cs-«,nopr.niscair.res.in/bitstream/123456789/52463/1/IJCA 16A...INDIAN J. CHEM., VOL. 16A, JUNE...
Transcript of cs-«,nopr.niscair.res.in/bitstream/123456789/52463/1/IJCA 16A...INDIAN J. CHEM., VOL. 16A, JUNE...
INDIAN J. CHEM., VOL. 16A, JUNE 1978
Compound
TABLE 2 - vas(OCO) IN ORGANOTINCARBOXYLATES
Vas (OCO), cm-1 Compound vas(OCO), cm-1
Solid Solution(solid)
1548 1640 PhSn(Ox).OCO.CH3 1645
1535Sn(Ox)2(OCOCH3). 1665
1632 PhSn(Ox)20CO,C2H5 1645Sn(Ox)2(OCO.C2H.). 1650
1576 1662 PhSn(Ox)20COCH.Cl 1672
1650Sn(Ox)2(OCOCH2CI). 1695
1722 PhSn(Ox)20CO.EF3 17251630 1630 Sn(MHBB), 1700
16151620 Sn(HNB). 1710
1620
Ph3SnOCO.CH.
Ph3SnOCO.CFaPh3Sn(MHBB)
PhaSn(HNB)
in the parent triphenyltin compounds in the solutionph,se (Table 2), thu.s showir g the " bser ce of <flyinterrnolecul. r coordinr tion. In the dioxir ate di-carboxyl:, tes, "as(OCO) occur ,. t slightly higherfrequcr.cies. Though the it.ere: se of coordir ation~umber a t the tin, t?m r:ises "as(OCO) by ir hibitirgintermolecular coordinc tion, the frcquer.cies " re stillmuch lower than those in organic esters. This issuggestive of considerable ionic char: cter in thetin-c. rboxyla te bor.d beca use, r.s shown la ter, intra-molecular chelation is ui.likely in these compounds.
The .i-arylazo carboxyl.tes, Sr,(NHBB)4 and Sn-(HNB)4' show two bar.ds of nee rly equal inter sityin the region for "as(OCO) (ref. 9). If the com-pour.ds were octa-coordina ted with e,:ch ligandactii.g as bider.tate group, or.ly a sir gle broadabsorption bai.d would be expected in the sameregion as that observed in the triphenyltin deri-v, tive, The appearance of two bar.ds, one r.earlyat the s. me frequency as that in the correspor.dirgtriphonyltin deriva tive a r.d the other a t a consider-ably higher frequency (,.....,1700cm'}, suggests thatonly two of the four ligar.ds act rs bidenta tegroups, while the rem iring two form ester-likeSn-OCOR bor.d, This is also supported by thespectrophotometric titr. tion of the two compoundswith N"OH in methanol. The titration curves showtwo breaks at 2 moles and 4 moles of NaOH permole of the tin compound" correspondir g to thetwo distinguisha ble types of C8 rboxyla te groups(coordina ted and ester-like). Thus, the tin 8 tomsin these two compounds arc hexa-coordinatcd a sin the oxina te deriva tives. This also shows theinrbility of the carboxyla te group to form ir.termole-cut r chelation in the hexa-coordii ated derivatives.
References
1. OKAWARA. R. & OHARA, M., Organa/in compounds,Vol. II (Marcel Dekker, New York), 1971, 253.
2. OKAWARA, R. & WADA, M., Adv. organometal, Chem.,5 (1967), 137.
3. POLLER, R. C., J. organometal, cu«, 3 (1965), 321.4. POLLER. R. C,; The chemistry of organotin. compounds
(Lagos), 1970, Ch. 12.5. FORD, R. F. E. & SAMS, J. R., J. organometal. Chem ..
31 (1971), 47.6. FORD, B. F. E., LIENGME, B. V. & SAMS, J. R., J.
organometal, cu«: 19 (1969), 53, 67.
544
7. FORD, B. F. E. & SAMS, J. R., J. organometal, Chem.,21 (1970), 345.
8. Roy, A.. Ph.D. thesis, North Bengal University, 1974.9. BANERJEE, S. C.. Ph.D. thesis, North Bengal University,
1975.10. DATTA, D., MAJEE, B. & GHOSH, A. K., J. organometal,
cs-«, 84 (1975), 231.
Reactions of Liquid Sulphur Trioxide withSome Oxo-organottn Compounds
RAM C. PAUL, RAMESH K. SHARMA.RITA WALIA &SURA] P. NARULA
Department of Chemistry, Panjab UniversityChandigarh 160014
Received 28 July 1977; accepted 30 December 1977
Equimolar ratio of liquid sulphur trioxide in carbontetrachloride and l1-oXO-bis[triphenyltin(IV)] in di-chloromethane react at - 20° to ~ive 1 : 1 solid adduct.The adduct changes to bis(triphenyltin) sulphate inrefluxing carbon tetrachloride. Two moles of liquidS03 react with one mole each of 11-0xo-bis[triphenyltin(IV)]. l1-oxo-bis[tri-n-propyltin(IV] and u-oxo-blsjtrt-n-butyltin(IV)] to ~ive the cor-responding bis(tri-organotin) dlsulphates. The structures of all thesecompounds have been established on the basis ofelemental analyses and infrared data.
OXO-ORGANOTIN(IV) cornpotr ds r re br sic innature- «r d form a ddition componr ds with
common Lewis 8 cids 2. The re: ctior s of liquidsulphur trioxide with some srch cornponr ds hr vebeen attempted ar d the results He reported inthis rote.
fl.-Oxo-bis [tripher yltir- (I V)], fl.-oxo-his [tri-a-propyl-tir(IV)], Woxo-bis[tri-n-brtyltir(IV)] rnd di-x-bt.tyl-tin oxide supplied by Akzo Chemic; Is, Kirby, UK,were used r s si-ch. Liquid sulphur trioxide wasobtr ir ed ,5 reported". The roactior s were crrriedout ur-der perfect dry cor ditior s.
Reaction of liquid suipltur trioxide icith fl.-oxo-bis-[triphcnyltin(IV)] in 1:1 molar ratio - Liquid S03(1·60 g; 20 mmoles) in carbon tetT<'chloride (50 ml)w: s dropped slowly into the well cooled (- 20°)
NOTES
solution 01 [J.-oxo-bis[triphenyltill(IV)J (14'30 g, 20mmoles) in dichlorornetho r e (50 ml) ur.der N2
a tmosphere. A white solid (15 g; 19 mmoles, 95%)W2 s obtained which was filtered under N2 < trnos-sphere, wr shed <led dried in vacuo (,....,10 mm) ar.danalysed.
The above compound (5'30 g; 6·7 mmoles) wtstaken in dry carbon tetrachloride (200 ml) ar dhca ted on a wu ter-bi.th for 1-2 hr, filtered, we shed S03.A-and dried in vacuo (,.....,10mm) r nd anr lysed. Itw.i s found to be bis rtriphen yltin (1V)] sulpha te,
The 2- bove rea ction wa s also carried in the molar [(CeH.)3Sn].SO.
ratio 2:1 to give a white solid in er ch crse. The [(CaH.laSnJ2S•07white solids were heated in dry CeIt for 1-2 hr.
The relevant physical and anc lytica l drta rre 'given in T~ ble 1. The 1: 1 adduct obtr ir-ed here [(tl-C3H7laSn].S207
is insoluble in most of the common orgcr ic solver:ts [( C H) S ) SOand hence its mol+r conductance and moleculc r n-, $ 3 n 2 2 7
weight could not be determined. It is a highmelting solid cr d could not be sublimed in vacuo(0·2 mm).
The IR data (vmax in crrr+) of the 1:1 adduct,bis(triphenyItin) sulphate, b.se ar.d liquid S03 showthat Vas(SO) of liquid S03 at 1390 is shifted tolower frequercy region " nd <' ppears c-t 1295 in thelR spectrum of the 8 dduct. vas(SrOSn) b: ndappears it 775 in Woxo-bis[(triphenyltin(IV)]4. Sircenope of the reacting species .bsorb c t 650 ar d630, the existence of these brr.ds in the spectrumof the rdduct mr y be rttribntcd to vas(Sr OSn).~OSO bands of liquid S03 at 650, 532 shifted to580 on ~dduct form? tion, Besides these, someminor spectral changes such as the shift of vs(SO)of liquid S03 r t 1068 to 1050 in the adduct, hrvealso been observed. These observations iridic. tedonor-acceptor bond formation as:
[(C6H5)3S"M) :+S03-+ [(C6H5)3Sn]i>:-+soaLitera ture records" that the adducts of liquid
S03 with diethyl ether and di((1-chloroethyl) etherundergo intra molecul: r migra tion on he, tir g toproduce diethyl sulphate t.nd di(~-chloroethyl) sul-pha te respectively. A similar ch" r:ge rlso occurs in1: 1 adduct and a cornpa rison of the IR spectrumof the product with those of the krown bisttri-organotin) sulpha tes7,8 suggests the r dduct to havebeen char.ged to bisttriphenyltin) sulph. te; Vmaxa t1130, 1090 (vasSO), 735 (PhY-CH), 690 (Ph), 580(a.soso or VsS03) i-r d 448 (vasSl.Ph3).
It is interestir g to r.ote thr t u-oxo-bisjtri-a-prcpyl-tin (IV)] , [L-oxo-bis[tri-n-br.tyltit.{IV)l ar.d di-n-butyl-tin oxide on rer ction with liquid S03 directly givethe corresporidi: g orgar.otin sulph: tes7,8. References
The compounds obtair-ed from two moles of liquidS03 and one mole of the oxo tir (IV) compourds8 re solids, ser sitive to moisture, iJ 50111 ble in mostof the common org8 nic sol-verts a I' d could I' ot besublimed even in vac-~t()(,--.,0·2 mm). Owir g to theirinsolubility, rnoler conductance rr d molccul: r weightdeterrnina tior s could not be C,' rried out.
Some major IR ebsorption brr.ds (vrnaxin em-I)of the a bove mer, tioned cornpour.ds rs well; s mete Idisulphe tes", for comparison, he ve been; ssigr.ed ; sfollows: The strong be nds a t 1298 ard 1280 in thecompourds ; re rssigr-ed to vasS03 mOd€59. Thebands cppearing in the region 1160-70 are due to 7.
TABLE 1- PHYSICAL AND ANALYTICAL DATA OF1: 1 ADDUCT, BIS(TRIPHENYLTIN) SULPHATE AND OF
DISULPHATES OBTAINED BY THE REACTION OF LIQUID SO.WITH .,.-OXO-BIS[TRIORGANOTIN(IV)]
Complex m.p. (0e) and Tin (%) Sulphurstate found (%) found
(reqd) (reqd)
>330 30·40 4-14White hygro- (29'72) (4'30)scopic solid>330 30'46 4·01White powder (29'72) (4'30)
300 (dec.) 26·50 7'02White hygro- (27'00) (7'32)scopic solid>330 35·17 9·62White powder (35'22) (9'55)>330 30·20 8·49White crystal- (31'30) (8·47)line solid
• A = fL-oXo-bis[triphenyltin(IV)].
VsSOa modes while those identified in the spectrrlregion 1040-50 •.re rrother symmetric (V'.S03) <; b-sorptior 59. The be ids due to ~a,SOS ha ve beenlocated a t 770-810 whereas due to ~sSOS havebeen at 715-60. ~asS03 <J bsorption frequencies ha vebeen observed in the rarge 570-90 while asosomodes seem to occur" t 550 in ill these compoui.ds.The b31 ds in the region 335-60 m. y correspoi d toeither ~SOS or V·S03 modes", Such b. r.ds in thekr.own disulphc tcs could be identified only in Ramanspectra. All these, bsorptioi s •.grce f, irly well withthose of the reported disulph: tes. va,S;C3, bsorp-tion occurrirg in the region 600-12 is in re. son, ble<' greemer t with simil. r L bsorpt ion in org, I ot.insulpha tes',8. This Foil ts to tl:e ple r c r SI C3moieties in these cornpour.ds.
On the br sis of tee ~.bove-mei tior ed studiesbisftriorgar.otin] disulphc tcs may be given the poly-meric structure (I).
1. MARCHAND, A., MENDELSOHN, J., LEBEDEFF, l\f. &VALADE, J., J. organometal. Chem., 17 (1969), 379.
2. PAUL, R. C., MAHAJAN, V. K., AHLUWALIA. S. C., SHARMA,R. K. & NARULA, S. P., Inorg. nucl. chem. LeU. 9(1973), 893. '
3. PAUL. R. c.. GONDAI-, S. K & NARULA, S. P., Indian J.Chem.,3 (1965), 243.
4. KRIEGSMANN, H .• HOFFMANN, H. & GEISSLER, H., Z.anorg, allg. cu«; 341 (1965), 24.
5. LOVEJOY, R. W., COLWELL, ]. H., EGGERS, D. F. &HALSEY, G. D., J. chem. Phys., 36 (1962), 612.
6. SUTER, C. M., EVANS, P. B. & KIEFER, J. M., J. Am.chem, soe., 60 (1938), 536.
KUNZE, U., LINDNER, E. & KOOLA, ]., J. organometal.Chem., 38 (1972), 51.
545
INDIAN J. CHEM., VOL. 16A, JUNE 1978
8. HERBER, R. H. & STAPFER, C. H., Tnorg, nucl. chemLeft., 7 (1971)' 617.
Q }JALAVIT, G. & NOEL, S., Rev. cu« minerale, 8 (1971),1.
Potentiometric Study on Some TernaryComplexes of Pr(III)
T. H. J\IHASKE* & K. N. MUNSHI
Department of Chemistry, Nagpur UniversityN agpur 440010
Rcceiued 18 October 1976; revised 10 October 1977accepted 1 November 1977
The formation constants of the ternary complexesof Pr(III) with nitrilotriacetic acid (NTA), Nvhydroxy-ethylethylenediaminetriacetic acid (HEDTA) and ethy-lenediaminetetracetic acid (EDTA) as primary Ilgands(A) and 8-hydroxyquinoIine-5-sulphonic acid (OSA)and 8-hydroxy-7 -iodoquinoline-5-sulphonic acid(IOSA) as secondary Iigands (L) have been investi-gated by potentiometric titration technique. Ternarycomplexes having 1: 1: 1 stoichiometry are formed.The formation constants (log K~!d are reported atthree different temperatures and at fixed ionic strengthJ1 = O'2M (NaCIO.). The formation constant of ter-nary chclates follow the order log K~:lt >log K~~TA>
log K~l~IA.
WE helve reported earlierl-3 mixed ligand chela tesof Pr(III) with bidenta te phenolic 2 cids and
carboxylic acids. The present investigation dealswith the dntcrmir.a.tion of the stability constantsof ternary complexes of Pr(III) with nitrilotriaceticacid (NTA), N-hydroxyethylethyleLediaminetriticetica cid (HEDTA) and ethylenedi".minetetr~cetic e cid(EDTA) ~s prim.ry Iig.r.ds (A) ar.d 8-hydroxy-quu.olir e-s-sulphonic a cid (OSA) ar.d 8-hydroxy-7-iodoquinolir:e-s-sulphonic a cid (IOSA) L S secon-dary ligands (L). The stability constants havebeen determii cd employing a modified form ofIrvir g and Rossottr' potentiometric titration tech-nique. The sic,bility COl sta nts of OSA complexeswith Pr(HI) 2 re reported" in litera ture but theconditio's of study are different. For comparisonof the values of stability constants of va riousten ary complexes, birary complexes have beenstudied under identical conditior s.
A stock solution 0·02M of PrCl3.7H20 ([Rare EathIndia Ltd) was prepared in a calculated quantityof perchloric acid to prevent hydrolysis. Solutionsof O·OlM NTA (BDH), O'OlM HEDTA (SigmaChemicd Co. Ltd), O·OIM EDTA (disodium salt,AK BDH), 0'004M OSA (E. Merck) and 0·004MIOSA (BDH) were prepr red in wa ter ard standard-ized potentiometrically. Sodil:m hydroxide (O·sM).sodium perchlorate (1M) and perchloric 2 cid (O'IM)solutions were prepared in doubly distilled wc ter.
An exp rnded sole pH meter with an accurr cy of0·02 PH units (Electronic Corporation of India Ltd)
*Pres")nt address: Department of Chemistry, VidarbhaMahavidyalaya, Amaravati (Maharashtra).
546
with a g12ss calomel electrode 3 ssernbly w: s used.An ag3r bridge, saturated with KN03 was usedto prevent the formation of chloro complexes.Measurements were done under N2 2 tmosphere ina thermostat-bath having an accuracy of ±0·1.
The experiment: 1 procedure involved the poten-tiometric titrations of three solutions for binarycomplex studies, viz. (i) free H004 (1·0 X 10-2M),(ii) HCI04 (1·0 X 1O-2M) + liga-id (L) (2·0 X 1O-3M) and(iii) HCI04 (l'Ox 10-2M)+ ligand (L) (2'OX 10-3M)+ metal (M) (4·0 X 10-4M); arid four solutior.s forternary complex studies, viz. (i) free HCI04 (1,0 X10-2M), (ii) HClO( (l'Ox 10-2M)+ secondary ligand(L) (2'0xlO-3M); (iii) HCI04 (1'0xl0-2M}+ primaryligand (A) (2'OxlO-3M)+ metv l (M) (2'0xI0-3M)and (iv) HClO( (1'0 X 1O-2M) + primary ligand(A) (2'Ox 10-3M) + metal (2'Ox 1O-3M) + secondrryligand (L)(2'Ox 10-3M). The ionic strergth of solu-tions (total vol. 100 ml) WeS mair.tcined a t 0·2M.The titra tions were ca rried out aga inst O·Silt sodiumhydroxide for binary complexes and agair.st 1'06MN<i,oH for ternary mixtures. As a represerita tivecase typical plots of PH against volume of NaOHare shown in Fig. 1 for Pr(III)-IOSA system.Similar plots are obtained for Pr(III)-OSA systemalso. The pH titration curves for represents tiveternary system of Pr(III)-NTA-IOSA are shown inFig. 2. Similar plots are obtained when HEDTAand EDTA are used as primary ligands and so alsowhen OSA is used 8S secondary ligand.
In the case of the mixed ligand systems presentedin this paper, primary ligands (A) form very stable1:1 complex with Pr(III) ion and the observe tionof prime ry complex curves indice ted tha t thecomplete formation of 1:1 complex (MA) takes placeat very law pH ~4'0 in the range where secondaryligand (L) could not get a tta ched with the bina ry
9P,ClIIHOSA
8
pH 6
5
4
3
2
10 20 30VOlume of NoOH lml>
Fig. 1 - Titration curves for Pr(III)-IOSA system at 35°and !.I. = 0'2M (NaCIO.l [(Al acid titration curve; (El ligand
titration curve; and (C) complex titration curve]