Structural analysis of phenyl-germanium, -tin, and -lead dithiocarboxylates [(RCSS)xMPh4-x, M = Ge, Sn, Pb; x = 1-3]: Affinity between thiocarbonyl sulfur and Group 14 elements

Article abstract of DOI:10.1016/S0022-328X(00)00453-8

A series of RCSSGePh₃, (RCSS)₂GePh₂, (RCSS)₃SnPh, and (RCSS)₂PbPh₂ were synthesized, and the structures of some p-tolyl derivatives [RCSSMPh₃ (R = 4-CH₃C₆H₄, M = Ge: 1d, Sn: 3d, Pb: 6d) and (4-CH₃C₆H₄CSS)₂SnPh₂ (4d)] and a o-tolyl derivative [(2-CH₃C₆H₄CSS)₃SnPh: (5c)] were analyzed by X-ray. The results indicate intramolecular non-bonded interactions between the thiocarbonyl sulfur and the central Group 14 element metals. The mono dithiocarboxylates (1d, 3d, and 6d) exhibit a distorted tetrahedral structure around the central Group 14 elements. Diphenyltin bis(dithiocarboxylate) (4d) is shown to take a distorted octahedron or skewed trapezoidal bipyramid, where the two dithiocarboxylate groups are bound to the Sn atom as an anisobidentate ligand, and the tin tris(dithiocarboxylate) (5c) exhibits a seven-coordinated pentagonal bipyramid. The distance between the thiocarbonyl sulfur and the Sn atom in 4-CH₃C₆H₄CSSMPh₃ (M = Ge, Sn, Pb) is shorter than those in the corresponding germanium and lead derivatives. Based on these distances, the affinity of Group 14 elements for sulfur atoms is deduced to decrease in the order Sn > Pb ≥ Ge > Si > C.

Full text of DOI:10.1016/S0022-328X(00)00453-8

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 611 (2000) 190–199
Structural analysis of phenyl-germanium, -tin, and -lead
dithiocarboxylates [(RCSS)xMPh4−x, M=Ge, Sn, Pb; x=1–3]:
affinity between thiocarbonyl sulfur and Group 14 elements
Shinzi Kato a,*, Kazuyasu Tani a, Nobuyuki Kitaoka a, Kohzaburoh Yamada b,
Hiroyuki Mifune b
a Department of Chemistry, Faculty of Engineering, Gifu Uni6ersity, 1-1 Yanagido, Gifu 501-1193, Japan
b Fuji Photo Film Co., Ltd., Ashigara Research Laboratories, 210 Nakanuma, Minamiashigara, Kanagawa 250-0193, Japan
Received 25 January 2000; accepted 15 March 2000
Abstract
A series of RCSSGePh3, (RCSS)2GePh2, (RCSS)3SnPh, and (RCSS)2PbPh2 were synthesized, and the structures of some p-tolyl
derivatives [RCSSMPh3 (R=4-CH3C6H4, M=Ge: 1d, Sn: 3d, Pb: 6d) and (4-CH3C6H4CSS)2SnPh2 (4d)] and a o-tolyl derivative
[(2-CH3C6H4CSS)3SnPh: (5c)] were analyzed by X-ray. The results indicate intramolecular non-bonded interactions between the
thiocarbonyl sulfur and the central Group 14 element metals. The mono dithiocarboxylates (1d, 3d, and 6d) exhibit a distorted
tetrahedral structure around the central Group 14 elements. Diphenyltin bis(dithiocarboxylate) (4d) is shown to take a distorted
octahedron or skewed trapezoidal bipyramid, where the two dithiocarboxylate groups are bound to the Sn atom as an
anisobidentate ligand, and the tin tris(dithiocarboxylate) (5c) exhibits a seven-coordinated pentagonal bipyramid. The distance
between the thiocarbonyl sulfur and the Sn atom in 4-CH3C6H4CSSMPh3 (M=Ge, Sn, Pb) is shorter than those in the
corresponding germanium and lead derivatives. Based on these distances, the affinity of Group 14 elements for sulfur atoms is
deduced to decrease in the order Sn\Pb]Ge\Si\C. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Dithiocarboxylates; X-ray structural analysis; Intramolecular interaction; Affinity
1. Introduction
single crystals. We report here the first X-ray structural
analyses of a series of phenyl Group 14 element deriva-
tives of dithiocarboxylates together with the synthesis
of phenyl-germanium dithiocarboxylates, phenyltin
tris(dithiocarboxylates), and diphenyllead bis(dithiocar-
boxylates).
In contrast to Group 14 element derivatives of
dithiocarbamates, dithiocarbonates, and dithiophosphi-
nates, little is known about the corresponding dithio-
carboxylate derivatives [1]. Previously, we reported the
synthesis of triphenyl-tin [2b] and lead arenecarbod-
ithioates [2d] and diphenyltin bis(arenecarbodithioates)
[2b]. The corresponding germanium derivatives
(RCSSGePh3, (RCSS)2GePh2) have not yet been syn-
thesized. In addition, there has been no report of the
X-ray structural analysis of organo-Group 14 element
derivatives of dithiocarboxylates ((RCSS)xMR4% −x, (R,
R%=alkyl, aryl; M=Si, Ge, Sn, Pb; x=1–4)), perhaps
due to the difficulty of purification and of obtaining
2. Results and discussion
2.1. Synthesis
The stoichiometric reactions of piperidinium dithio-
carboxylates with Ph3GeCl, Ph2GeCl2, PhSnCl3, and
Ph2PbCl2 proceeded readily at room temperature and
led to the quantitative formation of the expected
triphenylgermanium dithiocarboxylates 1, diphenylger-
manium bis(dithiocarboxylates) 2, phenyltin tris(dithio-
carboxylates) 5, and diphenyllead bis(dithiocarboxy-
* Corresponding author. Fax: +81-58-2932610.
E-mail address: shinzi@apchem.gifu-u.ac.jp (S. Kato).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00453-8

S. Kato et al. / Journal of Organometallic Chemistry 611 (2000) 190–199
191
lates) 7 (Scheme 1). These dithiocarboxylate derivatives
are less crystallizable than the corresponding thiocar-
boxylate derivatives. After several attempts, we success-
fully crystallized 1, 2, 5, and 7, except for
triphenylgermanium 2-methylbezenecarbodithioate (1c)
and phenyltin tris(dithioacetate) (5a). We also at-
tempted the synthesis and isolation of phenylgerma-
nium tris(dithiocarboxylates) ((RCSS)3GePh) and
Group 14 element derivatives of tetrakis(dithiocarboxy-
lates) ((RCSS)4M, M=Ge, Sn), but failed. For exam-
ple, the reaction of SnCl4 with 4 M amounts of sodium
or piperidinium 4-methylbenzenecarbodithioate af-
forded not the desired product 8, but rather dichlorotin
bis(4-methylbenzenecarbodithioate) and bis(4-methylth-
iobenzoyl) disulfide [3].
2.2. Molecular structures
2.2.1. Mono dithiocarboxylates Group 14 elements
deri6ati6es 1, 3, and 6
Selected bond lengths and angles in 1d, 3d, and 6d
are collected in Table 1. All molecular forms are similar
to the ORTEP drawing of the Sn derivatives 3d as is
shown in Fig. 1. The crystal data are listed in Table 2.
,
The C11–S11 bond lengths (ca. 1.64 A) are close to the
sum of their double bond covalent bond radii [4], and
,
all C11ꢀS12 bond lengths (1.71(1)–1.746(3) A) are
Scheme 1.
roughly intermediate between their single and double
bond covalent bond radii [4]. All M1ꢀS12 bond lengths
are also shown in MꢀS single bonds, respectively [4]. In
addition, they are comparable to the distances obtained
in germanium-dithiocarbonates [5], tin-dithiocarba-
mates and dithiocarbonates [6,7], and lead-dithiocarba-
mates [8] and dithiophosphates [9,10]. The M1ꢀS11
distances are longer than the sum of their covalent
bond radii [4], but significantly less than the sum of van
der Waals radii of both atoms [11], thus intramolecular
interaction should be considered. On the basis of such
interaction, the S12ꢀM1ꢀC31 angles significantly devi-
ate from the ideal tetrahedral angle. However, other
angles around the central Group 14 elements are rela-
tively comparable to tetrahedral angle. Therefore,
mono dithiocarboxylate derivatives show a distorted
tetrahedron.
Table 1
Selected bond lengths (A) and angles (°) of 4-CH3C6H4CSSMPh3
,
Ge (1d)
Sn (3d)
Pb (6d)
Bond lengths
M1ꢀS11
M1ꢀS12
C11ꢀS11
C11ꢀS12
M1ꢀC21
M1ꢀC31
M1ꢀC41
3.371(l)
2.2526(8)
1.637(3)
1.746(3)
1.942(3)
1.948(3)
1.934(3)
3.207(2)
2.446(l)
1.645(5)
1.737(5)
2.137(5)
2.146(4)
2.124(5)
3.362(5)
2.535(4)
1.64(2)
1.71(l)
2.19(2)
2.19(l)
2.16(2)
Bond angles
S11ꢀM1ꢀS12
S11ꢀC11ꢀS12
M1ꢀS11ꢀC11
M1ꢀS12ꢀC11
S12ꢀM1ꢀC21
S12ꢀM1ꢀC31
S12ꢀM1ꢀC41
C21ꢀM1ꢀC31
C21ꢀM1ꢀC41
C31ꢀM1ꢀC41
59.71(3)
122.2(2)
70.03(10)
105.9(l)
115.19(9)
96.75(8)
110.75(9)
108.0(1)
104.7(2)
106.1(6)
60.92(4)
120.8(3)
76.5(2)
100.4(2)
119.9(l)
94.4(l)
109.2(l)
114.5(l)
117.3(2)
119.3(6)
57.8(l)
122(l)
75.6(6)
102.6(6)
116.2(5)
93.9(4)
107.8(4)
110.1(1)
107.9(2)
110.5(5)
2.2.2. Bis(dithiocarboxylates) Group 14 element
deri6ati6es (4)
Diphenyltin bis(4-methylbenzenecarbodithioate) (4d)
crystallized as four independent molecules. The ORTEP
drawing and selected bond lengths and angles are
shown in Fig. 2 and Table 3. The two dithiocarboxyl
groups and the tin atom exist in the same plane. The
four CꢀS bond lengths of the two dithiocarboxylate
groups are nearly same values, and are roughly midway
between their single and double bond covalent bond
,
radii [4]. The SnꢀS bond lengths (av. 2.483(7) A) are
slightly longer than the sum of their covalent bond radii
[4], which they are comparable to the distances ob-
served in dimethyltin bis(dithiocarbamates) [12]. On the
,
other hand, the other Sn–S distances (av. 3.056(7) A)
are longer than the sum of their covalent bond radii,
,
which are ca. 0.7 A shorter than the sum of their van
Fig. 1. The ORTEP drawing of 4-CH3C6H4CSSSnPh3 (3d). Hydrogen
atoms have been omitted for clarity.
,
der Waals radii [11] and ca. 0.15 A shorter than those

192
S. Kato et al. / Journal of Organometallic Chemistry 611 (2000) 190–199
Table 2
Crystal data for 1d, 3d, 4d, 5c, and 6d
Empirical formula
Formula weight
Crystal system
C
471.17
Triclinic
26H22GeS2 (1d)
C26H22S2Sn (3d)
517.27
Triclinic
C28H24S4Sn (4d)
607.43
Monoclinic
C30H26S6Sn (5c)
697.59
Monoclinic
C26H22PbS2 (6d)
605.78
Triclinic
Unit-cell dimensions
,
a (A)
11.224(3)
12.508(3)
9.767(3)
90.23(3)
114.70(2)
69.33
11.327(2)
12.306(2)
9.835(l)
91.21(2)
112.56(1)
109.14(1)
1178.9(4)
9.126(6)
49.908(8)
23.955(7)
95.60(5)
34.703(2)
10. 112(2)
25.484(2)
137.036(2)
11.405(3)
12.434(3)
9.807(2)
91.44(3)
112.37(l)
110.20(2)
1187.2(6)
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
V (A )
3
,
1148.7(6)
10858(6)
P21/c (No. 14)
16
6095.0(9)
C2/c (No. 15)
8
(
(
(
Space group
Z
P1 (No. 2)
2
P1 (No. 2)
2
P1 (No. 2)
2
Dcalc (g cm−3
)
1.362
1.457
1.486
1.520
1.694
Crystal size (mm)
m (Mo–Ka) (cm−1
Temperature (°C)
2qmax (°)
0.40×0.25×0.20
15.24
23.0
0.10×0.10×0.45
12.70
23.0
0.51×0.46×014
104.74 c
23.0
0.29×0.23×0.17
12.68
23.0
0.23×0.14×0.09
73.03
23.0
)
55.0
55.0
119.8
55.0
55.0
Number of measured reflections
Number of unique reflections
Rint
4550
4277
0.013
5690
5414
0.024
17434
16274
0.106
7102
6988
0.019
5723
5450
0.080
Number of observations [I\3|(I)]
Number of variables
3380
262
3576
262
5880
1179
4503
335
1816
262
Reflection/parameter ratio
12.90
13.65
4.99
0.067, 0.093
0.0700
13.44
6.93
b
Residuals: R, a Rw
0.032, 0.034
0.0150
0.33, −0.25
0.038, 0.039
0.0200
0.51, −0.73
0.039, 0.040
0.0150
0.54, −0.62
0.040, 0.042
0.0350
0.63, 490
P value b
Max. and min. of residual electron
0.59, −0.93
−3
,
density (e A
)
Goodness of fit
1.55
1.42
1.90
1.65
1.07
a R=S(ꢀFoꢀ−ꢀFcꢀ)/SꢀFoꢀ.
b Rw=[S w(ꢀFoꢀ−ꢀFcꢀ)2/S wꢀFoꢀ2]1/2, w=[h2(Fo)+P2(Fo)2/4]−1
.
c v(CuꢀKa) (cm−1).
,
of mono derivative 3d (3.207(2) A). The longer SnꢀS
distances are far apart (S11ꢀSnꢀS21=152.1(3)°), while
the shorter Sn–S distances are close together
(S12ꢀSnꢀS22=84.2(3)°). The SꢀSnꢀCipso bond angles
(106.6(7)–110.4(7)°) are close to the tetrahedral angle,
while the CipsoꢀSnꢀCipso bond angles (129(1)°) are quite
different. Since there are two additional SnꢀS(x1) inter-
actions, the steric effects of S(x1) would increase the
CipsoꢀSnꢀCipso angles from an ideal tetrahedral angle to
129(1)° and would decrease the S12ꢀSnꢀS22 angle to
84.2(3)°. Thus, the two dithiocarboxylate groups are
coordinated as anisobidentate ligands toward the tin
atom. These results are typical for a highly distorted
octahedral or skew trapezoidal bipyramidal structure.
molecular form of 5c differs from the corresponding
thiocarboxylate derivative [13], where the two dithio-
carboxyl groups and the tin atom exist in the same
plane (Fig. 3(a)). In Table 4, the six CꢀS bond lengths
of the three dithiocarboxyl groups are comparable to
those in 4d, and can be separated into shorter CꢀS
,
bond lengths (av. 1.661(5) A) and longer CꢀS bond
,
lengths (av. 1.701(4) A). The former are significantly
longer than the sum of the double bond covalent bond
radii, while the latter are roughly intermediate between
2.2.3. Tris(dithiocarboxylates) Group 14 element
deri6ati6es 5
Although the crystallization of phenyltin tris(4-
methylbenzenecarbodithioate) (5d) was examined under
many different conditions, no suitable single crystals for
X-ray structural analysis was obtained. However, we
have succeeded in the preparation of single crystals of
phenyltin tris(2-methylbenzenecarbodithioate) (5c). The
Fig. 2. The ORTEP drawing of one molecule of (4-
CH3C6H4CSS)2SnPh2 (4d). Hydrogen atoms have been omitted for
clarity.

S. Kato et al. / Journal of Organometallic Chemistry 611 (2000) 190–199
193
Table 3
their single and double bond covalent bond radii [4].
,
Selected bond lengths (A) and angles (°) of diphenyltin bis(4-methyl-
benzenecarbodithioate) (4d)
The SnꢀS bond lengths of the two dithiocarboxylate
,
groups in the same plane are av. 2.597(1) A and av.
,
2.794(1) A, respectively, which are close to the distances
Bond lengths
Sn1ꢀS11
Sn1ꢀS12
C11ꢀS11
C11ꢀS12
Sn1ꢀC31
3.006(7)
2.482(7)
1.69(3)
1.69(3)
2.07(2)
SnlꢀS21
SnlꢀS22
C21ꢀS21
C21ꢀS22
SnlꢀC41
3.111(7)
2.484(7)
1.69(3)
1.66(3)
2.07(3)
observed in divalent tin compounds with bidentate
ligands [14,15]. Therefore, these seem to be coordinated
in a bidentate form toward the tin atom. The SnꢀS
bond lengths of the remaining dithiocarboxylate group
,
are 2.492(1) and 2.987(1) A, respectively, where the
Bond angles
former is close to the smallest SnꢀS bond lengths
observed in tris(dithiocarbamate) tin derivatives [16].
On the other hand, the latter is the longest of the six
SnꢀS bond lengths, and is longer than the sum of their
covalent bond radii [4]. However, these are shorter than
the sum of their van der Waals radii [11], and are also
Sn11ꢀSn1ꢀS21
Sn12ꢀSn1ꢀS22
S11ꢀSn1ꢀS12
S11ꢀC11ꢀS12
SnlꢀS11ꢀC11
Sn1ꢀS12ꢀC11
S12ꢀSnlꢀC31
S12ꢀSnlꢀC41
152.1(3)
84.2(3)
61.9(2)
115(1)
82.1(9)
100.1(10)
110.4(7)
106.6(7)
C31ꢀSnlꢀC41
S21ꢀSnlꢀS22
S21ꢀC21ꢀS22
SnlꢀS21ꢀC21
SnlꢀS22ꢀC21
S22ꢀSnlꢀC31
S22ꢀSnlꢀC41
129(l)
61.8(2)
121(1)
77.4(7)
99(1)
107.6(7)
108.6(7)
,
shorter than those of 3d (3.207(2) A) and 4d (av.
,
3.056(7) A). The S11ꢀSn1ꢀS21 angle (72.22(4)°) is com-
parable to the ideal pentagonal angle, and the
S32ꢀSn1ꢀC41 angle (160.7(1)°) is approximately linear.
These results are consistent with a seven-coordinated
pentagonal bipyramidal structure, where the S11, S12,
S21, S22, and S31 atoms are equatorial and S32 and
C41 are axial (Fig. 3(b)).
2.3. Comparison of germanium, tin, and lead
dithiocarboxylates
The results from X-ray structural analyses have been
explained as follows. In the mono derivatives 1d, 3d,
and 6d, the shorter CꢀS bond lengths are nearly the
Fig. 3. The ORTEP drawing of (2-CH3C6H4CSS)3SnPh (5c) (a). The
coordination surrounding the Sn1 atom (b). Hydrogen atoms have
been omitted for clarity.
,
same (1.637(3)–1.645(5) A), while the longer CꢀS bond
lengths slightly shorten in the order Ge\Sn\Pb. Pre-
sumably, delocalization of the dithiocarboxylate group
may occur in the lead derivative 6d. The shorter MꢀS
bond lengths indicate single bonds. It is noteworthy
that the distance between the sulfur of the shorter CꢀS
bond (thiocarbonyl sulfur) and the central tin atom is
shorter than S···Ge and S···Pb distances. The ratio of
these distances and the sum of the corresponding van
der Waals radii [11] become smaller in the order Sn 3d
(19%)\Pb 6d (12%)]Ge 1d (11%). This suggests that
the electron affinity of the tin atom for the sulfur atom
is much stronger than those of the germanium and lead
atoms. Sulfur does not generally show a stronger
affinity with silicon than oxygen [17]. In
CH3C(S)OSiH3, the distance between the thiocarbonyl
Table 4
,
Selected bond lengths (A) and angles (°) of phenyltin tris(2-methyl-
benzenecarbodithioate) (5c)
Bond lengths
Sn1-S11
Sn1ꢀS21
Sn1ꢀS31
Sn1ꢀC41
2.813(1)
2.751(1)
2.987(1)
2.138(1)
Sn1ꢀS12
Sn1ꢀS22
Sn1ꢀS32
2.594(1)
2.600(1)
2.492(1)
C11ꢀS11
C21ꢀS21
C31ꢀS31
1.663(5)
1.673(5)
1.648(4)
C12ꢀS11
C22ꢀS21
C32ꢀS31
1.701(4)
1.691(4)
1.712(4)
Bond angles (°)
S11ꢀSn1ꢀS12
S11ꢀSn1ꢀS21
S11ꢀSn1ꢀS31
65.00(4)
144.43(4)
72.22(4)
Sn1ꢀS11ꢀC11
Sn1ꢀS12ꢀC11
S11ꢀC11ꢀS12
84.3(2)
90.8(2)
119.9(3)
,
sulfur and the silicon atom is 3.185(9) A, indicating
very weak interaction, although less than the van der
Waals distance [11]. Thus, the affinity between sulfur
atom and Group 14 elements may decrease in the order
Sn\Pb]Ge\Si\C. These non-bonding interactions
are considered to reflect interaction between the sulfur
lone-pair and the non-bonding orbital (s* orbital) of
CꢀM or SꢀM (M=Ge, Sn, Pb). In comparing mono
3d, bis 4d, and tris derivatives 5c, the two CꢀS bond
lengths of 4d and 5c are nearly same value, which
S12ꢀSn1ꢀS22
S12ꢀSn1ꢀS32
S12ꢀSn1ꢀC41
82.79(4)
90.87(4)
101.5(1)
Sn1ꢀS21ꢀC21
Sn1ꢀS22ꢀC21
S21ꢀC21ꢀS22
79.4(2)
94.6(2)
121.9(3)
S21ꢀSnlꢀS22
S21ꢀSnlꢀS31
S22ꢀSn1ꢀS32
S22ꢀSn1ꢀC41
66.00(4)
72.22(4)
95.33(5)
100.8(1)
S31ꢀSnlꢀS32
S32ꢀSnlꢀC41
SnlꢀS31ꢀC31
SnlꢀS32ꢀC31
S31ꢀC31ꢀS32
64.10(4)
160.7(1)
84.5(2)
89.1(2)
120.3(3)

194
S. Kato et al. / Journal of Organometallic Chemistry 611 (2000) 190–199
3. Conclusion
suggests that the dithiocarboxylate groups in 4d and 5c
seem more strongly delocalized than those of 3d. The
SnꢀS bond lengths increase in the order 4dB3dB5c,
but the distances between the thiocarbonyl sulfur and
the tin atoms shorten in the order 3d\4d\5c. The
bidentate characters of dithiocarboxylate groups are
considered to increase with their number.
A series of germanium, tin, and lead derivatives of
dithiocarboxylates were synthesized, and their struc-
tures were analyzed by X-ray. These molecules show
the existence of intramolecular non-bonding interac-
tions between the thiocarbonyl sulfur atoms and the
central Group 14 element metals. Comparative studies
of the compounds RCSSMPh3 (M=Ge, Sn, Pb) re-
vealed that the distance between the thiocarbonyl sulfur
and the tin atom is shorter than those of the germa-
nium and lead derivatives. These non-bonding interac-
tions reflect the affinity between the sulfur atoms and
the Group 14 elements, i.e. this affinity decreases in the
order Sn\Pb]Ge\Si\C. Such order of the affinity
would contribute not only to the synthesis of the rele-
vant compounds but also elucidation of biological
mechanism in which the Group 14 elements and sulfur
participate.
2.4. Spectra
Thiocarbonyl stretching frequencies in the germa-
nium, tin, and lead derivatives are observed at 1160–
1200 cm−1 for aliphatic derivatives and 1210–1270
cm−1 for aromatic ones. The 13CꢁS chemical shifts
appear at l 230–250, and those of aliphatic are at
lower frequencies than those of aromatic. The 119Sn-
NMR chemical shifts are observed at l −125 to −130
for mono derivatives 3, l −250 to −400 for bis
derivatives 4, and l −650 to −740 for tris derivatives
5, and those of aliphatic derivatives are at a lower field
than those of aromatic derivatives. The coupling con-
stants of tin–carbon appear at 600 Hz and 800 Hz,
respectively, with a difference of 200 Hz. The thiocar-
bonyl stretching frequencies and the thiocarbonyl car-
bon and 119Sn chemical shifts of 4-methylbenzene
derivatives are shown in Table 5. The thiocarbonyl
stretching frequencies are nearly the same, but the
13CꢁS chemical shifts show 3 ppm downfield shift with
an increase in dithiocarboxylate groups. On the other
hand, the 119Sn chemical shifts show upfield shifts in the
order 3dB4dB5d, with a difference of 250 ppm be-
tween 3d and 4d and of 350 ppm between 4d and 5d. In
these spectroscopic data of mono-, bis-, and tris(4-
methylbenzenecarboxylates) germanium, tin, and lead
derivatives, the w(CꢁS) stretching frequencies are nearly
the same, but the 13CꢁS chemical shifts are in the order
GeBSnBPb and mono-Bbis-Btris(dithiocarboxy-
late) derivatives.
4. Experimental
Melting points were determined by a Yanagimoto
micromelting point apparatus, but not corrected. The
IR spectra were measured on Perkin–Elmer FT-IR
1640 spectrophotometer. H- (400 MHz) and 13C-NMR
1
spectra (100 MHz) were measured on a JEOL JNM-
a400 in CDCl3 containing Me4Si as an internal stan-
dard. 119Sn-NMR spectra (149 MHz) were also
measured on a JEOL JNM-a400 with Me4Sn as an
external standard. UV–vis spectra were obtained from
a JASCO U-Best 55. Elemental analyses were per-
formed by the Elemental Analysis Center of Kyoto
University. All solvents were dried and distilled prior to
use. Ph3GeCl, Ph2GeCl2, Ph3SnCl, Ph2SnCl2, PhSnCl3,
SnCl4–CH2Cl2 1.0 M solution, and Ph3PbCl are of
commercial grade were obtained from Aldrich.
Ph2PbCl2 was obtained from Alfa Chemical Co. Piperi-
dinium [18] and sodium dithiocarboxylates [2f] were
prepared by previously described methods. A series of
Table 5
RCSSMPh3 (M=Sn:
(RCSS)2SnPh2 4 [2b] were synthesized according to the
procedures reported previously.
3 [2b,f], Pb: 6 [2d]) and
Selected features in the spectroscopic data of (4-CH3C6H4CSS)x-
a
MPh4−x
b
c
d
No.
M
x
w(CꢁS) (cm−1
)
lCꢁS
l119
Sn
4.1. General procedures
1d
3d
6d
2d
4d
7d
5d
Ge
Sn
Pb
Ge
Sn
Pb
Sn
1
1220, 1212
1242, 1224
1219, 1210
1238, 1221
1239, 1221
1222
227.7
232.1
234.5
228.0
235.9
239.4
238.2
1
1
2
2
2
3
−138.8
The synthesis of triphenylgermanium 4-methylben-
zenecarbodithioate (1d) is described in detail as a typi-
cal procedure for compounds 1, 2, 5, and 7. For 3 [2b],
4 [2b], and 6 [2d], the additional spectral data and
elemental analysis are described.
−392.0
−739.5
1242, 1224
1a. Recrystallizing solvents: hexane; orange crystals
(28%); m.p. 89–90°C. IR (KBr): 1193 (CꢁS), 1158
a Standard: Me4Sn.
b In KBr.
1
(CꢁS) cm−1. H-NMR (CDCl3): l 2.91 (s, 3H, CH3),
c In CDCl3.
d In C6D6.
7.39–7.44 (m, 9H, Ar), 7.62–7.65 (m, 6H, Ar). 13C-

S. Kato et al. / Journal of Organometallic Chemistry 611 (2000) 190–199
195
NMR (CDCl3): l 43.8 (CH3), 128.0, 129.3, 134.7, 136.8,
236.6 (CꢁS). UV–vis (CH2Cl2) umax (log m): 222 (4.05),
289 (3.95), 309 (3.48), 518 (2.13) nm.
(log m): 222 (4.35), 273 (4.13), 316 (4.24), 531 (2.59) nm.
Anal. Found: C, 61.17; H, 3.95. C25H19ClGeS2 Calc.: C,
61.08; H, 3.90%.
1b. Recrystallizing solvents: 1:1 Et2O–hexane; purple
crystals (60%); m.p. 108–110°C. IR (KBr): 1218 (CꢁS)
2a. Recrystallizing solvents: hexane; orange crystals
(54%); m.p. 78–79°C. IR (KBr): 1197 (CꢁS), 1183
1
1
cm−1. H-NMR (CDCl3): l 7.39–7.44 (m, 11H, Ar),
(CꢁS) cm−1. H-NMR (CDCl3): l 2.61 (s, 6H, CH3),
7.68–7.71 (m, 7H, Ar), 8.19–8.22 (m, 2H, Ar). 13C-
NMR (CDCl3): l 127.1, 128.0, 128.5, 129.9, 132.5,
134.7, 134.8, 145.7, 228.7 (CꢁS). UV–vis (CH2Cl2) umax
(log m): 222 (4.36), 270 (4.46), 306 (4.13), 519 (2.58) nm.
Anal. Found: C, 65.62; H, 4.47. C25H20GeS2 Calc.: C,
65.68; H, 4.41%.
7.15 (t, J=6.6 Hz, 4H, PhGe), 7.38 (t, J=6.6 Hz, 4H,
PhGe), 7.48 (d, J=6.6 Hz, 2H, PhGe). 13C-NMR
(CDCl3): l 45.7 (CH3), 128.1, 130.2, 133.5, 135.9, 229.4
(CꢁS). UV–vis (CH2Cl2) umax (log m): 222 (4.14), 270
(3.42), 309 (3.39), 409 (3.00), 520 (3.58) nm.
2b. Recrystallizing solvents: 4:3 CH2Cl2–hexane; red
crystals (62%); m.p. 196–198°C. IR (KBr): 1237 (CꢁS),
1c. Reddish–purple oil (88%). IR (neat): 1240 (CꢁS)
1
1
cm−1. H-NMR (CDCl3): l 2.38 (s, 3H, CH3), 7.12–
1222 (CꢁS) cm−1. H-NMR (CDCl3): l 7.31–7.53 (m,
7.20 (m, 3H, Ar), 7.32–7.43 (m, 10H, Ar), 7.69–7.71
(m, 6H, Ar). 13C-NMR (CDCl3): l 19.7 (CH3), 125.5,
125.9, 128.6, 128.8, 130.0, 130.7, 132.2, 134.1, 134.8,
150.1, 235.7 (CꢁS).
8H, Ar), 7.67–7.74 (m, 2H, PhGe), 7.90–7.96 (m, 6H,
Ar), 8.07–8.22 (m, 4H, Ar). 13C-NMR (CDCl3): l
128.3, 128.5, 128.6, 128.7, 128.8, 131.0, 133.2, 133.7,
228.7 (CꢁS). UV–vis (CH2Cl2) umax (log m): 222 (4.39),
270 (4.52), 305 (3.17), 515 (2.63) nm. Anal. Found: C,
58.62; H, 3.81. C26H20GeS4 Calc.:C, 58.55; H, 3.78%.
1d. To a solution of Ph3GeCl (0.339 g, 1.00 mmol) in
Et2O (15 ml), piperidinium 4-methylbenzenecarbod-
ithioate (0.254 g, 1.00 mmol) was added and the mix-
ture was stirred at 20°C for 1 h. After addition of
CH2Cl2 (100 ml), the mixture was washed with water
(3×90 ml), followed by drying over MgSO4. The sol-
vents were removed under reduced pressure (30°C/2.7
kPa), and the resulting residue was dissolved into a
mixed solvent of CH2Cl2 (4.0 ml) and hexane (3.0 ml)
and allowed to stand in a refrigerator (−20°C) for 24
h to give 1d as purple crystals (0.306 g, 65%); m.p.
2c. Red oil (82%). IR (neat): 1241 (CꢁS) cm−1
.
1H-NMR (CDCl3): l 2.31 (s, 6H, CH3), 7.09–7.96 (m,
18H, Ar). 13C-NMR (CDCl3): l 19.8 (CH3), 125.5,
126.0, 128.6, 128.8, 129.2, 130.8, 132.5, 133.6, 134.3,
148.8, 235.7 (CꢁS).
2d. Recrystallizing solvents: 7:5 CH2Cl2–hexane; red
crystals (69%); m.p. 114–116°C. IR (KBr): 1238 (CꢁS),
1
1221 (CꢁS) cm−1. H-NMR (CDCl3): l 2.34 (s, 6H,
CH3), 7.17 (d, J=8.1 Hz, 4H, Ar), 7.21 (t, J=6.9 Hz,
6H, PhGe), 7.31 (d, J=8.1 Hz, 4H, Ar), 7.48 (d,
J=6.9 Hz, 4H, PhGe). 13C-NMR (CDCl3): l 21.6
(CH3), 127.1, 128.5, 128.7, 129.1, 130.2, 134.2, 142.2,
144.1, 228.0 (CꢁS). UV–vis (CH2Cl2) umax (log m): 222
(4.41), 271 (4.22), 324 (4.73), 515 (2.52) nm. Anal.
Found: C, 60.01; H, 4.33. C28H24GeS4 Calc.: C, 59.91;
H, 4.31%.
129–130°C. IR (KBr): 1220 (CꢁS), 1212 (CꢁS) cm−1
.
1H-NMR (CDCl3): l 2.37 (s, 3H, CH3), 7.15 (d, J=8.4
Hz, 2H, Ar), 7.39–7.47 (m, 9H, PhGe), 7.73–7.75 (m,
6H, PhGe), 8.19 (d, J=8.4 Hz, 2H, Ar). 13C-NMR
(CDCl3): l 21.5 (CH3), 127.2, 128.5, 128.7, 129.8, 134.6,
134.8, 143.2, 143.5, 227.7 (CꢁS). UV–vis (CH2Cl2) umax
(log m): 222 (4.46), 273 (4.71), 320 (4.27), 527 (2.65) nm.
Anal. Found: C, 66.30; H, 4.75. C26H22GeS2 Calc.: C,
66.27; H, 4.71%.
2e. Recrystallizing solvents: 5:4 CH2Cl2–hexane; red
crystals (60%); m.p. 119–121°C. IR (KBr): 1240 (CꢁS)
1
1e. Recrystallizing solvents: 1:1 CH2Cl2–hexane; pur-
ple crystals (60%); m.p. 117–118°C. IR (KBr): 1261
cm−1. H-NMR (CDCl3): l 3.77 (s, 6H, CH3O), 6.76
(d, J=9.0 Hz, 4H, Ar), 7.23–7.58 (m, 6H, Ar), 7.81–
7.99 (m, 4H, PhGe), 8.02 (d, J=9.0 Hz, 4H, Ar).
13C-NMR (CDCl3): l 55.5 (CH3O), 113.5, 128.4, 128.6,
129.3, 133.1, 134.1, 137.8, 164.1, 225.7 (CꢁS). UV–vis
(CH2Cl2) umax (log m): 222 (4.42), 272 (4.31), 349 (4.55),
516 (2.83) nm. Anal. Found: C, 56.69; H, 4.10.
C28H24GeO2S4 Calc.: C, 56.68; H, 4.08%.
(CꢁS), 1243 (CꢁS), 1228 (CꢁS) cm−1
.
1H-NMR
(CDCl3): l 3.79 (s, 3H, CH3O), 6.78 (d, J=8.9 Hz, 2H,
Ar), 7.36–7.43 (m, 9H, PhGe), 7.69–7.71 (m, 6H,
PhGe), 8.28 (d, J=8.9 Hz, 2H, Ar). 13C-NMR
(CDCl3): l 55.5 (CH3O), 113.0, 128.0, 128.4, 129.5,
129.8, 134.8, 138.9, 163.8, 225.5 (CꢁS). UV–vis
(CH2Cl2) umax (log m): 222 (4.50), 270 (5.42), 341 (4.40),
520 (2.81) nm. Anal. Found: C, 64.36; H, 4.75.
C26H22GeOS2 Calc.: C, 64.10; H, 4.55%.
2f. Recrystallizing solvents: 4:3 CH2Cl2–hexane; red
crystals (62%); m.p. 146–148°C. IR (KBr): 1236 (CꢁS)
1
cm−1. H-NMR (CDCl3): l 7.20 (d, J=8.7 Hz, 4H,
1f. Recrystallizing solvents: 4:3 CH2Cl2–hexane; pur-
ple crystals (57%); m.p. 120–121°C. IR (KBr): 1211
Ar), 7.30–7.50 (m, 6H, PhGe), 7.76–7.81 (m, 4H,
PhGe), 8.02 (d, J=8.7 Hz, 4H, Ar). 13C-NMR
(CDCl3): l 128.1, 128.5, 128.6, 130.2, 133.1, 134.1,
139.6, 142.5, 226.4 (CꢁS). UV–vis (CH2Cl2) umax
(log m): 222 (4.45), 273 (4.24), 312 (4.28), 516 (2.69) nm.
Anal. Found: C, 51.89; H, 3.11. C26H18Cl2GeS4 Calc.:
C, 51.86; H, 3.01%.
1
(CꢁS) cm−1. H-NMR (CDCl3): l 7.23 (d, J=8.3 Hz,
2H, Ar), 7.31–7.36 (m, 9H, PhGe), 7.60–7.62 (m, 6H,
PhGe), 8.08 (d, J=8.3 Hz, 2H, Ar). 13C-NMR
(CDCl3): l 128.0, 128.1, 128.4, 128.6, 130.0, 134.2,
134.4, 134.9, 226.6 (CꢁS). UV–vis (CH2Cl2) umax

196
S. Kato et al. / Journal of Organometallic Chemistry 611 (2000) 190–199
3a. Orange oil (92%). IR (neat): 1187 (CꢁS), 1174
4d [2b]. Recrystallizing solvents: 7:5 CH2Cl2–hexane;
orange crystals (88%). 13C-NMR (CDCl3): l 21.7
(CH3), 127.4, 128.6, 128.8, 129.4, 134.6, 140.3, 145.1,
145.4, 235.9 (CꢁS). 119Sn-NMR (CDCl3): l −392.0
(1JC–Sn=807 Hz). Anal. Found: C, 55.44; H, 4.07.
C28H24S4Sn Calc.: C, 55.36; H, 3.98%.
1
(CꢁS), 1152 (CꢁS) cm−1. H-NMR (CDCl3): l 2.94 (s,
3H, CH3), 7.36–7.40 (m, 9H, PhSn), 7.64–7.67 (m, 6H,
PhSn). 13C-NMR (CDCl3): l 42.0 (CH3), 128.8, 129.7,
136.5, 136.8, 242.0 (CꢁS). 119Sn-NMR (CDCl3): l
−127.4 (1JC–Sn=595 Hz). UV–vis (CH2Cl2) umax
(log m): 319 (3.94), 461 (1.74) nm.
3b [2b]. Recrystallizing solvents: 5:3 CH2Cl2–hexane;
red crystals (78%). 13C-NMR (CDCl3): l 127.9, 128.5,
128.9, 129.7, 136.5, 136.7, 136.8, 143.9, 233.1 (CꢁS).
119Sn-NMR (CDCl3): l −135.4 (1JC–Sn=597 Hz).
Anal. Found: C, 59.72; H, 4.15. C25H20S2Sn Calc.: C,
59.66; H, 4.01%.
3c [2b]. Recrystallizing solvents: 1:1 CH2Cl2–hexane;
red crystals (74%). 13C-NMR (CDCl3): l 20.1 (CH3),
125.5, 126.1, 128.9, 129.1, 129.8, 130.8, 132.4, 136.8,
138.7, 148.8, 240.1 (CꢁS). 119Sn-NMR (CDCl3): l
−126.5 (1JC–Sn=591 Hz). Anal. Found: C, 60.52; H,
4.39. C26H22S2Sn Calc.: C, 60.37; H, 4.29%.
4e. Recrystallizing solvents: 3:2 CH2Cl2–hexane; or-
ange crystals (81%); m.p. 169–170°C. 1H-NMR
(CDCl3): l 3.81 (s, 6H, CH3O), 6.78 (d, J=8.9 Hz, 4H,
Ar), 7.32–7.40 (m, 6H, PhSn), 7.90–7.93 (m, 4H,
PhSn), 8.32 (d, J=8.9 Hz, 4H, Ar). 13C-NMR
(CDCl3): l 55.6 (CH3O), 113.0, 128.8, 129.3, 130.0,
134.6, 136.0, 146.2, 164.9, 233.5 (CꢁS). 119Sn-NMR
(CDCl3): l −402.7 (1JC–Sn=812 Hz). Anal. Found: C,
52.61; H, 3.82. C28H24O2S4Sn Calc.: C, 52.59; H, 3.78%.
4f [2b]. Recrystallizing solvents: 6:5 CH2Cl2–hexane;
orange crystals (79%). 13C-NMR (CDCl3): l 128.1,
128.6, 129.1, 129.8, 134.7, 140.6, 141.0, 144.0, 234.6
(CꢁS). 119Sn-NMR (CDCl3): l −378.9 (1JC–Sn=826
Hz). Anal. Found: C, 48.22; H, 2.83. C26H18Cl2S4Sn
Calc.: C, 48.17; H, 2.80%.
3d [2b,f]. Recrystallizing solvents: 7:5 CH2Cl2–hex-
ane; red crystals (70%).
3e [2b]. Recrystallizing solvents: 5:4 CH2Cl2–hexane;
red crystals (75%). 13C-NMR (CDCl3): l 55.5 (CH3O),
113.0, 128.8, 129.5, 130.1, 134.6, 136.8, 139.8, 164.0,
5a. Orange oil (41%). IR (neat): 1196 (CꢁS), 1148
1
(CꢁS) cm−1. H-NMR (CDCl3): l 2.78 (s, 9H, CH3),
7.37–7.48 (m, 3H, PhSn), 7.77–7.79 (m, 2H, PhSn).
13C-NMR (CDCl3): l 48.5 (CH3), 128.8, 131.6, 134.5,
139.0, 250.5 (CꢁS). 119Sn-NMR (CDCl3): l −652.2.
UV–vis (CH2Cl2) umax (log m): 222 (5.12), 270 (4.52),
310 (3.85), 401 (2.75) nm.
229.8 (CꢁS). 119Sn-NMR (CDCl3): l −143.1 (1JC–Sn
=
597 Hz). Anal. Found: C, 58.61; H, 4.22. C26H22OS2Sn
Calc.: C, 58.56; H, 4.16%.
3f [2b]. Recrystallizing solvents: 6:5 CH2Cl2–hexane;
red crystals (69%). 13C-NMR (CDCl3): l 128.0, 128.7,
129.3, 130.3, 134.7, 141.3, 141.4, 143.6, 230.2 (CꢁS).
119Sn-NMR (CDCl3): l −130.4 (1JC–Sn=612 Hz).
Anal. Found: C, 55.92; H, 3.66. C25H19ClS2Sn Calc.: C,
55.84; H, 3.56%.
5b. Recrystallizing solvents: 5:1:7 CH2Cl2–AcOEt–
hexane; orange crystals (82%); m.p. 144–147°C. IR
.
(KBr): 1236 (CꢁS), 1221 (CꢁS) cm−1 1H-NMR
(CDCl3): l 7.32–7.40 (m, 9H, Ar), 7.54–7.58 (m, 3H,
Ar), 8.06–8.08 (m, 2H, Ar), 8.29–8.31 (m, 6H, Ar).
13C-NMR (CDCl3): l 127.3, 128.1, 129.1, 130.0, 131.1,
134.1, 144.4, 151.8, 239.4 (CꢁS). 119Sn-NMR (CDCl3):
l −737.2. UV–vis (CH2Cl2) umax (log m): 222 (4.52),
262 (4.33), 313 (4.96), 445 (3.70) nm. Anal. Found: C,
49.52; H, 3.14. C27H20S6Sn Calc.: C, 49.47; H, 3.08%.
5c. Recrystallizing solvents: 7:3:8 AcOEt–Et2O–hex-
ane; orange crystals (85%); m.p. 110–113°C. IR (KBr):
4a. Recrystallizing solvents: hexane; orange crystals
(87%); m.p. 98–99°C. IR (KBr): 1172 (CꢁS), 1151
1
(CꢁS) cm−1. H-NMR (CDCl3): l 2.64 (s, 6H, CH3),
7.24–7.35 (m, 6H, PhSn), 7.48–7.50 (m, 4H, PhSn).
13C-NMR (CDCl3): l 51.1 (CH3), 128.7, 129.8, 135.4,
140.5, 252.4 (CꢁS). 119Sn-NMR (CDCl3): l −251.5
(1JC–Sn=741 Hz). UV–vis (CH2Cl2) umax (log m): 320
(3.88), 417 (2.11) nm.
1
1226 (CꢁS) cm−1. H-NMR (CDCl3): l 2.54 (s, 9H,
4b [2b]. Recrystallizing solvents: 8:5 CH2Cl2–hexane;
orange crystals (82%). 13C-NMR (CDCl3): l 127.3,
128.0, 129.0, 130.0, 133.8, 134.7, 142.7, 144.8, 236.9
(CꢁS). 119Sn-NMR (CDCl3): l −385.0 (1JC–Sn=817
Hz). Anal. Found: C, 53.96; H, 3.52. C26H20S4Sn Calc.:
C, 53.90; H, 3.48%.
CH3), 7.13–7.16 (m, 6H, Ar), 7.23–7.26 (m, 3H, Ar),
7.44–7.46 (m, 3H, Ar), 7.56–7.58 (m, 3H, Ar), 8.08–
8.10 (m, 2H, Ar). 13C-NMR (CDCl3): l 20.9 (CH3),
125.6, 127.1, 129.1, 130.1, 130.2, 131.1, 131.2, 133.5,
145.0, 151.1, 246.5 (CꢁS). 119Sn-NMR (CDCl3): l
−710.7. Anal. Found: C, 51.66; H, 3.73. C30H26S6Sn
Calc.: C, 51.65; H, 3.76%.
4c. Recrystallizing solvents: 1:1 CH2Cl2–hexane; red
crystals (70%); m.p. 79–80°C. IR (KBr): 1233 (CꢁS)
1
cm−1. H-NMR (CDCl3): l 2.43 (s, 6H, CH3), 7.11–
5d. Recrystallizing solvents: 2:6:5 CH2Cl2–AcOEt–
hexane; orange crystals (77%); m.p. 130–132°C. IR
7.24 (m, 6H, Ar), 7.41–7.49 (m, 8H, Ar), 7.95–8.01 (m,
4H, Ar). 13C-NMR (CDCl3): l 20.5 (CH3), 125.6, 126.7,
129.1, 129.8, 131.0, 133.1, 134.7, 135.8, 144.2, 146.9,
.
(KBr): 1242 (CꢁS), 1224 (CꢁS) cm−1 1H-NMR
(CDCl3): l 2.24 (s, 9H, CH3), 7.04 (d, J=8.4 Hz, 6H,
Ar), 7.32–7.37 (m, 3H, PhSn), 7.70–7.80 (m, 2H,
PhSn), 8.21 (d, J=8.4 Hz, 6H, Ar). 13C-NMR
(CDCl3): l 22.0 (CH3), 127.5, 128.7, 128.9, 129.8, 131.1,
139.1, 145.4, 152.3, 238.2 (CꢁS). 119Sn-NMR (CDCl3):
244.2 (CꢁS). 119Sn-NMR (CDCl3): l −367.4 (1JC–Sn
=
805 Hz). UV–vis (CH2Cl2) umax (log m): 338 (4.32), 457
(2.93) nm. Anal. Found: C, 55.39; H, 4.00. C28H24S4Sn
Calc.: C, 55.36; H, 3.98%.

S. Kato et al. / Journal of Organometallic Chemistry 611 (2000) 190–199
197
l −739.5. UV–vis (CH2Cl2) umax (log m): 221 (5.21),
258 (4.73), 340 (5.01), 445 (2.45) nm. Anal. Found: C,
51.72; H, 3.82. C30H26S6Sn Calc.: C, 51.65; H, 3.76%.
5e. Recrystallizing solvents: 1:1 CH2Cl2–hexane; or-
ange crystals (78%); m.p. 157–159°C. IR (KBr): 1269
130.1, 137.0, 137.6, 143.4, 156.2 (1JC–Pb=543 Hz),
234.5 (CꢁS). UV–vis (CH2Cl2) umax (log m): 222 (4.43),
272 (4.57), 318 (4.38), 520 (2.23) nm.
6e [2d]. Recrystallizing solvents: 5:3 CH2Cl2–hexane;
1
red crystals (78%). H-NMR (CDCl3): l 3.68 (s, 3H,
1
(CꢁS), 1244 (CꢁS) cm−1. H-NMR (CDCl3): l 3.88 (s,
CH3O), 6.86 (d, J=9.0 Hz, 2H, Ar), 7.29 (t, J=7.3
Hz, 3H, PhPb), 7.42 (t, J=7.3 Hz, 6H, PhPb), 7.78 (d,
J=7.3 Hz, 6H, PhPb), 8.34 (d, J=9.0 Hz, 2H, Ar).
13C-NMR (CDCl3): l 55.3 (CH3O), 112.7, 127.4, 129.3,
129.9, 136.8, 138.4, 156.2 (1JC–Pb=545 Hz), 163.6,
232.0 (CꢁS). UV–vis (CH2Cl2) umax (log m): 222 (4.44),
272 (4.62), 344 (4.45), 515 (2.32) nm. Anal. Found: C,
50.39; H, 3.62. C26H22OPbS2 Calc.: C, 50.22; H, 3.57%.
6f [2d]. Recrystallizing solvents: 2:1 CH2Cl2–hexane;
red crystals (73%). 1H-NMR (CDCl3): l 7.18 (d, J=8.5
Hz, 2H, Ar), 7.31 (t, J=7.6 Hz, 3H, PhPb), 7.44 (t,
J=7.6 Hz, 6H, PhPb), 7.76 (d, J=7.6 Hz, 6H, PhPb),
8.17 (d, J=8.5 Hz, 2H, Ar). 13C-NMR (CDCl3): l
127.8, 128.8, 129.4, 130.1, 136.9, 138.0, 143.7, 155.9
(1JC–Pb=544 Hz), 233.2 (CꢁS). UV–vis (CH2Cl2) umax
(log m): 221 (4.43), 272 (4.71), 313 (4.34), 524 (2.18) nm.
Anal. Found: C, 47.99; H, 3.11. C25H19ClPbS2 Calc.: C,
47.95; H, 3.06%.
9H, CH3O), 6.79 (d, J=9.0 Hz, 6H, Ar), 7.34–7.41 (m,
3H, PhSn), 8.05–8.09 (m, 2H, PhSn), 8.32 (d, J=9.0
Hz, 6H, Ar). 13C-NMR (CDCl3): l 55.7 (CH3O), 113.1,
128.8, 129.7, 130.1, 131.1, 134.9, 152.8, 165.1, 235.5
(CꢁS). 119Sn-NMR (CDCl3):
l
−748.2. UV–vis
(CH2Cl2) umax (log m): 223 (5.13), 264 (4.69), 369 (4.95),
463 (2.47) nm. Anal. Found: C, 48.39; H, 3.56.
C30H26O3S6Sn Calc.: C, 48.32; H, 3.51%.
5f. Recrystallizing solvents: 2:4:7 CH2Cl2–AcOEt–
hexane; red crystals (53%); m.p. 137–140°C. IR (KBr):
1
1235 (CꢁS) cm−1. H-NMR (CDCl3): l 7.25–7.43 (m,
12H, Ar), 8.00–8.03 (m, 2H, PhSn), 8.21–8.23 (m, 3H,
PhSn). 13C-NMR (CDCl3): l 128.2, 128.7, 129.2, 130.2,
131.0, 139.8, 141.2, 151.5, 237.5 (CꢁS). 119Sn-NMR
(CDCl3): l −739.8. UV–vis (CH2Cl2) umax (log m): 223
(5.14), 263 (4.72), 331 (4.65), 429 (2.45) nm. Anal.
Found: C, 42.80; H, 2.31. C27H17Cl3S6Sn Calc.: C,
42.73; H, 2.26%.
7a. Recrystallizing solvents: hexane; orange crystals
(35%); m.p. 87–88°C. IR (KBr): 1162 (CꢁS), 1152
6a. Orange oil (86%). IR (neat): 1161 (CꢁS), 1132
1
1
(CꢁS) cm−1. H-NMR (CDCl3): l 2.92 (s, 3H, CH3),
(CꢁS) cm−1. H-NMR (CDCl3): l 2.67 (s, 6H, CH3),
7.29–7.44 (m, 9H, PhPb), 7.57–7.68 (m, 6H, PhPb).
13C-NMR (CDCl3): l 45.2 (CH3), 128.3, 128.8, 135.9,
153.2 (1JC–Pb=541 Hz), 259.9 (CꢁS). UV–vis (CH2Cl2)
umax (log m): 222 (4.41), 270 (4.55), 334 (3.74), 470 (1.66)
nm.
7.31 (t, J=7.5 Hz, 2H, PhPb), 7.44 (t, J=7.5 Hz, 4H,
PhPb), 7.92 (d, J=7.5 Hz, 4H, PhPb). 13C-NMR
(CDCl3): l 44.9 (CH3), 129.5, 130.2, 136.7, 137.0, 250.7
(CꢁS). UV–vis (CH2Cl2) umax (log m): 222 (4.61), 270
(4.54), 335 (4.41), 467 (2.11) nm.
6b [2d]. Recrystallizing solvents: 5:4 CH2Cl2–hexane;
purple crystals (60%). 1H-NMR (CDCl3): l 7.26 (t,
J=8.5 Hz, 1H, Ar), 7.33 (t, J=7.6 Hz, 3H, PhPb),
7.45 (t, J=7.6 Hz, 6H, PhPb), 7.50 (t, J=8.5 Hz, 2H,
Ar), 7.77 (d, J=7.6 Hz, 6H, PhPb), 8.26 (d, J=8.5 Hz,
2H, Ar). 13C-NMR (CDCl3): l 127.5, 127.7, 128.5,
129.3, 130.1, 132.3, 137.0, 156.0 (1JC–Pb=544 Hz),
235.4 (CꢁS). UV–vis (CH2Cl2) umax (log m): 222 (4.47),
271 (4.62), 303 (4.30), 519 (2.15) nm. Anal. Found: C,
50.89; H, 3.61. C25H20PbS2 Calc.: C, 50.74; H, 3.41%.
6c [2d]. Recrystallizing solvents: 5:7 Et2O–hexane;
orange crystals (83%). 1H-NMR (CDCl3): l 2.39 (s, 3H,
CH3), 7.08–7.15 (m, 4H, Ar), 7.34–7.53 (m, 9H, Ar),
7.64–7.92 (m, 6H, Ar). 13C-NMR (CDCl3): l 19.8
(CH3), 125.4, 125.7, 128.4, 129.4, 130.1, 130.6, 131.9,
137.0, 150.0, 155.6 (1JC–Pb=533 Hz), 242.2 (CꢁS).
UV–vis (CH2Cl2) umax (log m): 307 (3.83), 504 (2.23)
nm. Anal. Found: C, 51.75; H, 3.90. C26H22PbS2 Calc.:
C, 51.55; H, 3.66%.
7b. Recrystallizing solvents: 2:1 CH2Cl2–hexane; or-
ange crystals (74%); m.p. 196–198°C. IR (KBr): 1217
1
(CꢁS) cm−1. H-NMR (CDCl3): l 7.38 (t, J=7.7 Hz,
4H, PhPb), 7.42 (t, J=7.8 Hz, 4H, Ar), 7.51 (t, J=7.7
Hz, 2H, PhPb), 7.56 (t, J=7.8 Hz, 2H, Ar), 7.95 (d,
J=7.7 Hz, 4H, PhPb), 8.09 (d, J=7.8 Hz, 4H, Ar).
13C-NMR (CDCl3): l 128.3, 129.0, 130.2, 130.5, 133.5,
135.1, 138.4, 157.8, 243.3 (CꢁS). UV–vis (CH2Cl2) umax
(log m): 222 (4.49), 272 (4.09), 316 (4.49), 472 (2.67) nm.
Anal. Found: C, 46.82; H, 3.11. C26H20PbS4 Calc.: C,
46.76; H, 3.02%.
7c. Recrystallizing solvents: 4:5 Et2O–hexane; orange
crystals (83%); m.p. 211–214°C. IR (KBr): 1230 (CꢁS)
1
cm−1. H-NMR (CDCl3): l 2.35 (s, 6H, CH3), 7.10 (t,
J=7.3 Hz, 4H, Ar), 7.20 (t, J=7.3 Hz, 2H, Ar), 7.33
(d, J=7.3 Hz, 2H, Ar), 7.44 (t, J=7.5 Hz, 2H, PhPb),
7.57 (t, J=7.5 Hz, 4H, PhPb), 8.16 (d, J=7.5 Hz, 4H,
PhPb). 13C-NMR (CDCl3): l 20.0 (CH3), 125.5, 125.8,
129.0, 130.0, 130.3, 130.8, 132.1, 134.4, 151.1, 161.1,
244.0 (CꢁS) nm. Anal. Found: C, 48.42; H, 3.57.
C28H24PbS4 Calc.: C, 48.32; H, 3.48%.
6d [2d]. Recrystallizing solvents: 3:2 CH2Cl2–hexane;
1
red crystals (88%). H-NMR (CDCl3): l 2.34 (s, 3H,
CH3), 7.10 (d, J=8.2 Hz, 2H, Ar), 7.36 (t, J=7.6 Hz,
3H, PhPb), 7.48 (t, J=7.6 Hz, 6H, PhPb), 7.78 (d,
J=7.6 Hz, 6H, PhPb), 8.20 (d, J=8.2 Hz, 2H, Ar).
13C-NMR (CDCl3): l 21.6 (CH3), 127.8, 128.5, 129.3,
7d. Recrystallizing solvents: 2:1 CH2Cl2–hexane; or-
ange crystals (83%); m.p. 214–217°C. IR (KBr): 1222
1
(CꢁS) cm−1. H-NMR (CDCl3): l 2.35 (s, 6H, CH3),
7.13 (d, J=8.2 Hz, 4H, Ar), 7.35 (t, J=7.3 Hz, 2H,

198
S. Kato et al. / Journal of Organometallic Chemistry 611 (2000) 190–199
Et2O (0.1 ml), and hexane (0.5 ml) at 25°C for 6 days.
3d (0.151 g) was crystallized from CH2Cl2 (0.6 ml),
Et2O (0.1 ml), and hexane (0.5 ml) at 25°C for 5 days.
4d (0.120 g) was crystallized from CH2Cl2 (0.5 ml),
Et2O (0.3 ml), and hexane (0.5 ml) at 25°C for 10 days.
5c (0.107 g) was crystallized from CH2Cl2 (0.6 ml) and
hexane (0.5 ml) at 25°C for 9 days. 6d (0.131 g) was
crystallized from CH2Cl2 (0.8 ml), Et2O (0.3 ml), and
hexane (0.5 ml) at 25°C for 2 weeks.
PhPb), 7.49 (t, J=7.3 Hz, 4H, PhPb), 8.11 (d, J=7.3
Hz, 4H, PhPb), 8.20 (d, J=8.2 Hz, 4H, Ar). 13C-NMR
(CDCl3): l 21.7 (CH3), 127.2, 128.4, 129.2, 129.4, 130.0,
130.7, 134.9, 144.4, 239.4 (CꢁS). UV–vis (CH2Cl2) umax
(log m): 222 (4.44), 273 (4.06), 333 (4.70), 474 (2.70) nm.
Anal. Found: C, 48.37; H, 3.52. C28H24PbS4 Calc.: C,
48.32; H, 3.48%.
7e. Recrystallizing solvents: 3:2 CH2Cl2–hexane; or-
ange crystals (82%); m.p. 209–211°C. IR (KBr): 1261
1
(CꢁS), 1235 (CꢁS) cm−1. H-NMR (CDCl3): l 3.89 (s,
6H, CH3O), 6.91 (d, J=9.0 Hz, 2H, Ar), 7.44 (t,
J=7.8 Hz, 4H, PhPb), 7.50 (t, J=7.8 Hz, 2H, PhPb),
8.01 (d, J=7.8 Hz, 4H, PhPb), 8.19 (d, J=9.0 Hz, 2H,
Ar). 13C-NMR (CDCl3): l 55.6 (CH3O), 113.6, 129.2,
129.5, 129.6, 129.8, 135.7, 137.6, 164.0, 243.1 (CꢁS).
UV–vis (CH2Cl2) umax (log m): 222 (4.43), 271 (4.11),
348 (4.71), 470 (2.73) nm. Anal. Found: C, 46.27; H,
3.37. C28H24O2PbS4 Calc.: C, 46.20; H, 3.32%.
4.4. X-ray structural analysis
The measurements were carried out on a Rigaku
AFC7R four-circle diffractometer with graphite-
monochromated Mo–Ka (u=0.71069 A) and Cu–Ka
,
,
radiation (u=1.54178 A). All of the structures were
®
solved and refined using the TEXSAN crystallographic
software package on an IRIS Indigo computer. Lorentz
and polarization corrections were applied to the data,
and empirical absorption corrections (DIFABS [19] (3d,
4d, 5c, and 6d) and c-scans [20] (1d)) were also applied.
The structures were solved by direct method using
SHELXS-86 [21] for 1d, 3d, 4d, 5c, and 6d and expanded
using DIRDIF-94 [22]. Scattering factors for neutral
atoms were from Cromer and Waber [23] and anoma-
lous dispersion [24] was used. Crystal data and mea-
surement description are summarized in Table 2.
7f. Recrystallizing solvents: 4:3 CH2Cl2–hexane; or-
ange crystals (85%); m.p. 194–197°C. IR (KBr): 1226
1
(CꢁS) cm−1. H-NMR (CDCl3): l 7.38 (d, J=7.7 Hz,
4H, Ar), 7.42–7.52 (m, 6H, PhPb), 7.91–7.98 (m, 4H,
PhPb), 8.01 (d, J=7.7 Hz, 4H, Ar). 13C-NMR
(CDCl3): l 128.5, 128.8, 128.9, 129.0, 129.3, 130.2,
135.0, 140.1, 247.9 (CꢁS). UV–vis (CH2Cl2) umax
(log m): 222 (4.47), 272 (4.21), 322 (4.72), 478 (2.76) nm.
Anal. Found: C, 42.40; H, 2.51. C26H18Cl2PbS4 Calc.:
C, 42.38; H, 2.46%.
4.2. General procedure for reaction of SnCl4 with
piperidinium or sodium 4-methylbenzenecarbodithioate
5. Supplementary material
To a solution of piperidinium 4-methylbenzenecar-
bodithioate (1.016 g, 4.00 mmol) in CH2Cl2 (30 ml),
SnCl4–CH2Cl2 1.0 M solution (1.0 ml, 1.0 mmol) was
added and the mixture was stirred at 20°C for 1 h. The
solvent was removed under reduced pressure (20°C/2.7
kPa). The mixtures were dissolved into a solvent of
CH2Cl2 (15 ml). Filtration of the resulting precipitate
gave a mixture of dichlorotin bis(4-methylbenzenecar-
bodithioate) and bis(4-methylthiobenzoyl) disulfide [3]
as orange solid. Fractional crystallization of the solid
gave chemically pure dichlorotin bis(4-methylbenzene-
carbodithioate) in 8% yield: Yellow crystals; m.p. 191–
Crystallographic data for the structural analysis have
been deposited at the Cambridge Crystallogrphic Data
Centre (no. CCDC 139447 for compound 1d, CCDC
139448 for compound 3d, CCDC 139449 for compound
4d, CCDC 139450 for compound 5c and CCDC 139451
for compound 6d). Copies of this information maybe
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (Fax: +44-
1223-336033; e-mail: or www: http://www.ccdc.
cam.ac.uk).
193°C. IR (KBr): 1249 (CꢁS), 1228 (CꢁS) cm−1
.
1H-NMR (CDCl3): l 2.46 (s, 6H, CH3), 7.25 (d, J=8.3
Hz, 4H, Ar), 8.14 (d, J=8.3 Hz, 4H, Ar). 13C-NMR
(CDCl3): l 22.2 (CH3), 128.1, 129.4, 135.9, 149.1, 237.0
(CꢁS). 119Sn-NMR (CDCl3): l −715.3. Anal. Found:
C, 36.40; H, 2.61. C16H14Cl2S4Sn Calc.: C, 36.66; H,
2.69%.
Acknowledgements
This research was supported by a Grant-in-Aid for
Scientific Research on Priority Areas (No. 09239220)
and by a Grants-in-Aid for Scientific Research (No.
09355032) from the Ministry of Education, Science,
Sports and Culture of Japan. We thank Professor
Takashi Kawamura and Associate Professor Masahiro
Ebihara of Gifu University for their invaluable assis-
tance with X-ray crystallography.
4.3. Preparation of single crystals
1d (0.124 g) was crystallized from CH2Cl2 (0.4 ml),

S. Kato et al. / Journal of Organometallic Chemistry 611 (2000) 190–199
199
,
,
[11] Sum of van der Waals radii: Ge···S 3.78 A, Sn···S 3.96 A, Pb···S
References
,
3.82 A. A. Bondi, J. Phys. Chem. 68 (1964) 441.
[12] (a) T. Kimura, N. Yasuoka, N. Kasai, M. Kakudo, Bull. Chem.
Soc. Jpn. 45 (1972) 1649. (b) T.P. Lockhart, W.F. Manders, E.O.
Schlemper, J.J. Zuckermann, J. Am. Chem. Soc. 108 (1986)
4074.
[13] P. Singh, S. Bhattacharya, V.D. Gupta, H. No¨th, Chem. Ber.
129 (1996) 1093.
[1] (a) G.D. Thorn, R.A. Ludwig, The Dithiocarbamates and Re-
lated Compounds, Elsevier, Amsterdam, 1962. (b) D. Coucou-
vanis, Prog. Inorg. Chem. 11 (1970) 233. (c) D. Coucouvanis,
Prog. Inorg. Chem. 26 (1979) 301. (d) I. Haiduc, Rev. Inorg.
Chem. 3 (1981) 353.
[2] (a) S. Kato, M. Mizuta, Y. Ishii, J. Organomet. Chem. 55 (1973)
121. (b) S. Kato, T. Kato, Y. Shibahashi, E. Kakudo, M.
Mizuta, Y. Ishii, J. Organomet. Chem. 76 (1974) 215. (c) S.
Kato, A. Hori, H. Shiotani, M. Mizuta, N. Hayashi, T.
Takakuwa, J. Organomet. Chem. 82 (1974) 223. (d) T. Katada,
S. Kato, M. Mizuta, Chem. Lett. (1975) 1037. (e) S. Kato, A.
Hori, M. Mizuta, T. Katada, H. Ishihara, J. Organomet. Chem.
420 (1991) 13. (f) S. Kato, N. Kitaoka, O. Niyomura, Y. Kitoh,
T. Kanda, M. Ebihara, Inorg. Chem. 38 (1999) 496.
[14] J. Potenza, D. Mastropalo, Acta Crystallogr. Sect. B 29 (1973)
1830.
[15] P.F.R. Ewings, P.G. Harrison, T.J. King, J. Chem. Soc. Dalton
Trans. (1976) 1399.
[16] (a) J.S. Morris, E.O. Schlemper, J. Cryst. Mol. Struct. 8 (1978)
295. (b) J.S. Morris, E.O. Schlemper, J. Cryst. Mol. Struct. 9
(1979) 1. (c) D. Dakternieks, H. Zhu, D. Masi, C. Mealli, Inorg.
Chim. Acta 211 (1993) 155. (d) E. Kello, V. Vrabel, I. Skacani,
J. Holecek, Acta Crystallogr. Sect. C 51 (1995) 408.
[17] M.J. Barrow, E.A.V. Ebsworth, C.M. Huntley, D.W.H. Rankin,
J. Chem. Soc. Dalton Trans. (1982) 1131.
[18] S. Kato, T. Mitani, M. Mizuta, Int. J. Sulfur Chem. 8 (1973)
359.
[19] N. Walker, D. Stuart, Acta Crystallogr. Sect. A 39 (1983) 158.
[20] G.M. Sheldrick, in: G.M. Sheldrick, C. Kruger, R. Goddard
(Eds.), Crystallographic Computing 3, vol. 3, Oxford University
Press, UK, 1985, p. 175.
[3] (a) S. Kato, T. Kato, T. Kataoka, M. Mizuta, Int. J. Sulfur
Chem. 8 (1973) 437. (b) O. Niyomura, Y. Kitoh, K.-I. Na-
gayama, S. Kato, Sulfur Lett. 22 (1999) 195
,
[4] Covalent bond radii: CꢀS 1.81 A, CꢁS 1.61, GeꢀS 2.26, SnꢀS
,
2.44, PbꢀS 2.58 A. L. Pauling, The Chemical Bond, Cornell
University Press, Ithaca, New York, 1976.
[5] J.E. Drake, A.G. Mislankar, M.L.Y. Wong, Inorg. Chem. 30
(1991) 2174.
[6] (a) V.G.D. Kumar, C. Wei, E. Sinn, J. Organomet. Chem. 290
(1985) 291. (b) D. Dakternieks, H. Zhu, D. Masi, C. Mealli,
Inorg. Chem. 31 (1992) 3601.
[7] E.R.T. Tiekink, J. Organomet. Chem. 314 (1986) 85.
[8] F.A.K. Nasser, A. Wilson, Jr., J.J. Zuckermann, Organometal-
lics 4 (1985) 2073.
[9] M.G. Begley, P.G.C. Gaffney, A.S. Harrisona, J. Organomet.
Chem. 289 (1985) 281.
[21] A.C.T. North, D.C. Phililips, F.S. Mathews, Acta Crystallogr.
Sect. A 24 (1986) 351.
[22] The DIRDIF-94 program system was used; P.T. Beukskens, G.
Admiraal, G. Beurskiens, W.P. Bosman, R. de Gelder, R. Israel,
J.M.M. Smits, Technical Report of the Crystallography Labora-
tory, University of Nijmegen, The Netherlands, 1994.
[23] D.T. Cromer, J.T. Waber, International Tables for X-ray Crys-
tallography, vol. IV, Kynoch, Birmingham, UK, 1974, Table
2.2A.
[24] D.C. Creagh, W.J. McAuley, in: A.J.C. Wilson (Ed.), Interna-
tional Tables for X-ray Crystallography, vol. C, Kluwer, Boston,
1992, Table 4.2.6.8, pp. 219.
[10] S.N. Olafsson, T.N. Petersen, P. Andersen, Acta Chem. Scand.
50 (1996) 745.
.