Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Kieselguhr padded frit. A mixture of Ar*N(SnMe3)H (2) and Ar*NH2
55.7 Hz, Sn(CH3)3], 1.25 [s, 9 H, p-C(CH3)3], 1.46 [s, 18 H,
was obtained by fractional crystallization from a saturated toluene
solution. Yield Ar*N(SnMe3)H (2): 0.153 g (0.254 mmol, 25.4%).
Mp.: 191.8 °C (decom.). EA: calcd. (found): C 71.78 (72.086), H 6.19
o-C(CH3)3], 2.77 (broad, 1 H, NH), 7.18 (s, 2 H, arom. CH). 13C{1H}
NMR (298.2 K, CD2Cl2, 75.5 MHz): δ = –2.7 [s, 1J{13C-117Sn} = 369,
1J{13C-119Sn} = 386 Hz, Sn(CH3)3], 32.0 [s, p-C(CH3)3], 32.4 [s, o-
(6.023), N 2.33 (2.099)%. 1H NMR (298.2 K, CD2Cl2, 300.13 MHz): C(CH3)3], 34.8 [s, o-C(CH3)3], 36.4 [s, o-C(CH3)3], 122.7 (arom. C),
δ = –0.19 [s, 9 H, 2J{1H-117Sn} = 55.9, 2J{1H-119Sn} = 56.5 Hz, 140.8 (arom. C), 142.4 (arom. C), 148.5 (arom. C); (298.2 K, [D6]ben-
Sn(CH3)3], 2.03 (s, 3 H, p-CH3), 2.16 (broad, 1 H, NH), 5.73 (s, 2 H, zene, 75.5 MHz): δ = –2.9 [s, J{13C-117Sn} = 367, 1J{13C-119Sn} =
1
CHPh2), 6.47 [s, 2 H, (Ph2CH)2C6H2(CH3)N(SnC3H9)H] 7.01–7.30 384 Hz, Sn(CH3)3], 32.3 [s, p-C(CH3)3], 32.8 [s, o-C(CH3)3], 35.0 [s,
(m, 20 H, arom. CH); (298.2 K, [D6]benzene, 300.13 MHz): δ = 0.03
p-C(CH3)3], 36.6 [s, o-C(CH3)3], 122.8 (arom. C), 141.4 (arom. C),
[s, 9 H, 2J{1H-117Sn} = 53.6, 2J{1H-119Sn} = 55.9 Hz, Sn(CH3)3], 1.92 143.0 (arom. C), 148.4 (arom. C). 119Sn NMR (298.2 K, [D6]benzene,
(s, 3 H, p-CH3), 2.16 (broad, 1 H, NH), 6.02 (s, 2 H, CHPh2), 6.87
111.85 MHz): δ = 63.7 (s) ppm. Raman (laser: 632 nm, accumulation
time: 20 s, 10 Scans): ν˜ = 3420 (1), 2960 (2), 2915 (3), 2771 (1), 2703
(1), 1600 (2), 1469 (1), 1444 (1), 1422 (1), 1388 (1), 1360 (1), 1287
(1), 1242 (1), 1194 (3), 1188 (3), 1144 (1), 1119 (1), 1022 (1), 927
H, (1), 829 (2), 813 (1), 756 (1), 741 (1), 644 (1), 568 (1), 537 (5), 523
(2), 508 (10), 460 (1), 338 (1), 258 (1), 201 (1) cm–1. IR (ATR, 16
[s, 2 H, (Ph2CH)2C6H2(CH3)N(SnC3H9)H], 7.01–7.25 (m, 20 H, arom.
2
CH); (296.7 K, [D8]thf, 300.13 MHz): δ = 0.11 [s, 9 H, J{1H-117Sn}
= 54.8, 2J{1H-119Sn} = 57.4 Hz, Sn(CH3)3], 1.98 (s, 3 H, p-CH3), 2.21
(broad,
1 H, NH), 5.84 (s, 2 H, CHPh2), 6.47 [s, 2
(Ph2CH)2C6H2(CH3)N(SnC3H9)H], 7.01–7.24 (m, 20 H, arom. CH)
ppm. 13C{1H} NMR (298.2 K, CD2Cl2, 75.5 MHz): δ = –4.7 [1J{13C- scans): ν(NH) = 3417 (w) cm–1.
1
117Sn} = 371, J{13C-119Sn} = 386 Hz, Sn(CH3)3], 21.4 (s, CH3), 52.9
(s, CHPh2), 126.7 (s, arom. C), 128.8 (s, arom. C), 130.2 (s, arom. C),
Synthesis of Mes*N(SiMe3)SnMe3 (4): To a stirred solution of
136.6 (s, arom. C), 143.5 (s, arom. C), 144.9 (s. arom. C), 146.5 (s. Mes*N(SiMe3)H (0.668 g, 2.00 mmol) in thf (10 mL) was added a
arom. C); (298.2 K, [D6]benzene, 75.5 MHz): δ = –4.9 [s, 1J{13C- 2.5 m nBuLi solution in n-hexane (0.84 mL, 2.10 mmol) dropwise at
1
117Sn} = 361, J{13C-119Sn} = 378 Hz, Sn(CH3)3], 21.5 (s, CH3), 53.2 room temperature. After 10 min a solution of Me3SnCl (0.409 g,
(s, CHPh2), 126.9 (s, arom. C), 129.0 (s, arom. C), 130.5 (s, arom. C),
137.6 (s, arom. C), 145.4 (s, arom. C), 146.7 (arom. C) ppm. 119Sn
NMR (298.2 K, [D6]benzene, 111.85 MHz): δ = 65.1 (s) ppm. Raman
2.05 mmol) in thf (5 mL) was added dropwise at room temperature
and the reaction mixture was stirred for 2 h. Afterward the solvent was
removed in vacuo and the residue was extracted with n-hexane (7 mL).
(laser: 633 nm, accumulation time: 20 s, scans: 10): ν˜ = 3345 (1), 3060 The solvent was removed again after filtration through a Kieslguhr
(2), 3048 (3), 3041 (1), 2977 (1), 2915 (1), 2862 (1), 1599 (2), 1380
(1), 1296 (1), 1258 (2), 1237 (1), 1198 (1), 1187 (2), 1172 (2), 1157
(1), 1152 (1), 1129 (1), 1075 (1), 1032 (4), 1001 (10), 980 (2), 918
padded frit. The resulting solid was dried in vacuo. Yield: 0.957 g
(1.93 mmol, 96.4%). X-ray quality crystals could be obtained from a
saturated benzene solution at room temperature. Mp.: 80 °C. EA:
(1), 864 (1), 833 (2), 820 (1), 785 (1), 746 (1), 702 (1), 683 (19, 648 calcd. (found): C 58.07 (58.463), H 9.54 (9.134), N 2.82 (2.594)%.
(1), 634 (1), 618 (2), 604 (1), 532 (3), 510 (6), 472 (1), 438 (1), 339 1H NMR (296.9 K, CD2Cl2, 300.13 MHz): δ = 0.13 [s, 9 H, 2J{1H-
2
2
(1), 292 (1), 266 (1), 248 (1), 233 (1), 218 (1) cm–1. IR (ATR, 32
29Si} = 6.2 Hz, Si(CH3)3], 0.26 [s, 9 H, J{1H-117Sn} = 51.0, J{1H-
scans): ν˜ = 3342 (w), 3103 (w), 3082 (w), 3057 (w), 3022 (w), 2978 119Sn} = 53.3 Hz, Sn(CH3)3], 1.27 [s, 9 H, p-C(CH3)3], 1.47 [s, 18 H,
(w), 2906 (w), 2860 (w), 1597 (w), 1493 (m), 1452 (m), 1441 (m), o-C(CH3)3], 7.31 (s, 2 H, arom. CH); (298.2 K, [D6]benzene,
1391 (w), 1335 (w), 1315 (w), 1279 (w), 1257 (m), 1238 (w), 1215 300.13 MHz): δ = 0.27 [s, 18 H, 2J{1H-29Si} was not observed, 2J{1H-
(w), 1192 (w), 1176 (w), 1153 (w), 1128 (w), 1076 (w), 1032 (m), 117Sn} = 50.4, 2J{1H-119Sn} = 52.7 Hz, Si(CH3)3 and Sn(CH3)3], 1.32
1003 (w), 982 (w), 966 (w), 916 (w), 885 (w), 860 (w), 833 (m), 822 [s, 9 H, p-C(CH3)3], 1.58 [s, 18 H, o-C(CH3)3], 7.52 (s, 2 H, arom.
2
(w), 760 (s), 744 (m), 694 (s), 683 (s), 648 (m), 635 (m), 621 (m), 604 CH); (298.2 K, [D8]thf, 300.13 MHz): δ = 0.13 [s, 9 H, J{1H-29Si} =
2
2
(s), 557 (m), 530 (s) cm–1.
6.0 Hz, Si(CH3)3], 0.28 [s, 9 H, J{1H-119Sn} = 53.4, J{1H-117Sn} =
51.6 Hz], 1.27 [s, 9 H, p-C(CH3)3], 1.49 [s, 18 H, o-C(CH3)3], 7.34
Synthesis of Mes*N(SnMe3)H (3): To a stirred solution of Mes*NH2 (s, 2 H, arom. CH). 13C{1H} NMR (298.2 K, CD2Cl2, 75.5 MHz): δ
(0.261 g, 1.00 mmol) in thf (5 mL) was added a 2.5 m solution of = –0.6 [s, 1J{13C-117Sn} = 370, 1J{13C-119Sn} = 387 Hz, Sn(CH3)3],
nBuLi in n-hexane (0.42 mL, 1.05 mmol) at 0 °C. The solution was
stirred 30 min at room temperature and a solution of Me3SnCl C(CH3)3], 38.4 [s, o-C(CH3)3], 125.0 (s, arom. CH), 143.9 (s, arom.
(0.219 g, 1.10 mmol) in thf (5 mL) was added at 0 °C. This reaction C), 146.5 (s, arom. C), 148.2 (arom. C); (298.2 K, [D6]benzene,
mixture was stirred 4 h at room temperature and afterward the solvent 75.5 MHz): δ = –0.4 [s, 1J{13C-117Sn} = 369, 1J{13C-119Sn} = 387 Hz,
4.7 [s, Si(CH3)3], 31.7 [s, p-C(CH3)3], 34.8 [s, p-C(CH3)3], 35.2 [s, o-
was removed in vacuo. The residue was extracted with n-hexane
(5 mL) and filtered through Kieselguhr. Removal of the solvent re-
sulted in a colorless solid. Yield: 0.10 g (0.236 mmol, 23.6%).* X-ray
Sn(CH3)3], 5.0 [s, Si(CH3)3], 32.0 [s, p-C(CH3)3], 34.9 [s,
p-C(CH3)3], 35.5 [s, o-C(CH3)3], 38.6 [s, o-C(CH3)3], 125.3 (s, arom.
CH), 144.2 (s, arom. C), 146.5 (s, arom. C), 148.4 (s, arom. C). 29Si
quality crystals can be obtained from a saturated benzene solution. INEPT NMR (296.8 K, CD2Cl2, 59.6 MHz): δ = 2.5 (m); (298.2 K,
Repeated recrystallization at 45 °C from benzene yields a pure sample
[D6]benzene, 59.6 MHz): δ = 2.7 (m) ppm. 119Sn{1H} NMR (298.2 K,
of Mes*N(SnMe3)H (3). Crystals of Mes*N(SnMe3)2 were also ob- [D6]benzene, 111.85 MHz): δ = 53.7 (s) ppm. IR (ATR, 32 scans): ν˜
tained from such a reaction by fractional crystallization. Mp.: 68.9 °C = 3070 (w), 2958 (s), 2949 (2), 2904 (m), 2866 (m), 1622 (w), 1603
(lit.: 66–67 °C).[6] EA: calcd. (found): C 59.45 (60.381), H 9.27
(w), 1551 (w), 1462 (w), 1406 (m), 1391 (m), 1360 (m), 1283 (w),
1263 (m), 1250 (s), 1221 (m), 1182 (s), 1146 (m), 1109 (m), 1020 (w),
(9.466),
N
3.30% (3.366)%. 1H NMR (298.2 K, CD2Cl2,
2
2
300.13 MHz): δ = 0.29 [s, 9 H, J{1H-117Sn} = 52.7, J{1H-119Sn} = 926 (m), 914 (m), 891 (s), 837 (s), 770 (s), 756 (s), 721 (m), 702 (m),
55.1 Hz, Sn(CH3)3], 1.27 [s, 9 H, p-C(CH3)3], 1.46 [s, 18 H, o-C(CH3) 679 (m), 656 (m), 644 (m), 623 (m), 536 (s) cm–1. Raman (laser:
3], 2.73 (broad, 1 H, NH), 7.21 (s, 2 H, arom. CH); (298.2 K, [D6]ben-
633 nm, accumulation time: 30 s, 10 scans): ν˜ = 3071 (1), 2953 (3),
zene, 300.13 MHz): δ = 0.17 [s, 9 H, 2J{1H-117Sn} = 52.5, 2J{1H- 2905 (6), 1606 (1), 1471 (1), 1407 (1), 1285 (1), 1265 (1), 1203 (2),
119Sn}
=
54.2 Hz,
1192 (3), 1148 (2), 1110 (1), 934 (1), 916 (1), 847 (1), 821 (3), 703
(2), 680 (1), 647 (1), 639 (1), 626 (2), 569 (2), 539 (3), 509 (10), 456
(1), 406 (1), 304 (1), 189 (3), 177 (3), 150 (3), 126 (4), 100 (3), 80
Sn(CH3)3], 1.38 [s, 9 H, p-C(CH3)3], 1.56 [s, 18 H, o-C(CH3)3], 2.67
(broad, 1 H, NH), 7.47 (s, 2 H, arom. CH); (298.2 K, [D8]thf,
2
2
300.13 MHz): δ = 0.24 [s, 9 H, J{1H-117Sn} = 53.3, J{1H-119Sn} = (4) cm–1.
Z. Anorg. Allg. Chem. 0000, 0–0
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