Inorganic Chemistry
ARTICLE
[L1H2+Na+]: 460.3191, found: 460.3180. Anal. Calcd. for C29H43NO2
(%): C 79.59; H 9.90; N 3.20. Found: C 79.28; H 9.61; N 3.34.
[4-tBu-6-Ad-2-CH=N(4,6-tBu2-2-OHC6H2)C6H2OH] (L2H2).
[4-tBu-6-Ad-2-CH=N(4,6-tBu2-2-OC6H2)C6H2O]TiCl2 (2).
Complex 2 was synthesized in the same way as described above for
the synthesis of complex 1 with ligand L2H2 (2.50 g, 5 mmol) as
starting material. Pure complex 2 (2.19 g, 3.55 mmol, 71%) was
obtained as red crystals. 1H NMR (400 MHz, CDCl3) δ 8.72 (s, 1H),
7.73 (d, J = 2.4 Hz, 1H), 7.41 (d, J = 2.4 Hz, 1H), 7.30ꢀ7.38 (m, 5H),
7.23 (d, J = 2.4 Hz, 1H), 7.03 (d, J = 2.0 Hz, 1H), 1.76 (s, 6H), 1.41 (s,
9H), 1.35 (s, 9H), 1.33 (s, 9H). 13C NMR (100 MHz, CDCl3) δ
162.4, 157.6, 156.4, 150.4, 142.7, 142.4, 138.0, 137.7, 137.0, 131.6,
130.0, 129.8, 128.0, 126.5, 125.9, 124.8, 122.9, 108.9, 42.2, 34.7,
34.4, 34.1, 31.8, 31.6. 31.5, 29.8. HRMS (m/z) Calcd. for
[C35H47NO2Cl2Ti]+: 631.2463, found: 631.2471. Anal. Calcd. for
C35H47NO2Cl2Ti (%): C 66.46; H 7.49; N 2.21. Found: C 66.12; H
7.74; N 2.31.
1
The ligand L2H2 was prepared as a similar procedure of L1H2. H
NMR (400 MHz, CDCl3) δ 12.14 (s, 1H), 8.62 (s, 1H), 7.64 (d, J = 2.4
Hz, 1H), 7.33 (d, J = 2.4 Hz, 1H), 7.20ꢀ7.32 (m, 5H), 7.15 (d, J = 2.4
Hz, 1H), 6.91 (d, J = 2.0 Hz, 1H), 5.95 (s,1H), 1.77 (s, 6H), 1.39 (s,
18H), 1.31 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 164.4, 157.0, 150.5,
146.1, 142.4, 141.2, 136.6, 135.8, 135.6, 128.9, 128.8, 127.7, 125.7, 125.4,
122.9, 119.0, 112.8, 42.4, 35.1, 34.7, 34.4, 31.8, 31.7, 31.6, 29.6. HRMS
(m/z) Calcd. for [L2H2+Na+]: 538.3661, found: 538.3654. Anal. Calcd.
for C35H49NO2 (%): C 81.50; H 9.58; N 2.72. Found: C 81.13; H 9.78;
N 2.91.
[4-tBu-6-CMe2Ph-2-CH=N(4,6-tBu2-2-OHC6H2)C6H2OH] (L3H2).
The ligand L3H2 was prepared as a similar procedure of L1H2. 1H NMR (400
MHz, CDCl3) δ 12.68 (s, 1H), 8.68 (s, 1H), 7.42 (d, J = 2.4 Hz, 1H), 6.99 (d,
J = 2.0 Hz, 1H), 6.10 (s, 1H), 2.20 (s, 6H), 2.11 (s, 3H), 1.81 (s, 6H), 1.45 (s,
9H), 1.35 (s, 9H), 1.34 (s, 9H). 13C NMR (100 MHz, CDCl3) δ164.9, 157.9,
146.1, 142.3, 141.3, 137.4, 135.7, 135.6, 128.5, 127.1, 122.9, 118.7, 112.6, 40.3,
37.4, 37.2, 35.1, 34.6, 34.3, 31.7, 31.5. HRMS (m/z) Calcd. for [L3H2+Na+]:
522.3348, found: 522.3356. Anal. Calcd. for C34H45NO2 (%): C 81.72; H 9.08;
N 2.80. Found: C 81.23; H 8.88; N 3.01.
[4-tBu-6-CMe2Ph-2-CH=N(4,6-tBu2-2-OC6H2)C6H2O]TiCl2 (3).
Complex 3 was synthesized in the same way as described above for the
synthesis of complex 1 with ligand L3H2 (2.58 g, 5 mmol) as starting
material. Pure complex 3 (2.06 g, 3.25 mmol, 65%) was obtained as red
crystals. 1H NMR (400 MHz, CDCl3) δ 8.88 (s, 1H), 7.63 (d, J = 2.0 Hz,
1H), 7.42 (d, J = 2.0 Hz, 1H), 7.22 (s, 1H), 7.19 (d, 1H), 2.24 (s, 6H), 2.17
(s, 3H), 1.91 (d, J = 12 Hz, 3H), 1.80 (d, J = 12 Hz, 3H), 1.44 (s, 9H), 1.38
(s, 9H), 1.38 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 162.9, 158.7, 157.9,
146.0, 145.0, 141.2, 137.9, 135.1, 133.5, 128.6, 125.0, 123.6, 109.1, 40.6, 37.5,
36.9, 34.9, 34.8, 34.7, 31.6, 31.3, 29.4, 29.0. HRMS (m/z) Calcd. for
[C34H43NO2Cl2Ti]+: 615.2150, found: 615.2158. Anal. Calcd. for
C34H43NO2Cl2Ti (%): C 66.24; H 7.03; N 2.27. Found: C 66.92; H
7.31; N 2.41.
[4-tBu-6-CMe2Ph-2-CH=N(4-tBu-6-CMe2Ph-2-OHC6H2)
C6H2OH] (L4H2). The ligand L4H2 was prepared as a similar
procedure of L1H2. 1H NMR (400 MHz, CDCl3) δ 12.17 (s, 1H),
8.58 (s, 1H), 7.58 (d, J = 2.4 Hz, 1H), 7.38 (d, J = 2.0 Hz, 1H),
7.11ꢀ7.28 (m, 11H), 6.96 (s, 1H), 5.46 (s, 1H), 1.72 (s, 6H), 1.69
(s, 6H), 1.36 (s, 18H). 13C NMR (100 MHz, CDCl3) δ 164.4, 157.1,
150.6, 145.5, 142.6, 141.0, 136.6, 136.1, 135.3, 128.8, 128.2, 128.0,
127.6, 125.9, 125.8, 125.7, 125.4, 123.0, 118.9, 113.8, 42.4, 34.8,
34.4, 31.9, 31.7, 29.7, 29.6. HRMS (m/z) Calcd. for [L4H2+Na+]:
584.3504, found: 584.3488. Anal. Calcd. for C39H47NO2 (%): C
83.38; H 8.43; N 2.49. Found: C 83.78; H 8.18; N 2.70.
[4-tBu-6-CMe2Ph-2-CH=N(4- tBu-6-CMe2Ph-2-OC6H2)-
C6H2O]TiCl2 (4). Complex 4 was synthesized in the same way as
described above for the synthesis of complex 1 with ligand L4H2
(2.81 g, 5 mmol) as starting material. Pure complex 4 (2.48 g, 3.65
mmol, 73%) was obtained as red crystals. 1H NMR (400 MHz,
CDCl3) δ 8.72 (s, 1H), 7.77 (d, J = 2.0 Hz, 1H), 7.41 (d, J = 2.0 Hz,
1H), 7.14ꢀ7.32 (m, 12H), 1.82 (s, 6H), 1.78 (s, 6H), 1.39 (s, 9H),
1.33 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 162.1, 157.4, 148.9,
145.6, 145.0, 140.8, 140.6, 137.5, 135.1, 133.2, 129.0, 128.3, 128.1,
126.6, 126.1, 125.8, 125.6, 125.4, 123.7, 117.8, 109.5, 42.5, 42.1,
35.0, 34.8, 31.7, 31.4, 29.4, 28.7. HRMS (m/z) Calcd. for
[C39H45NO2Cl2Ti]+: 677.2307, found: 677.2317. Anal. Calcd.
for C39H45NO2Cl2Ti (%): C 69.03; H 6.68; N 2.06. Found: C
69.44; H 6.43; N 2.21.
[4-tBu-6-SiMe2Ph-2-CH=N(4-tBu-6-CMe2Ph-2-OHC6H2)-
C6H2OH] (L5H2). The ligand L5H2 was prepared as a similar
1
procedure of L1H2. H NMR (400 MHz, CDCl3) δ 12.13 (s, 1H),
8.63 (s, 1H), 7.51 (s, J = 2.4 Hz, 1H), 7.43 (d, J = 2.4 Hz, 1H), 7.36 (d,
J = 2.4 Hz, 1H), 7.17ꢀ7.30 (m, 5H), 7.05 (d, J = 2.0 Hz, 1H), 5.62 (s,
1H), 1.75 (s, 6H), 1.39 (s, 9H), 1.32 (s, 9H), 0.88 (s, 9H), 0.31 (s,
6H). 13C NMR (100 MHz, CDCl3) δ 164.6, 163.5, 150.6, 145.7,
142.8, 141.2, 138.3, 136.3, 135.3, 130.6, 128.3, 125.9, 125.7, 125.0,
123.1, 117.8, 113.8, 42.5, 34.8, 34.2, 31.9, 31.6, 29.8, 27.2, 17.8, ꢀ4.6.
HRMS (m/z) Calcd. for [L5H2+Na+]: 580.3587, found: 580.3594.
Anal. Calcd. for C36H51NO2Si (%): C 77.50; H 9.21; N 2.51. Found:
C 77.85; H 8.97; N 2.70.
t
[4-tBu-6-SiMe2 Bu-2-CH=N(4- tBu-6-CMe2Ph-2-OC6H2)-
C6H2O]TiCl2 (5). Complex 5 was synthesized in the same way as
described above for the synthesis of complex 1 with ligand L5H2
(2.79 g, 5 mmol) as starting material. Pure complex 5 (2.19 g, 3.25
mmol, 65%) was obtained as red crystals. 1H NMR (400 MHz,
CDCl3) δ 8.71 (s, 1H), 7.72 (s, 1H), 7.47 (s, 1H), 7.18ꢀ7.38 (m,
7H), 1.76 (s, 6H), 1.36 (s, 9H), 1.35 (s, 9H), 0.92 (s, 9H), 0.43 (s,
6H). 13C NMR (100 MHz, CDCl3) δ 167.8, 158.2, 156.6, 150.2,
145.1, 142.6, 140.6, 139.8, 135.3, 132.3, 128.0, 126.9, 125.5, 124.9,
124.7, 122.7, 109.7, 41.9, 35.1, 34.4, 32.1, 31.8, 31.3, 28.5, 26.9, 17.7,
ꢀ4.7. HRMS (m/z) Calcd. for [C36H49NO2Cl2SiTi]+: 673.2389,
found: 673.2395. Anal. Calcd. for C36H49NO2Cl2SiTi (%): C 64.09;
H 7.32; N 2.08. Found: C 64.43; H 7.12; N 2.21.
[4,6-tBu2-2-CH=N(4,6-tBu2-2-OC6H2)C6H2O]TiCl2 (1). A so-
lution of n-BuLi (6.5 mL, 1.6 M solution in n-hexane, 10.4 mmol) was
added dropwise to a stirred solution of ligand L1H2 (2.19 g, 5 mmol) in
toluene (20 mL) at ꢀ78 °C. The solution was allowed to warm to room
temperature and stirred for 2 h, and then was added dropwise to a
solution of TiCl4 (0.99 g, 5.21 mmol) in toluene (20 mL). After the
resulting mixture was allowed to warm to room temperature and stirred
for 24 h, a red solution was obtained. The solvents were removed under
vacuum, and the residue was extracted with CH2Cl2 (5 mL) and filtered.
The filtrate was concentrated to 2 mL and mixed with n-hexane (20 mL).
Cooling to room temperature afforded red crystals of complex 1 (2.33 g,
4.20 mmol, 84%). 1H NMR (400 MHz, CDCl3) δ 8.87 (s, 1H), 7.70 (d,
J = 2.4 Hz, 1H), 7.43 (d, J = 2.0 Hz, 1H), 7.22 (d, J = 1.6 Hz, 1H), 7.18 (d,
J = 1.2 Hz 1H), 1.54 (s, 9H), 1.46 (s, 9H), 1.38 (s, 9H), 1.35 (s, 9H). 13C
NMR (100 MHz, CDCl3) δ 162.8, 158.2, 155.9, 146.0, 145.3, 141.6,
137.7, 135.3, 133.7, 129.0, 125.2, 123.7, 109.3, 35.4, 35.1, 35.0, 34.9,
31.8, 31.4, 29.9, 29.6. HRMS (m/z) Calcd. for [C29H41NO2Cl2Ti]+:
553.1994, found: 553.1984. Anal. Calcd. for C29H41NO2Cl2Ti (%): C
62.82; H 7.45; N 2.53. Found: C 62.52; H 7.64; N 2.41.
t
[4-tBu-6-SiMe2 Bu-2-CH=N(4-tBu-6-CMe2Ph-2-OC6H2)-
C6H2O]TiCl2 THF (6). A solution of complex 5 (1.10 g, 1.62
3
mmol) was added dropwise to a stirred THF (10 mL) solvent at
ꢀ78 °C. The solution was allowed to warm to room temperature
and stirred for 24 h. The solvents were removed under vacuum, and
the residue was extracted with CH2Cl2 (5 mL) and filtered. The
filtrate was concentrated to 2 mL and mixed with hexane (20 mL).
Cooling to room temperature afforded red crystals of complex 6
(1.15 g, 1.54 mmol, 95%). 1H NMR (400 MHz, CDCl3) δ 8.29 (s,
1H), 7.56 (d, J = 2.4 Hz, 1H), 7.23ꢀ7.37 (m, 6H), 7.08 (t, J = 7.2 Hz,
10890
dx.doi.org/10.1021/ic2014286 |Inorg. Chem. 2011, 50, 10884–10892