94
M. Novotný et al. / Journal of Organometallic Chemistry 849-850 (2017) 88e97
(ppm, THF-d8)
d
: 1.09. Elemental analysis (%): found for C27H38Li-
analysis (%): found C34H48Li2N4O2Si2 - C(66.6), H(8.0), N(8.9),
calculated C(66.42), H(7.87), N(9.11).
N3O2Si - C(69.0), H(8.3), N(8.8), calculated C(68.76), H(8.12),
N(8.91).
4.1.10. Synthesis of 10 ({1, 4-[C(NDmp)(NSiMe3)]2C6H4}(Li·THF2)2)
3.710 g of DmpN(SiMe3)Li (18.62 mmol) was dissolved in 80 ml
of THF and a saturated solution of 1,4-dicyanobenzene (1.193 g,
9.31 mmol) in THF was added dropwise at ꢁ50 ꢀC. 6.702 g (64%) of
white powder was obtained. Decomposition at 112 ꢀC. 1H NMR
4.1.5. Synthesis of 5 ({4-(N≡C)C6H4C(Dipp)(NSiMe3)}Li·THF2)
4.39 g of DippN(SiMe3)Li (17.18 mmol) was dissolved in 80 ml of
THF and
a saturated solution of 1,4-dicyanobenzene (2.2 g,
17.18 mmol) in THF was added dropwise at ꢁ50 ꢀC. 5.11 g (56%) of
white powder was obtained. M. p. 106e108 ꢀC. 1H NMR (ppm, THF-
(ppm, THF-d8)
2.04 (s, H50, 12H), 0.25 (s, SiCH3, 18H). 13C NMR (ppm, THF-d8)
172.8 (Camidinate), 152.1 (C10), 142.4 (C1), 130.7 (C20), 127.5 (C2),125.7
(C30), 119.8 (C40), 19.6 (C50), 3.5 (CSi). 7Li NMR (ppm, THF-d8)
: 1.51.
d
: 6.74 (s, H2, 4H), 6.67 (d, H30, 4H), 6.47 (t, H40, 2H),
d8)
d
: 7.34 (d, H2, 2H), 7.08 (d, H3, 2H), 6.71 (d, 30H, 2H), 6.60 (t, 40H,
d:
1H) 3.34 (m, 50H, 2H), 1.05 (d, 60H, 6H), 1.00 (d, 60H, 6H), ꢁ0.26 (s,
SiCH3, 9H). 13C NMR (ppm, THF-d8)
d
: 169.8 (Camidinate), 148.5 (C10),
d
148.0 (C1), 141.3 (C20), 131.2 (C2), 128.3 (C3), 122.3 (C30), 121.7 (C40),
Elemental analysis (%): found for C46H72Li2N4O4Si2 - C(67.9), H(9.2),
N(6.7), calculated C(67.78), H(8.90), N(6.87).
119.1 (C4), 110.5 (C7), 28.4 (C50), 22.4 (C60), 3.2 (CSi). 7Li NMR (ppm,
THF-d8) d: 1.21. Elemental analysis (%): found for C31H46LiN3O2Si -
C(70.7), H(8.9), N(7.8), calculated C(70.55), H(8.79), N(7.96).
4.1.11. Synthesis of 11 ({1, 4-[C(NDipp)(NSiMe3)]2C6H4}(Li·THF2)2)
6.879 g of DippN(SiMe3)Li (26.93 mmol) was dissolved in 80 ml
of THF and a saturated solution of 1,4-dicyanobenzene (1.726 g,
13.47 mmol) in THF was added dropwise at ꢁ50 ꢀC. 6.76 g (54%) of
white powder was obtained. M. p. for 11 201e207 ꢀC, for 11a
4.1.6. Synthesis of 6 ({{1, 3-[C(NPh)(NSiMe3)]2C6H4}(Li·THF)2}n)
4.607 g of PhN(SiMe3)Li (26.90 mmol) was dissolved in 80 ml of
THF and a saturated solution of 1,3-dicyanobenzene (1.724 g,
13.46 mmol) in THF was added dropwise at ꢁ50 ꢀC. 6.534 g (64%) of
decomposition at 95 ꢀC. 1H NMR (ppm, THF-d8)
d: 6.64 (s, H2, 4H),
white powder was obtained. 1H NMR (ppm, THF-d8)
d
: 7.01 (s, H2,
6.60 (d, H30, 4H), 6.51 (t, H40, 2H), 3.29 (m, H50, 4H), 0.93 (d, H60,
1H), 6.79 (m, H4-6, 3H), 6.73 (dd, H30, 4H), 6.35 (t, H40, 2H), 6.25 (d,
24H), ꢁ0.37 (s, SiCH3, 18H). 13C NMR (ppm, THF-d8)
d: 172.9
H20, 4H), ꢁ0.26 (s, SiCH3, 18H). 13C NMR (ppm, THF-d8)
d: 173.2
(Camidinate), 148.9 (C10), 141.6 (C(1)), 141.0 (C20), 125.9 (C2), 122.2
(C30),121.2 (C40), 28.3 (C50), 22.6 (C60), 3.6 (CSi). 7Li NMR (ppm, THF-
(Camidinate), 154.6 (C10), 143.0 (C(1,3)), 129.1 (C2), 128.5 (C20), 127.9
(C(4,6)), 126.8 (C5), 124.6 (C30), 118.1 (C40), 4.0 (CSi). 7Li NMR (ppm,
d8) d: 1.27. Elemental analysis (%): found for C54H88Li2N4O4Si2 -
THF-d8)
d
: ꢁ0.47. Elemental analysis (%): found for C34H48Li2
C(70.2), H(9.7), N(5.9), calculated C(69.94), H(9.56), N(6.04).
-
N4O2Si2 - C(66.6), H(7.9), N(9.0), calculated C(66.42), H(7.87),
N(9.11).
4.1.12. Synthesis of 12 ({1-[C(NPh)(N'SiMe3)]-3-
[C(NDipp)(N'SiMe3)]C6H4}(Li·THF2)2)
4.1.7. Synthesis of 7 ({1, 3-[C(NDmp)(N'SiMe3)]2C6H4}(Li·THF2)2)
3.71 g of DmpN(SiMe3)Li (18.62 mmol) was dissolved in 80 ml of
THF and a saturated solution of 1,3-dicyanobenzene (1.193 g,
9.31 mmol) in THF was added dropwise at ꢁ50 ꢀC. 6.7 g (92%) of
3.735 g of 3 (7.08 mmol) was dissolved in 40 ml of THF and a
saturated solution of PhN(SiMe3)Li (1.212 g, 7.08 mmol) in THF was
added dropwise at ꢁ50 ꢀC. 4.27 g (72%) of white powder was ob-
tained. 1H NMR (ppm, THF-d8)
d: 7.24 (d, H6, 1H), 6.77 (m, ArH, 4H),
white powder was obtained. 1H NMR (ppm, THF-d8)
d
: 7.02 (d,
6.59 (m, ArH, 3H), 6.46 (d, H4, 1H), 6.27 (t, H400, 1H), 5.75 (d, H20,
H4,6, 2H), 6.84 (t, H5, 1H), 6.57 (d, H30, 4H), 6.40 (s, H2, 1H), 6.34 (t,
2H), 3.40 (m, H500, 2H), 1.05 (d, H600, 3H), 0.99 (d, H600, 9H), ꢁ0.18 (s,
H40, 2H), 1.93 (s, H50, 12H), ꢁ0.39 (s, SiCH3, 18H). 13C NMR (ppm,
SiCH3, 9H), ꢁ0.30 (s, SiCH3, 9H). 13C NMR (ppm, THF-d8)
d: 173.8
THF-d8)
d
: 172.0 (Camidinate), 151.9 (C10), 143.0 (C(1,3)), 130.5 (C20),
(Camidinate), 171.6 (Camidinate), 153.9 (C10), 149.1 (C100), 142.1 (C3),
142.0 (C1), 141.0 (C200), 128.6 (C2), 128.0 (C30), 127.6 (C4), 126.6 (C6),
125.9 (C5), 124.1 (C20), 122.5 (C300), 120.9 (C400), 117.5 (C40), 28.2
(C500), 25.2 (C600), 23.2 (C600), 4.1 (CSi), 3.5 (CSi). 7Li NMR (ppm, THF-
127.7 (C30), 126.9 (C(4,6)), 126.0 (C2), 125.6 (C5), 119.5 (C40), 19.9
(C50), 3.6 (SiC). 7Li NMR (ppm, THF-d8)
d
: 1.15. Elemental analysis
(%): found for C46H72Li2N4O4Si2 - C(67.9), H(9.2), N(6.7), calculated
C(67.78), H(8.90), N(6.87).
d8) d: 1.53, 1.41. Elemental analysis (%): found for C48H76Li2N4O4Si2
- C(68.5), H(9.2), N(6.4), calculated C(68.37), H(9.08), N(6.64).
4.1.8. Synthesis of 8 ({1, 3-[C(NDipp)(NSiMe3)]2C6H4}(Li·THF2)2)
5.015 g of DippN(SiMe3)Li (19.64 mmol) was dissolved in 80 ml
of THF and a saturated solution of 1,3-dicyanobenzene (1.258 g,
9.82 mmol) in THF was added dropwise at ꢁ50 ꢀC. 3.646 g (40%) of
white powder was obtained. Decomposition at 132 ꢀC. 1H NMR
4.1.13. Synthesis of 13 ({3-[C(NDmp)(NSiMe3)]-1-
[C(NDipp)(NSiMe3)]C6H4}(Li·THF2)2)
2.389 g of 3 (4.53 mmol) was dissolved in 40 ml of THF and a
saturated solution of DmpN(SiMe3)Li (0.902 g, 4.53 mmol) in THF
was added dropwise at ꢁ50 ꢀC. 3.015 g (76%) of white powder was
(ppm, THF-d8) d
: 6.84 (br, H4-6, 3H), 6.66 (d, H30, 4H), 6.50 (t, H40,
2H), 6.48 (s, H2, 1H), 3.45 (m, H50, 4H), 1.13 (d, H60, 12H), 0.95 (d,
obtained. 1H NMR (ppm, THF-d8)
d: 6.99 (d, H6, 1H), 6.72 (dd, H5,
H60, 12H), ꢁ0.70 (s, SiCH3, 18H). 13C NMR (ppm, THF-d8)
d
: 172.4
1H), 6.66 (d, H300, 1H, H300), 6.62 (s, H2, 4, 2H), 6.53 (t, H400, 1H), 6.46
(d, H30, 2H), 6.26 (t, H40,1H), 3.35 (m, H50, 2H),1.76 (s, H500, 6H), 0.94
(dd, H60, 12H), ꢁ0.44 (s, SiCH3, 9H), ꢁ0.46 (s, SiCH3, 9H). 13C NMR
(Camidinate), 148.7 (C10), 143.3 (C(1, 3)), 141.1 (C20), 126.2 (C(4,6)),
125.6 (C5), 123.2 (C2), 122.6 (C30), 121.2 (C40), 28.1 (C50), 25.5 (C60),
23.3 (C60), 3.6 (CSi; 1J(Si, C) ¼ 55.5 Hz). 7Li NMR (ppm, THF-d8)
(ppm, THF-d8) d
: 172.6 (Camidinate), 171.9 (Camidinate), 151.8 (C10),
d: ꢁ0.62. Elemental analysis (%): found for C54H88Li2N4O4Si2
-
148.5 (C100), 143.3 (C3), 142.8 (C1), 140.7 (C200), 130.8 (C20), 127.5
(C30), 127.3 (C2), 125.7 (C4), 125.6 (C6), 125.4 (C5), 122.6 (C300), 120.9
(C400), 119.7 (C40), 28.1 (C500), 25.4 (C600), 23.4 (C600), 19.7 (C50), 3.6
C(70.0), H(9.7), N(5.9) calculated C(69.94), H(9.56), N(6.04).
4.1.9. Synthesis of 9 ({1, 4-[C(NC6H6)(NSiMe3)]2C6H4}(Li·THF)n)
(CSi), 3.5 (CSi). 7Li NMR (ppm, THF-d8)
d: 1.46. Elemental analysis
4.459 g of PhN(SiMe3)Li (26.04 mmol) was dissolved in 80 ml of
THF and a saturated solution of 1,4-dicyanobenzene (1.668 g,
13.02 mmol) in THF was added dropwise at ꢁ50 ꢀC. 6.823 g of white
powder was obtained. Decomposition at 149 ꢀC. 13C NMR (ppm, CP-
(%): found for C50H80Li2N4O4Si2 - C(69.1), H(9.4), N(6.4), calculated
C(68.93), H(9.26), N(6.43).
4.1.14. Synthesis of 14 ({4-[C(NPh)(NSiMe3)]-1-[C(NDmp)(NSiMe3)]
C6H4}(Li·THF2)2)
4.805 g of 4 (10.21 mmol) was dissolved in 40 ml of THF and a
saturated solution of PhN(SiMe3)Li (1.75 g, 10.21 mmol) in THF was
MAS, 15 000 Hz, Fig. S2)
128.3 (C2, C20), 124.1 (C30), 118.3 (C40), 68.8 (THF), 26.0 (THF), 3.1
(SiC). 7Li NMR (ppm, CP-MAS, 15 000 Hz)
: ꢁ0.66. Elemental
d
: 174.8 (Camidinate), 151.3 (C10), 141.6 (C1),
d