Rastogi, D. K.

Teotia, M. P.

English

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NOTESTABLE 1 - DISTRIBUTIONOF NORMALMODES OF VIBRATIONSWITH THEIR SYMMETRYSPECIES·Complexes Stereochemistry Point group Symmetry Symmetry No. of IRspecies of species of activevMX vML bandsNiL.X.[L= Nia, Cpy, Ent, X = Br-] Polymeric octahedral Ci 2Ag+2Au Ag+Au 3Ni(Nia),I. Trans-octahedral D4h AIg+Alu AIg+BIg+Eu 2NiL,X, [L=Amp, Pzd, X=Cl-, Br-, 1- do do do do 2NO;]CoC12·2Apz do do do do 2Co(Amp).X. [X = CI-, NOi] do do do do 2[Ni(Nia)s)2+ [(CIO,).]2- Octahedral (cation) 0.,. TJu 1CoI •.Apz Tetrahedral3 C2v Al+Bl A1+B, 4CoX •.2Amp rX=Br-, 1-] do do do do 4FeX2.2Nia [X=Cl- 1-] do do do do 4*IR active species are underlined.values of V2 and v3• The colour, magnetic momentvalues and the values of spectral parameters arccharacteristic of tetrahedral Co(II) complexes.Fe (II) complexes are yellow in colour havingmagnetic moment values of about 4·9 BM indicat-ing the presence of four unpaired Electrons. Thesedata favour a tetrahedral geometry for thecomplexesw,The IR data of the tetrahedral Co(II) and Fe(II)complexes reveal that all the ligands coordinatethrough ring nitrogen. Amp and Nia act asmonodentate ligands coordinating through the ringnitrogen.We have worked out the point group symmetryof these complexes and calculated the number ofinfrared active bands. Nitrate groups and ligandshave been treated as single points. The results ofthese calculations are presented in Table l. Thepolymeric halogen bridged complexes belong to C.point group for which two v M-Br and one vM-N(ring) vibrations arc expected to be IR active. Thebands due to v M-Br mode are expected to appearbelow 200 cm+. A single hand due to vM-N (ripg)is observed around 250 cm+, favouring a polymericstructure for these complexess.In the monomeric octahedral complexes, we ob-serve one or two bands in the far IR region, due tovM-L mode and vM-X vibrations. These dataindicate that the complexes are trans-octahedralhaving D." symmetry. In the nitrate complexeswe observe a band at 315 cm-I which could beassigned to vM-O modc P. The cation of thecomplex [Ni(Nia)s]2+[(CI04)2]2-bdongs toOhsymmetryfor which one band due to vNi-L mode is expectedand is observed at 245 crrr".The tetrahedral complexes belong to CZv pointgroup having two IR active bands for both \lM-Xand vM-L modes. In the Fe(II) complexes, thetwo vFe-Cl bands are observed at 375 and 345 cm-1(ref. 12). The bands at 290 crrr+ may be tentativelyassigned to Fe-L mode.The authors express their sincere thanks to theUniversity of Montreal, Montreal, Canada, for pro-viding instrumentation facilities.Referencesfi: SINGH, P. P. & SHUKLA,LT. P., At/st. J. cu,«; 27 (1974),-: 1827.2. SINGH, P. P., KHAN, S. A. & SRIVASTAVA,A. K., IndianJ. Chern., 12 (1974), 192.3. TANADE,Y. & SUGA~O, S., J. phys. Soc. Japan, 9 (1954),753.4. BILLING, D. E. & UNDERHILL, A. E., J. chem. Soc., (A),(1968), 29.5. SINGH, P. P. & KHAN, S. A., Inorg. chim. Acta, 14 (1975),143.6. CLARK, R. J. H. & WILLIAMS, C. S., Inorg. Chem., 4(1965), 350.7. SINGH, P. P. & SETH, J. N., J. inorg, nucl, Chem., 37(1975), 593.8. HATHWAY, B. J. & UNDERHILL, A. E., J. chem, Soc.,(1961), 3090.9. ADDISON, C. C., AMOS, D. W., SUTTON, D. & HOYLE,W. R. R., J. chem, Soc., (A), (1967), 808.10. SINGH,P. P. & RIVEST, R., Can. J. Chem., 46 (1968), 1773.11. NUTTAL,R. H. & TAYLOR,D. W., Chem. Commun., (1968),1417.12. FERRARO,J. R., WAZNIA,W. & ROCH, G., Ricerca scient.,38 (1968), 433.Correlation of IR Data with the Stabilityof Pt(IV). Ir(III). Rh(III). Ru(III). Co(III)Cr(III). Ni(II). Pt(IJ). Pd(II) & Cu(II)Complexes of 3.3'-Diamino-4,4'-dihydroxy-diphenyl SulphoneM. P. TEOTIA & D. K. RASTOGIDepartment of Chemistry, Meerut College, Meerut 250001Received 3 1\1arch 1975; accepted 2 March 1976IR spectra of the octahedral Pt(IV). Ir(III), Rb(III),Ru(I1I), Co(I1I), Cr(III), Ni(II), Pt(II), Pd(II) and Cu(II)complexes of 3,3' -diamino-4,4' -dibydroxydipbenylsul-phone {D(AHP)S] have been studied in the reglon 4000-200 cm-! and the order of stability of the complexes isdiscussed in the lll1ht of IR data. IR spectral datasupportthe following order ofa- bonding :3da <4da< 5da.CORRELATION of the stability of transt ionmetal complexes with the infrared bands dueto vNH2, 1.)NH2and vM-N frequencies, in a numberof metal complexes with amines and ethylenediarnine, has been reported>?". In this note wr:present the correlation of the order of stabilitieswith IR and electronic spectral data of Pt(IV),Ir(III), RC(III) , Ru(III) , Co(III), Cr(III), Ni(II),813INDIAN J. CHEM., VOL. 14A, OCTOBER 1976Pt(II}, Pd(II} and Cu(II) complexes of 3,3'-diamino-4,4'-dihydroxyd:phenyl sulphone [D(AHP)S].Isolation and characterization of metal complexesof D(AHP)S have been described earlierll-16. IRspectra of D(AHP)S shows bands at 600, 535, 335and 300 cnr" which may be due to skeletal vibrationsof the frame work. A few bands in the region335-535 cmr! in the IR spectra of the complexes,which are absent in the spectrum of ligand, may beass'gned to vM-N. The M-N mode of vibration inoctahedral transition metal complexes of D(AHP)S,follows the sequence: Pt(IV} > Ir(III) > Rh(III)> Ru(III) > Co(III) > Cr(III) = Ni(II}.For square planar complexes, the increasing orderof vM-N frequency in Cu(II) < Pd(II) < Pt(Il).This order of bond strengths was supported byM-N stretching force constants as obtained fromthe normal coordinate analysis. It is thus interest-ing to note that the order. of. strength" ~f M-~ bondsin D(AHP}S complexes IS In conformity wi th theorder of the metal ions in the spectrochemical series.It is, further, substantiated by their order ofspli tting en ergiesl1-16.It is evident from Table 1 that a1' (NH2) vibrationsin the octahedral transition metal complexes ofD(AHP}S increase from Ni(II) to Pt(IV) in the order:Pt(IV) > Ir(III) > Rh(III) = Ru(III) > Co(III)> Cr(III) > Ni(II).For square planar complexes, the a,(NH2) vibra-tion follows the sequence: Pt(II) > Pd(II) > Cu(II).Therefore, it may be concluded that this decreasein a,(NHz) frequencies is in close agreement with thestrength of metal nitrogen bonds, 10 Dq values(Table 1) of the complexes and the spectrochemi-TABLE 1 - IR AND 10 Dq DATA OF THE TRANSITIONMETAL COMPLEXES OF D(AHP}S(Values in crrr")Complex 10 Dq v(M-N) 8r(NH.} vas(NH2)OCTAHEDRAL COMPLEXES[Pt(C12H10N .O.S} 30500 525 800 3200-3240(CI.)][Ir(C12HION,O.S} 25775 520 792 3232(CI)(H,O)][Rh(C12HloN.O.S} 21445 510 565 3266(CI)(H.O)][Ru(C1.HION.0.S} 21260 508 765 3270(CI)(H.O)][Co(~.HloN.O.S) 21175 505 760 3290-3300(CI)(H.O)][Cr(C12HlON,O.S) 16620 500 756 3310-3320(OH) (H.O)][Ni(C12H1ON.0.S} 10400 500 742 3325(NH.)]SQUARE PLANAR COMPLEXES[Pt(C12HloN,O,S)] 44750 515 775 3230-3260[Pd(C12H1ON,O.S)] 34520 510 765 3280[Cu(C12H,oN.o.S}] 492 708 3325814cal series of the metal ions as also pointed out earlierby Sacconi et al», Quagliano et al», Powell andShcppards and Nakamoto et aP8. One can, how-ever, t ealise that these frequencies are rarely purebecause of coupling of normal modes of vibra-tion of the same symmetry in the molecule.Two strong absorption bands around 3380 and3360 cm-1 ar.d one around 3300 crrr? have beenobserved in the spectra of D(AHP)S. The hgherfrequency bands are due to v.(NH2) and lowerfrequency band due to vas(NH2)' On complexationboth of these vibrations are consderably loweredindicating that nitrogen of the NH2 group servesas a coor d.nation centre. The vas(NHz) frequencyin octahedral complexes is generally found todecrease in the ord-r : Pt(IV) > Ir(III) > Rh(III)> Ru(IIl) > CollI) > Cr(III) > Ni(II).In the square planar complexes of D(AHP)S,vas(NH2) frequencies decrease in the order: Pt(II)> Pd(II} > Cu(II).The vas(NH;l) frequencies in the present complexesfollow the order: Co(IIl) > Cr(III) > Ni(II) which.s in agreement with the result obtained by earlierwork(~rsJ7-2o. It is also in agreement with the orderof a,(NH2), v(M-N) vibrations and the 10 Dq valuesof the complexes (Table 1). It can, therefore, beconcluded that the decrease in N-H stretchingfrequency corresponds to the increase in metalnitrogen bond strength.It may be inferred from the infrared spectralstudies of the octahedral and square planarcomplexes of D(AHP)S that the order of increaseor decrease in various IR frequencies follows thesequence of their stability derived from electronicspectral studies and the increase in a-bonding occursin the order: 3da < 4da < 5da derived fromelectronic spectral studies of these complexesU-17•References1. NAKAGAVA, 1. &,MIZUSHI:'>rA, S., Bull, chem, Soc. Japan,28 (1955), 581.2. SACCONI, L., SABATINI, A. & GANS, P., Tnorg, cu.«, 3(1964), 197i.3. SVATOS, G. 1., SWEAMY, D. M., MIZUSHIMA, S., CURRAN,C. & QUAGLIANO, J. V., J. Am. chem. Soc., 79 (1957),3513.4. SVATOS, G. F., CURI<AN, C. & QUAGLIANO, J. V., j. Am.chem. Soc., 77 (1955), 6159.5. CONDR.'l.TE, R. A. & NAKAMOTO, K., j. cheni. Phys., 42(1965), 259Q.6. POWELL, D. B. & SHEPPARD, N., J. chem. Soc., (1958),3108.7. POWELL, D. B. & SHEPPARD, N., J. chem. Soc., (1961),112..8. POWELL, D. B. & SHEPPARD, N., Spectrochim, Acta, 17(1961), 68.9. LEVER, A. B. P. & MONTOVANJ, E., Inorg. Chem., 10(1971), 817.10. LEVER, A. B. P. & MONTOVANI, E., Tnorg, chim, Acta, 5(1971), 429.11. TEOTIA, M. P., RASTOGI, n. K. & MALIK, v«. U., Lnorg .chim, Acta, 7 (1973), 339.12. TEOTIA, M. P., RASTOGI, D. I\:. & MALIK, W. U., J. inorg,nucl, Chem .. 35 (1973), 3015.13. TEOTIA, M. P., RASTOGI, D. K. & MALIK, \>"T. U., j. inorg,nucl. Chem., 35 (1973), 404'7.14. TEOTIA, M. P., DUA, S. tc.. SHARMA. K. C. 8tt RASTOGI,D. K., f. inorg, nucl, cne.«, 37 (1975), 685.15. TEOTIA, 1\1, P. & RASTOGI, D. K., Indian j. Chem., 13(1975), 7i1.16. TEOTIA, M. P., RASTOGI, D. K. & MALIK, \V. U., Indianj. cu«, 11 (1974), 1303.I17. JRWING. H. & WILLIAM. R. J. P .• J. chem, SOC .• (1953).7lln.18. FUJITA. J .. NAKAMOTO. K. ~KOBAYASHI. M.. J. Am.chem, Suc .• 78 (1956), 3295:19. KOBAYASHI. M. s. FUJITA. j., J. chem . Phys .• 23 (1955).. 1)54.20. TANAKA, -r .• KA:-IIADA, M.• FUJITA, J. ~ KYAMO. E.•Bull. chem. Soc. Japan. 37 (1965). 22fNd(III), Pr(III), Ce(III) & La(lII) Complexeswith 3-Formyl-4-hydroxy- & 3-0ximinomethyl-4'-ni troazobenzenesK. G. K. WARRIER. P. N. MOHAN DAS· & P. T. JOSEPHCSIR Trivandrum Complex, Trivandrum 19Received 6 November 1975; accepted 2 February 1976Nd(III), Pr(III), Ce(III), and La(III) form 1: 2 com-plexexs with 3-formyl-4-hydroxy-4' -nitroazobenzeneHF4NB, and 1:3 with 4-hydroxy 3-oximinomethyl-4'-nitroazobenzene (H04NB). The complexes have beenstudied using Calvin-Bjerrum pH titration techniquein 60% (wjw) ethanol-water medium at 28°±l°C. Thefree energies of formation of the complexes have beenevaluated. The order of stability is found to be: Nd»Pr>Ce>La. H04NB forms stabler complexes withthese metal ions.WE hav~ reT~orted previouslyl the ~f~ect of methylsubst itut ion on the stepwise stability of Nd(III),Pr(III), Ce(lU) and La(III) complexes with 3-formyl-4-hydroxyazobenzene. In this note we report thesynthesis of 3-formyl-4-hydro},,-y-4' -nitroazobenzene(HF4NB,I) and its oxime, 4-hydroxy-3-oximi~~~e-thyl-4'-nitroazobenzene (H04NB,II). The stabilitiesof Nd(UI). PrlIII). Ce(III) and La(IU) complexeswith these ligands have been studied,HF4NB was prepared by a method similarto that reported earlier-. The oxime, H04NB,was prepared from HF4NB by standard methods.The identities of the ligancis (I) and (II) wereconfirmed by their melting points and IR data whichagreed with those reported in literature".I ,R =01I,R=NOHExperimental procedure was the same as reportedearliers. The metal ion solutions were preparedfrom metal nitrates in conductivity water and aSystronic pH meter type 322 (accuracy 0·05) wasused for pH measurements.The protonation constants of the ligands HF4NBand H04NB were found to be 7·15 and 8·84 respec--Present address: Instt. fur Anorg. Chemie, UniversitatDusseldorf. Dusseldorf. West Germany.NOTESTABLE 1 - STABILITY CONSTANTS OF THE COMPLEXESMetal HF4NBlog ~3H04NBlog ~315·32±0·Q414·8514-92±0·Q414·6014-67±0·Q414·201H7±0·0414·10Nd(III) (a) 8·63±0·Q4(b) 8·20Pr(lII) (a) 8·35±O·Q4(b) 8·00Ce(III) (a) 8·25 ± 0·04(b) 7-95La(I1I) (a) 8·05 ±0·04(b) 7·95(a) Bjerrum values(b) Correction-term methodtively as calculated by the Irving and Rossettimethods and by direct calculations.Formation curves for the metal-ligand systemswere drawn between n and PA which in turn werecalculated by the method of Bjerrums and Calvin".The log K values for th~ systems were takendirectly from the formation curves an~ wererefined by computational method de~c~Ibed byRossotti and Rossottis. All metals precipitate be-yond PH 7·0 in the case of HF4N.b and 8·0 in thecase of H04NB. These form 1:2 complexes in thecase of HF4NB and 1:3 complexes in the case ofH04NB.Replacement of the formyl group of HF4NB .byan oximinomethyl group increases the complexingtendency of the ligand considerably as seen fro~pK values, Both the ligands behave as monoproticand bidentate ligands in complex formation.Instead of the oxygen of the formyl group in HF4NB,nitrogen of the oxime group in H04NB takes partin coordination. Similar structures for some oximecomplexes have been confirmed by X-ray analysis".As seen from Table 1. both the 1:2 and 1:3 complexesfollow the stability order Nd(lIl) > Pr(lIl)> Ce(IIl) > La (Ill ). La(IIl). Ce(lIl), Pr(Ill)and Nd(IlI) possess ionic radii 1·061, 1·034,1·013 and 0,995 A respectively and the stability ofmetal complex increases with increase in ionic radius.This is also justified by considering Z"/r values forthese metal ions. The complexing tendency of theligands may be expressed in the order H04NB >HF4NB.The values for the free energy changes duringcomplexation have also been calculated (-AF-::::. 12·0kcaljmole for complex formation with HF4NB and-::::.21·0 kcaljrnole for complex: formation withH04NB). These are in good agreement with thestability constants of the complexes.References1. WARRIER. K. G. K.. PAVITHRAN. C .• M..f.HAN DAS. P. N.& JOSEPH. P. T .• Indian]. Chem .• (in press).2. MOHAN DAS. P. N .• SUNAR."'O. P. & TRIVEDI. C. P.• IndianJ. Chem .. 11 (1973). 7~3. IRVING. H. & ROSSOTTI. H. S .• J. chem, Soc .• (1954), 2994.4. BJERRUM. J .• Metal ammine formation in aqueous solu-tions (P. Haase. Copenhagen). 1941. 35.S. CALVIN, M. & WILSON, K. W .• J. Am. chem, Soc .• 67 (1945).2003.6. ROSSOTTI. F. J. C. & ROSSOTTI. H.. The determination ofstability constants (McGraw-Hill, New York). 1961. 8.6.7. MELLOR. D. P .• Chem, Rev .• 33 (1943). 137.\(815

Correlation of IR Data with the Stability of Pt(IV), Ir(III), Rh(III), Ru(III), Co(III), Cr(III), Ni(II), Pt(IV), Pd(II) & Cu(II) Complexes of 3.3'-Diamino-4,4'-dihydroxydiphenyl Sulphone

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Correlation of IR Data with the Stability of Pt(IV), Ir(III), Rh(III), Ru(III), Co(III), Cr(III), Ni(II), Pt(IV), Pd(II) & Cu(II) Complexes of 3.3'-Diamino-4,4'-dihydroxydiphenyl Sulphone

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