M. Nanjo et al. / Journal of Organometallic Chemistry 672 (2003) 100Á
/108
105
Table 3
Reactions of tris(trimethylsilyl)germylzinc chloride (1a) with substrates
in diethyl ether
The solution was kept at ꢂ
/
20 8C. The colorless crystals
were filtered off, dried, and shown to be (Me3-
Si)3GeZnCl(thf) (1a) (0.88 g, 1.87 mmol) in 86% yield.
1H-NMR (C6D6) d 0.48 (s, 27H), 1.34Á
1.36 (m, 4H,
/
Substrate
Reaction conditions Products (yield/%)
THF), 3.60Á
3.62 (m, 4H, THF); 13C{1H}-NMR (C6D6)
/
d 4.7, 25.3 (THF), 68.8 (THF); 29Si{1H}-NMR (C6D6)
d 0.2.
H2O
HCl
r.t., 6 days
r.t., 2 h
(Me3Si)3GeH (43)
(Me3Si)3GeH (100)
no reaction
I2
Me3SiCl
r.t., 4 days
r.t., 4 days
(Me3Si)4Ge (17)
3.5. Preparation of tris(trimethylsilyl)germylzinc
bromide, (Me3Si)3GeZnBr (1b)
(Me3Si)3GeLi(thf)3 r.t., 2 h
(Me3Si)3SiLi(thf)3
[(Me3Si)3Ge]2Zn (100)
[(Me3Si)3Ge]2Zn (50)
[(Me3Si)3Si]2Zn (50)
[(Me3Si)3Ge]2Zn (50)
Me2Zn (50)
r.t., 2 h
MeLi
r.t., 2 h
ZnBr2 (4.05 g, 18.0 mmol) reacted with one molar
equivalent of (Me3Si)3GeLi(thf)3 (0.99 g, 1.92 mmol)
containing THF (10 ml) in Schlenk tube at r.t. for 3 h
under argon atmosphere. The solvent was taken off
under reduced pressure. The solid residue was washed
twice with pentane (10 ml). The organic layer was
filtered. The solvent was concentrated (3 ml), and then
PhMe2SiLi
PhMe2GeLi
r.t., 2 h
r.t., 2 h
[(Me3Si)3Ge]2Zn (50)
[(Me3Si)3Ge]2Zn (50)
8A with a 1-m 20% SE30 column. X-ray crystal-
lographic data and diffraction intensities were collected
on a MacScience DIP2030 diffractiometer utilizing
˚
kept at ꢂ20 8C. Colorless crystals separated, and these
/
graphite-monochromated MoÁ
/
Ka (lꢀ
/0.71073 A) ra-
were filtered off and judged probably to be (Me3-
Si)3GeZnBr(thf) (1b) (0.70 g, 1.37 mmol) in 71% yield.
diation. The structures were solved by direct methods
using the program system SIR-92. A refinement was
performed by a SILICON graphics O2 with MAXUS.
THF, diethyl ether, and other solvents were purified and
1H-NMR (C6D6) d 0.46 (s, 27H), 1.34Á
/
1.36 (m, 4H,
3.62 (m, 4H, THF); 13C{1H}-NMR (C6D6)
d 4.6, 25.3 (THF), 68.8 (THF); 29Si{1H}-NMR (C6D6)
d ꢂ1.0.
THF), 3.60Á
/
dried as reported in the literature.
/
3.2. Materials
3.6. Preparation of tris(trimethylsilyl)germylzinc iodide,
(Me3Si)3GeZnI (1c)
(Me3Si)3SiLi [5], (Me3Si)3GeLi [4], PhMe2GeLi [8],
PhMe2SiLi [8], (Me3Si)3GeH [4], (Me3Si)4Ge [4],
Ph3GeCl [9], and Ph3GeMe [10] were prepared as
reported in the literature. ZnCl2, ZnBr2, ZnI2, Me3SiCl,
and MeLi are commercially available.
ZnI2 (6.00 g, 18.8 mmol) reacted with one molar
equivalent of (Me3Si)3GeLi(thf)3 (1.00 g, 1.94 mmol)
containing THF (15 ml) in Schlenk tube at r.t. for 3 h
under argon atmosphere. The solvent was taken off
under reduced pressure. The solid residue was washed
twice with pentane (10 ml). The organic layer was
filtered. The concentration of the solvent under reduced
3.3. Structural studies
Germylzinc halides (1aÁ
/
c) and silylzinc chloride (2a,
pressure, and then kept at ꢂ20 8C. Colorless crystals
/
b) could be obtained in the form crystals suitable for X-
ray diffraction studies. A single crystal was sealed in a
capillary glass tube for the collection. Diffraction data
was collected at 200 K on a MacScience DIP2030 image
separated, and these were filtered off and judged to be
(Me3Si)3GeZnI(thf) (1c) (0.93 g, 1.67 mmol) in 86%
1
yield. H-NMR (C6D6) d 0.46 (s, 27H), 1.34Á
/
1.36 (m,
3.62 (m, 4H, THF); 13C{1H}-NMR
(C6D6) d 4.7, 25.3 (THF), 68.8 (THF).
4H, THF), 3.60Á
/
plate diffraction employing graphite-monochromated
˚
MoÁ
/
Ka radiation (lꢀ0.71073 A). Crystallographic
/
data for 1aÁ/c and 2a,b are listed in Table 4.
3.7. Preparation of tris(trimethylsilyl)silylzinc chloride,
(Me3Si)3SiZnCl (2a)
3.4. Preparation of tris(trimethylsilyl)germylzinc
chloride, (Me3Si)3GeZnCl (1a)
ZnCl2 (5.32 g, 39.0 mmol) reacted with one molar
equivalent of (Me3Si)3SiLi(thf)3 (1.64 g, 3.48 mmol)
containing THF (15 ml) in Schlenk tube at r.t. for 3 h
under argon atmosphere. The solvent was taken off
under reduced pressure. The solid residue was washed
twice with pentane (10 ml). The organic layer was
filtered. The solution was concentrated (3 ml), and
ZnCl2 (0.30 g, 2.17 mmol) reacted with one molar
equivalent of (Me3Si)3GeLi(thf)3 (1.12 g, 2.17 mmol)
containing diethyl ether (10 ml) in Schlenk tube at room
temperature (r.t.) for 1 day under argon atmosphere.
The concentration of the reaction mixture by removal of
diethyl ether followed by addition of pentane (10 ml).
The organic layer was filtered. After removal of solvent
under vacuum, pentane (3 ml) was added to the residue.
then kept at ꢂ20 8C. Crystals separated, and these
/
were filtered off. Colorless crystals flammable in air with
a composition of (Me3Si)3SiZnCl(thf) (2a) (1.19 g, 2.83
Nanjo, Masato
