4364 Organometallics, Vol. 25, No. 18, 2006
Gonza´lez-Maupoey et al.
mmol) in hexane (70 mL) at -78 °C. The reaction mixture was
slowly warmed to room temperature and stirred for 6 h. The solvent
was completely removed and the resulting solid extracted into
hexane. After concentrating the solution, a yellow powder was
obtained, which was recrystallized from cold hexane and character-
ized as 4 (0.27 g, 56% yield). Anal. Calcd for C31H43TiSiO2Cl: C,
CH2); 3.00 (s, 2H, Ti-CH2Ph); 2.34 (s, 2H, SiCH2Ph); 2.25 (s, 6H,
CH3Ph); 1.40 [s, 18H, C(CH3)3]; 0.11 (s, 6H, C5H4SiMe2(CH2Ph)).
13C NMR (125 MHz, C6D6, 25 °C): δ 161.4, 151.8, 141.9, 136.9,
136.6, 130.1, 129.1, 128.8, 128.5, 128.2, 127.8, 127.4, 126.6, 126.2
(aromatic); 123.5 (ipso-C5H4SiMe2(CH2Ph)); 123.1, 122.3 (C5H4-
SiMe2(CH2Ph)); 78.4 (Ti-CH2Ph); 38.5 (Si-CH2Ph); 37.1 (CH2);
35.8 [C(CH3)3]; 31.3 [C(CH3)3]; 21.5 (CH3-Ph); -0.02 (C5H4-
SiMe2(CH2Ph)).
1
66.54; H, 7.69. Found: C, 66.47; H, 7.82. H NMR (300 MHz,
C6D6, 25 °C): δ 7.09, 6.99 (AA′ spin system, 2 × 2H, Ph); 6.39
(m, 4H, C5H4SiMe2Cl); 3.82, 3.43 (AB spin system, 2 × 1H, ∆δ
) 0.39 ppm, 2JH-H ) 13.6 Hz, CH2); 2.14 (s, 6H, CH3Ph); 1.37 [s,
18H, C(CH3)3]; 1.35 (s, 3H, Ti-CH3); 0.48 (s, 6H, C5H4SiMe2Cl).
13C NMR (125 MHz, C6D6, 25 °C): δ 161.2, 136.8, 136.1, 130.3,
129.0, 126.1 (Ph); 121.3 (ipso-C5H4SiMe2Cl); 119.9, 119.6 (C5H4-
SiMe2Cl); 54.4 (Ti-CH3); 36.2 (CH2); 35.3 [C(CH3)3]; 30.9
[C(CH3)3]; 21.2 (CH3-Ph); 2.9 (C5H4SiMe2Cl).
Synthesis of Ti(η5-C5H4SiMe2-η1-MBMP)(CH2Ph)2 (8). A 2.0
M solution of MgCl(CH2Ph) (0.34 mL, 0.69 mmol) in THF was
added to a solution of Ti(η5-C5H4SiMe2-η1-MBMP)Cl2 (0.20 g, 0.34
mmol) in toluene (50 mL) at -78 °C, followed by stirring overnight.
After warming to room temperature, the solvent was completely
removed and the solid obtained extracted into hexane. Concentrating
the resulting solution gave a solid, which was recrystallized from
cold hexane and characterized as 8 (0.17 g, 72% yield). Anal. Calcd
for C44H54TiSiO2: C, 76.54; H, 7.83. Found: C, 76.43; H, 7.64.
1H NMR (300 MHz, C6D6, 25 °C): δ 7.20-6.90 (m, 14H,
aromatic); 6.37, 6.00 (AA′BB′ spin system, 2 × 2H, C5H4SiMe2);
3.85 (br s, 2H, CH2); 3.08, 2.77 (2 × 2H, Ti-CH2Ph); 2.22, 2.04
(s, 2 × 3H, CH3Ph); 1.58, 1.38 [s, 2 × 9H, C(CH3)3]; 0.13 (s, 6H,
C5H4SiMe2). 1H NMR (300 MHz, CD2Cl2, 25 °C): δ 7.15 (m, 4H,
m-CH2Ph), 6.89 (m, 2H, p-CH2Ph), 6.85 (m, 4H, o-CH2Ph); 7.06,
7.02, 6.54, 6.38 (two AA′ spin systems, 4 × 1H, Ph); 6.38, 6.25
(AA′BB′ spin system, 2 × 2H, C5H4SiMe2); 3.71 (br s, 2H, CH2);
2.98, 2.55 (2 × 2H, Ti-CH2Ph); 2.32, 2.21 (s, 2 × 3H, CH3Ph);
1.51, 1.37 [s, 2 × 9H, C(CH3)3]; 0.13 (s, 6H, C5H4SiMe2). 13C NMR
(125 MHz, C6D6, 25 °C): δ 162.3, 150.0, 140.3, 137.0, 132.4,
131.5, 130.9, 130.5, 128.9, 127.0, 125.7, 121.7 (Ph); 151.2, 128.6,
128.3, 126.5 (Ti-CH2Ph); 124.2, 123.0 (C5H4SiMe2); 88.4 (Ti-CH2-
Ph); 33.7 (CH2); 35.3, 35.0 [C(CH3)3]; 30.5 [C(CH3)3]; 21.4, 21.2
(CH3-Ph); 2.2 (C5H4SiMe2).
Synthesis of Ti(η5-C5H4SiMe3)(η2-MBMP)Me (5). Following
the procedure described for 4 using 0.57 mL (1.72 mmol) of a 3.0
M solution of MgClMe in THF and 0.50 g (0.86 mmol) of Ti(η5-
C5H4SiMe2Cl)(η2-MBMP)Cl in hexane (70 mL), a bright yellow
solid was obtained, which was characterized as 5 (0.29 g, 63%
yield). Anal. Calcd for C32H46TiSiO2: C, 71.35; H, 8.61. Found:
C, 71.14; H, 8.40. 1H NMR (300 MHz, C6D6, 25 °C): δ 7.12, 7.00
(AA′ spin system, 2 × 2H, Ph); 6.50, 6.33 (AA′BB′ spin system,
2 × 2H, C5H4SiMe3); 3.89, 3.44 (AB spin system, 2 × 1H, ∆δ )
2
0.45 ppm, JH-H ) 13.7 Hz, CH2); 2.15 (s, 6H, CH3Ph); 1.40 [s,
18H, C(CH3)3]; 1.36 (s, 3H, Ti-CH3); 0.20 (s, 9H, C5H4SiMe3).
13C NMR (125 MHz, C6D6, 25 °C): δ 161.2, 136.8, 135.9, 130.0,
129.0, 126.0 (Ph); 126.0 (ipso-C5H4SiMe3); 120.0, 119.5 (C5H4-
SiMe3); 53.5 (Ti-CH3); 36.1 (CH2); 35.2 [C(CH3)3]; 30.8 [C(CH3)3];
21.2 (CH3-Ph); -0.17 (C5H4SiMe3).
Synthesis of Ti(η5-C5H4SiMe2Cl)(η2-MBMP)(CH2Ph) (6). Fol-
lowing the procedure described for 4 using 0.26 mL (0.50 mmol)
of a 2.0 M solution of MgCl(CH2Ph) in THF and 0.30 g (0.50
mmol) of Ti(η5-C5H4SiMe2Cl)(η2-MBMP)Cl in hexane (70 mL),
a light brown powder was obtained, which was characterized as 6
(0.21 g, 65% yield). Anal. Calcd for C37H47TiSiO2Cl: C, 70.00;
H, 7.41. Found: C, 69.80; H, 7.23. 1H NMR (300 MHz, C6D6, 25
°C): δ 7.31 (m, 5H, CH2Ph); 7.06, 6.99 (AA′ spin system, 2 ×
Synthesis of Ti(η5-C5H4SiMe2-η1-MBMP)Me2 (9). Following
the procedure described for 8 using 0.34 mL (1.03 mmol) of a 3.0
M solution of MgClMe in THF and 0.30 g (0.52 mmol) of Ti(η5-
C5H4SiMe2-η1-MBMP)Cl2 in hexane (50 mL), a bright yellow solid
was obtained, which was recrystallized from cold toluene and
characterized as 9 (0.18 g, 65% yield). Anal. Calcd for C32H46-
TiSiO2: C, 71.35; H, 8.61. Found: C, 69.33; H, 8.49. The isolated
yellow solid consisted mainly of 9, but it contained some unremov-
able amount of MgCl2, which prevented us from obtaining correct
elemental analysis, though satisfactory spectroscopy data were
2H, Ph); 6.43, 6.26 (AA′BB′ spin system, 2 × 2H, C5H4SiMe2Cl);
2
3.88, 3.38 (AB spin system, 2 × 1H, ∆δ ) 0.50 ppm, JH-H
)
13.6 Hz, CH2); 3.31 (s, 2H, Ti-CH2Ph); 2.14 (s, 6H, CH3Ph); 1.45
[s, 18H, C(CH3)3]; 0.42 (s, 6H, C5H4SiMe2Cl). 1H NMR (300 MHz,
CDCl3, 25 °C): δ 7.34 (m, 5H, CH2Ph); 7.07, 6.96 (AA′ spin
system, 2 × 2H, Ph); 6.47, 6.40 (AA′BB′ spin system, 2 × 2H,
C5H4SiMe2Cl); 3.86, 3.40 (AB spin system, 2 × 1H, ∆δ ) 0.46
ppm, 2JH-H ) 13.4 Hz, CH2); 3.05 (s, 2H, Ti-CH2Ph); 2.30 (s, 6H,
CH3Ph); 1.45 [s, 18H, C(CH3)3]; 0.16 (s, 6H, C5H4SiMe2Cl). 13C
NMR (125 MHz, C6D6, 25 °C): δ 161.4, 136.9, 136.6, 129.1, 128.5,
126.6 (Ph); 151.8 (ipso-CH2Ph); 130.1 (p-CH2Ph); 126.2 (m-
CH2Ph); 123.5 (o-CH2Ph); 123.5 (ipso-C5H4SiMe2Cl), 123.1, 122.3
(C5H4SiMe2Cl); 78.4 (Ti-CH2Ph); 37.1 (CH2); 35.8 [C(CH3)3]; 31.3
[C(CH3)3]; 21.5 (CH3-Ph); -0.01 (C5H4SiMe2Cl).
1
obtained. H NMR (300 MHz, C6D6, 25 °C): δ 7.15, 7.10, 6.85,
6.79 (two AA′ spin systems, 4 × 1H, Ph); 6.51, 6.08 (AA′BB′
spin system, 2 × 2H, C5H4SiMe2); 3.73 (br s, 2H, CH2); 2.17, 2.05
(s, 2 × 3H, CH3Ph); 1.61, 1.43 [s, 2 × 9H, C(CH3)3]; 1.03 (s, 6H,
Ti-CH3); 0.25 (s, 6H, C5H4SiMe2). 13C NMR (125 MHz, C6D6, 25
°C): δ 162.0, 150.2, 140.2, 136.7, 132.1, 131.1, 130.4, 130.4, 129.3,
127.9, 126.9, 125.6 (Ph); 126.0 (ipso-C5H4SiMe2); 119.9, 118.7
(C5H4SiMe2); 57.6 (Ti-CH3); 33.8 (CH2); 35.3, 35.0 [C(CH3)3]; 30.7,
30.4 [C(CH3)3]; 21.4, 21.1 (CH3-Ph); 2.3 (C5H4SiMe2).
Polymerization Procedure. Polymerization runs were carried
out by following the general procedure. Polymerization of ethyl-
ene: A 250 mL Bu¨chi reactor equipped with a mechanical stirrer
was first evacuated and then charged with dried scavenger methy-
laluminoxane (MAO) and toluene (150 mL). A 10 mL pressure
tube was charged with the titanium complex in a toluene solution
previously preactivated (2 min) with 1 mL of MAO. The reactor
was purged with the monomer three times by pressurizing and
venting. The monomer was then equilibrated with the toluene in
the reactor for 30 min at the polymerization temperature and
pressure (kept constant at 1 atm over the run) with constant stirring.
The reaction was initiated by injecting the solution containing the
catalytic system under argon pressure. After the desired reaction
time was reached the reactor was vented and the polymer was
precipitated into 10% HCl in methanol, washed with clean
methanol, and dried in a vacuum oven at 60 °C to constant weight.
Synthesis of Ti(η5-C5H4SiMe2(CH2Ph))(η2-MBMP)(CH2Ph)
(7). Following the procedure described for 4 using 0.52 mL (1.00
mmol) of a 2.0 M solution of MgCl(CH2Ph) in THF and 0.30 g
(0.50 mmol) of Ti(η5-C5H4SiMe2Cl)(η2-MBMP)Cl in hexane (50
mL), a dark brown powder was obtained, which was characterized
as 7 (0.20 g, 58% yield). Anal. Calcd for C44H54TiSiO2Cl: C, 76.38;
H, 7.87. Found: C, 76.10; H, 7.50. 1H NMR (300 MHz, C6D6, 25
°C): δ 7.34-7.00 (m, 10H, CH2Ph); 7.10, 7.00 (AA′ spin system,
2 × 2H, Ph); 6.35 (m, 4H, C5H4SiMe2Bz); 3.97, 3.41 (AB spin
system, 2 × 1H, ∆δ ) 0.56 ppm, 2JH-H ) 13.7 Hz, CH2); 3.31 (s,
2H, Ti-CH2Ph); 2.07 (s, 2H, SiCH2Ph); 2.15 (s, 6H, CH3Ph); 1.48
[s, 18H, C(CH3)3]; 0.14 (s, 6H, C5H4SiMe2Bz). 1H NMR (300 MHz,
CDCl3, 25 °C): δ 7.30-6.90 (m, 10H, CH2Ph); 7.02, 6.91 (AA′
spin system, 2 × 2H, Ph); 6.42, 6.35 (m, 4H, C5H4SiMe2Bz); 3.81,
3.35 (AB spin system, 2 × 1H, ∆δ ) 0.46 ppm, 2JH-H ) 13.7 Hz,