Synthesis and structure of bis(4-iodophenoxy)triphenylantimony and 4-iodophenoxytetraphenylantimony

Article abstract of DOI:10.1007/s11172-016-1368-1

A reaction of triphenylantimony with 4-iodophenol in the presence of hydrogen peroxide furnished bis(4-iodophenoxy)triphenylantimony, which when treated with pentaphenylantimony gave 4-iodophenoxytetraphenylantimony. The structure of organoantimony compounds was studied by ¹H and ¹³C NMR spectroscopy and X-ray crystallography.

Full text of DOI:10.1007/s11172-016-1368-1

Russian Chemical Bulletin, International Edition, Vol. 65, No. 3, pp. 751—755, March, 2016
751
Synthesis and structure of bis(4ꢀiodophenoxy)triphenylantimony
and 4ꢀiodophenoxytetraphenylantimony
V. V. Sharutin, O. K. Sharutina, and V. S. Senchurin
South Ural State University,
76 prosp. im. V. I. Lenina, 454080 Chelyabinsk, Russian Federation.
Fax: +7 (351) 267 9900. Eꢀmail: vvsharutin@rambler.ru
A reaction of triphenylantimony with 4ꢀiodophenol in the presence of hydrogen peroxide
furnished bis(4ꢀiodophenoxy)triphenylantimony, which when treated with pentaphenylantiꢀ
mony gave 4ꢀiodophenoxytetraphenylantimony. The structure of organoantimony compounds
was studied by 1H and 13C NMR spectroscopy and Xꢀray crystallography.
Key words: triphenylantimony, hydrogen peroxide, 4ꢀiodophenol, pentaphenylantimony, bisꢀ
(4ꢀiodophenoxy)triphenylantimony, 4ꢀiodophenoxytetraphenylantimony, synthesis, structure.
Earlier, we have shown that antimony derivatives of
general formula Ph4SbX (X is an electronegative substituꢀ
ent) can be obtained from pentaphenylantimony and HX
(X = OR,1 OAr,2 OC(O)R,3 OSO2R,4 ON=CRR´ 5). No
less efficient method for the synthesis of the indicated
derivatives is the reaction of pentaphenylantimony and
antimony derivatives of general formula Ph3SbX2, in these
cases the target product has been isolated in almost quanꢀ
titative yield.6 Note that the synthesis of tetraphenylantiꢀ
mony aroxides by the ligand exchange reaction is described
in the only work.7
because it gives high yield the final product, the amount of
which reaches two moles calculated on one mole of the
starting pentaphenylantimony.11
The structures of the synthesized compounds 1 and 2
were established based on the analysis of 1H and 13C NMR
spectroscopy data and Xꢀray crystallography.
1H NMR spectra of compounds 1 and 2 exhibit douꢀ
blets for the protons of the aroxy groups with the ratio of
integral intensities of 1 : 1, which are significantly upfield
shifted as compared to the signals for the protons of the
phenyl groups. Such a tendency is also observed in the
13C NMR spectra, in which the signals for the carbon
atoms of the aroxy groups in compounds 1 and 2 are
The interest to the indicated issue is due to the biologꢀ
ical activity of some pentavalent antimony organic derivaꢀ
tives.8—10
observed in the region of
δ 76.697—79.745 and
The purpose of the present work is the synthesis of two
new antimony compounds: bis(4ꢀiodophenoxy)triphenylꢀ
antimony (1) and 4ꢀiodophenoxytetraphenylantimony (2).
Compound 1 was synthesized by the oxidative addiꢀ
tion reaction11 from triphenylantimony, 4ꢀiodophenol,
and hydrogen peroxide in diethyl ether at 20 °C:
76.639—77.364, respectively, whereas the signals for the
carbon atoms of the phenyl groups are found in the region
of δ 122.48—137.58 and 123.01—137.02, respectively.
Xꢀray diffraction studies of compounds 1 and 2 showed
that the antimony atoms have a distorted trigonal bipyrꢀ
amidal coordination, with the oxygen atoms of the aroxy
ligands occupying the axial positions (Figs 1 and 2). In
crystal 2, two types of crystallographically independent
molecules are present (a, b).
The axial angles OSbO and OSbC are equal to 172.15(8)°
(1) and 177.83(8)° (2A), 178.58(8)° (2B). The sums of the
angles CSbC in the equatorial plane are 360° (1) and
358.08° (2A), 357.48° (2B). In crystal 1, the antimony
atom lies virtually in the equatorial plane (the deviation is
0.008 Å), in 2A and 2B the central atom deviates from the
plane C3 to the side of axial carbon atom by 0.170 and
0.162 Å, respectively, which indicates a distortion of the
trigonal bipyramidal configuration of the molecules. Molꢀ
ecules 1 and 2 differ in conformation of the phenyl rings
relative to the equatorial plane. Thus, in crystal 1 the planes
It was found that compound 1 reacted with pentaphenꢀ
ylantimony in toluene with the formation of 4ꢀiodophenꢀ
oxytetraphenylantimony (2) in 76% yield:
This method for the synthesis of 2 applied to comꢀ
pounds of general formula Ph4SbX is very promising
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0751—0755, March, 2016.
1066ꢀ5285/16/6503ꢀ0751 © 2016 Springer Science+Business Media, Inc.

752
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 3, March, 2016
Sharutin et al.
C(34)
C(35)
C(33)
C(32)
C(36)
C(23)
C(26)
C(31)
C(52)
C(22)
I(2)
C(53)
C(24)
O(2)
C(16)
C(15)
C(14)
C(54)
C(21)
C(51)
I(1)
Sb(1)
C(25)
C(11)
C(41)
C(43)
O(1)
C(56)
C(55)
C(13)
C(46)
C(42)
C(12)
C(45)
C(44)
Fig. 1. Molecular structure of 1.
C(31)—C(36), C(41)—C(46), and C(51)—C(56) have the
following angles with the equatorial plane: 61.17°, 37.52°, and
50.94°, respectively. In crystal 2A, one of the phenyl rings is
virtually perpendicular to the equatorial plane (the correꢀ
sponding angle is equal to 81.88°), whereas the plane of the
other phenyl ring has the angle of 18.71° with the equatꢀ
orial plane, the third phenyl ring is arranged relative to the
equatorial plane at the angle of 43.49°. In crystal 2B, similar
angles are 77.52°, 15.65°, and 43.93°. In crystal 1, the planes
of the aroxy groups C(11)—C(16) and C(21)—C(26) have
the angles of 80.27° and 51.37° with the equatorial plane,
in crystals 2A and 2B similar angles are 76.59° and 77.17°.
I(2)
C(54)
C(53)
C(24)
C(23)
C(22)
C(52)
C(55)
C(25)
C(51)
C(6)
C(56)
C(5)
C(4)
C(21)
O(1)
C(26)
O(2)
C(63)
C(62)
I(1)
C(1)
Sb(1)
C(41)
C(64)
C(65)
C(66)
C(95)
C(94)
C(3)
C(61)
Sb(2)
C(2)
C(91)
C(11)
C(31)
C(46)
C(13)
C(92)
C(81)
C(34)
C(45)
C(44)
C(82)
C(83)
C(36)
C(86)
C(85)
C(84)
Fig. 2. Molecular structure of 2.

Synthesis of bis(4ꢀiodophenoxy)triphenylantimony
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 3, March, 2016
753
1H and 13C NMR spectra were recorded on an Agilent DD2
400 spectrometer (400 MHz) in CDCl3, using HMDS as an
internal standard (for 1H) and signal of the solvent as a reference
(for 13C).
Elemental analysis was performed on a Carlo Erba CHNSꢀ
O EA 1108 elemental analyzer. Melting points of compounds 1
and 2 were measured on a Stuart SMP 30 appliance.
Xꢀray diffraction studies of crystals 1 and 2 were performed
on a BrukerꢀNonius X8Apex diffractometer (MoꢀKα radiation,
λ = 0.71073 Å, graphite monochromator). Collection and proꢀ
cessing of data and refinement of unit cell parameters, as well as
correction for absorption were performed using the SMART and
SAINTꢀPlus14 programs. All the calculations on solution and
refinement of the structures were performed using the SHELXL/
PC15 programs. The structures were solved by direct method and
refined by the least squares method in anisotropic approximaꢀ
tion for nonhydrogen atoms. The main crystallographic data and
results of the structure refinement are given in Table 1, principal
bond distances and bond angles are summarized in Table 2.
The full Tables of atomic coordinates, bond distances and
bond angles were deposited with the Cambridge Crystallographic
The equatorial bonds Sb—C in crystal 1 are equal within
the experiment error limits (2.103(3), 2.104(3), 2.105(2) Å)
and are shorter than in crystals 2A (2.115(3)—2.128(3) Å)
and 2B (2.113(3)—2.124(3) Å). The length of the axial
bonds Sb—C in 2A and 2B is 2.195(3) and 2.193(3) Å,
respectively. Note that the Sb—O bond distances in comꢀ
pound 2 (2.1618(19) (A) and 2.1644(19) Å (B)) are comꢀ
parable with similar distances in the antimony aroxyꢀ
tetraphenyl compounds (cf. Ref. 12: 2.132(6)—2.221(4) Å),
but are considerably longer than the Sb—O bond distances
(2.0687(17) and 2.0657(16) Å) in compound 1, whose
values approximate the sum of the covalent radii of O and
Sb atoms equal to 2.07 Å (see Ref. 13).
Experimental
IR spectra of compounds 1 and 2 were recorded on a Bruker
Tensor 27 IR spectrometer in KBr pellets in the region of
4000—400 cm–1
.
Table 1. Crystallographic data, parameters of experiment and refinement for structures 1 and 2
Parameter
Value
1
2
М
Т/К
791.03
100.15
649.14
100.15
Crystal system
Space group
a/Å
b/Å
c/Å
α/deg
β/deg
γ/deg
V/Å3
Monoclinic
P21/c
15.4189(8)
8.9576(5)
20.8616(10)
90.00
110.6680(10)
90.00
2695.9(2)
4
Triclinic
–
P1
10.7650(4)
13.3173(6)
17.5920(8)
95.7570(10)
90.6120(10)
98.8940(10)
2478.23(18)
4
Z
ρ
calc/g cm–3
1.949
3.339
1.740
2.380
μ/mm–1
F(000)
1504.0
1264.0
Crystal size/mm
θ range of data collection/deg
Reflection collected
0.222×0.219×0.06
4.14—76.52
–26 ≤ h ≤ 25,
–8 ≤ k ≤ 14,
–35 ≤ l ≤ 26
21916
0.199×0.141×0.124
3.12—72.98
–17 ≤ h ≤ 17,
–21 ≤ k ≤ 22,
–2 ≤ l ≤ 27
28053
Reflection collected
Independent reflections
13040
22320
(Rint
)
(0.0312)
316
(0.0226)
603
Refinement variables
GOOF
Rꢀfactors on F2 > 2σ(F2)
1.000
0.999
R1
wR2
0.0390
0.0685
0.0416
0.0751
Rꢀfactors on all reflections
R1
wR2
0.0653
0.0774
0.0693
0.0854
Residual electron density
(min/max)/ e Å
1.44/–1.59
1.37/–1.86
–3

754
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 3, March, 2016
Sharutin et al.
Table 2. Principal bond distances and bond angles in the structures 1 and 2
Bond
d/Å
Angle
ω/deg
Molecule 1
Sb(1)—O(1)
Sb(1)—O(2)
Sb(1)—C(31)
Sb(1)—C(41)
Sb(1)—C(51)
O(1)—C(11)
O(2)—C(21)
I(1)—C(14)
I(2)—C(24)
C(11)—C(12)
C(11)—C(16)
C(12)—C(13)
2.0687(17)
2.0657(16)
2.103(3)
2.105(2)
2.104(3)
1.355(3)
1.361(3)
2.101(2)
2.097(2)
1.396(4)
1.400(4)
1.387(3)
O(1)—Sb(1)—C(31)
O(1)—Sb(1)—C(41)
O(1)—Sb(1)—C(51)
O(2)—Sb(1)—O(1)
O(2)—Sb(1)—C(31)
O(2)—Sb(1)—C(41)
O(2)—Sb(1)—C(51)
C(31)—Sb(1)—C(41)
C(31)—Sb(1)—C(51)
C(51)—Sb(1)—C(41)
C(11)—O(1)—Sb(1)
C(21)—O(2)—Sb(1)
94.93(8)
83.19(8)
93.43(8)
172.15(8)
91.94(9)
89.96(8)
87.59(8)
121.90(10)
111.39(10)
126.70(10)
133.28(16)
124.58(15)
Molecule 2
Sb(1)—O(1)
Sb(1)—C(41)
Sb(1)—C(31)
×Sb(1)—C(21)
Sb(1)—C(11)
I(1)—C(4)
Sb(2)—O(2)
Sb(2)—C(71)
Sb(2)—C(91)
Sb(2)—C(81)
Sb(2)—C(61)
I(2)—C(54)
2.1618(19)
2.195(3)
2.115(3)
2.128(3)
2.118(2)
2.102(3)
2.1644(19)
2.113(3)
2.124(3)
2.193(3)
2.122(3)
2.104(3)
1.337(3)
1.330(3)
1.392(4)
1.382(4)
1.394(4)
1.395(4)
1.398(4)
1.405(4)
1.403(4)
1.395(4)
O(1)—Sb(1)—C(41)
C(31)—Sb(1)—O(1)
C(31)—Sb(1)—C(41)
C(31)—Sb(1)—C(21)
C(31)—Sb(1)—C(11)
C(21)—Sb(1)—O(1)
C(21)—Sb(1)—C(41)
C(11)—Sb(1)—O(1)
C(11)—Sb(1)—C(41)
C(11)—Sb(1)—C(21)
O(2)—Sb(2)—C(81)
C(71)—Sb(2)—O(2)
C(71)—Sb(2)—C(91)
C(71)—Sb(2)—C(81)
C(71)—Sb(2)—C(61)
C(91)—Sb(2)—O(2)
C(91)—Sb(2)—C(81)
C(61)—Sb(2)—O(2)
C(61)—Sb(2)—C(91)
C(61)—Sb(2)—C(81)
C(1)—O(1)—Sb(1)
C(51)—O(2)—Sb(2)
177.83(8)
85.64(9)
96.00(10)
116.15(10)
124.76(10)
83.57(9)
96.95(10)
86.80(9)
91.09(10)
117.17(10)
178.58(8)
87.76(9)
116.57(10)
91.38(10)
123.74(10)
82.91(9)
96.48(10)
86.00(9)
117.95(10)
95.42(10)
131.23(16)
131.76(18)
O(1)—C(1)
O(2)—C(51)
C(15)—C(16)
C(15)—C(14)
C(71)—C(72)
C(71)—C(76)
C(41)—C(46)
C(41)—C(42)
C(91)—C(92)
C(91)—C(96)
Data Center: CCDC 998314 for 1 and CCDC 998315 for 2
(deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Bis(4ꢀiodophenoxy)triphenylantimony (1). A 30% aqueous
solution of hydrogen peroxide (160 mg) was added to a mixture
of triphenylantimony (500 mg, 1.42 mmol) and 4ꢀiodophenol
(623 mg, 2.82 mmol) in diethyl ether (20 mL) and the mixture
was allowed to stand for 24 h at 20 °C. Colorless crystals formed
were filtered and dried. The yield was 1020 mg (91%). M.p. 184 °C.
IR, ν/cm–1: 3091, 3067, 2925, 2854, 1567, 1274, 1243, 1169,
1098, 1069, 1022, 997, 829, 822, 743, 730, 693, 645, 635, 617,
534, 519, 592, 480, 459. 1H NMR, δ: 6.10 (d, 4 H, Ar, J = 8.72 Hz);
7.11 (d, 4 H, Ar, J = 8.71 Hz); 7.46 (m, 9 H, pꢀHPh, mꢀHPh); 8.04
(m, 6 H, oꢀHPh). 13C NMR, δ: 76.70—79.75 (Ar); 122.48—137.58
(Ph). Found (%): C, 45.38; H, 3.08. C30H23O2I2Sb. Calculatꢀ
ed (%): C, 45.54; H, 2.91.
was heated for 1 h at 80 °C. The reaction mixture was concenꢀ
trated to 0.5 mL and cooled to 10 °C. Crystals formed were
filtered, washed with hexane (5 mL) and dried. The yield was
571 mg (88%). M.p. 162 °C. IR, ν/cm–1: 3091, 3067, 3058, 3047,
3014, 2925, 2854, 1567, 1475, 1433, 1283, 1169, 1062, 997, 839,
822, 800, 729, 692, 634, 607, 511, 491, 464, 452. 1H NMR,
δ: 5.83 (d, 2 H, Ar, J = 8.74 Hz); 6.95 (d, 2 H, Ar, J = 8.74 Hz);
7.26—7.45 (m, 12 H, pꢀHPh, mꢀHPh); 7.68 (d, 8 H, oꢀHPh).
Found (%): C, 55.36; H, 3.81. C30H24OISb. Calculated (%):
C, 55.50; H, 3.70.
References
1. G. A. Razuvaev, N. A. Osanova, T. G. Brilkina, T. I. Zinoꢀ
vjieva, V. V. Sharutin, J. Organomet. Chem., 1975, 99, 93.
2. V. V. Sharutin, V. V. Zhidkov, D. V. Muslin, N. S. Lyapina,
G. K. Fukin, L. N. Zakharov, A. I. Yanovskii, Yu. T. Struchꢀ
4ꢀIodophenoxytetraphenylantimony (2). A mixture of bisꢀ
(4ꢀiodophenoxy)triphenylantimony (0.395 mg, 0.50 mmol) and
pentaphenylantimony (253 mg, 0.50 mmol) in benzene (5 mL)

Synthesis of bis(4ꢀiodophenoxy)triphenylantimony
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 3, March, 2016
755
kov, Russ. Chem. Bull. (Engl. Transl.), 1995, 44, 931 [Izv.
Akad. Nauk, Ser. Khim., 1995, 958].
3. V. V. Sharutin, O. K. Sharutina, A. P. Pakusina, V. K.
Bel´sky, J. Organomet. Chem., 1997, 536, 87.
4. V. V. Sharutin, O. K. Sharutina, L. P. Panova, V. K. Bel´sky,
Russ. J. Gen. Chem. (Engl. Transl.), 1997, 67, 1438 [Zh. Obshch.
Khim., 1997, 67, 1528].
5. V. V. Sharutin, O. K. Sharutina, O. V. Molokova, E. N.
Ettenko, D. B. Krivolapov, A. T. Gubaidullin, I. A. Litviꢀ
nov, Russ. J. Gen. Chem. (Engl. Transl.), 2001, 71, 1243
[Zh. Obshch.. Khim., 2001, 71, 1317].
6. V. V. Sharutin, V. S. Senchurin, O. K. Sharutina, A. P. Paꢀ
kusina, L. P. Panova, Russ. J. Gen. Chem. (Engl. Transl.),
1996, 66, 1710 [Zh. Obshch. Khim., 1996, 66, 1755].
7. V. V. Sharutin, O. K. Sharutina, P. E. Osipov, O. V. Subꢀ
acheva, Russ. J. Gen. Chem. (Engl. Transl.), 2001, 71, 983
[Zh. Obshch. Khim., 2001, 71, 1045].
11. V. V. Sharutin, V. S. Senchurin, Imennye reaktsii v khimii
elementoorganicheskikh soedinenii [Named Reactions in
Chemistry of Organoelement Compounds], Izdatelґskii Tsentr
YuUrGU, Chelyabinsk, 2011, 427 pp. (in Russian).
12. O. K. Sharutina, V. V. Sharutin, Molekulyarnye struktury orꢀ
ganicheskikh soedinenii surґmy(V) [Molecular Structures of
Antimony(V) Organic Compounds], Izdatelґskii Tsentr YuUrGU,
Chelyabinsk, 2012, 395 pp. (in Russian).
13. S. S. Batsanov, Zh. Inorg. Khim., 1991, 36, 3015 [J. Inorg.
Chem. USSR (Engl. Transl.), 1991, 36].
14. Bruker (1998). SMART and SAINTꢀPlus. Versions 5.0. Data
Collection and Processing Software for the SMART System.
Bruker AXS Inc., Madison, Wisconsin, USA.
15. Bruker (1998). SHELXTL/PC. Versions 5.10. An Integrated
System for Solving, Refining and Displaying Crystal Structures
From Diffraction Data. Bruker AXS Inc., Madison, Wisconsin,
USA.
8. E. R. T. Tiekink, Crit. Rev. Oncol./Hematol. 2002, 42, 217.
9. I. I. Ozturk, C. N. Banti, M. J. Manos, A. J. Tasiopoulos,
N. Kourkoumelis, K. Charalabopoulos, S. K. Hadjikakou,
J. Inorg. Biochem., 2012, 109, 57.
10. M. I. Ali, M. K. Rauf, A. Badshah, I. Kumar, C. M. Forsyth,
P. C. Junk, L. Kedzierski, P. C. Andrews, Dalton Trans.,
2013, 42, 16733.
Received August 24, 2015;
in revised form November 9, 2015