M. P o¨ tter et al. / Journal of Organometallic Chemistry 621 (2001) 261–266
265
+
was added and LiCl separated by filtration. The residue
obtained by evaporation of the solution was recrystal-
(SiOMe). MS (CI, isobutane) m/z (%): 482 (6) [M ],
+
+
467 (23) [M −CH ], 451 (51) [M −OCH ], 409 (100)
[M −SiMe ]. Anal. Found: C, 56.91; H, 10.31; N,
6.07. Calc. for C H N OSi (483.00): C, 57.19; H,
3
3
+
lized from pentane to give pale yellow prisms. Yield
3
1
1
0
1
1
.6 g (57%), m.p. 81–82°C. H-NMR (benzene-d ): l=
6
23 50
2
4
.15, 0.27 and 0.57 (3s, SiCH , 3×9H), 2.12 (s, NCH ,
2H), 3.19 (d, J=14 Hz, CH , 2H), 3.66 (d, J=
4 Hz, CH , 2H), 6.95–7.30 (m, aryl-CH, 3H). C-
10.43; N, 5.80%.
3
3
2
2
2
1
3
3.4. Crystal-structure determination of 9
2
NMR (benzene-d ): l=3.0, 7.2 and 8.3 (SiCH ), 17.5
6
3
(
SiꢁC), 45.7 (NCH ), 64.1 (CH ), 125.7, 127.8, 128.0
X-ray diffraction data were collected with a STOE-
IPDS diffractometer using graphite-monochromated
3
2
2
9
and 142.6 (arom. C). Si-NMR (benzene-d ): l=
6
−
19.6 (SiSiMe ), −8.3 (br, CSiMe ), 29.5 (SiꢁC):
Mo–K
0.4×0.2×0.2 mm , formula
weight 450.97, orthorhombic, space group Pbcn, a=
17.597(4), b=20.506(4), c=15.432(3) V=
200(2) K,
a
radiation. Crystals from pentane, crystal size
3
3
3
(THF-d ): l= −19.4 (SiSiMe ), −8.75 (CSiMe ), −
C H N Si , formula
22 46 2 4
8
3
3
8
.68 (CSiMe ), 28.3 (SiꢁC). MS m/z (%): 452 (16)
3
+ + +
[
M +2H], 451 (6) [M +H], 408 (89) [M +2H−
A;
,
+
3
NMe2], 395 (100) [M +2H−CH NMe ]. Anal.
5568(2) A
,
;
Z=8;
temperature
2
2
−
1
Found: C, 58.83; H, 10.29; N, 6.51. Calc. for
C H N Si (450.96): C, 58.60; H, 10.28; N, 6.21%.
v=0.224 mm , F(000)=1984, [ range 1.99–24.19°;
index ranges −205h520, 05k514, −175l517;
2
2
46
2
4
−
3
−3
dcalcd=1.076 g cm , peak/hole 0.28/−0.22 e A
,
,
3.2. [2,6-Bis(dimethylaminomethyl)phenyl]-
measured reflections 12 322, independent reflections
3504, observed reflections 2012, Rint=0.060, no. of
parameters 253, R1 [I\2|(I)] 0.042, wR2 (all data)
0.090. The structure was solved by direct methods
(trimethylsilyl)-[bis(trimethylsilyl)methyl]silanol (12)
Excess water was added to an ethereal solution of
1
.0 g (2.2 mmol) of 9. After stirring for 1 h, the organic
(SHELXS-86) [17] and refined by full-matrix least-
2
phase was separated, dried with Na SO and evapo-
squares techniques against F
(SHELXL-93) [18]. XP
2
4
rated. Kugelrohr-distillation of the residue (110°C, 2×
(Siemens Analytical X-ray Instruments, Inc.) was used
for structure representations.
−
2
10
mbar) afforded a colorless oil, yield 0.7 g (67%).
−
1
1
IR (cap.): w˜ =3350–3440 cm
(br, OH ). H-NMR
ass
(
9
2
benzene-d ): l=0.19, 0.23 and 0.49 (3s, SiCH , 3×
H), 0.42 (s, CH, 1H), 1.93 and 2.14 (2s, NCH3,
6
3
4. Supplementary material
×6H), 3.16 and 3.77 (2 br s, CH , 2×2H), 6.75–754
2
1
3
(
m, aryl-CH). C-NMR (benzene-d ): l=1.4, 3.8 and
Crystallographic data (excluding structure factors)
for the structure reported in this paper have been
deposited with the Cambridge Crystallographic Data
Centre as supplementary publication No. CCDC-
145939. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cam-
bridge CB2 1EZ (UK) (fax: +44-1223-336033; e-mail:
deposit@ccdc.cam.ac.uk).
6
4
.3 (SiCH ), 7.1 (CH), 44.4 and 45.4 (NCH ), 64.4 and
3
3
6
6.7 (CH ), 128.9, 129.7, 130.1 and 145.1 (arom. C).
2
2
9
Si-NMR (benzene-d ): l= −19.4 (SiSiMe ), −0.2
6
3
and 1.9 (CSiMe ), 3.2 (SiOH). MS m/z (%): 467 (7)
3
+
+
+
[
M −H], 423 (100) [M −HNMe ], 408 (100) [M −
2
CH NMe ]. Anal. Found: C, 56.10; H, 10.06; N, 5.67.
Calc. for C H N OSi (468.98): C, 56.34; H, 10.32; N,
2
2
2
2
48
2
4
5.97%.
3.3. [2,6-Bis(dimethylaminomethyl)phenyl]-
Acknowledgements
methoxy-(trimethylsilyl)-[bis(trimethylsilyl)methyl]silane
13)
Excess methanol (50 ml) was added to the ethereal
(
We gratefully acknowledge the support of our re-
search by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie. We thank Profes-
sor M. Michalik and Dr W. Baumann for recording the
NMR spectra and Professor N. Stoll for recording the
MS spectra.
solution of 0.17 g (0.37 mmol) of 9 and the solution was
refluxed for 1 h. After evaporation the residue was
recrystallized from methanol. Colorless crystals, m.p.
−
1
8
(
9°C, yield 0.15 g (84%). IR (nujol): w˜ =1113 cm
1
3 6
SiOCH ). H-NMR (benzene-d ): l=0.14, 0.20 and
0
.37 (3s, SiCH , 3×9H), 1.22 (s, CH, 1H), 2.18 (br s,
3
References
NCH , 12H), 3.32–3.81 (m, CH , 4H), 3.53 (s, OCH ,
3
3
2
3
1
3
H), 7.22–7.50 (m, aryl-CH, 3H). C-NMR (benzene-
[
1] (a) N. Wiberg, H. K o¨ pf, J. Organomet. Chem. 315 (1986) 9. (b)
N. Wiberg, G. Wagner, G. Reber, J. Riede, G. M u¨ ller,
Organometallics 6 (1987) 35. (c) N. Wiberg, K.-S. Joo, K.
Polborn, Chem. Ber. 126 (1993) 67. (d) N. Wiberg, G. Wagner,
G. M u¨ ller, J. Riede, J. Organomet. Chem. 271 (1984) 381.
d ): l=1.1, 3.2 and 3.7 (SiCH ), 8.3 (CH), 45.3
6
3
(NCH ), 52.0 (OCH ), 64.1 (CH ), 128.1, 128.2, 129.0
3 3 2
2
9
and 141.0 (arom. C). Si-NMR (benzene-d ): l=
−
6
21.3 (SiSiMe3), −0.8 and 2.5 (CSiMe ), 10.2
3