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CH), 120.8 (C6H4), 116.6 (pyrrole-CH), 110.2 (pyrrole-CH), 20.9
(p-CH3C6H4).
13C NMR (100.6 MHz, CDCl3): δ 169.9 (NCH), 146.1
(pyrrole-C), 124.6 (pyrrole-CH), 117.2 (pyrrole-CH), 110.4
Anal. calcd for C12H12N2 (184.24): C, 78.23; H, 6.57; N, (pyrrole-CH), 57.1 (NC(CH2)3), 42.9 (C(CH2)3), 36.4 (CH(CH2)3),
15.21%. Found C, 78.30; H, 6.53; N, 15.47%.
29.5 (CH(CH2)3).
Synthesis of (4-methoxyphenyl)(1H-pyrrol-2-ylmethylene)-
Anal. calcd for C15H20N2 (228.33): C, 78.90; H, 8.83; N,
amine (HL4). The synthesis of HL4 was performed according 12.27%. Found C, 79.09; H, 8.79; N, 12.46%.
to the same procedure as for HL1. Yield: 0.80 g, 40%.
1H NMR (400 MHz, CDCl3): δ 8.28 (1H, s, NCH), 7.21–7.178
Synthesis of complexes
Synthesis of L1AlMe2 (1a). To a stirred solution of HL1
(2H, m, C6H4), 6.94–6.91 (2H, m, C6H4), 6.85–6.83 (1H, m, pyrrole-
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H), 6.65 (1H, dd, JHH = 1.4, JHH = 3.6, pyrrole-H), 6.27 (1H, dd,
3JHH = 2.6, 3JHH = 3.6, pyrrole-H), 3.83 (3H, s, p-OCH3C6H4).
(0.80 g, 4.70 mmol) in toluene (20 mL) was slowly added AlMe3
13C NMR (100.6 MHz, CDCl3): δ 151.0 (p-OCH3C6H4), 148.4 (2.35 mL of a 2.0 M solution in toluene, 4.70 mmol). The reac-
(NCH), 144.7 (i-C6H4), 130.9 (pyrrole-C), 123.0 (pyrrole-CH), tion mixture was stirred at 100 °C for 24 hours, after which the
121.940 (C6H4), 116.2 (pyrrole-CH), 114.4 (C6H4), 110.2 volatiles were removed in vacuo to yield an orange oil. The
(pyrrole-CH), 55.49 (p-OCH3C6H4).
product was obtained as a yellow crystal by sublimation under
Anal. calcd for C12H12N2O (200.24): C, 71.98; H, 6.04; N, reduced pressure at room temperature. Yield: 0.45 g, 42%.
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13.99%. Found C, 71.13; H, 5.89; N, 13.33%.
Synthesis of (2-methylphenyl)(1H-pyrrol-2-ylmethylene)- 7.45–7.40 (2H, m, ArH), 7.35–7.31 (3H, m, ArH and pyrrole-H),
1H NMR (400 MHz, CDCl3): δ 8.36 (1H, d, JHH = 1.1, NCH),
amine (HL5). The synthesis of HL5 was performed according 7.30–7.25 (1H, m, ArH), 7.05 (1H, dd, JHH = 1.0, JHH = 3.7,
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to the same procedure as for HL1. Yield: 1.13 g, 59%.
1H NMR (400 MHz, CDCl3): δ 10.74 (1H, br s, pyrrole-NH), −0.62 (6H, s, Al(CH3)2).
8.23 (1H, s, NCH), 7.34–7.28 (2H, m, C6H4), 7.23–7.18 (1H, m,
13C NMR (100.6 MHz, CDCl3): δ 153.8 (NCH), 144.1 (ArC),
C6H4), 7.06–7.03 (1H, m, C6H4), 6.72 (1H, dd, 4JHH = 1.4, 3JHH
137.2 (pyrrole-CH), 136.4 (pyrrole-C), 129.9 (ArCH), 126.6
3.6, pyrrole-H), 6.54–6.56 (1H, m, pyrrole-H), 6.26 (1H, dd, (ArCH), 121.4 (ArCH), 120.4 (pyrrole-CH), 116.0 (pyrrole-CH).
3JHH = 2.6, 3JHH = 3.6, pyrrole-H), 2.42 (3H, s, o-CH3C6H4).
Anal. calcd for C13H15N2Al (226.25): C, 69.01; H, 6.68; N,
13C NMR (100.6 MHz, CDCl3): δ 151.0 (i-C6H4), 150.2 (NCH), 12.38%. Found: C, 68.95; H, 7.09; N, 12.19%.
pyrrole-H), 6.48 (1H, dd, JHH = 1.80, JHH = 3.7, pyrrole-H),
=
131.7 (o-C6H4), 130.6 (pyrrole-C), 130.4 (C6H4), 126.9 (C6H4),
Synthesis of L2AlMe2 (2a). To a stirred suspension of HL2
125.3 (C6H4), 123.7 (C6H4), 118.4 (pyrrole-CH), 116.7 (pyrrole- (1.60 g, 8.50 mmol) in toluene (20 mL) was slowly added AlMe3
CH), 110.1 (pyrrole-CH), 17.9 (o-CH3C6H4).
Anal. calcd for C12H12N2 (184.24): C, 78.23; H, 6.57; N, tion mixture was stirred at room temperature for 24 hours,
15.21%. Found C, 78.43; H, 6.44; N, 15.56%. after which the volatiles were removed in vacuo to leave an
(4.25 mL of a 2.0 M solution in toluene, 8.50 mmol). The reac-
Synthesis of (2-tert-butylphenyl)(1H-pyrrol-2-ylmethylene)- orange oil. After recrystallization in hexane at −20 °C, pale
amine (HL6). The synthesis of HL6 was performed according yellow crystals formed. Yield: 1.31 g, 63%.
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to the same procedure as for HL1. Yield: 1.57 g, 66%.
1H NMR (400 MHz, CDCl3): δ 8.26 (1H, d, JHH = 1.0, NCH),
1H NMR (400 MHz, CDCl3): δ 9.38 (1H, br s, pyrrole-NH), 7.34–7.32 (1H, m, pyrrole-H), 7.29–7.25 (2H, m, ArH), 7.13–7.07
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8.12 (1H, s, NCH), 7.40 (1H, dd, JHH = 1.5, JHH = 7.8, C6H4), (2H, m, ArH), 7.03 (1H, dd, JHH = 0.9, JHH = 3.7, pyrrole-H),
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7.24 (1H, td, JHH = 1.6, JHH = 7.5, C6H4), 7.16 (1H, td, JHH
1.6, JHH = 7.5, C6H4), 6.96–6.94 (1H, m, pyrrole-H), 6.84 (1H, Al(CH3)2).
=
6.46 (1H, dd, JHH = 1.1, JHH = 3.7, pyrrole-H), −0.63 (6H, s,
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dd, JHH = 1.6, JHH = 7.5, C6H4), 6.68 (1H, dd, JHH = 1.3,
13C NMR (100.6 MHz, CDCl3): δ 162.4 (ArCF), 159.9 (ArCF),
3JHH = 3.6, pyrrole-H), 6.33 (1H, dd, JHH = 2.7, JHH = 3.6, 153.9 (NCH), 140.4 (ArCN), 137.3 (pyrrolyl-CH), 136.2 (pyrrole-
pyrrole-H), 1.47 (9H, s, o-C(CH3)3C6H4). C), 121.8 (ArCH), 121.8 (pyrrole-CH), 121.5 (ArCH), 116.8
13C NMR (100.6 MHz, CDCl3): δ 151.64 (i-C6H4), 148.0 (ArCH), 116.6 (ArCH), 116.1 (pyrrole-CH).
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(NCH), 142.8 (o-C6H4), 131.4 (pyrrole-C), 127.1 (C6H4), 126.0
Anal. calcd for C14H14N2FAl (244.24): C, 63.93; H, 5.78; N,
(C6H4), 125.1 (C6H4), 122.6 (C6H4), 119.7 (pyrrole-CH), 115.4 11.47%. Found: C, 64.02; H, 5.41; N, 11.70%.
(pyrrole-CH), 110.4 (pyrrole-CH), 35.6 (o-C(CH3)3C6H4), 30.8
(o-C(CH3)3C6H4).
Synthesis of L3AlMe2 (3a). To a stirred suspension of HL3
(1.00 g, 5.43 mmol) in toluene (20 mL) was slowly added AlMe3
Anal. calcd for C15H18N2 (226.32): C, 79.61; H, 8.02; N, (2.71 mL of a 2.0 M solution in toluene, 5.43 mmol). The reac-
12.38%. Found C, 79.90; H, 8.04; N, 12.31%. tion mixture was stirred at room temperature for 45 min, after
Synthesis of (1-adamantyl)(1H-pyrrol-2-ylmethylene)amine which the volatiles were removed in vacuo to leave a yellow oil.
(HL7). The synthesis of HL7 was performed according to the Yield: 1.16 g, 89%.
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same procedure as for HL1. Yield: 1.11 g, 46%.
1H NMR (400 MHz, CDCl3): δ 8.32 (1H, d, JHH = 1.1, NCH),
1H NMR (400 MHz, CDCl3): δ 8.74 (1H, br s, pyrrole-NH), 7.32–7.30 (1H, m, pyrrole-H), 7.21 (4H, s, ArH), 7.00 (1H, dd,
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7.78 (1H, s, NCH), 6.95–7.01 (1H, m, pyrrole-H), 6.59 (1H, d, 4JHH = 0.9, JHH = 3.6, pyrrole-H), 6.45 (1H, dd, JHH = 1.8, JHH
4JHH = 1.6, pyrrole-H), 6.25 (1H, dd, JHH = 2.8, JHH = 3.2, = 3.7, pyrrole-H), 2.36 (3H, s, ArCH3), −0.63 (s, 6H, Al(CH3)2).
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pyrrole-H), 2.16 (3H, br s, CH), 1.82 (6H, d, JHH = 2.4, NCH2),
1.57–1.69 (6H, m, CH2).
13C NMR (100.6 MHz, CDCl3): δ 153.3 (NCH), 141.6 (ArCN),
136.7 (pyrrolyl-CH), 136.7 (pyrrole-CH), 136.6 (pyrrole-C),
This journal is © The Royal Society of Chemistry 2014
Dalton Trans., 2014, 43, 1348–1359 | 1355