Organometallics
Article
CDCl ) δ 22.8, 23.0, 23.2, 24.5, 25.9, 26.6, 27.9, 28.4, 29.0, 120.2,
dissolved in dry THF (5 mL) and stirred for 1 day at 40 °C.
Subsequently, the solvent was removed in vacuo, and the residue was
washed with diethyl ether (3 × 3 mL) and recrystallized from
3
1
1
21.4, 122.4, 124.1, 124.3, 125.1, 126.8, 127.4, 129.8, 130.2, 132.7,
36.1, 136.9, 137.6, 145.2, 146.2, 147.8, 152.3, 153.1, 180.2. Anal.
Calcd C H ClN Pd (832.36): C, 69.14; H, 7.13; N, 6.72. Found: C,
dichloromethane/diethyl ether to give 20 (64 mg, 34%) as a colorless
48
59
4
1
6
8.87; H, 7.12; N, 6.58.
SP-4-4-[1,3-Bis[2,6-diisopropylphenyl]-1,3-dihydro-2H-imi-
solid. mp 141 °C. H NMR (500 MHz, CDCl ) δ 0.76 (d, J = 6.6 Hz,
3
6 H), 1.01 (d, J = 6.9 Hz, 6 H), 1.19 (d, J = 6.9 Hz, 6 H), 1.48 (d, J =
dazol-2-ylidene]chloro[2-(1-(2,6-diisopropylphenyl)-1H-imida-
zol-2-yl-κN )-5-methoxyphenyl-κC]palladium(II) (17). The syn-
6
.3 Hz, 6 H), 1.53 (s, 3 H), 1.83 (s, 6 H), 2.99 (spt, J = 6.7 Hz, 2 H),
3
3
.27 (spt, J = 6.9 Hz, 2 H), 3.83 (s, 3 H), 5.93 (dd, J = 1.4, 7.7 Hz, 1
thesis of 17 was carried out as described above for 14 starting from
imidazole 5 (100 mg, 0.3 mmol) and palladium(II) acetate (67 mg, 0.3
mmol). Purification by column chromatography on silica gel
H), 6.48 (d, J = 1.6 Hz, 1 H), 6.50 (d, J = 7.6 Hz, 1 H), 6.54 (td, J =
.9, 7.6 Hz, 1 H), 6.67 (m, 3 H), 7.04 (d, J = 1.6 Hz, 1 H), 7.19 (dd, J
1.6, 7.6 Hz, 2 H), 7.25 (s, 2 H), 7.35 (dd, J = 1.6, 7.9 Hz, 2 H), 7.41
0
=
(
dichloromethane/ethyl acetate 70:1) gave 17 (32 mg, 12%) as a
13
(t, J = 7.6 Hz, 2 H). C NMR (125 MHz, CDCl ) δ 17.9, 22.6, 23.1,
1
3
light yellow solid. 295 °C (dec.). H NMR (500 MHz, CDCl ) δ 0.60
(
3
26.0, 26.2, 26.5, 28.5, 28.9, 55.4, 113.7, 119.5, 120.5, 122.8, 124.2,
d, J = 6.6 Hz, 6 H), 0.85 (d, J = 6.6 Hz, 6 H), 1.02 (d, J = 6.9 Hz, 6
1
24.4, 124.8, 127.5, 127.6, 128.4, 129.9, 135.7, 137.1, 137.3, 137.6,
H), 1.03 (d, J = 6.6 Hz, 6 H), 1.16 (d, J = 6.6 Hz, 6 H), 1.53 (d, J = 6.3
Hz, 6 H), 2.38 (spt, J = 6.9 Hz, 2 H), 3.17 (spt, J = 6.6 Hz, 2 H), 3.38
1
45.0, 147.6, 148.8, 152.2, 159.6, 178.2, 179.5. Anal. Calcd
C H N O Pd (831.39): C, 67.90; H, 6.79; N, 6.74. Found: C,
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56
4
3
(
(
spt, J = 6.6 Hz, 2 H), 3.63 (s, 3 H), 5.78 (d, J = 8.5 Hz, 1 H), 6.06
dd, J = 2.5, 8.5 Hz, 1 H), 6.14 (d, J = 2.5 Hz, 1 H), 6.49 (d, J = 1.6
6
7.80; H, 6.98; N, 6.67.
SP-4-4-Acetato[1,3-bis[2,6-diisopropylphenyl]-1,3-dihydro-
Hz, 1 H), 7.19 (dd, J = 1.4, 7.7 Hz, 2 H), 7.23 (s, 2 H), 7.25 (d, J = 7.9
Hz, 2 H), 7.33 (dd, J = 1.4, 7.7 Hz, 2 H), 7.42 (t, J = 7.6 Hz, 2 Hz),
2
H-imidazol-2-ylidene][2-(1-(2,6-diisopropylphenyl)-1H-imida-
3
zol-2-yl-κN )phenyl-κC]palladium(II) (21). Under argon, complex
0 (100 mg, 0.1 mmol) and IPr (83 mg, 0.2 mmol) were dissolved in
7
.43 (d, J = 1.6 Hz, 1 H), 7.47 (t, J = 7.6 Hz, 1 H). 13C NMR (125
1
MHz, CDCl ) δ 22.4, 23.0, 23.1, 24.5, 25.9, 26.7, 27.9, 28.4, 29.0, 54.4,
3
dry THF (5 mL) and stirred for 1 day at 40 °C. Subsequently, the
solvent was removed in vacuo, and the residue was washed with
diethyl ether (3 × 3 mL) and recrystallized from diethyl ether to give
1
1
05.8, 119.5, 122.1, 124.2, 124.3, 125.28, 125.33, 126.3, 129.9, 130.08,
30.14, 132.7, 136.1, 145.3, 146.4, 147.9, 153.2, 153.4, 157.6, 180.3.
Anal. Calcd C H ClN OPd (862.36): C, 68.12; H, 7.12; N, 6.49.
1
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61
4
21 (60 mg, 33%) as a colorless solid. mp 248 °C (dec.). H NMR (500
Found: C, 67.99; H, 7.20; N, 6.28.
MHz, CDCl ) δ 0.69 (d, J = 6.6 Hz, 6 H), 0.85 (d, J = 6.6 Hz, 6 H),
3
SP-4-4-[1,3-Bis[2,6-diisopropylphenyl]-1,3-dihydro-2H-imi-
1
.00 (d, J = 6.6 Hz, 6 H), 1.02 (d, J = 6.9 Hz, 6 H), 1.18 (d, J = 6.9 Hz,
dazol-2-ylidene]chloro[2-(1-(2,6-diisopropylphenyl)-1H-imida-
6
H), 1.49 (d, J = 6.6 Hz, 6 H), 1.63 (s, 3 H), 2.35 (spt, J = 6.9 Hz, 2
3
zol-2-yl-κN )-5-fluorophenyl-κC]palladium(II) (18). The synthesis
H), 2.97 (spt, J = 6.7 Hz, 2 H), 3.26 (spt, J = 6.6 Hz, 2 H), 5.83 (dd, J
of 18 was carried out as described above for 14 starting from imidazole
=
1.4, 7.7 Hz, 1 H), 6.46 (d, J = 7.6 Hz, 1 H), 6.49 (td, J = 0.9, 7.6 Hz,
6
(100 mg, 0.3 mmol) and palladium(II) acetate (71 mg, 0.3 mmol).
1
H), 6.52 (d, J = 1.6 Hz, 1 H), 6.63 (td, J = 1.4, 7.5 Hz, 1 H), 7.05 (d,
Purification by column chromatography on silica gel (dichloro-
J = 1.3 Hz, 1 H) 7.20 (dd, J = 1.4, 7.7 Hz, 2 H), 7.25 (m, 4 H), 7.36
methane/ethyl acetate 70:1) gave 18 (33 mg, 12%) as a colorless
1
(dd, J = 1.6, 7.6 Hz, 2 H), 7.43 (t, J = 7.6 Hz, 2 H), 7.46 (t, J = 7.9 Hz,
solid. mp 290 °C (dec.) H NMR (500 MHz, CDCl ) δ 0.68 (d, J =
3
13
1
2
1
1
H). C NMR (125 MHz, CDCl ) δ 22.6, 23.01, 23.04, 24.6, 25.96,
3
6
.6 Hz, 6 H), 0.85 (d, J = 6.9 Hz, 6 H), 1.03 (d, J = 6.9 Hz, 6 H), 1.04
6.04, 26.5, 27.9, 28.4, 28.9, 120.7, 121.6, 122.4, 124.31, 124.33, 124.4,
25.0, 127.3, 127.6, 130.0, 130.3, 132.6, 135.8, 137.1, 137.7, 145.1,
46.2, 147.5, 148.9, 152.8, 178.0, 179.7. Anal. Calcd C H N O Pd
(
d, J = 6.9 Hz, 6 H), 1.18 (d, J = 6.9 Hz, 6 H), 1.53 (d, J = 6.3 Hz, 6
H), 2.34 (spt, J = 6.8 Hz, 2 H), 3.24 (m, 4 H), 5.82 (dd, J = 5.8, 8.7
Hz, 1 H), 6.25 (td, J = 2.5, 8.7 Hz, 1 H), 6.31 (dd, J = 2.5, 9.8 Hz, 1
H), 6.54 (d, J = 1.6 Hz, 1 H), 7.20 (dd, J = 1.4, 7.7 Hz, 2 H), 7.24 (s, 2
H) 7.25 (d, 2 H, partial overlapping with solvent peak), 7.34 (dd, J =
5
0
62
4
2
(857.49): C, 70.04; H, 7.29; N, 6.53. Found: C, 69.67; H, 7.55; N,
6
.53.
13
SP-4-3-Acetonitrile[1,3-bis[2,6-diisopropylphenyl]-1,3-dihy-
1
.4, 7.7 Hz, 2 H), 7.43 (t, J = 7.6 Hz, 2 H), 7.48 (m, 2 H). C NMR
dro-2H-imidazol-2-ylidene][2-(1-(2,6-diisopropylphenyl)-1H-
(
125 MHz, CDCl ) δ 22.3, 23.0, 23.1, 24.5, 26.0, 26.6, 27.9, 28.5, 29.0,
3
3
imidazol-2-yl-κN )phenyl-κC]palladium(II) Tetrafluoroborate
2
3
1
1
1
1
−
08.9 (d, J = 23.0 Hz), 120.2, 122.2 (d, J = 8.4 Hz), 124.2,
C,F
C,F
(22). Complex 13a (50 mg, 0.07 mmol) and silver tetrafluoroborate
2
24.3, 124.36 (d, J = 18.2 Hz), 124.40, 125.4, 126.6, 130.0, 130.4,
C,F
(
(
15 mg, 0.08 mmol) were dissolved in DCM (4.5 mL) and acetonitrile
0.5 mL) and stirred at room temperature overnight. The reaction
32.3, 133.22, 133.24, 135.9, 145.2, 146.2, 147.8, 152.4, 155.3, 155.3,
1
19
60.6 (d, J = 250.7 Hz), 178.9. F NMR (282 MHz, CDCl ) δ
C,F
3
mixture was filtered through Celite, the solvent was reduced to 1 mL,
and diethyl ether (10 mL) was added, resulting in the precipitation of
an off-white solid. The solvent was removed with a pipet. Purification
by column chromatography on silica gel (dichloromethane/acetoni-
113.4. Anal. Calcd C H ClFN Pd (851.87): C, 67.68; H, 6.86; N,
48
58
4
6
.58. Found: C, 67.38; H, 6.93; N, 6.28.
SP-4-4-Acetato[1,3-bis[2,6-diisopropylphenyl]-1,3-dihydro-
3
2
H-imidazol-2-ylidene][2-(1-methyl-1H-imidazol-2-yl-κN )-
1
trile 9:1) gave 22 (52 mg, 91%) as a colorless solid. mp 130 °C. H
phenyl-κC]palladium(II) (19). Under argon, complex 7 (100 mg, 0.2
mmol) and IPr (120 mg, 0.3 mmol) were dissolved in dry THF (5
mL) and stirred for 1 day at 40 °C. Subsequently, the solvent was
removed in vacuo, and the residue was washed with diethyl ether (3 ×
NMR (500 MHz, CDCl ) δ 0.73−1.43 (m, 24 H), 2.35 (br. s., 3 H),
3
2
.76 (br. s., 2 H), 3.15 (br. s., 2 H), 3.75 (s, 3 H), 6.47 (d, J = 6.9 Hz, 1
H), 6.82 (m, 3 H), 6.99 (t, J = 7.4 Hz, 1 H), 7.14 (d, J = 6.9 Hz, 1 H),
1
3
7
.26−7.34 (m, 4 H), 7.36 (s, 2 H), 7.47 (t, J = 7.6 Hz, 2 H). C NMR
3
mL) and recrystallized from dichloromethane/diethyl ether to give
9 (98 mg, 44%) as a colorless solid. mp 205 °C (dec.). H NMR (500
1
(125 MHz, CDCl ) δ 22.57 (b), 23.0 (b), 26.4 (b), 28.7 (b), 28.9 (b),
3
1
3
5.3, 122.0, 122.9 (b), 122.9, 124.0 (b), 124.5 (b), 125.1 (b), 125.4
MHz, CDCl ) δ 0.82 (d, J = 6.6 Hz, 6 H), 1.00 (d, J = 6.9 Hz, 6 H),
3
(
(
b), 128.1, 130.7, 134.7, 137.2, 145.3 (b), 145.8 (b), 152.3 (C), 176.74
.22 (d, J = 6.9 Hz, 6 H), 1.37 (s, 3 H), 1.45 (d, J = 6.6 Hz, 6 H), 2.95
1
9
C). Two signals are missing, probably due to signal broading.
F
NMR (282 MHz, CDCl ) δ −153.36, −153.31. Anal. Calcd
3
C H BF N Pd (780.06): C, 60.05; H, 6.20; N, 8.98. Found: C,
=
7.6 Hz, 1 H), 7.07 (dd, J = 1.3, 7.6 Hz, 1 H), 7.18 (dd, J = 1.4, 7.7
39 48
4
5
5
9.73; H, 5.98; N, 8.41.
Suzuki−Miyaura Cross-Coupling. A 10 mL crimp vial with a
Hz, 2 H), 7.25 (s, 2 H), 7.33 (dd, J = 1.6, 7.9 Hz, 2 H), 7.39 (t, J = 7.9
Hz, 2 H). 13C NMR (125 MHz, CDCl ) δ 22.7, 23.3, 26.1, 26.3, 26.5,
3
magnetic stir bar was charged with a boronic acid and a base and
capped with a PTFE-faced butyl rubber septum. When the reaction
was run under argon, the vial was evacuated and filled with argon three
times. The aryl chloride, for determination of yields or conversions by
GC−MS, dodecane as internal standard, and a stock solution of the
2
1
8.4, 28.8, 35.2, 121.1, 121.3, 122.7, 124.2, 124.4, 124.7, 125.6, 127.4,
29.9, 135.7, 137.6, 138.0, 144.9, 147.7, 148.9, 152.2, 178.4, 179.6.
Anal. Calcd C H N O Pd (711.24): C, 65.86; H, 6.80; N, 7.88.
39
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4
2
Found: C, 66.15; H, 7.03; N, 7.88.
SP-4-4-Acetato[1,3-bis[2,6-diisopropylphenyl]-1,3-dihydro-
−3
2
1
H-imidazol-2-ylidene][2-(1-(2,6-dimethyl-4-methoxyphenyl)-
precatalyst (10 M in EtOH) were dissolved in a solvent and added
to the vial with a syringe. Subsequently, the reaction mixture was
stirred as indicated.
3
H-imidazol-2-yl-κN )phenyl-κC]palladium(II) (20). Under argon,
complex 9 (100 mg, 0.1 mmol) and IPr (88 mg, 0.2 mmol) were
3
974
dx.doi.org/10.1021/om5004336 | Organometallics 2014, 33, 3966−3976