupymass. The mass was washed with benzene to re-move excess ligand and the residue dissolved in theminimum amount of ethanol. The solution wasconcentrated by passing nitrogen when pale browncrystals were formed. These were washed withbenzene and dried in a current of nitrogen. Fe(L)2Iqand Fe(L)6(CI04)2 were prepared as above. Fe(LhBr;precipitated when ethanolic solutions of FeBr •.2HqOand 4-aminoantipyrine were mixed and concen-trated. The crystals were washed with ethanolfollowed by benzene and then dried. All the opera-tions were carried out in an atmosphere of nitrogen.Dry solid complexes are quite stable towards aerialoxidation.

Iron in the perchlorate complex was estimatedgravimetrically as Fe20a after decomposing thecomplex with conc. HNOa. Iron in the other com-ple:,~s was estimated grav~metrically as Fe20a afterigniting the complexes m air. Perchlorate wasdetermined by Kurz's method". The halides wereestimated by Volhard's method. The analyticalresults are given in Table 1.

IR spectra of the ligand and the complexes (nujolmull) in the region 600-4000 crrr-' were recorded on aPerkin-Elmer infrared spectrophotometer model 257.

TABLE 1 - COLOURAND ANALYTICALDATA OFFe(II) COMPLEXES

Complex" Colour Found (Calc.)--------:'Ifetal Anion

% 0/10

Fe(L).(ClO.h Deep brown 3'81 4·73

Fe(LhCI2 vene« ish(3-79) (4-81)10·74 13·13

Fe (L)2Br2 Brown(10'47) (13-29)

8'89 25'61

Fe(L)2I2 do(8'98) (25'68)7'87 35·29

(7-80) (35-44)

"L = 4-aminoantipyrine.

The spectra in the region 200-600 crrr" were obtain-ed on a Beckman spectrophotometer model 12.Conductance measurements were carried out ona Systronics direct reading conductivity meterusing a dip type cell having a cell constant of 0·571crrr '. Magnetic susceptibilities of the complexeswere determined by Gouy method using Hg[Co(CNS)4Jas the calibrant. The electronic spectra of thecomplexes in the solid state were recorded usingmull technique on a Unicam SP 700A recordingspectrophotometer.

The molar conductance values of the perchloratecomplex in nitrobenzene and methanol are 48·97and 190·1 ohrrr ' ern- mole+ respectively indicatingit to be a 1: 2 electrolytes. The chloro, bromo andiodo complexes behave as non-electrolytes in nitro-benzene showing ;\.'If of 8·29, 13·09 and 12·86 ohm-1ern- mole-' respectively. However, in methanolthe conductance values of the halo complexes arein the range 123·7-152·9 ohrrr ! ern" mole:". Thisshows that the halo complexes dissociate consider-ably in a coordinating solvent like methanol.

A comparison of the IR spectral bands of the freeligand and the complexes shows that the IR fre-quencies of the amino group do not undergo anyappreciable change on complexation. On the otherhand the carbonyl stretching frequency observedat 1635 crrr'! in the free ligand is shifted to 1600 cm-1in the spectra of complexes. This indicates thatcarbonyl oxygen acts as a donor atom in the C0m-plexes and that the amino group is not involved inbonding. A medium to strong intensity bandappearing in the range 470-480 cm-1 in the spectraof the complexes and absent in the ligand spectrumcan be attributed tentatively to the metal-oxygenstretching frequency". Similarly, a band observedin the region 310-320 cm! for the halo complexescan be assigned to the metal-halogen stretchingfrequency. In the perchlorate complex '13 and \14of the perchlorate group appear as strong bands at625 and 1090 crrr ! respectively indicating the ionicnature of the perchlorate.

Since the complexes are only sparingly solublein common solvents, the electronic spectra wererecorded in the solid state. The spectra of all thecomplexes appear to contain an intense band below400 nm as evidenced by the sharp decrease in theabsorption above this wavelength. This may beattributed to a charge-transfer process. Thoughthe solid state electronic spectra do not show anywell defined band between 750 and 1400 nm, all thecomplexes show a comparatively weak absorptionmaximum in the range 1150-1250 nm. This canbe attributed to the weak d-d transition expectedaround 1000 nm for octahedral complexes of Fe(II).

The effective magnetic moment values show thatall the complexes are of the spin-free type. Theperchlorate complex shows a magnetic moment of5·7 BM which is much higher than the spin onlyvalue of 4·9 BM. This is not surprising in view ofthe fact that this complex is likely to have a regularoctahedral configuration as suggested by the mole-cular formula. A large orbital contribution to themagnetic moments is expected for a regular octa-hedral complex of high spin Fe(II)1°. The magneticmoments of the other complexes (5·17-5·34 BM) are

NOTESin the ranges expected for tetrahedral or distortedoctahedral complexes of Fe(II)IO,l1. However theelectronic spectral data supports a distorted octa-hedral structure for the halo complexes.

The authors thank the authorities of the IndianInstitute of Science, Bangalore, for the electronicspectra and the Indian Institute of T chnology,Madras, for the IR spectra.

References1. RAVI, A., GOPALAKRISIlNAN, J. & PATEL, C. C., Indian

J. Chcm., S (1967), 356.2. GOPALAKRISH~AN, J. & PATEL, C. C., Indian J. Chem.,

S (1907), 364.3. GOPALAKRI5HSAN, J., RAVI, A. & PATEL, C. C., Bull.

chem . Sac. Japan, 40 (1967), 791.4. PRABHAKARJ\N, C. P. & PATEL, c. C., J. inorg . nucl .

Cheni., 34 (1972), 3485.5. BAILY, R. A. & PETERSON, T. R., Can, J. cu-«, 47

(1969),1681.6. WEISSBERGER, A., PROSCUER, P. s., l'{IDDlCK, J. A. &

TROOPS, E., Organic solvents, Vol. VII (Fnterscience,~ew York), 1956.

7. KuRZ, E., KOBER, G. & BERL, M., Analyt . ci».«, 30(1958), 1983.

8. WALMSLEY, J. A. & TYREE, S. Y., luorg . Chem., 2(1963), 312

9. NAKAMOTO, K., Angci» cu.«; 11 (1972), 666.10. FIGGIS, B. N. & LEWIS, J., in Progress in inorganic

chemistry, edited by F. A. Cotton, Vol. 6 (Iriterscience,New York), 1964.

11. FORSTER, D. & GOODGA'\IE, D. ~r. L., J. chon. Soc.,(1965), 454.

Addition Compounds of Uranyl Chloride,Bromide & Nitrate with Dlphenyl Sulph-oxide, Thianthrene-5-oxide, 2,9-Dimethyl-1,lO-phenanthroline & 6,6'-Dimethyl-2,2'-

blpyrldyl

MARGUERITE A. WASSEF

Chemistry Department, University College for WomenAin Shams University, Cairo, Egypt

Received 29 March 1975; accepted 23 July 1975

Addition compounds of uranyl chloride, bromide, andnitrate with diphenyl sulphoxide, thianthrene-S-oxide,2,9-dimethyl-l,lO-phenanthroline, and 6,6'-dimethyl-2,2'-bipyridyl have been prepared. IR data of thecomplexes are discussed and an attempt has been madeto explain the type of coordinate bond formed. Di-phenyl sulphide, diphenyl sulphone, and thianthrenedo not form addition compounds.

A FEW complexes of uranyl chloride, bromide andnitrate with organic ligands have been pre-

paredl-3 although a large number of the complexesof uranium(IV) halides are reported in the Iiterature+".The preparation and characterization of additioncompounds of the uranyl salts with the title ligandsare reported in this note. The addition compoundsformed are similar to those reported with uraniumtetrahalides,

All solvents were dried carefully by conventionalrnethods". Wherever necessary reactions werecarried out under Nz atmosphere. Uranium chlorineand bromine were determined by volumetric method

135