Oxidation of tri( o-tolyl)antimony by tert-butyl hydroperoxide. Molecular structures of bis[µ 2-oxo-tri(o-tolyl)antimony] and µ 2-oxo- bis[( tert-butylperoxy)tri( o-tolyl)antimony]
![Oxidation of tri( o-tolyl)antimony by tert-butyl hydroperoxide. Molecular structures of bis[µ 2-oxo-tri(o-tolyl)antimony] and µ 2-oxo- bis[( tert-butylperoxy)tri( o-tolyl)antimony]](/file/picture/147160326/oxidation-of-tri-o-tolyl-antimony-by-tert-butyl-hydroperoxide-molecular.png "Oxidation of tri( o-tolyl)antimony by tert-butyl hydroperoxide. Molecular structures of bis[µ 2-oxo-tri(o-tolyl)antimony] and µ 2-oxo- bis[( tert-butylperoxy)tri( o-tolyl)antimony]")
Автор: Sharutin V.V., Sharutina O.K., Artemeva E.V., Makerova M.S.
Журнал: Вестник Южно-Уральского государственного университета. Серия: Химия @vestnik-susu-chemistry
Рубрика: Металлоорганическая химия
Статья в выпуске: 4 т.7, 2015 года.
Бесплатный доступ
Tri( o-tolyl)antimony oxidation by equimolar amount of tert-butyl hydroperoxide in diethyl ether led to the formation of bis[µ 2-oxo-tri( o-tolyl)antimony] (1). At the molar ratio of reactants 1:2 or 1:4 µ 2-oxo- bis[( tert-butylperoxy)tri( o-tolyl)antimony] (2) has been formed. According to the X-ray analysis data, antimony atoms are in the trigonal bipyramidal coordination in molecules 1 and 2. The bond lengths Sb-O vary within the ranges 1.937(2)-2.078(2) Å (1) and 1.975(17)-2.216(15) Å (2).
Tri(ortho-tolyl)antimony, tert-butyl hydroperoxide, oxidation, bis[µ2-oxo-tri(o-tolyl)antimony], µ2-oxo-bis[(tert-butylperoxy)tri(o-tolyl)antimony], molecular structures, x-ray analysis
Короткий адрес: https://sciup.org/147160326
IDR: 147160326 | DOI: 10.14529/chem150404
Текст научной статьи Oxidation of tri( o-tolyl)antimony by tert-butyl hydroperoxide. Molecular structures of bis[µ 2-oxo-tri(o-tolyl)antimony] and µ 2-oxo- bis[( tert-butylperoxy)tri( o-tolyl)antimony]
Synthesis of bis [ µ 2 -oxo-tri( o -tolyl)antimony] (1). Tri(o-tolyl)antimony (200 mg, 0.50 mmol) was dissolved in diethyl ether (20 mL). Then tert -butyl hydroperoxide (66 mg of 70 % aqueous solution, 0.50 mmol) was added. The solution was left to stand for 24 hours at temperature 20 °С. When the solvent evaporated, colourless cristalline substance 1 was obtained; the product yield was 199 mg (95 %), MP: 216 °C.
IR spectrum (ν, cm - 1): 3048, 2921, 2854, 1584, 1446,1280, 1202, 1160, 1120, 1031,935, 918, 890,764, 750, 740, 655, 636, 491, 471, 435.
Synthesis of µ 2 -oxo- bis [( tert -butylperoxy)tri( o -tolyl)antimony] 2. Tri(o-tolyl)antimony (200 mg, 0.50 mmol) was dissolved in diethyl ether (20 mL). Then tert -butyl hydroperoxide (132 mg of 70 % aqueous solution, 1.00 mmol) was added. The solution was left to stand for 24 hours at temperature 20 °С. Colorless crystals 2 were obtained; yield 230 mg (92 %), MP: 162 °C.
The reaction with the molar ratio 1:4 was carried out at the same conditons. The product yield of substance 2 was 87 %.
IR spectrum of the substunce 1 was recorded on the Bruker Tensor 27 FT-IR (KBr pellets; 4000 - 400 cm - 1).
The X-ray diffraction analyses of crystalline substances 1 and 2 were made on the Bruker D8 QUEST automatic four-circle diffractometer (Mo K α -emission, λ = 0.71073 Å, 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 [16]. All calculations for structure determination and refinement were performed using the SHELXL/PC programs [17]. The structures 1 and 2 were determined by the direct method and refined by the least-squares method in the anisotropic approximation for non-hydrogen atoms.
The main crystallographic data and refinement results for structures 1 and 2 are listed in Table 1. The selected bond lengths and bond angles are given in Table 2.
Table 1
Crystallographic data and the experimental and structure refinement parameters for compound 1
|
Parameter |
Value |
|
|
1 |
2 |
|
|
Empirical formula |
C 42 H 42 O 2 Sb 2 |
C 50 H 60 O 5 Sb 2 |
|
Formula weight |
822.26 |
984.48 |
|
Т , К |
296(2) |
296(2) |
|
Crystal system |
Triclinic |
Triclinic |
|
Space group |
P-1 |
P1 |
|
a , Å |
11.0684(3) |
10.3355(4) |
|
b , Å |
11.1721(3) |
11.0049(5) |
|
c, Å |
17.0248(5) |
11.0848(4) |
|
α , deg |
80.7820(10) |
69.771(2) |
|
β, deg |
86.0600(10) |
84.636(2) |
|
γ , deg |
61.0370(10) |
81.907(2) |
|
V , Å3 |
1818.06(9) |
1169.88(8) |
|
Z |
2 |
1 |
|
ρ (calcd.), g/сm3 |
1.502 |
1.397 |
|
µ , mm–1 |
1.520 |
1.198 |
|
F (000) |
824.0 |
502.0 |
|
Crystal size, mm |
0.17×0.09×0.08 |
0.55×0.38×0.21 |
|
2 θ Range of data collection, deg |
7.38 - 58.28° |
3.98 - 47.5° |
|
Range of refraction indices |
- 15 ≤ h ≤ 15, - 15 ≤ k ≤ 15, - 23 ≤ l ≤ 23 |
- 11 ≤ h ≤ 11, - 12 ≤ k ≤ 12, - 12 ≤ l ≤ 12 |
|
Measured reflections |
32558 |
14775 |
|
Independent reflections |
9014 |
6981 |
|
R int |
0.0480 |
0.0245 |
|
Refinement variables |
421 |
521 |
|
GOOF |
1.030 |
1.159 |
|
R factors for F2 > 2 σ (F2) |
R 1 = 0.0314, wR 2 = 0.0551 |
R 1 = 0.0511, wR 2 = 0.1274 |
|
R factors for all reflections |
R 1 = 0.0564, wR 2 = 0.0611 |
R 1 = 0.0589, wR 2 = 0.1361 |
|
Residual electron density (min/max), e /Å3 |
0.49/ - 0.33 |
1.04/ - 2.17 |
Table 2
Selected bond lengthes and bond angles in the structures of compounds 1 - 2
|
Bond |
d , Å |
Angle \ |
ω , deg |
Bond |
d , Å |
Angle |
ω , deg |
|
1 |
2 |
||||||
|
Sb(1) - Sb(1a) |
3.1409(4) |
O(1a)Sb(1)C(1) |
165.14(10) |
Sb(1) - O(1) |
1.997(17) |
O(1)Sb(1)C(11) |
93.7(9) |
|
Sb(1) - O(1) |
1.9372(18) |
O(1)Sb(1)C(11) |
114.54(10) |
Sb(1) - C(11) |
2.145(14) |
O(1)Sb(1)O(2) |
167.6(6) |
|
Sb(1) - O(1a) |
2.0784(18) |
O(1a)Sb(1)C(11) |
89.40(9) |
Sb(1) - O(2) |
2.143(18) |
O(1)Sb(1)C(21) |
86.7(7) |
|
Sb(1) - C(1) |
2180(3) |
O(1)Sb(1)C(21) |
130.04(10) |
Sb(1) - C(21) |
2.166(17) |
O(1)Sb(1)C(1) |
95.3(8) |
|
Sb(1) - C(11) |
2.135(3) |
C(11)Sb(1) C(1) |
103.30(11) |
Sb(1) - C(1) |
2.18(2) |
С(11)Sb(1)C(21) |
116.3(10) |
Table 2 (end)
|
Bond |
d , Å |
Angle |
го , deg |
Bond |
d , Å |
Angle |
го , deg |
|
1 |
2 |
||||||
|
Sb(1) - C(21) |
2.150(3) |
C(11)Sb(1)C(21) |
111.93(11) |
Sb(2) - O(1) |
1.951(18) |
С(11)Sb(1)C(1) |
124.4(12) |
|
Sb(2) - Sb(2b) |
3.1441(3) |
C(21)Sb(1)Sb(1a) |
110.58(8) |
Sb(2) - C(41) |
2.150(17) |
O(2)Sb(1)C(11) |
87.2(9) |
|
Sb(2) - O(2) |
2.0585(17) |
C(21)Sb(1)C(1) |
96.05(11) |
Sb(2) - C(61) |
2.114(12) |
O(2)Sb(1)C(21) |
81.9(7) |
|
Sb(2) - O(2b) |
1.9473(17) |
O(2b)Sb(2)C(31) |
89.87(9) |
Sb(2) - C(51) |
2.114(12) |
O(2)Sb(1)C(1) |
94.3(8) |
|
Sb(2) - C(31) |
2.186(3) |
O(2)Sb(2)C(31) |
163.65(9) |
Sb(2) - O(4) |
2.129(17) |
С(1)Sb(1)C(21) |
118.9(10) |
|
Sb(2) - C(41) |
2.131(3) |
O(2b)Sb(2)C(41) |
108.70(10) |
О(2) - О(3) |
1.337(17) |
Sb(2)O(1)Sb(1) |
169.2(6) |
|
Sb(2) - C(51) |
2.151(3) |
O(2)Sb(2)C(41) |
92.51(10) |
O(4) - O(5) |
1.356(17) |
C(22)C(21)Sb(1) |
127.0(19) |
|
O(1) - Sb(1a) |
2.0784(18) |
O(2b)Sb(2)C(51) |
130.20(9) |
O(5) - C(35) |
1.51(2) |
C(46)C(41)Sb(2) |
114.2(15) |
|
O(2) - Sb(2b) |
1.9473(17) |
O(2)Sb(2)C(51) |
87.24(9) |
O(3) - C(31) |
1.451(17) |
C(42)C(41)Sb(2) |
124.6(15) |
|
Symmetry relation: a) 1 - x, - y, 2 - z; b) 2 - x, 1 - y, 1 - z |
|||||||
The full tables of atomic coordinates, bond lengths, and bond angles for the substance 1 was deposited with the Cambridge Crystallographic Data Centre (№ 1052677; ; .
Results and Discussion
It has been found that the oxidation of tri( o -tolyl)antimony by tert -butylhydroperoxide at the molar ratio 1:1 in diethyl ether goes with the formation of tri( o -tolyl)antimony oxide with dimeric structure: bis [μ 2 -oxo-tri( o -tolyl)antimony] ( 1 ):
2 ( o -Tol^Sb + 2 t -BuOOH ^ [( o -Tol^SbOh + 2 t -BuOH
According to X-ray diffraction data the crystal of compound 1 contains two types of crystallographically independent molecules ( А , B ). The antimony atoms have intermediate coordination between tri-gonal-bipyramidal and square-pyramidal coordination (Fig. 1).
Fig. 1. The structure of compound 1А (hydrogen atoms aren’t shown)
Two carbon atoms of the aryl substituents and μ2-bridging oxygen atom are placed in equatorial plane, the second μ2-bridging oxygen atom and carbon atom are in axial positions. The sum of equatorial OSbC and CSbC angles is 356.57(10)º for А and 350.83(10)º for B. The axial OSbC angles are significantly distorted, they are equal to 165.14(10)° and 163.65(9)°. The OSbO and SbOSb angles in the flat cyclic fragment [Sb2O2] equal 77.14(8)°, 102.86(8)° (А) and 76.62(8)°, 103.13(7)° (B). The Sb-Ceq bond lengths (2.135(3), 2.150(3) А А; 2.131(3), 2151(3) A B) and Sb-Oeq (1.937(2) А А; 1.943(2) A B) are less than Sb-Cax (2.180(3) А А; 2.186(3) A B) and Sb-Oax (2.078(2) А А; 2.058(2) A B). The distances between antimony atoms in the cycle (3.1409(5) (А), 3.1441(3) Å (B)) are considerably less than the double Van der Waals radius of antimony atom (4.4 Å [18]). The о-Tol3Sb fragments in compound 1 are in staggered conformation with respect to each other. Geometrical parameters of complex 1 are close to geometrical parameters of such compounds as (Ph3SbO)2 [19] and [(2-MeOC6H4)3SbO]2 [20].
When the concentration of tert -butylhydroperoxide has increased (1:2 or 1:4) the single organoan-timony product in the reaction mixture is μ 2 -oxo- bis [( tert -butylperoxo)tri( o -tolyl)antimony] ( 2 ), the product yield is 92 %:
2 ( o -Tol^Sb + 4 t -BuOOH ^ [( o -Tol^SbOOBu- t ]2O + 2 t -BuOH + H2O
The coordination polyhedron of antimony atoms in binuclear molecule 2 is an insignificantly distorted trigonal bipyramid (Fig. 2). The bipyramid distortion is characterized by deflection of Sb(1) and Sb(2) atoms from their respective equatorial planes by 0.02 Å and 0.08 Å to the direction of the bridging oxygen atom O(1), which leads to angle deviation between axial and equatorial bonds from the theoretical value 90 ° . The axial OSb(1,2)O angles are equal to 167.6(6) ° and 159.5(5) ° .
The equatorial CSb(1,2)C angles are changed in the range of 116.3(8) °- 124.4(12) ° . The Sb(1)O(1)Sb(2) angle is 169.2(6) ° . The SbOSb fragment has linear structure in the centrosymmetric molecule of μ 2 -oxo- bis [( tert -butylperoxo)triphenylantimony] [21].
Fig. 2. The structure of compound 2 (hydrogen atoms aren’t shown)
The equatorial bonds Sb(1)-Ceq and Sb(2)-Ceq are changed in the range of 2.14(1) - 2.18(2) A and 2.10(1) - 2.15(1) A.
The Sb(1,2)–О(1) distances are equal to 1.997(7) and 1.951(18) Å, and they are less than terminal distances Sb(1)–О(2) (2.143(18) Å) and Sb(2)–О(4) (2.129(17) Å) like in the molecule of μ 2 - oxo- bis [( tert -butylperoxo)triphenylantimony].
Conclusions
Thus, tert -butylhydroperoxide oxidizes tri( o -tolyl)antimony at the molar ratio of the reactants 1:1 into tri( o -tolyl)antimony oxide, which dimerizes into bis [μ 2 -oxo-tri( o -tolyl)antimony]. With tert butylhydroperoxide in excess (1:2 and 1:4) the reaction proceeds with the formation of the single orga-noantimony compound: q 2-oxo- bis [( tert -butylperoxo)tri( o -tolyl) antimony].
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