Reactions of P4S10 and pyPS2Cl with N,N′-diphenylurea and N,N′-diphenylthiourea

Article abstract of DOI:10.1016/j.poly.2007.05.032

The reaction of P₄S₁₀ (1) with N,N′-diphenylurea (PhNH)₂CO (2) results in new heterocyclic compounds: the pyridinium salt of 1,3-diphenyl-2-sulfido-2-thioxo-1,3-diaza-2λ⁵-phosphetidine (3) (with a P-N-C-N cycle) and the pyridinium salt of 1,4-diphenyl-2,5-disulfido-2,5-dithioxo-1,4-dithiadiaza-2λ⁵,5λ⁵-diphosphinane (4), containing the (P-S-N)₂ cycle and the cyclic thiophosphates [pyH]₂[P₂S₈] (5), [pyH]₂[P₂S₇] (6) and [pyH]₃[P₃S₉] (7). A similar reaction, but carried out with N,N′-diphenylthiourea (PhNH)₂CS (8), leads to the formation of 4 and 6. pyPS₂Cl (9), used as an alternative starting material, also yields compounds 3, 4, 5, and further [pyH][PS₂Cl₂] (10) and S₈ after reaction with 2. Compound 3 reacts with Pd(CH₃COO)₂, with the formation of the complex [Pd(Ph₂N₂COPS₂)₂] (11). The crystal structures of 3 and 7 were determined by single-crystal X-ray diffraction.

Full text of DOI:10.1016/j.poly.2007.05.032

Polyhedron 26 (2007) 4250–4256
www.elsevier.com/locate/poly
Reactions of P4S10 and pyPS2Cl with N,N0-diphenylurea
and N,N0-diphenylthiourea
a,b
a
a
a
´
´ˇ
´
Lenka Dastychova , Marie Sotolarova , Dalibor Dastych , Jan Taraba ,
a
a,
*
´ ˇ´
Marek Necˇas , Jirˇı Prıhoda
a
Department of Chemistry, Faculty of Science, Masaryk University, Kotla´rˇska´ 2, CZ-61137 Brno, Czech Republic
Department of Physical Electronics, Faculty of Science, Masaryk University, Kotla´rˇska´ 2, CZ-61137 Brno, Czech Republic
b
Received 12 March 2007; accepted 12 May 2007
Available online 5 June 2007
Abstract
The reaction of P4S10 (1) with N,N0-diphenylurea (PhNH)2CO (2) results in new heterocyclic compounds: the pyridinium salt of
1,3-diphenyl-2-sulfido-2-thioxo-1,3-diaza-2k5-phosphetidine (3) (with a P–N–C–N cycle) and the pyridinium salt of 1,4-diphenyl-2,5-
disulfido-2,5-dithioxo-1,4-dithiadiaza-2k5,5k5-diphosphinane (4), containing the (P–S–N)2 cycle and the cyclic thiophosphates
[pyH]2[P2S8] (5), [pyH]2[P2S7] (6) and [pyH]3[P3S9] (7). A similar reaction, but carried out with N,N0-diphenylthiourea (PhNH)2CS
(8), leads to the formation of 4 and 6. pyPS2Cl (9), used as an alternative starting material, also yields compounds 3, 4, 5, and further
[pyH][PS2Cl2] (10) and S8 after reaction with 2. Compound 3 reacts with Pd(CH3COO)2, with the formation of the complex
[Pd(Ph2N2COPS2)2] (11). The crystal structures of 3 and 7 were determined by single-crystal X-ray diffraction.
ꢀ 2007 Elsevier Ltd. All rights reserved.
Keywords: Chlorodithiophosphoric acid pyridiniumbetaine; Phosphorus pentasulfide; Diazaphosphetidine; Diazadiphosphinane; Cyclic thiophosphates;
Palladium(II) complex
1. Introduction
between 9 and H2S [4]. The formation of the [PS2] unit is
also assumed in many reactions of 9 with nucleophilic
reagents [5–14,31]. Thus these units and elemental sulfur
can participate in the formation of various compounds
containing the exocyclic PS2 group.
Phosphorus pentasulfide, P4S10 (1) is a very important
starting material for the syntheses of many linear phospho-
rus and sulfur containing compounds, but has been used
less extensively for the preparation of cyclic compounds
containing the exocyclic PS2 group [1,2], as compared with
pyPS2Cl (9). Commercially available P4S10 usually contains
lower phosphorus sulfides, P4S9, P2S5, P2S4, that can also
arise upon prolonged storage or thermal decomposition
of this compound [3], and the reactive units [PS2] [3],
[PS3] and elemental sulfur can also be found among the
decomposition products. The existence of the anion
py[PS3]ꢀ has been described as a product of the reaction
Many heterocyclic compounds containing the exocyclic
PS2 group were prepared by reactions of 9 with various
mono- [15], di- [14] and polyfunctional nucleophiles
[5–9,11,13], e.g., thiosemicarbazide [5,6] and urea [7,8]
derivatives. Reactions of 9 with monosubstituted thiosem-
icarbazide compounds of the type RNHC(S)NHNH2
(R = Me, Et) [5], carried out in the presence of pyridine,
led to the formation of five-membered P–N–C–N–N het-
erocycles, whereas the reaction with disubstituted
t
RNHC(S)N (Me) NH2 (R = iPr, Bu) yields different reac-
tion products, depending on the reaction conditions [6]. In
the presence of triethylamine, the triethylammonium salt of
1,3-diaza-2k5,4k5-diphosphetidine with a four-membered
*
Corresponding author. Tel.: +420 549 496 690; fax: +420 549 492 443.
´
E-mail address: prihoda@chemi.muni.cz (J. Prˇıhoda).
0277-5387/$ - see front matter ꢀ 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2007.05.032

L. Dastychova´ et al. / Polyhedron 26 (2007) 4250–4256
4251
Scheme 1.
P–N–P–N cycle was formed, whereas the pyridinium salt of
1,3,4-triaza-2k5-phospholane with a five-membered P–N–
N–C–S cycle was prepared in the absence of a HCl
acceptor.
reaction. The composition of the reaction mixture was fol-
lowed by 31P NMR spectroscopy. The integral rates of all
resonance signals presented in the 31P NMR spectrum are
shown in Table 1. Compound 13, containing unexpectedly
an oxygen atom in the molecule, is probably the product of
partial hydrolysis of sulfur containing precursors. Yellow
needle crystals were also formed at the same time and they
were assigned to the previously undescribed compound 7.
The reaction of 9 with urea leads to the formation of
the cyclic ammonium salt of 4,6-dioxo-2-sulfido-2-thioxo-
1,3,5-triaza-2k5-phosphinane [7]. The reaction of 9 with
N,N0-diphenylthiourea, (PhNH)2CS (8), yields, in the
presence of triethylamine and depending on the reaction
temperature, two different heterocyclic compounds con-
taining P–N–C–N and P–N–P–N cycles [8] (see Scheme 1).
The reaction of pyPS2Cl (9) with (PhNH)2CO (2), as
well as reactions of phosphorus pentasulfide (1) with 2
and 8 had not been studied as yet. Therefore they became
the subject of our investigation in this work.
2.2. Reaction of P4S10 (1) with N,N0-diphenylthiourea (8)
This reaction was carried out in a similar way to that
described above. Yellow crystals were formed after
15 min heating. The resonance signals, which were found
in the 31P NMR spectrum of the reaction mixture, are men-
tioned in Table 1. After cooling the reaction mixture, the
solvent was partially evaporated in vacuum at ambient
temperature, the solid was filtered off and rinsed with ace-
tonitrile. The 31P NMR spectrum of this solid, dissolved in
acetonitrile, proved that the solution contained only com-
pound 4.
2. Results and discussion
2.1. Reaction of P4S10 (1) with N,N0-diphenylurea (2)
The course of the reactions between 1 and nucleophilic
reagents has commonly the character of nucleophilic reduc-
tion in which, depending on the reaction conditions, a wide
variety of compounds arise [11,12].
2.3. Reaction of pyPS2Cl (9) with N,N0-diphenylurea (2)
The reaction of 1 with 2 was carried out in acetonitrile
and in the presence of pyridine in the molar ratio 1:4:4.
A number of reaction products arose in the course of the
The reaction between 9 and 2 (1:1) was carried out in
acetonitrile solution in the presence of pyridine as a HCl
acceptor. At first, the reaction mixture was refluxed for
Table 1
Identified 31P NMR signals in the studied reaction mixtures
Compound
d (ppm)
Reaction partners
P4S10 + (PhNH)2CO
Reflux (2 h) (%)
P4S10 + (PhNH)2CS
Reflux (20 min) (%)
pyPS2Cl + (PhNH)2CO
Reflux (1.5 h) (%)
After standing 3 months (20 ꢁC) (%)
3
88.1
109.1
120.3
130.4
84.0
89
4
7
83
1
1
9
4
1
4
94
4
5 [16]
6 [16]
10 [18]
12 [17]
13 [16]
7
25
87.4
32.1
1
7
2

4252
L. Dastychova´ et al. / Polyhedron 26 (2007) 4250–4256
1.5 h. Greenish crystals precipitated in the course of the
reaction and the 31P NMR chemical shift (88.1 ppm) corre-
sponds to compound 3. The composition of the remaining
reaction mixture is given in Table 1.
Further standing of the filtrate led to the crystallization
of another brown solid. Its resonance signal at 120.3 ppm
was found in the 31P NMR spectrum, and corresponds to
the resonance of compound 5. The final solid, which was
isolated from the filtrate after several weeks of standing,
was elemental sulfur, as identified by MS spectrometry.
the melting point of 3, and the second one at 184 ꢁC
belongs to the beginning of the thermal decomposition,
accompanied by a continuous mass loss. In the region
310–400 ꢁC, a few undistinguished minima were observed,
which can be ascribed to gradual decomposition of the
compound. At 424 ꢁC, the weight loss reached 72.9%,
which corresponds to the formation of POSN2 (theoretical
weight loss 72.2%). At 632 ꢁC further weight loss of up to
88.0% of the starting mass of the sample was observed.
This stage of decomposition corresponds to the expected
end-product of the composition PN (theoretical weight loss
88.3%). X-ray diffraction analysis of 3 confirmed that this
substance is the pyridinium salt of 1,3-diphenyl-2-sulfido-
2-thioxo-1,3-diaza-2k5-phosphetidine.
2.4. Identification and properties of the prepared compounds
2.4.1. Identification of 3
Two independent spin systems in the regions d = 7.8–
8.5 ppm and d = 8.7–9.6 ppm, and not linked together by
cross peaks, were identified in the 2D 1H–1H COSY
NMR spectrum of 3 (Fig. 1). These regions are sufficiently
apart from each other to enable their resolution without
difficulties. The integral rate of the first spin system is
approximately twice the integral rate of the second one,
2.4.2. Identification of 4
The formation of compound 4 was detected in all the
studied reaction systems (1 with 2 or 8; 9 with 2). The res-
onance signal of 4 was found at d = 109.1 ppm (s). This
chemical shift is characteristic for phosphorus (V) com-
pounds containing the PS2 group. The substance 4 was also
1
1
which is in agreement with integral values in the 1D H
studied by H NMR spectroscopy. Resonance signals in
NMR spectrum. From this and from comparison with
the 1H NMR spectra of 9 and 2 it follows that the molecule
of 3 contains one aromatic group coming from 9 (pyridine)
[19] and two aromatic phenyl groups coming from 2 [20].
The molecular peak at m/z = 306 in the MS spectrum of
3 corresponds to the mass of the anionic part (exact mass
304.997219). The thermal behavior of 3 was followed by
thermal analysis. There are two minima on the DTA curve.
The first endothermic minimum at 174 ꢁC corresponds to
the aromatic region (d = 7.18–7.59 ppm) belong to a phe-
nyl group, and signals in the region 7.99–8.68 ppm are
characteristic of the pyridinium cation [19]. Another reso-
1
nance signal at d = 8.47 ppm in the H NMR spectrum
can be assigned to the acid hydrogen bonded to pyridine.
MS spectrometry of 4 identified the molecular peak at
m/z = 436. This mass corresponds to a compound of the
composition C12H10N2P2S6 (exact mass 435.864356).
Therefore it was concluded that substance 4 is the pyridi-
Fig. 1. 2D 1H–1H COSY NMR spectrum of compound 3.

L. Dastychova´ et al. / Polyhedron 26 (2007) 4250–4256
4253
nium salt of 1,4-diphenyl-2,5-disulfido-2,5-dithioxo-1,4-
dithiadiaza-2k5, 5k5-diphosphinane. Its possible formation
is shown in the following equations:
2.4.4. The formation of [pyH][PS2Cl2] (10)
The formation of pyridinium dichlorodithiophosphate,
[pyH][PS2Cl2] (10) in the reaction between 2 and 9, can
be explained as proceeding via two routes. The first one
is that HCl, evolved in the first step of the substitution
reaction between 2 and 9, reacts with compound 9 with
the formation of [pyH][PS2Cl2] (10) [18]. The second route
is based on the assumed reaction between the heterocyclic
compound 3 and evolved HCl. This mechanism was proved
by carrying out the direct reaction of 3 with HCl, and
(PhNH)2CO (2) was found in the reaction mixture. The
ð1Þ
1
presence of both compounds was confirmed by H NMR
(2) [20] and 31P NMR (10) spectroscopy.
2 pyPS2Cl þ 2 ðPhNHÞ2CO þ1=4 S8 ! ð4Þ
ð9Þ
ð2Þ
þ 2 PhNCO þ 2 Hþ þ 2 Clꢀ
ð2Þ
ð3Þ
2.4.5. The formation of cyclic thiophosphates 5, 6 and 7
Cyclic phoshpates have been known for a long time. A
mixture of the anions [P2S8]2ꢀ (present in 5) and [P3S9]3ꢀ
(in 7) is formed as a result of disproportionation [P2S7]2ꢀ
(in 6) [16]. The anion [P3S9]3ꢀ is known as [NH4]3[P3S9]
[24] and was obtained in the reaction of P4S10 and P4S9
in liquid ammonia below ꢀ33 ꢁC. It was also prepared,
together with [P2S7]2ꢀ and [P2S8]2ꢀ, as the triethylammo-
nium salts in the reaction mixture of triethylamine, white
phosphorus and sulfur [16]. We also prepared [pyH]3[P3S9]
(7) in the reaction of 9 with benzamide in a yield 67% (with
respect to 1). The anion of compound 5 was identified (as a
salt with the cation [py2H]+) amongst the products of the
reaction of 1 and pyridine [25], and also in the reaction
mixture of 9 with 4-iso-propylthiosemicarbazide [10].
The formation of bis(pyridinium)-bis(l-disulfido)-tetra-
thio-cyclo-diphosphate, [pyH]2[P2S8] (5), bis(pyridinium)-
l-disulfido-pentathio-cyclo-diphosphate, [pyH]2[P2S7] (6)
and tris(pyridinium)-nonathio-cyclo-triphosphate, [pyH]3
[P3S9] (7) can be explained in our reaction systems on the basis
of the formation of [PS2] and [PS3] units and S8 (Scheme 2).
2 ½pyHꢁ½PS2Cl2ꢁ þ 2 ðPhNHÞ2CO þ1=4 S8 ! ð4Þ
ð10Þ
ð2Þ
þ 2 PhNCO þ 4 Hþ þ 4 Clꢀ
2.4.3. The complex properties of 3
The presence of two sulfur atoms in the PS2 group of 3
indicates that this substance can have an affinity to metal
ions such as Ni [21], Pd [22] and Pt [23]. Therefore we
allowed compound 3 to react with Pd(CH3COO)2 with
the aim of preparing the Pd complex (11). The reaction
was carried out in acetonitrile, with the starting com-
pounds in a molar ratio of 2:1. Immediately, a brown pre-
cipitate appeared. Mass spectrometry gave a molecular
peak at m/z 717, which corresponds to the mass of the
expected compound C26H20N4O2P2PdS4 (exact mass
715.897915).
2.4.6. Crystal structures of 3 and 7
Crystals of compound 3 are monoclinic and were grown
from acetonitrile solution. The molecular structure (Fig. 2)
has certain common features. The structure is formed by a
Compound 11 is sparingly soluble in common solvents
such as CH3CN, CH2Cl2 or pyridine, and is insoluble in
CH3OH. It is poorly soluble in dimethylformamide, in
which it decomposes within a few hours.
The thermal behavior of 11 was followed by thermal
analysis. The compound did not melt and only slow
decomposition was observed with increasing temperature.
The first endothermic effect occurs on DTA curve at
140.9 ꢁC and corresponds to the beginning of the decompo-
sition of 11. The sample was further heated up to 1000 ꢁC.
The weight loss was 82.0% at the temperature 999 ꢁC,
which corresponds to the formation of PdO (theoretical
weight loss 82.9%).
Scheme 2.

4254
L. Dastychova´ et al. / Polyhedron 26 (2007) 4250–4256
Table 2
four-membered approximately planar heterocycle contain-
ing P–N–C–N atoms. Each of the two N-phenyl ring planes
is tilted with respect to the plane of the P–N–C–N hetero-
cycle [6.83(5)ꢁ or 3.34(6)ꢁ]. The plane formed by the S–P–S
bonds is oriented almost perpendicularly (88.94(6)ꢁ) to the
plane of the heterocycle. The values of these angles are in
agreement with the expected sp3 hybridization of the P-
atom. The p-electron density of the proposed P@S bond
is delocalized over the exocyclic PS2 group, which was con-
Selected crystallographic data of compounds 3 and 7
Compound
3
7
Chemical formula
Formula weight
Crystal size (mm)
T (K)
Crystal system
Space group
Unit cell dimensions
C18H16N3OPS2
385.43
0.20 · 0.20 · 0.30
120
monoclinic
P2(1)/c
C20H24ClN4P3S9
737.33
0.30 · 0.30 · 0.25
120
orthorhombic
Pcca
˚
˚
a (A)
13.634(3)
10.205(2)
13.323(3)
95.22(3)
1846.0(6)
4
1.387
0.71069
0.386
17.897(3)
10.399(2)
16.919(5)
90
3148.8(13)
4
1.555
0.71069
0.892
firmed by the almost equal P–S bond lengths (1.94–1.96 A).
˚
b (A)
These values are comparable to those in similar substances,
[pyH][PS2(NPh)2CS] and [pyH][PS2NPh]2 [8]. Compound 3
can be considered as an almost ionic substance. In fact, the
pyridinium cation is bonded to the S atoms of the PS2
group (H3Aꢂ ꢂ ꢂS1 and H3Aꢂ ꢂ ꢂS2) through a van der Waals
interaction; the distances between the atoms are 2.671(5)
˚
c (A)
b (ꢁ)
Volume (A )
3
˚
Z
qcalc (g cmꢀ3
)
˚
k (A)
l (mmꢀ1
R1
wR2
)
˚
and 2.580(4) A. This type of interaction can also be
0.0373
0.0937
0.0427
0.1220
observed in similar substances, such as [pyH][PS2(NPh)2
˚
˚
CS] (2.42(4) A) and [pyH][PS2NPh]2 (3,3145(3) A) [8].
Compound 3 does not contain any other relevant
H-bridges. A comparison of the corresponding bond
lengths with the literature data [8] shows that there is no
significant difference either in the four-membered ring, or
in the exocyclic bonds. Only isolated molecules of 3 can
be found in the crystal structure. Selected crystallographic
data are given in Table 2.
The structure and composition of solid 7 were deter-
mined by X-ray diffraction to be tris(pyridinium)-nona-
thio-cyclo-triphosphate, [pyH]3[P3S9], and the structure is
shown in Fig. 3. The molecular structure of the [P3S9]3ꢀ
anion was previously determined by Falius et al. Com-
pound [pyH]3[P3S9] was prepared in the reaction between
elemental phosphorus and alkylammonium polysulfides
[16]. The anion is packed together with triethylammonium
cations, and the P3S3 ring adopts a nearly perfect chair con-
formation. In our compound 7, the six-membered ring
takes on a skew-boat arrangement. The bond distances
and angles are comparable between [Et3NH]3[P3S9] and 7.
The intracyclic P–S bond lengths range within 2.122(1)
Fig. 3. The molecular structure of 7.
˚
and 2.147(1) A, while the terminal P@S bonds are shorter,
˚
reflecting their increased p-character [1.966(1)–1.986(1) A].
3. Experimental
3.1. Physical measurements
1H, 13C and 31P NMR spectra were recorded on 300 and
500 MHz Bruker DRX Avance NMR spectrometers.
Chemical shifts are given in ppm (d scale) relative to tetra-
1
methylsilane (for H and 13C nuclei), or 85% H3PO4 for
31P. All samples were measured at 303 K in dimethylsulfox-
ide or acetonitrile in a coaxial cuvette system (an inner
4 mm cuvette with the sample placed in a 5 mm cuvette
containing a small amount of D2O). Compound 7 (dis-
solved in D2O) was measured directly in the 5 mm cuvette.
13C NMR spectra were measured with 1H decoupling. The
Fig. 2. The molecular structure of 3.

L. Dastychova´ et al. / Polyhedron 26 (2007) 4250–4256
4255
1
2D H–1H COSY NMR spectrum was measured with two
3060 (m); d(Carom–H): 1283 (sh), 1265 (sh), 1195 (m),
1168 (w), 1103 (w), 1058 (vw), 1047 (vw), 1023 (w), 1003
(m), 987 (w), 893 (w); PS: 756 (vs), 739 (vs), 693 (vs), 674
(s), 646 (vs).
90ꢁ pulses.
Mass spectra were measured using a multifunctional
quadrupole spectrometer TRIO 1000 Series II, Finnigan
MAT, Fisons Instruments. The ionization energy was
70 eV. The sample was inserted into the spectrometer by
the Direct Insert Probe.
3.2.2. Synthesis of the pyridinium salt of 1,4-diphenyl-2,5-
disulfido-2,5-dithioxo-1,4-dithiadiaza-2k5,5k5-diphosphinane
[pyH]2[PS2(SNPh)]2 (4)
FT-IR spectra were measured in Nujol using an Equi-
nox 55/S/NIR FT-IR Bruker spectrometer. Vibration fre-
quencies were compared with the literature data [26,27].
Elemental analyses (C, H, N, S) were performed on a
Fisons Instruments EA-1108 elemental analyzer. Phospho-
rus was determined gravimetrically as chinolinium
molybdatophosphate.
A suspension of 1 (0.226 g, 0.51 mmol) and 0.458 g
(2.01 mmol) of 8 in 25 ml of acetonitrile and 0.33 ml pyri-
dine (4.1 mmol) was refluxed for 20 min. Yellow crystals
of compound 4 formed after 15 min heating. The solvent
was partially evaporated after cooling of the reaction mix-
ture. The crystals that formed were filtered off and rinsed
with acetonitrile. Compound 4 was obtained in 48% yield
(with respect to 1).
Anal. Calc. for C22H22N4P2S6: N, 9.39; P, 10.38; S,
32.24. Found: N, 10.44; P, 11.78; S, 32.03%. M.p. 169.8–
172.5 ꢁC. IR (Nujol): mCH(pyH+): 3121 (vw), 3085 (sh),
3051 (vw); m(pyH+): 1629 (w), 1606 (sh), 1595 (m), 1537
(sh), 1481 (s); 1530 (sh), 1496 (sh), 1328 (w); d(Carom–H):
1279 (m), 1261 (w), 1237 (w), 1195 (w), 1159 (w), 944
(sh), 937 (sh), 900 (m), 876 (m), 865 (sh); PS: 755 (w),
743 (sh), 740 (w), 696 (m), 670 (sh), 666 (sh), 661 (s), 606
(w), 540 (s).
Thermal analysis up to 1000 ꢁC was carried out using a
Derivatograph C, MOM, in a ceramic pot in static air
atmosphere. The heating rate was 5 K minꢀ1
.
Crystal structure determinations were performed using a
four-circle diffractometer KUMA KM-4 with Mo Ka radi-
ation (k = 0.71069 A), and the software packages Xcalibur
˚
CCD system for the data collection/reduction [28] and
SHELXTL for the structure solution, refinement and drawing
preparation [29]. The structures were solved by direct
methods. Non-hydrogen atoms were refined anisotropi-
cally while hydrogen atoms were inserted in calculated
positions and isotropically refined assuming a ‘‘ride-on’’
model. Selected crystallographic data of compounds 3
and 7 are shown in Table 2.
3.2.3. Synthesis of tris(pyridinium)-nonathio-cyclo-
triphosphate [pyH]3[P3S9] (7)
A solution of 1 (0.313 g, 0.70 mmol) and 2 (0.610 g,
2.87 mmol) in 15 ml of acetonitrile and 0.46 ml
(5.64 mmol) of pyridine was refluxed for 2 h. Compound
2 dissolved gradually during heating and the reaction mix-
ture turned yellow. The reaction mixture was kept at ambi-
ent temperature for 3 months and yellow needle crystals of
7, soluble only in H2O, were formed in 15% yield (with
respect to 1).
Anal. Calc. for C15H18N3P3S9: C, 28.97; H, 2.92; N,
6.76; P, 14.94; S, 46.41. Found: C, 27.62; H, 2.81; N,
6.80; P, 14.92; S, 46.38%. M.p. 138.7–139.1 ꢁC. IR (Nujol):
d(C–H): 3041 (sh), 3062 (sh); m(pyH+): 1628 (m), 1610 (m),
1540 (m), 1485 (sh); 1517 (s), 1476 (s), 1377 (m), 750 (s);
m(PS): 667 (s), 676 (s), 609 (w), 649 (sh); m(P–S–P): 485
(s), 496 (s), 549 (s), 559 (s).
3.2. Procedures
All reactions and subsequent manipulations were carried
out in an atmosphere of dry nitrogen. pyPS2Cl (9) was pre-
pared according to a known procedure [30]. P4S10 (1) was
purchased from Merck, diphenylurea (2) and diphenylthiou-
rea (8) (Fluka) and Pd(CH3COO)2 (Sigma–Aldrich) were
used without further purification. Acetonitrile and pyridine
were purified according to known procedures [31] and dis-
tilled before use.
3.2.1. Synthesis of the pyridinium salt of 1,3-diphenyl-2-
sulfido-2-thioxo-1,3-diaza-2k5-phosphetidine
[pyH][PS2(NPh)2CO] (3)
2.786 g (13.29 mmol) of 9 and 2.800 g (13.19 mmol) of 2
in 40 ml CH3CN were placed into a Schlenk vessel and
1.026 g (12.97 mmol) of pyridine was added to the suspen-
sion. The reaction mixture was refluxed for 1.5 h. Com-
pound 2 gradually dissolved and the reaction mixture
turned yellow. After cooling, the first portion of greenish
crystals appeared. The supernatant solution was partially
evaporated and greenish crystals of 3 were filtered off.
The yield after recrystallization from acetonitrile was 73%
(with respect to 9).
3.2.4. Synthesis of bis(2,2-disulfido-4-oxo-1,3-diphenyl-1,3-
diaza-2k5-phosphetidino)palladium(II)
[Pd(Ph2N2COPS2)2] (11)
0.341 g (0.88 mmol) of 3 and 0.099 g (0.44 mmol) of
Pd(CH3COO)2 was stirred in acetonitrile at ambient tem-
perature for 12 h. The reaction product (11), a brown pow-
der, was filtered off. Yield: 57% (with respect to 3).
Anal. Calc. for C26H20N4O2P2PdS4: C, 43.55; H, 2.81;
N, 7.81; P, 8.64; S, 17.89. Found: C, 42.66; H, 2.66; N,
7.84; P, 8.63; S, 15.28%. Temperature 140.9 ꢁC (dec.). IR
(Nujol): m(Carom–H): 1593 (s); d(Carom–H): 1548 (m), 1486
(s), 1312 (s), 1287 (sh), 1112 (m), 1006 (s), 992 (sh), 898
Anal. Calc. for C18H16N3OPS2: N, 10.90; P, 8.04; S,
16.64. Found: N, 11.17; P, 7.91; S, 16.05%. M.p.
174.2 ꢁC. IR (Nujol): m(pyH+): 1634 (m), 1611 (sh), 1525
(m), 1496 (vs); mCH(pyH+): 3196 (vw), 3125 (w), 3082 (m),

4256
L. Dastychova´ et al. / Polyhedron 26 (2007) 4250–4256
[4] A. Dimitrov, I. Hartwich, B. Ziemer, et al., Z. Anorg. Allg. Chem.
631 (2005) 2439.
(w);PS: 752 (m), 719 (m), 692 (w), 689 (m), 680 (sh), 651
(m), 637 (w), 608 (w).
ˇ
´
ˇ
[5] R. Sevcˇık, J. Prıhoda, M. Necas, Polyhedron 24 (2005) 1855.
ˇ´
ˇ
´
[6] M. Jancˇa, M. Necˇas, Z. Zak, et al., Polyhedron 20 (2001) 2823.
[7] J. Neels, K.H. Jost, M. Meisel, Z. Anorg. Allg. Chem. 541 (1986)
307.
4. Conclusion
´
ˇ´
[8] V. Novomeˇstska, J. Marek, J. Prıhoda, Polyhedron 18 (1999)
New heterocyclic compounds with exocyclic PS2 and P–N
atoms in the cycle (pyridinium salts of 1,3-diphenyl-2-sulfido-
2-thioxo-1,3-diaza-2k5-phosphetidine, [pyH][PS2(NPh)2CO]
(3) and 1,4-diphenyl-2,5-disulfido-2,5-dithioxo-1,4-dithiadi-
aza-2k5,5k5-diphosphinane, [pyH]2[PS2(SNPh)]2 (4)) were
prepared from two P–S precursors – P4S10 (1) and pyPS2Cl
(9). In the reactions cyclic thiophosphates were formed.
We proved the formation of bis(l-disulfido)-tetrathio-
cyclo-diphosphate, [pyH]2[P2S8] (5), bis(pyridinium)-l-
disulfido-pentathio-cyclo-diphosphate, [pyH]2[P2S7] (6) and
tris(pyridinium)-nonathio-cyclo-triphosphate, [pyH]3[P3S9]
(7). A Pd-complex, bis(2,2-disulfido-4-oxo-1,3-diphenyl-
1,3-dia- za-2k5-phosphetidino)palladium(II), [Pd(Ph2N2-
COPS2)2] (11) was also prepared.
2723.
´
[9] J. Marek, J. Prˇıhoda, Z. Kristallogr. 212 (1997) 399.
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´
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umbetainu kyseliny chlorodithiofosforecˇne
nukleofily), Thesis, Masaryk University, Brno, Czech Republic,
s
vıcefunkcnımi
ˇ ´
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[11] M. Meisel, Beitra¨ge zur Chemie von Phosphorsa¨ure- und Thi-
ophosphorsa¨urebetainen, Dissertation, ZIAC der AdW der DDR,
Berlin, 1986.
[12] E. Fluck, H. Binder, Z. Anorg. Allg. Chem. 359 (1968) 102.
[13] J. Prˇ´ıhoda, J. Marek, Z. Krist.-New Cryst. Struct. 212 (1997)
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[14] M. Jancˇa, M. Necˇas, J. Prˇıhoda, Acta Crystallogr., Sect. E 58 (2002)
772.
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[15] G. Ohms, J. Zessin, Z. Zak, Phosphorus Sulfur Silicon 76 (1993)
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[16] H. Falius, A. Schliephake, D. Schomburg, Z. Anorg. Allg. Chem. 611
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Acknowledgements
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FT NMR Spectra, Aldrich Chemical Company, Inc., Milwaukee,
1993.
We thank our colleagues from the Faculty of Science,
Palacky University, Olomouc, Czech Republic for carrying
out the elemental analyses.
Appendix A. Supplementary material
[20] S.H. Lee, H. Matsushita, B. Clapham, K.D. Janda, Tetrahedron 60
(2004) 3439.
CCDC 638838 and 638971 contain the supplementary
crystallographic data for 3 and 7. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@
ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at
doi:10.1016/j.poly.2007.05.032.
[21] L.A. Kushch, V.V. Gritsenko, L.I. Buravov, A.G. Khomenko, G.V.
Shilov, O.A. Dyachenko, V.A. Merzhanov, E.B. Yagubskii, R.
Rousseau, E. Canadell, J. Mater. Chem. 5 (1995) 1633.
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[23] F. Bigoli, P. Deplano, M.L. Mercuri, M.A. Pellinghelli, L. Pilia, G.
Pintus, A. Serpe, E.F. Trogu, Inorg. Chem. 41 (2002) 5241.
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1378.
[26] M. Hora´k, D. Papousˇek, Infrared Spectroscopy and Molecular
´
Structure (Infracˇervena spektra a struktura molekul), Academia,
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