Synthesis and Structure of Tetraphenylstibonium and Tetraphenylphosphonium Hydrogen Sulfates

Article abstract of DOI:10.1023/A:1025676100508

Reactions of pentaphenylantimony and pentaphenylphosphorane with sulfuric acid yielded tetraphenylstibonium and tetraphenylphosphonium hydrogen sulfates, respectively; their crystal and molecular structure was determined.

Full text of DOI:10.1023/A:1025676100508

Russian Journal of General Chemistry, Vol. 73, No. 4, 2003, pp. 536 540. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 4, 2003,
pp. 569 572.
Original Russian Text Copyright
2003 by Sharutin, Pakusina, Egorova, Platonova, A. Gerasimenko, E. Gerasimenko, Zakharov, Fukin.
Synthesis and Structure of Tetraphenylstibonium
and Tetraphenylphosphonium Hydrogen Sulfates
V. V. Sharutin, A. P. Pakusina, I. V. Egorova, T. P. Platonova, A. V. Gerasimenko,
E. A. Gerasimenko, L. N. Zakharov, and G. K. Fukin
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received March 2, 2001
Abstract Reactions of pentaphenylantimony and pentaphenylphosphorane with sulfuric acid yielded tetra-
phenylstibonium and tetraphenylphosphonium hydrogen sulfates, respectively; their crystal and molecular
structure was determined.
The structures of antimony(V) derivatives Ar4SbX
(X = acid residue) are described in numerous papers
[1 20]. In these compounds, the Sb X bond lengths
vary within wide limits, with the antimony coordina-
tion polyhedron varying from virtually ideal tetrahed-
ron [17] to trigonal bipyramid [1 4, 10 20] and oc-
tahedron [5 9]. Among compounds of this series,
organoantimony derivatives of strong acids are the
least studied. To determine the structural features of
such compounds, we have prepared tetraphenylstibo-
nium (I) and tetraphenylphosphonium (II) hydrogen
sulfates from pentaphenylantimony and pentaphenyl-
phosphorane, respectively:
ly coincides with the difference between the covalent
Sb
radii of the Sb and P atoms (d
1.41 , dPcov 1.10
cov
[21]). Although the anions in both complexes are the
same, the S O bonds in them somewhat differ. In I,
the S=O bond lengths are 1.419(2), 1.436(2), and
1.473(1)
(average 1.443 ), and the S O(H) bond
length is 1.522(1) . These distances are shorter than
in II [S=O, 1.440(1), 1.444(2), and 1.474(1) (aver-
age 1.453 ); S O(H) 1.574(1) ]. The OSO angles
are in the range 105.69(8) 112.29(9) for I and
104.49(8) 114.16(8) for II. The SOH angle in I
[120.6(1) ] is larger than in II [110.2(1) ]. The differ-
ence between the geometries of the anions in I and II
may be due to the effect of the pyridine solvation
Ph5E + H2SO4
Ph4EOSO2(OH) + PhH,
O3
I, II
E = Sb (I), P (II).
O2
O1
S
According to single crystal X-ray diffraction, the
molecules of I and II (Figs. 1, 2) consist of hydrogen
sulfate anions (HOSO3) and Ph4E+ cations [E = Sb
(I), P (II)]. The Sb atom in the cation of I has a
distorted tetrahedral coordination. The CSbC angles
vary in the range 99.23(7) 120.25(6) , and the Sb C
bond lengths are 2.090(2), 2.102(2), 2.110(2), and
2.116(2) . It should be noted that, in tetraphenyl-
stibonium perchlorate having a similar structure, the
Sb coordination is virtually ideal tetrahedral: The
CSbC angles are 109.44(8) 109.49(8) , and the aver-
O4
C33
C34
C14
C32
C13
C12
C35
C36
C15
C16
C43
C44
C31
C11
C42
Sb
C21
C41
C26
age Sb C distance, 2.095
[13].
C46
C22
C23
C53
The P C bond lengths [1.7882(16) 1.7947(16)
]
and CPC angles [106.48(8) 112.67(7) ] in the cation
of II vary within narrower limits than in I, suggesting
more regular tetrahedral structure of the Ph4P+ cation.
Note that the difference between the average distances
Sb C (2.100 ) and P C (1.793 ) in I and II virtual-
C25
C24
Fig. 1. Molecular structure of tetraphenylstibonium
hydrogen sulfate.
1070-3632/03/7304-0536$25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS AND STRUCTURE OF TETRAPHENYLSTIBONIUM
537
C23
C22
C24
C21
C20
C16
C15
C19
P
C14
C2
C17
C18
C3
C13
C7
C1
C4
C8
C6
C12
C11
O2
S1
C5
C9
H1
O1
C10
O3
O4
Fig. 2. Molecular structure of tetraphenylphosphonium hydrogen sulfate (the pyridine solvation molecule is not shown).
molecule present in the crystal of II. The cation, ani-
on, and pyridine molecule in II are linked by weak
intermolecular hydrogen bonds H O H (Fig. 3).
Hydrogen atoms in the p-position of the phenyl rings
of the tetraphenylphosphonium ions also participate
in weak hydrogen bonding. The H O distances vary
within 2.433 2.579 (with the C H O angles vary-
ing within 145.2 157.6 ), which appreciably exceeds
the distance typical of hydrogen bonds {d(O H) <
EXPERIMENTAL
Single crystal X-ray diffraction study of I and II
was performed with Bruker SMART-1000CCD (for I;
MoK radiation, graphite monochromator, /2 scan-
ning, 2
radiation, graphite monochromator, /2 scanning,
32.41 ) diffractometers. C24H21O4SSb (I): mono-
30.03 ) and Siemens P3/PC (for II; MoK
2
clinic system; at 20 C a 12.308(2), b 10.273(1), c
2.1
[22]} but is less than the sum of the van der
[21]).
18.093(2)
;
105.850(2) , V 2200.8(5) 3, space
3
Waals radii of the O and H atoms (2.7
group P21/c, Z 4, dcalc 1.591 g cm . C29H26NO4PS
(II): triclinic system; at 20 C a 9.727(5), b 10.859(6),
We found that keeping of a solution of pentaphen-
ylantimony in liquid SO2 in the absence of H2SO4 for
12 h at 20 C, followed by removal of the solvent and
recrystallization of the residue from water, results in
quantitative formation of tetraphenylantimony ben-
zenesulfonate III; the reaction apparently involves
insertion of SO2 into the Sb C bond with the forma-
tion of tetraphenylantimony benzenesulfinate IV,
which is subsequently oxidized with atmospheric oxy-
gen to tetraphenylantimony benzenesulfonate:
c 13.167(7)
;
69.232(10) ,
76.251(10) ,
87.221(10) ; V 1262.2(12) 3, space group P1, Z 2,
3
dcalc 1.356 g cm . The H atoms in aryl substituents in
I and II were localized by differential electron density
syntheses and refined isotropically. The X-ray absorp-
tion was taken into account with the SADABS
program [23]. The structures of I and II were solved
by the direct method and refined by the full-matrix
least-squares method in the anisotropic approximation
for all nonhydrogen atoms to R 0.0475, RW 0.0690
using 6414 reflections with I > 2 (I) for I and to R
0.0764, RW 0.1868 using 8160 reflections with I >
2 (I) for II. X-ray diffraction study of II revealed a
disordered solvation molecule of pyridine.
Ph5Sb + SO2
[Ph4SbOS(O)Ph]
IV
O2
Ph4SbOSO2Ph.
III
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 4 2003

538
SHARUTIN et al.
C1C
P1C
N1SB
C19C
C7C
C13C
C4SB
O3B
H4SB
C17C
O4B
H17C
C13A
O2B
C1D
H22A
S1B
C19A
O1A
S1A
C7A
C22A
H22D
P1A
C7D
C13D
H17B
P1D
C19D
C1A
O4A
C22D
O2A
H4SA
C4SA
C17B
C13B
P1B
O3A
N1SA
C19B
C7B
C1B
Fig. 3. System of intermolecular hydrogen bonds in the crystal of tetraphenylphosphonium hydrogen sulfate pyridine solvate
(the phenyl substituents that do not participate in intermolecular interactions are not shown).
Selected interatomic distances (d) and bond angles ( ) in I and II
Compound I Compound II Compound I
Compound II
bond
d,
bond
d,
angle
, deg
angle
, deg
Sb C41
Sb C21
Sb C31
Sb C11
S O4
2.090(2)
2.102(2)
2.110(2)
2.116(2)
1.419(2)
1.436(2)
1.473(1)
1.522(1)
0.78(2)
P1 C1
P1 C7
P1 C13
P1 C19
S1 O1
S1 O2
S1 O3
S1 O4
O1 H1
1.7945(17)
1.7926(17)
1.7882(16)
1.7947(16)
1.5743(13)
1.4442(15)
1.4734(13)
1.4402(13)
0.86(2)
C41SbC21
C41SbC31
C21SbC31
C41SbC11
C21SbC11
C31SbC11
O4SO2
118.99(6)
111.05(6)
120.25(6)
99.23(7)
101.58(6)
100.47(6)
112.29(9)
111.2(1)
C13P1C7
C13P1C19
C7P1C19
C13P1C1
C7P1C1
C19P1C1
O4S1O2
O4S1O3
O2S1O3
O4S1O1
O2S1O1
O3S1O1
S1O1H1
108.22(7)
108.60(8)
112.67(7)
111.17(7)
109.72(7)
106.48(8)
114.16(8)
112.76(7)
112.30(8)
104.49(8)
106.65(7)
105.58(7)
110.2(1)
S O2
S O3
S O1
O4SO3
O1 H1
O2SO3
110.1(1)
O4SO1
109.41(9)
107.86(8)
105.69(8)
120.6(1)
O2SO1
O3SO1
SO1H1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 4 2003

SYNTHESIS AND STRUCTURE OF TETRAPHENYLSTIBONIUM
The data collection and editing and the refinement Khim., 1995, no. 5, p. 958.
539
of the unit cell parameters were performed by the
SMART and SAINT Plus programs [24]. All the cal-
culations for structure determination and refinement
were performed by SHELXTL/PC programs [25]. The
selected bond lengths and bond angles in the mole-
cules of I and II are listed in the table.
4. Sharutin, V.V., Sharutina, O.K., Osipov, P.E., Pu-
shilin, M.A., Muslin, D.V., Lyapina, N.Sh., Zhid-
kov, V.V., and Bel’skii, V.K., Zh. Obshch. Khim.,
1997, vol. 67, no. 9, p. 1528.
5. Bone, S.P. and Sowerby, D.B., J. Chem. Res. Synop.,
1979, no. 3, p. 82.
Tetraphenylstibonium hydrogen sulfate I. A mix-
ture of 1.00 g of pentaphenylantimony and 0.19 g of
sulfuric acid in 10 ml of liquid SO3 was kept for 12 h
at room temperature. The solvent was removed, and
the residue was recrystallized from water. Yield
0.93 g (89%), mp 213 214 C.
6. Bone, S.P. and Sowerby, D.B., Phosphorus, Sulfur,
Silicon, 1989, vol. 45, nos. 1 2, p. 23.
7. Sharutina, O.K., Sharutin, V.V., Senchurin, V.S.,
Fukin, G.K., Zakharov, L.N., Yanovskii, A.I., and
Struchkov, Yu.T., Izv. Ross. Akad. Nauk, Ser. Khim.,
1996, no. 1, p. 194.
Tetraphenylphosphonium hydrogen sulfate II
was prepared similarly to I from pentaphenylphos-
phorane and sulfuric acid in liquid SO2. The solvent
was removed, and the residue was recrystallized from
benzene. The crystal solvate [Ph4P]+[SO4H] 1/2C6H6
was isolated; yield 92%, mp 143 C. Found, %: C
68.63; H 5.20; P 6.10. C27H24O4PS. Calculated, %:
C 68.21; H 5.05; P 6.53. The single crystal X-ray dif-
fraction study was performed with a yellow crystalline
compound obtained by recrystallization of II from
pyridine.
8. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P., and
Belsky, V.K., J. Organomet. Chem., 1997, vol. 536,
no. 1, p. 87.
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10. Sharutin, V.V., Sharutina, O.K., Mel’nikova, I.G.,
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Reaction of pentaphenylantimony with SO2.
A mixture of 1 g of pentaphenylantimony and 10 ml
of liquid SO2 was kept for 12 h at room temperature.
The solvent was removed, and the residue was recrys-
tallized from water. Tetraphenylantimony benzenesul-
fonate crystal hydrate was obtained; yield 1.05 g
(88%), mp 100 C (101 C [16]).
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ACKNOWLEDGMENTS
The study was financially supported by the Russian
Foundation for Basic Research (project nos. 00-15-
97439 and 99-07-90133) in cooperation with the
Center for X-ray Structural Studies, Division of Gen-
eral and Technical Chemistry, Russian Academy of
Sciences (project no. 00-15-97359).
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