JP2006342106A - Transition metal compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing an alkyl complex of an imine bond-containing transition metal compound. <P>SOLUTION: This producing method comprises reacting a transition metal compound represented by formula (I): R<SB>n</SB>MX<SB>4-n</SB>(wherein M is a group 4 transition metal; n is an integer of 1 to 4; X is a hydrogen atom, a hydrocarbon group, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or the like; and R is a hydrocarbon group) with a ligand precursor selected from compounds containing an imino group such as a salicylaldimine and -O-E or >N-E (wherein E is H, Li, Na, K, Ca, Mg or the like). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel transition metal compound that can be used for olefin polymerization and a synthesis method thereof.

  It is disclosed that a group 4 transition metal compound having two phenoxy group and imine chelate type compounds as ligands has excellent performance as an olefin polymerization catalyst (Patent Document 1). Moreover, it has been shown that a transition metal compound having a pyrrolide group or an indolide group instead of a phenoxy group is a good catalyst for olefin polymerization (Patent Document 2). In these group of imine bond-containing transition metal compounds, the dihalide as a catalyst precursor is typically alkylated and activated with an organoaluminum compound cocatalyst such as methylalumoxane (MAO), and then subjected to olefin polymerization. The method to offer is taken. On the other hand, a method of activating other transition metal complexes such as metallocene without using an organoaluminum compound is known. In this case, an alkyl transition metal compound having at least one alkyl group is used as a catalyst precursor, and a catalytically active species is generated by a Lewis acid, a proton acid, an oxidizing agent, or the like.

  Almost no alkyl complexes of the above transition metal compounds have been known so far. The reason is that alkylating agents (alkyllithium, alkylmagnesium, alkylaluminum, alkylzinc, etc.) used for alkylation of metallocene halides or amide compounds, etc., can react with ligands containing imine bonds. This is because the side reaction of reducing the imine cannot be prevented, and in particular, when the central metal is titanium, the desired compound cannot be obtained by reduction to low-valent titanium. There is also known a method of synthesizing a dialkyl complex while removing an alkane by a reaction between a group 4 tetraalkyl complex and a ligand having an acidic proton. Typically, a relatively stable and bulky transition metal compound such as a tetrabenzyl complex is used for this reaction, but the reaction yield is low, the tetraalkyl complex must be synthesized separately, and the benzyl group is removed as a radical. And had drawbacks such as being able to react with imines within the molecule.

By not using an organoaluminum compound, effects such as improvement of the thermal stability of the cocatalyst and suppression of side reactions derived from organoaluminum can be considered. Therefore, a simple method for synthesizing an alkyl complex of an imine bond-containing transition metal compound is available. It was anxious.
Japanese Patent Laid-Open No. 11-315109 Japanese Patent Laid-Open No. 2001-72706

  Under the background described above, the present inventors have intensively studied to synthesize alkyl complexes of imine bond-containing transition metal compounds, and as a result, it is possible to synthesize such compounds in a specific method. The headline and the present invention have been completed.

The present invention
A transition metal compound (A) represented by the following general formula (I):
R _n MX _4-n ... (I)
[Wherein M represents a group 4 transition metal. n is an integer of 1 to 4, and X is a hydrogen atom, hydrocarbon group, halogen atom, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group , A heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and R is a hydrocarbon group. ]
By reacting one binding residue (y) selected from the following Group Y with a ligand precursor (B) including both a binding residue (z) selected from the following Group Z:
The present invention relates to a process for producing a transition metal compound (C) containing both R, the binding residue (y) and the binding residue (z).

[In the general formulas (II) and (II ′) showing the binding residues shown in Group Y above, R ^{25 to} R ²⁸ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, A bond residue shown in Group Z, indicating a heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group In the general formulas (III) and (III ′) showing, E is hydrogen, Li, Na, K, Rb, Cs, Mg, or Ca, or Mg-containing group, Ca-containing group, Si-containing group, or Sn-containing It is a group. ]

  In the method according to the present invention, the transition metal compound (A) can be used in the reaction step with the next ligand precursor (B) without isolation and purification, and in addition to the commonly used benzyl group. It is possible to produce the transition metal compound (C) into which various alkyl groups are introduced with good yield.

Hereinafter, the best mode for carrying out the present invention will be described.
Transition metal compound (A)
The transition metal compound (A) used in the present invention is represented by the following general formula (I).

R _n MX _4-n ... (I)
[Wherein M represents a group 4 transition metal. n is an integer of 1 to 4, and X is a hydrogen atom, hydrocarbon group, halogen atom, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group , A heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and R is a hydrocarbon group. ]

The hydrocarbon group as X in the general formula (I) is specifically, as a hydrocarbon group, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n A linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as hexyl; 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as vinyl, allyl, isopropenyl, etc. A linear or branched alkenyl group; a linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and the like A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms; cyclopentadienyl, indenyl, fluorenyl, etc. A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; And alkyl-substituted aryl groups such as -propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl. One or more hydrogen atoms of the hydrocarbon group may be substituted with halogen, for example, halogen having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl group, pentafluorophenyl group, chlorophenyl group, etc. A hydrocarbyl group. Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as a benzyl group and a cumyl group, etc. are mentioned. Furthermore, the hydrocarbon group may be substituted with other group 13 and 14 elements such as boron, aluminum, silicon, germanium, and tin, and examples thereof include a trimethylsilylmethyl group and a bis (trimethylsilyl) methyl group.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Examples of the oxygen-containing group include an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic acid anhydride group.

  Sulfur-containing groups include mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group, isothiocyanate group, sulfone ester group, sulfonamido group, thiocarboxyl group, Examples include a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group, and the like.

  Nitrogen-containing groups include amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups. The thing which became ammonium salt can be illustrated.

  Examples of the boron-containing group include a boranediyl group, a boranetriyl group, and a diboranyl group.

  Examples of the phosphorus-containing group include a phosphide group, a phosphoryl group, a thiophosphoryl group, and a phosphato group.

  Specific examples of the aluminum-containing group include AlR4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

  Examples of silicon-containing groups include monohydrocarbon-substituted silyl groups such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl groups such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, Trihydrocarbon-substituted silyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, tolylsilylsilyl, trinaphthylsilyl; hydrocarbon-substituted silyl silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; trimethylsilylphenyl and the like Examples include silicon-substituted aryl groups.

  Examples of the germanium-containing group and tin-containing group include those obtained by substituting silicon of the silicon-containing group with germanium and tin.

  As the hydrocarbon group as R in the general formula (I), the above-described hydrocarbon group as X can be used without limitation. One or more hydrogen atoms of the hydrocarbon group as R may be substituted with halogen, for example, 1 to 30 carbon atoms such as trifluoromethyl group, pentafluorophenyl group, chlorophenyl group, preferably 1 to There are 20 halogenated hydrocarbon groups. Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as a benzyl group and a cumyl group, etc. are mentioned. Furthermore, the hydrocarbon group may be substituted with other group 13 and 14 elements such as boron, aluminum, silicon, germanium, and tin, and examples thereof include a trimethylsilylmethyl group and a bis (trimethylsilyl) methyl group.

The transition metal compound (A) is an ether solvent or a hydrocarbon solvent, and MX ₄ [wherein, M and X have the same meaning as the transition metal compound (A) represented by the general formula (I). . And an alkylating agent can be synthesized. Specific examples are shown below, but the reaction is not limited thereto. As the reaction solvent, diethyl ether, dibutyl ether, THF, toluene, pentane, benzene and the like are preferable, and diethyl ether and THF are particularly preferable. MX ₄ [wherein, M and X are synonymous with the transition metal compound (A) represented by the general formula (I). ], Halides such as MF ₄ , MCl ₄ , MBr ₄ , MI ₄ , or adducts thereof with donor compounds, amides, M (NR ₂ ) ₄ , and alkoxides, M (OR) ₄ ( R = alkyl group, aryl group) and the like can be used, and halides and adducts thereof are preferably used. As the donor compound, THF, diethyl ether, 1,2-dimethoxyethane, 1,1,2,2-tetramethylethylenediamine and the like are used, and THF and 1,2-dimethoxyethane are preferable. As the alkylating agent, an alkyl lithium reagent, a Grignard reagent, an alkyl aluminum, an alkyl zinc, an alkyl tin compound, or the like can be used. Alkyllithium reagents and Grignard reagents are preferred, and the use of alkyllithium reagents is particularly preferred. The reaction product may be isolated and purified, or may be used in the next reaction as it is or after substitution with an appropriate solvent.

Ligand precursor (B)
The ligand precursor (B) used in the present invention includes both one binding residue (y) selected from the following Group Y and one binding residue (z) selected from the following Group Z.

[In the general formulas (II) and (II ′) showing the binding residues shown in Group Y above, R ^{25 to} R ²⁸ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, A bond residue shown in Group Z, indicating a heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group In the general formulas (III) and (III ′) showing, E is hydrogen, Li, Na, K, Rb, Cs, Mg, or Ca, or Mg-containing group, Ca-containing group, Si-containing group, or Sn-containing It is a group. ]

The hydrocarbon group as R ^{25 to} R ²⁸ in the general formula (II) or (II ′) may have a hydrogen atom substituted with a halogen, such as a trifluoromethyl group, a pentafluorophenyl group, a chlorophenyl group, etc. And a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

  Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as a benzyl group and a cumyl group, etc. are mentioned.

  Furthermore, the hydrocarbon group is a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic anhydride group, etc. Oxygen-containing group: amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group is ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group , Isothiocyanate ester group, sulfone ester group, Sulfur-containing groups such as sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, silicon-containing groups , A germanium-containing group, or a tin-containing group.

  Of these, the number of carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. 1-30, preferably 1-20 linear or branched alkyl groups; 6-30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc., preferably 6 An aryl group having ˜20; a halogen atom, an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group or aryloxy having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms A substituted aryl group substituted with 1 to 5 substituents such as a group is preferred.

  Examples of the oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group and phosphorus-containing group are the same as those exemplified above.

  Heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic groups thereof. Examples thereof include a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in the compound residue.

  Silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, hydrocarbon-substituted siloxy groups, and more specifically, methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups , Diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, triphenylsilyl group and the like are preferable. In particular, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and a dimethylphenylsilyl group are preferable. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

  Examples of the germanium-containing group and tin-containing group include those obtained by substituting silicon of the silicon-containing group with germanium and tin.

Next, the examples of R ^{25 to} R ²⁸ described above will be described more specifically.
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. Specific examples of the alkylthio group include a methylthio group and an ethylthio group. Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group. Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group. Specific examples of the acyl group include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, and p-methoxybenzoyl group. Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group. Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group. Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group. Specific examples of the imide group include an acetimide group and a benzimide group. Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group. Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group. Specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group. Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

R ²⁵ , R ²⁶ and R ²⁷ , R ²⁸ may be linked to each other to form an alicyclic ring, an aromatic ring, or a hydrocarbon ring containing a different atom such as a nitrogen atom, and these rings are further substituted. You may have.

  In the general formula (III) or (III ′), E is hydrogen, Li, Na, K, Rb, Cs, Mg or Ca, or an Mg-containing group, a Ca-containing group, a Si-containing group or a Sn-containing group. is there. When E is hydrogen, it is an alcohol or an amine, and the corresponding lithium salt or sodium salt can be obtained by reacting with an appropriate reagent such as alkyl lithium or sodium hydride.

  As the ligand precursor (B) including both the binding residues y and z represented by the general formula (II), (II ′), (III) or (III ′), the following formulas (IV) to (VII) ) Can be mentioned.

[In the above formulas (IV), (V), (VI) and (VII), R ^{1 to} R ²⁴ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group or a heterocyclic compound. Residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, E is hydrogen, Li, Na, K, Rb, Cs, Mg or Ca, or an Mg-containing group, Ca-containing group, Si-containing group or Sn-containing group. ]

In the general formulas (IV), (V), (VI) and (VII), R ^{1 to} R ²⁴ and E represent R ²⁵ to R in the general formula (II), (II ′), (III) or (III). it can be mentioned the same ones as exemplified for R ²⁸ and E. R ^{1 to} R ²⁴ are two or more of these groups, preferably adjacent groups connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. These rings may further have a substituent.

Transition metal compound (C)
The transition metal compound (C) according to the present invention can be efficiently obtained by reacting the transition metal compound (A) described above with the ligand precursor (B).

Reactions include aromatic solvents such as xylene, toluene and benzene, aliphatic hydrocarbon solvents such as hexane and pentane, ether solvents such as diethyl ether, THF and dibutyl ether, and halogenated carbonization such as methylene chloride, chloroform and chlorobenzene. It can be carried out in a hydrogen solvent and mixtures thereof. Since alkyl complexes are usually sensitive to water and oxygen, it is desirable to carry out the reaction in an inert atmosphere such as dry nitrogen, argon or helium. The charge molar ratio of (A) / (B) can be used between 0.01 and 10, but is preferably between 0.1 and 3, and more preferably between 0.3 and 1.5. As the ligand precursor (B), a mixture of two or more kinds may be used, or two or more kinds of ligand precursors (B) may be sequentially added and used. As a result, a transition metal compound in which different ligands are bonded to the same metal can be obtained. The reaction temperature is determined depending on the balance between the thermal stability of the reactive organism and the reaction rate determined by the combination of the substrates, and therefore varies greatly depending on the compound, but it is generally preferable to carry out the reaction between -78 ° C and 200 ° C. The reaction time is the same and cannot be generally stated, but it is usually carried out for 0.1 to 100 hours. In many cases, the reaction can be confirmed by the formation of a leaving inorganic salt or organic compound. Isolation of the reaction product is preferably carried out by separating the inorganic salt when it is produced and recrystallizing it after concentrating the filtrate or substituting it with a suitable solvent, or adding a poor solvent to precipitate as a solid. . The produced transition metal compound can be identified by various methods such as ¹ H or ¹³ C-NMR, structural analysis by X-ray diffraction, mass spectrometry spectrum, and elemental analysis. In this method, the transition metal compound (A) can be isolated and purified and used for the reaction with the next ligand precursor (B), but the transition metal compound (A) is particularly unstable. In some cases, the reaction solution obtained by synthesizing the transition metal compound (A) can be used in the reaction with the next ligand precursor (B) as it is or after replacing with a suitable reaction solvent.

As such a transition metal compound (C), transition metal alkyl complexes represented by the following general formulas (VIII) to (XI) are preferably exemplified. (In the formula, M, R ^{1 to} R ²⁴ , X and R are the same as defined above.)

  Hereinafter, although the invention content of this application is demonstrated in detail by an Example, this application is not restrict | limited by these Examples.

All the synthesis experiments of the transition metal compound MeTiBr ₃ (A) were performed under a dry nitrogen or argon atmosphere. Tetrabromotitanium (TiBr ₄ , 6.959 g, 18.94 mmol) was weighed into a 30 mL Schlenk tube, and 19 mL of dry pentane was added. The resulting slurry was cooled to −78 ° C., and 9 mL (9.0 mmol) of dimethylzinc in hexane (1.0 M) and 1 mL of pentane were added by syringe. The resulting slurry was returned to room temperature over 3 hours, and the resulting slurry was filtered through celite and washed with pentane. The filtrate was concentrated to about 2/3 while cooling to −78 ° C., filtered at −78 ° C., and the orange filtrate was allowed to stand at −78 ° C. overnight. The resulting dark purple solid was separated from the mother liquor by decantation and dried at low temperature (1.83 g). A second crystal was obtained by concentrating the mother liquor (2.00 g). Yield 70%, ¹ H NMR (benzene-d6) δ 1.96 (s).

Synthesis of Ligand Precursor (B) Salicylaldimine Compound (A) {C ₆ F ₅ N═CH (2-OH-3tBuC ₆ H ₃ ), 2.99 g, 8.71 mmol} in ether solution at −78 ° C. It was added dropwise to an ether slurry (10 mL) of cooled sodium hydride (211.5 mg, 8.81 mmol). The temperature was raised to room temperature overnight, and the mixture was further stirred at room temperature for 3 hours. The yellow solution obtained by filtering the product was concentrated, and the yellow solid produced by adding toluene and pentane was filtered off. After washing with toluene and pentane, it was dried on a high vacuum line to obtain 2.65 g of a yellow solid C ₆ F ₅ N═CH (2-ONa-3tBuC ₆ H ₃ ) (yield 83%).

Synthesis of transition metal compound (C) MeTiBr ₃ (311 mg, 1.03 mmol) and ligand precursor obtained above, C ₆ F ₅ N═CH (2-ONa-3tBuC ₆ H ₃ ) (760 mg, 2.08 mmol) ) In toluene at −78 ° C. for 2.5 hours. The refrigerant was removed, the produced solid was filtered off, and the filtrate was concentrated to about half. When pentane was added and cooled to −78 ° C., 494 mg of reddish purple crystals were obtained (yield 58%). As a result of analysis, it was found that a transition metal compound, [C ₆ F ₅ N═CH (2-O-3-tBuC ₆ H ₃ )] ₂ TiMeBr was obtained. ¹ H NMR (toluene-d8) .δ7.55 (s, 1H, HC = N), 7.47 (s, 1H, HC = N), 7.44 (dd, J = 3.6, 1.7 Hz, 1H, ArH), 7.41 (dd, J = 3.6, 1.7 Hz, 1H, ArH), 6.91 (dd, J = 7.9, 1.7 Hz, 1H, ArH), 6.81 (dd, J = 7.9, 1.7 Hz, 1H, ArH), 6.69 (dt , J = 7.6 Hz, 2H, ArH), 1.97 (d, J = 2.0 Hz, 3H, CH ₃ -Ti), 1.57 (s, 9H, tBu), 1.51 (s, 9H, tBu).

An experiment was conducted in the same manner as in Example 1 except that the salicylaldimine compound (a) was used instead of the salicylaldimine compound (a), and [C ₆ H ₅ N = CH (2-O-3-tBuC ₆ H ₃ )] ₂ TiMeBr was obtained (yield 53%). ¹ H NMR (benzene-d6) .δ7.62 (s, 1H, HC = N), 7.51 (s, 1H, HC = N), 7.42 (m, 2H, ArH), 6.84-6.65 (m, 14H, ArH), 2.00 (s, 3H, CH ₃ -Ti), 1.73 (s, 9H, tBu), 1.59 (s, 9H, tBu).

An experiment was conducted in the same manner except that the salicylaldimine compound (c) was used instead of the salicylaldimine compound (a) in Example 1, and [2,4,6-F ₃ -C ₆ H ₂ N═CH ( 2-O-3-tBuC ₆ H ₃ )] ₂ TiMeBr was obtained (yield 53%). ¹ H NMR (benzene-d6) .δ7.63 (s, 1H, HC = N), 7.59 (s, 1H, HC = N), 7.44 (dd, J = 7.6, 1.7 Hz, 2H, ArH), 6.82 -6.66 (m, 4H, ArH), 6.19 (m, 2H, ArH), 5.87 (m, 2H, ArH), 2.01 (d, J = 1.7 Hz, 3H, CH ₃ -Ti), 1.61 (s, 9H , tBu), 1.56 (s, 9H, tBu).

4mL of ether was added to 95.2 mg (0.340 mmol) of a 1: 1 adduct of tetrachlorotitanium and 1,2-dimethoxyethane to obtain a light yellow slurry. To this was added 0.30 mL (0.334 mmol) of a MeLi ether solution (1.14 M) at 0 ° C., kept at this temperature for 30 minutes, and then cooled to −78 ° C. Here, 239.1 mg (0.655 mmol) of toluene slurry was added to C ₆ F ₅ N═CH (2-ONa-3tBuC ₆ H ₃ ) synthesized in the same manner as in Example 1, and allowed to react overnight. The reaction mixture was evaporated to dryness and extracted with toluene. The extracted solution was concentrated, pentane was added, and the mixture was cooled to −78 ° C. to obtain a brown solid. The solid filtered off was washed with pentane to obtain the product [C ₆ F ₅ N═CH (2-O-3tBuC ₆ H ₃ )] ₂ TiMeCl. ¹ H NMR (benzene-d6) .δ7.59 (s, 1H, HC = N), 7.44 (s, 1H, HC = N), 7.42-7.36 (m, 2H, ArH), 6.89 (dd, J = 7.6, 1.7 Hz, 1H, ArH), 6.79 (dd, J = 7.9, 1.7 Hz, 1H, ArH), 6.66 (dt, J = 7.6, 2.3 Hz, 2H, ArH),), 2.04 (s,, 3H , CH ₃ -Ti), 1.50 (s, 9H, tBu), 1.45 (s, 9H, tBu).

The reaction was performed in substantially the same manner as in Example 4, except that 2 equivalents of MeLi to Ti were added. The product was purified by recrystallization from pentane. ¹ H NMR (benzene-d ₆ ) δ7.52 (s, 2H, HC = N), 7.45 (dd, J = 7.6, 1.7 Hz, 2H, ArH), 6.88 (dd, J = 7.6, 1.7 Hz, 2H , ArH), 6.72 (t, J = 7.7 Hz, 2H, ArH), 1.65 (s, 6H, CH3-Ti), 1.58 (s, 18H, tBu) and X-ray structural analysis, this product is It was found that [C ₆ F ₅ N═CH (2-O-3tBuC ₆ H ₃ )] ₂ TiMe ₂ .

  According to the present invention, the transition metal compound (A) can be used in the reaction step with the next ligand precursor (B) without isolation and purification, and various other than the commonly used benzyl group. It is possible to synthesize a transition metal compound (C) into which an alkyl group is introduced with good yield. The obtained transition metal compound (C) can use a wide range of cocatalysts as well as general cocatalysts for activating other transition metal alkyl complexes such as metallocenes, which causes deactivation. Since the use of organoaluminums can be minimized, effects such as improvement in thermal stability and activation efficiency of the catalyst can be expected.

Claims (3)

A transition metal compound (A) represented by the following general formula (I):
R _n MX _4-n ... (I)
[Wherein M represents a group 4 transition metal. n is an integer of 1 to 4, and X is a hydrogen atom, hydrocarbon group, halogen atom, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group , A heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and R is a hydrocarbon group. ]
A ligand precursor (B) comprising both a binding residue (y) selected from the following Group Y and a binding residue (z) selected from the following Group Z;
A process for producing a transition metal compound (C) comprising both R, the binding residue (y), and the binding residue (z), characterized by reacting

[In the general formulas (II) and (II ′) showing the binding residues shown in Group Y above, R ^{25 to} R ²⁸ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, A bonded residue shown in Group Z, indicating a heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group In the general formulas (III) and (III ′) showing, E is hydrogen, Li, Na, K, Rb, Cs, Mg, or Ca, or Mg-containing group, Ca-containing group, Si-containing group, or Sn-containing It is a group. ] The transition metal compound according to claim 1, wherein the ligand precursor (B) is selected from compounds represented by the following general formulas (IV), (V), (VI) and (VII): The manufacturing method of (C).

[In the above formulas (IV), (V), (VI) and (VII), R ^{1 to} R ²⁴ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group or a heterocyclic compound. A residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and E is hydrogen, Li, Na, K, Rb, Cs, Mg, or Ca, or an Mg-containing group, Ca-containing group, Si-containing group, or Sn-containing group. ] A transition metal compound (C) represented by the following general formulas (VIII), (IX), (X) and (XI) obtained by the method of claim 1 or claim 2.

[Wherein M represents a group 4 transition metal. R ^{1 to} R ²⁴ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring. Two groups out of the groups represented by R ^{1 to} R ²⁴ may be linked (however, R ¹ are not bonded to each other), and the ligands bonded to the same metal are the same. Or they may be different from each other. X is a hydrogen atom, hydrocarbon group, halogen atom, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, and R is a hydrocarbon group. ]