Synthesis and structures of triphenylantimony oximates

Article abstract of DOI:10.1023/A:1019634307064

The reactions of triphenylantimony or trimethylantimony with tert-butyl hydroperoxide in the presence of acetone oxime, acetophenone oxime, cyclohexanone oxime, or benzaldehyde oxime afforded monomeric triorganoantimony oximates Ph₃Sb(ON=CMe

Full text of DOI:10.1023/A:1019634307064

Russian Chemical Bulletin, International Edition, Vol. 51, No. 6, pp. 1051—1057, June, 2002
1051
Organometallic Chemistry
Synthesis and structures of triphenylantimony oximates
V. A. Dodonov,a A. V. Gushchin,aꢀ D. A. Gor´kaev,a G. K. Fukin,b T. I. Starostina,a L. N. Zakharov,b
Yu. A. Kurskii,b and A. S. Shavyrinb
aNizhnii Novgorod State University,
23 prosp. Gagarina, 603950 Nizhnii Novgorod, Russian Federation.
Fax: +7 (831 2) 65 8592. Eꢀmail: guav3@uic.nnov.ru
bG. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, 603600 Nizhnii Novgorod, Russian Federation.
Fax: +7 (831 2) 66 1497. Eꢀmail: lz@imoc.sinn.ru
The reactions of triphenylantimony or trimethylantimony with tertꢀbutyl hydroperoxide
in the presence of acetone oxime, acetophenone oxime, cyclohexanone oxime, or benzꢀ
aldehyde oxime afforded monomeric triorganoantimony oximates Ph3Sb(ON=CMe2)2,
Ph3Sb(ON=CMePh)2,
Ph3Sb[ON=C(CH2)5]2,
Ph3Sb(ON=CHPh)2,
and
Me3Sb(ON=CMe2)2 in 87—96% yields. Xꢀray diffraction analysis demonstrated that
Ph3Sb(ON=CMe2)2 and Ph3Sb(ON=CHPh)2 have trigonalꢀbipyramidal structures. An analoꢀ
gous reaction with dimethylglyoxime gave rise to polymeric triphenylantimony dioximate in
96% yield. The reaction with butaneꢀ2,3ꢀdione monoxime yielded chelate cyclic bis(triphenylꢀ
antimony) oxides.
Key words: triphenylantimony oximates, trimethylantimony oximates, oximes, acetone
oxime, acetophenone oxime, cyclohexanone oxime, benzaldoxime, butaneꢀ2,3ꢀdione oxime,
dimethylglyoxime, tertꢀbutyl hydroperoxide, molecular structure, Xꢀray diffraction analysis.
The structural chemistry of the triorganoantimony
derivatives R3SbX2 with oxygenꢀcontaining functional
groups has been extensively developed in recent years.
Antimony compounds with derivatives of monobasic
OHꢀacids (viz., monohydric alcohols and phenols, monoꢀ
carboxylic acids, hydroperoxides, and sulfonic acids) have
a trigonalꢀbipyramidal configuration with the monoꢀ
dentate ligands X in the axial positions.1,2 The structures
of derivatives of dibasic OHꢀacids (viz., glycols, diꢀ
hydroxybenzenes, dicarboxylic acids, and dibasic inorꢀ
ganic acids) are determined by the mutual arrangement
of the OH groups in dibasic acid HO—Y—OH. Polyꢀ
meric or cyclic oligomeric molecular structures of the
general formula (—R3Sb—OYO—)n are most commonly
occurring. The trigonalꢀbipyramidal fragments are linked
to each other, apparently, through the axial Sb—O
bonds.1,3,4
However, in the case of αꢀglycols and pyrocatechol,
the OH groups in dibasic OHꢀacids are located in close
proximity, which prevents both O ligands from occupyꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 965—971, June, 2002.
1066ꢀ5285/02/5106ꢀ1051 $27.00 © 2002 Plenum Publishing Corporation

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Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
Dodonov et al.
ing axial positions. As a result, both these ligands are
located in the equatorial plane and the configuration of
the Sb atom changes from a trigonal bipyramid to an
octahedron. The vacant axial position is occupied by a
molecule of the solvent or an electronꢀdonating addiꢀ
tive. These compounds exist as monomers.5
Triorganoantimony derivatives with βꢀdiketones in
which the Sb atom has a distorted octahedral configuraꢀ
tion and the ligand is bidentate or even tridentate have
attracted the particular attention.6
As part of continuing studies in this field, it was of
interest to study the structures of triphenylantimony deꢀ
rivatives with oximes of monoꢀ and dicarbonyl comꢀ
pounds serving as monoꢀ and bidentate Oꢀligands of
pentaꢀ and hexacoordinated antimony.
tertꢀbutyl hydroperoxide taken in a molar ratio of 1 : 2 : 1,
respectively,9 according to the following scheme
R3Sb + 2 HON=CR´R″ + ButOOH →
→ R3Sb(ON=CR´R″)2 + ButOH + H2O.
R = Ph, Me; R´, R″ = H, Alk, Ph
(3)
Bis(acetone oximato)triphenylantimony (1), bis(benzꢀ
aldoximato)triphenylantimony (2), bis(cyclohexanone
oximato)triphenylantimony (3), bis(acetophenone oxiꢀ
mato)triphenylantimony (4), and bis(acetone oximato)triꢀ
methylantimony (5) were prepared based on oximes of
monocarbonyl compounds, viz., acetone, benzaldehyde,
acetophenone, and cyclohexanone, respectively. Prodꢀ
ucts 1—5 were obtained in 87—96% yields (Table 1).
These compounds were isolated as colorless crystalꢀ
line compounds stable to atmospheric air and moisture.
All compounds are readily soluble in chloroform and
ether. Oximates 1 and 3 are also soluble in alcohols and
aromatic hydrocarbons. Oximate 5 is soluble in all usual
solvents. The molecular weights, which were determined
by the cryoscopic method in benzene, and the results of
analysis for the metal content, are in good agreement
with the calculated values (see Table 1).
Results and Discussion
Triorganoantimony(V) oximates are synthesized by
the reactions of sodium salts of oximes with triorganoꢀ
antimony(V) dihalides (reaction (1)), which are preꢀ
liminarily prepared by halogenation of triorganoantiꢀ
mony(III).7
R3SbX2 + 2 NaON=CR´R″ →
The structures of the compounds were studied by IR
spectroscopy, 1H and 13C NMR spectroscopy, and Xꢀray
diffraction analysis.
→ R3Sb(ON=CR´R″)2 + 2 NaX.
(1)
R = Me, Et, Ph; X = Cl, Br;
The IR spectra of oximates 1—4 have a Sb—Ph
stretching absorption band at 450—430 cm–1. The IR
spectrum of compound 5 shows a Sb—Me stretching
R´, R″ = Me, Et, Pr, Ph, cycloꢀC6H10
Previously, the following threeꢀstep scheme of the
synthesis through intermediate antimony alkoxides has
been employed:1
absorption band at 580 cm–1 10
In the spectra of all
.
oximates 1—5, the C=N stretching absorption bands are
observed in the region of 1615—1570 cm–1, i.e., they are
shifted to the lowꢀfrequency region by 40—50 cm–1 as
compared to the corresponding bands for free oximes.7
In the region of 3400—3000 cm–1, broad absorption bands
of the OH groups of free oximes are lacking.
The 1H NMR spectrum of oximate 4 has a singlet
(δ 2.36) of the Me group (Table 2). Consequently, the
acetophenone oximate ligands exist only in one of the
two possible (Z or E) forms. The spectrum of acetone
oximate 1 shows two singlets for the protons of the Me
R3Sb → R3SbCl2 → R3Sb(OR)2
→ R3Sb(ON=CR´R″)2.
→
(2)
We synthesized these compounds with the use of a
oneꢀstep oxidative procedure, which allows one to preꢀ
pare different functional antimony(V) derivatives in high
yields at room temperature starting directly from triꢀ
organoantimony.8 The reactions of Ph3Sb with aldehyde
and ketone oximes were carried out in the presence of
Table 1. Characteristics of triorganoantimony oximates R3Sb(ON=CR´R″)2 (1—5)
Compound
R
R´
R″
Yield
(%)
M.p.*
/°С
Found/Calculated
Sb (%)
М
1
2
3
4
5
Ph
Ph
Ph
Ph
Me
Me
H
Me
Ph
87
98
89
92
96
115 (88—90)1
188
24.3/24.5
20.6/20.5
21.3/21.1
19.7/19.6
39.6/39.2
492/497
471/469
574/577
627/621
308/311
(CH2)5
121
157
40 (40)7
Me
Me
Ph
Me
* The literature data are given in parentheses.

Structures of triorganoantimony(V) oximates
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
1053
1
Table 2. H and 13C NMR spectra of triorganoantimony oximates 1—5 (27 °C)*
Compound
δ
1Н
13С
C=N
H—C=
Me—C=N
Me—Sb
cycloꢀC6H10
C—Sb
C—(C=N)
1
2
3
4
5
7.10—8.20
7.15—8.20
7.15—8.20
7.10—8.22
—
1.52, 1.90
—
—
2.36
1.77, 1.82
—
—
—
—
1.58
—
—
—
—
—
—
5.11
—
—
—
—
154.20
—
—
—
—
1.25—2.70
—
—
21.85, 14.70
* The spectra of compounds 1—4 were recorded on a Tesla BSꢀ567 A spectrometer. The spectrum of compound 5 was
measured on a Bruker CXPꢀ200 spectrometer.
groups with equal intensities, which is indicative of the
nonequivalence of the Me groups at the C=N bond.
This is confirmed by the fact that the integral intensity
ratio of the signals for the protons of two methyl and three
phenyl groups is 6 : 15. An analogous nonequivalence of
the Me groups, though less pronounced, is observed in
the spectrum of oximate 5. The nonequivalence of the
alkyl groups in free oximes and their metal derivatives
has been noted previously, the splitting of the NMR
signals being dependent on the composition of the comꢀ
pound and the conditions of the measurements of the
NMR spectra.7 In the region δ 7.10—8.22, the signals for
the protons of all phenyl groups bound to the Sb atom or
involved in the oximate ligands are observed.
The 13C NMR spectrum of trimethylantimony acꢀ
etone oximate 5 confirmed the nonequivalence of
the Me groups of the acetone oximate fragment (see
Table 2).
According to the results of Xꢀray diffraction analysis,
the pentacoordinated Sb atom in molecules 1 and 2
C(10)
C(9)
C(8)
C(11)
C(12)
C(17)
C(18)
C(7)
C(24)
O(2)
C(16)
C(22)
C(13)
Sb(1)
C(15)
N(2)
C(14)
C(19)
C(23)
O(1)
C(2)
C(1)
C(21)
N(1)
C(20)
C(3)
C(6)
C(5)
C(4)
Fig. 1. Molecular structure of 1.

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Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
Dodonov et al.
C(4)
C(3)
C(5)
C(14A)
C(13A)
C(12A)
C(15A)
C(16A)
C(2)
C(6)
C(11A)
C(1)
C(17A)
N(1A)
Sb(1)
O(1A)
C(1A)
C(6A)
C(2A)
C(7)
O(1)
C(3A)
C(8)
C(9)
C(5A)
C(4A)
N(1)
C(8A)
C(11)
C(9A)
C(10)
C(12)
C(13)
C(17)
C(16)
C(14)
C(15)
Fig. 2. Molecular structure of 2.
(Figs. 1 and 2) has a distorted trigonalꢀbipyramidal coꢀ
ordination with three Ph groups in the equatorial posiꢀ
tions and two monodentate iminoxy groups in the axial
positions. In the crystal structures, molecules 1 are loꢀ
cated in general positions, whereas molecules 2 have
the symmetry C2 and are located on twofold axes
passing through the Sb(1) and C(7) atoms. The axial
O(1)—Sb(1)—O(2) (176.0(2)°) and O(1)—Sb(1)—O(1A)
(176.5(1)°) angles are close to 180°. In both compounds
(1 and 2), the sum of the equatorial C(Ph)—Sb—C(Ph)
angles is 360°. The Sb—C(Ph) distances in molecules 1
and 2 are in the ranges of 2.113(6)—2.120(6) and
2.106(3)—2.108(4) Å, respectively (Tables 3 and 4).
The benzene rings are noncoplanar. The Sb—O(1)
and Sb—O(2) distances in molecule 1 (2.044(4) and
2.050(4) Å, respectively) are somewhat smaller than the
corresponding distances in molecule 2 (2.065(2) Å) and
are substantially smaller than those in furfurol oximate
(2.150(3) Å)11 and, particularly, in tetraphenylantimony
cyane oximates (2.226(4)—2.259(1) Å)12 studied previꢀ
ously. Apparently, this is associated with a more covaꢀ
lent character of the bond between the iminoxy group
and the metal atom in oximates 1 and 2 and, on the
contrary, with a more ionic character of tetraphenylꢀ
antimony oximates.11,12
Table 3. Selected bond lengths (d) and bond angles (ω) in
molecule 1
Bond
d/Å
Angle
ω/deg
Sb(1)—O(1)
Sb(1)—O(2)
Sb(1)—C(7)
Sb(1)—C(13)
Sb(1)—C(1)
O(1)—N(1)
O(2)—N(2)
N(1)—C(19)
N(2)—C(22)
2.044(4)
2.050(4)
2.113(6)
2.119(7)
2.120(6)
1.410(7)
1.418(6)
1.269(9)
1.249(8)
O(1)—Sb(1)—O(2)
O(1)—Sb(1)—C(7)
O(2)—Sb(1)—C(7)
O(1)—Sb(1)—C(13)
O(2)—Sb(1)—C(13)
176.0(2)
91.3(2)
87.8(2)
84.8(2)
92.2(2)
C(7)—Sb(1)—C(13) 117.5(2)
O(1)—Sb(1)—C(1)
O(2)—Sb(1)—C(1)
C(7)—Sb(1)—C(1)
93.4(2)
90.5(2)
120.8(2)
C(19)—C(21) 1.497(12)
C(19)—C(20) 1.504(11)
C(22)—C(23) 1.493(9)
C(22)—C(24) 1.500(10)
C(13)—Sb(1)—C(1) 121.7(2)
N(1)—O(1)—Sb(1)
N(2)—O(2)—Sb(1)
113.1(4)
106.8(3)
C(19)—N(1)—O(1) 111.5(6)
C(22)—N(2)—O(2) 113.6(5)

Structures of triorganoantimony(V) oximates
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
1055
Table 4. Selected bond lengths (d) and bond angles (ω) in
molecule 2
The IR spectrum of compound 6 has absorption bands
at 1550 and 470 cm–1 assigned to the stretching vibraꢀ
tions of the C=N and Sb—Ph groups, respectively,
whereas the absorption band of the free OH group is not
observed.
Based on the results obtained, we assume that, unlike
the wellꢀknown transition metal dimethylglyoximates,
triphenylantimony dimethylglyoximate has a polymeric
structure. The cobalt(II) and nickel(II) complexes with
dimethylglyoxime are brightly colored mononuclear cheꢀ
lates in which both ligands are bound to one transition
metal atom through four N atoms.13 In addition, the
metal atom in cobalt(II) and nickel(II) complexes with
1,2ꢀdiphenylethaneꢀ1,2ꢀdione dioxime can be coordiꢀ
nated by one ligand through one N atom and one
O atom.14
In our opinion, the preparation of the iminoxy deꢀ
rivative of triphenylantimony with diacetyl (butaneꢀ2,3ꢀ
dione) monoxime was of particular interest. In this case,
unlike the aboveꢀconsidered triphenylantimony derivaꢀ
tives with oximes of monocarbonyl compounds 1—5,
one would expect the formation of a hexacoordinated
antimony derivative via chelation of the ligand to the
central metal atom or the formation of a heptacoordinated
antimony compound of the R3SbX2 type.
The synthesis was carried out by the reaction of
diacetyl monoxime with Ph3Sb in the presence of
ButOOH taken in a molar ratio of 1 : 1 : 1 in a 1 : 2
hexane—isopropyl alcohol mixture. A colorless compound
thus obtained is readily soluble in ether, chloroform, and
aromatic hydrocarbons. This compound melted with deꢀ
composition in an open tube at 146—161 °C (depending
on the rate of heating). The molecular weight (cryosꢀ
copy, benzene) is 954. The data obtained are indicative
of the formation of bis(iminoxytriphenylantimony) oxꢀ
ide in 86% yield according to reactions (6) and (7).
Bond
d/Å
Angle
ω/deg
Sb(1)—O(1)
Sb(1)—C(1)
Sb(1)—C(7)
O(1)—N(1)
N(1)—C(11)
2.065(2)
2.106(3)
2.108(4)
1.399(3)
1.259(4)
O(1)—Sb(1)—O(1A) 176.46(11)
O(1)—Sb(1)—C(1)
O(1A)—Sb(1)—C(1)
86.30(9)
91.87(9)
C(1)—Sb(1)—C(1A) 117.97(13)
O(1)—Sb(1)—C(7)
C(1)—Sb(1)—C(7)
N(1)—O(1)—Sb(1)
C(11)—N(1)—O(1)
91.77(5)
121.02(7)
110.9(2)
112.2(2)
C(11)—C(12) 1.460(4)
In molecule 1, the dimethyliminoxy groups
O(1)N(1)C(19)C(20)C(21) and O(2)N(2)C(22)C(23)C(24)
are planar (the average deviations of the atoms from the
planes are 0.02 and 0.007 Å, respectively) and the diꢀ
hedral angle between their mean planes is 63.5°. The
phenyliminoxy groups in molecule 2 are also planar (to
within 0.026 Å) and the dihedral angle between the
mean planes of these groups is 70.1°.
The O—N distances in molecules 1 and 2 have close
values (1.410(7) and 1.418(6) Å in 1 and 1.399(3) Å in 2).
Like the O—N distances, the C—N distances in molecules
1 and 2 vary within a narrow range of 1.249(8)—1.269(9) Å.
The Sb(1)—O(1)—N(1) (Sb(1)—O(2)—N(2)) and
O(1)—N(1)—C(19) (O(2)—N(2)—C(22)) angles in
molecule 1 are 113.1(4)° (106.8(3)°) and 111.5(6)°
(113.6(5)°), respectively, and are close to the correspondꢀ
ing angles in molecule 2 (Sb(1)—O(1)—N(1), 110.9(2)°;
O(1)—N(1)—C(11), 112.2(2)°).
We believe that monomeric antimony derivatives with
oximes of other monocarbonyl compounds also have
trigonalꢀbipyramidal structures.
In line with the goal to be sought, we synthesized the
SbV derivative with dimethylglyoxime. In the reactions
with equimolar amounts of Ph3Sb and ButOOH at room
temperature, dimethylglyoxime acts as a dibasic OHꢀ
acid to form triphenylantimony dimethylglyoximate (6)
in 96% yield (reaction (4)).
Ph3Sb + ButOOH + HX → ButOH + Ph3Sb(OH)X
(6)
HX = Me—C(NOH)—C(O)—Me
2 Ph3Sb(OH)X → (Ph3SbX)2O + H2O
(7)
n Ph3Sb + n ButOOH + n HON=C(Me)C(Me)=NOH →
→ [—Ph3SbON=C(Me)C(Me)=NO—]n
+
The calculated molecular weight is 922. Under the
action of concentrated HCl, Ph3SbCl2 was obtained in
ca. 100% yield with respect to the starting (Ph3SbX)2O.
According to the literature data, triphenylantimony(V)
monohydroxides Ph3Sb(OH)X, which contain not only
the OH group but also halide,1 carboxylate, βꢀdiꢀ
ketonate,10 or other groups, are unstable and readily unꢀ
dergo intermolecular dehydration to form the bridging
Sb—O—Sb bond.
6
+ n ButOH + n H2O.
(4)
Compound 6 is a colorless noncrystalline solid comꢀ
pound, which is insoluble in organic solvents and deꢀ
composes without melting at 230—240 °C. Under the
action of concentrated HCl, compound 6 underwent
acidolysis to eliminate Ph3SbCl2 in ca. 100% yield:
The IR spectrum of the resulting compound has an
absorption band at 440 cm–1 (ν(Sb—Ph)). The absorpꢀ
tion band at 1660 cm–1 belongs to vibrations of the carꢀ
bonyl group, which is involved in conjugation with the
[—Ph3SbON=C(Me)C(Me)=NO—]n + 2n HCl →
6
→ n Ph3SbCl2 + n HON=C(Me)C(Me)=NOH.
(5)

1056
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
Dodonov et al.
C=N group and coordinated to the Sb atom. Its freꢀ
quency is close to the corresponding value (1680 cm–1
)
for individual diacetyl monoxime in which conjugation
occurs. The absorption band of the free OH group is not
observed in the spectrum.
The 1H NMR spectrum shows six singlets of the
Meꢀgroups (δ 1.62—1.97) along with a multiplet for the
protons of the Ph groups (δ 7.2—8.1). The ratio between
the overall integral intensities of the signals for the proꢀ
tons of the Ph and Me groups is 15 : 6, which counts in
favor of the proposed general formula (Ph3SbX)2O. The
aboveꢀmentioned six signals of the Me groups can be
easily divided into three pairs (δ 1.62 and 1.71; 1.75 and
1.97; 1.79 and 1.95). The integral intensities of the sigꢀ
nals within each pair are equal, whereas the intensities
for the pairs differ from each other. Hence, it can be
concluded that there are three types of binding of the
ketoximate ligands MeC(NO)—C(O)Me to the Ph3Sb
groups. Each type includes one Me group bound to the
stronger electronꢀwithdrawing carbonyl C=O fragment
and one Me group bound to the weaker electronꢀwithꢀ
drawing azomethine fragment C=N.
The 13C NMR spectrum of this compound shows
three signals for the nonequivalent azomethine C atoms
(δ 156.2, 157.0, and 157.7), three signals for the nonꢀ
equivalent carbonyl C atoms (δ 199.6, 199.7, and 199.8),
and a group of signals for the nonequivalent methyl C
atoms (δ 8.07, 8.40, 24.48, 24.67, and 24.77).
antimony) oxide ketoximates. One would expect that a
twofold increase in the amount of the starting diacetyl
oxime in the course of the synthesis will give rise to
triphenylantimony bis(oximate) of the Ph3SbX2 type.
However, contrary to the expectations, we isolated the
same bis(triphenylantimony) oxide (Ph3SbX)2O. This fact
supports the conclusion that this structure is more favorꢀ
able. Previously, we have demonstrated6,10 that the oxiꢀ
dative oneꢀstep synthesis of βꢀdiketonate derivatives of
triphenylꢀ and trialkylantimony always yielded antiꢀ
mony(V) monodiketonates (independently of the amount
of the starting diketone).
Based on the molecular weights and the data from IR
and NMR spectroscopy, three types of bisꢀtriphenylꢀ
antimony oxide ketoximates (A—C) can be proposed.
First, the oximate ligand can close the sixꢀmembered
chelate ring at each Sb atom (A), as has been proved
previously6 for triorganoantimony βꢀdiketonates. Secꢀ
ond, the ligand can form bridging bonds between the Sb
atoms through both the O atoms of the iminoxy group
and the carbonyl group (B), which is accompanied by
the closure of the bicycle. Third, bridging bonds beꢀ
tween the Sb atoms can be formed with the participation
of the O atom and the N atom of the iminoxy group
without the involvement of the carbonyl group (C). Reꢀ
cently, the latter structural type has been found15 in
µꢀoxobis[(furfuraldoximato)triphenylantimony] studied
by Xꢀray diffraction analysis. For all these types of coorꢀ
dination, the intensities of the signals for the protons of
the Me substituent at the C=O group must be equal to
the intensities of the signals for the protons of the Me
substituent at the imine group. Actually, this situations is
Experimental
The IR spectra were recorded on a Specord IRꢀ75 specꢀ
trometer in Nujol mulls in the region of 4000—400 cm–1. The
1H and 13C NMR spectra were measured on Bruker CXPꢀ200
(200 MHz) and Tesla BSꢀ567 A (100 MHz) spectrometers
using HMDS as the internal standard and CDCl3 as the solvent.
Triphenylantimony,2 tertꢀbutyl hydroperoxide,16 benzaldeꢀ
hyde oxime, acetone oxime, acetophenone oxime,17 diacetyl
monoxime, and dimethylglyoxime18 were synthesized accordꢀ
ing to known procedures.
1
observed in the H NMR spectrum. At the moment, the
Bis(acetone oximato)triphenylantimony (1). A solution of
tertꢀbutyl hydroperoxide (2 mmol) in hexane (5 mL) was added
with continuous stirring to a solution of Ph3Sb (2 mmol) and
acetone oxime (4 mmol) in hexane (20 mL) during 20 min.
The mixture was kept at ∼20 °C for 2 h. The precipitate that
formed was separated, washed with hexane, and dried. Comꢀ
pound 1 was obtained in 86% yield. The physicochemical paꢀ
reliable assignment of all signals in the NMR spectra is
difficult to make. The calculated molecular weight for
the complexes A—C (922) is close to the experimental
value (954).
Probably, the aboveꢀconsidered oxidative procedure
afforded a mixture of chelate cyclic bis(triphenylꢀ

Structures of triorganoantimony(V) oximates
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
1057
rameters and the NMR spectroscopic data for compound 1 are
given in Tables 1 and 2, respectively.
2. I. E. Pokrovskaya, V. A. Dodonov, Z. A. Starikova, E. N.
Kanunnikova, T. M. Shchegoleva, and G. P. Lebedev,
Zh. Obshch. Khim., 1981, 51, 1247 [J. Gen. Chem. USSR,
1981, 51 (Engl. Transl.)].
3. V. A. Dodonov, A. Yu. Fedorov, R. I. Usyatinskii, S. N.
Zaburdyaeva, and A. V. Gushchin, Izv. Akad. Nauk, Ser.
Khim., 1995, 748 [Russ. Chem. Bull., 1995, 44, 730 (Engl.
Transl.)].
4. S. N. Zaburdyaeva, L. S. Korchemnaya, A. Yu. Fedorov,
and V. A. Dodonov, Zh. Obshch. Khim., 1999, 69, 86 [Russ.
J. Gen. Chem., 1999, 69 (Engl. Transl.)].
5. V. A. Dodonov, A. Yu. Fedorov, G. K. Fukin, S. N.
Zaburdyaeva, L. N. Zakharov, and A. V. Ignatenko, Main
Group Chemistry, 1999, 3, 15.
Triphenylantimony derivatives with aldehyde and ketone
oximes 2—4 were prepared analogously in a benzene solution.
The derivatives with dimethylglyoxime and diacetyl monoxime
were prepared in a 1 : 2 mixture of hexane and isopropyl alcohol.
Bis(acetone oximato)trimethylantimony (5). tertꢀButylhydroꢀ
peroxide (2 mmol) and acetone oxime (4 mmol) were placed in
a tube and dissolved in hexane (20 mL). Then calcined Na2SO4
was added. The resulting mixture was degassed and Me3Sb
(2 mmol) was recondensed into this tube under reduced presꢀ
sure. Then the mixture was kept at ∼20 °C for 2 h and the liquid
components were distilled off after which the residue slowly
crystallized. Compound 5 was obtained in 96% yield.
Xꢀray structure study of the crystals of the compounds
Ph3Sb(ONCMe2)2 (1) and Ph3Sb(ONCHPh)2 (2) was carried
out on a fourꢀcircle Siemens P3/PC diffratometer (graphite
monochromator, MoꢀKα radiation, θ/2θ scanning technique).
The crystals of 1 and 2 are monoclinic and tetragonal, respecꢀ
tively, at 20 °C a = 9.332(2) and 16.731(5) Å, b = 16.008(3)
and 16.731(5) Å, c = 15.743(3) and 19.867(6) Å, β = 99.78(2)°,
V = 2318(1) and 5562(3) Å3, space groups P21/n (Z = 4) and
I41/a (Z = 8), dcalc = 1.425 and 1.417 g cm–3 for compounds 1
and 2, respectively. The structures of complexes 1 and 2 were
solved by direct methods and refined by the fullꢀmatrix leastꢀ
squares method with anisotropic thermal parameters for all
nonhydrogen atoms. The positions of the H atoms of the Ph
groups in molecule 1 and all H atoms in molecule 2 were
revealed from difference electron density syntheses and refined
with isotropic thermal parameters. The positions of the H atꢀ
oms of the Me groups in molecule 1 were calculated from
geometric considerations (C—H 0.96 Å) and refined using the
riding model. The final R factors for complexes 1 and 2 were
R = 0.056 and 0.032, Rw = 0.107 and 0.073, S = 1.04 and 1.06
based on 4091 and 3160 reflections with I > 2σ(I ), respecꢀ
tively. All calculations were carried out with the use of the
SHELXꢀ97 program packages.19 The selected bond lengths and
bond angles in molecules 1 and 2 are given in Tables 3 and 4,
respectively. The atomic coordinates were deposited with the
Cambridge Structural Database.
6. A. V. Gushchin, R. I. Usyatinsky, G. K. Fukin, V. A.
Dodonov, and L. N. Zakharov, Main Group Chemistry,
1998, 2, 187.
7. V. K. Jain, R. Bohra, and R. C. Mehrotra, Inorg. Chim.
Acta, 1981, 51, 191.
8. V. A. Dodonov and A. V. Gushchin, Izv. Akad. Nauk, Ser.
Khim., 1993, 2043 [Russ. Chem. Bull., 1993, 42, 1955 (Engl.
Transl.)].
9. V. A. Dodonov, D. A. Gor´kaev, G. K. Fukin, A. V.
Gushchin, and T. I. Starostina, Abstrs. SchoolꢀConference
for Young Scientists, (Moscow, September 6—11, 1999), "Orꢀ
ganometallic Chemistry Towards the 21st Century," Moscow,
1999, RY101.
10. A. V. Gushchin, R. I. Usyatinskii, and V. A. Dodonov, Izv.
Akad. Nauk, Ser. Khim., 1995, 154 [Russ. Chem. Bull., 1995,
44, 149 (Engl. Transl.)].
11. V. V. Sharutin, O. K. Sharutina, O. V. Molokova, S. I.
Rokhmanenko, T. G. Troinina, D. B. Krivolapov, A. T.
Gubaidullin, and I. A. Litvinov, Zh. Obshch. Khim., 2000,
70, 1990 [Russ. J. Gen. Chem., 2000, 70 (Engl. Transl.)].
12. K. V. Domasevitch, N. N. Gerasimchuk, and A. Mokhir,
Inorg. Chem., 2000, 39, 1227.
13. E. V. Alekseevskii, R. K. Gol´ts, and A. P. Musakin,
Kolichestvennyi analiz [Quantitative Analysis], Goskhimizdat,
Leningrad, 1955, 135 pp. (in Russian).
14. S. V. Singh, S. Gupta, A. C. Ojha, and M. K. Rastogi, Ind.
J. Chem., Sec. A, 1991, 30, 545.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 00ꢀ15ꢀ97439)
in collaboration with the Center of Xꢀray Diffraction
Studies of the Division of the General and Technical
Chemistry of the Russian Academy of Sciences, by the
Program "Russian Universities" (Project No. 992839),
and by the Federal Target Program "Integration" (Project
No. A 0047).
15. O. K. Sharutina, Dr. Sci. (Chem.) Thesis, Blagoveshchensk
State Pedagogical University, Irkutsk, 2001, 50 pp. (in
Russian).
16. V. Karnojitzki, Les Peroxides Organiques, Hermann, Paris,
1959, 152 pp.
17. WeygandꢀHilgetag, OrganischenꢀChemischen Experimentierꢀ
kunst, Johann Ambrosius Barth Verlag, Leipzig, 1964,
800 pp.
18. Organic Syntheses, Collective Volume 2, Blatt, New
York, 1946.
19. W. Robinson and G. M. Sheldrick, in Crystallographic Comꢀ
puting Techniques and New Technologies, Eds. N. W. Isaacs
and M. R. Taylor, Oxford Univ. Press, Oxford (England),
1988, 366 pp.
References
1. K. A. Kocheshkov, A. P. Skoldinov, and N. N. Zemlyanskii,
Metody elementoorganicheskoi khimii. Sur´ma, vismut [Methꢀ
ods of Heteroorganic Chemistry. Antimony and Bismuth],
Nauka, Moscow, 1976, 483 pp. (in Russian).
Received July 19, 2001;
in revised form February 26, 2002