Synthesis and some properties of transition metal complexes based on the octathiophophetane ammonium salts

Article abstract of DOI:10.1002/hc.21152

Cyclic octathiotetraphosphetanes, and speciafically their ammonium salt, represent novel polyfunctional heterocyclic ligands that are valuable in the development of organometallic and coordinated chemistry. Coordination features of octathiotetraphosphetan

Full text of DOI:10.1002/hc.21152

Heteroatom Chemistry
Volume 00, Number 0, 2014
Synthesis and Some Properties of Transition
Metal Complexes Based on the
Octathiophophetane Ammonium Salts
Lidiya I. Kursheva,1 Nadezhda V. Yanberdina,1 Elena E. Zvereva,1
Aleksandеr E. Vandyukov,1 Mary Rose Reisenauer,2
Jolene D. Lujan,2 Robert W. Lebrun,2 Leslie D. Edwards,2
Snezna Rogelj,2 Liliya V. Frolova,3 Elvira S. Batyeva,1
and Oleg G. Sinyashin1
1A.E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Kazan
Scientific Center, Arbuzov Street 8, 420088, Kazan, Russia
2Biology Department, New Mexico Institute of Mining and Technology, 801 Leroy Place, Socorro,
New Mexico 87801
3Chemistry Department, New Mexico Institute of Mining and Technology, 801 Leroy Place,
Socorro, New Mexico 87801
Received 12 November 2013; revised 24 February 2014
ꢀC
2014 Wiley Periodicals, Inc. Heteroatom Chem.
ABSTRACT: Cyclic octathiotetraphosphetanes, and
speciafically their ammonium salt, represent novel
polyfunctional heterocyclic ligands that are valu-
able in the development of organometallic and
coordinated chemistry. Coordination features of
octathiotetraphosphetane ammonium salts with
structures differing only by piperidine and triethy-
lamine substituents in the reaction with transition
d-metals of I and VIII groups [Cu(I), Ag(I), Fe(II),
Co(II)] are described. Some similarities and differ-
ences in the behavior of piperidinium and triethy-
lammonium salts of the octathiotetraphosphetane
upon complexation with metal halides are discussed.
00:1–8, 2014; View this article online at wileyon-
linelibrary.com. DOI 10.1002/hc.21152
INTRODUCTION
Polyfunctional ligands are widely used in
organometallic and coordinated chemistry. Ac-
cordingly, various types of polynuclear complexes
(monomeric, dimeric, tetrameric, polymeric, as
well as clusters) based on the thioesters of P(III)
acids as the P,S-ligands were previously synthesized
and characterized by means of X-ray single crystal
diffraction.
Because of the disproportionate transformations
of ligands ranging from the monodentate type of
coordination via the P atom to the bidentate type
via P and S atoms in one molecule as well as via S
atoms only, different types of structure and coordi-
nation modes were found in complexes with Cu(I)
halides [1–6]. Therefore, ammonium salts of cyclic
Correspondence to: Lydiya I. Kursheva; e-mail: kursheva@
iopc.ru.
Dedicated to 77th birthday of Professor Okazaki.
Contract grant sponsor: RFBR.
Contract grant number: 12-03-00479-а.
Contract grant sponsor: DCSM RAS Programme 6.
Contract grant sponsor: National Institute of General Medical
Sciences from the National Institutes of Health (USA).
Contract grant number: P20 GM103451.
ꢀC
2014 Wiley Periodicals, Inc.
1

2
Kursheva et al.
octathiotetraphosphetanes represent such type of
novel heterocyclic ligands. These salts were obtained
ride due to the merely partial substitution of triethy-
lamine groups for Cu cations (Eq. (1)).
(1)
As shown before for the original ammonium
salts 1 and 2 as well as for the Cu(I) complex 3
with the ligand 1, IR/Raman spectroscopy can be
successfully used for the determining of the struc-
ture of product 4 [7–9]. Because of the high com-
plexity of spectral data, the calculations within the
framework of DFT are uniquely useful for spectral
interpretation when combined with comprehensive
experimental analysis and theoretical models. Calcu-
lated IR/Raman spectra revealed common spectral
earlier based on the reaction of white phosphorus
(P4) and elemental sulfur with aliphatic mercaptans
in the presence of amines [7–9].
RESULTS AND DISCUSSION
Recently, we obtained the Cu(I) chloride complex
of piperidinium salt of octathiotetraphosphetane,
[CuCl·{P(S) S−H2N+( CH2 )5}]4, whose structure
was determined by IR/Raman spectroscopy com-
bined with density functional theory (DFT) calcu-
lations [9]. The coordination behavior of triethy-
lammonium salt of octathiotetraphosphetane in the
reaction with Cu(I) halide was reported previously
[10]. Similarities and differences in the behavior
of octathiotetraphosphetane ammonium salts com-
pared with structures differing only by piperidine
and triethylamine substituents were revealed upon
complexation with Cu(I) halides. Continued inves-
tigation of this type of ligands’ ability to complex
with the transition d-metals of I and VIII groups,
as well as the behavior of octathiotetraphophetane
piperidinium and triethylammonium salts 1 and 2,
{[P(S)]4(S−H2RN+)4; R = ( СH2 )5 1; (C2H5)3 2]}
in reactions with Ag(I), Fe(II), or Co(II) halides, is
presented in this paper.
4−
characteristics corresponding both to P4S8 anion
of “free” ligand [9] and complex 4 [10]; both of which
are influenced by complexation.
It is noteworthy that the reaction of Cu(II)
halides (Cl, Br) with either ligand 1 and 2 resulted
in the formation of appropriate Cu(I) complexes 3,
4. This probably occurred due to reduction of Cu(II)
to Cu(I); indeed, the expected change in the color of
the reaction mixture was observed. In fact, a similar
redox process was reported for the reaction of tri-
alkyltrithiophosphites with Cu(II) halides [11]. Thus,
the reduction of Cu(II) into Cu(I) upon complexa-
tion both of thiophosphites and thiophosphetanes
is a common chemical pathway that results in the
formation of Cu(I) coordinated compounds and
by-products [9–11].
We have found that interaction of the salt 1 with
AgCl in the ratio 1:4, or with FeCl2 in the ratio 1:2,
both in acetonytrile, proceeded similarly to the reac-
tion with Cu(I) halide. Namely, all the piperidinium
fragments remain unchanged in molecules of both
Ag complex 5 and Fe complex 6. The reaction of the
ligand 1 with FeCl2 resulted in a powder-like com-
pound in which, according to the X-ray fluorescence
(XRF) data, the Fe, P, S, and Cl atoms are presented
in Eq. (2):
Spectral and calculated data revealed that the
formation of Cu(I) chloride complex with the piperi-
dinium salt 1 occurs without a change of the ligand
itself, that is all four piperidinium fragments remain
in complex 3, and each of sulfur atoms is coordi-
nated by CuCl [9].
.
ClCu
+
.
.
.
CuCl
.
.
. .S
S
.
.
.
-
.
+
-
NH2
S
P
P
P
P
S
N
H2 +
+
-
-
H2
S
S
.
.
.
NH2
N
.
[(−CH2−)5N+H2S−P(S)]4 + 2FeCl2
.
.
.
.
.
.
.
.
S
S
ClCu
CuCl
1
3
[(−CH2−)5N+H2S−P(S)]4 · 2FeCl2
25◦C
−−−−→
(2)
In contrast, the reaction of the triethylammo-
nium salt 2 and Cu(I) chloride resulted in formation
of the complex CuCl·{[P(S)]4(SCu)3S−HN+(C2H5)3}
4 [10] incorporating triethylammonium hydrochlo-
6
Our attempts to grow a crystal suitable for
X-ray single crystal diffraction failed even when
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Some Properties of Transition Metal Complexes Based on the Octathiophophetane Ammonium Salts
3
800
343.2
600
400
377.2
200
400.0
0
300
400
500
600
700
800
900
1000
m/z
FIGURE 2 Mass spectrum MALDI TOF of complex 8.
FIGURE 1 Mass spectrum MALDI TOF of fragments of com-
plex 6.
Corresponding XRF of this product has shown the
presence of Fe, P, S, and Cl elements.
It should be pointed out that the same reac-
tion of the triethylammonium salt 2 with Ag(I),
Fe(II), and Co(II) halides, even in the presence of
excess of metal halide, resulted in the formation
of complexes 7–9: (С2H5)3N+H−[SP(S)]4·Ag4Cl 7,
(С2H5)3N+H−[SP(S)]4·M2Cl (M: Fe 8; Co 9) compris-
ing one ammonium group in each molecule; this is
analogous to the outcome illustrated in Eq. (1).
The reaction of the salt 2 with AgCl in CHCl3
resulted in a yellow product 7 that decomposes at
temperature higher than 300°С. The interaction of
ligand 2 with FeCl2 in CHCl3 or CoCl2 in CH3CN
was carried out to give the appropriate powder-like
compounds 8 and 9. In mass spectrum MALDI TOF
of the Fe complex 8 (Fig. 2), the fragment ion peaks
are observed (m/z 377, 400, 343.2). These are similar
to the peaks of complex 6 (Fig. 1), which confirms the
metal–ligand binding in complex 8 via sulfur atoms.
Meanwhile, the absence of M+ peaks in mass spec-
tra for the complexes 6 and 8 can be explained by
the low stability of complexes due to the presence
of octathiotetraphosphetane ammonium salts under
laser ionization.
using different solvents. Powder X-ray study of this
compound was also impossible because of the strong
fluorescence. In the IR/Raman spectra of the new
complex 6, some bands at 2519–2414 сm−1 are ob-
served, corresponding to H2N+ group of reaction
product; these are redshifted by ꢀ50 cm−1 relative
to the spectrum of original salt 1. Common stretch-
ing vibration bonds of Р Р, P S, P S at bands 390/
567 сm−1 and 657/772 cm−1 are observed in both Ra-
man and IR spectra; this corresponds to the chang-
ing and splitting of spectra due to the distortion of
[P4S8]4− anion by coordination of P S and/or P
S
groups with Fe atoms. Nonetheless, in general, the
spectral characteristics of this area have not changed
dramatically. In accordance to the above discussed
experimental IR/Raman spectra and analytical data,
we proposed that in the complex 6 all sulfur atoms
of [P4S8]4− anion are coordinated with Fe atoms.
MALDI TOF mass spectrum of 6 (Fig. 1) shows
that the peak of M+(m/z 907) is absent while many
other fragment ions peaks are observed under laser
ionization. The appearance of peaks such as the m/z
365, 405 ([P4S8]4−), the m/z 223.7 (PS2C5H12Fe), and
the m/z 343.2 (P2S3C5H12Fe2) may indicate a metal–
ligand binding in complex 6 via sulfur atoms.
The interaction of the ligand 2 with Fe(III) chlo-
ride in methanol at room temperature (r.t.) resulted
in the formation of a powder-like product 8a, which
was decomposed at temperature higher than 250°C.
XRF of this product has shown the presence of Fe,
P, S, and Cl elements. In the IR spectra, the bands
at 633 and 465 cm−1 are observed; these are similar
Reaction of the ligand 1 with Fe(III) chloride
in acetonytrile at 40°C for 12 h resulted in the for-
mation of a light yellow product 6a; this product
decomposed at the temperature higher than 300°C.
Heteroatom Chemistry DOI 10.1002/hc

4
Kursheva et al.
vious reports [9]. The IR spectra of complexes with
Cu(I), Cu(II), and Co(II) (curves B, C, and F in Fig. 3)
show stretching vibration bands 645–667 cm−1 and
567–582 cm−1 of P S and P S groups, respectively.
Some changes and splitting of these bands can be
explained by coordination of the P S and/or P
S
groups with metal atoms; in general, however, the
spectral characteristics of this area are retained. Fur-
thermore, as shown in Fig. 3, the IR spectra of com-
plexes with Cu(I) and Cu(II) (curves B and C) are
identical to each other; that points to the similarities
of both products and, as a part of the course, the re-
duction of Cu(II) to Cu(I) under reaction conditions.
In case of complex with Ag(I) 7 (curve D), the band
of νP S 668 cm−1 is much weaker than the band
νP S 558–585 cm−1; this possibly indicates the ad-
ditional coordination between the P S group and
Ag atoms. The IR spectrum of complex with Fe(II) 8
(curve E) in the area 700–400 cm−1 comprises some
broad overlapping bands assigned to P S and P S
groups.
The bands belonging to the stretching and defor-
mation vibrations of [P4S8]4− anion are observed in
the far IR area 400–50 cm−1 of all products. These
bands are shifted by 10–30 cm−1 relative to their po-
sitions in the IR spectrum of triethylammonium salt
(Fig. 3, curve A, νP P 390 cm−1, δPS2 231 cm−1).
This is because [P4S8]4− fragments of the ligand are
influenced by complexation with metal atoms.
As shown in Fig. 3 (curve E), the IR spectrum of
reaction product with FeCl2 8 looks quite different
than the other spectra; this can be due to the spe-
cific structure of complex. To clarify the suggested
structure of the complex with Fe(II) 8, quantum-
chemical modeling was carried out. Selected models
were [P4S8]4− anion surrounded by either two Fe(II)
atoms (model a) or by two Fe(II) atoms and one chlo-
rine atom (model b). Optimized structures, shown in
Fig. 4, demonstrate that the anion retains its struc-
ture when four sulfur atoms are coordinated by two
ferric atoms.
The good agreement of the calculated IR spec-
tra of these models with the experimental spectra
of products (Fig. 5) suggests a possible coexistence
of these two structures in the product. According
to the calculations, band νFe Cl should appear at
430 cm−1 and Fe···S vibrations are predicted to pro-
duce bands in 350–250 cm−1 spectral region. Band
775 cm−1 can be explained by the antisymmetric
stretching vibrations of P-S fragment (model b).
Thus, when compared to the spectrum of “free” lig-
and, the additional IR bands in the low-frequency re-
gion of the spectra of complex may now be assigned
to metal–ligand vibrations.
FIGURE 3 IR spectra of octathiotetraphosphetane triethy-
lammonium salt 2 (A) and reaction products with CuCl 3 (B),
CuCl2 3(C), AgCl 6 (D), FeCl2 7 (E), and CoCl2 8 (F) in spec-
tral range 4000–400 cm−1
.
to the bands of “free” ligand 2 assigned to vibrations
of P and P S bonds. Characteristic bands rela-
S
tive to triethylammonium fragment at 2925 and 2854
cm−1 are available in 8a; those suggest the formation
of product identical to complex 8.
The structure of complexes 4, 7–9 was studied
and interpreted in detail by IR spectroscopy com-
bined with DFT calculations. The spectral charac-
teristics as a function of the nature of metal used
were then compared.
The experimental IR spectra of reaction prod-
ucts, measured at 25°С, are given in Fig. 3. Some
bands of the triethylammonium fragment (e.g., char-
acteristic vibrations of the alkyl groups) are detected
in the spectral range 3100–800 cm−1. Several new
bands, appearing in the range 1650–700 cm−1 of the
product spectra, but absent in the spectra of triethy-
lammonium salt, can be assigned to vibrations of the
triethylammonium cations coordinated by chlorine
ions of metallic salts.
Additional common bands are observed in the
range 700–400 cm−1 of IR spectra of the original tri-
ethylammonium salt 2 and the reaction products 4
and 7–9 (Fig. 3); these can be assigned to vibrations
of [P4S8]4− anion in the complexes according to pre-
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Some Properties of Transition Metal Complexes Based on the Octathiophophetane Ammonium Salts
5
In summary, the interaction of P,S-ligands,
based on octathiotetraphosphetane ammonium salts
with metals of I and VIII group, proceeds toward
the formation of coordination compounds whose
structure is determined both by the nature of metal
and the amine fragments in the thiophosphetane
molecule.
Because of the unique cyclic structure with
various functional groups, the original octathio-
phosphetane ammonium salts as well as their metal
complexes are of interest in the studies of cat-
alytic systems, nanoparticles, and bioheterocyclic
compounds among others. The biological activity of
tetraphosphetane derivatives (1, 2) and their metal
complexes (3–9) was the next subject of our inves-
tigations. Compounds were tested against Gram-
positive (Staphylococcus aureus, Streptococcus
pyogenes) and Gram-negative (Acinetobacter bau-
mannii, Pseudomonas aeruginosa) bacteria and did
not show any definitive antibacterial properties [12].
However, transition metal complexes of octathiote-
traphosphetane do show some antifungal and an-
ticancer activity. Cu complex 3 and Fe complex
8 showed some antifungal activity (MIC ꢀ50 μM
against Candida albicans). Cu complex 4, based
on the triethylammonium salt, demonstrates anti-
cancer activity (IC50 ꢀ25 μM against HeLa cervi-
cal cancer), but is not active against C. albicans. A
combination of these biological and ferromagnetic
properties may permit the development of pathogen-
targeting applications.
FIGURE 4 Optimized possible structures of the anionic part
of complex 8.
It is interesting that metal complexes exhibit dif-
ferent biological activity depending on the character
of the amino group near the sulfur atom as well as
the nature of the metal. Compounds having the tri-
ethylamine group at the sulfur atom exhibit the an-
ticancer activity and the antifungal activity as well,
whereas the compounds with the piperidine group
at the sulfur atom show antifungal activity only.
In addition, compound 1 dissolved in DMSO
induced potent (ꢀ12uM) and rapid (15 min) shed-
ding of the leukocyte adhesion molecule L-selectin
from primary peripheral blood neutrophils [13]. This
suggests that DMSO-dissolved piperidinium salt 1
of octathiotetraphosphetane possesses notable anti-
inflammatory activity, an aspect that will addition-
ally be investigated in the future.
FIGURE 5 Selected region of the experimental IR (curve A)
in comparison with the calculated IR spectra of some possible
models a (curve B) and b (curve C) of complex 8.
The proposed structure correlates well with the-
oretical and experimental IR bands in corresponding
spectra and demonstrates the credibility of combin-
ing the structural spectral analysis with DFT calcu-
lations. Common spectral characteristics found for
Cu(I), Ag(I), Fe(II), and Co(II) complexes, as well
4−
as for P4S8 anion of “free” ligands, demonstrate
4−
that all of the compounds obtained comprise P4S8
moiety, which is distorted by the coordination with
metal in the complexes.
It should be noticed that, according to the EPR
spectra, Fe-containing complexes exhibit promis-
ing magnetic properties: in Fe2+/Fe3+complexes, the
presence of diamagnetics Fe2+ (3d6) is preferable.
EPR spectrum of the Fe3+ complex is of special in-
terest since, due to the interactions of neighboring
Fe atoms, the formation of Fe3+ chains gives ferro-
magnetic properties to these compounds.
EXPERIMENTAL
NMR spectra were measured using Bruker CXP-
100 (Bruker, Germany, 36.48 МHz, 31Р) spectrom-
eters. IR spectra of all compounds were recorded
on an FTIR spectrometer “Tensor 27” (Bruker, Ger-
many) in the 4000–400 cm−1 middle IR range at an
Heteroatom Chemistry DOI 10.1002/hc

6
Kursheva et al.
optical resolution of 4 cm−1. Solid samples were pre-
pared as KBr pellets. Far-IR spectra were recorded
on an FTIR spectrometer “IFS-66v/s” (Bruker, Ger-
many) in the 600–100 cm−1 range at an optical res-
olution of 4 cm−1. Solid sample, mixed with Nujol,
was placed between polyethylene plates. FT Raman
spectra were recorded on a BRUKER RAM II mod-
ule (using a Ge detector) attached to a BRUKER
VERTEX 70 FTIR spectrometer (Bruker, Germany)
in the 4000–10 cm−1 range at an optical resolution
of 4 cm−1. The Nd:YAG laser with a wavelength of
1064 nm (power of 500 mW) was used as a source
of excitation. The samples were placed in standard
cylindrical aluminum sample pan.
XRF spectra were obtained using an energy
dispersive X-ray spectrometer EDX 800HS2 (Shi-
madzu, Japan). It has an active diameter of 5 mm. All
measurements were made using a 50W low-power
Rh tube (50 kV, 1000 μA) with an acquisition time
of 100 s (live time).
added gradually to a stirred mixture of 0.25 g
(0.3 mmol) tetraphosphetane 1 in 15–20 mL ace-
tonitrile or methanol at 28°C; the reaction mixture
was then stirred for 2 h at 50–60°C or 35–40°C, re-
spectively, until the reaction was completed (disap-
pearance of signal 31P NMR (D2O), δ: 122 of start-
ing ammonium salt [9]). During this time, a white
compound was converted to a light yellow one. The
precipitate was treated as defined in the general pro-
cedure to give complex 3 (0.24 g, 61.5%), mp > 300°C
(decomposed) [9]. IR (KBr, cm−1): 390 (Р Р), 567,
657 (P S), 2980–2880 (CH2), 2463, 2367 (NH2+).
Anal. calcd. for C20H48Cl4Cu4N4P4S8 (1117): C 21.40;
H 3.97; N 4.99; P 11.00; S 22.87. Found: C 21.12; H
3.25; N 4.77; P 10.20; S 22.93.
The same compound was isolated by the reaction
of piperidinium salt 1 with CuCl2.
Found: C 21.55; H 4.25; N 4.50; P 10.50; S 23.50.
Tetra(dithiotriethylammonium)tetraphosphetane
MALDI-TOF experiments were performed with
an Ultraflex III TOF/TOF (Bruker Daltonics, Ger-
many) mass spectrometer equipped with an Nd:YAG
laser and a collision cell. The spectra were mea-
sured in the positive ion linear modе. MS data were
processed using the software FlexAnalysis 3.0 from
Bruker Daltonics.
Copper(I) Chloride, 4.
(a) To 0.25 g (0.31 mmol) salt 2 in 8 mL CHCl3, grad-
ually at the stirring CuCl 0.125 g (1.26 mmol) was
added. The reaction mixture was then stirred
for 4 h at ambient temperature. After that, the
light yellow precipitate was treated as defined
in the general procedure to give complex 4
(0.22 g, 50.9%); mp > 300°С (decomposed). Anal.
calcd. for C6H16ClCu4NP4S8 (771.5): Cu 32.92; N
1.81; P 16.07; S 33.18. Found: Cu 33.56; N 2.17;
P 16.50; S 34.0.
EPR spectra were recorded on EPR spectrome-
ter SE/X-2544 (Radio PAN, Poland).
Computations
All quantum-chemical calculations were carried out
using the Gaussian-03 suite of programs [14]. The
hybrid metageneralized gradient DFT approxima-
tion M05–2X [15,16] was used in combination with
LanL2DZ (for the Fe atom) [17–19] and 6-31G* (for
all other atoms) basis sets [20, 21]. All stationary
points were characterized as minima by analysis of
the Hessian matrices. The simulated spectra are ob-
tained by convolution of computed band intensities
with a Lorentzian lineshape function (with a half-
width = 20 cm−1 for [P4S8]4− model and 10 cm−1 for
[P4S8]4−(FeCl) model).
Filtrate was concentrated in vacuum to give
triethylammonium hydrochloride (0.11 g), mp
230–254°С. Lit.: mp 254°С [22]. Anal. calcd. for
C6H16NCl: C 52.36; Н 11.63; Cl 25.8; N 10.18.
(137.5). Found: C 50.12; H 13.25; Cl 23.17; N
10.78. The liquid residue (δp 69.5 ppm) was not
identified.
(b) From 0.45 g (0.57 mmol) salt 2 in 5 mL CH3OH
and 0.225 g (2.27 mmol) CuCl in CH3OH-CH3CN
(1:1) after stirring for 5 h at ambient temper-
ature and following treatment of precipitate as
defined in the general procedure, complex 4 (0.2
g, 54.33%) was obtained; mp > 300 ºС (decom-
posed). Triethylammonium hydrochloride was
isolated from filtrate.
Piperidinium
salts of
tetrathioxotetraphosphetane
1
and
1,2,3,4-tetramercapto-1,2,3,4-
were synthesized
triethylammonium
2
Analogously from 0.25 g (0.31 mmol) salt 2 in
CHCl3 (16–18 mL) at 26–30°С, just prepared and
dried CuCl2 (0.08 g, 0.6 mmol) was added. (White
smog was isolated at that point.) One day later, com-
plex 4 (0.2 g, 83.3%) was prepared; mp 260–280°С
(decomposed). Anal. calcd. for C6H16ClCu4NP4S8
(771.5): Cu 32.92; N 1.81; P 16.07; S 33.18. Found:
Cu 33.65; N 2.34; P 16.75.
according to a procedure published earlier [9].
General procedure for the purification of new com-
plexes: All precipitates were separated from the solu-
tion by decantation, washed twice with acetonitrile
and diethyl ether, filtered, and dried.
Tetra(dithiopiperidinium)tetraphosphetane Cop-
per(I) Chloride, 3. CuCl (0.14 g, 1.4 mmol) was
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Some Properties of Transition Metal Complexes Based on the Octathiophophetane Ammonium Salts
7
(decomposed). IR (KBr, сm−1): 668 (P S), 558, 585
(P S). Anal. calcd. for C6H16Ag4Cl NP4S8 (949): Ag
45.46; N 1.47; P 13.06. Found: Ag 46.69; N 1.51; P
12.9.
Triethylammonium hydrochloride (0.2 g) was
isolated from filtrate, mp 235–240°С. Lit.: mp 254°С
[22].
Tetra(dithiopiperidinium)tetraphosphetane Ar-
gentum(I) Chloride, 5. To salt 1 (0.1 g, 0.138 mmol)
in 20 mL CH3CN, AgCl (0.08 g, 0.55 mmol) was
added. The reaction mixture was stirred at 35°С for
6 h. Yellow precipitate was treated as defined in the
general procedure to give 0.1 g (55.5%) complex 5,
mp 200–220°С. Anal. calcd. for C20H48Ag4Cl4N4P4S8
(1298): С 18.49; H 3.07; Ag 33.2; N 4.31; P 9.54.
Found: С 18.02; H 3.95; Ag 33.82; N 4.05; P 9.0.
The liquid residue (δр 3.99 ppm) was not identi-
fied.
Triethylammonium hydrochloride was isolated
from concentrated filtrate, mp 242–245°С. Lit.:
254°С [22]. Anal. calcd. for C6H16Cl N (135.5): С 52.3;
Н 11.7; Cl 25.8; N 10.16. Found: С 52.12; H 12.25; Cl
24.17; N 10.78. The liquid residue from the reaction
(δр 3.99 ppm) was not identified.
Tetra(dithiotriethylammonium)tetraphosphetane
Ferrum(II) Chloride, 8.
(a) To stirred solution of salt 2 (0.3 g, 0.38 mmol)
in 15 mL CHCl3, FeCl2 (0.1 g, 0.8 mmol) was
added. A gray reaction mixture was stirred at
r.t. for 8 h. The precipitate was separated and
treated as defined in the general procedure to
give complex 8 (0.07 g, 29.16%), mp 200–210°С
(decomposed). IR (KBr, сm−1): 392 (P P), 469,
772 (P S), 2854, 2924 (СH2), 2360 (NH+). Anal.
calcd. for C6H16 Fe2Cl NP4S8 (629): Fe 17.8; Cl
5.64; N 2.2; P 19.7. Found: Fe 17.09; Cl 4.96; N
1.8; P 18.95. EPR: g factor 2.000, wide of line:
81 mT. The dark yellow filtrate (δр 77.95 ppm)
was not identified.
(b) In a similar way, from 0.1 g (0.126 mmol) salt
2 in 8 mL CH3OH and 0.05 g (0.125 mmol)
FeCl2 after stirring for 8 h and following treat-
ment of precipitate, complex 8 was obtained
(0.03 g, 37.5%), mp > 300°С. IR (KBr, сm−1):
524, 644 (P S). Found: Fe 17.0; N 1.75; P
19.05. From concentrated filtrate, triethylammo-
nium hydrochloride was isolated, mp 252°С. Lit.:
254°С [22].
Tetra(dithiopiperidinnium)tetraphosphetane Fer-
rum(II) Chloride, 6.
(a) To salt 1 (0.1 g, 0.138 mmol) in CH3CN
(6 mL), Fe(II)chloride (0.035 g, 0.276 mmol) was
added. The brown reaction mixture was stirred
for 10.5 h at 25°С. Then, the mixture was cooled
to r.t. after which the yellow precipitate was
treated as defined in the general procedure to
give complex 6 (0.1 g, 79.49%), mp > 300°С.
IR (KBr, сm−1): 390 (P P), 469, 772 (P S),
637 (P(S)S), 2519, 2414 (HN+). Anal. calcd. for
C20H48 Cl4Fe2N4P4S8 (978): Fe 11.45; N 5.72; P
12.6; S 26.22. Found: Fe 11.84; N 5.9; P 12.22; S
27.40. EPR: g factor: 2.000, wide of lines: 76 mT.
(b) Analogously from 0.1 g (0.138 mmol) salt 1
and Fe(II) chloride (0.035 g, 0.276 mmol) in
methanol after stirring at 25°С for 8.5 h, complex
6 (0.06 g, 47.69%) was obtained, mp > 300°С. IR
(KBr, сm−1): 529 (P S), 628 (P S), 2526 (HN+).
Interaction of Salt 1 with FeCl3. To salt 1
(0.05 g, 0.069 mmol) in 8 mL methanol, Fe(III) chlo-
ride (0.02 g, 0.123 mmol) was added while stirring.
After heating for 20 h at 40°С, the reaction mixture
was cooled and precipitate was separated from the
solution and dried. Product 6a (0.01 g, 17.5%) was
obtained, mp > 300°С. IR (KBr, сm−1): 483 (P S),
633(P S), 2480, 2654 (NH+). XRF: Fe 56.97; P 17.29;
S 56.97. EPR: g factor 2.000.
Interaction of Salt 2 with FeCl3. To salt 2 (0.05
g, 0.063 mmol) in 3 mL CH3OH, a solution of FeCl3
(0.02 g, 0.12 mmol) in 4 mL CH3OH was added;
the reaction mixture became dark and a precipi-
tate formed. After stirring for 26 h at r.t., a brown
compound 8a (0.04 g, (80%) was obtained, mp >
250°С. IR (KBr, сm−1): 465, 772 (P S), 633(P S),
2925, 2854 (СH2), 2361 (NH+). XRF: Fe 16.56; Cl
4.8; P 19.11; S 32.4. EPR: g factor 2.000, wide of line:
42 mT.
Tetra(dithiotriethylammonium)tetraphosphetane
Argentum(I) Chloride, 7. To 0.26 g (0.33 mmol) salt
2, in 8 mL CHCl3, the excess of AgCl 0.2 g (1.39
mmol) in 3 mL CHCl3 was added. The dark gray
reaction mixture was stirred at ambient tempera-
ture for 3 h, then for 5 h at 35–40°С. After cooling,
a yellow powder was isolated from the solution,
treated to give complex 7 (0.2 g, 67%), mp > 300°С
Tetra(dithiotriethylammonium)tetraphosphetane
Cobalt(II) Chloride, 9. To salt 2 (0.1 g, 0.13 mmol)
in 5 mL CH3CN at stirring, CoCl2 (0.033 g, 0.25
mmol) in 1 mL CH3CN was added. Black precipitate
was treated as defined in the general procedure to
give complex 9 (0.031 g, 38.75%), mp 136–140°С.
IR (KBr, сm−1): 390 (P P), 231 (P(S) S). Anal.
Heteroatom Chemistry DOI 10.1002/hc

8
Kursheva et al.
[9] Badeeva, E. K.; Platova, E. V.; Kursheva, L. I.;
Zvereva, E. E.; Vandyukov, A. E.; Katsyuba, S. A.;
Kovalenko, V. I.; Batyeva, E. S.; Sinyashin, O. G. Het-
eroatom Chem 2011, 22(1), 24–30.
calcd. for C6H16ClCo2NP4S8 (635.5): С 11.3; H 2.51;
Co 18.50; N 2.2; P 19.5. Found: С 10.76; H 3.04; Co
18.61; N 2.75; P 19.63.
[10] Kursheva, L. I.; Batyeva, E. S.; Zvereva, E. E.;
Badeeva, E. K.; Platova, E. V.; Sinyashin, O. G. Phos-
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Heteroatom Chemistry DOI 10.1002/hc