Activation of C-S bond by group 10 metal complexes: Reaction of phosphine ligand tethered with three tert-butylthiophenyl groups with group 10 metal compounds

Article abstract of DOI:10.1246/bcsj.20160089

A new PS₃-type tripodal tetradentate ligand, P(2-t-BuSC₆H₄)₃ (1b), was synthesized by reaction of PCl₃ with 2-t-BuS(C₆H₄)Li. Reaction of ligand 1b with NiCl₂6H₂O resulted in the elimination of t-BuCl to afford the corresponding 5-coordinate nickel complex, [NiCl(P(2-SC₆H₄)(2-t-BuSC₆H₄)₂}] 6. In addition, ligand 1b reacted with [PdCl₂(PhCN)₂] and [PtCl₂(cod)] to give 4-coordinate square planar palladium and platinum complexes, [MCl(P(2-SC₆H₄)(2-t-BuSC₆H₄)₂}] (7: M = Pd, 8: M = Pt), respectively, via the elimination of t-BuCl. Further elimination of t-BuCl from palladium complex 7 proceeded by heating of 7 in CDCl₃ at 100°C for 4h to form dipalladium complex, [Pd₂₍P(2-SC₆H₄)₂(2-t-BuSC₆H₄))₂] (9). The isopropyl-substituted palladium and platinum complexes, [PdCl{P(2-i-PrSC₆H₄)₃}]Cl (3a) and [PtCl₂{P(2-i-PrSC₆H₄)₃}] (5), also underwent the elimination of i-PrCl by the thermolysis in CDCl₃ at 60 °C to afford the corresponding complexes, [MCl{P(2-SC₆H₄)(2-i-PrSC₆H₄)₂}] (11: M = Pd, 12: M = Pt). The structures of these complexes were determined by NMR spectroscopy, elemental analyses, and X-ray crystallography.

Full text of DOI:10.1246/bcsj.20160089

Activation of C-S Bond by Group 10 Metal Complexes: Reaction
of Phosphine Ligand Tethered with Three tert-Butylthiophenyl
Groups with Group 10 Metal Compounds
Nobuhiro Takeda,* Yusuke Tanaka, Rin Oma, Fumiaki Sakakibara, and Masafumi Unno
Division of Molecular Science, and International Education and Research Center for Silicon Science, Graduate School of
Science and Technology, Gunma University, 1-5-1 Tenjin-cho, Kiryu, Gunma 376-8515
E-mail: ntakeda@gunma-u.ac.jp
Received: March 17, 2016; Accepted: May 31, 2016; Web Released: May 24, 2016
Nobuhiro Takeda
Nobuhiro Takeda received his B.S. in 1992 and Ph.D. in 1997 from The University of Tokyo under the
supervision of Prof. Renji Okazaki. He worked as a postdoctoral fellow at Chiba University (1997–1998) and
Institute for Molecular Science (1998). He became an Assistant Professor at Kyushu University in 1998 and
moved to Kyoto University as an Assistant Professor in 2000. In 2006, he joined Gunma University as an
Associate Professor. His current research interest is focused on synthesis of new ligands and synthesis,
structure, and reactivity of their transition-metal complexes.
Abstract
new PS3-type tripodal tetradentate ligand, P(2-t-
cleavage of bonds between sp3 carbon and sulfur atoms
catalyzed by nickel(II)6,7 and palladium(II)8,9 complexes is
relatively rare, and such cleavage catalyzed by platinum(II)9,10
is very rare.
A
BuSC6H4)3 (1b), was synthesized by reaction of PCl3 with 2-t-
BuS(C6H4)Li. Reaction of ligand 1b with NiCl2¢6H2O resulted
in the elimination of t-BuCl to afford the corresponding 5-coor-
dinate nickel complex, [NiCl{P(2-SC6H4)(2-t-BuSC6H4)2}] 6.
In addition, ligand 1b reacted with [PdCl2(PhCN)2] and
[PtCl2(cod)] to give 4-coordinate square planar palladium and
platinum complexes, [MCl{P(2-SC6H4)(2-t-BuSC6H4)2}] (7:
M = Pd, 8: M = Pt), respectively, via the elimination of t-
BuCl. Further elimination of t-BuCl from palladium complex 7
proceeded by heating of 7 in CDCl3 at 100 °C for 4 h to form
dipalladium complex, [Pd2{P(2-SC6H4)2(2-t-BuSC6H4)}2] (9).
The isopropyl-substituted palladium and platinum complexes,
[PdCl{P(2-i-PrSC6H4)3}]Cl (3a) and [PtCl2{P(2-i-PrSC6H4)3}]
(5), also underwent the elimination of i-PrCl by the thermolysis
in CDCl3 at 60 °C to afford the corresponding complexes,
[MCl{P(2-SC6H4)(2-i-PrSC6H4)2}] (11: M = Pd, 12: M = Pt).
The structures of these complexes were determined by NMR
spectroscopy, elemental analyses, and X-ray crystallography.
In recent years, much attention has been focused on
transition-metal complexes with tripodal tetradentate ligands
due to not only their unique structure and properties but also the
potential for the activation of small molecules such as N2, O2,
and H2, the stabilization of reactive intermediates, and catalytic
activities.11-16 Recently, we reported the synthesis of a new trip-
odal tetradentate ligand, tris(2-isopropylthiophenyl)phosphine
(1a), and their group 10 metal complexes, that is, 5-coordinate
nickel(II) and palladium(II) complexes, 2 and 3a, 4, respec-
tively, and square planar platinum(II) complex 5 (Chart 1).17,18
In this paper, we report the synthesis of the tert-butyl deriv-
ative of phosphine ligand 1a, tris(2-tert-butylthiophenyl)phos-
phine (1b), and its reactions with group 10 metal complexes.
These reactions resulted in the cleavage of the C(sp3)-S bond
along with the elimination of tert-butyl chloride. In addition,
we report thermolysis of the isopropyl-substituted palladium
and platinum complexes, 3a and 5, resulting in the C(sp3)-S
bond cleavage with the elimination of isopropyl chloride.
C-S bond activation by transition metals has been attracting
much attention from the standpoint of catalytic and stoichio-
metric transformations using organosulfur compounds1 and
hydrodesulfurization (HDS), which is important in petrochem-
istry.2-4 In addition, alkylthio groups such as tert-butylthio and
benzylthio groups have been used as protective groups for
thiols, and the C-S bond of these S-alkyl thioethers are cleaved
by the reaction with (a) Na/NH3, (b) protic acid such as FSO3H-
SbF5 and HClO4/CH3CO2H, or (c) transition-metal compounds
such as silver(I), mercury(II), and copper(II).5 However, the
Cl
Cl
M
P
i-Pr
i-Pr
i-Pr
i-Pr
R
R
S
S
Pt Cl
S
S
S
i-Pr
S
X–
S
P
P
S
S
R
i-Pr
5
1a: R = i-Pr
1b: R = t-Bu
2: M = Ni, X = BF4
3a: M = Pd, X = Cl
4: M = Pd, X = BF4
Chart 1. Ligands 1a, b, and group 10 metal complexes with
ligand 1a.
922 | Bull. Chem. Soc. Jpn. 2016, 89, 922–930 | doi:10.1246/bcsj.20160089
© 2016 The Chemical Society of Japan

Table 1 shows selected bond lengths and angles for complexes
6-8. In nickel complex 6, the Ni1-S1 (thiolato) bond is slightly
shorter than the Ni1-S3 (thioether) bond. This tendency is con-
sistent with the reported properties that metal-thiolato bonds
are shorter than metal-thioether bonds.21 The Ni1-S2 bond is
longer than the other two Ni-S bonds, the S3-Ni1-S1 bond
angle is larger than the other two S-Ni-S bond angles, and the
Results and Discussion
Synthesis and Structure of Tris(2-tert-butylthiophenyl)-
phosphine Ligand (1b). Lithiation of tert-butyl phenyl sul-
fide19 with butyllithium in the presence of tetramethylethylene-
diamine (TMEDA) in hexane at 50 °C for 1 h,20 followed by
treatment with PCl3 at ¹40 to 25 °C yielded the desired ligand,
tris(2-tert-butylthiophenyl)phosphine (1b), in 43% yield
(Scheme 1). Phosphine 1b is stable in air and its structure
Cl
Ni
P
t-Bu
t-Bu
S
S
NiCl2·6H2O
BuOH, 50 °C, 24 h
1
was determined by H, 13C, and 31P NMR spectra, elemental
S
analysis, and X-ray crystallographic analysis.
t-Bu
t-Bu
S
S
The ORTEP drawing of 1b showed the pre-organized struc-
ture for the 4-coordination to metals with a C3 symmetry axis,
in which the three sulfur atoms are situated on the same side
with the lone pair of the phosphorus atom (Figure 1).
[PdCl2(PhCN)2]
CHCl3, 25 °C, 72 h
or
P
6: 89%
t-Bu
Cl
t-Bu
S
t-Bu
1b
[PtCl2(cod)]
S
S
S
CH2Cl2, 25 °C, 48 h
M
P
Reactions of Ligand 1b with Group 10 Metal Com-
pounds. When ligand 1b was treated with NiCl2¢6H2O in
butanol at 50 °C for 1 d, one tert-butyl group on the sulfur
atom of 1b was eliminated to form the corresponding chlorido-
(thiolato)nickel complex 6 in 89% yield (Scheme 2). Reactions
of 1b with [PdCl2(PhCN)2] in CHCl3 at 25 °C for 72 h and with
[PtCl2(cod)] in CH2Cl2 at 25 °C for 48 h also resulted in the
elimination of tert-butyl chloride to afford the corresponding
palladium and platinum complexes, 7 and 8, respectively. The
structures of these complexes, 6, 7, and 8, were determined by
7: M = Pd, 94%
8: M = Pt, 97%
Scheme 2. Reaction of ligand 1b with group 10 metal
complexes.
the H, 13C, and 31P NMR spectra, elemental analyses, and X-
1
ray crystallographic analyses.
The X-ray analyses showed 5-coordinate trigonal-bipyrami-
dal structure of nickel complex 6 (Figure 2) and 4-coordinate
square-planar structure of palladium and platinum complexes, 7
and 8 (Figures 3 and 4). In the latter structures, one thioether
moiety coordinates to the metal, while another uncoordinates.
t-Bu
t-Bu
t-Bu
t-Bu
S
S
S
S
PCl3
–40 °C ~ 25 °C
BuLi, TMEDA
hexane
50 °C, 1 h
P
Li
S
t-Bu
1b: 43%
Figure 2. ORTEP drawing of 6 with thermal ellipsoids
(50% probability). All H atoms have been omitted for
clarity.
Scheme 1. Synthesis of ligand 1b.
Figure 1. ORTEP drawing of 1b with thermal ellipsoids
(50% probability). All H atoms and solvent molecules have
been omitted for clarity.
Figure 3. ORTEP drawing of 7 with thermal ellipsoids
(50% probability). All H atoms and a solvent molecule
have been omitted for clarity.
Bull. Chem. Soc. Jpn. 2016, 89, 922–930 | doi:10.1246/bcsj.20160089
© 2016 The Chemical Society of Japan | 923

P1-Ni1-Cl1 bond angle is near 180°. These properties suggest
that the 5-coordinate structure of 6 can be explained by the
weak coordination of the S2 atom to the distorted square-planar
structure constructed by the Ni1, P1, Cl1, S1, and S3 atoms,
as in the case of cationic 5-coordinate nickel and palladium
complexes, 2, 3a, and 4.17 Also in the palladium and plati-
num complexes, 7 and 8, the M1-S1 (thiolato) bond is
slightly shorter than the M1-S2 (thioether) bond. The S1-M1-
S2 angles of 7 and 8 deviate from 180°, although the P1-M1-
Cl1 and other bond angles around the metal center are close
to 180 and 90°, respectively. Therefore, complexes 7 and 8
have distorted square-planar structures. The Pd1-S3 distance
(3.4911(7) ¡) of 7 is close to the sum of van der Waals radii of
Pd (1.63 ¡) and S (1.80 ¡),22 suggesting very weak interaction
between the Pd1 and S3 atoms. On the other hand, the Pt1-S3
distance (3.862(3) ¡) is longer than the sum of van der Waals
radii of Pt (1.72 ¡) and S (1.80 ¡),22 indicating no interaction
between the Pt1 and S3 atoms. The difference in the structure
among 6, 7, and 8 is consistent with the reported tendency
to form five-coordinate complex in the order of NiII > PdII >
PtII.23
The 1H and 13C NMR spectra of 6-8 showed that the two tert-
butyl groups are equivalent, although those in the crystalline
states are nonequivalent. Since these results suggest the rapid
interconversion between the two tert-butyl groups in solution
on the time scale of NMR spectrometry at room temperature,
variable temperature NMR experiments were examined. The
1H NMR spectrum of platinum complex 8 at ¹60 °C indicated
splitting of the methyl peak of the tert-butyl group into two
peaks at 1.18 and 1.28 ppm with the ratio of 1:1, and the
31P{1H} and 195Pt{1H} NMR spectra at ¹60 °C showed one set
of peaks, that is, one singlet peak with a pair of satellite peaks
on the 31P{1H} NMR spectrum and one doublet peak on the
195Pt{1H} NMR spectrum. These spectra at ¹60 °C are consis-
tent with 4-coordinate structures, A and B, and 5-coordinate
structure C shown in Chart 2. Since X-ray structural analysis
often indicates the most stable structure, it is considered that
the structure in solution at ¹60 °C is structure A observed in
X-ray crystallography (Figure 4). However, the possibility of
rapid interconversion between structures A and B by pyram-
idal inversion on the sulfur atom coordinating to the platinum
center cannot be rejected. Platinum complex 8, in solution at
room temperature, is thought to undergo rapid interconversion
between the coordinating and non-coordinating sulfur atoms
in the 4-coordinate structure. Similar rapid interconversion has
been observed in platinum complex 5.17 On the other hand, in
1
the H NMR spectrum of palladium complex 7 at ¹60 °C, the
broadening of peaks was observed. It is analogized that palla-
dium complex 7 also undergoes similar rapid interconversion
between the coordinating and non-coordinating sulfur atoms in
the 4-coordinate structure in solution at room temperature. As
for nickel complex 6, rapid interconversion between 4- and 5-
t-Bu
Cl
Pt
P
Cl
Pt
P
t-Bu
t-Bu
Cl
Pt
P
t-Bu
t-Bu
t-Bu
S
S
S
S
S
S
S
S
S
Figure 4. ORTEP drawing of 8 with thermal ellipsoids
(50% probability). All H atoms and solvent molecules have
been omitted for clarity.
A
B
C
Chart 2. Possible structures of complex 8 in solution.
Table 1. Selected bond lengths (¡) and angles (°)
6
7
8
11
12
M1-S1
M1-S2
M1-S3
M1-Cl1
2.2012(6)
2.6378(6)
2.2521(6)
2.2289(6)
2.1002(6)
90.03(2)
95.82(2)
93.45(2)
87.94(2)
84.79(2)
88.19(2)
177.96(3)
107.27(2)
108.92(2)
143.07(2)
359.26a)
2.3251(7)
2.3548(7)
3.4911(7)
2.3769(7)
2.1731(7)
96.28(3)
2.287(3)
2.297(3)
3.862(3)
2.360(3)
2.197(3)
91.01(11)
90.98(11)
2.3089(7)
2.3816(7)
3.1214(7)
2.3753(6)
2.1705(6)
91.76(2)
2.2895(11)
2.2919(11)
3.797(1)
2.3740(12)
2.1888(11)
93.01(4)
M1-P1
Cl1-M1-S1
Cl1-M1-S2
Cl1-Ni1-S3
P1-M1-S1
P1-M1-S2
P1-Ni1-S3
P1-M1-Cl1
S1-M1-S2
S2-Ni1-S3
S3-Ni1-S1
Sum of bond angles
95.85(3)
99.22(2)
90.82(4)
81.15(3)
87.98(3)
88.68(11)
88.81(11)
82.18(3)
87.99(2)
88.69(4)
87.69(4)
174.41(3)
160.46(3)
178.58(12)
158.72(12)
171.18(2)
164.51(2)
178.25(4)
162.08(4)
361.26b)
359.48b)
361.15b)
360.21b)
a) Sum of bond angles among S1-Ni1-S2, S2-Ni1-S3, and S3-Ni1-S1. b) Sum of bond angles around the metal.
924 | Bull. Chem. Soc. Jpn. 2016, 89, 922–930 | doi:10.1246/bcsj.20160089
© 2016 The Chemical Society of Japan

(A)
(B)
Figure 5. The 31P{1H} (A) and 1H (B) NMR spectra of the reaction mixture in the reaction of 1b with [PdCl2(PhCN)2] in CDCl3. (a)
is a new peak, (b) denotes 1b, (c) denotes 7, (d) denotes t-BuCl, and (e) denotes isobutene.
t-Bu
t-Bu
t-Bu
Cl
Pd
P
S
S
[PdCl2(PhCN)2]
t-Bu
S
S
t-Bu
P
S
S
S
[PdCl(L)]Cl (L = 1b)
S
P
S
Pd Pd
S
P
S
3b
CDCl3
100 °C, 4 h
t-Bu
S
t-Bu
1b
7
t-Bu
Cl
9: quant
t-Bu
– t-BuCl
S
S
S
Pd
P
t-Bu
+
t-BuCl
93%
+
H2C=CMe2
trace
×2
+ t-Bu+ + Cl–
t-BuCl or H2C=CMe2 + HCl
S
S
S
Pd
P
7
10
Scheme 3. Plausible mechanism for the formation of 7.
Scheme 4. Thermal reaction of palladium complex 7.
coordinate structures or rapid pyramidal inversion on the sulfur
atoms in the 5-coordinate structure is suggested in solution at
room temperature.
described above, therefore, these results are interesting. In
addition, this mechanism is consistent with the stability of the
isopropyl-substituted group 10 metal complexes 2-5.17 Since
tert-butyl cation is more stable than isopropyl cation, the tert-
butyl derivatives undergo easy elimination of tert-butyl cation
to afford complexes 6-8.
In order to investigate the reaction mechanism, the reaction of
ligand 1b with [PdCl2(PhCN)2] in CDCl3 in an NMR tube was
1
monitored by H and 31P{1H} NMR spectrometry. After stand-
ing of the reaction mixture at room temperature for 10 min,
the 31P{1H} NMR spectrum showed a large peak at 105.9 ppm
together with small peaks at 73.7 (for 7) and ¹15.7 (for 1b)
ppm. In the 1H NMR spectrum, a large peak at 1.26 ppm was ob-
served along with small peaks at 1.40 (for 1b), 1.50 (for 7), 1.61
Thermolysis of Palladium Complex 7. It is expected that
group 10 metal complexes 6-8 bearing two tert-butylthio
groups and one chlorido ligand can undergo the further elimi-
nation of tert-butyl chloride by thermal reaction to afford the
corresponding complexes coordinated by one phosphine part
and two thiolato parts. We examined thermal reaction of palla-
dium complex 7.
4
(for t-BuCl), and 1.72 (t, JHH = 1.2 Hz, for isobutene24) ppm
(Figure 5). Further reaction at room temperature for 3 days
resulted in the disappearance of these large peaks at ¤P 105.9
ppm and ¤H 1.26 ppm, which is assigned to [PdCl(L)]Cl (L =
1b) (3b), and almost quantitative formation of 7 (¤P 73.7 ppm,
When a CDCl3 solution of 7 was heated at 100 °C for 4 h in a
sealed tube, dipalladium complex 9 and t-BuCl, which is con-
1
firmed by H and 13C NMR spectra [¤H 1.62 ppm; ¤C 34.5 (q),
¤
1.51 ppm) was observed together with the formation of t-
67.1 (s) ppm], were quantitatively formed together with a trace
amount of isobutene (Scheme 4). The structure of complex 9
was determined by 1H, 13C, and 31P NMR spectra, UV-vis spec-
trum, elemental analysis and X-ray crystallographic analysis.
The X-ray analysis showed that the complex 9 has nearly
C2 symmetry and the two palladium atoms are bridged by
two thiolato ligands to give the Pd2S2 four-membered ring
(Figure 6). Each palladium atom is further coordinated by one
phosphine and one thiolato ligands. The sums of bond angles
around the two palladium atoms are near 360° (358.7° for Pd1
and 358.9° for Pd2), therefore, the two palladium atoms have
distorted square-planar structures. The angle between the two
planes (the plane including Pd1, P1, S1, S2, and S4 and the
plane including Pd2, P2, S1, S4, and S5) is 65.8° and the Pd2S2
four-membered ring has a bent structure. The two C6H4S(t-Bu)
groups on the phosphorus atoms are situated in the open side of
H
BuCl and isobutene with a molar ratio of 7:t-BuCl:isobutene =
5:4:1.
Thus, it is considered that the reaction of 1b with [PdCl2-
(PhCN)2] initially affords complex 3b, and then 3b undergoes
the cleavage of the C(t-Bu)-S bond activated by the coordi-
nation of the sulfur atoms to the acidic divalent palladium
center and the resulting tert-butyl cation affords t-BuCl or
isobutene via addition of chloride anion or elimination of H+,
respectively (Scheme 3). The formation of nickel complex 6
and platinum complex 8 can be explained by a similar mecha-
nism. Also in the C-S bond cleavage catalyzed by Lewis acids
such as H+, Ag+, Hg2+, Cu2+, etc., similar types of mechanism
have been postulated.5 Cleavage of C(sp3)-S bond activated by
nickel(II)6,7 and palladium(II)8,9 complexes is relatively rare,
and such cleavage catalyzed by platinum(II)9 is very rare as
Bull. Chem. Soc. Jpn. 2016, 89, 922–930 | doi:10.1246/bcsj.20160089
© 2016 The Chemical Society of Japan | 925

Cl
Pd
P
i-Pr
i-Pr
i-Pr
i-Pr
Cl
Pd
P
i-Pr
i-Pr
i-Pr
i-Pr
S
S
S
S
S
S
Cl–
S
CDCl3
60 °C, 7 h
3a
11: quant
Cl
Cl
S
S
Pt Cl
S
Pt
P
i-Pr
S
P
CDCl3
60 °C, 6 h
S
i-Pr
5
12: quant
Scheme 5. Thermal reaction of isopropyl derivatives 3a
and 5.
When thermal reaction of palladium complex 3a in CDCl3
was monitored by 1H NMR spectroscopy, heating of 3a at
60 °C for 7 h resulted in quantitative formation of complex 11
along with the formation of isopropyl chloride [¤H 1.52 (d,
Figure 6. ORTEP drawing of 9 with thermal ellipsoids
(50% probability). All H atoms and a solvent molecule
have been omitted for clarity. Selected bond lengths (¡)
and angles (deg): Pd1-Pd2, 3.0848(8); Pd1-P1, 2.218(2);
Pd1-S1, 2.369(2); Pd1-S2, 2.296(2); Pd1-S4, 2.420(2);
Pd2-P2, 2.195(2); Pd2-S4, 2.368(2); Pd2-S5, 2.313(2);
Pd2-S1, 2.414(2); P1-Pd1-S2, 87.60(7); P1-Pd1-S1,
84.36(7); S2-Pd1-S4, 98.04(7); S1-Pd1-S4, 88.69(7);
P2-Pd2-S5, 86.90(8); S5-Pd2-S1, 99.27(8); S4-Pd2-S1,
88.85(7); P2-Pd2-S4, 83.84(8).
3
3JHH = 7 Hz, 6H), 4.20 (d, JHH = 7 Hz, 1H) ppm; ¤C 27.2 (q),
53.9 (d) ppm] (Scheme 5). Thermal reaction of platinum com-
1
plex 5 in CDCl3 at 60 °C for 6 h monitored by H NMR spec-
troscopy also afforded platinum complex 12 together with iso-
propyl chloride. These reactions support the above-mentioned
mechanism for the formation of complexes 6-8 via [MCl(L)]Cl
(M = Ni, Pd, Pt; L = 1b). The easier elimination of tert-butyl
cation from 6-8 than that of isopropyl cation from 3a and 5
is probably due to the stability of tert-butyl cation compared
with isopropyl cation as described in the former section. These
cleavage reactions of the S-C (i-Pr) bond are interesting,
because S-C (i-Pr) bond cleavage using transition-metal com-
pounds is very rare despite the existence of the cleavage reac-
tions using alkaline metals,25 tin hydrides,26,27 or Lewis acids
such as AlCl3 and TiCl4.28
The structures of complexes 11 and 12 were determined by
1H, 13C, and 31P NMR spectra, elemental analysis, and X-ray
crystallography. The NMR spectra and X-ray crystallography
indicated the similar tendency to those of tert-butyl derivatives,
7 and 8 (Table 1 and Figures 7 and 8).
On the other hand, thermolysis of chloridonickel and
chloridopalladium tetrafluoroborates, 2 and 4, at 60 °C resulted
in no reaction. These results may be explained by the instability
of the expected products, cationic complexes having a vacant
coordination site, [M{P(2-SC6H4)(2-t-BuSC6H4)2}]BF4 (M =
Ni, Pd), as well as the case of the elimination of tert-butyl
group from 7.
the Pd2S2 ring with cis configuration in order to avoid steric
congestion. In the reflection of trans influence, the Pd-(¯2-S)
bonds (Pd1-S4, 2.420(2) and Pd2-S1, 2.414(2) ¡) situated in
the trans position of the phosphine ligands are longer than
the other Pd-S bonds. The bridged Pd-(¯2-S) bonds (Pd1-S1,
2.369(2) and Pd2-S4, 2.368(2) ¡) are slightly longer than the
Pd-(¯1-S) bonds (Pd1-S2, 2.296(2) and Pd2-S5, 2.313(2) ¡).
1
The H and 13C NMR spectra indicated that the two tert-butyl
groups are equivalent, and the 31P NMR spectrum showed the
1
only one peak. In addition, no change was observed in the H
and 31P NMR spectra of 9 at ¹60 °C. These results strongly
suggest that the structure in solution is similar to that in the
crystalline state. This nonfluxional structure of 9 may be
explained by the stronger bonds between palladium and thiolato
ligands compared with coordination of thioether ligands to the
palladium center.
The formation mechanism of complex 9 can be explained
by the elimination of tert-butyl chloride from chloridopalla-
dium complex 7 and the subsequent dimerization of the result-
ing unsaturated three-coordinate palladium(II) complex 10
(Scheme 4). Instability of intermediate 10 may rationalize the
elimination of tert-butyl chloride from 7 at higher temperature
compared with the temperature in the formation of 7 along with
tert-butyl chloride.
Conclusion
In summary, we synthesized a new PS3-type tripodal tetra-
dentate ligand 1b bearing tert-butylthio groups. Reaction of 1b
with group 10 metal complexes resulted in the elimination of
tert-butyl chloride to afford the corresponding complexes, 6-8.
In these reactions, it is considered that the corresponding group
10 metal complexes, [MCl(L)]Cl (M = Ni, Pd, Pt; L = 1b), are
initially formed and the C-S bond activated by the coordina-
tion of the sulfur atoms to the metal center is subsequently
cleaved along with the formation of tert-butyl cation. Further
elimination of tert-butyl chloride from 7 afforded dipalladium
complex 9. In addition, isopropyl derivatives, 11 and 12, were
Thermolysis of Group 10 Metal Complexes with Isopro-
pyl-Substituted Ligand, 3a and 5.
It is considered that
complexes 6-8 are formed via the elimination of tert-butyl
cation from the group 10 metal complexes bearing ligand 1b,
[MCl(L)]Cl (M = Ni, Pd, Pt; L = 1b) at 25 or 50 °C. This
consideration suggests the possibility of the elimination of
isopropyl chloride from the isopropyl derivatives 2-5.
926 | Bull. Chem. Soc. Jpn. 2016, 89, 922–930 | doi:10.1246/bcsj.20160089
© 2016 The Chemical Society of Japan

performed with Merck Silica Gel 60 (70-230 mesh ASTM).
1
The H NMR (600, 500, or 400 MHz), 13C NMR (150 or 126
MHz), 31P NMR (243 or 202 MHz), and 195Pt NMR (129 MHz)
spectra were measured in CDCl3 with a JEOL JNM-ECA600,
JNM-λ500, or JNM-ECS400 spectrometer using SiMe4 (0 ppm)
1
as internal standards for H NMR spectroscopy, CDCl3 (77.0
ppm) as those for 13C NMR spectroscopy, H3PO4 (85%) in D2O
(0 ppm) as an external standard for 31P NMR spectroscopy, and
Na2PtCl6 in D2O (0 ppm) as an external standard for 195Pt NMR
spectroscopy. The UV-vis spectra were recorded on a JASCO
V-550 UV-vis spectrometer. All melting points were deter-
mined on a Yanaco micro melting point apparatus MP-J3 and
are uncorrected. Elemental analyses were performed by the
Center for Material Research by Instrumental Analysis (CIA),
Gunma University.
Preparation of Tris(2-tert-butylthiophenyl)phosphine
(1b). To a mixture of tert-butyl phenyl sulfide19 (3.00 g, 18.0
mmol), TMEDA (5.40 mL, 36.0 mmol), and hexane (15 mL)
was added a hexane solution of butyllithium (1.65 M, 13.1
mL, 21.6 mmol) at 25 °C. After heating at 60 °C for 1 h, PCl3
(0.58 ml, 6.60 mmol) was added to the mixture at ¹40 °C. The
reaction mixture was stirred at this temperature for 3 h, then
gradually warmed to 25 °C over 12 h. After addition of a
saturated aqueous solution of NH4Cl, the mixture was extracted
with hexane. The organic layer was dried over anhydrous
MgSO4, and the solvents were removed under reduced pres-
sure. The residue was separated by WCC (SiO2, hexane:chlo-
roform = 1:1) to afford pure tris(2-tert-butylthiophenyl)phos-
phine (1b) (1.35 g, 2.56 mmol, 43%). 1b: colorless crystals, mp.
Figure 7. ORTEP drawing of 11 with thermal ellipsoids
(50% probability). All H atoms have been omitted for
clarity.
1
204.0-206.0 °C; H NMR (500 MHz, CDCl3): ¤ 1.41 (s, 27H),
6.47 (dd, 3JHH = 7.5 Hz, 4JHH = 1.2 Hz, 3H), 7.15 (ddd, 3JHH
=
7.5, 7.5 Hz, 4JHH = 1.2 Hz, 3H), 7.27 (ddd, 3JHH = 7.5, 7.5
4
Hz, 4JHH = 1.2 Hz, 3H), 7.62 (ddd, 3JHH = 7.5 Hz, JHH
=
3
1.5Hz, JHP = 4.2 Hz, 3H); 13C{1H} NMR (126 MHz, CDCl3):
¤ 31.2 (CH3), 48.4 (C), 127.9 (CH), 130.0 (CH), 133.9 (CH),
1
2
137.3 (d, JCP = 31 Hz), 138.3 (CH), 147.3 (d, JCP = 14 Hz);
31P{1H} NMR (202 MHz, CDCl3): ¤ ¹16.6 (s). Anal. Calcd
for C30H39PS3¢0.5H2O: C, 67.25; H, 7.52%. Found: C, 67.27;
H, 7.36%.
Figure 8. ORTEP drawing of 12 with thermal ellipsoids
(50% probability). All H atoms and minor parts of the
disordered isopropyl group have been omitted for clarity.
Reaction of 1b with NiCl2¢6H2O. A mixture of 1b (100
mg, 0.190 mmol), NiCl2¢6H2O (50 mg, 0.210 mmol), and
butanol (2.0 mL) was heated at 50 °C for 24 h. The reaction mix-
ture was allowed to stand at 25 °C to give [NiCl{P(2-SC6H4)-
(2-t-BuSC6H4)2}] (6) (95 mg, 0.168 mmol, 89%) as gray pre-
also formed by thermal reactions of 3a and 5, respectively. The
easier elimination of tert-butyl chloride than that of isopropyl
chloride is probably due to the stability of tert-butyl cation
compared with isopropyl cation. The C(sp3)-S bond cleavage
activated by group 10 metal is rare and, especially, the cleavage
activated by platinum(II) and the cleavage of the isopropyl-
sulfur bond activated by transition metals are very rare. These
C(sp3)-S bond cleavage reactions are very interesting.
1
cipitates. 6: gray crystals, mp 264 °C (decomp); H NMR (500
MHz, CDCl3): ¤ 1.50 (s, 18H), 6.98 (br s, 1H), 7.09-7.69 (m,
9H), 7.76 (br s, 2H). 13C{1H} NMR (126 MHz, CDCl3): ¤ 30.7
(CH3), 55.5 (C), 121.8 (d, JCP = 6 Hz, CH), 127.7 (CH), 128.6
(d, 1JCP = 45 Hz), 129.5 (CH), 131.8 (d, JCP = 9 Hz, CH), 132.3
(CH), 133.7 (CH), 135.3 (d, JCP = 9 Hz, CH), 138.1 (CH),
138.5 (d, 1JCP = 60 Hz), 139.2 (d, 2JCP = 19 Hz), 159.0 (d,
2JCP = 28 Hz). 31P{1H} NMR (202 MHz, CDCl3): ¤ 69.1 (s).
UV-vis (chloroform) -max 272 (¾ 10000), 326 (¾ 5100), 508 (¾
940), 649 (¾ 330) nm. Anal. Calcd for C26H30ClNiPS3¢0.5H2O:
C, 54.51, H, 5.45%. Found: C, 54.63; H, 5.35%.
It is expected that these results obtained in this paper can
contribute to the chemistry of organosulfur compounds and
group 10 metal complexes with thioether ligands.
Experimental Section
General Procedures. All reactions were carried out under
an argon atmosphere unless otherwise noted. Tetrahydrofuran
was purified by distillation from sodium diphenylketyl before
use. Other solvents used in reactions were purified by the
reported methods.29 Wet column chromatography (WCC) was
Reaction of 1b with [PdCl2(PhCN)2]. A mixture of 1b
(140 mg, 0.266 mmol), [PdCl2(PhCN)2] (100 mg, 0.261 mmol),
and chloroform (4.0 mL) was stirred at 25 °C for 72 h. After
filtration of the reaction mixture, the filtrate was concentrated.
Bull. Chem. Soc. Jpn. 2016, 89, 922–930 | doi:10.1246/bcsj.20160089
© 2016 The Chemical Society of Japan | 927

3
The residue was reprecipitated by the addition of hexane to a
dichloromethane solution of the mixture to afford [PdCl{P(2-
SC6H4)(2-t-BuSC6H4)2}] (7) (150 mg, 0.245 mmol, 94%). 7: red
3JHH = 8, 8 Hz, 2H), 7.53 (dd, JHH = 8, 8 Hz, 2H), 7.58 (d,
3JHH = 8 Hz, 2H), 7.63 (dd, 3JHH = 8, 8 Hz, 2H). 31P{1H} NMR
(202 MHz, CDCl3): ¤ 63.2 (s). UV-vis (chloroform) -max 294
(¾ 35000), 323 (¾ 21000), 366 (¾ 16000), 541 (¾ 640) nm.
Anal. Calcd. for C44H42P2Pd2S6¢CHCl3: C, 46.70; H, 3.74%.
Found: C, 46.37; H, 3.91%.
1
crystals, mp 151 °C (decomp); H NMR (500 MHz, CDCl3): ¤
1.51 (s, 18H), 7.02 (ddd, 3JHH = 8, 8 Hz, JHP = 3 Hz, 1H), 7.23-
7.31 (m, 4H), 7.39-7.44 (m, 3H), 7.54 (dd, 3JHH = 8, 8 Hz, 2H),
3
7.70 (dd, JHH = 8 Hz, JHP = 4 Hz, 2H). 13C{1H} NMR (126
Thermolysis of [PdCl{P(2-i-PrSC6H4)3}]Cl (3a). In a 5 º
NMR tube was placed a CDCl3 solution (0.5 mL) of 3a (30 mg,
0.045 mmol). After three freeze-pump-thaw cycles, the tube
was frozen, evacuated, and sealed. The solution was heated at
60 °C for 7 h, during which time the reaction was followed by
1H NMR spectroscopy. The sealed tube was opened, and the
reaction mixture was concentrated. The residue was reprecipi-
tated by the addition of hexane to a chloroform solution of
the mixture to afford [Pd{P(2-SC6H4)(2-i-PrSC6H4)2}] (11) in
a quantitative yield. 11: red crystals, mp 227 °C (decomp);
1H NMR (400 MHz, CDCl3): ¤ 1.33 (d, 3JHH = 7 Hz, 6H), 1.48
MHz, CDCl3): ¤ 31.4 (CH3), 55.0 (C), 122.4 (d, JCP = 9 Hz,
CH), 128.4 (d, 1JCP = 65 Hz), 129.3 (d, JCP = 20 Hz, CH),
129.4 (d, JCP = 3 Hz, CH), 130.2 (CH), 132.1 (CH), 132.9
(CH), 133.1 (d, JCP = 5 Hz, CH), 136.3 (d, JCP = 11 Hz, CH),
138.5 (d, 1JCP = 63 Hz), 139.0 (d, 2JCP = 17 Hz), 159.1 (d,
2JCP = 25 Hz). 31P{1H} NMR (202 MHz, CDCl3): ¤ 72.8 (s).
UV-vis (chloroform) -max 336.5 (¾ 1800), 384 (¾ 570), 451 (¾
110) nm. Anal. Calcd. for C26H30ClPPdS3¢CHCl3: C, 44.37; H,
4.27%. Found: C, 44.27; H, 4.14%.
Reaction of 1b with [PtCl2(cod)].
A mixture of 1b
3
3
(140 mg, 0.266 mmol), [PtCl2(cod)] (100 mg, 0.267 mmol), and
dichloromethane (2.0 mL) was stirred at 25 °C for 48 h. After
filtration of the reaction mixture, the filtrate was concentrated.
The residue was reprecipitated by the addition of hexane to a
chloroform solution of the mixture to afford [PtCl{P(2-SC6H4)-
(2-t-BuSC6H4)2}] (8) (180 mg, 0.257 mmol, 97%). 8: orange
(d, JHH = 7 Hz, 6H), 3.77 (sep, JHH = 7 Hz, 2H), 7.01 (ddd,
3JHH = 7, 7 Hz, JHP = 3 Hz, 1H), 7.24-7.42 (m, 7H), 7.55 (ddd,
3JHH = 8 Hz, JHH = 2 Hz, JHP = 2 Hz, 2H), 7.65 (dd, JHH
=
4
3
8 Hz, JHP = 4 Hz, 2H). 13C{1H} NMR (126 MHz, CDCl3): ¤
22.3 (CH3), 23.5 (CH3), 45.7 (CH), 122.4 (d, JCP = 9 Hz, CH),
1
128.5 (d, JCP = 66 Hz), 129.1 (d, JCP = 8 Hz, CH), 129.5 (d,
CP = 20 Hz, CH), 130.3 (CH), 132.7 (d, JCP = 2 Hz, CH),
132.9 (d, JCP = 5 Hz, CH), 133.0 (CH), 134.7 (d, JCP = 10 Hz,
1
crystals, mp 166 °C (decomp); H NMR (500 MHz, CDCl3): ¤
J
1.31 (s, 18H), 6.90 (ddd, 3JHH = 7, 7 Hz, JHP = 3 Hz, 1H), 7.20
3
3
1
2
(dd, JHH = 7, 7 Hz, 1H), 7.25-7.54 (m, 7H), 7.55 (dd, JHH
=
CH), 136.5 (d, JCP = 61 Hz), 139.8 (d, JCP = 18 Hz), 159.0
(d, 2JCP = 25 Hz). 31P{1H} NMR (202 MHz, CDCl3): ¤ 72.0
(s). Anal. Calcd. for C24H26ClPPdS3: C, 49.40; H, 4.49%.
Found: C, 49.24; H, 4.30%.
Thermolysis of [PtCl2{P(2-i-PrSC6H4)3}] (5). In a 5 º
NMR tube was placed a solution of 5 (13 mg, 0.017 mmol) in
CDCl3 (0.5 mL). The solution was heated at 60 °C for 6 h, dur-
ing which time the reaction was followed by 1H NMR spectros-
7 Hz, JHP = 3 Hz, 1H), 7.67 (dd, 3JHH = 8 Hz, JHP = 4 Hz, 2H).
13C{1H} NMR (126 MHz, CDCl3): ¤ 31.1 (CH3), 54.2 (C),
122.2 (d, JCP = 9 Hz, CH), 127.3 (d, JCP = 76 Hz), 129.0 (d,
CP = 4 Hz, CH), 129.3 (d, JCP = 17 Hz, CH), 130.3 (d, 1JCP
1
J
=
67 Hz), 131.9 (CH), 132.17 (d, JCP = 4 Hz, CH), 132.22 (d,
CP = 4 Hz, CH), 133.5 (d, JCP = 5 Hz, CH), 136.4 (d, JCP
J
=
9 Hz, CH), 141.4 (d, JCP = 16 Hz), 160.6 (d, JCP = 26 Hz).
1
1
31P{1H} NMR (202 MHz, CDCl3): ¤ 47.9 (s, JPPt = 3679 Hz).
copy. The H NMR spectrum of the reaction mixture showed
1
195Pt{1H} NMR (129 MHz, CDCl3): ¤ ¹4418 (s, JPPt = 3659
quantitative formation of [Pt{P(2-SC6H4)(2-i-PrSC6H4)2}] (12).
For isolation of 12, see: A solution of 5 (100 mg, 0.133
mmol) in chloroform (4 mL) was heated at 60 °C for 48 h. After
filtration of the reaction mixture, the filtrate was concentrated.
The residue was reprecipitated by the addition of hexane to a
chloroform solution of the mixture to give [Pt{P(2-SC6H4)(2-i-
PrSC6H4)2}] (12) (73 mg, 0.109 mmol, 82%). 12: orange crys-
tals, mp 213 °C (decomp); 1H NMR (600 MHz, CDCl3, 60 °C):
¤ 1.22 (br d, 3JHH = 6.6 Hz, 6H), 1.26 (br d, 3JHH = 6.6 Hz, 6H),
3.53 (br s, 2H), 6.90-6.95 (m, 1H), 7.14-7.19 (m, 1H), 7.31-
7.51 (m, 8H), 7.56-7.60 (m, 2H). 13C{1H} NMR (150 MHz,
CDCl3, 60 °C): ¤ 22.1 (s, CH3), 22.9 (s, CH3), 44.8 (br s, CH),
Hz). UV-vis (chloroform) -max 291.5 (¾ 13500), 343.5 (¾
3300), 394.5 (¾ 910) nm. Anal. Calcd. for C26H30ClPPtS3: C,
44.60; H, 4.32%. Found: C, 44.50; H, 4.79%.
Thermolysis of 7. In a 5 º NMR tube was placed a CDCl3
solution (0.6 mL) of 7 (30 mg, 0.049 mmol). After three freeze-
pump-thaw cycles, the tube was frozen, evacuated, and sealed.
The solution was heated at 100 °C for 4 h, during which time
the reaction was followed by 1H NMR spectroscopy. The sealed
tube was opened, and the reaction mixture was concentrated.
The residue was reprecipitated by the addition of hexane to a
chloroform solution of the mixture to afford [Pd{P(2-SC6H4)2-
(2-t-BuSC6H4)}]2 (9) in a quantitative yield.
1
122.4 (d, JCP = 8.6 Hz, CH), 127.5 (d, JCP = 74.6 Hz), 129.1
In order to obtain the yield of t-BuCl: In a pressure-resistant
NMR tube was placed a CDCl3 solution (0.6 mL) of 7 (29.3
mg, 0.048 mmol) and mesitylene (10 ¯L, 0.072 mmol as a
standard). The solution was gradually warmed to 100 °C and
heated at 100 °C for 4 h. The 1H NMR spectrum of the reaction
mixture indicated the formation of 9, t-BuCl (integral ratio of
mesitylene:t-BuCl = 1.0:0.62, 0.045 mmol, 93%) and a trace
amount of isobutene. 9: red crystals, mp 238 °C (decomp);
1H NMR (500 MHz, CDCl3): ¤ 1.47 (s, 18H), 6.85-6.97 (m,
(br s, CH), 129.7 (d, JCP = 11.0 Hz, CH), 131.3 (s, CH), 132.6
(s, CH), 132.7 (s, CH), 133.0 (br s, CH), 134.7 (br d, JCP = 6.0
1
2
Hz, CH), 135.5 (d, JCP = 67.5 Hz), 141.9 (br d, JCP = 15.9
2
Hz), 160.6 (br d, JCP = 21.5 Hz). 31P{1H} NMR (243 MHz,
CDCl3, 60 °C): ¤ 50.0 (s, 1JPPt = 3566 Hz). 31P{1H} NMR (243
MHz, CDCl3, 20 °C): ¤ 49.9 (s, 1JPPt = 3583 Hz). Anal. Calcd.
for C24H26ClPPtS3: C, 42.88; H, 3.90%. Found: C, 42.58; H,
4.18%.
X-Ray Crystallography of 1b¢H2O, 6, 7¢CH2Cl2,
3
3
4H), 6.99 (dd, JHH = 8, 8 Hz, 2H), 7.13 (dd, JHH = 8, 8 Hz,
8¢0.5CHCl3, 9¢CHCl3, 11, and 12.
Single crystals of
3
2H), 7.17 (dd, JHH = 8, 8 Hz, 2H), 7.26-7.23 (m, 2H), 7.36
1b¢H2O, 6, 7¢CH2Cl2, 8¢0.5CHCl3, 9¢CHCl3, 11, and 12 suita-
ble for X-ray structural analysis were obtained by slow recrys-
3
3
(d, JHH = 8 Hz, 2H), 7.41 (dd, JHH = 8, 8 Hz, 2H), 7.47 (dd,
928 | Bull. Chem. Soc. Jpn. 2016, 89, 922–930 | doi:10.1246/bcsj.20160089
© 2016 The Chemical Society of Japan

Table 2. Crystal data and refinement details for 1b¢H2O, 6,
and 7¢CH2Cl2
Table 3. Crystal data and refinement details for 8¢0.5CHCl3
and 9
1b¢0.5H2O
6
7¢CH2Cl2
8¢0.5CHCl3
9¢CHCl3
Empirical formula C30H39PS3¢
[C26H30-
[C26H30-
Empirical formula
[C26H30ClPPtS3]¢ [C44H42P2Pd2S6]¢
0.5H2O
ClNiPS3]
ClPPdS3]¢
CH2Cl2
696.43
123(2)
orthorhombic
P212121
0.5CHCl3
759.87
123(2)
monoclinic
P21/n (No. 14)
10.2504(13)
18.715(2)
15.3198(18)
90
96.6494(14)
90
2919.1(6)
4
1.729
5.320
CHCl3
1157.24
123(2)
monoclinic
P21/c (No. 14)
16.7717(11)
14.4580(9)
18.7029(13)
90
97.2771(9)
90
4498.6(5)
4
1.709
1.361
Formula weight
Temperature/K
Crystal system
Space group
a/¡
b/¡
c/¡
¡/deg
¢/deg
Formula weight
Temperature/K
Crystal system
Space group
535.81
123(2)
trigonal
P-3
563.81
123(2)
monoclinic
P21/c
(No. 14)
(No. 147)
(No. 19)
a/¡
b/¡
c/¡
¡/deg
¢/deg
£/deg
V/¡3
14.8175(17) 15.3031(10) 9.9862(5)
14.8175(17) 10.8984(7) 16.2536(8)
15.5377(10) 18.7218(9)
90 90
100.0947(7) 90
8.3455(11)
90
90
£/deg
V/¡3
120
1586.8(3)
2
90
90
3038.8(3)
4
1.522
1.149
Z
D
¹3
2551.3(3)
4
1.468
1.187
calc/Mg m
¹1
Z
D
Absorp coeff/mm
Crystal size/mm
¹3
calc/Mg m
1.136
0.30 © 0.20 ©
0.05
0.20 © 0.20 ©
0.20
¹1
Absorp coeff/mm 0.303
Crystal size/mm
0.50 © 0.10 © 0.30 © 0.30 © 0.30 © 0.15 ©
0.10 0.10 0.15
2.75 to 28.27° 2.66 to 25.50° 2.63 to 25.50°
ª range
2.52 to 27.00°
22516
6359
0.0472
99.9%
2.76 to 25.50°
30213
7889
0.0388
93.9%
No. of reflns measd
No. of indep reflns
Rint
ª range
No. of reflns measd 4739
No. of indep reflns 2427
17084
4736
20842
5509
Completeness
Rint
0.0413
92.4%
0.0202
99.6%
0.0216
97.6%
Data/Restraints/Parameters 6359/0/307
7889/0/524
1.264
Completeness
Data/Restraints/
Parameters
Goodness-of-fit
on F2
Goodness-of-fit on F2
1.225
Final R indices [I > 2·(I)]a)
R1 = 0.0919
wR2 = 0.1540
wR2 = 0.1949
R1 = 0.0933
wR2 = 0.1757
wR2 = 0.1957
0.0036(3)
R1 = 0.0822
wR2 = 0.0738
wR2 = 0.1761
R1 = 0.0825
wR2 = 0.0754
wR2 = 0.1763
0.0021(3)
1.519 and
¹1.132
2427/0/110 4736/0/289 5509/4/326
1.003 1.266 1.274
R indices (all data)a)
Final R indices
[I > 2·(I)]a)
R1 = 0.0698 R1 = 0.0315 R1 = 0.0192
wR2 = 0.1540 wR2 = 0.0738 wR2 = 0.1393
wR2 = 0.1960 wR2 = 0.0629 wR2 = 0.0503
R1 = 0.1328 R1 = 0.0317 R1 = 0.0192
wR2 = 0.1757 wR2 = 0.0754 wR2 = 0.1414
wR2 = 0.2261 wR2 = 0.0630 wR2 = 0.0503
¹0.003(18)
Extinction coefficient
Largest diff. peak and
R indices (all data)a)
2.556 and
¹2.271
¹3
hole/e ¡
2
2 2
a)
R1 = -««Fo« ¹ «Fc««/-«Fo«,
wR2 = [(-w(Fo ¹ Fc ) /
Absolute structure
parameter
2 2 1/2
-w(Fo ) ]
.
Largest diff. peak
and hole/e ¡
0.642 and
¹0.498
0.300 and
¹0.261
0.422 and
¹0.404
¹3
2
2 2
a)
R1 = -««Fo« ¹ «Fc««/-«Fo«,
wR2 = [(-w(Fo ¹ Fc ) /
2 2 1/2
-w(Fo ) ]
.
sition numbers CCDC-1020229, CCDC-1020230, CCDC-
1020231, CCDC-1020232, CCDC-1020233, CCDC-1020234,
and CCDC-1020235 for compounds 1b¢H2O, 6, 7¢CH2Cl2,
8¢0.5CHCl3, 9¢CHCl3, 11, and 12, respectively. Copies of the
data can be obtained free of charge via http://www.ccdc.cam.ac.
uk/conts/retrieving.html (or from the Cambridge Crystallo-
graphic Data Centre, 12, Union Road, Cambridge, CB2 1EZ,
U.K.; Fax: +44 1223 336033; e-mail: deposit@ccdc.cam.
ac.uk).
tallization from hexane/CHCl3. The crystals were mounted on
glass fibers. The intensity data were collected on a Rigaku
R-AXIS IV++ diffractometer with graphite monochromated
Mo K¡ radiation (- = 0.71070 ¡). The structures were solved
by direct methods (SHELXS-9730 or SIR-9731), and refined by
full-matrix least-squares procedures on F2 for all reflections
(SHELXL-9730). All the non-hydrogen atoms were refined
anisotropically. All hydrogens were placed using AFIX instruc-
tions. The crystal data and refinement details are shown in
Tables 2, 3, and 4. Crystallographic data have been depos-
ited with Cambridge Crystallographic Data Centre: Depo-
This work was partially supported by Grant-in-Aid for
Scientific Research (C) from Japan Society for the Promo-
tion of Science (JSPS). We are grateful to Professor Soichiro
Kyushin, Graduate School of Technology, Gunma Univer-
sity for his kind permission to use his single-crystal X-ray
diffractometer.
Bull. Chem. Soc. Jpn. 2016, 89, 922–930 | doi:10.1246/bcsj.20160089
© 2016 The Chemical Society of Japan | 929

Table 4. Crystal data and refinement details for 11 and 12
11 12
[C24H26ClPPdS3] [C24H26ClPPtS3]
9
L. Lindoy, S. E. Livingstone, T. N. Lockyer, Nature 1966,
211, 519.
10 Cleavage of C(sp3)-S bond by platinum(0) complex has
been reported: N. Nakata, N. Furukawa, T. Toda, A. Ishii, Angew.
Chem., Int. Ed. 2010, 49, 5784.
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
a/¡
583.45
672.14
123(2)
123(2)
11 A. S. Borovik, Acc. Chem. Res. 2005, 38, 54.
12 X. Hu, K. Meyer, J. Organomet. Chem. 2005, 690, 5474.
13 C. Pettinari, F. Marchetti, A. Drozdov, in Comprehensive
Coordination Chemistry II, ed. by A. B. P. Lever, T. J. Meyer,
Elsevier Pergamon, Oxford, 2004, Vol. 1, pp. 211-251. doi:10.
1016/B0-08-043748-6/01062-8.
14 G. Huttner, J. Strittmatter, S. Sandhöfner, in Comprehensive
Coordination Chemistry II, ed. by A. B. P. Lever, T. J. Meyer,
Elsevier Pergamon, Oxford, 2004, Vol. 1, pp. 297-322. doi:10.
1016/B0-08-043748-6/01082-3.
15 J.-C. Hierso, R. Amardeil, E. Bentabet, R. Broussier, B.
Gautheron, P. Meunier, P. Kalck, Coord. Chem. Rev. 2003, 236,
143.
16 R. R. Schrock, Acc. Chem. Res. 1997, 30, 9.
17 N. Takeda, Y. Tanaka, F. Sakakibara, M. Unno, Bull. Chem.
Soc. Jpn. 2010, 83, 157.
18 Group 10 metal complexes bearing analogous ligands,
tris(methylthiophenyl)phosphine, have been reported: a) G. Dyer,
D. W. Meek, Inorg. Chem. 1965, 4, 1398. b) G. Dyer, M. O.
Workman, D. W. Meek, Inorg. Chem. 1967, 6, 1404. c) L. P.
Haugen, R. Eisenberg, Inorg. Chem. 1969, 8, 1072. d) E. W. Abel,
J. C. Dormer, D. Ellis, K. G. Orrell, V. Šik, M. B. Hursthouse,
M. A. Mazid, J. Chem. Soc., Dalton Trans. 1992, 1073.
19 S. B. Harkins, J. C. Peters, J. Am. Chem. Soc. 2004, 126,
2885.
monoclinic
P21 (No. 4)
9.6288(5)
9.4346(5)
13.6426(9)
90
monoclinic
P21/n (No. 14)
8.7897(5)
18.7062(11)
15.5083(11)
90
b/¡
c/¡
¡/deg
¢/deg
£/deg
V/¡3
93.5854(8)
90
1236.92(12)
2
1.567
1.186
95.8935(10)
90
2536.4(3)
4
1.760
5.957
Z
¹3
D
calc/Mg m
¹1
Absorp coeff/mm
Crystal size/mm
0.30 © 0.20 ©
0.10
0.30 © 0.20 ©
0.10
ª range
2.63 to 27.50°
10439
5315
2.55 to 25.50°
13191
4688
No. of reflns meads
No. of indep reflns
Rint
0.0158
0.0233
Completeness
93.0%
99.1%
Data/Restraints/Parameters 5315/1/271
4688/0/299
1.367
Goodness-of-fit on F2
1.055
Final R indices [I > 2·(I)]a)
R1 = 0.0198
wR2 = 0.1540
wR2 = 0.0483
R1 = 0.0201
wR2 = 0.1757
wR2 = 0.0486
R1 = 0.0296
wR2 = 0.0738
wR2 = 0.0578
R1 = 0.0302
wR2 = 0.0754
wR2 = 0.0579
R indices (all data)a)
20 W. Bauer, P. A. A. Klusener, S. Harder, J. A. Kanters,
A. J. M. Duisenberg, L. Brandsma, P. v. R. Schleyer, Organo-
metallics 1988, 7, 552.
Absolute structure parameter ¹0.004(17)
21 A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G.
Watson, R. Taylor, J. Chem. Soc., Dalton Trans. 1989, S1.
22 A. Bondi, J. Phys. Chem. 1964, 68, 441.
Largest diff. peak and
0.389 and
0.763 and
¹0.739
¹3
hole/e ¡
¹0.532
2
2 2
23 G. A. Barclay, R. S. Nyholm, R. V. Parish, J. Chem. Soc.
1961, 4433.
24 The peak for CH2=C of isobutene was also observed at
4.65 ppm.
a)
R1 = -««Fo« ¹ «Fc««/-«Fo«,
wR2 = [(-w(Fo ¹ Fc ) /
2 2 1/2
-w(Fo ) ]
.
25 For a recent paper, see: T. Okamura, K. Kunisue, Y. Omi,
K. Onitsuka, Dalton Trans. 2013, 42, 7569.
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