T.S. Lobana et al. / Journal of Organometallic Chemistry 745-746 (2013) 460e469
461
C3H5NS(NeH))(
m
-S-C3H5NS(NeH))Cl]n [22a], [Ag2(
m
-S-C3H3NS(Ne
1439(sh),
n
(CeN) þ
d
(CeH); 1186(s),
n
(C]S); 1108(w), 986(m),
Me))(m3-I)2]n [22b] and {Ag(C5H5NS)Cl}n complexes have been re-
ported. Further, coordination chemistry of 2,4-dithiouracil
(C4H4N2S2, structure IV) is limited and there are only a few struc-
turally characterized complexes of CoIII, TiIII, RuII and CuI [17,23,24].
In view of our interest in the development of coordination
chemistry of silver(I) halides, we have reported complexes with a
few heterocyclic thioamides [17,19] and related N, S-donor ligands,
namely, thiosemicarbazones [25]. In this paper, reactions of silver(I)
halides (X ¼ Cl, Br) with a series of heterocyclic-2-thiones as shown
in Chart 1 [structures I (R ¼ H, Me, Et, Prn), II, III and IV] have been
carried out in the presence of PPh3 as co-ligand and the resulting
complexes characterized using analytical data, IR and multinuclear
NMR spectroscopy (1H and 31P) and single crystal X-ray crystal-
lography (1e4, 6e13).
915(m), n d ppm): 7.79 (s, 1H, NH),
(PeCPh). 1H NMR data (CDCl3,
7.26e7.44 (m, 16H, PPh3 þ CHCl3). 3.73 (s, 4H, C4,5H).
2.2.2. [Ag2(m-Cl)2(k
1-S-C3H5NS(NeMe))2(PPh3)2] 2
It was prepared by the method used for complex 1 (Yield 67%,
mp. 161e164 ꢁC). Found: C, 51.18; H, 4.52; N, 5.38. Calc. for
C
45H48Ag2Cl2N4P2S2: C, 51.06; H, 4.54; N, 5.29%. IR absorptions (
cmꢀ1): 3178(m),
(NeH); 3065e2880(w), (CeH); 1513(s),
1478(sh), (CeH); 1192(m), (C]S); 1093(s), (PeCPh);
(CeN) þ
958(w), ppm): 9.14 (s, 1H, NH),
(NeCH3). 1H NMR data (CDCl3,
7.50e7.33 (m, 15H, PPh3), 3.70 (d, 4H, C4,5H), 3.10 (s, 3H, CH3).
n/
n
n
n
d
n
n
d
d
2.2.3. [Ag2(m-Cl)2(k
1-S-C3H5NS(NeEt))2(PPh3)2] 3
It was prepared by a method used for complex 1 (Yield 66%, mp.
165e167 ꢁC). Found: C, 51.35; H, 4.61; N, 5.14. Calc. for
C
46H50Ag2Cl2N4P2S2: C, 51.51; H, 4.66; N, 5.22%. IR absorptions (n/
2. Experimental section
cmꢀ1): 3202(m),
1478(sh),
(CeN) þ
NMR data (CDCl3,
C4,5H, NeCH2), 1.20 (t, 3H, CH3).
n
(NeH); 3051e2885(w),
n
(CeH); 1516(s),
n
d(CeH); 1187(m),
n
(C]S); 1094(s),
n
(PeCPh). 1H
2.1. Materials and techniques
d
ppm): 7.50e7.39 (m, 15H, PPh3), 3.63 (m, 6H,
Silver(I) halides were freshly prepared from AgNO3 and potas-
sium halides (X ¼ Cl, Br) in methanol and dried in vacuo. Imida-
zolidine-2-thione, thiazolidine-2-thione, 1-methyl-imidazoline-2-
thione and 2,4-dithiouracil were procured from Aldrich Chem-
icals Ltd. and used as such. The N-alkyl-imidazolidine-2-thiones (1-
methyl-imidazolidine-2-thione, 1-ethyl-imidazolidine-2-thione, n-
2.2.4. [AgCl(k
1-S-C3H5NS(NeMe))(PPh3)2] 4
To silver(I) chloride (0.025 g, 0.17 mmol) suspended in aceto-
nitrile was added solid PPh3 (0.091 g, 0.34 mmol), and the contents
were stirred for 24 h. The white solid formed was filtered and dried
in vacuo. To this solid suspended in chloroform was added solid 1-
methyl-imdazolidine-2-thione (0.020 g, 0.17 mmol) and the con-
tents were stirred until a clear solution was obtained, which was
allowed to evaporate at room temperature. The solid obtained was
dissolved in dichloromethane and acetonitrile mixture. Slow
evaporation of the solution resulted in colorless crystals of 4 (Yield
68%, mp. 165e167 ꢁC). Found: C, 61.40; H, 4.95; N, 3.62. Calc. for
propyl-imidazolidine-2-thione
and
n-butyl-imidazolidine-2-
thione) were prepared as per the literature methods [26]. The C,
H and N analyses were obtained with Thermoelectron FLASHEA
1112 CHNS analyzer. The IR spectra were recorded using KBr pellets
in the range 4000e400 cmꢀ1 on Varian 660-IR Fourier transform
infrared spectrophotometer. The melting points were determined
with a Gallenkamp electrically heated apparatus. The 1H NMR
spectra were recorded on a JEOL AL300 FT spectrometer at 300 MHz
in CDCl3 with TMS as the internal reference. The 31P NMR spectra
were recorded on BRUKER AVANCE II 400 spectrometer operating
at a frequency of 161.9 MHz using o-phosphoric acid as the external
reference set at zero position.
C
40H38AgClN2P2S: C, 61.26; H, 4.85; N, 3.57%. IR absorptions (n/
cmꢀ1): 3212m (br),
n
(NeH); 3066e2799(m),
n
(CeH); 1515(s),
1479(s),
996(w),
n
(CeN) þ
d
(CeH); 1180(m),
n
(C]S); 1093(m), n(PeCPh);
d
(NeCH3). 1H NMR data (CDCl3,
d ppm): 8.64 (s, 1H,
NH), 7.42e7.26 (m, 16H, PPh3 þ CHCl3), 3.61 (m, 4H, C4,5H), 3.08 (m,
3H, CH3).
2.2. Synthesis of complexes
2.2.5. [AgCl(k
1-S-C3H5NS(NeEt)(PPh3)2)] 5
2.2.1. [Ag2(m-Cl)2(k
1-S-C3H5NS(NeH))2(PPh3)2] 1
It was prepared by a method used for complex 4 (Yield 66%, mp.
151e154 ꢁC). Found: C, 61.55; H, 4.95; N, 3.62. Calc. for
C
To silver(I) chloride (0.025 g, 0.17 mmol) suspended in aceto-
nitrile was added solid PPh3 (0.045 g, 0.17 mmol) and the contents
were stirred for 24 h. The white solid formed was filtered and dried
in vacuo. To this solid suspended in chloroform was added solid
imdazolidine-2-thione (0.018 g, 0.17 mmol) and the contents were
stirred until a clear solution was obtained, which was allowed to
evaporate at room temperature. The solid obtained was dissolved in
dichloromethane and acetonitrile mixture. A slow evaporation of
the solution resulted in colorless crystals of complex 1 (Yield 70%,
mp. 163e165 ꢁC). Found: C, 49.54; H, 4.16; N, 6.07. Calc. for
41H40AgClN2P2S: C, 61.71; H, 5.01; N, 3.51%. IR absorptions (n/
cmꢀ1): 3202(m),
1478(m),
(CeN) þ
NMR data (CDCl3,
n
(NeH); 3050e2885(m),
n
(CeH); 1517(s),
n
d
(CeH); 1193(m),
d
PPh3 þ CHCl3). 3.58 (m, 6H, C4,5H, NeCH2), 1.17 (m, 3H, CH3).
n
(C]S); 1094(m),
n
(PeCPh). 1H
ppm): 8.60 (s, 1H, NH), 7.70e7.26 (m, 16H,
2.2.6. [AgCl(k
1-S-C3H5NS(NePrn)(PPh3)2)] 6
It was prepared by a method used for complex 1 (Yield 67%, mp.
150e153 ꢁC). Found: C, 61.95; H, 5.10; N, 3.48. Calc. for
C
42H42AgClN2P2S: C, 62.11; H, 5.17; N, 3.45%. IR absorptions (
cmꢀ1): 3092(w),
(NeH); 3051e2871(m), (CeH); 1511(s),
1479(sh), (CeH); 1186(m), (C]S); 1094(m), (PeCPh).
(CeN) þ
n/
C
21H21AgClN2PS: C, 49.70; H, 4.14; N, 5.52%. IR absorptions (
n/
cmꢀ1): 3150(m),
n
(NeH); 3040e2865(w), (CeH); 1509(s),
n
n
n
n
d
n
n
1H NMR data (CDCl3,
d ppm): 7.43e7.26 (m, 16H, PPh3, CHCl3). 3.61
(m, 4H, C4H, NeCH2), 3.49 (t, 2H, C5H), 1.55 (m, 2H, eCH2), 0.87 (t,
6
4
5
5
5
4
4
1
NH
5
3H, CH3).
1
1
NR
N1H
HN3
HN 3
NMe
3S
4
2
3
2.2.7. [Ag2(m-Br)2(k
1-S-C3H5NS(NeMe))2(PPh3)2] 7
2
2
2
N
S
S
To silver(I) bromide (0.025 g, 0.13 mmol) suspended in aceto-
nitrile was added solid PPh3 (0.070 g, 0.26 mmol) and the contents
were stirred for 24 h. The white solid formed was filtered and dried
in vacuo. To this solid suspended in chloroform was added solid
1-methyl-imdazolidine-2-thione (0.016 g, 0.13 mmol) and the
H
S
II
S
S
I
IV
III
Chart 1. Various thio-ligands used.