Antimony Complexes {[2,6-(OMe)2C6H3]3SbCH2C(O)OEt}2+[Hg2I6]2? and {[2,6?(OMe)2C6H3]3SbME}2+[Hg2I4]2?· : Synthesis and Structure

Article abstract of DOI:10.1134/S0036023619010078

It has been established that ethyl iodoacelate and 1,4-diiodobutane alkylate triarylantimony Ar₃Sb with the formation of [Ar₃SbCH₂C(O)OEt]⁺I^? and [Ar₃Sb(CH₂)₄I]^+<

Full text of DOI:10.1134/S0036023619010078

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2019, Vol. 64, No. 1, pp. 28–35. © Pleiades Publishing, Ltd., 2019.
Russian Text © I.V. Egorova, V.V. Zhidkov, I.P. Grinishak, I.Yu. Bagryanskaya, N.V. Pervukhina, I.V. El’tsov, N.V. Kurat’eva, 2019, published in Zhurnal Neorganicheskoi Khimii,
2019, Vol. 64, No. 1, pp. 15–22.
COORDINATION
COMPOUNDS
Antimony Complexes
{[2,6-(OMe)2C6H3]3SbCH2C(O)OEt}+2 [Hg2I6]2–
and {[2,6-(OMe)2C6H3]3SbMe}+2 [HgI4]2– ⋅ DMSO:
Synthesis and Structure
I. V. Egorovaa, *, V. V. Zhidkova, I. P. Grinishaka, I. Yu. Bagryanskayab, c,
N. V. Pervukhinac, d, I. V. El’tsovc, and N. V. Kurat’evac, d
aBlagoveshchensk State Pedagogical University, Blagoveshchensk, 675000 Russia
bVorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
cNovosibirsk National Research State University, Novosibirsk, 630090 Russia
dNikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
*e-mail: bgpu.chim.egorova@mail.ru
Received December 7, 2017; revised February 19, 2018; accepted July 4, 2018
Abstract⎯It has been established that ethyl iodoacelate and 1,4-diiodobutane alkylate triarylantimony Ar3Sb
−
with the formation of [Ar3SbCH2C(O)OEt]+I– and [Ar3Sb(CH2)4I]+I–, [Ar3Sb(CH2)4SbAr3]2+ where
I2,
Ar = 2,6-(OMe) C H . The complexes
+ [Hg2I6]2– and
+[HgI4]2– ⋅ DMSO
Ar SbMe
2
Ar SbCH C O OEt
( )
[
]
[
]
2
6
3
3
2
3
2
have been synthesized by the reaction of [Ar3SbCH2C(O)OEt]+I– and [Ar3SbMe]+I– with mercury diiodide
and studied by X-ray diffraction. The antimony and iodine atoms have a distorted tetrahedral coordination.
The CSbC and IHgI angles are ranged within 103.28(14)°–116.68(14)°, 103.7(4)°–115.5(4)° and 98.122(9)°–
125.590(12)°, 102.66(2)°–115.64(2)°, respectively.
Keywords: tris(2,6-dimethoxyphenyl) antimony, ethyl iodoacetate, 1,4-diiodobutane, tris(2,6-dimethoxy-
phenyl) (ethoxycarbonylmethyl) antimony iodide, tris(2,6-dimethoxyphenyl)methyl antimony iodide, mer-
cury diiodide, X-ray diffraction analysis, nuclear magnetic resonance
DOI: 10.1134/S0036023619010078
INTRODUCTION
The reaction between alkyl halides and aryl anti-
mony(III) compounds is less profoundly studied. The
alkylation of dimethyl- and diethylantimony with
methyliodide leads to the formation of trialkylphenyl-
stibonium iodide [10]. It has not been managed to per-
form the addition of alkyl halides to antimony(III)
compounds with two or three aromatic substituents for
The addition of an alkyl iodide to alkyl mono- and
binuclear antimony(III) derivatives with the forma-
tion of Sb–C bonds leads to a wide variety of
tetraalkystibonium iodides with the general formula
[R3R'Sb]+I– (R = Me, Еt, n-Pr, n-Bu, iso-Bu, n-Am;
−
R' = Me, Еt) and [R2SbMe(CH2)nMeSbR2]2+ (R = a rather long time [3]. For this reason, stibonium salts
I2
Еt, tert-Bu; n = 4, 6), respectively [1–5]. The anti- [Аr3RSb]+[BF4]– (Аr = Ph, o-Tol, m-Tol, p-Tol, (3,4-
monyorganic compounds with the general formula
Me)2C6H3, (2,4-Me)2C6H3, (2,4,6-Me)3C6H2; R =
Me, Ph) are synthesized with the use of more active
[Alk3SbСН2Е]+Br–, where Alk = n-Bu; E = Ph,
CH=CH2, CH=CHC(O)OEt, C(O)OMe, CN, alkylating agents, such as trimethyloxonium or
diphenyliodinium fluoroborates [11–14]. The further
effect of sodium iodide leads to corresponding iodide
complexes [7, 10]. Trimethyloxonium tetrafluorobo-
rate and methyltrifluoromethanesulfonate alkylate the
binuclear antimonyorganic compound 1,2-(Ph2Sb)2C6H4
to result in the complexes [1,2-(Ph2MeSb)2C6H4][BF4]2
and [1,2-(Ph2MeSb)2C6H4][OTf], which are efficient
catalysts for the hydrosilylation of benzaldehyde under
CH=CHR; R=Me, n-Pr, iso-Pr, were synthesized by
the reaction of a alkyl bromide and tributylantimony.
These complexes are used in the synthesis of second-
ary alcohols from corresponding aldehydes R'CHO
(R' = Ph, 4-ClC6H4, 4-MeC6H4, PhCH=CH, pyri-
dine-2-yl, 4-BrC6H4) [6, 7]. The alkylation of triethyl-
and trimethylantimony with methyl was also per-
formed [8, 9].
28

ANTIMONY COMPLEXES
29
2
+
+
H3C
H3C
H3C
CH3
CH3
O
O
O
+
Sb CH2
I −
Sb CH2 Sb
2I−
4
4
3
3
3
O
H3C
O
O
3
2
d
+
+
H3C
H3C
H3C
H3C
H3C
O
O
O
O
SbCH3 I−
a
c
I−
Sb
Sb CH2
C
3
3
OEt
O3
H3C
O
O
1
b
b
+
+
H3C
H3C
O
O
O
−
O
−
2
2
Sb CH2
C
SbCH3 [HgI4]
[Hg2I6]
3
OEt
3
O
H3C
2
2
H3C
4
5
(a) ICH2C(O)OEt, (b) HgI2, (c) CH3I, (d) ICH2(CH2)2CH2I.
Fig. 1. Synthetic scheme for stibonium complexes.
mild conditions [15]. The method for the synthesis of
[Ph3MeSb]+Cl– by the reaction between bis(chloro-
methyl)zinc and triphenylantimony with the further
hydrolysis of the formed zincorganic compound is
also known [16]. The synthesis of triphenylalkylstibo-
mium zwitterions with the use of bromomethylin-
dium(III) dibromide or phenylmethanesulfonic acid
anhydride as alkylating agents in the presence of
hydrogen peroxide was also described [17, 18].
Tetraorganylantimony halides [Аr3RSb]+X– [Аr =
2,6-(OMe)2C6H3; R = Me, Et, n-Bu, СН2СН=СН2;
X = Cl, Br, I] were synthesized by the addition of alkyl
halides to triarylantimony [19].
EXPERIMENTAL
The possibility to perform the alkylation of tris(2,6-
dimethoxyphenyl)antimony with ethyl ester of iodo-
acetic acid and 1,4-diiodidebutane was studied.
Tris(2,6-dimethoxyphenyl)(ethoxycarbonylmethyl)anti-
mony iodide {[2,6-(OMe)2C6H3]3SbCH2C(O)OEt}+I–
(1),
tris(2,6-dimethoxyphenyl)(4-iodobytul)anti-
mony iodide {[2,6-(OMe)2C6H3]3Sb(CH2)4I}+I– (2),
and 1,4-di[tris(2,6-dimethoxyphenyl)antimonyl]butane
iodide {[2,6-(OMe)2C6H3]3Sb(CH2)4Sb[C6H3(OMe)2-
−
2,6]3}2+ (3) were synthesized and characterized by
I2
NMR spectroscopy.
The
mercury(II)
( )
complexes
+[Hg2I6]2– (4)
The objective of this work was to study the targeted
synthesis of stibonium complexes containing potential
coordinating centers, which represent the oxygen
atoms of carbonyl and/or methoxy groups in the
organic substituents at the antimony atom.
2,6-(OMe) C H SbCH C O OEt
[
]
{
}
2
6
3
2
3
2
and
+[HgI ]2–⋅ DMSO
2, 6- OMe C H SbMe
(
)
[
{
]
}
4
6
3
2
3
2
(5) were synthesized by the reaction between mercury
diiodide and compounds {[2,6-
1
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 64 No. 1 2019

30
EGOROVA et al.
(OMe)2C6H3]3SbMe}+I– and studied by X-ray diffrac-
tion.
The reactions were performed at room temperature
(Fig. 1).
added under stirring. The solvent was evaporated.
Light-green crystals of complex 4 (0.78 g, 97%) with
Tm = 185°C were thus synthesized.
IR spectrum (ν, cm–1): 3086, 3069, 3001, 2972,
2937, 2834, 1724, 1587, 1576, 1471, 1427, 1385, 1362,
1306, 1286, 1257, 1180, 1102, 1032, 1017, 889, 869,
804, 800, 781, 771, 740, 715, 708, 617, 596, 584, 499.
Synthesis of complex 1. To tris(2,6-dimethoxyphe-
nyl)antimony (1.03 g, 1.93 mmol) in chloroform
(10 mL), ethyl ester of monoiodoacetic acid (0.41 g,
1.93 mmol) was added under stirring. The reaction
mixture was allowed to stand for 12 h. The solvent was
evaporated, and the solid residue was washed with
diethyl ester (5 × 10 mL). Complex 1 (1.40 g, 97%)
with Tm = 184°C (decomp.) was thus synthesized. IR
For C56H68Hg2I6O16Sb2, anal. calcd. (%): C, 27.99;
H, 2.85; O, 10.65.
Found (%): C, 27.60; H, 2.73; O, 10.60.
Complex 5 was obtained by the same method from
tris(2,6-dimethoxyphenyl)methylstibonium
iodide
spectrum (ν, cm–1): 3059, 3000, 2973, 2941, 2835,
1728, 1716, 1587, 1576, 1475, 1429, 1400, 1388, 1363,
1305, 1256, 1184, 1173, 1126, 1102, 1022, 891, 866, 804,
792, 775, 740, 713, 615, 594, 499.
(0.50 g, 0.74 mmol) synthesized as described in [19]
and mercury diiodide (0.17 g, 0.37 mmol). Light-green
crystals of complex 5 (0.65 g, 97%) with Tm = 168°C
was thus separated.
For C28H34IO8Sb, anal. calcd. (%): C, 45.00; H,
4.59; O, 17.13.
IR spectrum (ν, cm–1): 3151, 3066, 3024, 3006,
2991, 2970, 2937, 2848, 2835, 1587, 1576, 1471, 1427,
1303, 1257, 1172, 1151, 1102, 1035, 1020, 950, 891, 829,
781, 773, 740, 717, 696, 594.
Found (%): C, 44.56; H, 4.10; O, 16.52.
1H NMR spectrum (δ, ppm): 0.88 t (3H, CH2–
CH3, J 7.2 Hz), 3.63 s (18H, CH3–O), 3.65 s (2H,
CH2–Sb), 3.85 q (2H, CH2–CH3, J 7.2 Hz), 6.65 d
(6H, 3,5-Ph, J 8.4 Hz), 7.49 t (3H, 4-Ph, J 8.4 Hz).
For
C50H60HgI4O12Sb2
⋅
0.92C2H6SO
(C51.84H65.52HgI4O12.92S0.92Sb2), anal. calcd. (%): C,
33.18; H, 3.53; O, 11.02.
13C{1H} NMR spectrum (δ, ppm): 13.65 (CH3–
CH2), 29.74 (CH2–Sb), 56.52 (CH3–O), 61.69
(CH3–CH2), 104.77 (1-Ph), 104.87 (3,5-Ph), 135.78
(4-Ph), 162.15 (2,5-Ph), 167.32 (C=O).
Synthesis of complexes 2 and 3. To 1,4-diiodobu-
tane (0.60 g, 1.94 mmol) in chloroform (70 mL),
a solution of tris(2,6-dimethoxyphenyl)antimony
(1.00 g, 1.88 mmol) in chloroform (100 mL) was added
drop by drop under stirring for 30 min. The solution
was stirred for 15 min. The solvent was evaporated, and
the residue was washed with diethyl ester (5 × 20 mL). A
colorless finely crystalline product (1.42 g) represent-
ing a mixture of two compounds 2 (~90%) and 3
(~10%) according to NMR data was separated.
Found (%): C, 33.07; H, 3.61; O, 10.70.
IR spectra of these complexes were recorded on a
FSM 2202 Fourier-transform IR spectrometer in the
region of 500–7000 cm–1 ad KBr pellets. Elemental
analysis was performed on a Carlo Erba 1106 CHN-
analyzer.
NMR spectra were recorded on a Bruker Avance
III 500 spectrometer with a working frequency of
500.03 MHz for 1H and 125.73 MHz for 13C. The spec-
tra were taken in the solution of a complex (25 mg) in
CDCl3 (0.6 mL). The solvent signals used as standards
were δ = 7.26 ppm for residual protons in the 1H NMR
spectrum and δ = 77.23 ppm for the 13C NMR spectra.
The assignment of signals was accomplished on the
basis of homonuclear 1H,1H-COSY and heteronuclear
13C,1H-HMBC and 13C,1H-HSQC two-dimensional
correlations.
Complex 2. 1H NMR spectrum (δ, ppm): 1.74 m
(2H, 2-Bu), 1.88 m (2H, 3-Bu), 2.77 m (2H, 1-Bu),
3.12 t (2H, 4-Bu, J 6.6 Hz), 3.62 s (18H, CH3–O),
6.64 d (6H, 3,5-Ph, J 8.3 Hz), 7.47 t (3H, 4-Ph, J 8.4
Hz).
X-ray diffraction analysis of complexes 4 and 5 was
performed on a Bruker KAPPA APEX II diffractome-
ter with an area CCD-detector (MoKα radiation,
graphite monochromator, ω–ϕ-scanning). The struc-
tures were solved by direct methods and refined by the
full-matrix least-squares technique in the anisotropic
approximation using the SHELXL-97 software [20].
The positions of hydrogen atoms were calculated geo-
metrically and refined “as riding” (the parameters of
hydrogen atoms were calculated in every refinement
cycle from the coordinates of corresponding carbon
atoms). In complex 5, the [HgI4]2– anion and a DMSO
molecule are partially disordered (the second position
13C{1H} NMR spectrum (δ, ppm): 6.11 (1-Bu),
25.65 (2-Bu), 25.73 (1-Bu), 35.00 (3-Bu), 56.52
(CH3–O), 104.29 (1-Ph), 104.73 (3,5-Ph), 135.43 (4-
Ph), 162.40 (2,5-Ph).
1
Complex 3. H NMR spectrum (δ, ppm): 1.73 m
(4H, 2,3-Bu), 2.77 m (4H, 1,4-Bu), 3.57 s (18H,
CH3–O), 6.63 d (6H, 3,5-Ph), 7.47 t (3H, 4-Ph).
13C{1H} NMR spectrum (δ, ppm): 26.00 (1,4-Bu),
27.32 (2,3-Bu), 56.71 (CH3–O), 104.13 (1-Ph),
104.87 (3,5-Ph), 135.52 (4-Ph), 162.40 (2,5-Ph).
Synthesis of complexes 4 and 5. To complex 1 (0.50 g, of a solvent molecule has not been determined). The
0.66 mmol) in DMSO (20 mL), a solution of mercury selected crystallographic characteristics, results of
diiodide (0.30 g, 0.66 mmol) in DMSO (10 mL) was X-ray diffraction experiment, and refinement details
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ANTIMONY COMPLEXES
31
Table 1. Crystallographic characteristics, data of X-ray diffraction experiment, and refinement details for the structures of
complexes 4 and 5
Parameter
4
5
Formula
C56H68Hg2I6O16Sb2
2403.18
C51.84H65.52HgI4O12.92S0.92Sb2
Formula weight
Temperature, K
Symmetry system
Space group
a, Å
b, Å
c, Å
β, deg
V, Å3
1876.57
173(2)
200(2)
Monoclinic
C2/c
P21/n
28.2103(12)
11.2798(5)
23.1211(8)
104.929(1)
7108.9(5)
17.8459(9)
30.1024(16)
24.3373(13)
106.236(2)
12552.7(11)
Z
4
8
calcd, g/cm3
2.245
1.986
ρ
μ(MoKα), mm–1
7.721
5.347
F(000)
Crystal size, mm
θ angle range, deg
4448
0.60 × 0.45 × 0.20
2.07–30.07
7109
0.65 × 0.45 × 0.35
1.26–26.37
Number of measured reflections
Number of independent reflections
Transmittance min/mаx
GOOF on F2
81829
295857
10421 (Rint = 0.0386)
0.0903/0.3073
1.012
25677 (Rint = 0.0626)
0.1287/0.2562
1.089
R-factor for I > 2σ(I)
R-factor for all reflections
Residual electron density, max/min, е/Å3
R1 0.0305, wR2 0.0799
R1 = 0.0376, wR2 = 0.0839
2.491/–2.252
R1 0.0524, wR2 0.0967
R1 = 0.1002, wR2 = 0.1092
1.773/–2.342
for the structures of complexes 4 and 5 are given in Table nals typical for a moiety with the C–I bond from this
13
1. The X-ray diffraction data for complexes 4 and 5
were deposited with the Cambridge Structure Data-
base (CCDC nos. 1549982 and 1549983).
complex in the high-field C NMR spectrum region
allows us to presume the substitution of both halide
atoms in 1,4-diiodobutane. Another confirmation of
symmetry in the structure of complex 3 is the exis-
tence of only two signals from the aliphatic moiety in
the 1H and 13C NMR spectra.
RESULTS AND DISCUSSION
The positions and intensities of signals in the one-
The composition of complexes 4 and 5 formed by
1
dimensional H and 13C NMR spectra of complexes
the reactions of HgI2 with complex 1 and {[2,6-
1–3 was in agreement with the presumable addition of
ethyliodoacetate and 1,4-diiodobutane to tris(2,6-
dimethoxyphenyl)antimony, but did not unambigu-
ously confirmed it. To perform the targeted assign-
ment of signals and confirm the structures of these sti-
bonium compounds, two-dimensional 13C,1H-corela-
tion spectra were recorded. The analysis of the
obtained data argues for the formation of the new Sb–
CAlk bond in complexes 1 and 2. Cross-peaks corre-
sponding to the interaction of the methylene group
bonded to the antimony atom with the unco-carbon
atom of the phenyl moiety can be clearly seen in the
two-dimensional spectra of these complexes (Fig. 2).
It has not been managed to detect this signal for com-
plex 3 due to a small content of this product in the ana-
lyzed mixture (~10%). However, the absence of sig-
(OMe)2C6H3]3SbMe}+I– is governed by the molar
ratio of reagents (1 : 1, 1 : 2). According to X-ray dif-
fraction data, the mercury atoms in the centrosym-
metric binuclear [Hg2I6]2– anion have a distorted tet-
rahedral coordination (IHgI angles are 98.122(9)°–
125.590(12)°, Fig. 3).
The terminal iodine atoms are more strongly
bonded to the mercury atoms (Hg–Iterm, 2.6874(4),
2.6945(3) Å) in comparison with the bicoordinated
bridging iodine atoms (Hg–Ibridge
,
2.9246(4),
2.9260(4) Å). Their values are comparable with the
parameters of the complexes
2+ [Hg2I6]2– and
Ph Sb
[
]
4
2+ [Hg2I6]2– (Hg–Iterm
,
2.6910(4) and
p-Tol Sb
[
]
4
2.6996(4) Å; 2.7028(3) and 2.7222(3) Å; Hg–Ibridge
,
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 64 No. 1 2019

32
EGOROVA et al.
1
2
ppm
ppm
10
0
20
40
60
80
30
50
70
90
110
100
ppm
ppm
120
140
160
180
130
150
170
104
105
106
104
105
2.8
ppm
2.7
3.7
ppm
3.6
7
6
5
4
3
2
0
7
6
5
4
3
2
1
0
ppm
ppm
13
1
Fig. 2. C, H-HMBC spectra of complexes 1 and 2.
O(06)
C(08)
C(05)
C(04)
I(1a)
I(3a)
C(23)
O(02)
C(16)
O(5)
C(07)
Hg(1a)
O(4)
C(14)
C(18)
Sb(1)
C(13)
C(6)
C(19)
C(20)
C(17)
C(22)
O(2)
C(5)
I(2a)
C(1)
C(2)
O(1)
C(8)
I(2)
C(9)
C(12)
C(4)
C(10)
Hg(1)
C(3)
C(21)
C(11)
O(3)
C(7)
O(6)
I(3)
I(1)
C(24)
C(15)
+
2–
Fig. 3. General view of the {[2,6-(OMe) C H ] SbCH C(O)OEt} cation and the [Hg I ] anion of complex 4. Hydrogen
2
6
3 3
2
2 6
atoms are omitted.
two [HgI4]2– anion (Fig. 5). The IHgI angles in the tetra-
hedral anions are 102.66(2)°–115.64(2)°. The Hg–I dis-
tances are nonequivalent (2.670(5)–2.956(7) Å), as also
2.8250(4) and 3.0748(5)Å; 2.8539(3) and 2.9163(3) Å)
[21]. The Hg(1)I(2)Hg(1a)I(2a) and I(1)I(3)I(1a)I(3a)
are almost mutually perpendicular, and the angle
between them is 87.47°. The terminal iodine atoms
link [Hg2I6]2– anions into chains running along axis c
by means of I···I contacts (3.944 Å) (Fig. 4).
takes place in the complex
2+[HgI4]2–
n-Tol Sb
[
]
4
(2.7719(13)–2.7908(12) Å) [21].
In the cations of complexes 4 and 5, the antimony
and oxygen atoms of methoxy groups are character-
ized by additional coordination (Sb···O distances are
The unit cell of complex 5 contains four structurally
nonequivalent {[2,6-(OMe)2C6H3]3SbMe}+ cations and
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ANTIMONY COMPLEXES
33
0
b
I(3)
I(3)'
a
Fig. 4. Fragment of the structural packing of complex 4. Hydrogen atoms are omitted.
2.853–2.895 Å, and the van der Waals radii of Sb and (H···O 2.493 Å), linking the cations of complex 4 into
O in sum are 3.7 Å [22]), which leads to the appear-
ance of the contribution from trigonal-bipyramidal
component to the tetrahedral structure (Figs. 3 and 5).
The CSbC bond angles (103.28(14)°–116.68(14)° in
complex 4 and 103.7(4)°–115.5(4)° in complex 5)
deviate from the value ideal for a tetrahedron. The
bond lengths are the following: Sb–CAlk, 2.140(4);
a chain running along axis b (Fig. 6). The incorpora-
tion of a solvent molecule into the coordination sphere of
the mercury atom takes place in the [HgI3(DMSO)]–
anion [24]. However, DMSO molecules in complex 5
participate only in the formation of weak hydrogen
bonds O···H–CAr (O···H, 2.48–2.67 Å) with the stibo-
nium cation.
Sb–CAr, 2.085(3)–2.093(3) Å in complex 4; Sb–CMe
,
2.085(10)–2.113(9); Sb–CAr, 2.051(9)–2.114(8) Å in
complex 5 (the Sb and C covalent radii in sum are
2.18 Å [22]).
Let us mention that the Sb–СAr bond lengths and
CSbC bond angles in cations 4 and 5 and oxide
tris(2,6-dimethoxyphenyl)antimony have close values
(2.073(4)–2.098(5) Å and 107.47(18)°–116.24(18)°
[23]).
The absorption bands in the IR spectra of com-
plexes 1–5 were identified in compliance with the data
[23, 25]. The vibration frequencies of bonds in the
spectra of complexes 1, 4, and 5 appear at 1102 cm–1
[νs(О–СAlk)]; 1022, 1256 (1), 1017, 1257 (4), 1020,
1257 (5) cm–1 [νаs(СМе–О–СAr)]; 2835, 2941 (1),
2834, 2937 (4), 2835, 2937 (5) cm–1 [νs,аs(С–Н)];
The carbonyl oxygen atoms participate in the for-
mation of hydrogen bonds СAr(21)–H(21)···O(06) 1716, 1728 (1), 1724 (4) cm–1 [νas(OCO)].
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 64 No. 1 2019

34
EGOROVA et al.
C(121)
C(122)
C(120)
C(119)
C(118)
C(124)
O(16)
C(17)
C(37)
O(31)
C(117)
O(11)
C(123)
C(12)
O(15)
C(13)
C(14)
C(44)
C(43)
C(47)
C(324)
O(36)
C(33)
C(11)
Sb(1)
O(14)
C(325)
C(125)
C(45)
C(46)
C(16)
C(24)
C(23)
C(34)
O(13)
C(115)
C(32)
Sb(3)
C(19)
C(25)
O(12)
C(116)
C(15)
C(18)
C(224)
C(424)
C(322)
C(317)
C(321)
C(320)
C(421)
C(420)
C(114)
C(26)
O(41)
C(27)
O(21)
C(41)
Sb(4)
C(35)
O(26)
O(33)
C(221)
C(113)
C(220)
C(111)
C(28)
O(32)
C(417)
O(43)
C(415)
O(22)
C(217)
C(319)
O(34)
O(35)
C(38)
C(112)
Sb(2)
O(23)
C(215)
C(419)
C(423)
C(425)
C(49)
C(311)
O(45)
C(219)
C(225)
C(29)
C(410)
C(316)
C(312)
C(313)
C(03)
C(411)
C(223)
O(24)
C(210)
O(44)
I(8)
C(214)
C(211)
C(214)
O(01)
C(416)
C(412)
I(1)
O(02)
C(04)
C(413)
C(216)
Hg(2)
I(5)
I(7)
I(6)
C(213)
Hg(1)
I(3)
S(2)
I(4)
S(1)
C(01)
C(02)
I(2)
Fig. 5. Indepenent part in the structure of complex 5. Hydrogen atoms, second anion–solvent disordering component, and some
atom notations are omitted.
c
0
O(06)
H(21A)
b
Fig. 6. Fragment of the structural packing of complex 4 with hydrogen bonds (dashed lines) forming the chains of cations along
axis b.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 64
No. 1
2019

ANTIMONY COMPLEXES
35
7. Y.-Z. Huang, L.-J. Zhang, C. Chen, and Z.-G. Guo, J.
Organomet. Chem. 412, 47 (1991). doi 10.1016/0022-
328X(91)86040-W
CONCLUSIONS
Tris(2,6-dimethoxyphenyl)antimony alkylation pro-
viding the possibility to broaden the series of stibonium
salts has been studied. The composition of the stibonium
8. K. Issleib and R. Linder, Justus Liebigs Ann. Chem.
707, 120 (1967). doi 10.1002/jlac.19677070119
cations
{[2,6-(OMe)2C6H3]3Sb(CH2)4I}+,
{[2,6-(OMe)2C6H3]3SbCH2C(O)OEt}+,
9. G. Balàzs, L. Balàzs, H. J. Breunig, and E. Lork, Appl.
and
Organomet.
Chem.
16,
155
(2002).
doi
{[2,6-(OMe)2C6H3]3Sb(CH2)4Sb[C6H3(OMe)2-2,6]3}2+
is governed by the nature of an alkylating agents, ethyl
iodoacetate and 1,4-diiodobutane. The synthetic
approach has been proposed, and the earlier unknown
10.1002/aoc.255
10. G. Grüttner and M. Wiernik, Chem. Ber. 48, 1759
(1915). doi 10.1002/cber.19150480271
11. M. C. Henry and G. Wittig, J. Am. Chem. Soc. 82, 563
(1960). doi 10.1021/ja01488a017
triarylalkylstibonium
2,6-(OMe) C H SbCH C O OEt
mercurates
12. D. Henning, G. Kempter, E. Ahrens, et al., Z. Chem.
+[Hg2I6]2– and
( )
+ [HgI4]2–
[
[
{
]
{
}
7, 463 (1967). doi 10.1002/zfch.19670071213
2
6
3
2
3
2
13. D. Henning, G. Kempter, and K.-D. Worlitzer, Z.
containing
2,6-(OMe) C H SbMe
]
}
2
6
3
3
2
Chem. 9, 306 (1969). doi 10.1002/zfch.19690090813
potential coordination centers in the organic substitu-
ents at the antimony atom have been structurally char-
acterized.
14. L. G. Makarova and A. N. Nesmeyanov, Izv. Akad.
Nauk SSSR, Otd. Khim. Nauk, 617 (1945).
15. M. Hirai, J. Cho, and F. P. Gabbai, Chem.-Eur. J. 22,
6537 (2016). doi 10.1002/chem.201600971
16. G. Wittig and K. Schwarzenbach, Justus Liebigs Ann.
ACKNOWLEDGMENTS
Chem. 650, 1 (1961). doi 10.1002/jlac.19616500102
The authors are grateful to the Chemical Service
Center of Shared Facilities of the Siberian Branch of
the Russian Academy of Sciences for X-ray diffraction
analysis.
17. L. A. Felix, C. A. F. Oliveira, R. K. Kross, et al., J.
Organomet. Chem. 603, 203 (2000). doi
10.1016/S0022-328X(00)00178-9
18. A. P. Pakusina, Extended Abstract of Doctoral Disser-
tation in Chemistry (Irkutsk, 2006).
19. M. Wada, S. Miyake, S. Hayashi, et al., J. Organomet.
Chem. 507, 53 (1996). doi 10.1016/0022-
328X(95)05716-3
20. G. M. Sheldrick, SHELX-97: Programs for Crystal
Structure Analysis (Release 97-2) (Univ. of Göttingen,
Göttingen, 1997).
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Translated by E. Glushachenkova
doi 10.1021/jo00004a010
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 64 No. 1 2019