Organometallics
Article
(m, 4H, 2CH2), 4.80−4.84 (m, 4H, 2CH2), 7.26−7.28 (m, 2H, Ar),
7.36−7.40 (m, 4H, Ar), 7.76−7.80 (m, 1H, Ar), 9.06−9.08 (m, 2H,
Ar). 13C{1H} NMR (CDCl3, 125 MHz): δ 14.0, 20.5, 31.3, 48.8, 110.5,
123.0, 124.7, 134.8, 138.1, 152.7, 161.6. Anal. Calcd for
C20H27Br2N3Pd: C, 41.73; H, 4.73; N, 7.30. Found: C, 41.39; H,
4.56; N, 7.51.
Dichloro(1,3-dibenzyl-1,3-dihydro-2H-benzimidazol-2-ylidene)-
(pyridine)palladium (4c). Yield 0.175 g (63%, method A), yellow
prismatic crystals, mp 268−270 °C dec. 1H NMR (CDCl3, 500 MHz):
δ 6.27 (s, 4H, 2CH2). 7.06−7.12 (m, 4H, 2CH2), 7.31−7.39 (m, 8H,
Ar), 7.61−7.63 (m, 4H, Ar), 7.75−7.78 (m, 1H, Ar), 8.99−9.00 (m,
2H, Ar), 13C{1H} NMR (CDCl3, 125 MHz): δ 53.3, 111.6, 123.4,
124.7, 128.1, 128.4, 129.1, 134.7, 135.2, 138.3, 151.4, 164.9. Anal.
Calcd for C26H23Cl2N3Pd: 56.29; H, 4.18; N, 7.57. Found: C, 56.26;
H, 4.36; N, 7.28.
Dibromo(1,3-dibenzyl-1,3-dihydro-2H-benzimidazol-2-ylidene)-
(pyridine)palladium (4d). Yield 0.288 g (91%, method B), yellow
prismatic crystals, mp 285−287 °C dec. The physical and spectral
characteristics of the product obtained are identical with those
described in the literature.19
(1,3-Dimethyl-1,3-dihydro-2H-imidazol-2-ylidene)diiodo-
(pyridine)palladium (5a). Yield 0.095 g (35%, method A), 0.242 g
(90%, method B), yellow prismatic crystals. The physical and spectral
characteristics of the product obtained are identical with those
described in the literature.20
8.44−8.45 (m, 2H, Ar). 13C{1H} NMR (CDCl3, 125 MHz): δ 24.1,
26.6, 29.4, 124.1, 124.5, 125.5, 130.4, 136.4, 137.1, 146.6, 153.5, 156.7.
Anal. Calcd for C32H41I2N3Pd: C, 46.42; H, 4.99; N, 5.08. Found: C,
46.61; H, 4.78; N, 5.29.
{1,3-Bis[2,6-bis(propan-2-yl)phenyl]-1,3-dihydro-2H-imidazol-2-
ylidene}dichloro(3-chloropyridine)palladium (5h). Yield 0.235 g
(69%, method A), yellow prismatic crystals, mp 238−240 °C (lit.
mp 240 °C).4a The physical and spectral characteristics of the product
obtained are identical with those described in the literature.4a
(2,4-Dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-ylidene)diiodo-
(pyridine)palladium (6a). Yield 0.102 g (38%, method A), 0.188 g
(70%, method B), yellow prismatic crystals, mp 163−165 °C. 1H
NMR (CDCl3, 500 MHz): δ 4.00 (s, 3H, CH3), 4.16 (s, 3H, CH3),
7.34−7.37 (m, 2H, Ar), 7.75−7.78 (m, 1H, Ar), 7.94 (s, 1H, CH of
triazole), 9.02−9.03 (m, 2H, Ar). 13C{1H} NMR (CDCl3, 125 MHz):
δ 36.4, 40.9, 124.8, 138.0, 143.3, 153.2, 154.0. Anal. Calcd for
C9H12I2N4Pd: C, 20.15; H, 2.25; N, 10.44. Found: C, 20.25; H, 2.50;
N, 10.21.
Dibromo(4-butyl-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-
ylidene)(pyridine)palladium (6b). Yield 0.179 g (74%, method B),
1
yellow prismatic crystals, mp 144−146 °C. H NMR (CDCl3, 500
MHz): δ 1.04 (t, J = 7.5 Hz, 3H, CH3), 1.44−1.51 (m, 2H, CH2),
2.12−2.18 (m, 2H, CH2), 4.28 (s, 3H, CH3), 4.49−4.52 (m, 2H,
CH2), 7.35−7.37 (m, 2H, Ar), 7.77−7.80 (m, 1H, Ar), 7.93 (s, 1H,
CH of triazole), 9.01−9.02 (m, 2H, Ar). 13C{1H} NMR (CDCl3, 125
MHz): δ 13.8, 19.9, 32.0, 40.6, 49.1, 124.8, 138.2, 142.5, 152.8, 155.1.
Anal. Calcd for C12H18Br2N4Pd: C, 29.75; H, 3.74; N, 11.56. Found:
C, 29.48; H, 3.55; N, 11.84.
(1-Butyl-3-methyl-1,3-dihydro-2H-imidazol-2-ylidene)dichloro-
(pyridine)palladium (5b). Yield 0.132 g (67%, method A), yellow
1
prismatic crystals, mp 118−120 °C. H NMR (CDCl3, 500 MHz): δ
1.02 (t, J = 7.5 Hz, 3H, CH3), 1.44−1.52 (m, 2H, CH2), 2.03−2.08
(m, 2H, CH2), 4.15 (s, 3H, CH3), 4.54 (t, J = 7.4 Hz, 2H, CH2), 6.89−
6.90 (m, 2H, 2CH of imidazole), 7.33−7.36 (m, 2H, Ar), 7.74−7.78
(m, 1H, Ar), 8.98−9.00 (m, 2H, Ar). 13C{1H} NMR (CDCl3, 125
MHz): δ 13.9, 20.0, 32.8, 38.1, 50.8, 121.7, 123.0, 124.6, 138.1, 148.7,
151.4. Anal. Calcd for C13H19Cl2N3Pd: C, 39.57; H, 4.85; N, 10.65.
Found: C, 39.29; H, 5.01; N, 10.38.
Dibromo(2,4-dibutyl-2,4-dihydro-3H-1,2,4-triazol-3-ylidene)-
(pyridine)palladium (6c). Yield 0.234 g (89%, method B), yellow
1
prismatic crystals, mp 106−108 °C. H NMR (CDCl3, 500 MHz): δ
1.01−1.05 (m, 6H, 2CH3), 1.46−1.52 (m, 4H, CH2), 2.09−2.17 (m,
4H, 2CH2), 4.50−4.53 (m, 2H, CH2), 4.64−4.67 (m, 2H, CH2),
7.34−7.37 (m, 2H, Ar), 7.76−7.79 (m, 1H, Ar), 7.94 (s, 1H, CH of
triazole), 9.01−9.02 (m, 2H, Ar). 13C{1H} NMR (CDCl3, 125 MHz):
δ 13.8, 13.9, 19.96, 20.0, 31.4, 31.9, 49.2, 53.2, 124.8, 138.2, 142.4,
152.8, 154.4. Anal. Calcd for C15H24Br2N4Pd: C, 34.21; H, 4.59; N,
10.64. Found: C, 34.42; H, 4.85; N, 10.69.
Dibromo(1-butyl-3-methyl-1,3-dihydro-2H-imidazol-2-ylidene)-
(pyridine)palladium (5c). Yield 0.191 g (79%, method B), yellow
1
prismatic crystals, mp 135−137 °C. H NMR (CDCl3, 500 MHz): δ
1.03 (t, J = 7.5 Hz, 3H, CH3), 1.46−1.50 (m, 2H, CH2), 2.05−2.08
(m, 2H, CH2), 4.09 (s, 3H, CH3), 4.48−4.51 (m, 2H, CH2), 6.90−
6.91 (m, 2H, 2CH of imidazole), 7.32−7.35 (m, 2H, Ar), 7.73−7.77
(m, 1H, Ar), 9.03−9.05 (m, 2H, Ar). 13C{1H} NMR (CDCl3, 125
MHz): δ 13.9, 20.1, 32.3, 38.6, 51.1, 121.7, 123.2, 124.6, 137.9, 147.5,
152.7. Anal. Calcd for C13H19Br2N3Pd: C, 32.29; H, 3.96; N, 8.69.
Found: C, 32.05; H, 4.12; N, 8.45.
Dichloro(2,4-dibenzyl-2,4-dihydro-3H-1,2,4-triazol-3-ylidene)-
(pyridine)palladium (6d). Yield 0.220 g (87%, method A), yellow
1
prismatic crystals, mp 142−144 °C. H NMR (CDCl3, 500 MHz): δ
5.85 (s, 2H, CH2), 5.94 (s, 2H, CH2), 7.34−7.43 (m, 8H, Ar), 7.51−
7.53 (m, 2H, Ar), 7.62−7.64 (m, 2H, Ar), 7.72 (s, 1H, CH of triazole),
7.78−7.81 (m, 1H, Ar), 8.95−8.96 (m, 2H, Ar). 13C{1H} NMR
(CDCl3, 125 MHz): δ 53.1, 56.9, 124.8, 128.7, 128.9, 129.31 (2C),
129.33, 129.5, 133.8, 134.7, 138.5, 142.8, 151.5, 157.1. Anal. Calcd for
C21H20Cl2N4Pd: C, 49.87; H, 3.99; N, 11.08. Found: C, 49.52; H,
4.02; N, 11.29.
[1,3-Bis(2,4,6-trimethylphenyl)-1,3-dihydro-2H-imidazol-2-
ylidene]dichloro(3-chloropyridine)palladium (5d). Yield 0.189 g
(64%, method A), yellow prismatic crystals. The physical and spectral
characteristics of the product obtained are identical with those
described in the literature.4a
{1,3-Bis[2,6-bis(propan-2-yl)phenyl]-1,3-dihydro-2H-imidazol-2-
ylidene}dichloro(pyridine)palladium (5e). Yield 0.235 g (73%,
method A), yellow prismatic crystals. The physical and spectral
characteristics of the product obtained are identical with those
described in the literature.21
{1,3-Bis[2,6-bis(propan-2-yl)phenyl]-1,3-dihydro-2H-imidazol-2-
ylidene}dibromo(pyridine)palladium (5f). Yield 0.272 g (74%,
method B), yellow prismatic crystals, mp 246 °C dec. 1H NMR
(CDCl3, 500 MHz): δ 1.12 (d, J = 6.8 Hz, 12H, 4CH3), 1.50 (d, J =
6.8 Hz, 12H, 4CH3), 3.25−3.31 (m, 4H, 4CH), 7.06−7.09 (m, 2H,
Ar), 7.16 (s, 2H, 2CH of imidazole), 7.36−7.37 (m, 4H, Ar), 7.49−
7.53 (m, 3H, Ar), 8.51−8.53 (m, 2H, Ar). 13C{1H} NMR (CDCl3, 125
MHz): δ 23.6, 26.5, 29.1, 124.16, 124.21, 125.4, 130.4, 135.6, 137.3,
146.8, 152.6, 155.3. Anal. Calcd for C32H41Br2N3Pd: C, 52.37; H, 5.63;
N, 5.73. Found: C, 52.23; H, 5.60; N, 5.52.
Dibromo(2,4-dibenzyl-2,4-dihydro-3H-1,2,4-triazol-3-ylidene)-
(pyridine)palladium (6e). Yield 0.264 g (89%, method B), yellow
1
prismatic crystals, mp 133−135 °C. H NMR (CDCl3, 500 MHz): δ
5.80 (s, 2H, CH2), 5.90 (s, 2H, CH2), 7.34−7.44 (m, 8H, Ar), 7.52−
7.53 (m, 2H, Ar), 7.62−7.63 (m, 2H, Ar), 7.70 (s, 1H, CH of triazole),
7.76−7.79 (m, 1H, Ar), 8.98−8.99 (m, 2H, Ar). 13C{1H} NMR
(CDCl3, 125 MHz): δ 53.4, 57.1, 124.8, 128.7, 128.9, 129.3, 129.44,
129.47, 129.52, 133.6, 134.5, 138.2, 142.8, 152.8, 156.5. Anal. Calcd for
C21H20Br2N4Pd: C, 42.42; H, 3.39; N, 9.42. Found: C, 42.54; H, 3.45;
N, 9.62.
Dibromo(4-butyl-2-tert-butyl-2,4-dihydro-3H-1,2,4-triazol-3-
ylidene)(pyridine)palladium (6f). Yield 0.200 g (76%, method B),
yellow prismatic crystals, mp 99−101 °C. 1H NMR (CDCl3, 500
MHz): δ 1.07 (t, J = 7.5 Hz, 3H, CH3), 1.49−1.57 (m, 2H, CH2), 2.07
(s, 9H, 3CH3), 2.13−2.19 (m, 2H, CH2), 4.69−4.72 (m, 2H, CH2),
7.33−7.36 (m, 2H, Ar), 7.75−7.78 (m, 1H, Ar), 7.98 (s, 1H, CH of
triazole), 8.99−9.00 (m, 2H, Ar). 13C{1H} NMR (CDCl3, 125 MHz):
δ 13.8, 20.1, 31.3, 31.5, 50.2, 62.6, 124.8, 138.1, 141.4, 151.6, 152.9.
Anal. Calcd for C15H24Br2N4Pd: C, 34.21; H, 4.59; N, 10.64. Found:
C, 34.26; H, 4.67; N, 10.35.
{1,3-Bis[2,6-bis(propan-2-yl)phenyl]-1,3-dihydro-2H-imidazol-2-
ylidene}diiodo(pyridine)palladium (5g). Yield 0.363 g (88%, method
1
B), yellow prismatic crystals, mp 210 °C dec. H NMR (CDCl3, 500
MHz): δ 1.11 (d, J = 6.8 Hz, 12H, 4CH3), 1.52 (d, J = 6.8 Hz, 12H,
4CH3) 3.38−3.45 (m, 4H, 4CH), 7.07−7.09 (m, 2H, Ar), 7.21 (s, 2H,
2CH of imidazole), 7.36−7.38 (m, 4H, Ar), 7.50−7.53 (m, 3H, Ar),
(4-Benzyl-2-tert-butyl-2,4-dihydro-3H-1,2,4-triazol-3-ylidene)-
dibromo(pyridine)palladium (6g). Yield 0.191 g (68%, method B),
1
yellow prismatic crystals, mp 119−121 °C. H NMR (CDCl3, 500
I
Organometallics XXXX, XXX, XXX−XXX