Synthesis and structures of a series of Ge-M (M=C, Si, and Sn) compounds derived from germyllithium containing three 2-(dimethylamino)phenyl groups on germanium

Article abstract of DOI:10.1016/S0022-328X(99)00386-1

Reactions of {tris[2-(dimethylamino)phenyl]germyl}lithium (1) with Group 14 electrophiles afford the corresponding carbogermane, silylgermane, and stannylgermane compounds containing three 2-(dimethylamino)phenyl groups on the germanium atom. X-ray structure analysis of these structures was performed and revealed that: (1) the steric repulsion between the amino groups and the substituents is mainly reflected by the torsion angle M-Ge-C_ipso-C_ortho; (2) the N...M atomic distances are within the sum of the van der Waals radii; (3) in a series of the silylgermanes, the Ge-Si bond lenght increases as the size of the silyl group increases: -SiH3<=SiMe2H<=SiMe3<=SiMe2-t-Bu.

Full text of DOI:10.1016/S0022-328X(99)00386-1

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 590 (1999) 15–24
Synthesis and structures of a series of GeꢀM (M=C, Si, and Sn)
compounds derived from germyllithium containing three
2-(dimethylamino)phenyl groups on germanium
Atsushi Kawachi, Yoko Tanaka, Kohei Tamao *
Institute for Chemical Research, Kyoto Uni6ersity, Uji, Kyoto 611-0011, Japan
Received 29 December 1998
Abstract
Reactions of {tris[2-(dimethylamino)phenyl]germyl}lithium (1) with Group 14 electrophiles afford the corresponding carboger-
mane, silylgermane, and stannylgermane compounds containing three 2-(dimethylamino)phenyl groups on the germanium atom.
X-ray structure analysis of these structures was performed and revealed that: (1) the steric repulsion between the amino groups
and the substituents is mainly reflected by the torsion angle MꢀGeꢀCipsoꢀCortho; (2) the N···M atomic distances are within the sum
of the van der Waals radii; (3) in a series of the silylgermanes, the GeꢀSi bond length increases as the size of the silyl group
increases: ꢀSiH35SiMe2H5SiMe35SiMe2t-Bu. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: 2-(Dimethylamino)phenyl group; Germyllithium; Silane; Germane; Stannane; Crystal structure
2. Results and discussion
1. Introduction
2.1. Preparations
Recently, we have reported on the preparation and
structure of {tris[2-(dimethylamino)phenyl]germyl}-
lithium (1) [1a]; the 2-(dimethylamino)phenyl group
functioning as the nitrogen donor induces a large
distortion of the geometry around the germanium
atom. The germyllithium 1 can be an ideal agent
[2,3] for constructing the germanium Group 14 element
linkage with the {tris[2-(dimethylamino)phenyl]-
germyl moiety, which is expected to be a novel tripodal
ligand. The skeleton can afford a cavity surrounded
by the three amino groups, as shown in Fig. 1
[4].
The germyllithium 1 was prepared from tris[2-
(dimethylamino)phenyl]germane (2) with tert-butyl-
lithium in THF as reported previously [1]. The
reactions of 1 with Group 14 electrophiles were carried
out as shown in Scheme 1.
The reaction of 1 with methyl iodide afforded the
methylgermane 3 in 82% yield. The germyllithium 1
In this context, we report here the reactions of 1
with Group 14 electrophiles and X-ray structure analy-
sis of the obtained GeꢀM (M=C, Si, and Sn) com-
pounds [5].
Fig. 1. GeꢀM (M=C, Si, and Sn) compounds with three 2-(dimethyl-
amino)phenyl groups.
* Corresponding author.
E-mail address: tamao@scl.kyoto-u.ac.jp (K. Tamao)
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00386-1

16
A. Kawachi et al. / Journal of Organometallic Chemistry 590 (1999) 15–24
Scheme 1.
also reacted with monochlorosilanes, Me2HSiCl,
Me3SiCl, and t-BuMe2SiCl to yield the corresponding
silylgermanes 4, 5, and 6 in 40, 91, and 57% yields,
respectively. The reactions of 1 with silicon tetrafluoride
(SiF4) and dichlorosilane (SiH2Cl2) were also successful.
Thus, 1 was treated with gaseous silicon tetrafluoride in
THF at −78°C to yield the (trifluorosilyl)germane 7.
Isolation of 7 was unsuccessful, because it was highly
moisture sensitive and barely crystallized, but its forma-
bond with a torsion angle of 168°, and another amino
group is almost perpendicular to the GeꢀSi bond with a
torsion angle of −93°. Due to the steric repulsion, the
,
SiꢀCt-Bu bond (1.922(4) A) is longer than the typical
,
SiꢀC bond (1.86ꢀ1.91 A) (so called ‘long’ SiꢀC bond)
[9], and the Ct-BuꢀSiꢀGe bond angle (114.0(1)°) is larger
than the tetrahedral angle. (2) In all cases except for the
two amino groups in 6, the N···M interatomic distances
are within the sum of the van der Waals radii (N, 1.54;
1
tion could be confirmed by H-, 29Si-, and 19F-NMR
,
,
,
C, 1.85; Si, 2.00; Sn, 2.20 A) [10]: 3, 3.19 A; 4, 3.39 A;
1
spectroscopy. The value of JSiꢀF (342 Hz) is reasonable
,
,
,
,
5, 3.48 A; 6, 4.56 A; 8, 3.13 A; 10, 3.42 A. These data
demonstrate that the N···M interatomic distances are
influenced by the substituents on M rather than M
itself; thus, the average of the distances is less than 3.2
when compared with the reported values [6], e.g. 356
Hz for F3SiSiH3 [7]. Furthermore, 7 was characterized
by converting it into the corresponding (trihydrosi-
lyl)germane 8 by reduction of the SiꢀF bonds with
LiAlH4 [8]. When 1 was treated with dichlorosilane in
THF at −40°C, the (chlorosilyl)germane 9 was ob-
tained as an oily compound, which could not be
purified because of the high moisture sensitivity. For-
mation of 9 was confirmed by 1H- and 29Si-NMR
spectroscopy and its conversion to 8 by reduction of the
SiꢀCl bonds with LiAlH4 [8]. The reaction of 1 with
trimethylstannyl chloride afforded the corresponding
stannylgermane 10 in 86% yield.
,
A for the non-substituted species (Ar3GeꢀMH3) 3 and 8
,
and are close to ca. 3.4 A for the methyl-substituted
species (Ar3GeꢀMMe2R) 4, 5, and 10. (3) Based on the
summation of three bond angles ꢀCꢀGeꢀC%, the ge-
ometries around the germanium atom are slightly de-
formed from the tetrahedral geometry in all cases. (4)
2.2. Structural studies of 3, 4, 5, 6, 8, and 10
The structures of the obtained GeꢀM (M=C, Si,
and Sn) compounds 3, 4, 5, 6, 8, and 10 were investi-
gated by X-ray diffraction as shown in Figs. 2–7,
respectively. Selected bond lengths, bond angles, and
torsion angles for 3, 4, 5, 6, 8, and 10 are listed in Table
1, and the X-ray diffraction data are shown in Table 2.
The following characteristic features should be noted.
(1) In all compounds, except 6, all of the three amino
groups are located on the frontal face of the GeꢀM
(M=C, Si, and Sn) bond. The steric repulsion between
the amino groups and the substituents is mainly
reflected in the torsion angle MꢀGeꢀCipsoꢀCortho. In 6,
due to the bulky t-butyl group on the silicon atom, one
amino group occupies the region opposite the GeꢀSi
Fig. 2. Molecular structure of 3. One of the two independent
molecules in a unit cell is shown. The thermal ellipsoids are drawn at
a 30% probability. Hydrogen atoms, except for H25a, b, and c on
C25, are omitted for clarity.

A. Kawachi et al. / Journal of Organometallic Chemistry 590 (1999) 15–24
17
Fig. 3. Molecular structure of 4. The thermal ellipsoids are drawn at
a 30% probability. Hydrogen atoms, except for H1 on the silicon
atom, are omitted for clarity.
Fig. 5. Molecular structure of 6. The thermal ellipsoids are drawn at
a 30% probability. Hydrogen atoms are omitted for clarity.
Fig. 6. Molecular structure of 8. One of the four independent
molecules in a unit cell is shown. The thermal ellipsoids are drawn at
a 30% probability. Hydrogen atoms, except for H1, 2, and 3 on the
silicon atom, are omitted for clarity.
Fig. 4. Molecular structure of 5. The thermal ellipsoids are drawn at
a 30% probability. Hydrogen atoms are omitted for clarity.
In a series of silylgermanes, the GeꢀSi bond length
increases as the size of the silyl group increases; ꢀSiH3
were observed in the region for the normal tetracoordi-
nate species [7].
,
,
(8) (2.326(6) A)5SiMe2H (4) (2.374(1) A)5SiMe3 (5)
,
,
(2.386(2) A)5SiMe2t-Bu (6) (2.445(1) A). (5) In the
,
stannylgermane 10, the GeꢀSn bond length (2.573(2) A)
3. Conclusions
is somewhat shorter than that of Ph3GeSnMe3
,
(2.6106(5)–2.652(2) A) [5d,e] and other GeꢀSn bond
The tris[2-(dimethylamino)phenyl]germane moiety can
adjust the size of the cavity to accept the substituents by
changing the torsion angle MꢀGeꢀCipsoꢀCortho. It was
found that in all compounds except 6, all of the three
amino groups were located on the frontal face of the
GeꢀM bond. Under these circumstances, the N···M
distances for the parent carbogermane 3 and silylger-
,
lengths (2.596(4)ꢀ2.636(1) A) [5b,c,d,e] reported so far,
whereas other corresponding bond lengths and angles
are similar to each other.
Whereas the steric interaction dominates the struc-
ture factors, the electronic interaction, that is, coordina-
tion by the amino groups to the atom M, seems to be
much less important, perhaps due to the low Lewis
acidity of M. The 29Si resonance of the silylgermanes
4ꢀ10 and the 119Sn resonance of the stannylgermane 10
,
mane 8 are less than 3.2 A, while the distances for the
methylated silylgermanes and stannylgermane 4, 5, and
,
10 are close to 3.4 A.

18
A. Kawachi et al. / Journal of Organometallic Chemistry 590 (1999) 15–24
Table 1
a,b
,
Selected bond lengths (A), bond angles (°), and torsion angles (°) for 3, 4, 5, 6, 8, and 10
MX3=
CH3 (3)
1.939(4)
1.967(3)
1.962(4)
1.969(4)
0.90(6)
SiH3 (8)
2.326(6)
SiMe2H (4)
SiMe3 (5)
SiMe2tBu (6)
SnMe3 (10)
GeꢀM
GeꢀC1
GeꢀC9
GeꢀC17
MꢀX
2.374(1)
1.972(4)
1.977(4)
1.973(4)
1.864(5) c
1.866(5) c
1.40(3) d
3.367(4)
3.419(4)
3.396(4)
324
2.386(2)
1.975(6)
1.971(5)
1.971(6)
1.874(7)
1.866(8)
1.859(7)1
3.440(6)
3.497(5)
3.513(5)
326
2.445(1)
1.974(4)
1.995(4)
1.975(4)
1.879(4) c
1.880(4) c
1.922(4) e
3.417(3)
4.775(4)
5.480(4)
322
2.573(2)
1.94(2)
1.99(2)
1.93(2)
2.11(2)
2.13(2)
2.12(2)
3.35(2)
3.43(1)
3.48(1)
317
1.94(2)
1.94(1)
1.97(2)
1.45
1.45
1.46
3.31(2)
3.03(2)
3.24(1)
328
318
−45(1)
−26(1)
−33(1)
5(2)
−11(2)
−1(2)
0.99(5)
1.24(7)
M···N1
M···N2
3.163(6)
3.233(6)
3.221(6)
320
318
39.5(4)
48.2(4)
20.1(4)
0.3(5)
M···N3
ꢀXꢀMꢀX% f
ꢀCꢀGeꢀC% f
MꢀGeꢀC1ꢀC2
MꢀGeꢀC9ꢀC10
MꢀGeꢀC17ꢀC18
GeꢀC1ꢀC2ꢀN1
GeꢀC9ꢀC10ꢀN2
GeꢀC17ꢀC18ꢀN3
315
312
323
317
−37.8(3)
−38.7(4)
−35.5(4)
−4.3(5)
−2.8(5)
−3.0(5)
35.1(5)
41.9(5)
38.9(5)
5.9(8)
3.3(8)
2.0(8)
−42.7(3)
−93.1(4)
168.3(3)
−6.7(5)
4.7(6)
−35(1)
−25(1)
−38(1)
−3(2)
−15(2)
−2(2)
3.8(5)
11.2(5)
4.7(5)
a Data for one of the two independent molecules are shown.
b Data for one of the four independent molecules are shown.
c SiꢀCMe
d SiꢀH.
.
e SiꢀCt-Bu
.
f Summation of the three bond angles.
l 7.200 ppm, 13C l 128.00 ppm) and CDCl3 (13C l 77.00
ppm). 19F, 29Si, and 119Sn chemical shifts were referenced
to external trichlorofluoromethane (0 ppm), tetramethyl-
silane (0 ppm), and tetramethylstannane (0 ppm), respec-
tively. Mass spectra were measured at 70 eV on a Jeol
JMS-700 mass spectrometer equipped with a MS-SEPU
data processing system. Melting points were measured
with a Yanaco-MP-S3 apparatus and were uncorrected.
IR spectra were recorded on a Jasco IR-810 spectropho-
tometer. The elemental analyses were performed at the
Microanalysis Division of the Institute for Chemical
Research, Kyoto University. Analytical samples were
purified by recrystallization.
tert-Butyllithium in pentane was purchased from
Kanto Chemical Co., Inc. Silicon tetrafluoride was
purchased from Nippon Sanso Co., Ltd. Dichlorosilane
was kindly donated by Shin-Etsu Chemical Co., Ltd.
Hexane was distilled under nitrogen over sodium wire.
THF and Et2O were distilled under nitrogen over sodium
benzophenone ketyl, LiAlH4, or sodium–potassium al-
loy. All reactions were carried out under an inert
atmosphere, unless otherwise noted.
Fig. 7. Molecular structure of 10. One of the two independent
molecules in a unit cell is shown. The thermal ellipsoids are drawn at
a 30% probability. Hydrogen atoms are omitted for clarity.
4. Experimental
4.2. Synthesis of {tris[2-(dimethylamino)phenyl]-
germyl}lithium (1) [1a]
4.1. General
To
a solution of tris[2-(dimethylamino)phenyl]-
1H (270 MHz), 13C (67.94 MHz), 19F (254.19 MHz),
29Si (53.67 MHz), and 119Sn (100.68 MHz) NMR spectra
germane (2) [1b] (220 mg, 0.50 mmol) in THF (1.0 ml)
was added tert-butyllithium in pentane (1.64 M, 1.00 ml,
1.64 mmol) at −40°C. The reaction mixture was stirred
t −40°C for 1h to give a yellow suspension of 1.
were recorded on a Jeol EX-270 spectrometer. 1H and 13
C
chemical shifts were referenced to internal benzene-d6 (1H

A. Kawachi et al. / Journal of Organometallic Chemistry 590 (1999) 15–24
19
Table 2
Summary of X-ray diffraction data for 3, 4, 5, 6, 8, and 10
3
4
5
6
8
10
Chemical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
C25H33N3Ge
448.15
C
492.27
26H37N3SiGe
C27H39N3SiGe
506.30
C30H45N3SiGe
548.38
C24H33N3SiGe
464.22
C27H39N3GeSn
596.91
0.50×0.40×0.20 0.40×0.30×0.50 0.40×0.20×0.40 0.30×0.20×0.50 0.50×0.50×0.50 0.30×0.30×0.30
Triclinic
Monoclinic
P21/c (no. 14)
11.076(2)
15.070(2)
16.037(3)
Monoclinic
P21/n (no. 14)
10.241(4)
15.154(3)
18.566(2)
Triclinic
Triclinic
Monoclinic
P21/n (no. 14)
19.019(4)
15.026(4)
20.822(4)
(
(
(
P1 (no. 2)
P1 (no. 2)
P1 (no. 2)
,
a (A)
16.926(2)
17.153(2)
8.923(2)
95.71(1)
90.26(1)
69.569(7)
2414.1(6)
4
10.570(2)
15.712(2)
9.915(1)
93.615(10)
105.38(1)
71.99(1)
1509.5(4)
2
22.51(1)
24.197(8)
9.432(2)
90.01(1)
89.98(3)
89.95(4)
5138(3)
8
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
91.79(2)
95.27(2)
104.25(1)
3
,
V (A )
Z
2675.6(7)
4
1.222
20.99
293
2869.0(10)
4
1.172
19.70
293
5767(2)
8
1.375
83.00
293
DCalc. (g cm−3
)
1.233
18.18
293
1.206
19.08
293
1.200
21.57
293
v(Cu–Ka) (cm−1
)
Temperature (K)
No. of reflections collected
7450
4395
4725
4762
15724
9427
No. of independent reflections 7168
(Rint=0.015)
5595
4157
(Rint=0.067)
3167
4448
(Rint=0.018)
3150
4481
(Rint=0.027)
3749
15270
(Rint=0.072)
5410
8952
(Rint=0.053)
4746
No. of observed reflections
(I\3|(I))
No. of variables
R
547
285
446
317
1045
0.073
0.097
1.50
578
0.040
0.065
1.12
0.042
0.055
1.71
0.055
0.080
1.88
0.045
0.077
1.33
0.079
0.114
1.77
Rw
Goodness-of-fit
stirred at r.t. for 8 h. After the solvent was removed
under reduced pressure, the residue was diluted with
benzene (10 ml) under an inert atmosphere. The result-
ing suspension was filtered, and the filtrate was concen-
trated to give a solid. Recrystallization of the solid from
hexane (2.0 ml) under an inert atmosphere yielded 4 as
colorless crystals (97 mg, 40% yield based on 2). M.p.:
165.5–166.5°C. 1H-NMR (C6D6): l 0.57 (d, 6H, J=3.5
Hz), 2.43 (s, 18H), 4.71 (septet, 1H, J=3.5 Hz), 6.90–
6.96 (m, 4H), 7.10–7.24 (m, 4H), 7.46–7.49 (m, 4H).
13C-NMR (CDCl3): l −3.05, 46.52, 120.14, 123.94,
129.22, 137.72, 139.34, 159.51. 29Si-NMR (C6D6): l
−27.6 (dd, JSiꢀH=188 Hz, JSiꢀH=7 Hz), IR (KBr,
cm−1): w(SiꢀH) 2110. MS: m/e 449 (M+, 8), 434 (M+–
Me, 1), 329 (82), 134 (100). Anal. Calc. for
C25H37N3GeSi: C, 63.43; H, 7.58; N, 8.54. Found: C,
63.35; H, 7.79; N, 8.54.
4.3. Synthesis of tris[2-(dimethylamino)phenyl]methyl-
germane (3)
Methyl iodide (1.10 ml, 16.5 mmol) was added to a
suspension of 1 (prepared from 0.49 mmol of 2) in THF
(1.0 ml) at −40°C, and then the mixture was stirred at
room temperature (r.t.) for 4 h. After the solvent was
removed under reduced pressure, the residue was diluted
with hexane (10 ml). The resulting suspension was
filtered and the filtrate was concentrated to give a solid.
Recrystallization of the solid from hexane (0.5 ml)
yielded 3 as colorless crystals (182 mg, 82% yield based
on 2). M.p.: 109.5–111.0°C. 1H-NMR (C6D6): l 1.59 (s,
3H), 2.45 (s, 18H), 6.98–7.00 (m, 3H), 7.15–7.25 (m,
6H), 7.47–7.49 (m, 3H). 13C-NMR (CDCl3): l 1.62,
46.24, 120.65, 123.68, 129.24, 137.02, 138.67, 159.91.
MS: m/e 449 (M+, 8), 434 (M+–Me, 1), 329 (82), 134
(100). Anal. Calc. for C25H33N3Ge: C, 67.00; H, 7.42; N,
9.38. Found: C, 67.19; H, 7.42; N, 9.39.
1
2
4.r5. Tris[2-(dimethylamino)phenyl](trimethylsilyl)-
germane (5)
4.4. A typical procedure for reaction of 1 with mono-
chlorosilanes: synthesis of tris[2-(dimethylamino)-
phenyl](dimethylsilyl)germane (4)
This compound was obtained in 45% yield (based on
2) after recrystallization from hexane. M.p.: 170.0–
171.5°C. 1H-NMR (C6D6): l 0.57 (s, 9H), 2.40 (s, 18H),
6.89–6.95 (m, 4H), 7.12–7.20 (m, 4H), 7.44–7.47 (m,
4H). 13C-NMR (CDCl3): l 1.21, 45.84, 46.74, 120.14,
123.97, 129.18, 138.31, 139.60, 159.75. 29Si-NMR
Dimethylchlorosilane (1.80 ml, 16.5 mmol) was added
to a suspension of 1 (prepared from 0.50 mmol of 2) in
THF (1.0 ml) at −40°C, and then the mixture was

20
A. Kawachi et al. / Journal of Organometallic Chemistry 590 (1999) 15–24
(C6D6): l −6.41. MS: m/e 507 (M+, 0.4), 492 (M+–Me,
Table 4
Positional parameters and Biso/Beq for 4
3), 434 (M+–SiMe3, 77), 120 (C6H4NMe2, 100). Anal.
Atom
x
y
z
Beq
Table 3
Positional parameters and Biso/Beq for 3
Ge(1)
Si(1)
N(1)
N(2)
N(3)
C(1)
C(2)
C(3)
C(4)
C(5)
0.19299(4)
0.1596(1)
0.3459(3)
0.2877(3)
0.11562(3)
0.21173(3)
0.12068(8)
0.0539(2)
0.3119(2)
0.1723(2)
0.1546(2)
0.0831(2)
0.0417(3)
0.0700(3)
0.1408(3)
0.1892(3)
−0.0352(3)
0.0801(3)
0.2888(2)
0.3264(3)
0.3761(3)
0.3898(3)
0.3543(3)
0.3045(3)
0.3091(4)
0.3697(3)
0.2826(2)
0.2572(2)
0.3138(3)
0.3949(3)
0.4211(3)
0.3652(2)
0.1582(4)
0.1096(3)
0.0948(3)
0.1627(4)
3.32(1)
4.30(3)
4.39(8)
4.95(9)
4.35(8)
3.70(9)
3.73(9)
4.9(1)
5.7(1)
5.2(1)
4.6(1)
6.6(1)
6.6(1)
3.69(9)
4.3(1)
5.9(1)
6.2(1)
5.1(1)
4.20(10)
7.9(2)
6.5(1)
3.34(8)
3.67(9)
4.9(1)
5.3(1)
5.0(1)
4.08(9)
7.5(2)
5.4(1)
5.9(1)
6.2(1)
−0.00670(8)
0.1530(2)
−0.0554(2)
0.1047(2)
0.2290(3)
0.2332(3)
0.3136(3)
0.3892(3)
0.3866(3)
0.3073(3)
0.1392(4)
0.1477(4)
0.1006(3)
0.0194(3)
0.0137(3)
0.0863(4)
0.1660(3)
0.1728(3)
−0.1407(4)
−0.0605(3)
0.1410(2)
0.1313(2)
0.1448(3)
0.1675(3)
0.1795(3)
0.1669(3)
0.0578(4)
0.1734(3)
−0.0656(3)
−0.0894(3)
Atom
x
y
z
Beq
Ge(1)
Ge(1%)
N(1)
N(1%)
N(2)
N(2%)
N(3)
N(3%)
C(1)
C(1%)
C(2)
C(2%)
C(3)
0.23638(2)
−0.26292(2)
0.3254(2)
−0.1735(2)
0.1907(2)
−0.3079(2)
0.0471(2)
−0.4524(2)
0.3094(2)
−0.1894(2)
0.3442(2)
−0.1551(2)
0.3920(3)
0.22420(2)
0.22252(3) −0.47940(5) 3.80(1)
0.06578(5) 3.50(1)
−0.0939(3)
0.2231(3)
0.2904(3)
0.3029(4)
0.2481(5)
0.1835(4)
0.1712(4)
0.3311(5)
0.4734(4)
0.3344(3)
0.3645(4)
0.4693(4)
0.5421(4)
0.5124(4)
0.4096(3)
0.3504(6)
0.1897(5)
0.0547(3)
0.0290(2)
0.0266(2)
0.3333(2)
0.3331(2)
0.3041(2)
0.2999(2)
0.1422(2)
0.1403(2)
0.0568(2)
0.0539(2)
0.0012(3)
−0.0062(4)
−0.4820(4)
−0.1983(4)
−0.1761(4)
0.2305(4)
−0.6256(4)
0.1923(4)
−0.6350(4)
0.1432(5)
−0.6188(5)
0.2388(6)
−0.7345(6)
0.3801(6)
−0.8656(6)
0.4297(5)
−0.8826(5)
0.3354(5)
−0.7683(5)
−0.0117(7)
−0.5024(8)
−0.1159(7)
−0.3739(7)
−0.0661(4)
−0.3392(4)
−0.1835(4)
−0.2085(4)
−0.2825(5)
−0.1115(5)
−0.2632(5)
−0.1458(6)
−0.1435(5)
−0.2762(6)
−0.0482(5)
−0.3704(5)
−0.3484(6)
−0.0380(6)
−0.1492(7)
−0.1781(8)
0.1995(4)
−0.5786(4)
0.2514(4)
−0.6304(4)
0.3200(5)
−0.6817(5)
0.3424(6)
−0.6906(6)
0.3024(6)
−0.6449(6)
0.2304(5)
−0.5900(5)
0.2533(6)
−0.6455(6)
0.3048(6)
−0.7212(5)
−0.0480(6)
−0.3808(7)
5.55(9)
5.57(9)
4.94(8)
5.10(8)
4.38(7)
4.57(8)
3.78(8)
3.91(8)
4.36(9)
4.36(9)
5.9(1)
5.9(1)
6.4(1)
6.4(1)
5.8(1)
5.9(1)
4.59(9)
4.88(10)
8.3(2)
8.7(2)
9.2(2)
9.6(2)
3.81(8)
4.26(9)
4.12(9)
4.63(9)
5.3(1)
6.6(1)
5.6(1)
7.4(1)
5.3(1)
6.1(1)
4.73(10)
5.2(1)
7.8(2)
7.1(1)
7.6(1)
8.2(2)
3.76(8)
3.86(8)
4.00(8)
4.19(9)
5.2(1)
5.7(1)
6.4(1)
6.9(1)
6.6(1)
6.4(1)
5.0(1)
5.1(1)
6.5(1)
6.7(1)
6.0(1)
5.9(1)
4.9(1)
5.3(1)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18) −0.0658(4)
C(19) −0.1565(4)
C(20) −0.1294(4)
C(21) −0.0120(4)
C(22)
C(23) −0.2068(5)
C(24) −0.0822(4)
C(25)
C(26)
C(3%)
C(4)
C(4%)
C(5)
C(5%)
C(6)
C(6%)
C(7)
C(7%)
C(8)
C(8%)
C(9)
−0.1067(3)
0.4088(3)
−0.0891(3)
0.3786(3)
−0.1195(3)
0.3284(3)
−0.1695(3)
0.2960(4)
−0.1981(4)
0.3925(5)
−0.1086(5)
0.3125(2)
−0.1864(2)
0.2810(2)
−0.2182(2)
0.3352(3)
−0.1649(3)
0.4206(3)
−0.0790(3)
0.4529(3)
−0.0465(3)
0.4000(2)
−0.1003(3)
0.1627(4)
−0.3281(3)
0.1533(3)
−0.3501(3)
0.1799(2)
−0.3193(2)
0.0957(2)
−0.4026(2)
0.0596(3)
−0.0009(3)
0.0285(3)
0.0277(3)
0.1121(3)
0.1098(3)
0.1681(2)
0.1662(3)
−0.0409(4)
−0.0453(4)
0.0129(4)
0.0128(5)
0.2526(2)
0.2534(2)
0.3009(2)
0.3060(3)
0.3163(3)
0.3297(3)
0.2864(3)
0.3034(4)
0.2407(3)
0.2511(3)
0.2235(3)
0.2276(3)
0.3154(4)
0.3032(4)
0.4220(3)
0.4220(4)
0.3274(2)
0.3239(2)
0.3566(2)
0.3513(2)
0.4387(3)
0.4300(3)
0.4891(3)
0.4788(3)
0.4598(3)
0.4531(3)
0.3798(3)
0.3762(3)
0.3430(3)
0.3390(4)
0.2280(3)
0.2211(3)
0.1823(3)
0.1808(4)
0.0789(4)
C(9%)
C(10)
C(10%)
C(11)
C(11%)
C(12)
C(12%)
C(13)
C(13%)
C(14)
C(14%)
C(15)
C(15%)
C(16)
C(16%)
C(17)
C(17%)
C(18)
C(18%)
C(19)
C(19%)
C(20)
C(20%)
C(21)
C(21%)
C(22)
C(22%)
C(23)
C(23%)
C(24)
C(24%)
C(25)
C(25%)
0.3016(4)
0.0518(4)
Calc. for C27H39N3GeSi: C, 64.05; H, 7.76; N, 8.30.
Found: C, 63.67; H, 7.75; N, 8.44.
4.6. Tris[2-(dimethylamino)phenyl](tert-butyldi-
methylsilyl)germane (6)
This compound was obtained in 57% yield (based on
2) after recrystallization from hexane. M.p.: 164.0–
165.0°C. H-NMR (C6D6): l 0.51 (s, 6H), 1.03 (s, 9H),
1
2.29 (s, 18H), 7.01–7.06 (m, 6H), 7.20–7.26 (m, 3H),
7.92–7.95 (m, 3H). 13C-NMR (CDCl3): l −2.69, 20.45,
28.20, 45.86, 119.87, 122.50, 128.64, 137.72, 138.92,
158.92. 29Si-NMR (C6D6): l 1.43. MS: m/e 549 (M+,
0.1), 534 (M+–Me, 0.9), 492 (M+–t-Bu, 4), 434 (M+–
SiMe2t-Bu, 100), 134 (99), 120 (98). Anal. Calc. for
C30H45N3GeSi: C, 65.71; H, 8.27; N, 7.66. Found: C,
66.03; H, 8.39; N, 7.71.
−0.4359(3)
0.1071(4)
−0.3866(4)
0.1912(4)
−0.3051(4)
0.2263(3)
−0.2728(3)
−0.0449(3)
−0.5426(3)
0.0771(3)
4.7. Synthesis of tris[2-(dimethylamino)phenyl](tri-
fluorosilyl)germane (7)
−0.4204(3)
0.1590(3)
−0.3398(3)
To a suspension of 1 (prepared from 0.50 mmol of 2)
in THF–toluene (1.0 ml/10.0 ml) was introduced at

A. Kawachi et al. / Journal of Organometallic Chemistry 590 (1999) 15–24
21
Table 6
−78°C with stirring an excess of gaseous silicon
Positional parameters and Biso/Beq for 6
tetrafluoride for ca. 5 min through a gas inlet tube from
the gas cylinder until the yellow color disappeared and
a white precipitate was formed. The mixture was warmed
to ambient temperature over 5 h. The formation of 7 was
confirmed by means of NMR spectra. 1H-NMR (C6D6):
l 2.48 (s, 18H), 6.90–6.96 (m, 3H), 7.07–7.10 (m, 3H),
7.15–7.20 (m, 3H), 7.40–7.43 (m, 3H). 13C-NMR
(CDCl3): l 45.99, 120.74, 124.80, 130.37, 135.96, 136.55,
159.16. 29Si-NMR (C6D6): l −69.64 (q, 1JSiꢀF=342 Hz).
19F-NMR (C6D6): l −132.2 (1JSiꢀF=342 Hz).
Atom
x
y
z
Beq
Ge(1)
Si(1)
N(1)
N(2)
N(3)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12) −0.0738(5)
C(13) −0.0856(5)
C(14) −0.0059(4)
C(15)
C(16)
C(17)
C(18) −0.0952(4)
C(19) −0.1942(5)
C(20) −0.1794(5)
C(21) −0.0683(5)
0.17147(4)
0.3803(1)
0.3319(3)
0.2021(4)
0.25371(3)
0.29898(7)
0.1998(2)
0.0872(2)
0.2405(3)
0.1417(3)
0.1274(3)
0.0442(3)
0.37358(4)
0.4540(1)
0.1355(3)
0.6036(4)
0.1926(4)
0.2685(4)
0.1711(4)
0.1096(5)
0.1387(6)
0.2267(6)
0.2909(5)
0.0237(4)
0.0984(5)
0.5283(4)
0.6134(4)
0.7035(4)
0.7180(5)
0.6442(5)
0.5512(4)
0.6546(7)
0.6245(6)
0.2467(4)
0.1695(4)
0.0702(5)
0.0530(5)
0.1333(5)
0.2293(4)
0.2631(6)
0.0697(6)
0.3215(5)
0.4839(5)
0.6241(4)
0.7447(5)
0.6660(6)
0.6017(5)
3.871(10)
4.20(2)
4.89(8)
5.45(8)
5.41(8)
4.45(8)
4.53(8)
6.3(1)
7.1(1)
6.7(1)
5.7(1)
5.6(1)
−0.1109(4)
0.2103(4)
0.2897(4)
0.3236(5)
0.2793(6)
0.1973(6)
0.1627(5)
0.2262(5)
0.4621(5)
0.0875(4)
0.1057(4)
0.0219(5)
−0.0228(4)
−0.0105(3)
0.0716(3)
0.2568(3)
0.1734(4)
0.2452(3)
0.1710(3)
0.1801(3)
0.2618(3)
0.3345(3)
0.3265(3)
0.0098(3)
0.0837(3)
0.3454(3)
0.3257(3)
0.3863(3)
0.4702(3)
0.4927(3)
0.4305(3)
0.2501(4)
0.1880(4)
0.3717(3)
0.1954(3)
0.3654(3)
0.3117(4)
0.3862(4)
0.4533(3)
4.8. Synthesis of tris[2-(dimethylamino)phenyl]-
(chlorosilyl)germane (9)
6.8(1)
4.26(8)
4.38(8)
5.4(1)
6.0(1)
5.8(1)
4.74(9)
7.6(1)
6.7(1)
4.08(8)
4.61(9)
6.0(1)
6.4(1)
5.5(1)
4.74(9)
7.5(1)
7.8(1)
5.35(10)
5.6(1)
4.88(9)
6.7(1)
7.1(1)
6.5(1)
Gaseous dichlorosilane was liquidized at −78°C and
diluted with THF to make a 1.5 M solution. The solution
(1.9 ml, 2.8 mmol) was added to a suspension of 1
(prepared from 0.48 mmol of 2) in THF (1.5 ml) at
−40°C, and was then stirred at r.t. for 8 h. After the
solvent was removed under reduced pressure, crude 9 was
obtained as oil. The yield was estimated by means of
NMR analysis (61%): toluene was used as an internal
standard. 1H-NMR (C6D6): l 2.44 (s, 18H), 5.29 (s, 2H),
0.1848(6)
0.3433(5)
0.0231(4)
Table 5
C(22)
C(23) −0.2194(6)
C(24) −0.1254(6)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
0.0320(4)
Positional parameters and Biso/Beq for 5
Atom
x
y
z
Beq
0.3986(4)
0.5334(4)
0.3900(4)
0.3825(6)
0.5258(6)
0.2721(6)
Ge(1)
Si(1)
N(1)
N(2)
N(3)
C(1)
C(2)
C(3)
C(4)
C(5)
0.19299(4)
0.1596(1)
0.3459(3)
0.2877(3)
0.11562(3)
0.21173(3)
0.12068(8)
0.0539(2)
0.3119(2)
0.1723(2)
0.1546(2)
0.0831(2)
0.0417(3)
0.0700(3)
0.1408(3)
0.1892(3)
−0.0352(3)
0.0801(3)
0.2888(2)
0.3264(3)
0.3761(3)
0.3898(3)
0.3543(3)
0.3045(3)
0.3091(4)
0.3697(3)
0.2826(2)
0.2572(2)
0.3138(3)
0.3949(3)
0.4211(3)
0.3652(2)
0.1682(4)
0.1096(3)
0.0948(3)
0.1627(4)
3.32(1)
4.30(3)
4.39(8)
4.95(9)
4.35(8)
3.70(9)
3.73(9)
4.9(1)
5.7(1)
5.2(1)
4.6(1)
6.6(1)
6.6(1)
3.69(9)
4.3(1)
5.9(1)
6.2(1)
5.1(1)
4.20(10)
7.9(2)
6.5(1)
3.34(8)
3.67(9)
4.9(1)
5.3(1)
5.0(1)
4.08(9)
7.5(2)
5.4(1)
5.9(1)
6.2(1)
−0.00670(8)
0.1530(2)
−0.0554(2)
0.1047(2)
0.2290(3)
0.2332(3)
0.3136(3)
0.3892(3)
0.3866(3)
0.3073(3)
0.1392(4)
0.1477(4)
0.1006(3)
0.0194(3)
0.0137(3)
0.0863(4)
0.1660(3)
0.1728(3)
−0.1407(4)
−0.0605(3)
0.1410(2)
0.1313(2)
0.1448(3)
0.1675(3)
0.1795(3)
0.1669(3)
0.0578(4)
0.1734(3)
−0.0656(3)
−0.0894(3)
−0.0939(3)
0.2231(3)
0.2904(3)
0.3029(4)
0.2481(5)
0.1835(4)
0.1712(4)
0.3311(5)
0.4734(4)
0.3344(3)
0.3645(4)
0.4693(4)
0.5421(4)
0.5124(4)
0.4096(3)
0.3504(6)
0.1897(5)
0.0547(3)
6.91–6.97 (m, 4H), 7.06–7.15 (m, 4H), 7.44–7.47 (m,
4H). 13C-NMR (C6D6): 45.81, 121.05, 125.75, 131.47,
135.06, 136.97, 159.34. 29Si-NMR (C6D6): l −39.27 (dd,
1JSiꢀH=245 Hz).
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18) −0.0658(4)
C(19) −0.1565(4)
C(20) −0.1294(4)
C(21) −0.0120(4)
C(22)
C(23) −0.2068(5)
C(24) −0.0822(4)
C(25)
C(26)
4.9. Reduction of
tris[2-(dimethylamino)phenyl](silyl)germane (8)
9
with LiAlH4: synthesis of
A solution of dichlorosilane in THF (2.0 M, 4.0 ml,
8.1 mmol) was added to a suspension of 1 (prepared from
2.0 mmol of 2) in THF (5.0 ml) at −40°C, and was then
stirred at r.t. for 5 h. The mixture was added to a
suspension of LiAlH4 (310 mg, 8.1 mmol) in THF (10 ml)
at 0°C and stirred for 1 h. The reaction mixture was
diluted with THF (60 ml), followed by the successive
addition of H2O (0.3 ml), 15% NaOH aqueous solution
(0.3 ml), and H2O (0.9 ml) at 0°C. The resulting
suspension was filtered, and the filtrate was concentrated
to give an oily material. Crystallization of the oil
from hexane yielded 8 as colorless crystals (350 mg,
0.0789(4)
0.3016(4)
0.0518(4)

22
A. Kawachi et al. / Journal of Organometallic Chemistry 590 (1999) 15–24
Table 7
Table 7 (Continued)
Positional parameters and Biso/Beq for 8
C(43)
C(44)
C(45)
C(46)
C(47)
C(48)
C(49) −0.0408(8)
C(50) −0.1006(10)
C(51) −0.1408(9)
C(52) −0.116(2)
C(53) −0.058(1)
C(54) −0.0223(8)
C(55) −0.1815(9)
C(56) −0.1158(9)
C(57)
C(58)
C(59)
C(60)
C(61)
C(62)
0.371(1)
0.4012(8)
0.442(1)
−0.057(2)
−0.075(2)
−0.022(2)
0.049(2)
−0.067(2)
0.049(2)
0.153(2)
0.125(2)
0.233(3)
0.360(2)
0.386(2)
0.284(2)
−0.023(2)
−0.123(2)
0.145(1)
0.199(1)
0.287(2)
0.329(2)
0.276(2)
0.183(2)
0.270(2)
0.120(2)
−0.100(2)
−0.241(2)
−0.328(2)
−0.283(3)
−0.147(3)
−0.059(2)
−0.244(2)
−0.424(2)
0.349(2)
0.377(2)
0.271(3)
0.143(3)
0.118(2)
0.217(2)
0.525(3)
0.622(2)
0.357(2)
0.304(2)
0.211(2)
0.174(2)
0.226(2)
0.319(2)
0.233(2)
0.380(2)
0.600(2)
0.742(2)
0.826(2)
0.784(3)
0.649(3)
0.560(2)
0.743(2)
0.921(2)
7.0(6)
7.7(7)
7.1(6)
5.9(5)
9.0(7)
9.9(7)
5.5(5)
6.1(6)
9.0(7)
9.6(8)
9.1(7)
6.9(6)
10.5(8)
8.6(6)
4.4(4)
4.6(4)
6.0(5)
6.8(6)
5.7(5)
6.0(5)
8.7(7)
9.0(7)
5.5(5)
7.5(7)
10.2(8)
10.1(9)
8.2(7)
6.4(5)
11.7(8)
12.4(9)
5.2(5)
5.6(5)
8.2(7)
9.8(9)
8.4(7)
6.9(6)
11.4(8)
8.4(6)
4.5(4)
4.7(4)
6.0(5)
6.3(6)
6.0(5)
5.5(5)
9.4(7)
8.8(7)
5.9(5)
7.0(6)
8.8(7)
9.0(8)
8.2(7)
6.0(5)
11.2(8)
13.4(10)
Atom
x
y
z
Beq
5.08(5)
0.4130(9)
0.4037(9)
0.3520(10)
0.2300(9)
0.301(1)
0.4926(9)
0.5031(8)
0.3683(9)
0.3130(8)
0.2848(7)
0.2882(7)
0.3069(9)
0.3257(9)
0.3241(10)
0.3014(8)
0.2470(9)
0.3130(8)
0.2161(7)
0.1637(7)
0.1446(7)
0.1772(9)
0.2289(8)
0.2484(7)
0.1331(9)
0.0757(8)
0.3035(7)
0.2919(9)
0.334(1)
Ge(1)
Ge(2)
Ge(3)
Ge(4)
Si(1)
Si(2)
Si(3)
Si(4)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(9)
N(10)
N(11)
N(12)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
0.25861(9)
0.24120(8)
0.01280(8)
0.51297(8)
0.2880(3)
0.2121(3)
0.97847(8)
0.47851(8)
0.24658(7)
0.25355(7)
0.9029(2)
0.4030(2)
0.1784(2)
0.3217(2)
0.9983(6)
0.9771(7)
0.8698(6)
0.4766(7)
0.4997(7)
0.3682(6)
0.2713(6)
0.1319(6)
0.2340(8)
0.2300(6)
0.3680(6)
0.2692(8)
1.0082(7)
1.0168(8)
1.0406(9)
1.0565(8)
1.0479(8)
1.0238(7)
1.045(1)
0.6897(2)
0.1897(2)
0.0216(2)
0.4786(2)
0.8252(6)
0.3257(6)
5.08(5)
4.77(5)
4.78(5)
8.7(2)
8.8(2)
8.0(2)
7.9(2)
7.0(5)
6.6(5)
6.2(4)
7.3(5)
7.3(5)
6.2(4)
6.7(5)
5.9(4)
7.9(5)
6.6(5)
5.6(4)
7.5(5)
6.3(6)
6.3(6)
8.3(7)
8.1(7)
7.9(7)
5.9(5)
10.8(8)
11.3(8)
4.6(4)
5.3(5)
8.2(7)
8.7(7)
8.0(7)
6.5(6)
8.7(7)
10.5(8)
4.3(4)
4.9(5)
6.6(6)
7.2(6)
7.4(7)
6.2(5)
9.3(7)
9.3(7)
4.8(5)
5.5(5)
8.4(7)
9.3(8)
8.4(7)
7.0(6)
11.0(8)
9.1(7)
5.3(5)
6.8(6)
8.3(7)
9.1(8)
8.3(7)
6.5(6)
11.1(8)
11.9(9)
4.3(4)
5.5(5)
−0.0360(3)
0.4640(3)
0.3902(6)
0.2033(7)
0.2198(7)
0.2961(7)
0.1115(7)
0.2766(8)
−0.1208(6)
0.0197(7)
0.0644(7)
0.3768(7)
0.5230(6)
0.5665(8)
0.3206(9)
0.378(1)
−0.1098(6)
0.6102(6)
0.762(2)
0.986(1)
0.535(1)
0.489(1)
0.262(2)
0.034(1)
−0.013(2)
0.159(1)
−0.274(1)
0.514(2)
0.339(1)
0.775(1)
0.568(2)
0.619(2)
0.539(3)
0.397(3)
0.346(2)
0.426(2)
0.856(2)
0.784(2)
0.808(2)
0.948(2)
1.038(2)
0.993(3)
0.856(3)
0.771(2)
0.945(2)
1.134(2)
0.570(1)
0.513(2)
0.440(2)
0.423(2)
0.476(2)
0.551(2)
0.553(2)
0.438(2)
0.311(2)
0.449(2)
0.541(2)
0.491(3)
0.351(3)
0.267(2)
0.634(2)
0.445(2)
0.069(2)
0.116(2)
0.040(3)
−0.099(3)
−0.154(2)
−0.072(2)
0.358(2)
0.282(2)
0.066(1)
0.015(2)
0.0741(7)
0.0725(8)
0.1180(9)
0.1654(9)
0.1682(7)
0.1249(9)
C(63) −0.0251(9)
C(64)
C(65)
C(66)
C(67)
C(68)
C(69)
C(70)
C(71)
C(72)
C(73)
C(74)
C(75)
C(76)
C(77)
C(78)
C(79)
C(80)
C(81)
C(82)
C(83)
C(84)
C(85)
C(86)
C(87)
C(88)
C(89)
C(90)
C(91)
C(92)
C(93)
C(94)
C(95)
C(96)
0.0339(10)
0.0477(7)
0.0689(9)
0.090(1)
0.4195(10)
0.407(1)
0.351(1)
0.093(1)
0.386(1)
0.0734(10)
0.0528(8)
0.120(1)
0.3982(8)
0.3563(9)
0.2048(10)
0.223(1)
0.2151(6)
0.2126(7)
0.1927(9)
0.175(1)
0.1763(9)
0.1964(7)
0.2545(10)
0.1872(8)
0.2828(6)
0.3352(7)
0.3572(7)
0.3236(8)
0.2715(8)
0.2514(7)
0.3668(9)
0.4239(8)
0.1983(7)
0.213(1)
0.3080(8)
0.3983(10)
0.436(1)
0.2385(7)
0.2183(7)
0.2149(9)
0.2284(10)
0.2462(8)
0.2510(8)
0.144(1)
0.043(1)
C(8)
C(9)
0.960(1)
0.4569(9)
0.3975(9)
0.3582(9)
0.382(1)
1.0413(7)
1.0319(8)
1.079(1)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
1.1302(9)
1.1390(9)
1.0946(8)
0.9609(8)
0.9619(9)
0.9627(7)
0.9125(8)
0.9014(8)
0.941(1)
0.9918(10)
1.0034(7)
0.8138(9)
0.8686(8)
0.5411(6)
0.5308(8)
0.575(1)
0.6286(9)
0.6383(9)
0.5932(8)
0.4616(9)
0.4609(9)
0.5078(6)
0.5172(7)
0.5396(9)
0.5575(8)
0.5489(8)
0.5239(7)
0.545(1)
0.439(1)
0.4778(8)
0.3170(9)
0.3841(9)
0.5767(7)
0.5718(7)
0.6164(9)
0.6626(9)
0.6667(8)
0.6237(9)
0.4750(10)
0.5349(9)
0.5501(7)
0.5693(8)
0.590(1)
0.211(1)
0.1888(7)
0.1799(8)
0.129(1)
0.0864(9)
0.0960(9)
0.1484(10)
0.1988(10)
0.267(1)
0.2610(7)
0.2816(7)
0.2864(9)
0.2712(9)
0.2532(9)
0.2472(8)
0.286(1)
0.171(1)
0.117(1)
0.1023(8)
0.1427(8)
0.299(1)
0.5929(10)
0.5754(9)
0.5530(7)
0.619(1)
0.548(1)
0.280(1)
0.356(1)
0.1796(7)
0.1254(10)
0.0798(9)
0.092(1)
0.148(1)
0.1923(9)
0.102(1)
0.063(1)
0.3099(7)
0.3196(9)
1
38% yield based on 2). M.p.: 88.0–90.0°C. H-NMR
(C6D6): l 2.45 (s, 18H), 4.17 (s, 3H), 6.94–6.98 (m,
3H), 7.08–7.15 (m, 3H), 7.53–7.57 (m, 3H). 13C-NMR
(CDCl3): l 45.99, 120.40, 124.04, 129.45, 136.55,
138.94, 159.26. 29Si-NMR (C6D6): l −81.14 (q,
1JSiꢀH=196 Hz). IR (KBr, cm−1): w(SiꢀH) 2140. MS:
m/e 465 (M+, 10), 464 (M+–1, 29), 463 (M+–2, 13),
0.462(1)
0.4627(8)
0.4112(9)

A. Kawachi et al. / Journal of Organometallic Chemistry 590 (1999) 15–24
23
.
462 (M+–3, 21), 434 (M+–SiH3, 33), 120 (C6H4NMe2,
100). Anal. Calc. for C24H33N3GeSi: C, 62.09; H, 7.16;
N, 9.05. Found: C, 61.83; H, 7.28; N, 8.95.
Table 8
Positional parameters and Biso/Beq for 10
Atom
x
y
z
Beq
5.84(3)
Sn(1)
Sn(2)
Ge(1)
Ge(2)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
0.08862(6)
0.23829(7)
0.15340(10)
0.10955(10)
0.0306(8)
0.2662(7)
0.0822(8)
0.0984(9)
0.1668(9)
0.2098(8)
0.0898(9)
0.037(1)
0.13464(7)
0.21569(8)
0.2783(1)
0.2815(1)
0.327(1)
0.1569(9)
0.1982(9)
0.0963(10)
0.257(1)
0.424(1)
0.382(1)
0.393(1)
0.462(2)
0.525(2)
0.518(1)
0.445(1)
0.305(2)
0.355(2)
0.313(1)
0.250(1)
0.280(2)
0.370(2)
0.430(1)
0.401(1)
0.097(1)
0.131(1)
0.2726(9)
0.2344(10)
0.231(1)
0.270(1)
0.310(1)
0.311(1)
0.114(1)
0.264(1)
0.114(1)
0.018(1)
0.131(1)
0.247(1)
0.160(1)
0.140(1)
0.206(2)
0.287(2)
0.306(1)
0.038(2)
0.043(1)
0.2425(10)
0.229(1)
0.189(2)
0.166(2)
0.180(2)
0.219(1)
0.210(2)
0.354(2)
0.4114(10)
0.465(1)
0.555(1)
0.594(1)
0.545(1)
0.454(1)
0.468(2)
0.407(1)
0.087(2)
0.296(2)
0.198(2)
0.36171(6)
4.10. Synthesis of tris[2-(dimethylamino)phenyl](tri-
methylstannyl)germane (10)
−0.07507(7)
0.41126(8)
−0.10100(9)
0.2865(8)
0.3553(6)
0.5211(7)
−0.1770(7)
0.0566(7)
−0.1479(8)
0.3959(8)
0.3389(9)
0.332(1)
6.81(3)
4.81(4)
5.08(4)
7.5(4)
5.7(3)
6.0(4)
7.3(4)
7.5(4)
7.2(4)
6.0(4)
7.0(5)
9.9(7)
10.7(9)
9.6(7)
6.6(5)
10.8(8)
10.5(8)
5.5(4)
6.1(5)
7.5(6)
8.2(6)
7.3(5)
6.5(5)
9.6(7)
6.7(5)
5.8(4)
5.8(4)
8.0(6)
8.6(6)
7.4(6)
6.4(5)
8.6(6)
9.0(7)
9.5(7)
7.7(5)
8.0(6)
6.4(5)
7.5(6)
8.4(6)
9.0(7)
8.2(7)
6.6(5)
12.2(9)
10.4(7)
5.5(4)
7.0(5)
8.8(7)
9.2(7)
9.4(7)
7.1(5)
11.2(8)
9.0(6)
4.9(4)
5.2(4)
7.6(6)
9.0(7)
7.5(6)
6.2(5)
12.0(9)
8.4(6)
10.4(7)
12.5(9)
10.4(8)
A solution of trimethylchlorostannane (370 mg, 1.86
mmol) in THF (0.50 ml) was added to a suspension of
1 (prepared from 0.49 mmol of 2) in THF (1.0 ml) at
−40°C, and was then stirred at r.t. for 6 h. After the
solvent was removed under reduced pressure, the
residue was diluted with benzene (10 ml). The resulting
suspension was filtered, and the filtrate was concen-
trated to give a solid. Recrystallization of the solid
from hexane (1.0 ml) yielded 10 as colorless crystals
(218 mg, 74% yield based on 2). M.p.: 189.0–190.0°C.
1H-NMR (C6D6): l 0.47 (s, 9H), 2.37 (s, 18H), 6.92 (m,
3H), 7.06–7.08 (m, 3H), 7.53–7.55 (m, 3H). 13C-NMR
(CDCl3): l −5.46, 46.67, 119.59, 123.74, 137.61,
138.63, 159.71. 119Sn-NMR (C6D6): l −78.82. MS:
m/e 599 (M+, 0.1), 584 (M+–Me, 55), 582 (66), 580
(61), 434 (M+ꢀSnMe3, 100). Anal. Calc. for
C27H39N3GeSn: C, 54.33; H, 6.59; N, 7.04. Found: C,
54.23; H, 6.58; N, 7.04.
−0.012(1)
−0.007(2)
0.048(1)
0.0944(10)
−0.044(1)
0.071(1)
0.2350(9)
0.2718(9)
0.319(1)
0.331(1)
0.298(1)
0.2469(10)
0.285(1)
0.303(1)
0.1883(9)
0.1530(9)
0.185(1)
0.255(1)
0.289(1)
0.257(1)
0.066(1)
0.024(1)
0.090(1)
0.135(1)
0.382(2)
0.439(1)
0.4439(9)
0.246(1)
C(8)
C(9)
0.2410(10)
0.3724(8)
0.3441(9)
0.3068(10)
0.300(1)
0.3291(10)
0.3648(9)
0.308(1)
0.4245(9)
0.5064(9)
0.5490(9)
0.6195(7)
0.6444(10)
0.603(1)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
4.11. X-raystructuredeterminationsfor 3, 4, 5, 6, 8, and10
All crystal data and refinement parameters are
summarized in Table 2. Data were collected on a Rigaku
AFC7R diffractometer with graphite monochromated
Cu–Ka radiation using the ꢀ−2q scan technique
(2qmax=120°). The structure was solved by heavy-atom
Patterson methods [11] and expanded using Fourier
0.5353(8)
0.549(1)
0.521(1)
0.262(1)
0.413(1)
C(27) −0.022(1)
0.3661(10)
−0.1874(9)
−0.216(1)
−0.2794(9)
−0.311(1)
−0.287(1)
−0.2233(8)
−0.217(1)
−0.133(1)
−0.0354(9)
0.0325(9)
0.075(1)
C(28)
C(29)
C(30)
C(31) −0.038(1)
C(32) −0.043(1)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39) −0.018(1)
C(40) −0.052(1)
C(41) −0.015(1)
C(42)
C(43)
C(44)
C(45)
C(46)
C(47)
C(48)
C(49)
C(50)
C(51)
C(52)
C(53)
C(54)
0.0486(9)
0.051(1)
0.005(1)
2
techniques [12] and refined on ꢁFꢁ . Empirical absorption
corrections based on azimuthal scans of several
reflections were applied for all of the compounds except
6. The non-hydrogen atoms were refined anisotropically.
All hydrogen atoms bonded to the carbon atoms were
located at the expected positions by a geometrical
calculation and fixed at these positions. The hydrogen
atoms bonded to silicon atoms in 4 and 8 were found on
the difference Fourier map and refined isotropically. The
final atomic coordinates and isotropic temperature
factors of 3, 4, 5, 6, 8, and 10 are listed in Tables 3–8,
respectively.
0.002(1)
0.135(2)
0.066(1)
0.0597(9)
0.093(1)
0.055(1)
0.050(1)
−0.015(1)
−0.0567(9)
0.1131(9)
0.0702(10)
−0.1014(7)
−0.1176(7)
−0.107(1)
−0.0834(10)
−0.0678(9)
−0.0769(8)
−0.135(1)
−0.218(1)
−0.032(1)
−0.011(1)
−0.161(1)
0.208(1)
0.170(1)
0.1061(8)
0.1579(8)
0.159(1)
0.109(2)
0.053(1)
0.0511(9)
0.280(1)
0.183(1)
0.243(1)
0.317(1)
0.281(1)
5. Supplementary material
Crystallographic data (excluding structure factors) for
the structures reported in this paper have been deposited
with the Cambridge Crystallographic Data Center as
supplementary CCDC nos. 113088–113093. Copies of
this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge, CB2

24
A. Kawachi et al. / Journal of Organometallic Chemistry 590 (1999) 15–24
.
[5] (a) L. Pa´rka´nyi, A. Ka´lma´n, K.H. Pannell, F. Cervantes-Lee, R.N.
Kapoor, Inorg. Chem. 35 (1996) 6622. (b) H.K. Sharma, F.
Cervantes-Lee, L. Pa´rka´nyi, K.H. Pannell, Organometallics 15
(1996) 429. (c) S.P. Mallela, R.A. Geanangel, Inorg. Chem. 33
(1994) 1115. (d) L. Pa´rka´nyi, A. Ka´lma´n, K.H. Pannel, H. Sharma,
J. Organomet. Chem. 484 (1994) 153. (e) K.H. Pannel, L. Pa´rka´nyi,
H. Sharma, F. Cervantes-Lee, Inorg. Chem. 31 (1992) 522. (f) L.
Pa´rka´nyi, C. Hernandez, K.H. Pannell, J. Organomet. Chem. 301
(1986) 145.
[6] E.A. Williams, in: S. Patai, Z. Rappoport (Eds.), The Chem-
istry of Organic Silicon Compounds, Wiley, New York, 1989,
ch. 8.
[7] J.E. Drake, N.P.X. Westwood, J. Chem. Soc. A. (1971) 3300.
[8] M. Kumada, M. Ishikawa, S. Maeda, J. Organomet. Chem. 2
(1964) 278.
1EZ, UK (Fax: +44-1223-336-033; e-mail: deposit@-
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
Acknowledgements
We thank the Ministry of Education, Science, Sports
and Culture, Japan, for the Grants-in-Aid for Scientific
Research (Grant Nos. 07405043 and 09239103). Y.T.
thanks the Japan Society for the Promotion of Science
(fellowship for Japanese Junior Scientists).
[9] W.S. Sheldrick, in: S. Patai, Z. Rappoport (Eds.), The Chemistry
of Organic Silicon Compounds, Wiley, New York, 1989, ch. 3.
[10] (a) J. Emsley, The Elements, 2nd ed., Clarendon Press, Oxford,
1992. (b) F.A. Cotton, G. Wilkinson, P. Gauss, Basic Inorganic
Chemistry, second ed., Wiley, New York, 1987.
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[11] PATTY and ORIENT: P.T. Beurskens, G. Admiraal, G. Beurskens,
W.P. Bosman, S. Garcia-Granda, R.O. Gould, J.M.M. Smits, C.
Smykalla, 1992. The DIRDIF program system, Technical Report
of the Crystallography Laboratory, University of Nijmegen, The
Netherlands.
[12] DIRDIF92 and DIRDIF94: P.T. Beurskens, G. Admiraal, G.
Beurskens, W.P. Bosman, S. Garcia-Granda, R.O. Gould, J.M.M.
Smits, C. Smykalla, 1992 and 1994. The DIRDIF program system,
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of Nijmegen, The Netherlands.
[2] P. Riviere, M. Riviere-Baudet, J. Satge, in: A.G. Davies (Ed.),
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Oxford, 1995, pp. 137–216 and references cited therein.
[3] (a) K.M. Baines, R.J. Groh, B. Joseph, U.R. Parshotam,
Organometallics 11 (1992) 2176. (b) A. Castel, P. Riviere, J. Satge´,
H.Y. Ko, Organometallics 9 (1990) 205.
[4] Recent examples of this type of compound: (a) R.A. Gossage, G.D.
McLennan, S.R. Stobart, Inorg. Chem. 35 (1996) 1729. (b) M.
Ray, A.P. Golombek, M.P. Hendrich, V.G. Young, A.S. Borovik,
J. Am. Chem. Soc. 118 (1996) 6084.