K. Tamao et al. / Journal of Organometallic Chemistry 574 (1999) 193–205
201
3.5. Synthesis of 2,2-dimethyl-1,3-diphenyl-1,1,3,3-
tetrafluorotrisilane (9a)
2H), 7.01–7.08 (m, 6H), 7.16 (d, J=11 Hz, 2H), 7.41–
7.46 (m, 8H), 7.68 (dd, J=1.2 and 8.1 Hz, 2H), 8.60 (d,
3
J=7.3 Hz, 2H). 13C-NMR: l −2.62 (d, J(C–F)=4.9
The tetraethoxytrisilane (8a; 3.1 g, 7.0 mmol) was
added to a solution of pyridine (HF)x (1.2 ml; large
excess amount), in ether (15 ml) at −78°C in Teflon
flask. After 18 min, the mixture was concentrated using
a water pump at −50 to −40°C. To the residue was
added quickly dry hexane (15 ml) with stirring. The
upper clear layer was separated and the residue was
further extracted with dry hexane for two times. The
combined extract was concentrated and distilled bulb-
to-bulb to give 9a (2.0 g, 84% yield): b.p. 120–123°C
(bath temperature)/0.3 mmHg. 1H-NMR: l 0.18 (s,
Hz), 45.61, 49.28 (d, J=2.5 Hz), 117.18, 125.79,
126.11, 126.26, 127.78, 128.63, 130.62 (d, J=9.7 Hz),
131.09, 132.62, 134.86, 135.08, 139.00 (d, J=7.3 Hz),
139.55 (d, J=13.5 Hz), 152.78. 19F-NMR: l −
150.5(bs). 29Si-NMR: l −0.05 (d, J(Si–F)=315 Hz),
2
−43.3 (t, J(Si–F)=40 Hz). Solid state CP/MAS 13C-
NMR: l −5.76, −4.98, 42.62, 45.44, 52.04, 55.15,
119.85, 125.19, 127.72, 129.86, 132.19, 133.06, 134.81,
138.60, 141.42, 153.27. Solid state CP/MAS 15N-NMR:
l 16.6, 26.9. Solid state CP/MAS 29Si-NMR: l −43.2,
1
1
−6.0 (d, J(Si–F)=294 Hz), 10.2 (d, J(Si–F)=338 Hz).
meso-1: m.p. 161.3–162.8°C. 1H-NMR: l 0.52 (s,
6H), 2.00 (bs, 6H), 2.23 (s, 6H), 6.92 (dd, J=1.0 and
7.6 Hz, 2H), 6.97–7.08 (m, 6H), 7.21 (t, J=7.6 Hz,
2H), 7.42 (dd, J=7.0 and 8.0 Hz, 2H), 7.51 (dd, J=1.0
and 8.0 Hz, 2H), 7.53 (dd, J=1.9 and 7.3 Hz, 4H), 7.72
(dd, J=1.0 and 8.0 Hz, 2H). 8.57 (d, J=7.0 Hz, 2H).
6H), 7.05–7.15 (m, 6H), 7.58 (dd, J=1.6 and 7.8 Hz,
2
4H). 13C-NMR: l −8.39, 128.77, 132.03 (t, J(C–F)
=
13.4 Hz), 132.13, 133.19. 29Si-NMR: l −56.3 (quintet,
J
(Si–F)=30 Hz), −5.4 (tt, 2J(Si–F)=353 and 9 Hz).
19F-NMR: l −133.3. Anal. Calc. for C14H16F4Si3: C,
48.81; H, 4.68. Found: C, 48.78; H, 4.69%.
3
13C-NMR: l −2.57 (d, J(C–F)=8.6 Hz), 45.41, 49.60
3.6. Synthesis of 2,2,3,3-tetramethyl-1,4-diphenyl-
1,1,4,4-tetrafluorotetrasilane (9b)
(d, J=2.4 Hz), 116.97, 125.86, 126.17, 126.26, 127.73,
128.63, 130.95, 131.06, 132.80, 134.85, 135.19, 138.75
(d, J=7.3 Hz), 139.64 (d, J=14.7 Hz), 152.87. 19F-
In a similar manner, the reaction of 8b (4.9 g, 9.6
mmol) with pyridine (HF)x (1.7 ml) in ether (20 ml)
gave 9b (3.5 g, 8.8 mmol, 91% yield): b.p. 173–183°C
(bath temperature)/0.6 mmHg. 1H-NMR: l 0.28 (s,
12H), 7.12–7.16 (m, 6H), 7.59–7.63 (m, 4H). 13C-
NMR: l −7.09, 128.70, 131.85, 133.12 (br), 133.32 (t,
NMR: l −152.7(bs). 29Si-NMR: l −2.0 (d, J(Si–F)
=
309 Hz), −42.5 (t, 2J(Si–F)=39 Hz). Solid state
CP/MAS 13C-NMR: l 1.43, 1.82, 44.56, 49.03, 50.39,
51.26, 116.45, 122.86, 126.46, 128.01, 128.98, 132.97,
134.71, 139.38, 141.71, 150.84, 151.91. Solid state CP/
MAS 15N-NMR: l 12.0, 21.1. Solid state CP/MAS
2
1
2J(C–F)=12 Hz). 29Si-NMR: l −47.4 (t, J(Si–F)=28
29Si-NMR: l −41.7, −15.6 (d, J(Si–F)=287 Hz), 8.9
Hz), −3.0 (t, J(Si–F)=356 Hz). 19F-NMR: l −132.9.
Anal. Calc. for C16H22F4Si4: C, 47.72; H, 5.51. Found:
C, 47.82; H, 5.50%.
(d, J(Si–F)=338 Hz).
1
3.8. Synthesis of 1,4-difluoro-2,2,3,3-tetramethyl-1,4-
bis[8-(dimethylamino)-1-naphthyl]-1,4-
diphenyltetrasilane (2)
3.7. Synthesis of 1,3-difluoro-2,2-dimethyl-1,3-bis[8-
(dimethylamino)-1-naphthyl]-1,3-diphenyl-trisilane (1)
In a similar manner to that described for the prepara-
tion of 1, the reaction of 9b (1.13 g, 2.8 mmol) with
8-(dimethylamino)-1-naphthlyllithium (1.4 g, 5.6 mmol)
in dry ether (12 ml) give 2 (1.7 g, 85% yield) as colorless
To a suspension of 8-(dimethylamino)-1-naphthlyl-
lithium [7] (1.5 g, 5.8 mmol) in dry ether (12 ml) was
added quickly 9a (1.0 g, 2.9 mmol) at −78°C with
stirring. The mixture was allowed to warm to r.t.,
stirred overnight, and concentrated in vacuo. The
residue was dissolved in benzene (7 ml), and filtered
through a sintered glass filter to remove LiF. The
filtrate was concentrated under reduced pressure to
leave solids, which was recrystallized from a mixture of
toluene (3 ml) and hexane (2 ml) at −25°C to give 1
(1.5 g, 79% yield) as colorless crystals (mixture of dl
and meso isomers). The dl and meso isomer of 1 could
be separated by the repeated recrystallization from
hexane: Anal. Calc. for C38H40N2F2Si3 (dl and meso
mixture): C, 70.54; H, 6.23; N, 4.33. Found: C, 70.35;
H, 6.32; N, 4.27%.
1
crystals as a mixture of dl and meso isomers. H-NMR
(dl: meso=1: 1): l 0.19 (s, 6H), 0.35 (s, 6H), 0.57 (s,
6H), 0.72 (s, 6H), 1.86 (s, 6H), 1.87 (s, 6H), 2.14 (s,
6H), 2.15 (s, 6H), 6.86, 6.88 (dd, J=1.0 and 7.3 Hz,
2H), 7.05–7.12 (m, 6H), 7.15–7.24 (m, 2H), 7.42, 7.44
(dd, J=6.8 and 8.1 Hz, 2H), 7.48–7.57 (m, 6H), 7.70,
7.73 (dd, J=1.0 and 8.3 Hz, 2H), 8.54, 8.56 (d, J=6.8
Hz, 2H). 13C-NMR (dl: meso=1: 1): l −3.71 (d,
3
3J(C–F)=3.7 Hz), −3.42 (d, J(C–F)=3.7 Hz), −3.14,
−2.92, 45.79, 49.39 (d, J=2.4 Hz), 116.86, 125.84,
126.13, 126.26, 127.78, 128.67, 130.95, 131.93 (d, J=11
Hz), 132.73, 135.01, 135.13, 138.24 (d, J=7.3 Hz),
140.33 (d, J=14.7 Hz), 152.94. 19F-NMR (dl: meso=
1: 1): l −145.0 (bs). 29Si-NMR (dl: meso=1: 1): l 0.0
1
dl-1: m.p. 150–151°C. H-NMR: l 0.56 (s, 6H), 2.06
(bs, 6H), 2.13 (s, 6H), 6.90 (dd, J=0.8 and 7.3 Hz,
2
(d, J(Si–F)=308 Hz), −38.6 (t, J(Si–F)=39 Hz). Anal.