Khandelwal, B. L.

Raina, (Miss) Krishna

English

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for 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),211.63INDIAN J. CHEM., VOL. 14A, JANUARY 19763. MORGAN,G. T. & KELLETT, R. E., J. chem, Soc., (1926),1080. TABLE 1 - PRODUCTS OF THE REACTIONS OF DIALKYLTIN4. WYNNE, K. J. & PEARSON, P. S., Lnorg . Chem., 10 (1971), DIALKOXIDESWITHDIETHYLHYDROXYLAMINE2735.5. WYNNE, K. J., CLARK, A. J. & BERG, M., J. chem, SOC.,Dalton, (1972), 2370.6. GEARY, W. J., Coord. chem . Rev., 7 (1971), 81.7. COLTHUP,N. B., DALY, L. H. & WIBERLEY, S. E., Intro-duction to infrared and Raman spectroscopy, InternationalEdition (Academic Press, London), 1964, 230.N,N-Diethylamino-oxy Derivatives ofDialkyltin(IV)(Miss) C. K. SHARMA,V. D. GUPTA& R. C. MEHROTRA*Department of Chemistry, University of RajasthanJaipur 302004Received 25 January 1975; accepted 27 February 1975Diethylamio-oxy derivatives of dialkyltin(IV) havebeen synthesized and characterized on the basis ofelemental analysis, molecular weight determinationand IR data.IN continuation of our previous work on N,N-diethylhydroxylamine deriv~tjv~s of ti~aniu~l,boron and alurninium-, the derivatives of dialkyltin(IV) are reported in this n?te. . .. .Dimethyl-, diethyl- and dibutyltin dm:opropox~desand dibutyltin diethoxide, prepared by.the scdl,:mmethod, react with diethylhydroxylamine to giveproducts, R2Sn(OR')2-X [0 (C2H5)2]X (Table 1). Thereactions can be represented as follows:R2Sn(OR')2+X(C2Hs)2NOH >R2Sn(OR'h_x[ON(C2Hs)2]x+xR'OH;(R = CH3, C2HS and C4H9; R' = C2HS and C3H;and x = 1 and 2).The general method of prepa.ratio? of ~he com-pound is as follows: Dialkyl~m d~alkoxldes a~c1diethylhydrcxylamine were mixed .1D benzene. IIIstoichiometric ratios and left overnight. Reactionmixtures were heated at a bath temperature of80-90° for 4-8 hr. In reactions (1-3) the benzenewas removed and the products distilled under reducedpressure. In other cases, insoluble products wereseparated by filtration and washed subseq,:en~ly.Dibutyltin derivatives (Table 1, Nos. 1-3) are l1qUl~S,miscible with organic solvents. These <l:r~volatileand can be distilled with slight decomposition underreduced pressure. ..The molecular complexity of soluble diethylamine-oxy derivatives of dibutyl tin (IV) was foun~ to. beabout three as revealed by mol. wt detern:llnatlO~.Compounds derived from dimethyl- and dIet~yltllldiisopropoxides are insoluble and can be consideredto be polymeric. . .IR spectra of the compounds' exhibit Vas and VSN-O around 950 and 910 crrr! respectively". Thecharacteristic absorptions' of isopropoxy groupoccur at 1140 1055-1050 crrr ' and that of ethoxygroup at 1180-'1103 and 1010 em-I. The bands i.n theregions 620-609 and 521-510 cm-1 have been assigned*Present address: Delhi University, Delhi 110007.64SI Molar Product Found (%) (calc.)No. ratio ofreactants Sn N1: 1 (C.H9)2Sn(OC.Hs) 32·39 3·85[ON(C.Hsh], b.p. (32-46) (3-83)113-16°/1 mm; 27%2 1:2 (C.HgJzSn [0N (C2Hs).h, 29'27 6'83b.p , 103-6°/1 mm; 40% (29'04) (6'84)3 1: 1 (C.H9).Sn (OC3H?i) 31·29 3·60[ON(C2Hsh], b.p. (31'33) (3-64)110%'5 mm; 35%4 1: 1 (CHa).Sn(OC3H?i) 39·93 4·70[ON(C.Hs)2]' insoluble (40'05) (4'73}and infusible; 99%5 1:2 (CHs).Sn[ON(C.Hs).]2, 36·72 8·60insoluble and in- (36'53) (8'62)fusible; 97%6 1:1 (C2HshSn (OC3H?i) 36'81 4·46[ON(C2H5h], soluble (36'64) (4'33)in hot benzene andinfusible; 98%7·937 1:2 (C2HshSn[ON(C2H5)2J., 33'98insoluble and in- (33'67) (7'94)fusible; 96%Products 1-3 are yellow liquids and of 4-7 are white solids.to Vas and Vas Sn-C respectively. Vas and Vs Sn-O appeararound 572-560 and 475-466 em"! respectively'.References1. SINGH, A., SHARMA,C. K., RAI, A. K., GUPTA, V. D. &MEHROTRA,R. C.,]. chem, Soc. (A), (1971), 2440.2. SHARMA,C. K., GUPTA, V. D. & MEHROTRA,R. C., Indian]. Chem., 12 (1974), 218.3. NOEL, R. M.• MUNOZ, A. & MATHIS, F., Chem, Abstr., 60(1964), 10064.4. RAO, C. N. R.. Chemical applications of infrared spectroscopy(Academic Press, New York), 1963.5. TANAKA,T .• Organometal . chem, Rev., 5 (1970), 7.Mn(Il), Fe(Il), Co{ll), NUll) & Cu(ll) Com-plexes with BenzoylhydrazineR. C. AGGARWAL& K. K. NARANGChemistry Department, Banaras Hindu University, Varanasi 5Received 16 December 1974; accepted 3 March 1975Benzoylbydrazine (BH) complexes of the typesM(BH)3S0•.3iH.0 where M=Ni(II), Co(II) or Fe(II);M'(BH).SO•.2H20 where M'=Cu(II) or Mn(II);M"(BH)3Cl2.3H.0 where M"= Ni(II), Co(II) or Mn(II) andNi(BH)3Xwhere X=HgCI!-, HgCl2I~-,HgI:-, CdCI.I~-orCdl:- have been synthesized and characterized by ana-lysis and physicochemical studies. The complexes arespin-free and octahedral where BH acts as a bidentatecoordinating ligand. Molar extinction coefficient (3)and approximate oscillator strength (f) of the elec-tronic bands have been calculated for complexesof the type M·(BH)sCIa- Sulphate group is bonded tometals directly or to BH by hydrogen bonding.IN continuation of our work1,2 on benzoylhydrazine(BH) complexes of Ti(IV) and some non-tra~-sition metal ions, the preparation and characteri-

Chlorotellurium Compounds of Aryl Ethers

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Chlorotellurium Compounds of Aryl Ethers

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