Phenylation of Antimony(V) Organic Compounds with Pentaphenylantimony. The Structure of Tetraphenylantimony Chloride

Article abstract of DOI:10.1023/A:1022377815791

Tetraphenylantimony chloride and bromide were synthesized through the reaction of pentaphenylantimony with diphenylantimony trichloride or tribromide taken at a molar ratio of 2:1 in toluene. When the initial compounds were taken at a molar ratio of 1:1, triphenylantimony dichloride or dibromide was formed. The phenylation of triphenylantimony sulfate with pentaphenylantimony yielded tetraphenylantimony sulfate. According to the X-ray diffraction data, the antimony atom in the tetraphenylantimony chloride molecule has a distorted trigonal bipyramidal configuration with the chlorine atom in the axial position. The Sb-Cl distance is equal to 2.686(1) and Sb-C distances are equal to 2.113(4) and 2.165(4) A (av. 2.130 A).

Full text of DOI:10.1023/A:1022377815791

Russian Journal of Coordination Chemistry, Vol. 29, No. 2, 2003, pp. 89–92. Translated from Koordinatsionnaya Khimiya, Vol. 29, No. 2, 2003, pp. 95–98.
Original Russian Text Copyright © 2003 by Sharutin, Sharutina, Pakusina, Platonova, Zadachina, Gerasimenko.
Phenylation of Antimony(V) Organic Compounds
with Pentaphenylantimony. The Structure
of Tetraphenylantimony Chloride
V. V. Sharutin, O. K. Sharutina, A. P. Pakusina, T. P. Platonova,
O. P. Zadachina, and A. V. Gerasimenko
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 109, Vladivostok, 690022 Russia
Received July 23, 2001
Abstract—Tetraphenylantimony chloride and bromide were synthesized through the reaction of pentapheny-
lantimony with diphenylantimony trichloride or tribromide taken at a molar ratio of 2 : 1 in toluene. When the
initial compounds were taken at a molar ratio of 1 : 1, triphenylantimony dichloride or dibromide was formed.
The phenylation of triphenylantimony sulfate with pentaphenylantimony yielded tetraphenylantimony sulfate.
According to the X-ray diffraction data, the antimony atom in the tetraphenylantimony chloride molecule has
a distorted trigonal bipyramidal configuration with the chlorine atom in the axial position. The Sb–Cl distance
is equal to 2.686(1) and Sb–C distances are equal to 2.113(4) and 2.165(4) Å (av. 2.130 Å).
Pentaphenylantimony is known to phenylate triphen- antimony sulfate is poorly soluble in toluene, at 90–
ylantimony dihalides to give tetraphenylantimony 100°C, this reaction virtually terminates in 6 h.
halides [1, 2]; however, reactions of pentaphenylaniti-
Ph5Sb + Ph3SbSO4
(Ph4Sb)2SO4.
mony with diphenylantimony trihalides were not
described in the literature. As a continuation of our
studies on phenylating properties of pentaphenylanti-
mony, its reactions with diphenylantimony trichloride
and tribromide, triphenylantimony sulfate, and acetyl-
acetonatotriphenylantimony chloride were investi-
gated.
The reaction of acetylacetonatotriphenylantimony
with pentaphenylantimony in toluene at room tempera-
ture is also accompanied by the exchange of the ligands
between the antimony atoms:
Ph5Sb + Ph3SbCl(Äcac)
Ph4SbCl + Ph4Sb(Äcac),
where Acac is the acetylacetone residue.
Melting points and IR spectra of the compounds
synthesized via reactions of redistribution of radicals
coincide with the analogous parameters of the known
antimony compounds.
Thus, pentaphenylantimony can be used as the
effective phenylating agent in reactions with anti-
mony(V) derivatives.
The structure of tetraphenylantimony chloride (I)
was determined in [3]; in this work, the structure of I
was refined. According to X-ray diffraction data, the
antimony atom in molecule I has a trigonal bipyramidal
coordination with the axial Cl atom that is typical of
antimony(V) compounds with the coordination number
of 5 (see figure). The Sb–Ceq and Sb–Cax bond lengths are
equal to 2.113(4), 2.117(4), 2.126(4), and 2.165(4) Å,
respectively. The Sb atom extends from the equatorial
plane toward the axial phenyl group, as a result of
which the CeqSbCl angles are less than the perfect angle
of 90°, while the CeqSbCax angles exceed 90°. The sum
RESULTS AND DISCUSSION
It was established that the reactions of pentapheny-
lantimony with diphenylantimony trichloride (taken at
a molar ratio of 2 : 1 and 1 : 1) in toluene at room tem-
perature are accompanied by the redistribution of radi-
cals between the antimony atoms to give tetraphenylan-
timony chloride or tetraphenylantimony chloride and
triphenylantimony dichloride, respectively, in high
yields:
2Ph5Sb + Ph2SbCl3
Ph5Sb + Ph2SbCl3
3Ph4SbCl,
Ph4SbCl + Ph3SbCl2.
For these reactions to be complete, the reaction mix-
ture should be heated at 90–100°C for a short time.
Reactions of pentaphenylantimony with diphenyl-
antimony tribromide follow the same route.
When pentaphenylantimony reacts with triphenyl- of the equatorial angles is equal to 357.2°, but their val-
antimony sulfate, the phenyl ligands also migrate from ues are different (115.9(1)°, 117.8(1)°, and 123.5(2)°).
one antimony atom to another one. Although triphenyl- The angles formed by the phenyl rings and the equato-
1070-3284/03/2902-0089$25.00 © 2003 åÄIä “Nauka /Interperiodica”

90
SHARUTIN et al.
C(44)
C(43)
C(42)
C(45)
C(46)
C(41)
C(13)
C(32)
C(14)
C(15)
C(33)
C(12)
Sb
C(11)
C(16)
C(34)
C(35)
C(22)
C(31)
C(21)
C(36)
C(23)
C(24)
Cl
C(26)
C(25)
The structure of molecule I.
rial plane are equal to 6.5° (ë(11)–ë(16)), 35.2° removed and the residue was recrystallized from water.
(C(21)–C(26)), and 98.5° (C(31)–C(36)). The
C(41)SbCl angle is equal to 173.6(1)°. A linear geome-
try of the Cl–Sb–C(41) fragment is violated due to
shifting of the Sb–Cl bond toward the phenyl ring
(C(11)–C(16)) lying virtually in the equatorial plane.
Different values of the axial angles and deviations of
the equatorial angles from the theoretical value of 120°
can be explained by the effect of the molecular packing
in crystal I.
Crystals I were thus obtained in a yield of 0.84 g (91%),
mp 198°C. The residue insoluble in water was dis-
solved in alcohol containing hydrogen chloride. After
cooling an alcohol solution, 0.75 g (89%) of tripheny-
lantimony dichloride (mp 143°C) was obtained. Tet-
raphenylantimony bromide (90%) and triphenylanti-
mony dibromide (77%) were synthesized using the
same procedure.
Reaction of pentaphenylantimony with triphenyl-
antimony sulfate. A mixture of 1.00 g of pentapheny-
lantimony and 0.88 g of triphenylantimony sulfate in
15 ml of toluene was heated in a glass evacuated
ampoule at 90–100°C for 6 h; the solvent was removed;
the residue was dissolved in a hot water and the
obtained solution was filtered off. After the solvent was
evaporated, 1.60 g (85%) of tetraphenylantimony sul-
fate was obtained, mp 233°C (234–237°C [5]).
As in some other antimony compounds with the gen-
eral formula Ph4SbX, the Sb–Cl distance (2.686(1) Å) in
complex I exceeds the sum of the covalent radii of Sb
and Cl atoms (2.40 Å [4]), thus indicating that this bond
is a polar bond.
EXPERIMENTAL
Reaction of pentaphenylantimony with diphenyl-
antimony trichloride. a) A mixture of 1.00 g of pen-
taphenylantimony and 0.39 g of diphenylantimony
trichloride crystal hydrate in 15 ml of toluene was
allowed to stand at 100°ë for 1 h; the solvent was
removed and the residue was recrystallized from water.
The yield of crystals I was 1.30 g (95%), mp 202°C
(202–210°C [5]). Tetraphentlantimony bromide was
synthesized using the same procedure. The yield was
90%, mp 218°C (216–218°C [5]). b) A mixture of
1.00 g of pentaphenylantimony and 0.78 g of diphenyl-
antimony trichloride crystal hydrate in 15 ml of toluene
Reaction of pentaphenylantimony with acetylac-
etonatotriphenylantimony chloride. A mixture of
1.00 g of pentaphenylantimony and 0.96 g of acetylac-
etonatotriphenylantimony chloride in 10 ml of toluene
was heated in a glass evacuated ampoule for 1 h. After
cooling, the solvent was removed and the residue was
recrystallized from a heptane–toluene (5 : 1) mixture;
0.87 g of tetraphenylantimony acetylacetonate was
obtained, mp 209°C (decomposition) (209°C [6]). The
residue was recrystallized from water; 0.81 g (88%) of
was allowed to stand at 100°C for 1 h; the solvent was crystals I was obtained, mp 198°C.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 29 No. 2 2003

PHENYLATION OF ANTIMONY(V) ORGANIC COMPOUNDS
91
Table 1. Crystallographic parameters and results of refine- Table 2. Coordinates of atoms (×104) and their equivalent
ment of structure I
isotropic thermal parameters (×103) in structure I
Ueq, Å2
Parameter
I
Atom
x
y
z
Empirical formula
C24H20ClSb
465.60
Sb
8524(1)
10994(1)
8323(4)
7959(5)
7733(6)
7883(5)
8268(5)
8478(5)
9542(4)
9289(5)
9930(5)
1100(1)
1701(1)
1481(3)
2352(4)
2588(5)
1949(5)
1090(4)
851(3)
7503(1)
7217(1)
6053(3)
5831(3)
4893(4)
4197(4)
4410(3)
5345(3)
7957(3)
7522(3)
7821(4)
8569(4)
9026(3)
8715(3)
8517(2)
9051(3)
9725(3)
9865(3)
9342(4)
8659(3)
7631(3)
7050(3)
7188(5)
7870(5)
8451(5)
8325(4)
46.9(1)
72.5(3)
52(1)
91(2)
114(2)
103(2)
91(2)
71(1)
48(1)
65(1)
83(1)
87(2)
83(2)
65(1)
51(1)
66(1)
84(2)
84(2)
90(2)
73(1)
54(1)
73(1)
108(2)
124(2)
114(2)
81(1)
M
Cl
Crystal system
T
Monoclinic
293(2) K
P21/n
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(21)
C(22)
C(23)
Space group
Unit cell parameters:
a, Å
10.144(1)
b, Å
14.635(2)
c, Å
14.019(2)
β, deg
V, Å3
90.023(3)
–82(3)
2081.1(2)
–907(3)
–1683(3)
–1645(4)
–838(4)
–41(3)
Z
4
ρ(calcd), g/cm3
µMo, mm–1
F(000)
1.486
1.458
C(24) 10776(5)
C(25) 11007(5)
C(26) 10406(4)
928
Crystal size, mm
θ, deg
Prism (0.15 × 0.14 × 0.12)
2.44–22.99
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
8220(4)
7071(5)
6838(6)
7699(7)
8836(6)
9102(5)
6588(4)
5573(5)
4307(5)
4079(6)
5072(6)
6318(5)
2160(3)
2136(3)
2803(4)
3482(4)
3536(3)
2853(3)
489(3)
Range of indices
–10 ≤ h ≤ 11, –12 ≤ k ≤ 16,
–15 ≤ l ≤ 15
Total number of reflections
Independent reflections
Reflections with I > 2σ(Ι)
Number of refined parameters
GOOF
9019
2891 (Rint = 0.0421)
2227
235
0.938
R-factors for F2 > 2σ(F2)
R1 = 0.0255, wR2 = 0.0557
R1 = 0.0387, wR2 = 0.0593
764(3)
R-factors for all reflections
436(5)
–213(5)
–498(5)
–145(3)
IR spectra were recorded on a Hitachi-215 spectro-
photometer (suspension in mineral oil between sodium
chloride plates).
X-ray diffraction analysis of a naturally faceted
single crystal was carried out on a SMART-1000 CCD
diffractometer (MoKα radiation, graphite monochroma-
tor). The data were collected in sets of 606, 450, and
235 scans at ϕ = 0°, 90°, and 180°, respectively; ω-scan-
ning with a step of 0.3° and the step counting time of
10 s; the crystal–detector distance was 45 mm. Correc-
tion for absorption of X-rays by the sample was applied
using equivalent reflections.
Table 3. Selected bond lengths and angles in structure I
Bond
d, Å
Angle
ω, deg
Sb–C(21)
2.113(4)
2.117(4)
2.126(4)
2.165(4)
2.686(1)
1.363(6)
1.364(5)
1.378(6)
1.360(7)
1.350(7)
C(21)SbC(11)
C(21)SbC(31)
C(11)SbC(31)
C(21)SbC(41)
C(11)SbC(41)
C(31)SbC(41)
C(21)SbCl
123.5(2)
117.8(1)
115.9(1)
94.6(2)
95.8(2)
96.6(2)
81.8(1)
81.9(1)
89.8(1)
173.6(1)
Sb–C(11)
Sb–C(31)
Sb–C(41)
Sb–Cl
The structure was solved by direct methods and
refined by the least-squares method in an anisotropic
approximation for non-hydrogen atoms. The positions
of the hydrogen atoms were determined geometrically
and refined in the rider model. The data were collected
and processed and the unit cell parameters were refined
using the SMART and SAINT-Plus programs [7]. All
the calculations for the determination and refinement of
C(11)–C(12)
C(11)–C(16)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
C(11)SbCl
C(31)SbCl
C(41)SbCl
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 29 No. 2 2003

92
SHARUTIN et al.
3. Lebedev, V.A., Bochkova, R.I., Kuz’min, E.A., et al.,
Dokl. Akad. Nauk SSSR, 1981, vol. 260, no. 5, p. 1124.
the structure were performed using the SHELXTL/PC
programs [8].
4. Batsanov, S.S., Zh. Neorg. Khim., 1991, vol. 36, no. 11,
Selected crystallographic data and the results of the
structure refinement are presented in Table 1. The coor-
dinates and thermal parameters of non-hydrogen atoms
are given in Table 2, and the main bond lengths and
angles are listed in Table 3.
p. 3015.
5. Kocheshkov, K.A., Skoldinov,A.P., and Zemlyanskii, N.N.,
Metody elementoorganicheskoi khimii. Sur’ma, vismut
(Methods of Organoelement Chemistry. Antimony and
Bismuth), Moscow: Nauka, 1976.
6. Sharutin, V.V., Sharutina, O.K., Zadachina, O.P., et al.,
Zh. Obshch. Khim., 2000, vol. 70, no. 5, p. 746.
7. SMART and SAINT-Plus. Versions 5.0. Data Collection
and Processing Software for the SMART System, Madi-
son, WI, USA: Bruker AXS Inc., 1998.
8. SHELXTL/PC. Versions 5.10. An Integrated System for
Solving, Refining and Displaying Crystal Structures
From Diffraction Data, Madison, WI, USA, Bruker
AXS Inc.: 1998.
REFERENCES
1. Sharutin, V.V., Senchurin, V.S., Sharutina, O.K., et al.,
Zh. Obshch. Khim., 1996, vol. 66, no. 10, p. 1755.
2. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., and
Panova, L.P., Zh. Obshch. Khim., 1998, vol. 68, no. 2,
p. 345.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 29 No. 2 2003