Synthesis and structure of tetra-and triarylantimony oximates

Article abstract of DOI:10.1023/A:1013220911661

Pentaphenyl-and penta-p-tolylantimony were reacted with benzophenone oxime or triarylantimony bis(benzophenonoximate) in toluene to obtain tetraarylantimony benzophenonoximate. Triarylantimony bis(benzophenonoximates) were prepared by oxidative addition f

Full text of DOI:10.1023/A:1013220911661

Russian Journal of General Chemistry, Vol. 71, No. 8, 2001, pp. 1243 1247. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 8, 2001,
pp. 1317 1321.
Original Russian Text Copyright
2001 by Sharutin, Sharutina, Molokova, Ettenko, Krivolapov, Gubaidullin, Litvinov.
Synthesis and Structure of Tetra-
and Triarylantimony Oximates
V. V. Sharutin, O. K. Sharutina, O. V. Molokova, E. N. Ettenko,
D. B. Krivolapov, A. T. Gubaidullin, and I. A. Litvinov
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received April 12, 2000
Abstract Pentaphenyl- and penta-p-tolylantimony were reacted with benzophenone oxime or triarylanti-
mony bis(benzophenonoximate) in toluene to obtain tetraarylantimony benzophenonoximate. Triarylantimony
bis(benzophenonoximates) were prepared by oxidative addition from tryarylstibine and oxime in ether in the
presence of hydrogen peroxide. X-ray diffraction analysis of tetraphenylantimony benzophenonoximate was
performed to show that coordination of the antimony atom is trigonal-bipyramidal and the oxime oxygen
atom is axial.
It is known that pentaarylstibines I react with anti-
mony derivatives of the general formula Ar3SbX2
(Ar = Ph, p-Tol; X = Cl, Br, OC(O)R, OSO2Ar , NO3,
SCN), giving unsymmetrical antimony derivatives
Ar4SbX in high yields [1 4]. Analogous dispropor-
tionation reactions involving compound I and triaryl-
antimony dioximates has not yet been studied.
The products are colorless crystalline substances
soluble in aromatic hydrocarbons and polar organic
solvents.
The yields of tetraarylantimony oximates in this
case reach 98% (see Table 1).
Triarylantimony bis(benzophenonoximates) were
obtained by oxidative addition of benzophenone
oxime to triarylantimony in the presence of hydrogen
peroxide.
We found that tetraarylantimony benzophenon-
oximates can be prepared by the above-mentioned re-
action in 92% yield from pentaphenyl- and penta-p-
tolylantimony and triarylantimony bis(benzophenon-
oximates) in toluene.
Ar3Sb + 2HON=CPh2 + H2O2
+ 2H2O.
Ar3Sb(ON=CPh2)2
Ar5Sb + Ar3Sb(ON=CPh2)2
2Ar4SbON=CPh2,
Note that this method was first used for preparing
triphenylantimony diacetate and then analogous anti-
mony derivatives of the general formula Ar3SbX2,
where X is an electronegative group [1, 3 6], but the
synthesis of triarylantimony dioximates by this
method has not been reported.
Ar = Ph, 4-MeC6H4.
The IR spectra and the melting points of the tetra-
arylantimony benzophenonoximates prepared by this
method were consistent with respective characteristics
of the compounds obtained from pentaarylantimony
and benzophenone oxime.
According to X-ray diffraction data, the antimony
atom in compound IIa has a usual trigonal-bipyr-
amidal coordination typical of five-coordinate anti-
mony compounds (Fig. 1). The O2 and C7 atoms are
axial, the O2Sb1C7 bond angle is 174.9(2) , equatorial
angles vary from 118.8(2) to 120.2(2) , and their sum
is 348.2(3) . The angles between axial and equatorial
substituents are in the range 81.2(2) 95.4(2) , and
acute angles involve oxygen atoms (Table 2). Equa-
torial Sb C bonds are equal to each other within the
experimental errors and are slightly shorter than the
axial Sb C7 bond. The Sb O bond [2.146(4) ] is
close to Sb C. This is much shorter than in the penta-
The reactions of pentaphenyl- or penta-p-tolylanti-
mony with oximes give tetraarylantimony oximates.
Ar5Sb + HON=CRR
Ar4SbON=CRR + ArH,
I
IIa IIj
Ar = Ph; R = R = Ph (a), R = H, R = C6H3(OH)-2-(Br)-5
(b), R = H, R = C6H4(NO2)-3 (c), R, R = cyclohexyl (d).
Ar = C6H4(Me)-4; R = Ph, R = Me (e), R = H, R =
C4H3O (f), R = R = Ph (g), R = H, R = C6H3(OH)-2-
(Br)-5 (h), R = H, R = C6H4(NO2)-3 (i), R, R = cyclo-
hexyl (j).
1070-3632/01/7108-1243$25.00 2001 MAIK Nauka/Interperiodica

1244
SHARUTIN et al.
Table 1. Yields, melting points, and elemental analyses of tetraarylantimony oximates
Found, %
Calculated, %
H
Comp.
no.
Yield, % mp,
C
Formula
C
H
N
C
N
IIa
IIb
IIc
IId
IIe
IIf
IIg
IIh
IIi
90
96
92
70
98
97
98
87
97
84
168
70.02
56.97
62.31
66.20
70.44
67.03
71.65
60.53
64.02
67.69
4.89
3.95
4.58
5.76
6.57
5.88
5.90
4.89
4.73
6.81
2.37
2.02
4.95
2.79
2.61
2.62
2.38
1.86
4.00
2.11
C37H30NOSb
C31H25BrNO2Sb
C31H25N2O3Sb
C30H30NOSb
C36H36NOSb
C33H32NO2Sb
C41H38NOSb
C35H33BrNO2Sb
C35H33N2O3Sb
C34H38NOSb
70.93
57.67
62.52
66.42
69.68
66.44
72.14
59.91
64.52
68.23
4.79
3.88
4.20
5.53
5.81
5.37
5.57
4.71
5.07
6.35
2.24
2.17
4.71
2.58
2.26
2.35
2.05
2.00
4.30
2.34
150
139
122
Oil
148
166
125
158
IIj
valent antimony derivative Ph4SbON=C(NO)Me
(2.266 and 2.235 , respectively [7]) which is struc-
Single-crystal X-ray diffraction analysis of
tetraphenylantimony benzophenonoximate IIa. The
turally similar to the obtained oximates. The geometry intensities of 5575 reflections, 3138 of which had I >
of the Ph2C=NO substituent is usual. The trigonal-
3 , were measured at 20 C on an Enraf Nonius
CAD-4 automatic four-circle K-diffractometer (MoK
radiation, MoK 0.71073 , graphite monochro-
mator, /2 scanning, < 29.96 ). Crystals of IIa,
C37H30NOSb, are monoclinic; at 20 C, a 11.565(1),
planar coordination of the C25 atom and the N2 C25
bond length of 1.281(7)
structure. The crystal packing of molecules IIa is
determined by multiple CH contacts and dispersion
agree with the proposed
interactions between parallel benzene rings (Fig. 2).
b
16.545(8),
c
15.713(3)
,
94.09(2) , V
2999(2) 3, Z 4, dcalc 1.39 g/cm3, space group P21/n.
EXPERIMENTAL
Absorption corrections were not applied ( Mo
9.52 cm ). The structure was solved by the direct
method using the SIR program [8] and refined first
1
The IR spectra were registered on a Hitachi-215
spectrometer (suspension in Vaseline oil).
C21
C22
C10
C11
C20
C23
C24
C28
C12
C14
C19
C9
C8
C7
C29
Sb1
C27
C15
N2
O2
C33
C26
C13
C30
C16
C18
C6
C25
C31
C34
C32
C37
C1
C17
C2
C35
C5
C36
C3
Fig. 1. Geometry of complex IIa in crystal.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 8 2001
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SYNTHESIS AND STRUCTURE OF TETRA- AND TRIARYLANTIMONY OXIMATES
1245
Fig. 2. Crystal packing of molecules IIa.
isotropically and then anisotropically. Hydrogen
atoms were revealed from differential electron density
series and refined isotropically in the final stage. Final
divergence factors: R 0.038 and RW 0.043, on 2905
unique reflections with F2 > 3 . All calculations were
peformed using the MolEN program complex [9] on a
DEC AlphaStation 200 compter. Analysis of inter-
molecular contacts and the molecular drawings were
performed by the WINPL98 program [10].
Triphenylantimony bis(benzophenonoximate).
To a solution of 1.00 g of triphenylstibine and 0.76 g
of benzophenone oxime in 20 ml of ether, 0.32 ml of
31% aqueous hydrogen peroxide was added. The
Table 2. Pricipal geometric parameters of structure Ia:
bond lengths (d, ) and bond angles ( , deg)
Bond
d
Bond
d
Sb1 O2
Sb1 C1
Sb1 C7
Sb1 C13
Sb1 C19
2.146(4)
2.135(6)
2.180(5)
2.120(6)
2.132(6)
O2 N2
1.387(6)
1.281(7)
1.501(8)
1.499(8)
Tetraarylantimony oximates were obtained accord-
ing to the following typical procedures.
N2 C25
C25 C26
C25 C32
Tetraphenylantimony
benzophenonoximate
(IIa). a. A mixture of 1.00 g of pentaphenylantimony,
0.39 g of benzophenone oxime, and 10 ml of toluene
was kept for 1 h at 90 C. The solvent was removed,
and the residue was crystallized from a 3:1 heptane
benzene mixture. Yield 1.11 g (90%), mp 168 C.
Angle
Angle
O2Sb1C1
O2Sb1C7
O2Sb1C13
O2Sb1C19
C1Sb1C7
C1Sb1C13
C1Sb1C19
C7Sb1C13
81.2(2)
174.9(2)
88.8(2)
86.6(2)
94.2(2)
118.8(2)
120.2(2)
95.4(2)
C7Sb1C19
C13Sb1C19
Sb1O2N2
O2N2C25
N2C25C26
N2C25C32
C26C25C32
93.8(2)
119.2(2)
112.2(3)
114.3(5)
114.9(5)
126.3(5)
118.6(5)
b. A mixture of 0.40 g of pentaphenylantimony and
0.59 g of triphenylantimony bis(benzophenonoximate)
in 10 ml of toluene was kept for 1 h at 90 C. The
solvent was removed, and the residue was crystallized
from a 3:1 heptane benzene mixture. Yield 0.96 g
(97%), mp 168 C.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 8 2001

1246
SHARUTIN et al.
Table 3. Atomic coordinates in structure IIa, equivalent isotropic termal parameters of non-hydrogen atoms B =
3
3
4/3
(ai aj)B(i, j) ( 2), and isotropic thermal parameters of hydrogen atoms
i= 1 j= 1
Atom
x
y
z
B
Atom
x
y
z
B
Sb1
O2
0.90643(4)
1.0640(3)
1.1400(4)
0.8628(5)
0.9479(6)
0.9173(7)
0.8037(7)
0.7175(6)
0.7484(6)
0.7443(5)
0.6506(5)
0.5477(5)
0.5324(6)
0.6222(6)
0.7241(6)
0.8819(5)
0.8632(7)
0.8432(7)
0.8412(6)
0.8582(6)
0.8809(6)
1.0113(5)
0.9797(6)
1.0521(6)
1.1475(7)
1.1073(6)
1.1760(6)
1.2472(5)
1.3303(5)
1.3005(6)
1.3769(7)
1.4808(7)
1.5105(7)
1.4360(6)
1.2942(5)
0.22897(2) 0.28967(3)
0.2548(2) 0.3652(3)
0.1898(3) 0.3687(3)
0.3460(3) 0.3348(4)
0.4021(4) 0.3600(5)
0.4773(4) 0.3899(6)
0.4970(4) 0.3956(5)
0.4419(4) 0.3701(4)
0.3665(4) 0.3394(4)
0.2143(3) 0.2116(4)
0.1704(4) 0.2405(4)
0.1656(4) 0.1915(5)
0.2055(4) 0.1152(5)
0.2510(4) 0.0865(5)
0.2550(4) 0.1353(4)
0.1272(3) 0.3684(4)
0.0515(4) 0.3309(5)
0.0141(4) 0.3827(5)
0.0062(4) 0.4677(5)
0.0681(5) 0.5057(5)
0.1339(4) 0.4541(4)
0.2172(3) 0.1842(4)
0.1624(4) 0.1191(4)
0.1548(4) 0.0532(5)
0.2030(5) 0.0474(5)
0.2647(4) 0.1780(4)
0.2572(5) 0.1098(5)
0.2097(3) 0.3702(4)
0.1399(4) 0.3715(4)
0.0704(4) 0.3265(5)
0.0061(5) 0.3276(6)
0.0112(5) 0.3729(6)
0.0786(5) 0.4187(5)
0.1443(4) 0.4185(5)
0.2938(3) 0.3638(4)
2.959(7)
3.46(9)
3.3(1)
3.3(1)
5.1(2)
6.1(2)
5.2(2)
4.6(2)
4.1(2)
3.0(1)
3.9(2)
4.6(2)
4.8(2)
4.7(2)
4.0(2)
3.1(1)
4.9(2)
6.5(2)
6.0(2)
5.2(2)
4.6(2)
3.0(1)
4.5(2)
5.6(2)
6.3(2)
4.4(2)
6.1(2)
3.1(1)
3.9(2)
4.9(2)
7.0(2)
7.5(2)
6.6(2)
5.2(2)
3.2(1)
C33
C34
C35
C36
C37
H2
1.3745(6)
1.4153(6)
1.3762(7)
1.2990(6)
1.2573(6)
0.531(4)
0.989(6)
0.785(7)
0.143(4)
0.189(5)
0.667(5)
0.495(4)
0.3089(4) 0.3034(4)
0.3859(4) 0.2919(5)
0.4502(4) 0.3386(6)
0.4348(4) 0.3972(5)
0.3584(4) 0.4104(4)
4.7(2)
5.7(2)
5.7(2)
5.3(2)
4.1(2)
4(1)
N2
C1
C2
C3
0.110(3)
0.512(5)
0.544(5)
0.045(3)
0.170(3)
0.148(3)
0.137(3)
0.207(3)
0.222(3)
0.215(2)
0.041(4)
0.059(3)
0.052(4)
0.074(3)
0.177(3)
0.136(4)
0.119(3)
0.182(6)
0.199(3)
0.291(3)
0.066(3)
0.033(3)
0.030(3)
0.085(3)
0.189(3)
0.270(3)
0.106(3)
0.000(3)
0.473(4)
0.152(3)
0.853(3)
0.398(5)
0.418(5)
0.882(3)
0.826(3)
0.301(3)
0.209(3)
0.081(3)
0.531(3)
0.623(2)
0.276(4)
0.351(4)
0.504(4)
0.565(3)
0.475(3)
0.121(4)
0.010(4)
0.004(6)
0.720(3)
0.107(3)
0.293(3)
0.293(3)
0.366(4)
0.450(3)
0.451(3)
0.275(3)
0.758(3)
0.178(3)
0.426(4)
0.958(3)
C4
H3
10(2)
C5
H4
13(3)
4(1)
5(1)
5(1)
4(1)
5(1)
4(1)
C6
H5
C7
H6
C8
H8
C9
H9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
C31
C32
H10 0.458(5)
H11 0.108(4)
H12 0.278(3)
H14 0.843(6)
H15 0.827(5)
H16 0.826(6)
H17 0.866(4)
H18 0.900(4)
H20 0.921(5)
H21 1.031(5)
H22 1.185(8)
H23 0.626(4)
H24 1.241(4)
H27 1.228(5)
H28 1.354(5)
H29 1.535(5)
H30 1.576(5)
H31 1.462(4)
H33 1.409(4)
H34 0.959(4)
H35 0.087(4)
H36 1.270(5)
H37 0.710(4)
0.8(8)
10(2)
5(1)
8(2)
5(1)
4(1)
8(2)
7(2)
14(3)
2(1)
3(1)
5(2)
6(2)
6(2)
5(1)
5(1)
4(1)
3(1)
5(1)
7(2)
4(1)
REFERENCES
resulting mixture was kept for 12 h at 20 C. Colorless
crystals formed and were filtered off and dried to
obtain 1.52 g (72%) of triphenylantimony bis(benzo-
phenonoximate), mp 104 C.
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ACKNOWLEDGMENTS
The X-ray diffraction analysis was performed at the
Department of X-ray studies of the Spectral Analytical
Center for Collective Use of the Russian Foundation
for Basic Research (project no. 96-03-40006).
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SYNTHESIS AND STRUCTURE OF TETRA- AND TRIARYLANTIMONY OXIMATES
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 8 2001