Method for converting carbon dioxide and bicarbonates into formic acid derivatives using a cobalt complex as a catalytic system
A bicarbonate, catalytic conversion technology, applied in organic compound/hydride/coordination complex catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of low hydrogenation yield and high cost
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Embodiment 1
[0064] Preparation of Ligand T2
[0065]
[0066] 1a) Preparation of T2 (tris(2-(diphenylphosphine)phenyl)phosphine):
[0067] Under argon, in a 100 ml three-necked flask equipped with a thermometer and a reflux condenser, 1.5 g (4.4 mmol) of (2-bromophenyl)diphenylphosphine was dissolved in 30 ml of anhydrous THF (tetrahydrofuran) with magnetic stirring middle. The mixture was cooled to -78°C by means of a cooling bath, and 3 ml of a 1.6N solution of n-butyllithium in hexane (4.8 mmol) were added to the mixture at this temperature by means of a funnel within 10 minutes. Stir at this temperature for 30 minutes. Next, 0.13 ml of phosphorus trichloride dissolved in 5 ml of anhydrous THF was added at this temperature within 5 minutes. The reaction mixture can be warmed to room temperature with stirring over one hour, followed by heating at reflux temperature (about 65° C.) for one hour. It was then cooled and the solution was concentrated in vacuo until dryness. 30ml dry ...
Embodiment 2
[0070] Preparation of cobalt complexes
[0071] 2a) Synthesis of [Co(H)T1]:
[0072] 335 mg of T1 (0.5 mmol) were stirred in 5 ml of dry acetone under argon. By adding 129mg, (1 equiv) Co(acac) 2 and 5ml of ethanol to form a black solution. After 10 minutes 38 mg (2 equivalents) of NaBH in 3 ml of ethanol were added 4 . A yellow deposit formed. After 15 minutes it was filtered, washed with ethanol and dried in vacuo. exist 1 A quadruple doublet (J = 42.2 Hz quartet, 70.5 Hzd) was generated between δ -9.32 and -10.01 in H NMR.
[0073] 2b) [Co(H) 2 T1] + x - A generic synthesis of:
[0074] Under argon, 190 mg of the complex [Co(H)T1] was dissolved in 10 ml of distilled THF. Next, 1.5 equivalents of trifluoromethanesulfonic acid (0.035 ml) were added to the solution, whereby its color changed from orange to deep red to black. After stirring for 10 minutes, the corresponding stoichiometric amount of anion source (NaBF 4 , NaBPh 4 , NH 4 PF 6 ) was added to 5ml o...
Embodiment 3
[0086] The formation of sodium formate: 9.5mg (0.028mmol) Co (BF 4 ) 2 ·6H 2 O and 18.75 mg (1 equivalent) of T1 were dissolved in 40 ml of dry methanol. 1.6gNaHCO 3 Place in a 100ml Parr autoclave and transfer the pre-formed catalyst solution into the autoclave. The autoclave was purged three times with hydrogen and the hydrogen was pressurized to 60 bar at room temperature. Next, the reaction mixture was heated to 80° C. and stirred at this temperature for 20 hours. After the reaction time was over, the autoclave was cooled and the pressure was slowly released. The solution was concentrated to dryness in vacuo, and the 1 H NMR at D 2 The yield was determined in O using THF as internal standard (relaxation time 20 sec). All reactions were performed in duplicate to ensure reproducibility.
[0087] When using drill source Co(BF 4 ) 2 ·6H 2 In situ preparation of cobalt catalysts in the presence of O and the ligand tris[(2-diphenylphosphine)ethyl]phosphine (T1) (mole...
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