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DOI: 10.14529/chem160207
PECULIARITIES OF THE REACTIONS OF TRI(META-TOLYL)ANTIMONY AND TRI(ORTHO-TOLYL)ANTIMONY WITH 2-NITROBENZALDOXIME. THE MOLECULAR STRUCTURES
OF B/S(2-NITROBENZALDOXIMATO)TRI(META-TOLYL)ANTIMONY, ^2-OXO-BIS[(2-NITROBENZALDOXIMATO)TRI(META-TOLYL)ANTIMONY] AND
B/S(2-NITROBENZALDOXIMATO)TRI(ORTHO-TOLYL)ANTIMONY
V.V. Sharutin, vvsharutin@rambler.ru O.K. Sharutina, sharutinao@mail.ru E.V. Artemeva, katriona_dr@mail.ru M.S. Makerova, marina.mms74@mail.ru
South Ural State University, Chelyabinsk, Russian Federation
Bis(2-nitrobenzaldoximato)tri(meta-tolyl)antimony (1), f2-oxo-bis[(2-nitrobenzaldoximato)-tri(meta-tolyl)antimony] (2) and bis(2-nitrobenzaldoximato)tri(ortho-tolyl)antimony (3) have been obtained by the reactions of tri(meta-tolyl)antimony and tri(ortho-tolyl)antimony with 2-nitrobenzaldoxime in the presence of an oxidizing agent (hydrogen peroxide or tert-butyl hydroperoxide). Compounds 1-3 have been characterized by X-ray diffraction analysis.
Keywords: tri(m-tolyl)antimony, tri(o-tolyl)antimony, 2-nitrobenzaldoxime, tert-butyl hydroperoxide, hydrogen peroxide, oxidizing reactions, bis(2-nitrobenzaldoximato)-tri(m-tolyl)antimony, f 2-oxo-bis[(2-nitrobenzaldoximato)tri(m-tolyl)antimony], bis(2-nitrobenzaldoximato)tri(o-tolyl)antimony, molecular structures, X-ray analysis.
Introduction
The oxidative synthesis is an effective single-stage way of synthesis of antimony (V) derivatives Ar3SbX2. It has been found that the products of oxidative addition reactions of triarylantimony and oximes, depending on the oxime nature and the reaction conditions, are Ar3SbX2 or (Ar3SbX)20 (Ar = Ph, p-Tol, o-Tol; X = ONCHR, ONCRR') [1-6]. According to X-ray analysis data, the X ligands are monodentate, they form only one bond with the antimony atom through the oxygen atom. However, both types of molecules have decreased distances between the antimony atom and the iminoxy group nitrogen atoms, but it does not appreciably distort trigonal bipyramidal coordination of the central atom. By the example of derivatives containing furfuraloximate ligands it has been shown that the type of ligand coordination can be dependent on the nature of aryl radicals at the antimony atom. Thus, furfuraloxime ligands in the molecule of bis(f2-furfuraloximato)-(f2-oxo)-bis[triphenylantimony] are bidentate bridging ligands. These ligands are coordinated by the oxygen atom to the first antimony atom and by the nitrogen atom to the second antimony atom. This fact increases antimony coordination number to six [7]. However, the molecule of f2-oxo-bis[(furfuraloximato)tri(o-tolyl)antimony] has the regular molecular structure for this type of compounds, typically with monodentate ligands [6]. 2-Oxybenzaldoxime has different coordination types and denticity in the derivatives of triphenyl- and tris(5-bromo-2-methoxyphenyl)bismuth [2, 8, 9].
Further investigation of the oxidative addition reactions of triarylantimony with different types of oximes and determination of the product molecular structures are of obvious chemical interest.
Thus, the reactions of tri(o-tolyl)- and tri(m-tolyl)antimony with 2-nitrobenzaldoxime in the presence of an oxidizing agent (hydrogen peroxide or tert-butyl hydroperoxide) and the product molecular structures are discussed at this paper.
Experimental
Synthesis of 6/s[2-nitrobenzaldoximato]tri(m-tolyl)antimony (1)
a) Tri(m-tolyl)antimony (100 mg, 0.25 mmol) and 2-nitrobenzaldoxime (42 mg, 0.25 mmol) were dissolved in the mixture of diethyl ether (25 ml) and heptane (5 mL). Then hydrogen peroxide (28 mg, 30 % aqueous, 0.25 mmol) was added. The solution was left to stand for 24 hours at 20 °C. After the solvent evaporation, the solid residue was repeatedly washed with warm toluene. The light-yellow crystals 1 (56 mg, 36 %, MP: 124 °C) were obtained from the toluene. The microcrystalline powder, poorly soluble in toluene, had MP = 247 °C.
b) Tri(m-tolyl)antimony (100 mg, 0.25 mmol) and 2-nitrobenzaldoxime (84 mg, 0.50 mmol) were dissolved in the mixture of diethyl ether (25 ml) and heptane (5 mL). Then hydrogen peroxide (28 mg, 30 % aqueous, 0.25 mmol) was added. The solution was left to stand for 24 hours at 20 °C. After the solvent evaporation the light-yellow crystals 1 (MP: 121 °C) were obtained; the yield was 98 mg (46 %).
IR spectrum (v, cm -1): 1609, 1585, 1557, 1522, 1476, 1450, 1402, 1377, 1348, 1302, 1207, 1163, 1123, 1099, 1040, 976, 959, 912, 885, 849, 793, 779, 743, 689, 665, 644, 577, 550, 513, 503, 449, 428.
Synthesis of ^2-oxo-6/s[(2-nitrobenzaldoximato)tri(m-tolyl)antimony] (2)
a) Tri(m-tolyl)antimony (100 mg, 0.25 mmol) and 2-nitrobenzaldoxime (84 mg, 0.5 mmol) were dissolved in the mixture of diethyl ether (25 ml) and heptane (5 mL). Then fert-butyl hydroperoxide (32 mg, 70 % aqueous, 0.25 mmol) was added. The solution was left to stand for 24 hours at 20 °C. After the solvent evaporation the solid residue was repeatedly washed with small portions of diethyl ether. The light-yellow crystals 2 were obtained; the product yield was 122 mg (56 %), MP: 127 °C.
b) Tri(m-tolyl)antimony (100 mg, 0.25 mmol) and 2-nitrobenzaldoxime (42 mg, 0.25 mmol) were dissolved in the mixture of diethyl ether (25 ml) and heptane (5 mL). Then fert-butyl hydroperoxide (32 mg, 70 % aqueous, 0.25 mmol) was added. The solution was left to stand for 24 hours at 20 °C. After the solvent evaporation the light-yellow crystals 2 (MP: 127 °C; yield 155 mg (89 %)) were obtained.
IR spectrum (v, cm -1): 1647, 1609, 1582, 1557, 1522, 1477, 1450, 1439, 1404, 1381, 1341, 1296, 1204, 1167, 1142, 1123, 1097, 1074, 1042, 970, 947, 922, 885, 847, 779, 741, 691, 642, 575, 544, 521, 503, 478, 426.
Synthesis of 6/s[2-nitrobenzaldoximato]tri(o-tolyl)antimony (3)
a) Tri(o-tolyl)antimony (100 mg, 0.25 mmol) and 2-nitrobenzaldoxime (85 mg, 0.50 mmol) were dissolved in ether (30 mL). Then hydrogen peroxide (28 mg, 30 % aqueous, 0.25 mmol) was added. The solution was left to stand for 24 hours at 20 °C. When the solvent was evaporated, fine-crystalline precipitate was crystallized from toluene with the addition of heptane to give light-yellow crystals 3; yield was 175 mg (94 %), MP: 181 °C.
IR spectrum (v, cm -1): 1606, 1584, 1522, 1472, 1443, 1427, 1382, 1346, 1325, 1296, 1277, 1206, 1164, 1123, 1081, 1036, 966, 955, 912, 885, 849, 787, 745, 696, 644, 578, 543, 514, 489, 436.
b) Tri(o-tolyl)antimony (100 mg, 0.25 mmol) and 2-nitrobenzaldoxime (85 mg, 0.50 mmol) were dissolved in the solution of benzene with addition of heptane (5:1; 30 mL). Then fert-butyl hydroperoxide (32 mg, 70% aqueous, 0.25 mmol) was added. The solution was left to stand for 24 hours at 20 °C. The light-yellow crystals 3 were obtained; the product yield was 184 mg (99 %), MP: 187 °C.
c) Tri(o-tolyl)antimony (100 mg, 0.25 mmol) and 2-nitrobenzaldoxime (42 mg, 0.25 mmol) were dissolved in the solution of benzene with addition of heptane (5:1; 30 mL). Then hydrogen peroxide (28 mg, 30% aqueous, 0.25 mmol) was added. The solution was left to stand for 24 hours at 20 °C. The solid precipitate was washed with small portions of heated toluene. The light-yellow crystals (MP: 187 °C) 3 and white fine powder (MP > 300 °C) were obtained.
d) Tri(o-tolyl)antimony (100 mg, 0.25 mmol) and 2-nitrobenzaldoxime (42 mg, 0.25 mmol) were dissolved in the solution of benzene with the addition of heptane (5:1; 30 mL). Then fert-butyl hydroperoxide (32 mg, 70 % aqueous, 0.25 mmol) was added. The solution was left to stand for 24 hours at 20 °C. The light-yellow crystals 3 (MP: 187 °C) and white fine powder (MP > 300 °C) were obtained.
IR spectra of compounds 1-3 were recorded on Shimadzu IRAffinity-1S FTIR spectrometer (KBr pellets; 4000-400 cm-1).
X-ray diffraction analysis of crystalline substances 1-3 was performed on Bruker D8 QUEST automatic four-circle diffractometer (Mo Ka- emission, X = 0.71073 A, graphite monochromator).
The data were collected and analyzed, the unit cell parameters were refined, and the absorption correction was applied using the SMART and SAINT-Plus programs [10]. All calculations for structure determination and refinement were performed using the SHELXL/PC program [11]. Molecular structures 1-3 were determined by the direct method and refined by the least-squares method, in the anisotropic approximation for non-hydrogen atoms.. The selected crystallographic data and the structure refinement results are listed in Table 1. Selected bond lengths and bond angles are summarized in Table 2.
The full tables of atomic coordinates, bond lengths, and bond angles were deposited with the Cambridge Crystallographic Data Centre (CCDC 1048763, 1048167, 1048131 for compounds 1, 2 and 3, respectively; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Table 1
Crystallographic data and the experimental and structure refinement parameters for compounds 1-3
Parameter Value
1 2 3
Empirical formula C35H3iN4OeSb C56H52N4O7 Sb2 CssH31N4O6Sb
Formula weight 725.39 1136.52 725.39
T, K 273.15 273.15 273.15
Crystal system Monoclinic Triclinic Monoclinic
Space group P21/n P-1 P21/n
a, A 18.079(2) 11.3885(7) 19.7939(6)
b, A 9.5431(10) 12.2767(6) 8.4059(2)
c, A 20.628(2) 21.9637(13) 21.0674(6)
a, deg 90.00 99.923(3) 90.00
P, deg 112.008(4) 95.110(3) 109.6450(10)
Y, deg 90.00 107.511(3) 90.00
V, A3 3299.6(6) 2852.1(3) 3301.28(16)
Z 4 2 4
P(calcd.), g/Cm3 1.460 1.323 1.459
mm-1 0.887 0.997 0.886
F(000) 1472.0 1148.0 1472.0
Crystal size, mm 0.38 x 0.21 x 0.12 0.41 x 0.24 x 0.19 0.34 x 0.19 x 0.1
8 Range of data collection, deg 4.98-47.32° 2.93-25.47° 2.63-26.45°
Range of refraction indices 20 < h < 20, -10 < k < 10, -23 < l < 23 -13 < h < 13, -14 < k < 14, -26 < l < 26 -24 < h < 24, -10 < k < 10, -25 < l < 26
Measured reflections 20432 44671 29107
Independent reflections 4898 10271 6776
Rint 0.0721 0.0817 0.0372
Refinement variables 418 628 418
GOOF 1.254 1.083 1.023
R factors for F2 > 2ct(F2) R1 = 0.0795, wR2 = 0.1974 R1 = 0.0632, wR2 = 0.1443 R1 = 0.0296, wR2 = 0.0641
R factors for all reflections R1 = 0.1071, wR2 = 0.2088 R1 = 0.1133, wR2 = 0.1688 R1 = 0.0444, wR2 = 0.0698
Residual electron density (min/max), e/A3 1.70/-0.64 1.19/-1.15 0.47/-0.31
Table 2
Selected bond lengths and bond angles in the structures of compounds 1-3
Bond d, Â Angle ra, deg
1
Sb(1)-C(1) 2.114(10) O(1)Sb(1)O(4) 173.8(3)
Sb(1)-C(11) 2.118(10) C(1)Sb(1)C(21) 117.9(4)
Sb(1)-C(21) 2.126(10) C(11)Sb(1)C(21) 124.9(4)
Sb(1)-0(1) 2.076(7) C(1)Sb(1)C(11) 117.2(4)
Sb(1)-O(4) 2.089(7) N(1)O(1)Sb(1) 118.4(6)
0(1)-N(1) 1.377(11) O(1)N(1)C(37) 110.8(9)
O(4)-N(3) 1.378(10) N(3)O(4)Sb(1) 108.7(5)
N(1)-C(37) 1.260(13) O(4)N(3)C(47) 112.0(9)
N(3)-C(47) 1.267(13) C(1)Sb(1)O(1) 93.7(4)
Sb(1)-N(1) 2.988(8) C(1)Sb(1)O(4) 86.1(3)
Sb(1)-N(2) 2.848(8) C(11)Sb(1)O(1) 81.9(4)
2
Sb(1)-C(1) 2.111(8) O(1)Sb(1)O(2) 177.6(2)
Sb(1)-C(11) 2.100(7) C(11)Sb(1)C(21) 122.5(3)
Sb(1)-C(21) 2.127(8) C(1)Sb(1)C(11) 115.3(3)
Sb(1)-0(1) 1.977(5) C(1)Sb(1)C(21) 121.5(3)
Sb(1)-O(2) 2.117(6) N(1)O(2)Sb(1) 109.7(5)
0(2)-N(1) 1.381(8) O(2)N(1)C(37) 111.2(7)
O(5)-N(3) 1.371(9) Sb(1)O(1)Sb(2) 143.0(3)
N(1)-C(37) 1.213(11) N(3)O(5)Sb(2) 109.0(5)
N(3)-C(77) 1.242(11) O(5)N(3)C(77) 110.0(7)
Sb(2)-C(41) 2.107(7) C(61)Sb(2)C(41) 122.7(3)
Sb(2)-C(61) 2.131(8) C(51)Sb(2)C(41) 113.2(3)
Sb(2)-C(51) 2.117(8) C(51)Sb(2)C(61) 123.5(4)
Sb(2)-0(1) 1.986(5) O(1)Sb(1)C(1) 89.9(3)
Sb(2)-O(5) 2.117(6) O(1)Sb(1)C(21) 92.1(3)
Sb(1)-N(1) 2.892(8) O(1)Sb(2)C(61) 91.8(3)
Sb(2)-N(3) 2.871(8) O(1)Sb(2)C(51) 89.3(3)
3
Sb(1)-C(1) 2.124(3) O(1)Sb(1)O(4) 172.17(7)
Sb(1)-C(11) 2.116(3) C(1)Sb(1)C(21) 112.7(1)
Sb(1)-C(21) 2.113(3) C(11)Sb(1)C(21) 124.9(1)
Sb(1)-0(1) 2.087(2) C(1)Sb(1)C(11) 122.3(1)
Sb(1)-O(4) 2.086(2) N(1)O(1)Sb(1) 114.4(1)
0(1)-N(1) 1.374(4) O(1)N(1)C(37) 112.1(2)
O(4)-N(3) 1.377(2) N(3)O(4)Sb(1) 111.2(1)
N(1)-C(37) 1.259(3) O(4)N(3)C(47) 113.4(2)
N(3)-C(47) 1.258(3) C(1)Sb(1)O(1) 93.24(9)
Sb(1)-N(1) 2.935(2) C(1)Sb(1)O(4) 91.35(9)
Sb(1)-N(3) 2.886(2) C(11)Sb(1)O(4) 82.94(8)
Results and Discussion
Previously it has been shown that the oxidative addition reaction of triphenyl- or tri(p-tolyl)antimony and oxime at the molar ratio 1:1 leads to binuclear organoantimony compound with the bridging oxygen atom with the general formula (Ar3Sb0NCRR')20 [5,6].
As it has been found out, the structure of the product of tri(rn-tolyl)antimony reaction with 2-nitrobenzaldoxime does not depend on the molar ratio of the reactants, but is determined by the oxidizing agent nature. Thus, at the molar ratio 1:2:1 or 1:1:1 the product of this reaction in the presence of fert-butyl hydroperoxide is &7's[2-nitrobenzaldoximato]tri(m-tolyl)antimony (1):
rn-To^Sb + 2 HON=CHC6HNO2-2 + H2O2 ^ m-Tol3Sb(ON=CHC6HNO2-2)2 + 2 H2O.
1
If fert-butyl hydroperoxide has been used as the oxidizing agent, the interaction of tri(m-tolyl)antimony with 2-nitrobenzaldoxime leads to the formation of ju2-oxo-bis[2-nitrobenzaldoximato]tri(m-tolyl)antimony (2) both at the equimolar ratio and at the excess of oxime:
2 m-Tol3Sb+2 HON=CHC6H4NO2-2+2 i-BuOOH ^ [m-Tol3Sb(ON=CHC6H4NO2-2)]2O+2 i-BuOH+H2O
2
The interaction of tri(o-tolyl)antimony with 2-nitrobenzaldoxime, irrespective of the molar ratio and the oxidizing agent nature, goes with the formation of bis [2-nitrobenzaldoximato]tri(o-tolyl)antimony (3):
o-To^Sb + 2 HON=CHC6HNO2-2 + ROOH ^ o-Tol3Sb(ON=CHC6HNO2-2)2 + H2O + ROH;
R = H, Bu-i 3
At the molar ratio 1:1:1 both compound 3 and tri(o-tolyl)antimony oxide, which has been separated from the main product by recrystallization from toluene, are formed.
Special experiments have shown that the nature of a solvent (hexane, diethyl ether, a mixture of benzene and heptane) does not affect the product structure.
Compounds 1-3 are crystalline substances, which are resistant to the effect of air moisture and oxygen; they are freely soluble in aromatic and aliphatic hydrocarbons.
The synthesized triarylantimony dioximates have been identified by infrared spectroscopy and X-ray analysis.
In the IR-spectra of compounds 1-3 there are intensive absorption bands, characterizing nitro group vibrations. Thus, the absorption band due to NO2-group vibrations does not change its position, and it appears at 1522 cm-1 in all spectra. The band, corresponding to NO2-group symmetric vibrations (1348, 1344, 1346 cm-1) in the spectra of 1-3, does not shift much. The C-NO2 vibrations are characterized by the band at 849, 847, 849 cm-1 in these spectra. Note that the corresponding bands in the spectrum of pure 2-nitrobenzaldoxime are located at 1522, 1346, and 853 cm-1. In the IR spectra there are bands at 449, 478 and 436 cm-1 due to the Sb-C(Ar) vibration of the C3-symmetric [12] SbC3 fragment. The characteristic bands at 1600 cm-1 (C=N bonds), 960 cm-1 (N-O bonds) have also been found.
According to X-ray diffraction analysis data, the antimony atoms in the molecules of compounds 1, 2 and 3 have distorted trigonal-bipyramidal coordination with axial oxygen atoms (Fig. 1-3). In binuclear molecule 2 Sb (1) and Sb (2) atoms are connected by a bridging oxygen atom, Sb(1)O(1)Sb(2) bond angle is equal to 143.0(3)°.
Fig. 1. The structure of compound 1
Fig. 2. The structure of compound 2
Fig. 3. The structure of compound 3
Sums of CSbC bond angles are equal to 360° (1), 359.3(3)°, 359.5(3)° (2), 359.8(1)° (3), at that the values of the individual angles differ from the theoretical angle by less than 8°. The Sb atoms are shifted from the correlated planes [C3] at 0.002 A (1), 0.091, 0.098 A (2), 0.052 A (3). The axial OSbO angles are equal to 173.8(3), 177.6(2), 172.17(7) in 1-3, respectively. The OSbC angles vary within the ranges 81.8(4)°-95.0(4)° (1), 82.3(3)°-96.0(3)°, 83.2(2)°-96.5(3)° (2), 82.94(8)°-93.24(9)° (3).
The Sb-C bond intervals are 2.113(10)-2.123(10) A (1), 2.102(8)-2.129(8) A, 2.106(8)-2.131(8) A (2), 2.113(2)-2.124(3) A (3). The Sb-O bond lengths in 1 (2.078(7), 2.090(7) A) and 3 (2.086(2), 2.087(2) A) have similar values, they are less than equatorial bond lengths. The analogous distances in molecule 2 (2.117(6), 2.116(6) A) are greater than the distances in 1 and 3. The lengths between antimony atoms and the bridging oxygen atom are equal to 1.977(5) and 1.987(5) A.
In molecules 1-3 the Sb- • N distances between Sb atom and N atoms of iminoxy groups (2.848(8), 2.988(8) A (1), 2.871(8), 2.892(8) A (2), 2.886(2), 2.935(2) A (3)) are considerably less than the sum of
Van der Waals radiuses of Sb and N atoms (3.8 Á [13]). Obviously, there is no correlation between Sb-O bond lengths and strength of Sb-N contacts. Decrease of Sb-N distances does not result in the expected N-O bond lengthening [1.377(11), 1.379(11) Á (1), 1.373(9), 1.382(8) Á (2), 1.374(4), 1.377(2) Á (3)].
The structure organization of 1-3 crystals is due to weak intermolecular 0--H hydrogen bonds between oxygen atoms of nitro groups and hydrogen atoms of methyl groups or aromatic rings, as well as to C-H- • • n interactions.
Conclusions
It has been found that the product of the oxidative addition reaction of tri(m-tolyl)antimony with 2-nitrobenzaldoxime has the structure that is determined by the oxidizing agent type. The reaction of tri(o-tolyl)antimony and 2-nitrobenzaldoxime proceeds with the formation of tri(o-tolyl)antimony dioximate, irrespective of the oxidizing agent nature and the molar ratio of the reactants.
References
1. Sharutin V.V., Sharutina O.K., Molokova O.V., Pakusina A.P., Gerasimenko A.V., Sergienko A.S., Bukvetskii B.V., Popov D.Yu. [Synthesis and Structures of Tetra- and Triarylantimony Oxi-mates]. Russian Journal of Coordination Chemistry, 2002, vol. 28, no. 8, pp. 544-553. DOI: 10.1023/A:1019701511840
2. Sharutin V.V., Sharutina O.K., Molokova O.V. [Synthesis and structure of Tetra- and Triphenylantimony Salicylaldoximates]. Russian Journal of Inorganic Chemistry. 2012, vol. 57, no. 6, pp. 832-837. DOI: 10.1134/S0036023612010226
3. Sharutin V.V., Sharutina O.K., Molokova O.V., Pakusina A.P., Gerasimenko A.V., Gerasimenko E.A. [Synthesis and Structure of Triphenylantimony Bis(Acetophenoneoximate)]. Russian Journal of Coordination Chemistry, 2002, vol. 28, no. 7, pp. 464-467. DOI: 10.1023/A:1016293009968
4. Dodonov V.A., Gushhin A.V., Gor'kaev D.A., Fukin G.K., Starostina T.I., Zaharov L.N., Kurskij Ju.A., Shavyrin A.S. [Synthesis and Structure of Triphenylantimony Oximates]. Russian Chemical Bulletin, 2002, no. 6, pp. 1051-1057. DOI: 10.1023/A:1019634307064
5. Sharutin V.V., Molokova O.V., Sharutina O.K., Gerasimenko A.V., Pushilin M.A. [Synthesis and Structure of Triarylantimony Dioximates]. Russian Journal of General Chemistry, 2004, vol. 74, no. 10, pp. 1485-1491. DOI: 10.1007/s11176-005-0041-4
6. Sharutin V.V., Molokova O.V., Sharutina O.K., Smirnova S.A. [Oxidative Addition Reactions of Tri(2-methylphenyl)antimony]. Russian Journal of Inorganic Chemistry, 2012, vol. 57, no. 9, pp. 1252-1258. DOI: 10.1134/S0036023612090185
7. Sharutin V.V., Sharutina O.K., Molokova O.V., Pakusina A.P., Bondar' E.A., Krivolapov D.B., Gubajdullin A.T., Litvinov I.A. [Synthesis and Structure of (j,-Oxo-bis[triphenyl(furfuraloximato) antimony]. Russian Journal of General Chemistry, 2001, vol. 71, no. 9, pp. 1426-1430. DOI: 10.1023/A: 1013910120594
8. Sharutin V.V., Sharutina O.K. [Specific Features of the Reaction between Tris(5-bromo-2-methoxyphenyl)antimony and 2-Oxybenzaldoxime: Structure of Bis(^3-2-oxybenzaldoximato-O,O',N)-(^2-oxo)-bis(5-bromo-2-methoxyphenyl)diantimony]. Russian Journal of Inorganic Chemistry, 2014, vol. 59, no. 11, pp. 1263-1267. DOI: 10.1134/S0036023614110229
9. Dong L., Yin H., L. Wen, Wang D. Bis(2-hydroxybenzaldehyde oximato-KO)triphenylanti-mony(V). Acta Crystallogr. , 2009, vol. 65E, no. 11, pp. m1438. DOI: 10.1107/S1600536809043542
10. Bruker (2000) SMART. Bruker Molecular Analysis Research Tool, Versions 5.625 Bruker AXS, Madison, Wisconsin, USA.
11. Bruker (2000) SAINTPlus Data Reduction and Correction Program Versions 6.02a, Bruker AXS, Madison, Wisconsin, USA.
12. Doak G.O., Long G.G., Freedman L.D. The Infrared Spectra of Some Phenylsubstituted Pentavalent Antimony Compounds. J. Organomet. Chem., 1965, vol. 4, no. 1, pp. 82-91.
13. Batsanov S.S. [Atomic Radii of the Elements]. Russian Journal of Inorganic Chemistry, 1991, vol. 36, no. 12, pp. 3015-3037. (in Russ.)
Received 15 March 2016
УДК 546.863+546.865+547.1 52+547.53.024+548.312.5 DOI: 10.14529/chem 1 e0207
ОС ОБЕННОСТИ ВЗАИМОДЕЙСТВИЯ ТРИ(МЕТА-ТОЛИЛ)СУРЬМЫ И ТРИ(ОРТО-ТОЛИЛ)СУРЬМЫ С 2-НИТРОБЕНЗАЛЬДОКСИМОМ. МОЛЕКУЛЯРНЫЕ СТРУКТУРЫ БИС(2-НИТРОБЕНЗАЛЬДОКСИМАТО)ТРИ(МЕТА-ТОЛИЛ)СУРЬМЫ, ^2-ОКСО-БИС[(2-НИТРОБЕНЗАЛЬДОКСИМАТО)ТРИ(МЕТА-ТОЛИЛ)СУРЬМЫ] И БИС(2-НИТРОБЕНЗАЛЬДОКСИМАТО)-ТРИ(ОРТО-ТОЛИЛ)СУРЬМЫ
В.В. Шapymин, О.К. Шapymинa, Е.В. Аpmемьевa, М.С. Мaкеpoвa
Южно-Уральский государственный университет, г. Челябинск
Bзaимодействием три(меmа-толил)сyрьмы и три(орmо-толил)сyрьмы с 2-нитробензaльдоксимом в присутствии окислителя (пероксидa водородa или трет-бyтилгидропероксидa) синтезировяны бuс(2-нитробензaльдоксимaто)три(меmа-толил)сyрьмa (1), i«2-оксо-бuс[(2-нитробензaльдоксимaто)три(меmа-толил)сyрьмa] (2) и бuс(2-нитробензaльдоксимaто)три(oрmо-толил)сyрьмa (3). Соединения 1-3 охaрaктеризовaны методом рентгеноструктурного aнaлизa.
Ключевые слова: mрu(м-mолuл)сyрьма, mрu(о-mолuл)сyрьма, 2-нumро-бензальдоксuм, mреmбymuлгuдропероксuд, перок^д водорода, ошсленж, бж(2-нumробензальдоксuмаmо)mрu(м-mолuл)сyрьма, ß2-оксо-бuс[(2-нumробензальдоксuмаmо)-mрu(м-mолuл)сyрьма], бuс(2-нumробензальдоксuмаmо)mрu(o-mолuл)сyрьма, молекулярные структуры, рентгеноструктурный аналпз.
Литература
1. Синтез и строение оксимятов тетрa- и триярилсурьмы / B.B. Шярутин, O.K. шярутиня, O.B. Молоковя и др. // ^орд. химия. - 2002. - Т. 28. - № 8. - С. 581-590.
2. Шярутин, B.B. Синтез и строение сялициляльдоксимятов тетрa- и трифенилсурьмы /
B.B. Шярутин, O.K. Шярутиш, O.B. Молоковя // Журн. неоргaн. химии. - 2012. - Т. 57. - № 6. -
C. 902-907.
3. Синтез и строение бис(яцетофеноноксимятя) трифенилсурьмы / B.B. Шярутин, O.K. Шярутиня, O.B. Молоковя и др. // ^орд. химия. - 2002. - Т. 28. - № 7. - С. 497-500.
4. Синтез и строение оксимятов трифенилсурьмы / B.A. Додонов, A.B. Гущин, Д.А. Горькяев и др. // Изв. РАН. Сер. хим. - 2002. - № 6. - С. 965-971.
5. Синтез и строение диоксимятов триярилсурьмы / B.B. Шярутин, O.B. Молоковя, O.K. Шярутиня и др. // Журн. общ. химии. - 2004. - Т. 74. - Bbm. 10. - С. 1600-1607.
6. Реякции окислительного присоединения три(2-метилфенил)сурьмы / B.B. Шярутин, O.B. Молоковя, O.K. Шярутиня, С.А. Смирновя // Журн. неоргян. химии. - 2012. - Т. 57. - № 9. -
C. 1334-1340.
7. Синтез и строение ц-оксобис[трифенил(фурфуряльоксимято)сурьмы] / B.B. Шярутин, O.K. Шярутиня, O.B. Молоковя и др. // Журн. общ. химии. - 2001. - Т. 71. - Bbm. 9. - С. 14261510.
8. Шярутин, B.B. Oсобенности взяимодействия mрuс(5-бром-2-метоксифенил)сyрьмы с 2-оксибензяльдоксимом. Строение бuс(ц3-2-оксибензaльдоксимaто-O,O',N)- (ц2-оксо)-бuс(5-бром-2-метоксифенил)дисурьмы / B.B. Шярутин, O.K. Шярутиня // Журн. неоргян. химии. - 2014. -Т. 59. - № 11. - С. 1507-1511. DOI: 10.7868/S0044457X14110221.
9. Bis(2-hydroxybenzaldehyde oximato-K0)triphenylantimony(V) / L. Dong, H. Yin, L. Wen,
D. Wang // Acta Crystallogr. - 2009. - V. 65E, № 11. - P. m1438. DOI: 10.1107/S1600536809043542
10. Bruker (2000) SMART. Bruker Molecular Analysis Research Tool, Versions 5.625 Bruker AXS, Madison, Wisconsin, USA.
11. Bruker (2000) SAINTPlus Data Reduction and Correction Program Versions 6.02a, Bruker AXS, Madison, Wisconsin, USA.
12. Doak, G.O. The infrared spectra of some phenylsubstituted pentavalent antimony compounds / G O. Doak, G.G. Long, L.D. Freedman // J. Organomet. Chem. - 1965. - V. 4. - N. 1. - P. 82-91.
13. Бацанов, С.С. Атомные радиусы элементов / С.С. Бацанов // Журн. неорган. химии. -1991. - Т. 36. - Вып. 12. - С. 3015-3037.
Шарутин Владимир Викторович - доктор химических наук, профессор, старший научный сотрудник УНИД, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: vvsharutin@rambler.ru.
Шарутина Ольга Константиновна - доктор химических наук, профессор, кафедра аналитической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: sharutinao@mail.ru.
Артемьева Екатерина Владимировна - студент химического факультета, ЮжноУральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: katriona_dr@mail.ru.
Макерова Марина Сергеевна - студент химического факультета, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: marina.mms74@mail.ru.
Поступила в редакцию 15 марта 2016 г.
ОБРАЗЕЦ ЦИТИРОВАНИЯ
Peculiarities of the reactions of tri(meta-tolyl)antimony and tri(ortho-tolyl)antimony with 2-nitrobenzaldoxime. The molecular structures of bis(2-nitrobenzaldoximato)tri(meta-tolyl)antimony, ^2-oxo-bis[(2-nitrobenzaldoximato)tri(meta-tolyl)antimony] and bis(2-nitrobenzaldoximato)tri(ortho-tolyl)antimony / V.V. Sharutin, O.K. Sharutina, E.V. Artemeva, M.S. Makerova // Вестник ЮУрГУ. Серия «Химия». - 2016. - Т. 8, № 2. - С. 61-69. DOI: 10.14529/chem160207
FOR CITATION
Sharutin V.V., Sharutina O.K., Artemeva E.V., Makerova M.S. Peculiarities of the Reactions of Tri(meta-tolyl)antimony and Tri(ortho-tolyl)antimony with 2-Nitro-benzaldoxime. The Molecular Structures of Bis(2-nitrobenzaldoximato)tri(meta-tolyl)antimony, ^-Oxo-bis[(2-mtrobenzaldoximato)tri(meta-tolyl)antimony] and Bis(2-mtrobenzaldoximato)tri(ortho-tolyl)antimony. Bulletin of the South Ural State University. Ser. Chemistry. 2016, vol. 8, no. 2, pp. 61-69. DOI: 10.14529/chem160207
