Synthesis, dissociation behavior and crystal structures of palladium(II) complexes with N,N-dimethylthiocarbamoyl, Me2NC=S, containing ligand: Structures of [Pd(PPh3)2(η1-SCNMe2)(Cl)], [Pd(PPh3)(Cl)]2(μ,η2-SCNMe2)2, [Pd(PPh3)2{η1-C(SMe)(NMe2)}(η2-S2CO)], and [Pd{η1-SC(O)NMe2}Pd(Cl)](μ,η2-SCNMe2)(μ,η2-dppm)2

Article abstract of DOI:10.1002/jccs.200400044

Treatment of Pd(PPh₃)₄ with N,N-dimethylthiocarbamoyl chloride, Me₂NC(=S)Cl, in dichloromethane at -20 °C produces complex [Pd(PPh₃)₂(η¹-SCNMe₂)(Cl)] (1). In solution state, complex 1 shows the intramolecular dissociation of the chloride or intermolecular dissociation of the triphenylphosphine ligands to form η²-thiocarbamoyl complex [Pd(PPh₃)₂(η²-SCNMe₂)][Cl] (2) or the bridging η²-thiocarbamoyl dipalladium complex [Pd(PPh₃)Cl]₂(μ,η²-SCNMe₂)₂ (3). Treatment of 1 with MeOCS₂K yields [Pd(PPh₃){η¹-C(SMe)(NMe₂)}(η²-S₂CO)] (5a). The Fischer-type carbene-complex 5a is formed via methyl migration of the methyldithiocarbonate to thiocarbamoyl ligand. Complex 1 reacts with EtOCS₂K resulting in the formation of η²-dithiocarbonate complex [Pd(PPh₃)(η¹-SCNMe₂)(η²-S₂COEt)] (4b) and carbene-complex [Pd(PPh₃){η¹-C(SEt)(NMe₂)}(η²-S₂CO)] (5b) with ratios of 10:1 from the integration of ³¹P{¹H} NMR spectra. By continuously stirring the mixtures 4b and 5b in CH₂Cl₂ solution for 2 h, complex 5b was formed as the final product. Complex [Pd(η¹-SCNMe₂)(η²-Phen)(Cl)] (6) or [Pd{η¹-SC(O)NMe₂}Pd(Cl)](μ,η²-SCNMe₂)- (μ,η²-dppm)₂ (7) is accessible by the reaction of 1 with phen (1,10-phenanthroline) or dppm {bis(diphenylphosphino) methane} in dichloromethane at room temperature. All of the complexes are identified by spectroscopic methods and complexes 1, 3, 5a, and 7 are determined by single-crystal X-ray diffraction. The complexes 1 and 3 crystallize in the monoclinic space group P2₁/n and P2₁/c with Z = 4, respectively, whereas 5a and 7 belong to the triclinic space group P1 with Z = 2. The cell dimensions are as follows: for 1, a = 12.8248(1) ?, b = 18.6358(2) ?, c = 14.9692(1) ?, β = 105.1513(4)°; for 3, a = 9.8782(1) ?, b = 11.7238(1) ?, c = 20.7353(2) ?, α = 103.9126(5)°, β = 97.8453(3)°, γ = 104.9669(5)°; for 5a, a = 16.3638(2) ?, b = 9.3374(1) ?, c = 15.7117(2) ?, β = 98.2957(6)°; for 7, a = 12.1128(1) ?, b = 14.0133(2) ?, c = 17.7873(2) ?, α = 82.1939(5), β = 79.6190(6)°, γ = 80.9551(5)°.

Full text of DOI:10.1002/jccs.200400044

Journal of the Chinese Chemical Society, 2004, 51, 279-290
279
Synthesis, Dissociation Behavior and Crystal Structures of Palladium(II)
Complexes with N,N-dimethylthiocarbamoyl, Me2NC=S, Containing
Ligand: Structures of [Pd(PPh3)2(h1-SCNMe2)(Cl)],
[Pd(PPh3)(Cl)]2(m,h2-SCNMe2)2, [Pd(PPh3)2{h1-C(SMe)(NMe2)}(h2-S2CO)], and
[Pd{h1-SC(O)NMe2}Pd(Cl)](m,h2-SCNMe2)(m,h2-dppm)2
Ying-Chih Lina* (
Shou-Ling Huang c (
aDepartment of Chemistry, National Taiwan University, Taiwan 106, R.O.C.
), Kuang-Hway Yihb* (
), Gene-Hsiang Leec (
),
) and Yu Wanga (
)
bDepartment of Applied Cosmetology, Hungkuang University, Shalu, Taichung, Taiwan 433, R.O.C.
cInstrumentation Center, College of Science, National Taiwan University, Taiwan, R.O.C.
Treatment of Pd(PPh3)4 with N,N-dimethylthiocarbamoyl chloride, Me2NC(=S)Cl, in dichloromethane at
-20 °C produces complex [Pd(PPh3)2(01-SCNMe2)(Cl)] (1). In solution state, complex 1 shows the intra-
molecular dissociation of the chloride or intermolecular dissociation of the triphenylphosphine ligands to
form 02-thiocarbamoyl complex [Pd(PPh3)2(02-SCNMe2)][Cl] (2) or the bridging 02-thiocarbamoyl dipall-
adium complex [Pd(PPh3)Cl]2(µ,02-SCNMe2)2 (3). Treatment of 1 with MeOCS2K yields [Pd(PPh3){01-
C(SMe)(NMe2)}(02-S2CO)] (5a). The Fischer-type carbene-complex 5a is formed via methyl migration of
the methyldithiocarbonate to thiocarbamoyl ligand. Complex 1 reacts with EtOCS2K resulting in the forma-
tion of 02-dithiocarbonate complex [Pd(PPh3)(01-SCNMe2)(02-S2COEt)] (4b) and carbene-complex
[Pd(PPh3){01-C(SEt)(NMe2)}(02-S2CO)] (5b) with ratios of 10:1 from the integration of 31P{1H} NMR spec-
tra. By continuously stirring the mixtures 4b and 5b in CH2Cl2 solution for 2 h, complex 5b was formed as the
final product. Complex [Pd(01-SCNMe2)(02-Phen)(Cl)] (6) or [Pd{01-SC(O)NMe2}Pd(Cl)](µ,02-SCNMe2)-
(µ,02-dppm)2 (7) is accessible by the reaction of 1 with phen (1,10-phenanthroline) or dppm {bis(diphenyl-
phosphino)methane} in dichloromethane at room temperature. All of the complexes are identified by spectro-
scopic methods and complexes 1, 3, 5a, and 7 are determined by single-crystal X-ray diffraction. The com-
plexes 1 and 3 crystallize in the monoclinic space group P21/n and P21/c with Z = 4, respectively, whereas 5a
and 7 belong to the triclinic space group P1 with Z = 2. The cell dimensions are as follows: for 1, a =
12.8248(1) Å, b = 18.6358(2) Å, c = 14.9692(1) Å, b = 105.1513(4)E; for 3, a = 9.8782(1) Å, b = 11.7238(1) Å,
c = 20.7353(2) Å, a = 103.9126(5)E, b = 97.8453(3)E, ( = 104.9669(5)E; for 5a, a = 16.3638(2) Å, b =
9.3374(1) Å, c = 15.7117(2) Å, b = 98.2957(6)E; for 7, a = 12.1128(1) Å, b = 14.0133(2) Å, c = 17.7873(2) Å,
a = 82.1939(5), b = 79.6190(6)E, ( = 80.9551(5)E.
Keywords: N,N-dimethylthiocarbamoyl chloride; Intramolecular intermolecular dissociation;
02-thiocarbamoyl; Fischer-type carbene; Methyl migration; Palladium complex.
INTRODUCTION
Thiocarbamoyl (thiocarboxamide) complexes have
previously been prepared by a variety of synthetic routes1
from the reaction of metal carbonylates with N,N-dimethyl-
thiocarbamoyl chloride, Me2NC(=S)Cl, via nucleophilic dis-
placement of chloride,2 nucleophilic attack by an amine on an
electrophilic thiocarbonyl complex,3 reaction of hydrosulfide
with haloaminocarbene4 or isonitrile5 ligands, electrophilic
attack at a coordinated isothiocyanate,6 cleavage of a
dithiocarbamate ligand,7 or C-H activation of thioform-
amides.8 Oxidative addition9 of both chloride and N,N-di-
methylthiocarbamoyl ligand to metal complex is most gener-
ally used and is relevant to the work to be described herein.
The thiocarbamoyl metal complexes are known in Nb, Ta
(VB),10 Mo, W (VIB),7b,11 Ru, Rh, and Ir (VIIIB),9c,12 al-
though rare Pd thiocarbamoyl complex has also been studied.
In a previous communication,13 we have reported that
* Corresponding author. Tel: +886-4-26318652-5308; fax: +886-4-26321046; e-mail: khyih@sunrise.hk.edu.tw

280 J. Chin. Chem. Soc., Vol. 51, No. 2, 2004
Lin et al.
the first N,N-dimethylthiocarbamoyl, S2CNMe2, complexes
of palladium metal are accessible via the oxidative addition
reaction of tetrakis(triphenylphosphine)palladium with thio-
carbamoyl chloride. In contrast to thiocarbamoyl complexes
of the above-mentioned metals, the palladium examples are a
particularly reactive species. Especially, in solution state, the
sulfur atom of the thiocarbamoyl ligand assists the dissocia-
tion of either the chloride or the triphenylphosphine ligand to
form the 02-thiocarbarmoyl complexes. Because of the abil-
ity of amino lone pair to contribute via conjugation to the
metal-ligand bonding, the thiocarbamoyl ligands show a
strong tendency to adopt bidentate coordination.
SCNMe2)][Cl] (2) or the triphenylphosphine ligand of 1 to
form the bridging 02-thiocarbarmoyl dipalladium complex
[Pd(PPh3)Cl]2(µ,02-SCNMe2)2 (3). Continuous stirring of di-
chloromethane solution of these mixtures at room tempera-
ture for 8 h produces complex 3 with 93% isolate yield. We
did not isolate complex 2 in the dissociative reaction because
it can be synthesized from the reaction of 1 and ammonium
hexafluorophosphate, NH4PF6, in acetone with 92% isolate
yield at ambient temperature.14 The yellow complex 3 is more
stable and has poorer solubility in common solvents than that
of 1. Only one example, [Pd(PPh3)2(01-CH2SCH3)Cl],15 is
known, the dissociation of either the phosphine or the chlo-
ride ligand occurred in CH2Cl2 solution to form monomer
complexes [Pd(PPh3)(02-CH2SCH3)Cl] and [Pd(PPh3)2(02-
CH2SCH3)][Cl]. From the above description, one can con-
clude that the sulfur atom of the thiocarbamoyl ligand assists
triphenylphosphine or chloride dissociation of 1 to form 3 or
2.
On the basis of these experimental results, we report
the dissociation behavior and reactions of [Pd(PPh3)2(01-
SCNMe2)(Cl)] (1) with anionic dithio, neutral nitrogen and
phosphorus ligands as well as the novel carbene-complexes
formation from the alkyl-thiocarbamoyl coupling reaction in
this article. Four X-ray crystal structure analyses have been
carried out to provide accurate structural parameters.
Nucleophilic displacement of the chloride in 1 with
-
-
anionic dithiocarbonate ligands, MeOCS2 or EtOCS2 , in
methanol at room temperature produces carbene-complex
[Pd(PPh3){01-C(SMe)(NMe2)}(02-S2CO)] (5a) with 90%
isolate yield (Scheme II) or the mixtures of 02-dithiocar-
bonate complex [Pd(PPh3)(01-SCNMe2)(02-S2COEt)], 4b
and carbene-complex [Pd(PPh3){01-C(SEt)(NMe2)}(02-
S2CO)] (5b) in good yields with a 10:1 ratio according to the
integration of 31P{1H} NMR spectrum (Fig. 1). The dichloro-
methane solution of 4b slowly undergoes ethyl-thiocarba-
moyl coupling reaction at ambient temperature for 2 h to give
5b in 75% yields. The air-stable yellow-orange compounds
5a and 5b are soluble in polar solvent, and insoluble in di-
ethyl ether and n-hexane. Both complexes 5a and 5b include
a dithiocarbonate, S2CO-2, group. Dithiocarbonate metal
complexes have previously been prepared by a variety of syn-
RESULTS AND DISCUSSION
Syntheses
Treatment of Pd(PPh3)4 with N,N-dimethylthiocar-
bamoyl chloride, Me2NC(=S)Cl, in dichloromethane at -20
°C yields the air-stable yellow complex [Pd(PPh3)2(01-
SCNMe2)(Cl)] (1) with 92% isolate yield (Scheme I). The
air-stable yellow compound 1 is soluble in dimethylsulf-
oxide, dichloromethane and acetonitrile, slightly soluble in
methanol, and insoluble in n-hexane and diethyl ether.
The dichloromethane solution of 1 processes intra- and
intermolecular dissociation of either the chloride of 1 to form
the chelating 02-thiocarbarmoyl complex [Pd(PPh3)2(02-
Scheme I
Cl
PPh3
Cl
Ph3P
Pd
Pd
2PPh3
+
intermolecular
dissociation
C
NMe2
C
S
S
Me2N
Cl
3
PPh3
Me2NC(S)Cl
Ph P
Pd
PPh3
Ph3P Pd
Ph3P
PPh3
3
Me2N
C
1
S
PPh3
PPh3
S
Pd
Cl
intramolecular
dissociation
C
NMe2
2

N,N-dimethylthiocarbamoyl Palladium Complexes
J. Chin. Chem. Soc., Vol. 51, No. 2, 2004 281
plex from the alkyl-thiocarbamoyl coupling reaction is the
first example in the literature.
Scheme II
O
OR
S
C
S
C
The respective reactions of 1 and phen or dppm in di-
chloromethane results in the isolation of [Pd(01-SCNMe2)-
(02-Phen)(Cl)] (6) or [Pd{01-SC(O)NMe2}Pd(Cl)](µ,02-
SCNMe2)(µ,02-dppm)2 (7) with 73% or 45% isolate yield.
We expected the reaction of 1 with phen would produce a
triphenylphosphine and chloride displaced complex [Pd-
(PPh3)(01-SCNMe2)(02-Phen)][Cl]. Instead, the product of
this reaction was found to be a two triphenylphosphine lig-
ands displaced complex 6 that was confirmed by spectro-
scopic data (described below). Another 20% yield of uniden-
tified product was detected that includes similar spectro-
scopic data as that of 7. Formation of thiocarbamate complex
7 is proposed to proceed via one triphenylphosphine dis-
placement by sulfur atom of thiocarbamoyl of 1 to afford a
bridging thiocarbamoyl dimetal complex, followed by one
chloride and three triphenylphosphines displacement by two
dppm ligands to form an unstable species containing bridging
thiocarbamoyl, dppm and a chelating thiocarbamoyl interme-
diate 7’ (Scheme III) or via intermolecular dissociation of
two triphenylphosphine ligands forming 3, followed by two
chloride and two triphenylphosphine displacement by two
dppm ligands to form [Pd2(µ,02-SCNMe2)2(µ,02-dppm)2]-
[Cl]2 and then one of the chloride re-coordinated to metal
forming complex 7’. In isolation and recrystallization, com-
plex 7’ reacted with oxygen to give the final thiocarbamate
product 7. The air-stable brown and yellow complexes 6 and
7 are soluble in chlorinated solvents and DMSO, and insolu-
ble in diethyl ether and n-hexane. The isolated compounds 1,
3-7 were already of good purity, but analytically pure sam-
ples could be obtained by slow n-hexane diffusion into a di-
chloromethane solution at +4 °C. All characterization data
are consistent with the proposed constitution.
Ph3P
Ph3P
Pd
Pd
r.t, 2h
S
S
Me2N
C
Me2N
C
5a: R = Me
5b: R = Et
S R
S
4b: R = Et
EtOCS2K
MeOCS2K
Cl
PPh3
Ph3P
Pd
Me2N
C
1
S
dppm
O2
Phen
H2
C
PPh2
Ph2P
Me2N
N
S
C
Pd
Pd
Pd
N
Cl
Me2N
O
Cl
C
S
C
NMe2
Ph2P
PPh2
6
S
C
H2
7
thetic routes including reactions of (i) metal carbonyl sulfide
complexes with COS16 (ii) metal carbon disulfide complexes
with dioxygen17 (iii) dealkylation,18 iodide abstraction,19 and
hydrolysis20 of alkoxydithiocarbamate metal complexes. To
our knowledge, formation of dithiocarbonate carbene-com-
IR and MS Spectroscopy
In the infrared spectra of 1, 4-6 the C-N stretches for the
SCNMe2 group are in the region of 1429-1436 cm-1, typical
for a 01-bound SCNMe2 group21 with partially multiple C-N
bond of the thiocarbamoyl ligand. The peaks at 1516 and
1526 cm-1 in the IR spectra of 5a and 5b indicate a de-
localized C(SR)NMe2 group. The IR spectra of 5a and 5b
show the C=O stretching band of the co-ordinated carbonate
ligand at 1675, 1603 and at 1681, 1605 cm-1, respectively,
which are indicative of a chelate dithiocarbonate ligand.16-20
The FAB mass spectra of 1, 3-5 show parent peaks with the
typical Pd isotope distribution corresponding to [M+] molec-
Fig. 1. 1H NMR spectra of the mixtures 4b and 5b in
CDCl3.

282 J. Chin. Chem. Soc., Vol. 51, No. 2, 2004
Lin et al.
Scheme III
H2
C
Me2N
PPh2
Ph2P
O2
dppm
S
C
Pd
Pd
Cl
Cl
C
S
C
H2
C
Me2N
NMe2
Ph2P
PPh2
PPh2
Ph2P
H2
Cl
PPh3
7'
S
C
Pd
Ph3P
Pd
S
Pd
O
Cl
Me2N
C
S
C
C
1
NMe2
Ph2P
H2
C
Me2N
PPh2
2
H2
PPh2
Ph2P
7
O2
C
S
Pd
3
7'
Pd
2Cl
C
S
NMe2
Ph2P
PPh2
C
H2
ular masses, respectively. In the FAB mass spectra, base
peaks with the typical Pd isotope distribution are respectively
in agreement with the [M+ - Cl] and [M+ - dppm - O] molecu-
lar masses of 6 and 7.
nuclei, respectively.
The 31P{1H} NMR spectrum of 3 shows two doublet
resonances at * 23.1 and * 35.1 due to the chemical in-
equivalence of the two PPh3 ligands and the relatively more
downfield resonance than those of 1 (* 16.6), 3 (* 19.8), 4b (*
24.8), and 7 (* 1.97, 9.91) shows the cationic character of 2.
From the description, it is clear that the compound 2 is
side-on bound through the C-S moiety of the SCNMe2 ligand.
NMR Spectroscopy
The room-temperature 1H NMR spectra of 1 are com-
plicated because of the dissociation of either the chloride or
the triphenylphosphine ligand of 1 to form the mononuclear
complex [Pd(PPh3)2(02-SCNMe2)][Cl] (2) or the dipalladium
complex [Pd(PPh3)Cl]2(µ,02-SCNMe2)2 (3). Clear spectra of
complex [Pd(PPh3)2(02-SCNMe2)][PF6] and 3 and vari-
1
The H NMR spectrum of 6 shows eight resonances
with the same ratios and the 13C{1H} NMR spectrum exhibits
twelve singlet resonances, which are attributed to the in-
equivalent environments of the phen ligand. The relative
down-field 13C{1H} NMR spectrum of 1, appears as one sin-
glet resonance at * 221.6 for the carbon atom of the thiocar-
bamoyl group.
1
able-temperature (298-233 K) H NMR spectra of the mix-
ture distinguished the three complexes unambiguously (Sup-
porting Information, spectrum A). Two methyl resonances of
1
the SCNMe2 ligand are observed in the H NMR spectra of
The methyl group of the SCNMe2 ligand in 7 shows
1
complexes 1-7, consistent with hindered rotation about the
partially multiple C-N bond. The 13C{1H} NMR spectra of
the methyl signals of complexes 1-7 are in the region from *
38.9 to * 53.4. The low-field section of the 13C{1H} NMR
spectra consists of one resonance attributable on intensity
grounds to the thiocarbamoyl carbon atom in the region from
* 212.8 to * 234.3. In the 1H NMR spectra of 5a and 5b, one
resonance at * 2.88 and three resonances at * 1.20 and 3.45,
4.03 and the corresponding 13C{1H} NMR signals at * 21.2
similar H NMR and 13C{1H} NMR resonances as those of
1-6, two singlet resonances appear at * 173.2 and * 223.0
which are assigned to the carbon atoms of the SCNMe2 and
SC(=O)NMe2 ligands, respectively.
X-ray single-crystal structures of 1, 3, 5a, and 7
To confirm the first thiocarbamoyl palladium and the
methyl-thiocarbamoyl coupling carbene-complex, the afore-
mentioned compounds 1, 3, 5a, and 7 have been performed
by single-crystal X-ray diffraction studies. Single crystals of
1, 3, 5a, and 7 were grown by slow n-hexane diffusion into a
dichloromethane solution at +4 °C. ORTEP plots with atom
labels of 1, 3, 5a and 7 are shown in Figs. 2-5. Crystal data
and refinement details, selected interatomic distances (Å)
22
and at * 13.4, * 33.4 are attributed to the S-CH3 and the
S-CH2CH323 groups, respectively. The 13C{1H} NMR spectra
of 5a and 5b reveal two singlets at lowest field, which are as-
signed to the carbon atoms of the carbene (* 247.9 and *
246.7) and dithiocarbonate (* 199.0 and * 199.1) carbon

N,N-dimethylthiocarbamoyl Palladium Complexes
J. Chin. Chem. Soc., Vol. 51, No. 2, 2004 283
and angles (deg), and atomic coordinates and equivalent
isotropic displacement coefficients for important atoms of
complexes 1, 3, 5a and 7 are listed in Tables 1, 2 and 3, re-
spectively.
sitions: P(2)-Pd-P(1), 173.75(3)°; Cl(1)-Pd-C(1), 166.32(10)°.
Complex 3 is a dimer with each SCNMe2 unit bridging
through a carbon atom of the thiocarbamoyl group to one
metal center and sulfur atom to the other metal forming a
six-membered ring and boat-form geometry. Within the
SCNMe2 ligands themselves, the geometries are consistent
with significant partial double bond character in the C-S and
In complex 1, the SCNMe2 ligand is s bound to Pd atom
through the carbon atom of the thiocarbamoyl group. The
S-Pd bond distance of 3.033 Å in 1 indicates no bonding in-
teraction between the sulfur atom and palladium metal atom.
The palladium atom has a distorted square planar geometry in
which two triphenylphosphine and the carbon atom of the
thiocarbamoyl ligand and the chloride ligand are in trans po-
Fig. 4. An ORTEP drawing with 50% thermal ellip-
soids and atom-numbering scheme for the com-
plex [Pd(PPh3){01-C(SMe)(NMe2)}(02-S2CO)]
(5a).
Fig. 2. An ORTEP drawing with 50% thermal ellip-
soids and atom-numbering scheme for the com-
plex [[Pd(PPh3)2(01-SCNMe2)(Cl)] (1).
Fig. 3. An ORTEP drawing with 50% thermal ellipsoids and atom-numbering scheme for the complex
[Pd(PPh3)Cl]2(µ,02-SCNMe2)2 (3).

284 J. Chin. Chem. Soc., Vol. 51, No. 2, 2004
Lin et al.
Table 1. Crystal Data and Refinement Details for Complexes 1, 3·CH2Cl2, 5a and 7·3CH2Cl2
1
3·CH2Cl2
5a
7·3CH2Cl2
chemical formula
formula weight
crystal system
space group
a, Å
b, Å
c, Å
a, deg
b, deg
g, deg
V, Å3
Z
rcalcd, g cm-3
m, (Mo Ka), mm-1
l, Å
C39H36ClNP2SPd
754.54
monoclinic
P21/n
12.8248(1)
18.6358(2)
14.9692(1)
90
105.1513(4)
90
3453.28(5)
4
1.451
0.797
0.71073
150(1)
C43H44Cl4N2P2S2Pd2
1069.46
triclinic
P1
9.8782(1)
11.4238(1)
20.7353(2)
103.9126(5)
97.8453(3)
104.9669(5)
2166.76(4)
2
C23H24NOPS3Pd
563.98
monoclinic
P21/c
16.3638(2)
9.3374(1)
15.7117(2)
90
98.2957(6)
90
2375.56(5)
4
C59H62Cl7N2OP4S2Pd2
1464.06
triclinic
P1
12.1128(1)
14.0133(2)
17.7873(2)
82.1939(5)
79.6190(6)
80.9551(5)
2914.86(6)
2
1.639
1.281
0.71073
150(1)
1.577
1.128
0.71073
150(1)
1.668
1.164
0.71073
150(1)
T, K
q range, deg
Independent rflns
no. of variables
Ra
Rw
Sc
1.78-27.50
7906
407
0.043
0.090
1.02-27.50
9924
497
0.041
0.097
1.26-27.50
5458
272
0.039
0.090
1.48-27.50
13381
682
0.069
0.181
b
1.0459
1.103
1.119
1.017
a R = S||Fo| - |Fc||/S|Fo|. b Rw = [Sw(|Fo| - | Fc|)2]1/2; w = 1/s2(|Fo|). c Quality-of-fit = [Sw(|Fo| - |Fc|)2/(Nobserved
parameters)]1/2
-
N
.
SC-N bonds. Thus, the C-S bond distances (1.731(4) and
1.718(4) Å) are comparable to the C-S double bond in ethyl-
enethiourea although they are longer than those in free CS2
(1.554 Å). The SC-N bond distances (1.316(5) and 1.318(5)
Å) are typical for a C-N bond having partial double bond
character and are certainly much shorter than the normal C-N
(1.47 Å) single bond.
In complex 5a, the palladium atom has a distorted
square planar geometry and the carbene carbon, Pd, S, and N
are coplanar to within 0.030 Å. The bond angles about C(2)
(126.7, 113.5, and 119.8°) clearly show the sp2 character of
the carbon. One of the sulfur atoms of dithiocarbonate ligand
is trans to the triphenylphosphine: S(2)-Pd-P(1), 171.56(3)°,
while the other is trans to the carbene ligand: S(1)-Pd-C(2),
170.61(10)°. The Pd-C(2) bond distance, 2.043(4) Å, is lon-
ger than the other PdII-carbon(carbonyl) distances, and simi-
lar to those of Pd-C(carbene) distances.24 Within the carbene,
C(SMe)(NMe2), the geometry is consistent with significant
partial double bond character in the S(3)-C(2) (1.731(4) Å)
and C(2)-N(1) (1.308(4) Å) bonds. This implies PB-PB over-
lap, involving the empty P orbital of C(2) atom. Because of
Fig. 5. An ORTEP drawing with 30% thermal ellip-
soids and atom-numbering scheme for the
complex [Pd{01-SC(O)NMe2}Pd(Cl)](µ,02-
SCNMe2)(µ,02-dppm)2 (7).

N,N-dimethylthiocarbamoyl Palladium Complexes
J. Chin. Chem. Soc., Vol. 51, No. 2, 2004 285
Table 2. Selected Interatomic Distances (Å) and Angles (deg) for 1, 3, 5a and 7
H2
C
Me2N
O
PPh2
Ph2P
Cl
Cl
S
C
Cl
PPh3
PPh3
Ph3P
Ph3P
S
C
Pd
Pd
S
Pd
Ph3P
Pd
S
S
Pd
Pd
C
NMe2
Me2N
C
O
Me2N
C
C
Cl
C
S
C
S
Me2N
S Me
1
NMe2
3
Ph2P
PPh2
5a
7
H2
Pd-P
Pd-Cl
Pd-C
2.3531(9), 2.3401(9)
2.4067(9)
1.982(3)
2.3046(10), 2.3013(9)
2.3721(10), 2.3677(9)
1.969(4), 1.989(4)
2.2889(9)
-
2.043(4)
2.3488(16)(av), 2.3345(17)(av)
2.3579(16)
2.008(6)
Pd-S
C=S
C-N
N-Me
C-Pd-X (Cl, S)
Pd-S-C
Pd-C-S
3.033
1.679(4)
1.320(4)
2.3573(10), 2.3733(9)
1.731(4), 1.718(4)
1.316(5), 1.318(5)
2.3306(9), 2.3250(9)
1.731(4)
1.308(5)
1.502(5), 1.441(5)
170.61(10)
2.317(2), 2.3556(17)
1.715(6), 1.692(13)
1.315(8), 1.415(15)
1.359(15)-1.477(9)
168.09(18)
1.458(5), 1.457(5)
166.32(10)
-
1.465(5)-1.474(5)
178.55(11), 178.05(10)
116.93(19), 117.7(2)
116.93(19), 117.7(2)
88.11(12), 87.91(13)
119.8(2)
96.7(2), 105.0(5)
120.6(3)
111.61(18)
B-electron donation by both nitrogen and sulfur atoms, the
aminothiocarbene is a very weak B-acceptor and has binding
properties towards low-valent transition metals similar to
those of phosphines or pyridines. The Pd-S(1) bond distance,
2.3306(9) Å, is longer than the Pd-S(2) bond distance,
2.3250(9) Å, due to the high trans influence of carbene ligand
than PPh3 ligand and the two Pd-S bonds are within the nor-
mal Pd-S length range (2.23~2.32 Å).25 The bond distances
within the dithiocarbonate ligand, S-C(av), 1.773(4) Å, and
C(1)-O(1), 1.207(4) Å, fall in the range of values found for
other dithiocarbonate complexes, and are indicative of an
overall electronic delocalization within the S2CO group.16
Complex 7 consists of two palladium centers bridged
by two mutually trans dppm groups, with the Cl, SC(=O)NMe2,
and SCNMe2 ligands bound in the equatorial plane which is
approximately perpendicular to the Pd-P vectors. Pd(1) or
Pd(2) has an essentially square-planar coordination in which
the two phosphines are mutually trans and the chloride or sul-
fur atom of the SC(=O)NMe2 ligand is trans to the carbon or
sulfur atom of the bridging SCNMe2 ligand, forming a
A-frame type dinuclear compound. Thiocarbamate complex
7 represents a rare example of a binuclear palladium species
with M2+3 core, and the two metals can be formally regarded
as Pd(II) and Pd(I) with 16- and 17-electron configurations,
respectively. The bond distances C(4)-O(1) (1.248(14) Å),
C(1)-N(1) (1.315(8) Å), and C(4)-N(2) (1.415(15) Å) are typ-
ical for a C-O and C-N bond having partial double bond char-
acter and are certainly much shorter than a normal C-O (1.43
Å) and C-N (1.47 Å) single bond.
The Pd-PPh3 bond lengths of 1, 3 and 5a are in the re-
gion of 2.2889(9) – 2.3531(9) Å, and appear to be normal.
The Pd-Cl (2.3579(16) – 2.4067(9) Å) and Pd-S distances are
both within the range of values reported for other palladiumII
complexes.
CONCLUSION
In this article we report the syntheses, dissociation be-
havior and X-ray crystal structures of thiocarbamoyl Pd com-
plexes. We have prepared [Pd(PPh3)2(01-SCNMe2)(Cl)] (1)
by the oxidative addition of Me2NC(=S)Cl to Pd(PPh3)4. The
sulfur atom of the thiocarbamoyl ligand assisting the dissoci-
ation of either the chloride or the triphenylphosphine ligand
to form 2 or 3 has been confirmed. The bridging thiocar-
bamoyl dinuclear complex [Pd(PPh3)Cl]2(µ,02-SCNMe2)2
(3) including six-membered ring is a good starting material
for preparation of dinuclear compound. Novel alkyl-thiocar-
bamoyl coupling reaction produces the first uncyclic N,S-
heteroatom Fischer-type carbene-complexes 5a,b26 from the
reaction of 1 with alkyldithiocarbonate ligands. The p inter-
action between the carbene-carbon and SR or NMe2 and the
more chelate ability of the dithiocarbonate ligand than the
alkyldithiocarbonate ligand are two important factors in

286 J. Chin. Chem. Soc., Vol. 51, No. 2, 2004
Lin et al.
Table 3. Atomic Coordinates and Equivalent Isotropic
Displacement Coefficients for Important Atoms of 1, 3,
5a and 7
Cl(1)
S(1)
S(2)
P(1)
P(2)
P(3)
P(4)
O(1)
N(1)
N(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
-339(1)
4288(1)
2114(2)
1360(1)
3238(1)
2004(1)
3939(1)
3888(8)
3168(5)
2416(10)
3099(5)
2197(6)
4234(6)
2912(12)
3038(18)
1415(12)
2644(5)
3414(5)
800(1)
891(1)
522(2)
2521(1)
2456(1)
-877(1)
-906(1)
609(7)
1076(4)
43(7)
940(4)
1138(5)
1220(6)
382(8)
7264(1)
6480(1)
8902(1)
6700(1)
7650(1)
6764(1)
7754(1)
9513(5)
5317(3)
10360(5)
6070(4)
4913(4)
4791(4)
9608(7)
10925(10)
10500(10)
6793(4)
6995(4)
35(1)
30(1)
54(1)
27(1)
30(1)
26(1)
29(1)
95(3)
33(1)
86(3)
26(1)
37(2)
44(2)
80(3)
141(7)
131(7)
28(1)
31(1)
Atom
x
y
z
Beq
Compound 1
Pd
Cl(1)
S(1)
P(1)
P(2)
N(1)
C(1)
C(2)
C(3)
652(1)
671(1)
-25(1)
2425(1)
-1061(1)
753(2)
479(3)
668(3)
1085(3)
2954(3)
3500(3)
-1228(3)
-1531(3)
1949(1)
2746(1)
406(1)
1542(1)
2358(1)
1157(2)
1132(2)
534(2)
1816(2)
887(2)
2215(2)
3333(2)
2132(2)
7165(1)
5905(1)
7332(1)
7305(1)
7203(1)
8875(2)
7962(2)
9441(3)
9395(3)
8214(2)
7529(2)
7154(2)
8226(2)
17(1)
25(1)
27(1)
18(1)
18(1)
21(1)
19(1)
34(1)
28(1)
20(1)
21(1)
20(1)
19(1)
41(11)
C(4)
-400(13)
3013(5)
-1384(5)
C(10)
C(22)
C(28)
E.S.Ds. refer to the last digit printed.
Compound 3
Pd(1)
Pd(2)
Cl(1)
Cl(2)
S(1)
S(2)
P(1)
P(2)
N(1)
N(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
3176(1)
1589(1)
2390(1)
-623(1)
2806(1)
4183(1)
2267(1)
263(1)
5075(3)
4014(3)
3878(4)
6059(4)
5541(4)
3415(4)
5250(4)
3518(4)
4701(1)
5285(1)
5573(1)
3739(1)
3733(1)
6715(1)
2756(1)
6686(1)
3698(3)
7473(3)
4001(3)
4042(4)
3020(4)
6613(3)
8548(4)
7389(4)
1985(1)
3333(1)
1146(1)
3177(1)
3281(1)
2742(1)
1215(1)
3421(1)
2694(2)
4017(2)
2682(2)
2229(2)
3146(2)
3446(2)
4066(2)
4655(2)
18(1)
17(1)
27(1)
24(1)
23(1)
26(1)
20(1)
18(1)
23(1)
25(1)
21(1)
29(1)
29(1)
20(1)
35(1)
32(1)
forming the carbene-complexes. Three bonding modes of the
thiocarbamoyl ligand have been observed; these include
monodentate coordination through carbon atom (complexes
1 and 6), bidentate through carbon and sulfur atoms by
chelation (complex 2) and bridging between two metal cen-
ters (complexes 3 and 7).
EXPERIMENTAL SECTION
General Procedures
All manipulations were performed under nitrogen us-
ing vacuum-line, drybox, and standard Schlenk techniques.
NMR spectra were recorded on a Bruker AM-500 WB FT-
NMR spectrometer and are reported in units of * (ppm) with
residual protons in the solvent as an internal standard (CDCl3,
* 7.24; DMSO-d6, * 2.45). IR spectra were measured on a
Nicolate Avator-320 instrument and were referenced to a
polystyrene standard, using cells equipped with calcium fluo-
ride windows. Mass spectra were recorded on a JEOL SX-
102A spectrometer. Solvents were dried and deoxygenated
by refluxing over the appropriate reagents before use. n-Hex-
ane, diethyl ether, THF and benzene were distilled from so-
dium-benzophenone. Acetonitrile and dichloromethane were
distilled from calcium hydride, and methanol was distilled
from magnesium. All other solvents and reagents were of re-
agent grade and were used as received. Elemental analyses
and X-ray diffraction studies were carried out at the Regional
Compound 5a
Pd
S(1)
S(2)
S(3)
8143(1)
7403(1)
9073(1)
9600(1)
7083(1)
8365(2)
9062(2)
8298(2)
8958(2)
9254(3)
8595(3)
9592(3)
-264(1)
-873(1)
127(1)
-1049(1)
-664(1)
-537(3)
1515(3)
-453(4)
254(4)
2500(1)
3609(1)
3743(1)
1356(1)
1408(1)
5117(2)
1348(2)
4344(2)
1679(2)
1831(3)
1630(2)
725(3)
19(1)
25(1)
30(1)
43(1)
18(1)
40(1)
29(1)
27(1)
29(1)
41(1)
37(1)
50(1)
P(1)
O(1)
N(1)
C(1)
C(2)
C(3)
-2663(5)
2773(4)
1886(5)
C(4)
C(5)
Compound 7
Pd(1)
Pd(2)
1586(1)
3376(1)
828(1)
749(1)
6730(1)
7769(1)
25(1)
31(1)

N,N-dimethylthiocarbamoyl Palladium Complexes
J. Chin. Chem. Soc., Vol. 51, No. 2, 2004 287
Center of Analytical Instrumentation located at National Tai-
wan University. PdCl2·xH2O was purchased from Strem
Chemical, EtOCS2K, dppm, and 1,10-phenanthroline were
purchased from Merck.
Found: C, 51.28; H, 4.21; N, 2.80.
Preparation of [Pd(PPh3)2(01-SCNMe2)(02-S2COEt)] (4b)
MeOH (10 mL) was added to a flask (100 mL) contain-
ing [Pd(PPh3)2(01-SCNMe2)(Cl)] (1) (0.754 g, 1.0 mmol)
and EtOCS2K (0.14 g, 1.0 mmol) at room temperature. After
stirring for 5 min, a pale-yellow precipitate was formed. The
precipitate was collected by filtration (G4) and was washed
with MeOH (10 mL) and diethyl ether (2 ´ 10 mL) and then
dried in vacuo yielding 0.51 g (88%) of [Pd(PPh3)2(01-
SCNMe2)(02-S2COEt)] (4b). IR (KBr, cm-1) L (CN) 1436
Preparation of [Pd(PPh3)2(01-SCNMe2)(Cl)] (1)
CH2Cl2 (20 mL) was added to a flask (100 mL) contain-
ing Pd(PPh3)4 (1.154 g, 1.0 mmol) and Me2NC(=S)Cl (0.142
g, 1.15 mmol) at -20 EC. The stirred mixture was allowed to
warm to room temperature for about 10 min. The solvent was
concentrated to 10 mL, and 20 mL of diethyl ether was added
to the solution. The yellow solids were formed which were
isolated by filtration (G4), washed with n-hexane (2 × 10 mL)
and subsequently dried under vacuum yielding 0.74 g (98%)
of [Pd(PPh3)2(01-SCNMe2)(Cl)] (1). IR (KBr, cm-1) L (CN)
1481 (m), 1436 (m). 1H NMR (500 MHz, CDCl3, 298 K): *
2.31, 2.62 (s, 6H, NCH3), 7.30-8.03 (m, 30H, Ph). 31P{1H}
NMR (202 MHz, CDCl3, 298 K): * 16.5 (br, PPh3). 13C{1H}
NMR (125 MHz, CDCl3, 298 K): * 41.2 (br, NCH3), 128.1-
135.3 (m, Ph), 223.5 (s, NCS). MS (FAB, NBA, m/z): 754.5
[M+], 492 [M+ - PPh3]. Anal. Calcd. for C39H36ClNP2SPd:
C, 62.08; H, 4.81; N, 1.86%. Found: C, 62.10; H, 4.86; N,
1.84.
1
3
(m). H NMR: * 1.40 (t, 3H, OCH2CH3, JH-H = 7.0), 2.95,
3.30 (s, 6H, NCH3), 4.55 (m, 2H, OCH2CH3), 7.37-7.62 (m,
15H, Ph). 31P{1H} NMR: * 24.8 (br, PPh3). 13C{1H} NMR: *
13.8 (s, OCH2CH3), 38.9, 40.8 (s, NCH3), 67.8, 68.0 (s,
OCH2CH3), 128.3-134.2 (m, Ph), 210.0 (s, OCS2), 233.2 (s,
NCS). MS (FAB, NBA, m/z): 578 [M+].
Preparation of [Pd(PPh3){01-C(SMe)(NMe2)}(02-S2CO)]
(5a)
MeOH (10 mL) was added to a flask (100 mL) contain-
ing [Pd(PPh3)2(01-SCNMe2)(Cl)] (1) (0.754 g, 1.0 mmol) and
MeOCS2K (0.146 g, 1.0 mmol) at room temperature. After
stirring for 5 min, a yellow-orange precipitate was formed.
The precipitate was collected by filtration (G4), washed with
n-hexane (2 ´ 10 mL) and then dried in vacuo to yield 0.51 g
(90%). Of complex [Pd(PPh3){01-C(SMe)(NMe2)}(02-
S2CO)] (5a). IR (KBr, cm-1) L (CO) 1675 (vs), 1603 (vs). 1H
NMR: * 2.88 (s, 3H, SCH3), 2.96, 3.52 (s, 6H, 2NCH3),
7.30-7.57 (m, 15H, Ph). 31P{1H} NMR: * 28.0 (PPh3).
13C{1H} NMR: * 21.2 (s, SCH3), 43.6, 52.0 (s, NCH3),
128.2-134.2 (m, C of Ph), 199.0 (s, S2CO), 247.9 (d, NCSMe,
JP-C = 14.6). MS (FAB, NBA, m/z): 564 [M+]. Anal. Calcd for
C23H24NOPS3Pd: C, 48.98; H, 4.30; N, 2.48%. Found: C,
49.85; H, 4.56; N, 2.38.
Preparation of [Pd(PPh3)2(02-SCNMe2)][Cl] (2)
1H NMR (500 MHz, CDCl3, 233 K): * 2.39, 3.58 (s, 6H,
NCH3), 7.15-7.72 (m, 30H, Ph). 31P{1H} NMR (202 MHz,
2
CDCl3, 233 K): * 23.1, 35.1 (d, JP-P = 40.7 Hz, PPh3).
13C{1H} NMR (125 MHz, CDCl3, 233 K): * 46.1, 53.4 (s,
NCH3), 128.1-135.3 (m, Ph), 212.8 (s, NCS).
Preparation of [Pd(PPh3)Cl]2(µ,02-SCNMe2)2 (3)
To [Pd(PPh3)2(01-SCNMe2)(Cl)] (1) (0.754 g, 1.0
mmol) dissolved in CH2Cl2 (10 mL) with continuous stirring
under a stream of dry nitrogen for 8 h, 20 mL of n-hexane was
added, and a yellow precipitate was formed. The precipitate
was collected by filtration (G4), washed with n-hexane (2 ´
10 mL) and then dried in vacuo to yield 0.46 g (93%) of
[Pd(PPh3)Cl]2(µ,02-SCNMe2)2 (3). IR (KBr, cm-1) L (CN)
1483 (m), 1436 (m). 1H NMR (500 MHz, CDCl3, 298 K): *
2.49, 3.42 (s, 12H, NCH3), 7.28-8.02 (m, 30H, Ph). 31P{1H}
NMR (202 MHz, CDCl3, 298 K): * 19.8 (s, PPh3). 13C{1H}
NMR (125 MHz, CDCl3, 298 K): * 39.9, 49.1 (s, NCH3),
128.4-135.8 (m, Ph), 234.3 (s, NCS). MS (FAB, NBA, m/z):
984.5 [M+], 722.5 [M+ - PPh3], 460.5 [M+ - 2PPh3]. Anal.
Calcd for C42H42Cl2N2P2S2Pd2: C, 51.23; H, 4.30; N, 2.85%.
Preparation of [Pd(PPh3){01-C(SEt)(NMe2)}(02-S2CO)]
(5b)
The synthesis and work-up were similar to those used in
the preparation of complex 5a. The complex [Pd(PPh3){01-
C(SEt)(NMe2)}(02-S2CO)] (5b) was isolated in 75% yield as
a yellow-orange microcrystalline solid. IR (KBr, cm-1) L
(CO) 1681 (vs), 1605 (vs). 1H NMR: * 1.20 (t, 3H, SCH2CH3,
JH-H = 7.5), 2.89, 3.54 (s, 6H, 2NCH3), 3.45, 4.03 (m, 2H,
SCH2), 7.40-7.57 (m, 15H, Ph). 31P{1H} NMR: * 28.0 (PPh3).
13C{1H} NMR: * 13.4 (s, SCH2CH3), 33.4 (s, SCH2), 43.6,

288 J. Chin. Chem. Soc., Vol. 51, No. 2, 2004
Lin et al.
52.2 (s, NCH3), 128.4-134.0 (m, C of Ph), 199.1 (s, S2CO),
246.7 (d, NCSEt, JP-C = 15.2). MS (FAB, NBA, m/z): 578
[M+]. Anal. Calcd for C24H26NOPS3Pd: C, 49.87; H, 4.53; N,
2.42%. Found: C, 50.15; H, 4.38; N, 2.28.
N, 2.32%. Found: C, 55.84; H, 4.50; N, 2.28.
Single-Crystal X-ray Diffraction Analyses of 1, 3, 5a
and 7
Single crystals of 1, 3, 5a, and 7 suitable for X-ray dif-
fraction analyses were grown by recrystallization from 20/1
n-hexane/CH2Cl2. The diffraction data were collected at
room temperature on an Enraf-Nonius CAD4 diffractometer
equipped with graphite-monochromated Mo K" (8 = 0.71073
Å) radiation. The raw intensity data were converted to struc-
ture factor amplitudes and their esd’s after corrections for
scan speed, background, Lorentz, and polarization effects.
An empirical absorption correction, based on the azimuthal
scan data, was applied to the data. Crystallographic computa-
tions were carried out on a Microvax III computer using the
NRCC-SDP-VAX structure determination package.27
A suitable single crystal of 1 was mounted on the top of
a glass fiber with glue. Initial lattice parameters were deter-
mined from 24 accurately centered reflections with 2 values
in the range from 1.78 to 27.50°. Cell constants and other per-
tinent data were collected and are recorded in Table 1. Reflec-
tion data were collected using the 2/22 scan method. Three
check reflections were measured every 30 min throughout the
data collection and showed no apparent decay. The merging
of equivalent and duplicate reflections gave a total of 24507
unique measured data, of which 7906 reflections with I >
2F(I) were considered observed. The first step of the struc-
ture solution used the heavy-atom method (Patterson synthe-
sis), which revealed the positions of metal atoms. The re-
maining atoms were found in a series of alternating differ-
ence Fourier maps and least-squares refinements. The quan-
tity minimized by the least-squares program was w(|Fo|-
|Fc|)2, where w is the weight of a given operation. The analyti-
cal forms of the scattering factor tables for the neutral atoms
were used.28 The non-hydrogen atoms were refined aniso-
tropically. Hydrogen atoms were included in the structure
factor calculations in their expected positions on the basis of
idealized bonding geometry but were not refined in least
squares. All hydrogens were assigned isotropic thermal pa-
rameters 1-2 Å2 larger then the equivalent Biso value of the
atom to which they were bonded. The final residuals of this
refinement were R = 0.043 and Rw = 0.090.
Preparation of [Pd(01-SCNMe2)(02-Phen)(Cl)] (6)
CH2Cl2 (40 mL) was added to a flask (100 mL) contain-
ing [Pd(PPh3)2(01-SCNMe2)(Cl)] (1) (0.754 g, 1.0 mmol) and
phen (0.18 g, 1.0 mmol), and the solution was stirred at room
temperature. After stirring 1 h, MeOH (10 mL) was added to
the solution; brown solids were formed which were isolated
by filtration (G4), washed with n-hexane (2 ´ 10 mL) and
subsequently dried under vacuum yielding 0.30 g (73%) of
[Pd(01-SCNMe2)(02-Phen)(Cl)] (6). IR (KBr, cm-1) L (CN)
1
1436 (m). H NMR (500 MHz, DMSO-d6, 298 K): * 3.66,
4.06 (s, 6H, NCH3), 7.50, 7.84, 7.88, 7.94, 8.39, 8.53, 8.63,
8.75 (s, 8H, Phen). 13C{1H} NMR (125 MHz, DMSO-d6, 298
K): * 41.5, 49.4 (s, NCH3), 125.3, 127.4 (s, 5, 6-C of Phen),
126.6, 127.0 (s, 3, 8-C of Phen), 128.9, 129.6 (s, C of Phen),
139.3, 140.3 (s, 4, 7-C of Phen), 143.3, 144.5 (s, C of Phen),
150.4, 151.7 (s, 2, 9-C of Phen), 221.6 (s, NCS). MS (FAB,
NBA, m/z): 374 [M+ - Cl]. Anal. Calcd for C15H14ClN3SPd:
C, 43.92; H, 3.44; N, 10.25%. Found: C, 43.80; H, 3.26; N,
10.58.
Preparation of [Pd{01-SC(O)NMe2}Pd(Cl)](m,02-
SCNMe2)(m,02-dppm)2 (7)
CH2Cl2 (30 mL) was added to a flask (100 mL) contain-
ing [Pd(PPh3)2(01-SCNMe2)(Cl)] (1) (0.754 g, 1.0 mmol) and
dppm (0.384 g, 1.0 mmol) at room temperature. After stirring
for 2 h, 20 mL of diethyl ether was added to the solution and a
yellow precipitate was formed. The precipitate was collected
by filtration (G4), washed with diethyl ether (2 ´ 10 mL) and
then dried in vacuo. Further purification was accomplished
by slowly diffusion of n-hexane (40 mL) to a CH2Cl2 solution
(5 mL) of the yellow product yielding 0.41 g (45%) of
[Pd{01-SC(O)NMe2}Pd(Cl)](µ,02-SCNMe2)(µ,02-dppm)2
(7). IR (KBr, cm-1) L (CN) 1483 (m), 1424 (m). 1H NMR (500
MHz, CDCl3, 298 K): * 3.75, 3.97 (m, PCH2, 4H), 2.49, 2.91
(s, 12H, NCH3), 6.65-8.34 (m, 48H, Ph). 31P{1H} NMR (202
MHz, CDCl3, 298 K): * 1.97, 9.91 (m, dppm). 13C{1H} NMR
(125 MHz, CDCl3, 298 K): * 30.9 (br, PCH2), 41.1, 43.4, 47.7
(s, NCH3), 127.1-135.0 (m, Ph), 173.2 (s, SCO), 223.0 (s,
NCS). MS (FAB, NBA, m/z): 809 [M+ - dppm- O], 686 [M+ -
dppm- O - Me2NCS - Cl], 578 [M+ - dppm- Me2NCS - Cl -
Pd]. Anal. Calcd for C56H56ClN2OP4S2Pd2: C, 55.62; H, 4.67;
The procedures for 3, 5a and 7 were similar to those for
1. The final residuals of this refinement were R = 0.041 and
Rw = 0.097 for 3, for R = 0.039 and Rw = 0.090 for 5a and R =
0.069 and Rw = 0.181 for 7. Selected bond distances and an-

N,N-dimethylthiocarbamoyl Palladium Complexes
J. Chin. Chem. Soc., Vol. 51, No. 2, 2004 289
1972, 8, 39. (c) Dean, W. K. J. Organomet. Chem. 1980,
190, 353. (d) Dean, W. K.; Charles, R. S.; Van Derveer, D. G.
Inorg. Chem. 1977, 16, 3328.
gles and selected final atomic coordinates are listed in Tables
2 and 3.
10. Gilletti, P. F.; Femec, D. A.; Brown, T. M. Inorg. Chem.
1992, 31, 4008.
ACKNOWLEDGMENT
11. (a) Nieter-Burgmayer, S. J.; Templeton, J. L. Inorg. Chem.
1985, 24, 3939. (b) Brower, D. C.; Tonker, T. L.; Morrow, J.
R.; Rivers, D. S.; Templeton, J. L. Organometallics 1986, 5,
1094. (c) Carmona, E.; Gurierrez-Puebla, E.; Monge, A.;
Perez, P. J.; Sanchez, L. J. Inorg. Chem. 1989, 28, 2120. (d)
Jeffery, J. C.; Went, M. J. J. Chem. Soc. Dalton Trans. 1990,
567. (e) Anderson, S.; Cook, D. J.; Hill, A. F. Organo-
metallics 2001, 20, 2468.
We thank the National Science Council of Taiwan, the
Republic of China (NSC92-2113-241-001) for support.
Supporting Information Available
Plot of VT NMR spectra of the mixtures of 1, 2 and 3 in
CDCl3, X-ray crystallographic files, in CIF format, for the
structures of complexes 1, 3, 5a, and 7.
12. (a) Thewissen, D. H. M. W.; Noltes, J. G. Inorg. Chim. Acta.
1982, 59, 181. (b) Gibson, J. A. E.; Cowie, M. Organo-
metallics 1984, 3, 722.
13. Yih, K. H.; Lee, G. H.; Wang, Y. Inorg. Chem. Commun.
2003, 6, 577.
14. Yih, K. H.; Lee, G. H.; Wang, Y. J. Chin. Chem. Soc. 2004,
51, 31.
Received August 28, 2003.
15. Yoshida, G.; Kurosawa, H.; Okawara, R. J. Organomet.
Chem. 1976, 113, 85.
REFERENCES
16. (a) Gaffney, T. R.; Ibers, J. A. Inorg. Chem. 1982, 21, 2860.
(b) Werner, H.; Bertleff, W.; Zimmer-Gasser, B.; Schubert,
U. Chem. Ber. 1982, 115, 1004. (c) Gaffney, T. R.; Ibers, J.
A. Inorg. Chem. 1982, 21, 2851. (d) Bianchini, C.; Meli, A.;
Orlandini, A. Inorg. Chem. 1982, 21, 4166.
1. Angelici, R. J. Acc. Chem. Res. 1972, 18, 335. A review of
carbamoyl and thiocarbamoyl complexes.
2. (a) Dean, W. K.; Treichel, P. M. J. Organomet. Chem. 1974,
66, 87. (b) Dean, W. K.; Treichel, P. M. Chem. Commun.
1972, 803. (c) Dean, W. K. J. Organomet. Chem. 1977, 135,
195.
17. (a) Cecconi, F.; Ghilardi, C. A.; Midollini, S.; Moneti, S.;
Orlandini, A.; Scapacci, G. J. Chem. Soc., Dalton Trans
1989, 211. (b) Bianchini, C.; Ghilardi, C. A.; Meli A.;
Orlandini, A. J. Organomet. Chem. 1985, 286, 259. (c)
Bianchini, C.; Meli, A. J. Chem. Soc., Dalton Trans 1983,
2419. (d) Bianchini C.; Meli, A. Inorg. Chem. 1987, 26,
4268. (e) Bianchini, C.; Mealli, C.; Meli A.; Sabat, M. J.
Chem. Soc., Chem. Commun. 1985, 1024.
3. (a) Busetto, L.; Grazianin, M.; Belluco, U. Inorg. Chem.
1971, 10. 78. (b) Petz, W. J. Organomet. Chem. 1981, 205,
203.
4. Roper, W. R.; Wright, A. H. J. Organomet. Chem. 1982, 233,
C59.
5. Treichel, P. M.; Knebel, W. J.; Hess, R. W. J. Am. Chem. Soc.
1971, 93, 5424.
18. (a) Colton, R.; Traeger, J. C.; Tedesco, V. Inorg. Chim. Acta
1993, 210, 193. (b) Colton, R.; Tedesco, V. Inorg. Chim. Acta
1992, 202, 95. (c) Colton, R.; Tedesco, V. Inorg. Chim. Acta
1991, 183, 161.
6. Roper, W. R.; Grundy, K. R. J. Organomet. Chem. 1976, 113,
C45.
7. (a) Brower, D. C.; Tonker, T. L.; Templeton, J. L. Organo-
metallics, 1985, 4, 745. (b) Herrick, R. S.; Burgmayer, S. J.
N.; Templeton, J. L. J. Am. Chem. Soc. 1983, 105, 2599. (c)
Mayr, A.; McDermott, G. A.; Domes, A. M.; Holder, A. K. J.
Am. Chem. Soc. 1986, 108, 310. (d) Anderson, S.: Hill, A. F.
J. Chem. Soc., Dalton Trans. 1993, 587. (e) Ichimura, A.;
Yamamoto, Y.; Kajino, T.; Kitigawa, T.; Kuma, H.; Kushi, Y.
Chem. Commun. 1988, 1130.
19. Doherty, J.; Fortune, J.; Manning, A. R.; Stephens, F. S. J.
Chem. Soc., Dalton Trans 1984, 1111.
20. Rossi, R.; Marchi, A.; Margon, L.; Casellato, U.; Graziani,
R. J. Chem. Soc., Dalton Trans 1990, 2923.
21. Gal, A. W.; Ambrosius, H. P. M. M.; Van der Ploeg, A. F. J.
M.; Bosman, W. P. J. Organomet. Chem. 1978, 149, 81.
22. Yih, K. H.; Lin, Y. C.; Cheng, M. C.; Wang, Y. J. Chem. Soc.,
Chem. Commun. 1993, 1380.
8. Luo, X. L.; Kubas, G. J.; Bums, C. J.; Butcher, R. J.
Organometallics 1995, 14, 3370.
23. Yih, K. H.; Lin, Y. C.; Cheng, M. C.; Wang, Y. J. Chem. Soc.,
Dalton Trans 1995, 1305.
9. (a) Gibson, J. A. E.; Cowie, M. Organometallics 1984, 3,
722. (b) Corain, B.; Martelli. M. Inorg. Nucl. Chem. Lett.
24. (a) Cardin, D. J.; Cetinkaya B.; Lappert, M. F. Chem. Rev.

290 J. Chin. Chem. Soc., Vol. 51, No. 2, 2004
Lin et al.
1972, 72, 545 and references cited therein. (b) Butler, W. M.;
Enemark, J. H. Inorg. Chem. 1973, 12, 451. (c) Anderson, O.
P.; Packard, A. B. Inorg. Chem. 1978, 17, 1333. (d) Wilson,
R. D.; Kamitori, K.; Ogoshi, H.; Yoshida, Z.; Ibers, J. A. J.
Organomet. Chem. 1979, 173, 199.
W. R.; Stone, F. G. A. J. Organomet. Chem. 1973, 50, C54.
(c) Calo, V.; Del Sole, R.; Nacci, A.; Schingaro, E.; Scordari,
F. Eur. J. Org. Chem. 2000, 869.
27. Gabe, E. J.; Lee, F. L.; Lepage, Y. Crystallographic Comput-
ing 3; Sheldrick, G. M.; Kruger, C.; Goddard, R. Eds. Claren-
don Press: Oxford, England, 1985; p 167.
25. Bozec, H. L.; Dixneuf, P. H.; Carty, A. J.; Taylor, N. J. Inorg.
Chem. 1978, 17, 2568.
28. International Tables for X-ray Crystallography; Reidel:
Dordrecht, The Netherlands, 1974; Vol. IV.
26. (a) Browning, J.; Green, M.; Spenser, J. L.; Stone, F. G. A. J.
Chem. Soc., Dalton Trans 1974, 97. (b) Fraser, P. J.; Roper,