CN101348501B - 2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof - Google Patents

Abstract

The invention discloses a 2-imdo group-9-phenyl group-1, 10-phenanthrolines transition metal complex and a preparation method thereof and an application thereof. The structural formula of the 2-imdo group-9-phenyl group-1, 10-phenanthrolines transition metal complex of the invention is shown as the formula(I), wherein M is transition metal, and R and R<1> are independently selected from hydrogen,alkyl and phenyl respectively. In the invention, the ligand and the transition metal complex of 2-imdo group-9-phenyl group-1, 10-phenanthrolines containing N^N^N ligand are designed and synthesized;when the transition metal complex is used to catalyze the ethylene oligomerization reaction, the transition metal complex performs good catalytic activity and high selectivity of 1-butylene, so that the transition metal complex has broad industrial application prospect.

Description

2-imino-9-phenyl-1,10-phenanthroline transition metal complex and its preparation method and application

technical field

The invention relates to a 2-imino-9-phenyl-1,10-phenanthroline transition metal complex and a preparation method thereof, as well as a catalyst composition composed of the transition metal complex and the catalyst composition in Applications in catalytic ethylene oligomerization.

Background technique

Linear α-olefin is a very important organic chemical intermediate, which has different properties and uses according to the length of its carbon chain. C ₄ ~ C ₈ are comonomers for the production of linear low density polyethylene (LLDPE); C ₈ ~ C ₁₂ can be used as basic raw materials for the production of high-grade lubricants; C ₁₀ ~ C ₁₈ are used for the production of surfactants, detergents and An important raw material for cleaning agents; high-carbon α-olefins are widely used in oilfield chemistry and paper setting agents. At present, the industrial production of linear α-olefins is mainly realized by the method of ethylene oligomerization. In recent years, the demand for α-olefins in the world has been increasing year by year. According to data, the world's demand for α-olefins reached 3.4 million tons in 2002, maintaining a scale of 4.9% growth in world demand; the market for α-olefins Considered to be the core factor of economic growth in the United States and Western Europe, this huge market consumes full-fraction α-olefins, such as: in Western Europe, high-grade lubricants for transportation vehicles are polymers of α-olefins; both household and industrial cleaning agents are It is an ethoxylate compound of α-olefin, ether-based sulfate, etc.; and high-carbon α-olefin is widely used in oilfield chemistry and paper setting agent. Since the 1970s, research on homogeneously catalyzed ethylene oligomerization by transition metal complexes has attracted people's attention. Shell first discovered the Shell Higher Olefin Preparation Process, namely the SHOP (Shell Higher Olefin Process) process. Related patents: US Patent3686351, 19720711 and US Patent3676523, 19720822, which are O—P bridging type coordination nickel catalyst (formula A), ethylene oligomerization catalytic activity is about 10 ⁵ g·mol ^-1 (Ni)·h ^-1 , the 99% of the products obtained in the process are linear olefins, of which α-olefins account for 98%, and have been industrialized and widely used.

(式A)

(Formula A)

While improving the existing catalysts, people are also working hard to study new catalysts, simplify the synthesis and preparation process of catalysts, and improve the catalytic activity of catalysts and the selectivity of catalytic products. In recent years, a variety of late-transition metal catalyst systems with O, N, P and other heteroatoms as ligands have been developed. Among them, catalysts with nitrogen atoms as coordination teeth have received extensive attention, such as the recent patent: Jpn.Kokai Tokkyo Koho JP 11060627, A22 Mar 1999 Heisei; PCTInt.Appl. WO9923096A114May1999; PCTInt.Appl. WO9951550A114 Oct 1999.

Ethylene oligomerization and polymerization follow the same reaction mechanism, therefore, ethylene oligomerization and polymerization are two types of products with different properties that catalyze the ethylene reaction. Half of the usage of polymer materials is polyolefin resin. Compared with other resin materials, olefin resin has excellent environmental coordination. It is used as a key promotion material in the automobile industry of developed countries. In 2003, the world production volume reached Among them, polyethylene is the synthetic resin with the fastest development, the largest output, and a wide range of uses, reaching 51.1 million tons that year. Industrialized polyethylene catalysts include Ziegler-Natta type catalysts (DE Pat889229 (1953); IT Pat545332 (1956) and IT Pat536899 (1955); Chem. Rev., 2000, 100, 1169 and related literature in this special series), Phillips type catalysts (Belg.Pat.530617 (1955); Chem.Rev.1996, 96, 3327) and metallocene-type catalysts (W.Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin: Springer, 1999), and post-transitions developed in recent years Highly efficient ethylene oligomerization and polymerization catalysts of the metal metal complex type. In 1995, Brookhart etc. reported a class of α-diimine Ni(II) complexes, which can polymerize ethylene with high activity, and its structure is shown in the following formula (J.Am.Chem.Soc., 1995,117,6414 -6415):

In 1998, Brookhart and Gibson et al. reported the complexes of pyridine diimide iron (II) and cobalt (II) at the same time. By adjusting the substituents on the benzene ring, ethylene can be well oligomerized or polymerized. Its structure is as follows Formula B (J.Am.Chem.Soc., 1998, 120, 4049-4050; Chem.Commun.1998, 849-850):

(Formula B)

At present, the industry mainly uses Ni, Cr, Zr and ZN catalysts to produce α-olefins, mainly concentrated in three major companies, namely BP, Chevron Phillips and Shell, and several companies have independent production processes and technologies. Shell's oligomerization process is mainly to synthesize high-carbon chain α-olefins, which are used in detergents and detergent intermediates. The catalytic activity of ethylene oligomerization is about 10 ⁵ g·mol ^-1 (Ni)·h ^-1 , 99% of the obtained products are linear olefins, of which α-olefins account for 98%. Since the process uses high-pressure oligomerization, the equipment cost and operating cost are relatively high, so the current development goal is still low-pressure oligomerization. Nickel-based catalysts require high-pressure catalytic technology and technology, and there is a potential danger of double bond displacement to generate internal olefins, and the operating conditions are harsh; other types of catalysts are modified and modified on the basis of production of polyolefin catalysts, and are often damaged by careless operation. Cause high polyolefin formation and block the discharge port. Therefore, the research and development of new highly active ethylene oligomerization catalysts is the key to the development of new ethylene oligomerization processes.

Contents of the invention

The object of the present invention is to provide a 2-imino-9-phenyl-1,10-phenanthroline transition metal complex and a preparation method thereof.

The 2-imino-9-phenyl-1,10-phenanthroline transition metal complex of the present invention has a structural formula as shown in formula I,

Wherein, M is a transition metal;

R and ^R1 are each independently selected from hydrogen, alkyl and phenyl.

Preferably, M is Fe, Co or Ni; R ^is selected from hydrogen, methyl, ethyl, isopropyl; R is selected from methyl and phenyl. More preferably, the metal complexes of the present invention are selected from any of the following complexes:

M=Fe, R=Me, ^R1 =Me; M=Fe, R=Me, ^R1 =Et;

M=Fe, R=Me, R ¹ =iPr; M=Fe, R=Ph, R ¹ =Me;

M=Fe, R=Ph, R ¹ =Et; M=Fe, R=Ph, R ¹ =iPr;

M=Co, R=Me, ^R1 =Me; M=Co, R=Me, ^R1 =Et;

M=Co, R=Me, R ¹ =iPr; M=Co, R=Ph, R ¹ =Me;

M=Co, R=Ph, R ¹ =Et; M=Co, R=Ph, R ¹ =iPr;

M=Ni, R=Me, ^R1 =Me; M=Ni, R=Me, ^R1 =Et;

M=Ni, R=Me, ^R1 =iPr; M=Ni, R=Ph, ^R1 =Me;

M=Ni, R=Ph, R ¹ =Et; M=Ni, R=Ph, R ¹ =iPr;

Here, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, and Ph represents a phenyl group.

The preparation method of this transition metal complex comprises the steps:

1) Use 2-acetyl-9-phenyl-1,10-phenanthroline or 2-benzoyl-9-phenyl-1,10-phenanthroline and alkyl-substituted aniline to synthesize 2- Amino-9-phenyl-1,10-phenanthroline ligand;

2) The complex can be obtained by reacting the 2-imino-9-phenyl-1,10-phenanthroline ligand obtained in step 1) with a transition metal salt.

Wherein, step 1) reacts with p-toluenesulfonic acid as catalyst.

Another object of the present invention is to provide uses of the metal complexes of the present invention.

The metal complex of the present invention can constitute a catalyst composition for ethylene oligomerization.

The catalyst composition includes a main catalyst and a cocatalyst, wherein the main catalyst is the 2-imino-9-phenyl-1,10-phenanthroline transition metal complex of the present invention, and the cocatalyst is selected from aluminoxane, Alkyl aluminum compounds and alkyl aluminum chlorides.

Preferably, the aluminoxane is methylalumoxane, modified methylalumoxane; alkylaluminum and alkylaluminum chloride include trimethylaluminum, triethylaluminum, diethylaluminum chloride, diethylaluminum Ethyl Aluminum Chloride. The molar ratio of metal aluminum in the cocatalyst to the central metal Al/M of the main catalyst is 100 to 2000.

In the catalyst composition, an auxiliary ligand triphenylphosphine can also be added to improve the catalytic activity and prolong the life of the catalyst. The molar ratio of the triphenylphosphine to the main catalyst is 50-1:1.

The application of the above catalyst composition in catalyzing ethylene oligomerization also belongs to the protection scope of the present invention. Preferably, the oligomerization reaction temperature is 20 to 80°C, and the ethylene pressure is 10-0.1 MPa.

The present invention designs and synthesizes 2-imino-9-phenyl-1,10-phenanthroline ligand and transition metal complex containing N＾N＾N ligand, and the metal complex is used to catalyze ethylene Oligomerization reaction, showing excellent catalytic activity and high 1-butene selectivity, has a wide range of industrial application prospects.

Description of drawings

Fig. 1 is the crystal structure figure of ligand 2;

Fig. 2 is the crystal structure figure of complex 2;

Fig. 3 is the crystal structure diagram of complex 7;

Fig. 4 is the crystal structure figure of complex 10;

Figure 5 is a crystal structure diagram of complex 12;

Figure 6 is a crystal structure diagram of complex 13;

FIG. 7 is a crystal structure diagram of complex 17.

Detailed ways

Complexes of the present invention can be synthesized according to the following equation:

Specific steps are as follows:

1. Use 2-acetyl-9-phenyl-1,10-phenanthroline or 2-benzoyl-9-phenyl-1,10-phenanthroline to react with substituted aniline to synthesize 2-imino -9-phenyl-1,10-phenanthroline ligand;

2. Use 2-imino-9-phenyl-1,10-phenanthroline ligands to react with transition metal salts (such as FeCl ₂ 4H ₂ O, CoCl ₂ , NiCl ₂ 6H ₂ O, etc.), complexes can be obtained.

Wherein, 2-acetyl-9-phenyl-1,10-phenanthroline main synthesis steps are: (1) 2-acetyl-1,10-phenanthroline, ethylene glycol and p-toluenesulfonic acid in toluene ( 100mL) was refluxed for 18 hours until no water was generated in the oil-water separator. After removing the solvent toluene, the residue was purified by perbasic alumina column, rinsed with petroleum ether/ethyl acetate (1:2), and the second fraction was condensed product. (2) The phenyllithium solution is added dropwise to the toluene suspension of the product obtained in step (1), and the original yellow color becomes brown. After the dropwise addition, the reaction solution was stirred and reacted at 0°C for 3 hours under the protection of nitrogen. Then, water was added carefully and stirred to stop the reaction, the yellow organic layer was separated, the aqueous layer was extracted several times with dichloromethane, and then the organic phases were combined and dried over anhydrous sodium sulfate. The organic layer was concentrated, and the residue was purified by silica gel column to obtain a yellow oil. The yellow oil obtained above was dissolved in acetone, p-toluenesulfonic acid was added as a catalyst, and heated to reflux for 15 hours, the product precipitated from the solution, and after filtration, a light yellow solid product 2-acetyl-9-phenyl-1 was obtained. 10-Phenanthroline.

The main synthesis steps of 2-benzoyl-9-phenyl-1,10-phenanthroline are: add phenyllithium solution dropwise to 2-cyano-1,10- In the toluene suspension of phenanthroline, after the dropwise addition was completed, it was slowly warmed to room temperature and stirred overnight. The reaction was quenched by slow addition of water, the red organic layer was separated, the aqueous layer was extracted several times with dichloromethane, then the organic phases were combined and dried over anhydrous sodium sulfate. The organic layer was concentrated, and the residue was purified by silica gel column to obtain 2-benzoyl-9-phenyl-1,10-phenanthroline as a yellow solid product.

Preferably, complexes with the following substitutions can be obtained:

1: M=Fe, R=Me, R ¹ =Me; 2: M=Fe, R=Me, R ¹ =Et;

3: M=Fe, R=Me, R ¹ =iPr; 4: M=Fe, R=Ph, R ¹ =Me;

5: M=Fe, R=Ph, R ¹ =Et; 6: M=Fe, R=Ph, R ¹ =iPr;

7: M=Co, R=Me, R ¹ =Me; 8: M=Co, R=Me, R ¹ =Et;

9: M=Co, R=Me, R ¹ =iPr; 10: M=Co, R=Ph, R ¹ =Me;

11: M=Co, R=Ph, R ¹ =Et; 12: M=Co, R=Ph, R ¹ =iPr;

13: M=Ni, R=Me, R ¹ =Me; 14: M=Ni, R=Me, R ¹ =Et;

15: M=Ni, R=Me, R ¹ =iPr; 16: M=Ni, R=Ph, R ¹ =Me;

17: M=Ni, R=Ph, R ¹ =Et; 18: M=Ni, R=Ph, R ¹ =iPr;

Concrete preparation process is as follows:

1. General method of ligand synthesis

1.2-Acetyl-9-phenyl-1,10-phenanthroline and alkyl-substituted aniline were refluxed in toluene with p-toluenesulfonic acid as a catalyst for 1 day, after the reaction solution was concentrated, it was perbasic alumina column, and petroleum After washing with ether/ethyl acetate (20:1), the second fraction was divided into the product, and the solvent was removed to obtain a yellow solid, which was the corresponding ligand.

2.2-Benzoyl-9-phenyl-1,10-phenanthroline and alkyl-substituted aniline use p-toluenesulfonic acid as a catalyst, use ethyl orthosilicate as solvent and dehydrating agent, at 140-150°C Heating and reacting for 1.5 days, removing tetraethyl orthosilicate under reduced pressure, then perbasic alumina column, washing with petroleum ether/ethyl acetate (6:1), the second stream was divided into products, and the solvent was removed to obtain a yellow solid. is the corresponding ligand.

All the above synthesized 2-imino-9-phenyl-1,10-phenanthroline ligands were confirmed by NMR, IR and elemental analysis.

2. General method for the synthesis of iron (II), cobalt (II), and nickel (II) complexes

Mix FeCl ₂ 4H ₂ O, CoCl ₂ or NiCl ₂ 6H ₂ O and 2-imino-9-phenyl-1,10-phenanthroline ligand in a molar ratio (1:1), add tetrahydrofuran Or ethanol as a solvent, stirred at room temperature for 9 hours, precipitated, filtered and washed with ether and dried to obtain 2-imino-9-phenyl-1,10-phenanthroline complex.

The complex of the present invention can also be used to form a catalyst composition for ethylene oligomerization, which includes a main catalyst and a co-catalyst (ie, an activator) for activation of the main catalyst. The main catalyst is the 2-imino-9-phenyl-1,10-phenanthroline complex of the present invention, and aluminoxane, alkylaluminum compound and alkylaluminum chloride can be used as cocatalysts use. Examples of aluminoxanes include methylalumoxane (MAO), triisobutylaluminum-modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Aluminoxanes can be produced by the hydrolysis of various trialkylaluminum compounds, MMAO can be produced by the hydrolysis of trimethylaluminum and higher trialkylaluminums such as triisobutylaluminum; Examples of alkylaluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, and the like. Preferably, aluminoxane and alkylaluminum chloride, such as methylaluminoxane (MAO), triisobutylaluminum modified methylaluminoxane (MMAO) and diethylaluminum chloride are used catalyst.

For the above catalyst composition, under the synergistic effect of the cocatalyst methylaluminoxane (abbreviated as MAO) or triisobutylaluminum modified methylaluminoxane (abbreviated as MMAO), the iron(II) complex The compound shows good oligomerization activity to ethylene, and the product is mainly butene, and the selectivity to 1-butene is as high as 99% or more; (II) complex shows higher activity to ethylene oligomerization, and the oligomer of generation is mainly butene, hexene, octene etc., and also reaches more than 95% to the selectivity of 1-butene; Under the synergistic effect of the catalyst diethylaluminum chloride (Et ₂ AlCl), the nickel(II) complex exhibits moderate oligomerization activity towards ethylene, however, the addition of the auxiliary ligand triphenylphosphine can greatly improve the activity of the nickel complex. Catalytic activity and extended catalyst life.

The complex of the present invention and its catalytic process for ethylene oligomerization are described below with specific examples.

Example 1

1. Preparation of 2-acetyl-9-phenyl-1,10-phenanthroline:

1) 2-acetyl-1,10-phenanthroline (2.823g, 10.0mmol), ethylene glycol (3.254g, 52.4mmol) and p-toluenesulfonic acid (206mg) were refluxed in toluene (100mL) for 18 hours until No water is generated in the oil-water separator, after removing the solvent toluene, the residue is purified by an alkaline alumina column, rinsed with petroleum ether/ethyl acetate (1:2), and the second stream is separated into the product, and a light yellow solid is obtained after concentration 1.691 g, 50% yield. The melting point is 119-121°C.

FT-IR (KBr disc): 3054, 2993, 2980, 2938, 2900, 1619, 1589, 1552, 1505, 1490, 1476, 1445, 1391, 1376, 1256, 1232, 1204, 1147, 1129, 1106, 1029, 1009, 953, 855, 789, 752, 675cm-1.

¹ H NMR (400MHz, CDCl3): δ=9.24(d, J=4.4Hz, 1H), 8.25(d, J=8.4Hz, 1H), 8.22(d, J=8.4Hz, 1H), 7.93(d , J=8.4Hz, 1H), 7.77(s, 2H), 7.61(dd, J=4.4Hz, 1H), 4.18(t, J=6.4Hz, 2H), 4.01(t, J=6.4Hz, 2H ), 1.98(s, 3H).

¹³ C NMR (100MHz, CDCl3): δ=161.5, 150.5, 146.4, 145.8, 136.8, 136.0, 129.0, 128.1, 126.7, 126.3, 122.9, 119.5, 65.2, 25.6.

Elemental analysis (C ₁₆ H ₁₄ N ₂ O ₂ ) theoretical value (%): C72.16, H5.30, N10.52; experimental value (%): C72.18, H5.23, N11.00.

2) Ether solution (20mL) of bromobenzene (0.9mL, 8.5mmol) was added dropwise to 2 equivalents of metal lithium (118mg, 17.0mmol) in ether suspension (30mL) to prepare phenyllithium solution at room temperature and under nitrogen protection . Under the protection of nitrogen at 0°C, the prepared phenyllithium solution was added dropwise to the toluene suspension (40 mL) of the product obtained in step 1) (1.333 g, 5.0 mmol), and the original yellow color became brown. After the dropwise addition, the reaction solution was stirred and reacted at 0°C for 3 hours under the protection of nitrogen. Then, water (100 mL) was added carefully to stop the reaction with stirring, the yellow organic layer was separated, the aqueous layer was extracted several times with dichloromethane, then the organic phases were combined and dried over anhydrous sodium sulfate. The organic layer was concentrated, and the residue was purified by silica gel column to obtain a yellow oil. The yellow oil obtained above was dissolved in acetone (50 mL), and p-toluenesulfonic acid (170 mg) was added as a catalyst, heated to reflux for 15 hours, the product precipitated out of the solution, and after filtration, a light yellow solid product 2-acetyl-9 was obtained. -Phenyl-1,10-phenanthroline 0.710 g, yield 47.5%. The melting point is 184-186°C.

FT-IR (KBr disc): 3103, 3026, 2916, 1694, 1633, 1620, 1597, 1565, 1537, 1495, 1367, 1285, 1219, 1190, 1120, 1034, 1011, 888, 817, 766, 741, 678,566cm-1.

¹ H NMR (300MHz, CDCl3): δ=8.44(d, J=7.2Hz, 2H), 8.34(d, J=3.0Hz, 2H), 8.30(d, J=8.4Hz, 1H), 8.17(d , J=8.4Hz, 1H), 7.88(d, J=8.7Hz, 1H), 7.78(d, J=8.7Hz, 1H), 7.59(t, J=7.2Hz, 2H), 7.50(t, J =7.2Hz, 1H), 3.14(s, 3H).

¹³ C NMR (75MHz, CDCl3): δ=200.3, 156.6, 152.3, 145.4, 144.8, 138.5, 136.5, 130.4, 129.3, 128.4, 128.1, 127.3, 127.0, 125.3, 119.7, 119.6, 25.2.

Elemental analysis (C ₂₀ H ₁₄ N ₂ O) theoretical value (%): C80.52, H4.73, N9.39; experimental value (%): C80.00, H4.77, N9.36.

2. Preparation of 2-acetyl-9-phenyl-1,10-phenanthroline (2,6-dimethylaniline) ligand [ligand 1]: 2-acetyl-9-phenyl-1, 10-phenanthroline (0.225g, 0.75mmol) and 2,6-dimethylaniline (0.184g, 1.5mmol) were added with 80mg p-toluenesulfonic acid as a catalyst, refluxed in 20ml toluene under nitrogen protection for 1 day, after concentration The residue was perbasic alumina column, rinsed with petroleum ether/ethyl acetate (20:1), the second fraction was divided into product, and the solvent was removed to obtain 0.104 g of yellow solid, with a yield of 34.6%. The melting point is 190-192°C.

FT-IR (KBr disc): 3041, 3018, 2914, 1635, 1605, 1590, 1546, 1506, 1485, 1467, 1362, 1293, 1204, 1118, 1091, 855, 761, 739, ^{687 cm -1} .

¹ H NMR (300MHz, CDCl ₃ ): δ8.80(d, J=8.4Hz, 1H); 8.45(d, J=7.8Hz, 2H); 8.34(d, J=8.7Hz, 2H); 8.18( d, J=8.4Hz, 1H); 7.85(d, J=3.9Hz, 2H); 7.56(t, J=7.5Hz, 2H); 7.47(t, J=7.2Hz, 1H); 7.11(d, J=7.5Hz, 2H); 6.97(t, J=7.5Hz, 1H); 2.62(s, 3H); 2.09(s, 6H).

¹³ C NMR (75MHz, CDCl ₃ ): δ168.0, 156.9, 155.8, 149.0, 146.0, 145.1, 139.2, 137.1, 136.5, 129.8, 129.6, 128.9, 127.9, 127.8, 127.5, 127.3, 126.1, 1235.1, 120.6, 119.9, 18.0, 16.7.

Elemental analysis (C ₂₈ H ₂₃ N ₃ ) theoretical value (%): C83.76, H5.77, N10.47; experimental value (%): C83.69, H5.76, N10.40.

3. Preparation of [2-acetyl-9-phenyl-1,10-phenanthroline (condensed 2,6-dimethylaniline)]iron(II) [complex 1]: 2- Acetyl-9-phenyl-1,10-phenanthroline (2,6-dimethylaniline) ligand (0.0806g, 0.2mmol) and FeCl ₂ ·4H ₂ O (0.040g, 0.2mmol) In the Schlenk tube, after vacuuming and filling nitrogen three times, add 4ml of degassed tetrahydrofuran, the reaction solution first forms a green precipitate from a green solution, stir and react at room temperature for 9 hours, filter the obtained precipitate, and the filtrate is green; After washing and drying, 0.1043 g of light green powder was obtained, with a yield of 98.4%.

FT-IR (KBr disc): 3059, 2953, 2918, 2867, 1615, 1590, 1555, 1504, 1491, 1468, 1451, 1435, 1374, 1299, 1205, 865, 792, 772, 745, 702 ^{cm -1} .

Elemental analysis (C ₂₈ H ₂₃ Cl ₂ FeN ₃ ·1/2CH ₂ Cl ₂ ): C59.98, H4.24, N7.36; experimental value (%): C59.61, H4.34, N7.28.

4. Ethylene oligomerization at normal pressure: A 250ml three-neck round bottom flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.6 mg (5 μmol) of complex 1 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) to make Al/Fe=500 (molar ratio, the same below). At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. After the reaction, a small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.59×10 ³ g·mol ^-1 (Fe)·h ^-1 , and the oligomer produced was only butene, Wherein the 1-butene content is 96.1%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 2

1. The preparation of complex 1 is the same as in Example 1.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, evacuated while hot and replaced with _N gas for 3 times. 2.6 mg (5 μmol) of complex 1 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.3 ml of modified methylaluminoxane (MMAO) (1.93 mol/l heptane solution) to make Al/Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. After the reaction, a small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 4.78×10 ⁵ g·mol ^-1 (Fe)·h ^-1 , and the oligomer produced was only 1-butyl alkene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 3

1. The preparation of complex 1 is the same as in Example 1.

2. Pressurized (1MPa) ethylene oligomerization: Add 50ml of toluene, 1.7ml of methylalumoxane (MAO) (1.46mol/l toluene solution), 20ml of complex 1 (5.0μmol) in toluene and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 4.08×10 ⁵ g·mol(Fe) ^-1 ·h ^-1 , the oligomer The contents are respectively: C ₄ 99.2%, C ₆ 0.8%, and the selectivity to 1-butene is 99.8%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 4

1. The preparation of complex 1 is the same as in Example 1.

2. Pressurized (1MPa) ethylene oligomerization: 50ml toluene, 1.3ml triisobutylaluminum modified methylalumoxane (MMAO), 1.93mol/l heptane solution), 20ml complex 1 (5.0 μmol) of toluene solution and toluene were sequentially added into a 250-ml stainless steel autoclave so that the total volume was 100 ml, and Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 2.69×10 ⁶ g·mol ^-1 (Fe)·h ^-1 , the oligomer The contents are respectively: C ₄ 99.4%, C ₆ 0.6%, and all the butenes produced are 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 5

1. Preparation of 2-acetyl-9-phenyl-1,10-phenanthroline (2,6-diethylaniline) ligand [ligand 2]: 2-acetyl-9-phenyl-1, 10-phenanthroline (0.446g, 1.5mol), 2,6-diethylaniline (0.4906g, 3.2mmol) and 118mg p-toluenesulfonic acid in 20ml toluene, heated and refluxed for 8 hours, the reaction of the raw materials was complete, and the Toluene was removed by evaporation, the residue was dissolved in dichloromethane, loaded on neutral alumina, passed through a neutral alumina column, rinsed with petroleum ether/ethyl acetate (6:1), evaporated to dryness, washed and dried with ether to obtain Orange solid 0.284g, yield 44.2%. The melting point is 181-183°C.

FT-IR (KBr disc): 3060, 3037, 2960, 2929, 2868, 1639, 1608, 1589, 1546, 1507, 1486, 1452, 1418, 1369, 1296, 1258, 1194, 1119, 1099, 862, 828, 762, 740, 686 cm ^-1 .

¹ H NMR (300MHz, CDCl ₃ ): δ8.80(d, J=8.4Hz, 1H); 8.45(d, J=7.5Hz, 2H); 8.33(d, J=8.4Hz, 2H); 8.17( d, J=8.4Hz, 1H); 7.80(d, J=3.9Hz, 2H); 7.56(t, J=7.5Hz, 2H); 7.47(t, J=6.9Hz, 1H); 7.16(d, J=7.2Hz, 2H); 7.07(t, J=7.2Hz, 1H); 2.64(s, 3H); 2.42(q, J=7.2Hz, 4H); 1.16(t, J=7.2Hz, 6H) .

¹³ C NMR (75MHz, CDCl ₃ ): δ167.7, 156.9, 155.9, 148.0, 146.0, 145.1, 139.2, 137.1, 136.5, 131.1, 129.8, 129.6, 128.9, 127.8, 127.5, 127.3, 126.1, 1236.4, 120.5, 119.8, 24.7, 17.0, 13.8.

Elemental analysis (C ₃₀ H ₂₇ N ₃ ) theoretical value (%): C83.88, H6.34, N9.78; experimental value (%): C83.66, H6.40, N9.60.

Its crystal structure is shown in Figure 1.

2. Preparation of [2-acetyl-9-phenyl-1,10-phenanthroline (condensed 2,6-diethylaniline)]iron(II) [complex 2] chloride: the 2- Acetyl-9-phenyl-1,10-phenanthroline (2,6-diethylaniline) ligand (0.0864g, 0.2mmol) and FeCl ₂ ·4H ₂ O (0.0401g, 0.2mmol) In the Schlenk tube, after evacuating and filling nitrogen three times, add 4ml of degassed tetrahydrofuran, the reaction solution first forms a green precipitate from a green solution, stir and react at room temperature for 9 hours, filter the obtained precipitate, and the filtrate is brown-yellow; After washing with ether and drying, 0.1073 g of gray-blue powder was obtained, with a yield of 95.9%.

FT-IR (KBr disc): 3063, 2966, 2929, 2872, 1617, 1584, 1558, 1504, 1490, 1442, 1374, 1289, 1243, 1205, 1193, 1152, 1141, 1060, 859, 786, 759, 744,701cm ^-1 .

Elemental analysis (C ₃₀ H ₂₇ Cl ₂ FeN ₃ ) theoretical value (%): C64.77, H4.89, N7.55; experimental value (%): C64.26, H4.59, N7.50.

Its crystal structure is shown in Figure 2.

3. Ethylene oligomerization at normal pressure: A 250ml three-neck round bottom flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.8 mg (5 μmol) of complex 2 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) to make Al/Fe=500. At 40°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 590 g.mol ^-1 (Fe)·h ^-1 , and the oligomerization product was only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 6

1. The preparation of complex 2 is the same as in Example 5.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.8 mg (5 μmol) of complex 2 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.3 ml of triisobutylaluminum-modified methylaluminoxane (MMAO) (1.93 mol/l heptane solution) to make Al/Fe=500. At 40°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 1.63×10 ⁴ g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product was only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 7

1. The preparation of complex 2 is the same as in Example 5.

2. Pressurized (1MPa) ethylene oligomerization: add 50ml toluene, 1.7ml methylaluminoxane (MAO) (1.46mol/l toluene solution), 20ml complex 2 (5.0μmol) toluene solution and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 2.91×10 ⁵ g·mol ^-1 (Fe)·h ^-1 , the oligomer The contents are respectively: C ₄ 98.7%, C ₆ 1.3%, and the selectivity to 1-butene is 99.8%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 8

1. The preparation of complex 2 is the same as in Example 5.

2. Pressurized (1MPa) ethylene oligomerization: 50ml toluene, 1.3ml triisobutylaluminum modified methylalumoxane (MMAO) 1.93mol/l heptane solution), 20ml complex 2 (5.0μmol ) toluene solution and toluene were sequentially added into a 250-ml stainless steel autoclave to make the total volume 100ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 4.79×10 ⁵ g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product Only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 9

1. Preparation of 2-acetyl-9-phenyl-1,10-phenanthroline (2,6-diisopropylaniline) ligand [ligand 3]: 2-acetyl-9-phenyl- 1,10-phenanthroline (0.295g, 1.0mol), 2,6-diethylaniline (0.4482g, 2.5mmol) and 96mg of p-toluenesulfonic acid in 20ml of toluene, heated and refluxed for 21 hours, the reaction of raw materials was complete , toluene was removed by rotary evaporation, the residue was dissolved in dichloromethane and loaded on neutral alumina, passed through the neutral alumina column, rinsed with petroleum ether/ethyl acetate (10:1), and the second stream was divided into products, After evaporating to dryness, washing and drying with ether, 0.24 g of an orange solid was obtained, with a yield of 53.1%. The melting point is 256-258°C.

FT-IR (KBr disc): 3061, 2962, 2924, 2865, 1635, 1607, 1589, 1579, 1546, 1507, 1486, 1462, 1436, 1420, 1381, 1366, 1294, 1247, 1189, 1117, 1097, 860, 780, 761, 741 ^{, 685 cm-1} .

¹ H NMR (400MHz, CDCl ₃ ): δ=8.82 (d, J=8.4Hz, 1H); 8.45 (d, J=7.6Hz, 2H); 8.33 (dd, J=8.4Hz, 2H); 8.17( d, J=8.4Hz, 1H); 7.88(d, J=4.0Hz, 2H); 7.56(t, J=7.6Hz, 2H); 7.47(t, J=7.2Hz, 1H); 7.21(d, J=7.6Hz, 2H); 7.13(t, J=7.6Hz, 1H); 2.86(sept, J=6.8Hz, 2H); 2.66(s, 3H); 1.18(dd, J=6.8Hz, 12H) .

¹³ C NMR (75MHz, CDCl ₃ ): δ=167.7, 156.9, 155.8, 146.7, 146.0, 145.2, 139.2, 137.1, 136.5, 135.8, 129.9, 129.7, 129.0, 127.8, 127.5, 127.3, 126.1, 123.7 120.6, 119.9, 28.3, 23.3, 23.0, 17.3.

Elemental analysis (C ₂₆ H ₂₇ N ₃ ) theoretical value (%): C83.99, H6.83, N9.18; experimental value (%): C84.00, H6.84, N8.98.

2. the preparation of [2-acetyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-diisopropylaniline)] iron (II) [complex 3]: the 2 -Acetyl-9-phenyl-1,10-phenanthroline (2,6-diisopropylaniline) ligand (0.0918g, 0.2mmol) and FeCl ₂ ·4H ₂ O (0.0401g, 0.2mmol ) was placed in a Schlenk tube, after being vacuumed and filled with nitrogen three times, 4ml of degassed tetrahydrofuran was added, and the reaction solution was first to generate a green precipitate from a green solution, stirred and reacted at room temperature for 9 hours, and the gained precipitate was filtered, and the filtrate was green; After washing with ether and drying, 0.0776 g of light green powder was obtained, with a yield of 66.2%.

FT-IR (KBr disc): 3062, 2969, 2926, 2865, 1611, 1590, 1557, 1501, 1490, 1463, 1440, 1374, 1330, 1286, 1247, 1185, 1152, 1138, 870, 786, 748, 701cm ^-1 .

Elemental analysis (C ₃₂ H ₃₁ Cl ₂ FeN ₃ ) theoretical value (%): C65.77, H5.35, N7.19; experimental value (%): C65.15, H5.32, N6.95.

3. Ethylene oligomerization at normal pressure: A 250ml three-neck round bottom flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.9 mg (5 μmol) of complex 3 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) to make Al/Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: no oligomer was obtained. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 10

1. The preparation of complex 3 is the same as in Example 9.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.9 mg (5 μmol) of complex 3 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.3 ml of triisobutylaluminum-modified methylaluminoxane (MMAO) (1.93 mol/l heptane solution) to make Al/Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 1.99×10 ³ g.mol ^-1 (Fe)·h ^-1 , and the oligomerization product was only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 11

1. The preparation of complex 3 is the same as in Example 9.

2. Pressurized (1MPa) ethylene oligomerization: Add 50ml of toluene, 1.7ml of methylaluminoxane (MAO) (1.46mol/l toluene solution), 20ml of complex 3 (5.0μmol) in toluene and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 6.21×10 ³ g·mol(Fe) ^-1 ·h ^-1 , and the oligomerization product Only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 12

1. The preparation of complex 3 is the same as in Example 9.

2. Pressurized (1MPa) ethylene oligomerization: 50ml toluene, 1.3ml triisobutylaluminum modified methylalumoxane (MMAO) 1.93mol/l heptane solution), 20ml complex 3 (5.0μmol ) toluene solution and toluene were sequentially added into a 250-ml stainless steel autoclave to make the total volume 100ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 1.90×10 ⁴ g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product Only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 13

1.2-Benzoyl-9-phenyl-1,10-phenanthroline preparation: bromobenzene (3.2mL, 30.5mmol) ether solution (20mL) was added dropwise to 2 equivalents of metal lithium (439mg, 63.2mmol) The diethyl ether suspension (30 mL) was prepared into a phenyllithium solution at room temperature under nitrogen protection. At -78°C under the protection of nitrogen, the phenyllithium solution prepared above was added dropwise to 2-cyano-1,10-phenanthroline (2.053g, 10.0mmol) in toluene suspension (50mL), dropwise After the addition was complete, warm to room temperature slowly and stir overnight. The reaction was quenched by slow addition of water, the red organic layer was separated, the aqueous layer was extracted several times with dichloromethane, then the organic phases were combined and dried over anhydrous sodium sulfate. The organic layer was concentrated, and the residue was purified by a silica gel column to obtain 1.245 g of a yellow solid product 2-benzoyl-9-phenyl-1,10-phenanthroline with a yield of 21.3%. The melting point is 162-164°C.

FT-IR (KBr disc): 3060, 3034, 1645, 1616, 1595, 1575, 1545, 1505, 1486, 1446, 1420, 1364, 1319, 1288, 1183, 1152, 1093, 1023, 944, 878, 865, 768, 716, 692 cm ^-1 .

¹ H NMR (300MHz, CDCl ₃ ): δ=8.93(d, J=7.2Hz, 2H), 8.55-8.39(m, 4H), 8.30(d, J=8.4Hz, 1H), 8.16(d, J =8.4Hz, 1H), 7.89(d, J=8.7Hz, 1H), 7.81(d, J=8.7Hz, 1H), 7.72-7.62(m, 3H), 7.56-7.49(m, 3H).

¹³ C NMR (100MHz, CDCl ₃ ): δ=191.4, 156.5, 153.4, 145.9, 144.6, 138.8, 136.7, 136.6, 132.7, 132.5, 129.8, 129.6, 128.6, 128.3, 127.8, 127.5, 1264.3, 122.5 119.6.

Elemental analysis (C ₂₅ H ₁₆ N ₂ O) theoretical value (%): C83.31, H4.47, N7.77; experimental value (%): C82.94, H4.45, N7.73.

2. Preparation of 2-benzoyl-9-phenyl-1,10-phenanthroline (2,6-dimethylaniline) ligand [ligand 4]: 2-benzoyl-9-phenyl- 1,10-Phenanthroline (0.76g, 2.1mmol) and 2,6-Dimethylaniline (0.585g, 4.8mmol) were added with 100mg p-toluenesulfonic acid as catalyst, in 5ml ethyl orthosilicate at 140°C React for about 36 hours, and use an oil-water separator to separate the ethanol generated, remove the tetraethyl orthosilicate under reduced pressure, and dissolve the residue with dichloromethane, and use petroleum ether/ethyl acetate ( 6:1) rinse, the second stream was separated into the product, and the solvent was removed to obtain 0.376 g of a yellow solid with a yield of 38.4%. The melting point is 142-144°C.

FT-IR (KBr disc): 3055, 2943, 1616, 1589, 1577, 1544, 1505, 1484, 1441, 1368, 1319, 1290, 1207, 1088, 1024, 969, 858, 773, 765, 740, 716, 694cm ^-1 .

¹ H NMR (400MHz, CDCl ₃ ): δ=8.87(d, J=8.4Hz, 1H); 8.37(d, J=8.4Hz, 1H); 8.26-8.24(m, 3H); 8.11(d, J =8.4Hz, 1H); 7.82(s, 2H); 7.57(d, J=8.0Hz, 2H); 7.46(t, J=7.2Hz, 4H); 7.38(t, J=7.2Hz, 2H); 6.96(d, J=7.2Hz, 2H); 6.86(t, J=7.2Hz, 1H); 2.12(s, 6H).

¹³ C NMR (100MHz, CDCl ₃ ): δ=166.1, 155.9, 155.7, 148.2, 145.7, 144.7, 138.5, 136.3, 136.0, 135.4, 129.6, 129.2, 129.1, 128.9, 128.3, 127.9, 127.3, 126.7 126.7, 125.5, 125.2, 122.7, 121.7, 118.9, 18.2.

Elemental analysis (C ₃₃ H ₂₅ N ₃ ) theoretical value (%): C85.50, H5.44, N9.06; experimental value (%): C85.14, H5.47, N8.94.

3. Preparation of [2-benzoyl-9-phenyl-1,10-phenanthroline (condensed 2,6-dimethylaniline)]iron(II) [complex 4] chloride: 2- Benzoyl-9-phenyl-1,10-phenanthroline (2,6-dimethylaniline) ligand (0.0698g, 0.15mmol) and 1 equivalent of FeCl ₂ ·4H ₂ O (0.0312g, 0.15mmol) was placed in a Schlenk tube, vacuumized and filled with nitrogen three times, then 6ml of degassed absolute ethanol was added, the reaction solution first changed from yellow-green to green and a gray-green precipitate was formed, stirred and reacted at room temperature for 12hrs, filtered, and the filtrate It was green, and the precipitate was washed with ether and dried to obtain 0.0772 g of gray-green powder with a yield of 86.9%.

FT-IR (KBr disc): 3056, 2922, 1620, 1588, 1549, 1489, 1445, 1368, 1300, 1212, 1155, 1001, 863, 774, 744, 703 ^{cm -1} .

Elemental analysis (C ₃₃ H ₂₅ Cl ₂ FeN ₃ ·H ₂ O) theoretical value (%): C65.15, H4.47, N6.91; experimental value (%): C65.12, H4.11, N6. 85.

4. Ethylene oligomerization at normal pressure: A 250ml three-neck round bottom flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. Add 3.0 mg (5 μmol) of complex 4 and then re-evacuate and replace with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) to make Al/Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.95×10 ³ g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product was only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 14

1. The preparation of complex 4 is the same as in Example 13.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, evacuated while hot and replaced with _N gas for 3 times. Add 3.0 mg (5 μmol) of complex 4 and then re-evacuate and replace with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.3 ml of triisobutylaluminum-modified methylaluminoxane (MMAO) (1.93 mol/l heptane solution) to make Al/Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.64×10 ⁵ g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product was only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 15

1. The preparation of complex 4 is the same as in Example 13.

2. Pressurized (1MPa) ethylene oligomerization: Add 50ml of toluene, 1.7ml of methylalumoxane (MAO) (1.46mol/l toluene solution), 20ml of complex 4 (5.0μmol) in toluene and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 1.94×10 ⁶ g·mol ^-1 (Fe)·h ^-1 , the oligomer The contents are respectively: C ₄ 99.2%, C ₆ 0.8%, and the selectivity to 1-butene is 99.9%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 16

1. The preparation of complex 4 is the same as in Example 13.

2. Pressurized (1MPa) ethylene oligomerization: 50ml toluene, 1.3ml triisobutylaluminum modified methylalumoxane (MMAO) 1.93mol/l heptane solution), 20ml complex 4 (5.0μmol ) toluene solution and toluene were sequentially added into a 250-ml stainless steel autoclave to make the total volume 100ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 2.11×10 ⁶ g·mol ^-1 (Fe)·h ^-1 , the oligomer The contents are respectively: C ₄ 99.1%, C ₆ 0.9%, and the selectivity to 1-butene is 100%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 17

1. Preparation of 2-benzoyl-9-phenyl-1,10-phenanthroline (2,6-diethylaniline) ligand [ligand 5]: 2-benzoyl-9-phenyl -1,10-phenanthroline (0.57g, 1.58mmol) and 2,6-diethylaniline (0.4978g, 3.27mmol) were added with 112mg p-toluenesulfonic acid as catalyst, in 5ml ethyl orthosilicate at 140 ℃ for 12 hours, and the ethanol produced was separated with an oil-water separator, and the ethyl orthosilicate was removed under reduced pressure, and the residue was dissolved and loaded with dichloromethane. (4:1) rinsing, the second stream was divided into products, and the solvent was removed to obtain 0.5664 g of a yellow solid with a yield of 72.8%. The melting point is 187-189°C.

FT-IR (KBr disc): 3060, 3034, 2962, 2918, 1618, 1586, 1542, 1504, 1485, 1440, 1363, 1294, 1200, 1090, 965, 869, 763 ^{, 697 cm -1} .

¹ H NMR (400MHz, CDCl ₃ ): δ=8.85(d, J=8.0Hz, 1H); 8.37-8.22(m, 4H); 8.09(d, J=8.0Hz, 1H); 7.80(s, 2H ); 7.58(s, 2H); 7.45-7.36(m, 6H); 7.01-6.97(m, 3H); 2.61(q, J=7.2Hz, 2H); 2.34(q, J=7.2Hz, 2H) ; 1.16 (t, J=7.2Hz, 6H).

¹³ C NMR (100MHz, CDCl ₃ ): δ=165.7, 156.2, 156.1, 147.6, 146.1, 145.1, 138.9, 136.7, 136.4, 135.4, 131.1, 130.3, 129.6, 129.2, 128.7, 128.5, 1235.7, 127.7 127.2, 125.8, 125.5, 123.4, 122.1, 119.2, 24.5, 13.5.

Elemental analysis (C ₃₅ H ₂₉ N ₃ ) theoretical value (%): C85.51, H5.95, N8.55; experimental value (%): C85.03, H5.94, N8.48.

2. Preparation of [2-benzoyl-9-phenyl-1,10-phenanthroline (2,6-diethylaniline)]iron(II) [complex 5] chloride: 2- Benzoyl-9-phenyl-1,10-phenanthroline (2,6-diethylaniline) ligand (0.0745g, 0.15mmol) and FeCl ₂ ·4H ₂ O (0.0310g, 0.15mmol) Place in a Schlenk tube, vacuumize and fill with nitrogen three times, then add 5ml of degassed absolute ethanol, the reaction solution turns from yellow-green to green and a dark brown precipitate is formed, stir and react at room temperature for 9hrs, filter, the filtrate is green, The precipitate was washed with ether and dried to obtain 0.0673 g of dark brown powder with a yield of 71.8%.

FT-IR (KBr disc): 3061, 2966, 2874, 1594, 1553, 1490, 1444, 1368, 1291, 1261, 1107, 1059, 1000, 868, 781, 702 ^{cm -1} .

Elemental analysis (C ₃₅ H ₂₉ Cl ₂ FeN ₃ ) theoretical value (%): C67.98, H4.73, N6.80; experimental value (%): C67.94, H4.78, N6.57.

3. Ethylene oligomerization at normal pressure: A 250ml three-neck round bottom flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 5 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) to make Al/Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 520 g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product was only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 18

1. The preparation of complex 5 is the same as in Example 17.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, evacuated while hot and replaced with _N gas for 3 times. 3.1 mg (5 μmol) of complex 5 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.3 ml of triisobutylaluminum-modified methylaluminoxane (MMAO) (1.93 mol/l heptane solution) to make Al/Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 5.13×10 ⁴ g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product was only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 19

1. The preparation of complex 5 is the same as in Example 17.

2. Pressurized (1MPa) ethylene oligomerization: Add 50ml of toluene, 1.7ml of methylaluminoxane (MAO) (1.46mol/l toluene solution), 20ml of complex 5 (5.0μmol) in toluene and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 5.16×10 ⁵ g·mol ^-1 (Fe)·h ^-1 , the oligomer The contents are respectively: C ₄ 98.6%, C ₆ 1.4%, and the selectivity to 1-butene is 100%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 20

1. The preparation of complex 5 is the same as in Example 17.

2. Pressurized (1MPa) ethylene oligomerization: 50ml toluene, 1.3ml triisobutylaluminum modified methylalumoxane (MMAO) 1.93mol/l heptane solution), 20ml complex 5 (5.0μmol ) toluene solution and toluene were sequentially added into a 250-ml stainless steel autoclave to make the total volume 100ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 5.43×10 ⁵ g·mol(Fe) ^-1 ·h ^-1 , the oligomer The contents are respectively: C ₄ 98.7%, C ₆ 1.3%, and the selectivity to 1-butene is 100%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 21

1. Preparation of 2-benzoyl-9-phenyl-1,10-phenanthroline (2,6-diisopropylaniline) ligand [ligand 6]: 2-benzoyl-9-phenyl -1,10-phenanthroline (0.3938g, 1.09mmol) and 2,6-diisopropylaniline (0..4328g, 2.44mmol) were added with 112mg of p-toluenesulfonic acid as catalyst, in 5ml of ethyl orthosilicate React at about 140°C for 12 hours, and use an oil-water separator to separate the generated ethanol, remove tetraethyl orthosilicate under reduced pressure, and dissolve the residue in dichloromethane, and use petroleum ether/ Ethyl acetate (6:1) was rinsed, and the second stream was separated into the product, and the solvent was removed to obtain 0.42 g of a yellow solid with a yield of 74.0%. The melting point is 170-171°C.

FT-IR (KBr disc): 3063, 2958, 2860, 1611, 1588, 1544, 1506, 1487, 1463, 1430, 1358, 1291, 1194, 1091, 966, 858, 777, 757, ^{701 cm -1} .

¹ H NMR (300MHz, CDCl ₃ ): δ=8.84(d, J=7.2Hz, 1H); 8.38-8.24(m, 4H); 8.11(d, J=8.4Hz, 1H); 7.82(s, 2H ); 7.62 (s, 2H); 7.49-7.39 (m, 6H); 7.04 (s, 3H); 3.00 (m, 2H); 1.19 (s, 6H); 0.97 (s, 6H).

¹³ C NMR (100MHz, CDCl ₃ ): δ=164.9, 155.9, 145.7, 144.6, 138.5, 136.3, 136.0, 135.2, 134.5, 130.3, 129.1, 128.7, 128.4, 128.2, 128.1, 127.2, 127.1, 126. 125.4, 123.2, 122.4, 121.8, 111.8, 28.1, 23.7, 21.6.

Elemental analysis (C ₃₇ H ₃₃ N ₃ ) theoretical value (%): C85.51, H6.40, N8.09; experimental value (%): C84.91, H6.36, N7.84.

2. Preparation of [2-benzoyl-9-phenyl-1,10-phenanthroline chloride (2,6-diisopropylaniline)]iron(II) [complex 6]: 2 -Benzoyl-9-phenyl-1,10-phenanthroline (2,6-diisopropylaniline) ligand (0.0795g, 0.15mmol) and FeCl ₂ ·4H ₂ O (0.0309g, 0.15 mmol) was placed in a Schlenk tube, vacuumed and filled with nitrogen three times, then 5ml of degassed absolute ethanol was added, the reaction solution first changed from yellow-green to green with brown-green precipitates and then turned to brown-gray, stirred at room temperature for 12hrs , filtered, the filtrate was green, the precipitate was washed with ether and dried to obtain 0.0856 g of brown powder, with a yield of 86.6%.

FT-IR (KBr disc, cm ⁻¹ ): 3031, 2959, 2866, 1620, 1587, 1550, 1488, 1459, 1436, 1364, 1319, 1274, 1206, 995, 872, 850, 704.

Elemental analysis (C ₃₇ H ₃₃ Cl ₂ FeN ₃ ) theoretical value (%): C68.75, H5.15, N6.50; experimental value (%): C68.42, H5.23, N6.59.

3. Ethylene oligomerization at normal pressure: A 250ml three-neck round bottom flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.2 mg (5 μmol) of complex 6 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) to make Al/Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: no oligomerization activity. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 22

1. The preparation of complex 6 is the same as in Example 21.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.2 mg (5 μmol) of complex 6 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of triisobutylaluminum-modified methylalumoxane (MMAO) (1.93 mol/l heptane solution) to make Al/Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.75×10 ³ g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product was only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 23

1. The preparation of complex 6 is the same as in Example 21.

2. Pressurized (1MPa) ethylene oligomerization: add 50ml toluene, 1.7ml methylaluminoxane (MAO) (1.46mol/l toluene solution), 20ml complex 6 (5.0μmol) toluene solution and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 4.09×10 ³ g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product Only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 24

1. The preparation of complex 6 is the same as in Example 21.

2. Pressurized (1MPa) ethylene oligomerization: 50ml toluene, 1.3ml triisobutylaluminum modified methylalumoxane (MMAO) 1.93mol/l heptane solution), 20ml complex 6 (5.0μmol ) toluene solution and toluene were sequentially added into a 250-ml stainless steel autoclave to make the total volume 100ml, Al/Fe=500. When the polymerization temperature reaches 40°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 4.65×10 ³ g·mol ^-1 (Fe)·h ^-1 , and the oligomerization product Only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 25

1. Preparation of [2-acetyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-dimethylaniline)] cobalt (II) [complex 7]: 2- Acetyl-9-phenyl-1,10-phenanthroline (2,6-dimethylaniline) ligand (0.0806g, 0.2mmol) and anhydrous CoCl ₂ (0.0274g, 0.2mmol) were placed in Schlenk In the tube, 4ml of absolute ethanol was added, the solution was green at the beginning, then gradually became turbid and produced a green precipitate, stirred at room temperature for 12 hours, filtered, washed with ether, and dried to obtain 0.07g of green powder, with a yield of 65.6%.

FT-IR (KBr disc, cm ^-1 ): 3063, 2945, 2914, 1619, 1585, 1557, 1504, 1490, 1451, 1437, 1374, 1290, 1256, 1206, 1142, 989, 919, 865, 791, 772, 745, 700, 653, 609.

Elemental analysis (C ₂₈ H ₂₃ Cl ₂ CoN ₃ ·H ₂ O) theoretical value (%): C61.22, H4.59, N7.65; experimental value (%): C61.46, H4.34, N7. twenty four.

Its crystal structure is shown in Figure 3.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.6 mg (5 μmol) of complex 7 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 6.85×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 94.3% , C ₆ 5.7%, selectivity to 1-butene is 97.0%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 26

1. The preparation of complex 7 is the same as in Example 25.

2. Pressurized (1MPa) ethylene oligomerization: Add 50ml of toluene, 1.7ml of methylaluminoxane (MAO) (1.46mol/l toluene solution), 20ml of complex 7 (5.0μmol) in toluene and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Co=500. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 4.32×10 ⁶ g·mol(Co) ^-1 ·h ^-1 , the oligomer The contents are respectively: C ₄ 92.1%, C ₆ 7.6%, and the selectivity to 1-butene is 99.8%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 27

1. Preparation of [2-acetyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-diethylaniline)] cobalt (II) [complex 8]: 2- Acetyl-9-phenyl-1,10-phenanthroline (2,6-diethylaniline) ligand (0.065g, 0.15mmol) and anhydrous CoCl ₂ (0.0207g, 0.16mmol) were placed in Schlenk In the tube, 4ml of absolute ethanol was added, the solution was green at the beginning, and a green precipitate was formed soon, stirred at room temperature for 12h, filtered, washed with ether, and dried to obtain 0.068g of green powder with a yield of 80.3%.

FT-IR (KBr disc): 3061, 2969, 2924, 2865, 1613, 1582, 1557, 1501, 1489, 1463, 1441, 1375, 1330, 1288, 1185, 1153, 869, 786, 749, 700 ^{cm -1} .

Elemental analysis (C ₃₀ H ₂₇ Cl ₂ CoN ₃ ) theoretical value (%): C64.41, H4.86, N7.51; experimental value (%): C64.25, H4.92, N7.27

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.8 mg (5 μmol) of complex 8 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 6.71×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 91.9% , C ₆ 5.4%, C _{≥ 8} 2.7%, the selectivity to 1-butene is 97.9%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 28

1. The preparation of complex 8 is the same as in Example 27.

2. Pressurized (1MPa) ethylene oligomerization: Add 50ml of toluene, 1.7ml of methylalumoxane (MAO) (1.46mol/l toluene solution), 20ml of complex 8 (5.0μmol) in toluene and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Co=500. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 4.06×10 ⁶ g·mol ^-1 (Co)·h ^-1 , the oligomer The contents are respectively: C ₄ 95.7%, C ₆ 4.0%, C _{≥ 8} 0.3%, and the selectivity to 1-butene is 99.7%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 29

1. the preparation of [2-acetyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-diisopropylaniline)] cobalt (II) [complex 9]: 2 -Acetyl-9-phenyl-1,10-phenanthroline (2,6-diisopropylaniline) ligand (0.0937g, 0.2mmol) and anhydrous CoCl ₂ (0.0279g, 0.21mmol) In the Schlenk tube, add 6ml of absolute ethanol, the solution was green at the beginning, and soon formed a green precipitate, stirred at room temperature for 24h, filtered, washed with ether, and dried to obtain 0.103g of green powder with a yield of 85.6%.

FT-IR (KBr disc): 3450, 3062, 2964, 2932, 2875, 1618, 1585, 1558, 1504, 1490, 1441, 1375, 1290, 1193, 859, 787, 760, 745, ^{701 cm -1} .

Elemental analysis (C ₃₂ H ₃₁ Cl ₂ CoN ₃ ) theoretical value (%): C65.43, H5.32, N7.15; experimental value (%): C64.48, H5.55, N6.61.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.9 mg (5 μmol) of complex 9 were added followed by re-evacuation and displacement with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 5.23×10 ⁵ g·mol(Co) ^-1 ·h ^-1 , and the oligomer contents were: C ₄ 80.0% , C ₆ 16.5%, C _{≥ 8} 3.5%, the selectivity to 1-butene is 95.4%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 30

1. The preparation of complex 9 is the same as in Example 29.

2. Pressurized (1MPa) ethylene oligomerization: Add 50ml of toluene, 1.7ml of methylalumoxane (MAO) (1.46mol/l toluene solution), 20ml of complex 9 (5.0μmol) in toluene and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Co=500. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 6.52×10 ⁶ g·mol ^-1 (Co)·h ^-1 , the oligomer The contents are: C ₄ 75.7%, C ₆ 23.0%, C _{≥ 8} 1.3%, and the selectivity to 1-butene is 99.7%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 31

1. Preparation of [2-benzoyl-9-phenyl-1,10-phenanthroline chloride (2,6-dimethylaniline)] cobalt (II) [complex 10]: 2 -Benzoyl-9-phenyl-1,10-phenanthroline (2,6-dimethylaniline) ligand (0.0696g, 0.15mmol) and anhydrous CoCl ₂ (0.0212g, 0.15mmol) Add 6ml of absolute ethanol to the Schlenk tube. The solution is green at the beginning, and then gradually forms a brown precipitate. Stir at room temperature for 15h, filter, wash with ether, and dry to obtain 0.0714g of reddish-brown powder with a yield of 80.2%.

FT-IR (KBr disc): 3057, 2919, 1612, 1597, 1555, 1490, 1445, 1371, 1317, 1289, 1213, 999, 863, 774, 748, 721, ^{703 cm -1} .

Elemental analysis (C ₃₃ H ₂₅ Cl ₂ CoN ₃ ·CH ₂ Cl ₂ ) theoretical value (%): C60.20, H4.01, N6.19; experimental value (%): C60.25, H4.02, N6 .28.

Its crystal structure is shown in Figure 4.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, evacuated while hot and replaced with _N gas for 3 times. 2.9 mg (5 μmol) of complex 10 were added and then evacuated and replaced 3 times with ethylene. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 5.58×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 84.4% , C ₆ 14.8%, C _{≥ 8} 0.8%, the selectivity to 1-butene is 96.4%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 32

1. The preparation of complex 10 is the same as in Example 31.

2. Pressurized (1MPa) ethylene oligomerization: add 50ml toluene, 1.7ml methylaluminoxane (MAO) (1.46mol/l toluene solution), 20ml complex 10 (5.0μmol) toluene solution and toluene in sequence Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Co=500. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 4.90×10 ⁶ g·mol ^-1 (Co)·h ^-1 , the oligomer The contents are respectively: C ₄ 84.5%, C ₆ 13.4%, C _{≥ 8} 2.1%, and the selectivity to 1-butene is 99.8%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 33

1. Preparation of [2-benzoyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-diethylaniline)] cobalt (II) [complex 11]: 2 -Benzoyl-9-phenyl-1,10-phenanthroline (2,6-diethylaniline) ligand (0.0856g, 0.174mmol) and anhydrous CoCl ₂ (0.0268g, 0.2mmol) Add 8ml of absolute ethanol to the Schlenk tube, the solution is green at the beginning, and then gradually forms a brown precipitate, stirred at room temperature for 12h, filtered, washed with ether, and dried to obtain 0.084g of dark brown powder with a yield of 77.6%.

FT-IR (KBr disc): 3063, 2963, 2934, 2875, 1613, 1596, 1552, 1498, 1490, 1442, 1371, 1319, 1288, 1108, 995, 872, 782, 751, 720, 701 ^{cm -1} .

Elemental analysis (C ₃₅ H ₂₉ Cl ₂ CoN ₃ ·CH ₂ Cl ₂ ) theoretical value (%): C61.21, H4.42, N5.95; experimental value (%): C60.68, H4.28, N5 .63.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 0.25 ml of diethylaluminum chloride solution (2.0 mol/l hexane solution) to make Al/Co=100. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: no oligomerization activity. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 34

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 0.5 ml of diethylaluminum chloride solution (2.0 mol/l hexane solution) to make Al/Co=200. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: no oligomerization activity. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 35

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.3 ml of triisobutylaluminum-modified methylalumoxane (MMAO) (1.93 mol/l heptane solution) to make Al/Co=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then analyzed by GC: the oligomerization activity was 5.93×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 77.1% , C ₆ 16.2%, C _{≥ 8} 6.7%, the selectivity to 1-butene is 96.1%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 36

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 0.35 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=100. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 0.76×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 90.7% , C ₆ 5.9%, C _{≥ 8} 3.4%, the selectivity to 1-butene is 98.0%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 37

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, evacuated while hot and replaced with _N gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 0.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=200. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.33×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 86.3% , C ₆ 10.6%, C _{≥ 8} 3.1%, the selectivity to 1-butene is 97.0%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 38

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 6.42×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 78.5% , C ₆ 15.2%, C _{≥ 8} 6.3%, the selectivity to 1-butene is 96.7%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 39

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 3.4 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=1000. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then analyzed by GC: the oligomerization activity was 5.70×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 77.8% , C ₆ 15.1%, C _{≥ 8} 7.1%, the selectivity to 1-butene is 97.4%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 40

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 5.1 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=1500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 5.42×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer content was: C ₄ 76.0% , C ₆ 16.7%, C _{≥ 8} 7.3%, the selectivity to 1-butene is 96.1%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 41

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 6.8 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=2000. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 4.31×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 82.2% , C ₆ 14.8%, C _{≥ 8} 3.0%, the selectivity to 1-butene is 98.2%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 42

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 0°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then analyzed by GC: the oligomerization activity was 3.64×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 91.0% , C ₆ 7.6%, C _{≥ 8} 1.4%, the selectivity to 1-butene is 98.4%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 43

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 40°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then analyzed by GC: the oligomerization activity was 5.05×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer content was: C ₄ 81.1% , C ₆ 16.0%, C _{≥ 8} 2.9%, the selectivity to 1-butene is 95.9%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 44

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, evacuated while hot and replaced with _N gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 60°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 1.41×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 72.4% , C ₆ 19.2%, C _{≥ 8} 8.4%, the selectivity to 1-butene is 97.2%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 45

1. The preparation of complex 11 is the same as in Example 33.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 11 were added and then evacuated and replaced with ethylene 3 times. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 80°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 0.874×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 72.5% , C ₆ 16.6%, C _{≥ 8} 10.9%, the selectivity to 1-butene is 96.3%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 46

1. The preparation of complex 11 is the same as in Example 33.

2. Pressurized (1MPa) ethylene oligomerization: 50ml toluene, 1.7ml methylaluminoxane (MAO) (1.46mol/l toluene solution), 20ml complex 11 (5.0μmol) toluene solution and toluene were added sequentially Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Co=500. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 7.33×10 ⁶ g·mol ^-1 (Co)·h ^-1 , the oligomer The contents are respectively: C ₄ 80.5%, C ₆ 16.8%, C _{≥ 8} 2.7%, and the selectivity to 1-butene is 99.7%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 47

1. Preparation of [2-benzoyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-diisopropylaniline)] cobalt (II) [complex 12]: 2-benzoyl-9-phenyl-1,10-phenanthroline (2,6-diisopropylaniline) ligand (0.0785g, 0.15mmol) and anhydrous CoCl ₂ (0.021g, 0.15mmol ) was placed in a Schlenk tube, and 6ml of absolute ethanol was added. At the beginning, the solution was green, and then a brown precipitate was gradually generated, stirred at room temperature for 12h, filtered, washed with ether, and dried to obtain 0.0769g of a reddish-brown powder, with a yield of 78.4%. .

^{- 1} .

Elemental analysis (C ₃₇ H ₃₃ Cl ₂ CoN ₃ ·CH ₂ Cl ₂ ) theoretical value (%): C62.14, H4.80, N5.72; experimental value (%): C62.17, H4.82, N5 .54.

Its crystal structure is shown in Figure 5.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.2 mg (5 μmol) of complex 12 were added and then evacuated and replaced 3 times with ethylene. 30 ml of toluene was injected with a syringe, and 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) was added to make Al/Co=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.85×10 ⁵ g·mol ^-1 (Co)·h ^-1 , and the oligomer contents were: C ₄ 55.2% , C ₆ 28.1%, C _{≥ 8} 16.7%, the selectivity to 1-butene is 94.3%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 48

1. The preparation of complex 12 is the same as in Example 47.

2. Pressurized (1MPa) ethylene oligomerization: 50ml toluene, 1.7ml methylaluminoxane (MAO) (1.46mol/l toluene solution), 20ml complex 12 (5.0μmol) toluene solution and toluene were added sequentially Into a 250-ml stainless steel autoclave, bring the total volume to 100 ml, Al/Co=500. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 2.80×10 ⁶ g·mol ^-1 (Co)·h ^-1 , the oligomer The contents are respectively: C ₄ 46.7%, C ₆ 34.0%, C _{≥ 8} 19.3%, and the selectivity to 1-butene is 100%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 49

1. the preparation of [2-acetyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-dimethylaniline)] nickel (II) [complex 13]: the 2- Acetyl-9-phenyl-1,10-phenanthroline (2,6-dimethylaniline) ligand (0.0957g, 0.238mmol) and NiCl ₂ ·6H ₂ O (0.0602g, 0.251mmol) In the Schlenk tube, 10ml of absolute ethanol was added, a precipitate was formed quickly, stirred at room temperature for 15 hours, the obtained precipitate was filtered, washed with ether, and dried to obtain 0.1131g of orange powder with a yield of 89.3%.

FT-IR (KBr disc): 3445, 3056, 1611, 1587, 1556, 1503, 1489, 1453, 1376, 1294, 1204, 1148, 862, 793, 773, 745, ^{702 cm -1} .

Elemental analysis (C ₂₈ H ₂₃ Cl ₂ N ₃ Ni·1/2CH ₂ Cl ₂ ) theoretical value (%): C59.68, H4.22, N7.33; experimental value (%): C59.89, H4. 44, N7.20.

Its crystal structure is shown in Figure 6.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.6 mg (5 μmol) of complex 13 and 50 μmol of triphenylphosphine were added, followed by evacuation and displacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 3.74×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 98.0% , C ₆ 2.0%, selectivity to 1-butene is 17.5%. Extend the reaction to 60min: the oligomerization activity is 3.49×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , the oligomer contents are respectively: C ₄ 96.7%, C ₆ 3.3%, the choice of 1-butene sex at 4.3%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 50

1. The preparation of complex 13 is the same as that in Example 49.

2. Pressurized (1MPa) ethylene oligomerization: 50ml of toluene, 0.75ml of diethylaluminum chloride (2.0mol/l hexane solution), 20ml of complex 13 (5.0μmol) and 100μmol of triphenylphosphine in toluene The solution was sequentially added into a 250-ml stainless steel autoclave to make the total volume 100 ml, Al/Ni=300. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 3.68×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , the oligomer The contents are respectively: C ₄ 98.1%, C ₆ 1.9%, and the selectivity to 1-butene is 36.2%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 51

1. Preparation of [2-acetyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-diethylaniline)] nickel (II) [complex 14]: 2- Acetyl-9-phenyl-1,10-phenanthroline (2,6-diethylaniline) ligand (0.0779g, 0.18mmol) and NiCl ₂ ·6H ₂ O (0.0458g, 0.19mmol) In the Schlenk tube, add 10ml of absolute ethanol, an orange precipitate is formed quickly, stir at room temperature for 15hrs, filter the resulting precipitate, the filtrate is yellow, wash the precipitate with ether, and dry to obtain an orange powder 0.091g, the yield is 89.7%.

FT-IR (KBr disc): 3442, 3062, 2958, 2871, 1616, 1584, 1559, 1502, 1489, 1442, 1377, 1302, 1292, 1192, 1060, 859, 787, 762, 744, 701 ^{cm -1} .

Elemental analysis (C ₃₀ H ₂₇ Cl ₂ N ₃ Ni·1/2CH ₂ Cl ₂ ) theoretical value (%): C60.89, H4.69, N6.98; experimental value (%): C60.46, H4. 96, N6.67.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.8 mg (5 μmol) of complex 13 and 50 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then analyzed by GC: the oligomerization activity was 3.29×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 97.3% , C ₆ 2.7%, selectivity to 1-butene is 15.9%. Extend the reaction to 60min: the oligomerization activity is 4.67×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , the oligomer contents are respectively: C ₄ 97.0%, C ₆ 3.0%, the choice of 1-butene sex at 5.8%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 52

1. The preparation of complex 14 is the same as in Example 51.

2. Pressurized (1MPa) ethylene oligomerization: 50ml of toluene, 0.75ml of diethylaluminum chloride (2.0mol/l hexane solution), 20ml of complex 14 (5.0μmol) and 100μmol of triphenylphosphine in toluene The solution was sequentially added into a 250-ml stainless steel autoclave to make the total volume 100 ml, Al/Ni=300. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 6.15×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , the oligomer The contents are respectively: C ₄ 98.7%, C ₆ 1.3%, and the selectivity to 1-butene is 50.2%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 53

1. Preparation of [2-acetyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-diisopropylaniline)] nickel (II) [complex 15]: 2 -Acetyl-9-phenyl-1,10-phenanthroline (2,6-diisopropylaniline) ligand (0.0933g, 0.204mmol) and NiCl ₂ ·6H ₂ O (0.0494g, 0.206mmol ) was placed in a Schlenk tube, 5 ml of absolute ethanol was added, and stirred at room temperature for 15 hrs. The resulting orange precipitate was filtered, washed with ether, and dried to obtain 0.0916 g of orange powder with a yield of 76.5%.

FT-IR (KBr disc): 3426, 3060, 2967, 2865, 1609, 1586, 1558, 1489, 1443, 1378, 1330, 1293, 1185, 1151, 869, 787, 761, 749, 702 ^{cm -1} .

Elemental analysis (C ₃₂ H ₃₁ Cl ₂ N ₃ Ni CH ₂ Cl ₂ ) theoretical value (%): C58.97, H4.95, N6.25; experimental value (%): C58.44, H5.02, N6.20.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 2.9 mg (5 μmol) of complex 15 and 50 μmol of triphenylphosphine were added, followed by evacuation and displacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 3.33×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 97.5% , C ₆ 2.5%, selectivity to 1-butene is 14.0%. Extend the reaction to 60min: the oligomerization activity is 3.68×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , the oligomer contents are respectively: C ₄ 96.1%, C ₆ 3.9%, the choice of 1-butene sex at 3.2%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 54

1. The preparation of complex 15 is the same as in Example 53.

2. Pressurized (1MPa) ethylene oligomerization: 50ml of toluene, 0.75ml of diethylaluminum chloride (2.0mol/l hexane solution), 20ml of complex 15 (5.0μmol) and 100μmol of triphenylphosphine in toluene The solution was sequentially added into a 250-ml stainless steel autoclave to make the total volume 100 ml, Al/Ni=300. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 3.96×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , the oligomer The contents are respectively: C ₄ 98.9%, C ₆ 1.1%, and the selectivity to 1-butene is 63.4%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 55

1. The preparation of [2-benzoyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-dimethylaniline)] nickel (II) [complex 16]: the 2 - Benzoyl-9-phenyl-1,10-phenanthroline (2,6-dimethylaniline) ligand (0.0936g, 0.202mmol) and NiCl ₂ 6H ₂ O (0.0491g, 0.205mmol ) was placed in a Schlenk tube, 5ml of absolute ethanol was added, and the reaction was stirred at room temperature for 15hrs. The resulting precipitate was filtered, and the filtrate was yellow. The precipitate was washed with ether and dried to obtain 0.115g of yellow powder, with a yield of 96.0%.

FT-IR (KBr disc): 3388, 1618, 1592, 1554, 1486, 1445, 1378, 1290, 1212, 1057, 1038, 1004, 868, 778, 754, 723 ^{, 703 cm -1} .

Elemental analysis (C ₃₃ H ₂₅ Cl ₂ N ₃ Ni·H ₂ O) Theoretical value (%): C64.85, H4.45, N6.88; Experimental value (%): C65.09, H4.16, N6 .82.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.0 mg (5 μmol) of complex 16 and 50 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 3.47×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 97.8% , C ₆ 2.2%, selectivity to 1-butene is 15.2%. Extend the reaction to 60min: the oligomerization activity is 4.71×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , the oligomer contents are: C ₄ 95.7%, C ₆ 4.3%, the choice of 1-butene sex at 2.8%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 56

1. The preparation of complex 16 is the same as in Example 55.

2. Pressurized (1MPa) ethylene oligomerization: 50ml of toluene, 0.75ml of diethylaluminum chloride (2.0mol/l hexane solution), 20ml of complex 16 (5.0μmol) and 100μmol of triphenylphosphine in toluene The solution and toluene were sequentially added into a 250-ml stainless steel autoclave to make the total volume 100 ml, Al/Ni=300. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 3.91×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , the oligomer The contents are respectively: C ₄ 98.1%, C ₆ 1.9%, and the selectivity to 1-butene is 38.9%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 57

1. The preparation of [2-benzoyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-diethylaniline)] nickel (II) [complex 17]: the 2 -Benzoyl-9-phenyl-1,10-phenanthroline (2,6-diethylaniline) ligand (0.0987g, 0.201mmol) was suspended in 4ml of absolute ethanol, and 4ml of it was added dropwise The ethanol solution of NiCl ₂ 6H ₂ O (0.0496g, 0.209mmol) had no obvious change at the beginning, then gradually changed from yellow to orange, stirred at room temperature for 9hrs, filtered, the filtrate was yellow, and the precipitate was washed with ether and dried to obtain orange The powder is 0.113g, and the yield is 90.6%.

FT-IR (KBr disc): 3061, 2963, 1597, 1558, 1489, 1443, 1377, 1291, 1209, 1148, 1108, 1065, 1040, 1004, 867, 784, 706 ^{cm -1} .

Elemental analysis (C ₃₅ H ₂₉ Cl ₂ N ₃ Ni·1/2CH ₂ Cl ₂ ) theoretical value (%): C64.24, H4.56, N6.33; experimental value (%): C64.50, H4. 75, N6.60.

Its crystal structure is shown in Figure 7.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 17 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) to make Al/Ni=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: no oligomerization activity. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 58

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 17 and 50 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of methylaluminoxane (MAO) (1.46 mol/l toluene solution) to make Al/Ni=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: no oligomerization activity. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 59

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 17 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of triisobutylaluminum-modified methylaluminoxane (MMAO) (1.93 mol/l heptane solution) to make Al/Ni=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 4.8×10 ³ g·mol ^-1 (Ni)·h ^-1 , the oligomerization product was only butene, and for 1-butane The selectivity of alkenes was 92.8%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 60

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.1 mg (5 μmol) of complex 17 and 50 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 1.7 ml of modified methylaluminoxane (MMAO) (1.93 mol/l heptane solution) to make Al/Ni=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 1.28×10 ⁴ g·mol ^-1 (Ni)·h ^-1 , and the oligomerization product was only butene. The selectivity of alkenes is 41.6%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 61

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.0 mg (5 μmol) of complex 17 was added, followed by re-evacuation and displacement with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 1.43×10 ⁴ g·mol ^-1 (Ni)·h ^-1 , the oligomerization product was only butene, and 1-butene The selectivity to alkenes was 78.5%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 62

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.0 mg (5 μmol) of complex 17 and 10 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then analyzed by GC: the oligomerization activity was 9.63×10 ⁴ g·mol ^-1 (Ni)·h ^-1 , and the oligomer content was: C ₄ 97.8% , C ₆ 2.2%, selectivity to 1-butene is 27.1%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 63

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.0 mg (5 μmol) of complex 17 and 25 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.29×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 98.1% , C ₆ 1.9%, selectivity to 1-butene is 24.0%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 64

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, evacuated while hot and replaced with _N gas for 3 times. 3.1 mg (5 μmol) of complex 17 and 50 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 3.31×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 98.1% , C ₆ 1.9%, selectivity to 1-butene is 15.9%. Extend the reaction to 60min: the oligomerization activity is 3.71×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , the oligomer contents are respectively: C ₄ 96.5%, C ₆ 3.5%, the choice of 1-butene Sex is 3.5%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 65

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, evacuated while hot and replaced with _N gas for 3 times. 3.0 mg (5 μmol) of complex 17 and 100 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then analyzed by GC: the oligomerization activity was 6.82×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 97.7% , C ₆ 2.3%, selectivity to 1-butene is 8.5%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 66

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.0 mg (5 μmol) of complex 17 and 100 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.75×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 98.8% , C ₆ 1.2%, the selectivity to 1-butene is 27.2%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 67

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, evacuated while hot and replaced with _N gas for 3 times. 3.1 mg (5 μmol) of complex 17 and 50 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 0°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 1.14×10 ⁵ g·mol(Ni) ^-1 ·h ^-1 , and the oligomer contents were: C ₄ 99.2% , C ₆ 0.8%, the selectivity to 1-butene is 34.6%. Extend the reaction to 60min: the oligomerization activity is 1.91×10 ⁵ g·mol(Co) ^-1 ·h ^-1 , the oligomer contents are respectively: C ₄ 98.4%, C ₆ 1.6%, the choice of 1-butene sex at 16.3%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 68

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.0 mg (5 μmol) of complex 17 and 50 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 40°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.36×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 97.2% , C ₆ 2.8%, selectivity to 1-butene is 22.7%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 69

1. The preparation of complex 17 is the same as in Example 57.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.0 mg (5 μmol) of complex 17 and 50 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 60°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 1.58×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 95.4% , C ₆ 4.6%, selectivity to 1-butene is 20.2%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 70

1. The preparation of complex 17 is the same as in Example 57.

2. Pressurized (1MPa) ethylene oligomerization: Add 50ml of toluene, 0.75ml of diethylaluminum chloride (2.0mol/l hexane solution), 20ml of complex 17 (5.0μmol) toluene solution to 250- ml stainless steel autoclave, make the total volume 100ml, Al/Ni=300. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 2.26×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , the oligomer The contents are respectively: C ₄ 98.9%, C ₆ 1.1%, and the selectivity to 1-butene is 97.1%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 71

1. The preparation of complex 17 is the same as in Example 57.

2. Pressurized (1MPa) ethylene oligomerization: 50ml of toluene, 0.75ml of diethylaluminum chloride (2.0mol/l hexane solution), 20ml of complex 17 (5.0μmol) and 50μmol of triphenylphosphine in toluene The solution and toluene were sequentially added into a 250-ml stainless steel autoclave to make the total volume 100 ml, Al/Ni=300. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 5.87×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , the oligomer The contents are respectively: C ₄ 100%, the selectivity to 1-butene is 93.0%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 72

1. The preparation of complex 17 is the same as in Example 57.

2. Pressurized (1MPa) ethylene oligomerization: 50ml of toluene, 0.75ml of diethylaluminum chloride (2.0mol/l hexane solution), 20ml of complex 17 (5.0μmol) and 50μmol of triphenylphosphine in toluene The solution and toluene were sequentially added into a 250-ml stainless steel autoclave to make the total volume 100 ml, Al/Ni=300. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 5.17×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , the oligomer The contents are respectively: C ₄ 97.5%, C ₆ 2.5%, and the selectivity to 1-butene is 36.5%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 73

1. The preparation of [2-benzoyl-9-phenyl-1,10-phenanthroline chloride (condensed 2,6-diisopropylaniline)] nickel (II) [complex 18]: the 2-benzoyl-9-phenyl-1,10-phenanthroline (2,6-diisopropylaniline) ligand (0.0827g, 0.159mmol) and NiCl ₂ ·6H ₂ O (0.0401g, 0.168mmol) was placed in a Schlenk tube, 10ml of absolute ethanol was added, stirred and reacted at room temperature for 15hrs, the resulting precipitate was filtered, the filtrate was yellow, the precipitate was washed with ether, and dried to obtain 0.0776g of orange powder, with a yield of 75.1%.

FT-IR (KBr disc): 3440, 3057, 2962, 2866, 1621, 1595, 1554, 1490, 1439, 1377, 1322, 1293, 1207, 1151, 1101, 1024, 872, 784, 763, 707 ^{cm -1} .

Elemental analysis (C ₃₇ H ₃₃ Cl ₂ N ₃ Ni·0.5CH ₂ Cl ₂ ) Theoretical value (%): C65.11, H4.95, N6.07; Experimental value (%): C65.01, H5.04 , N5.85.

2. Ethylene oligomerization at normal pressure: A 250ml three-necked round-bottomed flask equipped with a magnetic stirrer was continuously dried at 130°C for 6hrs, vacuumed while hot and replaced with _N2 gas for 3 times. 3.0 mg (5 μmol) of complex 16 and 50 μmol of triphenylphosphine were added, followed by evacuation and replacement with ethylene three times. Inject 30 ml of toluene with a syringe, and then add 0.75 ml of diethylaluminum chloride (2.0 mol/l hexane solution) to make Al/Ni=300. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. A small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 5.88×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , and the oligomer contents were: C ₄ 97.5% , C ₆ 2.5%, selectivity to 1-butene is 10.6%. Extend the reaction to 60min: the oligomerization activity is 3.89×10 ⁵ g·mol ^-1 (Ni)·h ^-1 , the oligomer contents are respectively: C ₄ 96.4%, C ₆ 3.6%, the choice of 1-butene sex at 6.6%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Example 74

1. The preparation of complex 18 is the same as in Example 73.

2. Pressurized (1MPa) ethylene oligomerization: 50ml of toluene, 0.75ml of diethylaluminum chloride (2.0mol/l hexane solution), 20ml of complex 18 (5.0μmol) and 0.1mmol of triphenylphosphine The toluene solution and the toluene were sequentially added into a 250-ml stainless steel autoclave so that the total volume was 100 ml, and Al/Ni=300. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, keep the ethylene pressure of 1 MPa, and stir for 30 minutes. After the reaction, the pressure was released, and a small amount of the mixture was taken out and neutralized with 5% dilute hydrochloric acid for gas chromatography (GC) analysis: the oligomerization activity was 5.77×10 ⁶ gmol ^-1 (Ni)·h ^-1 , and the oligomer content was respectively It is: C ₄ 98.4%, C ₆ 1.6%, and the selectivity to 1-butene is 34.9%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained.

Claims (7)

1. 2-imino-9-phenyl-1,10-phenanthroline transition metal complex of formula I structure, it is characterized in that: described complex is that M, R and R are selected from following any ^one Combined complexes:

(Formula I); M=Fe, R=Me, ^R1 =Me; M=Fe, R=Me, ^R1 =Et; M=Fe, R=Me, R ¹ =iPr; M=Fe, R=Ph, R ¹ =Me; M=Fe, R=Ph, R ¹ =Et; M=Fe, R=Ph, R ¹ =iPr; M=Co, R=Me, ^R1 =Me; M=Co, R=Me, ^R1 =Et; M=Co, R=Me, R ¹ =iPr; M=Co, R=Ph, R ¹ =Me; M=Co, R=Ph, R ¹ =Et; M=Co, R=Ph, R ¹ =iPr; M=Ni, R=Me, ^R1 =Me; M=Ni, R=Me, ^R1 =Et; M=Ni, R=Me, ^R1 =iPr; M=Ni, R=Ph, ^R1 =Me; M=Ni, R=Ph, R ¹ =Et; M=Ni, R=Ph, R ¹ =iPr; Here, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, and Ph represents a phenyl group. 2. the preparation method of 2-imino-9-phenyl-1,10-phenanthroline transition metal complex described in claim 1, comprises the steps: 1) Using p-toluenesulfonic acid as a catalyst, use 2-acetyl-9-phenyl-1,10-phenanthroline or 2-benzoyl-9-phenyl-1,10-phenanthroline and alkyl Synthesis of 2-imino-9-phenyl-1,10-phenanthroline ligands by reaction of substituted anilines; 2) The complex can be obtained by reacting the 2-imino-9-phenyl-1,10-phenanthroline ligand obtained in step 1) with a transition metal salt. 3. a catalyst composition, comprises procatalyst and procatalyst, and described procatalyst is 2-imino-9-phenyl-1,10-phenanthroline transition metal complexes described in claim 1, and described The cocatalyst is selected from the group consisting of aluminoxanes, alkylaluminum compounds and alkylaluminum chlorides; The aluminoxane is methylalumoxane and modified methylalumoxane; the alkylaluminum is trimethylaluminum and triethylaluminum; the alkylaluminum chloride is diethylaluminum chloride, dichloroaluminum Ethylaluminum. 4. The catalyst composition according to claim 3, characterized in that: the molar ratio of metal aluminum in the co-catalyst to the central metal M of the main catalyst is 100 to 2000. 5. The catalyst composition according to claim 3, characterized in that: the catalyst composition also contains triphenylphosphine; the molar ratio of the triphenylphosphine to the main catalyst is 50-1:1. 6. the application of catalyst composition described in claim 3 in catalytic ethylene oligomerization. 7. The application according to claim 6, characterized in that: the temperature of the oligomerization reaction is 20 to 80° C., and the ethylene pressure is 10-0.1 MPa.

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