H. Zhan et al. / Journal of Organometallic Chemistry 894 (2019) 1e9
3
added to a 50 mL round bottom flask equipped with a stirring bar
in freshly distilled triethylamine (10 mL) and CH
2
Cl
2
(30 mL) solu-
and a condenser. Bromine (90 mg, 0.56 mmol) was added dropwise
tion mixture was added CuI (5 mg, 0.015 mmol), Pd(OAc)
2
(5 mg,
to the flask at room temperature. After stirring at room tempera-
ture for 10 min, the reaction mixture was heated to 60 C and
stirred for an additional hour. After cooling, the reaction mixture
2 2
was poured into water (45 mL) and extracted with CH Cl . The
combined organic layer was dried over anhydrous sodium sulfate,
filtered and concentrated under reduced pressure. The crude
0.015 mmol) and PPh (20 mg, 0.044 mmol). After the solution was
3
ꢀ
ꢀ
stirred for 30 min at 0 C, trimethylsilylacetylene (0.15 mL,
0.87 mmol) was added and the suspension was stirred for 30 min in
an ice-bath before being warmed to room temperature. After
reacting for 30 min at room temperature, the mixture was heated to
ꢀ
64 C for 1e2 days. Once the reaction was completed based on TLC
product was recrystallized from the solvent mixture of CH
2
Cl
2
and
monitoring, the solvent mixture was evaporated under reduced
methanol to give the product L1-Br as a purple solid (156 mg, 86%).
pressure. The crude product was purified by column chromatog-
1
H NMR (400 MHz, CDCl
d, J ¼ 4.2 Hz, 2H, Ar), 3.98 (t, J ¼ 7.9 Hz, 4H, C
H, C 17), 1.41e1.25 (m, 20H, C
17), 0.88 (t, J ¼ 7.0 Hz, 6H, C
C NMR (100 MHz, CDCl /ppm): 161.05 (C]O), 139.01, 135.36,
31.66, 131.11, 119.16, 107.82 (Ar), 53.43, 42.29, 31.76, 29.98, 29.15,
3
,
d
/ppm): 8.68 (d, J ¼ 4.2 Hz, 2H, Ar), 7.24
17), 1.73e1.68 (m,
17);
raphy on silica gel with a solvent combination of CH
2 2
Cl /hexane
(
8
H
(1:1.5) as eluent to provide the pure product L1-TMS (148 mg, 71%)
1
4
8
H
8
H
8
H
as a purple solid. H NMR (400 MHz, CDCl
J ¼ 4.1 Hz, 2H, Ar), 7.33 (d, J ¼ 4.1 Hz, 2H, Ar), 4.03 (t, J ¼ 7.9 Hz, 4H,
17), 1.74e1.60 (m, 4H, C 17), 1.43e1.27 (m, 20H, C 17), 0.88 (t,
J ¼ 7.0 Hz, 6H, C 17), 0.29 (s, 18H, TMS); C NMR (100 MHz, CDCl
/ppm): 161.40 (C]O),139.45,135.58,134.04,130.61,128.71,108.96,
3
, d/ppm): 8.86 (d,
1
3
3
, d
1
2
C
8
H
8
H
8
H
þ
13
6.82, 22.63, 14.10 (C
8
H17); FAB-MS: m/z 681.9 [M] .
8
H
3
,
The similar procedure was used to prepare L2-Br.
d
1
L2-Br: Purple solid, yield: 81%. H NMR (400 MHz, CDCl
3
,
d/
104.62 (Ar), 96.91, 77.62 (C^C), 42.61, 32.05, 30.28, 29.45, 29.43,
þ
ppm): 8.66 (d, J ¼ 4.2 Hz, 2H, Ar), 7.22 (d, J ¼ 4.2 Hz, 2H, Ar),
27.12, 22.91, 14.40 (C
8
H
17), 0.28 (TMS); FAB-MS: m/z 716.2 [M] .
3
.99e3.88 (m, 4H, EH), 1.83e1.82 (m, 2H, EH), 1.39e1.24 (m, 16H,
The same procedures were applied to prepare compounds L2-
13
EH), 0.90e0.85 (m, 12H, EH); C NMR (100 MHz, CDCl
3
,
d
/ppm):
TMS and L3-TMS.
1
1
4
61.38 (C]O), 139.38, 135.42, 131.46, 131.11, 119.04, 107.94 (Ar),
L2-TMS: Purple solid, yield: 83%. H NMR (400 MHz, CDCl
3
,
d
/
5.96, 39.05, 30.10, 28.26, 23.48, 23.03, 14.04, 10.43 (EH). FAB-MS:
ppm): 8.82 (d, J ¼ 4.2 Hz, 2H, Ar), 7.32 (d, J ¼ 4.2 Hz, 2H, Ar),
þ
m/z 682.2 [M] .
4.01e3.94 (m, 4H, EH), 1.86e1.84 (m, 2H, EH), 1.39e1.22 (m, 16H,
13
EH), 0.90e0.85 (m, 12H, EH), 0.29 (s, 18H, TMS); C NMR (100 MHz,
CDCl /ppm): 161.77 (C]O), 139.87, 135.56, 133.84, 130.71, 128.62,
2.2.3. Synthesis of L3-HT
3
, d
Pd(PPh (13 mg, 0.011 mmol) was added to a solution of
compound L2-Br (150 mg, 0.22 mmol) and tributyl(4-
hexylthiophen-2-yl)stannane (312 mg, 0.68 mmol) in dry toluene
3
)
4
109.14 (Ar), 104.52, 96.94 (C^C), 46.34, 39.33, 30.39, 28.61, 23.80,
þ
23.34, 14.33, 10.71 (EH), ꢁ0.0035 (TMS). FAB-MS: m/z 716.4 [M] .
1
L3-TMS: Deep purple solid, yield: 77%. H NMR (400 MHz, CDCl
3
,
(
20 mL) under the nitrogen atmosphere. The reaction mixture was
d
/ppm): 8.89 (d, J ¼ 4.2 Hz, 2H, Ar), 7.28 (d, J ¼ 4.2 Hz, 2H, Ar), 7.05
(s, 2H, Ar), 4.05e4.02 (m, 4H, EH), 2.67 (d, J ¼ 7.4 Hz, 4H, C 13),1.90
(m, 2H, EH), 1.66e1.61 (m, 4H, C 13), 1.53e1.29 (m, 28H,
13þEH), 0.92e0.86 (m, 18H, C 13þEH), 0.26 (s, 18H, TMS);
NMR (100 MHz, CDCl /ppm): 161.69 (C]O), 150.12, 142.27,
refluxed for 1e2 days. Once the reaction was completed based on
TLC monitoring, the solvent was removed. The residue was purified
by silica gel column chromatography eluting with CH
6
H
6
H
13
2
Cl
2
/hexane
C
6
H
6
H
C
(
1:1.5) to give the compound L3-HT (164 mg, 87%) as a purple solid.
3
, d
1
H NMR (400 MHz, CDCl
d, J ¼ 4.1 Hz, 2H, Ar), 7.15 (s, 2H, Ar), 6.92 (s, 2H, Ar), 4.10e3.99 (m,
H, EH), 2.61 (t, J ¼ 7.6 Hz, 4H, C 13), 1.92e1.91 (m, 2H, EH),
.68e1.60 (m, 4H, C 13), 1.53e1.28 (m, 28H, C
13þEH), 0.93e0.86
/ppm): 161.63 (C]
O), 144.67, 143.14, 139.44, 136.63, 135.81, 127.87, 126.45, 124.44,
21.06, 108.21 (Ar), 45.93, 39.94, 31.66, 30.46, 30.38, 28.98, 28.60,
3
,
d
/ppm): 8.90 (d, J ¼ 4.1 Hz, 2H, Ar), 7.28
139.40, 136.69, 135.76, 128.50, 125.98, 125.08, 119.16, 108.62 (Ar),
103.64, 96.98 (C^C), 46.05, 39.32, 31.64, 30.43, 30.07, 29.66, 28.98,
28.65, 23.75, 23.22, 22.69, 14.21, 10.66 (C
MS: m/z 1049.5 [MþH] .
(
4
1
6
H
6
H13þEH), 0.10 (TMS). FAB-
þ
6
H
6
H
3
, d
13
(
m,18H, C
6
H
13þEH); C NMR (100 MHz, CDCl
2.2.6. Synthesis of ligands L1, L2 and L3
1
L1: To a solution of L1-TMS (80 mg, 0.11 mmol) in 8 mL of CH
2 2
Cl
2
3.67, 23.15, 22.62, 14.12, 10.58 (C
6
H
13þEH). FAB-MS: m/z 856.5
and 5 mL of methanol was added K CO (33 mg, 0.24 mmol) and the
2
3
þ
[M] .
mixture was stirred for 4e5 h at room temperature under the ni-
trogen atmosphere. Once the reaction was completed based on TLC
monitoring, the mixture was poured into 20 mL water and the
organic phase was extracted by CH Cl . The combined organic layer
2 2
was washed with saturated brine, dried over anhydrous sodium
2
.2.4. Synthesis of L3-Br
N-Bromosuccinimide (NBS) (36 mg, 0.20 mmol) was added to a
solution of compound L3-HT (86 mg, 0.1 mmol) in chloroform
15 mL), and the reaction mixture was stirred overnight at room
(
sulfate, filtered and concentrated under reduced pressure. The
temperature in the dark. Once the reaction was completed based on
TLC monitoring, the solvent was removed. The residue was purified
crude product was recrystallized from CH
2
Cl
a purple solid of L1 (47 mg, 75%). H NMR (400 MHz, CDCl
8.88 (d, J ¼ 4.1 Hz, 2H, Ar), 7.40 (d, J ¼ 4.1 Hz, 2H, Ar), 4.03 (t,
J ¼ 7.9 Hz, 4H, C 17), 3.60 (s, 2H, C^CH), 1.74e1.71 (m, 4H, C
1.42e1.28 (m, 20H, C
(100 MHz, CDCl /ppm): 161.12 (C]O), 139.26, 135.20, 134.20,
2
and methanol to give
1
3
, d/ppm):
by column chromatography on silica gel eluting with CH
ane (1:2) and precipitated from the solvent mixture of CH
methanol to give the pure product L3-Br (85 mg, 85%) as a deep
2
Cl
2
/hex-
2
Cl
2
and
8
H
8
H
17),
13
8
H17), 0.87 (t, J ¼ 7.0 Hz, 6H, C
8
H17); C NMR
1
purple solid. H NMR (400 MHz, CDCl
Ar), 7.20e7.19 (m, 2H, Ar), 7.00e6.98 (m, 2H, Ar), 4.07e4.98 (m, 4H,
EH), 2.57e2.54 (m, 4H, C 13), 1.90e1.88 (m, 2H, EH), 1.64e1.57 (m,
13), 1.39e1.28 (m, 28H, C
13þEH), 0.92e0.86 (m, 18H,
13þEH); C NMR (100 MHz, CDCl /ppm): 161.56 (C]O),
3
,
d
/ppm): 8.87e8.84 (m, 2H,
3
, d
130.64, 127.16, 108.78 (Ar), 85.58, 76.23 (C^C), 42.35, 31.76, 30.01,
þ
6
H
29.16, 26.83, 22.63, 14.10 (C
8
H
17); FAB-MS: m/z 572.4 [M] ; IR (KBr):
ꢁ
1
4
C
1
H, C
6
H
6
H
n
(C^C) 2094 cm
The same procedures were applied to prepare other ligands L2
and L3.
L2: Purple solid, yield: 82%. H NMR (400 MHz, CDCl
.
13
6
H
3
, d
43.56, 141.91, 139.32, 136.50, 135.56, 128.18, 125.77, 124.56, 110.01,
1
108.40 (Ar), 45.93, 39.22, 31.59, 30.34, 29.63, 29.58, 28.91, 28.57,
3
, d/ppm):
2
3.65, 23.12, 22.59, 14.11, 10.55 (C
6
H13þEH); FAB-MS: m/z 1014.3
8.84 (d, J ¼ 4.1 Hz, 2H, Ar), 7.38 (d, J ¼ 4.1 Hz, 2H, Ar), 4.00e3.97 (m,
þ
[M] .
4H, EH), 3.60 (s, 2H, C^CH), 1.85e1.84 (m, 2H, EH), 1.37e1.25 (m,
1
3
1
3
6H, EH), 0.90e0.87 (m, 12H, EH); C NMR (100 MHz, CDCl , d/
2
.2.5. Synthesis of L1-TMS, L2-TMS and L3-TMS
L1-TMS: To an ice-cooled mixture of L1-Br (199 mg, 0.29 mmol)
ppm): 161.45 (C]O), 139.64, 135.24, 134.05, 130.71, 127.04, 108.91
(Ar), 85.51, 76.26 (C^C), 46.02, 39.11, 30.09, 28.25, 23.47, 23.05,