Al Complexes with Bidentate N,N-Dialkylaniline–arylamido Ligands
product (0.84 g, 83%) was obtained as a yellow oil. C23H34N2
(338.53): calcd. C 81.60, H 10.12, N 8.28; found C 81.53, H 10.15,
N 8.32. H NMR (300 MHz, CDCl3, 293 K): δ = 7.46 (d, 1 H, Ph-
materials. The product (0.50 g, 89%) was obtained as a colorless
crystalline solid. C19H27AlN2 (310.41): calcd. C 73.52, H 8.77, N
9.02; found C 73.50, H 8.75, N 9.00. 1H NMR (300 MHz, C6D6,
1
H), 7.28 (t, 1 H, Ph-H), 7.21–7.12 (m, 5 H, Ph-H), 4.10 (s, 2 H, 293 K): δ = 7.25 (d, 2 H, Ph-H), 7.13 (t, 1 H, Ph-H), 6.93 (m, 3 H,
CH2N), 3.53 (br., 1 H, NH), 3.42 [m, 2 H, CH(CH3)2], 3.06 (q, 4
Ph-H), 6.69 (m, 1 H, Ph-H), 4.32 (s, 2 H, CH2N), 2.52 (s, 6 H,
H, NCH2CH3), 1.24 [d, 12 H, CH(CH3)2], 1.03 (t, 6 H, NCH2CH3) NCH3), 2.36 (s, 6 H, CH3), –0.65 (s, 6 H, AlCH3) ppm. 13C{1H}
ppm. 13C{1H} NMR (75 MHz, CDCl3, 293 K): δ = 142.93, 137.39, NMR (75 MHz, C6D6, 293 K): δ = 150.81, 1415.98, 138.29, 136.26,
129.53, 128.31, 124.16, 123.75, 123.55, 123.07, 122.75, 118.50,
52.46, 48.30, 27.52, 24.37, 12.20 ppm.
130.74, 129.03, 127.40, 127.05, 123.84, 118.62, 57.19, 44.94, 19.57,
–9.78 ppm.
ortho-C6H4(NEt2)CH2NHC6H3Me2-2,6 (2g): This compound was
prepared in the same way as described above for 2a with 1g (1.12 g,
4.0 mmol) and LiAlH4 (0.23 g, 6.0 mmol) as starting materials. The
ortho-C6H4(NMe2)(CH2NC6H4Me-4)AlMe2 (3d): This compound
was prepared in the same way as described above for 3a with 2d
(0.72 g, 3.0 mmol) and AlMe3 (3.0 mL, 3.0 mmol) as starting mate-
product (1.02 g, 91%) was obtained as a yellow oil. C19H26N2 rials. The product (0.82 g, 92%) was obtained as a colorless crystal-
(282.42): calcd. C 80.80, H 9.28, N 9.92; found C 80.83, H 9.23, N
line solid. C18H25AlN2 (296.39): calcd. C 72.94, H 8.50, N 9.45;
9.94. 1H NMR (300 MHz, CDCl3, 293 K): δ = 7.45 (d, 1 H, Ph-
found C 72.96, H 8.45, N 9.48. 1H NMR (300 MHz, CDCl3,
H), 7.26 (t, 1 H, Ph-H), 7.19 (m, 2 H, Ph-H), 7.01 (d, 2 H, Ph-H), 293 K): δ = 7.37–7.28 (m, 6 H, Ph-H), 7.00 (d, 1 H, Ph-H), 6.69
6.84 (t, 1 H, Ph-H), 4.18 (s, 2 H, CH2N), 3.68 (br., 1 H, NH), 3.08 (d, 1 H, Ph-H), 4.49 (s, 2 H, CH2N), 2.92 (s, 6 H, NCH3), 2.25 (s,
(q, 4 H, NCH2CH3), 2.38 (s, 6 H, CH3), 1.06 (t, 6 H, NCH2CH3) 3 H,CH3), –0.85 (s, 6 H, AlCH3) ppm. 13C{1H} NMR (75 MHz,
ppm. 13C{1H} NMR (75 MHz, CDCl3, 293 K): δ = 146.70, 137.80, CDCl3, 293 K): δ = 151.93, 145.32, 134.62, 131.78, 129.62, 128.45,
129.96, 129.60, 128.85, 127.61, 124.30, 123.10, 121.95, 118.03,
65.64, 48.76, 18.56, 12.52 ppm.
127.64, 123.77, 118.61, 114.38, 53.87, 44.91, 20.52, –10.20 ppm.
ortho-C6H4(NMe2)(CH2NC6H5)AlMe2 (3e): This compound was
prepared in the same way as described above for 3a with 2e (0.56 g,
2.5 mmol) and AlMe3 (2.5 mL, 2.5 mmol) as starting materials. The
product (0.66 g, 93%) was obtained as a colorless crystalline solid.
C17H23AlN2 (282.36): calcd. C 72.31, H 8.21, N 9.92; found C
72.35, H 8.25, N 9.83. 1H NMR (300 MHz, CDCl3, 293 K): δ =
ortho-C6H4(NEt2)CH2NHC6H5 (2h): This compound was prepared
in the same way as described above for 2a with 1h (1.39 g,
5.5 mmol) and LiAlH4 (0.31 g, 8.3 mmol) as starting materials. The
product (1.22 g, 87%) was obtained as a yellow oil. C17H22N2
(254.37): calcd. C 80.27, H 8.72, N 11.01; found C 80.21, H 8.75,
N 11.04. 1H NMR (300 MHz, CDCl3, 293 K): δ = 7.37 (d, 1 H, 7.37–7.30 (m, 4 H, Ph-H), 7.20 (t, 2 H, Ph-H), 6.77 (d, 2 H, Ph-
Ph-H), 7.25–7.17 (m, 4 H, Ph-H), 7.06 (t, 1 H, Ph-H), 6.66 (m, 3
H, Ph-H), 4.40 (s, 2 H, CH2N), 3.65 (br., 1 H, NH), 3.02 (q, 4 H,
H), 6.62 (t, 1 H, Ph-H), 4.50 (s, 2 H, CH2N), 2.93 (s, 6 H, NCH3),
–0.84 (s, 6 H, AlCH3) ppm. 13C{1H} NMR (75 MHz, CDCl3,
NCH2CH3), 1.05 (t, 6 H, NCH2CH3) ppm. 13C{1H} NMR 293 K): δ = 154.03, 154.01, 134.13, 131.53, 128.79, 128.27, 127.41,
(75 MHz, CDCl3, 293 K): δ = 148.58, 136.04, 129.12, 127.36,
123.93, 122.62, 118.28, 117.08, 113.61, 112.8, 48.01, 44.69,
12.62 ppm.
118.37, 114.66, 114.26, 53.39, 44.64, –10.51 ppm.
ortho-C6H4(NEt2) (CH2NC6H3iPr2-2,6)AlMe2 (3f): This com-
pound was prepared in the same way as described above for 3a with
2f (0.34 g, 1.0 mmol) and AlMe3 (1.0 mL, 1.0 mmol) as starting
materials. The product (0.36 g, 92%) was obtained as a colorless
crystalline solid. C25H39AlN2 (394.57): calcd. C 76.10, H 9.96, N
ortho-C6H4(NMe2)(CH2NC6H3iPr2-2,6)AlMe2 (3a): AlMe3 (1.0
in toluene, 2.0 mL, 2.0 mmol) was added to a solution of 2a (0.62 g,
2.0 mmol) in toluene (20 mL) at –10 °C with stirring. The reaction
mixture was gently heated to 80 °C for 24 h. After removal of the
solvent, the product was recrystallized from hexane to give the de-
sired complex as a colorless crystalline solid (0.62 g, 84%).
1
7.10; found C 76.15, H 9.93, N 7.18. H NMR (300 MHz, CDCl3,
293 K): δ = 7.51 (d, 1 H, Ph-H), 7.36 (m, 3 H, Ph-H), 7.24–7.11
(m, 3 H, Ph-H), 4.35 (s, 2 H, CH2N), 3.69 [m, 2 H, CH(CH3)2],
C23H35AlN2 (366.52): calcd. C 75.37, H 9.63, N 7.64; found C 3.50 (m, 4 H, NCH2CH3), 1.25 [d, 12 H, CH(CH3)2], 1.19 (t, 6 H,
75.40, H 9.61, N 7.65. 1H NMR (300 MHz, CDCl3, 293 K): δ = NCH2CH3), –1.04 (s, 6 H, AlCH3) ppm. 13C{1H} NMR (75 MHz,
7.32 (m, 3 H, Ph-H), 7.02 (m, 1 H, Ph-H), 6.94–6.93 (m, 2 H, Ph- CDCl3, 293 K): δ = 149.52, 142.84, 135.82, 130.81, 129.45, 127.56,
H), 6.71 (m, 1 H, Ph-H), 4.45 (s, 2 H, CH2N), 3.95 [m, 2 H,
126.67, 124.31, 123.15, 121.69, 60.81, 44.40, 27.14, 25.92, 24.38,
CH(CH3)2], 2.41 (s, 6 H, NCH3), 1.41 [q, 12 H, CH(CH3)2], –0.63 9.20, –8.52 ppm.
(s, 6 H, AlCH3) ppm. 13C{1H} NMR (75 MHz, CDCl3, 293 K): δ
= 149.12, 147.93, 145.99, 136.09, 130.60, 127.60, 127.16, 124.87,
124.11, 118.74, 60.74, 44.91, 27.52, 26.23, 25.15, –9.97 ppm.
ortho-C6H4(NEt2) (CH2NC6H3Me2-2,6)AlMe2 (3g): This com-
pound was prepared in the same way as described above for 3a with
2g (0.42 g, 1.5 mmol) and AlMe3 (1.5 mL, 1.5 mmol) as starting
materials. The product (0.44 g, 87%) was obtained as a colorless
crystalline solid. C21H31AlN2 (338.47): calcd. C 74.52, H 9.23, N
ortho-C6H4(NMe2)(CH2NC6H3Et2-2,6)AlMe2 (3b): This com-
pound was prepared in the same way as described above for 3a with
2b (0.62 g, 2.2 mmol) and AlMe3 (2.2 mL, 2.2 mmol) as starting
materials. The product (0.65 g, 87%) was obtained as a colorless
crystalline solid. C21H31AlN2 (338.47): calcd. C 74.52, H 9.23, N
1
8.28; found C 74.48, H 9.27, N 8.23. H NMR (300 MHz, CDCl3,
293 K): δ = 7.32 (d, 1 H, Ph-H), 7.29 (t, 1 H, Ph-H), 7.24 (m, 2 H,
Ph-H), 7.05 (d, 2 H, Ph-H), 6.91 (t, 1 H, Ph-H), 4.34 (s, 2 H,
CH2N), 3.55 (m, 4 H, NCH2CH3), 2.31 (s, 6 H, CH3), 1.20 (t, 6 H,
1
8.28; found C 74.39, H 9.32, N 8.34. H NMR (300 MHz, CDCl3,
293 K): δ = 7.32–7.28 (m, 3 H, Ph-H), 6.99–6.94 (m, 3 H, Ph-H), NCH2CH3), –1.03 (s, 6 H, AlCH3) ppm. 13C{1H} NMR (75 MHz,
6.71 (m, 1 H, Ph-H), 4.38 (s, 2 H, CH2N), 3.0 (q, 4 H, CH2CH3), CDCl3, 293 K): δ = 150.84, 143.42, 138.32, 136.09, 130.89, 128.20,
2.40 (s, 6 H, NCH3), 1.38 (t, 6 H, CH2CH3), –0.63 (s, 6 H, AlCH3) 126.94, 126.59, 123.02, 121.66, 57.30, 44.40, 19.18, 9.06, –8.25 ppm.
ppm. 13C{1H} NMR (75 MHz, CDCl3, 293 K): δ = 149.64, 146.00,
144.21, 136.13, 130.69, 127.52, 127.10, 126.68, 124.27, 118.73,
59.37, 45.02, 24.50, 16.38, –9.90 ppm.
ortho-C6H4(NEt2) (CH2NC6H5)AlMe2 (3h): This compound was
prepared in the same way as described above for 3a with 2h (0.51 g,
2.0 mmol) and AlMe3 (2.0 mL, 2.0 mmol) as starting materials. The
ortho-C6H4(NMe2)(CH2NC6H3Me2-2,6)AlMe2 (3c): This com-
pound was prepared in the same way as described above for 3a with
2c (0.46 g, 1.8 mmol) and AlMe3 (1.8 mL, 1.8 mmol) as starting
product (0.52 g, 84%) was obtained as a colorless crystalline solid.
C19H27AlN2 (310.41): calcd. C 73.52, H 8.77, N 9.02; found C
73.56, H 8.73, N 9.07. 1H NMR (300 MHz, CDCl3, 293 K): δ =
Eur. J. Inorg. Chem. 2009, 3613–3621
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