Synthesis and characterization of O,O′-(o-, m-, or p-ditolyl) dithiophosphate ligands

Article abstract of DOI:10.1080/10426500601090917

O,O ′-(ortho-, meta-, or para-ditolyl) dithiophosphate ligands have been isolated as triethylammonium salts, (o-, m-or p-CH3C6H4O)2PS2HNEt3, by an auto-catalytic reaction of cresols with P2S5 in the presence of Et3N in a 4:1:2 molar ratio in toluene under

Full text of DOI:10.1080/10426500601090917

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Phosphorus, Sulfur, and Silicon
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Synthesis and Characterization
of O,O′-(o-, m-, or p-Ditolyl)
Dithiophosphate Ligands
Aran Kumar a , Kuldeep R. Sharma a & Sushil K.
Pandey a
a Department of Chemistry , University of Jammu ,
Jammu, India
Published online: 20 Apr 2007.
To cite this article: Aran Kumar , Kuldeep R. Sharma & Sushil K. Pandey (2007)
Synthesis and Characterization of O,O′-(o-, m-, or p-Ditolyl) Dithiophosphate Ligands,
Phosphorus, Sulfur, and Silicon and the Related Elements, 182:5, 1023-1031, DOI:
10.1080/10426500601090917
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Phosphorus, Sulfur, and Silicon, 182:1023–1031, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500601090917
Synthesis and Characterization of O,O ꢀ-(o-, m-, or
p-Ditolyl) Dithiophosphate Ligands
Aran Kumar
Kuldeep R. Sharma
Sushil K. Pandey
Department of Chemistry, University of Jammu, Jammu, India
O,O ꢀ-(ortho-, meta-, or para-ditolyl) dithiophosphate ligands have been isolated as
triethylammonium salts, (o-, m- or p-CH C H O) PS HNEt , by an auto-catalytic
3
6
4
2
2
3
reaction of cresols with P S in the presence of Et3N in a 4:1:2 molar ratio in toluene
2
5
under anhydrous conditions. These triethylammonium salts could be converted into
sodium/ammonium salts, (o-, m-, or p-CH C H O) PS Na/NH , by their direct
3
6
4
2
2
4
reaction with sodium metal in equimolar ratio or passing dry ammonia gas in
toluene. These salts were characterized by elemental analyses (C, H, N, and S) and
1
13
31
mass, IR, and NMR ( H, C, and P) spectroscopic studies.
Keywords Cresyl; dithiophosphates; ditolyl; triethylammonium
INTRODUCTION
O,O ꢀ-dialkyl dithiophosphoric acids, (RO)2PS2H (where R = Me, Et,
Prn, Pri, or But), and cyclic analogous, O,O ꢀ-alkylene dithiophosphoric
acids, OGOPS2H (where G = 1,2- and 1,3-glycols), as well as their al-
kali metal salts have occupied a unique position as versatile chelating
ligands in the last three decades.1−4 These ligands are known to form a
variety of complexes with transition and non-transition elements.3−12
In general, a universal bi-dentate nature of these ligands has been
established.7−10,12 However, they have also depicted other bonding
modes, e.g., monodentate, bridging, or chelating toward several met-
als and metalloids.2,6,13 These ligands are known to form polymeric
complexes.10Various dithiophosphate complexes find extensive appli-
cations in agriculture,11 industries,13,14 extraction,15 and analytical
processes.16 A literature survey revealed that a substantial amount of
Received July 30, 2006; accepted October 6, 2006.
Address correspondence to Sushil K. Pandey, Department of Chemistry, University of
Jammu, Baba Saheb Ambedkar Road, New University Campus, Jammu, 180 006 India.
E-mail: kpsushil@rediffmail.com
1023

1024
A. Kumar et al.
work has been done with these ligands but scant information is avail-
able on the synthesis and characterization O,O ꢀ-ditolyl dithiophosphate
ligands and their derivatives. The synthesis of (p-CH3C6H4O)2PS2H
and its salts is reported; however, these have been characterized mainly
on the basis of UV and IR spectroscopy.17 Only a few reports are avail-
able on this subject, and they lack either the description of a conve-
nient route to synthesis or proper characterization.18−22 In addition,
forced conditions, such as a higher temperature ranging 115–150◦C,
were applied for synthesis, and there also were difficulties in separa-
tion. Recently, some metal complexes with ditolyl dithiophosphate lig-
ands have been synthesized and characterized.23,24 Some derivatives of
ditolyl dithiophosphates have found applications both in industries25−27
and agriculture.28 Therefore, it was thought worthy to investigate the
chemistry of O,O ꢀ-(o-, m-, or p-ditolyl) dithiophosphates, and we report
here on the convenient synthesis and characterization of O,O ꢀ-(o-, m-,
or p−ditolyl) dithiophosphate ligands.
RESULTS AND DISCUSSION
Reactions of P2S5 with ortho-, meta-, or para-hydroxytoluenes (cresols)
in the presence of triethylamine, Et3N, in a 4:1:2 stoichiometry in
toluene were quite facile at 40–50◦C and yielded sticky solid com-
pounds corresponding to (RO)2PS2HNEt3, where R = o CH3C6H4O (1),
m CH3C6H4O (2), and p CH3C6H4O (3) (Scheme 1).
SCHEME 1
Zemlyanskii and Glushkova have obtained crude (p-CH3C6H4O)2
PS2H by the reaction of P2S5 with cresol at 150◦C, which on reaction
with K2CO3 gave potassium salt in a 60% yield.20 We have found that
cresols do not show any reactivity with P2S5 in the absence of triethy-
lamine even on refluxing in toluene over a week’s time. It is to be noted
also that the reactions of P2S5 with alcohols or glycols also are a bit
sluggish and are completed usually in 4–6 h. Therefore, it is impli-
cated that Et3N has not only acted as a reactant but also played a cat-
alytic role in these reactions. It may be presumed that an ionic species,
[CH3C6H4O]−Et3NH+, initially formed, which then reacted with P2S5
in a rather facile way (Scheme 2).
Compounds (1–3) are fairly soluble in common organic solvents like
toluene, chloroform, methylenedichloride, or benzene, and are insoluble

O,O ꢀ-(o-, m-, or p-Ditolyl) Dithiophosphate Ligands
1025
SCHEME 2
in carbon tetrachloride or n-hexane. These were obtained in a quantita-
tive yield and appear to be moisture sensitive but sufficiently stable to
handle if they are not directly exposed to moisture. These compounds
get crystallized in 2–3 days just by leaving them at r.t. or by keeping
the toluene-hexane solution at 0◦C. These triethylammonium salts of
O,O ꢀ-(ortho-, meta-, or para-ditolyl) dithiophosphates (1–3) were easily
converted into sodium salts by their direct reaction with sodium metal
in toluene in a 1:1 molar ratio (Scheme 3).
SCHEME 3
Passing dry NH3 gas through a toluene solution of triethylammo-
nium salts (1–3) for 8–10 min resulted in the formation of ammonium
salts of O,Oꢀ-ditolyl dithiophosphates (Scheme 4).
SCHEME 4
Sodium and ammonium salts are soluble in CH3OH or EtOH, spar-
ingly soluble in chloroform, and insoluble in most of the hydrocarbon
solvents. Efforts were made to convert triethylammonium salts of O,O ꢀ-
(o-, m-, or p-ditolyl) dithiophosphates into O,O ꢀ-(o-, m-, or p-ditolyl)
dithiophosphoric acids, (CH3C6H4O)2PS2H, by their reaction with dry
hydrochloric gas (HCl), but this was not successful to isolate because
the final product was embedded with impurities, which could not be
separated. However, this could be achieved by the reaction of triethy-
lammonium salts of O,O ꢀ- (o-, m-, or p-ditolyl) dithiophosphates with
acetic acid in toluene or benzene ,which results in the formation of
a compound corresponding to (CH3C6H4O)2PS2H in a 50–60% yield

1026
A. Kumar et al.
SCHEME 5
(Scheme 5). This work is still under progress, especially in view of the
characterization and optimization of yield.
The micro-elemental analyses (C, H, N, and S) of all the previously
discussed compounds (1–9) were found consistent to their molecular
composition. The monomeric nature of compounds (1–3) has been found
by their molecular weight determinations in freezing benzene. All these
compounds have shown the presence of the molecular ion peak in mass
spectra.
IR spectra were recorded in the range 4000–200 cm−1, and the
tentative assignments were done on the basis of relevant literature
reports.1−5 IR spectra have shown a broad absorption for νNH vibra-
tions in the region 3581–3425 cm−1 in compounds (1–3) and (7–9), while
these absorptions were absent in compounds (4–6). In all the compounds
ν(P) O C and νP O (C), stretching vibrations were found in the re-
gion 1189–1108 cm−1 and 950–860 cm−1, respectively. Bands in region
563–540 cm−1 and 702–672 cm−1 may be assigned to νP S and νP S
(symmetric and asymmetric) vibrations. The νCH stretching vibrations
due to the tolyl group appeared in the region 2950–2910 cm−1
.
In 1H NMR spectra, a triplet and quartet were observed for CH3 and
CH2 protons of Et3N moiety in the compounds (1–3) at δ 1.25–1.29 ppm
(J = 7.2 Hz) and δ 3.09–3.11 ppm, respectively. The chemical shift for the
NH proton in compounds (1–3) and (7–9) appeared as a broad signal
at δ 9.24–9.64 ppm. The chemical shifts of CH3 (attached to tolyl) and
for tolyl ring protons were observed at δ 2.10–2.29 ppm and δ 6.82–7.44
ppm with a usual splitting pattern. The sodium and ammonium salts
of the cresyl dithiophosphates have shown the chemical shifts for all
the protons except the protons due to Et3NH group.
The 13C NMR spectral study of compounds (4–9) was not possible
due to their poor solubility in CDCl3. However, the 13C NMR spectral
data of compounds (1–3) have provided rather useful information. In 13
C
spectra of compounds (1–3), the chemical shifts for CH3 and CH2 car-
bons of the Et3NH moiety were observed in the regions δ 8.49–8.52 and
δ 46.18–46.23 ppm, respectively. This upfield shift is due to the presence
of a nitrogen atom bonded to it carrying a positive charge. For compound
(1), chemical shifts for the CH3 carbons of both tolyl rings were found
at δ 17.45–17.48 ppm. Chemical shifts for para- and meta-carbon were
found in the regions δ 126.07–131.22 and δ 124.29–125.86 ppm, respec-
tively. The shift for carbon, to which methyl groups are attached, was

O,O ꢀ-(o-, m-, or p-Ditolyl) Dithiophosphate Ligands
1027
found in the region δ 130.76–131.05 ppm, where a shift for ortho-carbon
(unsubstituted ones) was found in the normal region δ 120.81–123.94
ppm, suggesting that none of the protons of these carbon atoms are in-
volved in hydrogen bonding. The absence of hydrogen bonding is also
confirmed by no significant change in the chemical shift for C O. The
13C spectrum of compound (2) has shown a chemical shift for the CH3
carbon of the two tolyl rings at δ 17.50 and δ 17.46 ppm. Chemical shifts
for ortho-, meta-, and para- carbons were found in the regions δ 121.80–
123.79, δ 124.37–126.04, and δ 126.26–130.99 ppm, respectively. Shifts
for three ortho-carbons were found in the region δ 121.80–123.97 ppm,
while one of the ortho-carbons was observed with an upfield shift at δ
115.17 ppm. This abnormal shift value might be due to intramolecular
hydrogen bonding between protons attached to the carbon and oxygen
atom. This hydrogen bonding is further supported by the chemical shift
for C O, which occurred at δ 154.73 ppm as compared to a shift for aro-
matic C O without hydrogen bonding at 150–152 ppm.29,30 In the 13
C
spectrum of compound (3), chemical shifts for the CH3 carbon of both
tolyl rings were found at δ 17.48 and δ 17.45 ppm. The chemical shift for
para-carbon, to which methyl groups are attached, was found in the re-
gion δ 126.82–131.20 ppm. The shifts for meta- and ortho-carbon were
found in the region δ 122.34–124.00 ppm and δ 124.38–126.62 ppm,
while one of the ortho-carbons was observed with an upfield shift at δ
115.09 ppm, which is due to the presence of intramolecular hydrogen
bonding akin to [(m CH3C6H4O)2PS2HNEt3].
31P NMR spectra (proton-decoupled) have shown the chemical shift
as a singlet in each case in the downfield region. Chemical shifts for
compounds (1–9) were found in the region δ 105.22–109.14 ppm, re-
spectively. Occurrence of a singlet in each case indicated the equivalent
nature of phosphorus nucleus in the molecule.
EXPERIMENTAL
General Procedures and Reagents
All the experimental manipulations were carried out strictly under an-
hydrous conditions, and a nitrogen atmosphere and also by using mod-
ified Schlenk techniques. Triethylamine (Thomas Baker, b.p. 88.8◦C)
and cresols (Highmedia, b.p. 191◦C ortho-, 203◦C meta-, and 202◦C
para-), were freshly distilled prior to use. P2S5(Spectrochem) was pro-
cured commercially and it was used as such. Toluene was dried by
refluxing over sodium metal and kept under a nitrogen atmosphere.
Micro-elemental analysis (C, H, and N) was done on a Vario EL III ele-
mental analyzer, while sulfur was estimated as BaSO4 by Messenger’s

1028
A. Kumar et al.
method. Infrared spectra were recorded in KBr on an FTIR Perkin
Elmer-377 spectrophotometer. 1H and 13C NMR spectra were measured
on Jeol FX 90Q 90MHz using TMS as an external reference. 31P NMR
spectra were recorded by means of a Brucker DRX 300 (120 MHz) us-
ing 85% H3PO4 as an external reference. The mass spectrophotometeric
analysis (EI) was carried out on ESQUIRE-300 (Brucker-Daltonics).
Synthesis
(o-CH3C6H4O)2PS2HNEt3 (1)
A toluene solution (∼40 mL) of freshly distilled ortho-cresol (9.37 g,
8.99 mmol) was added dropwise to a toluene (∼80 mL) suspension of
P2S5 (5.0 g, 2.24 mmol). After stirring the contents for 5–7 min at
∼50◦C, a toluene solution (∼40 mL) of Et3N (4.55 g, 4.59 mmol) was
added dropwise to it. All the P2S5 was dissolved in 15–20 min, result-
ing in a clear mixture. Evaporation of excess of toluene under reduced
pressure resulted in the compound (o-CH3C6H4O)2PS2HNEt3 (1) in a
quantitative yield as a colorless sticky solid. Yield 18.1 g (97.8%); m.p.
56–58◦C; MS(EI, m/z): 410 (28%) (M+); Anal. calcd. for C20H30O2PS2N
(411.54): C, 58.31; H, 7.28; S, 15.55% Found: C, 58.29; H, 7.30; S, 15.54;
IR (KBr, cm−1): 3581b, 2950b, 1615m, 1502s, 1488s, 1108s, 909s, 680s,
1
596s, and 540m; H NMR (CDCl3, δ ppm): 1.25 (t, 9H, CH3 of Et3N,
J = 7.2 Hz), 2.23 (s, 6H, CH3 of cresol), 3.09 (m, 6H, CH2 of Et3N),
7.0–7.25 (m, 8H , C6H4), 9.24 (s, 1H, -NH); 31P NMR (CDCl3, δ ppm):
105.65 (s).
(m-CH3C6H4O)2PS2HNEt3 (2)
The procedure adopted for the synthesis of (2) was similar to those
used for (1). For the reaction, 7.49 g (6.9 mmol) of meta-cresol, 4 g
(1.8 mmol) of P2S5, and 6.64 g (3.59 mmol) of Et3N were used, and the
product was a colorless sticky solid. Yield 14.5 g (98%); m.p. 55–57◦C;
MS(EI, m/z): 411.54 (31%, M+); Anal. calcd. for C20H30O2PS2N (411.54):
C, 58.31; H, 7.28; S, 15.55%. Found: C, 58.29; H, 7.30; S, 15.55%; IR
(KBr, cm−1): 3513b, 2940b, 1585s, 1502s, 1139s, 950s, 687s, and 563m;
1H NMR (CDCl3, δ ppm): 1.25 (t, 9H , CH3 of Et3N, J = 7.2 Hz), 2.29
(s, 6H, CH3 of cresol), 3.11 (m, 6H, CH2 of Et3N), 6.92–7.25 (m, 8H ,
C6H4), 9.25 (s, 1H, -NH); 31P NMR (CDCl3, δ ppm): 105.34 (s).
(p-CH3C6H4O)2PS2HNEt3(3)
A similar synthetic procedure as in the cases of (1) or (2) was used for
the preparation of (3). The reaction of 6.20 g (5.80 mmol) para-cresol,
3.35 g (1.5 mmol) P2S5, and 3.04 g (3.01 mmol) of Et3N was carried out,
which resulted in compound (3) as a colorless sticky solid. Yield 12.16

O,O ꢀ-(o-, m-, or p-Ditolyl) Dithiophosphate Ligands
1029
g (98%); m.p. 57◦C; MS(EI, m/z): 411.54 (27%, M+); Anal. calcd. for
C20H30O2PS2N (411.54): C, 58.31; H, 7.28; S, 15.55%. Found: C, 58.30;
H, 7.27; S, 15.53%; IR (KBr, cm−1): 3543b, 2945b, 1608s, 1486s, 1189s,
1
1122s, 935s, 683s, and 550m; H NMR (CDCl3, δ ppm): 1.25 (t, 9H,
CH3 of Et3N, J = 7.2 Hz), 2.25 (s, 3H, –CH3 of cresol), 3.11 (m, 6H,
CH2 of Et3N), 7.03–7.33 (m, 8H, C6H4), 9.25 (s, 1H, -NH); 31P NMR
(CDCl3, δ ppm): 105.6 (s).
(o-CH3C6H4O)2PS2Na (4)
A weighed amount of sodium metal (0.28 g, 1.2 mmol) was added to
a toluene solution (∼100 mL) of (o CH3C6H4O)2PS2HNEt3 (1) (4.93 g,
1.2 mmol), and the mixture was stirred for 3 h at ∼55◦C, which resulted
in white precipitates. The contents were cooled and then filtered by a
funnel fitted with a G-4 sintered disc. Finally, the residue was dried
under reduced pressure that gave compound (4) as a white solid. Yield
3.95 g (97.5%); m.p. 188◦C; MS(EI, m/z): 333.35 (22%, M+); Anal. calcd.
for C14H14O2PS2Na (333.35): C, 50.39; H, 4.20; S, 19.20%. Found: C,
50.40; H, 4.22; S, 19.18; IR (KBr, cm−1): 2920b, 1618m, 1502s, 1211m,
1
1159s, 876s, 691s, 556m, and 520m; H NMR (CDCl3, δ ppm): 2.20 (s,
6H, CH3 of cresol), 6.82–7.30 (m, 8H, C6H4); 31P NMR (CH3OH, δ
ppm): 109.24 (s).
(m-CH3C6H4O)2PS2Na (5)
3.66 g (0.89 mmol) of (m-CH3C6H4O)2PS2HNEt3 (2) and 0.21 g (0.89
mmol) of sodium metal were used for the preparation of (5). All the
experimental manipulations were similar as used for compound (4).
Compound (5) was obtained as a white solid. Yield 2.35 g (97.1%); m.p.
188◦C; MS(EI, m/z): 333.35 (24%, M+); Anal. calcd. for C14H14O2PS2Na
(333.35): C, 50.39; H, 4.20; S, 19.20%. Found: C, 50.38; H, 4.20; S,
19.20%; IR (KBr, cm−1): 2910b, 1622m, 1512s, 1217m, 1150s, 886s, 672s,
and 550m; 1H NMR (CDCl3, δ ppm): 2.24 (s, 6H, CH3 of cresol), 6.95–
7.44 (m, 8H, C6H4); 31P NMR (CH3OH, δ ppm): 109.19 (s).
(p-CH3C6H4O)2PS2Na (6)
The method used for this synthesis was similar as used for com-
pounds (4–5). 4.23 g (1.0 mmol) of (3) and 0.23 g (1.0 mmol) of sodium
metal were used, which resulted in the formation of compound (6) as
a white solid. Yield 3.38 g (98.8%); m.p. 188◦C; MS(EI, m/z): 333.35
(20%, M+); Anal. calcd. for C14H14O2PS2Na (333.35): C, 50.39; H, 4.20;
S, 19.20%. Found: C, 50.40; H, 4.20; S, 19.19%; IR (KBr, cm−1): 2912w,
1
1620m, 1508s, 1214m, 1151s, 883s, 672s, and 552m; H NMR (CDCl3,

1030
A. Kumar et al.
δ ppm): 2.24 (s, 6H, CH3 of cresol), 6.94–7.24 (m, 8H, C6H4); 31P NMR
(CH3OH, δ ppm): 109.11 (s).
(o-CH3C6H4O)2PS2NH4 (7)
Dry ammonia gas was passed through a toluene solution (∼100 mL)
of (o-CH3C6H4O)2PS2HNEt3 (1) (2.46 g, 0.60 mmol) for 8–10 minutes at
r.t., which resulted in the formation of white precipitates. Compound (7)
was obtained as a white powder after filtration by using a funnel fitted
with a G-4 sintered disc and drying under reduced pressure. Yield 1.87
g (95.89%); m.p. 64◦C; MS(EI, m/z): 327.41 (26%, M+); Anal. calcd. for
C14H14O2PS2NH4 (327.41): C, 51.35; H, 5.54; S, 19.50; N, 4.27%. Found:
C, 50.90; H, 4.21%; S, 19.10; N, 4.25%; IR (KBr, cm−1): 3425b, 2920b,
1
1615m, 1500s, 1211m, 1158s, 860s, 688s, and 558m; H NMR (CDCl3,
δ ppm): 2.23 (s, 6H, CH3 of cresol), 6.85–7.34 (m, 8H, C6H4), 9.54 (s,
4H, NH4); 31P NMR (CH3OH, δ ppm): 109.34 (s).
(m-CH3C6H4O)2PS2NH4 (8)
m-CH3C6H4O)2PS2HNEt3 (2) (1.23 g, 0.30 mmol) was used for the
synthesis of compound (8), while using a similar method as for com-
pound (7). Yield 1.05 g (85.36%); m.p. 68◦C; MS(EI, m/z): 327.41 (23%,
M+); anal. calcd. for C14H14O2PS2NH4 (327.41): C, 51.35; H, 5.54; S,
19.5; N, 4.27%. Found: C, 50.44; H, 4.15; S, 19.11; N, 4.24%; IR (KBr,
cm−1): 3431b, 2920b, 1618m, 1510s, 1212m, 1159s, 880s, 702s, and
556m; 1H NMR (CDCl3, δ ppm): 2.23 (s, 6H, CH3 of cresol), 6.83–7.33
(m, 8H, C6H4), 9.64 (s, 4H, NH4); 31P NMR (CH3OH, δ ppm): 109.60 (s).
(p-CH3C6H4O)2PS2NH4 (9)
p-CH3C6H4O)2PS2HNEt3 (2) (1.64 g, 0.4 mmol) was used for the syn-
thesis of compound (8), while using a similar method as for compound
(7). Yield 1.50 g (91.46%); m.p. 66◦C; MS(EI, m/z): 327.41 (27%, M+);
anal. calcd. for C14H14O2PS2NH4 (327.41): C, 51.35; H, 5.54; S, 19.5;
N, 4.27%. Found: C, 50.80; H, 5.21; S, 19.00; N, 4.25%; IR (KBr, cm−1):
1
3435b, 2933b, 1617m, 1508s, 1201m, 1166s, 878s, 700s, and 562m; H
NMR (CDCl3,δ ppm): 2.21 (s, 6H, CH3 of cresol), 6.88–7.30 (m, 8H,
C6H4), 9.31 (s, 4H, NH4); 31P NMR (CH3OH, δ ppm): 109.2 (s).
REFERENCES
[1] J. R. Wasson, G. M. Wolterman, and H. J. Stocklosa, Top. Curr. Chem., 35, 65 (1973).
[2] I. Haiduc, Rev. Inorg. Chem., 3, 353 (1981).
[3] H. P. S. Chauhan, Coord. Chem. Rev., 79, 207 (1998).
[4] B. P. S. Chauhan, G. Srivastava, and R. C. Mehrotra, Coord. Chem. Rev., 55, 207
(1984).

O,O ꢀ-(o-, m-, or p-Ditolyl) Dithiophosphate Ligands
1031
[5] S. K. Pandey, G. Srivastava, and R. C. Mehrotra, Trans. Met. Chem., 16, 252 (1991).
[6] H. Preut, V. D. Ngo, and F. Huber, Acta Crystallogr. Sec. C, 43, 164 (1987).
[7] R. Chander, B. L. Kalsotra, and S. K. Pandey, Trans. Met. Chem., 28, 405 (2003).
[8] U. N. Tirpathi, Phosph.- Sulf. and Silicon, 159, 47 (2000).
[9] S. K. Pandey, G. Srivastava, and R. C. Mehrotra, Synth. React. Inorg. Met.-Org.
Chem., 19, 795 (1989).
[10] T. Ito and H. H. Igrashi, Acta Crystallogr. Sect. B, 25, 2303 (1969).
[11] U. N. Tirpathi, P. P. Bipin, R. Mirza, and S. Shukla, J. Coord. Chem., 55, 1111 (2002).
[12] R. Chander, B. L. Kalsotra, and S. K. Pandey, Ind. J. Chem., 34A, 1134 (2004).
[13] T. A. Guiton and C. G. Pantano, Sol-Gel Processing of Sulphide. [Abstract 5th Inter-
national Workshop on Glasses, Ceramics and Gels, Rio de Janeiro (1989).
[14] D. R. Baker, U. S. Pat. 4 012 421/1977; Chem. Abstr., 87, 6201 (1977).
[15] G. A. Marinkina, I. L Kotlyarevskii, and I. S. Levin, Zh. Prikl., Khim., 50, 427 (1977);
Chem. Abstr., 86, 146568p (1977).
[16] N. A. Ulakhovich, G. K. Budhnikov, I. V. Postnova, and N. K. Shakukurova, Zabod
Lab., 46, 587 (1980); Chem. Abstr., 93, 125128z (1980).
[17] E. I. Markova, D. A. Akhmedzade, and N. F. Dzhanikbekov, Zerb. Khim. (Russ.), 1,
135 (1984); Chem. Abstr., 101, 22136d (1984).
[18] Nippon Chemical Industrial Co. Ltd., Jpn. Pat. JP58032889 A2 19830225 (1983);
Chem. Abstr., 99, 5829f (1983).
[19] M. Oktawiec, Prace Inst. Ministerswa Hutnictwa, 9, 320 (1957); Chem. Abstr., 52,
72179 (1957).
[20] N. I. Zemlyanskii and L. V. Glushkova, Zh. Obsch. Khim., 36(12), 2193 (1966); Chem.
Abstr., 66, 75776d (1967).
[21] I. P. Komkov and V.M. Levitskaya, Khim. Khim. Tekh., 10, 1014 (1967); Chem.
Abstr., 68, 39241h (1968).
[22] D. A. Akhmedzade, V. D. Yasnopol’skii, and N. F. Dzhanibekov, Akad. Nauk USSR,
11, 92 (1980); Chem. Abstr., 95, 42534u (1981).
[23] S. Wu, Z. Liu, Y. Zhang, and P. Li, Gaz. Chim. Italiana, 123, 647 (1993); Chem.
Abstr., 121, 35806m (1994).
[24] Q. Hao, H. K. Fun, S. Chantrapromma, I. A. Razak, F. Jian, X. Yang, et al., Acta.
Crystallogr., 57, 717 (2001).
[25] J. A. McCleverty, R. S. Z. Kowalski, N. A. Bailey, R. Mulvaney, and D. A. O’Cleirigh,
J. Chem. Soc. Dalt. Trans., 4, 627 (1983).
[26] N. N. Glebova, O. K. Sharaev, E. I. Tienyakova, and B. A. Dolgoplosk, Vysokomolekul.
Soedin. Seriya, 37, 1145 (1995); Chem. Abstr., 125, 143371g (1996).
[27] W. E. McEwen, V. C. Si, and B. J. Kalbacher, Phosph., Sulf. and Silicon, 11, 191
(1981).
[28] Q. Xie, N. Luo, J. Li, and X. Jing, Youji Huaxue, 12, 159 (1992); Chem. Abstr., 117,
26650w (1992).
[29] A. Kumar, S. Koul, T. K. Rajdan, and K. K. Kapoor, Tetrahedron Lett., 47, 837 (2006).
[30] J. Wang, Y. Shen, W. Hu, M. Hseish, F. Lin, and M. Hsu, J. Med. Chem., 49, 1442
(2006).