Propylene dimerization catalyzed by zirconocene complexes
2.32 mmol) were reacted to afford the product as red crystals
(0.406g, 30.6%). 1H NMR (400 MHz, 298 K, CDCl3): δ 8.02 (d,
J = 8.6Hz, 1H, 7-Ind―H), 7.93 (d, J = 8.4Hz, 1H, 4-Flu―H), 7.86 (d,
J = 8.4Hz, 1H, 1-Flu―H), 7.79 (d, J = 8.4Hz, 1H, 5-Flu―H), 7.68
(t, J = 7.6Hz, 1H, 3-Flu―H), 7.58 (d, J = 7.2 Hz, 2H, 3,5-Ph―H), 7.53
(d, J = 8.6 Hz, 1H, 8-Flu―H), 7.45 (t, J = 7.6Hz, 1H, 2-Flu―H), 7.28(t,
J = 7.5Hz, 1H, 6-Flu―H), 7.21–7.14 (m, 3H, 2,4,6-Ph―H), 7.07 (t,
J = 7.6Hz, 1H, 7-Flu―H), 6.94 (t, J = 7.5 Hz, 1H, 6-Ind―H), 6.81
(t, J = 7.5Hz, 1H, 5-Ind―H), 6.40 (d, J = 8.6 Hz, 1H, 4-Ind―H), 6.13
(s, 1H, 2-Ind―H), 4.69-4.60 (m, 1H, CH2Flu), 4.22–4.13 (m, 1H,
CH2Ind), 4.00–3.93 (m, 2H, IndCH2CH2Flu), 2.64–2.54 (m, 1H,
CH2CH3), 2.10–1.99 (m, 2H, CH2CH3), 1.83–1.74 (m, 1H, CH2CH3),
0.48 (t, J = 7.4Hz, 3H, CH2CH3), 0.32 (t, J = 7.4Hz, 3H, CH2CH3). 13C
NMR (100MHz, 298 K, CDCl3): δ 144.7 (1-Ph―C), 131.4 (7a-Ind―C),
129.0 (1,4-Flu―C), 128.8 (4b-Flu―C), 128.7 (7-Ind―C), 127.8 (3,5-
Ph―C), 127.71 (4a-Flu―C), 127.66 (5-Flu―C), 126.7 (3-Flu―C),
126.4 (9a-Flu―C), 126.0 (2,6-Ph―C), 125.7 (8-Flu―C), 125.5 (8a-
Flu―C), 125.13 (6-Ind―C), 125.09 (2-Flu―C), 124.72 (4-Ph―C),
124.69 (3a-Ind―C), 123.97 (5-Ind―C), 123.95 (6-Flu―C), 123.3
(4-Ind―C), 123.1 (9-Flu―C), 121.6 (7-Flu―C), 121.1 (1-Ind―C),
117.2 (3-Ind―C), 103.9 (2-Ind―C), 49.8 (C(C2H5)), 32.3 (CH2CH2),
30.8 (CH2CH3), 30.0 (CH2CH2), 27.7 (CH2CH3), 9.3 (CH2CH3), 8.1
(CH2CH3). Anal. Calcd for C35H32Cl2Zr: C, 68.38; H, 5.25; found: C,
68.29; H, 5.23%.
0.8 Hz, 1H, 6-Flu―H), 7.08 (dt, J = 8.0, 1.0 Hz, 1H, 7-Flu―H), 7.05–
7.02 (m, 1H, 5-Ph―H), 6.98–6.93 (m, 2H, 6-Ind―H, 4-Ph―H),
6.85–6.78 (m, 2H, 4,5-Ind―H), 6.69 (dd, J = 7.4, 0.6 Hz, 1H, 3-
Ph―H), 6.35 (s, 1H, 2-Ind―H), 4.75–4.66 (m, 1H, CH2Flu), 4.28–
4.19 (m, 1H, CH2Ind), 4.00–3.93 (m, 2H, IndCH2CH2Flu), 2.20–2.15
(m, 2H, CH2CH2CH3), 1.97 (s, 3H, CCH3), 1.41 (s, 3H, Ph―CH3),
1.25–1.16 (m, 1H, CH2CH2CH3), 0.75 (t, J = 7.2 Hz, 3H, CH2CH2CH3),
0.60–0.49 (m, 1H, CH2CH2CH3). 13C NMR (100 MHz, 298 K, CDCl3): δ
144.7 (1-Ph―C), 136.5 (2-Ph―C), 132.5 (6-Ph―C), 131.8
(7a-Ind―C), 128.9 (7-Ind―C), 128.6 (1-Flu―C), 127.8 (4-Flu―C),
127.3 (4a,4b-Flu―C), 127.1 (5-Ph―C), 126.9 (5-Flu―C), 126.6
(9a-Flu―C), 126.0 (3-Flu―C), 125.8 (8a-Flu―C), 125.41 (8-Flu―C),
125.37 (6-Ind―C), 125.1 (2-Flu―C), 125.0 (6-Flu―C), 124.8
(4-Ph―C), 124.5 (5-Ind―C), 124.3 (3-Ph―C), 124.0 (4-Ind―C),
123.5 and 123.4 (9-Flu―C, 1-Ind―C), 122.0 (3a-Ind―C), 120.0
(3-Ind―C),
119.1
(7-Flu―C),
104.2
(2-Ind―C),
44.3
(CH3CCH2CH2CH3), 39.1 (CH3CCH2CH2CH3), 33.0 (CH2CH2), 29.9
(CH2CH2), 25.5 (CCH3), 22.1 (Ph―CH3), 17.3 (CH2CH2CH3), 14.7
(CH2CH2CH3). EI/HRMS: [M]+ calcd for C36H34Cl2Zr, 626.1085;
found, 626.1088.
Ethylene-1-(9-fluorenyl)-2-{1-[3-(3-(3-(2-methylphenyl)pentyl))indenyl]}
zirconium dichloride (6)
Following the procedure described above, L6H2 (0.99 g,
2.11 mmol), n-BuLi (1.77 ml, 2.39 mol lÀ1, 4.23 mmol) and ZrCl4
(0.50 g, 2.15 mmol) were reacted to afford the product as red
Ethylene-1-(9-fluorenyl)-2-{1-[3-(2-(2-(2-methylphenyl)propyl))indenyl]}zirconium
dichloride (4)
1
crystals (0.71 g, 53.1%). H NMR (400 MHz, 298 K, CDCl3): δ 8.06
Following the procedure described above, L4H2 (1.89 g,
4.29 mmol), n-BuLi (3.60 ml, 2.39 mol lÀ1, 8.60 mmol) and ZrCl4
(1.03 g, 4.42 mmol) were reacted to afford the product as red
(d, J = 8.6 Hz, 1H, 7-Ind―H), 7.89 (d, J = 8.4 Hz, 1H, 4-Flu―H),
7.87 (d, J = 8.6 Hz, 1H, 1-Flu―H), 7.76 (d, J = 8.4 Hz, 1H, 5-Flu―H),
7.66 (t, J = 7.6 Hz, 1H, 3-Flu―H), 7.54 (d, J = 8.6 Hz, 1H, 8-Flu―H),
7.47 (d, J = 8.6 Hz, 1H, 6-Ph―H), 7.42 (t, J = 7.6 Hz, 1H, 2-Flu―H),
7.29 (t, J = 7.7 Hz, 1H, 6-Flu―H), 7.10 (t, J = 5.6 Hz, 1H, 7-Flu―H),
7.08 (t, J = 5.6 Hz, 1H, 5-Ph―H), 6.98 (t, J = 7.2 Hz, 1H, 4-Ph―H),
6.93 (dd, J = 8.4, 4.0 Hz, 1H, 4-Ph―H), 6.84 (d, J = 3.6 Hz, 2H, 4,5-
Ind―H), 6.75 (d, J = 7.4 Hz, 1H, 3-Ph―H), 6.18 (s, 1H, 2-Ind―H),
4.74–4.65 (m, 1H, CH2Flu), 4.26–4.17 (m, 1H, CH2Ind), 3.95 (dd,
J = 14.6, 7.8 Hz, 2H, IndCH2CH2Flu), 2.69–2.60 (m, 1H, CH2CH3),
2.58–2.48 (m, 1H, CH2CH3), 2.39–2.30 (m, 1H, CH2CH3), 2.21–2.12
(m, 1H, CH2CH3), 1.30 (s, 3H, Ph―CH3), 1.06 (t, J = 7.3 Hz, 3H,
CH2CH3), 0.60 (t, J = 7.4 Hz, 3H, CH2CH3). 13C NMR (100 MHz,
1
crystals (0.97 g, 34.4%). H NMR (400 MHz, 298 K, CDCl3): δ 8.13
(d, J = 8.6 Hz, 1H, 7-Ind―H), 7.89 (d, J = 7.4 Hz, 2H, 1,4-Flu―H),
7.76 (d, J = 8.4 Hz, 1H, 5-Flu―H), 7.68–7.64 (m, 1H, 3-Flu―H),
7.50 (d, J = 8.6 Hz, 1H, 8-Flu―H), 7.46–7.42 (m, 2H, 2-Flu―H,
6-Ph―H), 7.30–7.26 (m, 1H, 6-Flu―H), 7.10–7.02 (m, 2H, 7-Flu―H,
5-Ph―H), 7.00–6.94 (m, 2H, 6-Ind―H, 4-Ph―H), 6.90–6.82 (m, 2H,
4,5-Ind―H), 6.75 (dd, J = 7.4, 0.6 Hz, 1H, 3-Ph―H), 6.28 (s, 1H,
2-Ind―H), 4.75–4.66 (m, 1H, CH2Flu), 4.28–4.19 (m, 1H, CH2Ind),
4.00–3.94 (m, 2H, IndCH2CH2Flu), 2.03 (s, 3H, C(CH3)2), 1.65 (s,
3H, C(CH3)2), 1.51 (s, 3H, Ph―CH3). 13C NMR (100 MHz, 298 K,
CDCl3): δ 147.5 (1-Ph―C), 136.2 (2-Ph―C), 132.6 (6-Ph―C),
131.8 (7a-Ind―C), 129.0 (7-Ind―C), 127.5 and 127.4 (4a,4b-
Flu―C), 127.2 (1-Flu―C), 127.0 (4-Flu―C), 126.5 (9a-Flu―C),
126.1 (5-Flu―C), 126.0 (3-Flu―C), 125.8 (8a-Flu―C), 125.7
(6-Ind―C), 125.6 (8-Flu―C), 125.3 (5-Ph―C), 125.0 (4-Ph―C),
124.9 (2-Flu―C), 124.5 (3-Ph―C), 124.2 (6-Flu―C), 124.0
(5-Ind―C), 123.42 (9-Flu―C), 123.40 (4-Ind―C), 123.38
(1-Ind―C), 122.0 (3a-Ind―C), 120.1 (3-Ind―C), 119.4 (7-Flu―C),
104.1 (2-Ind―C), 41.0 (C(CH3)2), 32.8 (CH2CH2), 29.9 (CH2CH2),
29.1 (C(CH3)2), 27.1 (C(CH3)2), 22.2 (PhCH3). Anal. Calcd for
C34H30Cl2ZrÁ0.25CH2Cl2: C, 66.14; H, 4.94; found: C, 66.35; H,
4.83%.
298 K, CDCl3):
δ 142.2 (1-Ph―C), 137.1 (2-Ph―C), 132.6
(6-Ph―C), 131.1 (7a-Ind―C), 129.1 (7-Ind―C), 128.8 (1-Flu―C),
127.9 (4a,4b-Flu―C), 127.6 (4-Flu―C), 126.8 (5-Flu―C), 126.3
(9a-Flu―C), 126.2 (3-Flu―C), 125.9 (5-Ph―C), 125.60 (8-Flu―C),
125.57 (8a-Flu―C), 125.2 (6-Ind―C), 125.04 (2-Flu―C), 124.98
(6-Flu―C), 124.5 (4-Ph―C), 124.0 (5-Ind―C), 123.9 (3-Ph―C),
123.6 (9-Flu―C), 123.2 (1-Ind―C), 123.0 (4-Ind―C), 121.7
(3a-Ind―C), 120.8 (3-Ind―C), 118.5 (7-Flu―C), 104.3 (2-Ind―C),
49.0 (C(C2H5)), 32.8 (CH2CH2), 31.4 (CH2CH3), 30.5 (CH2CH3), 30.0
(CH2CH2), 21.8 (Ph―CH3), 11.7 (CH2CH3), 10.2 (CH2CH3). Anal.
Calcd for C36H34Cl2ZrÁ0.5CH2Cl2: C, 65.31; H, 5.26; found: C,
65.40; H, 5.32%.
Ethylene-1-(9-fluorenyl)-2-{1-[3-(2-(2-(2-methylphenyl)pentyl))indenyl]}zirconium
dichloride (5)
Ethylene-1-(9-fluorenyl)-2-{1-[3-(2-(2-(2-methoxylphenyl)propyl))indenyl]}
zirconium dichloride (7)
Following the procedure described above, L5H2 (1.10 g,
2.35 mmol), n-BuLi (2.65 ml, 1.79 mol lÀ1, 4.74 mmol) and ZrCl4
(0.57 g, 2.45 mmol) were reacted to afford the product as red
Following the procedure described above, L7H2 (0.84 g,
1.84 mmol), n-BuLi (2.33 ml, 1.59 mol lÀ1, 3.68 mmol), and ZrCl4
(0.44 g, 1.89 mmol) were reacted to afford the product as red
1
1
crystals (0.372 g, 25.2%). H NMR (400 MHz, 298 K, CDCl3): δ 8.13
crystals (0.234 g, 20.6%). H NMR (400 MHz, 298 K, CDCl3): δ 8. 07
(d, J = 8.7 Hz, 1H, 7-Ind―H), 7.89 (d, J = 8.6 Hz, 2H, 1,4-Flu―H),
7.76(d, J = 8.4 Hz, 1H, 5-Flu―H), 7.66 (dt, J = 8.2, 1.0 Hz, 1H, 3-
Flu―H), 7.51–7.44 (m, 3H, 2,8-Flu―H, 6-Ph―H), 7.28 (dt, J = 6.9,
(d, J = 8.6 Hz, 1H, 7-Ind―H), 7.89 (t, J = 8.4 Hz, 2H, 1,4-Flu―H),
7.76 (d, J = 8.4 Hz, 1H, 5-Flu―H), 7.66 (t, J = 7.6 Hz, 1H, 3-Flu―H),
7.50 (d, J = 8.4 Hz, 1H, 8-Flu―H), 7.45 (t, J = 7.6 Hz, 1H, 2-Flu―H),
Appl. Organometal. Chem. 2014, 28, 413–422
Copyright © 2014 John Wiley & Sons, Ltd.
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