INDIAN J. CHEM., VOL. 16A, FEBRUARY 1978

conclusion of cis arrangement of halogens is doubtfulas the absorption ,....,200 due to symmetric vSn-CIhas been questionedll, the out-of-plane ring bendingbeing reported to appear almost at the sameposition. Some distortions in these arrangementscannot be overruled as concluded from M6ssbauerdata10•

In the diphenyllead dihalide adducts only theasymmetric vPb-Ph ,....,225 cm-l could be observedwhich does not significantly. differ in position fromthe parent Lewis acidsl3. The Pb-X, Pb-O andsymmetric· Pb-.Ph absorptions in these complexesare expected to fall much below the recorded regiondue to the heavier mass of the central metal atomlead, as compared to tinls•l4. Significant deviations.from the structures of the corresponding tin com­poun,ds discussed above are not expected7•9•15 in thelead complexes.

In the two penta-coordinated adducts (RaSnCl.Apy)the asymmetric Sn-aryl (,....,270) and the Sn-Cl(,....,280) vibrations were observed and the complexesare being assigned the widely reported trigonalbipyramidal ligand geometry, with a· planar RsSnmoiety?·g·l6.

Phenyltin trichloride is reported to show strong..,Sn-Cl and vSn-Ph at 385-364 and 250-248respectively1? The Sn-Ph vibration in the complexrem3!ins unaffected (242), while the polarisation of

13+ 3-Sn-Cl bond (O--7Sn- - - - -Cl) subsequently resultsin a fall of frequency (300 m, 295 wand 290 w).The presence of two Sn-O linkages suggest a cisarrangement of the ligands and the multiplicity ofSn-Cl vibrations is suggestive of the chlorine atomsbeing in cis positions18. Dipole moment studies byearlier workers19 also confirm such an arrangementfor similar compounds.

Financial support, in the form of fellowship,from, the CSIR, New Delhi to one of us (M.K.)is gratefully acknowledged. Thanks are also due toInternational Lead and Zinc Research Organization,USA, for the gift sample of tetraphenyllead anddiphenyllead dichlorides.

.References

1. JENSEN, K. A. & FRIEDIGER, A., Kgl. Danske Videnskab.Selskab, Mat. Fys. Med. No. 20, 20 (1943).

2. VIEBEL, 5., EGGERSEN,E. & LINHOLT, S. L., Acta. chem.scand., 8 (1954), 763.

:3. PRABHAKARAN,C. P. & PATEL, C. C., J. inorg. nucl.Chem., 34 (1972), 3485.

4. S~VANT, V. V., RAMAMURTHY,P. & PATEL, C. C., J.less-common Met., 22 (1970), 479.

5. PANYUSHKIN,V. T., GARNOVSKII,A. K. & GRANDBURG,I. I., Lh. Obshch. Khim., 38 (1968), 1154.

-6. VIJAYAN, M. & VISHWAMITRA,M. A., Acta Cryst., 21(1966), 522.

7. DAS, V. G. K. & KITCHING, W., J. organometal. Chem.,13 (1968), 523.

:8. LANGER, H. G. & BLUT, A. H., J. organometal. Chem.,5 (1966), 288.

9. MATWIYOFF, N. A. & DRAGO, R. S., lnorg. Chem., 3(1964), 337.

10. LIENGME, B. V., RANDALL,R S. & SAMS, J. R, Can.J. Chem., 50 (1972), 3212.

11. SRIVASTAVA,T. N., TANDON,S. K. & BAJPAI, B., lnorg.chim. Acta, 13 (1975). 109.

12. PbLLER, R. C., The chemistry of organotin compoundS(Logos Press, London), 1970, 227-29.

13. CLARK,R J. H., DAVIES, A. G. & PUDDEPHATT, R. J.,lnorg. chem., 8 (1969), 437.

17+

14. MACDIARMID, A. G., Organometallic compounds ofGroup lVB elements, Vol. 2, Part II (Marcel Dekker,New York), 1972.

15. HAUPT, H. J. & HUBER, R, J. organometal. Chem., 33(1971), 175.

16. POLLER, R C., The chemistry of organotin compoundS(Logos Press, London), 1970, 185-98.

17. POLLER, R C. & TOLEY, D. L. B., J. chem. Soc., A(1967), 1578.

18. JAURA, K. L., CHANDER, K. & SHARMA, K. K., Z.anorg. allgem. Chem., 375 (1970), 107.

19. MULLINS, F. P., Can. J. Chem., 49 (1971), 2719.

Dichloromethoxy( fluorosulphato )titanium(IV)& Its Complexes with Pyridine,

Ethylenediamine & Dimethyl Sulphoxide

R. C. PAUL, SUDHIR BAJAJ, R C. KUMAR & R. D. VERMA

Department of Chemistry, Panjab University, Chandigarh

Received 20 November 1976; accepted 15 November 1977

Dichloromethoxy(ftuorosulphato )titanium(IV) hasbeen prepared by reacting trichloromethoxytitanium(IV) with ftuorosulphuric acid. Its IR spectrumindicates that the ftuorosulphate group acts as atridentate ligand having C3v symmetry. TiCI.(OCHa)(SOaF) forms 1: 1 complexes with pyridine. ethylene­diamine and dimethyl sulphoxide. The IR spectraof the complexes reveal the covalent nature (Cs sym­metry) of ftuorosulphate group and also the mode ofcoordination of the Lewis bases.

FRAZER and coworkers have reported the pre-pardtion of alkoxychlorosulphatotitanium(IV)compounds by the interaction of alkoxytitanium(IV)and sulphuryl chloride1. In this note we report thepreparation and the characteriza.tion of hithertounknown dichloromethoxy(fluorosulpha to)titanium­(IV) and its coordination complexes with pyridine,ethylenediamine a.nd dimethyl sulphoxide.

Dichloromethoxy(fluorosulpha to) titanium (IV) (A)was prepared by adding dropwise freshly distilledfluorosulphuric acid (2,2 g) to trichloromethoxy­titarlium(IV)2 (4·0 g) in 25 ml sulphuryl chloride.Hydrogen chloride gas was evolved at room tem­perature. To ensure the completion of the reaction,the reaction mixture was refluxed till the ensuinggases gave no test for HCl gas. The compoundformed was filtered, washed with sulphuryl chloridefollowed by carbon tetrachloride and finally driedin vacuo [Found: S, 12·70; Ti, 18,98; Cl, 27·59;F, 8·02; C, 4·60; H, 1-30. TiC12(OCHa)(SOaF)requires S, 12·85; Ti, 19·27; Cl, 28·51; F, 7,63;C, 4·82; H, 1·20%].

Complex of (A) with pyridine was prepared byadding, to a chilled suspension of (A) in CC14,asolution of pyridine in CC14in 1: 2 molar ratio.The reaction mixture was stirred for 2 hr. Thecomplex formed W2S filtered, washed with CC14anddried in vacuo [Found: Ti, 14,20; S, 10·80; Cl,22·40; F, 6·14; C, 22,95; H, 2·50; N, 4·16.TiCl2(OCHa)(SOaF).Py requires Ti, 14·63; S, 9,75;CI, 21·64; F, 5·79; C, 21·95; H, 2·44; N, 4-26%]_The complexes of (A) with ethylenediamine anddimethyl sulphoxide were prepared in a similar way.

NOTES

For the complex A.en [Found: Ti, 15·26; Cl, 22·74;S, 10·48;. F, 6,28; C, 11·45; H, 3,75; N, 9·53.Reqd.: Tl, 15·53; CI, 22·97; S, 10,35; F, 6·15; C,11·55; H, 3·56; N, 9·05%]. For the complex

A.DMSO [Found: Ti, 14·89; Cl, 21-32; S, 20·08;F, 5·96; C, 10·60; H, 2·85. Reqd.: Ti, 14·67; Cl,21?0; ~, 19·57; F, 5,81; C, 11:00; H, 2·75%].

Tltamum, sulphur and fluonne were determined,gravimetrically 2S Ti02, BaS04 and (C6HslaSnFrespectively. Chlorine was determined by Volha.rd'smethod. The parent compound and its coordination,complexes are yellow, hygroscopic solids, insoluble in,common organic solventS. Their melting points are>260°.

It is now well established that the symmetry()f the fluorosulphate group is reduced from Cav(when it is ionic) to Cs when it acts as a mono- orbidentate groupa-5. However, if it acts as a tri­<Ientate ligard its symmetry still remains Cav. Thislowering of the symmetry (when it acts as amOl1O- or bidentate ligand) results in an incre2seof its fundamental vibrations from six to nine,all of which are IiR and Raman active. The IRabsorption bands for the fluorosulphate group in (A)>can be assigned on the basis of Cav symmetrywhich is maintained not because of the anionicSOaF-, but due to the metal-anion coordination,in which all the three oxygen atoms of the fluoro­sulphate group are involved in coordination in anequivalent position resulting in hexa-coordination oftitanium. That the fluorosulphate group in (A) isnot ionic becomes evident from a comparison of itsIR spectra (',1max in em-I) with that of CsSOaF(ref. 6). The ',12mode shows a significant shift from715 in the cesium salt to 820. There is consistent,though smaller, shift in VI and Va modes (VI shiftsfrom 1078 to 1090, while Vashifts from 558 to 580).'.14' ',Is and ',16modes appear at 1230, 560 and 420respectively. There is, thus, a probability that theiluorosulphate group in (A) is tridentate having aCav symmetry.

The presence of the methoxy group in (A) issupported by its analytical data as well as by itsIR spectrum. The IR spectrum of (A) as a mullin hexachlorobutadiene shows bands at 2920 and2885, which may be attributed to vC-H. Otherbands usually attributed to an alkoxy group arealso present in (A) and also in its coordination>complexes under discussion. In pure methanol, thebands at 1035-65 are attributed to vO-C; whilein Ti(OCHa)Cla these bands are found at a lowerposition; i.e. 980-1000. The bands at 975-1025indicate the presence of OCHa group in (A).

The splitting of all the three E modes, in thecoordination complexes of (A) indicate the reducedsymmetry (C5) of the fluorosulphate group. Theyappear at 1340, 1260 (\14) and 680, 588 (\15) inA.Py, at 1370, 1310 (',14),656, 579 (\15)& 420, 370(\16)in A.en and at 1370, 1260 (\14), 655, 579 (',Is)

& 435, 345 (\16) in A.DMSO respec~ively .. -r:heformation of 1:1 complexes of (A) WIth pyndmeand dimethyl sulphoxide suggest that the fluoro­sulphate group behaves .as a :nonodentate c~valentliga~d and that titann~m .IS penta-coor~ma~ed.In 'the case of ethylenedlamme complex, tltanmmseems to acquire hexa-coordination. In pure liquid

pyridine the 16b vibrations (out-of-plane ring de­formation) appears at 403, while the 6a and 8bvibrations (in-plane ring deformation) appear at601 and 1578 respectively'. These vibrations inTiCI2(OCHa) (SOaF).Py show significant shift to higherregion and appear at 419,624 and 1600 respectively,indicating the coordination of pyridine to themetal. The prominent bands at 3505 (\IN-·H)

and ~655 (N -H bending) in ethylenediamine8 shiftto 3445 and 1600 respectively in the complexTiCI2(OCHa)(SOaF).eIl. The vC~N band appearingat 1225 in the pure base shows no significantchange. The trend in the shift of the N - Hfrequencies indicates that titanium is coordinated toethylenediamine and has acquired hexa-coordination.Pure dimethyl sulphoxide shows two characteristicbands 'at 1050 and 690 assigned to vS=O and\lC-S respectively9. The vS=O in the complexTiCI2(OCHa)(SOaF).DMSO appears at 990. The lower­ing of this frequency indicates the coordination ofdimethyl sulphoxide to titanium through its oxygenatom, since the coordination through sulphur atomwould have increased the \lS=O as is knownin its complexes with platinum and palladium(II)halidesIo,ll. The upward shift in the vC-S to 720further justifies the suggested mode of coordination.References

1. FRAZER, M. J., GERRARD, W. & PARRETT, F. \V., J.chem. Soc., (1965), 3687.

2. BEERMAN;C. & BESTIAN, R., Angew. Chem., 71 (1959), 618.3. GOUBEAU, R. & MILNE, J. B., Can. J. Chem., 45 (1967),

2322.4. YEATS, P. A., POH, B. L. FORD, B. F. E., SAMS, J. R. &

AUBKE, F., J. chem. Soc. (A), (1970), 2188.5. CARTER, R. A., JONES, S. P. L. & AUBKE, F., Inorg.

Chem., 9 (1970), 2485.6. RUOFF, A., MILNE, J. B•• KAUFMANN, G. & LEROY, M.,

Z. anorg. allg. Chem., 372 (1970), 119.7. GILL, N. S., NUTTALL, R. H., SCAIFE, D. E. & SHARP,

D. W. A., ]. inorg. nucl. Chem., 18 (1961), 79.8. NAKAMOTO, K., Infrared spectra of inorganic and co­

ordination compounds (Wiley Interscience, New York),1970, 224.

9. LAPPERT, M. F. & SMITH, J. K., J. chem. Soc., (1961), 3224.10. COTTON, F. A. & FRANCIS, R.o J. Am. chem. Soc., 82

(1960), 2986.11. COTTON, F. A., FRANCIS, R. & HORROCKS (Jr), W. D.,

J. phys. Chem., 64 (1960), 1534.

Stability Constants of Co(II), Ni(II), Cu(II),Zn(II), Cd(II), UO~+ & V02+ Chelates ofo-(N -a,-furfuralideneimino )benzoic Acid

D. C. SEHGAL, P. K. KANUNGO & R. K. i\'IEHTA

Department of Chemistry, University of Jodhpur, Jodhpur

Received 16 APril 1977; accepted 18 July 1977

Stability constants of Co(II), Ni(II) , Cu(II), Zn(II),Cd(II), UO~+ and V02+ complexes with o-(N-o.-fur­furalideneimino)benzoic acid have been determinedpotentiometrically in aqueous media using Calvin­Bjerrum pH titration technique. The measurementshave been carried out at three different ionic strengthsand temperatures. Thermodynamic stability con­stants have been obtained by extrapolating the experi­mental values to zero ionic stren~th. Values of freeenergy change have also been calculated.

175