Synthesis and Structure of Triarylantimony Bis(arenesulfonates)

Article abstract of DOI:10.1023/A:1024945617228

Triarylantimony bis(arenesulfonates) were prepared by reaction of triarylantimonies with hydrogen peroxide in the presence of arenesulfonic acids. The steric structure of the products was assessed. Triarylantimony bis(arenesulfonates) were reacted with so

Full text of DOI:10.1023/A:1024945617228

Russian Journal of General Chemistry, Vol. 73, No. 3, 2003, pp. 354 357. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 3, 2003,
pp. 380 384.
Original Russian Text Copyright
2003 by Sharutin, Sharutina, Platonova, Pakusina, Panova, Fukin, Zakharov.
Synthesis and Structure of Triarylantimony Bis(arenesulfonates)
V. V. Sharutin, O. K. Sharutina, T. P. Platonova, A. P. Pakusina,
L. P. Panova, G. K. Fukin, and L. N. Zakharov
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received March 2, 2001
Abstract Triarylantimony bis(arenesulfonates) were prepared by reaction of triarylantimonies with
hydrogen peroxide in the presence of arenesulfonic acids. The steric structure of the products was assessed.
Triarylantimony bis(arenesulfonates) were reacted with sodium salts to obtain sodium arenesulfonates and the
corresponding triarylantimony derivatives.
Antimony(V) compounds of the general formula
Ph3SbX2 (X is an electronegative substituent) feature
a trigonal-bipyramidal coordination of the central
atom. However, the coordination of Sb may be di-
storted by intramolecular interactions with ligands X,
as, for instance, in triphenylantimony diarene- and
dialkanecarboxylates [1 3]. In triphenylantimony bis-
(benzenesulfonates), too, decreased distances between
the antimony atom and the oxygen atoms of the sulfo
groups, which are formally not bound with each other
triphenylantimony bis(4-methylbenzenesulfonate) and
bis(2,4-dimethylbenzenebenzenesulfonate), 176.1(2)
and 176.8(1) , respectively.
The mean Sb Ce bond lengths in disulfonates I and
II are close to each other, 2.098(9) and 2.089(3)
,
respectively. The Sb O bond lengths are 2.124(5) and
2.107(5) (I) and 2.124(2), and 2.158(2) (II). The
Sb O distances in triphenylantimony bis(benzenesul-
fonate) {2.128(2) and 2.106(3)
[4]} are close to
each other and almost concide with analogous dis-
tances in compound I. In compounds I and II, shor-
tened Sb O=S contacts are revealed. The Sb O6 and
Sb O3,6 distances are 3.427 (I) and 3.438, and
[the Sb O=S distances are 3.274(4) and 3.445(4)
]
are observed, implying weak intramolecular interac-
tion between these atoms [4]. However, in triphenyl-
antimony bis(4-methylbenzenesulfonate) [5] and tri-
3.334
(II), which is smaller than the sum of the
phenylantimony
bis(2,4-dimethylbenzenesulfonate)
Van der Waals radii of these atoms (3.7 [7]). Note
that the Sb O=S intramolecular interactions result in
lengthening of the corresponding S=O distances. The
S2 O6 [1.423(6) ] (I) and S1 O3 [1.436(2) ] and
S2 O6 distances [1.440(3) ] (II) almost coincide
with the S=O distances [1.412(7) 1.434(3) ], where
the O atoms are not involved in additional interactions
with Sb. Moreover, equatorial CSbC angles in I and
II are slightly enlarged from the side of the intra-
molecular contact. On this basis we can propose that
the Sb O interactions in disulfonates I and II
are weak.
[6] no such interaction was revealed.
We performed an X-ray diffraction study of tri-m-
tolylantimony bis(benzenesulfonate) (I) and tri-p-
tolylantimony bis(2,5-dimethylbenzenesulfonate) (II),
prepared by an oxidative addition reaction from tri-
arylantimonies and hydrogen peroxide in the presence
of arenesulfonic acids.
Ar3Sb + H2O2 + 2HOSO2Ar
Ar3Sb(OSO2Ar )2 + 2H2O,
I, II
Ar = m-Tol, Ar = Ph (I); Ar = p-Tol, Ar = C6H3Me2-2,5
(II).
The fact that compound II contains two intramo-
lecular contacts, whereas compound I contains one
such contact appears to be a consequence of the steric
situation in the coordination sphere of the Sb atoms.
In compound II, the methyl substituents in the aryl
rings are in the para positions, while in disulfonate I,
in the meta positions. Thus, in the latter compound,
stronger steric hindrances to additional coordination
of Sb take place. This is indirectly evidenced by the
magnitudes of the SbOS angles: 136.2(4) and
131.5(3) in I and 129.82(13) and 127.57(14) in II.
Compounds I and II have a trigonal-bipyramidal
arrangement of the substituents at the central atom
(Figs. 1 and 2). The sums of equatorial CSbC angles
are 360 (I) and 359.82(12) (II). The antimony atoms
scarcely deviate from the equatorial plane: The devia-
tions of Sb from the C1C8C15 plane are 0.0090 (I) and
0.0391
(II)]. Axial angles are 170.6(2) (I) and
174.33(8) (II). The respective angle in triphenyl-
antimony bis(benzenesulfonate) is 178.3(1) , and in
1070-3632/03/7303-0354$25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS AND STRUCTURE OF TRIARYLANTIMONY BIS(ARENESULFONATES)
355
C4
C7
C3
C2
C5
C26
C6
C27
C25
C1
O3
O4
C24
C33
Sb1
C32
C31
C22
O5
C23
C16
C8
S1
O2
C10
O1
C9
S2
C21
C13
C15
C12
C17
C30 C29
C20
O6
C11
C18
C14
C19
Fig. 1. Geneal view of the molecule of tri-m-tolylantimony bis(benzenesulfonate) (I).
C7
C4
C3
C2
C5
C6
C28
C1
O6
O5
S2
O1
Sb1
C23
O2
C24
C25
O4
C9 C35
S1 C16
C17
C8
C30
C13
C12
C36
C15
C22
C31
C11
O3
C19
C20
C26
C27
C18
C14
C37
C32
C19
C34
C21
C33
C29
Fig. 2. General view of the molecule of tri-p-tolylantimony bis(2,5-dimethylbenzenesulfonate) (II).
Molecules of compound I in crystal form a com-
plex system of weak intermolecular O H interactions
(Fig. 3). The O H distances are 2.429 2.543 , and
the angle at the H atom is 154.1 166.0 , which much
exceeds the geometrical criterion for H bond
{d(O H) < 2.1 [8]}, but is much smaller than the
sum of the Van der Waals radii of O and H (2.7
[7]).
fonate) with metal chlorides, as shown in [4], involve
substitution of the benzenesulfonate moieties by
chlorine. We found that triarylantimony bis(arenesul-
fonates) react with sodium fluoride, bromide, nitrate,
and acylates in a similar way.
Ar3Sb(OSO2Ar )2 + 2NaX
Ar3SbX2 + 2NaOSO2Ar ,
Ar = Ph, m-Tol, p-Tol; Ar = Ph, C6H4Me-4, C6H3Me2-2,3,
C6H3Me2-2,4, C6H3Me2-2,5; X = F, Br, NO3; OC(O)Me,
OC(O)Ph.
Reactions of triphenylantimony bis(benzenesul-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 3 2003

356
SHARUTIN et al.
S1A
S2D
S2C
Sb1A
H30A
H30C
O6A
S2A
Sb1C
H14K
S1D
S1C
C1E
Sb1E
O2D
O5B
S2B
H12B
O6B
H30E
Sb1B
S1B
Fig. 3. System of intermolecular bonds in the crystal of tri-m-tolylantimony bis(benzenesulfonate) (I).
The reactions of triarylantimony bis(arenesulfo-
14.045(3)
;
100.450(4),
110.345(4),
nates) with sodium halides were performed in aqueous
alcohols, while those with sodium acetate, benzoate,
and nitrate, in toluene with heating. The yields of the
target products reached 70 90%.
112.706(3) ; V 1680.0(5) 3; space group P-1, Z 2,
dcalc 1.513 g/cm3. The structures were solved by the
direct method and refined by full-matrix least squares
anisotropically for all non-hydrogen atoms to R
0.0802, RW [on 6327 reflections with I > 2 (I)] for I
and to R 0.0551 and RW 0.1127 [on 7718 reflections
with I > 2 (I] for II. Substituent hydrogen atoms in I
and II were located by Fourier synthesis and refined
isotropically.
EXPERIMENTAL
The IR spectra were measured on a Hitachi-215
spectrometer in mineral oil.
Sigle-crystal X-ray diffraction analysis of com-
pounds I and II was performed on a Siemens P3/PC
automatic four-circle diffractometer ( MoK radiation,
Data collection and treatment, as well as refine-
ment of unit cell parameters were performed using the
SMART and SAINT Plus programs [9]. All structural
calculations were performed using SHELXTL/PC
programs [10]. The principal bond lengths and bond
angles are listed in the table.
graphite monochromator, /2 scanning, 2
for I and 2 27.54 for II. Crystal data for I,
C33H31O6S2Sb, monoclinic; at 20 C, a 14.495(3), b
26.06
12.773(3),
3228.1(11)
c
17.680(4)
;
99.54(3) ,
V
3; space group P2(1)/c, Z 4, dcalc
Triarylantimony bis(arenesulfonates) I, II. To
a mixture of 2.53 mmol of triarylantimony and
5.06 mmol of arenesulfonic acid in 20 ml of diethyl
1.460 g/cm3. Crystal data for II, C37H39O6S2Sb, tri-
clinic; at 20 C, a 11.928(2), b 12.453(2), c
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 3 2003

SYNTHESIS AND STRUCTURE OF TRIARYLANTIMONY BIS(ARENESULFONATES)
357
Principal bond lengths (d) and bond angles ( ) in com-
pounds I and II
dibromide, mp 215 C, and 87% of sodium 2,4-di-
methylbenzenesulfonate, mp >250 C. The IR spectra
of the resulting compounds are identical to those of
authentic samples.
Compound I
Compound II
Reaction of tri-p-tolylantimony bis(2,3-di-
methylbenzenesulfonate) with sodium nitrate. A
mixture of 0.5 g of tri-p-tolylantimony bis(2,3-di-
bond
d,
bond
d,
Sb C1
Sb C8
Sb C15
Sb O1
Sb O4
S1 O1
S1 O2
S1 O3
S1 C22
S2 O4
S2 O5
S2 O6
S2 C28
2.112(9)
2.084(8)
2.097(9)
2.124(5)
2.107(5)
1.492(6)
1.412(7)
1.424(8)
1.766(9)
1.522(5)
1.430(6)
1.423(6)
1.757(9)
Sb C1
Sb C8
Sb C15
Sb O1
Sb O4
S1 O1
S1 O2
S1 O3
S1 C22
S2 O4
S2 O5
S2 O6
S2 C30
2.087(3)
2.092(3)
2.087(3)
2.158(2)
2.124(2)
1.522(2)
1.434(3)
1.436(2)
1.775(3)
1.525(2)
1.432(3)
1.440(3)
1.777(3)
methylbenzenesulfonate) and 0.1
g
of sodium
nitrate in 30 ml of toluene was heated for 6 h at
90 C. Fine crystals precipitated and were filtered
off. The toluene was removed to obtain 0.3 g (90%)
of tri-p-tolylantimony dinitrate, mp 172 C. The
weight of the toluene-insoluble sodium 2,3-dimethyl-
benzenesulfonate was 0.21 g (79%), mp >250 C.
The reaction of triphenylantimony bis(2,4-dimethyl-
benzenesulfonate) with sodium benzoate was per-
formed in a similar way to obtain 75% of triphenyl-
antimony dibenzoate, mp 171 C, and 89 % of sodium
2,4-dimethylbenzenesulfonate, mp >250 C. The IR
spectra of the resulting compounds are identical to
those of authentic samples.
angle
, deg
angle
, deg
ACKNOWLEDGMENTS
C8SbC15
C8SbC1
C15SbC1
O4SbO1
S1O1Sb
S1O4Sb
116.7(4)
126.7(3)
116.6(4)
170.6(2)
136.2(4)
131.5(3)
C8SbC15
C8SbC1
C15SbC1
O4SbO1
S1O1Sb
S1O4Sb
119.96(12)
115.24(12)
124.62(12)
174.33(8)
129.82(13)
127.57(14)
The work was financially supported by the Russian
Foundation for Basic Research (project nos. 00-15-
97439 and 99-07-90133) and the Center for X-ray
Studies, Division of General and Technical Chemistry,
Russian Academy of Sciences (project no. 00-15-
97359).
REFERENCES
ether at 20 C we added 2.53 mmol of hydrogen per-
oxide as a 27% aqueous solution. After 12 h, the
solvent was removed, and the residue was recrystal-
lized from toluene to obtain compound I, yield 87%,
mp 145 C. IR spectrum, , cm : 1320 s, 1140 s,
1140 s (SO2). Found, %: C 55.23; H 4.34. C33H31
O6S2Sb. Calculated, %: C 55.85; H 4.37.
1. Sowerby, D.B., J. Chem. Res. Synop., 1979, vol. 3,
no. 1, p. 80.
2. Lebedev, V.A., Bochkova, R.I., Kuzubova, L.F., Kuz’-
min, E.A., and Sharutin, V.V., Dokl. Akad. Nauk
SSSR, 1982, vol. 265, no. 2, p. 332.
3. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P., and
Bel’skii, V.K., Zh. Obshch. Khim., 1997, vol. 67,
no. 9, p. 1536.
4. Ruther, R., Huber, F., and Preut, H., Z. Anorg. Allg.
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Bel’skii, V.K., Zh. Obshch. Khim., 1997, vol. 67,
no. 9, p. 1531.
6. Sharutin, V.V., Sharutina, O.K., Platonova, T.P., Pa-
kusina, A.P., Krivolapov, D.B., Gubaidullin, A.T.,
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no. 12, p. 3015.
1
Tri-p-tolylantimony
bis(2,5-dimethylbenzenesul-
fonate) (II) was obtained in a similar way, yield 88%,
1
mp 182 C. IR spectrum, , cm : 1320 s, 1170 v.s,
1080 s (SO2). Found, %: C 57.77; H 5.32. C37H39
O6S2Sb. Calculated, %: C 58.04; H 5.10.
Reaction of triphenylantimony bis(2,4-di-
methylbenzenesulfonate) with sodium fluoride. To
a solution of 1 g of triphenylantimony bis(2,4-dime-
thylbenzenesulfonate) in 15 ml of ethanol we added a
solution of 0.12 g of sodium fluoride in 5 ml of water.
After 1 h, the solvent was removed, and the residue
was recrystallized from toluene to obtain 0.42 g (74%)
of triphenylantimony difluoride, mp 99 C. The weight
of the toluene-insoluble sodium 2,4-dimethylbenzene-
sulfonate (mp >250 C) was 0.50 g (88%).
8. Zefirov, Yu.V., Zh. Org. Khim., 1975, vol. 11, no. 11,
p. 2636.
9. SMART and SAINT. Area Detector Control and Integ-
ration Software, Madison: Bruker, 1998.
10. SHELXTL, Version 5.10, Madison: Bruker, 1998.
The reaction with sodium bromide was performed
in a similar way to obtain 71% of triphenylantimony
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 3 2003