Synthesis and characterization of platinum and palladium pyrrolidinedithiocarbamate complexes

Article abstract of DOI:10.1007/s11243-013-9701-0

Treatment of (PPh₃)₂MCl₂ (M = Pd or Pt) with ammonium pyrrolidinedithiocarbamate (NH₄S₂CNC ₄H₈) in a 1:1 molar ratio gave (PPh₃)M(Cl) (κ ² S,S-S₂CNC₄H₈) [M = Pt (1), Pd (2)]. On the other hand, the interaction of these compounds in a 1:2 [M:L] molar ratio gave (PPh₃)Pt(κS-S₂CNC ₄H₈)(κ ² S,S-S₂CNC ₄H₈) (3), which contains both terminal and chelated dithiocarbamato ligands, or a yellow insoluble solid for M = Pd. The bis(diphenylphosphino)ethane platinum or palladium dichlorides [(dppe)MCl ₂] reacted with the same ligand to give the salts [(dppe)M(κ ² S,S-S₂CNC₄H₈)]Cl (M = Pt (4), Pd (5) which have only one chelating dithiocarbamato ligand. The new compounds were characterized by ¹H-, ¹³C{¹H}- and ³¹P-n.m.r. spectroscopy, mass spectrometry, elemental analysis and X-ray single crystal structure analysis.

Full text of DOI:10.1007/s11243-013-9701-0

Transition Met Chem (2013) 38:377–383
DOI 10.1007/s11243-013-9701-0
Synthesis and characterization of platinum and palladium
pyrrolidinedithiocarbamate complexes
•
Laith Almazahreh Mohammad El-khateeb
•
•
Mohammad Harb Helmar Gorls Wolfgang Weigand
•
¨
Received: 8 October 2012 / Accepted: 15 January 2013 / Published online: 6 February 2013
Ó Springer Science+Business Media Dordrecht 2013
Abstract Treatment of (PPh3)2MCl2 (M = Pd or Pt) with
ammonium pyrrolidinedithiocarbamate (NH4S2CNC4H8)
in a 1:1 molar ratio gave (PPh3)M(Cl)(j2S,S-S2CNC4H8)
[M = Pt (1), Pd (2)]. On the other hand, the interaction of
these compounds in a 1:2 [M:L] molar ratio gave (PPh3)Pt-
(jS-S2CNC4H8)(j2S,S-S2CNC4H8) (3), which contains both
terminal and chelated dithiocarbamato ligands, or a yellow
insoluble solid for M = Pd. The bis(diphenylphosphino)-
ethane platinum or palladium dichlorides [(dppe)MCl2]
reacted with the same ligand to give the salts [(dppe)M-
(j2S,S-S2CNC4H8)]Cl (M = Pt (4), Pd (5) which have only
one chelating dithiocarbamato ligand. The new compounds
Introduction
The dithiocarbamates (R2NCS2-) are versatile ligands
capable of bonding to transition as well as main group
metals [1–4]. They have been widely investigated because
of their importance in fields such as the chemical industry,
biology and biochemistry [5–10]. Coordination complexes
of dithiocarbamato ligands of Ni, Pd and Pt are known in
the literature [11–19]. Complexes of Pt(II) and Pd(II)
containing dithiocarbamato groups together with mono- or
diamine ligands have been described by Faraglia and others
[17–20]. These complexes include neutral [M(S2CNR2)-
(amine)(Cl)] or cationic complexes such as [M(S2CNR2)-
(amine)2]?. Some of these complexes were tested in vitro
against KB tumor cells; sub-line of the ubiquitous KER-
ATIN-forming tumor cell line Hela. The derivatives
[M(S2CNEt2)(bipy)]? and [M(S2CNEt2)(phen)]? showed
antitumor activity against leukemic cells [21]. The analo-
gous L-methioninol (=Mol) [M(S2CNR2)(Mol)]? (R = Me,
CH2CO2Et) complexes have been prepared by the reaction of
L-methioninol with [M(S2CNR2)Cl]n in a 1:1 molar ratio,
while reaction of the same reactants in 1:2 molar ratio gave the
binuclear species [M2(S2CNR2)2(Mol)Cl2] [22].
1
were characterized by H-, 13C{1H}- and 31P-n.m.r. spec-
troscopy, mass spectrometry, elemental analysis and X-ray
single crystal structure analysis.
¨
L. Almazahreh Á H. Gorls Á W. Weigand
Institut fu¨r Anorganische und Analytische Chemie,
¨
Friedrich-Schiller-Universtat Jena, Humboldt Strasse 8,
07743 Jena, Germany
M. El-khateeb (&)
Complexes of Pd and Pt with mixed tertiary phosphines
and dithiocarbamates have also been described by several
groups [23–28]. The interaction of (Ph2P(CH2)nPPh2)-
Chemistry Department, Jordan University of Science
and Technology, Irbid 22110, Jordan
e-mail: kateeb@just.edu.jo
-
PdCl2 (n = 1–4) with R2NCS2 in acetonitrile gave the
chelate complexes [(Ph2P(CH2)nPPh2)PdS2CNR2]? [23, 26].
The analogous Pt and Ni complexes [(Ph2P(CH2)2PPh2)-
M(S2CNEt2)]? were made in a similar way [27]. Com-
plexes of Pt(IV) and Pd(II) of the type [Pt(S2CNR2)2-
(PPh3)Cl2] and Pd(S2CNR2)2PPh3 were prepared from
the corresponding dichlorides; [Pt(S2CNR2)2Cl2] or
[M(S2CNR2)2] suspended in CS2, with phosphines dissolved
in toluene [28].
Present Address:
M. El-khateeb
Chemistry Department, Faculty of Science and Arts at Alkamil,
King Abdulaziz University, Alkamil 21931,
Kingdom of Saudi Arabia
M. Harb
Chemistry Department, Faculty of Science at Qunfudah,
Umm Al-Qura University, Qunfudah,
Kingdom of Saudi Arabia
123

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Transition Met Chem (2013) 38:377–383
Preparation of (PPh3)Pt(jS,S2CNC4H8)-
Our effort in this area involves the preparation of
(j2S,S-S2CNC4H8) (3)
CpRu(PPh3)(S2CNC4H8) using ammonium pyrrolidine-
dithiocarbamate and the chloride CpRu(PPh3)2Cl [29].
The dithiocarboxylates CpRu(PPh3)S2CR (R = 2-C4H3O,
2-C4H3S, C:CR’) have been obtained by a similar substi-
tution reaction [30]. In the present study, we describe the
interaction of ammonium pyrrolidinedithiocarbamate with
(PPh3)2MCl2 and (dppe)MCl2 (M = Pd, Pt) which gave
different products depending on the phosphine ligands and
the molar ratio of reactants.
A solution of (PPh3)2PtCl2 (0.11 g, 0.14 mmol) and ammo-
nium pyrrolidinedithiocarbamate (46 mg, 0.28 mmol) in
THF (50 cm3) was stirred for 48 h. After filtration, the
THF was removed under reduced pressure. The resulting
solid was extracted with CH2Cl2 and extracts concentrated
to dryness. Crystals suitable for X-ray diffraction analysis
of (3) were obtained by diffusion of pentane into a CH2Cl2
1
solution at 4 °C. Yield: 81 %. H-n.m.r. (CDCl3): d 1.95
(m, 4H, NCH2CH2); 2.04 (m, 4H, NCH2CH2); 3.60 (t, 4H,
3
3
2NCH2CH2, J = 6.8 Hz); 3.91 (t, 4H, 2NCH2CH2, J =
6.8 Hz); 7.35–7.55 (m, 15H, PPh3). 13C-n.m.r. (CDCl3):
d 25.1, 26.1 (CH2); 50.8, 55.1 (NCH2); 127.6, 129.5, 133.1
(PPh3); 200.5 (CS2). 31P-n.m.r. (CDCl3): d 17.43 (195Pt
Experimental
Materials and methods
2
satellites, JPPt = 4603 Hz). DEI-MS (m/z): 749 (M?).
All reactions were performed using standard Schlenk and
vacuum-line techniques under argon atmosphere. Sol-
vents (Fisher Scientific) were reagent grade, dried and
freshly distilled prior to use according to standard meth-
ods. Other chemicals (Acros) were used without further
purification.
C28H31N2PPtS4.0.25C5H10.2CH2Cl2 calcd.: C, 40.0; H,
4.1; N, 3.0; S, 13.7 %. Found: C, 40.4; H, 4.3; N, 2.8; S,
13.4 %.
Preparation of [(dppe)M(j2S,S-S2CNC4H8)]Cl (4, 5)
The 1H-, 13C{1H}- and 31P{1H}-n.m.r. spectra were
recorded on either a Bruker AVANCE 200 or 400 MHz
spectrometer using the solvent residual peak (1H, 13C{1H})
or 85 % H3PO4 (31P{1H}) as reference. The mass spectra
were recorded with a Finnigan MAT SSQ 710 instrument.
Elemental analyses were obtained with a Leco CHNS-932
apparatus.
A solution of (dppe)MCl2 (0.19 mmol) and ammonium
pyrrolidinedithiocarbamate (32 mg, 0.19 mmol) in THF
(50 cm3) was stirred at room temperature for 18 h. The
resulting yellow mixture was filtrated, and the solvent was
evaporated under reduced pressure. The obtained solid was
washed several times with hexane and extracted with
CH2Cl2. The final product was recrystallized by diffusion
of pentane into CHCl3 solutions at 4 °C.
Preparation of (PPh3)M(Cl)(j2S,S-S2CNC4H8)
(M = Pt (1), Pd (2))
[(dppe)Pt(j2S,S-S2CNC4H8)]Cl (4)
Yield: 88 %. 1H-n.m.r. (CDCl3): d 2.05 (m, 4H, NCH2CH2);
2.89 (d, 4H, PCH2, JHP = 18.8 Hz); 3.71 (t, 4H, NCH2
A solution of (PPh3)2MCl2 (0.14 mmol) and ammonium
pyrrolidinedithiocarbamate (23 mg, 0.14 mmol) in THF
(50 cm3) was stirred for 18 h. After filtration, the THF was
removed under reduced pressure. The resulting solid was
extracted with CH2Cl2, and the solvent was removed under
vacuum.
2
CH2, J = 5.8 Hz); 7.44–7.79 (m, 20H, PPh2). 13C-n.m.r.
3
(CDCl3): d 28.2 (CH2); 49.8 (NCH2); 49.6 (PCH2); 127.3,
129.7, 132.5 (PPh2); 200.3 (CS2). 31P-n.m.r. (CDCl3): d 46.6
2
(
195Pt satellites, JPPt = 3888 Hz). DEI-MS (m/z): 739
(M?-Cl). C31H32ClNP2PtS2 calcd.: C, 48.0; H, 4.2; N, 1.8; S,
Complex (1) is a known compound [31], and its struc-
ture has recently been reported.
8.3 %. Found: C, 48.3; H, 4.4; N, 1.6; S, 8.0 %.
(PPh3)M(Cl)(j2S,S-S2CNC4H8) (2): Crystals suitable for
X-ray diffraction analysis were obtained from CHCl3/
pentane solutions at 4 °C. Yield: 75 %. 1H-n.m.r. (CDCl3):
[(dppe)Pd(j2S,S-S2CNC4H8)]Cl (5)
3
d 1.97 (m, 4H, NCH2CH2); 3.55 (t, 4H, 2NCH2CH2, J =
1
6.8 Hz); 7.31–7.64 (m, 15H, PPh3). 13C-n.m.r. (CDCl3):
d 25.3 (CH2); 48.9 (NCH2); 128.2, 131.2, 132.7 (PPh3)
202.0 (CS2). 31P-n.m.r. (CDCl3): d 30.6. DEI-MS (m/z):
629 (M?). C23H23ClN2PPdS4Á0.5CHCl3 calcd.: C, 46.3; H,
3.9; N, 2.3; S, 10.5 %. Found: C, 46.9; H, 4.4; N, 2.2; S,
10.9 %.
Yield: 75 %. H-n.m.r. (CDCl3): d 1.95 (t, 4H, NCH2CH2,
2
3J = 6.8 Hz); 2.81 (d, 4H, PCH2, JHP = 22.2 Hz); 3.74
3
(t, 4H, NCH2CH2, J = 6.5 Hz); 7.48–7.75 (m, 20H, PPh2).
13C-n.m.r. (CDCl3): d 28.7 (CH2); 53.3 (NCH2); 44.0
(PCH2); 126.7, 127.5, 128.3 (PPh2); 201.6 (CS2). 31P-n.m.r.
(CDCl3): d 63.27. DEI-MS (m/z): 651 (M?-Cl). C31H32
123

Transition Met Chem (2013) 38:377–383
379
ClNP2Pd S2Á1.33H2OÁCHCl3 calcd.: C, 46.3; H, 4.3; N, 1.7;
Treating (PPh3)2PtCl2 with two equivalents of the dithio-
carbamato ligand (NH4S2CNC4H8) gave complex (3) which
has both terminal and chelating thiocarbamato ligands in
addition to one PPh3 ligand. The analogous reaction of the
Pd-species produced only yellow insoluble materials regard-
less of the reaction solvent. Complex (3) is stable in the solid
S, 7.7 %. Found: C, 46.9; H, 4.5; N, 1.7; S, 7.9 %.
Structure determination
1
state and in solution. The H-n.m.r. spectrum of (3) showed
The intensity data for the compounds were collected on a
Nonius KappaCCD diffractometer using graphite-mono-
chromated Mo-Ka radiation. Data were corrected for Lorentz
and polarization effects but not for absorption effects
[32–34]. Crystallographic data as well as structure solution
and refinement details are summarized in Table 1. The
structures were solved by direct methods (SHELXS [35]) and
refined by full-matrix least squares techniques against Fo2
(SHELXL-97 [35]). All hydrogen atom positions were
included at calculated positions with fixed thermal parame-
ters. All non-hydrogen and non-disordered atoms were
refined anisotropically [35]. The crystals of compound (5)
were very small, so the completeness of the data is less than
90 %. Nevertheless, the ratio of data with I [2r(I) to
parameters is good enough. Compounds (2) and (3) were
co-crystallized with disordered solvent molecules. For com-
pound (2), the methylene chloride is disordered of an
inversion center. The molecule is refined with occupancy
factor of 0.5. For (3), the solvent molecule is co-crystallized
with 50 % and is disordered in 2 and 4 positions. The carbon
positions were refined isotropically with occupancy factors of
0.25 and 0.25 XP (SIEMENS Analytical X-ray Instruments,
Inc.) was used for structure representations. Crystallographic
data have been deposited with the Cambridge Crystallo-
graphic Data Centre, CCDC No. 877671 for (2), CCDC-
806387 for (3) and 806388 for (5).
the presence of two sets of the two different methylene
protons of the pyrrolidine rings. The first set appears as
multiplets due to the CH2 groups remote from the N-atom at
1.95 and 2.04 ppm, while the other set is assigned to the CH2
groups bonded to nitrogen, appearing as triplets at 3.60 and
3.91 ppm. In the 13C-n.m.r. spectrum of (3), the methylene
carbon atoms also gave different signals, at 25.1 and
26.1 ppm for one set and at 50.8 and 55.1 for the set bonded
to nitrogen. In addition, the spectrum contains three peaks for
the carbon atoms of the phenyl groups of the PPh3 ligand and
a weak peak at 200.5 ppm for the carbon atom bonded to the
two sulfur atoms. In the 31P-n.m.r. spectrum of (3), one
singlet at 17.43 ppm with platinum satellites (JP-Pt
=
4603 Hz) was observed. The mass spectrum of (3) displayed
the molecular ion peak at m/z = 749 g/mol, in addition to
peaks resulted from the fragmentation of this molecule.
The reaction of the bis(diphenylphosphino)ethane com-
plexes (dppe)MCl2 (M = Pt, Pd) with dithiocarbamate
afforded the salts [(dppe)Pt(j2S,S-S2CNC4H8)]Cl (4) and
[(dppe)Pd(j2S,S-S2CNC4H8)]Cl (5), respectively, as shown
in Scheme 2. These complexes are stable both in solution
and in the solid state and are soluble in polar organic sol-
vents. The 1H-n.m.r. spectra of (4) and (5) showed the two
methylene groups of the pyrrolidine ring in the ranges of
1.95–2.05 and 3.71–3.74 ppm which are comparable to
those of (2) and (3). The ethylene group of the dppe ligand
resonates at 2.89 and 2.81 ppm for (4) and (5), respec-
tively. The spectra of (4) and (5) also showed phenyl res-
onances in the range of 7.44–7.79 ppm. The 13C-n.m.r.
spectra of (4) and (5) showed the methylene groups of the
pyrrolidine ring at 28.2 and 49.8 ppm for (4) and at 28.7
and 53.3 ppm for (5), with that of the dppe ligand at 49.6
and 44.0 ppm for (4) and (5), respectively. The spectra also
showed a singlet at 200.3 and 201.6 ppm for (4) and (5),
respectively, which is assigned to the CS2-carbon. The 31P
n.m.r. spectrum of (4) showed a singlet at 46.6 ppm with a
Pt–satellites (JP-Pt of 3888 Hz) and that of (5) showed a
singlet at 63.3 ppm. The mass spectra of (4) and (5) both
showed the molecular peak as [(dppe)M(S2CNC4H8)]?.
Results and discussion
Stirring a THF solution of equimolar amounts of (PPh3)2MCl2
and the dithiocarbamato ligand (NH4S2CNC4H8) in THF
resulted in the formation of the (PPh3)MCl(j2S,S-S2CNC4H8)
complexes (Scheme 1).
Complex (1) has been recently described [31] while (2)
is new. Complex (2), which has a chloride, one PPh3 and
one chelating dithiocarbamato ligands, has been charac-
terized by spectroscopic methods, elemental analysis and
structural determination. The 1H-n.m.r. spectrum of (2)
contains the resonances of the pyrrolidine protons at 1.97
and 3.55 ppm. The multiplet at 7.31–7.64 ppm is due to the
phenyl protons. The single P-atom reveals its presence at
30.6 ppm in the 31P-n.m.r. spectrum of (2). The 13C-n.m.r.
spectrum of (2) showed six resonances corresponding to
the six different carbon types, in which the CS2-carbon was
observed at 200.5 ppm.
Crystal structures of (2), (3) and (5)
ORTEP views of the complexes (PPh3)Pd(Cl)(j2S,S-S2-
CNC4H8) (2), (PPh3)Pt(jS-S2CNC4H8)(j2S,S-S2CNC4H8)
(3) and [(dppe)Pd(j2S,S-S2CNC4H8)]Cl, (5) with the
atom numbering schemes are shown in Figs. 1, 2, 3,
123

380
Transition Met Chem (2013) 38:377–383
Table 1 Crystallographic data
and refinement details for
(PPh3)Pd(Cl)(j2S,S-S2CNC4H8)
(2), (PPh3)Pt(jS,S2CNC4H8)
(j2S,S-S2CNC4H8) (3) and
[(dppe)Pd(j2S,S-
Compound
Formula
(2)
(3)
(5)
C23H23ClNPPdS,
0.5 CHCl3
C28H31N2PPtS4,
0.25 C5H10, 2 CH2Cl2
[C31H32NP2PdS2]?
Cl- CHCl3, 1.25 H2O
fw (g mol-1
)
610.05
937.74
828. 37
-140(2)
Monoclinic
P 21/n
T/ °C
Crystal system
-140(2)
Triclinic
P ¯ı
-90(2)
S2CNC4H8)]Cl, (5)
Triclinic
P ¯ı
Space group
˚
a/A
9.5519(2)
10.0336(3)
14.5244(4)
88.728(2)
87.543(2)
63.202(3)
1241.37(6)
2
9.3394(4)
14.9178(8)
15.6487(9)
116.102(3)
95.682(3)
98.091(3)
1906.36(17)
2
32.5310(6)
12.7723(2)
34.4507(4)
90
˚
b/A
˚
c/A
a/°
b/°
c/°
97.888(1)
90
3
˚
V/A
14178.7(4)
16
Z
q (g cm-3
l (cm-1
)
1.632
1.634
1.555
)
12.62
42.46
10.62
Measured data
Data with I [ 2r(I)
Unique data/Rint
wR2 (all data, on F2)a)
R1 (I [ 2r(I))a)
sb)
10,849
13,492
56,100
5,214
6,637
15,372
5,619/0.2190
0.1820
8,638/0.0501
0.1247
25,707/0.0973
0.2279
a
Definition of the R indices:
R1 = (R||Fo| - |Fc||)/R|Fo|;
wR2 = {R[w(F2o - Fc2)2]/
R[w(F2o)2]}1/2
0.0673
0.0514
0.0741
1.012
1.039
1.068
w-1 = r2(F2o) ? (aP)2 ? bP;
P = [2F2c ? Max(F2O]/3
-3
˚
Res. dens./e A
1.651/- 2.336
Multi-scan
877671
1.138/- 2.358
Multi-scan
806387
2.124/- 1.416
Multi-scan
806388
Absorpt method
CCDC No.
b
s = {R[w(F2o - Fc2)2]/
(No - Np)}1/2
Scheme 1 Reactions of
(PPh3)2MCl2 with
NH4S2CNC4H8 at different
molar ratio
Ph3P
Cl
S
M
N
S
1:1
1:2
M
Pt
Pd
(1), (2)
S
=
Ph3P
Ph3P
Cl
Cl
M
+
N
H4NS
S
S
Ph3P
Pt
N
N
S
S
(3)
Scheme 2 Preparation of the
salts [(dppe)M(k2S,S-
S2CNC4H8)]Cl
Ph2
Ph2
P
S
P
Cl
Cl
S
N
M
N
+
M
Cl
H4NS
P
P
S
Ph2
Ph2
M Pt
=
Pd
(5)
(4),
˚
˚
respectively. The crystals of these complexes contain sol-
vent molecules which are omitted from the views of
Figs. 1, 2, 3. Selected bond distances and angles for the
structures of (2), (3) and (5) are summarized in Table 2.
These complexes assume a common square planar geom-
etry around the metal center. The Pd–S distance
(2.2886(11) A) and the Pd–P bond length (2.2853(9) A) of
(2) lie within the range found for the complexes (PPh3)Pd-
(Cl)(j2S,S-S2CNEt2) and (PPh3)Pd(jS-S2PPh2)(j2S,S-S2-
PPh2) [36, 37]. The chelate S–Pd–S angle of (2) is con-
tracted to 75.61(4)°, leaving more space for the other
angles around Pd which are in the range of 92.99(4)
123

Transition Met Chem (2013) 38:377–383
381
Fig. 1 ORTEP drawing
of (PPh3)Pd(Cl)(j2S,S-
S2CNC4H8) (2), the ellipsoids
represent a probability of 40 %,
hydrogen atoms and solvent
molecules are omitted for clarity
Fig. 2 ORTEP drawing
of (PPh3)Pt(jS,S2CNC4H8)
(j2S,S-S2CNC4H8) (3), the
ellipsoids represent a proba-
bility of 40 %, hydrogen atoms
and solvent molecules are
omitted for clarity
Fig. 3 ORTEP drawing
of [(dppe)Pd(j2S,S-S2CNC4H8)]
Cl, (5), the ellipsoids represent a
probability of 40 %, hydrogen
atoms, counter Cl ion and
solvent molecules are omitted
for clarity
123

382
Transition Met Chem (2013) 38:377–383
2
2
˚
Table 2 Selected bond lengths (A) and bond angles (°) of (PPh3)Pd(Cl)(j S,S-S2CNC4H8) (2), (PPh3)Pt(jS,S2CNC4H8)(j S,S-S2CNC4H8) (3)
and [(dppe)Pd(j2S,S-S2CNC4H8)]Cl, (5)
(2)
(3)
(5)
Molecule
A
B
C
D
Pd-P1
Pd-S2
Pd-Cl1
Pd-S1
S1-C1
S2-C1
N1-C1
2.2853(9)
2.2886(11)
2.3354(12)
2.3503(9)
1.708(4)
Pt-P1
2.2537(17)
2.3270(16)
2.3360(15)
2.3603(18)
1.725(7)
1.716(7)
1.740(7)
1.692(7)
89.42(6)
100.62(6)
95.09(6)
74.77(6)
86.9(2)
Pd-P1
Pd-P2
Pd-S1
Pd-S2
S1-C1
S2-C1
N1-C1
2.2722(2)
2.272(2)
2.340(2)
2.3603(2)
1.722(7)
1.704(8)
1.336(9)
2.271(2)
2.2663(2)
2.3514(2)
2.364(2)
1.711(9)
1.734(7)
1.316(10)
2.2750(2)
2.289(2)
2.346(2)
2.3601(2)
1.724(7)
1.716(9)
1.316(9)
2.258(2)
2.2827(2)
2.3449(2)
2.361(2)
1.717(9)
1.740(7)
1.306(10)
Pt-S3
Pt-S1
Pt-S2
S1-C1
1.738(4)
S2-C1
1.302(5)
S3-C6
S4-C6
P1-Pd-S2
P1-Pd-Cl1
S2-Pd-S1
Cl1-Pd-S1
C1-S1-Pd
C1-S2-Pd
96.57(4)
94.58(4)
75.61(4)
92.99(4)
85.75(13)
87.03(15)
P1-Pt-S3
P1-Pt-S1
S3-Pt-S2
S1-Pt-S2
C1-S1-Pt
C1-S2-Pt
P1-Pd-P2
P1-Pd-S1
P2-Pd-S2
S1-Pd-S2
C1-S1-Pd
C1-S2-Pd
85.47(8)
97.21(7)
101.32(7)
75.83(7)
84.5(3)
84.99(7)
101.37(7)
98.27(7)
75.63(7)
85.5(2)
84.73(8)
96.99(8)
102.71(8)
75.40(7)
85.4(3)
84.20(7)
100.13(7)
100.45(7)
75.89(7)
85.7(2)
86.3(2)
84.2(2)
84.7(3)
85.2(2)
84.7(3)
–96.57(4)°. For compound (3), the Pt–S distances of the
chelating dithiocarbamate ligand of 2.3360(15) and
˚
2.3603(18) A are longer than the Pt–S distances (terminal:
chelate ring, is smaller than the angles within the five-
membered dppe chelate ring or the other non-chelated
angles.
˚
2.3270(16) A) within the same molecules. The Pt–P bond
Acknowledgments We thank the deanship of scientific research at
Jordan University of Science and Technology for financial support.
L.A. and M.H. wish to thank DAAD – Germany for scholarship.
˚
length in (3) is 2.2537(17) A. These values are also compa-
rable to those found in the diethylcarbamato analog (PPh3)Pt-
(jS,S2CNEt2)(j2S,S-S2CNEt2) [38]. The S–Pt–S chelate
angle of 74.61(14)° is smaller than the corresponding S–Pt–S
and P–Pt–S bond angles within (3).
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