4310 Organometallics, Vol. 22, No. 21, 2003
Leung et al.
reaction was stirred for 2 days. The volatiles were removed
under reduced pressure, and the residue was extracted with
hexane/Et2O, 1:1. After filtration and concentration of the
filtrate, compound 4 was obtained as orange-red crystals.
Yield: 0.63 g (79%).
Method B: A solution of 2 (1.16 g, 1.82 mmol) in Et2O (30
mL) was added slowly to a stirred solution of GeCl2‚dioxane
(0.21 g, 0.91 mmol) in Et2O (30 mL) at -90 °C. The yellow
suspension was raised to ambient temperature and stirred for
2 days. The precipitate was filtered. Hexane was added to the
filtrate and concentrated under reduced pressure. 4 was
obtained as orange-red crystals. Yield: 0.24 g (42%).
in [Tbt(Tip)GedS], but similar to those distances re-
ported for typical Ge-S single bonds (2.17-2.25 Å).20
The Ge-Se distances of 2.357(4) and 2.370(4) Å in 7 are
in the range 2.337-2.421 Å for some Ge-Se single
bonds reported, but slightly shorter than the Ge-Se
distance of 2.426(2) Å in [{CPh(SiMe3)2C5H4N-2}2Ged
Se].5 The Ge-Te bond distances of 2.585(4) and 2.577(4)
Å in 8 are slightly shorter than that in alkylidene-
telluragermirane (2.591(3) Å)21 and [Ge{N(SiMe3)2}(µ-
Te)]2 (2.595(2), 2.596(2) Å).14d
[(µ-NdP h 2P )(Me3SiNdP h 2P )CdGe(OSiMe3)]2 (5). A so-
lution of 4 (0.70 g, 0.55 mmol) in toluene (30 mL) was added
to Me3NO (0.095 g, 1.27 mmol) in toluene (30 mL) at -90 °C
with stirring. The reaction mixture faded gradually when
raised to ambient temperature. The pale yellow solution was
stirred at room temperature for 17 h. The volatiles were
removed under reduced pressure, and the residue was ex-
tracted with Et2O. It was filtered and concentrated, yielding
pale yellow crystals of 5. Yield: 0.33 g (46%). Mp: 196 °C (dec).
Anal. Found: C, 57.27; H, 5.73; N, 4.03. Calcd for C62H76N4P4O2-
Exp er im en ta l Section
Gen er a l P r oced u r es. All manipulations were carried out
under an inert atmosphere of dinitrogen gas by standard
Schlenk techniques. Solvents were dried over and distilled
from CaH2 (hexane) and/or Na (Et2O, toluene, and THF).
Sulfur, selenium, and tellurium powders were purchased from
Aldrich Chemicals and used without further purification.
GeCl2‚dioxane22 and [Ge{N(SiMe3)2}2]23 were prepared by
reported procedures. The 1H, 13C, 31P, 77Se, and 125Te NMR
spectra were recorded on Bru¨ker WM-300 or Varian 400
spectrometers. The NMR spectra were recorded in benzene-
d6 or THF-d8, and the chemical shifts δ are relative to SiMe4,
85% H3PO4, Ph2Se2, and Me2Te2 for 1H, 13C, 31P, 77Se, and
125Te NMR, respectively.
1
Si4Ge2: C, 57.69; H, 5.93; N, 4.34. H NMR (C6D6): δ -0.02
(s, 18H, SiMe3), 0.71 (s, 18H, OSiMe3), 6.51-8.73 (m, 40H, Ph).
13C{1H} NMR (C6D6): δ 2.29 (SiMe3), 3.76 (OSiMe3), 127.03
1
(m, Ph), 129.36 (m, Ph), 130.95 (d, J P-C ) 60.6 Hz, p-Ph′),
1
132.21 (d, J P-C ) 45.6 Hz, m-Ph′), 133.18 (s, o-Ph′), 133.40
1
(d, J P-C ) 42.9 Hz, ipso-Ph′). 31P{1H} NMR (C6D6): δ 18.66,
[HC(P P h 2dNSiMe3)2Li‚THF ] (2). BunLi (6.3 mL, 10.11
mmol, 1.6 M solution in n-hexane) was added slowly to the
solution of [(Me3SiNdPPh2)2CH2] (5.65 g, 10.11 mmol) in THF
(60 mL) at -90 °C. The brown suspension was raised to
ambient temperature and stirred overnight. Volatiles were
removed under reduced pressure, and the residue was ex-
tracted by Et2O. The precipitate was filtered. Hexane was
added to the filtrate and concentrated under reduced pressure.
Compound 2 was obtained as pale yellow crystals. Yield: 4.52
g (70%). Mp: 128-131 °C. Anal. Found: C, 65.68; H, 7.57; N,
4.49. Calcd for C35H47N2LiOP2Si2: C, 66.01; H, 7.44; N, 4.40.
1H NMR (C6D6): δ 0.22 (s, 18H, SiMe3), 1.22-1.26 (m, 4H,
THF), 1.67 (t, J P-H ) 2.7 Hz, 1H, PC(H)P), 3.61-3.65 (m, 4H,
THF), 7.02-7.08 (m, 12H, Ph), 7.74-7.81 (m, 8H, Ph). 13C-
44.61.
[(Me3SiNdP P h 2)2CdGe(µ-S)]2 (6). A solution of 4 (0.34 g,
0.27 mmol) in THF (30 mL) was added dropwise to the
colorless solution of powdered sulfur (0.017 g, 0.53 mmol) in
THF (30 mL) at 0 °C with stirring. The resultant yellow
solution was raised to room temperature and stirred for 36 h.
After filtration and concentration of the filtrate, compound 6
was obtained as white crystals. Yield: 0.11 g (30%). Mp: 175-
176 °C. Anal. Found: C, 56.16; H, 5.80; N, 4.05. Calcd for
C
62H76N4Ge2P4S2Si2: C, 56.29; H, 5.79; N, 4.24. 1H NMR (THF-
d8): δ -0.46 (s, 18H, SiMe3), -0.32 (s, 18H, SiMe3), 7.17-7.40
(m, 24H, Ph), 7.41-7.44 (m, 4H, Ph), 7.61-7.72 (m, 8H, Ph),
7.80-7.88 (m, 4H, Ph). 13C{1H} NMR (THF-d8): δ 2.16, 4.14
1
{1H} NMR (C6D6): δ 4.35 (SiMe3), 23.56 (t, J P-C ) 128.8 Hz,
2
(SiMe3), 128.20 (d,1J P-C ) 48.3 Hz, m-Ph), 128.58 (t, J P-C
)
24.0 Hz, o-Ph), 128.87 (d, 1J P-C ) 50.4 Hz, ipso-Ph), 130.08 (s,
PCP), 25.31, 68.66 (THF), 127.77 (s, p-Ph), 129.23 (s, m-Ph),
2
1
1
131.37 (t, J P-C ) 5.2 Hz, o-Ph), 142.08 (d, J P-C ) 95.5 Hz,
p-Ph), 131.15 (s, p-Ph′), 132.32 (s, m-Ph′), 132.59 (d, J P-C
)
ipso-Ph). 31P{1H} NMR (C6D6): δ 29.42.
67.2 Hz, o-Ph′), 133.71 (d, J P-C ) 46.2 Hz, ipso-Ph′). 31P{1H}
NMR (THF-d8): δ 10.69, 57.52. FAB-MS: m/z found 663.1040;
calcd for C31H38N2GeP2SSi 663.1054 ([M/2 + H]+).
1
[HC(P P h 2dNSiMe3)2GeCl] (3).
A solution of [HC-
(PPh2dNSiMe3)2Li‚THF] (2) (0.91 g, 1.43 mmol) in Et2O (20
mL) was added slowly to the solution of GeCl2‚dioxane (0.33
g, 1.43 mmol) in Et2O (20 mL) at 0 °C. The yellow suspension
was raised to ambient temperature and stirred for 18 h. The
precipitate was filtered. Hexane was added to the filtrate and
concentrated under reduced pressure. Compound 3 was ob-
tained as pale yellow crystals. Yield: 0.70 g (73%). Mp: 254
[(Me3SiNdP P h 2)2CdGe(µ-Se)]2 (7). A solution of 4 (0.68
g, 0.54 mmol) in THF (30 mL) was added dropwise to the
colorless solution of powdered selenium (0.089 g, 1.13 mmol)
in THF (30 mL) at 0 °C with stirring in the absence of light.
The resultant orange solution was raised to room temperature
and stirred for 2 days. It was filtered and concentrated,
obtaining yellow crystals of 7. Yield: 0.17 g (23%). Mp: 328
°C (dec). Anal. Found: C, 51.87; H, 5.58; N, 3.95. Calcd for
°C (dec). Anal. Found: C, 57.08; H, 6.15; N, 4.24. Calcd for
1
C
31H39ClGeN2P2Si2‚1/2 hexane: C, 57.68; H, 6.40; N, 3.96. H
62H76N4Ge2P4Se2Si2: C, 52.49; H, 5.54; N, 3.95. 1H NMR
NMR (THF-d8): δ -0.15 (s, 18H, SiMe3), 3.50 (t, J P-H ) 12
C
Hz, 1H, PC(H)P), 7.29-7.37 (m, 13H, Ph), 7.66-7.72 (m, 7H,
(THF-d8): δ -0.48 (s, 18H, SiMe3), -0.25 (s, 18H, SiMe3),
7.18-7.42 (m, 24H, Ph), 7.49-7.58 (m, 4H, Ph), 7.61-7.68 (m,
8H, Ph), 7.78-7.85 (m, 4H, Ph). 13C{1H} NMR (THF-d8): δ
Ph). 13C{1H} NMR (THF-d8): δ 3.01 (SiMe3), 37.14 (t, J P-C
)
1
2
270.9 Hz, PCP), 128.58 (t, J P-C ) 24.0 Hz, m-Ph and p-Ph),
2
131.14 (s, o-Ph), 132.31 (t, J P-C ) 21.0 Hz, ipso-Ph). 31P{1H}
1
2.50, 4.39 (SiMe3), 128.49 (d, J P-C ) 47.7 Hz, m-Ph), 128.81
(s, o-Ph), 129.18 (d, 1J P-C ) 50.7 Hz, ipso-Ph), 130.37 (s, p-Ph),
131.46 (s, p-Ph′), 132.68 (s, m-Ph′), 132.90 (d, 1J P-C ) 43.8 Hz,
NMR (THF-d8): δ 13.97.
[(Me3SiNdP P h 2)2CdGefGedC(P P h 2dNSiMe3)2] (4).4
Method A: A solution of 3 (1.30 g 1.95 mmol) in toluene (30
mL) was added to a stirred solution of [Ge{N(SiMe3)2}2] (0.49
g, 1.25 mmol) in toluene (30 mL) at room temperature. The
1
o-Ph′), 133.91 (d, J P-C ) 46.8 Hz, ipso-Ph′). 31P{1H} NMR
(THF-d8): δ 13.97, 60.80. 77Se NMR (THF-d8): δ 860.88. FAB-
MS: m/z found 711.0510; calcd for C31H38N2GeP2SeSi2 711.0499
([M/2 + H]+).
(20) Tokitoh, N.; Matsumoto, T.; Manmaru, K.; Okazaki, R. J . Am.
Chem. Soc. 1993, 115, 8855.
(21) Kishikawa, K.; Tokitoh, N.; Okazaki, R. Organometallics 1997,
16, 5127.
(22) Fjeldberg, T.; Haaland, A.; Schilling, B. E. R.; Lappert, M. F.;
Thorne, A. J . J . Chem. Soc., Dalton Trans. 1986, 1551.
[(Me3SiNdP P h 2)2CdGe(µ-Te)]2 (8). A solution of 4 (0.72
g, 0.57 mmol) in THF (30 mL) was added slowly to the colorless
solution of powdered tellurium (0.15 g, 1.18 mmol) in THF (30
mL) at 0 °C with stirring in the absence of light. The resultant
red solution was raised to room temperature and stirred for 2