JP2002265484A - Trinuclear complex and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily producing a trinuclear complex. SOLUTION: This method for producing a trinuclear complex comprises reacting a binuclear complex of the general formula I or I' (R<1> to R<4> and A are each a hydrocarbon group or the like; M<1> and M<2> are each a metal of the groups (3-5) or lanthanide series; and L<1> to L<4> are each an anionic ligand) with a borane derivative of the general formula B(R<5> )3 (R<5> is H, a hydrocarbon group, an alkoxy group or the like) and water, and the trinuclear complex is provided thereby.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a trinuclear complex and a method for producing the same, and more particularly, to a cationic metallocene trinuclear complex and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Cationic complexes of metallocenes can be used as catalysts, especially as polymerization catalysts for olefins, and their value is high.

In particular, a trinuclear complex has three reaction points near the polymerization reaction, and is expected to have high activity as a catalyst. An object of the present invention is to provide a trinuclear complex simply.

[0004]

In SUMMARY OF to the present invention, the binuclear olefin complex represented by the following formula (I) or formula (I ')

Embedded image ^{(Wherein, R 1, R 2, R} 3 and R ⁴ are each, independently of one another, identical or different, represent a hydrogen atom or a C ₁ -C ₁₀ hydrocarbon group, A is substituted which may be C ₁
-C ₄₀ hydrocarbon group, a halogen atom, substituted; silicon may have a substituent group; which may have a substituent germanium atom; which may have a substituent oxygen atom A phosphorus atom which may be substituted; a tin atom which may have a substituent; a nitrogen atom which may have a substituent, or a sulfur atom which may have a substituent, and M ¹ and M ² is
L ¹ , L ² , L ² independently of one another and being the same or different and representing metals of groups 3 to 5 of the periodic table or of the lanthanide series;
³ and L ⁴ are independent of each other and are the same or different and represent an anionic ligand. However, L ¹ and L ^2, or, L ³
And L ⁴ may be cross-linked. ), The following formula (I
A borane derivative represented by I) and B (R ⁵ ) ₃ (II) (wherein R ⁵ is a hydrogen atom; a C ₁ -C ₂₀ hydrocarbon group which may have a substituent; C ₁ ~
C ₂₀ alkoxy group; C ₆ -C optionally having substituent (s)
_{20 an} aryloxy group; an amino group which may have a substituent; a silyl group which may have a substituent, or a hydroxyl group. ), A trinuclear complex produced by reacting with water.

According to the present invention, there is provided a method for producing a trinuclear complex, wherein the dinuclear olefin complex represented by the following formula (I) or (I ′) is

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently of one another and are the same or different and are a hydrogen atom or a C ₁ -C ₁₀ hydrocarbon group, and A has a substituent C ₁ that may be
-C ₄₀ hydrocarbon group, a halogen atom, substituted; silicon may have a substituent group; which may have a substituent germanium atom; which may have a substituent oxygen atom A phosphorus atom which may be substituted; a tin atom which may have a substituent; a nitrogen atom which may have a substituent, or a sulfur atom which may have a substituent, and M ¹ and M ² is
L ¹ , L ² , L ² independently of one another and being the same or different and representing metals of groups 3 to 5 of the periodic table or of the lanthanide series;
³ and L ⁴ are independent of each other and are the same or different and represent an anionic ligand. However, L ¹ and L ² or L ³
And L ⁴ may be cross-linked. ), The following formula (I
A borane derivative represented by I) and B (R ⁵ ) ₃ (II) (wherein R ⁵ is a hydrogen atom; a C ₁ -C ₂₀ hydrocarbon group which may have a substituent; C ₁ ~
C ₂₀ alkoxy group; C ₆ -C optionally having substituent (s)
_{20 an} aryloxy group; an amino group which may have a substituent; a silyl group which may have a substituent, or a hydroxyl group. ), A method for producing a trinuclear complex, characterized by reacting with water.

In the present invention, R ¹ , R ² , R ³ and R ⁴ are preferably hydrogen atoms.

In the present invention, M ¹ and M ² are each independently of each other, the same or different, and are metals of Group 4 or 5 of the periodic table or lanthanide series, and the anionic ligand is It is preferably a delocalized cyclic η ⁵ -coordination ligand. Further, it is more preferable that the delocalized cyclic η ⁵ -coordination system ligand is an optionally substituted cyclopentadienyl group, indenyl group, fluorenyl group or azulenyl group.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, one embodiment of the present invention will be described in more detail.

In the present invention, the dinuclear olefin complex represented by the following formula (I) or (I ′)

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , A, M ¹ , M ² , L ¹ ,
L ^2, L ³ and L ⁴ are each as defined above. ), A borane derivative represented by the following formula (II), and B (R ⁵ ) ₃ (II) (wherein R ⁵ has the above meaning.) Trinuclear formed by reacting with water A complex is provided.

[0010] In this specification, the hydrocarbon group may be a non-cyclic saturated or unsaturated, may be cyclic, saturated or unsaturated. When the hydrocarbon group is acyclic, it may be linear or branched. Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, allyl groups, alkyldienyl groups, polyenyl groups, aryl groups,
Examples include an alkylaryl group, an arylalkyl group, a cycloalkyl group, a cycloalkenyl group, a (cycloalkyl) alkyl group, and the like.

The C ₁ -C ₁₀ hydrocarbon groups include C ₁ -C ₁₀
Alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₃ -C ₁₀ allyl group, C ₄ -C ₁₀ alkadienyl group, C ₄ -C ₁₀ polyenyl group, C ₆ -C ₁₀ Aryl group,
C ₆ -C ₁₀ alkylaryl group, C ₆ -C ₁₀ arylalkyl group, C ₄ -C ₁₀ cycloalkyl group, C ₄ -C ₁₀ cycloalkenyl group, (C ₃ ~C ₆ cycloalkyl) C ₁ -C ₄ Alkyl groups can be mentioned.

A C ₁ -C ₁₀ alkyl group, a C ₂ -C ₁₀ alkenyl group, a C ₂ -C ₁₀ alkynyl group, a C ₃ -C ₁₀ allyl group,
₄ -C ₁₀ alkadienyl group, and, C ₄ -C ₁₀ polyenyl group, respectively, C ₁ -C ₅ alkyl group, C ₂ -C ₅ alkenyl group, C ₂ -C ₅ alkynyl group, C ₃ -C ₅ allyl group,
C ₄ -C ₅ alkadienyl group, and is preferably a C ₄ -C ₅ polyenyl group.

Examples of alkyl groups useful in the practice of the present invention include, but are not limited to, methyl, ethyl, propyl, n-butyl, t-butyl, and the like.

Examples of aryl groups useful in the practice of the present invention include, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, naphthyl, and the like.

In the present invention, R ¹ , R ² , R ³ and R ⁴ are preferably a hydrogen atom.

A represents C ₁ -C which may have a substituent.
₄₀ hydrocarbon group; halogen atom; silicon which may have a substituent; germanium atom which may have a substituent; oxygen atom which may have a substituent; A good phosphorus atom; a tin atom which may have a substituent;
A nitrogen atom which may have a substituent, or a sulfur atom which may have a substituent.

The C ₁ -C ₄₀ hydrocarbon group includes a C ₁ -C ₄₀ alkyl group, a C ₂ -C ₄₀ alkenyl group, a C ₂ -C ₄₀ alkynyl group,
C ₃ -C ₄₀ allyl group, C ₄ -C ₄₀ alkadienyl group, C ₄ -
C ₄₀ polyenyl group, C ₆ -C ₄₀ aryl group, C ₆ -C ₄₀ alkylaryl group, C ₆ -C ₄₀ arylalkyl group, C ₄ -C
_{A 40} cycloalkyl group, a C ₄ -C ₄₀ cycloalkenyl group,
(C ₃ -C ₂₀ cycloalkyl), and the like C ₁ -C ₂₀ alkyl group.

C₁-C₄₀Alkyl group, C_Two-C₄₀Alkenyl
Group, C_Two-C₄₀Alkynyl group, C_Three-C ₄₀Allyl group, C_Four-C
₄₀An alkyldienyl group and C_Four-C₄₀Polyenyl group
Is C₁-C₂₀Alkyl group, C_Two-C₂₀Alkene
Group, C_Two-C₂₀Alkynyl group, C_Three-C₂₀Allyl group, C_Four-
C₂₀An alkyldienyl group and C_Four-C₂₀Polyenyl group
And each is preferably C₁-C_TenAlkyl
Group, C_Two-C_TenAlkenyl group, C_Two-C_TenAlkynyl group, C
_Three-C_TenAllyl group, C_Four-C_TenAn alkyldienyl group, and
C_Four-C_TenMore preferably, it is a polyenyl group.

C₆-C₄₀Aryl group, C₆-C₄₀Alkyria
Reel base, C₆-C₄₀Arylalkyl group, C_Four-C₄₀Shiku
Loalkyl group, C_Four-C₄₀A cycloalkenyl group, and
(C_Three-C₂₀Cycloalkyl) C₁-C₂₀Alkyl groups are
Each C₆-C₂₀Aryl group, C₆-C₂₀Alkylarylene
Group, C₆-C₂₀Arylalkyl group, C_Four-C₂₀Cycloa
Alkyl group, C_Four-C₂₀A cycloalkenyl group and (C_Three-
C_TenCycloalkyl) C ₁-C_TenAlkyl groups are preferred,
Each C₆-C_TenAryl group, C₆-C₁₂Alkyl ants
Group, C₆-C₁₂Arylalkyl group, C_Four-C_TenCyclo
An alkyl group and C_Four-C_TenFurther cycloalkenyl groups
preferable.

Substituents may be introduced into silicon, germanium, oxygen, phosphorus, tin, nitrogen, and sulfur atoms. Examples of the substituent include, for example,
Examples include a halogen atom, an amino group, a hydroxyl group, a silyl group, an alkoxy group, and an aryloxy group.

Examples of alkoxy groups useful in the practice of the present invention include, but are not limited to, methoxy, ethoxy, 2-methoxyethoxy, t-butoxy, and the like.

Examples of aryloxy groups useful in the practice of this invention include, but are not limited to, phenoxy,
Naphthoxy, phenylphenoxy, 4-methylphenoxy, 2-tolyloxy, 3-tolyloxy, 4-tolyloxy, naphthyloxy, biphenyloxy, 4-phenoxyphenyloxy, 4-fluorophenyloxy,
3-carbomethoxyphenyloxy, 4-carbomethoxyphenyloxy and the like.

Examples of amino groups useful in the practice of the present invention include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino, and the like.

[0024] Examples of useful silyl groups in the practice of the present invention, but are not limited to, trimethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, dimethylethylsilyl, methyl methoxyphenyl silyl, methylethylphenoxy Silyl and the like.

M ¹ and M ² are independent of each other and are the same or different and represent a metal belonging to Groups 3 to 5 of the periodic table or a lanthanide series. As M ¹ and M ² , metals of Group 4 or 5 of the periodic table or lanthanide series are preferable, and metals of Group 4 of the periodic table, that is, titanium, zirconium and hafnium are more preferable.

L ¹ , L ² , L ³ and L ⁴ are independent of each other;
The same or different indicates an anionic ligand. However, L ¹ and L ² or L ³ and L ⁴ may be crosslinked.

[0027] The anionic ligands are delocalized cyclic η
⁵ - coordination type ligand, C ₁ -C ₂₀ alkoxy groups, C ₆ -C ₂₀
It is preferably an aryloxy group or a dialkylamide group.

L ¹ , L ² , L ³ and L ⁴ are delocalized cyclic η
It is preferably a ⁵ -coordination ligand. Delocalized cyclic eta ⁵ - Example of the coordination type ligand is an unsubstituted cyclopentadienyl group and substituted cyclopentadienyl groups. This substituted cyclopentadienyl group is, for example, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, t-butylcyclopentadienyl, dimethylcyclopentadienyl, Diethylcyclopentadienyl,
Diisopropylcyclopentadienyl, di-t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl group, 2-methylindenyl group, 2-methyl-4-phenylindenyl group, tetrahydroindenyl group, benzoin A benzyl group, a fluorenyl group, a benzofluorenyl group, a tetrahydrofluorenyl group and an octahydrofluorenyl group.

In the delocalized cyclic η ⁵ -coordination system ligand, one or more atoms of the delocalized cyclic π system may be substituted with a hetero atom. In addition to hydrogen, one such as an element of group 14 of the periodic table and / or an element of groups 15, 16 and 17 of the periodic table.
It can contain more than one heteroatom.

Delocalized ring η^Five-Coordination ligands, for example
For example, a cyclopentadienyl group is
May be cross-linked by one or more cross-linking ligands.
It may be. Examples of the bridging ligand include C
H_Two, CH_TwoCH_Two, CH (CH_Three) CH_Two, CH (C
_FourH₉) C (CH_Three)_Two, C (CH_Three)_Two, (CH_Three)_TwoSi,
(CH_Three) _TwoGe, (CH_Three)_TwoSn, (C₆H_Five)_TwoSi,
(C₆H_Five) (CH_Three) Si, (C₆H _Five)_TwoGe, (C
₆H_Five)_TwoSn, (CH_Two)_FourSi, CH_TwoSi (CH_Three)_Two,
o-C₆H_FourOr 2,2 ′-(C₆H_Four)_TwoIs mentioned.

Two or more delocalized cyclic η^Five-Coordination coordination
, For example, cyclopentadienyl groups,
May be cross-linked by one or more cross-linking groups.
It may be. Examples of the crosslinking group include, for example, CH_Two, C
H_TwoCH_Two, CH (CH_Three) CH_Two, CH (C_FourH₉) C (C
H_Three)_Two, C (CH_Three)_Two, (CH_Three)_TwoSi, (CH_Three)_TwoG
e, (CH_Three)_TwoSn, (C₆H_Five)_TwoSi, (C₆H_Five)
(CH_Three) Si, (C₆H_Five) _TwoGe, (C₆H_Five)_TwoSn,
(CH_Two)_FourSi, CH_TwoSi (CH_Three)_Two, O-C₆H_Fouror
Is 2,2 ′-(C₆H_Four)_TwoIs mentioned.

The dinuclear olefin complex represented by the above formula (I) or the above formula (I ') has two or more metallocene moieties.
(moiety) as a ligand. Such compounds are known as polynuclear metallocenes. The polynuclear metallocene may have any substitution mode and any bridged form. The independent metallocene moieties of the polynuclear metallocene may each be the same or different. Examples of the polynuclear metallocene are described in, for example, EP-A-632063, JP-A-4-80214, JP-A-4-85310, and EP-A-654476.

The trinuclear complex according to the present invention is produced by reacting the above-mentioned dinuclear olefin complex with a borane derivative represented by the following formula (II) and water.

B (R ⁵ ) ₃ (II) (wherein, R ⁵ has the above meaning.) R ⁵ is a hydrogen atom; C _{1 to} C ₂₀ which may have a substituent.
Hydrocarbon group; C ₁ -C ₂₀ alkoxy group optionally having a substituent; C ₆ -C ₂₀ aryloxy group optionally having a substituent; amino group optionally having a substituent A silyl group which may have a substituent, or a hydroxyl group.

R ⁵ is preferably an aryl group which may have a substituent or an alkyl group which may have a substituent, such as a pentafluorophenyl group, a fluorophenyl group and a phenyl group. Is more preferred.

Typically, water and a dinuclear olefin complex represented by the above formula (I) or (I ') are added to a solvent for the borane derivative, and the mixture is stirred. The order of addition is not limited, and the borane derivative and water may be added to the solvent of the binuclear olefin complex.

For example, as a dinuclear olefin complex, when M ¹ and M ² are the same group M and L ¹ , L ² , L ³ and L ⁴ are the same group L, the following trinuclear complex is obtained. Probably generated.

[0038]

Embedded image The binuclear complex represented by the above formula (I) or (I ′) did not react with water as it was. However, by adding the borane derivative of the above formula (II) to the binuclear complex, the borane derivative draws out the ligand A bound to the metal M in the binuclear complex and becomes a borate. On the other hand, since a site where water can attack the metal M is generated in the binuclear complex,
Water OH ^- is bonded to the metal, considered trinuclear complex is produced progressed as reaction. A hydrogen atom may be added to the oxygen atom of the generated trinuclear complex. In addition,
This reaction mechanism is only a hypothesis, and the present invention is not limited to this reaction mechanism.

The amount of the borane derivative represented by the above formula (II) is preferably from 0.1 mol to 20 mol based on 1 mol of the total amount of the dinuclear olefin complex (I) or (I ′). It is more preferably from 0.2 mol to 5 mol, even more preferably from 0.3 mol to 1.0 mol.

The amount of water is preferably from 0.1 mol to 20 mol, and more preferably from 0.5 mol to 5 mol, per 1 mol of the total amount of the dinuclear olefin complex (I) or (I ′). More preferably, it is even more preferably from 0.5 mol to 3 mol.

The reaction is preferably carried out at -100 ° C to 300 ° C.
, And particularly preferably -80 ° C to 200 ° C.
C., more preferably in the temperature range of 0.degree. C. to 200.degree. The pressure is, for example, from 0.1 bar to 250
It is in the range of 0 bar, preferably in the range of 0.5 bar to 10 bar.

As the solvent, a solvent capable of dissolving the dinuclear olefin complex represented by the above formula (I) or (I ') is preferable. As the solvent, an aliphatic or aromatic organic solvent is used. Ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; amides such as N, N-dimethylformamide; sulfoxides such as dimethylsulfoxide; Aromatic hydrocarbons such as benzene and toluene are used.

The dinuclear olefin complex represented by the above formula (I) or (I ') used in the present invention is, for example,
An organometallic compound represented by the following formula (IV) is reacted with an organometallic compound represented by the following formula (V) to obtain a reaction mixture, and the reaction mixture is added to a nucleophilic compound represented by the following formula (III) It can be synthesized by adding a reagent.

[0044]

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , A, M ¹ , M ² , L ¹ ,
L ^2, L ³ and L ⁴ are each as defined above. X ¹ and X ²
Is independent of each other and is the same or different and represents a first leaving group. However, X ¹ and X ² exclude the case where they are hydrocarbon groups. Y ¹ and Y ² are independently of each other, the same or different, and represent a C ₁ -C ₃₀ hydrocarbon group which may have a substituent. Z represents a second leaving group. X ¹ and X ² are independent of each other and are the same or different and each represent a leaving group. However, this does not apply to hydrocarbon groups. The leaving group, for example, F, Cl, Br, a halogen atom such as I, p-toluenesulfonyl group, a tosylate group (-O-S (= O) 2 -C 6 H 4 -CH 3), trifluoperazine Romethanesulfonic acid ester (triflate), C ₁ -C
_{A 20} alkoxy group (preferably a C ₁ -C ₁₀ alkoxy group, more preferably a C ₁ -C ₆ alkoxy group),
₆ -C ₂₀ aryloxy group, a tri-lower alkyl silyl group, and the like. As the leaving group, a halogen atom, a tosylate group, a C ₁ -C ₂₀ alkoxy group and a tri-lower alkylsilyloxy group are preferred, and Cl and Br are more preferred.

Y ¹ and Y ² are independently of each other and are the same or different and each represent a C ₁ -C ₃₀ hydrocarbon group which may have a substituent. It is preferably a C ₁ -C ₁₀ hydrocarbon group, more preferably a C ₁ -C ₅ hydrocarbon group, and even more preferably an ethyl group.

Z represents a leaving group. For example, Li, N
Examples thereof include alkali metals such as a and K, and metal halides such as MgX (wherein X represents a halogen atom). Examples of the nucleophilic reagent represented by the above formula (III) include a lithium reagent and a Grignard reagent.

The amount of the nucleophile represented by the formula (III) is preferably from 0.1 mol to 20 mol, more preferably from 0.5 mol to 10 mol, per 1 mol of the organometallic compound (V). Is more preferable, and even more preferably 0.9 mol to 2.5 mol.

The amount of the organometallic compound represented by the above formula (IV) is preferably 0.1 mol to 10 mol with respect to 1 mol of the organometallic compound represented by the above formula (V). More preferably from 0.5 mol to 3 mol,
Even more preferably, it is between 0.9 mol and 1.5 mol.

The synthesis reaction of the dinuclear olefin complex represented by the above formula (I) or (I ′) is preferably carried out at -100 ° C.
The reaction is carried out in a temperature range of -300 ° C, particularly preferably -80.
C. to 100 C., more preferably -50 C. to 5C.
It is performed in a temperature range of 0 ° C. The pressure is, for example, in the range from 0.1 bar to 2500 bar, preferably 0.5 bar.
It is in the range from 10 bar to 10 bar.

As the solvent for the synthesis reaction of the binuclear olefin complex, a solvent capable of dissolving the organometallic compound represented by the above formula (IV) and the organometallic compound represented by the above formula (V) is preferable. As the solvent, an aliphatic or aromatic organic solvent is used. Ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; amides such as N, N-dimethylformamide; sulfoxides such as dimethylsulfoxide; Aromatic hydrocarbons such as benzene and toluene are used.

In the present invention, as the organometallic compound represented by the formula (IV), for example, the following metallocene can be used.

Bis (cyclopentadienyl) dichlorozirconium; bis (methylcyclopentadienyl) dichlorozirconium; bis (butylcyclopentadienyl) dichlorozirconium; bis (indenyl) dichlorozirconium; bis (fluorenyl) dichlorozirconium; (Indenyl) (fluorenyl) dichlorozirconium; bis (cyclopentadienyl) dichlorotitanium; (dimethylsilanediyl) bis (indenyl) dichlorozirconium; (dimethylsilanediyl) bis (tetrahydroindenyl) dichlorozirconium; (dimethylsilanediyl) ( (Indenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-ethyl) Ndeniru) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-4,
(5-benzoindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-ethyl-4,5-benzoindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-4-phenylindenyl)
Dichlorozirconium; (dimethylsilanediyl) bis (2-ethyl-4-phenylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-4,6-diisopropylindenyl) dichlorozirconium.

In the present invention, as the organometallic compound represented by the formula (V), for example, the above-mentioned dichloro compound or the like can be converted into a strong base such as an alkali metal such as sodium or an alkaline earth metal such as magnesium. It can be used after reduction or conversion to a dialkyl form.

Bis (cyclopentadienyl) diethyl zirconium; bis (methylcyclopentadienyl) diethyl zirconium; bis (butylcyclopentadienyl) diethyl zirconium; bis (indenyl) diethyl zirconium; bis (fluorenyl) diethyl zirconium; Indenyl) (fluorenyl) diethyl zirconium; (3-methyl-5-naphthylindenyl)
(2,7-di-tert-butylfluorenyl) diethyl zirconium; (3-methyl-5-naphthylindenyl) (3,4,7-trimethoxyfluorenyl) diethyl zirconium; (pentamethylcyclopentadiene (Enyl) (tetrahydroindenyl) diethyl zirconium; (cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) diethyl zirconium; (indenyl) (1-buten-4-ylcyclopentadienyl) diethyl zirconium [1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) diethyl zirconium;

Bis (cyclopentadienyl) diethyltitanium; dimethylsilanediylbis (indenyl) diethylzirconium; dimethylsilanediylbis (tetrahydroindenyl) diethylzirconium; dimethylsilanediyl (cyclopentadienyl) (indenyl) diethylzirconium; Dimethylsilanediylbis (2-methylindenyl) diethyl zirconium; dimethylsilanediylbis (2-ethylindenyl) diethylzirconium; dimethylsilanediylbis (2-methyl-4,
5-benzoindenyl) diethyl zirconium; dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) diethylzirconium; dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] Acenaphthylene-7-ylidene) diethyl zirconium; dimethylsilanediyl (2-methyl-4,
5-benzoindenyl) (2-methyl-4-phenylindenyl) diethyl zirconium; dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) diethyl zirconium; Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) diethyl zirconium; dimethylsilanediyl (2
-Ethylindenyl) (2-ethyl-4-phenylnaphthyl) diethyl zirconium; dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl)
Diethyl zirconium; dimethylsilanediylbis (2
-Methyl-4-phenylindenyl) diethyl zirconium; dimethylsilanediylbis (2-ethyl-4-phenylindenyl) diethylzirconium; dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) diethylzirconium; Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) diethyl zirconium; dimethylsilanediylbis (2-methyl-4-naphthylindenyl) diethylzirconium; dimethylsilanediylbis (2-ethyl-
4-naphthylindenyl) diethyl zirconium;

Methylphenylsilanediylbis (indenyl) diethylzirconium; methylphenylsilanediyl (cyclopentadienyl) (indenyl) diethylzirconium; methylphenylsilanediylbis (tetrahydroindenyl) diethylzirconium; methylphenylsilanediylbis (2 -Methylindenyl) diethyl zirconium; methylphenylsilanediylbis (2-ethylindenyl) diethylzirconium; methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) diethylzirconium; methylphenylsilanediylbis ( 2-ethyl-4,5-benzoindenyl) diethyl zirconium; methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] a Naphthylene-7-ylidene) diethyl zirconium; methylphenyl silane diyl (2-
Methyl-4,5-benzoindenyl) (2-methyl-4
-Phenylindenyl) diethyl zirconium; methylphenylsilanediyl (2-ethylindenyl) (2-
Methyl-4-phenylindenyl) diethyl zirconium; methylphenylsilanediyl (2-methyl-4,5
-Benzoindenyl) (2-ethyl-4-phenylindenyl) diethyl zirconium; methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2
-Ethyl-indenyl) diethyl zirconium; methylphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) diethyl zirconium;

Methylphenylsilanediylbis (2-methyl-4phenylindenyl) diethyl zirconium;
Methylphenylsilanediylbisdiethylzirconium; methylphenylsilanediylbis (2-methyl-
4,6-diisopropylindenyl) diethyl zirconium; methylphenylsilanediylbis (2-ethyl-
4,6-diisopropylindenyl) diethyl zirconium; methylphenylsilanediylbis (4-naphthylindenyl) diethyl zirconium; methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) diethyl zirconium; diphenylsilanediylbis ( Indenyl) diethyl zirconium; diphenylsilanediylbis (2-methylindenyl) diethylzirconium; diphenylsilanediylbis (2-ethylindenyl) diethylzirconium; diphenylsilanediyl (cyclopentadienyl) (indenyl) diethylzirconium; diphenylsilane Diylbis (2-methyl-4,5-benzoindenyl) diethyl zirconium; diphenylsilanediylbis (2-ethyl-4,5
-Benzoindenyl) diethyl zirconium; diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4phenylindenyl) diethylzirconium; diphenylsilanediyl (2-ethyl-
4,5-benzoindenyl) (2-methyl-4phenylindenyl) diethyl zirconium; diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2
-Ethyl-4phenylindenyl) diethyl zirconium; diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4naphthylindenyl) diethyl zirconium; diphenylsilanediyl (2-methylindenyl) (4phenylindenyl) diethyl zirconium; diphenylsilanediylbis (2
-Methyl-4phenylindenyl) diethyl zirconium; diphenylsilanediylbis (2-ethyl-4phenylindenyl) diethylzirconium; diphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) diethylzirconium;

Diphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) diethyl zirconium; diphenylsilanediylbis (2-methyl-4
-Naphthylindenyl) diethyl zirconium; diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) diethyl zirconium; 1-silacyclopentane-1,1-bis (indenyl) diethyl zirconium; 1-silacyclopentane-1 1-bis (2-methylindenyl) diethyl zirconium; 1-silacyclopentane-1,1-bis (2-ethylindenyl) diethyl zirconium; 1-silacyclopentane-1,1-
Bis (2-methyl-4,5-benzoindenyl) diethyl zirconium; 1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) diethyl zirconium; 1-silacyclopentane- 1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) diethyl zirconium; 1
-Silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) diethyl zirconium; 1-silacyclopentane-1- (2-methyl- 4,5-benzoindenyl)
-1- (2-ethyl-4-phenylindenyl) diethyl zirconium; 1-silacyclopentane-1- (2-
Ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-naphthylindenyl) diethyl zirconium;
1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) diethyl zirconium; 1-silacyclopentane-1,1-bis (2-
Methyl-1-phenylindenyl) diethyl zirconium; 1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) diethyl zirconium;
1-silacyclopentane-1,1-bis (2-methyl-
4,6-diisopropylindenyl) diethyl zirconium; 1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) diethyl zirconium; 1-silacyclopentane-1,1-bis ( 2-methyl-4-naphthylindenyl) diethyl zirconium; 1-silacyclopentane-1,1-bis (2
-Ethyl-4-naphthylindenyl) diethyl zirconium; bis (cyclopentadienyl) diethyltitanium;
Ethylene-1,2-bis (indenyl) diethyl zirconium; ethylene-1,2-bis (tetrahydroindenyl) diethyl zirconium; ethylene-1- (cyclopentadienyl) -2- (1-indenyl) diethyl zirconium; ethylene -1- (cyclopentadienyl)
-2- (2-indenyl) diethyl zirconium; ethylene-1- (cyclopentadienyl) -2- (2-methyl-1-indenyl) diethyl zirconium; ethylene-1,2-bis (2-methylindenyl) Diethyl zirconium; ethylene-1,2-bis (2-ethylindenyl) diethyl zirconium; ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) diethyl zirconium; ethylene-1,2-bis (2-ethyl-
4,5-benzoindenyl) diethyl zirconium;

Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) diethyl zirconium; ethylene-1- (2-methyl-4,5-benzoin Denenyl) -2
-(2-methyl-4-phenylindenyl) diethyl zirconium; ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) diethyl zirconium; ethylene -1- (2
-Methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) diethyl zirconium; ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2 -Ethyl-4-naphthylindenyl) diethyl zirconium; ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) diethyl zirconium; ethylene-1,2-bis (2-methyl-4- Phenylindenyl) diethyl zirconium;
Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) diethyl zirconium; ethylene-1,2-
Bis (2-methyl-4,6-diisopropylindenyl) diethyl zirconium; ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) diethyl zirconium; ethylene-1,2-bis (2- Methyl-4-naphthylindenyl) diethyl zirconium; ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) diethyl zirconium; propylene-
2,2-bis (indenyl) diethyl zirconium; propylene-2-cyclopentadienyl-2- (1-indenyl) diethyl zirconium; propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) Diethyl zirconium; propylene-2-cyclopentadienyl-2- (9-fluorenyl) diethyl zirconium; propylene-2-cyclopentadienyl-2
-(2,7-dimethoxy-9-fluorenyl) diethyl zirconium; propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) diethyl zirconium; propylene-2-cyclopentane Dienyl-2- (2,7-dibromo-9-fluorenyl) diethyl zirconium; propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) diethyl zirconium; propylene-2-
Cyclopentadienyl-2- (2,7-dimethyl-9-
Fluorenyl) diethyl zirconium; propylene-2
-(3-methylcyclopentadienyl) -2- (2,7
-Diethyl 9-fluorenyl) diethyl zirconium;
Propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) diethyl zirconium; propylene-2- (3-trimethylsilylcyclopentadienyl) -2- (3 , 6
-Di-tert-butyl-9-fluorenyl) diethyl zirconium; propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-
Fluorenyl] diethyl zirconium; propylene-2
-Cyclopentadienyl-2- (3-tert-butyl-9-fluorenyl) diethyl zirconium; propylene-2,2-bis (tetrahydroindenyl) diethyl zirconium; propylene-2,2-bis (2-methylindenyl) ) Diethyl zirconium; propylene-2,
2-bis (2-ethylindenyl) diethyl zirconium; propylene-2,2-bis (2-methyl-4,5-
Benzoindenyl) diethyl zirconium; propylene-2,2-bis (2-ethyl-4,5-benzoindenyl) diethyl zirconium; propylene-2,2-bis (4,5-dihydro-8-methyl-7H- Cyclopent [e] acenaphthylene-7-ylidene) diethyl zirconium; propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) diethyl zirconium; propylene-2 -(2
-Ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) diethyl zirconium; propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2 -Ethyl-4-phenylindenyl) diethyl zirconium; propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) diethyl zirconium; propylene-2- (2-methylindenyl) -2- (4-
Phenyl-2,2-bis (2-methyl-4-phenylindenyl) diethyl zirconium; propylene-2,2-bis (2-ethyl-4-phenylindenyl) diethyl zirconium; propylene -2,2-bis (2-methyl-
4,6-diisopropylindenyl) diethyl zirconium; propylene-2,2-bis (2-ethyl-4,6
-Diisopropylindenyl) diethyl zirconium;
Propylene-2,2-bis (2-methyl-4-naphthylindenyl) diethyl zirconium;
2-bis (2-ethyl-4-naphthylindenyl) diethyl zirconium;

1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) diethyl zirconium] hexane; 1,6-bis [methylsilylbis (2-
Methyl-4,5-benzoindenyl) diethylzirconium] hexane; 1,6-bis [methylsilylbis (2
-Ethyl-4-phenylindenyl) diethyl zirconium] hexane; 1,6-bis [methylsilylbis (2
-Methyl-4-naphthylindenyl) diethyl zirconium] hexane; 1,6-bis [methylsilylbis (2
-Methyl-4,6-diisopropylindenyl) diethylzirconium] hexane; 1,6-bis [methylsilyl (2-methyl-4phenylindenyl) (4,5-benzoindenyl) diethylzirconium] hexane; 1
-[Methylsilylbis (tetrahydroindenyl) diethylzirconium] -6- [ethylstannyl (cyclopentadienyl) (fluorenyl) diethylzirconium] hexane; 1,6-disila-1,1,6,6-tetramethyl-1 1,6-bis [methylsilylbis (2-methyl-4phenylindenyl) diethylzirconium] hexane; 1,4-disila1,4-bis [methylsilylbis (2-methyl-4phenylindenyl) diethylzirconium] [1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (pentamethylcyclopentadienyl diethylzirconium); [1,4-bis ( 9-fluorenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis ( Cyclopentadienyl diethyl zirconium); [1,4-bis (1-indenyl) -1,
1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyl diethylzirconium);
[1- (1-indenyl) -6- (2-phenyl-1-
Indenyl) -1,1,6,6-tetraethyl-1,6
-Disila-4-oxahexane] bis (tert-butylcyclopentadienyl diethylzirconium);
[1,10-bis (2,3-dimethyl-1-indenyl) -1,1,10,10-tetramethyl-1,10-
Digermadecane] bis (2-methyl-4-phenylindenyldiethylzirconium); (1-methyl-3-t
tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7-chlorofluorenyl) diethyl zirconium; (4,7-dichloroindenyl) (3,6
-Dimesitylfluorenyl) diethyl zirconium; bis (2,7-di-tert-butyl-9-cyclohexylfluorenyl) diethyl zirconium; (2,7-dimesitylfluorenyl) [2 7-bis (1-naphthyl) fluorenyl] diethyl zirconium; dimethylsilylbis (fluorenyl) diethyl zirconium; dibutylstannylbis (2-methylfluorenyl) diethyl zirconium; 1,1,2,2-tetraethyldisilanediyl (2- Methylindenyl) (4-phenylfluorenyl) diethyl zirconium; propylene-1- (2
-Indenyl) -2- (9-fluorenyl) diethyl zirconium; 1,1-dimethyl-1-silaethylenebis (fluorenyl) diethyl zirconium; [4- (cyclopentadienyl) 4,7,7-trimethyl (tetrahydroindenyl) [4- (cyclopentadienyl) 4,7-dimethyl-7-phenyl (5,6-dimethyltetrahydroindenyl) diethylzirconium; [4- (cyclopentadienyl) -4,
7-dimethyl-7- (1-naphthyl) (7-phenyltetrahydroindenyl)] diethyl zirconium; [4
-(Cyclopentadienyl) -4,7-dimethyl-7-
Butyl (6,6-diethyltetrahydroindenyl)]
[4- (3-tert-butylcyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] diethyl zirconium; [4
-(1-indenyl) -4,7,7-trimethyl (tetrahydroindenyl)] diethylzirconium; bis (cyclopentadienyl) diethylhafnium; bis (indenyl) diethylvanadium; bis (fluorenyl) diethylscandium; (indenyl) (Fluorenyl) diethylniobium; (2-methyl-7-naphthylindenyl) (2,6-di-tert-butylfluorenyl) diethyltitanium; (pentamethylcyclopentadienyl) (tetrahydroindenyl) butyl Hafnium; (cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) diethylhafnium.

[0061]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
However, the present invention is not limited to the following examples.

The reaction was performed under a nitrogen atmosphere. As a solvent
Used toluene was steamed from sodium and benzophenone.
Stayed. Zirconocene dichloride from Nichia
(C₆F _Five)_ThreeB is Aldrich (Aldrich Chemical Company,
Inc). Zirconium binuclear complex (Cp
_Two(ZrMe)_Two (CH_TwoCH_Two) Was synthesized by a known method.

The ¹ H-NMR and ¹³ C-NMR spectra were obtained from Bruke
r Measured using ARX-400 or JEOL JNM-AL300 NMR spectrometer, using THF-d8 as a solvent. Gas chromatographic analysis was performed using a silica glass capillary column SHIMADZU.
CBP1-M25-O25 and SHIMADZU C-R6A-Chromatopac inte
The measurement was performed with a SHIMADZU GC-14A gas chromatograph equipped with a grator.

Embodiment 1

Embedded image To a toluene solution (10 mL) of (C ₆ F ₅ ) ₃ B (154 mg, 0.3 mmol) was added distilled water (10.8 μL, 0.6 mmol) and a dinuclear complex (Cp ₂ ZrMe) ₂
(CH ₂ CH ₂ ) (150 mg, 0.3 mmol) was added at room temperature, and the mixture was stirred at room temperature for 1 hour to produce a white precipitate. The solvent was removed by filtration, and the obtained precipitate was washed with toluene and dried under reduced pressure. Trinuclear zirconium complex (1
67 mg, 0.115 mmol) was obtained with an isolation yield of 77%. The structure was determined by X-ray crystal structure analysis.

¹ H-NMR (THF-d8) δ2.48 (s, 6H), 3.23
(s, 3H), 6.50 (s, 30H), 7.25-7.38 (m, 10H); ¹³ C-NMR
(THF-d8) δ21.98, 42.60, 114.55, 126.52, 129.40, 1
30.16, 138.02 (JC-F = 261 Hz), 138.93, 140.01 (JC-
F = 244 Hz), 149.55 (JC-F = 251 Hz).

[0066]

According to the present invention, various trinuclear complexes can be selectively obtained.

Continued on the front page F term (reference) 4H050 AB40 BE60 BE90 4J028 AA01A AB01A AC01A AC10A AC28A BA00A BA01B BB00A BB00B BC13B EB01 4J128 AA01 AB01 AC01 AC10 AC28 AD00 BA00A BA01B BB00A BB00B BC13B EB01

Claims (8)

[Claims] 1. A dinuclear olefin complex represented by the following formula (I) or (I ′): (Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently of each other, the same or different, and each represents a hydrogen atom or a C ₁ -C ₁₀ hydrocarbon group, and A has a substituent. A C ₁ -C ₄₀ hydrocarbon group which may be substituted; a halogen atom; silicon which may have a substituent; a germanium atom which may have a substituent; an oxygen atom which may have a substituent; A phosphorus atom which may have a substituent; a tin atom which may have a substituent; a nitrogen atom which may have a substituent, or a sulfur atom which may have a substituent. Wherein M ¹ and M ² are independent of each other and are the same or different and represent a metal belonging to Groups 3 to 5 of the periodic table or a lanthanide series; L ¹ , L ² , L ³ and L ⁴ are each other independently, the same or different and each represents an anionic ligand. However, L ¹ and L ^2, or, L ³ and L ⁴ . It may be crosslinked) and borane derivatives represented by the following formula ^{(II), B (R 5} ) 3 (II) ( wherein, R ⁵ is a hydrogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; which may have a substituent group C ₁ ~
C ₂₀ alkoxy group; C ₆ -C optionally having substituent (s)
_{20 an} aryloxy group; an amino group which may have a substituent; a silyl group which may have a substituent, or a hydroxyl group. ) A trinuclear complex formed by reacting with water. 2. The trinuclear complex according to claim 1, wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms. 3. The method according to claim ^1, wherein M ¹ and M ² are independent of each other and are the same or different and are metals of Group 4 or 5 of the periodic table or lanthanide series, wherein said anionic ligand is delocalized. cyclic eta ⁵ - is a coordination type ligand, trinuclear complex according to claim 1 or 2. 4. The method according to claim 1, wherein the delocalized cyclic η ⁵ -coordination ligand is
The trinuclear complex according to claim 3, which is an optionally substituted cyclopentadienyl group, indenyl group, fluorenyl group, or azulenyl group. 5. A process for producing a trinuclear complex, wherein a dinuclear olefin complex represented by the following formula (I) or (I ′) is represented by the following formula: (Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently of each other, the same or different, and each represents a hydrogen atom or a C ₁ -C ₁₀ hydrocarbon group, and A has a substituent. A C ₁ -C ₄₀ hydrocarbon group which may be substituted; a halogen atom; silicon which may have a substituent; a germanium atom which may have a substituent; an oxygen atom which may have a substituent; A phosphorus atom which may have a substituent; a tin atom which may have a substituent; a nitrogen atom which may have a substituent, or a sulfur atom which may have a substituent. Wherein M ¹ and M ² are independent of each other and are the same or different and represent a metal belonging to Groups 3 to 5 of the periodic table or a lanthanide series; L ¹ , L ² , L ³ and L ⁴ are each other independently, the same or different and each represents an anionic ligand. However, L ¹ and L ^2, or, L ³ and L ⁴ . It can be crosslinked) and borane derivatives represented by the following formula ^{(II), B (R 5} ) 3 (II) ( wherein, R ⁵ is a hydrogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; which may have a substituent group C ₁ ~
C ₂₀ alkoxy group; C ₆ -C optionally having substituent (s)
₂₀ aryloxy group; optionally substituted amino group; an optionally substituted silyl group, or a hydroxyl group. A method for producing a trinuclear complex, characterized by reacting with water. 6. The process for producing a trinuclear complex according to claim 5, wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms. 7. A M ¹ and M ² are, independently of one another, identical or different, is a metal of Group 4 of the periodic table or a Group 5 or the lanthanide series, wherein the anionic ligand is delocalized The method for producing a trinuclear complex according to claim 5, wherein the method is a cyclic η ⁵ -coordination ligand. 8. The delocalized cyclic η ⁵ -coordination system ligand,
The method for producing a trinuclear complex according to claim 7, which is an optionally substituted cyclopentadienyl group, indenyl group, fluorenyl group, or azulenyl group.