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G. Attilio Ardizzoia et al. / Inorganica Chimica Acta 362 (2009) 3507–3512
1H NMR (CDCl3, RT): 2.42 (s, 3H), 7.27 (d, 2H, J = 8.0 Hz), 7.34 (d,
2H, J = 8.0 Hz), 7.62 (t, 1H, J = 7.5 Hz), 7.79 (t, 1H, J = 7.6 Hz), 7.89
(d, 1H, J = 8.1 Hz), 8.19 (d, 1H, J = 8.5 Hz), 8.27 (d, 1H, J = 8.6 Hz),
8.39 (d, 1H, J = 8.6 Hz), 8.84 (s, 1H, HC@N). 13C NMR (CDCl3, RT):
20.66 (CH3), 118.59, 120.56, 126.90, 127.48, 127.83, 129.50,
129.75, 130.13, 131.90, 136.77, 144.99, 147.79, 154.51, 163.67
(HC@N). Anal. Calc. for C17H14N2: C, 82.90; H, 5.73; N, 11.37. Found:
C, 82.60; H, 5.65; N, 11.29%.
2.5. Synthesis of quim2
To a solution of 0.50 g (3.18 mmol) of 2-quinolinecarboxalde-
hyde in 10 ml of toluene, 0.42 g (3.47 mol) of
a-methylbenzyl-
amine were added. The solution was stirred at 70 °C for 8 h, then
the solvent was removed under reduced pressure and the crude
product suspended in 2 ml of methanol. An orange solid was iso-
lated after filtration. Yield: 72%.
1H NMR (CDCl3, RT): 1.68 (d, 3H, J = 6.6 Hz), 4.74 (q, 1H,
J = 6.6 Hz), 7.29 (t, 1H, J = 8.1 Hz), 7.39 (t, 2H, J = 7.4 Hz), 7.50 (d,
2H, J = 7.6 Hz), 7.61 (t, 1H, J = 7.5 Hz), 7.76 (t, 1H, J = 7.6 Hz), 7.86
(d, 1H, J = 8.1 Hz), 8.14 (d, 1H, J = 8.5 Hz), 8.21 (d, 1H, J = 8.5 Hz),
8.29 (d, 1H, J = 8.5 Hz), 8.66 (s, 1H, HC@N). 13C NMR (CDCl3, RT):
24.43 (CH3), 54.76 (CH), 120.61, 125.67, 126.77, 126.84, 127.80,
128.39, 128.53, 129.54, 129.70, 136.72, 143.97, 147.84, 157.84,
162.96 (HC@N). Anal. Calc. for C18H16N2: C, 83.04; H, 6.19; N,
10.76. Found: C, 82.50; H, 6.22; N, 10.74%.
Chart 1.
performed on a Shimadzu GC-17A gas chromatograph with a
PS225 capillary column (25 m, 0.25 mm) equipped with
QP5000 mass selective detector.
a
2.6. Synthesis of copper(I) complexes 1–4
2.2. Synthesis of pyim1
In a typical experiment, a suspension of 0.50 g (0.565 mmol) of
[Cu(PPh3)3Cl] in diethylether was treated with an equimolar
amount of the corresponding imine. The resulting suspension
was stirred at room temperature for 18 h, after which time a
brick-red precipitate formed. The solid was filtered off and dried
in vacuum. Yield: 77% (1); 81% (2); 86% (3); 91% (4).
To a solution of 2.25 g (21 mmol) of 2-pyridinecarboxaldehyde
in 10 ml of methanol, 2.95 g (23 mmol) of 4-chloroaniline were
added. The solution was stirred at 40 °C for 8 h, then it was reduced
to half the volume and chilled in an ice-bath. A yellow solid was
formed, which was filtered and dried in vacuum. Yield: 78%.
1H NMR (CDCl3, RT): 7.23 (d, 2H, J = 6.6 Hz), 7.37 (d, 2H,
J = 6.7 Hz), 7.38 (t, 1H, J = 5.0 Hz), 7.81 (t, 1H, J = 7.7 Hz), 8.18 (d,
1H, J = 7.9 Hz), 8.58 (s, 1H, HC@N), 8.72 (d, 1H, J = 4.7 Hz). 13C
NMR (CDCl3, RT): 121.50, 123.71, 125.08, 129.16, 131.37, 137.48,
139.45, 151.12, 152.36, 162.02, 162.65 (HC@N). Anal. Calc. for
C12H9ClN2: C, 66.52; H, 4.19; N, 12.93. Found: C, 66.39; H, 3.97;
N, 12.79%.
[Cu(pyim1)(PPh3)Cl], 1: 1H NMR (CD2Cl2, RT): 7.31–7.44 (m,
19H), 7.61 (t, 1H, J = 6.2 Hz), 8.01 (t, 1H, J = 6.7 Hz), 8.14 (d, 1H,
J = 5.9 Hz), 8.68 (s, 1H, HC = N), 8.70 (d, 1H, J = 4.9 Hz). 13C NMR
(CD2Cl2, RT): 120.87, 123.22, 124.92, 128.16, 128.35, 129.54,
130.96, 133.49, 137.28, 137.56, 139.12, 150.85, 151.98, 161.38,
164.14 (HC@N). 31P NMR (CD2Cl2, RT): ꢀ4.08 ppm (s). Anal. Calc.
for C30H24N2Cl2PCu: C, 62.34; H, 4.19; N, 4.85. Found: C, 62.22;
H, 4.31; N, 4.64%.
[Cu(pyim2)(PPh3)Cl], 2: 1H NMR (CD2Cl2, RT): 2.38 (s, 3H), 2.60 (s,
3H), 7.13 (d, 2H, J = 7.4 Hz), 7.23–7.34 (m, 17H), 7.48 (d, 1H,
J = 5.6 Hz), 7.54 (d, 1H, J = 5.4 Hz), 7.75 (t, 1H, J = 5.5 Hz), 8.41 (s,
1H, HC@N). 13C NMR (CD2Cl2, RT): 20.46 (CH3), 25.98 (CH3),
118.73, 120.38, 124.76, 128.12, 128.38, 131.11, 133.43, 136.69,
137.22, 137.87, 147.99, 155.10, 158.01, 162.49 (HC@N). 31P NMR
(CD2Cl2, RT): ꢀ4.30 ppm (s). Anal. Calc. for C32H29N2ClPCu: C,
67.24; H, 5.11; N, 4.90. Found: C, 67.09; H, 5.28; N, 4.77%.
Brick-red crystals suitable for X-ray analysis of species 2 were
obtained by slow diffusion of diethylether into a dichloromethane
solution of the complex.
2.3. Synthesis of pyim2
To a solution of 0.50 g (4.13 mmol) of 6-methylpyridine-2-car-
boxaldehyde in 10 ml of ethanol, 0.48 g (4.48 mol) of p-toluidine
was added. The solution was stirred at 80 °C for 6 h, then it was re-
duced to half the volume and a yellow solid formed. It was filtered
and dried in vacuum. Yield: 81%.
1H NMR (CDCl3, RT): 2.38 (s, 3H), 2.64 (s, 3H), 7.21 (d, 1H,
J = 7.6 Hz), 7.23 (d, 2H, J = 8.6 Hz), 7.25 (d, 2H, J = 8.7 Hz), 7.68 (t,
1H, J = 7.7 Hz), 8.02 (d, 1H, J = 7.7 Hz), 8.62 (s, 1H, HC@N). 13C
NMR (CDCl3, RT): 21.46 (CH3), 24.78 (CH3), 119.31, 121.57,
125.09, 130.22, 137.02, 137.25, 148.85, 154.60, 158.76, 160.36
(HC@N). Anal. Calc. for C14H14N2: C, 79.67; H, 6.79; N, 13.32. Found:
C, 79.95; H, 6.72; N, 13.33%.
[Cu(quim1)(PPh3)Cl], 3: 1H NMR (CD2Cl2, RT): 2.39 (s, 3H), 7.16
(d, 2H, J = 8.1 Hz), 7.22 (t, 1H, J = 7.4 Hz), 7.28–7.37 (m, 16H),
7.53–7.56 (m, 4H), 7.58 (d, 1H, J = 7.6 Hz), 8.27 (d, 1H, J = 8.3 Hz),
8.65 (s, 1H, HC@N). 13C NMR (CD2Cl2, RT): 19.71 (CH3), 117.99,
121.06, 126.31, 126.76, 127.43, 128.09, 128.31, 129.15, 129.39,
130.81, 132.07, 133.51, 136.12, 137.18, 144.74, 146.89, 156.62,
165.07 (HC@N). 31P NMR (CD2Cl2, RT): ꢀ5.56 ppm (s). Anal. Calc.
for C35H29N2ClPCu (3): C, 69.19; H, 4.81; N, 4.61. Found: C, 69.57;
H, 4.98; N, 4.20%.
2.4. Synthesis of quim1
To a solution of 0.50 g (3.18 mmol) of 2-quinolinecarboxalde-
hyde in 10 ml of toluene, 0.37 g (3.45 mol) of p-toluidine were
added. The solution was stirred at 70 °C for 8 h, during which time
a yellow solid formed. It was filtered and dried in vacuum. Yield:
88%.
[Cu(quim2)(PPh3)Cl], 4: 1H NMR (CD2Cl2, RT): 1.81 (d, 3H,
J = 6.7 Hz), 4.91 (q, 1H, J = 6.6 Hz), 7.24–7.39 (m, 20H), 7.52 (d,
1H, J = 6.3 Hz), 7.65 (t, 1H, J = 6.8 Hz), 7.79 (t, 1H, J = 6.4 Hz), 7.84