Main Group Heterocycles from Lithiated Phosphinimines
Organometallics, Vol. 26, No. 12, 2007 3043
mL) and dried under vacuum to give a white solid (0.156 g, 67%).
31P NMR (C6D6): 74.6. 11B NMR (C6D6): -1.3. Anal. Calcd for
C22H25BF10NOP: C, 47.94; H, 4.57; N, 2.54. Found: C, 48.27; H,
4.75; N, 2.55.
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3
1H NMR: 2.79 (m, CH), 2.02 (m, CH2), 1.06 (dd, JHH ) 7, JPH
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3
) 7, 3H, Me), 0.95 (d, JPH ) 14, 9H, tBu), 0.91 (d, JPH ) 14,
9H, tBu), 0.09 (s, 9H, SiMe3). 13C{1H} NMR: 139.3 (d, JCF
)
1
Synthesis of ((C6F5)2B(Cl)CH2)tBu2PNH2, 16. Compound 15
(0.330 g; 1.81 mmol) was dissolved in 7 mL of Me3SiCl. The clear
solution was stirred at room temperature for 24 h. The excess
solvent was removed under vacuum to give a white solid, which
was washed by pentane and dried under vacuum (0.31 g; 0.56
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242, C6F5), 137.9 (d, JCF ) 237, C6F5), 39.5 (d, JPC ) 40, tBu),
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1
38.8 (d, JPC ) 40, tBu), 34.6 (d, JPC ) 55, PCHMe), 29.6 (s,
tBu), 28.7 (s, tBu), 19.8 (s, PCHMe), 6.9 (s, SiMe3). 19F NMR:
3
-129.40 (br, 4F, o-F), -159.31 (t, JFF ) 21, 1F, p-F), -161.23
(t, JFF ) 20.6 Hz, 1F, p-F), -165.43 (br, 4F, m-F). 31P NMR:
3
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2
mmol; 93%). H NMR (C6D6): 2.62 (bs, 2H, NH2), 1.99 (d, JPH
90.1. 11B NMR: -1.5. Anal. Calcd for C26H33BF10NPSi: C, 50.42;
) 11 Hz, 2H, CH2), 0.53 (d, JPH ) 15 Hz, 9H, tBu). 13C{1H}
3
NMR (C6D6): 148.6 (d, 1JCF ) 244 Hz, o-C6F5), 140.0 (d, 1JCF
)
H, 5.37; N, 2.26. Found: C, 50.58; H, 5.19; N, 2.39.
250 Hz, p-C6F5), 138.0 (d, 1JCF ) 244 Hz, m-C6F5), 124.3 (br, ipso-
Synthesis of [(Me2AlCMe2)iPr2PNSiMe3], 12, and
[((Me2N)2BCMe2)iPr2PNSiMe3], 13. These compounds were
prepared in a similar fashion, and thus only one preparation is
detailed. A solution of nBuLi (4.40 mL; 8.81 mmol) in hexanes
was added dropwise to a solution of 11 (1.816 g; 7.34 mmol) in
toluene (30 mL) at 25 °C. After stirring for 12 h, the clear yellow
solution was cooled to -78 °C and (Me2N)2BBr (1.04 mL, 7.34
mmol) was added dropwise over a 15 min period. The slurry was
gradually warmed to 25 °C and stirred for an additional 12 h. The
mixture was passed through Celite, and the volatile products were
removed in Vacuo. The thick oil 13 was washed with cold pentanes
(3 × 1 mL) and dried (1.740 g, 67%). 12: Yield: 0.341 g, 54%.
1H NMR: 1.78 (m, 2H, CMe2H), 1.42 (d, 6H, 3JP-H ) 19, CMe2),
0.95 (dd, 6H, 3JP-H ) 15, 3JH-H ) 7, CMe2H), 0.92 (dd, 6H, 3JP-H
C), 35.08 (d, 1JPC ) 48 Hz, tBu), 25.8 (s, tBu), 11.2 (br, CH2). 19
F
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NMR (C6D6): -132.8 (d, JFF ) 20 Hz, 4F, o-F), -159.7 (t, JFF
) 20 Hz, 2F, p-F), -165.1 (m, 4F, m-F). 31P NMR (C6D6): 72.6.
11B NMR (C6D6): -4.8. Anal. Calcd for C21H22BF10NPCl: C,
45.39; H, 3.99; N, 2.52. Found: C, 45.27; H, 3.75; N, 2.55.
Synthesis of [((C6F5)2BCH2)tBu2PNH)], 17. Compound 16
(0.080 g; 0.14 mmol) was dissolved in 5 mL of toluene. nBuLi
(2.5 M) (0.06 mL; 0.15 mmol) was added dropwise at room
temperature. The clear solution turned cloudy due to LiCl formation.
After stirring for 6 h, the LiCl was removed by filtration through
Celite and toluene by vacuum to give a white solid (0.069 g; 0.13
mmol; 93%). 1H NMR (C6D6): 1.99 (bs, 2H, NH), 1.58 (d, 2JPH
10 Hz, 2H, CH2), 0.57 (d, 3JPH ) 14 Hz, 9H, tBu). 13C{1H} NMR
)
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1
) 15, JH-H ) 7, CMe2H), 0.15 (s, 9H, SiMe3), -0.36 (s, 6H,
(C6D6): 147.9 (d, JCF ) 242 Hz, o-C6F5), 140.0 (d, JCF ) 248
1
AlMe2). 13C{1H} NMR: 26.8 (d, JP-C ) 42, CMe2H), 23.8 (br,
1
1
Hz, p-C6F5), 137.85 (d, JCF ) 249 Hz, m-C6F5), 35.6 (d, JPC
)
35 Hz, tBu), 25.5 (s, tBu), 7.55 (br, CH2). 19F NMR (C6D6): -136.2
(br, 4F, o-F), -160.1 (t, 3JFF ) 20 Hz, 2F, p-F), -164.47 (m, 4F,
m-F). 31P NMR (C6D6): 89.7. 11B NMR (C6D6): -4.7. Anal. Calcd
for C21H21BF10NP: C, 48.58; H, 4.08; N, 2.70. Found: C, 48.82;
H, 4.40; N, 2.71.
CMe2), 22.2 (s, CMe2), 17.4 (s, CMe2H), 16.7 (s, CMe2H), 3.4 (s,
SiMe3), -7.5 (br, AlMe2). 31P{1H} NMR: 60.4. 27Al NMR: 168.0
(br, ν1/2 ≈ 2500 Hz). Anal. Calcd for C15H37AlNPSi: C, 56.74; H,
11.74; N, 4.41. Found: C, 56.58; H, 11.49; N, 4.39. 13: 1H NMR:
2.82 (s, 12H, NMe), 2.00 (sep, 2H, 3JH-H ) 7, CMe2H), 1.19 (dd,
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6H, JP-H ) 14, JH-H ) 7, CMe2H), 1.15 (d, 6H, JP-H ) 15,
Synthesis of [((C6F5)2BCH2)tBu2PNH](AlMe3), 18. Compound
17 (65 mg; 0.13 mmol) was dissolved in 5 mL of toluene, then
cooled to -35 °C. AlMe3 (14.3 µL; 0.15mmol) was added dropwise
at the same temperature. After stirring the solution for 1 h, toluene
was removed by vacuum to give a white solid, which was washed
with pentane and dried under vacuum (0.067 g; 0.11 mmol; 90%).
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CMe2), 1.01 (dd, 6H, JP-H ) 14, JH-H ) 7, CMe2H), 0.19 (s,
9H, SiMe3). 13C{1H} NMR: 40.8 (s, NMe), 29.0 (d, JP-C ) 56,
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CMe2H), 27.5 (d, JP-C ) 59, CMe2), 21.6 (s, CMe2H), 19.0 (d,
2JP-C ) 2 Hz, CMe2), 18.4 (s, CMe2H), -0.42 (s, SiMe3). 31P{1H}
NMR: 18.0. 11B{1H} NMR: 25.3. Anal. Calcd for C16H41BN3-
PSi: C, 55.64; H, 11.96; N, 12.17. Found: C, 55.58; H, 11.77; N,
12.09.
2
1H NMR (C6D6): 1.77 (br s, NH), 1.38 (d, JPH ) 16 Hz, 2H,
3
CH2), 0.70 (s, 6H, AlMe2), 0.64 (d, JPH ) 15 Hz, 9H, tBu), 0.14
1
(s, 3H, AlMe). 13C{1H} NMR (C6D6): 150.5 (d, JCF ) 233 Hz,
Synthesis of [((C6F5)2B(Cl)CH2)tBu2PNH(SiMe3)], 14. Com-
pound 2 (0.350 g; 0.591 mmol) was dissolved in 5 mL of CH2Cl2,
then added to a CH2Cl2 solution of [Me3NH]Cl (0.073 g; 0.763
mmol) at 25 °C. After stirring the solution for 24 h, the solvent
was removed under vacuum to give a white solid. The solid was
washed with toluene (3 × 5mL), then dried under vacuum (0.270
g; 0.43 mmol; 73%). 1H NMR: 5.04 (d, 2JPH ) 12, NH), 2.09 (d,
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o-C6F5), 140.8 (d, JCF ) 287 Hz, p-C6F5), 137.5 (d, JCF ) 279
Hz, m-C6F5), 36.3 (d, JPC ) 51 Hz, tBu), 26.7 (s, tBu), 17.3. 19F
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NMR (C6D6): -123.32 (d, JFF ) 16 Hz, 4F, o-F), -156.48 (t,
3JFF ) 18 Hz, 2F, p-F), -162.61 (m, 4F, m-F). 31P NMR (C6D6):
74.2. 11B NMR (C6D6): 83.9 (br). Anal. Calcd for C24H30BF10-
NPAl: C, 48.75; H, 5.11; N, 2.37. Found: C, 48.57; H, 4.75; N,
2.22.
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2JPH ) 11, 2H, CH2), 0.66 (d, JPH ) 14, 18H, tBu), 0.09 (s, 9H,
1
SiMe3). 13C{1H} NMR: 148.5 (d, JCF ) 240, o-C6F5), 140.1 (d,
Synthesis of [(((C6F5)2B(OMe)CH2)tBu2PNH)(AlMe2)], 19.
Compound 15 (0.250 g; 0.450 mmol) was dissolved in 5 mL of
toluene, then cooled to -35 °C. AlMe3 (48 µL; 0.50 mmol) was
added dropwise. Gas evolution was observed. After stirring the
solution for 2 h, toluene was removed by vacuum to give a white
solid, which was washed with pentane and dried under vacuum
(0.230 g; 0.38 mmol; 84%). 1H NMR (C6D6): 3.05 (s, 3H, OMe),
1.58 (d, 2JPH ) 17 Hz, 2H, CH2), 0.55 (d, 3JPH ) 14 Hz, 9H, tBu),
-0.35 (s, 6H, AlMe). 13C{1H} NMR (C6D6): 148.9 (d, 1JCF ) 237
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1JCF ) 248, p-C6F5), 138.0 (d, JCF ) 266, m-C6F5), 36.1 (d, JPC
) 48, tBu), 26.6 (s, tBu), 14.6 (br, CH2), 2.7 (s, SiMe3). 19F NMR:
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-132.46 (d, JFF ) 18, 4F, o-F), -159.47 (t, JFF ) 20, 2F, p-F),
-164.86 (m, 4F, m-F). 31P NMR: 77.6. 11B NMR: -4.3. Anal.
Calcd for C24H30BF10NPSi: C, 45.91; H, 4.82; N, 2.23. Found: C,
45.72; H, 5.22; N, 2.55.
Synthesis of ((C6F5)2B(OMe)CH2)tBu2PNH2, 15. Compound
2 (1.00 g; 1.69 mmol) was dissolved in 5 mL of CH2Cl2. Then 35
mL of dry methanol was added, and the resulting cloudy solution
was stirred at room temperature for 24 h. The solvent and excess
methanol were removed under vacuum to give a white solid (0.850
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Hz, o-C6F5), 140.5 (d, JCF ) 251 Hz, p-C6F5), 138.0 (d, JCF
)
1
268 Hz, m-C6F5), 55.48(s, OMe), 35.87 (d, JPC ) 49 Hz, tBu),
26.5 (s, tBu), 8.90 (br, CH2), -8.0 (s, AlMe). 19F NMR (C6D6):
-133.40 (d, 3JFF ) 18 Hz, 4F, o-F), -157.74 (t, 3JFF ) 18 Hz, 2F,
p-F), -163.87 (m, 4F, m-F). 31P NMR (C6D6): 69.1. 11B NMR
(C6D6): 0.41. Anal. Calcd for C24H30BF10NOPAl: C, 47.47; H,
4.98; N, 2.31. Found: C, 47.27; H, 4.75; N, 2.21.
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g; 1.54 mmol; 91%). H NMR (C6D6): 3.22 (s, 3H, OMe), 3.05
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(s, 2H, NH2), 1.50 (m, 2H, PCH2), 0.55 (d, JPH ) 14 Hz, 9H,
1
tBu). 13C{1H} NMR (C6D6): 149.2 (d, JCF ) 234 Hz, o-C6F5),
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139.8 (d, JCF ) 247 Hz, p-C6F5), 137.87 (d, JCF ) 245 Hz,
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m-C6F5), 52.9 (s, OMe), 34.84 (d, JPC ) 49 Hz, tBu), 25.81 (s,
X-ray Data Collection and Reduction. Crystals were manipu-
lated and mounted in capillaries in a glovebox, thus maintaining a
dry, O2-free environment for each crystal. Diffraction experiments
tBu), 8.21 (br, PCH2). 19F NMR (C6D6): -134.5 (d, 3JFF ) 17 Hz,
4F, o-F), -160.5 (t, 3JFF ) 20 Hz, 2F, p-F), -165.2 (m, 4F, m-F).