Dithiolium compounds of tin(IV) and antimony(III)

3330

Notes Dq = 4751 cm -~ F~-- 168cm -1 F 4 = 56cm -~.

With these parameters AI --* E transition is located at 24,411 cm -1 which agrees fairly well with the experimental value of 23,200 cm -1. The spectra of this complex in aqueous solution are shown in Fig. 4. It may be observed that the spectra are completely different as compared to crystal spectra. Consequently the geometry of the complex in solution is different from that in solid state. The spectral measurements were made on the set up described previously. The complexes were prepared by methods due to M. C. Steele[3] and F. Holzl[4]. Both of these complexes were found to be diamagnetic.

Department of Chemistry University College of Science Calcutta 9 India

M. BASU S. BASU

J. inorg,nucl.Chem.,1969,Vol.31,pp. 3330to3332. PergamonPress. Printedin Great Britain

Dithiolium compounds of tin(IV) and antimony(Ill) (First received 14 February 1969; in revised form 10 March 1969) IN REC~.raT work successful syntheses of dithiolium tetrabromo- and tetrachloro- metallates of transition metals have been reported [ 1-5]. This type of compound for non-transition metals, however, has not been reported as yet. Well-known, however, are the acetylacetonates of tin, lead or antimony for example. This fact led us to undertake the syntheses of dithio-/3-diketone complexes of these metals. For this purpose we applied the synthetic technique applicable to this type of compound of transition metals [2, 6, 7]. The acetylacetonates were dissolved in absolute ethanol and were treated with free halogen and hydrogen sulfide. Sometimes the reaction was also carded out in the presence of hydrogen halide catalyst. Though we did not succeed in obtaining dithio-/3-diketonates of these metals, dithiolium compounds of them were synthesized. In synthesizing the complexes of transition metals, hydrogen halide was indispensable as the catalyst, while for the compounds of tin and antimony, hydrogen halide was not required as shown in the experimental part. The presence of excessive hydrogen halide sometimes gave the adducts of hydrogen halide, which were often very sensitive to moisture. In this manner, the complexes of tin(IV) and antimony(III) were obtained, whereas those of tin(II) or antimony(V) were not, even when the oxidation numbers of the metals of starting salts were 2 and 5, respectively. This fact seems to be attributable to t h e relative redox potentials of dithiolium, tin and antimony. Tri~-:. were made by this method to synthesize the lead(II) complex, but this was not achieved possibly owing to too low reactivity oflead(II) chloride. EXPERIMENTAL Instruments. I.R. spectra were obtained by a Nujol and hexachloro-l,3-butadiene mull procedure using a type DS-301 i.r. spectrophotometer of Japan Spectroscopic Co., Ltd. An Hitachi EPS-2 typed 1. 2. 3. 4. 5. 6. 7.

K. Knauer, P. Hemmerich andJ. D. W. Van Voorst, Angew. Chem. 6, 262 (1967). A. Furuhashi, K. Watanuki and A. Ouchi, Bull. chem. Soc. Japan 41, 110 (1968). A. Furuhashi, T. Takeuchi and A. Ouchi, Bull. chem. Soc. Japan 41, 2049 (1968). Y. Takahashi, M. Nakatani and A. Ouchi, Bull. chem. Soc. Japan 42, 274 (1969). G. H. Hearth, R. L. Martin and I. M. Stewart, Aust. J. Chem. 22, 83 (1969). A. Ouchi, M. Hyodo and Y. Takahashi, Bull. chem. Soc. Japan 40, 2819 (1967). A. Ouchi, M. Nakatani and Y. Takahashi, Bull. chem. Soc. Japan 41, 2044 (1968).

Notes

3331

automatic recording spectrophotometer was used to obtain electronic spectra. Magnetic moments were measured with a Gouy balance at room temperature (15°C). Syntheses of complexes. In Table 1 are shown the elemental analyses as well as the chemical formulas of the products calculated from the analytical data, the colors of solid compounds, and the yields of the syntheses. Table 1. Analyses of complexes

Color

Yield (%)

Sn(C~H7S2)2CIe

yellow

20

Sb(CsH7S2)2Cls'HCI

green

27

Sb(CsHrS2)CI4

yellow

15

Sb(C10HuS2)CI4

orange

< 10

Chemical formulae

Metal Calcd. Found Calcd. Found Calcd. Found Calcd. Found

19-99 20.45 20.36 20.30 30.84 30.45 26.67 26.06

Analyses (%) C H 20.23 20.45 20.09 19.40 15.21 15.37 26.27 26.91

2.37 2"63 2-53 2.39 1.79 1.58 1.99 2-04

S

CI

21.60 21.40 21.45 20.40 16.24 17-65 14.04 13.21

35.82 35.81 35.57 36.43 35.92 35.67 31-05 31.75

C~HrS2:3,5-dimethyl- 1,2-dithiol- 1-ium. C10H7S2: 3-methyl-5-phenyl- 1,2-dithiol- 1-ium.

3,5-dimethyl-l,2-dithiol-l-ium hexachlorostannate(IV). 2.3 g (0-010 mol) of tin(lI) chloride dihydrate were dissolved, after dehydration by direct heating, in 30 ml of absolute ethanol together with 1.8 g (0.018 mol) of acetylacetone. To the solution, under ice cooling, chlorine was passed for a few minutes, then hydrogen sulfide for 1 hr. To the solution thus obtained, was added an equivolume of petroleum ether. It was kept overnight at 5°C to obtain a crystalline product. This was filtered off, washed with carbon sulfide, ethyl ether and lastly by petroleum ether, dried in a nitrogen atmosphere under reduced pressure overnight at room temperature. A tin(IV) compound was prepared by the same method. In this process, hydrogen chloride should not be passed into the solution as the catalyst; if introduced, it produces a hydrogen chloride adduct, probably Sn(C5H7S2hCI6"nHCI, which is not stable, strongly deliquescent, and even in a nitrogen atmosphere decomposes rapidly at room temperature, though not as fast at 0°C. 3,5-dimethyl-l,2-dithiol-l-ium pentachloroantimonate(lll).hydrogen chloride. To 1.8 g (0.018 mol) of acetylacetone and 2.3 g (0.010 mol) of antimony(Ill) chloride, both dissolved in 30 ml of absolute ethanol, were added, under ice cooling, hydrogen chloride, chlorine and hydrogen sulfide in that order. An equivolume of petroleum ether was then added, and the mixture kept overnight at 5°C. The crystalline product thus obtained was washed and dried. 3,5-dimethyl-l,2-dithiol-l-ium tetrachloroantimonate(lll). Chlorine first, then hydrogen sulfide were bubbled through the mixed ethanolic solution of acetylacetone and antimony(lll) chloride. It was possible to use antimony(V) chloride in place of antimony(Ill) chloride, in which case chlorine was not necessary; the produce was obtained merely by passing hydrogen sulfide into the starting ethanolic solution. 3-methyl-5-phenyl-l,2-dithiol-l-ium tetrachloroantimonate(III) was obtained by almost the same method as that of the former compound, using benzoylacetone in place of acetylacetone. RESULTS AND DISCUSSIONS These new dithiolium halogenometallates are all diamagnetic at room temperature, hardly soluble in such nonpolar organic solvents as carbon tetrachloride, benzene or chloroform, but soluble in such polar ones as ethanol or water, in which they undergo dissociation into metal halide and dithiolium ions. The u.v. absorption spectra of the ethanolic solutions of these compounds are closely similar to each other, provided that the dithiolium moiety in the compounds is the same. The compounds containing 3,5-dimethylq,2-dithiol-l-ium show always two main peaks: 37,700 cm -1 (log ~ = 3.8) and 34,500cm -~ (log C= 4.0). Those containing 3-methyl-5-phenyl-l,2-dithiol-l-ium show always three main absorptions: 41,000 cm -1 (log ~ = 3.8), 34,100 cm -1 (log ~ = 4.0) and 28,300 cm -1 (log E =

3332

Notes

4.4). The i.r. spectra of these compounds, as well as those of dithiolium perchlorate or halogenometallates of transition metals, are almost alike in 1800-600 cm -1 region provided that the contained dithiolium is the same one. The typical pattern of the i.r. spectra of some compounds are shown in Table 2. From these results these compounds are assumed to consist of halogeno metallate anion and Table 2. I.R. spectra of complexes (cm -a) Sn(CsHTSz)sCIo

1475 1442 1421 1392 1368

Sb(C~HTSz)CI4

Fe(CsHTS2)2CI4 Sb(CloHaS2)C4

s sh sh w m

1477s 1442 sh 1422sh 1369 m

1470 s 1430 s 1420s 1375 s 1353s

1233m 1203 s

1299m 1201s

1230 m 1200s

1101 w 1021s 1012s 998 s 851s

1100 w lOlOm lO04sh 985 sh 871s

1073 w 1007 m 997 m 982w 860s

705 s

705 s

710w 696 s

Fe(ClaHoSs)Ch

1589 m 1469s

1593 w 1475s

1372 1343 1322 1254

w w w s

1372 w 1340w 1312 w 1258s

1144w 1100 w 1015w 998 m 929 w 859 m

1145m 1098 w 1018m 998 m 923 s 877 s 865 s 760s

771 722 706 680

s w m s

708 w 675 s

dithiolium cation. Such a structure was suggested by R. L. Martin for the transition metal compounds of dithiolium [5]. The X-ray structural analysis of Fe(C~HTS~hCI4 recently made by R. Mason, E. D. McKenzie et al. [8], as well as by H. C. Freeman, K. H. Knauer et al. [9], likewise support the suggested structure. Since some of the compounds are not yellow but green or reddish-orange in color, some sort of anion-cation interaction is also expected to exist as pointed out by R. L. Martin [5].

Acknowledgements - T h e authors wish to thank Professor Yukichi Yoshino, Dr. Kunihiko Watanuki and Dr. Toshio Takeuchi for their helpful discussions. The support of a Scientific Research Grant from the Ministry of Education of Japan given for this investigation is also gratefully acknowledged.

Department of Chemistry College of General Education University of Tokyo Komaba, Meguro-ku, Tokyo Japan 153

MITSUHISA NAKATANI YOSHIAKI TAKAHASHI AKIRA OUCHI

8. R. Mason, E. D. McKenzie, G. B. Robertson and G. A. Rusholme, Chem. Comm. 1673 (1968). 9. H. C. Freeman, G. H. W. Milburn, C. E. Nockoids, P. Hemmerich and K. H. Knauer, Chem. Comm. 55 (1969). J. inorg, nuel. Chem.,1969, Vol. 31,pp. 3332to3333.

Pergamon Press.

Prlnted in Great Britain

Proton conductivity in ammonium perchiorate (Received 30January 1969) WE HAVE obtained some evidence of proton conductivity in solid ammonium perchlorate (A.P.). A.P. pellets were prepared by pressing under a pressure of 3 tlcm 2 till they were transparent. Elec-