Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
3
1.6 Hz, 1 H). 13C{1H} NMR (125.8 MHz, CDCl3, 298 K): δ = 20.0, (500.3 MHz, [D8]THF, 298 K): δ = 0.52 (d, JH,H = 6.9 Hz, 6 H), 0.82
3
3
23.5, 24.0, 25.0, 25.7, 26.3, 28.3, 28.8, 29.9, 34.9, 55.1, 120.6, 124.2,
124.4, 125.5, 125.8, 126.4, 129.7, 139.5, 142.6, 147.6, 148.9,
(d, JH,H = 6.9 Hz, 6 H), 0.89 (s, 18 H),1.10 (d, JH,H = 6.9 Hz, 6
3
3
H),1.26 (d, JH,H = 6.9 Hz, 6 H), 3.54 (m, JH,H = 6.9 Hz, 2 H), 4.37
3
152.8 ppm. 29Si{1H} NMR (99.4 MHz, CDCl3, 298 K):
δ
=
(m, JH,H = 6.9 Hz, 2 H), AB spin system with A at δ = 3.17 ppm and
–12.0 ppm.
B at δ = 5.13 ppm (2JH,H = 14.4 Hz, 4 H), 5.43 (s, Si–H satellites
298 Hz, 1 H, SiH), 6.09 (t, 3JH,H = 7.3 Hz, 2 H), 6.43 (dd, 3JH,H = 7.3,
4JH,H = 1.6 Hz, 2 H), 6.73 (m, 4 H), 6.81 ppm (m, 4 H). 13C{1H} NMR
(125.8 MHz, [D8]THF, 298 K): δ = 24.0, 24.3, 26.1, 26.5, 28.2, 29.1,
30.6, 34.4, 57.1, 113.1, 123.0, 123.1, 123.2 (2s), 123.5, 132.6, 137.3,
148.7, 148.8, 153.4, 160.0 ppm. 29Si{1H} NMR (99.4 MHz, [D8]THF,
298 K): δ = –118.7 ppm.
Synthesis of HSi[N(SiMe3)2][OC6H3(CH2NDipp)-2-tBu-6] (4):
Compound 2 (423 mg, 1.1 mmol) was dissolved in 20 mL of n-pentane
and LiN(SiMe3)2 (276 mg, 1.2 mmol) was added portionwise. The as-
obtained suspension was stirred for 4 d and filtered using celite. The
filtrate was dried in vacuo, whereby a colorless solid was isolated. The
solid was purified by crystallization from n-pentane (210 mg, 38%).
Colorless crystals suitable for single-crystal X-ray diffraction were
grown from n-pentane solution at –18 °C. C29H50N2OSi3·0.45H2O (M
= 535.09 g·mol–1): C 65.10 (calcd. 65.09); H 9.63 (9.59), N 5.36
(5.24)%. The elemental analysis measurement was performed under
non inert conditions and thus, the compound partially hydrolyzed. M.p.
148–151 °C. 1H NMR (500.3 MHz, CDCl3, 298 K): δ = 0.16 (s, 18
Supporting Information (see footnote on the first page of this article):
1H NMR spectra of 2 and 4, IR spectra of 1-6, nomenclature of 6 and
crystal data collections and refinement information are given.
Acknowledgements
3
3
H) 0.89 (d, JH,H = 6.9 Hz, 3 H), 1.01 (d, JH,H = 6.9 Hz, 3 H), 1.24
3
3
(d, JH,H = 6.9 Hz, 3 H),1.32 (d, JH,H = 6.9 Hz, 3 H), 1.47 (s, 9 H),
We gratefully acknowledge financial support by the DFG research
group 1497 “Organic-Inorganic Nanocomposites through twin poly-
merization”. We also thank Janine Freytag and Ute Stöß for elemental
analyses as well as Anja Veit for recording the IR spectra and support
in synthesis.
2.92 (m, 3JH,H = 6.9 Hz, 1 H), 3.81 (m, JH,H = 6.9 Hz, 1 H), AB spin
3
system with A at δ = 3.55 ppm and B at δ = 4.91 ppm (2JH,H = 15.3 Hz,
2 H), 4.84 (s, Si–H satellites 257 Hz, 1 H, SiH), 6.79 (dd, 3JH,H = 7.3,
4JH,H = 1.6 Hz, 1 H), 6.84 (t, 3JH,H = 7.6 Hz, 1 H), 7.12 (m, 2 H), 7.20
3
3
4
(t, JH,H = 7.6 Hz, 1 H), 7.24 ppm (dd, JH,H = 7.3, JH,H = 1.6 Hz, 1
H). 13C{1H} NMR (125.8 MHz, CDCl3, 298 K): δ = 4.3, 23.5, 23.9,
25.6, 26.6, 28.2, 28.3, 30.0, 34.8, 55.8, 120.8, 123.3, 124.7, 125.2,
125.4, 126.7, 129.8, 140.2, 141.6, 148.9, 149.2, 152.0 ppm. 29Si{1H}
NMR (99.4 MHz, CDCl3, 298 K): δ = –44.2, 4.6 ppm.
Keywords: Pentacoordinated silicon; Molecular hydrido-
silicate; Silanes; Chirality; Amino alcohols
Synthesis of Cl2Si[OC6H3(CH2NDipp)-2-tBu-6] (5): Compound 1
(3.00 g, 8.8 mmol) was dissolved in 10 mL of n-pentane and n-butyl-
lithium (7.42 mL, 18.6 mmol) was slowly added. The as-obtained sus-
pension was stirred for 2 h and filtered, whereby the lithium salt was
isolated as a colorless solid and dried in vacuo. Silicon tetrachloride
(7.51 g, 44.2 mmol) was dissolved in 20 mL of n-pentane and the lith-
ium salt was added portionwise. Subsequently, the suspension was
stirred for 16 h, filtered using celite, and the solvent was removed in
vacuo, while a colorless solid was isolated. The material was purified
by crystallization from n-pentane at –18 °C and isolated as microcrys-
talline material (2.64 g, 68%). C23H31Cl2NOSi (M = 436.49 g·mol–1):
References
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3
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3
3
4
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Synthesis of [HSi{OC6H3(CH2NDipp)-2-tBu-6}2]K (6): Compound
5 (1410 mg, 3.2 mmol) was dissolved in 50 mL of THF and potassium
(280 mg, 7.1 mmol) was added as little pieces. The suspension was
heated at reflux for 16 h and cooled down to room temperature. Sub-
sequently, the latter was filtered using celite and the filtrate was dried
in vacuo. The as-obtained solid was dissolved in 3 mL of THF and n-
hexane was carefully added, while two layers are formed. The mixture
was left for 3 d in a freezer at –18 °C, which gave colorless crystals
(61 mg, 5%). Colorless crystals suitable for single-crystal X-ray dif-
fraction were grown from THF/n-hexane solution at –18 °C.
C46H63N2O2KSi (M = 743.21 g·mol–1): C 74.44 (calcd. 74.34); H 8.60
(8.54), N 3.81 (3.77)%; no melting point up to 200 °C. 1H NMR
Z. Anorg. Allg. Chem. 0000, 0–0
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