Inorganic Chemistry
Article
Materials. Toluene, THF, and hexane were dried by refluxing with
sodium and benzophenone ketyl; the latter serves as an indicator.
CH2Cl2 was distilled from P2O5. rac-LA was purchased from Daigang
BIO Engineer Ltd. of China and was recrystallized from toluene three
times. CDCl3 was purchased from J&K Scientific, Ltd. in Beijing and
was dried over activated molecular sieves. KN(SiMe3)2 and NaN-
(SiMe3)2 were purchased from J&K Scientific Ltd. and used as
received. 18-Crown-6 and 15-crown-5 were purchased from local
companies and were used as received.
was slowly added KN(SiMe3)2 (1.0 mL of a 1.00 M solution in THF,
1.0 mmol) at 0 °C under a nitrogen atmosphere. During this process,
the colorless solution changed to red. After the solution was stirred for
4 h at room temperature, the red precipitate formed was separated by
filtration. The solid residue was washed with 20 mL of hexane and
dried in vacuo to give complex 1 as a red powder (0.438 g, 77%). Red
crystals of 1 suitable for X-ray diffraction studies were obtained from a
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benzene solution at room temperature. H NMR (400 MHz, toluene-
d8, 25 °C): δ 8.52 (d, J = 8.8 Hz, Ar-H, 1H), 8.10 (s, Ar-H, 1H), 7.81
(d, J = 8.4 Hz, Ar-H, 2H), 7.51 (t, J = 7.6 Hz, Ar-H, 1H), 7.33−7.22
(m, Ar-H, 3H), 7.21−7.10 (m, Ar-H, 3H), 6.71 (t, J = 7.0 Hz, 1H),
2.92 (s, crown ether-H, 24H). 13C NMR (100 MHz, toluene-d8, 50
°C): δ 132.91, 132.71, 132.06, 131.12, 129.93, 126.46, 123.63, 123.40,
121.08, 70.05. Anal. Calcd for C32H37KO7: C, 67.37; H, 6.23. Found:
C, 67.11; H, 6.51.
Syntheses. Synthesis of 2-(9-Anthryl)phenol (H1L). A sample of 2-
bromophenol (1.88 g, 11 mmol) was dissolved in 80 mL of THF and
cooled to −20 °C using a low-temperature reactor. Under a nitrogen
n
atmosphere 22 mmol of BuLi (8.8 mL, 2.5 M hexane solution) was
added. The solution became white and was slowly warmed to room
temperature over the course of 2 h. To this solution was slowly added
11 mmol of anthrone (2.13 g dissolved in 100 mL of THF), and the
yellow solution which formed was stirred overnight. The solution was
hydrolyzed with 30 mL of 6 M HCl and stirred for 1 h. The mixture
was extracted with diethyl ether. The organic layer was washed three
times with 500 mL of water, dried with MgSO4, and evaporated to
dryness, affording a brown solid. This crude product was purified by
column chromatography over silica gel (CH2Cl2/petroleum ether = 1/
5), affording 0.96 g (32%) of 2-(9-anthryl)phenol as an off-white solid.
1H NMR (300 MHz, chloroform-d, 25 °C): δ 8.52 (s, Ar-H, 1H), 8.03
(d, J = 8.4 Hz, Ar-H, 2H), 7.65 (d, J = 8.7 Hz, Ar-H, 2H), 7.53−7.35
(m, Ar-H, 5H), 7.25 (dd, J = 7.5, 1.8 Hz, Ar-H, 1H), 7.17−7.09 (m,
Ar-H, 2H), 4.49 (s, −OH, 1H). 13C NMR (100 MHz, chloroform-d,
25 °C): δ 153.73, 132.12, 131.50, 130.79, 129.83, 129.63, 128.56,
127.96, 126.33, 126.01, 125.50, 123.95, 120.69, 115.70. Anal. Calcd for
C20H14O: C, 88.33; H, 4.99. Found: C, 88.76; H, 5.22.
Synthesis of Complex 2. According to the procedure described
above for 1, H2L (0.326 g, 1.0 mmol) was converted to complex 2 as a
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red brown powder (0.502 g, 80%). H NMR (300 MHz, benzene-d6,
25 °C): δ 8.78 (d, J = 8.5 Hz, Ar-H, 2H), 8.17 (s, Ar-H, 1H), 7.88 (d, J
= 9.5 Hz, Ar-H, 2H), 7.72 (dd, J = 8.6, 2.9 Hz, Ar-H, 1H), 7.48 (d, J =
2.9 Hz, Ar-H, 1H), 7.30 (ddd, J = 8.3, 6.4, 1.4 Hz, Ar-H, 2H), 7.22
(ddd, J = 8.6, 6.4, 1.5 Hz, Ar-H, 2H), 7.19 (s, Ar-H, 1H), 2.85 (s,
crown ether-H, 24H), 1.50 (s, ArC(CH3)3, 9H). 13C NMR (100 MHz,
benzene-d6, 50 °C): δ 132.75, 132.14, 131.39, 129.73, 126.39, 125.49,
124.86, 123.41, 120.35, 69.94, 33.93, 32.69. Anal. Calcd for
C36H45KO7: C, 68.89; H, 7.50. Found: C, 68.76; H, 7.21.
Synthesis of Complex 3. According to the procedure described
above for 1, H3L (0.300 g, 1.0 mmol) was converted to complex 3 as a
deep red powder (0.510 g, 85%). Clear red crystals of 3 suitable for X-
ray diffraction studies were obtained from a toluene solution at room
1
Synthesis of 2-(9-Anthryl)-4-tert-butylphenol (H2L). According to
the procedure described above for H1L, 2-bromo-4-tert-butylphenol
(1.14g, 5 mmol) was converted to 2-(9-anthryl)-4-tert-butylphenol as
temperature. H NMR (300 MHz, benzene-d6, 25 °C): δ 8.56 (d, J =
8.4 Hz, Ar-H, 2H), 8.20 (s, Ar-H, 1H), 7.87 (d, J = 8.0 Hz, Ar-H, 2H),
7.47−7.30 (m, Ar-H, 1H), 7.37−7.19 (m, Ar-H, 5H), 7.07 (d, J = 2.8
Hz, Ar-H, 1H), 3.54 (s, −OCH3, 3H), 2.99 (s, crown ether-H, 24H).
13C NMR (100 MHz, benzene-d6, 50 °C): δ 132.53, 131.71, 130.38,
125.57, 125.05, 124.68, 124.20, 118.62, 116.78, 70.21, 56.24. Anal.
Calcd for C33H39KO8: C, 65.99; H, 6.60. Found: C, 65.76; H, 6.52.
Synthesis of Complex 4. According to the procedure described
above for 1, H4L (0.382 g, 1.0 mmol) was converted to complex 4 as a
deep red powder (0.455 g, 67%). Red crystals of 4 suitable for X-ray
diffraction studies were obtained from a benzene solution at room
temperature. Because of the poor solubility of 4, the expected
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an off-white powder (0.62 g, 38%). H NMR (300 MHz, chloroform-
d, 25 °C): δ 8.57 (s, Ar-H, 1H), 8.08 (d, J = 8.4 Hz, Ar-H, 2H), 7.70
(d, J = 8.9 Hz, Ar-H, 2H), 7.43−7. 57 (m, Ar-H, 3H), 7.42 (ddd, J =
8.6, 6.5, 1.4 Hz, Ar-H, 2H), 7.27 (d, J = 2.5 Hz, Ar-H, 1H), 7.09 (d, J =
8.6 Hz, Ar-H, 1H), 4.37 (s, −OH, 1H), 1.34 (s, ArC(CH3)3, 9H). 13
C
NMR (75 MHz, chloroform-d, 25 °C): δ 151.38, 143.40, 131.56,
130.82, 130.53, 129.03, 128.57, 127.78, 126.58, 126.26, 126.20, 125.47,
123.22, 115.04, 34.25, 31.62. Anal. Calcd for C24H22O: C, 88.66; H,
7.08. Found: C, 88.31; H, 6.79.
Synthesis of 2-(9-Anthryl)-4-methoxyphenol (H3L). According to
the procedure described above for H1L, 2-bromo-4-methoxyphenol
(1.01 g, 5 mmol) was converted to 2-(9-anthryl)-4-methoxyphenol as
a light yellow powder (0.56 g, 37%). 1H NMR (300 MHz, chloroform-
d, 25 °C): δ 8.54 (s, Ar-H, 1H), 8.05 (d, J = 8.3 Hz, Ar-H, 2H), 7.70
(d, J = 8.6 Hz, Ar-H, 2H), 7.48 (ddd, J = 8.3, 6.5, 1.4 Hz, Ar-H, 2H),
7.41 (ddd, J = 8.1, 6.5, 1.5 Hz, Ar-H, 2H), 7.09 (d, J = 8.9 Hz, Ar-H,
1H), 7.02 (dd, J = 8.9, 2.9 Hz, Ar-H, 1H), 6.81 (d, J = 2.8 Hz, Ar-H,
1H), 4.21 (s, −OH, 1H), 3.77 (s, −OCH3, 3H). 13C NMR (75 MHz,
chloroform-d, 25 °C): δ 153.47, 147.79, 131.50, 130.64, 129.73,
128.57, 127.99, 126.38, 126.03, 125.52, 124.49, 116.54, 116.46, 115.65,
55.76. Anal. Calcd for C20H16O: C, 88.63; H, 5.10. Found: C, 83.98;
H, 5.37.
information on 13C NMR was not achieved. H NMR (300 MHz,
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benzene-d6, 25 °C): δ 8.76 (d, J = 8.7 Hz, Ar-H, 2H), 8.07 (s, Ar-H,
1H), 7.88 (d, J = 2.9 Hz, Ar-H, 1H), 7.82 (d, J = 7.6 Hz, Ar-H, 2H),
7.28 (d, J = 2.9 Hz, Ar-H, 1H), 7.24 (ddd, J = 8.2, 6.4, 1.4 Hz, Ar-H,
2H), 7.13−7.19 (m, Ar-H, 2H), 2.75 (s, crown ether-H, 24H), 2.02 (s,
ArC(CH3)3, 9H), 1.55 (s, ArC(CH3)3, 9H). Anal. Calcd for
C40H53KO7: C, 70.48; H, 7.92. Found: C, 70.14; H, 7.80.
Synthesis of Complex 5. According to the procedure described
abuove for 1, H1L (0.270 g, 1.0 mmol) was converted to give complex
5 as a brown powder (0.250 g, 49%). 1H NMR (300 MHz, benzene-d6,
25 °C): δ 8.64 (dd, J = 8.7, 1.2 Hz, 2H), 8.16 (s, Ar-H, 1H), 7.81−7.91
(m, Ar-H, 2H), 7.69 (ddd, J = 8.2, 7.0, 2.0 Hz, Ar-H, 1H), 7.46 (dd, J =
7.3, 2.0 Hz, Ar-H, 1H), 7.33 (dd, J = 8.3, 1.2 Hz, Ar-H, 1H), 7.24−7.30
(m, Ar-H, 2H), 7.20 (d, J = 1.4 Hz, Ar-H, 1H), 7.17−7.18 (m, Ar-H,
1H), 6.88 (td, J = 7.2, 1.3 Hz, Ar-H, 1H), 2.76 (s, crown ether-H,
20H). 13C NMR (100 MHz, benzene-d6, 50 °C): δ 132.90, 132.63,
131.97, 130.84, 129.91, 126.75, 124.92, 123.80, 123.68, 121.12, 68.94.
Anal. Calcd for C30H33NaO6: C, 70.12; H, 6.25. Found: C, 70.30; H,
6.49.
Synthesis of Complex 6. According to the procedure described
above for 1, H2L (0.326 g, 1.0 mmol) was converted to complex 6 as a
dark red powder (0.396 g, 70%). 1H NMR (300 MHz, benzene-d6, 25
°C): δ 8.70 (d, J = 8.9 Hz, Ar-H, 2H), 8.17 (s, Ar-H, 1H), 7.87 (d, J =
8.5 Hz, Ar-H, 2H), 7.70 (d, J = 10.6 Hz, Ar-H, 1H), 7.48 (d, J = 2.7
Hz, Ar-H, 1H), 7.16−7.35 (m, Ar-H, 5H), 2.73 (s, crown ether-H,
20H), 1.48 (s, ArC(CH3)3, 9H). 13C NMR (100 MHz, benzene-d6, 50
°C): δ 132.68, 132.02, 131.06, 130.88, 129.83, 129.64, 128.52, 126.55,
126.37, 125.58, 125.14, 124.73, 123.95, 123.77, 123.54, 123.41, 120.57,
Synthesis of 2-(9-Anthryl)-4,6-di-tert-butylphenol (H4L). Accord-
ing to the procedure described above for H1L, 2-bromo-4,6-di-tert-
butylphenol (1.42 g, 5 mmol) was converted to 2-(9-anthryl)-4,6-di-
tert-butylphenol as a pale brown powder (0.57 g, 30%). 1H NMR (300
MHz, chloroform-d, 25 °C): δ 8.52 (s, 1H), 8.02 (d, J = 7.9 Hz, Ar-H,
2H), 7.71 (d, J = 8.8 Hz, Ar-H, 2H), 7.51 (d, J = 2.4 Hz, Ar-H, 1H),
7.45 (ddd, J = 8.3, 6.6, 1.3 Hz, Ar-H, 2H), 7.39 (ddd, J = 8.2, 6.6, 1.6
Hz, Ar-H, 2H), 7.11 (d, J = 2.4 Hz, Ar-H, 1H), 4.54 (s, −OH, 1H),
1.50 (s, 9H, ArC(CH3)3), 1.34 (s, 9H, ArC(CH3)3). 13C NMR (100
MHz, chloroform-d, 25 °C): δ 149.91, 142.13, 135.36, 131.65, 131.10,
131.02, 128.58, 127.82, 126.50, 126.37, 126.27, 125.49, 123.81, 123.70,
35.17, 34.45, 31.77, 29.77. Anal. Calcd for C28H30O: C, 87.72; H, 7.68.
Found: C, 87.91; H, 7.90.
Synthesis of Complex 1. To a solution of H1L (0.270 g, 1.0 mmol)
and 18-crown-6 ether (0.264 g, 1.0 mmol) in tetrahydrofuran (20 mL)
F
Inorg. Chem. XXXX, XXX, XXX−XXX