A copper (i) coordination compound, its preparation method and application

Abstract

The application discloses a copper (I) coordination compound and a preparation method and application thereof. Specifically, the chemical formula of the copper (I) coordination compound is [Cu(dmp)(R 1 R 2 C3HN2PPh3)]BF4, wherein dmp is 2,9-dimethyl-1,10-phenanthroline, R 1 R 2 C3HN2PPh3(R 1 =R 2 =H(1a); R 1 =H, R 2 =Me(1b); R 1 =H, R 2 =Ph(1c); R 1 =R 2 =Me(1d)) is an is-bidentate phosphine pyrazole ligand; four kinds of mononuclear copper (I) complexes [Cu(dmp)(R 1 R 2 C3HN2PPh3)]BF4(R 1 =R 2 =H(2a); R 1 =H, R 2 =Me(2b); R 1 =H, R 2 =Ph(2c); R 1 =R 2 =Me(2d)) are obtained by modifying R 1 R 2 groups on the pyrazole phosphine ligand, and different modified groups can affect the structure, absorption, emission, redox potential and photocatalytic activity of the complexes. The coordination compound can catalyze the intermolecular atom transfer radical addition reaction of olefins and halogenated hydrocarbons under visible light irradiation, and has the characteristics of high conversion efficiency, wide application range and mild reaction conditions.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalytic chemistry and relates to four copper (I) coordination compounds, in particular to a class of bidentate mononuclear copper (I) coordination compounds containing an imine phosphine ligand and a diimine ligand, and a preparation method and use thereof. Background Art

[0002] Visible-light-mediated photocatalytic reactions harness sunlight to promote useful chemical transformations. The most commonly used molecular photosensitizers in these reactions are traditional polypyridyl complexes of ruthenium or iridium. Despite their advantages in visible-light absorption, long excited-state lifetimes, suitable redox properties, and photostability, their rarity, high cost, and high toxicity have fueled the development of alternatives such as organic dyes or earth-abundant transition metal photosensitizers. However, these organic dyes still suffer from drawbacks such as weak solution fluorescence and instability.

[0003] In recent years, studies have reported that copper (I) complexes with two phosphinoxazoline (N^P) ligands exhibit high stability in the process of photocatalytic hydrogen production, with photocatalytic activity exceeding 24 hours; and studies have also reported that diimine-bisisocyanide copper (I) complexes catalyze the addition reaction of alkyl olefins with alkyl halides. However, the double-chelated mononuclear copper (I) complex [Cu(N^N)(N^P)] + There are few reports containing one imine-phosphine ligand and one diimine ligand. Summary of the Invention

[0004] In view of the above situation, the object of the present invention is to provide four copper (I) coordination compounds and their preparation methods and uses.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A copper (I) coordination compound having the chemical formula [Cu(dmp)(R 1 R 2 C3HN2PPh3)]BF4, where dmp is 2,9-dimethyl-1,10-phenanthroline, R 1 、R 2 Independently selected from hydrogen, alkyl or aryl; preferably, the alkyl is a C1-C6 alkyl, such as methyl; the aryl is phenyl.

[0007] In the copper (I) coordination compound of the present invention, dmp and R 1 R 2 C3HN2PPh3 as a five-membered chelating ligand; each copper (I) center is bound to a dmp and an R 1 R 2 The three N atoms and one P atom in C3HN2PPh coordinate to form a highly distorted tetrahedron.

[0008] The crystals of the copper (I) coordination compound of the present invention belong to the triclinic system, and the space groups are P ī, the unit cell parameters are 2a: a = 10.6131(17) Å, b = 13.336(2) Å, c = 13.515(2) Å, α = 102.248(4)°, β =94.419(5)°, γ = 107.571(4)°, V = 1761.5(5) nm 3 , Z = 2; 2b: a = 10.8101(14) Å, b =12.1918(17) Å, c = 16.312(2) Å, α = 98.412(4)°, β = 108.062(4)°, γ = 100.700(4)°, V = 1960.0(5) nm 3 , Z = 2; 2c: a = 12.0193(3) Å, b = 18.5661(6) Å, c = 18.5678(8) Å, α =89.141(3)°, β = 72.401(3)°, γ = 75.892(3)°, V = 3822.6(2) nm 3 , Z = 4; 2d: a = 9.5309(5) Å, b = 12.5267(7) Å, c = 16.7613(9) Å, α = 77.384(2)°, β = 74.714(2)°, γ =79.755(2)°, V = 1868.30(18) nm 3 , Z = 2.

[0009] The preparation method of the copper (I) coordination compound of the present invention comprises the following steps: preparing (2-fluorophenyl)diphenylphosphine with o-fluoroiodobenzene and diphenylphosphine as raw materials; then preparing a bidentate phosphine pyrazole ligand with (2-fluorophenyl)diphenylphosphine and pyrazole as raw materials; and then preparing a copper (I) coordination compound with the bidentate phosphine pyrazole ligand, tetrafluoroborate, copper tetraacetonitrile, and 2,9-dimethyl-1,10-phenanthroline as raw materials. Preferably, o-fluoroiodobenzene and diphenylphosphine are used in the presence of a palladium catalyst to prepare (2-fluorophenyl)diphenylphosphine; (2-fluorophenyl)diphenylphosphine and pyrazole are used in the presence of an inorganic base to prepare the bidentate phosphine pyrazole ligand; the bidentate phosphine pyrazole ligand, tetrafluoroborate, copper tetraacetonitrile, and 2,9-dimethyl-1,10-phenanthroline are used in an inert gas to prepare the copper (I) coordination compound; the chemical formula of pyrazole is R 1 R 2 C3H2N2,R 1 、R 2 are independently selected from hydrogen, alkyl or aryl. Further preferably, the palladium catalyst is an inorganic palladium compound; the inorganic base is a carbonate; and the inert gas is selected from any one of nitrogen and argon.

[0010] Specifically, the preparation method of the copper (I) coordination compound of the present invention comprises the following steps:

[0011] (1) Add o-fluoroiodobenzene, diphenylphosphine, and palladium chloride to a thick-walled pressure-resistant bottle at a molar ratio of o-fluoroiodobenzene: diphenylphosphine: palladium chloride = 1:1: (0.001-0.005). Add a base and a solvent under an inert gas atmosphere, seal the reaction vessel, heat to 85°C, and react for 24 hours. After the reaction is complete, cool the reaction system to room temperature, extract with ethyl acetate, combine the organic phases, dry, filter, concentrate under reduced pressure, and purify by silica gel column chromatography to obtain pure (2-fluorophenyl)diphenylphosphine as a white solid.

[0012] (2) Pyrazole, (2-fluorophenyl)diphenylphosphine, and cesium carbonate were added to a thick-walled pressure-resistant bottle in a molar ratio of pyrazole: (2-fluorophenyl)diphenylphosphine: cesium carbonate = 3:1: (1-5). Under an inert gas atmosphere, a solvent was added, the reaction vessel was sealed, and the mixture was heated to 180°C and reacted for three days. The mixture was stirred at 180°C for three days. After the reaction, the temperature of the reaction system was lowered to room temperature, and the mixture was extracted with ethyl acetate. The organic phases were combined, dried, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain a pure bidentate phosphine pyrazole ligand as a white solid.

[0013] (3) According to the molar ratio of tetrafluoroborate tetraacetonitrile copper: bidentate phosphine pyrazole ligand: 2,9-dimethyl-1,10-phenanthroline = 1:1:1, tetrafluoroborate tetraacetonitrile copper, bidentate phosphine pyrazole ligand and 2,9-dimethyl-1,10-phenanthroline are first added to the reaction vessel respectively, and a solvent is added under an inert gas atmosphere to prepare a solution. The phosphine ligand solution is first added dropwise to the copper solution, and after stirring at room temperature for 1 hour, the 2,9-dimethyl-1,10-phenanthroline solution is added thereto and stirred at room temperature for 1 hour. After the reaction is completed, the reaction mixture is concentrated, a poor solvent is added to precipitate it, and the copper (I) coordination compound is obtained after washing and drying.

[0014] In the present invention, the inert gas is selected from any one of nitrogen and argon; the solvents are toluene and N,N-dimethylacetamide, dichloromethane and acetonitrile, respectively, and the poor solvent is ether; the heating is completed by an oil bath.

[0015] The present invention discloses the use of a bidentate phosphine pyrazole ligand in the preparation of a copper (I) coordination compound and the use of the copper (I) coordination compound as a photocatalyst for an atomic radical transfer (ATRA) reaction, specifically the use of the copper (I) coordination compound in the photocatalytic ATRA reaction of aryl olefins with alkyl halides. The present invention discloses for the first time a bichelated mononuclear copper (I) complex [Cu(N^N)(N^P)] as a photocatalyst. + , which can catalyze the reaction of aromatic olefins and alkyl halides ATRA under visible light irradiation; the copper (I) coordination compound disclosed in the present invention has strong absorption in the visible light region, and the maximum absorption band edge can reach 600nm; it also has the characteristics of a long excited state lifetime, appropriate redox properties, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Schematic diagram of the crystal structure of the copper (I) coordination complex of the present invention. Implementation Method

[0017] The preparation method of the copper (I) coordination complex of the present invention comprises the following steps: first, adding copper tetrafluoroborate tetraacetonitrile, bidentate phosphine pyrazole ligand, and 2,9-dimethyl-1,10-phenanthroline to a reaction vessel in a molar ratio of 1:1:1:1; then, adding a solvent under an inert gas atmosphere to form a solution. First, the phosphine ligand solution is dropwise added to the copper solution, stirred at room temperature for 1 hour, and then the 2,9-dimethyl-1,10-phenanthroline solution is added thereto, and stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture is concentrated, a poor solvent is added to precipitate, and the precipitation is washed and dried to obtain the copper (I) coordination complex.

[0018] In the above preparation method, the inert gas is selected from any one of nitrogen and argon; the solvents are ultra-dry dichloromethane and ultra-dry acetonitrile; and the poor solvent is diethyl ether.

[0019] The chemical structures of the bidentate phosphine pyrazole ligands (1a, 1b, 1c, 1d) and copper (I) coordination compounds (2a, 2b, 2c, 2d) of the present invention and the reaction diagrams are as follows:

[0020]

[0021] The present invention will be further described below with reference to the accompanying drawings and specific examples. Unless otherwise specified, the reagents, materials, instruments, etc. used in the following examples can be obtained through commercial means.

[0022] Example 1 Preparation of 1-(2-(diphenylphosphanyl)phenyl)-1H-pyrazole (1a).

[0023] Pyrazole (0.41 g, 6 mmol), (2-fluorophenyl)diphenylphosphine (0.56 g, 2 mmol), and Cs2CO3 (1.95 g, 6 mmol) were placed in a 35 mL thick-walled pressure bottle. Under a nitrogen atmosphere, degassed anhydrous N,N-dimethylacetamide (DMA, 5 mL) was added. The mixture was stirred in an oil bath at 180°C for 3 days. After the reaction was complete, it was cooled to room temperature and extracted with CHCl2 (2 × 10 mL). The combined organic layers were backwashed with water (2 × 10 mL), filtered, and evaporated. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents (yield: 0.05 g, yield: 77%).

[0024] The NMR data of the obtained product are as follows:

[0025] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.59 (d, 1H), 7.50–7.40 (m, 3H), 7.35–7.25 (m, 11H), 7.02 (dd, J = 7.3, 3.1 Hz, 1H), 6.25 (t, 1H); 13 C NMR (101MHz, CDCl3, ppm): δ = 144.6 (d, J = 21.2 Hz), 140.4, 136.6 (d, J = 11.2 Hz),134.8, 133.9 (d, J= 20.5 Hz), 131.2 (d, J = 5.3 Hz), 129.7, 128.9, 128.8, 128.6(d, J = 7.2 Hz), 128.2, 126.3 (d, J = 2.6 Hz), 106.3; 31 P NMR (162 MHz, CDCl3, ppm): δ = –14.5.

[0026] Example 2 Preparation of 1-(2-(diphenylphosphanyl)phenyl)-3-methyl-1H-pyrazole (1b).

[0027] 3-Methylpyrazole (0.49 g, 6 mmol), (2-fluorophenyl)diphenylphosphine (0.56 g, 2 mmol), and Cs2CO3 (1.95 g, 6 mmol) were placed in a 35 mL thick-walled pressure bottle. Under a nitrogen atmosphere, degassed anhydrous N,N-dimethylacetamide (DMA, 5 mL) was added. The mixture was stirred in an oil bath at 180°C for 3 days. After the reaction was complete, it was cooled to room temperature and extracted with CHCl2 (2 × 10 mL). The combined organic layers were backwashed with water (2 × 10 mL), filtered, and evaporated. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents (yield: 0.04 g, yield: 63%).

[0028] The NMR data of the obtained product are as follows:

[0029] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.48 (dd, J = 7.3, 3.6 Hz, 1H), 7.41(t, J = 7.0 Hz, 1H), 7.35 (t, J = 2.0 Hz, 1H), 7.33–7.21 (m, 11H), 7.01 (dd, J =6.8, 3.7 Hz, 1H), 6.03 (d, J = 2.2 Hz, 1H), 2.24 (s, 3H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 149.7, 144.7 (d, J = 21.2 Hz), 136.8 (d,J = 10.7 Hz), 134.8,134.0 (d, J = 20.5 Hz), 133.2 (d, J = 19.9 Hz), 131.8 (d, J = 5.6 Hz), 129.6,128.8, 128.5 (d, J = 7.0 Hz), 127.8, 126.0 (d, J = 2.5 Hz), 106.2, 13.6; 31 P NMR (162 MHz, CDCl3, ppm): δ = –14.4.

[0030] Example 3 Preparation of 1-(2-(diphenylphosphanyl)phenyl)-3-phenyl-1H-pyrazole (1c).

[0031] 3-Phenylpyrazole (0.86 g, 6 mmol), (2-fluorophenyl)diphenylphosphine (0.56 g, 2 mmol), and Cs2CO3 (1.95 g, 6 mmol) were placed in a 35 mL thick-walled pressure bottle. Under a nitrogen atmosphere, degassed anhydrous N,N-dimethylacetamide (DMA, 5 mL) was added. The mixture was stirred in an oil bath at 180°C for 3 days. After the reaction was complete, it was cooled to room temperature and extracted with CHCl2 (2 × 10 mL). The combined organic layers were backwashed with water (2 × 10 mL), filtered, and evaporated. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents (yield: 0.05 g, yield: 61%).

[0032] The NMR data of the obtained product are as follows:

[0033] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.60 (dd, J = 2.4, 1.0 Hz, 1H), 7.57–7.54 (m, 2H), 7.52 (ddd, J = 7.8, 4.0, 1.2 Hz, 1H), 7.43 (td, J = 7.7, 1.4 Hz,1H), 7.32–7.23 (m, 14H), 7.06 (ddd, J = 7.7, 3.6, 1.3 Hz, 1H), 6.62 (d, J= 2.4 Hz, 1H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 152.3, 144.7 (d, J = 21.3 Hz), 137.4(d, J = 10.7 Hz), 135.5, 134.0 (d, J = 20.3 Hz), 133.2, 133.1, 133.0, 131.8 (d, J = 3.7 Hz), 129.7, 128.7, 128.5, 128.4 (d, J = 5.9 Hz), 127.8 (d, J = 26.3Hz), 125.8, 125.0 (d, J = 2.8 Hz), 104.0; 31 P NMR (162 MHz, CDCl3, ppm): δ = –13.7.

[0034] Example 4 Preparation of 1-(2-(diphenylphosphanyl)phenyl)-3,5-dimethyl-1H-pyrazole (1d).

[0035] 3,5-Dimethylpyrazole (0.58 g, 6 mmol), (2-fluorophenyl)diphenylphosphine (0.56 g, 2 mmol), and Cs2CO3 (1.95 g, 6 mmol) were placed in a 35 mL thick-walled pressure bottle. Under a nitrogen atmosphere, degassed anhydrous N,N-dimethylacetamide (DMA, 5 mL) was added. The mixture was stirred in an oil bath at 180°C for 3 days. After the reaction was complete, it was cooled to room temperature and extracted with CHCl2 (2 × 10 mL). The combined organic layers were backwashed with water (2 × 10 mL), filtered, and evaporated. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents (yield: 0.02 g, yield: 26%).

[0036] The NMR data of the obtained product are as follows:

[0037] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.38 (dd, J = 7.6, 1.3 Hz, 1H), 7.32–7.24 (m, 12H), 7.10 (ddd, J= 7.6, 3.4, 1.2 Hz, 1H), 5.81 (s, 1H), 2.13 (s, 3H), 1.97 (s, 3H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 148.2, 143.5 (d, J = 22.3Hz), 140.3, 138.0 (d, J = 18.1 Hz), 136.5 (d, J = 11.4 Hz), 134.3, 134.0 (d, J =20.8 Hz), 129.4, 128.8, 128.7, 128.3 (d, J = 7.2 Hz), 128.1 (d, J = 2.5 Hz),105.4, 13.5, 11.7 (d, J = 4.5 Hz); 31 P NMR (162 MHz, CDCl3, ppm): δ = –14.2.

[0038] Example 5 Preparation of [Cu(dmp)(2a)]BF4.

[0039] To a solution of [Cu(CH3CN)4]BF4 (0.0315 g, 0.10 mmol) in acetonitrile (5 mL) was added a solution of 1a (0.0328 g, 0.10 mmol) in C2Cl2 (5 mL). After stirring at room temperature for 1 hour, a solution of 2,9-dimethyl-1,10-phenanthroline (dmp) (0.0208 g, 0.10 mmol) in C2Cl2 (5 mL) was added. Stirring was continued for 1 hour to obtain a clear yellow solution. After completion of the reaction, the reaction solution was concentrated to approximately 5 mL. Et2O (20 mL), a poor solvent, was then added to the solution to precipitate orange crystals of 2a. These crystals were isolated by filtration, washed with Et2O, and dried in vacuo (yield: 0.02 g; yield: 36%, calculated based on Cu).

[0040] Melting point: 226–228 °C.

[0041] Mass spectrum: Calculated value: 599.1426; Measured value: 599.1426.

[0042] The NMR data of the obtained product are as follows:

[0043] 1 H NMR (400 MHz,d 6 -DMSO, ppm): 8.79 (t, J = 8.1 Hz, 2H), 8.65 (s, 1H), 8.24 (d, J = 16.6 Hz, 2H), 8.00 (t, J = 7.2 Hz, 2H), 7.84 (d, J = 23.3 Hz, 2H),7.57 (m, 4H), 7.46 (s, 4H), 7.29 (s, 4H), 6.98 (d, J = 29.1 Hz, 1H), 6.55 (d, J =54.3 Hz, 1H), 2.44 (s, 6H); 3 C NMR (101 MHz, d 6 -DMSO, ppm): δ = 157.7, 156.6,142.2, 141.7, 141.4, 141.1, 137.1, 136.3, 132.6, 132.3 (t, J = 15.2 Hz), 131.3(d, J = 38.8 Hz), 130.5, 129.7 (t, J = 36.3 Hz), 128.2 (d, J = 8.9 Hz), 126.1 (d, J =6.2 Hz), 125.5, 124.8, 124.6, 106.9, 24.9, 24.1; 31 P NMR (162 MHz, d 6 -DMSO,ppm): δ = –8.3.

[0044] The obtained product was subjected to single crystal X-ray diffraction test, and its crystallographic parameters are shown in Table 1. The crystal structure is shown in Figure 1 shown.

[0045]

[0046] The above data show that the target product [Cu(dmp)(2a)]BF4 was successfully obtained in this example.

[0047] Example 6 Preparation of [Cu(dmp)(2b)]BF4.

[0048] To a solution of [Cu(CH3CN)4]BF4 (0.0315 g, 0.10 mmol) in acetonitrile (5 mL) was added a solution of 1b (0.0342 g, 0.10 mmol) in C2Cl2 (5 mL). After stirring at room temperature for 1 hour, a solution of 2,9-dimethyl-1,10-phenanthroline (dmp) (0.0208 g, 0.10 mmol) in C2Cl2 (5 mL) was added. Stirring was continued for 1 hour to obtain a clear yellow solution. After the reaction, the reaction solution was concentrated to approximately 5 mL. Et2O (20 mL), a poor solvent, was then added to the solution to precipitate orange crystals of 2b. These crystals were isolated by filtration, washed with Et2O, and dried in vacuo (yield: 0.02 g; yield: 33%, calculated based on Cu).

[0049] Melting point: 158–163 °C.

[0050] Mass spectrum: Calculated value: 613.1582; ​​Measured value: 613.1582.

[0051] The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, d 6 -DMSO, ppm): δ = 8.80 (d, J =8.1 Hz, 2H), 8.59 (s, 1H), 8.26 (d, J = 8.6 Hz, 2H), 8.02 (m, 2H), 7.85 (t, J =7.2 Hz, 1H), 7.73 (s, 1H), 7.62 (t, J = 7.2 Hz, 1H), 7.52 (s, 2H), 7.44 (s, 4H), 7.33–7.11 (m, 4H), 7.00 (t, J = 7.8 Hz, 1H), 6.51 (s, 1H), 2.45 (s, 6H); 13 CNMR (101 MHz, d 6 -DMSO, ppm): δ = 159.3, 158.2, 153.3, 142.7 (d, J = 4.4 Hz),138.8, 138.0, 136.1, 133.6 (d, J = 16.1 Hz), 132.9 (d, J= 32.4 Hz), 131.5 (d, J =7.2 Hz),131.2 (d, J = 5.5 Hz), 129.8 (d, J = 9.5 Hz), 128.2 (d, J = 4.6 Hz), 127.8(d, J = 16.5 Hz), 126.6, 126.5, 126.4, 126.2, 108.9, 26.2, 25.7, 13.5; 31 P NMR (162 MHz, d 6 -DMSO, ppm): δ = –11.9.

[0052] The obtained product was subjected to single crystal X-ray diffraction test, and its crystallographic parameters are shown in Table 2. The crystal structure is shown in Figure 1 shown.

[0053]

[0054] The above data show that the target product [Cu(dmp)(2b)]BF4 was successfully obtained in this example.

[0055] Example 7 Preparation of [Cu(dmp)(2c)]BF4.

[0056] To a solution of [Cu(CH3CN)4]BF4 (0.0315 g, 0.10 mmol) in acetonitrile (5 mL) was added a solution of 1c (0.0404 g, 0.10 mmol) in C2Cl2 (5 mL). After stirring at room temperature for 1 hour, a solution of 2,9-dimethyl-1,10-phenanthroline (dmp) (0.0208 g, 0.10 mmol) in C2Cl2 (5 mL) was added. Stirring was continued for 1 hour to obtain a clear yellow solution. After completion of the reaction, the reaction solution was concentrated to approximately 5 mL. Et2O (20 mL), a poor solvent, was then added to the solution to precipitate yellow crystals of 2c. These crystals were isolated by filtration, washed with Et2O, and dried in vacuo (yield: 0.04 g; yield: 59%, calculated as Cu).

[0057] Melting point: 233–236 °C.

[0058] Mass spectrum: Calculated value: 675.1739; Measured value: 675.1739.

[0059] The NMR data of the obtained product are as follows:

[0060] 1 H NMR (400 MHz, d 6 -DMSO, ppm): δ = 8.62 (s, 1H), 8.59 (d, J = 8.3 Hz,2H), 8.10 (s, 2H), 7.86 (t, J = 7.5 Hz, 1H), 7.74 (d, J = 8.3 Hz, 3H), 7.67 (t, J =7.5 Hz, 1H), 7.49 (t, J = 7.1 Hz, 2H), 7.42 (t, J = 6.9 Hz, 4H), 7.23 (m, 4H),7.07 (t, J = 7.7 Hz, 1H), 6.88 (d, J = 2.3 Hz, 1H), 6.85 (d, J = 7.3 Hz, 2H), 6.54(t, J = 6.7 Hz, 1H), 6.22 (s, 2H), 2.30 (s, 6H); 13 C NMR (101 MHz, d 6 -DMSO, ppm):δ = 158.74, 158.20, 156.33, 142.93 (d, J = 11.8 Hz), 142.70, 138.39, 137.95,136.75, 133.75 (d, J = 16.0 Hz), 133.16, 132.77, 131.74, 131.42, 131.20 (d, J =6.9 Hz), 130.47, 129.76 (d, J = 9.6 Hz), 128.70, 128.27, 127.63, 127.16,126.66, 126.44, 126.22, 125.91, 107.06, 26.33, 25.72; 31 P NMR (162 MHz, d 6 -DMSO,ppm): δ = –11.3。

[0061] The obtained product was subjected to single crystal X-ray diffraction test, and its crystallographic parameters are shown in Table 3. The crystal structure is shown in Figure 1 shown.

[0062]

[0063] The above data show that the target product [Cu(dmp)(2c)]BF4 was successfully obtained in this example.

[0064] Example 8: Preparation of [Cu(dmp)(2d)]BF4.

[0065] To a solution of [Cu(CH3CN)4]BF4 (0.0315 g, 0.10 mmol) in acetonitrile (5 mL) was added a solution of 1d (0.0356 g, 0.10 mmol) in C2Cl2 (5 mL). After stirring at room temperature for 1 hour, a solution of dmp (2,9-dimethyl-1,10-phenanthroline) (0.0208 g, 0.10 mmol) in C2Cl2 (5 mL) was added. Stirring was continued for 1 hour to obtain a clear yellow solution. After completion of the reaction, the reaction solution was concentrated to approximately 5 mL. Et2O (20 mL), a poor solvent, was then added to the solution to precipitate orange crystals of 2d. These crystals were isolated by filtration, washed with Et2O, and dried in vacuo (yield: 0.03 g; yield: 48%, calculated as Cu).

[0066] Melting point: 220–234 °C.

[0067] Mass spectrum: Calculated value: 627.1739; Measured value: 627.1740.

[0068] The NMR data of the obtained product are as follows:

[0069] 1 H NMR (400 MHz, d 6 -DMSO, ppm): δ = 8.78 (d, J = 8.2 Hz, 2H), 8.24 (d, J =9.0 Hz, 2H), 8.14–7.90 (m, 3H), 7.81 (t, J = 7.4 Hz, 1H), 7.74–7.58 (m, 2H), 7.58–7.47 (m, 2H), 7.45 (m, 4H), 7.33–7.08 (m, 3H), 6.95 (t, J= 7.7 Hz, 1H), 6.25 (s, 1H), 2.42 (s, 4H), 2.40 (s, 2H); 13 C NMR (101 MHz, d 6 -DMSO, ppm): δ =159.3, 158.2, 152.5, 144.5, 142.7 (d, J = 7.1 Hz), 138.8, 138.0, 133.7 (d, J =16.4 Hz), 132.9, 132.3, 131.4 (t, J = 21.5 Hz), 130.7 (d, J = 33.7 Hz), 129.8(d, J = 9.5 Hz), 127.8 (d, J = 15.2 Hz), 126.6, 126.5, 126.4, 126.2, 108.9,26.2, 25.7, 13.5, 12.9; 31 P NMR (162 MHz, d 6 -DMSO, ppm): δ = –12.2.

[0070] The obtained product was subjected to single crystal X-ray diffraction test, and its crystallographic parameters are shown in Table 4, and the crystal structure is shown in Figure 1 shown.

[0071]

[0072] The above data show that the target product [Cu(dmp)(2d)]BF4 was successfully obtained in this example.

[0073] Application Example Catalysis of the ATRA reaction of styrene and carbon tetrabromide under visible light irradiation.

[0074]

[0075] A mixture of carbon tetrabromide (0.2 mmol), styrene (2 equiv, 0.4 mmol), and 2c (1 mol%) was added to a 10 mL reaction tube. Ultra-dry MeCN (1 mL) was added under a nitrogen atmosphere. The mixture was stirred at room temperature and irradiated with a household 45 W energy-saving lamp for 24 hours, cooled with a fan. The reaction mixture was extracted three times with ethyl acetate (3 × 5 mL), backwashed with 3 × 5 mL of water and brine, dried over anhydrous Na₂SO₄, and concentrated to dryness under reduced pressure. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents. Yield: 93% (HPLC), 91% (isolation).

[0076] The NMR data of the obtained product are as follows:

[0077] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.49 (d, J = 7.0 Hz, 2H), 7.37 (t, J =7.3 Hz, 2H), 7.31 (t, J = 7.2 Hz, 1H), 5.33 (dd, J = 7.7, 4.1 Hz, 1H), 4.09(qd, J = 15.6, 5.9 Hz, 2H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 140.8, 129.0, 128. 9, 128.2, 66.5, 50.1, 35.0.

[0078] In the absence of a catalyst, the product yield was 11%. Replacing catalyst 2c with other catalysts, with all other conditions remaining the same, with the ATRA reaction of styrene and carbon tetrabromide under visible light irradiation resulted in the following HPLC yields: 2a 81%; 2b 87%; 2d 86%. No product was obtained with Cu(MeCN)4BF4. fac -[Ir(ppy)3] 75%; Rhodamine 6G 12%.

[0079] The present invention designs a series of copper (I) coordination compounds, the chemical formula of which is [Cu(dmp)(R 1 R 2 C3HN2PPh3)]BF4(2a-2d);These complexes were characterized by elemental analysis, IR spectroscopy and X-ray diffraction; The R 1 、R 2The effects of substituent changes on the crystal structure and photocatalytic activity of copper(I) complexes were investigated. Among these complexes, compound 2c exhibits the lowest energy absorption in the visible spectrum of the solution. Compared with 2a, 2b, and 2d, 2c exhibits lower energy emission and a longer emission lifetime in the solid state and possesses the highest photocatalytic activity in the ATRA reaction. These results provide a perspective for studying the effects of substituents on heterodiacid ligands in copper coordination complexes.

Claims

1. A copper (I) coordination compound, characterized in that: The chemical structural formula of the copper (I) coordination compound is as follows: ； where R 1 、R 2 are independently selected from hydrogen, methyl or phenyl.

2. The copper (I) coordination compound according to claim 1, characterized in that: The crystals of the copper (I) coordination compound belong to the triclinic system, and the space group is Pī.

3. The method for preparing the copper (I) coordination compound according to claim 1, wherein: (2-Fluorophenyl)diphenylphosphine was prepared using o-fluoroiodobenzene and diphenylphosphine as raw materials; then a bidentate phosphine pyrazole ligand was prepared using (2-fluorophenyl)diphenylphosphine and pyrazole as raw materials; and finally a copper (I) coordination compound was prepared using the bidentate phosphine pyrazole ligand, tetraacetonitrile copper tetrafluoroborate, and 2,9-dimethyl-1,10-phenanthroline as raw materials.

4. The method for preparing the copper (I) coordination compound according to claim 3, wherein: (2-Fluorophenyl)diphenylphosphine is prepared from o-fluoroiodobenzene and diphenylphosphine in the presence of a palladium catalyst; a bidentate phosphine pyrazole ligand is prepared from (2-Fluorophenyl)diphenylphosphine and pyrazole in the presence of an inorganic base; and a copper (I) coordination compound is prepared from a bidentate phosphine pyrazole ligand, tetraacetonitrile copper tetrafluoroborate, and 2,9-dimethyl-1,10-phenanthroline in an inert gas.

5. The method for preparing the copper (I) coordination compound according to claim 3, wherein: The palladium catalyst is an inorganic palladium compound; the inorganic base is a carbonate.

6. Use of the copper (I) coordination compound according to claim 1 as an ATRA reaction photocatalyst in the photocatalytic ATRA reaction of aryl olefins and alkyl halides.

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