CN111620914B - Side-arm metallocene tetravalent transition metal complex containing neutral benzyl heteroatom ligand and application thereof - Google Patents

Side-arm metallocene tetravalent transition metal complex containing neutral benzyl heteroatom ligand and application thereof Download PDF

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CN111620914B
CN111620914B CN202010658644.5A CN202010658644A CN111620914B CN 111620914 B CN111620914 B CN 111620914B CN 202010658644 A CN202010658644 A CN 202010658644A CN 111620914 B CN111620914 B CN 111620914B
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母瀛
宋婷婷
佟小波
张晋伟
李丰
刘宁
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Jilin University
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Abstract

The invention relates to the field of ethylene oligomerization catalysis, and particularly discloses a kind of single-metallocene tetravalent transition metal complex containing a neutral benzyl heteroatom ligand side arm and an application thereof, wherein the single-metallocene tetravalent transition metal complex containing the neutral benzyl heteroatom ligand side arm has a structure shown as a formula 1 or a formula 2:
Figure DDA0002577672480000011
the single-metallocene tetravalent transition metal complex containing the neutral benzyl heteroatom ligand side arm is activated by a proper cocatalyst and used for catalyzing ethylene hydrocarbon oligomerization, and the 1-hexane can be selectively generated by high-activity catalysis of ethylene oligomerization through adjusting the substituent on the ligand and the reaction conditionsAlkene or C10And C10The synthesis method of the alpha-olefin is suitable for industrial production, and solves the problem that the existing catalyst can not catalyze ethylene oligomerization to synthesize C with high selectivity10And C10The above problems with alpha-olefins.

Description

Side-arm metallocene tetravalent transition metal complex containing neutral benzyl heteroatom ligand and application thereof
Technical Field
The invention belongs to the field of ethylene oligomerization catalysis, and particularly relates to a single-metallocene tetravalent transition metal complex containing a neutral benzyl heteroatom ligand side arm and application thereof.
Background
Alpha-olefin is used as an important organic chemical raw material and is widely applied to the fields of polyethylene comonomers, surfactants, high-grade lubricating oil, plasticizers, detergents, oil additives and the like. Among them, linear low density polyethylene and polyolefin elastomers produced by copolymerizing ethylene with α -olefin as a comonomer have wide applications in the fields of medical instruments, automobiles, electronics, packaging, building materials, industrial and agricultural industries, and the like. Alpha-olefins are also important feedstocks for the synthesis of PAO (Poly Alpha olefins) as a high-grade lubricant base oil.
In recent years, with the continuous development of the polyolefin industry, the demand for α -olefins in the world has increased. The industrial production method of alpha-olefin mainly includes paraffin cracking, alkane dehydrogenation, alcohol dehydration and ethylene oligomerization, etc., and according to statistics, ethylene oligomerization is the main method for producing alpha-olefin at present.
Among them, the most common catalytic system for ethylene oligomerization is a catalytic system containing metallic chromium, such as Philips trimerization catalytic system, but heavy metal chromium has high toxicity and causes environmental pollution. With the development of science and technology, in recent years, reports of catalyzing ethylene oligomerization by using other transition metal compounds are sequentially provided, and the transition metal compounds are mainly transition metal compounds of fourth and fifth sub-groups. For example, Hessen et al, 2001 and 2002, have reported using [ (. eta.) (eta.)5-C5H4C(Me)2RTiCl3]MAO (methylaluminoxane) catalytic system (Angew. chem.2001,113,2584) and [ (. eta.5-C5H3R(bridge)ArTiCl3]Research results of high selectivity of 1-hexene production by catalyzing ethylene oligomerization by using a/MAO catalytic system (Organometallics 2002,21, 5122; J.Am.chem.Soc.2009,131, 5298). Huangjiling et al developed several thiophene or tetrahydrofuran side-arm containing half-sandwich titanium complexes that can catalyze the trimerization of ethylene to 1-hexene (chem.commun.,2003,22, 2816; j.mol.call.a, 2004,214,227; j.mol.call.a, 2014,387, 20). A series of indenyl half-sandwich titanium complexes containing thiophene side-arms, which can catalyze the trimerization of ethylene to obtain 1-hexene with higher activity under the activation of MAO (applied organometallic chem.2019, 33, 4666), were reported by Azimunavahsi et al in 2018.
Most of the fourth subgroup single metallocene complex systems reported so far for catalyzing ethylene trimerization to generate 1-hexene have low catalytic activity, are difficult to be used for industrial production, can only catalyze ethylene trimerization to generate 1-hexene, and cannot selectively produce other alpha-olefins. Therefore, the selective production of C by catalyzing ethylene oligomerization is developed10And the above novel catalysts for alpha-olefins are an important subject to be solved in the art.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a single-metallocene tetravalent transition metal complex containing a neutral benzyl heteroatom ligand side arm, a synthetic method and application thereof in catalyzing ethylene oligomerization. By developing a single-metallocene tetravalent transition metal complex containing a neutral benzyl heteroatom ligand side arm and adjusting the substituent on the ligand and the reaction conditions, the ethylene oligomerization can be catalyzed with high activity to selectively generate 1-hexene or C10And C10The above alpha-olefins. The selective formation of C by oligomerization of ethylene by catalysis has not been described so far10And the above reports of alpha-olefins. C10The alpha-olefin as the comonomer can obviously improve the mechanical and processing properties of polyolefin products, and has good application prospect when being used as a plasticizer, a detergent, an oil additive and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
one kindA single-metallocene tetravalent transition metal complex containing a side arm of a neutral benzyl heteroatom ligand, and the molecular formula of the complex is { Cp#C6H4-o-CH2A}MX1X2X3The structure is shown as formula 1 or formula 2:
Figure BDA0002577672470000021
wherein, the central metal M is any one of Ti (titanium element), Zr (zirconium element) or Hf (hafnium element);
Cp#is any one of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, substituted fluorenyl, cycloheptatrienyl or substituted cycloheptatrienyl;
the coordinating atom A being NR1R2、PR3R4、OR5Or SR6Wherein N is nitrogen, P is phosphorus, O is oxygen, S is sulfur, R is sulfur1And R2Each independently selected from alkyl group with 1-30 carbon atoms, cycloalkyl group with 1-30 carbon atoms, aryl substituted alkyl group with 1-30 carbon atoms, silyl substituted alkyl group with 1-30 carbon atoms, alkenyl group with 1-30 carbon atoms, phenyl group with 1-30 carbon atoms or aryl group with 1-30 carbon atoms, or R1And R2Linked as alkylene or alkenylene; r3And R4Each independently selected from alkyl group with 1-30 carbon atoms, cycloalkyl group with 1-30 carbon atoms, aryl substituted alkyl group with 1-30 carbon atoms, silyl substituted alkyl group with 1-30 carbon atoms, alkenyl group with 1-30 carbon atoms, phenyl group with 1-30 carbon atoms or aryl group with 1-30 carbon atoms, or R1And R2Linked as alkylene or alkenylene; r5Is alkyl with 1-30 carbon atoms, cycloalkyl with 1-30 carbon atoms, aryl substituted alkyl with 1-30 carbon atoms, silyl substituted alkyl with 1-30 carbon atoms, phenyl with 1-30 carbon atoms or aryl with 1-30 carbon atoms; r6Is alkyl with 1-30 carbon atoms, cycloalkyl with 1-30 carbon atoms, aryl substituted alkyl with 1-30 carbon atoms, silyl substituted alkyl with 1-30 carbon atoms, phenyl with 1-30 carbon atoms or aryl with 1-30 carbon atoms;
X1、X2and X3Each independently selected from alkyl with 1-30 carbon atoms, aryl substituted alkyl with 1-30 carbon atoms, silyl substituted alkyl with 1-30 carbon atoms, aryl with 1-30 carbon atoms, amino with 1-30 carbon atoms, alkoxy with 1-30 carbon atoms or halogen;
depending on the degree of crowding of the coordination environment around the central metal M, the coordinating atom A may or may not coordinate with the central metal M.
As a further scheme of the invention: in the single-metallocene tetravalent transition metal complex containing neutral benzyl heteroatom ligand side arms and having the structure shown in formula 1 or formula 2, M is Ti, Zr or Hf; cp#Is any one of cyclopentadienyl, monomethylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, dimethyldiphenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, monomethylindenyl, dimethylindenyl, benzindenyl, 2-methylbenzindenyl, 2-methyl-4-phenylindenyl, fluorenyl, dimethylfluorenyl, di-t-butylfluorenyl, cycloheptatrienyl or dibenzocycloheptatrienyl; a is NR1R2、PR3R4、OR5Or SR6，R1And R2The same or different, each is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, o-tolyl, p-tolyl, 3, 5-dimethylphenyl or 3, 5-di-tert-butylphenyl, or R1And R2Linked as 1, 4-butylene, 1, 5-pentylene, or 1, 4-butadienylene; r4And R5The same or different, each is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, o-tolyl, p-tolyl, 3, 5-dimethylphenyl or 3, 5-di-tert-butylphenyl, or R1And R2Linked as 1, 4-butylene, 1, 5-pentylene, 1, 4-butadienylene, R5Is methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, trimethylsilyl, phenyl, ortho-tolyl, para-tolyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, R6Is methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, trimethylsilyl, phenyl, ortho-tolyl, para-tolyl, 3, 5-dimethylphenyl or 3, 5-di-tert-butylphenyl; x1、X2And X3The same or different, respectively is any one of methyl, benzyl, neopentyl, trimethylsilylmethyl, dimethylamino, diethylamino, diisopropylamino, bistrimethylsilylamino, methoxyl, ethoxyl, isopropoxy, chlorine or bromine.
As a still further scheme of the invention: in the single-metallocene tetravalent transition metal complex containing neutral benzyl heteroatom ligand side arms and having the structure shown in formula 1 or formula 2, M is Ti, Zr or Hf; cp#Is cyclopentadienyl, tetramethylcyclopentadienyl, dimethyldiphenylcyclopentadienyl, 3, 4-diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, 2-methylbenzindenyl, fluorenyl, 4, 7-dimethylfluorenyl or 4, 7-di-tert-butylfluorenyl; a is NR1R2、PR3R4、OR5And SR6，R1And R2Identical or different, each being methyl, ethyl, isopropyl, tert-butyl or phenyl, or R1And R2Linked as 1, 4-butylene, 1, 5-pentylene, or 1, 4-butadienylene; r3And R4Identical or different, each being methyl, ethyl, isopropyl, tert-butyl or phenyl, or R1And R2Linked as 1, 4-butylene, 1, 5-pentylene, or 1, 4-butadienylene; r5Is methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, trimethylsilyl, 2, 6-dimethylphenyl, 2, 6-diethyltolyl or 2, 6-diisopropyltolyl; r6Is methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, trimethylsilyl, 2, 6-dimethylphenyl, 2, 6-diethyltolyl or 2, 6-diisopropyltolyl; x1、X2And X3The same or different, respectively, methyl, benzyl, trimethylsilylmethyl, dimethylamino, methoxy, isopropoxy, chloro or bromo.
The preparation process of the single-metallocene tetravalent transition metal complex containing the neutral benzyl heteroatom ligand side arm is as follows:
general method for ligand precursor Synthesis
The ligands used in this patent were synthesized by literature methods (Dalton Trans.,2019,20,17840-17851; CN 11065538A), and a typical synthesis procedure is as follows:
under inert atmosphere, adding 1.0-1.2 equivalent of N-butyllithium into N, N-disubstituted aromatic amine, P-disubstituted O-bromobenzylphosphine, O-substituted benzyl ether or S-substituted benzyl thioether, reacting for a certain time under proper conditions, and determining to generate corresponding ortho lithiation products of N, N-disubstituted benzylamine, P-disubstituted O-bromobenzylphosphine, O-substituted benzyl ether or S-substituted benzyl thioether. Slowly adding 1.0-1.2 equivalents of cyclopentenone, substituted cyclopentenone, indanone, substituted indanone, fluorenone, substituted fluorenone, tropone or substituted tropone into the reaction system under proper conditions. After reflux reaction for a certain time, cooling to room temperature, adding saturated ammonium chloride aqueous solution to quench reaction, separating out organic compounds, dehydrating or dehydroxylating under acidic condition, and finally obtaining corresponding ligand precursor by reduced pressure distillation or column chromatography separation.
Secondly, a general synthesis method of the ligand-side arm metallocene tetravalent transition metal complex containing neutral benzyl heteroatom
The preparation process of the single-metallocene tetravalent transition metal complex containing the neutral benzyl heteroatom ligand side arm comprises the following steps: under inert atmosphere, 1.0-1.2 equivalents of n-butyllithium are used for treating the corresponding ligand under proper conditions, and the corresponding ligand lithium salt is generated after stirring for a certain time (0.5-2.0 hours) at room temperature. Slowly adding the ligand lithium salt generated by the reaction into equivalent corresponding metal halide ether solution at a proper temperature (-78 to 25 ℃), stirring for a certain time (10 to 16 hours) at room temperature, evaporating the solvent to obtain a crude product, and recrystallizing by using a mixed solvent of dichloromethane and normal hexane to obtain the pure single-metallocene tetravalent transition metal trihalide containing the neutral benzyl heteroatom ligand side arm. If necessary, the obtained single metallocene tetravalent transition metal trihalide containing neutral benzyl heteroatom ligand side arm is reacted with appropriate alkali metal or alkaline earth metal reagent of alkyl, alkoxy or amino to obtain corresponding metallocene alkyl, alkoxy or amino compound. Or corresponding ligand lithium salt reacts with trialkyl-substituted metal halide, trialkoxy-substituted metal halide or triamino-substituted metal halide ether solvent to generate corresponding ligand mono-metallocene alkyl complex, alkoxy complex or amino complex containing neutral amine or phosphine ligand side arm.
It should be noted that the method for synthesizing the neutral benzyl heteroatom ligand-containing side-arm metallocene tetravalent transition metal complex is not limited to the aforementioned method, and those skilled in the art can synthesize the neutral benzyl heteroatom ligand-containing side-arm metallocene tetravalent transition metal complex by various methods based on the existing chemical knowledge.
The invention relates to an application of a single-metallocene tetravalent transition metal complex containing a neutral benzyl heteroatom ligand side arm, which is used for catalyzing ethylene oligomerization by taking the single-metallocene tetravalent transition metal complex containing the neutral benzyl heteroatom ligand side arm as a main catalyst and taking alkyl aluminoxane, modified alkyl aluminoxane, an alkyl aluminum/organic boron compound composite system or other reagents capable of playing the same activation role as a cocatalyst. By adjusting the substituent group on the ligand and the reaction condition, the ethylene oligomerization can be catalyzed with high activity to selectively generate 1-hexene or C10And C10The above alpha-olefin; wherein the molar ratio of aluminum in the cocatalyst to metal in the main catalyst is 5-10000:1, the molar ratio of boron in the cocatalyst to metal in the main catalyst is 0-2:1, and the polymerization temperature is-20 to 200 ℃.
As a still further scheme of the invention: in the application of the ligand side arm metallocene tetravalent transition metal complex containing neutral benzyl heteroatom, the alkyl aluminoxane is Methyl Aluminoxane (MAO) or Modified Methyl Aluminoxane (MMAO); the alkyl aluminum is preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl aluminum chloride, triisopropyl aluminum, tricyclopentyl aluminum, triisofluorenyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl methoxy aluminum, dimethyl ethoxy aluminum, diethyl aluminum chloride, ethyl dichloro aluminum, methyl propylAluminum oxide or aluminum sesquiethylate chloride; the organoboron compound is preferably B (C)6F5)3、Ph3CB(C6F5)4、Me3CB(C6F5)4、PhMe2HNB(C6F5)4Or PhQ2HNB(C6F5)4(ii) a Wherein Ph represents a phenyl group and Me represents a methyl group, at PhQ2HNB(C6F5)4Q in (1) is an alkyl group having 2 to 18 carbon atoms.
As a still further scheme of the invention: in the application of the ligand side arm single-metallocene tetravalent transition metal complex containing neutral benzyl heteroatom, the alkyl aluminoxane is preferably methyl aluminoxane or modified methyl aluminoxane; the alkyl aluminum is further preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride or sesquiethyl aluminum chloride; the organoboron auxiliary is preferably Ph3CB(C6F5)4。
As a still further scheme of the invention: in the application of the present invention, the catalytic olefin polymerization reaction can be carried out in any solvent which does not adversely affect the catalyst system, and can also be carried out under the solvent-free condition. The pressure of ethylene can be determined as desired. The ethylene pressure ranges from 0 to 150 atmospheres. The polymerization temperature may vary from-20 ℃ to 200 ℃, with a preferred temperature range being-20 ℃ to 120 ℃.
As a still further scheme of the invention: in the application of the ligand side arm metallocene tetravalent transition metal complex containing neutral benzyl heteroatom, the specific steps for catalyzing olefin polymerization reaction are as follows: adding a main catalyst and a cocatalyst into a polymerization kettle, and reacting for 5-720 minutes under the conditions of a certain temperature and ethylene pressure. After the polymerization reaction is completed, the obtained polymer is quenched with an acidic solution.
As a still further scheme of the invention: the ethylene oligomerization product is detected by gas chromatography, and analyzed by retention value and peak area.
Compared with the prior art, the invention has the beneficial effects that:
1. the synthesis method of the single-metallocene tetravalent transition metal complex containing the neutral benzyl heteroatom ligand side arm is simple, low in cost and high in yield;
2. compared with a chromium catalyst with high toxicity, the single-metallocene tetravalent transition metal complex containing the neutral benzyl heteroatom ligand side arm is environment-friendly and has little pollution as the catalyst;
3. the single-metallocene tetravalent transition metal complex containing the neutral benzyl heteroatom ligand side arm has a stable structure, and is good in stability, long in service life and high in catalytic activity in the catalytic reaction process;
4. the side-arm single-metallocene tetravalent transition metal complex containing the neutral benzyl heteroatom ligand is used for catalyzing ethylene oligomerization reaction, has high catalytic activity, and can generate 1-hexene or C with high selectivity by adjusting the substituent on the ligand and the reaction conditions10And C10The alpha-olefin solves the problem that the existing catalyst can not catalyze the ethylene oligomerization to synthesize C with high selectivity10And C10The alpha-olefin can be used as a plasticizer, a cleaning agent, an emulsifier, a flotation agent and a binder, can be polymerized into lubricating oil base oil, can be copolymerized with ethylene, propylene and the like into linear low-density polyethylene and polyolefin elastomer as a comonomer, and has wide application fields.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. These are all protection enclosures of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. The materials, reagents and the like used are commercially available unless otherwise specified. The ligands used in the following examples can be synthesized by methods described in the literature (Dalton Trans.,2019,20, 17840-17851; CN 11065538A).
The following examples illustrate the preparation of 30 exemplary neutral benzyl heteroatom containing ligand-pendant metallocene tetravalent transition metal complexes of the present invention.
Example 1: preparation of 2-tetramethylcyclopentadienyl-N, N-dimethylbenzylamine titanium trichloride (C1)
Weighing 2-tetramethylcyclopentadienyl-N, N-dimethylbenzylamine (0.26g, 1.0mmol) in a 50mL Schlenk bottle under an inert atmosphere, adding 30mL of anhydrous tetrahydrofuran, adding a hexane solution of nBuLi (N-Butyllithium) (0.40mL,1.0 mmol) by a syringe, reacting at room temperature for 1h, slowly adding the lithium salt solution to an equivalent of 1mol/L TiCl at-78 ℃4In 20mL of tetrahydrofuran solution (1.0mL, 1.0mol), reacting overnight at room temperature, removing the reaction solvent in vacuum, adding 15mL of dichloromethane, filtering, removing inorganic salts generated in the reaction, adding a proper amount of N-hexane, concentrating and filtering insoluble substances, and cooling and crystallizing at-30 ℃ in a refrigerator of a glove box to obtain a reddish brown solid, namely 2-tetramethylcyclopentadienyl-N, N-dimethylbenzylamine titanium trichloride (0.19g, yield 45.6%).
Example 2: synthesis of complex N- (2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) benzyl) pyrrole trimethyltitanium (noted as C2)
N- (2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) benzyl) pyrrole (0.40g, 1.0mmol) is weighed into a 50mL Schlenk bottle under an inert atmosphere, 20mL of anhydrous ether is added, a hexane solution of nBuLi (0.40mL,1.0 mmol) is added through a syringe, and the reaction is carried out at room temperature for 1h to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4DME (i.e. C)4H10Cl4O2Ti, DME 1,2-Dimethoxyethane for short, representing ethylene glycol dimethyl ether) (0.28g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the reaction was cooled to-30 ℃ with a low temperature bath, methyllithium (1.88mL, 3.0mmol,1.6mol/L) was slowly added for 10min, the above ligand lithium salt solution was added, the reaction was carried out at this temperature for 30min, then the reaction was carried out at room temperature for 12h, the reaction solvent was removed in vacuo, 15mL of n-hexane was added, filteredRemoving inorganic salt generated in the reaction, concentrating, removing insoluble substances from filtrate, putting into a refrigerator of a glove box, and cooling and crystallizing at-30 ℃ to obtain orange solid, namely N- (2- (2, 5-dimethyl-3, 4-diphenyl cyclopentadienyl) benzyl) pyrrole trimethyltitanium (0.36g, yield 74.0%).
Example 3: preparation of N- (2-fluorenyl) tetrahydropyrrole tribenzyltitanium (noted as C3)
N- (2-fluorenyl) tetrahydropyrrole (0.33g, 1.0mmol) is weighed into a 50mL Schlenk flask under an inert atmosphere, 20mL of anhydrous ether is added, a hexane solution of nBuLi (0.40mL,1.0 mmol) is added by a syringe, and the reaction is carried out at room temperature for 1h to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4Adding DME (0.28g and 1.0mmol) into 50mL of Schlenk, adding 20mL of anhydrous ether, cooling the reaction system to-30 ℃ by using a low-temperature bath, slowly adding benzyl potassium (0.39g and 3.0mmol), reacting for 10min, adding the above ligand lithium salt solution, reacting for 30min at the temperature, reacting for 12h at room temperature, removing the reaction solvent in vacuum, adding 15mL of N-hexane, filtering, removing inorganic salts generated by the reaction, concentrating, removing insoluble substances from the filtrate, placing the filtrate into a refrigerator of a glove box, and cooling and crystallizing at-30 ℃ to obtain an orange yellow solid, namely N- (2-fluorenyl) tetrahydropyrrole tribenzyltitanium (0.50g and the yield of 76.9%).
Example 4: preparation of 2- (4, 7-dimethylfluorenyl) -N, N-diethylbenzylamine trimethoxytitanium (noted as C4)
Under an inert atmosphere, 2- (4, 7-dimethylfluorenyl) -N, N-diethylbenzylamine (0.36g, 1.0mmol) is weighed into a 50mL Schlenk bottle, 20mL of anhydrous ether is added, a hexane solution of nBuLi (0.40mL,1.0 mmol) is added through a syringe, and the reaction is carried out at room temperature for 1h to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4DME (0.28g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the reaction system was cooled to-30 ℃ with a low temperature bath, sodium methoxide (0.16g, 3.0mmol) was slowly added, the reaction was carried out for 10min, the above ligand lithium salt solution was added, the reaction was carried out at this temperature for 30min, then the reaction was carried out at room temperature for 12h, the reaction solvent was removed in vacuo, 15mL of n-hexane was added, filtration was carried out, the inorganic salt formed by the reaction was removed, the filtrate was concentrated and the insoluble matter was removed, and the mixture was placed in an ice bag of a gloveThe crystals were cooled in a chamber at-30 ℃ to obtain orange solid 2- (4, 7-dimethylfluorenyl) -N, N-diethylbenzylamine trimethoxytitanium (0.35g, 71.1%).
Example 5: synthesis of 2-indenyl-N, N-diphenylbenzylamine tris-dimethylaminotitanium (noted as C5)
Under an inert atmosphere, 2-indenyl-N, N-diphenylbenzylamine (0.37g, 1.0mmol) is weighed into a 50mL Schlenk bottle, 20mL of anhydrous ether is added, a hexane solution of nBuLi (0.40mL,1.0 mmol) is added by a syringe, and the reaction is carried out at room temperature for 1h to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4DME (0.28g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the reaction system was cooled to-30 ℃ with a low temperature bath, sodium dimethylamide (0.20g, 3.0mmol) was slowly added, the reaction was carried out for 10min, the above ligand lithium salt solution was added, the reaction was carried out at this temperature for 30min, the reaction was carried out at room temperature for 12h, the reaction solvent was removed in vacuo, 15mL of N-hexane was added, filtration was carried out, the inorganic salt formed by the reaction was removed, the filtrate was concentrated and the insoluble matter was removed, and the filtrate was placed in a glove box refrigerator and cooled to-30 ℃ for crystallization to obtain an orange yellow solid, i.e., 2-indenyl-N, N-diphenylbenzylamine tridimethylaminotitanium (0.36 g.
Example 6: synthesis of N- (2- (2-methylindenyl)) zirconium pyridine trichloride (denoted as C6)
N- (2- (2-methylindenyl)) pyridine (0.30g, 1.0mmol) is weighed into a 50mL Schlenk flask under an inert atmosphere, 20mL of anhydrous ether is added, a solution of nBuLi (0.40mL, 1.00mmol) in hexane is added by a syringe, and the mixture is reacted at room temperature for 1h, the lithium salt solution is slowly added to ZrCl with an equivalent weight at-78 DEG C4·THF2(0.38g, 1.0mmol) in 20mL of ether, reacted at room temperature overnight, the reaction solvent was removed in vacuo, 15mL of dichloromethane was added, filtered, the inorganic salt formed by the reaction was removed, an appropriate amount of N-hexane was added, the insoluble matter was concentrated and filtered, and the mixture was placed in a glove box freezer and crystallized by cooling at-30 ℃ to give a yellow solid, i.e., N- (2- (2-methylindenyl)) zirconium pyridine trichloride (0.33g, 66.1%).
Example 7: synthesis of 2- (2-methyl-4-phenylindenyl) -N, N-dimethylbenzylamine trimethylzirconium (noted as C7)
Under the inert atmosphere, the reaction kettle is filled with a solvent,2- (2-methyl-4-phenylindenyl) -N, N-dimethylbenzylamine (0.34g, 1.0mmol) was weighed into a 50mL Schlenk flask, 30mL of anhydrous ether was added, a solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) in N-hexane was added by syringe, and the reaction was carried out at room temperature for 1 hour to precipitate a lithium salt having a large amount of ligand. Under inert atmosphere, ZrCl is added4·THF2(0.38g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the solution of the lithium salt of the ligand was slowly added to the ether solution of the metal chloride at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃, methyllithium (1.88mL, 3.0mmol,1.6mol/L) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed in vacuo, 15mL of N-hexane was added, inorganic salts formed by the reaction were removed by filtration, insoluble materials were concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled to-30 ℃ for crystallization to obtain a yellow solid, i.e., 2- (2-methyl-4-phenylindenyl) -N, N-dimethylbenzylamine trimethylzirconium (0.31g, 66.1%).
Example 8: synthesis of 2- (1, 3-dimethylindenyl) -N, N-dimethylbenzylamine tris (trimethylsilylmethyl) zirconium (denoted as C8)
2- (2-methyl-4-phenylindenyl) -N, N-dimethylbenzylamine (0.34g, 1.0mmol) was weighed into a 50mL Schlenk flask under an inert atmosphere, 30mL of anhydrous ether was added, a solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) in N-hexane was added by syringe and reacted at room temperature for 1 hour, and a large amount of a lithium salt of the ligand was precipitated. Under inert atmosphere, ZrCl is added4·THF2(0.38g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the lithium salt solution of the above ligand was slowly added to the ether solution of metal chloride at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃, trimethylsilyllithium (0.28mL, 3.0mmol) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed under vacuum, 15mL of N-hexane was added, inorganic salts formed by the reaction were removed by filtration, insoluble matters were concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled to-30 ℃ for crystallization to obtain a yellow solid, i.e., 2- (1, 3-dimethylindenyl) -N, N-dimethylbenzylamine tris (trimethylsilylmethyl) zirconium (0.42g, 66.0%).
Example 9: synthesis of 2-tetramethylcyclopentadienyl-N, N-dimethylbenzylamine hafnium trichloride (denoted as C9)
Weighing 2-tetramethylcyclopentadienyl-N, N-dimethylbenzylamine (0.26g, 1.0mmol) in a 50mL Schlenk bottle under an inert atmosphere, adding 30mL of anhydrous ether, adding a N-hexane solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) by using a syringe, reacting for 1h at room temperature, precipitating a lithium salt with a large amount of ligand to generate the inert atmosphere, and adding HfCl4·THF2(0.46g, 1.0mmol) is added into 50mL Schlenk, 20mL of anhydrous ether is added, the lithium salt solution of the ligand is slowly added into the ether solution of the metal chloride at room temperature, the reaction is carried out for 12h, the reaction solvent is removed in vacuum, 15mL of N-hexane is added, the inorganic salt generated by the reaction is removed, the insoluble matter is concentrated and filtered, and the mixture is placed into a refrigerator of a glove box to be cooled and crystallized at the temperature of minus 30 ℃ to obtain white solid, namely 2-tetramethylcyclopentadienyl-N, N-dimethylbenzylamine hafnium trichloride (0.35g, 64.9%).
Example 10: synthesis of N- (2-tetramethylcyclopentadienyl) piperidinemethylhafnium (denoted as C10)
Weighing 2-tetramethylcyclopentadienyl-N, N-dimethylbenzylamine (0.30g, 1.0mmol) in a 50mL Schlenk bottle under an inert atmosphere, adding 30mL of anhydrous ether, adding a N-hexane solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) by using a syringe, reacting for 1h at room temperature, precipitating a lithium salt with a large amount of ligand to generate the inert atmosphere, and adding HfCl4·THF2(0.46g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the lithium salt solution of the ligand was slowly added to the ether solution of the metal chloride at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃, methyllithium (1.88mL, 3.0mmol,1.6mol/L) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed in vacuo, 15mL of N-hexane was added, inorganic salts formed by the reaction were removed by filtration, insoluble materials were concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled at-30 ℃ for crystallization to obtain a white solid, namely N- (2-tetramethylcyclopentadienyl) piperidino-trimethylhafnium (0.34g, 65.6%).
Example 11: synthesis of 2-tetramethylcyclopentadienyl-N, N-diisopropylbenzylamine tris (trimethylsilylmethyl) hafnium (denoted as C11)
Weighing 2-tetramethyl ring under inert atmospherepentadienyl-N, N-diisopropylbenzylamine (0.54g, 1.0mmol) in a 50mL Schlenk flask, 30mL of anhydrous ether was added, a solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) in N-hexane was added via syringe, the reaction was carried out at room temperature for 1h, a lithium salt having a large amount of ligand was precipitated under an inert atmosphere, and HfCl was added4·THF2(0.46g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the lithium salt solution of the above ligand was slowly added to the ether solution of metal chloride at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃, trimethylsilyllithium (0.28g, 3.0mmol) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed under vacuum, 15mL of N-hexane was added, inorganic salts formed by the reaction were removed by filtration, insoluble matters were concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled to-30 ℃ for crystallization to obtain a white solid, i.e., 2-tetramethylcyclopentadienyl-N, N-diisopropylbenzylamine tris (trimethylsilylmethyl) hafnium (0.46g, 61.3%).
Example 12: synthesis of 2-tetramethylcyclopentadienyl-P, P-dimethylbenzylphosphine titanium trichloride (noted as C12)
Weighing 2-tetramethylcyclopentadienyl-P, P-dimethylbenzyl (0.27g, 1.0mmol) in a 50mL Schlenk bottle under an inert atmosphere, adding 30mL anhydrous tetrahydrofuran, adding a n-BuLi (0.40mL,1.0 mmol) hexane solution by a syringe, reacting at room temperature for 1h, slowly adding the lithium salt solution to an equivalent of 1mol/L TiCl at-78 DEG C4In 20mL of tetrahydrofuran solution (1.0mL, 1.0mol), reacting overnight at room temperature, removing the reaction solvent in vacuum, adding 15mL of dichloromethane, filtering, removing inorganic salts generated in the reaction, adding a proper amount of N-hexane, concentrating and filtering insoluble substances, and cooling and crystallizing at-30 ℃ in a refrigerator of a glove box to obtain a reddish brown solid, namely 2-tetramethylcyclopentadienyl-N, N-dimethylbenzylamine titanium trichloride (0.29g, 68.1%).
Example 13: synthesis of 2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) -P, P-diethylbenzylphosphinotrimethyltitanium (noted as C13)
2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) -P, P-diethylbenzylphosphine (0.42g, 1.0mmol) is weighed into a 50mL Schlenk bottle under an inert atmosphere, 20mL of anhydrous ether is added, a hexane solution of nBuLi (0.40mL,1.0 mmol) is added through a syringe, and the reaction is carried out at room temperature for 1h to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4Adding DME (0.28g, 1.0mmol) into 50mL Schlenk, adding 20mL of anhydrous ether, cooling the reaction system to-30 ℃ by using a low-temperature bath, slowly adding methyllithium (1.88mL, 3.0mmol,1.6mol/L), reacting for 10min, adding the above ligand lithium salt solution, reacting for 30min at the temperature, then reacting for 12h at room temperature, removing the reaction solvent in vacuum, adding 15mL of n-hexane, filtering, removing inorganic salts generated by the reaction, concentrating, removing insoluble substances from the filtrate, placing the filtrate into a refrigerator of a glove box, and cooling and crystallizing at-30 ℃ to obtain an orange yellow solid, namely 2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) -P, P-diethylbenzylphosphine trimethyltitanium (0.31g, 60.1%).
Example 14: synthesis of 2-fluorenyl-P, P-dimethylbenzylphosphine trimethoxytitanium (noted as C14)
Under an inert atmosphere, weighing 2-fluorenyl-P, P-dimethylbenzylphosphine (0.32g, 1.0mmol) into a 50mL Schlenk bottle, adding 20mL of anhydrous ether, adding a hexane solution of nBuLi (0.40mL,1.0 mmol) by using a syringe, and reacting at room temperature for 1h to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4Adding DME (0.28g and 1.0mmol) into 50mL of Schlenk, adding 20mL of anhydrous ether, cooling the reaction system to-30 ℃ by using a low-temperature bath, slowly adding sodium methoxide (0.16g and 3.0mmol), reacting for 10min, adding the ligand lithium salt solution, reacting for 30min at the temperature, reacting for 12h at room temperature, removing the reaction solvent in vacuum, adding 15mL of n-hexane, filtering, removing inorganic salts generated by the reaction, concentrating, removing insoluble matters from the filtrate, placing the filtrate into a refrigerator of a glove box, and cooling and crystallizing at-30 ℃ to obtain an orange-yellow solid, namely 2-fluorenyl-P, P-dimethylbenzyl phosphine trimethoxy titanium (0.26g and 57.0%).
Example 15: synthesis of 2- (4, 7-dimethylfluorenyl) -P, P-diethylbenzylphosphinotribenzylzirconium (noted as C15)
2- (4, 7-dimethylfluorenyl) -P, P-diethylbenzylphosphine (0.37g, 1.0mmol) was weighed into a 50mL Schlenk flask under an inert atmosphere, 30mL of anhydrous ether was added, and nBuLi (0.40mL,1.0mmol, 2.5 m) was added via syringeol/L) of the mixed solution, reacting for 1h at room temperature, precipitating lithium salt with a large amount of ligand to generate ZrCl in inert atmosphere4·THF2(0.38g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the lithium salt solution of the ligand was slowly added to the ether solution of the metal chloride at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃, benzyl potassium (0.39g, 3.0mmol) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed under vacuum, 15mL of n-hexane was added, filtration was carried out, the inorganic salt formed by the reaction was removed, the insoluble matter was concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled to-30 ℃ for crystallization to obtain a yellow solid, i.e., 2- (4, 7-dimethylfluorenyl) -P, P-diethylbenzylphosphinotribenzylzirconium (0.39g, 53.0%).
Example 16: synthesis of 2-indenyl-P, P-diisopropylbenzylphosphinotridimethylamino zirconium (noted as C16)
Weighing 2-indene-P, P-diisopropyl benzyl phosphine (0.32g, 1.0mmol) in a 50mL Schlenk bottle under inert atmosphere, adding 30mL of anhydrous ether, adding a n-hexane solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) by using a syringe, reacting for 1h at room temperature, precipitating a lithium salt with a large amount of ligand to generate the ZrCl under inert atmosphere4·THF2(0.38g, 1.0mmol) is added into 50mL Schlenk, 20mL of anhydrous ether is added, the lithium salt solution of the ligand is slowly added into the ether solution of the metal chloride at room temperature, the reaction is carried out for 30min at the temperature, the reaction bottle is cooled to-30 ℃, sodium dimethylamide (0.20g, 3.0mmol) is slowly added, the temperature is slowly increased to room temperature, the reaction is carried out for 12h, the reaction solvent is removed in vacuum, 15mL of n-hexane is added, the inorganic salt generated by the reaction is removed by filtration, the insoluble matter is concentrated and filtered, the mixture is placed into a refrigerator of a glove box to be cooled and crystallized at-30 ℃, and yellow solid, namely 2-indene-P, P-diisopropylbenzylphosphine tris (dimethylamino) zirconium (0.39g, 71.8%) is obtained.
Example 17: synthesis of 2- (2-methyl-4-phenylindenyl) -P, P-dimethylbenzylphosphine tris (trimethylsilylmethyl) hafnium (denoted C17)
2- (2-methyl-4-phenylindenyl) -P, P-dimethylbenzylphosphine (0.36g, 1.0mmol) was weighed into a 50mL Schlenk flask under inert atmosphere, 30mL of anhydrous ether was added, and injection was performedAdding n-hexane solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) into the reaction vessel, reacting for 1h at room temperature, precipitating lithium salt with a large amount of ligand to generate an inert atmosphere, and adding HfCl into the reaction vessel4·THF2(0.46g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the lithium salt solution of the above ligand was slowly added to the ether solution of metal chloride at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃ and trimethylsilyllithium (0.28g, 3.0mmol) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed under vacuum, 15mL of n-hexane was added, inorganic salts formed by the reaction were removed by filtration, insoluble matters were concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled to-30 ℃ for crystallization to obtain a white solid, i.e., 2- (2-methyl-4-phenylindenyl) -P, P-dimethylbenzylphosphine tris (trimethylsilyl) hafnium (0.51g, 64.1%).
Example 18: synthesis of 2- (4, 7-di-tert-butylfluorenyl) -P, P-dimethylbenzylphosphine triisopropoxyhium (recorded as C18)
Weighing 2- (4, 7-di-tert-butylfluorenyl) -P, P-dimethylbenzylphosphine (0.43g, 1.0mmol) in a 50mL Schlenk bottle under an inert atmosphere, adding 30mL of anhydrous ether, adding a n-hexane solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) by using a syringe, reacting for 1h at room temperature, precipitating a lithium salt with a large amount of ligand to generate an inert atmosphere, and adding HfCl4·THF2(0.46g, 1.0mmol) is added into 50mL Schlenk, 20mL of anhydrous ether is added, the lithium salt solution of the ligand is slowly added into the ether solution of the metal chloride at room temperature, the reaction is carried out for 30min at the temperature, the reaction bottle is cooled to-30 ℃, sodium isopropoxide (0.25g, 3.0mmol) is slowly added, the temperature is slowly increased to room temperature, the reaction is carried out for 12h, the reaction solvent is removed in vacuum, 15mL of n-hexane is added, the inorganic salt generated by the reaction is removed by filtration, the insoluble matter is concentrated and filtered, the mixture is placed into a refrigerator of a glove box to be cooled and crystallized at-30 ℃, and white solid, namely 2- (4, 7-di-tert-butylfluorenyl) -P, P-dimethylbenzylphosphine triisopropoxyhium (0.38g, 58.2%) is obtained.
Example 19: synthesis of methyl (2-tetramethylcyclopentadienyl benzyl) ether titanium trichloride (noted as C19)
Weighing methyl (2-tetramethyl cyclopentadienyl benzyl) ether (0) under inert atmosphere24g, 1.0mmol) in a 50mL Schlenk flask, 30mL of anhydrous tetrahydrofuran was added, a solution of nBuLi (0.40mL,1.0 mmol) in hexane was added via syringe and the reaction was carried out at room temperature for 1h, the above lithium salt solution was slowly added to an equivalent of 1mol/L TiCl at-78 deg.C4In 20mL of tetrahydrofuran solution (1.0mL, 1.0mol), reacting overnight at room temperature, removing the reaction solvent in vacuum, adding 15mL of dichloromethane, filtering, removing inorganic salts generated in the reaction, adding a proper amount of n-hexane, concentrating, filtering off insoluble substances, and cooling and crystallizing at-30 ℃ in a refrigerator of a glove box to obtain a reddish brown solid, namely methyl (2-tetramethylcyclopentadienyl benzyl) ether titanium trichloride (0.21g, 53.2%).
Example 20: synthesis of ethyl (2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) benzyl) ether trimethyltitanium (noted as C20)
Ethyl (2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) benzyl) ether (0.38g, 1.0mmol) was weighed into a 50mL Schlenk flask under an inert atmosphere, 20mL of anhydrous ether was added, and a hexane solution of nBuLi (0.40mL,1.0 mmol) was added via a syringe and reacted at room temperature for 1 hour to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4Adding DME (0.28g, 1.0mmol) into 50mL Schlenk, adding 20mL of anhydrous ether, cooling the reaction system to-30 ℃ by using a low-temperature bath, slowly adding methyllithium (1.88mL, 3.0mmol,1.6mol/L), reacting for 10min, adding the above ligand lithium salt solution, reacting for 30min at the temperature, then reacting for 12h at room temperature, removing the reaction solvent in vacuum, adding 15mL of n-hexane, filtering, removing inorganic salts generated by the reaction, concentrating, removing insoluble substances from the filtrate, placing the filtrate into a refrigerator of a glove box, and cooling and crystallizing at-30 ℃ to obtain an orange yellow solid, namely ethyl (2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) benzyl) ether trimethyltitanium (0.32g, 67.8%).
Example 21: synthesis of isopropyl (2-fluorenylbenzyl) ether tris (trimethylsilylmethyl) zirconium (noted as C21)
Weighing isopropyl (2-fluorenylbenzyl) ether (0.31g, 1.0mmol) in a 50mLSchlen bottle under an inert atmosphere, adding 30mL of anhydrous ether, adding a n-hexane solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) by using a syringe, and reacting for 1h at room temperature to obtain lithium with a large amount of ligandSalt precipitates. Under inert atmosphere, ZrCl is added4·THF2(0.38g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the lithium salt solution of the above ligand was slowly added to the ether solution of metal chloride at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃, trimethylsilyllithium (0.28g, 3.0mmol) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed under vacuum, 15mL of n-hexane was added, the inorganic salt formed by the reaction was removed by filtration, the insoluble matter was concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled to-30 ℃ for crystallization to obtain a yellow solid, i.e., isopropyl (2-fluorenylbenzyl) ether tris (trimethylsilylmethyl) zirconium (0.49g, 73.6%).
Example 22: synthesis of isopropyl (2-indenylbenzyl) ether trimethylhafnium (denoted C22)
Weighing isopropyl (2-indenyl benzyl) ether (0.26g, 1.0mmol) in a 50mL Schlenk flask under an inert atmosphere, adding 30mL of anhydrous ether, adding a solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) in n-hexane by a syringe, reacting for 1h at room temperature, precipitating a lithium salt with a large amount of ligand to generate HfCl under an inert atmosphere4·THF2(0.46g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the solution of the lithium salt of the ligand was slowly added to the solution of metal chloride in ether at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃, methyllithium (1.88mL, 3.0mmol,1.6mol/L) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed in vacuo, 15mL of n-hexane was added, inorganic salts formed by the reaction were removed by filtration, insoluble materials were concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled at-30 ℃ for crystallization to give a white solid, i.e., trimethyl hafnium isopropyl (2-indenylbenzyl) ether (0.29g, 59.4%).
Example 23: synthesis of methyl (2- (2-methyl-4-phenylindenyl) benzyl) ether trimethoxyhafnium (noted as C23)
Methyl (2- (2-methyl-4-phenylindenyl) benzyl) ether (0.33g, 1.0mmol) was weighed into a 50mL Schlenk flask under an inert atmosphere, 30mL of anhydrous ether was added, a solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) in n-hexane was added by syringe and reacted at room temperature for 1 hour, and a large amount of a lithium salt of a ligand was precipitatedForming HfCl in inert atmosphere4·THF2(0.46g, 1.0mmol) is added into 50mL Schlenk, 20mL of anhydrous ether is added, the lithium salt solution of the ligand is slowly added into the ether solution of the metal chloride at room temperature, the reaction is carried out for 30min at the temperature, the reaction bottle is cooled to-30 ℃, sodium methoxide (0.16g, 3.0mmol) is slowly added, the temperature is slowly raised to room temperature, the reaction is carried out for 12h, the reaction solvent is removed in vacuum, 15mL of n-hexane is added, the inorganic salt generated in the reaction is removed by filtration, the insoluble matter is concentrated and filtered, the mixture is placed into a refrigerator of a glove box to be cooled and crystallized at-30 ℃, and white solid, namely methyl (2- (2-methyl-4-phenylindenyl) benzyl) ether trimethoxyhafnium (0.41g, 68.6 percent) is obtained.
Example 24: synthesis of methyl (2-tetramethylcyclopentadienyl benzyl) sulfide trimethyltitanium (noted as C24)
Under an inert atmosphere, methyl (2-tetramethylcyclopentadienyl benzyl) sulfide (0.26g, 1.0mmol) is weighed into a 50mL Schlenk bottle, 20mL of anhydrous ether is added, a hexane solution of nBuLi (0.40mL,1.0 mmol) is added by a syringe, and the reaction is carried out for 1h at room temperature, so as to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4Adding DME (0.28g, 1.0mmol) into 50mL Schlenk, adding 20mL of anhydrous ether, cooling the reaction system to-30 ℃ by using a low-temperature bath, slowly adding methyllithium (1.88mL, 3.0mmol,1.6mol/L), reacting for 10min, adding the above ligand lithium salt solution, reacting for 30min at the temperature, reacting for 12h at room temperature, removing the reaction solvent in vacuum, adding 15mL of n-hexane, filtering, removing inorganic salts generated by the reaction, concentrating, removing insoluble substances from the filtrate, placing the filtrate into a refrigerator of a glove box, and cooling and crystallizing at-30 ℃ to obtain an orange yellow solid, namely methyl (2-tetramethyl cyclopentadienyl benzyl) sulfide trimethyltitanium (0.25g, 71.4%).
Example 25: synthesis of methyl (2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) benzyl) thioethertrimethoxy titanium (noted as C25)
Methyl (2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) benzyl) sulfide (0.38g, 1.0mmol) is weighed into a 50mL Schlenk bottle under an inert atmosphere, 20mL of anhydrous ether is added, a hexane solution of nBuLi (0.40mL,1.0 mmol) is added through a syringe, and the reaction is carried out at room temperature for 1h to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4Adding DME (0.28g and 1.0mmol) into 50mL of Schlenk, adding 20mL of anhydrous ether, cooling the reaction system to-30 ℃ by using a low-temperature bath, slowly adding sodium methoxide (0.16g and 3.0mmol), reacting for 10min, adding the ligand lithium salt solution, reacting for 30min at the temperature, reacting for 12h at room temperature, removing the reaction solvent in vacuum, adding 15mL of n-hexane, filtering, removing inorganic salts generated by the reaction, concentrating, removing insoluble substances from the filtrate, placing the filtrate into a refrigerator of a glove box, and cooling and crystallizing at-30 ℃ to obtain an orange yellow solid, namely methyl (2- (2, 5-dimethyl-3, 4-diphenylcyclopentadienyl) benzyl) thioether trimethoxytitanium (0.52g and 59.4%).
Example 26: synthesis of tris (dimethylamino) titanium ethyl (2-fluorenylbenzyl) sulfide (C26)
Ethyl (2-fluorenylbenzyl) sulfide (0.32g, 1.0mmol) was weighed into a 50mL Schlenk flask under an inert atmosphere, 20mL of anhydrous ether was added, a hexane solution of nBuLi (0.40mL,1.0 mmol) was added by syringe, and a reaction was carried out at room temperature for 1h to obtain a ligand lithium salt solution.
Under inert atmosphere, TiCl4Adding DME (0.28g and 1.0mmol) into 50mL of Schlenk, adding 20mL of anhydrous ether, cooling the reaction system to-30 ℃ by using a low-temperature bath, slowly adding sodium dimethylamide (0.20g and 3.0mmol), reacting for 10min, adding the above ligand lithium salt solution, reacting for 30min at the temperature, reacting for 12h at room temperature, removing the reaction solvent in vacuum, adding 15mL of n-hexane, filtering, removing inorganic salts generated by the reaction, concentrating, removing insoluble substances from the filtrate, placing the filtrate into a refrigerator of a glove box, and cooling and crystallizing at-30 ℃ to obtain an orange yellow solid, namely ethyl (2-fluorenylbenzyl) thioether tris (dimethylamino) titanium (0.27g and 54.5%).
Example 27: synthesis of methyl (2- (4, 7-dimethylfluorenyl) benzyl) sulfide tris (trimethylsilylmethyl) zirconium (noted as C27)
Isopropyl (2-fluorenylbenzyl) ether (0.33g, 1.0mmol) was weighed into a 50mL Schlenk flask under an inert atmosphere, 30mL of anhydrous ether was added, a solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) in n-hexane was added via syringe, and the reaction was carried out at room temperature for 1 hour to precipitate a large amount of lithium salt with ligand. Inertia deviceUnder the condition of sexual atmosphere ZrCl is added4·THF2(0.38g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the lithium salt solution of the above ligand was slowly added to the ether solution of metal chloride at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃, trimethylsilyllithium (0.28g, 3.0mmol) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed under vacuum, 15mL of n-hexane was added, the inorganic salt formed by the reaction was removed by filtration, the insoluble matter was concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled to-30 ℃ for crystallization to obtain a yellow solid, i.e., methyl (2- (4, 7-dimethylfluorenyl) benzyl) sulfide tris (trimethylsilylmethyl) zirconium (0.47g, 69.1%).
Example 28: synthesis of methyl (2-indenylbenzyl) sulfide trimethylzirconium (noted as C28)
Methyl (2-indenyl benzyl) sulfide (0.25g, 1.0mmol) was weighed into a 50mL Schlenk flask under an inert atmosphere, 30mL of anhydrous ether was added, a solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) in n-hexane was added by syringe and reacted at room temperature for 1h to precipitate a large amount of lithium salt of the ligand. Under inert atmosphere, ZrCl is added4·THF2(0.38g, 1.0mmol) was added to 50mL Schlenk, 20mL of anhydrous ether was added, the solution of the lithium salt of the ligand was slowly added to the solution of metal chloride in ether at room temperature, reaction was carried out at this temperature for 30min, the reaction flask was cooled to-30 ℃, methyllithium (1.88mL, 3.0mmol,1.6mol/L) was slowly added, the temperature was slowly raised to room temperature, reaction was carried out for 12h, the reaction solvent was removed in vacuo, 15mL of n-hexane was added, inorganic salts formed by the reaction were removed by filtration, insoluble materials were concentrated and filtered off, and the mixture was placed in a glove box freezer and cooled to-30 ℃ for crystallization to give a yellow solid, i.e., trimethylzirconium methyl (2-indenylbenzyl) sulfide (0.21g, 54.3%).
Example 29: synthesis of methyl (2- (2-methyl-4-phenylindenyl) benzyl) sulfide trimethoxyhafnium (noted as C29)
Methyl (2- (2-methyl-4-phenylindenyl) benzyl) sulfide (0.34g, 1.0mmol) is weighed into a 50mL Schlenk flask under inert atmosphere, 30mL of anhydrous ether is added, a solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) in n-hexane is added by a syringe and the mixture is reacted for 1h at room temperature, and lithium salt with a large amount of ligand is precipitatedForming HfCl in inert atmosphere4·THF2(0.46g, 1.0mmol) is added into 50mL Schlenk, 20mL of anhydrous ether is added, the lithium salt solution of the ligand is slowly added into the ether solution of the metal chloride at room temperature, the reaction is carried out for 30min at the temperature, the reaction bottle is cooled to-30 ℃, sodium methoxide (0.16g, 3.0mmol) is slowly added, the temperature is slowly raised to room temperature, the reaction is carried out for 12h, the reaction solvent is removed in vacuum, 15mL of n-hexane is added, the inorganic salt generated in the reaction is removed by filtration, the insoluble matter is concentrated and filtered, the mixture is placed into a refrigerator of a glove box to be cooled and crystallized at-30 ℃, and white solid, namely methyl (2- (2-methyl-4-phenylindenyl) benzyl) trimethoxyhafnium sulfide (0.48g, 78.2%) is obtained.
Example 30: synthesis of hafnium tribenzyl ethyl (2- (4, 7-di-tert-butylfluorenyl) benzyl) sulfide (noted as C30)
Weighing ethyl (2- (4, 7-di-tert-butylfluorenyl) benzyl) sulfide (0.43g, 1.0mmol) in a 50mL Schlenk bottle under an inert atmosphere, adding 30mL of anhydrous ether, adding a n-hexane solution of nBuLi (0.40mL,1.0mmol, 2.5mol/L) by using a syringe, reacting for 1h at room temperature, precipitating a lithium salt with a large amount of ligand to generate the HfCl under the inert atmosphere4·THF2(0.46g, 1.0mmol) is added into 50mL Schlenk, 20mL of anhydrous ether is added, the lithium salt solution of the ligand is slowly added into the ether solution of the metal chloride at room temperature, the reaction is carried out for 30min at the temperature, the reaction bottle is cooled to-30 ℃, benzyl potassium (0.39g, 3.0mmol) is slowly added, the temperature is slowly increased to room temperature, the reaction is carried out for 12h, the reaction solvent is removed in vacuum, 15mL of n-hexane is added, the inorganic salt generated by the reaction is removed by filtration, the insoluble matter is concentrated and filtered, the mixture is placed into a refrigerator of a glove box to be cooled and crystallized at-30 ℃, and white solid, namely ethyl (2- (4, 7-di-tert-butylfluorenyl) benzyl) sulfide tribenzyl hafnium (0.54g, 61.4 percent) is obtained.
Example 31
Heating the polymerization kettle equipped with magnetic stirrer to 120 deg.C, evacuating for 1 hr, charging 0.1MPa ethylene gas, adding 60mL toluene solution containing aluminum alkyl, then adding 20mL toluene solution containing 1. mu. mol main catalyst (i.e., the metallocene-type tetravalent transition metal complex with neutral benzyl heteroatom ligand side arm prepared in examples 1-30, respectively C1-C30) and 1.5 equivalents Ph3CB(C6F5)4Adding the toluene solution into a reaction kettle, increasing the pressure of ethylene to 0.5MPa, stirring for reaction for 30 minutes, and adding 1mL of ethanol as a terminator to terminate the oligomerization of ethylene. The reaction solution was then allowed to cool to room temperature, the gaseous product was collected in a gas metering tank, and the liquid product was collected in a conical flask. The gas-liquid product was measured and analyzed by gas chromatography, the data obtained are shown in table 1.
TABLE 1 results of ethylene oligomerization[1]
Figure BDA0002577672470000231
Figure BDA0002577672470000241
[1]The cocatalyst is iBu3Al；[2]The cocatalyst is Me3Al；[3]The cocatalyst is Et3Al；[4]The cocatalyst is Et2AlCl；[5]The cocatalyst is Et3Al2Cl3。
Example 32
Heating a polymerization kettle provided with a magnetic stirrer to 120 ℃, vacuumizing for 1 hour, filling ethylene gas with 0.1MPa, adding 60mL of toluene solution containing alkylaluminoxane, then adding 20mL of toluene solution containing 1 mu mol of main catalyst (namely, respectively, the metallocene tetravalent transition metal complex containing the side arm of the neutral benzyl heteroatom ligand prepared in the examples 1-30) into the reaction kettle, raising the ethylene pressure to 0.5MPa, stirring for reacting for 30 minutes, and adding 1mL of ethanol as a terminator to terminate the ethylene oligomerization reaction. Then, the temperature of the reaction solution was decreased to room temperature, the gas product was collected in a gas metering tank, the liquid product was collected in a conical flask, and the gas-liquid product was measured and then subjected to gas chromatography analysis, the data obtained being shown in table 2.
TABLE 2 ethylene oligomerization results 1[1]
Figure BDA0002577672470000251
Figure BDA0002577672470000261
In Table 2, [1] the cocatalyst was methylaluminoxane; [2] the cocatalyst is modified methylaluminoxane.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.

Claims (5)

1. A kind of ligand side arm metallocene tetravalent transition metal complex containing neutral benzyl heteroatom, its structure is shown as formula 1 or formula 2:
Figure DEST_PATH_IMAGE002
wherein, the central metal M is Ti, Zr or Hf; cp#Is cyclopentadienyl, tetramethylcyclopentadienyl, dimethyldiphenylcyclopentadienyl, 3, 4-diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, 2-methylbenzindenyl, fluorenyl, 4, 7-dimethylfluorenyl or 4, 7-di-tert-butylfluorenyl; a is NR1R2、PR3R4、OR5Or SR6Wherein R is1And R2Identical or different, are each methyl, ethyl, isopropyl, tert-butyl or phenyl, or R1And R2Linked to 1, 4-butylene, 1, 5-pentylene or 1, 4-butadienylene, R3And R4Identical or different, are each methyl, ethyl, isopropyl, tert-butyl or phenyl, R5Is methyl, ethyl, n-propyl, isopropyl or tert-butyl, R6Is methyl, ethylAlkyl, n-propyl, isopropyl or tert-butyl; x1、X2And X3The same are methyl, benzyl, trimethylsilylmethyl, dimethylamino, methoxy, isopropoxy, chloro or bromo respectively.
2. The use of the single metallocene tetravalent transition metal complex with neutral benzyl heteroatom ligand side arm as claimed in claim 1, wherein the single metallocene tetravalent transition metal complex with neutral benzyl heteroatom ligand side arm is used as a main catalyst, and alkyl aluminoxane and modified alkyl aluminoxane are used as cocatalyst for catalyzing ethylene oligomerization reaction; can catalyze ethylene oligomerization with high activity to selectively generate 1-hexene or C10And C10The above alpha-olefin; wherein the molar ratio of aluminum in the cocatalyst to metal in the main catalyst is 5-10000:1, and the polymerization reaction temperature is-20 to 150 ℃.
3. The use of the ligand-side arm metallocene tetravalent transition metal complex containing a neutral benzyl heteroatom according to claim 2, wherein the specific process of catalyzing ethylene oligomerization reaction is as follows: adding a main catalyst and a cocatalyst into a polymerization kettle in the presence of ethylene, stirring and reacting for 0-600 minutes at the temperature of-20-200 ℃, adding a proper amount of ethanol to terminate the ethylene oligomerization reaction, cooling the temperature of a reaction system to room temperature, collecting gas products into a gas metering tank, collecting liquid products into a conical flask, and carrying out component analysis by gas chromatography after metering the gas-liquid products.
4. The use of a ligand-side arm metallocene tetravalent transition metal complex with a neutral benzyl heteroatom as claimed in claim 3 wherein said alkylaluminoxane is methylaluminoxane or modified methylaluminoxane; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride or ethyl aluminum sesquichloride.
5. Use of a neutral benzyl heteroatom ligand-containing pendant metallocene tetravalent transition metal complex according to claim 4, wherein: the molar ratio of aluminum in the cocatalyst to metal in the main catalyst is 60-5000:1, and the polymerization reaction temperature is-20 to 120 ℃.
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