2-Lithiumamide-2-fluoro-1,3-diaza-2,4-disilacyclobutanes
C(CH3)3, 9 H, 7.16 C(3, 5)H, 1 H, 7.22 C(4)H, 1 H, 7.91 C(2, 6)H, 1
1,3-Di-tert-butyl-2-fluoro-2-(3,5-dimethylanilino)-4,4-
dimethyl-1,3-diaza-2,4-disila-cyclobutane (6)
4
H, 7.95 C(1)H, 1H. 13C NMR: δ = 4.55 Si–CBH3 (d, JCF = 0.10 Hz),
5.25 Si–CAH3, 20.72 Si–C(CH3)3, 29.18 Si–C(CH3)3, 34.13 N–C(CH3)
3
5
C18H34FN3Si2 (367.7), yield 66%, m.p. 56 °C, MS (EI): m/z (%) 352
3, 50.01 N–C(CH3)3 (d, JCF = 1.67 Hz), 126.87 C(3, 5) (d, JCF
=
1
(100) [M – Me]+. H NMR: δ = 0.43 Si–CBH3, 3 H, 0.54 Si–CAH3,
6
1.5 Hz), 129.05 C(4), 135.96 C(2, 6) (d, JCF = 2.15 Hz), 136.46 C(1)
6
d, JCF = 20.52 Hz). 19F NMR: δ = 44.87 SiF (d, JSiF = 12.16 Hz).
4
1
3 H, 1.18 N–(C(CH3)3, 18 H, 2.26 C(3,5)–CH3 (q, JHH = 0.6 Hz), 6
H, 3.84 NH, 1 H, 6.47 C(4)H, 1 H, 6.59 C(3, 5)H, 2H. 13C NMR: δ
29Si NMR: δ = –58.35 SiF (d, JSiF = 268.05 Hz), –14.22 Si–C(CH3)
1
4
4
3
= 3.63 Si–CA (d, JCF = 6.5 Hz), 4.94 Si–CB (d, JCF = 0.8 Hz), 21.25
(d, JSiF = 0.57 Hz), –5.46 Si(CH3)2.
3
4
C(3,5)–CH3, 33.51 N–(C(CH3)3 (d, JCF = 0.7 Hz), 49.95 N–C(CH3)3
3
4
(d, JCF = 1.7 Hz), 115.09 C(2,6) (d, JCF = 0.7 Hz), 120.82 C(4),
138.35 C(3,5), 144.48 C(1) (d, JCF = 6.0 Hz). 19F NMR: δ = 2.83.
3
Bis(1,3-di-tert-butyl-2-fluoro-4,4-dimethyl-1,3-diaza-2,4-
disila-cyclobutan)-2-ethylenediamine (11)
29Si NMR: δ = –63.13 SiF (d, JSiF = 260.4 Hz), –4.59 Si(CH3)2.
1
C22H54F2N6Si4 (553.1), yield 20%, m.p. 195 °C, MS (EI): m/z (%)
537 (100) [M – Me]+. 1H NMR: δ = 0.26 Si–CBH3, 6 H, 0.30 Si–
CAH3, 6 H, 1.15 N–C(CH3)3, 36 H, 1.29 NH, 2 H, 2.86 CH2, 4H. 13C
1,3-Di-tert-butyl-2-fluoro-2-(2,4,6-trimethylanilino)-4,4-
dimethyl-1,3-diaza-2,4-disila-cyclobutane (7)
4
4
NMR: δ = 4.22 Si–CA (d, JCF = 6.7 Hz), 4.50 Si–CB (d, JCF
=
=
C19H36FN3Si2 (381.7), yield 59%, m.p. 54 °C, MS (EI): m/z (%) 366
4
3
1
(100) [M – Me]+. H NMR: δ = 0.36 Si–CBH3, 3 H, 0.38 Si–CAH3,
0.7 Hz), 33.71 N–C(CH3)3 (d, JCF = 0.5 Hz), 44.15 CH2 (d, JCF
3
3.0 Hz), 49.55 N–C(CH3)3 (d, JCF = 1.7 Hz). 29Si NMR: δ = –57.80
3 H, 1.10 N–(C(CH3)3, 18 H, 2.15 C2,6–CH3, 6 H, 2.20 C4–CH3, 3 H,
1
15
4
3.27 NH, 1 H, 6.78 C3,5 H, 2H. 13C NMR: δ = 3.45 Si–CA (d, JCF
=
=
SiF (d, JSiF = 260.0 Hz), –6.17 Si(CH3)2.
N NMR: δ = –353.812
2
2
4
5
NH (d, JNF = 12.8 Hz), –309.70 NC(CH3)3 (d, JNF = 4.5 Hz).
6.4 Hz), 5.17 Si–CB (d, JCF = 0.9 Hz), 19.71 C2,6–CH3 (d, JCF
4
1.1 Hz), 20.39 C4–CH3, 33.48 N–C(CH3)3, (d, JCF = 0.8 Hz), 49.81
3
4
N–C(CH3)3 (d, JCF = 1.7 Hz), 128.76 C(2,6) (d, JCF = 0.5 Hz),
129.05 C(3,5), 130.07 C(4), 138.53 C(1) (d, 3JCF = 3.3 Hz). 19F NMR:
1,3-Di-tert-butyl-1,3,5,8-tetraaza-2,4-disilaspiro[3,4]octane
(12)
δ = 37.76 SiF (3JFH = 3.2 Hz). 29Si NMR: δ = –61.94 SiF (d, JSiF
=
1
267.1 Hz), –4.08 Si(CH3)2.
C12H30N4Si2 (286.6), yield 17%, b.p. 95 °C (0.09 mbar), m.p. 49 °C,
1
MS (EI): m/z (%) 271 (100) [M – Me]+. H NMR: δ = 0.21 Si(CH3)
2, 6 H, 1.13 N–C(CH3)3, 18 H, 3.11 CH2, 4H. 13C NMR: δ = 4.71 Si–
1,3-Di-tert-butyl-2-fluoro-2-(2,6-diisopropylanilino)-4,4-
dimethyl-1,3-diaza-2,4-disila-cyclobutane (8)
(CH3)2, 33.69 N–C(CH3)3, 42.18 CH2, 49.32 N–C(CH3)3. 29Si NMR:
15
δ = –38.46 Si–N4, –7.66 Si(CH3)2.
N NMR: δ = –356.49 NH.
C22H42FN3Si2 (423.8), yield 44%, b.p. 119 °C (0.1 mbar), MS (EI):
m/z (%) 408 (100) [M – Me]+. 1H NMR: δ = 0.35 Si–CBH3, 3 H, 0.38
3
Si–CAH3, 3 H, 1.07 N–C(CH3)3, 18 H, 1.21 CH(CH3)2 (d, JHH
=
Spirocyclic Compounds 13–15
6.8 Hz), 12 H, 3.54 CH(CH3)2 (3JHH = 6.8 Hz), 2 H, 3.25 NH, 1 H,
7.05 C3,5 H, 2 H, 7.07 C4 H, 1H. 13C NMR: δ = 3.70 Si–CA (d, JCF
4
A solution of the amino (2, 4) or hydrazino (3) compounds (0.1 mol)
in n-hexane (100 mL) was cooled to 0 °C and n-C4H9Li (0.1 mol, 23%
in n-hexane) was added. The mixture was warmed to reflux for 2 h
and compounds 13 and 14 were separated from LiF in vacuo and ana-
lytically pure obtained by recrystallisation from n-hexane. In the case
of 15 it was necessary to temper the formed lithium salt of 4 to 200 °C
to separate it from LiF. The mixture was solved in n-hexane (100 mL)
under reflux and afterwards cooled. The formed crystals of 13–15 were
recrystallised from n-hexane.
4
= 6.4 Hz), 5.21 Si–CB (d, JCF = 0.9 Hz), 23.59 CH(CH3)2, 20.39
5
4
CH(CH3)2 (d, JCF = 0.8 Hz), 33.48 N–C(CH3)3 (d, JCF = 0.9 Hz),
3
49.65 N–C(CH3)3 (d, JCF = 1.8 Hz), 122.80 C(4), 122.93 C(3, 5),
138.08 C(2, 6) (d, JCF = 2.1 Hz), 141.53 C(1) (d, JCF = 0.7 Hz). 19F
4
3
NMR: δ = 39.29 SiF (d, JFH = 3.9 Hz). 29Si NMR: δ = –61.96 SiF
3
1
15
(d, JSiF = 271.2 Hz), –3.62 Si(CH3)2.
2JNF = 11.1 Hz), –308.58 N–(CH3)3 (d, JNF = 3.8 Hz).
N NMR: δ = –328.14 NH (d,
2
1,3-Di-tert-butyl-2-fluoro-2-(2,3,4,5,6-pentafluoroanilino)-
1,3-diaza-2,4-disila-cyclobutane (9)
Compound (13)
C16H25F6N3Si2 (429.58), yield 78%, b.p. 78 °C/ (0.02 mbar), MS (EI):
1
m/z (%) 414.2 (100) [M – Me]+. H NMR: δ = 0.37 Si–CAH3, 3 H,
C20H50N6Si4 (486), m.p. 91 °C, MS (EI): m/z (%) 471 (100) [M –
Me]+. 1H NMR: δ = 0.31 Si–(CH3)2, 12 H, 1.27 N–C(CH3)3, 36H.
13C NMR: δ = 5.52 Si–(CH3)2, 34.16 N–C(CH3)3, 49.77 NC(CH3)3.
29Si NMR: δ = –58.84 Si–N, –8.46 Si(CH3)2.
0.39 Si–CBH3, 3 H, 1.12 NC(CH3)3, 18 H, 3.85 N–H, 1H. 13C NMR:
4
7
δ = 3.06 Si–CA (dt, JCF = 8.40, JCF = 1.94 Hz), 4.69, 33.62 N–
3
C(CH3)3, 49.94 N–(C(CH3)3 (d, JCF = 1.62 Hz), 121.33 C(2, 6) (m),
132.89 C(4) (m), 136.56 C(3, 5) (m), 139.90 C(1) (m). 19F NMR: δ
= –35.47 SiF (t, JFF = 5.80 Hz), 2.53 F(2,6) (m), 7.46 F(3,5) (m),
7.89 F(4) (tt, JFF = 27.64, JFF = 10.52, JFF = 5.73 Hz). 29Si NMR:
δ = –64.16 SiF (d, JSiF = 262.63 Hz), –2.86 Si(CH3)2.
–333.17 N–H (dt, JNF = 20.16, JNFortho = 1.72 Hz), –309.09 N–
C(CH3)3 (dt, JNF = 5.02, JNFortho = 0.99 Hz).
5
3
4
7
Compound (14)
1
15
N
NMR: δ =
C20H52N8Si4 (516), yield 30%, MS (EI): m/z (%) 502 (100) [M –
2
3
Me]+.
2
5
1,3-Di-tert-butyl-2-fluoro-2-(di-tert-butyl-phenyl-silylamino)-
1,3-diaza-2,4-disila-cyclobutane (10)
Compound (15)
C28H66N6Si4 (598), yield 24%, m.p. 184 °C, MS (EI): m/z (%) 583
1
C22H48FN3Si3 (457.31), yield 56%, m.p. 120 °C. H NMR: δ = 0.47 (100) [M – Me]+. 1H NMR: δ = 0.37 Si–(CH3)2, 12 H, 1.36 N–
Si–CBH3, 3 H, 0.52 Si–CAH3, 3 H, 1.25 Si–C(CH3)2Ph, 6 H, 1.32 N–
CA(CH3)3, 36 H, N–(CB(CH3)3 18H. 13C NMR: δ = 6.36 Si–(CH3)2,
Z. Anorg. Allg. Chem. 2011, 2183–2192