Alkali metal and trimethylsilyl carbamoselenothioates - Synthesis, structure, and some reactions

Article abstract of DOI:10.1002/zaac.200600369

This paper describes the synthesis and some reactions of potassium, rubidium , cesium and trimethylsilyl carbamoselenothioates. The potassium salts were synthesized in 70-80% yields by reacting the corresponding thiocarbamoyl chlorides with potassium selenide in acetonitrile. Furthermore, the rubidium and cesium salts were obtained in good yields by treating the trimethylsilyl esters with the corresponding metal fluorides. The crystal structure of acetonitrile-solvated potassium N,N-dimethylcarbamoselenothioate consisted of dimeric units, featuring μ-carbamoselenothioate anions associated with potassium cations that are located on the upper and lower sides of a plane involving two opposing carbamoselenothioate groups. These heavier alkali metal salts readily reacted with alkyl halides to give both S- and Se-alkyl esters. The reaction of the potassium salts with trimethylsilyl chlorides forms S- and Se-trimethylsilyl carbamoselenothioates which are in equilibrium. The reaction of the salts and silyl esters with organo Group-14 and -15 elements halides gave exclusively the corresponding Se-substituted products in good yields.

Full text of DOI:10.1002/zaac.200600369

DOI: 10.1002/zaac.200600369
Alkali Metal and Trimethylsilyl Carbamoselenothioates ؊ Synthesis, Structure,
and some Reactions
Kohji Kawai, Kazumasa Ibi, and Masahiro Ebihara
Gifu / Japan, Gifu University, Department of Chemistry, Faculty of Engineering,
Shinzi Kato*
Kasugai, Aichi / Japan, Chubu University, Department of Applied Chemistry, Faculty of Engineering
Received October 16th, 2006; revised December 6th, 2006.
Abstract. This paper describes the synthesis and some reactions of
potassium, rubidium , cesium and trimethylsilyl carbamoseleno-
thioates. The potassium salts were synthesized in 70Ϫ80 % yields
by reacting the corresponding thiocarbamoyl chlorides with potass-
ium selenide in acetonitrile. Furthermore, the rubidium and cesium
salts were obtained in good yields by treating the trimethylsilyl
esters with the corresponding metal fluorides. The crystal structure
of acetonitrile-solvated potassium N,N-dimethylcarbamoseleno-
thioate consisted of dimeric units, featuring µ-carbamoselenothio-
ate anions associated with potassium cations that are located on
the upper and lower sides of a plane involving two opposing carba-
moselenothioate groups. These heavier alkali metal salts readily re-
acted with alkyl halides to give both S- and Se-alkyl esters. The
reaction of the potassium salts with trimethylsilyl chlorides forms
S- and Se-trimethylsilyl carbamoselenothioates which are in equi-
librium. The reaction of the salts and silyl esters with organo
Group-14 and -15 elements halides gave exclusively the correspond-
ing Se-substituted products in good yields.
Keywords: Potassium carbamoselenothioate; Silyl selenothioester;
Germanium; Tin; Lead
Introduction
There are formally 6 groups of alkali metal carbamodichal-
cogenoates for each alkali metal, in which two oxygen
atoms of carbamate group are replaced by sulfur, selenium
or tellurium (Scheme 1). However, except for alkali metal
carbamodithioates [1], little is known about their chemistry
[2], although they are considered to be an important class
of compounds both synthetically and theoretically because
of heteroallylic anion systems (A, B, C or D) (Scheme 2). To
the best of our knowledge, there has been no report on
the synthesis of alkali metal carbamoselenothioates. Soon
starting this study in the end of 1986, we found Henriksen’s
report [3], in which the synthesis of two sodium carbamo-
selenothioates was described from the reaction of thio-
carbamoyl chloride with sodium selenide. This method was
almost same with our method by using potassium selenide.
After then, we have developed the synthetic methods a
series of alkali metal carbochalcogenoates [4, 5], and sodium
and potassium carbamoselenoates [6] and carbamotellu-
roates [7]. Moreover, O-trimethylsilyl carboselenoate [8] and
Scheme 1
Scheme 2
carbamoselenoates [9] have been found to readily react with
rubidium and cesium fluorides to give the corresponding
heavy alkali metal carbamoselenoates in good yields. As a
part of our studies on the synthesis of new carbochalcog-
enoic and carbamochalcogenoic acid derivatives, we report
* Prof. Dr. Shinzi Kato
Maruno-uchi 2-14-32, Lions-City Maruno-uchi 1105,
Naka-ku, Nagoya 460-0002 / Japan
Phone/Fax: ϩ 81-52-222-2442
E-mail: kshinzi@nifty.com
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625

K. Kawai, K. Ibi, M. Ebihara, S. Kato
here the synthesis and characterization of potassium, rubid-
ium, cesium, and triorganosilyl carbamoselenothioates and
some of their reactions with organo Group-14 and -15 ele-
ment halides.
Results and Discussion
Synthesis of Salts
First, the conditions for the reaction of N,N-dimethylthio-
carbamoyl chloride (1a) with potassium selenide to give
potassium N,N-dimethylcarbamoselenothioate (3a) were
examined. The reaction conditions shown in Scheme 3 ap-
peared to be preferred. Thus, an acetonitrile solution of 1a
was added dropwise to a suspension of excess freshly pre-
pared potassium selenide in the same solvent and the mix-
ture was stirred at room temperature 0 °C for 3 hours. Fil-
tration of the insoluble part (KCl and excess K2Se) and
removal of the solvent under reduced pressure gave 3a in a
yield of 76 % as yellow crystals. (Scheme 3) Under the same
conditions, the reaction with diethylthiocarbamoyl chloride
(1b) led to potassium N,N-diethylcarbamoselenothioates
(3b) in 72 % yield as an oil. In contrast to the use of
potassium selenide, the reactions with sodium selenide gave
the corresponding sodium carbamoselenothioates 2a and
2b in 84 and 74 % yields, respectively. On the other hand,
rubidium 4 and cesium carbamoselenothioates 5 were ob-
tained by reacting trimethylsilyl N,N-dimethylcarbamo-
selenothioates (9) with rubidium and cesium fluorides in
respective yields of 77 and 79 %. (Scheme 4) However, the
reaction of 9 with potassium fluoride resulted in the yield
of below 65 % under the same coditions. The reactions with
NaF, MgF2, CaF2, SrF2, and BaF2 led to the recovery of
the starting salts.
Scheme 4
Table 1 Typical spectral data of compounds 2؊19
13C NMRa / δ
CϭS
77Se NMRb
δ
Compd
CSSe
CϭSe
2a
2b
3a
3b
4
207.0
204.4
206.5
204.7
206.8
207.0
499.9
582.4
505.7
583.8
575.7
529.2
486.4
539.7
Ϫ
5
6a
6b
7
195.2
200.5
192.9
194.7
193.9
190.8
8
Ϫ
-c
-c
9a
9b
10
11
12
13
14
15
16
17
18
19
188.5
189.6
191.1
191.3
191.5
191.5
193.1
195.7
191.1
196.1
529.0
590.5
592?
633.9
655.7
670.4
624.8
Ϫ
624.8
Ϫ
a CD3OD, standard: TMS. b CD3OD, standard: (CH3)2Se. c No 77Se signals
were observed.
3.20Ϫ3.70. In the 13C NMR spectra, two signals due to the
non-equivalent N-CH3 groups and a signal due to -CSSe
carbon appear near δ 44.2 and in the region of δ 204Ϫ207,
respectively. The 77Se- NMR spectra show a signal due to
the carbamoselenothioate selenium atom in the range of δ
499Ϫ584. The influence of alkali metal cations on the
-CSSe carbon and 77Se signals appeared to be little.
Scheme 3
The obtained salts 2Ϫ5 are pale yellow to yellow oil or
crystals and relatively stable towards oxygen and moisture.
They can be stored in a refrigerator below 0 °C for one
month. The structures of 2Ϫ5 were characterized by their
1H, 13C, and 77Se -NMR spectra and by conversion into
methyl 6, phenacyl 7 or 2-acetophenoneoxime esters 8.
Moreover, the structure of 3a was confirmed by single-crys-
tal X-ray analyses. Their spectral data are shown in Table
Crystal structure and Packing
In general, it is difficult to obtain alkali metal carbamochal-
cogenoates as single crystals. To the best of our knowledge,
X-ray structure analyses have only been reported for lith-
ium [1c], sodium [1b], potassium [1b, 1d], and cesium N,N-
dialkylcarbamodithioates [1a]. After we made several at-
tempts to obtain single crystals of 2Ϫ5, the acetonitrile-
solvated salt K[Me2NCSSe](MeCN) of 3a allowed us to
characterize it crystallographically. The structure of the sol-
vated salt is shown in Figure 1, where the atoms E(11),
1
1. In the H-NMR spectra of N,N-dimethyl derivatives 2a,
3a, 4, and 5, two characteristic signals due to the non-
equivalent N-CH3 groups are observed in the region of δ
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Alkali Metal and Trimethylsilyl Carbamoselenothioates
E(12), E(21) and E(22) represent either sulfur or selenium
atoms, which can not be defined due to disorder [10]. Simi-
lar large disorders have been observed for the sulfur and
selenium atoms in ammonium [11] and alkali metal car-
boselenothioates [12]. The final atomic positional param-
eters are listed in Table 2. Selected bond distances and
angles are shown in Table 3. The unit cell and coordination
around the potassium metals are shown in Figure 2. The
salt consists of discrete dimeric units, where the potassium
metals are located on the upper and lower sides of the
planes which include two facing carbamoselenothioate
groups, and deviates somewhat from the center of a square
that consists of two sulfur and two selenium atoms of the
two carbamoselenothioate groups. The CϪE(11) and
Table 3 Selected bond distances and angles of dimeric 3a·MeCN
˚
Bond distances/A
E(11)ϪK(11)
E(12)ϪK(11)
E(11)ϪK(12)
E(12)ϪK(12)
E(21)ϪK(11)
E(22)ϪK(11)
E(21)ϪK(12)
E(22)ϪK(12)
E1ЈϪK(11)
3.38(1)
3.44(1)
3.45(1)
3.32(2)
3.32(2)
3.31(2)
3.41(1)
3.29(1)
3.32(1)
3.50(1)
3.37(1)
E4ЈϪK(12)
3.40(1)
E(11)ϪC(11)
E(12)ϪC(11)
E(21)ϪC(21)
E(22)ϪC(22)
K(11)ϪN(31)
K(12)ϪN(41)
N(11)ϪC(11)
N(21)ϪC(21)
K(11)ϪK(21)
1.864(5)
1.826(5)
1.858(5)
1.806(4)
2.944(4)
3.055(4)
1.291(2)
1.305(2)
3.967(5)
E2ЈϪK(11)
E3ЈϪK(21)
Angles/°
E(11)ϪC(11)ϪE(12)
E(21)ϪC(21)ϪE(22)
E(11)ϪK(11)ϪE(12)
E(12)ϪK(12)ϪE(21)
E(21)ϪK(11)ϪE(22)
E(21)ϪK(12)ϪE(22)
117.6(1)
118.0(1)
56.0(1)
55.4(1)
56.4(1)
55.7(1)
Torsion angles/°
N(11)ϪC(11)ϪE(11)ϪK(11)
N(11)ϪC(11)ϪE(12)ϪK(11)
N(11)ϪC(11)ϪE(21)ϪK(12)
N(11)ϪC(11)ϪE(22)ϪK(12)
E(11)ϪC(11)ϪN(11)ϪC(12)
E(12)ϪC(11)ϪN(11)ϪC(13)
155.2(1)
156.2(1)
155.2(1)
156.2(1)
14.0(7)
6.0(4)
˚
CϪE(12) (CϪS or CϪSe) bond distances (1.806Ϫ1.864 A)
in the carbamoselenothioate groups are significantly longer
˚
than common CϭS (1.61Ϫ1.63 A) in dithioesters [13] and
˚
the CϭSe double bonds (1.785(4)Ϫ1.792(7) A) in S-organyl
selenothioesters [14]. On the other hand, the CϪE(21) and
CϪE(22) bond lengths are longer than the C(sp2)-S single
bond (1.72Ϫ1.74 A) in dithioesters [13] or comparable with
Fig. 1 The ORTEP drawing of dimeric 3a·MeCN [E(11), E(12),
E(21), E(22) ϭ S or Se]. Hydrogen atoms are omitted for clarifica-
tion. Thermal ellipsoids are 20 % propability level.
˚
those of S-organyl selenothioesters [14] and the C(sp2)ϪSe
˚
single bonds [1.868(5) A] in Se-organyl selenoesters [15].
The CϪE(11) and CϪE(12) (CϪS or CϪSe) bond distances
˚
(1.806Ϫ1.864 A) are longer than those [1.757(9),
Table 2 Crystallographic data for dimeric of 3a·MeCN
˚
1.787(4) A] in ammonium carboselenothioate [11], indicat-
ing the contribution of a lone-pair electron on the nitrogen
atom, resulting in a partial CϪN double bond character. In
fact, the C(11)ϪN(11) and C(21)ϪN(21) distances of
empirical formula
formula weight
color
crystal system
unit-cell dimentions
C8H15K2N3S2Se2
454.46
yellow, prismatic
orthorhombic
˚
˚
˚
1.291(2) and 1.305(2) A, respectively, are substantially
a ϭ 13.041(3) A
˚
b ϭ 24.597(2) A
shorter than those [1.34 Ϫ1.36 (8) A] of alkali metal carba-
˚
c ϭ 12.795(2) A
˚
modithioates [1] and close to the sum (1.29 A) of the CϭN
3
˚
volume of unit cell /A
space group
4104(2)
Pbca (#61)
32
double bond radii [16]. These findings allowed us to con-
clude that among the canonical structures IϪIII in Scheme
5, III may be preferable due to electronic delocalization on
the N-CSSe group. The K(11)-E(11), K(11)-E(12), K(21)-
E(11) and K(21)-E(12) bond distances fall in the range of
Z value
Dcalc/(g/cm3)
6.553
crystal size/mm
7.14x4.85x3.42
301.48
23.1( 1)
0.71069
55.0°
5261
2010
81
µ(Mo-Kα/cmϪ1
temp/°C
˚
λ
MoKα/A
˚
˚
3.29Ϫ3.45 A which is comparable to that (3.25Ϫ3.45 A) of
the corresponding KϪS distances in K2(4-CH3C6H4CSS)2
[17]. The number of contacts between K and surrounding
atoms is 7 (one nitrogen from CH3CN and three sulfur and
selenium atoms, respectively, two sulfur and two selenium
atoms of which are in the same plane as the two facing
CSSe groups). The number of contacts for S and Se atoms
2θmax/deg
no. of measured reflections
no. of observations (I > 3σ(I))
no. of variables
b
residuals: Ra, Rw
0.0689; 0.0684
5.33
goodness of fit indicator
a R ϭ Σ(ΗFoΗϪΗFcΗ)/ΣΗFoΗ. b Rw ϭ [Σ(ΗFoΗϪΗFcΗ)2/ΣwΗFoΗ2]1/2, w ϭ [σ2(Fo)ϩ
p2(Fo)2/4]Ϫ1
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627

K. Kawai, K. Ibi, M. Ebihara, S. Kato
Fig. 2 (a) Unit cell of 3a·MeCN viewed down c-axis and (b) coor-
dination at potassium, and sulfur or selenium atoms [(E(11), E(12),
E(21), E(21), ElЈ, E2Ј, E3Ј, E4Ј ϭ S or Se)]. Hydrogen atoms are
omitted for clarify. Purple balls are potassium atom. Pink balls are
sulfur or selenium atom. Gray balls are carbon atom. Blue balls
are nitrogen atom.
Fig. 3 Arrangement of the potassium, ions in the crystals of
3a·MeCN. The solvated MeCN molecules and hydrogen atoms are
omitted for the clarification. (a) viewed down b-axis. (b) view down
a-axis.
Scheme 5
Reactions
With alkyl halides: We previously reported that the meth-
ylation of tetraalkylammonium carboselenothioates with
iodomethane occurred at both of their sulfur and selenium
atoms to give S- and Se-methyl carboselenothioates [11].
Compound 3a reacted with iodomethane at 0 °C to give the
expected S- 6a and Se-alkyl carbamoselenothioates 6b in
good yields (6a/6b ϭ 1 : 9) (Scheme 6).
Similarly, the sodium 2, rubidium 4 and cesium salts 5
gave the corresponding alkylated products at both the sul-
fur and selenium atoms in 70Ϫ90 % yields. The equimolar
reactions of 3a with phenacyl bromide or 2-chloroaceto-
phenone oxime exclusively gave the corresponding Se-sub-
is two and three, respectively. The E(11)ϪC(11)ϪE(12) and
E(21)ϪC(21)ϪE(22) angles are normal, 117.6 and 117.9°,
respectively. In contrast, the E(11)ϪK(11)ϪE(12) and
E(21)ϪK(11)ϪE(22) angles are relatively narrow 56.0 and
56.4°, respectively. In Figure 3, the arrangement of the pot-
assium atoms in the crystals of 3a is shown. It is noted that
the metal atoms are arranged tessellately where each four
metal cations form an irregular quadrilateral with angles
of 85Ϫ102° (44 tessellated 2D) [18] (Fig. 3a). Alkali metal
carbochalcogenoate and carbamochalcogenoate-arrange-
ments containing such cations have yet to be reported.
628
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Z. Anorg. Allg. Chem. 2007, 625Ϫ634

Alkali Metal and Trimethylsilyl Carbamoselenothioates
Scheme 7
Scheme 6
stituted esters 7 or 8 in quantitative yields, respectively.
These alkylations may occur at both atoms because heating
of a mixture of 6a and 6b (8 : 2) at 80 °C showed no change
in the ratio of these compounds [19]. More S-methylated
products are produced (10Ϫ30 %) than in the methylation
of tetraalkylammonium carboselenothioate (< 2 %) [11].
With trimethylsilyl chloride: In contrast to carbochalcog-
enoic acids, carbamochalcogenoic acids can not be isolated
because they are in rapid equilibrium with the starting com-
pounds such as amines, carbonylchalcogenide or carbon di-
chalcogenides. Previously, we found that O-triorganosilyl
carbochalcogenoates (RCEOSiRЈ3, E ϭ S, Se, Te), which
are readily obtained by reacting the corresponding alkali
metal carbochalcogenoates with triorganosilyl halides, act
as carbochalcogenoic acids [20]. In these reactions, O-trior-
ganosilyl carbochalcogenoates are formed via chalcogen-
substituted products (RCOESiMe3, E ϭ S, Se, Te) [21].
Similarly, alkali metal carbamo-thioates and -selenoates re-
acted with O-trimethylsilyl chloride to give the correspond-
ing O-silylated carbamochalcogenoates in good yields [9]. It
would be interesting to determine whether sodium 2 and
potassium carbamoselenothioates 3 react with trimethylsilyl
chloride to give both S- 9a and Se-trimethylsilyl carbamose-
lenoates 9b or only one of them. When 3a and excess tri-
methylsilyl chloride were stirred in hexane at 0 °C, the solu-
tion gradually changed from colorless to yellow. Filtration
of the resulting precipitates (KCl) and removal of the sol-
vent and excess trimethylsilyl chloride under reduced press-
ure gave pale yellow crystals with a melting point of
124Ϫ126 °C. The 1H-NMR spectrum of these crystals
showed broad signals near δ 0.5 and 2.8Ϫ3.1 (proton ra-
tio ϭ 9 : 12), which are attributable to SiCH3 and N-CH3
protons, respectively. (Scheme 7) In the 13C-NMR spectrum
at room temperature, two broad signals are observed in the
region of δ 180Ϫ195, where thio- or seleno-carbonyl carbon
signals appear. When these spectra were measured at a
lower temperature of Ϫ15 °C, the broad signals near δ 0.5
became markedly sharp at δ 0.54 and 0.94, which is attribu-
table to SSiCH3 and SeSiCH3 protons. (Fig. 4a) In the 13C-
Fig. 4 1H and 13C Variable temperature NMR spectra in CDCl3
for trimethylsilyl N,N-dimethylcarbamoselenothioate 9
NMR spectrum, the two broad signals at δ 180Ϫ195 be-
came sharp signals at δ 190.8 and 192.9, which can be attri-
buted to the CϭS and CϭSe carbons, respectively [22].
(Fig. 4b) When the temperature was allowed to rise to
65 °C, the two sharp signals at δ 0.54 and 0.94 due to
SeSiCH3 and SSiCH3 protons and the two sharp signals at
δ 190.8 and 192.9 due to the CϭS and CϭSe carbons
coalesced, respectively. These results clearly indicate that
tautomeric equilibrium exists between the thioxo- 9a and
selenoxo-forms 9b over Ϫ15 °C. This is the first example of
tautomeric equilibrium of organosilyl group between differ-
Z. Anorg. Allg. Chem. 2007, 625Ϫ634
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K. Kawai, K. Ibi, M. Ebihara, S. Kato
(629Ϫ670 ppm) of the Group-15 element-substitured carba-
moselenothioates 14Ϫ19 were observed at upfield region of
9Ϫ127 ppm than those of the corresponding Group-14 ele-
ment-substituted derivatives 10Ϫ13.
Experimental Section
General. The melting point was determined by a Yanagimoto
micromelting point apparatus and uncollected. The IR spectra were
1
measured on PERKIN-ELMER FT-IR 1640. The H-NMR spec-
tra were recorded on JEOL JNM-GX-270 (270 MHz) and JEOL
α-400 (100 MHz) with tetramethylsilane as an internal standard.
The 13C-NMR spectra were obtained from JEOL JNM-GX-270
(68 MHz) and JEOL αϪ400 (100 MHz). The 31P NMR spectra
were recorded on JEOL α-400 (162 MHz) with phosphoric acid as
external standard. The 77Se-NMR spectra were obtained from
JEOL α-400 (76 MHz) with dimethylselenide as an external stand-
ard. The 119Sn-NMR spectra were obtained from JEOL α-400
(149 MHz) with tetramethylstannane as an external standard. The
mass spectra were taken on Shimadzu Qp1000 (A) (EI/CI model)
and 9020DF (EI/CI model) high resolution mass spectrometer. The
high resolution mass spectroscopy (HRMS) was taken on a Shim-
adzu GCM 9020DF high resolution mass spectrometer. The High
Performance Liquid Chromatography (HPLC) was carried out by
Japan Analytical Industry Co. (column: JAIGEL 1H, 2H; eluent:
CHCl3). Elemental analyses were performed by the Elemental
Center of Kyoto University.
Scheme 8
Materials. Methanol, diethyl ether and hexane were refluxed with
sodium metal using benzophenone as indicator and distilled before
use. Acetonitrile and dichloromethene were distilled over phos-
phorus pentoxide. The following reagents were commercial grade
and used without further purification: selenium (powder), sodium
and potassium metals, methyl and ethyl iodides, phenacyl bromide,
and trichloroantimony (from Nacalai tesque Co. Kyoto), tri-
phenyltin chloride, dichlorophenylphosphine, triphenyllead bro-
mide, N,N-dimethylthiocarbamoyl and N,N-diethylthiocarbamoyl
chlorides (from Aldrich), and trichloro-arsenic and antimony (from
Wako Pure Chemical Industries Ltd. Osaka). Trimethylsilyl chlo-
ride is obtained from Shin-etsu Chemical Industry Ltd. and was
distilled before use. Diphenylarsenic chloride [25], phenylarsenic di-
chloride [26], diphenylantimony chloride and bromide [27, 28], and
2-Chloroacetophenone oxime [29] were prepared according to the
literatures.
ent chalcogen atoms [23] and in sharp contrast to the results
with the corresponding O-triorganosilyl carbamo-thioates
[9] and -selenoates [9] and carbochalcogenoates [20Ϫ22],
which show no tautomeric equilibrium between O- and E-
silylated esters (E ϭ chalcogen atoms).
With organo Group-14 and -15 element halides: The first
carbamoselenothioic acid main group derivatives were re-
ported in 1970 by Kametani and Tanaka, who isolated
Me2NCSSeSnClMe and Me2NCSSeSnMe2 from the reac-
tion of 1a with trimeric dimethyltin selenide [24]. To the
best of our knowledge, no other main group element deriva-
tives have been reported, most likely due to the difficulty of
their synthesis. Previously, we found that O-trimethylsilyl
carboselenoates react with organo Group-14 and -15 metal
halides to give exclusively the corresponding Se-substituted
carboselenoates [22b]. A series of selenocarbamic acid Se-
substituted organo Group-14 element esters were obtained
by using sodium [6], potassium [6] and O-trimethylsilyl car-
bamoselenoates [9]. As expected, the reactions of the pot-
assium salt 3a or the silylester 9 with triphenyl-ger-
manium, -tin, and -lead halides and with aryl-phosphoric, -
arsenic and -antimony halides proceeded readily at room
temperature to give the expected Se-substituted derivatives
10Ϫ19 in good yields, Scheme 8. Compounds 10Ϫ19 were
identified by elemental analyses and by the similarity of
X-Ray crystallography
All measurements were carried out on a Rigaku AFC7R dif-
fractometer with graphite monochromated Mo-Kα radiation (λ ϭ
˚
0.71069 A). The structure was solved and refined using the teXan
crystallographic software package on an IRIS Indigo computer. X-
Ray quality crystals of 3a were obtained by slow diffusion of hex-
ane into methanol solution containing a small amount of aceto-
nitrile. Used crystals were cut from the grown needles. In order to
avoid the decomposition of the sample, a crystal mounted on a
glass fiber was coated with an epoxy resin. The cell dimensions
were determined by least-squares refinement of diffractometer
angles for 25 automatically centered reflections. Three standard re-
flections were measured every 150 reflections and no decay was
detected. Lorentz and polarization corrections were applied to the
data and empirical absorption corrections (DIFABS) [30] were also
applied. The structure was solved by direct methods SIR88 [31]
1
their IR and H-, 13C- and 77Se-NMR spectra to those of
of the authentic samples prepared from 2 with the corre-
sponding organo Group 14 element halides. Their typical
spectral data are shown in Table 1. The 77Se-NMR signals
630
www.zaac.wiley-vch.de
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 625Ϫ634

Alkali Metal and Trimethylsilyl Carbamoselenothioates
CH3). Ϫ 13C-NMR (CD3OD): δ ϭ 44.1, 44.3 (CH3), 206.5 (CϭSSe). Ϫ
77Se-NMR (CD3OD): δ ϭ 505.7.
and expanded using DIRDIF 92 [32]. Scattering factors for neutral
atoms were from Cromer and Waber [33]. Anomalous dispersion
effects were included in Fcalc [34]; the values for ∆fЈ and ∆FЉ were
those of Creagh and McAuley [35]. The function minimized was
Σw(ΗFoΗ ϪΗFcΗ)2, and the weighting scheme employed was w ϭ
[σ2(Fo) ϩ σ2(Fo)2/4]Ϫ1. Full-matrix least-squares refinement was ex-
ecuted with non-hydrogen atoms anisotropic. The final least square
cycle included fixed hydrogen atoms at calculated positions of
which each isotropic thermal parameter was set to 1.2 times of that
of the connecting atom.
Potassium N,N-diethylcarbamoselenothioate (3b) (Method A). A
solution of N,N-diethylthiocarbamoyl chloride (1b) (3.713 g, 24.
48 mmol) in acetonitrile (20 ml) was added to a suspension of pot-
assium selenide (6.412 g, 40.80 mmol) in the same solvent (20 ml)
at 0 °C under argon atmosphere. The mixture was stirred at 0 °C
for 3 h (The color of the solution changed from yellow to red).
Filtration of the insoluble part (potassium chloride and excess of
potassium selenide) and removal of the solvent from the filtrate
under reduced pressure gave 3b as pale yellow oil. Yield: 4.129 g
(72 %).
Preparation of single crystals. Microcrystals of compound 3a (0.1 g)
were dissolved in degassed MeOH (4 ml) and hexane (1 ml) was
added slowly and allowed to stand in refrigerator (Ϫ17 °C) for
two weeks.
IR (neat) /cmϪ1: 2974, 2932, 2872, 2251, 2189, 1679, 1488, 1418, 1380, 1353,
1297, 1270, 1197, 1144, 1094, 1075, 1006, 959, 915, 880, 825, 778, 652, 564,
542. Ϫ 1H-NMR (CD3OD): δ ϭ 1.32 (b, CH3), 3.77 (b, CH3), 4.02 (b, CH2).
Ϫ
13C-NMR (CD3OD): δ ϭ 204.7 (CSSe). Ϫ 77Se-NMR (CD3OD): δ ϭ
583.8.
Syntheses of alkali metal carbamoselenothioates
Method B (from Me2NCSSeSiMe3 and KF). Potassium fluoride
(0.162 g, 2.79 mmol) was added to a solution of freshly prepared
trimethylsilyl N,N-dimethylcarbamoselenothioate (9) (0.840 g,
3.51 mmol) in dichloromethane (20 ml) at 25 °C under argon at-
mosphere. The mixture was stirred at 25 °C for 3 h. Filtration of
the resulting precipitates, followed by recrystallization from a
mixed solvent (6.5 ml) of acetonitrile/ether (3 : 1) at Ϫ25 °C, gave
3a as pale yellow crystals. Yield: 0.375 g (65 %).
(2؊5)
All manipulations of air-sensitive materials were performed under
a dry nitrogen atmosphere or an argon atmosphere. The prep-
aration of 2a, 3a, 3b, and 4a are described in detail as typical
procedures for potassium 3, rubidium 4 and cesium salts 5, respec-
tively. The compounds 2a, 3a, 3b, 4 and 5 were determined by
conversion into their methyl esters.
Rubidium N,N-dimethylcarbamoselenothioate (4). Rubidium fluor-
ide (0.408 g, 3.90 mmol) was added to a solution of freshly
prepared trimethylsilyl N,N-dimethylcarbamoselenothioate (9)
(1.560 g, 6.48 mmol) in dichloromethane (20 ml) at 25 °C under
argon atmosphere. The mixture was stirred at 25 °C for 3 h. Fil-
tration of the resulting precipitates, follwed by recrystallization
from a mixed solvent (6.5 ml) of acetonitrile/ether (3 : 1) at Ϫ25 °C,
Sodium N,N-dimethylcarbamoselenothioate (2a). A solution of N,N-
dimethylthiocarbamoyl chloride (1a) (3.948 g, 31.94 mmol) in
acetonitrile (20 mL) was added to a suspension of sodium selenide
(7.98 g, 65.87 mmol) in the same solvent (20 mL) at 0 °C under
argon atmosphere. The mixture was stirred at 0 °C for 3 h (the
color of the solution changed from yellow to orange). Filtration of
the insoluble part (sodium chloride and excess of sodium selenide)
and removal of the solvent from the filtrate under reduced pressure
gave 2a as pale yellow crystals. Yield: 5.103 g (84 %).
gave
4 as pale yellow crystals. Yield: 0.765 g (77 %). Mp
124Ϫ134 °C (dec).
IR (KBr) /cmϪ1: 1655, 1492, 1373, 1245, 1188, 1124, 1944, 943, 920, 851,
754. Ϫ 1H-NMR (CD3OD): δ ϭ 3.54 (s, CH3), 3.68 (s, CH3). Ϫ 13C-NMR
(CD3OD): δ ϭ 44.4 (CH3), 206.8 (CϭS). Ϫ 77Se-NMR (CD3OD): δ ϭ 575.7.
IR (KBr) /cmϪ1: 2919, 1630, 1493, 1364, 1244 1120, 1038, 971, 961, 937,
632, 521. Ϫ 1H-NMR (CD3OD): δ ϭ 3.24 (s, CH3), 3.28 (s, CH3). Ϫ 13C-
NMR (CD3OD): δ ϭ 44.3 (CH3), 45.1 (CH3), 207.0 (CSSe). Ϫ 77Se-NMR
(CD3OD): δ ϭ 99.9.
Cesium N,N-dimethylcarbamoselenothioate (5). Similarly to 4, the
reaction of 9 (0.600 g, 2.52 mmol) with cesium fluoride (0.339 g,
2.23 mmol), followed by recrystallization from a mixed solvent
(6.5 ml) of acetonitrile/ether (3 : 1) at Ϫ25 °C, gave 5 as pale yellow
crystals.Yield: 0.531 g (79 %). Mp: 151Ϫ153 °C (dec.).
IR (KBr) /cmϪ1: 2919, 2367, 1483, 1353, 1240, 1110, 935, 865. Ϫ 1H-NMR
(CD3OD): δ ϭ 3.53 (s, CH3), 3.67 (s, CH3). Ϫ 13C-NMR (CD3OD): δ ϭ
44.3, 207.0 (CϭS). Ϫ 77Se-NMR (CD3OD): δ ϭ 529.2.
Sodium N,N-diethylcarbamoselenothioate (2b). Similarly to 2a, the
reaction of N,N-diethylthiocarbamoyl chloride (1b) (4.909 g,
32.37 mmol) in acetonitrile (20 ml) with sodium selenide (7.98 g,
65.87 mmol) in the same solvent (20 ml) at 0 °C gave 2b as pale
yellow oil. Yield: 5.225 g (74 %).
IR (neat) /cmϪ1: 3358, 2935, 1460, 1417, 1377, 1353, 1266, 1196, 1136, 1093,
960, 894, 772, 538. Ϫ 1H-NMR (CD3OD): δ ϭ 1.31 (b, CH3), 3.77 (b, CH3),
4.02 (b, CH2). Ϫ 13C-NMR (CD3OD): δ ϭ 11.0, 12.0 (CH3), 48.2, 49.1
(CH2), 204.4 (CSSe). Ϫ 77Se-NMR (CD3OD): δ ϭ 582.4.
Reactions of compound 3a to leading to Group-14
and -15 elements derivatives
Potassium N,N-dimethylcarbamoselenothioate (3a) (Method A). A
solution of N,N-dimethylthiocarbamoyl chloride (1a) (3.027 g,
24.46 mmol) in acetonitrile (20 ml) was added to a suspension of
potassium selenide (5.517 g, 35.10 mmol) in the same solvent
(20 ml) at 0 °C under argon atmosphere. The mixture was stirred
at 0 °C for 3 h. Filtration of the insoluble part (potassium chloride
and excess of potassium selenide) and removal of the solvent from
the filtrate under reduced pressure gave 1.784 g of crude 3a as
orange crystals. Recrystallization from a mixed solvent (2.8 ml) of
metanol/ether (1.2 : 1) at Ϫ25 °C gave 3a as pale yellow crystals.
Yield: 3.858 g (76 %). Mp 155Ϫ168 °C (dec).
Methyl N,N-dimethylcarbamoselenothioate (6). Iodomethane (5 ml,
78.0 mmol) was added to potassium N,N-dimethylcarbamoseleno-
thioate (3a) (0.618 g, 3.00 mmol) at 0 °C under argon atmosphere.
The mixture was stirred at 0 °C for 3 h. Filtration of the insoluble
part (potassium iodide) and removal of excess of iodomethane from
the filtrate under reduced pressure gave a mixture of Se-methyl (6a)
and S-methyl N,N-dimethyl carbamoselenothioate 6b (6a/6b ϭ
7 : 1) as yellow solid; 0.468 g (86 %).
6a: IR (KBr) /cmϪ1: 2908, 1508, 1378, 1241, 1148, 1053, 968, 908, 862, 726.
Ϫ
13H-NMR (CDCl3): δ ϭ 2.75 (s, 3H, CH3Se); 3.40 ? (s, 3H, CH3N), 3.56
IR (KBr) /cmϪ1: 3447, 2920, 1654, 1604, 1480, 1437, 1397, 1359, 1246, 1124,
(s, 3H, CH3N). Ϫ 13C-NMR (CDCl3): δ ϭ 24.2 (s, CH3Se), 42.6, 49.4
(CH3N), 195.2 [C(ϭS)Se, JC-Se ϭ 136.5 Hz]. Ϫ 77Se-NMR (CDCl3): 486.4.
1043, 970, 943, 865, 552. Ϫ 1H-NMR (CD3OD): δ ϭ 3.53 (s, CH3), 3.68 (s,
Z. Anorg. Allg. Chem. 2007, 625Ϫ634
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
631

K. Kawai, K. Ibi, M. Ebihara, S. Kato
Ϫ HRMS m/z (EI, 20 eV) for C4H9SSe: 182.96187 (calcd. 182.96209); MS
(CIDI, 70 eV) m/z (%): 184 [Mϩ1] (2), 137 [(CH3)2NCSe], 89 [(CH3)2NCS].
IR (KBr) /cmϪ1: 3049, 3013, 1507, 1484, 1431, 1375, 1242, 1146, 1088, 998,
965, 854, 758, 695, 550, 475, 462. Ϫ 1H-NMR (CDCl3): δ ϭ 3.32 (s, 3H,
CH3), 3.45 (s, 3H, CH3), 7.37Ϫ7.74 (m, 15H, Ph). Ϫ 13C-NMR (CDCl3):
δ ϭ 44.0, 46.4 (CH3), 128.2, 128.5, 129.5, 130.1, 134.1, 135.5, 135.7 (Ph),
188.5 (CϭS). Ϫ 77Se-NMR (CDCl3): δ ϭ 529.0.
6b: IR (KBr) /cmϪ1: 2919, 1500, 1449, 1371, 1244, 1144, 1049, 962, 904, 852.
Ϫ
1H-NMR (CDCl3): δ ϭ 2.75 (s, 3H, CH3S); 3.37 (s, 3H, CH3N), 3.40 ? (s,
3H, CH3N). - 13C-NMR (CDCl3): δ ϭ 15.2 (CH3S), 42.8, 45.4 (CH3N),
200.5 [(CϭSe), JC-Se ϭ 230.1 Hz]. Ϫ 77Se-NMR (CDCl3): δ ϭ 539.7 (Cϭ
Se). Ϫ HRMS m/z (EI, 20 eV) for C4H9SSe: 182.96187 (calcd. 182.96209);
Ϫ MS (CIDI, 70 eV) m/z (%): 184 [Mϩ1] (3), 137 [(CH3)2NCSe], 89
[(CH3)2NCS].
Se-Triphenyltin N,N-dimethylcarbamoselenothioate (11). A solution
of triphenyltin chloride (0.309 g, 0.8 mmol) in dichloromethane
(15 ml) was added to a suspension of potassium N,N-dimethylcar-
bamoselenothioate (3a) (0.520 g, 2.5 mmol) in the same solvent
(15 ml) at 0 °C under argon atmosphere. The mixture was stirred
at 25 °C for 3 h. Filtration of the insoluble part (potassium chloride
and excess of 3a) and removal of the solvent from the filtrate under
reduced pressure gave crude Se-triphenyltin N,N-dimethylcarbamo-
selenothioate (11) (Yield: 0.410 g (99 %)). Recrystallization from a
mixed solvent (6.5 ml) of hexane/dichloromethane (3 : 1) at Ϫ25 °C
gave 11 as colorless crystals.Yield: 0.373 g (90 %). Mp 151Ϫ153 °C.
Se-Phenacyl N,N-dimethylcarbamoselenothioate (7). A solution of
phenacyl bromide (0.412 g, 2.07 mmol) in dichloromethane (10 ml)
was added to a suspension of potassium N,N-dimethylselenothi-
ocarbamate (3a) (0.412 g, 2.00 mmol) in the same solvent (20 ml)
at 0 °C under argon atmosphere. The mixture was stirred at 25 °C
for 3 h. Filtration of the insoluble part (potassium bromide) and
removal of the solvent from the filtrate under reduced pressure,
followed by recrystallization from a mixed solvent (5.0 ml) of hex-
ane/dichoromethane (1 : 4) at Ϫ25 °C gave 7a as pale yellow crys-
tals. Yield: 0.547 g (96 %). Mp 103Ϫ105 °C.
IR (KBr) /cmϪ1: 2966, 2919, 2837, 1684, 1593, 1507, 1448, 1375, 1268, 1197,
1149, 957, 850, 746, 686, 627, 534. Ϫ 1H-NMR (CDCl3): δ ϭ 3.30 (s, 3H,
CH3), 3.49 (s, 3H, CH3), 4.77 (s, JC-Se ϭ 13.4 Hz, 2H, CH2), 7.36Ϫ8.00 (m,
5H, Ph). Ϫ 13C-NMR (CDCl3): δ ϭ 42.7, 42.8 (CH3), 45.8 (CH2) 128.5,
128.6, 133.4, 133.8, 135.6 (Ph), 192.5 (CϭO), 194.7 (CϭS).
1
The IR and H- and 13C-NMR spectra of 11 were exactly consist-
ent with those of the authentic samples by the reaction of 2a or
trimethylsilyl ester 9 with triphenyltin chloride. C21H21NSSeSn
(517.11): C, 48.38 (calcd. 48.78), H, 4.04 (calcd. 4.09) %.
IR (KBr) /cmϪ1: 3059, 2367, 1577, 1518, 1480, 1429, 1406, 1382, 1331, 1242,
1151, 1071, 1020, 997, 959, 862, 732, 696, 548, 458. Ϫ 1H-NMR (CDCl3):
δ ϭ 3.28 (s, 3H, CH3), 3.45 (s, 3H, CH3), 7.31Ϫ7.84 (m, 15H, Ph). Ϫ 13C-
NMR (CDCl3): δ ϭ 44.0, 48.4 (CH3), 128.2, 128.5, 128.9, 129.1, 136.4, 136.7,
137.1, 141.1 (Ph), 189.6 (CϭS). Ϫ 77Se-NMR (CDCl3): δ ϭ 590.5; 119Sn-
NMR (CDCl3): δ ϭ Ϫ337.0 (JSn-Seϭ 779 Hz).
Se-(N,N-Dimethylcarbamoselenothioate)acetophenone oxime (8).
Similarly to 7, the reaction of 2-chloroacetophenone oxime
(0.445 g, 2.95 mmol) with 3a (0.515 g, 2.50 mmol), followed by
recrystallization from a mixed solvent (6.0 ml) of hexane/dichloro-
methane (1 : 2) at Ϫ25 °C, gave 8a as colorless crystals. Yield:
0.685 g (91 %). Mp 136Ϫ139 °C. C11H14N2OSSe (301.26): C, 43.65
(calcd. 43.86), H, 4.78 (calcld. 4.68) %.
IR (KBr) /cmϪ1: 3217, 3060, 2915, 2859, 1450, 1450, 1376, 1319, 1243, 1148,
1051, 960, 941, 850, 754, 701, 688, 658, 646, 550, 476. Ϫ 1H-NMR (CDCl3):
δ ϭ 3.32 (s, 3H, CH3), 3.54 (s, 3H, CH3), 4.71 (s, JH-Se ϭ 13.2 Hz), 7.36Ϫ7.78
(m, 5H, Ph), 9.76 (s, 1H, OH). Ϫ 13C-NMR (CDCl3): δ ϭ 42.7, 46.0 (CH3),
28.4 (CH2, JC-Se ϭ 66 Hz), 128.1, 128.5, 128.9, 129.1, 136.4, 136.7, 137.1,
141.1 (Ph), 156.4 (CN), 193.9 (CϭS).
Se-Diphenyltin bis(N,N-dimethylcarbamoselenothioate) (12). Simi-
larly to 11, the reaction of diphenyltin dichloride (0.688 g,
2.00 mmol) with 3a (0.825 g, 4.00 mmol), followed by recrystalliza-
tion the resulting from dichloromethane/hexane (1.1 : 1) at Ϫ17 °C,
gave 12 as slight yellow needles. Yield: 0.576 g (47 %). Ϫ Mp
205Ϫ208 °C. C22H22N2S2Se2Sn (607.11): C, 35.33 (calcd. 35.61), H,
3.63 (3.65) %.
IR (KBr) /cmϪ1: 3064, 3038, 2365, 1542, 1475, 1428, 1395, 1331, 1302, 1260,
1237, 1153, 1060, 1020, 996, 944, 873, 855, 802, 729, 695, 536. Ϫ 1H-NMR
(CDCl3): δ ϭ 33.28 (s, 3H, CH3), 3.31 (s, 3H, CH3), 7.40Ϫ8.14 (m, 15H,
Ph). Ϫ 13C-NMR (CDCl3): δ ϭ 344.6 (CH3), 48.9 (CH3), 128.1Ϫ141.3 (Ph),
191.1 (CϭS).
Trimethylsilyl N,N-dimethylcarbamoselenothioate (9). Trimethylsilyl
chloride (3.0 ml, 4.50 mmol) was added to a suspension of potass-
ium N,N-dimethylcarbamoselenothioate 3a (1.274 g, 6.18 mmol) in
hexane (20 ml) at 0 °C under argon atmosphere. The mixture was
stirred at 25 °C for 3 h (the color of the solution changed from
colorless to pale yellow). Filtration of the insoluble part (potassium
chloride) and removal of the solvent and excess of trimethylsilyl
chloride from the filtrate under reduced pressure gave a mixture of
9a, 9b as pale yellow crystals.Yield: 1.420 g (96 %). Mp
124Ϫ126 °C.
IR (KBr) /cmϪ1: 2964, 2369, 2345, 1522, 1508, 1458, 1389, 1361, 1262, 1094,
1020. 905, 867, 803, 905, 474. Ϫ 1H-NMR (CDCl3, at Ϫ15 °C): δ ϭ 0.54 (s,
CH3SiS), 0.94 (s, CH3SiSe), 2.78 [s, CH3NC(S)], 2.85 [s, CH3NC(Se)], 2.97
[s, CH3NC(S)], 3.09 [s, CH3NC(Se)]. Ϫ 13C-NMR (CDCl3, at Ϫ15 °C): δ ϭ
2.3 (CH3SiS), 2.7 (CH3SiSe), 44.7, 46.2 [CH3NC(S)], 43.9, 48.3
Se-Triphenyllead N,N-dimethylcarbamoselenothioate (13). Similarly
to 11, the reaction of triphenyllead chloride (0.474 g, 1.00 mmol)
with 3a (0.247 g, 1.20 mmol), followed by recrystallization from
hexane/dichloromethane (4 : 1) at Ϫ25 °C, gave 13 as pale yellow
crystals. Yield: 0.563 g (93 %). The IR and 1H-and 13C-NMR spec-
tra of 13 were exactly consistent with those of the authentic sample
prepared by the reaction of 9 with triphenyllead chloride. Mp
195Ϫ198 °C.
IR (KBr) /cmϪ1: 3059, 3042, 1568, 1507, 1474, 1430, 1403, 1375, 1327, 1242,
1187, 1147, 1059, 1014, 995, 954, 860, 722, 691, 549. Ϫ 1H-NMR (CDCl3):
δ ϭ 3.33 (s, 3H, CH3), 3.42 (s, 3H, CH3), 7.30Ϫ7.99 (m, 15H, Ph). Ϫ 13C-
NMR (CDCl3): δ ϭ 45.0, 48.4 (CH3), 128.8, 129.0, 129.7, 137.0, 156.1 (Ph),
191.3 (CϭS). Ϫ 77Se-NMR (CDCl3): δ ϭ 633.9.
[CH3NC(Se)], 190.8 (CϭS, JC-Se
226.1 Hz). Ϫ HRMS m/z (EI, 20 eV) calcd. for C6H15SSeSi: 240.98391
(calcd. 240.98589).
ϭ 131.2 Hz), 192.9 (CϭSe, JC-Se ϭ
Se-Diphenylphosphonic N,N-dimethylcarbamoselenothioate (14).
Similarly to 11, the reaction of diphenylphosphonic chloride
(0.352 g, 1.59 mmol) with 3a (0.329 g, 1.60 mmol) in the same sol-
vent (10 ml), followed by recrystallization from a mixed solvent
(4.0 ml) of hexane/dichloromethane (1 : 1) at Ϫ25 °C, gave 14 as
pale yellow needles.Yield: 0.364 g (65 %). Mp 125Ϫ127 °C. The IR
Se-Triphenylgermanium N,N-dimethylcarbamoselenothioate (10).
Similarly to 11, the reaction of triphenylgermyl bromide (0.500 g,
1.30 mmol) with 3a (0.309 g, 1.50 mmol), followed by recrystalliza-
tion from a mixed solvent (3.0 ml) of hexane/dichloromethane
(2 : 1) at Ϫ25 °C, gave 10 as colorless crystals.Yiled: 0.497 g (81 %).
Mp 137Ϫ145 °C. The IR and 1H-and 13C-NMR spectra of 10 were
exactly consistent with those of the authentic sample prepared by
the reaction of trimethylsilyl N,N-dimethylcarbamoselenothioate
(9) with triphenylgermanium chloride.
1
and H and 13C NMR spectra of 14 were exactly consistent with
those of the authentic samples by the reaction of trimethylsilyl ester
9 with diphenylphosphonic chloride. C15H16NPSSe (352.29): C,
51.24 (calcd. 51.14), H, 4.53 (4.58) %.
IR (KBr) /cmϪ1: 2966, 2925, 2362, 1560, 1499, 1428, 1397, 1367, 1262, 1238,
1139, 1091, 1066, 1024, 964, 852, 801, 741, 696, 508, 485. Ϫ 1H-NMR
632
www.zaac.wiley-vch.de
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 625Ϫ634

Alkali Metal and Trimethylsilyl Carbamoselenothioates
(CDCl3): δ ϭ 3.40 (s, 3H, CH3), 3.48 (s, 3H, CH3), 7.31Ϫ7.64 (m, 10H, Ph).
Ministry of Education, Science, Sports and Culture of Japan. We
thank Associate Prof. Mao Minoura of Kitasato University for
helpful advices with X-ray structure analysis and also Profs.
Hideharu Ishihara and Toshiaki Murai, and Dr. Takahiro Kanda of
Gifu University for the measuring of high resolution mass spectra.
Ϫ
13C-NMR (CDCl3): δ ϭ 44.7, 44.8 (CH3), 128.3, 128.4, 129.2, 133.4, 133.7
(Ph), 191.5 (CϭS). Ϫ 77Se-NMR (CDCl3): δ ϭ 655.7.
Se-Diphenylarsenic N,N-dimethylcarbamoselenothioate (15). Simi-
larly to 11, the reaction of diphenylarsenic chloride (0.264 g,
1.00 mmol) with 3a (0.229 g, 1.11 mmol), followed by recrystalliza-
tion from a mixed solvent (1.0 ml) of hexane/dichloromethane (4 :
1) at Ϫ25 °C, gave 15 as pale yellow crystals. Yield: 0.339 g (86 %).
Mp 125Ϫ127 °C. C15H16AsNSSe (396.24): C, 45.26 (calcd. 45.47),
H, 4.07 (4.07) %.
IR (KBr) /cmϪ1: 3064, 3044, 2368, 1479, 1577, 1505, 1478, 1429, 1366, 1268,
1236, 1137, 1064, 1021, 998, 962, 477, 457. Ϫ 1H-NMR (CDCl3): δ ϭ 3.43
(s, 3H, CH3), 3.48 (s, 3H, CH3), 7.34Ϫ7.61 (m, 10H, Ph). Ϫ 13C-NMR
(CDCl3): δ ϭ 44.8, 45.2 (CH3), 128.6, 133.6, 137.8 (Ph), 191.5 (CϭS). Ϫ
77Se-NMR (CDCl3): δ ϭ 670.4.
References
[1] U. Aava, A. Hess, Arkiv Kemi 1968, 30, 149; M. Colapietrom,
A. Domenico, A. Vaciago, J. Chem. Soc., Chem. Commun.
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D. Price, Z. Anorg. Allg. Chem. 2003, 629, 192.
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lurium, Special Periodical Report, 1Ϫ6, The Chemical Society,
London, 1970Ϫ1981; J. Willemse, J. A. Cras, J. J. Steggerda,
in: Structure and Bonding, J. D. Dunitz (eds.), Springer Verlag,
Heidelberg, 1976, pp. 83Ϫ126; J. A. Cras, J. Willemse, in: Com-
prehensive Coordination Chemistry, Vol. 2, G. Wilkinson, R. G.
Gillard, J. A. McClerverty (eds.), Pergamon Press, Oxford,
1987, pp. 579; G. Winter, Rev. Inorg. Chem. 1980, 2, 253; T. P.
Hanusa, in: Comprehensive Coordination Chemistry, Vol. 3, G.
F. R. Parkin (ed), Elsevier Pergamon, New York, 2004, pp. 1;
P. J. Heard, Prog. Inorg. Chem. 2005, 53, 1; G. Hogarth, Prog.
Inorg. Chem. 2005, 53, 71; E. R. T. Tiekink, I. Haiduc, Prog.
Inorg. Chem. 2005, 54, 127.
Se-Phenylarsenic bis(N,N-dimethylcarbamoselenothioate) (16).
Similarly to 11, the reaction of phenylarsenic dichloride (0.334 g,
1.50 mmol) with 3a (0.722 g, 3.50 mmol), followed by recrystalliza-
tion from a mixed solvent (23 ml) of hexane/dichloromethane (9 :
14) at Ϫ25 °C gave 16 as pale yellow crystals. Yield: 0.657 g (90 %).
Mp 125Ϫ127 °C. C6H17AsNS2Se2 (486.24): C, 29.36 (calcd. 29.64),
H, 3.72 (3.72) %.
IR (KBr) /cmϪ1: 3057, 2920, 1517, 1474, 1427, 1381, 1296, 1235, 1147, 1069,
1020, 990, 946, 854, 952, 687, 546, 459. Ϫ 1H-NMR (CDCl3): δ ϭ 3.43 (s,
6H, CH3), 3.46 (s, 6H, CH3), 7.34Ϫ7.61 (m, 5H, Ph). Ϫ 13C-NMR (CDCl3):
δ ϭ 44.8, 44.9 (CH3), 128.1, 128.8, 134.3 (Ph), 193.1 (CϭS). Se-NMR
(CDCl3): δ ϭ 624.8.
Se-Arsenic tris(N,N-dimethylcarbamoselenothioate) (17). Similarly
to 11, the reaction of trichloroarsenic (0.112 g, 0.62 mmol) with 3a
(0.425 g, 2.06 mmol), followed by recrystallization from a mixed
solvent (5.5 ml) of hexane/dichloromethane (3 : 8) at Ϫ25 °C gave
17 as pale yellow crystals. Yield: 0.337 g (95 %). Mp 224Ϫ228 °C.
C18H18AsNS2Se2 (576.24): C, 18.79 (calcd. 18.80), H, 3.23 (3.15) %.
IR (KBr) /cmϪ1: 2955, 2922, 2849, 1508, 1379, 1263, 1240, 1144, 1102, 1044,
951, 858, 801, 730, 695, 546). Ϫ 1H-NMR (CDCl3): δ ϭ 3.45 (s, CH3), 3.50
(s, CH3). Ϫ 13C-NMR (CDCl3): δ ϭ 44.0 (CH3), 195.7 (CϭS).
[3] L. Henriksen, Synthesis 1985, 204.
[4] S. Kato, O. Niyomura, Topics Curr. Chem. 2005, 251, 13.
[5] N. Kano, T. Kawashima, Topics Curr. Chem. 2005, 251, 141.
[6] S. Kato, T. Kawachi, K. Ibi, S. Nakaiida, K. Kawai, Het-
eroatom Chem. 1995, 6, 215.
[7] K. Ibi, T. Imase, S. Kato, F. Ando, J. Koketsu, submitted to
Z. Anorg. Allg. Chem. 2007, 633, 635.
[8] (a) Y. Kawahara, S. Kato, T. Kanda, T. Murai, H. Ishihara, J.
Chem. Soc., Chem.Commun. 1993, 277; (b) Y. Kawahara, S.
Kato, T. Kanda, T. Murai, Bull. Chem. Soc. Jpn. 1994, 67,
1881; (c) Y. Kawahara, S. Kato, T. Kanda, T. Murai, M. Ebih-
ara, Bull. Chem. Soc. Jpn. 1994, 68, 3507.
Se-Diphenylantimony N,N-dimethylcarbamoselenothioate (18).
Similarly to 11, the reaction of diphenylantimony chloride (0.538 g,
1.73 mmol) with 3a (0.428 g, 2.08 mmol), followed by recrystalliza-
tion from a mixed solvent (1.1 ml) of hexane/dichloromethane (8 :
3) at Ϫ25 °C, gave 18 as colorless crystals.Yiled: 0.538 g (70 %).
1
The IR and H- and 13C-NMR spectra of 18 were exactly consist-
ent with those of the authentic samples by the reaction of 2a or
trimethylsilyl ester
9 with diphenylantimony chloride. Mp
115Ϫ117 °C. C15H16NSSbSe (443.07): C, 0.55 (calcd. 40.66); H,
3.64 (3.67) %.
[9] M. Ibi, K. Kawai, S. Kato, F. Ando, J. Kouketsu, submitted
to Z. Anorg. Allg. Chem. 2007, 633, 621.
IR (KBr) /cmϪ1: 2371, 2346, 1508, 1428, 1370, 1232, 1136, 1059, 957, 728,
694, 458. Ϫ 1H-NMR (CDCl3): δ ϭ 43.43 (s, 6H, CH3), 7.30Ϫ7.67 (m, 10H,
Ph). Ϫ 13C-NMR (CDCl3): δ ϭ 45.0, 45.9 (CH3), 128.8, 136.1, 140.0 (Ph),
191.1 (CϭS). Ϫ 77Se-NMR (CDCl3): δ ϭ 4624.8.
[10] In Fig. 1, the occupancies of the sulfur atoms in E(11) and
E(12) are 52.5 and 47.5 %, respectively, whereas E(21) and
E(22) are 63.9 and 36.1 %, respectively, and the reverse results
are obtained for the selenium atoms.
[11] T. Murai, T. Kamoto, S. Kato, J. Am. Chem. Soc. 2000, 122,
9850.
[12] O. Niyomura, K. Sakai, T. Murai, S. Kato, S. Yamaguchi, K.
Tamao, Chem. Lett. 2001, 968.
Se-Antimony tris(N,N-dimethylselenothiocarbamate) (19). Similarly
to 11, the reaction of trichloroantimony (0.228 g, 1.00 mmol) with
3a (0.722 g, 3.50 mmol), followed by recrystallization from a mixed
solvent (23 ml) of hexane/dichoromethane (14 : 9) at Ϫ25 °C, gave
19 as yellow crystals. Yield: 0.580 g (93 %). Mp 205Ϫ207 °C.
C18H18NSSb2Se2 (623.07): C, 17.43 (calcd. 17.3), H, 3.09 (2.91) %.
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ˇ
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Adiwidjaja, J. Voss, J. Chem. Res. (S), 1977, 256.; (M) 1977,
2923.
IR (KBr) /cmϪ1: 2919, 2366, 1508, 1400, 1374, 1242, 1144, 945, 863, 732,
547. Ϫ 1H-NMR (CDCl3): δ ϭ 43.47 (s, CH3). Ϫ 13C-NMR (CDCl3): δ ϭ 4
44.0, 45.9 (CH3), 196.1 (CϭS).
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Fujii, T. Kanda, S. Kato, J. Am. Chem. Soc. 1997, 119, 8592.
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Acknowledgments. This research was supported partially by a
Grant-in-Aid for Scientific Research on Priority Areas from the
Z. Anorg. Allg. Chem. 2007, 625Ϫ634
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
633

K. Kawai, K. Ibi, M. Ebihara, S. Kato
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 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 625Ϫ634