2
D. Polo-Cerón et al. / Polyhedron xxx (2014) xxx–xxx
spectrometer. Microanalyses were carried out with a Perkin-Elmer
2400 or LECO CHNS-932 microanalyzer. Polymer molecular
weights and distribution were determined by GPC (Waters 150C
Plus or Alliance GPC-2000) in 1,2,4-trichlorobenzene at 150 °C,
using standard polystyrene calibration.
(4.0 mL, 6.40 mmol, 1.6 M in hexane). Yield 0.90 g, 88%. C25H26Li2
(340.4): Calc. C, 88.22; H, 7.70. Found: C, 87.81; H, 7.67%.
2.2.9. Synthesis of Li2{CH2CH2CH2(C9H5Pr-3)2} (12)
The preparation of 12 was carried out in an identical manner to
that of 10. CH2CH2CH2(C9H6Pr)2 (9) (0.92 g, 2.55 mmol) and LiBu
(3.5 mL, 5.60 mmol, 1.6 M in hexane). Yield 0.79 g, 84%. C27H30Li2
(368.4): Calc. C, 88.02; H, 8.21. Found: C, 87.83; H, 8.17%.
2.2. Synthesis of compounds
2.2.1. Synthesis of Li(C9H6Me-1) (4)
LiBu (7.7 mL, 12.30 mmol, 1.6 M in hexane) was added drop-
wise to a solution of C9H7Me-1 (1) (1.63 g, 12.30 mmol) in Et2O
(40 mL) at À78 °C. The mixture was warmed to 25 °C and stirred
for 4 h. Solvent was then removed in vacuo giving a white solid,
which was washed with hexane (2 Â 50 mL) and dried under vac-
uum to give the title compound as a white powder. Yield 1.57 g,
94%. C10H9Li (136.1): Calc. C, 88.24; H, 6.66. Found: C, 87.93; H,
6.62%.
2.2.10. Synthesis of [Zr{CH2CH2CH2(
solution of Li2{CH2CH2CH2(C9H5Me-3)2} (10) (0.76 g,
g
5-C9H5Me-3)2}Cl2] (13)
A
2.44 mmol) in THF (40 mL) was added to ZrCl4 (0.57 g, 2.44 mmol)
in THF at 0 °C. The reaction mixture was stirred under reflux for
18 h. Solvent was removed in vacuum and a toluene:hexane mix-
ture (9:1) (125 mL) added to the resulting solid. The mixture was
filtered and the filtrate concentrated (20 mL) and cooled to
À30 °C to yield crystals of the title complex. Yield 0.54 g, 48%. 1H
NMR (400 MHz, CDCl3, 25 °C): d = 1.84 (2H), 2.60 (4H) (m, CH2CH2-
CH2), 3.28 (s, 6H, 2 Â CH3), 6.42 (2H), 7.00–7.40 (8H) (m, 2 Â C9H5).
13C{1H} NMR (100 MHz, CDCl3): d = 22.1 (CH2CH2CH2), 25.8 (CH3),
30.6 (CH2CH2CH2), 105.8, 115.3, 121.0, 123.5, 126.1, 126.7, 126.9,
127.2, 128.7, 129.3 (2 Â C9H5). C23H22Cl2Zr (460.6): Calc. C, 59.98;
H, 4.81. Found: C, 59.49; H, 4.74%.
2.2.2. Synthesis of Li(C9H6Et-1) (5)
The preparation of 5 was carried out in an identical manner to
that of 4. C9H7Et-1 (2) (1.52 g, 10.40 mmol) and LiBu (6.5 mL,
10.40 mmol, 1.6 M in hexane). Yield 1.39 g, 89%. C11H11Li (150.1):
Calc. C, 87.99; H, 7.38. Found: C, 87.62; H, 7.31%.
2.2.3. Synthesis of Li(C9H6Pr-1) (6)
2.2.11. Synthesis of [Zr{CH2CH2CH2(g
5-C9H5Et-3)2}Cl2] (14)
The preparation of 6 was carried out in an identical manner to
that of 4. C9H7Pr-1 (3) (1.82 g, 11.34 mmol) and LiBu (7.1 mL,
11.34 mmol, 1.6 M in hexane). Yield 1.69 g, 91%. C12H13Li (164.1):
Calc. C, 87.79; H, 7.98. Found: C, 87.48; H, 7.96%.
The preparation of 14 was carried out in an identical manner to
that of 13. Li2{CH2CH2CH2(C9H5Et-3)2} (11) (0.60 g, 1.76 mmol)
and ZrCl4 (0.41 g, 1.76 mmol). Yield 0.28 g, 33%. 1H NMR
(400 MHz, CDCl3, 25 °C): d = 0.91 (m, 6H, 2 Â CH2CH3), 2.47 (4H),
2.74 (2H) (m, CH2CH2CH2), 3.05 (m, 4H, 2 Â CH2CH3), 5.99 (2H),
7.11 (2H), 7.24 (2H), 7.52 (4H) (m, 2 Â C9H5). 13C{1H} NMR
(100 MHz, CDCl3): d = 20.2 (CH2CH2CH2), 22.7 (CH2CH3), 26.8 (CH2-
CH3), 36.9 (CH2CH2CH2), 103.5, 113.3, 120.7, 123.9, 127.1, 127.8,
128.2, 128.6, 129.7, 130.3 (2 Â C9H5). C25H26Cl2Zr (488.6): Calc. C,
61.45; H, 5.36. Found: C, 61.09; H, 5.29%.
2.2.4. Synthesis of CH2CH2CH2(C9H6Me)2 (7)
1,3-Dibromopropane (0.99 g, 4.90 mmol) in THF (30 mL) was
added to a solution of Li(C9H6Me-1) (4) (1.47 g, 10.80 mmol) in
THF (50 mL) at 0 °C. The reaction mixture was allowed to warm
to room temperature and stirred for 6 h. Solvent was removed in
vacuo and hexane (150 mL) was added to the resulting dark orange
oil. The mixture was filtered and the solvent removed from the fil-
trate under reduced pressure to yield the title compound as a yel-
low solid. Yield 1.21 g, 82%. C23H24 (300.4): Calc. C, 91.95; H, 8.05.
Found: C, 91.87; H, 8.07%.
2.2.12. Synthesis of [Zr{CH2CH2CH2(g
5-C9H5Pr-3)2}Cl2] (15)
The preparation of 15 was carried out in an identical manner to
that of 13. Li2{CH2CH2CH2(C9H5Pr-3)2} (12) (0.50 g, 1.36 mmol)
and ZrCl4 (0.32 g, 1.36 mmol). Yield 0.27 g, 39%. 1H NMR
(400 MHz, CDCl3, 25 °C): d = 0.83 (m, 6H, 2 Â CH2CH2CH3), 1.36
(m, 4H, 2 Â CH2CH2CH3), 2.30 (4H), 2.79 (2H) (m, CH2CH2CH2),
3.00 (m, 4H, 2 Â CH2CH2CH3), 6.04 (2H), 7.13 (2H), 7.27 (2H),
7.55 (4H) (m, 2 Â C9H5). 13C{1H} NMR (100 MHz, CDCl3): d = 20.2
(CH2CH2CH2), 21.7, 23.9, 31.3 (CH2CH2CH3), 37.4 (CH2CH2CH2),
100.2, 117.4, 121.4, 125.3, 128.6, 129.1, 130.5, 131.1, 134.0, 138.3
(2 Â C9H5). C27H30Cl2Zr (516.7): Calc. C, 62.77; H, 5.85. Found: C,
62.31; H, 5.81%.
2.2.5. Synthesis of CH2CH2CH2(C9H6Et)2 (8)
The preparation of 8 was carried out in an identical manner to
that of 7. Li(C9H6Et-1) (5) (1.58 g, 10.50 mmol) and 1,3-dibromo-
propane (0.99 g, 4.90 mmol). Yield 1.04 g, 64%. C25H28 (328.5):
Calc. C, 91.41; H, 8.59. Found: C, 91.32; H, 8.62%.
2.2.6. Synthesis of CH2CH2CH2(C9H6Pr)2 (9)
The preparation of 9 was carried out in an identical manner to
that of 7. Li(C9H6Pr-1) (6) (1.72 g, 10.45 mmol) and 1,3-dibromo-
propane (0.99 g, 4.90 mmol). Yield 1.27 g, 72%. C25H28 (356.5):
Calc. C, 91.95; H, 9.05. Found: C, 91.89; H, 9.04%.
2.3. Data collection and structural refinement of 14 and 15
The data of 14 and 15 were collected with a CCD Oxford
Xcalibur S (k(Mo Ka) = 0.71073 Å) using x and u scans mode.
2.2.7. Synthesis of Li2{CH2CH2CH2(C9H5Me-3)2} (10)
Semi-empirical from equivalents absorption corrections were
carried out with SCALE3 ABSPACK [6]. All the structures were
solved by direct methods [7]. Structure refinement was carried
out with SHELXL-97 [8]. All non-hydrogen atoms were refined
anisotropically, and hydrogen atoms were calculated with the
riding model and refined isotropically. Table 1 lists crystallo-
graphic details and refinement details.
LiBu (4.4 mL, 7.00 mmol, 1.6 M in hexane) was added dropwise
to a solution of CH2CH2CH2(C9H6Me)2 (7) (1.01 g, 3.32 mmol) in
Et2O (40 mL) at À78 °C. The mixture was warmed to 25 °C and stir-
red for 4 h. Solvent was then removed in vacuo giving a white solid,
which was washed with hexane (2 Â 50 mL) and dried under vac-
uum to give the title compound as a white powder. Yield 0.97 g,
93%. C23H22Li2 (312.3): Calc. C, 88.45; H, 7.10. Found: C, 88.29; H,
7.02%.
2.4. Ethylene polymerization
2.2.8. Synthesis of Li2{CH2CH2CH2(C9H5Et-3)2} (11)
The preparation of 11 was carried out in an identical manner to
that of 10. CH2CH2CH2(C9H6Et)2 (8) (1.00 g, 3.01 mmol) and LiBu
A 1 L glass autoclave was heated to 60 °C. Under an inert N2
atmosphere, the zirconocene catalyst ([Zr] = 3 Â 10À5 mol LÀ1),
and MAO (10% in toluene, [Al] = 3 Â 10À2 mol LÀ1) and toluene