O-triorganosilyl carbamoselenoates - Synthesis and reactions

Article abstract of DOI:10.1002/zaac.200600368

A series of O-triorganosilyl carbamoselenoates were isolated in good yields from the reaction of sodium or potassium carbamoselenoates with triorganosilyl chlorides. The O-silyl carbamoselenoates readily reacted with RbF and CsF and with organogermanium, -tin, and -lead halides and gave the corresponding heavy alkali metal and Se-substituted Group 14 organometal and carbamoselenoates in moderate to good yields.

Full text of DOI:10.1002/zaac.200600368

DOI: 10.1002/zaac.200600368
O-Triorganosilyl Carbamoselenoates ؊ Synthesis and Reactions
Kazumasa Ibia, Kohji Kawaia, Shinzi Katob,*, Fumio Andob, and Jugo Koketsub
a Gifu / Japan, Gifu University, Department of Chemistry, Faculty of Engineering
b Kasugai / Japan, Chubu University, Department of Applied Chemistry, School of Engineering
Received October 16th, 2006; revised December 6th, 2006.
Abstract. A series of O-triorganosilyl carbamoselenoates were
isolated in good yields from the reaction of sodium or potassium
carbamoselenoates with triorganosilyl chlorides. The O-silyl carba-
moselenoates readily reacted with RbF and CsF and with organo-
germanium, -tin, and -lead halides and gave the corresponding
heavy alkali metal and Se-substituted Group 14 organometal and
carbamoselenoates in moderate to good yields.
Keywords: Silyl carbamoselenoate; Rubidiun carbamoselenoate;
Cesium carbamoselenoate; Tin selenoeste; Lead carbamotelluroate
Introduction
synthesis of organo Group 14 metal and rubidium and ces-
ium carbamoselenoates.
There are 15 possible carbamochalcogenoic acids in which
one or two oxygen atoms of the R2NCOO group in car-
bamic acid are replaced by S, Se or Te atom (I, Scheme 1).
Similar to carbamic acids, these carbamochalcogenoic ac-
ids can not be isolated due to
Results and Discussion
Treatment of freshly prepared sodium or potassium carba-
moselenoates with an excess of trimethylsilyl chloride gave
the expected O-trimethylsilyl carbamoselenoates 3 in good
yields (Scheme 2). For example, when sodium 1a or potass-
ium
Scheme 1
an equilibrium between the acid and the starting the start-
ing compounds: amines and carbon chalcogenides. There-
fore, their alkali metal and ammonium salts have been used
for the synthesis of carbamochalcogenoic acid derivatives
such as thio- and dithiocarbamato transition metal com-
plexes [1]. Although these alkali metal and ammonium salts
are useful carbamochalcogenoating agents, most of them
are insoluble in common aprotic solvents such as ether and
benzene. Aprotic solvent-soluble carbamochalcogenoating
agents are needed. Previously, we have found that O-trior-
ganosilyl carboselenoates and carbotelluroates act as the
corresponding carbochalcogenoating agents in aprotic sol-
vents [2]. Moreover, we have established a method for the
preparation of a series of sodium and potassium carbamo-
selenoates [3]. We report here the synthesis of O-triorganos-
ilyl carbamoselenoates and some reactions leading to the
Scheme 2
N,N-dimethylcarbamoselenoates 2a and excess trimethyl-
silyl chloride (5 ml) were stirred at room temperature for
5 h, the reaction solution gradually changed from colorless
to pale yellow. Removal of the precipitates, solvent and ex-
cess Me3SiCl, and distillation of the resulting residue under
reduced pressure afforded O-trimethylsilyl N,N-dimethylca-
rbamoselenoate 3a in 78 % yield. Similarly the reactions of
sodium or potassium N,N-diethyl- 1b or N,N-diphenyl-car-
bamoselenoates 1c with trimethylsilyl and (t-butyl)dimeth-
* Prof. Dr. Shinzi Kato
Maruno-uchi 2-14-32, Lions-City Maruno-uchi 1105,
Naka-ku, Nagoya 460-0002 / Japan
Phone/Fax: 81-52-222-2442
E-mail: kshinzi@nifty.com
Z. Anorg. Allg. Chem. 2007, 633, 621Ϫ624
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
621

K. Ibi, K. Kawai, S. Kato, F. Ando, J. Koketsu
Table 2 The 13CϭO and 77Se Chemical shifts of alkali metal
N,N-dimethylcarbamoselenoates
ylsilyl halides led to the corresponding O-triorganosilyl car-
bamoselenoates 3bϪ3f in moderate to good yields.
The obtained O-silyl esters 3 are pale yellow liquid or
crystals and readily dissolve in hexane, ether and dichloro-
methane. They are thermally stable, but sensitive toward
oxygen and moisture. Upon exposure to air, they gradually
decomposed with the liberation of red selenium. Under
oxygen-free and dry conditions, however, they can be stored
in a refrigerator (Ϫ17 °C) for at least one month.
M(Me2COSe)
No.
δ, (in CD3OD)
Ref.
M
13CϭO
77Sea
1a
2a
Na
K
179.8
179.7
179.6
585.2
584.6
584.8
[3]
[3]
4
5
Rb
Cs
180.1
180.3
587.6
589.8
Table 1 shows the 13C and 77Se NMR spectra of 3. The
13C and 77Se signals of the R2NC(Se)O- group are observed
within relatively narrow ranges of 184Ϫ190 ppm and
741Ϫ886 ppm, respectively. (Table 1)
a Standard: Me2Se; shifts were determined relative to diphenyl diselenide and
related to Me2Se with δ (Ph2Se2) ϭ 464.1 ppm.
a downfield shift in the order of potassium, rubidium and
cesium salts.
Table 1 The 13C and 77Se chemical shifts of the NC(ϭSe)O group
in compounds 3
The O-silyl esters 3 also reacted with organo-ger-
manium, -tin, and -lead halides at room temperature to af-
ford the corresponding Se-substituted Group 14 metal car-
bamoselenoates 6؊8 in good yields. (Scheme 4) Com-
pounds 6؊8 would be formed via transition state A or B in
Figure 1, although no spectroscopic data to support this
conjecture are currently available.
compd
No.
δ, CDCL3
13CϭSe
77Seb
3a
3b
3c
3d
3e
3f
185.3
186.0
184.6
184.3
189.5
190.1
758.6
762.9
741.6
751.2
876.4
885.4
a Standard: Me2Se; shifts were determined relative to diphenyl diselenide and
related to Me2Se with δ (Ph2Se2) ϭ 464.1 ppm.
To the best of our knowledge, the synthesis of rubidium
and cesium carbamoselenoates has not yet been reported,
most likely due to the difficulty of preparing rubidium and
cesium amides. Previously, we found that O-trimethylsilyl
carboselenoates react with RbF and CsF at room tempera-
ture to afford the corresponding heavy alkali metal carbose-
lenoates in good yields [4]. Under similar conditions, treat-
ment of O-trimethylsilyl N,N-dimethylcarbamoselenoate 3a
with RbF and CsF gave the expected rubidium 4 and ces-
ium carbamoselenoates 5 in yields of 87 % and 93 %,
respectively. (Scheme 3)In the case of KF, potassium carba-
moselenoate 2a resulted in a low yield of 36 %. In addition,
the reactions with LiF and NaF did not occur even with a
prolonged reaction time.
Scheme 4
Scheme 3
The 13C and 77Se NMR spectra of the carbamoselenoate
group in alkali metal N,N-dimethylcarbamoselenoates are
shown in Table 2. The values are observed within narrow
ranges of δ 179Ϫ181 ppm and 584Ϫ590 ppm, respectively.
Metal cations appeared to have very little effect on the car-
bonyl carbon chemical shifts of alkali metal carbamose-
lenoates, while the 77Se NMR signal shows a tendency for
Fig. 1 Plausible transition states for the formation of Se-substi-
tuted Group 14 metal carbamoselenoates 6؊8.
622
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 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 621Ϫ624

O-Triorganosilyl Carbamoselenoates
dium N,N-diethylcarbamoselenoate 1b (1.777 g, 8.80 mmol) gave 3c
as yellow liquid. Yield: 1.621(73 %). B.p. 48Ϫ50 °C/0.35 torr.
IR (KBr) [neat / cmϪ1]: 2969, 2935, 1509, 1459, 1399, 1304, 1243, 1210, 1105,
900, 834, 645, 496. Ϫ 1H-NMR (CDCl3): δ ϭ 0.46 (s, 9H, CH3Si), 1.10 (t,
J ϭ 7.3 Hz, 3H, CH3C), 1.20 (t, J ϭ 7.3 Hz, 3H, CH3C), 3.39 (q, 3H,
CH2N), 3.84 (q, 3H, CH2N). Ϫ 13C-NMR (CDCl3): δ ϭ 0.88 (CH3Si), 11.8,
12.7 (CH3C), 43.4, 49.3 (CH2N), 184.4 (CϭSe). Ϫ 77Se-NMR (CDCl3): δ ϭ
741.6. Ϫ MS (CIDI, 70 eV), m/z (rel. intensity, %) 267 [Mϩ ϩ1] (2.0), 164
Experimental Section
The melting points were measured by a Yanagido micromelting
point apparatus and uncorrected. The IR spectra were measured
on a PERKIN ELMER FT-IR 1640. The H NMR spectra were
1
recorded on a JEOL JMN-GX 270 (270 MHz) with tetramethylsil-
ane as an internal standard. The 13C NMR spectra were obtained
from a JEOL JMN-GX 270 (67.9 MHz). The 77Se NMR spectra
were obtained from a JEOL JMN-GX 270 (51.5 MHz) with di-
methyl selenide as an external standard. The 119Sn NMR spectra
were obtained from a JEOL a-400 (149 MHz) with tetramethyltin
as an external standard. The mass spectra were recorded on
Shimadzu GCMS QP1000 (A) (EI/CI, model). The high resolution
mass spectroscopy (HRMS) was taken on Shimadzu GCMS
9020DF high resolution mass spectrometer. Elemental analyses
were done at the Elemental Analyses Center of Kyoto University.
[Et2NCSe] (39.2), 100 [Et2NCO] (100).
Ϫ HRMS (20 eV) calcd for
C9H21NOSeSi: m/z 253.36398 (calcd. 253.04002).
O-(t-Butyl)dimethylsilyl N,N-diethylcarbamoselenoate (3d). The re-
action of (t-butyl)dimethylsilyl chloride (0.920 g, 9.0 mmol) with
sodium N,N-diethylcarbamoselenoate 1b (1.480 g, 7.33 mmol) in
dichloromethane (20 ml) at 20 °C for 14 h gave 3d as pale yellow
liquid. Yield: 1.716 (80 %). B.p. 119Ϫ121 °C/0.22 torr. C11H25NO-
SeSi (295.09): C, 44.88 (calcd. 44.68), H, 8.56 (8.70) %.
IR (KBr) [neat / cmϪ1]: 975, 2931, 2872, 1485, 1399, 1306, 1240, 1209, 1096,
941, 834, 784, 647, 498. Ϫ 1H-NMR (CDCl3): δ ϭ 0.32 (s, 6H, CH3Si), 0.73
(t, 9H, [(CH3)3CSi]), 0.96 (t, 3H, CH3C), 1.04 (t, 3H, CH3C), 3.28 (q, 2H,
CH2N), 3.40 (q, 2H, CH2N). Ϫ 13C-NMR (CDCl3): δ ϭ Ϫ4.04 (CH3Si),
11.4, 12.5 (CH3CH2N), 17.4 [C(CH3)3], 25.2 [C(CH3)3], 42.6, 48.8
(CH3CH2N), 184.3 (CϭSe). Ϫ 77Se-NMR (CDCl3): δ ϭ 751.2. MS (EI,
20 eV): m/z (rel. intensity, %) 295 [Mϩ] (52.1), 238 [Mϩ-(t-Bu)] (100), 100
Materials: Sodium and potassium carbamoselenoates were pre-
pared according to the method described previously [3]. Carbamoyl
chlorides, potassium, rubidium and cesium fluorides, and trimeth-
ylsilyl and (t-butyl)dimethylsilyl chlorides are purchased from
Nacarai tesque (Kyoto, Japan). Triphenylgermanium, triphenyltin
and triphenyllead chlorides were obtained from Alfa Products and
used without further purification. Diphenyltin dichloride was pre-
pared according to literature [5]. Dichloromethane and acetonitrile
were distilled from phosphorus pentaoxide and degassed prior to
use. Ether and hexane were distilled from sodium metal prior use
and degassed. All manipulations were carried out under argon.
[Et2NCO]ϩ (88.7).
Ϫ HRMS (20 eV) calcd for C11H25NOSeSi: m/z
295.08903 (calcd. 295.08694).
O-Trimethylsilyl N,N-diphenylcarbamoselenoate (3e). Similarly to
3a, the reaction of trimethylsilyl chloride (1.85 ml, 14.4 mmol) with
sodium N,N-diphenylcarbamoselenoate 1c (0.860 g, 0.96 mmol),
followed by dichloromethane/hexane (1:8), gave 3c as pale yellow
crystals. Yield: 1.763 (53 %). M.p. 45Ϫ48 °C (dec).
IR (KBr) /cmϪ1: 3050, 2980, 2881, 2840, 1591, 1516, 1493, 1314, 1250, 1135,
950, 870, 795, 690, 601, 506. Ϫ 1H-NMR (CDCl3): δ ϭ 0.37 (s, 9H, CH3Si),
7.2Ϫ7.4 (m, 10H, arom). Ϫ 13C-NMR (CDCl3): δ ϭ 0.67 (CH3Si), 126.2,
127.8, 129.3, 143.2 (arom), δ 189.5 (CϭSe). Ϫ 77Se-NMR (CDCl3): δ ϭ
876.4. Ϫ MS (CI, 70 eV): m/z (rel. intensity, %) 350 [Mϩ ϩ1] (67.0), 170
[Ph2NH] (100), 100 [Ph2N] (57). Ϫ HRMS (20 eV) calcd. for C10H19NOSeSi:
m/z 391.08847 (calcd. 391.08694).
O-Triorganosilyl carbamoselenoates (3)
The preparation of O-trimethylsilyl N,N-dimethylcarbamoseleno-
ate 3a is described in detail as typical procedures:
O-Trimethylsilyl N,N-dimethylcarbamoselenoate (3a). Trimethylsilyl
chloride (1.19 ml, 9.40 mmol) was added to a solution of sodium
N,N-dimethylcarbamoselenoate 1a (1.363 g, 7.84 mmol) in aceto-
nitrile (10 ml) and the mixture was stirred at 20 °C for 14 h. Sodium
chloride was filtered out and the solvent and excess of trimethylsilyl
chloride were removed under reduced pressure (0.3 torr). Vacuum
distillation of the resulting residue gave 3a as pale yellow liquid.
Yield: 2.740 g (78 %). B.p. 78Ϫ81 °C/0.7 torr.
IR (KBr) [neat / cmϪ1]: 2972, 2881, 2840, 1574, 1044, 1018, 933, 773, 659,
613, 500. Ϫ 1H-NMR (CDCl3): δ ϭ 0.40 (s, 9H, CH3Si), 3.03 (s, 3H, CH3N),
3.37 (s, 3H, CH3N). Ϫ 13C-NMR (CDCl3): δ ϭ 0.62 (CH3Si), 37.7, 44.2
(CH3N), δ 185.3 (CϭSe). Ϫ 77Se-NMR (CDCl3): δ ϭ 758.6. Ϫ MS (CIDI,
70 eV), m/z (rel. intensity, %): 225 [Mϩ ϩ1] (100), 136 [Me2NCSe] (9.8). Ϫ
HRMS (20 eV) calcd for C6H15NOSeSi: m/z 225.00702 (calcd. 225.00874).
O-Dimethyl-t-butylsilyl N,N-diphenylcarbamoselenoate (3f). Simi-
larly to 3d, the reaction of dimethyl-t-butylsilyl chloride (0.990 g,
6.58 mmol) with sodium N,N-diphenylcarbamoselenoate 1c
(1.650 g, 5.54 mmol), followed by dichloromethane/hexane (1:8),
gave 3f as pale yellow crystals. Yield: 0.525 (24 %). M.p.
52Ϫ54 °C (dec).
IR (KBr) /cmϪ1: 3050, 2972, 2940, 1564, 1502, 1394, 1302, 1284, 1149, 998,
826, 689, 622, 503. Ϫ 1H-NMR (CDCl3): δ ϭ 0.22 (s, 6H, CH3Si), 0.72 [t,
9H, (CH3)3CSi], 7.0Ϫ7.5 (m, 10H, arom). Ϫ 13C-NMR (CDCl3): δ ϭ Ϫ3.89
(CH3Si), 18.1 [SiC(CH3)3], 25.1 [C(CH3)3], 117.8, 126.8, 127.9, 129.4 (Ar),
190.1 (CϭSe). Ϫ 77Se-NMR (CDCl3): δ ϭ 885.6. Ϫ MS (EI, 20 eV): m/z
(rel. intensity, %) 390 [Mϩ] (33.8), 334 [Mϩ-(t-Bu)] (100), 196 [Ph2NCO]ϩ
(99.2). Ϫ HRMS (20 eV) calcd for C10H19NOSeSi: m/z 349.03945 (calcd.
349.04002).
O-Dimethyl-t-butylsilyl N,N-dimethylcarbamoselenoate (3b). Simi-
larly to 3a, the reaction of dimethyl-t-butylsilyl chloride (0.806 g,
5.36 mmol) with sodium N,N-dimethylcarbamoselenoate 1a
(0.741 g, 3.66 mmol) gave 3b as pale yellow liquid. Yield: 0.580
(60 %). B.p. 130Ϫ131 °C/0.35 torr.
IR (KBr) [neat / cmϪ1]: 2940, 2870, 1255, 1089, 867, 835, 773, 668, 496. Ϫ
1H-NMR (CDCl3): δ ϭ 0.50 (s, 6H, CH3Si), 0.91 [t, 9H, (CH3)3CSi], 3.07 (s,
3H, CH3N), 3.40 (s, 3H, CH3N). Ϫ 13C-NMR (CDCl3): δ ϭ Ϫ3.73 (CH3Si),
18.1 [C(CH3)3], 25.6 [C(CH3)3], 38.2 (CH3N), δ 186.0 (CϭSe). Ϫ 77Se-NMR
(CDCl3): δ ϭ 762.9. Ϫ MS (EI, 20 eV): m/z (rel. intensity, %): 267 [Mϩ]
(18.2), 210 [Mϩ-t-Bu] (100). Ϫ HRMS (20 eV) calcd for C9H21NOSeSi: m/z
267.05707 (267.05566).
Potassium N,N-dimethylcarbamoselenoate (2a). Similarly to 4, the
reaction of 3a (1.386 g, 6.16 mmol) with potassium fluoride
(0.965 g, 6.35 mmol) gave 2a as white micro crystals. Yield: 1.62 g
(36 % as 2a). M.p. 90Ϫ96 °C (dec.).
IR (KBr) /cmϪ1: 2926, 2185, 1653, 1534, 1421, 1400, 1357, 1257, 1100, 904,
678. Ϫ 1H-NMR (CDCl3): δ 2.92 (s, CH3), 3.27 (s, CH3). Ϫ 13C-NMR
(CDCl3): δ ϭ 38.4 (CH3), 43.8 (CH3), 179.7 (CϭO). Ϫ 77Se-NMR (CDCl3):
δ ϭ 584.6.
Rubidium N,N-dimethylcarbamoselenoate (4). Rubidium fluoride
(0.5.99 g, 5.75 mmol) was added to a solution of freshly prepared
O-trimethylsilyl N,N-dimethylcarbamoselenoate 3a (1.274 g,
5.66 mmol) in acetonitrile (15 ml) at 0 °C and the mixture was
stirred at this temperature for 1 h (the color changed from orange
O-Trimethylsilyl N,N-diethylcarbamoselenoate (3c). Similarly to 3a,
the reaction of trimethylsilyl chloride (1.57 ml, 13.2 mmol) with so-
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623

K. Ibi, K. Kawai, S. Kato, F. Ando, J. Koketsu
to yellow). The excess of RbF was filtered out and removed the
solvent under reduced pressure. The resulting residue was washed
with ether (2 x 5 ml) and then petro-ether (bp: <45 °C, 5 ml) gave
hexane (3:1) gave 7b as colorless needles. Yield: 0.796 g, (91 %).
M.p. 143Ϫ145 °C. The IR and 1H NMR spectra were consistent
with those of the authentic sample prepared by the reaction of
potassium N,N-dimethylcarbamoselenoate with diphenyltin di-
chloride.
4
as white micro crystals. Yield: 1.16 g (87 % as 4). M.p.
105Ϫ106 °C (dec.).
IR (KBr) /cmϪ1: 3050, 2980, 1600, 1560, 1470, 1430, 1360, 1250, 1100, 990,
980, 740, 695, 625, 440 cmϪ1. Ϫ 1H-NMR (CDCl3): δ ϭ 2.85 (s, 3H, CH3),
3.09 (s, 3H, CH3), 7.3Ϫ7.9 (m, 10H, arom). Ϫ 13C-NMR (CDCl3): δ ϭ 36.1
(CH3), 42.3 (CH3), 128.5, 129.5, 135.7, 140.9 (arom), 166.2 (CϭO). Ϫ 77Se-
NMR (CDCl3): δ ϭ 744.3 (745.2) [3].
IR (KBr) /cmϪ1: 2926, 2187, 1655, 1535, 1420, 1400, 1358, 1257, 1100, 902,
678. Ϫ 1H-NMR (CDCl3): δ ϭ 2.94 (s, CH3), 3.30 (s, CH3). Ϫ 13C-NMR
(CDCl3): δ ϭ 38.4 (CH3), 43.7 (CH3), 180.1 (CϭO). Ϫ 77Se-NMR (CDCl3):
δ ϭ 587.6.
Cesium N,N-dimethylcarbamoselenoate (5). Similarly to 4, the reac-
tion of 3a (1.386 g, 6.16 mmol) with cesium fluoride (0.965 g,
6.35 mmol) gave 5 as white micro crystals. Yield: 1.62 g (93 % as
5). M.p. 118Ϫ126 °C (dec.).
IR (KBr) /cmϪ1: 2928, 2185, 1653, 1533, 1420, 1400, 1355, 1247, 1100, 900,
675. Ϫ 1H-NMR (CDCl3): δ ϭ 2.92 (s, CH3), 3.27 (s, CH3). Ϫ 13C-NMR
(CDCl3): δ ϭ 37.4 (CH3), 43.8 (CH3), 180.3 (CϭO). Ϫ 77Se-NMR (CDCl3):
δ ϭ 589.8.
Se-Triphenyllead N,N-dimethylcarbamoselenoate (8). Triphenyllead
chloride (1.939 ml, 4.17 mmol) was added to a solution of O-tri-
methylsilyl N,N-dimethylcarbamoselenoate 3a (0.939 g, 4.17 mmol)
in hexane (10 ml). The mixture was stirred at 20 °C for 2 h. Fil-
tration of the resulting precipitates, followed by recrystallization
from a mixed solvent of ether and hexane (3:1) gave 8. Yield:
2.077 g (84 %). M.p. 110Ϫ112 °C.
IR (KBr) /cmϪ1: 3057, 2957, 1625, 1471, 1430, 1354, 1253, 1093, 993, 797,
728, 695. Ϫ 1H-NMR (CDCl3): δ ϭ 2.86 (s, 3H, CH3), 3.08 (s, 3H, CH3),
7.2Ϫ7.9 (m, 15H, arom). Ϫ 13C-NMR (CDCl3): δ ϭ 36.3 (CH3), 42.4 (CH3),
128.6, 129.7, 137.7, 153.9 (arom), 163.2 (CϭO). Ϫ 77Se-NMR (CDCl3): δ ϭ
757.1 (758.6) [3].
The preparation of 6b, 7a and 8 are described in detail as typical
procedures. The IR of 6؊8 were exactly consistent with those of
authentic samples, respectively [3].
Se-Trimethylgermanium N,N-dimethylcarbamoselenoate (6a). Simi-
larly to 6b, the reaction of 3a (0.474 g, 2.12 mmol) with trimeth-
ylgermanium chloride (0.310 ml, 2.12 mmol) gave 6a as colorless
liquid. Yield: 0.469 g (83 %). B.p. 74Ϫ75 °C/0.65 torr.
IR (neat, KBr) /cmϪ1: 2908, 1647, 1438, 1403, 1359, 1257, 1093, 897, 832,
760, 673, 609, 568. Ϫ 1H-NMR (CDCl3): δ ϭ 0.71 (s, 9H, GeCH3), 2.97 (s,
3H, NCH3), 3.11 (s, 3H, NCH3). Ϫ 13C-NMR (CDCl3): δ 2.4 (GeCH3), 35.8
(CH3), 39.8(CH3), 163.3 (CϭO). Ϫ 77Se-NMR (CDCl3): δ ϭ 702.3 (703.5)
[3].
Acknowledgments. This work was supported by the Grant-in-Aids
for Scientific Research (B) and on Priority Areas provided by the
Ministry of Education, Science, Sport and Culture, Japan. We thank
Professor Hideharu Ishihara and Dr. Takahiro Kanda for measure-
ment of HRMS.
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Se-Triphenylgermanium N,N-dimethylcarbamoselenoate (6b). Tri-
phenylgermanium chloride (0.673 ml, 2.00 mmol) was added to a
yellow solution of O-trimethylsilyl N,N-dimethylcarbamoselenoate
3a (0.448 g, 2.0 mmol) in dichloromethane (10 ml). The mixture
was stirred at 20 °C for 5 h. Filtration of black precipitates and
evaporation of the filtrate under reduced pressure followed by
recrystallization from a mixed solvent of dichloromethane/hexane
(1:2) gave 6b as colorless needles. Yield: 0.748 g (82 %). M.p.
128Ϫ131 °C.
IR (neat, KBr) /cmϪ1: 3100, 3050, 2980, 1647, 1492, 1430, 1252, 1089, 894,
737, 697. Ϫ 1H-NMR (CDCl3): δ ϭ 2.81 (s, 3H, NCH3), 3.08 (s, 3H, NCH3),
7.3Ϫ7.7 (m, 15H, arom). Ϫ 13C-NMR (CDCl3): δ ϭ 36.4 (GeCH3), 40.6
(CH3), 128.4, 128.6, 129.5, 134.9 (arom), 161.5 (CϭO). Ϫ 77Se-NMR
(CDCl3): δ ϭ 711.6 (712.4) [3].
[2] H. Ishihara, S. Kato, Tetrahedron Lett. 1972, 3751Ϫ3753; S.
Kato, H. Kageyama, Y. Kawahara, T. Murai, H. Ishihara,
Chem. Ber. 1992, 125, 417Ϫ422.
[3] S. Kato, T. Kawachi, K. Ibi, S. Nakaiida, K. Kawai, T. Kanda,
T. Murai, H. Ishihara, Heteroatom. Chem. 1995, 215Ϫ221.
[4] Y. Kawahara, S. Kato, T. Kanda, T. Murai, H. Ishihara, J.
Chem. Soc., Chem.Commun. 1993, 277Ϫ278; Y. Kawahara, S.
Kato, T. Kanda, T. Murai, Bull. Chem. Soc. Jpn. 1994,
1881Ϫ1885.
[5] R. Lieber, F. M. Feace, Inorg. Synth. 1966, 8, 57.
[6] S. Kato, O. Niyomura, Topics Curr. Chem. 2005, 251, 13Ϫ85;
N. Kano, T. Kawashima, Topics Curr. Chem. 2005, 251,
141Ϫ180.
[7] B. J. McCormick, R. Bereman, D. Baird, D. Coord. Chem.
Rev. 1984, 54, 99Ϫ130; H. G. Gysling, in: The Chemistry of
Organic Selenium and Tellurium Compounds, Vol. 1, S. Patai
and Z. Rappoport (eds), John Wiley Sons Interscience, 1986,
pp 679Ϫ855; L. Henriksen, in: The Chemistry of Organic Sel-
enium and Tellurium Compounds, Vol. 2, S. Patai (ed), John
Wiley Sons Interscience, New York, 1987, pp 393Ϫ420.
Se-Triphenyltin N,N-dimethylcarbamoselenoate (7a). Triphenyltin
chloride (1.193 ml, 3.09 mmol) was added to a solution of O-tri-
methylsilyl N,N-dimethylcarbamoselenoate 3a (0.693 g, 3.09 mmol)
in dichloromethane (10 ml). The mixture was stirred at 20 °C for
5 h. Filtration of the resulting precipitates and recrystallization
from a mixed solvent of ether and hexane (3: 1) yielded 7a as color-
less needles. Yield: 0.7960 g (88 %). M.p. 112Ϫ114 °C.
IR (KBr) /cmϪ1: 3082, 1628, 1480, 1425, 1360, 1250, 1100, 1075, 990, 730,
695, 450. Ϫ 1H-NMR (CDCl3): δ ϭ 2.79 (s, 3H, CH3), 3.03 (s, 3H, CH3),
7.3Ϫ7.7 (m, 15H, arom). Ϫ 13C-NMR (CDCl3): δ ϭ 36.2 (CH3), 42.2 (CH3),
128.6, 129.6, 136.5, 139.9 (arom), 163.5 (CϭO). Ϫ 77Se-NMR (CDCl3): δ ϭ
725.8 (726.5) [3]. Ϫ 119Sn-NMR (CDCl3): δ ϭ Ϫ272 (JSn-Se ϭ 857 Hz).
Se-Diphenyltin bis(N,N-dimethylcarbamoselenoate) (7b). Similarly
to 6a, the reaction of O-trimethylsilyl N,N-dimethylcarbamoseleno-
ate 7a (0.683 g, 3.05 mmol) and diphenyltin dichloride (0.518 g,
1.53 mmol) followed by recrystallization from dichloromethane/
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