m × 0.25 μm × 0.25 mm). N2 was used as the carrier gas. GC-MS measurements were performed on a 7890A-G C/5975C-MSD
instrument with a 19091S-433HP-5MS column (30 m × 250 μm × 0.25 μm). Helium was used as the carrier gas. IR spectra was
measured from 4000 to 500 cm-1 with a Bruker TENSOR 27 FT-IR instrument. UV spectra was recorded from 900 to 200 nm with a
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UNICO UV-2802 UV-Vis spectrophotometer. H and 13C NMR spectra (500 and 125 MHz, respectively) were recorded with a
Bruker AV 500 MHz spectrometer. The thermograv imetric curve was measured with NETZSCH STA-449C Thermogravimetric
Analyzer and N2 was used as the protective gas. Analysis of cobalt content was performed on an ICP-AES (IRIS INTREPID Ⅱ
XSP).
4.02 Preparation of NaCo(CO)4
All chemicals were chilled for 2 h at 0 °C. Excess NaOH was put in a 100 mL round-bottom flask which was placed at once on a
Schlenk line. After thorough evacuation, the flask was opened to a continuous flow of N2 and charged with Co2(CO)8 (1.22 g,
stabilized by n-hexane). Then, THF (40 mL) was added slowly with stirring, while a gentle stream of N2 was maintained. The solution
was stirred for 1-2 h, and then formed a pinkish purple precipitate . The light yellow solution was separated from the precipitate by
centrifuging for 5min at the speed of 3000r/min, and the precipitate was washed with THF 40 mL to afford NaCo(CO)4.
4.03 Preparation of Chloro-Substituted 1-Butyl-3-poly (ethylene glycol) Imidazole
Refrigerated imidazole (1.36 g, 20 mmol) and n-hexane (15 mL) were placed into an autoclave (75 mL). Refrigerated ethylene oxide
(21.5 mL, 425.6 mmol) liquid was subsequently added into the autoclave with stirring, which was then closed and flushed with N2.
The mixture in the autoclave was stirred at room temperature for 4 h, and then at 60 °C for 6 h. The reactor was then cooled to room
temperature and depressurized. After removing the solvent by reduced pressure distillation, the mixture was dried under vacuum to
obtain compound 2 as a dark brown viscous liquid. Cold (~0℃)Et2O was added to wash out the unreacted imidazole. The top Et2O
layer was decanted off, and the product was repeatedly washed with fresh Et2O, after which it was dried in vacuo fo about 12h to
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abtain the pure compound 2[41]. 3-poly (ethylene glycol) Imidazole (compound 2): H NMR (5ooMHz, CDCl3, δ): 7.55 (s, 1H,
N-CH=N), 7.38 (br s, 1H, N+CHCH), 7.01 (br s, 1H, N+CH), 4.12 (s, 1H, OH), 2.78-3.64 (br m, 47.1H, CH2CH2O). The average
number of ethylene oxide units in the polyether chain was calculated using the increased weight of the products [42,43]. Then 1-butyl
chloride (9.28 g, 100 mmol) as reactant and solvent, and compound 2 (20 mmol) were placed in an autoclave and stirred under N2
(6.0 MPa) for 10 h at 90 °C. The reactor was then cooled to room temperature and depressurized. Unreacted materials were
removed by vacuum distillation, and chloro-subs tituted1-butyl-3-poly (ethylene glycol) imidazole was obtained. The mixture was
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used in next step , without further purification. H NMR (5ooMHz, CDCl3, δ): 7.61 (s, N-CH=N), 7.37 (br s, N+CH), 7.03 (br s,
N+CH), 4.30 (br s, 2H, N+CH2), 4.12 (s, OH), 2.78-3.64 (br m, CH2CH2O), 1.89 (br s, 2H, N+CH2CH2), 1.39 (br s, 2H,
N+CH2CH2CH2), 0.97(br s, 3H, N+CH2CH2CH2CH3). 13C NMR (125,7MHz, CDCl3,δ): 136.21,122.76,121.15,71.87,69.68,69.46,
60.52,48.79,31.26,18.62,12.72.
4.04 Synthesis of Compounds 4a-c
All procedures were completed on a Schlenk line under a N2 flow. NaCo(CO)4-THF solution (60 ml, containing 5.4 mmol of
[Co(CO)4]-) was placed in a 3-necked flask, and compound 3 in THF (15 ml, containing 5.4 mmol of 3) was added with stirring at
room temperature. The ion exchange reaction completed rapidly, forming a NaCl precipitate, which could be removed through
filtering by sand core funnel under N2 protection. Then the remaining solution was added to H2O/CH2Cl2 biphasic system, the
compound 4 and its solvent THF could preferentially enter into CH2Cl2 organic phase. Both NaCo(CO)4 and by-products were
then dissolved and commixed in water[25]. Therefore, after simple phase-separation, product 4 was obtained directly from orangic
solution. Solvent THF and CH2Cl2 could be removed by reduced pressure distillation, compounds 4a-c were obtained. 13C
NMR(125,7MHz,CDCl3,δ) : 136.21,122.76,121.15,71.87,69.68,69.46,60.52,48.79,31.26,18.62,12.72.FT-IR (KBr): γmax/cm-1
3381.33, 3142.10, 2821.85, 2003.74, 1885.89, 1660.08, 1564.74, 1454.85, 1350.71, 1297.69, 1250.22, 1108.48, 950.28, 885.60,
845.16, 754.60.
4.05 Hydroesterification of 4-isobutylstyrene Catalyzed by 4c in the TPSC System
Freshly distilled 4-isobutylstyrene (17.4 mmol) and methanol (18.5 mmol), Pyridine (2.1 mmol), catalyst 4c (1.27 mmol), and 25
mL THF/n-heptane mixture (v/v = 1.5:1) were added to an autoclave (75 mL). The autoclave was closed, the air in the autoclave
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was replaced with N2 and CO for 3 times in turn. The mixture was heated to 100~160°C and stirred for 16~32h under the pressure