Y. Zhang et al. / Journal of Molecular Catalysis A: Chemical 373 (2013) 85–95
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1H NMR (400 MHz, CDCl3): ı 7.42 (d, J = 7.2 Hz, 1H, Ind-H), 7.34–7.28
(m, 2H, Ind-H), 7.12–7.00(m, 5H, Ind-H, 4Ph-H), 6.53–6.49 (m,
1H, Ind-H), 3.41 (s, 2H, Ind-H), 2.41–2.32 (m, 2H, C5H10), 2.29 (s,
3H, PhCH3), 2.24–2.14 (m, 2H, C5H10), 1.71–1.54 (m, 5H, C5H10),
(Ind-C), 147.8 (Ind-C), 131.6 (Ph-C), 130.1 (Ind-C), 129.4 (Ind-C),
128.8 (Ind-C), 128.5 (Ind-C), 127.6 (Ind-C), 126.9 (Ph-C), 126.6 (Ph-
C), 125.8 (Ph-C), 121.0 (Ind-C), 114.5 (Ind-C), 41.8 (CMe2-C), 31.4
(CMe2-C), 27.4 (CMe2-C). MALDI-TOF-MS (m/z): 351.0 (M+−Cl). IR
(cm−1): 2963, 2876, 1599, 1464, 1077, 1053, 752, 695. Anal. Calcd.
for C18H17Cl3Ti·(0.15C5H12): C, 56.53; H, 4.76; found: C, 56.72; H,
5.21%.
1
1.53–1.41 (m, 1H, C5H10). 13C{ H} NMR (125 MHz, CDCl3): ı 150.0
(Ind-C), 145.1 (Ind-C), 144.2 (Ph-C), 143.9 (Ind-C), 134.9 (Ind-C),
129.3 (Ind-C), 128.8 (Ind-C), 126.8 (Ind-C), 125.2 (Ph-C), 123.7 (Ph-
C), 123.5 (Ph-C), 122.3 (Ind-C), 44.1 (Ind-C), 37.3 (C5H10-C), 36.4
(C5H10-C), 26.5 (C5H10-C), 22.9 (C5H10-C), 20.8 (PhMe-C).
[Ind-CMe2-(p-MePh)]TiCl3 (C2). The procedure was similar to
that of C1. L2 (1.5 g, 6 mmol), n-BuLi (2.5 mL, 6 mmol) and TiCl4
(0.66 mL, 6 mmol) were used to give deep red crystals (1.5 g, 62%).
mp: 123.3–125.1 ◦C. 1H NMR (400 MHz, CDCl3): ı = 7.70–7.66 (m,
1H, Ind-H), 7.36–7.34 (m, 1H, Ind-H), 7.34–7.32 (m, 1H, Ph-H),
7.32–7.28(m, 1H, Ind-H), 7.28–7.25 (m, 1H, Ph-H), 7.25–7.22 (m, 1H,
Ph-H), 7.03–7.96 (m, 4H, 3Ind-H, Ph-H), 2.24 (s, 3H, PhCH3), 1.98
Synthesis of 3-{[1-(4-tert-butylphenyl)]cyclohexyl}indene (L6).
The procedure was similar to that of L2. p-tert-Butylphenyl
lithium (6.3 g, 45 mmol) and 6-cyclohexylidenebenzofulvene (8.8 g,
45 mmol) were used to give L6 as white solids (4.5 g, 30%).
mp: 93.1–95.6 ◦C. 1H NMR (400 MHz, CDCl3): ı 7.42 (d, J = 6.4 Hz,
1H, Ind-H), 7.38–7.30 (m, 2H, Ind-H), 7.29–7.23 (m, 2H, Ph-H),
7.21–6.97 (m, 3H, Ind-H, 2Ph-H), 6.50 (s, 1H, Ind-H), 3.41 (s, 2H, Ind-
H), 2.44–2.33 (m, 2H, C5H10), 2.25–2.11 (m, 2H, C5H10), 1.72–1.35
1
(s, 3H, CH3), 1.90 (s, 3H, CH3). 13C{ H} NMR (125 MHz, CDCl3): ı
148.9 (Ind-C), 144.8 (Ind-C), 136.1 (Ph-C), 131.6 (Ind-C), 130.2 (Ind-
C), 129.4 (Ind-C), 129.2 (Ind-C), 128.8 (Ind-C), 127.6 (Ph-C), 127.1
(Ph-C), 125.7 (Ph-C), 121.0 (Ind-C), 114.63 (Ind-C), 41,6 (CMe2-C),
31.4 (CMe2-C), 27.5 (CMe2-C), 20.8 (PhMe-C). MALDI-TOF-MS (m/z):
367.0 (M+−Cl) IR (cm−1): 2964, 2877, 1599, 1445, 1096, 1028, 901,
832, 751, 696. Anal. Calcd. for C19H19Cl3Ti: C, 56.83; H, 4.77; found:
C, 56.78; H, 4.71%.
1
(m, 6H, C5H10), 1.28 [s, 9H, C(CH3)3]. 13C{ H} NMR (125 MHz,
CDCl3): 149.9 (Ind-C), 148.1 (Ind-C), 145.2 (Ph-C), 144.1 (Ind-C),
144.0 (Ind-C), 129.5 (Ind-C), 126.5 (Ind-C), 125.3 (Ind-C), 124.9
(Ph-C), 123.7 (Ph-C), 123.6 (Ph-C), 122.5 (Ind-C), 44.1 (Ind-C),
37.4 (C5H10-C), 36.4 (CMe3-C), 34.2 (C5H10-C), 31.4 (CMe3-C), 26.6
(C5H10-C), 23.0 (C5H10-C).
[Ind-C(cyclo-C5H10)-Ph]TiCl3 (C3). The procedure was similar to
that of C1. L3 (1.6 g, 6 mmol), n-BuLi (2.5 mL, 6 mmol) and TiCl4
(0.66 mL, 6 mmol) were used to give deep red crystals of C3 (620 mg,
15%). mp: 143.4–145.1 ◦C. 1H NMR (400 MHz, CDCl3): ı 7.79 (d,
J = 8.8 Hz, 1H, Ind-H), 7.66 (d, J = 8.8 Hz, 1H, Ind-H), 7.44 (d, J = 7.2 Hz,
2H, Ph-H), 7.42–7.37 (m, 1H, Ph-H), 7.35–7.27 (m, 3H, Ind-H),
7.21–7.14 (m, 2H, Ph-H), 7.09 (d, J = 4.4 Hz, 1H, Ind-H), 3.07 (d,
J = 14.4 Hz, 1H, C5H10), 2.75–2.65 (m, 2H, C5H10), 2.23–2.11 (m,
1H, C5H10), 1.85–1.65 (m, 4H, C5H10), 1.50–1.30 (m, 2H, C5H10).
Synthesis of 3-{[1-(4-flurophenyl)]cyclohexyl}indene (L7). The
procedure was similar to that of L2. p-Fluorophenyl lithium (5.1 g,
50 mmol) and 6-cyclohexylidenebenzofulvene (9.8 g, 50 mmol)
were used to give L7 as white solids (3.9 g, 27%). mp: 78.2–79.7 ◦C
1H NMR (400 MHz, CDCl3): ı 7.42 (d, J = 7.2 Hz, 1H, Ind-H), 7.40–7.33
(m, 2H, Ind-H), 7.11–6.89(m, 5H, Ind-H, 4Ph-H), 6.53 (m, 1H, Ind-
H), 3.41 (s, 2H, Ind-H), 2.39–2.30 (m, 2H, C5H10), 2.22–2.08 (m,
2H, C5H10), 1.70–1.56 (m, 5H, C5H10), 1.51–1.39 (m, 1H, C5H10).
1
13C{ H} NMR (125 MHz, CDCl3): ı 150.7 (Ind-C), 142.3 (Ind-C),
1
13C{ H} NMR (125 MHz, CDCl3): ı 145.2 (Ind-C), 143.6 (Ind-C),
131.9 (Ph-C), 129.2 (Ind-C), 129.1 (Ind-C), 128.6 (Ind-C), 128.5 (Ind-
C), 128.3 (Ind-C), 127.8 (Ph-C), 127.2 (Ph-C), 126.5 (Ph-C), 119.9
143.0 (Ph-C), 143.0 (Ind-C), 129.6 (Ph-C), 128.5 (Ind-C), 128.4 (Ind-
C), 125.3 (Ind-C), 123.9 (Ind-C), 123.6 (Ind-C), 122.2(Ph-C), 114.8
(Ph-C), 114.6 (Ph-C), 44.0 (Ind-C), 37.4 (C5H10-C), 36.5 (C5H10-C),
26.4 (C5H10-C), 22.9 (C5H10-C).
(Ind-C), 115.0 (Ind-C), 45.0 (C5H10-C), 36.4 (C5H10-C), 34.9 (C5H10
-
C), 25.9 (C5H10-C), 22.5 (C5H10-C), 22.2 (C5H10-C). MALDI-TOF-MS
(m/z): 393.1 (M+−Cl). IR (cm−1): 2925, 2858, 1599, 1466, 1057,
1030, 750, 700. Anal. Calcd. for C21H21Cl3Ti: C, 58.98; H, 4.95; found:
C, 59.21; H, 5.23%.
Synthesis of 3-[2-(2-phenyladmantyl)]indene (L8). The procedure
was similar to that of L2. Phenyllithium (3.4 g, 40 mmol) and 6-(2-
adamantylidene)benzofulvene (9.9 g, 40 mmol) were used to give
pure L8 as white solids (8.8 g, 67%). mp: 121.1–123.3 ◦C. 1H NMR
(400 MHz, CDCl3): ı = 7.80 (d, J = 8.0 Hz, 1H, Ind-H), 7.60 (d, J = 8.0 Hz,
2H, Ind-H), 7.38 (d, J = 8.0 Hz, 1H, Ind-H), 7.26 (t, J = 8.0 Hz, 2H, Ph-
H), 7.20 (t, J = 8.0 Hz, 1H, Ph-H), 7.15–7.03 (m, 2H, Ph-H), 6.50 (t,
J = 2.0 Hz, 1H, Ind-H). 3.43–3.20 (m, 4H, 2 C9H14, 2Ind-H), 2.40–1.65
[Ind-C(cyclo-C5H10)-(o-MePh)]TiCl3 (C4). The procedure was
similar to that of C1. L4 (1.7 g, 6 mmol), n-BuLi(2.5 mL, 6 mmol) and
TiCl4 (0.66 mL, 6 mmol) were used to give deep red crystals of C4
(900 mg, 33%). mp: 159.7–162.1 ◦C. 1H NMR (400 MHz, CDCl3): ı
7.89 (d, J = 8.0 Hz, 1H, Ind-H), 7.67 (d, J = 8.0 Hz, 1H, Ind-H), 7.52
(s, 1H, Ph-H), 7.64–7.27 (m, 4H, 3Ph-H, Ind-H), 7.22–7.17 (m, 1H,
Ind-H), 7.13 (t, J = 7.2 Hz, 1H, Ind-H), 6.99–6.90 (m, 1H, Ind-H), 3.10
(d, J = 13.6 Hz, 1H, C5H10), 2.98 (d, J = 13.2 Hz, 1H, C5H10), 2.59 (t,
J = 12.8 Hz, 1H, C5H10), 2.2–1.8 (m, 3H, C5H10), 1.88 (s, 3H, PhCH3),
1.72 (d, J = 10.8 Hz, 2H, C5H10), 1.55–1.35 (m, 1H, C5H10), 1.20–1.05
1
(m, 12H, C9H14). 13C{ H} NMR (125 MHz, CDCl3): ı 150.6 (Ind-C),
145.9 (Ind-C), 145.3 (Ph-C), 143.8 (Ind-C), 129.1 (Ind-C), 127.9 (Ind-
C), 126.9 (Ind-C), 125.5 (Ind-C), 124.9 (Ph-C), 123.7 (Ph-C), 123.7
(Ph-C), 122.0 (Ind-C), 50.6 (Ind-C), 38.1 (C10H14-C), 37.3 (C10H14-C),
33.9 (C10H14-C), 33.4 (C10H14-C), 27.7 (C10H14-C), 27.3 (C10H14-C).
1
(m, 1H, C5H10). 13C{ H} NMR (125 MHz, CDCl3): ı 150.7 (Ind-C),
142.1 (Ind-C), 137.1 (Ph-C), 130.5 (Ind-C), 129.1 (Ind-C), 128.7 (Ind-
C), 127.9 (Ind-C), 127.3 (Ind-C), 127.0 (Ph-C), 125.7 (Ph-C), 125.3
(Ph-C), 123.8 (Ph-C), 123.5 (Ph-C), 120.6 (Ind-C), 114.3 (Ind-C),
44.9 (C5H10-C), 37.6 (C5H10-C), 35.7 (C5H10-C), 26.3 (C5H10-C), 23.3
(C5H10-C), 23.0 (C5H10-C), 22.4 (PhMe-C). MALDI-TOF-MS (m/z):
407.0 (M+−Cl). IR (cm−1): 2922, 2859, 1509, 1447, 1187, 1076, 736.
Anal. Calcd. for C22H23Cl3Ti·(0.11 C6H14): C, 60.33; H, 5.48; found:
C, 60.77; H, 5.94%.
[Ind-C(cyclo-C5H10)-(p-MePh)]TiCl3 (C5). The procedure was
similar to that of C1. L5 (1.7 g, 6 mmol), n-BuLi (2.5 mL, 6 mmol) and
TiCl4 (0.66 mL, 6 mmol) were used to give deep red crystals of C5
(1.6 g, 60%). mp: 146.7–148.1 ◦C. 1H NMR (400 MHz, CDCl3): ı 7.77
(d, J = 8.8 Hz, 1H, Ind-H), 7.61 (d, J = 8.8 Hz, 1H, Ind-H), 7.39–7.32 (m,
1H, Ind-H), 7.29–7.23 (m, 2H, Ph-H), 7.21 (d, J = 2.0 Hz, 1H, Ind-H),
7.12–6.99 (m, 4H, 2Ind-H, 2Ph-H), 2.99 (d, J = 13.6 Hz, 1H, C5H10),
2.64 (d, J = 7.2 Hz, 2H, C5H10), 2.24 (s, 3H, PhCH3), 2.15–2.05 (m,
2.2.2. Synthesis of titanium complexes C1–C8
Synthesis of [Ind-CMe2-Ph]TiCl3 (C1). To a solution of 0.84 g
(3.6 mmol) of L1 in 40 mL light petroleum ether, cooled to −78 ◦C
was added dropwise 1.5 mL (3.6 mmol) of n-BuLi. The reaction
mixture was warmed to r.t. and stirred overnight. Then 0.39 mL
(3.6 mmol) of TiCl4 was added to the mixture at −78 ◦C, the resul-
tant dark red solution was warmed to r.t. and stirred overnight. The
solvent and the unreacted TiCl4 were removed in vacuo. The residue
was extracted with light petroleum ether. After cooling the filtrate
to −20 ◦C, deep red crystals of C1 were obtained (423 mg, 30%). mp:
118.3–120.1 ◦C. 1H NMR (400 MHz, CDCl3): ı 7.74–7.69 (m, 1H, Ind-
H), 7.37–7.32 (m, 3H, Ph-H), 7.32–7.30 (m, 1H, Ind-H), 7.30–7.27
(m, 1H, Ph-H), 7.25–7.21 (m, 2H, Ind-H), 7.19–7.16 (m, 1H, Ph-H),
7.15–7.13 (m, 1H, Ind-H), 7.13–7.11 (m, 1H, Ind-H), 2.03 (s, 3H,
1
CH3), 1.95 (s, 3H, CH3). 13C{ H} NMR (125 MHz, CDCl3): ı 148.5