Reaction of sulfur chlorides with metal β-diketonates

Article abstract of DOI:10.1007/s11176-005-0227-9

Metal β-diketonates react with sulfur dichloride to form sulfenyl chlorides irrespective of β-substituent. Bulky phenyl and tert-butyl groups do not prevent formation of fully substituted complexes. The possibility of preparing sulfenyl chloride derivatives of rhodium, ruthenium, and vanadium β-diketonates was demonstrated. A new procedure was suggested for preparing chlorosulfenyl-substituted β-diketonates. Disulfur dichloride reacts with metal chelates with the substitution of both chlorine atoms and formation of polynuclear complexes in which the diketonate groups are linked by disulfide bridges. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11176-005-0227-9

Russian Journal of General Chemistry, Vol. 75, No. 3, 2005, pp. 335 341. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005,
pp. 367 374.
Original Russian Text Copyright
2005 by Svistunova, Shapkin, Nikolaeva.
Reaction of Sulfur Chlorides with Metal -Diketonates
I. V. Svistunova, N. P. Shapkin, and O. V. Nikolaeva
Far-Eastern State University, Vladivostok, Russia
Received August 1, 2003
Abstract Metal -diketonates react with sulfur dichloride to form sulfenyl chlorides irrespective of
-substituent. Bulky phenyl and tert-butyl groups do not prevent formation of fully substituted complexes. The
possibility of preparing sulfenyl chloride derivatives of rhodium, ruthenium, and vanadium -diketonates was
demonstrated. A new procedure was suggested for preparing chlorosulfenyl-substituted -diketonates. Di-
sulfur dichloride reacts with metal chelates with the substitution of both chlorine atoms and formation of
polynuclear complexes in which the diketonate groups are linked by disulfide bridges.
It was shown previously that sulfur dichloride
reacts with metal acetylacetonates with the substitu-
tion of one chlorine atom and formation of sulfenyl
chloride derivatives [1]:
Our goal was to apply reaction (1) to complexes of
other -diketones and to extend the range of metals
whose complexes can be brought into this reaction.
We obtained the SCl derivatives of the following
metal chelates:
O
O
O
O
H + nSCl2
SCl
+ nHCl, (1)
M
M
R1
SCl
R1
n
n
O
O
O
O
I IV
H + 3SCl2
+ 3HCl,
M
M
M = Cr (I), Co (II), Al (III), n = 3; M = Be (IV), n = 2.
3
3
(2)
R2
V XV
R2
Sulfur dichloride was added to a suspension of
acetylacetonate in pentane. The reactant ratio chelate :
SCl2 : pentane (g/ml/ml) was 1 : 1 : 10, which corre-
sponded to a 1.8-fold excess of SCl2. After stirring for
10 min, the product was filtered off.
M = Cr, R1 = R2 = Ph (V); M = Co, R1 = R2 = Ph (VI);
M = Al, R1 = R2 = Ph (VII); M = Cr, R1 = CH3, R2 = Ph
(VIII); M = Cr, R1 = t-Bu, R2 = CH3 (IX); M = Cr, R1 =
CH3, R2 = H (X); M = Co, R1 = CH3, R2 = H (XI); M =
The procedure is simple and convenient. However,
it is applicable to only a limited range of metal com-
plexes, namely, to those exhibiting high kinetic stabil-
ity. Iron(III) and copper(II) acetylacetonates decom-
pose under the conditions of reaction (1). Among
compounds I IV, the chromium complex I is the most
stable. It can be stored for an unlimited time and can
be purified by recrystallization. The cobalt (II) and
aluminum (III) chelates decompose during storage or
recrystallization.
Cr, R1 = R2 = H (XII); M = Rh, R1 = CH3, R2 = CH3
(XIII); M = Ru, R1 = CH3, R2 = CH3 (XIV); M = V, R1 =
CH3, R2 = CH3 (XV).
-Phenyl substituents drastically decrease the reac-
tivity of the chelate ring. In the reaction of chromium
dibenzoylmethanate [Cr(dbmH)3] with sulfur dichlo-
ride under the conditions described in [1], the conver-
sion of the starting chelate was incomplete (TLC
monitoring). The decreased reactivity of dibenzoyl-
methanates in halogenation and nitration was reported
previously [7, 8].
Collman et al. [2] prepared an SCl-substituted ace-
tylacetonate by reaction (1) starting from dichloro-
substituted chromium acetylacetonate.
The high reactivity of the SCl group was used to
prepare chromium and cobalt acetylacetonates con-
taining at the central carbon atom the thiophosphate
[1, 3], thioamide [3], vinylthio [4], or chloroethylthio
[5] group, and also siloxane polymers containing
metal chelate groups [6].
The fully substituted complex was obtained at in-
creased concentration of SCl2. The optimal reactant
ratio (g/ml/ml) is Cr(dbmH)3 : SCl2 : hexane = 1 : 2 :
5, which corresponds to a 7.5-fold excess of SCl2.
The optimal reaction time is 15 min. Further, even
1070-3632/05/7503-0335 2005 Pleiades Publishing, Inc.

336
SVISTUNOVA et al.
slight, increase in the SCl2 concentration results in
decomposition of Cr(dbmH)3.
Since the reaction in solution yields a purer product
(according to elemental analysis), it is preferable to
perform the synthesis of VIII in solution.
The fully substituted complex can also be obtained
at a lower SCl2 concentration, but the reaction time
in this case should be as long as several hours. In this
case, side decomposition reactions become more pro-
nounced, decreasing the yield and quality of the
product.
Complex VIII is quite stable (it does not decom-
pose noticeably during storage for several days), but,
in contrast to the related acetylacetonate and dibenzo-
ylmethanate derivatives, its attempted recrystallization
failed. Therefore, the crude product was purified by
precipitation from a benzene solution with hexane.
Compound V is quite stable, and it can be readily
recrystallized. As shown by the analysis for S, Cl, and
C, this is a trisubstituted complex. The IR spectrum
The IR spectrum of VIII in the range 1600
1
1500 cm contains a strong band of chelated C=O
1
1
of this compound in the range 1600 1500 cm con-
(1530 cm ) and a weak band originating from vibra-
1
1
tains a strong band at 1508 cm assignable to the
tions of phenyl groups (1581 cm ). The spectrum of
chelating C=O groups [9] and two weak bands at
1597 and 1582 cm , apparently belonging to phenyl
the unsubstituted complex in this range contains two
strong bands at 1553 and 1515 cm (C=O chelate,
1
1
groups. The spectrum of Cr(dbmH)3 in the same range
C=C) and two medium-intensity bands at 1588 and
1
1
contains two strong bands at 1533 and 1524 cm
1487 cm .
(C=O chelate, C=C) and a medium-intensity band at
The possibility of the substitution in complexes
containing tert-butyl groups was checked with chro-
mium pivaloylacetonate [Cr(pvacH)3] as example.
Treatment of a solution of Cr(pvacH)3 in hexane with
a small excess of SCl2 gave complex IX in almost
quantitative yield. Cr(pvacH)3 is readily soluble in
hexane; therefore, it is impossible to perform the reac-
tion in a suspension. For analysis we took the crude
complex, because its solubility in all inert organic
solvents is too high to perform recrystallization.
1
1591 cm . It is believed that the presence of a single
band of chelated C=O is characteristic of complexes
substituted at the central C atom [9].
Attempts to prepare Co(dbmSCl)3 and Al(dbmSCl)3
under the conditions described above failed. Cobalt
and aluminum dibenzoylmethanates decomposed
under the action of a large excess of SCl2.
When the reaction is performed in solution, large
excess of SCl2 becomes unnecessary. The reactions
of Cr(acacH)3 and Cr(dbmH)3 with a small excess of
SCl2 yielded fully substituted complexes similar to
those prepared under heterogeneous conditions.
The heaviest ion observed in the mass spectrum of
IX is the molecular ion. Its isotopic pattern corre-
sponds to the presence of three chlorine atoms.
The reaction is performed at a low temperature
(0 10 C) in chloroform or THF. THF is preferable,
because the product in this case, according to elemen-
tal analysis, does not require additional purification.
From chloroform, the product is isolated as a crystal
solvate decomposing upon recrystallization.
Kluiber [1] noted that the formation of sulfenyl
chlorides, and not sulfides, in reaction (1) was unex-
pected. This feature was due to the steric effect of
-methyl groups preventing the SCl group of the sul-
fenyl chloride to react with the molecule of unsubsti-
tuted acetylacetonate. Therefore, it was of particular
interest to study the reaction of SCl2 with chelates
containing no -substituents. As substrates for such a
reaction we chose chromium and cobalt formylaceto-
nates [Cr(fracH)3, X; Co(fracH)3, XI] and chromium
malondialdehydate Cr(mdaH)3 (XII).
SCl-Substituted cobalt (VI) and aluminum (VII)
dibenzoylmethanates were prepared by the reaction in
solution. The IR spectra of these compounds are simi-
lar to that of (V). The elemental analysis of the cobalt
complex is reasonably consistent. However, the com-
pound obtained from the Al complex shows strong
deviations in the content of elements, apparently be-
cause the Al complex is less stable and decomposes to
a greater extent.
In the reaction with SCl2, Cr(fracH)3 and Co(fracH)3
behave similarly to acetylacetonates. The reaction
products were obtained by the traditional procedure
[1] in high yields. The results of analysis for S, Cl,
and C are consistent with the composition of the SCl-
substituted chelates.
Cr(bzacSCl)3 (VIII) can be prepared in hexane at
the reactant ratio used in [1] [chelate : SCl2 : hexane =
1 : 1 : 10 (g/ml/ml)], which corresponds to a 2.8-fold
excess of SCl2. The yield of the product obtained by
this procedure is 70 80%. When the reaction is per-
formed in THF, the yield of VIII reaches 94 97%.
Complex XI is similar to Co(acacSCl)3 in proper-
ties. It decomposes upon recrystallization or storage
for 1 2 days, losing the solubility in organic solvents
(benzene, chloroform). Complex X is less stable than
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005

REACTION OF SULFUR CHLORIDES WITH METAL -DIKETONATES
337
its acetylacetonate analog. It decomposes upon recrys-
tallization or storage for several weeks.
Ruthenium complex XIV was prepared under sim-
ilar conditions.
An unexpected result was obtained with the com-
plex containing no substituents at the -carbon atoms.
On adding SCl2 to a suspension of Cr(mdaH)3 in
hexane, the crystals of the chelate changed the color
from violet to beige, characteristic of I and X, but the
IR spectrum of the reaction product was identical to
that of the starting malondialdehydate. A TLC exami-
nation also revealed only the starting complex. Due to
difficult availability of Cr(mdaH)3, we did not study
the influence of the reaction time and SCl2 concentra-
tion on the course of the substitution.
Compounds XIII and XIV are similar to the Cr
complex in the stability. Their analytical data are reas-
onably consistent with the formulas of the trisubsti-
tuted chelates. The IR spectra are typical of substi-
tuted acetylacetonates. They contain a single band in
1
the range 1600 1500 cm (instead of two bands in
the spectra of unsubstituted complexes), assignable to
vibrations of the chelated C=O group [9]; weak bands
1
of C H bending vibrations at 1200 and 800 cm [9]
disappear. The mass spectra of these compounds con-
tain molecular peaks; their isotopic pattern corre-
sponds to the presence of three Cl atoms.
When performed in solution, the reaction yielded
a complex whose IR spectrum in the range 1600
1
V(acacSCl)3 was prepared by the traditional proce-
dure [1]. Complex XV decomposes within a day. It
was characterized by the IR spectrum, typical of a
substituted acetylacetonate, and by elemental analysis.
The content of C and Cl is approximately consistent
with the formula of the trisubstituted chelate. The
observed deviations are due to partial oxidation of the
product and impossibility of its purification.
1500 cm contained a single absorption band, charac-
teristic of substituted metal chelates. The elemental
analysis was approximately consistent with the formu-
la of the trisubstituted complex. Apparently, the reac-
tion yielded Cr(mdaSCl)3 contaminated with decom-
positions tion products. We failed to obtain the pure
complex, as it decomposed during attempted recrystal-
lization.
Thus, SCl2 reacts with metal chelates containing
one or no -substituents similarly to the reaction with
acetylacetonates. Hence, the shielding effect of -sub-
stituents is not responsible for the fact that only one
SCl group is involved in the reaction. The presence of
phenyl or tert-butyl substituents does not prevent the
reaction of the metal chelates with SCl2. The SCl
derivatives of acetylacetonates and formylacetonates
are better prepared in suspension, whereas with the
benzoylacetonate, dibenzoylmethanate, pivaloylaceto-
nate, and malondialdehydate derivatives the synthesis
in solution is preferable. Chlorosulfenyl derivatives
of diketonates containing no -substituents show de-
creased stability, which complicates their isolation and
identification.
Gallium and vanadyl acetylacetonates decompose
under the action of SCl2 and the released HCl.
A mass-spectrometric study of I IX, XIII, and XIV
revealed the presence of molecular peaks in the spec-
tra of SCl-substituted chromium, aluminum, berylli-
um, rhodium, and ruthenium acetylacetonates and in
the spectrum of Cr(pvacSCl)3. The spectra of the
other complexes contain no heavy ions and are of no
interest. Apparently, compounds II and V VIII cannot
be heated without decomposition to a temperature
required for vaporization in the ionization chamber.
Cobalt complex II decomposes even on slight heating;
phenyl-substituted complexes V VIII are insufficient-
ly volatile.
To extend the range of metals whose complexes
can be converted into SCl derivatives, we studied the
reaction of SCl2 with Rh(III), Ru(III), Ga(III), V(III),
and vanadyl(IV) acetylacetonates. The reactions were
performed under the conditions described in [1]. We
obtained previously unknown chlorosulfenyl deriva-
tives of Rh(III) (XIII), Ru(III) (XIV), and V(III) (XV)
acetylacetonates.
In the series of SCl-substituted acetylacetonates,
the molecular peaks decrease in intensity with an in-
crease in the molecular weight of the complexes. The
most common fragmentation pathway is successive
removal of atoms of one of substituents and then of
the ligand as a whole (dik = acac or pvac) (Table 1).
[M(dikSCl)3] +
[M(dikSCl)2(acacS)]+
[M(dikSCl)3] +
[M(dikSCl)2(acacS)]+,
[M(dikSCl)2(acac)]+, (4)
[M(dikSCl)2]. (5)
(3)
Taking into account the decreased reactivity of
Rh(acacH)3 in electrophilic substitutions [2], to pre-
pare Rh(acacSCl)3 we took the reactants in the follow-
ing ratio (g/ml/ml): chelate : SCl2 : hexane = 1 : 2 :
10, corresponding to a fourfold excess of SCl2. Since
Rh(acacH)3 is more stable than Cr(III) and Co(III)
acetylacetonates [2], increased concentration of SCl2
does not cause decomposition of the complex.
The ligand removal is the major fragmentation
pathway for the aluminum and beryllium complexes.
Further fragmentation depends on the metal ion.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005

338
SVISTUNOVA et al.
Table 1. Relative intensity of peaks (%) in the mass spectra of I, III, IV, IX, XIII, and XIV
Ion
I
III
IV
IX
XIII
XIV
[M(dikSCl)3]+
34
14
3
19
20
30
11
5
18
9
12
27
39
8
2
4
10
7
6
[M(dikSCl)2(dikS)]+
[M(dikSCl)2(dik)]+
[M(dikSCl)2Cl]+
[M(dikSCl)2]+
100
35
60
27
3
[M(dikSCl)(dikS)]+
[M(dikSCl)(dik)]+
[M(dikSCl)(OC(CH3)C=S)Cl]+
[M(dikSCl)(OC(CH3)C=S)]+
[M(dikSCl)(dik)(Cl)]+
[M(dikSCl)(dik)]+
29
16
55
75
41
13
5
8
41
32
12
6
[M(dikSCl)(Cl)]+
[M(dikSCl)]+
6
55
32
3
The fragmentation of chromium complexes I and IX
can be described by Eq. (6):
only several peaks. Identification of the other peaks
was prevented by their large number, low intensity,
and complex isotopic patterns (ruthenium has six
major isotopes).
[Cr(dikSCl)2]+
[Cr(dikSCl)(OC(CH3)=C=S)]+, (6)
RC(O)Cl
1
We have measured the H NMR spectra of com-
R = CH3, t-Bu.
plexes III, IV, and XIII (Table 2). In all these cases,
the methyl groups give two separate signals of equal
intensity, which suggests their nonequivalence. To
account for this fact, we can assume the bent structure
of the SCl group with its arrangement in the chelate
ring plane and braked rotation around the C S bond.
In this case, the methyl groups differ in the distance
from the chlorine atom.
It is interesting that, in the case of IX, from which
two ions with different substituents can form accord-
ing to Eq. (6), only the ion formed by the loss of
pivaloyl chloride is formed.
The ruthenium compound showed the most com-
plex fragmentation pattern. We were able to identify
1
We failed to obtain the H NMR spectrum of II.
Table 2. Spectral characteristics of chlorosulfenyl deriva-
tives of metal -diketonates I VI, VIII XI, XIII, and XIV
All the samples of this compound contained an im-
purity of paramagnetic Co compounds whose forma-
tion was caused by impurities formed in the synthesis
of sulfenyl chloride.
1H NMR
spectrum,
, ppm
Comp.
no.
Absorption spectrum,
, nm (log )
Compound
The electronic absorption spectra of I XIV show
that the SCl group appreciably alters the spectra of all
the metal chelates. Instead of a set of separate bands
I
II
Cr(acacSCl)3
Co(acacSCl)3
292(4.19), 550(2.11)
291(4.50), 576(2.31)
of d
and
transitions, all the spectra contain
4
3
4
III
IV
V
Al(acacSCl)3 2.66, 2.70 284(4.31)
Be(acacSCl)2 2.66, 2.70
a single broad band exceeding in the intensity the
bands of the unsubstituted complex (Table 2). This
result is unusual, since the spectra of the other thio-
substituted complexes {Cr(acacSC2H4Cl)3, Cr[acac
SPO(OEt)2]3, Cr(acacSCN)3 [10]} are similar to the
spectrum of the unsubstituted complex.
Cr(dbmSCl)3
Co(dbmSCl)3
291(4.70), 559(2.29)
VI
277(4.77), 590(2.60)
271(4.55), 552(2.21)
298(4.37), 538(2.10)
276(4.30), 552(1.86)
278(4.33), 580(2.06)
VIII Cr(bzacSCl)3
IX
X
XI
Cr(pvacSCl)3
Cr(fracSCl)3
Co(fracSCl)3
It appeared impossible to make an empirical as-
signment of the band observed in the spectra of the
SCl-substituted complexes, since it does no coincide
in the position and shape with any of the bands of the
unsubstituted complex.
XIII Rh(acacSCl)3 2.76, 2.82 292(4.56)
XIV Ru(acacSCl)3 265(4.32), 345( ),
535(3.43)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005

REACTION OF SULFUR CHLORIDES WITH METAL -DIKETONATES
339
Our next goal was to study for comparison the
reaction of the metal chelates with the closest analog
of SCl2, S2Cl2.
by TLC and IR spectroscopy. Thus, sulfuryl chloride
reacts with unsubstituted chelates and can be used as
a chlorinating agent.
Treatment of a suspension of Cr(acacH)3 in hexane
with S2Cl2 under the conditions described in [1]
resulted in the formation of a sticky rubbery mass
blocking the stirrer even before adding the whole vol-
ume of S2Cl2. The reaction product was not studied
in detail.
Treatment of XVI with a large excess of SO2Cl2
yielded a single product, which showed chromato-
graphic mobility and hence was not a chlorosulfenyl
derivative. Apparently, the reaction stops at the step
of formation of the fully chlorinated dimer [Cr(acac
Cl)2(acacS )]2. The -methyl groups probably limit
the penetration of sulfuryl chloride molecules to the
disulfide group and thus prevent its cleavage.
The reaction of S2Cl2 with excess Cr(acacH)3
yielded several products that could be chromato-
graphed, which indicates that these products contained
no SCl groups. Along with the unchanged acetylace-
tonate, we isolated from the reaction mixture a prod-
uct giving in the mass spectrum the peak at m/z 760
as the heaviest ion. This peak corresponds to a com-
pound in which two acetylacetonate fragments are
linked with a disulfide bridge: (Hacac)2Cr(acacS
Sacac)Cr(acacH)2. The presence of strong peaks of
[(Hacac)2Cr(acacS)]+ and [(Hacac)2Cr(acac)]+ (rela-
tive intensity 100% each) confirms this formula. The
IR spectrum of this compound in the range 1700
EXPERIMENTAL
1
The IR spectra in the range 4000 400 cm were
recorded on an Impact-400 spectrometer (KBr pellets).
The UV spectra were taken on Hitachi-220A and
Specord µ-40 spectrometers in chloroform in 1-cm
3
cells (solution concentration 10 M for the visible
5
range and 10 M for the UV range). The mass spec-
tra were taken on an LKB-9000 device at an ionizing
1
voltage of 70 eV. The H NMR spectra were recorded
1
1600 cm shows a superposition of two bands corre-
on a Bruker WH-250 spectrometer (250 MHz, CDCl3)
relative to TMS. The TLC analysis was performed
with Sorbfil PTSKh-P-V plates, with benzene or
benzene acetone (10 : 1) as eluent. The analytical data
for the compounds obtained are given in Table 3.
sponding to the vibrations of four unsubstituted rings
and a band of two substituted rings. Thus, the reaction
of S2Cl2 with Cr(acacH)3 involves both SCl groups,
in accordance with Eq. (7):
Preparation of tris(2-chlorosulfenyl-1,3-diphe-
Cr(acacH)3 + S2Cl2
nyl-1,3-propanedionato)chromium(III)
V
in
a
(Hacac)2Cr(acacS Sacac)Cr(acacH)2.
(7)
suspension. A 2-ml portion of SCl2 was added drop-
wise to a stirred suspension of 12 ml of finely ground
chromium dibenzoylmethanate in 5 ml of hexane.
After stirring for 15 min, the precipitate was filtered
off, washed with hexane, vacuum-dried, and recrystal-
lized from benzene hexane. Yield 0.81 g (63%);
brown crystalline substance, mp 160 163 C.
XVI
The other spots in the chromatogram apparently
belong to oligomers consisting of three, four, or more
metal chelate fragments.
With the aim to prepare the monochlorosulfenyl
derivative, we treated compound XVI with 1 equiv of
SO2Cl2.
Preparation of tris(2-chlorosulfenyl-1,3-diphe-
nyl-1,3-propanedionato)chromium(III) V in solu-
tion. A solution of 1.9 ml of SCl2 in 5 ml of THF was
added dropwise at 10 C to a stirred solution of 3.6 g
of chromium dibenzoylmethanate in 100 ml of THF.
After stirring for 40 min, the solvent was distilled off
in a vacuum at room temperature. The residue was
recrystallized from benzene hexane. Yield 3.25 g
(70%); brown crystalline substance, mp 162 164 C.
The reaction yielded three chromatographically
mobile products. No compounds with zero chromato-
graphic mobility were obtained. Since chlorosulfenyl
derivatives of all the diketonates studied show zero
mobility on silica gel (probably because of the reac-
tion of SCl groups with silanol groups), we can con-
clude that the chlorosulfenyl derivative was not ob-
tained. The IR spectra of the three complexes formed
by the reaction are indicative of successive substitu-
tion of the chelate rings with chlorine atoms.
Tris(2-chlorosulfenyl-1,3-diphenyl-1,3-propane-
dionato)cobalt(III) VI was prepared similarly from
2 g of cobalt dibenzoylmethanate, 50 ml of THF, and
1.0 ml of SCl2. The residue after distilling off the
solvent was washed with hexane. Yield 98%. The
product was analyzed without additional purification.
Sulfuryl chloride was not used previously as a
chlorinating agent for metal diketonates. To check this
possibility, we treated Cr(acacH)3 with sulfuryl chlo-
ride. We obtained Cr(acacCl)3, which was identified
Tris(2-chlorosulfenyl-1,3-diphenyl-1,3-propane-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005

340
SVISTUNOVA et al.
Table 3. Analytical data for V XVI
Found, %
Comp. no.
Calculated, %
Cl
Formula
C
Cl
S
C
S
Va
58.47
58.50
58.04
61.27
50.31
48.74
40.60
28.20
28.44
24.85
31.71
30.71
31.16
11.50
11.60
11.06
10.45
14.01
14.83
15.52
21.12
20.30
23.45
17.23
17.80
10.31
10.97
10.37
8.82
12.35
13.42
C45H30Cl3CrO6S3
C45H30Cl3CrO6S3
C45H30Cl3CoO6S3
C45H30AlCl3O6S3
C30H24Cl3CrO6S3
C30H24Cl3CrO6S3
C24H36Cl3CrO6S3
C12H12Cl3CrO6S3
C12H12Cl3CoO6S3
C9H6Cl3CrO6S3
58.67
58.67
58.23
60.31
49.02
49.02
42.70
28.44
28.06
23.26
30.04
30.13
32.89
47.36
11.54
11.54
11.46
11.87
14.47
14.47
15.75
20.99
20.70
22.89
17.73
17.79
19.42
10.44
10.44
10.36
10.73
13.09
13.09
14.25
18.98
18.72
20.70
16.04
16.09
17.56
8.43
Vb
VI
VII
VIIIa
VIIIb
IX
X
XI
XII
XIII
XIV
XVc
XVId
19.31
19.12
21.49
16.74
16.23
C15H18Cl3O6RhS3
C15H18Cl3O6RuS3
C15H18Cl3O6S3V
C30H40Cr2O12S2
8.80
a
b
c
d
For the complex prepared in hexane.
For the complex prepared in solution.
V(acacSCl) .
[Cr(acacH) (acacS)] .
2 2
3
dionato)aluminum VII was prepared similarly from
2 g of aluminum dibenzoylmethanate, 50 ml of THF,
and 1.1 ml of SCl2. The residue after removing the
solvent was washed with hexane. Yield 93%. The
product was analyzed without additional purification.
um-dried. Yield 0.73 g (90%); beige powder. The
product was analyzed without additional purification.
Tris(2-chlorosulfenyl-1,3-butanedionato)co-
balt(III) XI was prepared similarly. Yield 74%. The
product was analyzed without additional purification.
Preparation of tris(2-chlorosulfenyl-1-phenyl-
1,3-butanedionato)chromium(III) VIII in suspen-
sion. A 1.0-ml portion of SCl2 was added dropwise
to a stirred suspension of 1 g of finely ground chro-
mium benzoylacetonate in 10 ml of hexane. After stir-
ring for 15 min, the precipitate was filtered off,
washed with hexane, and vacuum-dried. Yield 0.96 g
(70%); brown powder. For analysis, the sample was
reprecipitated from benzene with hexane.
Tris(2-chlorosulfenyl-1,3-propanedionato)chro-
mium(III) XII was prepared similarly to Cr(dbmSCl)3.
Yield 63%. The product was analyzed without addi-
tional purification.
Tris(2-chlorosulfenyl-2,4-pentanedionato)rhodi-
um(III) XIII. A 1-ml portion of SCl2 was added drop-
wise to a stirred suspension of 0.5 g of Rh(acacH)3
in 5 ml of hexane. After stirring for 10 min, the pre-
cipitate was filtered off, washed with hexane, and
dried in air. Yield 0.69 g (92%); yellow powder. The
product was recrystallized from benzene hexane;
decomposition point 120 130 C.
Preparation of tris(2-chlorosulfenyl-1-phenyl-
1,3-butanedionato)chromium(III) VIII in solution
was performed similarly to Cr(dbmSCl)3. The product
was analyzed without additional purification; mp
130 135 C (dec.).
Tris(2-chlorosulfenyl-2,4-pentanedionato)ruthe-
nium(III) XIV was prepared similarly. Yield 89%.
The product was analyzed without additional purifica-
tion.
Tris(3-chlorosulfenyl-5,5-dimethyl-2,4-hexane-
dionato)chromium(III) IX was prepared similarly to
Cr(dbmSCl)3 from 0.5 g of Cr(pvacH)3, 30 ml of
hexane, and 0.4 ml of SCl2. Yield 0.65 g (92%);
brown resinous substance. The product was analyzed
without additional purification.
Tris(2-chlorosulfenyl-2,4-pentanedionato)vana-
dium(III) XV was prepared similarly from 0.5 g of
V(acacH)3, 5 ml of hexane, and 0.5 ml of SCl2. Yield
80%. The product was analyzed without additional
purification.
Tris(2-chlorosulfenyl-1,3-butanedionato)chromi-
um(III) X. A 0.5-ml portion of SCl2 was added drop-
wise to a stirred suspension of 0.5 g of Cr(fracH)3 in
5 ml of hexane. After stirring for 10 min, the precipi-
tate was filtered off, washed with hexane, and vacu-
[3,3 -Dithiobis(2,4-pentanedionato)]tetrakis(2,4-
pentanedionato)dichromium(III) XVI. A solution of
0.4 ml of S2Cl2 in 10 ml of chloroform was added
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005

REACTION OF SULFUR CHLORIDES WITH METAL -DIKETONATES
341
with stirring to a solution of 3.5 g of Cr(acacH)3 in
50 ml of chloroform. After 5 min, 2 ml of triethyl-
amine was added. The solvent was removed in a vac-
uum at room temperature. The reaction products were
isolated chromatographically on silica gel, eluent
benzene acetone (stepwise elution, from 400 : 1 to
400 : 10). We recovered 0.5 g (14%) of unchanged
Cr(acacH)3, mp 209 212 C (published data: mp
214 C [11]) and isolated 2.4 g of violet crystalline
complex XVI (yield 63%) after recrystallization from
benzene heptane.
4. Svistunov, G.M., Shapkin, N.P., Razov, V.I., and
Glushchenko, V.Yu., Zh. Obshch. Khim., 1990,
vol. 60, no. 6, p. 1359.
5. Svistunov, G.M., Reutov, V.A., and Shapkin, N.P.,
Zh. Obshch. Khim., 1988, vol. 58, no. 5, pp. 1178
1179.
6. Shapkin, N.P., Svistunov, G.M., and Shapkina, V.Ya.,
Vysokomol. Soedin., Ser. A, 1989, vol. 31, no. 3,
p. 573.
7. Singh, P.R. and Sahai, R., Indian J. Chem., 1969,
vol. 7, no. 5, p. 628.
8. Singh, P.R. and Sahai, R., Aust. J. Chem., 1969,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005