Y. Takeuchi, Y. Takase / Journal of Organometallic Chemistry 689 (2004) 3275–3277
3277
Table 1
Selected bond lengths (A) and bond angles (ꢁ) for 4
solvent, the residue was recrystallized from
CHCl + hexane (1:2) to obtain colorless plates 4, (115
˚
3
Bond lengths
Bond angles
mg, 0.225 mmol); m.p. 267–269 ꢁC. Anal. Calc. for
Ge(1)–O(1)
Ge(1)–O(2)
Ge(1)–O(3)
Ge(1)–Cl(1)
Ge(1)–Cl(2)
Ge(1)–Cl(3)
Ge(1)–C(1)
2.736(2)
2.806(2)
2.808(2)
2.1589(8)
2.1684(6)
2.1651(6)
2.052(2)
Cl(1)–Ge(1)–Cl(2)
Cl(1)–Ge(1)–Cl(3)
Cl(1)–Ge(1)–C(1)
Cl(2)–Ge(1)–Cl(3)
Cl(2)–Ge(1)–C(1)
Cl(3)–Ge(1)–C(1)
102.11(3)
100.19(3)
117.37(6)
101.10(3)
116.83(6)
116.45(6)
C H Cl GeO : C, 51.57; H, 4.13. Found: C, 51.65;
3
2
2
21
3
1
H, 4.17%. H NMR (CDCl , 500 MHz); d 3.69,
3
(
7
–OMe), 6.41 (dd, H6), 6.83 (t, H5), 6.93 (d, H3),
13
.37(m, H4): C NMR (CDCl , 125 MHz); d 58.9
3
(–OMe), 68.3 (C), 110.1 (C3), 120.7 (C5), 126.9 (C1),
129.4 (C4), 130.0 (C6), 156.6 (C2).
3.3. X-ray crystallography
chemical shifts were reported in d (ppm) with respect
to Me Si. C NMR spectra were determined on the
same instrument operating at 125 MHz and the
chemical shifts were reported in d (ppm) with respect
1
3
Crystal data for 4 were collected on a Rigaku MSC
Mercury CCD diffractometer with graphite monochro-
4
˚
mated Mo Ka (k = 0.7107 A). The structure was solved
by direct methods using the programs SIR 92 and were
refined by full-matrix least-squares procedures using
Crystal Structure. Final atomic parameters of 4 were
deposited at the Cambridge Crystallographic Data Cen-
tre [8]. The crystallographic data are summarized in Ta-
ble 2. Perspective views of the molecules (Fig. 1) were
made by the use of ORTEP for À3 [9].
to Me Si. Elemental analysis was carried out by
4
the Microanalytical Laboratory, Department of
Chemistry, School of Science, the University of
Tokyo.
3
.2. Trichlorogermyl{tris[(2-methoxy)phenyl]}methane
4)
(
The syntheses of 6 and 7 were performed with the
method in the literature [6]. With the aid of Shlenk
Acknowledgments
apparatus, tris-(2-methoxyphenyl)methane (7) (681 mg,
2
(
HMPA (1.5 ml) was added. To this mixture was added
Y.T. thanks the financial support (The High-tech Re-
search Center Project) from The Ministry of Education,
Culture, Sports, Science and Technology. We thank
Prof. T. Kawashima, the University of Tokyo, for valu-
able discussion.
.04 mmol) in benzene (20 ml) was reacted with n-BuLi
10.4 mmol). After the solvent was exchanged to THF,
GeCl (3.93 g, 18.4 mmol), and the mixture was refluxed
4
for 40 h. After removal of the solvent, the residue was
separated and purified by column chromatography
(
SiO /CHCl :hexane) and GPC. After removal of the
2 3
References
[
[
[
[
[
1] K.-Y. Akiba (Ed.), Chemistry of Hypervalent Compounds, Wiley-
VCH, 1998.
2] C. Chuit, R.J.P. Corriu, C. Rey e´ , J.C. Young, Chem. Rev. 93
Table 2
Crystallographic data for 4
Formula
C
22
H
21Cl
3 3
GeO
(
1993) 1371.
Formula weight
Crystal color, habit
Crystal dimensions (mm)
Crystal system
512.36
3] R.J.P. Corriu, M. Nazhar, M. Poirier, G. Royo, J. Organomet.
Chem. 306 (1986) C5.
Colorless, platelet
0.20 · 0.20 · 0.20
Monoclinic
4] Y. Takeuchi, H. Yamamoto, K. Tanaka, K. Ogawa, J. Harada, T.
Iwamoto, H. Yuge, Tetrahedron 54 (1998) 9811.
Space group
˚
1
P2 /c
5] Y. Sugiyama, T. Matsumoto, H. Yamamoto, M. Nishikawa, M.
Kinoshita, T. Takei, W. Mori, Y. Takeuchi, Tetrahedron 59 (2003)
a (A)
˚
11.423(7)
10.975(5)
18.73(2)
103.415(7)
2283.9(30)
4
b (A)
8
689.
˚
c (A)
[
[
[
6] J. Kobayashi, K. Goto, T. Kawashima, M.W. Schidt, S. Nagase,
J. Am. Chem. Soc. 124 (2002) 3703.
7] J. Kobayashi, K. Kazunori, T. Kawashima, Silicon Chem. 1 (2002)
b (ꢁ)
V (A )
˚
3
Z
3
51.
3
Calculated density (g/cm )
Reflection collected
Unique
1.490
48384
5457
8] CCDC contains the supplementary crystallographic data for this
R
int
0.038
1
3
2 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223
36033; e-mail: deposit@ccdc.cam.ac.uk; Summary of Data
F
0 0 0
1040.00
0.033
R
1
(all data)
(all data)
Goodness-of-fit
CCDC 240694.
9] ORTEP-3 for Windows L.J. Farrugia, J. Appl. Cryst. (1997)
wR
2
0.081
[
0.997
5
65.