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Chemistry
Academician A. N. NESMEYANOV, A. E. BORISOV, and N. V. NOVIKOVA
ON THE ATOMIC REFRACTION OF ANTIMONY
The atomic refraction of phosphorus for the sodium \(D\) line has been reliably determined by many investigators on the basis of the study of a large number of organophosphorus compounds \((^{1-6})\). For arsenic it has been calculated from several alkyl and mixed alkyl-aryl organoarsenic compounds \((^{7})\). The atomic refractions are completely unknown for both trivalent and pentavalent antimony.
Table 1
Constants of alkenyl compounds of antimony, mercury, and arsenic
| Nos. | Compound | \(n_D^t\) | \(d_4^t\) | \(t^\circ\) | \(MR\) | Difference in mol. refr. | Atomic refr. of metal |
|---|---|---|---|---|---|---|---|
| 1 | \(\left(\begin{matrix}\mathrm{CH_3}& &\mathrm{H}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\end{matrix}\right)_3\mathrm{Sb}\) | 1,5511 | 1,2870 | 20 | 60,74 | 0,32 | 17,28 |
| 2 | \(\left(\begin{matrix}\mathrm{CH_3}&&\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\mathrm{H}\end{matrix}\right)_3\mathrm{Sb}\) | 1,5590 | 1,3092 | 20 | 60,42 | 0,32 | 16,96 |
| 3 | \(\left(\begin{matrix}\mathrm{CH_3}&&\mathrm{H}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\end{matrix}\right)_5\mathrm{Sb}\) | 1,5490 | 1,17025 | 20 | 88,92 | 0,45 | 16,48 |
| 4 | \(\left(\begin{matrix}\mathrm{CH_3}&&\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\mathrm{H}\end{matrix}\right)_5\mathrm{Sb}\) | 1,5610 | 1,1972 | 20 | 88,483 | 0,45 | 16,05 |
| 5 | \(\left(\begin{matrix}\mathrm{Cl}&&\mathrm{H}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\end{matrix}\right)_3\mathrm{Sb}\) | 1,6298 | 1,7617 | 50 | 61,85 | 0,83 | 17,54\((^9)\) |
| 6 | \(\left(\begin{matrix}\mathrm{Cl}&&\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\mathrm{H}\end{matrix}\right)_3\mathrm{Sb}\) | 1,6180 | 1,7580 | 50 | 61,02 | 0,83 | 16,71\((^9)\) |
| 7 | \(\left(\begin{matrix}\mathrm{CH_3}&&\mathrm{H}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\end{matrix}\right)_3\mathrm{SbCl_2}\) | 1,5820 | 1,5056 | 20 | 70,02 | — | 14,63 |
| 8 | \(\left(\begin{matrix}\mathrm{CH_3}&&\mathrm{H}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\end{matrix}\right)_3\mathrm{SbBr_2}\) | 1,6270 | 1,8596 | 20 | 77,16 | — | 15,97 |
| 9 | \(\left(\begin{matrix}\mathrm{CH_2{=}C{-}}\\[-2pt]\vert\\[-2pt]\mathrm{CH_3}\end{matrix}\right)_3\mathrm{Sb}\) | 1,5475 | 1,2879 | 20 | 60,38 | — | 16,92 |
| 10 | \((\mathrm{CH_2{=}CH})_3\mathrm{Sb}\) | 1,5614 | 1,4341 | 20 | 45,84 | — | 16,23 |
| 11 | \((\mathrm{CH_2{=}CH})_5\mathrm{Sb}\) | 1,5590 | 1,2986 | 20 | 63,91 | — | 14,57 |
| 12 | \((\mathrm{CH_2{=}CH})_3\mathrm{SbBr_2}\) | 1,6480 | 2,1153 | 20 | 62,38 | — | 15,05 |
| 13 | \(\left(\begin{matrix}\mathrm{CH_3}&&\mathrm{H}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\end{matrix}\right)_2\mathrm{Hg}\) | 1,5622 | 2,2120 | 20 | 41,40 | 0,19 | 12,43\((^{10})\) |
| 14 | \(\left(\begin{matrix}\mathrm{CH_3}&&\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\mathrm{H}\end{matrix}\right)_2\mathrm{Hg}\) | 1,5628 | 2,2297 | 20 | 41,21 | 0,19 | 12,24\((^{10})\) |
| 15 | \(\begin{matrix}\mathrm{Cl}&&\mathrm{H}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\mathrm{AsCl_2}\end{matrix}\) | 1,6105 | 1,8877 | 20 | 38,10 | 0,71 | 11,43\((^{11})\) |
| 16 | \(\begin{matrix}\mathrm{Cl}&&\mathrm{AsCl_2}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\mathrm{H}\end{matrix}\) | 1,5888 | 1,8682 | 20 | 37,39 | 0,71 | 10,72\((^{11})\) |
| 17 | \(\begin{matrix}\mathrm{Cl}&&\mathrm{H}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\mathrm{AsCl_2}\end{matrix}\) | 1,6076 | 1,8793 | 25 | 37,61 | 0,22 | 10,94\((^{12})\) |
| 18 | \(\begin{matrix}\mathrm{Cl}&&\mathrm{AsCl_2}\\[-2pt]&\mathrm{C{=}C}&\\[-2pt]\mathrm{H}&&\mathrm{H}\end{matrix}\) | 1,5859 | 1,8598 | 25 | 37,39 | 0,22 | 10,72\((^{12})\) |
In studying the stereochemistry of organometallic compounds of the ethylene series, we synthesized a number of liquid stereoisomers of propenyl compounds of trivalent and pentavalent antimony* \((^{8})\) and determined the atomic refractions of antimony from molecular refractions calculated by the Lorentz—Lorenz formula.
From the atomic refractions of antimony given in Table 1, it follows that they, like the atomic refractions of phosphorus, depend on the valence state of antimony and on the nature of the bonds.
Comparison of the molecular refractions of the corresponding pairs of cis- and trans-isomers—namely, tri-(propenyl)antimony (Nos. 1, 2), penta-(propenyl)antimony (Nos. 3, 4), tri-(β-chlorovinyl)antimony (Nos. 5, 6), dipropenylmercury (Nos. 13, 14), and β-chlorovinyldichloroarsine (Nos. 15, 16, 17, 18)—leads to the conclusion that the trans-isomers possess greater molecular refraction than their cis-isomers. This increased polarizability of trans-isomers (as compared with the cis-isomer) of alkenyl organoelement compounds is fully consistent with their increased reactivity in the sense of the greater ease of cleavage of the C—M bond, which we have noted repeatedly \((^{13-16})\).
Institute of Organoelement Compounds
Academy of Sciences of the USSR
Received
20 IV 1960
CITED LITERATURE
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* The synthesis and isolation of the reaction products of organoantimony compounds were carried out in a dry stream of nitrogen.