Group 14 Metal Enamido, Alkenyl, Imido and Alkenyl-Amido Complexes
FULL PAPER
pressure and stored at Ϫ30 °C. Compound 4 was obtained as yel-
low crystals. Yield: 0.45 g (37%); m.p.: 201Ϫ203 °C.
GeCl4 (0.54 mL, 4.69 mmol) in THF (20 mL) at Ϫ90 °C. The yel-
low solution was warmed to ambient temperature and stirred for
C38H54N4PbSi4: calcd. C 51.49, H 6.14, N 6.32; found C 51.12, H two days. The volatiles were removed under reduced pressure and
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6.06, N 6.27. H NMR (300 MHz, [D8]THF, 25 °C): δ ϭ Ϫ0.28 (s,
9 H, SiMe3), Ϫ0.21 (s, 9 H, SiMe3), 6.95Ϫ7.01 (m, 1 H, 5-py),
the residue was extracted with toluene. The yellow mixture was
filtered and concentrated to give yellow crystals of the title com-
7.18Ϫ7.24 (d, J ϭ 8.0 Hz, 1 H, 3-py), 7.35Ϫ7.41 (m, 3 H, Ph), pound. Yield: 0.84 g (48%); m.p.: 226Ϫ227 °C. C32H36Cl4Ge2N4Si2:
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7.42Ϫ7.48 (m, 2 H, Ph), 7.55Ϫ7.64 (m, 1 H, 4-py), 8.45 (d, J ϭ 4.1 calcd. C 46.88, H 4.43, N 4.83; found C 46.51, H 4.31, N 4.63. H
Hz, 1 H, 6-py) ppm. 13C{1H} NMR (300 MHz, [D8]THF, 25 °C):
NMR (300 MHz, C6D6, 25 °C): δ ϭ 0.03 (s, 4 H, SiMe3), 0.31 (s,
δ ϭ 1.17, 2.34 (SiMe3), 119.48 (CSiMe3), 121.80, 123.43, 125.29, 5 H, SiMe3), 6.86 (t, J ϭ 7.1 Hz, 1 H, 5-py), 6.98 (d, J ϭ 7.1 Hz,
128.52, 129.64, 131.79, 135.90, 142.62, 148.02, 150.03, 159.77 (Ph 1 H, 3-py), 7.08Ϫ7.15 (m, 3 H, Ph), 7.17Ϫ7.22 (m, 2 H, Ph), 7.41
and Py), 164.63 (NCPh).
(t, J ϭ 7.7 Hz, 1 H, 4-py), 7.73 (d, J ϭ 5.5 Hz, 1 H, 6-py) ppm.
13C{1H} NMR (300 MHz, C6D6, 25 °C): δ ϭ 2.60 (SiMe3), 119.13
(CSiMe3), 122.97, 126.04, 127.80, 128.91, 129.67, 132.07, 133.09,
139.98, 145.62 (Ph and Py), 167.73 (NCPh) ppm.
[Ge{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (5): A solution of 1
(0.94 g, 1.36 mmol) in Et2O (30 mL) was added slowly to a solution
of GeCl2·dioxane (0.66 g, 2.85 mmol) in Et2O (30 mL) at 0 °C. The
yellow suspension was warmed to ambient temperature and stirred
for 18 h. The precipitate was then filtered. Hexane was added to
the filtrate and concentrated, yielding pale-yellow crystals of 5.
Yield: 0.76 g (62%); m.p.: 124Ϫ125 °C. C19H27ClGeN2Si2: calcd. C
50.98, H 6.08, N 6.25; found C 50.77, H 5.91, N 6.13. 1H NMR
(300 MHz, [D8]THF, 25 °C): δ ϭ Ϫ0.22 (s, 9 H, SiMe3), Ϫ0.18 (s,
9 H, SiMe3), 7.33Ϫ7.40 (m, 4 H, Ph), 7.41Ϫ7.49 (d, 1 H, 5-py),
7.49Ϫ7.63 (m, 1 H, Ph), 7.63Ϫ7.66 (d, J ϭ 7.4 Hz, 1 H, 3-py), 7.95
(t, J ϭ 7.1 Hz, 1 H, 4-py), 8.70 (d, J ϭ 5.5 Hz, 1 H, 6-py) ppm.
13C{1H} NMR (300 MHz, [D8]THF, 25 °C): δ ϭ 1.62, 3.08
(SiMe3), 95.62 (CSiMe3), 120.69, 126.33, 127.97, 129.28, 130.06,
131.11, 133.53, 140.47, 144.38, 145.61, 155.57 (Ph and Py), 164.94
(NCPh) ppm.
[{(C5H4N-2)C(SiMe3)C(Ph)N}(µ-SiHCl)]2 (9): A solution of 1
(1.28 g, 1.84 mmol) in THF (30 mL) was added slowly to a solution
of HSiCl3 (0.41 mL, 4.05 mmol) in THF (20 mL) at Ϫ90 °C. The
yellow solution was warmed to ambient temperature and stirred
for two days. The volatiles were removed under reduced pressure
and the residue was extracted with toluene. The yellow mixture
was filtered and concentrated to give yellow crystals of the title
compound. Yield: 0.97 g (79%); m.p.: 232Ϫ233 °C.
C32H38Cl2Si4N4: calcd. C 58.07, H 5.79, N 8.46; found C 58.55, H
1
5.62, N 7.64. H NMR (300 MHz, [D8]THF, 25 °C): δ ϭ Ϫ0.16 (s,
6 H, SiMe3), 0.41 (s, 3 H, SiMe3), 5.46 (s, 1 H, SiH), 6.92Ϫ6.96 (t,
J ϭ 6.0 Hz, 1 H, 5-py), 6.99Ϫ7.02 (d, J ϭ 7.4 Hz, 1 H, 3-py),
7.11Ϫ7.19 (m, 2 H, Ph), 7.36Ϫ7.37 (m, 3 H, Ph), 7.41Ϫ7.44 (m, 1
H, 4-py), 7.80Ϫ7.82 (d, J ϭ 5.8 Hz, 1 H, 6-py) ppm. 13C{1H}
NMR (300 MHz, [D8]THF, 25 °C): δ ϭ 2.90, 3.13 (SiMe3), 101.36
(CSiMe3), 118.44, 123.80, 126.05, 127.92, 128.35, 128.91, 129.59,
139.36, 141.80, 155.89 (Ph and Py) 162.51 (NCPh) ppm.
[Sn{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (6): A solution of 1
(0.86 g, 1.23 mmol) in Et2O (30 mL) was added slowly to a solution
of SnCl2 (0.47 g, 2.47 mmol) in Et2O (30 mL) at 0 °C. The yellow
suspension was warmed to ambient temperature and stirred for
18 h. The precipitate was then filtered. The filtrate was removed
under reduced pressure and the residue was extracted with THF/n-
hexane (1:10) and concentrated to yield 6 as a yellow solid. Yield:
0.51 g (42%); m.p.: 210Ϫ213 °C. C19H27ClN2Si2Sn: calcd. C 46.22,
H 5.51, N 5.67; found C 46.29, H 5.58, N 5.88. 1H NMR
(300 MHz, [D8]THF, 25 °C): δ ϭ Ϫ0.28 (s, 9 H, SiMe3), Ϫ0.27 (s,
9 H, SiMe3), 7.13Ϫ7.26 (m, 1 H, 5-py), 7.30Ϫ7.35 (m, 3 H, Ph),
7.35Ϫ7.40 (m, 2 H, Ph), 7.44Ϫ7.47 (m, 1 H, 4-py), 7.56Ϫ7.59 (d,
J ϭ 8.7 Hz, 1 H, 3-py), 8.48 (d, J ϭ 6.0 Hz, 1 H, 6-py) ppm.
13C{1H} NMR (300 MHz, [D8]THF, 25 °C): δ ϭ 0.96, 1.96
(SiMe3), 100.12 (CSiMe3), 118.72, 127.56, 128.69, 130.89, 135.14,
140.72, 147.36, 160.03 (Ph and Py), 162.93 (NCPh) ppm. 119Sn{1H}
NMR (149 MHz, [D8]THF, 25 °C): δ ϭ Ϫ197.95 ppm.
[{(C5H4N-2)C(H)C(Ph)N}(µ-GeCl2)]2 (11):
A solution of 10
(0.84 g, 1.53 mmol) in THF (30 mL) was added slowly to a solution
of GeCl4 (0.38 mL, 3.36 mmol) in THF (20 mL) at Ϫ90 °C. The
yellow suspension was warmed to ambient temperature and stirred
for two days. The volatiles were removed under reduced pressure
and the residue was extracted with toluene. The yellow mixture
was filtered and concentrated to give yellow crystals of the title
compound. Yield: 0.39 g (37%); m.p.: 210Ϫ211 °C.
C26H36Cl4Ge2N4: calcd. C 46.23, H 2.90, N 8.29; found C 46.03,
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H 3.08, N 8.23. H NMR [300 MHz, C6D6/[D8]THF (2:1), 25 °C]:
δ ϭ 5.09 (s, 1 H, HCC), 6.57 (t, J ϭ 6.6 Hz, 1 H, 5-py), 6.68 (d,
J ϭ 8.5 Hz, 1 H, 3-py), 6.91 (t, J ϭ 8.0 Hz, 1 H, 4-py), 7.10Ϫ7.14
(m, 5 H, Ph), 8.65 (d, J ϭ 6.3 Hz, 1 H, 6-py) ppm. 13C{1H} NMR
(300 MHz, C6D6/[D8]THF 2:1, 25 °C): δ ϭ 96.51 (HCC), 116.70,
119.56, 121.62, 124.71, 125.92, 126.85, 129.69, 130.36, 139.85,
142.27, 145.48 (Ph and Py), 155.79 (NCPh) ppm.
[Pb{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (7): A solution of 1
(1.25 g, 1.80 mmol) in THF (20 mL) was added slowly to a solution
of PbCl2 (1.10 g, 3.96 mmol) in THF (20 mL) at Ϫ90 °C. The yel-
low suspension was warmed to ambient temperature and stirred
for 18 h. The volatiles were then removed under reduced pressure
and the residue was extracted with toluene. The yellow mixture
was filtered and concentrated to give yellow crystals of the title
compound. Yield: 0.73 g (69%); m.p.: 190Ϫ192 °C.
C19H27ClN2PbSi2: calcd. C 39.19, H 4.67, N 4.81; found C 38.94,
X-ray Crystallographic Study: Single crystals were sealed in Linde-
mann glass capillaries under nitrogen. The X-ray data of 2Ϫ5, 7Ϫ9,
and 11 were collected on a Rigaku R-AXIS II imaging plate using
˚
graphite-monochromated Mo-Kα radiation (λ ϭ 0.71073 A) from
a rotating-anode generator operating at 50 kV and 90 mA. Crystal
data for 2Ϫ5, 7Ϫ9, and 11 are summarized in Table 5 and 6. The
structures were solved by direct phase determination using the
computer program SHELXTL-PC[27] on a PC 486 and refined by
full-matrix least-squares with anisotropic thermal parameters for
the non-hydrogen atoms. Hydrogen atoms were introduced in their
idealized positions and included in structure factor calculations
with assigned isotropic temperature factor calculations.
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H 4.53, N 4.73. H NMR (300 MHz, C6D6, 25 °C): δ ϭ Ϫ0.07 (s,
9 H, SiMe3), Ϫ0.08 (s, 9 H, SiMe3), 6.40 (m, 1 H, 5-py), 6.90 (m,
1 H, 3-py), 7.07 (m, 1 H, 4-py), 7.23Ϫ7.27 (m, 2 H, Ph), 7.47Ϫ7.50
(m, 3 H, Ph), 8.24 (d, J ϭ 4.1 Hz, 1 H, 6-py) ppm. 13C{1H} NMR
(300 MHz, C6D6, 25 °C): δ ϭ 2.07, 2.94 (SiMe3), 89.40 (CSiMe3),
120.50, 123.30, 128.63, 129.00, 130.67, 130.79, 138.33, 145.26,
159.49 (Ph and Py), 166.23 (NCPh) ppm.
CCDC-250383 to -250390 (2Ϫ5, 7Ϫ9 and 11, respectively) contain
the supplementary crystallographic data for this paper. These data
[Ge{C(C5H4N-2)C(Ph)N(SiMe3)}Cl2]2 (8): A solution of 1 (1.48 g,
2.13 mmol) in THF (30 mL) was added slowly to a solution of can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
Eur. J. Inorg. Chem. 2005, 513Ϫ521
Leung, Wing-Por
