1204 J. Am. Chem. Soc., Vol. 120, No. 6, 1998
Mao et al.
PhMe2SiC(I)dCMeCMedC(I)SiMe2Ph (10). A 100 mL round-
bottom flask was charged with 8 (1.00 g, 1.75 mmol), I2 (0.95 g, 3.74
mmol), and THF (20 mL). The resulting red solution was stirred for
12 h, the THF was removed by vacuum transfer, and the resulting
residue was extracted into pentane (3 × 20 mL). The pentane solution
was washed with saturated Na2S2O3 solution until colorless and then
dried over Na2SO4. Pentane was removed to give 0.73 g (69%) of the
product as a pale yellow oil. 1H NMR (benzene-d6, 300 MHz): δ
7.61 (m, 4 H, C6H5,), 7.19 (m, 4 H, C6H5), 7.17 (m, 2 H, C6H5), 1.71
(s, 6 H, C4Me2), 0.58 (s, 6 H, SiMe2Ph), 0.52 (s, 6 H, SiMe2Ph). 13C-
{1H} NMR (benzene-d6, 100.6 MHz): δ 164.22 (C4Me2I2), 138.26
(C6H4, C), 133.84 (C6H4, CH), 129.61 (C6H4, CH), 128.30 (C6H4, CH),
100.45 (C4Me2I2), 20.19 (C4Me2I2), 1.30 (SiMe2Ph), 0.73 (SiMe2Ph).
EIMS: M+ - I- (475) and M+ - 2I- (348) were observed as the most
intense peaks. The isotope pattern for these peaks were in good
agreement with those obtained from simulation.
[1,4-Me2SiC6H4SiMe2C4Me2H2]n (11). A 100 mL round-bottom
flask was charged with 5 (0.95 g, 1.93 mmol) and THF (20 mL). An
aqueous HCl solution (6 M, 20 mL) was added to the flask, and then
the resulting mixture was stirred for 2 h at room temperature. The
reaction mixture was poured into 200 mL of methanol, and the white
precipitate was collected to afford 0.52 g (98%) of 11 as a white powder.
1H NMR (benzene-d6, 300 MHz): δ 7.62 (s, 4 H, C6H4), 6.02 (s, 2 H,
C4Me2H2), 1.96 (s, 6 H, C4Me2), 0.42 (s, 12 H, SiMe2). 13C{1H} NMR
(benzene-d6, 100.6 MHz): δ 155.88 (C4Me2H2, C), 140.35 (C6H4, C),
133.67 (C6H4, C), 124.39 (C4Me2H2, CH), 20.76 (C4Me2H2), -0.78
(SiMe2). Mn ) 4200, Mw ) 12 000. UV-vis (THF, nm): 232, 262.
Anal. Calcd for C16H24Si: C, 70.51; H, 8.88. Found: C, 69.26; H,
8.99.
trapped benzene molecule): C, 63.48; H, 6.56. Found: C, 60.70; H,
6.93. EIMS: (no parent peak M+ at 1470), m/z ) 765 and 710 as the
highest-mass peaks, assignable to the fragments MeCtCMe2SiC6H4-
SiMe2(C4Me2ZrCp2)-SiMe2C6H4SiMe2CtCMe and (Cp2Zr)MeCtCMe2-
Si-C6H4SiMe2CtCMe(ZrCp2). The isotope pattern for these peaks
were successfully simulated.
[1,4-Me2SiC6H4SiMe2C4Me2H2]3 (16). A 100 mL round-bottom
flask was charged with 15 (0.95 g, 1.93 mmol) and THF (20 mL). An
aqueous HCl solution (6 M, 20 mL) was added to the flask, and the
resulting mixture was stirred for 2 h at room temperature. This mixture
was poured into 200 mL of methanol, and the white precipitate was
collected to afford 0.52 g (98%) of 16 as a white powder. 1H NMR
(benzene-d6, 300 MHz): δ 7.62 (s, 4 H, C6H4), 6.03 (s, 2 H, C4Me2H2),
1.97 (s, 6 H, C4Me2), 0.43 (s, 12 H, SiMe2). 13C{1H} NMR (benzene-
d6, 100.6 MHz): δ 155.88 (C4Me2H2, C), 140.31 (C6H4, C), 133.67
(C6H4, CH), 124.27 (C4Me2H2, CH), 20.76 (C4Me2H2), -0.74 (SiCH2).
UV-vis (THF, nm): 232, 254. Anal. Calcd for C48H72Si6: C, 70.51;
H, 8.88. Found: C, 70.70; H, 10.03. EIMS showed M+ ) 816.
HRMS calcd for C48H72Si6, 816.424973; found, 816.425052.
[1,4-Me2SiC6H4SiMe2C4Me2I2]3 (17). A 100 mL round-bottom
flask was charged with 15 (0.951 g, 1.93 mmol), I2 (1.00 g, 3.94 mmol),
and THF (20 mL). The resulting red solution was stirred for 12 h,
and then the reaction mixture was poured into 200 mL of methanol.
The precipitate was collected to afford 0.75 g (74%) of 17 as white
crystals. 1H NMR (benzene-d6, 500 MHz): δ 7.601, 7.592, 7.590, 7.586
(4 singlets, 4 H, C6H4); 1.628, 1.604, 1.602, 1.573 (4 singlets, 6 H,
C4Me2); 0.601, 0.599, 0.593, 0.588, 0.586 (overlapped singlets, 12 H,
SiMe2). 13C NMR{1H} (benzene-d6, 100.6 MHz): δ 164.24, 164.13,
164.06 (overlapped singlets, C4Me2I2); 139.74, 139.67 (overlapped
singlets, C6H4, C); 133.82, 133.80, 133.73 (overlapped singlets, C6H4,
CH); 100.60, 100.47, 100.07, 100.00 (4 singlets, C4Me2I2); 20.22, 20.18,
20.08, 20.05 (4 singlets, C4Me2I2); 2.82, 2.78, 1.71, 1.69, -0.17, -0.32,
-1.06, -1.08 (8 singlets, SiCH2). UV-vis (THF, nm): 233, 280. Anal.
Calcd for C48H66Si6I6: C, 36.65; H, 4.23. Found: C, 37.35; H, 4.45.
EIMS showed the most intense peaks at M+ - 127 (I-) ) 1445; M+
- 254 (2I-) ) 1318; M+ - 381 (3I-) ) 1191; M+ - 508 (4I-) )
1064; M+ - 635 (5I-) ) 937. The isotope pattern for these peaks
was in good agreement with that obtained from simulation.
[1,3-Me2SiC6H4SiMe2C4Me2H2]n (12). The method for 11 was
followed (using 6), to afford 0.38 g (70%) of 12 as a gummy solid. 1H
NMR (benzene-d6, 400 MHz): δ 8.06 (s, 1 H, C6H4), 7.61 (d, J ) 7.6,
2 H, C6H4), 7.29 (t, J ) 7.6, 1 H, C6H4), 6.03 (s, 2 H, C4Me2H2), 1.98
(s, 6 H, C4Me2), 0.45 (s, 12 H, SiMe2). 13C{1H} NMR (benzene-d6,
100.6 MHz): δ 155.88 (C4Me2H2, C), 140.35 (C6H4, C), 133.67 (C6H4,
C), 124.39 (C4Me2H2, CH), 20.76 (C4Me2H2), -0.780 (SiMe2). Mn )
1700, Mw ) 3500. Anal. Calcd for C14H24Si2: C, 70.51; H, 8.88.
Found: C, 61.77; H, 8.30.
[4,4′-Me2SiC6H4C6H4SiMe2C4Me2H2]n (13). The method for 11
was followed (using 7) to afford 0.56 g (91%) of 13 as a white powder.
1H NMR (benzene-d6, 400 MHz): δ 7.66 (d, J ) 8.0, 4 H, C6H4), 7.61
(d, J ) 8.0, 4 H, C6H4), 6.08 (s, 2 H, C4Me2H2), 2.03 (s, 6 H, C4Me2),
0.46 (s, 12 H, SiMe2). 13C{1H} NMR (benzene-d6, 100.6 MHz): δ
155.98 (C4Me2H2, C), 142.18 (C6H4, C), 138.57 (C6H4, C), 134.78
(C6H4, CH), 127.04 (C6H4, CH), 124.48 (C4Me2H2, CH), 20.76
(C4Me2H2), -0.72 (SiMe2). Mn ) 6200, Mw ) 13 000. Anal. Calcd
for C22H28Si2: C, 75.79; H, 8.09. Found: C, 74.80; H, 8.11.
[1,4-Me2SiC6H4SiMe2C4Me2I2]n (14). A 100 mL round-bottom
flask was charged with 5 (0.95 g, 1.93 mmol), I2 (1.00 g, 3.94 mmol),
and THF (20 mL). The resulting red solution was stirred for 12 h,
and then the reaction mixture was poured into 200 mL of methanol.
The resulting precipitate was collected to afford 0.75 g (74%) of 14 as
a gray powder. 1H NMR (benzene-d6, 300 MHz): δ 7.71 (s, 4 H,
C6H4), 1.73 (s, 6 H, C4Me2), 0.60 (s, 6 H, SiMe2), 0.53 (s, 6 H, SiMe2).
13C NMR{1H} (benzene-d6, 100.6 MHz): δ 164.31 (C4Me2I2), 139.62
(C6H4, C), 133.84 (C6H4, CH), 100.31 (C4Me2I2), 20.31 (C4Me2I2), 1.12
(SiMe2), 0.99 (SiMe2), 0.79 (SiMe2). Mn ) 5000, Mw ) 8800. UV-
vis (THF, nm): 214, 233. Anal. Calcd for C12H22Si2I2: C, 36.65; H,
4.23; I, 48.41. Found: C, 36.74; H, 4.28; I, 48.22.
[1,4-Me2SiC6H4SiMe2C4Me2ZrCp2]3 (15). A 100 mL THF solution
of polymer 5 (5.21 g) was heated at reflux for 24 h, and then the solution
was concentrated to 30 mL and added to 70 mL of diethyl ether. The
resulting solution was cooled to -20 °C to give the product as yellow
cubic crystals in 93% yield (4.82 g). The compound was recrystallized
from a THF/diethyl ether solution containing a slight amount of
benzene. 1H NMR (benzene-d6, 300 MHz): δ 7.87 (s, 4 H, C6H4),
6.09 (s, 10 H, C5H5), 1.79 (s, 6 H, C4Me2), 0.31 (s, 12 H, SiMe2). 13C-
{1H} NMR (benzene-d6, 100.6 MHz): δ 198.93 (ZrC4Me2), 149.88
(ZrC4Me2), 142.82 (C6H4, C), 133.76 (C6H4, CH), 111.51 (C5H5), 27.68
(ZrC4Me2), 1.35 (SiMe2). Mn ) 4600, Mw ) 13 000. UV-vis (THF,
nm): 214, 226, 326. Anal. Calcd for C78H96Si6Zr3 (not including the
[1,3-Me2SiC6H4SiMe2C4Me2ZrCp2]2 (18). A 20 mL THF solution
of polymer 6 (1.0 g) was heated in a thick-wall glass reactor at 80 °C
for 24 h. During this period, yellow crystals precipitated from solution.
Pentane (10 mL) was added to the reaction mixture, and the supernatant
was filtered away to give 18 as yellow crystals in 85% yield (0.85 g).
1H NMR (toluene-d8, 400 MHz, 110 °C): δ 8.20 (s, 2 H, C6H4), 7.56
(d, JHH ) 7.6 Hz, 4 H, C6H4), 7.34 (t, JHH ) 7.6 Hz, 2 H, C6H4), 6.10
(s, 10 H, C5H5), 6.11 (s, 10 H, C5H5), 1.92 (s, 12 H, C4Me2), 0.52 (s,
12 H, SiMe2), 0.04 (s, 12 H, SiMe2). Due to its low solubility, a 13C-
{1H} NMR spectrum was not recorded. Anal. Calcd for C52H64Si4-
Zr2: C, 63.48; H, 6.56. Found: C, 63.44; H, 6.51.
[1,3-Me2SiC6H4SiMe2C4Me2H2]2 (19). A 100 mL round-bottom
flask was charged with 18 (0.50 g, 1.0 mmol) and THF (20 mL). An
aqueous HCl solution (6 M, 20 mL) was added to the flask, and then
the resulting mixture was stirred for 2 h at room temperature. The
yellow crystals of 18 dissolved, and a colorless solution formed. This
solution was poured into 100 mL of methanol, and the white precipitate
was collected to afford 0.20 g (72%) of 19 as a white powder. 1H
NMR (benzene-d6, 400 MHz): δ 8.02 (s, 2 H, C6H4), 7.54 (d, JHH
)
7.2 Hz, 4 H, C6H4), 7.33 (t, JHH ) 7.2 Hz, 2 H, C6H4), 5.98 (s, 4 H,
C4Me2H2), 1.94 (s, 12 H, C4Me2), 0.36 (s, 24 H, SiMe2). 13C{1H} NMR
(benzene-d6, 100.6 MHz): δ 156.15 (C4Me2H2, C), 140.61 (C6H4, C),
138.74, 134.41 (C6H4, CH), 124.92 (C4Me2H2, CH), 123.71, 21.06
(C4Me2H2), -0.37 (SiCH3). EIMS showed M+ ) 544. HRMS calcd
for C32H48Si4, 544.283316; found, 544.282772.
[Me2SiC6H4SiMe2C6H4SiMe2C4Me2ZrCp2]2 (20). A 250 mL Schlenk
flask was charged with Cp2ZrCl2 (0.58 g, 2.00 mmol), 4 (0.81 g, 2.00
mmol), and THF (80 mL). The flask was cooled to -78 °C, and then
n-butyllithium (1.6 M/hexane, 2.50 mL, 4.00 mmol) was added
dropwise. The flask was allowed to warm to room temperature over
7 h, and it was heated for 1 h at 65 °C. The volatile materials were
removed under vacuum. The resulting residue was extracted with a
mixture of dichloromethane and hexane (5:1, 80 mL), and the extract