Inorganic Chemistry
Article
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washed with water (2 × 100 mL) and brine (80 mL). The organic
phase was dried over magnesium sulfate, and the solvent was finally
removed under reduced pressure. The yellow, oily crude product was
recrystallized in dichloromethane, and 2b was obtained as chunky,
colorless crystals (93 mg, 21%).
1H NMR (acetone-D6): δ = 13.31 (br, 3H, NH), 4.21 (s, 6H, J
(H,29Si) = 3.5 Hz, CH2), 0.35 (s, 3H, J (H,29Si) = 7.3 Hz, CH3).
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13C{1H} NMR (acetone-D6): δ = 150.4 (CO), 56.4 (1J (C,29Si) = 60.2
Hz, CH2), −8.8 (1J (C,29Si) = 56.0 Hz, CH3); 14N NMR (acetone-D6):
δ = −45 (NO2); 29Si NMR (acetone-D6): δ = −3.2. Raman (800
mW): 3180 (6), 2975 (19), 2941 (54), 2910 (13), 1761 (36), 1612
(20), 1433 (18), 1333 (42), 1298 (22), 1234 (10), 1012 (100), 823
(6), 758 (8), 632 (17), 465 (20), 432 (7) cm−1. IR: 3232 (w), 3172
(w), 3028 (vw), 2773 (vw), 1757 (m), 1609 (s), 1445 (m), 1422 (m),
1322 (m), 1286 (m), 1260 (w), 1233 (m), 1201 (m), 1163 (vs), 1091
(m), 1009 (m), 999 (m), 935 (m), 863 (m), 822 (m), 788 (m), 742
(m) cm−1. MS (FAB−) [m/z]: 399.3 [M−H]−. C7H12N6O12Si
(400.29 g mol−1): C 21.00, H 3.02, N 20.99; C 21.01, H 3.08, N
20.69. Mp.: 133 °C. Dec. point: 138 °C. Sensitivities (BAM): impact 5
J; friction 240 N (grain size <100 μm).
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1H NMR (DMSO-D6): δ = 3.98 (s, 4H, CH2), 0.16 (s, 6H, J
(H,29Si) = 7.0 Hz, CH3). 13C{1H} NMR (DMSO-D6): δ = 150.0
(CO), 57.4 (1J (C,29Si) = 57.4 Hz, CH2), −6.2 (1J (C,29Si) = 53.9 Hz,
CH3). 15N NMR (DMSO-D6): δ = −41.7 (NO2), −185.7 (NH). 29Si
NMR (DMSO-D6): δ = −0.6; −0.4 (acetone-D6). Raman (800 mW):
2970 (29), 2944 (39), 2905 (74), 1735 (38), 1623 (24), 1423 (19),
1382 (36), 1332 (13), 1006 (51), 897 (38), 750 (12), 707 (10), 677
(12), 604 (100), 464 (43), 416 (12), 309 (12), 230 (29) cm−1. IR:
3224 (w), 3171 (w), 3124 (w), 3011 (w), 2819 (vw), 1764 (m), 1726
(s), 1615 (s), 1604 (s), 1554 (w), 1513 (vw), 1446 (m), 1415 (m),
1377 (m), 1321 (m), 1284 (s), 1264 (m), 1240 (s), 1223 (s), 1193
(vs), 1094 (w), 1069 (m), 1002 (s), 937 (m), 894 (m), 859 (m), 834
(s), 811 (m), 758 (m), 742 (m), 719 (w), 674 (vw) cm−1. MS (DEI+)
[m/z]: 295.3 [M]+, 147.2 [C5H11O3Si]+. C6H12N4O8Si (296.27 g
mol−1): C 24.32, H 4.08, N 18.91. Found: C 24.24, H 4.36, N 19.06.
Mp: 100 °C. Dec point: 142 °C. Sensitivities (BAM): impact 3 J;
friction 192 N (grain size 100−500 μm).
Modified Synthesis for Tetrakis(chloromethyl)silane Si-
(CH2Cl)4. Into a stirred mixture consisting of tetrachlorosilane (11.5
g, 67.7 mmol), bromochloromethane (52.4 g, 405 mmol), and THF
(150 mL) was added a precooled n-butyl lithium solution in n-hexane
(113 mL, 2.5 M, 283 mmol of n-BuLi) within 4 h. The mixture and
also the n-butyl lithium solution were cooled to −78 °C with an
ethanol/dry ice cooling. After the addition was complete, the reaction
mixture was stirred at −78 °C for a further 5 h and then warmed to 20
°C overnight. The mixture was concentrated under reduced pressure,
and the resulting precipitate was removed by filtration and washed
with n-hexane. This procedure was repeated one more time to remove
most of the THF, and the concentrated solution was cooled in the
refrigerator overnight. A colorless crystalline crude product precip-
itates, and is filtered off and washed with n-hexane to yield crude
tetrakis(chloromethyl)silane. Recrystallization from small amounts of
boiling n-hexane yielded 3.95 g (26%) of the pure Si(CH2Cl)4 as fine
colorless needles.
Tris(carbamoylmethyl) Methylsilane (3a). To an ice-cooled
solution of tris(hydroxymethyl)methylsilane (1.00 g, 7.3 mmol) in dry
acetonitrile (50 mL) was added chlorosulfonyl isocyanate CSI (3.54 g,
25.0 mmol) slowly under dry nitrogen atmosphere. After 5 min at 0
°C, the ice bath was removed, and the colorless solution was stirred for
another hour at ambient temperature. The reaction was cooled again
with an ice-bath. Water (15 mL) was added carefully, and the stirring
was continued for 10 min at 0 °C. The organic solvent was removed in
vacuo. The aqueous phase was extracted with ethyl acetate (3 × 50
mL), and the combined organic phases were washed with water (50
mL) and brine (50 mL). The organic solution was dried over
magnesium sulfate, and the solvent was removed under reduced
pressure. The crude product was obtained as colorless oil, which
started to crystallize after a short period of time. The recrystallization
in a mixture of dichloromethane and dioxane (50:50) yielded 520 mg
(27%) of 3a as colorless crystals.
Tetrakis(carbamoylmethyl)silane (4a). To an ice-cooled sol-
ution of tetrakis(hydroxymethyl) silane (0.17 g, 1.1 mmol) in dry
acetonitrile (15 mL) was added chlorosulfonyl isocyanate CSI (0.68 g,
4.8 mmol) slowly under dry nitrogen atmosphere. After 5 min at 0 °C,
the ice bath was removed, and the colorless solution was stirred for
another hour at ambient temperature. The reaction was cooled again
with an ice-bath. Water (7 mL) was added carefully, and the stirring
was continued for 10 min at ambient temperature. The organic solvent
was removed in vacuo, and ice was added to the aqueous phase. With
the help of ultrasound, 4a precipitated out of the cold solution as
colorless, pure solid (252 mg, 70%).
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1H NMR (DMSO-D6): δ = 6.45 (br, 6H, NH2), 3.68 (s, 6H, J
2
(H,29Si) = 3.4 Hz, CH2), 0.10 (s, 3H, J (H,29Si) = 6.9 Hz, CH3).
13C{1H} NMR (DMSO-D6): δ = 157.9 (CO), 53.7 (CH2), −7.6
(CH3). 29Si NMR (DMSO-D6): δ = −5.5. Raman (800 mW): 3261
(3), 3200 (9), 2973 (19), 2954 (3), 2945 (20), 2910 (100), 2861 (8),
1695 (20), 1633 (6), 1633 (6), 1444 (26), 1306 (12), 1265 (8), 1217
(14), 1121 (20), 1083 (10), 1071 (6), 1015 (9), 904 (40), 835 (30),
768 (5), 711 (10), 647 (4), 610 (41), 537 (6), 501 (19), 367 (12), 341
(3), 317 (9), 278 (7), 237 (3), 209 (6) cm−1. IR: 3420 (m), 3332 (m),
3269 (m), 3207 (m), 2943 (vw), 2907 (w), 1779 (w), 1701 (vs), 1615
(s), 1429 (m), 1279 (m), 1246 (m), 1215 (m), 1121 (m), 1063 (vs),
903 (m), 840 (vs), 801 (m), 784 (s), 776 (s), 748 (m), 711 (m), 651
(m), 609 (m) cm−1. MS (DEI+) [m/z]: 250.2 [C7H14N2O6Si]+, 191.2
[C5H11N2O4Si]+. C7H15N3O6Si (265.30 g mol−1): C 31.69, H 5.70, N
15.84. found: C 31.80, H 5,65 N, 15.60. Mp: 108 °C.
1H NMR (DMSO-D6): δ = 6.45 (s, 8H, NH2), 3.70 (s, 8H, CH2).
13C{1H} NMR (DMSO-D6): δ = 158.1 (CO), 53.4 (1J (C,29Si) = 64.5
Hz, CH2). 29Si NMR (DMSO-D6): δ = −15.5. Raman (800 mW):
3331 (12), 3284 (2), 2969 (65), 2940 (100), 2860 (7), 1703 (49),
1593 (10), 1446 (55), 1271 (20), 1235 (19), 1120 (29), 1076 (22),
908 (76), 753 (25), 650 (6), 616 (20), 515 (8), 231 (21) cm−1. IR:
3435 (m), 3334 (w), 3199 (vw), 2933 (vw), 1691 (s), 1592 (m), 1435
(w), 1376 (vs), 1269 (w), 1227 (w), 1120 (w), 1060 (vs), 895 (m),
837 (vw), 816 (m), 780 (s), 674 (vw) cm−1. MS (DEI+) [m/z]: 250.2
[C6H12N3O6Si]+. C8H16N4O8Si (324.32 g mol−1): C 29.63, H 4.97, N
17.28. Found: C 29.34, H 4,96, N 17.05. Mp: 138 °C.
Tris(nitrocarbamoylmethyl) Methylsilane (3b). Anhydrous
nitric acid (>99.5%, 1 mL) was slowly dropped into concentrated
sulfuric acid (1 mL) at 0 °C. With strong stirring, tris-
(carbamoylmethyl) methylsilane (3a, 195 mg, 0.73 mmol) was
added in small portions, and the suspension was stirred for 1 h at 0
°C. The clear solution was then poured onto ice/water (200 mL) with
heavy stirring. The aqueous solution was extracted ice-cold three times
with ethyl acetate (3 × 50 mL), and the combined organic phases were
washed with water (2 × 100 mL) and brine (80 mL). The organic
phase was dried over magnesium sulfate, and the solvent was finally
removed under reduced pressure. The resulting colorless solid was
dissolved in acetonitrile (1 mL), and large amounts of chloroform (50
mL) were added, resulting in precipitation of a colorless solid containg
solvent molecules. The filtrated solid was again dissolved in
acetonitrile, and the solvent was evaporated with time. After being
dried under high vacuum, 3b was obtained as colorless white solid (50
mg, 17%).
Tetrakis(nitrocarbamoylmethyl)silane (Sila-PETNC, 4b). A
0.19 g (0.6 mmol) portion of tetrakis(carbamoylmethyl) silane (4a)
was solved in concentrated sulfuric acid (2 mL) in small portions at 0
°C. With strong stirring, anhydrous acid (>99.5%, 2 mL) was added
dropwise with caution to the clear solution. After 1 h at 0 °C, the
solution was poured onto ice/water (150 mL) with heavy stirring, and
a colorless precitipate formed. After filtering the colorless solid and
washing with cold water, sila-PETNC was obtained as pure product
(240 mg, 79%).
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1H NMR (acetone-D6): δ = 13.40 (br, 4H, NH), 4.31 (s, 8H, J
(H,29Si) = 3.5 Hz, CH2). 13C{1H} NMR (acetone-D6): δ = 150.7
(CO), 55.6 (1J (C,29Si) = 62.3 Hz, CH2). 15N NMR (acetone-D6): δ =
−45.3 (NO2), −190.4 (NH, br). 29Si NMR (acetone-D6): δ = −9.8.
Raman (800 mW): 3178 (5), 2968 (17), 2935 (43), 2844 (3), 1773
(36), 1609 (15), 1433 (15), 1335 (41), 1302 (22), 1228 (13), 1180
(6), 1099 (3), 1014 (100), 952 (4), 853 (3), 822 (9), 748 (5), 489 (2),
H
Inorg. Chem. XXXX, XXX, XXX−XXX