Organometallics
Note
Avance DPX 300 or a Bruker Avance DRX 500 spectrometer, using
C6D6 as solvent. Chemical shifts δ are given relative to SiMe4. EI-MS
spectra were obtained using a Finnigan MAT 8230 spectrometer.
(CCDC-911154), and 8 (CCDC-911155). This material is
Elemental analyses were performed at the Institut fur Anorganische
̈
AUTHOR INFORMATION
Corresponding Author
Notes
■
Chemie, Universitat Gottingen. For elemental analysis compounds
̈
̈
were dried under vacuum for 6 h to remove the solvent molecules.
Synthesis of 5. To a toluene (30 mL) solution of 1 (0.42 g, 0.98
mmol) in a Schlenk flask (100 mL) was added trimethylsilyl azide (3)
(0.12 g, 1.04 mmol) in toluene (20 mL) drop by drop at −78 °C. The
solution was warmed to room temperature and stirred for 6 h. The
solvent was reduced in vacuo (10 mL) and stored at −26 °C in a
freezer to obtain single crystals of 5 in 4 days. Yield: 0.40 g, 78%. Anal.
Calcd for C30H42N4Si2 (514.85): C, 69.99; H, 8.22; N, 10.88. Found:
C, 69.86; H, 8.16; N, 10.81. 1H NMR (300 MHz, C6D6, 25 °C): δ 0.57
(s, 9H, Si(CH3)3), 1.03 (s, 18H, tBu), 6.76−7.21 (m, ArH), 7.58−7.63
(m, ArH) ppm. 29Si{1H} NMR (99.36 MHz, C6D6, 25 °C): δ −71.65
(LSi), −20.80 (SiNSiMe3) ppm. EI-MS: m/z 514 [M+].
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We thank the Deutsche Forschungsgemeinschaft (DFG) for
supporting this work. R.A. is grateful to the Alexander von
Humboldt Stiftung for a research fellowship.
REFERENCES
■
Synthesis of 6. Toluene (40 mL) was added to a Schlenk flask
(100 mL) containing 1 (0.32 g, 0.75 mmol) and adamantyl azide (4)
(0.14 g, 0.79 mmol). The reaction mixture was stirred at room
temperature for 6 h. The solvent was reduced in vacuo (10 mL) and
stored at −26 °C to obtain single crystals of 6 in a week. Yield: 0.32 g,
74%. Anal. Calcd for C37H48N4Si (576.89): C, 77.03; H, 8.39; N, 9.71.
Found: C, 77.01; H, 8.33; N, 9.63. 1H NMR (500 MHz, C6D6, 25 °C):
δ 1.20 (s, 18H, tBu), 1.42−2.32 (m, AdH), 6.83−7.19 (m, ArH),
7.73−7.78 (m, ArH) ppm. 29Si{1H} NMR (99.36 MHz, C6D6, 25 °C):
δ −66.60 (LSi) ppm. EI-MS: m/z 576 [M+].
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mmol) in a Schlenk flask (100 mL) was added trimethylsilyl azide (3)
(0.12 g, 1.04 mmol) in toluene (20 mL) drop by drop at −78 °C. The
solution was warmed to room temperature and stirred for 6 h. The
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B.; Goedecke, C.; Frenking, G. Chem. Commun. 2012, 48, 8186−8188.
61.42; H, 9.71; N, 14.26. H NMR (300 MHz, C6D6, 25 °C): δ 0.62
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(s, 9H, Si(CH3)3), 1.05 (s, 18H, tBu), 2.75 (s, 6H, N(CH3)2), 6.72−
7.03 (m, ArH) ppm. 29Si{1H} NMR (59.63 MHz, C6D6, 25 °C): δ
−59.15 (LSi), −21.18 (SiNSiMe3) ppm. EI-MS: m/z 390 [M+].
Synthesis of 8. Toluene (40 mL) was added to a Schlenk flask
(100 mL) containing 2 (0.38 g, 1.25 mmol) and adamantyl azide (4)
(0.23 g, 1.29 mmol). The reaction mixture was stirred at room
temperature for 6 h. The solvent was reduced in vacuo (10 mL) and
stored at −26 °C to obtain single crystals of 8 in 4 days. Yield: 0.49 g,
86%. Anal. Calcd for C27H44N4Si (452.75): C, 71.63; H, 9.80; N,
12.37. Found: C, 71.54; H, 9.76; N, 12.36. 1H NMR (300 MHz, C6D6,
25 °C): δ 1.20 (s, 18H, tBu), 1.38−2.23 (m, AdH), 2.87 (s, 6H,
N(CH3)2), 6.99−7.14 (m, ArH) ppm. 29Si{1H} NMR (99.36 MHz,
C6D6, 25 °C): δ −67.19 (LSi) ppm. EI-MS: m/z 452 [M+].
̈
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Crystal Structure Determination. Crystals were taken out of the
mother liquor under argon atmosphere using NVH oil. Diffraction
data were collected at 100 K on a Bruker three-circle diffractometer
equipped with a SMART 6000 CCD area detector and a Cu Kα
rotating anode. The data sets of 5, 6, and 8 were collected to the edge
of the Ewald sphere with high completeness and high multiplicity. Raw
data were integrated with SAINT,21 and an empirical absorption
correction with SADABS22 was applied. The structures were solved by
direct methods (SHELXS-97) and refined against F2 by full-matrix
least-squares methods using all data SHELXL.23 SHELXLE24 was used
as refinement GUI. All non-hydrogen atoms were refined with
anisotropic displacement parameters. Hydrogen atoms were con-
strained to ride on their parent atom with displacement parameters
constrained to 1.2 or 1.5 of the Uiso of their parent atom. Anisotropic
displacement parameters of carbon and nitrogen atoms were restrained
in the refinement of 8 using SIMU, ISOR, and RIGU25 commands.
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ASSOCIATED CONTENT
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S
* Supporting Information
Crystal and structure refinement parameters for compounds 5,
6, and 8 (Table S1). CIF files for 5 (CCDC-911153), 6
360
dx.doi.org/10.1021/om301149q | Organometallics 2013, 32, 358−361