5220 Organometallics, Vol. 21, No. 24, 2002
Ding et al.
plates. Mass spectra were obtained on a Finnigan Mat 8230
instrument. The compound [HC(CMeNAr)2]GeCl12 was pre-
pared by literature procedures. Other chemicals were pur-
chased from Aldrich and used as received.
which time the color changed from orange-red to pale yellow.
Concentration (ca. 10 mL) and storage of the solution in a -32
°C freezer for 24 h afforded yellow crystals of 9 (yield 0.362 g,
61%). Mp: 188-191 °C. Anal. Calcd for C33H53GeN3Si: C,
66.90; H, 9.02; N, 7.09. Found: C, 66.85; H, 9.09; N, 7.19. EI-
MS: m/e 593 (M+), 578 (M+ - Me, 100). 1H NMR (toluene-d8):
δ -0.36 (s, 9 H, SiMe3), 0.25 (s, 1 H, NH), 0.79 (s, 3 H, GeMe),
1.25 -1.50 (m, 24 H, CHMe2), 1.58 (s, 3 H, â-Me), 3.22 (s, 1 H,
â-CH2), 3.40 (sept, 2 H, CHMe2), 3.50 (sept, 2 H, CHMe2), 3.75
(sept, 2 H, CHMe2), 3.85 (sept, 2 H, CHMe2), 3.86 (s, 1 H,
â-CH2), 5.25 (s, 1 H, γ-CH), 7.10-7.20 (m, 6 H, 2,6-iPr2C6H3).
29Si NMR (toluene-d8): δ 5.94. IR (Nujol): 3361 cm-1 (NH).
[HC(CMeNAr )2]GeMe2(I) (Ar ) 2,6-iP r 2C6H3; 10). A
solution of MeI (0.142 g, 0.1 mmol) in dichloromethane (10 mL)
was added to a stirred solution of 5 (0.506 g, 1.0 mmol) in
dichloromethane (20 mL) at room temperature. After the
addition the reaction mixture was stirred for 10 h, during
which time the color changed from orange-red to yellow.
Removing the volatiles, washing the residue with n-hexane
(2 × 5 mL), and drying under vacuum afforded a pale yellow
powder of 10 (0.589 g, 91%). Mp: 217-219 °C. Anal. Calcd
for C31H47GeIN2 (647.2): C, 57.53; H, 7.32; N, 4.33. Found:
[HC(CMeNAr )2]GeMe (Ar ) 2,6-iP r 2C6H3; 5). A solution
of MeLi (1.4 mL, 1.6 M in diethyl ether, 2.24 mmol) was added
dropwise to a stirred solution of [HC(CMeNAr)2]GeCl (1; 1.05
g, 2.0 mmol) in diethyl ether (40 mL) at -78 °C. The reaction
mixture was warmed to room temperature and was stirred for
3 h. After removal of all volatiles, the residue was extracted
with n-hexane (30 mL). Storage of the extract in a -32 °C
freezer for 3 days afforded orange-red crystals of 5 (0.90 g,
89%). Mp: 131-132 °C. Anal. Calcd for C30H44GeN2 (506.3):
C, 71.31; H, 8.78; N, 5.54. Found: C, 71.56; H, 8.84; N, 5.53.
1
EI-MS (70 eV): m/e (%) 506 (M+, 5), 491 (M+ - Me, 100). H
NMR (C6D6): δ 0.64 (s, 3 H, GeMe), 1.16 (d, 6 H, CHMe2), 1.17
(d, 6 H, CHMe2), 1.29 (d, 6 H, CHMe2), 1.38 (d, 6 H, CHMe2),
1.55 (s, 6 H, â-Me), 3.45-3.50 (sept, 2 H, CHMe2), 3.65-3.73
(sept, 2 H, CHMe2), 4.80 (s, 1 H, γ-CH), 7.10-7.15 (m, 6 H,
2,6-iPr2C6H3).
[HC(CMeNAr )2]Gen Bu (Ar ) 2,6-iP r 2C6H3; 6). Deep red
crystals of 6 can be obtained in a way similar to that for 5 in
high yield (85%). Mp: 152-155 °C. Anal. Calcd for C33H50
-
C, 57.66; H, 7.13; N, 4.58. EI-MS (70 eV): m/e (%) 521 (M+
-
1
GeN2 (547.3): C, 72.41; H, 9.21; N, 5.12. Found: C, 72.01; H,
I, 20), 505 (M+ - I - CH4, 100). H NMR (CD3CN): δ 0.83 (s,
6 H, GeMe2), 1.19 (d, 12 H, CHMe2), 1.28 (d, 12 H, CHMe2),
2.02 (s, 6 H, â-Me), 2.80-3.00 (sept, 4 H, CHMe2), 5.85 (s, 1
H, γ-CH), 7.38-7.50 (m, 6 H, 2,6-iPr2C6H3).
9.10; N, 5.01. EI-MS (70 eV): m/e (%) 547 (M+, 5), 491 (M+
-
1
nBu, 100). H NMR (C6D6): δ 0.65 (t, 3 H, (CH2)3Me), 0.80-
1.05 (m, 6 H, (CH2)3Me), 1.12 (d, 6 H, CHMe2), 1.16 (d, 6 H,
CHMe2), 1.35 (d, 6 H, CHMe2), 1.42 (d, 6 H, CHMe2), 1.52 (s,
6 H, â-Me), 3.45-3.60 (sept, 2 H, CHMe2), 3.65-3.82 (sept, 2
H, CHMe2), 4.72 (s, 1 H, γ-CH), 7.05-7.15 (m, 6 H, 2,6-
iPr2C6H3).
X-r a y Cr ysta llogr a p h y. Single crystals of 5, 6, 8, and 9
were taken from the flask under nitrogen gas and mounted
on a glass fiber in a rapidly cooled perfluoropolyether.25 Data
were collected on a Stoe AED2 four-circle diffractometer (5 and
8) at 200(2) K or on a Stoe-Siemens-Huber four-circle diffrac-
tometer (6 and 9) equipped with a Siemens SMART area
detector at 133(2) K. Monochromated Mo KR radiation (λ )
0.710 73 Å) was used. The structures were solved by direct
methods (SHELXS-9626) and refined against F2 using SHELXL-
97.27 All non-hydrogen atoms were refined anisotropically. All
hydrogen atoms bonded to carbon were included in geo-
metrically ideal positions and refined with the riding model.
The hydrogen atom bonded to nitrogen (9) was refined with a
distance restraint. All disordered groups were refined with
distance restraints and restraints for the anisotropic displace-
ment parameters.
[HC(CMeNAr )2]GeMe(S) (Ar ) 2,6-iP r 2C6H3; 7). A solu-
tion of 5 (0.506 g, 1.0 mmol) in toluene (20 mL) was added to
a stirred suspension of elemental sulfur (0.032 g, 1.0 mmol)
and the mixture refluxed for 4 h. After removal of the volatiles,
the residue was washed with n-hexane (2 × 5 mL) and then
extracted with toluene (15 mL). Adding n-hexane (5 mL) to
the extract and keeping the solution at room temperature for
3 days afforded pale yellow crystals of 7 in a yield of 65%. The
physical data are in agreement with those in ref 14.
[HC(CMeNAr )2]GeMe(Se) (Ar ) 2,6-iP r 2C6H3; 8). A solu-
tion of 5 (0.506 g, 1.0 mmol) in toluene (20 mL) was added to
a stirred suspension of elemental selenium (0.079 g, 1.0 mmol)
in toluene (10 mL) at room temperature. The reaction mixture
was stirred for 2 days. After filtration a yellow solution was
obtained. Concentration (ca. 10 mL) and storage of the yellow
solution in a -32 °C freezer for 24 h afforded yellow crystals
of 8 (yield 0.508 g, 87%). Mp: 210-213 °C dec. Anal. Calcd
for C30H44GeN2Se: C, 61.67; H, 7.58; N, 4.79. Found: C, 61.29;
H, 7.47; N, 4.80. EI-MS: m/e 584 (M+), 569 (M+ - Me), 506
Ack n ow led gm en t. This work was supported by the
Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen Industrie.
Su p p or tin g In for m a tion Ava ila ble: Figures showing
ORTEP diagrams and tables giving full details of the crystal-
lographic data and data collection parameters, atom coordi-
nates, bond distances, bond angles, anisotropic thermal pa-
rameters, and hydrogen coordinates for 5, 6, and 8. This
material is available free of charge via the Internet at
http://pubs.acs.org.
1
(M+ - Se). H NMR (C6D6): δ 1.06 (d, 6 H, CHMe2), 1.09 (d, 6
H, CHMe2), 1.10 (s, 3 H, GeMe), 1.25 (d, 6 H, CHMe2), 1.46 (s,
6 H, â-Me), 1.63 (d, 6 H, CHMe2), 2.92-3.02 (sept, 2 H,
CHMe2), 3.80-3.90 (sept, 2 H, CHMe2), 4.81 (s, 1 H, γ-CH),
7.01-7.15 (m, 6 H, 2,6-iPr2C6H3). 77Se NMR (C6D6): δ -349.
[HC(C(CH2)NAr )CMeNAr ]GeMe(N(H)SiMe3) (Ar ) 2,6-
iP r 2C6H3; 9). A solution of Me3SiN3 (0.106 g, 0.1 mmol) in
n-hexane (10 mL) was added to a stirred solution of 5 (0.506
g, 1.0 mmol) in n-hexane (20 mL) at room temperature. After
the addition, the reaction mixture was stirred for 12 h, during
OM0203328
(25) Kottke, T.; Stalke, D. J . Appl. Crystallogr. 1993, 26, 615.
(26) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467.
(27) Sheldrick, G. M. SHELXL-97; Universita¨t Go¨ttingen, Go¨ttingen,
Germany, 1997.