Synthesis and photocatalytic application of carbazole terpyridyl nickel catalyst

Abstract

The invention belongs to the technical field of preparation of transition metal organic photocatalysts, and particularly relates to design and a preparation method of a carbazole terpyridyl nickel catalyst. The invention aims to design and synthesize a carbazole terpyridyl nickel catalyst with light / nickel synergistic catalytic activity. The preparation method comprises the following specific synthesis steps: reacting different types of alpha-pyridone pyridinium and alpha, beta-unsaturated ketone in methanol, and carrying out suction filtration, washing, drying and other operations to obtain the corresponding carbazole terpyridyl ligand. The carbazole terpyridyl ligand and anhydrous nickel bromide are subjected to a heating reflux reaction in a tetrahydrofuran solution, and the corresponding carbazole terpyridyl nickel catalyst is obtained through methanol washing, suction filtration, drying and other operations. The terpyridyl nickel catalyst has high catalytic activity in a C-N, C-O and C-S coupling reaction promoted by visible light.

Description

Technical Field

[0001] This invention belongs to the field of transition metal organophotocatalyst preparation technology, specifically relating to the preparation of a class of carbazole-modified terpyridine nickel catalysts. Background Technology

[0002] In recent years, with the deepening development of green chemistry concepts, the development of sustainable transition metal organocatalytic systems has attracted much attention from chemists. The rapid development of photocatalysis technology has introduced new impetus to the field of transition metal organocatalysis, providing catalytic systems with milder reaction conditions, broader substrate applicability, and better selectivity. The design and use of catalysts determine the efficiency and selectivity of the catalytic system. Among them, 2,2':6',2"-tripyridine (abbreviated as terpyridine), as a tridentate nitrogen ligand, is widely used in the design of various types of transition metal organocatalysts due to its excellent coordination properties, electronic regulation capabilities, and skeletal rigidity. For example, nickel terpyridine complexes are stable transition metal catalysts that have shown excellent catalytic performance in photocatalytic reactions such as carbon dioxide reduction, carbon-carbon coupling, and carbon-nitrogen coupling. However, in these developed catalytic systems, nickel terpyridine complexes require additional photocatalysts (such as iridium and ruthenium complexes) to exert their catalytic effect, constructing a photo / nickel dual catalytic pathway, which increases the complexity of the reaction system and the reaction cost. Therefore, designing and developing a novel class of nickel terpyridine complexes that simultaneously play the dual central role of transition metal catalysis and photocatalysis is of great significance for effectively simplifying catalytic reaction systems and reducing reaction costs.

[0003] 2,4,5,6-Tetra(9-carbazolyl)-isophthalonitrile (abbreviated as 4CzIPN) is a class of organic photosensitizers widely used in photocatalytic reactions. In-depth structural analysis of 4CzIPN revealed that carbazole is a strong electron-donating group, while the cyano group is a strong electron-withdrawing group. Therefore, the inventors of this patent envision introducing carbazole into the terpyridine framework to leverage its strong electron-donating effect, while the nickel center coordinated with nitrogen can act as an electron-withdrawing center. This effectively simulates a catalytic mechanism similar to that of the 4CzIPN photosensitizer. The inventors believe that this designed carbazole-terpyridine nickel complex not only effectively utilizes the catalytic properties of nickel but also acts as a photocatalyst, thus avoiding the use of external noble metal photocatalysts or organic photosensitizers. The successful development of this carbazole-terpyridine nickel complex is of great scientific significance for developing a simple and efficient photo / nickel synergistic catalytic system. Summary of the Invention

[0004] The purpose of this invention is to design and prepare a carbazole terpyridine nickel catalyst with high catalytic activity, and to further demonstrate the photo / nickel synergistic catalytic activity of the catalyst itself using CN, CO, and CS coupling reactions. The specific structure of the carbazole terpyridine nickel catalyst with photo / nickel synergistic catalytic activity designed and synthesized in this invention is shown below:

[0005]

[0006] Where: H represents hydrogen. Cat.1-Cat.3 are abbreviations for three types of carbazole terpyridine nickel catalysts.

[0007] This invention involves reacting different types of α-pyridone pyridinium salts and α,β-unsaturated ketones in methanol, followed by filtration, washing, and drying to obtain the corresponding carbazole terpyridine ligands. The carbazole terpyridine ligands are then reacted with anhydrous nickel bromide in tetrahydrofuran solution under reflux, followed by washing with methanol, filtration, and drying to obtain the corresponding carbazole terpyridine nickel catalyst.

[0008] The reaction formula is as follows:

[0009]

[0010] The synthesis method of the carbazole terpyridine nickel catalyst designed in this invention is as follows:

[0011] Under a nitrogen atmosphere, α-pyridone pyridinium salt (1, 2 mmol), α,β-unsaturated ketone (2, 2 mmol), ammonium acetate (20 mmol), and methanol (10 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 90°C for 12 hours. After cooling to room temperature, the solid was obtained by filtration and washed three times with methanol. After vacuum drying, the target product, carbazole terpyridine ligand (L), was obtained.

[0012] Under a nitrogen atmosphere, carbazole terpyridine ligand (L) (1 mmol), anhydrous nickel bromide (1.3 mmol), and tetrahydrofuran (15 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 70°C for 12 hours. After cooling to room temperature, the solid was obtained by filtration and washed three times with water. After vacuum drying, the target product, carbazole terpyridine nickel catalyst, was obtained.

[0013] The carbazole terpyridine nickel catalyst designed and synthesized in this invention was used for visible light-promoted CN, CO and CS coupling reactions, further demonstrating the excellent photo / nickel synergistic catalytic activity of the catalyst itself.

[0014] The specific operational procedure for the visible light-promoted CN coupling reaction is as follows:

[0015] Under a nitrogen atmosphere, 3-iodopyridine (0.4 mmol), catalyst Cat.1 (1 mol%), tetrahydropyrrole (1.2 mmol), and N,N-dimethylformamide (4 mL) were added sequentially to a Schlenk flask. The mixture was stirred for 12 hours under blue LED light (427 nm). After the reaction was complete, the mixture was extracted with ethyl acetate (3 × 25 mL), and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product was purified by column chromatography and dried under vacuum to obtain a colorless oily product. The reaction formula is as follows:

[0016]

[0017] The specific operational procedure for the visible light-promoted CO coupling reaction is as follows:

[0018] Under a nitrogen atmosphere, 3-iodopyridine (0.4 mmol), catalyst Cat.1 (1 mol%), 3-phenylpropanol (1.2 mmol), 2-tert-butyl-1,1,3,3-tetramethylguanidine (tBuMG, 1.2 mmol), and N,N-dimethylformamide (5 mL) were added sequentially to a Schlenk flask. The mixture was stirred for 24 hours under blue LED light (427 nm). After the reaction was complete, the mixture was extracted with ethyl acetate (3 × 25 mL), and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product was purified by column chromatography and dried under vacuum to obtain a colorless oily product. The reaction formula is as follows:

[0019]

[0020] The specific operational procedure for the visible light-promoted CS coupling reaction is as follows:

[0021] Under a nitrogen atmosphere, 3-iodopyridine (0.4 mmol), catalyst Cat.1 (1 mol%), 4-methoxybenzylthiol (1.2 mmol), and N,N-dimethylacetamide (4 mL) were added sequentially to a Schlenk flask. The mixture was stirred for 12 hours under blue LED light (427 nm). After the reaction was complete, the mixture was extracted with ethyl acetate (3 × 25 mL), and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product was purified by column chromatography and dried under vacuum to obtain a colorless oily product. The reaction formula is as follows:

[0022] Attached Figure Description

[0023] Figure 1 This is a high-resolution mass spectrometry analysis of the carbazole terpyridine nickel catalyst Cat.1 prepared in Example 1.

[0024] Figure 2 This is a high-resolution mass spectrometry analysis of the carbazole terpyridine nickel catalyst Cat2 prepared in Example 2.

[0025] Figure 3 This is a high-resolution mass spectrometry analysis of the carbazole terpyridine nickel catalyst Cat.3 prepared in Example 3.

[0026] Figure 4 The image shows the 1H NMR spectrum of the product of the CN coupling reaction catalyzed by the carbazole terpyridine nickel catalyst Cat.1 implemented in Example 4.

[0027] Figure 5 The image shows the 1H NMR spectrum of the product of the CO coupling reaction catalyzed by the carbazole terpyridine nickel catalyst Cat.1 implemented in Example 7.

[0028] Figure 6 The image shows the 1H NMR spectrum of the product of the CS coupling reaction catalyzed by the carbazole terpyridine nickel catalyst Cat.1 implemented in Example 9. Detailed Implementation

[0029] The present invention will be further described in detail below through embodiments, but the present invention is not limited to the following embodiments.

[0030] Example 1: Preparation of Carbazole Tripyridine Nickel Catalyst Cat.1:

[0031]

[0032] Synthesis of compound S1: Under a nitrogen atmosphere, carbazole (10 mmol), 1-(5-bromopyridin-2-yl)acetone (10 mmol), 18-crown ether-6 (1 mmol), potassium carbonate (12.5 mmol), and NN′-dimethyl-1,3-dimethylurea (20 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 190°C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature and quenched with 2M hydrochloric acid (25 mL). The aqueous phase was extracted with dichloromethane (3 × 80 mL), and the organic phases were combined. The organic phase was washed sequentially with 25% ammonia (60 mL) and water (100 mL), and dried with anhydrous sodium sulfate. The organic solvent was removed by filtration and vacuum. The product, compound S1, was purified by column chromatography (using petroleum ether:ethyl acetate = 10:1 as eluent) and vacuum drying to obtain a white solid. Yield: 1.7 g, 61%.

[0033] NMR analysis: 1H NMR (600MHz, CDCl3): δ=8.99 (d, J=1.98Hz, 1H), 8.31 (q, J=2.91Hz, 1H), 8.16 (d, J=7.76Hz, 2H), 8.09 (dd, J=2.46Hz, J=8.31Hz, 1H), 7.48-7.44 (m, 4H), 7.37-7.34 (m, 2H), 2.82 (s, 3H).

[0034] Synthesis of compound 1a: Compound S1 (3 mmol), elemental iodine (3.3 mmol), and pyridine (10 mL) were added sequentially to a round-bottom reaction flask. The mixture was stirred at 90°C for 4 hours. After the reaction was complete, the mixture was cooled to room temperature. The pyridine was removed by filtration, and the filter cake was washed with diethyl ether (3 × 20 mL). After recrystallization from ethanol and vacuum drying, the target product compound 1a was obtained as a gray solid. Yield: 1.2 g, 81%.

[0035] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=9.26 (d, J=1.9Hz, 1H), 9.09 (d, J=5.8Hz, 2H), 8.78 (t, J=7.8Hz, 1H), 8.49 (dd, J=8.3H z, J=2.2Hz, 1H), 8.37 (d, J=8.3Hz, 1H), 8.34-8.31 (m, 4H), 7.55-7.51 (m, 4H), 7.41-7.38 (m, 2H), 6.63 (s, 2H).

[0036] Synthesis of compound 2a: Under a nitrogen atmosphere, S2 (1 mmol), S1 (1 mmol), potassium hydroxide (2 mmol), and methanol (2 mK) were added sequentially to a round-bottom reaction flask. The mixture was stirred at 60°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature. The mixture was filtered, and the filter cake was washed with methanol (3 × 10 mL). After purification by column chromatography (using dichloromethane as eluent) and vacuum drying, the target product compound 2a was obtained as a yellow solid. Yield: 0.359 g, 51%.

[0037] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=9.01 (s, 1H), 8.54 (d, J=16.0Hz, 1H), 8.46 (d, J=8.1Hz, 1H), 8. 20-8.11 (m, 10H), 7.91 (s, 1H), 7.62 (d, J=8.0Hz, 4H), 7.52-7.44 (m, 8H), 7.37 (s, 6H).

[0038] Synthesis of carbazole terpyridine ligand L1: Under a nitrogen atmosphere, 1a (2 mmol), 2a (2 mmol), ammonium acetate (20 mmol), and methanol (10 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 90 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature. The mixture was filtered, and the filter cake was washed with methanol (3 × 15 mL). After vacuum drying, the target product, carbazole terpyridine ligand L1, was obtained as a yellow solid. Yield: 1.8 g, 91%.

[0039] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=9.00 (t, J=3.0Hz, 5H), 8.32 (d, J=1.8Hz, 2H), 8.20 (q, J=7.7Hz, 7.5H), 8.15 (dd, J=8.3Hz, J=2.5Hz ,2.5H), 8.00 (t, J=1.8Hz, 1H), 7.67 (d, J=8.2Hz, 4H), 7.52 (t, J=6.2Hz, 8H), 7.48 (t, J=7.3Hz, 4H), 7.36 (q, J=7.3Hz, 9H).

[0040] Synthesis of Carbazole Tripyridine Nickel Catalyst Cat.1: Under a nitrogen atmosphere, L1 (1 mmol), anhydrous nickel bromide (1.3 mmol), and tetrahydrofuran (15 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 70 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature. The filter cake was filtered and washed with water (3 × 10 mL), and then dried under vacuum to obtain the red solid target product, carbazole tripyridine nickel catalyst Cat.1. Yield: 1.2 g, 97%.

[0041] Example 2: Preparation of Carbazole Tripyridine Nickel Catalyst Cat.2:

[0042]

[0043] Synthesis of compound 2b: Under a nitrogen atmosphere, S3 (1 mmol), S1 (1 mmol), potassium hydroxide (2 mmol), and methanol (2 mL) were added sequentially to a round-bottom reaction flask. The mixture was stirred at 60°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature. The mixture was filtered, and the filter cake was washed with methanol (3 × 10 mL). After purification by column chromatography (using petroleum ether: dichloromethane = 1:1 as eluent), and vacuum drying, the target product compound 2b was obtained as a yellow solid. Yield: 0.399 g, 74%.

[0044] NMR analysis: 1H NMR (600MHz, CDCl3): δ=9.08 (d, J=2.0Hz, 1H), 8.52 (d, J=4.2Hz, 1H), 8.50 (d, J=3.3Hz, 1H), 8.19-8.11 (m, 6H) , 8.01 (d, J = 8.3Hz, 2H), 7.68 (d, J = 8.2Hz, 2H), 7.54-7.44 (m, 8H), 7.39 (t, J = 7.4Hz, 2H), 7.34 (t, J = 7.4Hz, 2H).

[0045] Synthesis of carbazole terpyridine ligand L2: Under a nitrogen atmosphere, 1a (2 mmol), 2a (2 mmol), ammonium acetate (20 mmol), and methanol (10 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 90 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature. The mixture was filtered, and the filter cake was washed with methanol (3 × 15 mL). After vacuum drying, the target product, carbazole terpyridine ligand L2, was obtained. Yield: 1.4 g, 86%.

[0046] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=9.06 (d, J=2.4Hz, 2H), 9.03 (d, J=8.4Hz, 2H), 9.01 (s, 2H), 8.24 (d, J=8.3Hz ,2H), 8.21-8.16(m, 8H), 7.80(d, 2H), 7.53(d, J=8.2Hz, 6H), 7.50-7.47(m, 6H), 7.38-7.33(m, 6H).

[0047] Synthesis of Carbazole Tripyridine Nickel Catalyst Cat.2: Under a nitrogen atmosphere, L2 (1 mmol), anhydrous nickel bromide (1.3 mmol), and tetrahydrofuran (15 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 70 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature. The filter cake was filtered and washed with water (3 × 10 mL), and then dried under vacuum to obtain the target product, carbazole tripyridine nickel catalyst Cat.2, as a yellow solid. Yield: 0.972 g, 95%.

[0048] Example 3: Preparation of Carbazole Tripyridine Nickel Catalyst Cat.3:

[0049]

[0050] Synthesis of compound 1b: Compound S4 (3 mmol), elemental iodine (3.3 mmol), and pyridine (10 mL) were added sequentially to a round-bottom reaction flask. The mixture was stirred at 90°C for 4 hours. After the reaction was complete, the mixture was cooled to room temperature. The pyridine was removed by filtration, and the filter cake was washed with diethyl ether (3 × 20 mL). The product, compound 1b, was obtained as a gray solid after recrystallization from ethanol and drying under vacuum. Yield: 0.831 g, 85%.

[0051] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=8.83-8.78 (m, 4H), 8.63-8.54 (m, 1H), 8.22-8.11 (m, 4.5H), 8.02-8.11 (m, 0.5H), 7.82-7.80 (m, 1H).

[0052] Synthesis of compound 2c: Under a nitrogen atmosphere, S2 (1 mmol), S4 (1 mmol), potassium hydroxide (2 mmol), and methanol (2 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 60°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature. The mixture was filtered, and the filter cake was washed with methanol (3 × 10 mL). After purification by column chromatography (using petroleum ether: dichloromethane = 1:1 as eluent), and vacuum drying, the target product compound 2c was obtained as a yellow solid. Yield: 0.286 g, 63%.

[0053] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=8.69 (t, J=2.34Hz, 1H), 8.44 (d, J=16.08Hz, 1H), 8.20-8.17 (m, 5H), 8.0 7-8.05 (m, 3H), 7.89-7.86 (m, 2H), 7.57 (d, J=8.22Hz, 4H), 7.49-7.46 (m, 5H), 7.35-7.33 (m, 4H).

[0054] Synthesis of carbazole terpyridine ligand L3: Under a nitrogen atmosphere, 1b (2 mmol), 2c (2 mmol), ammonium acetate (20 mmol), and methanol (10 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 90 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature. The mixture was filtered, and the filter cake was washed with methanol (3 × 15 mL). After vacuum drying, the target product, carbazole terpyridine ligand L3, was obtained as a white solid. Yield: 1.1 g, 85%.

[0055] NMR analysis: 1H NMR (600MHz, CDCl3): δ = 8.83 (s, 1H), 8.68 (d, J = 8.5Hz, 2H), 8.64-8.61 (m, 1H), 8.23-8.18 (m, 5H), 8.12 (d, J = 7.6Hz, 1H), 8.09-8.04 (m, 1H), 7.92-7.86 (m, 3H), 7.65 (d, J=8.3Hz, 1H), 7.60 (d, J=8.2Hz, 3H), 7.50-7.47 (m, 4H), 7.37-7.33 (m, 7H).

[0056] Synthesis of Carbazole Tripyridine Nickel Catalyst Cat.3: Under a nitrogen atmosphere, L3 (1 mmol), anhydrous nickel bromide (1.3 mmol), and tetrahydrofuran (15 mL) were added sequentially to a Schlenk flask. The mixture was stirred at 70 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature. The filter cake was filtered and washed with water (3 × 10 mL), and then dried under vacuum to obtain the target product, carbazole tripyridine nickel catalyst Cat.3, as a yellow solid. Yield: 0.824 g, 96%.

[0057] Example 4: Carbazole terpyridine nickel catalyst Cat.1 for catalyzing CN coupling reaction:

[0058]

[0059] Under a nitrogen atmosphere, 3-iodopyridine (0.4 mmol), catalyst Cat.1 (1 mol%), tetrahydropyrrole (1.2 mmol), and N,N-dimethylformamide (4 mL) were added sequentially to a Schlenk reaction tube. The mixture was stirred for 12 hours under blue LED light (427 nm). After the reaction was complete, the mixture was extracted with ethyl acetate (3 × 25 mL), and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product was purified by column chromatography (PE:EA = 20:1), followed by vacuum drying to obtain a colorless oily target product. Yield: 0.056 g, 94%.

[0060] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=7.42-7.43(m, 2H), 6.53-6.55(m, 2H), 3.30-3.32(m, 4H), 2.01-2.04(m, 4H).

[0061] Example 5: Carbazole terpyridine nickel catalyst Cat.1 for catalyzing CN coupling reaction:

[0062]

[0063] Under a nitrogen atmosphere, 2-iodopyrazine (0.4 mmol), catalyst Cat.1 (1 mol%), tetrahydropyrrole (1.2 mmol), and N,N-dimethylformamide (4 mL) were added sequentially to a Schlenk reaction tube. The mixture was stirred for 12 hours under blue LED light (427 nm). After the reaction was complete, the mixture was extracted with ethyl acetate (3 × 25 mL), and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product was purified by column chromatography (PE:EA = 20:1), followed by vacuum drying to obtain a colorless oily target product. Yield: 0.052 g, 89%.

[0064] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=8.04 (q, J=1.4Hz, 1H), 7.89 (d, J=1.3Hz, 1H), 7.78 (d, J=2.7Hz, 1H), 3.51 (t, J=6.7Hz, 4H), 2.07-2.04 (m, 4H).

[0065] Example 6: Carbazole terpyridine nickel catalyst Cat.3 for catalyzing CN coupling reaction:

[0066]

[0067] Under a nitrogen atmosphere, 3-iodopyridine (0.4 mmol), catalyst Cat.3 (1 mol%), tetrahydropyrrole (1.2 mmol), and N,N-dimethylformamide (4 mL) were added sequentially to a Schlenk reaction tube. The mixture was stirred for 12 hours under blue LED irradiation (427 nm). After the reaction was complete, the mixture was extracted with ethyl acetate (3 × 25 mL), and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product was purified by column chromatography (PE:EA = 20:1), followed by vacuum drying to obtain a colorless oily target product. Yield: 0.031 g, 53%.

[0068] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=7.42-7.43(m, 2H), 6.53-6.55(m, 2H), 3.30-3.32(m, 4H), 2.01-2.04(m, 4H).

[0069] Example 7: Carbazole terpyridine nickel catalyst Cat.1 for catalyzing CO coupling reaction:

[0070]

[0071] Under a nitrogen atmosphere, 3-iodopyridine (0.4 mmol), catalyst Cat.1 (1 mol%), benzyl alcohol (1.2 mmol), 2-tert-butyl-1,1,3,3-tetramethylguanidine (tBuMG, 1.2 mmol), and N,N-dimethylformamide (5 mL) were added sequentially to a Schlenk reaction tube. The mixture was stirred for 24 hours under blue LED light (427 nm). After the reaction was complete, the mixture was extracted with ethyl acetate (3 × 25 mL), and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product was purified by column chromatography (PE:EA = 10:1), followed by vacuum drying to obtain a colorless oily target product. Yield: 0.057 g, 77%.

[0072] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=8.45 (s, 1H), 8.29 (s, 1H), 7.50-7.41 (m, 5H), 7.32 (t, J=6.4Hz, 2H), 5.17 (s, 2H).

[0073] Example 8: Carbazole terpyridine nickel catalyst Cat.1 for catalyzing CO coupling reaction:

[0074]

[0075] Under a nitrogen atmosphere, triiodopyridine (0.4 mmol), catalyst Cat.1 (1 mol%), (E)-2-hexen-1-ol (1.2 mmol), 2-tert-butyl-1,1,3,3-tetramethylguanidine (tBuMG, 1.2 mmol), and N,N-dimethylformamide (5 mL) were added sequentially to a Schlenk reaction tube. The mixture was stirred for 24 hours under blue LED light (427 nm). After the reaction was complete, the mixture was extracted with ethyl acetate (3 × 25 mL), and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product was purified by column chromatography (PE:EA = 10:1), followed by vacuum drying to obtain a colorless oily target product. Yield: 0.057 g, 81%.

[0076] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=8.32 (s, 1H), 8.20 (t, J=3.1Hz, 1H), 7.20 (t, J=2.8Hz, 2H), 5.88-5.83 (m, 1H), 5.71- 5.66 (m, 1H), 4.52 (dd, J = 6.1Hz, J = 1.0Hz, 2H), 2.09-2.05 (m, 2H), 1.46-1.40 (m, 2H), 0.91 (t, J = 7.4Hz, 3H).

[0077] Example 9: Carbazole terpyridine nickel catalyst Cat.1 for catalyzing CS coupling reaction:

[0078]

[0079] Under a nitrogen atmosphere, triiodopyridine (0.4 mmol), catalyst Cat.1 (1 mol%), 4-methoxybenzylthiol (1.2 mmol), and N,N-dimethylacetamide (4 mL) were added sequentially to a Schlenk reaction tube. The mixture was stirred for 12 hours under blue LED irradiation (427 nm). After the reaction was complete, the mixture was extracted with ethyl acetate (3 × 25 mL), and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product was purified by column chromatography (PE:EA = 10:1), followed by vacuum drying to obtain a colorless oily target product. Yield: 0.084 g, 97%.

[0080] NMR analysis: 1 H NMR (600MHz, CDCl3): δ=8.43 (d, J=1.7Hz, 1H), 8.36 (d, J=3.8Hz, 1H), 7.44-7.41 (m, 3H), 7.14 (q, J=4.2Hz, 1H), 6.92-6.90 (m, 2H), 3.83 (s, 3H).

Claims

1. A carbazole-terpyridine nickel catalyst, characterized in that, The specific structure of the catalyst is shown below: Where: H is hydrogen. Cat.1-Cat.3 is an abbreviation for three carbazole terpyridine nickel catalysts.

2. The application of the carbazole terpyridine nickel catalyst according to claim 1 in visible light-promoted CN, CO and CS coupling reactions.

Images