Kaul, K. N.

Mehta, R. K.

Ozha, D. D.

English

NOPR

NOTESTABLE 1 - TEMPERATURECOEFFICIENTOF E.M.F. AND IlG, IlH AND IlS FOR THE CELL REACTIONSCell reaction e.m.f. dE/dT IlG303°K .IlH303°K IlS303°Kat 303°K (V deg-1) (cal.) (cal.) (cal. deg-1)(V)Ni+ (CllH2SCOO)2CU?(CllH23COO)2N i-j-Cu 0·1242 -0·000826 -5728 -17268 -38'11Ni+ (C13H27COO)2CU?(C13H27COO)2Ni +Cu 0·1287 -0·00075 -5936 -16416 -34'59Ni + (C15H31COO).CU?(C15H31COO) 2Ni+Cu 0·1315 -0'0007 -6064 -15845 -32-28Ni + (Cl~H3'COO) 2CU?(C17H3,COO) 2Ni+ Cu 0'1343 -0'00066 -6194 -15415 -30·44TABLE 2-E.M.F. OF THE CELL OF THE TYPE (A)Pot. Temp. e.m.f. dE/dT Meansoap (0C) (V) (V/deg) dE/dT(Cx103) (Vjdeg)MSOAP DERIVED FROMLAURICACID5 25 0·12858 25 0·128510 25 0·128510 30 0'1242 -0'0008610 40 0·1162 -0,00080 -0·00082610 45 0·1120 -0,00082SOAP DERIVED FROMMYRISTICACID1 25 0·13252'5 25 0·13255 25 0·13255 30 0·1287 -0'000765 35 0·1250 -0'000745 40 0'1212 -0'00076 -0'000755 45 0'1175 -0,00074SOAP DERIVED FROMPALMITICACID1'0 25 0·13501'5 25 0·13502'5 25 0·13502·5 30 0·1315 -0'000702'5 35 0·1280 -0'000702'5 40 0·1246 -0'00068 -0·00072'5 45 0·1210 -0·00072SOAP DERIVED FROM STEARICACID0·5 25 0'13750·7 25 0·13750'8 25 0'13750'8 30 0·1343 -0·000640'8 35 0·1310 -0,000660'8 40 0·1276 -0'00068 -0,000660'8 45 0·1243 -0,00066The e.m.f. values recorded at different temperaturesare given in Table 2.The reaction taking place in the cell isNi +CUD2~NiD2 +Cuwhere D stands for laurate, myristate, palmitateor stearate ion.Both the electrodes involved in the cell underconsideration are reversible with respect to thedetergent anion. The e.m.f. of t.he cell'S should. beindependent of the concentration of potassiumsoap and should be equal to algebraic difference ofstandard reduction or oxidation potential of elec-trodes. The concentration ranges of potassiumsoaps investigated were from 1X 10-2 to 5 X 10-3,5 X 10-3 to 1X 10-3 2·5 X 10-3 to 1X 10-3 and 8 X 10-4to 5X 10-4M for potassium laurate, myristate, palmi-tate and stearate respectively. These concentrationsof potassium soaps are just below the critical micelleconcentration (cmc) values", It is evident fromTable 2 that the e.m.f. of the cells are independentof the concentration of potassium soap solution.The following equations have been used for cal-culating t:...G, t:...H and t:...S at 303°K:t:...G=-nEFt:...S= nF (dE/dT)pb.H = -nEF +nFT (dE/dT)pThe values of the e.m.f. of the cells at 303°K, thetemperature coefficient of e.m.f. and the values of t:...G,t:...Hand t:...Sfor the cell reactions are given in Table 1.References1. MALIK, WAHID U. & JAIN, A. K., ]. electroanal . Chem.,14 (1967), 37.2. MALIK, WARID U., AHMAD, S. 1. & JAIN, A. K.,Kolloid-Z., 218 (1967), 155.3. MALIK, WARlD U. & JAIN, A. K., Aust. ]. Chem., 22(1969). 465.4. MALIK, WAHID U. & JAIN, AJAY K.,]. electroanal, Chem •.16 (196R), 271. .5. MALIK, WARID U. & JAIN, A. K., Indian J. Chem., 6(1968), 140.Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II),Pd(II), Cd(II) & U02(II) Chelates of SchiffBases Derived from o-AminobenzenesulphonicAcid & 2-Aminoethanesulphonic Acid &2-Hydroxy-l-naphthaldehydeD. D. OZHA, K. N. KAUL & R. K. MEHTADepartment of Chemistry, University of Jodhpur, JodhpurReceived 10 September 1974; accepted 3 March 1975N - (2 - Hydroxy - 1 - naphthalidene)orthanilic acid(H2NO) and N-(2-hydroxy-l-naphthalidene)taurine(H2NT), the two structurally similar Schiff bases, formsolid chelates with Mn(II), Fe(II), Co(II), Ni(II), Cu(II),Zn(II), Pd(II), Cd(II) and U02(II). Elemental analyses,molecular weight, magnetic moment values and elec-tronic spectral data indicate nearly octahedral stereo-chemistry for Mn(II), Fe(II), Co(II), Ni(II) and U02(II)chelates, whereas Cu(II) chelates display a tetra-gonal configuration. Zn(lI) and Cd(lI) chelates aretetrahedral in structure and the Pd(lI) chelate possessessquare-planar geometry.A PERUS~L of t~e literature- reveals that nosystematic studies have been carried out onSchiff bases derived from o-aminobenzenesulphonic61INDIAN J. CHEM., VOL. 14A, JANUARY 1976acid (orthanilic acid) or 2-aminoethanesulphonicacid (taurine) and 2-hydroxy-l-naphthaldehydez,3.The two Schiff bases, which are structurallysimilar, are expected to behave as biprotic tridentateligands.Metal salts (BDH) were of AR grade. Orthanilicacid (LR) , taurine (LR) and 2-hydroxy-1-naphth-aldehyde (AR) supplied by Fluka were used.Gallenkamp semimicro ebulliometer was usedto determine the molecular weights of the solidchelates using dioxane as the solvent. Magneticsusceptibility measurements were made on Gouyapparatus using mercury(II) tetrathiocyanatocobal-tate as the reference. The electronic absorptionspectra of the compounds were determined on aVEB Carl Zeiss, Jena, VSU-2P spectrophotometerat room temperature.Preparation of ligands and their metal chelaies=«H2NO and H2NT were synthesized by the methodof Pfeiffer et a/.2. These gave satisfactory elementalanalyses. Their metal chelates with Mn(II), Fe(II),Co(II), Ni(II), Cu(II) , Zn(II) , Pd(II), Cd(II) andUOz(II) were prepared by the method of Yamadaet al:". The pyridine adducts of these chelateswere obtained by the method reported earlier+,Elemental analyses and magnetic' moment dataof the chelates are given in Table 1.In general, the metal chelates display 1: 1 (metal-ligand) stoichiometry. The molecular weight datasuggest that Mn(II), Fe(II), Co(II), Ni(II) andCu(II) chelates have the composition [MLX3J whereM = metal ion; X = H20 or Py and LHz= H2NO[C17H13NSOJ or H2NT [C13H13NS04J. Their mag-netic moments indicate the presence of 5, 4, 3, 2and 1 unpaired electron in the Mn(II), Fe(II), Co(II),Ni(II) and Cu(II) chelates respectively.A little lower value (5·81 and 5'83) of the magneticmoment of Mn(II) chelates than the normal valueof 5·92 BM for octahedral or tetrahedral Mn(II)complexes- may be due to spin-exchange in thesolid state or due to the presence of a little Mn(III)species which may have been formed due to aerialoxidation", The high magnetic moments of Co(II)chelates may be due to spin-orbit coupling. TheCu(II) chelates exhibit magnetic moments of 1'92and 1·94 BM at 298°K. The magnetic momentof planar chelates are generally lower (1'8-1'9 BM)than those of octahedral complexes (1'9-2.0 BM).As the planar stereochemistry may be consideredas the limiting case of tetragonally distorted octa-hedral stereochemistry, the separation of the inter-action terms (i.e. between ground term zBu andthe components of 2T 2g term) is larger in square-planar chelates than that in the octahedral chelateswhich possibly explains the lower magnetic momentsof square-planar chelatess-". The magnetic momentsof perfect tetrahedral chelates are higher than thosefor square-planar or octahedral chelates due tospin-orbit coupling and are temperature dependant.The observed bands in the electronic spectra ofthe chelates correspond to the transitions 6A~-+4Eg(G) and 6AJg-+4Eg(D)f or the Mn(II) chelates,5T2g-+5Eg(D) for the Fe(II) chelates, 4Tlg(E)-+4A2g(F) and 4Tu (F)-+4T1g (P) for the Co(II)chelates, 3A 2g-+3Tlg (F) and 3A2g-+3TIg(P) forthe Ni(II) chelates, and 2E -+2Tzg for the Cu(II)chelates. These data supported by the magneticmoment data confirm nearly octahedral structureTABLE 1 - ELEMENTALANALYSESANDMAGNETICMOMENTDATAOF THEMETALCHELATESOFN-2-(HYDROXY-l-NAPHTHALIDENE)ORTHANILICACID ANDN -(2-HYDROXY-I-NAPHTHALIDENE)TAURINEMetal chelate* Hydrated chelatest Pyridine add ucts[lef! (BM) N (%) S (%) [lef! (BM) N (%) S (%)at 298°K Found Found at 298°K Found Found(Calc.) (Calc.) (Calc.) (Calc.)CHELATES OF N-(2-HYDROXY-I-NAPHTHALIDENE)ORTHANILICACID[Mn(C17HllNS04)XS] 5·81 3·19 (3,22) 7-26 (7·37) 5·87 8·94 (9'07) 5·10 (5'18)[Fe(C17HllNS04)XS] 5·45 3·18 (3'21) 7·25 (7'35) 5·40 8·95 (9'06) 5·11 (5'17)[CO(C17HllNS04) X3] 5·16 3-09 (3'19) 7·19 (7'30) 5·10 8'86 (9,02) 5·12 (5'15)[Ni(C17H11NSO.)X3] 3·08 3·10 (3'19) 7-21 (7·31) 3·17 8·88 (9,02) 4·97 (5'15)[Cu(C17HllNS04)X3] 1·92 3·08 (3,16) 7·16 (7'23) 1·90 8'79 (8'95) 5·00 (5,11)[Pd(C17HllNSO.)X] 3·05 (3,11) 7·09 (7,12) 5·32 (5-49) 6·11 (6'27)[Cd(C17HllNSO.)X] 2·98 (3·07) 6·94 (7,03) 5·29 (5'42) 6·05 (6'20)[Zn(~7HllNSO.)X] 3·31 (3042) 7·72 (7'83) 5·79 (5'96) 6·71 (6'81)[U02(C17HllNS04)X] 2·17 (2'28) 5·14 (5'22) 4·05 (4,15) 4·62 (4'74)CHELATESOF N-(2-HYDROXY-I-NAPHTHALIDENE)TAURINE[Mn(C13HllNSO.)Xs] 5·83 3·58 (3-62) 8·13 (8'29) 5·89 9·72 (9'84) 5·51 (5'62)[Fe(~3HllNS04)X3] 5·44 3·59 (3-61) 8·12 (8'27) 5·38 9·70 (9'82) 5·49 (5'61)[CO(~SHllNSO,)X3] 5·10 3045 (3'59) 8'10 (8'20) 5·14 9'61 (9'77) 5·32 (5'58)[Ni(C13HllNSO.)X3] 3·10 3046 (3'59) 8·12 (8'21) 3'20 9-64 (9'77) 5·30 (5'59)[Cu(ClsHllNS04)X3] 1·94 3047 (3'54) 8·06 (8'11) 1·91 9·52 (9'69) 5·35 (5'54)[Pd(C13HllNSO.)X] 3·32 (3049) 7-81 (7'98) 4·31 (4'51) 5·00 (5'16)[Cd(C13HllNS01)X] 3-32 (3043) 7·86 (7,86) 4-22 (4-47) 4·91 (5'11)[Zn(C13HllNSO.)X] 3·76 (3-88) 8·82 (8'87) 4·67 (4'83) 5·39 (5'52)[U02(C13H11NSO,,)X] 2·42 (2-47) 5·59 (5·66) 3040 (3'57) 3'92 (4,08)*X=H20 or pyridine; satisfactory metal analyses were obtained.[Estimation of water molecules gave satisfactory results.62for Mn(II) , Fe (II) , Co(II) and Ni(II) chelates andtetragonal configuration for the Cu(II) chelates.The tetragonal structure of Cu(II) chelates is alsoexpected from jahn-Teller effect". Infrared analysisof the metal chelates in the region of 3·1 to 4·0 f.I.confirms the presence of coordinated water moleculesin the complexes.The Zn(I1), Cd (II) , Pd(I1) and U02(II) chelatesshow 1: 1 (metal-ligand) stoichiometry (Table 1).The molecular weight determination shows thecomplexes to be monomeric in nature. Therefore,the complexes may be represented by the formula[MLX] , where M = metal ion, LH2= H2NO(Cl7Hl3NS04] or H2NT lCl3H12NS04] and X =H20 or Py. All the hydrated chelates and theirpyridine adducts have been found to be diamagnetic,as expected. These results can be best explainedby assigning a tetrahedral structure for Zn(II) andCd(II) chelates. U02(II) chelates possess an octa-hedral structure in conformity with the usual be-haviour of U02(II) ion".Pd(II) highly favours a square-planar configura-tion. Yamada et aI.s have suggested a square-planar configuration for a number of N-alkyl-salicylideneiminato Pd(II) chelates. Solution spec-tra in dioxane and pyridine of the Pd(II) chelatesindicate three absorption bands at 22200, 26500and 30600 cm! which can be assigned to the tran-sitions lA lL:;..lBlg, lAIg-,>-lE1g and lAIg-,>-lA2urespectively. Thus the Pd(II) chelates exhibit asquare-planar configuration.References1. COTTON, F. A., Prog. inorg. Chem., 7 (1966), 88.2. PFEIFFER, P., OFFERMANN, W. & \VERNER, H., ]. praht.Chem., 159 (1942), 313.3. YAMADA, S., Coord. chem . Rev., 1 (1966), 415.4. MEHTA, R. K., RAO, S. P. & KAPOOR, R. C., Indian ].Chem., 7 (1969), 937.5. FIGGIS, B. N. & HARRIS, C. M.,]. chem. Soc., (1959), 855.6. HOLM, R. H., EVERETT (Jr), G. M. & CHAKRAVORTY, A.,Prog. inorg . Chem., 7 (1966), 83.7. FIGGIS, B. N. & LEWIS, J.,Prog. inorg. Chem., 6 (1964), 37.8. JAHN, H. A. & TELLER, E., Proc. R. Soc., 161 (1937),220.9. SELBIN, J., Angew. Chem . intern. ss«, 5 (1966), 712.Chlorotellurium Compounds of Aryl Ethers(Miss) KRISHNA RAINA & B. L. KHANDELWALDepartment of Chemistry, Indian Institute of TechnologyNew Delhi 110029Received 28 ] anuary 1975; accepted 24 March 1975Conductance studies and molecular weight measure-ments on ethoxyphenyltellurium trichloride andbis(methoxyphenyl)tellurium dichloride suggest theirpresence in molecular form in organic solvents. IR andNMR studies show the presence of TeCl3 group in thepara position to ethoxy or methoxy group in the ring,in both the compounds.INthe present note, structural aspects of p-ethoxy-phenyltellurium trlchloride'P (I) and bis(p-me-thoxyphenyl)tellurium dichloride" ~II) are discussed.Recently, infrared and NMR studies of p-methoxy-phenyltellurium trichloride have been reporteds-".NOTESCompounds I (m.p. 180-82°) and II (m.p. 190°)Were prepared by literature methods=" and crystal-lized from chloroform and methanol respectively.Conductivities of these compounds at differentconcentrations have been measured in acetonitrileat 30° ± 10. The conductivity increases with dilu-tion. However, the molar conductances are lowerthan the values expected" for 1: 1 electrolytes (120-160 ohm? ern'? mole+) in the concentration rangeof 10-3M. This suggests that the compounds arepresent in the solution mainly in the molecularform. Molecular weight determination in benzeneby cryoscopic method further supports this conten-tion.The asymmetric and symmetric C-O-C stretchingsin phenetole and anisole appear at 1240 and 1040em+ whereas compound I exhibits these bands at1260 and 1050 cm-l and compound II at 1270 and1045 cm'". This shift to higher frequency sideindicates 0- or p-substitution of TeCl3 group in thering. The appearance of a very intense band(1580 crrr-) in both these compounds could be dueto a change in the dipole moment because of thepresence of para-substituted TeC13 group in thering. Further support for para-substitution is ob-tained from the overtone and combination bandswhich appear at 1880, 1780 and 1710 cm-l as ex-pected". A medium intensity band at 455 cm-lin compound 1 and at 480 cm-! in compound IIcorresponds to the tellurium-carbon bond. Thecompounds 1 and II show bands at 320 and 290crrr" respectively assigned to Te-Cl bond.PMR spectra of 1 and II have been recorded indeutro-acetonitrtle. These spectra are of A2X2type and give a definite proof of the para-substi-tution of chlorotellurium group in the ring. Spec-trum (I) scale) of bis(methoxyphenyl)telluriumdichloride shows two quartets at 8'30 and 7·12 ppm.Their intensities show each of them to be due toa pair of protons in idential chemical environment.The ] Hortho-Hmeta is 9,0 ± 0'3 Hz. The methoxygroups give rise to a singlet at 3·87 ppm.The NMR spectrum of II shows even finer struc-tural details. The protons ortho to OC2HS group(HA and HAl) in II are chemically equivalent asare the protons ortho to TeCls group (Hx and Hx-).] AX and] A'X' should be the same (",7-10 Hz).The ortho and meta aromatic protons (with respectto TeC13 group) show a multiplet at 8·27 and 7·80ppm respectively. ]. •.x which is equal to ] A'X'is 9,3 ± 0·3 Hz. The spectrum also shows couplingbetween HA and HA' (as also between Hx and Hx').] AA' is equal to ] xx- and is 2·2 ± 0·3 Hz. Thisspectrum Can be better described as of the typeAA'XX'. A quartet and a triplet appearing at4·14 and 1,38 ppm respectively are due to the ethylgroup (JC,H,-CH.= 7·0 ± 0·3 Hz).Authors wish to thank Mr J. W. Akitt of theUniversity of Leeds, UK, for his help in recordingand valuable comments on the NMR spectra.References1. MORGAN, G. T. & DREW, H. D. K.,J.chem.Soc.,(1925),2307.2. REICHEL, L. & KIRSCHBAUM, E., Liebig's Ann., 523 (1936),211.63

Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Cd(II) & UO2(II) Chelates of Schiff Bases Derived from o-Aminobenzenesulphonic Acid & 2-Aminoethanesulphonic Acid & 2-Hydroxy-1-naphthaldehyde

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Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Cd(II) & UO2(II) Chelates of Schiff Bases Derived from o-Aminobenzenesulphonic Acid & 2-Aminoethanesulphonic Acid & 2-Hydroxy-1-naphthaldehyde

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