A perfluorophenyl-substituted salicylaldimine nickel complex, its preparation method and application

Abstract

The present invention discloses a class of perfluorophenyl-substituted salicylaldimine nickel complexes, a preparation method thereof, and an application thereof in highly active catalytic norbornene polymerization. The preparation method includes the following steps: first metallizing a neutral ligand with sodium hydride, then reacting it with a nickel metal raw material compound in an organic medium, and then obtaining the target compound through filtration, concentration, and recrystallization steps. The perfluorophenyl-substituted salicylaldimine nickel complex of the present invention is a highly efficient norbornene addition polymerization catalyst. The perfluorophenyl-substituted salicylaldimine nickel complex of the present invention has very obvious advantages: the raw materials are easily available, the synthesis route is simple, the product yield is high, the polymerization performance can be regulated by adjusting the substituent structure, and it has a wide application prospect. Its structural formula is shown as follows:

Description

Technical Field

[0001] The present invention relates to a class of nickel complexes of perfluorophenyl-substituted salicylaldimine, and the application of such complexes in the polymerization of norbornene. Background Art

[0002] The research and development of cycloolefin polymers as new polymer materials have been quite active. In particular, addition polymers of norbornene (NBE) and its derivatives have always been one of the research hotspots in polymer materials. Due to the cyclic structure of the main chain, the interaction between molecular chains of polynorbornene is very large, making the polymer exhibit a very high melting point and can be used as a high-temperature resistant protective material; its good mechanical properties, such as high tensile fracture value and low tension, make it have good adhesion to metals; and its high transparency, low dielectric constant, low water absorption, high gas barrier property, acid and alkali resistance, chemical corrosion resistance, etc., as well as good solubility in halogenated aromatic hydrocarbons, make it applicable to microelectronic devices, liquid crystal display protective coatings, etc.; in addition, polynorbornene also has broad application prospects in aspects such as drugs and food packaging.

[0003] The addition polymerization of norbornene was first reported in the early 1960s using TiCl4 / AlR3 as the catalyst, but the research on addition polymerization is far less in-depth than that on ring-opening polymerization (Chim.Ind.(Milan), 1963, 45, 1478). Since the discovery of the metallocene / methylaluminoxane (MAO) catalytic system by Kaminsky, great progress has been made in the addition polymerization of NBE catalyzed by metallocenes (Angew.Chem.Int.Ed., 1985, 24, 507-508). The development of late transition metal catalysts in the late 20th century further promoted the development of NBE addition polymerization. In 1993, Deming and Novak used allyl nickel trifluoroacetate catalyst for NBE polymerization, and high catalytic activity could be obtained without the addition of a cocatalyst (Macromolecules, 1993, 26, 7089-7093). In 1998, the Deffieux group reported a nickel stearate complex, which could catalyze the addition polymerization of norbornene relatively rapidly when chlorobenzene was used as the solvent (Macromol.Chem.Phys., 1998, 199, 2221-2227). In addition, nickel acetylacetonate complex, nickel bicyclooctadiene complex, and nickel 2-ethylacetate complex can all catalyze NBE polymerization under the cocatalysis of MAO, and the catalytic activity of nickel acetylacetonate complex has a great dependence on the reaction temperature (Polym.Bull., 1998, 41, 433–440; Polym.Prep., 2002, 43, 1161-1163). During this period, the Grubbs group reported a nickel catalyst with salicylaldimine as a neutral ligand in 1998 (Organometallics, 1998, 17, 3149-3151), and in 2000, it was reported that such catalysts could tolerate heteroatoms and achieve the homopolymerization and copolymerization of norbornene derivatives containing polar groups, thus attracting great interest and attention (Science, 2000, 287, 460-462). The Li Yuesheng group studied the polymerization of norbornene catalyzed by salicylaldimine nickel complex and found that the solvent had a great influence on the polymerization reactivity of norbornene, and the activity was the highest in dichloromethane; the ligand substituents had little influence on the catalyst activity (J.Polym.Sci.Polym.Chem., 2002, 40, 2680-2685). In 2003, the Sun Wenhua group found that the electronic effect of substituents had a certain influence on the activity of salicylaldimine nickel complex catalyzing norbornene polymerization, but the steric effect had no significant influence on the catalytic activity (Organometallics, 2003, 22, 3678-3683).The Lee group studied a series of 6,6'-bis(alkoxymethyl)-2,2'-bipyridine nickel catalysts, which showed good activity under the action of MMAO (modified methylaluminoxane). When the substituents were bulky groups, the activity became stronger (Bull. Korean Chem. Soc., 2006, 27, 475 - 476). The Wu Qing group synthesized a class of [N,N] six-membered chelating nickel complexes based on diimine, diketimine salt, fluorinated diketimine ester and aniline imine ligands in 2008 and used them in the study of norbornene polymerization. According to the experimental results, it was speculated that the nickel center with high electrophilicity could reduce the activation energy of norbornene monomer insertion and was beneficial to the coordination and insertion of norbornene in the growing chain, resulting in enhanced catalytic activity and increased product molecular weight (J. Mol. Catal. A: Chem., 2008, 280, 81 - 86). In 2011, the Bouwman group reported the polymerization of norbornene catalyzed by a series of N-heterocyclic carbene nickel complexes under the action of MAO. The results showed that the complexes containing a bis-halide bis-carbene structure had higher activity, while the presence of anionic groups in the structure had a negative impact on the polymerization activity (Appl. Organometal. Chem., 2011, 25, 76–81). In 2013, the Chen group synthesized [O,N,N,O] tetradentate ketimine nickel complexes and studied the polymerization of norbornene using MAO as a cocatalyst. It was found that the electronic effect had no influence on the polymerization activity, while a smaller steric hindrance was beneficial to improving the polymerization activity (J. Mol. Catal. A: Chem., 2013, 380, 104 - 111). In 2017, the Zhang group reported the polymerization of norbornene catalyzed by the [N,P,P] tridentate nickel complex / MAO system and found that connecting three methylene groups between P and N could more flexibly adapt to the geometry of the metal complex and form a more stable active species, making it show higher catalytic activity (Eur. Polym. J., 2017, 93, 358 - 367). In 2018, the Cai and Eisen groups cooperated to synthesize aryloxyimidazoline-2-imine nickel complexes, which were catalytically active for the polymerization of norbornene under the action of cocatalysts such as MAO, MMAO, Et2AlCl and EtAlCl2 (Organometallics, 2018, 37, 1172 - 1180). In 2020, the Xiao and Cai groups reported bis(N-acylimidazoline-2-imine) nickel complexes, which catalyzed the polymerization of norbornene using B(C6F5)3 as a cocatalyst (Polym. Chem., 2020, 11, 5542–5547).

[0004] Norbornene polymers have a very high glass transition temperature, excellent mechanical properties, good transparency, thermal stability, and chemical corrosion resistance, so they have broad application prospects. In recent years, great progress has been made in the polymerization research of norbornene. On this basis, in-depth research on nickel complex catalysts, developing catalysts with high activity, thermal stability, and longer lifespan to suit the actual industrial application process, enabling them to efficiently and controllably catalyze the polymerization of norbornene, has very strong practical significance. Summary of the Invention

[0005] One of the objectives of the present invention is to disclose a class of nickel complexes of perfluorophenyl-substituted salicylaldimine.

[0006] Another objective of the present invention is to disclose a preparation method of a class of nickel complexes of perfluorophenyl-substituted salicylaldimine.

[0007] A third objective of the present invention is to disclose the application of a class of nickel complexes of perfluorophenyl-substituted salicylaldimine as catalysts in the polymerization of norbornene.

[0008] Technical concept of the present invention:

[0009] Salicylaldimine ligands are easily available. The ligands can be efficiently prepared through simple Schiff base condensation reactions. Their structure regulation is simple, and the electronic effect and steric effect can be adjusted by changing substituents. Using such ligands to synthesize nickel complex catalysts, highly active catalysts for catalyzing the polymerization of norbornene can be relatively easily obtained through ligand optimization and adjustment. In the present invention, by introducing perfluorophenyl at the ortho position of the phenoxy group, both the planar structure characteristics of the benzene ring that can rotate in space are utilized, ultimately acting on the steric hindrance of the complex on the insertion of norbornene, and the electronegativity of fluorine atoms is used to adjust the electricity of the benzene ring, ultimately affecting the electricity of the metal center, in order to achieve highly active catalysis of norbornene polymerization and obtain norbornene polymers with controllable molecular weights.

[0010] The perfluorophenyl-substituted salicylaldimine ligands (I) and their metal nickel complexes (II) provided by the present invention are characterized by having the following general formula:

[0011]

[0012] In formulas (I) and (II):

[0013] R 1 represents hydrogen, an alkyl group with a straight-chain, branched-chain, or cyclic structure of C1-C6, or a perfluoroalkyl group with a straight-chain, branched-chain, or cyclic structure of C1-C6;

[0014] R 2 represents an aryl group of C6-C 18 and a perfluoroaryl group of C6-C 18 of C7-C30 mono- or poly-aryl substituted alkyl;

[0015] R 3 represents an alkyl group having a C1-C6 straight-chain, branched-chain or cyclic structure, an aryl group having a C6-C 18 aryl;

[0016] R 4 and R 5 represent an aryl group having a C6-C 18 aryl; R 4 and R 5 may be the same or different.

[0017] More characteristically, in formulas (I) and (II):

[0018] R 1 is preferably hydrogen, an alkyl group having a C1-C4 straight-chain, branched-chain or cyclic structure, a perfluoroalkyl group having a C1-C4 straight-chain, branched-chain or cyclic structure;

[0019] R 2 is preferably an aryl group having a C6-C 12 aryl, a perfluoroaryl group having a C6-C 12 aryl, a mono- or poly-aryl substituted alkyl group having a C7-C 20 aryl;

[0020] R 3 is preferably an alkyl group having a C1-C4 straight-chain, branched-chain or cyclic structure, an aryl group having a C6-C 12 aryl;

[0021] R 4 and R 5 are preferably an aryl group having a C6-C 12 aryl.

[0022] In formulas (I) and (II):

[0023] R 1 is preferably hydrogen, methyl, trifluoromethyl; R 2 is preferably phenyl, perfluorophenyl, diphenylmethyl; R 3 is preferably methyl, phenyl; R 4 and R 5 are preferably phenyl.

[0024] Preferred perfluorophenyl-substituted salicylaldimine ligands have the following structural formula:

[0025]

[0026] The metal nickel-nickel complex structure of the preferred salicylaldimine ligand is:

[0027]

[0028] The preparation method of the perfluorophenyl-substituted salicylaldimine ligand (I) and its nickel complex (II) of the present invention is as follows:

[0029]

[0030] Perfluorophenyl-substituted salicylaldehyde shown by formula (III) and substituted aniline shown by formula (IV) are subjected to a Schiff base condensation reaction in an organic medium. The reaction temperature is 25 - 150 °C, and the reaction time is 2 - 72 hours. Then, the ligand compound (I) is collected from the reaction product;

[0031] Optionally, after the perfluorophenyl-substituted salicylaldimine ligand compound shown by formula (I) is metallized with NaH, it is reacted with the nickel metal raw material compound trans-Ni[(PR 4 3)R 5 2Cl] in an organic medium. The reaction temperature is 0 - 100 °C, and the reaction time is 2 - 96 hours. Then, the perfluorophenyl-substituted salicylaldimine nickel target compound (II) is collected from the reaction product;

[0032] In the above preparation method, the substituents R 1 ~R 5 are consistent with the corresponding groups of the perfluorophenyl-substituted salicylaldimine ligand (I) and its nickel metal complex (II) satisfying the present invention.

[0033] More characteristically, in the above preparation method, the nickel metal raw material compound is preferably trans-bis(triphenylphosphine)phenyl nickel chloride;

[0034] The molar ratio of the perfluorophenyl-substituted salicylaldimine ligand compound (I) to the nickel metal raw material compound is 1:0.5 - 1.5;

[0035] The organic medium is selected from one, two, three, four, or five of tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether, and n-hexane.

[0036] In the preparation method of the perfluorophenyl-substituted salicylaldimine ligand (I) of the present invention, the synthesis of the perfluorobenzene-substituted salicylaldehyde shown by formula (III) can be carried out according to the following route by referring to the literature method:

[0037]

[0038] Among them, after reacting substituted or unsubstituted phenol with sodium hydride in N,N-dimethylformamide to obtain the sodium salt, it is reacted with chloromethyl methyl ether to protect the phenolic hydroxyl group. Then, in tetrahydrofuran, it is successively reacted with n-butyllithium and hexafluorobenzene to obtain a product substituted with a perfluorophenyl group. Finally, it is deprotected with hydrochloric acid in methanol to obtain perfluorophenyl-substituted phenol (Org. Lett., 2018, 20, 7039-7043; Chem. Lett., 2016, 45, 857-859).

[0039] Reacting the perfluorophenyl-substituted phenol with paraformaldehyde under the catalysis of magnesium chloride to obtain the target product pentafluorophenyl-substituted salicylaldehyde (III) (Chem-Eur. J., 2016, 22, 18714-18717).

[0040]

[0041] In the preparation method of the perfluorophenyl-substituted salicylaldimine ligand (I) of the present invention, the synthesis of the substituted aniline shown in formula (IV) can be carried out according to the following several routes by referring to the literature method:

[0042] (1) Suzuki coupling of 4-methyl-2,6-dibromoaniline or 2,4,6-tribromoaniline with phenylboronic acid under the action of tetrakis(triphenylphosphine)palladium (Polymer Chemistry, 2013, 4, 2963-2967):

[0043]

[0044] (2) Prepared by reacting diphenylmethanol with aniline by heating to 160 °C under the catalysis of ZnCl2 / HCl (Macromolecules, 2016, 49, 8855-8862):

[0045]

[0046] (3) Reacting 4-methyl-2,6-dibromoaniline with bis(pinacolato)diboron under the catalysis of 1,1'-bis(diphenylphosphino)ferrocene dichloropalladium to obtain an intermediate product, and then reacting it with bromopentafluorobenzene under the catalysis of tetrakis(triphenylphosphine)palladium to obtain the target product (Macromolecules, 2015, 48, 5504-5510):

[0047]

[0048] The perfluorophenyl-substituted salicylaldimine nickel complex of the present invention is a catalyst that can efficiently initiate the addition polymerization of norbornene under the activation of an aluminoxane cocatalyst.

[0049] The aluminoxane cocatalyst described above may be methylaluminoxane (MAO), modified methylaluminoxane (MMAO), or an alkylaluminum with a linear or branched structure having 1 to 4 carbon atoms.

[0050] Using the perfluorophenyl-substituted salicylaldimine nickel complex described in the present invention as a catalyst, under the activation of an aluminoxane cocatalyst, norbornene is polymerized; the molar ratio of the catalyst to the monomer during polymerization is 1:1 to 20,000; the molar ratio of the catalyst to the aluminoxane cocatalyst during polymerization is 500 to 10,000.

[0051] More particularly, using the perfluorophenyl-substituted salicylaldimine nickel complex described in the present invention as a catalyst, norbornene is polymerized at 0 to 120 °C, preferably 30 to 90 °C, under the activation of methylaluminoxane; the molar ratio of the catalyst to the monomer during polymerization is 1:1 to 20,000, preferably 1:2500 to 10,000; the molar ratio of the catalyst to the aluminoxane cocatalyst during polymerization is 500 to 10,000, preferably 1000 to 4000.

[0052] When using the perfluorophenyl-substituted salicylaldimine nickel complex described in the present invention as a catalyst for the polymerization of norbornene, there is no special requirement for the mixing order of the perfluorophenyl-substituted salicylaldimine nickel complex, methylaluminoxane, and norbornene.

[0053] When using the perfluorophenyl-substituted salicylaldimine nickel complex described in the present invention as a catalyst for the polymerization of norbornene, the polymerization solvent is preferably one or more of toluene, m-xylene, o-xylene, mesitylene, and trichlorobenzene, specifically it can be one, two, three, four, or five.

[0054] The catalyst provided by the present invention is simple to prepare, has stable properties, and at the same time has high catalytic activity, and has broad application prospects. The present invention will be further illustrated by examples below, but the present invention is not limited thereto. Detailed Embodiments

[0055] Example 1

[0056] Synthesis of 4-trifluoromethyl-2-perfluorophenylphenol

[0057] Under argon protection, a solution of 4-(trifluoromethyl)phenol (16.22 g, 100.0 mmol) in 40 mL of N,N-dimethylformamide was added dropwise to a suspension of NaH (60%, 9.20 g, 230 mmol) in 150 mL of N,N-dimethylformamide (cooled in an ice-water bath). The reaction was carried out at room temperature overnight. Under an ice-water bath, chloromethyl methyl ether (18 mL, 237 mmol) was added dropwise. The reaction was continued at room temperature for 4 hours, quenched with water, extracted with dichloromethane, the organic phase was washed with saturated brine, and dried over anhydrous magnesium sulfate. The organic phase was filtered, concentrated, and then distilled under reduced pressure (70 °C / 8 mmHg) to obtain 4-(methoxymethoxy)-trifluoromethylbenzene, a colorless oily liquid (17.67 g, 85.7%).

[0058] Under argon protection, a solution of n-BuLi in hexane (2.5 M, 8 mL, 20 mmol) was added dropwise to a solution of 4-(methoxymethoxy)-trifluoromethylbenzene (4.12 g, 20.0 mmol) in 30 mL of tetrahydrofuran (cooled in a liquid nitrogen-ethanol bath). The reaction was carried out at room temperature overnight. Under an ice-water bath, the above mixture was added dropwise to a solution of perfluorobenzene (11.16 g, 60.0 mmol) in 40 mL of dry tetrahydrofuran. The reaction was continued at room temperature overnight. The solvent was removed by rotary evaporation, water was added, and the mixture was extracted with ethyl acetate. The organic phases were combined, dried over anhydrous magnesium sulfate. The organic phase was filtered, concentrated, and purified by column chromatography (silica gel, petroleum ether) to obtain a white solid (3.23 g, 43.4%).

[0059] Under an ice-water bath, hydrochloric acid (36%, 20 mL, 234 mmol) was slowly added dropwise to a solution of the above white solid in about 40 mL of methanol. The reaction was stirred at room temperature overnight. The solvent was removed by rotary evaporation, extracted with ethyl acetate, the organic phase was washed with saturated NaHCO3 solution until neutral, dried over anhydrous magnesium sulfate, filtered, and the organic phase was concentrated and purified by column chromatography (silica gel, petroleum ether:ethyl acetate = 5:1) to obtain 4-(trifluoromethyl)-2-(perfluorophenyl)phenol, a white solid (2.55 g, 89.5%).

[0060]

[0061] 1 H NMR (400 MHz, CDCl3, 298 K): δ 7.61 (dd, J1 = 1.7 Hz, J2 = 8.6 Hz, 1H, ArH), 7.50 (s, 1H, ArH), 7.05 (d, J = 8.4 Hz, 1H, ArH), 6.65 (s, 1H, OH). 1919F NMR (380 MHz, CDCl3, 298 K): δ -61.66 (s, 3F, CF3), -139.50 to -139.68 (m, 2F, Ar-F), -154.05 to -154.23 (m, 1F, Ar-F), -161.94 to -162.16 (m, 2F, Ar-F).

[0062] Example 2

[0063] Synthesis of 5-(Trifluoromethyl)-3-(perfluorophenyl)salicylaldehyde

[0064] 4-(Trifluoromethyl)-2-(perfluorophenyl)phenol (8.56 g, 23.0 mmol) and hexamethylenetetramine (11.24 g, 80.2 mmol) were dissolved in about 30 mL of trifluoroacetic acid and refluxed at 110 °C overnight. After cooling to 60 °C, dilute hydrochloric acid (2.3 M, 50 mL) was added, and the mixture was refluxed at 110 °C for 6 h. The mixture was extracted with ethyl acetate, and the organic phase was washed with saturated NaHCO3 solution until neutral and dried over anhydrous magnesium sulfate. After concentration of the organic phase, it was purified by column chromatography (silica gel, petroleum ether:ethyl acetate = 5:1) to obtain a yellow crystalline solid (4.78 g, 58.4%).

[0065]

[0066] 1 1H NMR (400 MHz, CDCl3, 298 K): δ 7.61 (dd, J1 = 1.7 Hz, J2 = 8.6 Hz, 1H, ArH), 7.50 (s, 1H, ArH), 7.05 (d, J = 8.4 Hz, 1H, ArH), 6.65 (s, 1H, OH). 19 19F NMR (380 MHz, CDCl3, 298 K): δ -62.07 (s, 3F, CF3), -139.13 to -139.33 (m, 2F, Ar-F), -153.86 to -154.44 (m, 1F, Ar-F), -161.55 to -162.62 (m, 2F, Ar-F).

[0067] Example 3

[0068] Synthesis of 3-(Perfluorophenyl)-5-methylsalicylaldehyde

[0069] Except that 2-(Pentafluorophenyl)-4-methylphenol (6.23 g, 22.7 mmol) was used as the raw material, other operation steps were the same as those in Example 2, and a yellow solid (3.46 g, 50.4%) was obtained.

[0070]

[0071] 1 1H NMR (400 MHz, CDCl3) δ 11.23 (d, J = 3.5 Hz, 1H, OH), 9.93 (d, J = 3.5 Hz, 1H, CHO), 7.50 (s, 1H, ArH), 7.33 (s, 1H, ArH), 2.41 (d, J = 3.2 Hz, 3H, CH3). 19 19F NMR (380 MHz, CDCl3, 298 K): δ -139.57~-139.76 (m, 2F, Ar-F), -154.41~-154.63 (m, 1F, Ar-F), -162.22~-162.45 (m, 2F, Ar-F).

[0072] Example 4

[0073] Synthesis of Ligand L1

[0074] Add 5-methyl-3-(pentafluorophenyl)salicylaldehyde (0.91 g, 3.0 mmol) and 2,6-bis(pentafluorophenyl)-4-methylaniline (1.32 g, 3.0 mmol) into a 100 mL eggplant-shaped flask, dissolve them with 50 mL of ethanol, heat to 80 °C and reflux overnight. Solids precipitate out. Filter, wash the solids with ethanol, and remove the solvent by vacuum drying to obtain bright yellow solids (1.56 g, 71.9%).

[0075]

[0076] 1 1H NMR (400 MHz, CDCl3, 298 K): δ 12.25 (s, 1H, OH), 8.00 (s, 1H, ArCH=N), 7.29 (s, 2H, ArH), 7.14 (d, J = 1.6 Hz, 1H, ArH), 6.98 (d, J = 1.6 Hz, 1H, ArH), 2.48 (s, 3H, CH3), 2.30 (s, 3H, CH3). 13 13C NMR (100 MHz, CDCl3, 298 K): δ 167.14, 167.10, 156.58, 145.52, 138.97, 136.19, 134.08, 133.99, 133.76, 133.69, 128.45, 119.23, 118.02, 114.98, 112.72, 20.84, 20.74, 20.18, 20.09. 1919F NMR (380 MHz, CDCl3, 298 K): δ -139.18 to -139.35 (m, 4F, Ar-F), -139.94 to -140.09 (m, 2F, Ar-F), -153.25 to -153.43 (m, 2F, Ar-F), -155.18 to -155.36 (m, 1F, Ar-F), -160.98 to -161.18 (m, 4F, Ar-F), -162.58 to -162.78 (m, 2F, Ar-F).

[0077] Example 5

[0078] Synthesis of Ligand L2

[0079] Except that 5-trifluoromethyl-3-pentafluorophenylsalicylaldehyde (0.85 g, 2.40 mmol) and 2,6-bis(perfluorophenyl)-4-methylaniline (1.07 g, 2.40 mmol) were used as raw materials, other operation steps were the same as in Example 4, and a yellow solid (1.37 g, 73.5%) was obtained.

[0080]

[0081] 1 1H NMR (400 MHz, CDCl3, 298 K): δ 13.10 (s, 1H, OH), 8.10 (s, 1H, ArCH=N), 7.59 (d, J = 1.2 Hz, 1H, ArH), 7.48 (d, J = 1.6 Hz, 1H, ArH), 7.32 (s, 1H, ArH), 7.41–7.34 (m, 5H, ArH), 7.33–7.27 (m, 2H, ArH), 7.32 (s, 2H, ArH), 2.49 (s, 3H, CH3). 13 13C NMR (100 MHz, CDCl3, 298 K): δ 166.17, 166.12, 161.24, 145.14, 144.52, 142.55, 139.05, 136.99, 132.72, 130.82, 124.73, 122.03, 121.69, 119.24, 117.88, 116.46, 112.40, 20.88, 20.78. 1919F NMR (380 MHz, CDCl3, 298 K): δ -61.80 (s, 3F, CF3), -139.21 to -139.38 (m, 4F, Ar-F), -139.56 to -139.72 (m, 2F, Ar-F), -152.56 to -152.75 (m, 2F, Ar-F), -153.44 to -153.62 (m, 1F, Ar-F), -160.50 to -160.71 (m, 4F, Ar-F), -161.79 to -161.99 (m, 2F, Ar-F).

[0082] Example 6

[0083] Synthesis of ligand L3

[0084] Except that 5-methyl-2-hydroxy-3-(pentafluorophenyl)benzaldehyde (1.51 g, 5.0 mmol) and 2,6-diphenyl-4-methylaniline (1.29 g, 5.0 mmol) were used as raw materials, other operation steps were the same as in Example 4, and a yellow solid (2.43 g, 89.5%) was obtained.

[0085]

[0086] 1 1H NMR (400 MHz, CDCl3, 298 K): δ 13.04 (s, 1H, OH), 7.93 (s, 1H, ArCH=N), 7.39–7.29 (m, 8H, ArH), 7.28–7.21 (m, 4H, ArH), 7.01 (d, J = 2.0 Hz, 1H, ArH), 6.71 (d, J = 2.0 Hz, 1H, ArH), 2.44 (s, 3H, CH3), 2.20 (s, 3H, CH3). 13 13C NMR (100 MHz, CDCl3, 298 K): δ 167.92, 167.88, 156.72, 142.32, 139.45, 135.68, 135.40, 135.31, 134.87, 133.68, 133.59, 131.00, 130.94, 129.75, 128.37, 127.54, 127.01, 118.96, 114.25, 21.01, 20.91, 20.17, 20.10. 19 19F NMR (380 MHz, CDCl3, 298 K): δ -139.57 to -139.73 (m, 2F, Ar-F), -155.80 to -155.99 (m, 1F, Ar-F), -162.86 to -163.8 (m, 2F, Ar-F).

[0087] Example 7

[0088] Synthesis of Ligand L4

[0089] Except that the raw materials used were 5-methyl-2-hydroxy-3-pentafluorophenylbenzaldehyde (1.51 g, 5.0 mmol) and 2,4,6-triphenylaniline (1.61 g, 5.0 mmol), other operation steps were the same as those in Example 4, and a bright yellow solid (2.73 g, 90.2%) was obtained.

[0090]

[0091] 1 H NMR (400 MHz, CDCl3, 298 K): δ 12.93 (s, 1H, OH), 8.00 (s, 1H, ArCH=N), 7.71–7.65 (m, 5H, ArH), 7.50–7.41 (m, 6H, ArH), 7.41–7.34 (m, 5H, ArH), 7.33–7.27 (m, 2H, ArH), 7.04 (s, 1H, ArH), 6.76 (s, 1H, ArH), 2.23 (s, 3H, CH3). 13 C NMR (100 MHz, CDCl3, 298 K): δ 168.09, 168.04, 156.73, 143.95, 140.09, 139.32, 138.89, 135.63, 135.49, 133.79, 133.71, 129.82, 128.50, 127.69, 127.62, 127.24, 127.07, 118.83, 114.34. 19 F NMR (380 MHz, CDCl3, 298 K): δ -139.55–-139.73 (m, 2F, Ar-F), -155.72–-155.90 (m, 1F, Ar-F), -162.81–-163.07 (m, 2F, Ar-F).

[0092] Example 8

[0093] Synthesis of Ligand L5

[0094] Except that the raw materials used were 5-methyl-2-hydroxy-3-pentafluorophenylbenzaldehyde (1.50 g, 5.0 mmol) and 2,6-dibenzyl-4-methylaniline (2.20 g, 5.0 mmol), other operation steps were the same as those in Example 4, and a bright yellow solid (3.09 g, 85.4%) was obtained.

[0095]

[0096] 11H NMR (400 MHz, CDCl3, 298 K): δ 13.16 (s, 1H, OH), 7.24–7.12 (m, 12H, ArH), 7.08 (s, 1H, ArCH=N), 7.05–6.97 (m, 8H, ArH), 6.82 (s, 1H, ArH), 6.66 (s, 1H, ArH), 6.23 (d, J = 0.8 Hz, 1H, ArH), 5.41 (s, 2H, Ph2CH), 2.22 (s, 3H, CH3), 2.22 (s, 3H, CH3). 13 13C NMR (100 MHz, CDCl3, 298 K): δ 168.82, 168.72, 156.59, 145.42, 143.40, 135.31, 134.76, 133.89, 133.83, 129.65, 128.99, 128.26, 127.47, 126.28, 118.42, 114.1452.45, 52.34, 21.47, 21.41, 20.20, 20.12. 19 19F NMR (380 MHz, CDCl3, 298 K): δ -139.46–-139.63 (m, 2F, Ar-F), -155.54–-155.71 (m, 1F, Ar-F), -162.73–-162.94 (m, 2F, Ar-F).

[0097] Example 9

[0098] Synthesis of Ligand L6

[0099] Except that 5-trifluoromethyl-2-hydroxy-3-pentafluorophenylbenzaldehyde (1.78 g, 5.0 mmol) and 2,6-diphenyl-4-methylaniline (1.30 g, 5.0 mmol) were used as raw materials, other operation steps were the same as those in Example 4, and a bright yellow solid (2.53 g, 84.7%) was obtained.

[0100]

[0101] 1 1H NMR (400 MHz, CDCl3, 298 K): δ 14.00 (s, 1H, OH), 7.99 (s, 1H, ArCH=N), 7.46 (s, 1H, ArH), 7.39–7.32 (m, 8H, ArH), 7.32–7.27 (m, 2H, ArH), 7.25 (s, 1H, ArH), 7.16 (d, J = 1.6 Hz, 1H, ArH), 2.46 (s, 3H, CH3). 1313C NMR (100 MHz, CDCl3, 298 K): δ 166.76, 166.71, 161.80, 141.02, 139.10, 136.48, 135.07, 131.11, 131.04, 130.24, 129.63, 128.54, 127.28, 124.98, 122.29, 120.99, 120.65, 120.32, 118.60, 115.70, 21.04, 20.94. 19 19F NMR (380 MHz, CDCl3, 298 K): δ -61.69 (s, 3F, CF3), -139.20–-139.37 (m, 2F, Ar-F), -154.20–-154.38 (m, 1F, Ar-F), -162.17–-162.41 (m, 2F, Ar-F).

[0102] Example 10

[0103] Synthesis of Ligand L7

[0104] Except that the raw materials used were 5-(trifluoromethyl)-2-hydroxy-3-(pentafluorophenyl)benzaldehyde (1.87 g, 5.24 mmol) and 2,4,6-triphenylaniline (1.69 g, 5.25 mmol), 50 mL of ethanol was added for dissolution, and the mixture was heated to 80 °C and refluxed overnight. A solid precipitated. After filtration, the solid was washed with ethanol, and the other operation steps were the same as those in Example 4 to obtain a bright yellow solid (2.93 g, 84.8%).

[0105]

[0106] 1 1H NMR (400 MHz, CDCl3, 298 K): δ 13.86 (s, 1H, OH), 8.06 (s, 1H, ArCH=N), 7.72–7.69 (m, 1H, ArH), 7.68 (s, 1H, ArH), 7.52–7.45 (m, 3H, ArH), 7.46–7.35 (m, 9H, ArH), 7.35–7.29 (m, 2H, ArH), 7.20 (d, J=1.6 Hz, 1H, ArH). 1313C NMR (100 MHz, CDCl3, 298 K): δ 166.96, 166.91, 161.96, 142.71, 139.86, 139.55, 138.99, 135.67, 131.61, 13.30, 129.70, 128.98, 128.66, 127.80, 127.51, 127.09, 126.85, 124.97, 122.27, 121.18, 120.85, 120.51, 118.62, 115.76. 19 19F NMR (380 MHz, CDCl3, 298 K): δ -61.71 (m, 3F, CF3), -139.20–-139.34 (m, 2F, Ar-F), -154.09–-154.28 (m, 1F, Ar-F), -162.10–-162.37 (m, 2F, Ar-F).

[0107] Example 11

[0108] Synthesis of Ligand L8

[0109] Except that 5-(trifluoromethyl)-2-hydroxy-3-(pentafluorophenyl)benzaldehyde (2.40 g, 6.74 mmol) and 2,6-dibenzyl-4-methylaniline (2.96 g, 6.74 mmol) were used as raw materials, other operation steps were the same as those in Example 4, and a bright yellow solid (4.33 g, 82.6%) was obtained.

[0110]

[0111] 1 1H NMR (400 MHz, CDCl3, 298 K): δ 13.99 (s, 1H, OH), 8.06 (s, 1H, ArCH=N), 7.25–7.13 (m, 12H, ArH), 7.05–6.96 (m, 8H, ArH), 6.70 (s, 1H, ArH), 6.66 (s, 1H, ArH), 6.58 (d, J=2.0 Hz, 1H, ArH), 5.35 (s, 2H, Ph2CH), 2.17 (s, 3H, CH3). 13 13C NMR (100 MHz, CDCl3, 298 K): δ 168.33, 161.52, 144.54, 143.11, 134.80, 129.21, 128.39, 124.95, 120.97, 120.63, 118.23, 115.50, 52.71, 52.61, 21.50, 21.44. 1919F NMR (380 MHz, CDCl3, 298 K): δ -61.86 (s, 3F, CF3), -139.11–-139.31 (m, 2F, Ar-F), -153.87–-154.04 (m, 1F, Ar-F), -161.97–-162.19 (m, 2F, Ar-F).

[0112] Example 12

[0113] Synthesis of ligand L9

[0114] Except that 2-hydroxy-3-(pentafluorophenyl)benzaldehyde (1.48 g, 5.15 mmol) and 2,6-diphenyl-4-methylaniline (1.30 g, 5.03 mmol) were used as raw materials, other operation steps were the same as those in Example 4, and a yellow crystalline solid (2.38 g, 89.4%) was obtained.

[0115]

[0116] 1 1H NMR (400 MHz, CDCl3, 298 K): δ 13.30 (s, 1H, OH), 7.97 (s, 1H, ArCH=N), 7.40–7.30 (m, 8H, ArH), 7.28–7.22 (m, 4H, ArH), 7.22–7.17 (dd, J1=1.2 Hz, J2=7.6 Hz, 1H, ArH), 6.94–6.88 (dd,, J1=1.6 Hz, J2=7.6 Hz, 1H, ArH), 6.81 (t, 1H, ArH), 2.44 (s, 3H, CH3). 13 13C NMR (100 MHz, CDCl3, 298 K): δ 167.93, 167.89, 158.92, 142.08, 139.44, 134.67, 130.96, 127.04, 119.15, 118.28, 114.58, 21.02, 20.92. 19 19F NMR (380 MHz, CDCl3, 298 K): δ -138.80–-139.04 (m, 2F, Ar-F), -159.00–-159.22 (m, 1F, Ar-F), -163.11–-163.38 (m, 2F, Ar-F).

[0117] Example 13

[0118] Synthesis of ligand L10

[0119] Except that the raw materials used were 2-hydroxy-3-(pentafluorophenyl)benzaldehyde (1.56 g, 5.40 mmol) and 2,4,6-triphenylaniline (1.74 g, 5.40 mmol), other operation steps were the same as those in Example 4, and a yellow solid (2.71 g, 84.8%) was obtained.

[0120]

[0121] 1 1H NMR (400 MHz, CDCl3, 298 K): δ 13.19 (s, 1H, OH), 8.04 (s, 1H, ArCH=N), 7.69 (m, 4H, ArH), 7.50–7.41 (m, 6H, ArH), 7.41–7.34 (m, 5H, ArH), 7.33–7.27 (m, 2H, ArH), 7.23 (d, J = 7.5 Hz, 1H, ArH), 6.95 (dd, J1 = 1.4, J2 = 7.3 Hz, 1H, ArH), 6.84 (t, J = 7.6 Hz, 1H, ArH). 13 13C NMR (100 MHz, CDCl3, 298 K): δ 167.02, 166.97, 157.82, 142.63, 138.97, 138.22, 137.90, 134.49, 133.86, 132.43, 128.73, 127.88, 127.43, 126.56, 126.18, 125.99, 118.03, 117.40, 117.30, 113.58. 19 19F NMR (380 MHz, CDCl3, 298 K): δ -139.47–-139.68 (m, 2F, Ar-F), -155.54–-155.74 (m, 1F, Ar-F), -162.77–-163.00 (m, 2F, Ar-F).

[0122] Example 14

[0123] Synthesis of nickel complex Ni1

[0124] Under argon protection, sodium hydride (58 mg, 2.4 mmol) was dispersed in 10 mL of tetrahydrofuran, and then ligand L1 (719 mg, 1.0 mmol) was slowly added, and the reaction was carried out overnight at room temperature. After filtration, the solvent was removed by vacuum distillation from the filtrate to obtain a light yellow foamy solid. 10 mL of toluene was added, and trans-bis(triphenylphosphine)phenylnickel chloride (660 mg, 0.95 mmol) was added, and the reaction was carried out overnight at room temperature. After filtration, the filtrate was concentrated and n-hexane was added to adjust the polarity, and a yellow solid (683 mg, 64.2%) was precipitated.

[0125]

[0126] 1 1H NMR (400 MHz, C6D6, 298 K): δ 8.64–8.53 (m, 1H, ArCHN), 7.04–6.84 (m, 10H, ArH), 6.86–6.73 (m, 3H, ArH), 6.72 (s, 1H, ArH), 6.49 (t, J = 7.2 Hz, 1H, ArH), 6.29 (t, J = 7.2 Hz, 2H, ArH) 1.95 (s, 3H, CH3), 1.94 (s, 3H, CH3). 13 13C NMR (100 MHz, C6D6, 298 K): δ 168.82, 161.78, 150.67, 141.09, 140.60, 139.07, 137.49, 135.55, 135.37, 133.55, 135.37, 133.91, 133.79, 133.70, 131.01, 130.57, 129.81, 125.95, 123.34, 122.67, 122.46, 119.24, 31.82, 22.91, 20.23, 19.81, 14.21. 19 19F NMR (380 MHz, C6D6, 298 K): δ -134.47–-135.76 (m, 2F, Ar-F), -135.10–-135.36 (m, 2F, Ar-F), -138.52–-138.78 (m, 2F, Ar-F), -153.57–-153.83 (m, 2F, Ar-F), -158.69–-158.87 (m, 1F, Ar-F), -161.17–-161.41 (m, 2F, Ar-F), -162.35–-162.58 (m, 2F, Ar-F), -162.69–-162.91 (m, 2F, Ar-F). 31 31P NMR (162 MHz, C6D6, 298 K): δ 34.67. Calcd. for C 57 H 31 F 15 NNiOP: C, 61.10; H, 2.79; N, 1.25. Found: C, 60.61; H, 3.19; N, 1.20%.

[0127] Example 15

[0128] Synthesis of nickel complex Ni2

[0129] Except that the raw materials used were ligand L2 (773 mg, 1.0 mmol), sodium hydride (58 mg, 2.4 mmol), and trans-bis(triphenylphosphine)phenylnickel chloride (660 mg, 0.95 mmol), the other operation steps were the same as in Example 14, and a yellow solid (651 mg, 58.3%) was obtained.

[0130]

[0131] 1 1H NMR (400 MHz, C6D6, 298 K): δ 8.59–8.42 (m, 1H, ArH), 7.83 (d, J = 1.2 Hz, 1H, ArCHN), 7.30 (d, 1H, ArH), 7.09–6.92 (m, 9H, ArH), 6.92–6.82 (m, 6H, ArH), 6.72–6.63 (m, 4H, ArH), 6.44 (t, J = 7.2 Hz, 1H, ArH), 6.23 (t, J = 7.2 Hz, 2H, ArH). 1.92 (s, 3H, CH3). 13 13C NMR (100 MHz, C6D6, 298 K): δ 165.24, 149.85, 139.88, 139.40, 137.17, 136.03, 134.10, 133.62, 133.52, 133.29, 130.48, 130.06, 128.01, 127.78, 126.15, 122.71, 122.35, 120.97, 119.30, 116.93, 20.19. 19 19F NMR (380 MHz, C6D6, 298 K): δ -60.97 (m, 3F, CF3), -134.80–-135.00 (m, 2F, Ar-F), -135.04–-135.26 (m, 2F, Ar-F), -138.57–-138.76 (m, 2F, Ar-F), -153.10–-153.33 (m, 2F, Ar-F), -157.62–-157.82 (m, 1F, Ar-F), -161.01–-161.26 (m, 2F, Ar-F), -162.05–-162.39 (m, 4F, Ar-F). 31 31P NMR (162 MHz, C6D6, 298 K): δ 34.94. Calcd. for C 57 H 28 F 18 NNiOP: C, 58.29; H, 2.40; N, 1.19. Found: C, 57.91; H, 2.47; N, 1.19%.

[0132] Example 16

[0133] Synthesis of Nickel Complex Ni3

[0134] Except that the raw materials used were ligand L3 (164 mg, 0.3 mmol), sodium hydride (18 mg, 0.75 mmol), and trans-bis(triphenylphosphine)phenylnickel chloride (208 mg, 0.3 mmol), other operation steps were the same as in Example 14, and a yellow solid (243 mg, 86.1%) was obtained.

[0135]

[0136] 1 H NMR (400 MHz, C6D6, 298 K): δ 8.02 (d, J = 8.8 Hz, 1H, ArCH=N), 7.45 (m, 4H, ArH), 7.32–7.22 (m, 4H, ArH), 7.23–7.16 (m, 2H, ArH), 7.13–6.97 (m, 10H, ArH), 6.97–6.82 (m, 10H, ArH), 6.77 (d, J = 2.0 Hz, 1H, ArH), 6.69 (d, J = 2.0 Hz, 1H, ArH), 6.44 (t, J = 7.2 Hz, 1H, ArH), 6.28 (t, J = 7.6 Hz, 2H, ArH), 2.04 (s, 3H, CH3), 1.95 (s, 3H, CH3). 13 C NMR (100 MHz, C6D6, 298 K): δ 168.52, 161.61, 147.04, 145.09, 144.57, 140.40, 138.04, 137.77, 135.83, 135.48, 134.86, 134.20, 134.10, 131.31, 131.14, 130.94, 130.87, 129.53, 129.18, 128.42, 128.07, 127.78, 127.56, 127.12, 125.55, 124.79, 122.07, 121.54, 119.52, 119.27, 20.54, 19.81. 19 F NMR (380 MHz, C6D6, 298 K): δ -138.74–-138.94 (m, 2F, Ar-F), -159.15–-159.34 (m, 1F, Ar-F), -163.28–-163.48 (m, 2F, Ar-F). 31 P NMR (162 MHz, C6D6, 298 K): δ 36.52. Anal. Calcd. for C 57 H 41F5NNiOP·0.6C6H7: C, 73.81; H, 4.64; N, 1.41. Found: C, 74.01; H, 4.73; N, 1.46%.

[0137] Example 17

[0138] Synthesis of nickel complex Ni4

[0139] Except that the raw materials used were ligand L4 (908 mg, 1.5 mmol), sodium hydride (86 mg, 3.6 mmol), and trans-bis(triphenylphosphine)phenylnickel chloride (974 mg, 1.4 mmol), the other operation steps were the same as those in Example 14, and a yellow solid (964 mg, 68.8%) was obtained.

[0140]

[0141] 1 H NMR (400 MHz, C6D6, 298 K): δ 8.02 (d, J = 8.8 Hz, 1H, ArCH=N), 7.48 (d, J = 7.2 Hz, 4H, ArH), 7.37–7.24 (m, 8H, ArH), 7.24–7.16 (m, 4H, ArH), 7.14–6.99 (m, 10H, ArH), 6.98–6.85 (m, 8H, ArH), 6.86 (d, J = 2.0 Hz 1H, ArH), 6.73 (d, J = 2.0 Hz, 1H, ArH), 6.45 (t, J = 7.2 Hz, 1H, ArH), 6.29 (t, J = 7.2 Hz, 2H, ArH), 1.96 (s, 3H, CH3). 13 C NMR (100 MHz, C6D6, 298 K): δ 168.30, 161.17, 148.39, 144.82, 144.31, 140.78, 140.22, 138.93, 138.06, 137.93, 136.46, 135.48, 134.21, 134.10, 131.24, 131.18, 130.80, 129.60, 129.16, 128.89, 127.79, 127.29, 124.88, 122.18, 121.69, 119.49, 119.40, 19.82. 19 F NMR (380 MHz, C6D6, 298 K): δ -138.74–-139.97 (m, 2F, Ar-F), -159.00–-159.21 (m, 1F, Ar-F), -163.17–-163.43 (m, 2F, Ar-F). 31P NMR (162 MHz, C6D6, 298 K): δ 36.39. Anal. Calcd. for C 62 H 43 F5NNiOP: C, 74.27; H, 4.32; N, 1.40. Found: C, 73.92; H, 4.39; N, 1.55%.

[0142] Example 18

[0143] Synthesis of Nickel Complex Ni5

[0144] Except that the raw materials used were ligand L5 (1.09 g, 1.5 mmol), sodium hydride (86 mg, 3.6 mmol), and trans-bis(triphenylphosphine)phenylnickel chloride (974 mg, 1.4 mmol), the other operating steps were the same as in Example 14, and a yellow solid (1.14 g, 67.8%) was obtained.

[0145]

[0146] 1 H NMR (400 MHz, C6D6, 298 K): δ 7.55 (t, J = 8.4 Hz, 6H, ArH), 7.26 (d, J = 7.6 Hz, 2H, ArH), 7.11–7.00 (m, 14H, ArH), 7.00–6.91 (m, 11H, ArH), 6.90–6.82 (m, 4H, ArH), 6.74 (d, J = 2.0 Hz, 1H, ArCH=N), 6.56 (t, J = 6.8 Hz, 1H, ArH), 6.39 (t, J = 7.2 Hz, 2H, ArH), 5.39 (d, J = 1.6 Hz, 1H, Ph2CH), 2.01 (s, 3H, CH3), 1.82 (s, 3H, CH3). 13 C NMR (100 MHz, C6D6, 298 K): δ 168.83, 184.36, 145.36, 144.15, 143.85, 138.25, 137.90, 137.18, 135.90, 134.53, 134.22, 134.12, 131.34, 130.90, 130.61, 130.23, 129.91, 128.85, 128.26, 128.02, 127.78, 126.36, 126.27, 121.83, 120.93, 120.16, 118.09, 53.51, 31.82, 21.12, 14.21. 1919F NMR(380MHz, C6D6, 298K): δ -138.95–-139.17 (m, 2F, Ar-F), -159.07–-159.28 (m, 1F, Ar-F), -163.01–-163.23 (m, 2F, Ar-F). 31 31P NMR(162MHz, C6D6, 298K): δ 36.69. Anal. Calcd. for C 71 H 53 F5NNiOP·0.5C6H 14 : C, 76.36; H, 5.20; N, 1.20. Found: C, 76.03; H, 5.44; N, 1.25%.

[0147] Example 19

[0148] Synthesis of nickel complex Ni6

[0149] Except that the raw materials used were ligand L6 (896 mg, 1.5 mmol), sodium hydride (86 mg, 3.6 mmol), and trans-bis(triphenylphosphine)phenylnickel chloride (974 mg, 1.4 mmol), other operation steps were the same as those in Example 14, and a yellow solid (1.07 g, 71.7%) was obtained.

[0150]

[0151] 1 1H NMR(400MHz, C6D6, 298K): δ 7.82 (d, J = 8.0 Hz, 1H, ArCHN), 7.40–7.17 (m, 12H, ArH), 7.08–6.94 (m, 10H, ArH), 6.94–6.83 (m, 6H, ArH), 6.80 (s, 2H, ArH), 6.76 (d, J = 7.2 Hz, 2H, ArH), 6.43 (t, J = 6.8 Hz, 1H, ArH), 6.25 (t, J = 7.2 Hz, 1H, ArH), 2.02 (s, 3H, CH3). 13 13C NMR(100MHz, C6D6, 298K): δ 168.44, 165.12, 146.24, 143.63, 143.11, 139.96, 137.75, 135.61, 135.24, 134.05, 133.94, 133.70, 132.20, 131.02, 130.90, 130.77, 130.32, 129.76, 129.18, 128.42, 128.02, 121.78, 127.32, 125.55, 124.97, 121.83, 119.39, 20.50.19 F NMR (380 MHz, C6D6, 298 K): δ -60.54 (s, 3F, CF3), -138.62–-138.84 (m, 2F, Ar-F), -157.99–-158.18 (m, 1F, Ar-F), -162.63–-162.86 (m, 2F, Ar-F). 31 P NMR (162 MHz, C6D6, 298 K): δ 36.16. Anal. Calcd. for C 57 H 38 F8NNiOP: C, 68.84; H, 3.85; N, 1.41. Found: C, 68.89; H, 3.96; N, 1.36%.

[0152] Example 20

[0153] Synthesis of Nickel Complex Ni7

[0154] Except that the raw materials used were ligand L7 (989 mg, 1.5 mmol), sodium hydride (86 mg, 3.6 mmol), and trans-bis(triphenylphosphine)phenylnickel chloride (974 mg, 1.4 mmol), the other operating steps were the same as in Example 14, and a yellow solid (0.94 g, 63.5%) was obtained.

[0155]

[0156] 1 H NMR (400 MHz, C6D6, 298 K): δ 7.82 (d, J = 8.4 Hz, 1H, ArCHN), 7.38–7.26 (m, 10H, ArH), 7.26–7.16 (m, 9H, ArH), 7.07–6.96 (m, 9H, ArH), 6.94–6.85 (m, 6H, ArH), 6.80 (d, J = 7.6 Hz, 2H, ArH), 6.42 (t, J = 7.2 Hz, 1H, ArH), 6.24 (t, J = 7.6 Hz, 2H, ArH). 1313C NMR(100MHz, C6D6, 298K): δ 168.28, 165.23, 147.56, 143.38, 142.86, 140.52, 139.79, 139.25, 137.78, 136.23, 134.05, 133.95, 133.73, 132.34, 131.07, 130.70, 130.25, 129.80, 129.10, 128.94, 128.20, 128.02, 127.78, 127.51, 127.28, 125.06, 121.97, 120.71, 119.35, 115.81, 115.48. 19 19F NMR(380MHz, C6D6, 298K): δ -60.58(s, 3F, CF3), -138.66– -138.84(m, 2F, Ar-F), -157.89– -158.07(m, 1F, Ar-F), -162.56– -162.80(m, 2F, Ar-F). 31 31P NMR(162MHz, C6D6, 298K): δ 36.03. Calcd. for C 62 H 40 F8NNiOP: C, 70.47; H, 3.82; N, 1.33. Found: C, 70.65; H, 3.80; N, 1.33%.

[0157] Example 21

[0158] Synthesis of Nickel Complex Ni8

[0159] Except that the raw materials used were ligand L8 (1.76 g, 1.5 mmol), sodium hydride (86 mg, 3.6 mmol), and trans-bis(triphenylphosphine)phenylnickel chloride (974 mg, 1.4 mmol), the other operating steps were the same as in Example 14, and a yellow solid (1.33 g, 80.9%) was obtained.

[0160]

[0161] 11H NMR (400 MHz, C6D6, 298 K): δ 7.50 (t, J = 8.4 Hz, 6H, ArH), 7.25 (d, J = 2.4 Hz, 1H, ArCHN), 7.21 (d, J = 7.6 Hz, 2H, ArH), 7.11–6.99 (m, 17H, ArH), 6.98–6.84 (m, 11H, ArH), 6.80 (s, 1H, ArH), 6.53 (t, J = 7.2 Hz, 1H, ArH), 6.36 (t, J = 7.2 Hz, 2H, ArH), 6.11–6.00 (m, 2H, Ph2CH), 1.77 (s, 3H, CH3). 13 13C NMR (100 MHz, C6D6, 298 K): δ 167.79, 163.23, 146.45, 143.06, 142.68, 142.58, 142.03, 136.67, 136.33, 133.66, 133.02, 132.82, 132.72, 129.62, 129.27, 129.18, 128.83, 127.58, 127.30, 127.09, 126.75, 126.72, 126.51, 128.48, 125.23, 125.11, 66.41, 52.36, 24.41, 19.80. 19 19F NMR (380 MHz, C6D6, 298 K): δ -60.81 (s, 3F, CF3), -138.84– -139.00 (m, 2F, Ar-F), -157.94– -158.10 (m, 1F, Ar-F), -162.54– -162.76 (m, 2F, Ar-F). 31 31P NMR (162 MHz, C6D6, 298 K): δ 37.05. Calcd. for C 71 H 50 F8NNiOP·1.4C4H8O: C, 72.12; H, 4.84; N, 1.10. Found: C, 71.64; H, 4.73; N, 1.32%.

[0162] Example 22

[0163] Synthesis of nickel complex Ni9

[0164] Except that ligand L9 (927 mg, 1.0 mmol), sodium hydride (58 mg, 2.4 mmol), and trans-bis(triphenylphosphine)phenylnickel chloride (660 mg, 0.95 mmol) were used as raw materials, other operation steps were the same as those in Example 14, and a yellow solid (662 mg, 75.2%) was obtained.

[0165]

[0166] 1 1H NMR (400 MHz, C6D6, 298 K): δ 8.03 (d, J = 8.4 Hz, 1H, ArCHN), 7.37 (d, 4H, ArH), 7.30–7.17 (m, 6H, ArH), 7.13–6.95 (m, 12H, ArH), 6.95–6.77 (m, 11H, ArH), 6.50–6.37 (m, 2H, ArH), 6.29 (t, J = 7.2 Hz, 2H, ArH), 2.03 (s, 3H, CH3). 13 13C NMR (100 MHz, C6D6, 298 K): δ 168.67, 163.37, 146.78, 140.35, 137.98, 136.16, 135.89, 134.90, 134.18, 134.08, 131.19, 131.10, 130.96, 130.75, 129.56, 129.18, 128.42, 128.08, 128.02, 127.78, 127.15, 125.55, 124.80, 121.61, 120.10, 119.61, 113.56, 20.51. 19 19F NMR (380 MHz, C6D6, 298 K): δ -138.80–-139.04 (m, 2F, Ar-F), -159.00–-159.22 (m, 1F, Ar-F), -163.11–-163.38 (m, 2F, Ar-F). 31 31P NMR (162 MHz, C6D6, 298 K): δ 36.28. Calcd. for C 56 H 39 F5NNiOP·0.4C7H8: C, 73.30; H, 4.42; N, 1.45. Found: C, 73.23; H, 4.53; N, 1.24%.

[0167] Example 23

[0168] Synthesis of nickel complex Ni10

[0169] Except that the raw materials used were ligand L10 (989 mg, 1.0 mmol), sodium hydride (58 mg, 2.4 mmol), and trans-bis(triphenylphosphine)phenylnickel chloride (660 mg, 0.95 mmol), the other operation steps were the same as those in Example 14, and a yellow solid (696 mg, 74.1%) was obtained.

[0170]

[0171] 1 1H NMR (400 MHz, C6D6, 298 K): δ 8.03 (d, J = 8.8 Hz, 1H, ArCHN), 7.40 (m, 4H, ArH), 7.36–7.28 (m, 4H, ArH), 7.28–7.16 (m, 8H, ArH), 7.12–6.96 (m, 11H, ArH), 6.96–6.83 (m, 9H, ArH), 6.49–6.39 (m, 2H, ArH), 6.28 (t, J = 7.2 Hz, 2H, ArH). 13 13C NMR (100 MHz, C6D6, 298 K): δ 167.19, 162.23, 146.85, 143.26, 142.74, 139.45, 138.90, 137.69, 136.70, 135.24, 135.11, 134.92, 132.91, 132.81, 129.87, 129.40, 128.35, 127.90, 127.63, 126.75, 126.51, 126.31, 126.07, 126.01, 123.63, 123.61, 120.48, 118.79, 118.46, 112.37. 19 19F NMR (380 MHz, C6D6, 298 K): δ -138.83–-139.04 (m, 2F, Ar-F), -158.88–-159.09 (m, 1F, Ar-F), -163.04–-163.30 (m, 2F, Ar-F). 31 31P NMR (162 MHz, C6D6, 298 K): δ 36.14. Calcd. for C 61 H 41 F5NNiOP·0.5C4H8O: C, 73.84; H, 4.43; N, 1.37. Found: C, 73.40; H, 4.18; N, 1.46%.

[0172] Example 24

[0173] Under argon protection, a toluene solution of norbornene (0.5 g / mL, 3.8 mL, 20 mmol) was added to a polymerization flask, and an appropriate amount of toluene was added to make the final total volume 10 mL. A toluene solution of catalyst Ni1 (20 μmol / mL, 0.1 mL, 2 μmol) was measured and added to the polymerization flask. The reaction temperature was controlled at 30 ± 1 °C, methylaluminoxane (1 M, 4 mL, 4 mmol) was added, and the reaction was carried out for 5 minutes. Then, hydrochloric acid / ethanol was added to terminate the reaction. The mixture was filtered, the residue was washed with ethanol, and vacuum dried at 60 °C for 12 h. [NBE]0 = 2.0 M, [Ni]0 = 0.0002 M, [Ni]0:[NBE]0 = 1:10000, [Ni]0:[Al]0 = 1:2000, yield: 58.3%, activity 6.64×10 6 g / (mol-Ni·h).

[0174] Examples 25 - 31

[0175] Using Ni1 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 1, other operations were the same as in Example 24.

[0176] Examples 32 - 37

[0177] Using Ni2 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 2, other operations were the same as in Example 24.

[0178] Examples 38 - 44

[0179] Using Ni3 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 3, other operations were the same as in Example 24.

[0180] Examples 45 - 50

[0181] Using Ni4 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 4, other operations were the same as in Example 24.

[0182] Examples 51 - 55

[0183] Using Ni5 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 5, other operations were the same as in Example 24.

[0184] Examples 56 - 59

[0185] Using Ni6 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 6, other operations were the same as in Example 24.

[0186] Examples 60 - 63

[0187] Using Ni7 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 7, other operations were the same as in Example 24.

[0188] Examples 64 - 68

[0189] Using Ni8 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 8, other operations were the same as in Example 24.

[0190] Examples 69 - 72

[0191] Using Ni9 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 9, other operations were the same as in Example 24.

[0192] Examples 73 - 76

[0193] Using Ni10 as the catalyst, norbornene was polymerized under different conditions. Except for the specific polymerization conditions as described in Table 10, other operations were the same as in Example 24.

[0194]

[0195]

[0196]

[0197]

Claims

1. A perfluorophenyl-substituted salicylaldimine ligand (I), characterized in that, Has the following general formula: In formula (I): R 1 represents hydrogen, a C1-C6 linear or branched alkyl group, or a C1-C6 perfluorinated linear or branched alkyl group; R 2 represents an aryl group having 6 to 18 carbon atoms, a perfluoroaryl group having 6 to 18 carbon atoms, or a mono- or poly-aryl-substituted alkyl group having 7 to 30 carbon atoms; R 3 represents an alkyl group with a straight-chain or branched-chain structure of C1 to C6, an aryl group of C6 to C 18 .

2. The perfluorophenyl-substituted salicylaldimine ligand (I) according to claim 1, wherein R 1 is hydrogen, an alkyl group with a straight-chain or branched-chain structure having 1 to 4 carbon atoms, a perfluoroalkyl group with a straight-chain or branched-chain structure having 1 to 4 carbon atoms; R 2 is an aryl group having 6 to 12 carbon atoms, a perfluoroaryl group having 6 to 12 carbon atoms, a mono- or poly-aryl-substituted alkyl group having 7 to 20 carbon atoms; R 3 is an alkyl group with a straight-chain or branched-chain structure having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms.

3. The perfluorophenyl-substituted salicylaldimine ligand (I) according to claim 1, wherein R 1 is hydrogen, methyl, or trifluoromethyl; R 2 is phenyl, perfluorophenyl, or diphenylmethyl; R 3 is methyl or phenyl.

4. A perfluorophenyl-substituted salicylaldimine nickel complex (II), characterized in that, Has the following general formula: In formula (II): R 1 represents hydrogen, a C1-C6 linear or branched alkyl group, or a C1-C6 perfluorinated linear or branched alkyl group; R 2 represents an aryl group having 6 to 18 carbon atoms, a perfluoroaryl group having 6 to 18 carbon atoms, or a mono- or poly-aryl-substituted alkyl group having 7 to 30 carbon atoms; R 3 represents an alkyl group with a straight-chain or branched-chain structure of C1 to C6, an aryl group of C6 to C 18 ; R 4 and R 5 represent aryl groups having 6 to 18 carbon atoms; R 4 and R 5 may be the same or different.

5. The nickel complex (II) of perfluorophenyl-substituted salicylaldimine according to claim 4, characterized in that, R 1 is hydrogen, an alkyl group with a linear or branched C1-C4 structure, or a perfluoroalkyl group with a linear or branched C1-C4 structure; R 2 is an aryl group with C6-C 12 a perfluoroaryl group with C6-C 12 a mono- or poly-aryl-substituted alkyl group with C7-C 20 ; R 3 is an alkyl group with a linear or branched C1-C4 structure, or an aryl group with C6-C 12 ; R 4 , R 5 are aryl groups with C6-C 12 .

6. The perfluorophenyl-substituted salicylaldimine metal nickel complex (II) according to claim 4, characterized in that, R 1 is hydrogen, methyl, trifluoromethyl; R 2 is phenyl, perfluorophenyl, diphenylmethyl; R 3 is methyl, phenyl; R 4 and R 5 is phenyl.

7. The preparation method of the perfluorophenyl-substituted salicylaldimine nickel complex (II) according to any one of claims 4 to 6, comprising the following steps: Subject the substituted aniline (IV) and perfluorobenzene-substituted salicylaldehyde (III) to a Schiff base condensation reaction at a reaction temperature of 25 to 150 °C and a reaction time of 2 to 72 hours, and then collect the ligand compound (I) from the reaction product; Then, after metalating the perfluorophenyl-substituted salicylaldimine ligand compound shown in formula (I) with NaH, react it with a nickel metal raw material compound in an organic medium at a reaction temperature of 0 to 100 °C and a reaction time of 2 to 96 hours, and then collect the perfluorophenyl-substituted salicylaldimine nickel target compound (II) from the reaction product; Substituent R in the above preparation method 1 ~R 5 is consistent with each corresponding group of the nickel (II) complex of perfluorophenyl-substituted salicylaldimine described in any one of Claims 4 to 6.

8. The method according to claim 7, wherein The nickel metal raw material compound is trans-bis(triphenylphosphine)phenyl nickel chloride; the molar ratio of the perfluorophenyl-substituted salicylaldimine ligand compound to the nickel metal raw material compound is 1:0.5 to 1.5; the organic medium is selected from one, two, three, four, or five of tetrahydrofuran, ether, toluene, benzene, petroleum ether, and n-hexane.

9. Use of the perfluorophenyl-substituted salicylaldimine nickel complex according to any one of claims 4 to 6, characterized in that, Under the activation of an aluminum-containing cocatalyst, it is used for the addition polymerization of norbornene.

10. The application according to claim 9, characterized in that, The aluminum-containing cocatalyst is methylaluminoxane (MAO), modified methylaluminoxane (MMAO), or an alkylaluminum with a straight-chain or branched-chain structure of C1 to C4.

11. The application according to claim 9, wherein Using the perfluorophenyl-substituted salicylaldimine nickel complex according to any one of claims 4 to 6 as a catalyst, under the activation of an aluminum-containing cocatalyst, polymerize norbornene; the molar ratio of the catalyst to the monomer during polymerization is 1:1 to 20000; the molar ratio of the catalyst to the aluminum-containing cocatalyst during polymerization is 500 to 10000.

12. The application according to claim 9, wherein Using the perfluorophenyl-substituted salicylaldimine nickel complex according to any one of claims 4 to 6 as a catalyst, under the activation of methylaluminoxane, polymerize norbornene at 0 to 120 °C; the molar ratio of the catalyst to the monomer during polymerization is 1:1 to 20000; the molar ratio of the catalyst to the aluminum-containing cocatalyst during polymerization is 500 to 10000.

13. The application according to claim 9, characterized in that, Using the perfluorophenyl-substituted salicylaldimine nickel complex according to any one of claims 4 to 6 as a catalyst, under the activation of methylaluminoxane, polymerize norbornene at 30 to 90 °C; the molar ratio of the catalyst to the monomer during polymerization is 1:2500 to 10000; the molar ratio of the catalyst to the aluminum-containing cocatalyst during polymerization is 1000 to 4000.

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