Reaction of triphenylbismuth bis(arenesulfonates) with triphenylstibine

Article abstract of DOI:10.1023/A:1012385524010

Tetraphenylantimony arenesulfonates and diphenylbismuth arenesulfonates were prepared by reaction of triphenylbismuth bis(arenesulfonates) with triphenylstibine in toluene at 25°C. The crystal and molecular structure of diphenylbismuth 2,4-dimethylbenzene

Full text of DOI:10.1023/A:1012385524010

Russian Journal of General Chemistry, Vol. 71, No. 1, 2001, pp. 79 82. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 1, 2001,
pp. 87 90.
Original Russian Text Copyright
2001 by Sharutin, Sharutina, Pavlushkina, Egorova, Pakusina, Krivolapov, Gubaidullin, Litvinov.
Reaction of Triphenylbismuth Bis(arenesulfonates)
with Triphenylstibine
V. V. Sharutin, O. K. Sharutina, I. I. Pavlushkina, I. V. Egorova, A. P. Pakusina,
D. B. Krivolapov, A. T. Gubaidullin, and I. A. Litvinov
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received November 9, 1999
Abstract Tetraphenylantimony arenesulfonates and diphenylbismuth arenesulfonates were prepared by
reaction of triphenylbismuth bis(arenesulfonates) with triphenylstibine in toluene at 25 C. The crystal and
molecular structure of diphenylbismuth 2,4-dimethylbenzenesulfonate was studied by single crystal X-ray
diffraction. The molecules of the compound in the crystal form chains of Ph2BiOSO2C6H3Me2-2,4 fragments
linked with oxygen atoms of the sulfo group of the bridging arenesulfonate ligand.
It is known that triphenylstibine reacts with tri-
phenylbismuth dichloride with transfer of both phenyl
groups and chlorine atoms to antimony, yielding tetra-
phenylantimony chloride and triphenylantimony di-
chloride [1]. In this work we studied the reaction of
triphenylstibine with triphenylbismuth bis(arenesulfo-
nates). We found that the reaction yields tetraphenyl-
antimony arenesulfonate, with the second product
being diphenylbismuth arenesulfonate.
Ph3Bi(OSO2Ar)2 + Ph3Sb
+ Ph4SbOSO2Ar
Ar = 2,4-C6H3Me2 (I), 2,5-C6H3Me2 (II).
Ph2BiOSO2Ar
3
3
Table 1. Atomic coordinates, equivalenty isotropic thermal parameters
(
2), and isotropic
B = 4/3
(ai aj )B(i, j )
i = 1 j = 1
thermal parameters of H atoms (Biso
,
2) in the structure of I
Atom
x
y
z
B
Atom
x
y
z
B
Bi1
S1
0.42857(4)
0.6775(2)
0.5676(6)
0.7018(7)
0.2895(6)
0.5636(9)
0.670(1)
0.759(1)
0.743(1)
0.641(1)
0.552(1)
0.3219(8)
0.222(1)
0.156(1)
0.193(1)
0.286(1)
0.353(1)
0.6331(8)
0.621(1)
0.577(1)
0.542(1)
0.555(1)
0.27421(4)
0.0844(2)
0.1218(6)
0.1620(7)
0.4380(6)
0.4044(9)
0.4373(9)
0.517(1)
0.565(1)
0.535(1)
0.456(1)
0.2491(8)
0.317(1)
0.294(1)
0.212(1)
0.146(1)
0.166(1)
0.0490(8)
0.0573(9)
0.156(1)
0.2487(9)
0.240(1)
0.27200(2) 2.992(7)
C25
C26
C27
H2
0.6008(9)
0.494(1)
0.609(1)
0.69(1)
0.850(9)
0.81(1)
0.625(8)
0.482(7)
0.20(1)
0.1422(9)
0.355(1)
0.140(1)
0.397(9)
0.535(8)
0.62(1)
0.562(7)
0.449(6)
0.371(9)
0.33(1)
0.2998(6)
0.4515(8)
0.2086(6)
0.359(6)
0.335(5)
0.197(8)
0.109(5)
0.126(5)
0.139(6)
0.022(7)
0.105(5)
0.038(5)
0.098(8)
0.452(5)
0.517(4)
0.301(6)
0.465(6)
0.461(6)
0.390(6)
0.166(5)
0.175(6)
0.195(5)
3.3(2)
6.4(4)
5.1(3)
8(3)a
6(3)a
12(4)a
3(2)a
3(2)a
8(3)a
12(4)a
4(2)a
4(2)a
11(4)a
6(3)a
3(2)a
7(3)a
7(3)a
7(3)a
8(3)a
3(2)a
6(3)a
4(2)a
0.3205(2)
0.2483(4)
0.3923(4)
0.2849(4)
0.2439(6)
0.3137(7)
0.2978(9)
0.2170(8)
0.1511(7)
0.1648(7)
0.1322(6)
0.0906(7)
0.0073(8)
0.0400(7)
0.0016(8)
0.0827(8)
0.3569(6)
0.4417(6)
0.4693(6)
0.4159(7)
0.3324(6)
3.22(6)
3.6(2)
4.2(2)
3.8(2)
3.2(2)
4.0(3)
6.2(4)
6.1(4)
5.9(4)
4.8(3)
2.6(2)
6.6(4)
9.1(4)
5.1(3)
8.5(4)
7.9(4)
2.7(2)
3.5(3)
4.4(3)
4.1(3)
4.0(3)
O11
O2
O3
H3
C1
H4
C2
H5
C3
H6
C4
H8
C5
H9
0.10(1)
C6
H10
H11
H12
H21
H22
H24
H261
H262
H263
H271
H272
H273
0.148(8)
0.309(8)
0.39(1)
0.641(9)
0.568(7)
0.54(1)
0.42(1)
0.54(1)
0.43(1)
0.187(7)
0.102(7)
0.12(1)
C7
C8
C9
0.000(8)
0.157(7)
0.308(8)
0.326(9)
0.416(9)
0.393(9)
0.071(7)
0.205(8)
0.121(7)
C10
C11
C12
C20
C21
C22
C23
C24
0.578(8)
0.578(9)
0.687(8)
a
The atoms were refined isotropically.
1070-3632/01/7101-0079$25.00 2001 MAIK Nauka/Interperiodica

80
SHARUTIN et al.
Fig. 1. Geometry of I in the crystal.
the bottom. Previously diarylbismuth arenesulfonates
The reaction occurs in toluene at 25 C, and within
were prepared by dearylation of triarylbismuth with
arenesulfonic acid [2].
12 18 h coarse crystals of diphenylbismuth arenesul-
fonate grow on the ampule walls, and a finely crystal-
line precipitate of a mixture of diphenylbismuth and
tetraphenylantimony arenesulfonates is formed on
The single crystal X-ray diffraction study of di-
phenylbismuth 2,4-dimethylbenzenesulfonate showed
(Fig. 1, Table 1) that the crystalline compound has the
polymeric structure.
Table 2. Selected bond lengths (d, ) and bond angles
( , deg) in the structure of I
Bond
d
Bond
d
Bi1 O1
Bi1 C1
S1 O1
S1 O3
2.406(7)
2.22(1)
1.481(6)
1.475(8)
Bi1 O3
Bi1 C7
S1 O2
2.459(7)
2.240(8)
1.425(8)
1.76(1)
S1 C20
The bismuth atom, with the stereochemically active
lone electron pair considered as a phantom ligand, has
a trigonal-bipyramidal configuration. The O1BiO3
angle is 175.1(2) . The angles between the pseudo-
axial oxygen atoms and the ipso carbon atoms of the
phenyl rings vary from 85.8(3) to 91.1(3) . The Bi C
bond lengths are equal within the experimental error,
whereas the Bi O bond lengths differ noticeably
(Table 2). The S O bond lengths show an inverse
correlation with the Bi O bond lengths: The bond
with the O atom forming the shorter bond with Bi is
longer. Thus, there is no leveling of the Bi O bonds
Angle
Angle
O1Bi1O3
O1Bi1C7
O3Bi1C7
O1S1O2
O1S1C20
O2S1C20
Bi1O1S1
175.1(2)
85.8(3)
91.1(3)
112.2(4)
106.6(4)
107.7(5)
119.7(4)
O1Bi1C1
O3Bi1C1
C1Bi1C7
O1S1O3
O2S1O3
O3S1C20
Bi1O3S1
90.6(3)
85.8(3)
94.7(3)
108.4(4)
114.8(4)
106.5(4)
117.7(4)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001

REACTION OF TRIPHENYLBISMUTH BIS(ARENESULFONATES) WITH TRIPHENYLSTIBINE
81
Fig. 2. Crystal packing of I. Projection along the 0Y-axis.
in the crystal, which allows the Bi O1 bond to be con-
sidered as mainly valence bond, and the Bi O3 bond,
as a coordination bond.
Single crystal X-ray diffraction study of
C20H19O3SBi (I) was performed on an Enraf-Nonius
CAD-4 automatic four-circle diffractometer. The crys-
tals are monoclinic; at 20 C a 10.702(1), b 11.639(2),
The linear structure of the O Bi O group is favor-
c 15.893(2)
;
104.94(1) , V 1912.6(5) 3, Z 4,
able for the hyperconjugation between the O3 lone
3
dcalc 1.90 g cm , space group P21/a. The unit cell
electron pair and the Bi O1 antibonding orbital (n
*
parameters and the intensities of 4285 reflections,
interaction), which results in noticeable lengthening of
the Bi O1 bond and formation of an =O3 Bi O1
three-center bond.
2072 of which were observed with I
3 , were
measured at 20 C using MoK radiation ( MoK
0.71074 , graphite monochromator, /2 scanning,
29.96 ). The absorption was taken into account
The polymeric chains in the crystal are directed
along the 0X-axis and have no short contacts corre-
sponding to strong intermolecular interactions. The
C H P and stacking interactions between parallel
aromatic rings are observed only within the chain
(Fig. 2).
1
empirically ( Mo 93.1 cm ). The structure was
solved by the heavy atom method and refined first in
the isotropic and then in the anisotropic approxima-
tion. All hydrogen atoms were revealed from the dif-
ferential electron density series and refined isotropi-
cally in the final refinement cycles. The structure was
refined to R 0.037 and RW 0.038 for 2088 unique
reflections with F2 3 . The atomic coordinates are
given in Table 1, and the main geometric parameters,
in Table 2. All calculations were performed with a
EXPERIMENTAL
The IR spectra were taken on a Hitachi-215 spec-
trometer (mull in mineral oil between NaCl plates).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001

82
SHARUTIN et al.
DEC AlphaStation 200 computer using the MolEN
program package [3]. The intermolecular contacts
were analyzed and the molecular drawings obtained
using the WINPL98 program [4].
benzenesulfonate and tetraphenylantimony 2,5-di-
methylbenzenesulfonate 58 and 89%, respectively.
ACKNOWLEDGMENTS
Diphenylbismuth 2,4-dimethylbenzenesulfonate.
A mixture of 1.00 g of triphenylstibine, 2.29 g of
triphenylbismuth bis(2,4-dimethylbenzenesulfonate),
and 30 ml of toluene was allowed to stand at 25 C for
72 h. Coarse crystals that formed on the ampule wall
were collected, dried, and weighed. Diphenylbismuth
2,4-dimethylbenzenesulfonate was obtained; yield
1.00 g (64%), mp 211 C. Found, %: C 43.75; H 3.53;
S 5.67. C20H19O3SBi. Calculated, %: C 43.80; H
3.47; S 5.84. The mother liquor was evaporated, and
the residue was recrystallized from water. Tetraphen-
ylantimony 2,4-dimethylbenzenesulfonate was ob-
tained; yield 1.58 g (91%), mp 211 C. IR spectrum,
The single crystal X-ray diffraction study was per-
formed at the department of X-ray diffraction studies
of the Spectrum-Analytical Center for Collective Use
of the Russian Foundation for Basic Research (pro-
ject no. 96-03-40006).
REFERENCES
1. Zinov’eva, T.I., Dodonov, V.A., and Pryakhina, O.I.,
Abstracts of Papers, VI Konferentsiya po metalloorga-
nicheskoi khimii (VI Conf. on Organometallic Chem-
istry), Nizhni Novgorod, 1995, p. 163.
2. Deacon, G.B., Felder, P.W., Domagala, M., Huber, F.,
and Ruther, R., Inorg. Chim. Acta, 1986, vol. 113,
no. 1, pp. 43 48.
3. Straver, L.H. and Schierbeek, A.J., MolEN. Structure
Determination System, Nonius B.V., 1994, vols. 1, 2.
4. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46,
1
, cm : 1240 (S=O), 1000 (S O). Found, %: C
62.23; H 4.95. C32H29O3SSb. Calculated, %: C
62.44; H 4.72.
Reaction of triphenylstibine with triphenylbismuth
bis(2,5-dimethylbenzenesulfonate) was performed
similarly. Yields of diphenylbismuth 2,5-dimethyl-
no. 1, pp. 34 36.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001