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Academician A. N. NESMEYANOV, K. N. ANISIMOV, N. E. KOLOBOVA,
M. Ya. ZAKHAROVA
BIMETALLIC DERIVATIVES OF CHROMIUM, MOLYBDENUM, AND TUNGSTEN CARBONYLS
Our previous investigations in this field were devoted to developing methods for the synthesis of chromium, molybdenum, and tungsten carbonyls (¹–⁵) and to studying the properties of bimetallic derivatives of rhenium carbonyl (⁶). In the present work we report mixed bimetallic derivatives of the type: C₅H₅(CO)₃Me—Me′(C₆H₅)₃ and [C₅H₅(CO)₃Me]₂—Me(C₆H₅)₂ (where Me = Cr, Mo, W; Me′ = Sn, Pb), which were obtained by the interaction of sodium salts of tricarbonyl-π-cyclopentadienylmolybdenum (tungsten, chromium) with triphenyltin (lead) chlorides in tetrahydrofuran solution. The compounds obtained are white or greenish-yellow crystalline substances, soluble in common organic solvents and insoluble in water. They are all quite stable in organic solvents. On treatment with hydrogen chloride, C₅H₅(CO)₃Mo—Sn(C₆H₅)₃ and C₅H₅(CO)₃W—Sn(C₆H₅)₃ in CCl₄ solution at −15° for 30 min gave, in almost quantitative yields, C₅H₅(CO)₃Mo—Sn(C₆H₅)Cl₂ and C₅H₅(CO)₃W—Sn(C₆H₅)Cl₂.
An analogous action of hydrogen chloride on [C₅H₅(CO)₃Mo]₂—Sn(C₆H₅)₂ and [C₅H₅(CO)₃W]₂—Sn(C₆H₅)₂ led to the preparation of [C₅H₅(CO)₃Mo]₂—SnCl₂ and [C₅H₅(CO)₃W]₂—SnCl₂.
The halogenated derivative compounds obtained are light-yellow crystalline substances, stable in air and soluble in common organic solvents.
Analyses, molecular weights, and IR spectra confirm the structure of the substances we synthesized. For C₅H₅(CO)₃Mo—Sn(C₆H₅)₃, Zavalishin, Khotsyanova, and Struchkov* carried out an X-ray structural investigation, the results of which will be published. It follows from this work that the Mo—Sn distance in the substance described is 2.85 ± 0.02 Å, which exceeds the sum of the atomic radii of the two metals according to the data of reference (⁷) by only 0.08 Å. Similar, but considerably larger, excesses (by 0.5–0.6 Å) of the metal—metal distance were also found in the bimetallic carbonyls Mn₂(CO)₁₀ and Re₂(CO)₁₀ (⁸). Thus, the Mo—Sn bond, and by analogy probably the other metal–metal bonds in the compounds we describe, are covalent bonds. This is also indicated by the solubility of our bimetallic compounds in hexane and other hydrocarbons.
Experimental Part
1. C₅H₅(CO)₃Mo—Sn(C₆H₅)₃. Into a 250 ml round-bottom flask equipped with a stirrer, reflux condenser, dropping funnel, and nitrogen inlet, 0.25 g of dispersed Na in tetrahydrofuran was introduced, and with constant stirring 0.7 g of freshly distilled cyclopentadiene was added in small portions. To the resulting C₅H₅Na solution, 2.7 g of Mo(CO)₆ was added. The reaction mixture was heated at a temperature
* The X-ray structural investigation of C₅H₅(CO)₃Mo—Sn(C₆H₅)₃ was carried out in the structural analysis laboratory of our institute.
60–70° until the evolution of CO ceased. To the mixture, cooled to room temperature, 3.9 g of \((\mathrm{C}_6\mathrm{H}_5)_3\mathrm{SnCl}\) in 15 ml of tetrahydrofuran was added with stirring. The precipitated sodium chloride was filtered off, the solvent was removed, and the remaining mass was subjected to sublimation \((75^\circ/1\ \mathrm{mm})\), as a result of which 0.1 g of \(\mathrm{Mo}(\mathrm{CO})_6\) was isolated. The residue after removal of molybdenum carbonyl was dissolved in a mixture of petroleum ether with benzene and chromatographed on \(\mathrm{Al}_2\mathrm{O}_3\). After recrystallization from a mixture of petroleum ether and toluene, 3.5 g of tricarbonyl-\(\pi\)-cyclopentadienylmolybdenumtriphenyltin with m.p. 212.5–213.5° was obtained.
\[ \begin{array}{ll} \mathrm{C}_{26}\mathrm{H}_{20}\mathrm{O}_3\mathrm{MoSn}.& \begin{array}{l} \text{Found, \%: } \mathrm{C}\ 52.66,\ 52.56;\quad \mathrm{H}\ 3.70,\ 3.42\\ \text{Calculated, \%: } \mathrm{C}\ 52.43;\quad \mathrm{H}\ 3.36 \end{array} \end{array} \]
Mol. wt. (cryoscopically in benzene)—found 581, 600; calculated 595.
I.R. spectrum* \((\nu,\ \mathrm{cm}^{-1})\): 446 (m); 482 (w); 512 (m); 575 (m); 590 (m); 680 (w); 725 (m); 747 (m); 822 (m); 840 (w); 996 (w); 1026 (w); 1074 (w); 1161 (w); 1192 (w); 1302 (w); 1336 (w); 1385 (m); 1408 (m); 1431 (m); 1462–1468 (w); 1481 (w); 1905–1924 (s); 1990 (s); 2860 (s); 2930 (s); 2952 (s); 3028 (m); 3070 (m); 3129 (m);
\([\mathrm{C}_5\mathrm{H}_5(\mathrm{CO})_3\mathrm{Mo}]_2\mathrm{Sn}(\mathrm{C}_6\mathrm{H}_5)_2\). To \(\mathrm{C}_5\mathrm{H}_5\mathrm{Na}\), prepared from 1.7 g of Na and 5.2 g of cyclopentadiene in tetrahydrofuran, 19.5 g of \(\mathrm{Mo}(\mathrm{CO})_6\) was added. After the evolution of CO ceased, 10 g of \(\mathrm{Cl}_2\mathrm{Sn}(\mathrm{C}_6\mathrm{H}_5)_2\) in 30 ml of tetrahydrofuran was added to the mixture. The substance isolated, after sublimation and chromatography, in an amount of 8.5 g was recrystallized three times from a mixture of hexane with benzene; it had m.p. 190–191.5°.
\[ \begin{array}{ll} \mathrm{C}_{28}\mathrm{H}_{20}\mathrm{O}_6\mathrm{Mo}_2\mathrm{Sn}.& \begin{array}{l} \text{Found, \%: } \mathrm{C}\ 43.87,\ 44.12;\quad \mathrm{H}\ 2.82,\ 2.83\\ \text{Calculated, \%: } \mathrm{C}\ 44.03;\quad \mathrm{H}\ 2.35 \end{array} \end{array} \]
Mol. wt.: found 840, 840, calculated 863.
I.R. spectrum \((\nu,\ \mathrm{cm}^{-1})\) (paste in Vaseline oil): 449 (m); 474 (m); 504 (m); 558 (s); 573 (m); 590 (m); 675 (w); 700 (w); 712 (w); 727 (m); 741 (m); 824 (s); 839 (w); 847 (w); 857 (w); 865 (w); 919 (w); 930 (w); 1010 (w); 1068 (w); 1196 (w); 1262 (w); 1310 (w); 1340 (w); 1384 (w); 1432 (m); 1470 (m); 1582 (w); 1892 (s); 1912 (s); 1923 (s); 1987 (s); 2380 (w); 2860 (s); 2930 (s); 2960 (s); 3050 (w); 3070 (w); 3113 (w).
\(\mathrm{C}_5\mathrm{H}_5(\mathrm{CO})_3\mathrm{W}—\mathrm{Sn}(\mathrm{C}_6\mathrm{H}_5)_3\). 17.6 g of \(\mathrm{W}(\mathrm{CO})_6\) was added to \(\mathrm{C}_5\mathrm{H}_5\mathrm{Na}\), prepared from 1.15 g of Na and 3.5 g of \(\mathrm{C}_5\mathrm{H}_6\) in diglyme. After evolution of CO at room temperature, 8 g of \((\mathrm{C}_6\mathrm{H}_5)_3\mathrm{SnCl}\) in 30 ml of diglyme was added. After sublimation, chromatography, and twofold recrystallization from a heptane–toluene mixture, 6 g of substance with m.p. 229–230.5° was isolated.
\[ \begin{array}{ll} \mathrm{C}_{26}\mathrm{H}_{20}\mathrm{O}_3\mathrm{WSn}.& \begin{array}{l} \text{Found, \%: } \mathrm{C}\ 46.08,\ 46.07;\quad \mathrm{H}\ 3.06,\ 3.21\\ \text{Calculated, \%: } \mathrm{C}\ 45.68;\quad \mathrm{H}\ 2.92 \end{array} \end{array} \]
Mol. wt.: found 706, 728, calculated 705.
I.R. spectrum \((\nu,\ \mathrm{cm}^{-1})\) (crystals in Vaseline oil): 449 (m); 479 (m); 490 (m); 570 (m); 582 (m); 680 (w); 725 (s); 737 (s); 799 (w); 832 (m); 862 (w); 1000 (w); 1017 (w); 1023 (w); 1073 (w); 1162 (w); 1193 (w); 1262 (w); 1305 (w); 1338 (w); 1382 (w); 1434 (m); 1469 (m); 1486 (w); 1581 (w); 1778 (w); 1854 (w); 3025 (w); 3065 (m); 3130 (w).
\([\mathrm{C}_5\mathrm{H}_5(\mathrm{CO})_3\mathrm{W}]_2\mathrm{Sn}(\mathrm{C}_6\mathrm{H}_5)_2\). 15 g of \(\mathrm{W}(\mathrm{CO})_6\) was added to a solution of \(\mathrm{C}_5\mathrm{H}_5\mathrm{Na}\) in 25 ml of diglyme, prepared from 1 g of Na and 2.5 g of \(\mathrm{C}_5\mathrm{H}_6\). After evolution of CO at room temperature, 13 g of \((\mathrm{C}_6\mathrm{H}_5)_2\mathrm{SnCl}_2\) was added. The reaction mass was treated by the method described above. A yellow crystalline product with m.p. 207–209° was obtained.
\[ \begin{array}{ll} \mathrm{C}_{28}\mathrm{H}_{20}\mathrm{O}_6\mathrm{W}_2\mathrm{Sn}.& \begin{array}{l} \text{Found, \%: } \mathrm{C}\ 35.50,\ 35.46;\quad \mathrm{H}\ 2.03,\ 2.10\\ \text{Calculated, \%: } \mathrm{C}\ 35.78;\quad \mathrm{H}\ 2.13 \end{array} \end{array} \]
* The I.R. spectra were measured by Yu. N. Sheinker and G. G. Dvoryantseva, for which we express our gratitude to them.
Mol. wt.: found 850, 867; calculated 939.
$C_5H_5(CO)_3W — Pb(C_6H_5)_3$. To $C_5H_5Na$, obtained from 1.15 g of Na and 3.5 g of cyclopentadiene in 30 ml of diglyme, 17.6 g of $W(CO)_6$, dissolved in 40 ml of diglyme, was added. The reaction mixture was heated at 120–130° until the evolution of CO ceased. Then, at room temperature, 10.5 g of $(C_6H_5)_3PbCl$ in 30 ml of diglyme was added. After sublimation, chromatography, and repeated recrystallization (heptane—benzene), 4 g of a yellow compound with m.p. 210–211.5° was isolated.
$C_{26}H_{20}O_3WPb$. Found %: C 41.04, 40.97; H 2.88, 2.81
Calculated %: C 40.5; H 2.6
Mol. wt.: found 860, 773; calculated 771.
IR spectrum ($\nu$, cm$^{-1}$): 442 (m); 478 (m); 487 (m); 558 (m); 578 (m); 730 (m); 750 (s); 833 (m); 1000 (m); 1019 (m); 1060 (w); 1172 (w); 1190 (w); 1300–1331 (w); 1383 (w); 1410 (m); 1434 (m); 1465–1480 (m); 1573 (w); 1880 (s); 1892 (s); 1908 (s); 1978 (s); 2860 (s); 2930 (s); 2965 (s); 3025 (m); 3070 (m); 3130 (m).
$C_5H_5(CO)_3Mo — Pb(C_6H_5)_3$. To $C_5H_5Na$, prepared from 0.1 g of Na and 0.3 g of $C_5H_6$ in tetrahydrofuran, 1.32 g of $Mo(CO)_6$ was added. After evolution of CO, 1.8 g of $(C_6H_5)_3PbCl$ in 20 ml of tetrahydrofuran was added. A yellow crystalline product was isolated in an amount of 0.6 g, m.p. 205°.
$C_{26}H_{20}O_3MoPb$. Found %: C 46.14, 46.00; H 3.04, 3.12
Calculated %: C 45.68; H 2.93
Mol. wt.: found 704, 660, 681; calculated 683.
IR spectrum ($\nu$, cm$^{-1}$) (paste in Vaseline oil): 445 (s); 468 (w); 482 (m); 500 (s); 568 (s); 586 (s); 730 (s); 747 (s); 823 (s); 1000 (m); 1020 (m); 1060 (w); 1160 (w); 1190 (w); 1263 (w); 1300 (w); 1330 (w); 1384 (m); 1435 (s); 1470 (m); 1573 (w); 1900–1930 (s); 1988 (s); 2866 (s); 2940 (s); 3020 (m); 3040 (m); 3060 (m); 3100 (w); 3125 (w).
$C_5H_5(CO)_3Cr — Sn(C_6H_5)_3$. To $C_5H_5Na$, obtained from 0.3 g of Na and 0.85 g of $C_5H_6$ in diglyme (25 ml), 3 g of $Cr(CO)_6$ was added. The reaction mixture was heated until the evolution of CO ceased. At room temperature, 2.5 g of $(C_6H_5)_3SnCl$ in 25 ml of diglyme was added. A white crystalline product with m.p. 220–222° was obtained.
$C_{26}H_{20}O_3CrSn$. Found %: C 56.57, 56.44; H 3.66, 3.67
Calculated %: C 56.62; H 3.63
Mol. wt.: found 530, 510; calculated 551.
$C_5H_5(CO)_3Mo — Sn(C_6H_5)Cl_2$. 3 g of $C_5H_5(CO)_3Mo — Sn(C_6H_5)_3$ in 20 ml of $CCl_4$ at −15° for 15 min was treated with dry HCl. The small precipitate that formed was filtered off, and the filtrate was removed in vacuo. 2.1 g (95%) of a slightly yellowish-greenish compound with m.p. 109–110° was isolated (recrystallization from an $n$-heptane—benzene mixture, 4:1).
$C_{14}H_{10}O_3MoO_3SnCl_2$ (512). Found %: C 32.79, 32.88; H 2.06, 2.05; Cl 14.36, 14.45
Calculated %: C 32.80; H 1.95; Cl 13.86
$C_5H_5(CO)_3W — Sn(C_6H_5)Cl_2$. By the action of dry HCl on a solution of 1.5 g of $C_5H_5(CO)_3W — Sn(C_6H_5)_3$ in 30 ml of $CCl_4$ at −15° for 15 min, 0.65 g (52%) of a yellow crystalline substance with m.p. 112–114° (from heptane) was isolated.
$C_{14}H_{10}O_3WSnCl_2$. Found %: C 28.20, 28.27; H 1.84, 1.87; Cl 11.58, 11.83
Calculated %: C 28.00; H 1.67; Cl 11.83
Mol. wt.: found 600; calculated 600.
$[C_5H_5(CO)_3Mo]_2 — SnCl_2$. A solution of 1 g of $[(C_5H_5(CO)_3Mo]_2 — Sn(C_6H_5)_2$ in 25 ml of $CCl_4$ at −15° for 2 h was treated with dry HCl. After removal
the solvent, the residue was recrystallized from benzene. This gave 0.7 g (71.4%) of yellow crystals with m.p. 200–201°.
\[ \mathrm{C}_{16}\mathrm{H}_{16}\mathrm{O}_{6}\mathrm{Mo}_{2}\mathrm{SnCl}_{2}. \quad \begin{array}{ll} \text{Found, \%:} & \mathrm{C}\ 28.34,\ 28.35;\ \mathrm{H}\ 1.51,\ 1.53;\ \mathrm{Cl}\ 11.18,\ 11.47 \\ \text{Calculated, \%:} & \mathrm{C}\ 28.23;\ \mathrm{H}\ 1.47;\ \mathrm{Cl}\ 10.44 \end{array} \]
Molecular weight: found 663, 685; calculated 680.
\[ [\mathrm{C}_{5}\mathrm{H}_{5}(\mathrm{CO})_{3}\mathrm{W}]_{2}\!-\!\mathrm{SnCl}_{2}. \]
Dry HCl was passed for 30 min at −15° through a solution of 0.8 g of \([\mathrm{C}_{5}\mathrm{H}_{5}(\mathrm{CO})_{3}\mathrm{W}]_{2}\!-\!\mathrm{Sn}(\mathrm{C}_{6}\mathrm{H}_{5})_{2}\) in \(\mathrm{CCl}_{4}\). The solvent was removed; the residue gave a dry crystalline product, which was recrystallized from a heptane–benzene mixture. This gave 83.3% of a yellow crystalline substance with m.p. 225–226°.
\[ \mathrm{C}_{16}\mathrm{H}_{10}\mathrm{O}_{6}\mathrm{W}_{2}\mathrm{SnCl}_{2}. \quad \begin{array}{ll} \text{Found, \%:} & \mathrm{C}\ 22.42,\ 22.29;\ \mathrm{H}\ 1.05,\ 1.02;\ \mathrm{Cl}\ 8.29,\ 8.45 \\ \text{Calculated, \%:} & \mathrm{C}\ 22.43;\ \mathrm{H}\ 1.17;\ \mathrm{Cl}\ 8.29 \end{array} \]
Institute of Organoelement Compounds
Academy of Sciences of the USSR
Received
8 II 1964
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