Synthesis and characterization of cyclometallated palladium(II) and platinum(II) complexes with amide-thiolate ligands

Article abstract of DOI:10.1016/j.jorganchem.2006.08.051

The redox reaction of bis(2-benzamidophenyl) disulfide (H₂L-LH₂) with [Pd(PPh₃)₄] in a 1:1 ratio gave mononuclear and dinuclear palladium(II) complexes with 2-benzamidobenzenethiolate (H₂L^-), [Pd(H₂L-S)₂(PPh₃)₂] (1) and [Pd₂(H₂L-S)₂ (μ-H₂L-S)₂(PPh₃)₂] (2). A similar reaction with [Pt(PPh₃)₄] produced only the corresponding mononuclear platinum(II) complex, [Pt(H₂L-S)₂(PPh₃)₂] (3). Treatment of these complexes with KOH led to the formation of cyclometallated palladium(II) and platinum(II) complexes, [Pd(L-C,N,S)(PPh₃)]^- ([4]^-) and [Pt(L-C,N,S) (PPh₃)]^- ([5]^-). The molecular structures of 2, 3 and [4]^- were determined by X-ray crystallography.

Full text of DOI:10.1016/j.jorganchem.2006.08.051

Journal of Organometallic Chemistry 692 (2007) 257–262
www.elsevier.com/locate/jorganchem
Synthesis and characterization of cyclometallated palladium(II)
and platinum(II) complexes with amide-thiolate ligands
*
Tatsuya Kawamoto , Satoko Suzuki, Takumi Konno
Department of Chemistry, Graduate School of Science, Osaka University, 1-16 Machikaneyama, Toyonaka, Osaka 560-0043, Japan
Received 28 February 2006; accepted 7 April 2006
Available online 30 August 2006
Abstract
The redox reaction of bis(2-benzamidophenyl) disulfide (H2L-LH2) with [Pd(PPh3)4] in a 1:1 ratio gave mononuclear and dinuclear
palladium(II) complexes with 2-benzamidobenzenethiolate (H2Lꢀ), [Pd(H2L-S)2(PPh3)2] (1) and [Pd2(H2L-S)2 (l-H2L-S)2(PPh3)2] (2). A
similar reaction with [Pt(PPh3)4] produced only the corresponding mononuclear platinum(II) complex, [Pt(H2L-S)2(PPh3)2] (3). Treat-
ment of these complexes with KOH led to the formation of cyclometallated palladium(II) and platinum(II) complexes, [Pd(L-
C,N,S)(PPh3)]ꢀ ([4]ꢀ) and [Pt(L-C,N,S) (PPh3)]ꢀ ([5]ꢀ). The molecular structures of 2, 3 and [4]ꢀ were determined by X-ray
crystallography.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Palladium(II) complexes; Platinum(II) complexes; Amide ligand; Cyclometallation; S–S bond activation
1. Introduction
the possibility of oxidation on sulfur atoms in reaction pro-
cesses [12].
Cyclometallated compounds, which are generated
through the activation of C–H bonds, have been exten-
sively investigated, because of their novel and outstanding
applications in organic and organometallic synthesis [1–4].
In this respect, a large number of cyclometallated com-
plexes with azobenzene and Schiff base moieties have been
reported. We have also reported cyclometallated palla-
dium(II) and platinum(II) complexes having a rare triden-
tate-C,N,S Schiff base ligand [5]. However, there are only a
few examples of cyclometallated complexes with amide
ligands, even though amide ligands adopt a planar coordi-
nation framework as do Schiff base ligands [6–9]. In partic-
ular, little is known about the structures and properties of
complexes with amide-thiolate ligands [7]. This seems to be
due to the high reactivity of sulfur atoms in amide ligands,
leading to sulfenate, sulfinate, or disulfide species [10,11].
Thus, we planed to apply redox reactions between low oxi-
dation metals and disulfide compounds in order to rule out
In this paper, we report that the reactions of bis(2-benz-
amidophenyl) disulfide with [Pd(PPh3)4] or [Pt(PPh3)4]
produce palladium(II) and platinum(II) complexes with
monodentate-S amide-thiolate ligands, which are con-
verted into cyclometallated palladium(II) and platinum(II)
complexes with tridentate-C,N,S amide-thiolate ligands by
treatment with base. The molecular structures of some of
these complexes are also reported.
2. Results and discussion
2.1. Synthesis
The reaction of bis(2-benzamidophenyl) disulfide (H2L-
LH2) with an equimolar amount of [Pd(PPh3)4] in benzene
under an anaerobic condition led to the formation of a
mixture of two compounds (1 and 2) that are separated
by fractional precipitation or recrystallization of a mixed
sample. Complexes 1 and 2 were assigned to have a mono-
nuclear and a dinuclear structures in [Pd(H2L-S)2(PPh3)2]
and [Pd2(H2L-S)2(l-H2L-S)2(PPh3)2] (H2Lꢀ = 2-benzami-
*
Corresponding author. Tel.: +81 6 6850 5766; fax: +81 6 6850 5785.
E-mail address: kaw@ch.wani.osaka-u.ac.jp (T. Kawamoto).
0022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.08.051

258
T. Kawamoto et al. / Journal of Organometallic Chemistry 692 (2007) 257–262
dobenzenethiolate), respectively, by the elemental analyses
and the IR and 1H NMR spectroscopies, along with the X-
ray analysis for 2. Similar treatment of H2L-LH2 with
[Pt(PPh3)4] gave a yellow compound (3). It was found from
the IR and 1H NMR spectra and the X-ray analysis that 3
contains
a
single mononuclear species, [Pt(H2L-
S)2(PPh3)2], which is analogous to the mononuclear 1.
Treatment of a mixture of 1 and 2 with KOH in ethanol
gave a yellow solution, from which a yellow powder ([(n-
Bu)4N][4]) was isolated by adding (n-Bu)4NBr. X-ray anal-
ysis demonstrated that [4]ꢀ is a desired cyclometallated
complex, [Pd(L-C,N,S)(PPh3)]ꢀ, in which a PdII centre is
coordinated by C, N, and S atoms from an amide-thiolate
ligand (L3ꢀ). An analogous cyclometallated complex (K[5])
was also obtained by treatment of 3 with KOH in ethanol,
which was assigned by the elemental analysis and the IR
and NMR spectroscopic studies (Scheme 1).
Fig. 1. Molecular structure of [Pd2(H2L-S)2(l-H2L-S)2(PPh3)2] (2).
2.2. Molecular structures of [Pd2(H2L–S)2(l-H2L–
S)2(PPh3)2] (2), [Pt(H2L–S)2(PPh3)2] (3) and
[(n-Bu)4N][Pd(L-C,N,S)(PPh3)] ([(n-Bu)4N][4])
˚
sulfur atoms with distances of N1–Hꢁ ꢁ ꢁS1 = 2.35(6) A
˚
and N2–Hꢁ ꢁ ꢁS2 = 2.57(7) A [15,16].
The molecular structure of 2 is shown in Fig. 1, and its
selected bond distances and angles are given in Table 1. In
2, there is a crystallographic inversion centre at the
midpoint of the Pd1ꢁ ꢁ ꢁPd10 vector. Two palladium(II)
atoms are bridged by two thiolato sulfur atoms from two
amide-thiolate ligands (H2Lꢀ). The Pdꢁ ꢁ ꢁPd separation in
The molecular structure of 3 is shown in Fig. 2, and its
selected bond distances and angles are given in Table 2. In
3, the platinum(II) centre resides in a square-planar geom-
etry that is defined by two sulfur atoms from two H2Lꢀ
ligands and two phosphorus atoms from two triphenyl-
phosphine ligands. The two phosphorus atoms are cis to
˚
˚
2 is 3.5504(8) A, which is indicative of the absence of a
each other. The Pt–S bond distances (av. 2.359(9) A) are
bonding interaction [5]. Each palladium(II) centre resides
in a square-planar geometry that is defined by two sulfur
atoms from two bridging H2Lꢀ ligands, one sulfur atom
from a terminal H2Lꢀ ligand and one phosphorus atom
from triphenylphosphine. The Pd–Sterminal (av. 2.333(2)
almost the same as those of a previously reported plati-
num(II) complex, [Pt(PPh3)2(TIPT)2] (HTIPT = 2,4,6-tri-
˚
isopropylbenzenethiol) (av. 2.359(4) A) [17]. The Pt–P
˚
bond distances (av. 2.292(9) A) are also comparable to
˚
those found in [Pt(PPh3)2(TIPT)2] (av. 2.323(4) A). The
phenyl rings from two H2Lꢀ ligands face each other with
˚
˚
˚
A), Pd–Sbridging (2.406(2) A) and Pd–P (2.291(2) A) bond
distances are within the range of normal values [13,14].
Two triphenylphosphine ligands are trans to each other
across two palladium(II) atoms. Each phenyl ring of the
terminal and bridging H2Lꢀ ligands is oriented so as to
face a phenyl of triphenylphosphine with distances of
˚
a distance of ca. 3.54 A. In addition, two intraligand
hydrogen bonds are observed between an amide and a thio-
˚
lato groups with distances of N1–Hꢁ ꢁ ꢁS1 = 2.291(8) A and
˚
N2–Hꢁ ꢁ ꢁS2 = 2.580(9) A [15,16].
X-ray analysis of [(n-Bu)4N][4] revealed the presence of
a discrete complex anion and a (n-Bu)4N+ counter cation.
The structure of the complex anion [4]ꢀ is shown in
˚
3.370(10) and 3.497(10) A, respectively. In addition, amide
protons form an intraligand hydrogen bond with thiolato
Scheme 1.

T. Kawamoto et al. / Journal of Organometallic Chemistry 692 (2007) 257–262
259
˚
Table 1
benzoylhydrazone) (Pd–C = 2.007(5) A and Pd–N =
1.971(5) A) [18].
˚
Selected bond distances (A) and angles (°) for [Pd2(H2L-S)2(l-H2L-
S)2(PPh3)2] (2)
˚
Pd1–S1
Pd1–S2
Pd1–S2#1
Pd1–P1
2.321(2)
2.345(2)
2.406(2)
2.291(2)
C1ꢁ ꢁ ꢁC43
3.370(10)
3.497(10)
2.35(6)
2.57(7)
3.5504(8)
98.6(1)
2.3. Spectroscopic studies
C14ꢁ ꢁ ꢁC31
N1–Hꢁ ꢁ ꢁS1
N2–Hꢁ ꢁ ꢁS2
Pd1ꢁ ꢁ ꢁPd1#1
S2–Pd1–P1
S2#1–Pd1–P1
Pd1–S2–Pd1#1
The IR spectrum of each complex obtained in this study
shows a carbonyl mC@O band (1661 cmꢀ1 for 1, 1676 cmꢀ1
for 2, 1667 cmꢀ1 for 3, 1655 cmꢀ1 for [(n-Bu)4N][4] and
1624 cmꢀ1 for K[5]), which shifts to lower energy relative
to the mC@O band for the starting disulfide ligand H2L-
LH2 (1678 cmꢀ1). Each of 1 and 2 gives an amide mN–H
band (3358 cmꢀ1 for 1 and 3320 cmꢀ1 for 2), while two
mN–H bands are observed for 3 (3352 cmꢀ1 and 3304
cmꢀ1), which are compatible with the presence of weak
and strong N–Hꢁ ꢁ ꢁS interactions detected by the X-ray
analysis (Table 2). No mN–H band is noticed for [(n-
Bu)4N][4] and K[5], indicative of the formation of a M–N
bond (M = Pd, Pt).
S1–Pd1–S2
S1–Pd1–S2#1
S1–Pd1–P1
S2–Pd1–S2#1
170.7(1)
91.1(1)
87.3(1)
83.3(1)
177.2(1)
96.7(1)
Symmetry transformations used to generate equivalent atoms: #1 ꢀx, ꢀy,
ꢀz.
The 1H NMR spectra of the complexes measured in
CDCl3 or DMSO-d6 are shown in Figs. S1–S3. Since the
1H NMR spectrum of 1 exhibits one singlet signal at d
8.81 due to amide protons, as does the spectrum of 3 (d
8.71), it is reasonable to assume that 1 has a symmetrical
mononuclear structure in [Pd(H2L-S)2(PPh3)2] with a cis
configuration, which is analogous to the structure in 3
([Pt(H2L-S)2(PPh3)2]). The relative downfield shift of
amide protons for 1 and 3 would be attributed to the for-
mation of intraligand hydrogen bonds with thiolato
groups. On the other hand, two amide proton signals are
1
observed at d 9.24 and 8.68 in the H NMR spectrum of
2. This is consistent with the symmetrical structure of 2
found in crystal, which reveals the presence of two bridging
and two terminal H2Lꢀ ligands. As shown in Fig. S3, the
1H NMR spectral feature of K[5] is very similar to that
of [(n-Bu)4N][4] over the whole region, showing a signifi-
cant downfield shift (d 8.80 for [4]ꢀ and d 8.86 for [5]ꢀ)
for the phenyl proton adjacent to the cyclometallated atom
(Fig. 3). This result implies that [5]ꢀ has a mononuclear
structure in [Pt(L-C,N,S)(PPh3)] bearing a cyclometallated
tridentate-C,N,S ligand (L3ꢀ), which is analogous to the
structure in [4]ꢀ ([Pd(L-C,N,S)(PPh3)]).
Fig. 2. Molecular structure of [Pt(H2L-S)2(PPh3)2] (3).
Table 2
˚
Selected bond distances (A) and angles (°) for [Pt(H2L-S)2(PPh3)2] (3)
Pt1–S1
Pt1–S2
Pt1–P1
Pt1–P2
2.352(9)
2.366(9)
2.307(9)
2.276(9)
91.7(3)
C1ꢁ ꢁ ꢁC14
3.55(5)
3.53(5)
2.291(8)
2.580(9)
C2ꢁ ꢁ ꢁC15
N1–Hꢁ ꢁ ꢁS1
N2–Hꢁ ꢁ ꢁS2
S2–Pt1–P1
S2–Pt1–P2
P1–Pt1–P2
S1–Pt1–S2
S1–Pt1–P1
S1–Pt1–P2
170.9(3)
81.6(3)
176.9(3)
89.5(3)
97.6(3)
3. Conclusions
It was found in this study that the redox reaction
between the disulfide H2L-LH2 and [Pd(PPh3)4] produces
a mixture of the mononuclear [Pd(H2L-S)2(PPh3)2] (1)
and the dinuclear [Pd2(H2L-S)2(l-H2L-S)2(PPh3)2] (2),
which was successfully separated. On the other hand, only
the mononuclear [Pt(H2L-S)2(PPh3)2] (3) was obtained for
the corresponding reaction with [Pt(PPh3)4], which is most
likely due to the stronger Pt–P bonds compared with the
Pd–P bonds. Interestingly, treatment of a mixture of 1
and 2 with OHꢀ results in the cyclometallated [Pd(L-
C,N,S)(PPh3)]ꢀ ([4]ꢀ). The first step of this reaction is
the cleavage of amide N–H bond by OHꢀ, which leads
to the formation of Pd–N bond accompanied by the loss
Fig. 3, and its selected bond distances and angles are given
in Table 3. The palladium(II) centre resides in a square-
planar geometry that is defined by one sulfur, one nitrogen
and one carbon atom from a L3ꢀ ligand, besides one
phosphorus atom from triphenylphosphine. Thus, the
L3ꢀ ligand acts as a rare tridentate-C,N,S chelator that
is derived from the cyclometallation reaction of the
˚
pendant phenyl ring. The Pd–C (2.023(6) A) and Pd–N
ꢀ
˚
(2.022(5) A) bond distances in [4] are slightly longer
than those in a related cyclometallated palladium(II) com-
plex, [Pd(L0)(MeCN)] (H2L0 = phenyl 2-pyridyl ketone

260
T. Kawamoto et al. / Journal of Organometallic Chemistry 692 (2007) 257–262
4.2. Synthesis of complexes
4.2.1. [Pd(H2L–S)2(PPh3)2] (1) and [Pd2(H2L–S)2-
(l-H2L–S)2(PPh3)2] (2)
To a solution of H2L-LH2 (0.51 g, 1.12 mmol) in 50 ml
of degassed benzene under an argon atmosphere was added
[Pd(PPh3)4] (1.18 g, 1.02 mmol). The reaction mixture was
stirred for 1 h at room temperature, and the resulting red
precipitate of a mixture of 1 and 2 (0.97 g) was collected
by filtration. When the filtrate was allowed to stand in a
refrigerator for 2 days, a red powder of a mixture of 1
and 2 (68 mg) was again precipitated, which was filtered
off. The second filtrate was further allowed to stand in a
refrigerator for 2 days. The precipitated red powder of 1
was collected by filtration. Yield: 35 mg. A pure sample
of 2 was obtained by recrystallization of the first red pre-
cipitate (32 mg) from CH2Cl2/n-hexane. Yield: 10 mg. Sin-
gle crystals of 2 suitable for a structure determination were
grown by slow diffusion of pentane into a CH2ClCH2Cl
solution of 2. Anal. Calcd. for [Pd(H2L-S)2(PPh3)2] Æ
1.5C6H6, C71H59N2O2P2PdS2: C, 70.78; H, 4.94; N, 2.33.
Found: C, 70.88; H, 5.02; N, 2.30%. Anal. Calcd. for
Fig. 3. Molecular structure of [Pd(L-C,N,S)(PPh3)]ꢀ ([4]ꢀ).
[Pd2(H2L-S)2(l-H2L-S)2(PPh3)2] Æ 0.25CH2Cl2, C88.25H70.5
-
Cl0.5N4O4P2Pd2S4: C, 63.40; H, 4.25; N, 3.35. Found: C,
63.35; H, 4.30; N, 3.49%. IR (m cmꢀ1): 3358vw (N–H),
~
Table 3
1661 m (C@O) for 1, 3320vw (N–H), 1676 m (C@O) for
2. H NMR (CDCl3): d 8.81 (s, 2H, NH), 7.97 (d, 2H,
˚
Selected bond distances (A) and angles (°) for [(n-Bu)4N][Pd(L-
C,N,S)(PPh3)] ([(n-Bu)4N][4])
1
Ph CH), 7.65–7.10 (m, 42H, Ph CH), 6.84 (t, 2H, Ph
CH), 6.60 (t, 2H, Ph CH) for 1, 9.24 (s, 2H, NH), 8.68
(s, 2H, NH), 8.20 (d., 2H, Ph CH), 8.05 (d, 2H, Ph CH),
7.66 (d, 2H, Ph CH), 7.45–6.90 (m, 58H, Ph CH), 6.82 (t,
2H, Ph CH) for 2.
Pd1–S1
Pd1–P1
S1–Pd1–P1
S1–Pd1–N1
S1–Pd1–C9
2.312(2)
2.243(2)
94.7(1)
85.3(2)
167.1(2)
Pd1–N1
Pd1–C9
P1–Pd1–N1
P1–Pd1–C9
N1–Pd1–C9
2.022(5)
2.023(6)
177.4(2)
97.7(2)
82.5(2)
4.2.2. [Pt(H2L–S)2(PPh3)2] (3)
of a H2Lꢀ and a PPh3 ligands. The coordination of amide
nitrogen atom affords the access of a pendant phenyl ring
to the metal centre, followed by the C–H activation.
Cyclometallation of phenyl ring caused by such short con-
tact has been found in the corresponding Schiff base com-
plexes [5,19,20]. The analogous cyclometallated [Pt(L-
C,N,S)(PPh3)]ꢀ ([5]ꢀ) was also formed by treatment of 3
with OHꢀ. Thus, it was evidenced that the redox reaction
between a low oxidation metal (Pd0 or Pt0) and an amide-
disulfide compound (H2L-LH2), followed by treatment
with base, is a simple and convenient synthetic route to
create cyclometallated metal complexes with amide-thio-
late ligands, which does not suffer oxidation at thiolato
groups.
To a solution of H2L-LH2 (0.18 g, 0.39 mmol) in 40 ml
of degassed benzene under an argon atmosphere was added
[Pt(PPh3)4] (0.48 g, 0.39 mmol). The reaction mixture was
stirred at room temperature for 2 h, followed by allowing
to stand in a refrigerator for 4 h. The resulting yellow
powder of 3 was collected by filtration. Yield: 0.24 g. Single
crystals of 3 suitable for a structure determination were
grown by slow diffusion of pentane into a CHCl3 solution
of 3. Anal. Calcd. for [Pt(H2L-S)2(PPh3)2], C62H50-
N2O2P2PtS2: C, 63.31; H, 4.28; N, 2.38. Found: C, 63.37;
H, 4.53; N, 2.35%. IR (m cmꢀ1): 3352 w, 3304 w (N–H),
~
1
1667 m (C@O). H NMR (CDCl3): d 8.71 (s, 2H, NH),
8.04 (d, 2H, Ph CH), 7.79 (d, 2H, Ph CH), 7.65–7.10 (m,
40H, Ph CH), 6.69 (t, 2H, Ph CH), 6.55 (t, 2H, Ph CH).
4. Experimental
4.2.3. [(n-Bu)4N][Pd(L-C,N,S)(PPh3)]-
([(n-Bu)4N][4])
4.1. General
An ethanolic solution of KOH (0.035 g, 0.63 mmol) was
added to a solution of a mixture of 1 and 2 (0.20 g) in 20 ml
of ethanol under an argon atmosphere. The reaction mix-
ture was refluxed for 2 h to give a yellow solution, which
was concentrated to ca. 10 ml with a rotary evaporator.
The addition of (n-Bu)4NBr (0.22 g) dissolved in a small
The reagents were purchased from commercial sources
and not purified further. Bis(2-benzamidophenyl) disulfide
(H2L-LH2) was synthesized by the modified method
reported in [21].

T. Kawamoto et al. / Journal of Organometallic Chemistry 692 (2007) 257–262
261
amount of ethanol to the concentrated solution afforded a
yellow powder of [(n-Bu)4N][4], which was collected by fil-
tration. Yield: 0.14 g. Single crystals of [(n-Bu)4N][4] suit-
able for a structure determination were obtained by
recrystallization of the yellow powder from hot ethanol.
Anal. Calcd. for [(n-Bu)4N][Pd(L-C,N,S)(PPh3)] Æ 0.2 KBr,
C47H59Br0.2K0.2N2OPPdS: C, 65.55; H, 6.90; N, 3.25.
PhN,S-chelate CH), 6.73 (d, 1H, PhC,N-chelate CH), 6.66 (t,
1H, PhN,S-chelate CH), 6.50 (t, 1H, PhC,N-chelate CH), 6.44
(t, 1H, PhC,N-chelate CH), 6.36 (t, 1H, PhN,S-chelate CH),
6.26 (d, 1H, PhN,S-chelate CH) [22].
4.3. Physical measurements
Found: C, 65.37; H, 7.11; N, 3.30%. IR (m cmꢀ1): 1655 m
The infrared spectra were measured on a JASCO FT/
IR-5000 spectrophotometer using the nujol mulls and the
NMR spectra on a JEOL EX 270 instrument. Tetrameth-
ylsilane was used as the internal standard (d 0). Elemental
analyses were performed at Osaka University.
~
1
(C@O). H NMR (DMSO-d6): d 8.80 (d, 1H, PhC,N-chelate
CH), 7.65–7.55 (m, 6H, PhPPh3 CH), 7.50–7.35 (m, 9H,
PhPPh3 CH), 7.16 (d, 1H, PhN,S-chelate CH), 6.70 (d, 1H,
PhC,N-chelate CH), 6.67 (t, 1H, PhN,S-chelate CH), 6.54 (t,
1H, PhC,N-chelate CH), 6.42 (t, 1H, PhC,N-chelate CH), 6.36
(t, 1H, PhN,S-chelate CH), 6.20 (d, 1H, PhN,S-chelate CH) [22].
4.4. X-ray structure analysis
4.2.4. K[Pd(L-C,N,S)(PPh3)] (K[5])
The crystallographic date of 2, 3 and [(n-Bu)4N][4] are
listed in Table 4. Each of a red crystal of 2, a yellow crystal
of 3 and a yellow crystal of [(n-Bu)4N][4] was sealed in a
Lindemann glass-capillary tube with the mother liquor.
X-ray diffraction data were collected on a Mac Science
MXC3 diffractometer with Mo Ka radiation (k =
To a solution of 3 (0.22 g, 0.19 mmol) in 20 ml of etha-
nol under an argon atmosphere was added an ethanolic
solution of KOH (0.039 g, 0.70 mmol). The reaction mix-
ture was refluxed for 2 h to give a yellow solution, which
was concentrated to ca. 5 ml with a rotary evaporator.
The concentrated solution was allowed to stand in a refrig-
erator for 2 h, and the resulting yellow powder of K[5] was
collected by filtration. Yield: 0.13 g. Anal. Calcd. for
K[Pd(L-C,N,S)(PPh3)] Æ 2.5H2O, C31H28KNO3.5PPtS: C,
48.50; H, 3.68; N, 1.82. Found: C, 48.50; H, 4.13; N,
˚
0.71073 A) at room temperature; the h–2h scans were used.
The intensities of three standard reflections for each com-
plex were measured every 100 reflections. Over the course
of data collection the standards of 2 decreased by 24.3%
and a linear correction factor was applied to account for
this. The standards of 3 and [(n-Bu)4N][4] showed no
significant decay effects. The structure of 2 was solved by
direct methods using PATTY in DIRDIF and those of 3
1.50%. IR (m cmꢀ1): 1624 m (C@O). 1H NMR (DMSO-
~
d6): d 8.86 (d, 1H, PhC,N-chelate CH), 7.70–7.55 (m, 6H,
PhPPh3 CH), 742 (s(br), 9H, PhPPh3 CH), 7.11 (d, 1H,
Table 4
Crystallographic data of complexes
[Pd2(H2L-S)2(l-H2L-S)2-
(PPh3)2]Æ3C5H12 (2)
[Pt(H2L-S)2(PPh3)2] Æ
1.5CHCl3 (3)
[(n-Bu)4N][Pd(L-C,N,S)(PPh3)] Æ
2C2H5OH ([(n-Bu)4N][4])
Empirical formula
Formula weight
Temperature (K)
Wavelength (A)
Crystal system
Space group
C
103H106N4O4P2Pd2S4
C63.5H51.5Cl4.5N2O2P2PtS2
1355.32
293(2)
0.71073
Monoclinic
P21/a
C51H71N2O3PPdS
929.60
293(2)
0.71073
Triclinic
1867.05
293(2)
0.71073
Triclinic
˚
ꢀ
ꢀ
P1
P1
Unit cell dimensions
˚
a (A)
13.997(7)
14.904(6)
11.839(5)
101.64(3)
101.57(4)
66.11(3)
2192(2)
1
29.32(1)
15.338(6)
12.731(4)
10.173(5)
27.298(9)
9.522(5)
96.86(3)
104.03(4)
81.95(3)
2530(2)
2
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
96.69(3)
3
˚
V (A )
5687(3)
4
1.58
2.66
10869
Z
Dcalc (Mg mꢀ3
)
1.42
0.58
9201
1.22
0.47
10005
l (mmꢀ1
)
Number of unique
reflections measured
Number of reflections
in refinement
7462 (I > 2.0 r(I))
7501 (I > 2.0 r(I))
8567 (I > 2.0r(I))
Ra
0.071
0.086
0.088
0.098
0.081
0.097
b
Rw
P
P
a
R = iF j ꢀ jF i/ jFoj.
h
i.
h
i
o
c
1=2
P
P
2
2
2
2
b
wR ¼
wðj F oj ꢀ j F cj Þ
wðF 2oÞ
.

262
T. Kawamoto et al. / Journal of Organometallic Chemistry 692 (2007) 257–262
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with full-matrix least-squares calculations. Hydrogen
˚
atoms were located at fixed positions (C–H 0.96 A).
´
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Acknowledgements
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This work was partially supported by a Grant-in-Aid for
Scientific Research on Priority Areas (No. 16033235) from
the Ministry of Education, Culture, Sports, Science and
Technology of Japan.
Appendix A. Supplemental material
Crystallographic data for the structural analyses have
been deposited with the Cambridge Crystallographic Data
Centre, CCDC Nos. 299784–299786. Copies of the data
can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK, fax: int. code +44
1223 336 033; e-mail for inquiry: fileserv@ccdc.cam.ac.uk;
[15] T. Okamura, S. Takamizawa, N. Ueyama, A. Nakamura, Inorg.
Chem. 37 (1998) 18.
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J. Chem. Soc., Dalton Trans. (1996) 4239.
1
e-mail for deposition: deposit@ccdc.cam.ac.uk. H NMR
spectra of complexes 1, 2, 3, [(n-Bu)4N][4] and K[5] are
available (Figs. S1–S3). Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2006.08.051.
[19] T. Kawamoto, I. Nagasawa, H. Kuma, Y. Kushi, Inorg. Chim. Acta
265 (1997) 163.
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[22] Assignment was made by selective homonuclear decoupling
measurements.
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