DAI ET AL.
3 of 9
ammonium hydroxide (15 ml). After reaction for 2 h, the
reaction mixture was heated up to 40ꢀC and reaction for
24 h. After the reaction is finished, the liquid is con-
densed to half the volume, cooled, and precipitated out of
the product. After filtration, the coarse product was rec-
rystallized with anhydrous ethanol to obtain white solid
(7.2 g, 52.3% yield). 1H NMR (CDCl3) δ (ppm): 6.44
(s, 2H, 5-H, 500-H), 7.35 (t, 2H, 4-H, 400-H), 7.81 (m, 2H,
30-H, 50-H), 8.10 (d, 2H, 3-H, 300-H), 8.63 (d, 2H, 6-H, 600-
H), 10.27 (s, 1H, OH). 13C NMR (D2O) δ (ppm): 125.1,
125.4, 128.8, 142.7, 143.0, 146.0, 148.5, 148.7, 166.7. MS:
m/z = 250.1.
solution was changed to 3–4 followed by evaporation
of ethanol in the solution. The precipitate was filtrated
and washed with water and ethanol (10 ml). At last,
being recrystalled with methanol and a white solid was
1
obtained after drying (1.02 g, 55% yield). H NMR
(CD3OD) δ ppm: 9.08 (m, 4H, 6-H, 600-H, 3-H, 300-H), 8.91
(s, 2H, 30-H, 50-H), 8.72 (td, 2H, 4-H, 400-H), 8.14 (td, 2H,
5-H, 500-H), 8.02 (d, 2H, 3-H, 5-H, ph), 7.05 (d, 2H, ph).
13C NMR (CD3OD) δ (ppm): 160.5, 156.3, 155.9, 149.8,
149.1, 136.8, 131.7, 129.4, 123.7, 121.2, 118.4, 116.5. MS:
m/z = 326.1.
2.1.6 | Synthesis of the cobalt complexes
with L1–L5
2.1.4 | Synthesis of 40-carboxylic acid-
2,20:60,200-terpyridine L4
Co(iso-octoate)2 (1 mmol) and ligands (1 mmol) were
added into methanol (30 ml) in the flask, and then, the
solution complex was stirred at 65ꢀC for 2 days. Filtering
out the solid, the filtrate by rotary evaporation device to
remove the methanol and the brown solid was attained.
The solid was dissolved in CH2Cl2, and then n-hexane
was dropped slowly into the solution, solid precipitate
from the solution. After filtrating, the solvent was
removed from the filtrate by rotary evaporation device
and form solid. The solid was dried in the vacuum drying
oven. The molecular structures and parameter of L1-Co
and L2-Co are shown in Tables S1–S12.
2-Acetylpyridine (2.42 g, 20 mmol) and furfural (0.96 g,
10 mmol) were added into ethanol (45 ml), and then
KOH (1.68 g, 30 mmol) and ammonia water (25–28%,
30 ml) were added into the solution under magnetic stir-
ring. The solution was stirred at room temperature for
8 h and the solid precipitate out of solution. The white
solid was obtained by filtration and washed with cold
ethanol (10 ml); the white solid was obtained and then
dried at 55ꢀC under vacuum (1.96 g, 58% yield). And
then, the attained solid (0.9 g, 6.7 mmol) are combined in
H2O (50 ml) made basic (pH 10) with addition KOH.
KMnO4 (1.9 g, 12 mmol) was added into the solution and
heated to reflux for 3 h. The reaction mix is cooled to
room temperature and filtered to remove MnO2. The pH
of the filtrate is adjusted to pH 5 with addition of HCl
(aq, conc.), forming an initial precipitate. The precipitate
was then removed by filtration and washed with water
and copious amounts of diethyl ether and dry to obtain a
2.2 | Catalysis hydrosilylation
General procedure for the catalytic hydrosilylation of ole-
fins was as follows: cobalt salt (0.004 mmol) was charged
into a 10-ml pressure glass tube with sealed cover. Then,
olefin (4.0 mmol) and diphenylsilane (0.88 g, 4.4 mmol)
were charged into the flask, and the resulting mixture
was stirred at 25ꢀC to 60ꢀC for desired time under the
sealed condition. The product was obtained by decanta-
tion separation. The conversion of olefins and selectivity
were determined and quantified by GC analysis on an
Agilent 7890B. And the structure of the products
were determined by GC–MS analysis on an Agilent
7890B-5977B apparatus equipped with a HP-5MS column
(30 m × 0.25 mm × 0.25 μm). Gas chromatography: Trace
DSQ GC Column, split = 50:1, flow = 1.1 ml min−1 con-
stant flow, inlet temperature = 250ꢀC, column tempera-
ture = 55ꢀC (held for 1 min), then 15ꢀC min−1 up to
120ꢀC, then 20ꢀC min−1 up to 200ꢀC, and then
15ꢀC min−1 up to 280ꢀC, (held for 5 min). 1H NMR
(400 MHz) and 13C NMR (100.6 MHz) spectra were
recorded on a Bruker Advance spectrometer. The data of
NMR were listed in the Supporting Information.
1
pure white solid (0.67 g, 60% yield). H NMR (DMSO)
δ (ppm): 7.49–8.02 (m, 4H, 4-H, 5-H, 400-H, 500-H),
8.60–8.61 (m, 2H, 3-H, 300-H), 8.72–8.73 (m, 2H, 6-H, 600-
H), 8.74 (s, 2H, 30-H, 50-H), 13.73 (s, 1H, COOH). 13C
(DMSO) δ (ppm): 167.35, 157.21, 155.49, 150.71, 141.86,
138.77, 126.03, 122.10, 120.87. MS: m/z = 278.1.
2.1.5 | Synthesis of 40-phenol-2,20:60,200-
terpyridine L5
2-Acetylpyridine (1.21 g, 10 mmol) and NaOH (2.0 g)
were added into 15-ml ethanol. After stirring at room
temperature for 20 min, 4-hydroxybenzaldehyde (0.61 g,
5 mmol) was added into the solution and stirred for
10 min, aqueous NH3 (8 ml, 25%) was added to the solu-
tion, and the mixture was stirred at 50ꢀC for 8 h. A large
amount of green solid was obtained when the pH of the