Mukherjee, R. N.

Raghunand, R.

Zingde, M. D.

English

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IR spectra, elemental analysis and other properties(Table 1) are in good agreement with the formulaesuggested for the derivatives. The IR spectra ofthese compounds also indicate that the linkage be-tween the cyclopentadienyl and indenyl rings andthe metal atom has the character of delocalized~-bonds9,lo and the nitro and nitrito groupsare attached to the metal by covalent a-bonds.References1. ANAND, S. P., MULTANI, R. K. & JAIN, B. D., CUY!'. su.,17 (1968), 487.2. RASTOGI, M. K. & MULTANI, R. K., J. inorg, nucl. Chem.,37 (1975), 1995.3. WESTON, R. E. & BRODASKY, T. F., J. chem. Phys., 27(1957), 683.4. CHALL, J., DUNCANSON, L. A., GATEHOUSE, B. M., LEWIS,J" NYHOLM, R. S., TOBE, M. L., TODD, r.F. & VENANZI,L. M., J. chem: Soc., (1959), 4073.5. SMITH, D. C., PAN, C. & i{EILSEN, J. R., J. ohem. Phys.,28 (1950), 706.6. TARTE, P., J. chem. Phys., 20 (1952), 1572.7. NAKAMOTO, K., Infrared spectra of inorganic and coordi-nation compounds (John Wiley, New york), 1963, 151.8. BASOLO, F. & HAMMAKER, G. S., Lnorg, Chem., 1 (1962),1.9. FRITZ, H. P., Adv. organometal. Chem., 1 (1964), 279.10. SCHARF, G. W. & BROWN, R. K., Can. J. Chem., 38 (1960),697.Di-(p-chlorophenyl)dithiophosphinatoDerivatives of Fe(I1I), Co(III) & Ru(I1I)R. N. MUKHERJEE, R. RAGHUNAND & M. D. ZINGDEDepartment of Chemistry, Indian Institute of TechnologyPowai, Bombay 400076Received 5 September 1975; accepted 7 N ouember 1975Spectral studies in the infrared and visible regionsand the magnetic studies over a temperature range(800 to 3000K) of M(III) (M = Fe, Co, Ru) derivatviesof di(p-chlorophenyl)dithiophosphinic acid (CldtpiH)have been investigated. These complexes have beenassigned octahedral stereochemistry and Dq, BandII values computed wherever possible. A novel mixedcomplex of Co(III) containing Cldtpi- and dimethyl-glyoxilllato anion (Dmg) has been characterized.THE electron spin resonance, magnetic andspectroscopic studies of dichlorophenyldithio-phosphinato (Cldtpi") complexes of some transitionmetals were reportec+" earlier. The reducing pro-perty of this ligand and the stabilization of Co(U)in Co(Cldtpi)2 which is in contrast to the behaviourof other dithio Iigands such as dithiophosphates,dithiocarbamates and xanthates were noted. There-fore, the synthesis of Fe(III) and Co (III) complexesof this ligand are of interest and are reported heretogether with a novel mixed complex of Co (III)containing Cldtpi" and dimethylglyoximato anion[Drng"}. The complex of Ru(III) is included forcomparison with iron.Fe(Cldtpi)3 - A concentrated aqueous solutionof ferric Chlo~'de was neutralized with sodiumcarbonate and fter filtration treated with a slightexcess of Na(CI pi) in water. The required complexcame down as a -black precipitate, and was washedwith water and dried in vacuo (Found S, 18·92; Fe,5·60. CssH2,CI6FePaSs requires S, 19·05; Fe, 5,53%).NOTESThe room temperature magnetic moment of 5.85BM indicated a do high spin configuration and themeasurements carried over a temperature range of80° to 3000K indicated the: ground state to be 'AIin .a? .octahedral stereoc~emistry and no spinequilibrium, The electromc spectrum, which issimilar to that of other dithio complexes is dominatedby intense charge transfer bands with bands at16600, 18900 and 23500 cm+, A slight bathochro-mic shift of the absorption bands is noticed as theligand field strength decreases from xanthate todithiophosphinate. However, no major change inthe nature of the spectra is observed between thelow spin Fe(ethyl xanthate), to the high spinFe(Cldtpi)s·R1t(CtdtPi)3 - Ruthenium trichloride trihydrate(0,5 g) in water (10 ml) was mixed with an aq.solution of Na(Cldtpi) (2 g) and the violet solutionso obtained allowed to stand overnight. The deepviolet compound which was obtained, was repeatedlywashed with water and dried (Found: 5, 18·3.C36H21.CIsPsRuSe requires 5, 18·23%).The complex is stable in air unlike Fe (III)complex and is sparingly soluble in methanol. Itis highly soluble in benzene and is monomeric, likeother Ru(III) complexes-, The electronic spectrumexhibited bands around 18400,22300 and 24200 em?(sit). The shift of the bands to lower frequency incomparisons to the spectrum ot tris (diethyldithio-phosphato)ruthenium(III) [Ru(Et2dtp)aJ, is due tothe lower position of dithiophosphina1es in thespectrochemical series. The band around 18400crrr+ have been assigned to the transition' tlg -Hg•The magnetic moments at 293°K and 83°K were1·70 and 1·62 BM respectively. The value of 1·70BM is lower than 2·1 BM expected for a six co-ordinate Ru(III) complex. This might be due tofactors- such as axial distortion, extensive tlgelectron delocalization, mixing with higher energycomponents of the 21 term or may be due to quench-ing of the orbital angular momentum by spin orbitcoupling which removes the degeneracy of IT 2gground state.Co(CldtPi)s - Aqueous solutions of sodium cobal-tinitrite and Na(Cldtpi) were mixed together andthe required brown complex immediately precipi-tated. It was washed with water and dried undervacuum (Found: 5, 18·72; Co, 5·74. C8sH2,ClsCoP.5.requires 5, 18·99; Co, 5,81%).The complex is quite stable unlike Co(Et2PS2).which decomposed even under nitrogen atmosphere'.The diamagnetic nature of the compound is indicativeof d' low spin system. The solid state and solutionelectronic spectra of freshly prepared samples aresimilar exhibiting bands at 12600 (IAI8-+IT u) and17900 (IAlc+IT 19). Based on available data", thecomplex can be assigned an octahedral geometry.The ligand field parameters Dq, B and ~ werecalculated as 1392 crrr+. 331 cm-l and 0·32 respec-tively.Co(Cldtpi)2(Dmg) - Cobalt chloride hexahydratedissolved in methanol and a filtered sohn ion ofdimethylglyoxime in methanol were mixed togetherand air was bubbled through the solution for 3 hi.To this a methanolic solution of CldtpiH was added623INDIAN J. CHEM., VOL. 14A, AUGUST 1976dropwise with vigorous stirring. After slight eva-poration the required brown precipitate separatedout, which was filtered, washed with methanol anddried in vacuo (Found: S, 15'8; Co, 7·25; N, 3·..•.5.C••H ••Cl,CoN,OsPsS, requires S, 15'64; Co, 7'31;N,3·2 ..•.%).The brown complex is diamagnetic, indicatinga low spin Co(IU) system. A broad moderatelyintense band at 1510 em? in the IR spectrum maybe ascribed to vC=N, which is slightly lower thanis usually observed for the other dimethylglyoximatocomplexes of trivalent ions", The two mediumstrong bands at 1075 and 1235 crrr-, assigned to thevN-O are due to unequal N-O linkages. This is inconformity with the X-ray studies of Ni(U) and Cu-(II) complexes of dimethylglyoxime", A weak bandaround 865 crrr! could be due to OH deformationvibration. The spectrum of the complex in thevisible region indicated a broad band with peaksaround 19200 and 20600 crrr-, and a shoulder at14900 cm+, The split band around 20000 ern+may be due to lAu-+IT It transition in an octahedralsymmetry with splitting occurring due to thespectrochemical differences between the ligandscoordinated to the metal atom.References1. MUKHERJEE, R. N. & ZINGDE. M. D.• J. inorg. nucl.CM",., 35 (1973). 696.2. MUKHERJEE, R. N. & ZINGDE. M. D.. Indian J. Che". .•Il (1974). 848.3. JORGENSEN, C. K.. Acta chern. scand .• 16 (1962). 1048.4. GROBELNY, R.. ]EZOWSKA-TRZEBIATOWSKA. B. & \VOJ-CIECHOWSKI. W.• J. inorg, nucl. Chern.• 28 (1966). 2715.5. HEATH, G. A. & MARTIN. R. L.• Austr. J. Chern.• 23 (1970).1721-6. KUCHAN. W. & JUDAT. A.• Chern. BeT .• 100 (1967). 991.7. LEVER. A. P. B .• Inorganic electronic spectl'oscoPY (Else-vier. New Delhi). 1968.S. BURGER. K., RUFF. I. & RUFF. F., J. inorg, nucl. Chern.•27 (1965), 179.Studies on Ion Association: Stabilities ofAzido Complexes of Ni(II), Zn(II) & Cd(II)REBATI C. DAS. MIHIR K. MISRA & BATA K. NANDADepartment of Chemistry. University College ofEngineering. Burla 768018. Orissa.Received 13 November 1975; accepted 3 December 1975The association constants of monoasldo complexes,MNt, for M = Ni(II), Zn(lI) and Cd(II) have beendetermined potentiometrically usina silver-silver azideelectrode. The results have been compared with thoseof monothiocyanato and monoselenocyanato complexes.Inner-sphere bondina is indicated in the complexes.THERMODYNAMICS of formation of thiocyanatoand selenocyanato complexes of some bi- andtrivalent metal ions have been studied by Das andcoworkersv", It was thought useful to extend thework to another pseudo-halide ion, Ns. The presentpaper reports the stability constants of azido com-plexes of Ni(II). Zn(II) and Cd(II) at 250 determinedby potentiometric method using silver-silver azideelectrode.62..•.Stock solution of metal perchlorates were preparedby dissolving the corresponding carbonates (AR) indilute perchloric acid (Merck, GR) and were estimatedby standard gravimetric procedures. Sodium azide(Reidel) was crystallized twice before use.Silver-silver azide electrodes, prepared by themethod of Taylor and Nimss, were equilibrated inthe cell solutions for ..•.8 hr before use. The electrodeset-up has been described in a previous paper andwas kept in an air-thermostat (25° ± 1°). E.m.f.measurements were made with a OSAW potentio-meter (model 30071) in conjunction with a multifiexgalvanometer.lAg. AgN,(s) II NaN3(aq.))) Satd. II NaNa(aq.) ) AgNa(s),NH.NO, M(C10,)t(aq.) Ag.(Half-cell I) (Half-cell II)(A)The cell of the type (A) was set up.It has been observed earlier that in such a cell thesmall liquid-junction potential which may be existingdoes not seriously vitiate stability constant results.The e.m.f. of the cell is given by the expressionE =RT I a(I)F n a(Il)where a represents the activity of the N; ion. a(I)being known from the concentration and activitycoefficient of Ni in half-cell I, a(U) were easily cal-culated from Eq. (1). Concentrations of differentspecies in equilibrium [Mz+. Ni. MN;. M(Na)s] inthe half-cell II were calculated by a series ofapproximations and refinements as detailed in ourearlier work-. Both Kl and approximate value ofKz[MN;] 1Kl = [M2+][NaJ'JJ+ ... (2)and... (1)'" (3)(assuming activity coefficients of species of similarcharge to be equal) were calculated using Eqs. (2)and (3) respectively and the values are presentedin Table 1. The activity coefficients of the ions inthe solutions were calculated from the ionic strengthswith the help of Davies equations.A comparison can be made of our results withthose found in the literature. Gerding" has calori-metrically determined the free-energy, enthalpyand entropy changes of formation of the azidocomplexes of Cd (II) in 3M solution of sodiumperchlorate at 25°. The!::J..Gof formation of CdN1was found to be -9·25 kJ mole+ against ourthermodynamic value, !::J..Go= -13·5 kJ rnole+, atzero ionic strength (calculated from the relationship:aGo = -RT in K). It is difficult to compare thetwo results as, in very high ionic strength, it is notpossible to evaluate the activity coefficient terms.However. qualitatively one expects lower stabilityat higher ionic strength in agreement with ourfindings.

Di-(p-chlorophenyl)dithiophosphinato Derivatives of Fe(III), Co(III) & Ru(III)

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Di-(p-chlorophenyl)dithiophosphinato Derivatives of Fe(III), Co(III) & Ru(III)

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