JP2012211118A - Transition metal complex, method for production thereof, trimerizing catalyst, and method for producing 1-hexene - Google Patents

Abstract

（Ｍは元素の周期律表の第４族の遷移金属原子を表し、Ｘ^１、Ｘ^２、Ｘ^３、及び、Ｒ^１、からＲ^{１ ４}は、水素原子、ハロゲン原子、ハロゲン原子を有してもよい炭素原子数１〜２０のアルキル基、アルコキシ基、炭素原子数６〜２０のアリール基、アリールオキシ基、炭素原子数７〜２０のアラルキル基、アラルキルオキシ基等である。）
【選択図】なしThe present invention provides a novel transition metal complex serving as a catalyst component capable of producing 1-hexene by a trimerization reaction of ethylene.
A transition metal complex represented by the formula (1) is provided.

(M represents a transition metal atom of Group 4 of the Periodic Table of the ^{Elements, X 1, X 2, X} 3 and,, ^{R 1, R 1 4} from has a hydrogen atom, a halogen atom, a halogen atom And may be an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group, etc.)
[Selection figure] None

Description

  The present invention relates to a transition metal complex, a method for producing the transition metal complex, a catalyst for trimerization, and a method for producing 1-hexene.

  The α-olefin is an industrially important raw material monomer produced by oligomerization of ethylene with a metal catalyst. However, since the oligomerization of ethylene usually gives a mixture of α-olefins according to the Shultz-Flory distribution, the development of a catalyst system capable of producing selective α-olefins is very important industrially.

For example, Patent Document 1, the half-metallocene titanium complex represented by formula (Cp-B (R) n Ar) TiR 1 3 is the presence of an activating co-catalyst component, a catalyst component for the trimerization of selective ethylene Has been reported to work as.
Among these selective ethylene trimerization catalysts, carbon atoms such as [1- (1-methyl-1- (3,5-dimethylphenyl) ethyl) -3-trimethylsilylcyclopentadienyl] titanium trichloride It has been reported that the half-metallocene titanium complex in which cyclopentadiene and substituted aryl group are bonded uses MAO (methylaluminoxane) as an activation promoter component and acts as an efficient ethylene trimerization catalyst at 30 ° C. (For example, refer nonpatent literature 1).

  [Diphenylmethyl-cyclopentadienyl] titanium trichloride having a diphenylmethyl group as a substituent of cyclopentadiene was synthesized as a half metallocene titanium complex in which a cyclopentadiene and an aryl group were bonded, and its molecular structure was determined. However, there is no report on its use as an ethylene trimerization catalyst (see Non-Patent Document 2).

Special table 2004-524959

Organometallics 2002, 21, 5122-5135. J. et al. Organomet. Chem. 1999, 592, 84-94.

  Under such circumstances, the problem to be solved by the present invention is to provide a novel transition metal complex that becomes a catalyst component capable of producing 1-hexene by the trimerization reaction of ethylene.

（式中、Ｍは元素の周期律表の第４族の遷移金属原子を表し、
Ｘ^１、Ｘ^２、Ｘ^３、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、それぞれ独立に、
水素原子、ハロゲン原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基、
−Ｓｉ（Ｒ^１６）_３（３つのＲ^１６はそれぞれ独立に、水素原子、ハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、３つのＲ^１６にある炭素原子数の合計が１〜２０である。）で示される置換シリル基、
または−Ｎ（Ｒ^１７）_２（２つのＲ^１７はそれぞれ独立にハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、２つのＲ^１７にある炭素原子数の合計が２〜２０である。）で示される２置換アミノ基を表し、
Ｒ^１５は、
水素原子、ハロゲン原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基、
−Ｓｉ（Ｒ^１６）_３（３つのＲ^１６はそれぞれ独立に、水素原子、ハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、３つのＲ^１６にある炭素原子数の合計が１〜２０である。）で示される置換シリル基、
または−Ｎ（Ｒ^１７）_２（２つのＲ^１７はそれぞれ独立にハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、２つのＲ^１７にある炭素原子数の合計が２〜２０である。）で示される２置換アミノ基を表し、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５のうち少なくとも一つは、ハロゲン原子、該アルキル基、該アルコキシ基、該アリールオキシ基、該アラルキル基、該アラルキルオキシ基、該置換シリル基または該２置換アミノ基であり、
Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよい。） That is, the first of the present invention relates to the transition metal complex represented by the general formula (1).

(In the formula, M represents a transition metal atom of Group 4 of the periodic table of elements,
X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ Are independent of each other
Hydrogen atom, halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or -N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). Represents a disubstituted amino group represented by:
R ¹⁵ is
Hydrogen atom, halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or -N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). Represents a disubstituted amino group represented by:
At least ^{one of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is A halogen atom, the alkyl group, the alkoxy group, the aryloxy group, the aralkyl group, the aralkyloxy group, the substituted silyl group, or the disubstituted amino group,
Of R ¹ , R ² , R ³ and R ⁴ , two groups bonded to two adjacent carbon atoms are bonded to form a ring together with the two carbon atoms to which the two groups are bonded. Of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , two groups bonded to two adjacent carbon atoms are bonded to each other, and the two groups are bonded to each other. May form a ring together with two carbon atoms present, and two groups bonded to two adjacent carbon atoms among R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are bonded. Then, the two carbon atoms to which the two groups are bonded together may form a ring. )

  A second aspect of the present invention relates to a trimerization catalyst obtained by bringing the transition metal complex into contact with an activation promoter component.

  The third aspect of the present invention relates to a method for producing 1-hexene in which ethylene is trimerized in the presence of a trimerization catalyst.

  A fourth aspect of the present invention relates to a method for producing the transition metal complex represented by the general formula (1).

  ADVANTAGE OF THE INVENTION By this invention, the transition metal complex suitable for the catalyst component which can manufacture 1-hexene by the trimerization reaction of ethylene can be provided.

In the present invention, the term “substituent” includes a halogen atom constituting a compound or group.
Furthermore, in the present invention, the substituted cyclopentadiene compounds represented by the general formulas (2) and (4) have isomers having different double bond positions on each cyclopentadienyl ring. The substituted cyclopentadienyl compound represents any one of them or a mixture thereof.

<Transition metal complex (1) (catalyst component for trimerization)>
Hereinafter, the transition metal complex represented by the general formula (1) will be described in detail.
In the transition metal complex (1), M represents a Group 4 element in the periodic table of elements, and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom. Among these, a titanium atom is preferable.

In the transition metal complex (1), the substituents X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are defined as described above, and specific examples thereof are shown below.

  The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.

  Specific examples of the “alkyl group having 1 to 20 carbon atoms” of the alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, heptyl group, n-octyl group, n-nonyl group, n-decyl Group, n-dodecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and n-eicosyl group. Among these, preferable alkyl groups are those having 1 to 10 carbon atoms, and more preferable examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and an amyl group. In addition, the “optionally having a halogen atom as a substituent” in the “alkyl group optionally having a halogen atom as a substituent” means that part or all of the hydrogen atoms in the alkyl group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom are as described above. In addition, when it has a halogen atom as a substituent, it is preferable that it is the range of the C1-C20, and the range of the C1-C10 is further more preferable. Examples of the alkyl group having a suitable halogen atom as a substituent include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, and a tribromomethyl group. , Fluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group and the like.

  Specific examples of the “aryl group having 6 to 20 carbon atoms” of the aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include a phenyl group, a 2-tolyl group, and 3-tolyl. Group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2 , 3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2 , 3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propyl Phenyl group, isopropyl Phenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, Examples include n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group and anthracenyl group. Among these, preferred aryl groups are aryl groups having 6 to 10 carbon atoms, and more preferred are phenyl groups. In addition, “optionally having a halogen atom as a substituent” in “an aryl group optionally having a halogen atom as a substituent” means that a part or all of the hydrogen atoms in the aryl group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom are as described above. In addition, when it has a halogen atom as a substituent, the carbon atom number is preferable in the range of 6-20, and the range of 6-10 is further more preferable. A particularly preferred aryl group having a halogen atom as a substituent is a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a chlorophenyl group, a bromophenyl group, or an iodophenyl group. Etc.

  Specific examples of the “aralkyl group having 7 to 20 carbon atoms” of the aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent include a benzyl group and a (2-methylphenyl) methyl group. , (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl Group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2 , 3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3 4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group , (Ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group (N-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) ) Methyl group, naphthylmethyl group, anthracenylmethyl group and the like. Among these, a preferable aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and more preferably a benzyl group. In addition, “optionally having a halogen atom as a substituent” in “an aralkyl group optionally having a halogen atom as a substituent” means that a part or all of the hydrogen atoms in the aralkyl group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom are as described above. In addition, when it has a halogen atom as a substituent, the carbon atom number is preferable in the range of 7-20, and the range of 7-10 is further more preferable.

  Specific examples of the “alkoxy group having 1 to 20 carbon atoms” of the alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include a methoxy group, an ethoxy group, an n-propoxy group, Isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy Group, n-undecyloxy group, n-dodecyloxy group, tridecyloxy group, tetradecyloxy group, n-pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, n -An eicosyloxy group etc. are mentioned. Among these, preferable alkoxy groups are those having 1 to 10 carbon atoms, and more preferable examples include a methoxy group, an ethoxy group, and a tert-butoxy group. In addition, “optionally having a halogen atom as a substituent” in “an alkoxy group optionally having a halogen atom as a substituent” means that some or all of the hydrogen atoms in the alkoxy group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom are as described above. In addition, when it has a halogen atom as a substituent, it is preferable in it being the range of the C1-C20, and the range of 1-10 is more preferable.

  Specific examples of the “alkoxy group having 2 to 20 carbon atoms” of the alkoxy group having 2 to 20 carbon atoms which may have a halogen atom as a substituent include an ethoxy group, an n-propoxy group, and an isopropoxy group. , N-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n -Undecyloxy group, n-dodecyloxy group, tridecyloxy group, tetradecyloxy group, n-pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, n-eicosyl An oxy group etc. are mentioned. Among these, preferable alkoxy groups are those having 2 to 10 carbon atoms, and more preferable examples include an ethoxy group and a tert-butoxy group. In addition, “optionally having a halogen atom as a substituent” in “an alkoxy group optionally having a halogen atom as a substituent” means that some or all of the hydrogen atoms in the alkoxy group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom are as described above. In addition, when it has a halogen atom as a substituent, it is preferable in it being the range of the C2-C20, and the range of 2-10 is further more preferable.

  Specific examples of the “aryloxy group having 6 to 20 carbon atoms” of the aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include a phenoxy group, a 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group Group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2, , 4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec- Examples include butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group. Among these, preferable aryloxy groups are aryloxy groups having 6 to 10 carbon atoms, and more preferable examples include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, and 4-methylphenoxy group. it can. In addition, the “optionally having a halogen atom as a substituent” in the “aryloxy group optionally having a halogen atom as a substituent” means that part or all of the hydrogen atoms in the aryloxy group are partially or entirely. , May be replaced by a halogen atom, and specific examples of the halogen atom are as described above. In addition, when it has a halogen atom as a substituent, the carbon atom number is preferable in the range of 6-20, and the range of 6-10 is further more preferable.

  Specific examples of the “aralkyloxy group having 7 to 20 carbon atoms” of the aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent include a benzyloxy group, (2-methylphenyl) ) Methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethyl) Phenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group , (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (Methylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n -Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy Group, naphthylmethoxy group, anthracenylmethoxy group and the like. Among these, a preferable aralkyloxy group is an aralkyloxy group having 7 to 10 carbon atoms, and more preferably a benzyloxy group. In addition, in the “aralkyloxy group optionally having a halogen atom as a substituent”, the “optionally having a halogen atom as a substituent” means that part or all of the hydrogen atoms in the aralkyloxy group are partially or entirely. , May be replaced by a halogen atom, and specific examples of the halogen atom are as described above. In addition, when it has a halogen atom as a substituent, the carbon atom number is preferable in the range of 7-20, and the range of 7-10 is further more preferable.

—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; In the substituted silyl group represented by the formula (1), each R ¹⁶ independently represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc.), aryl group Hydrocarbyl groups such as (phenyl groups); halogenated hydrocarbyl groups in which some or all of the hydrogen atoms in the hydrocarbyl group are replaced by halogen atoms Yes, the total number of carbon atoms of three R ¹⁶ is in the range of 1-20. The total number of carbon atoms of the three R ¹⁶ is preferably in the range of 3-18. Specific examples of the substituted silyl group include a methyl silyl group, an ethyl silyl group, a phenyl silyl group, a hydrocarbyl group such as a group in which some or all of the hydrogen atoms of the hydrocarbyl group are replaced with halogen atoms, or A monosubstituted silyl group having one halogenated hydrocarbyl group; a dimethylsilyl group, a diethylsilyl group, a diphenylsilyl group, or a group in which some or all of the hydrogen atoms of the hydrocarbyl group are replaced with halogen atoms. Disubstituted silyl groups having two hydrocarbyl groups and / or halogenated hydrocarbyl groups such as: trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group , Tri-sec-butylsilyl group, tri-tert-butylsilane Group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, hydrocarbyl in these groups Examples thereof include a hydrocarbyl group such as a group in which part or all of the hydrogen atoms in the group are replaced with a halogen atom and / or a trisubstituted silyl group having three halogenated hydrocarbyl groups. Of these, a trisubstituted silyl group is preferable, and a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a group in which some or all of the hydrogen atoms of these groups are replaced with halogen atoms are more preferable. .

—N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). In the disubstituted amino group shown, each R ¹⁷ independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms of the two R ¹⁷ is in the range of 2 to 20, A range of 10 is more preferred. Such hydrocarbyl group and halogenated hydrocarbyl group are the same as those described as the hydrocarbyl group and halogenated hydrocarbyl group of the substituted silyl group. Further, these two R ¹⁷ may be bonded to each other and form a ring together with the nitrogen atom to which they are bonded. Examples of the disubstituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butyl. Amino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, bistrimethylsilylamino group, bis- tert-Butyldimethylsilylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroindolyl group, dihydroisoindolyl group, groups in which some or all of the hydrogen atoms in these groups are replaced by halogen atoms, etc. Is mentioned. Of these, preferred are a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a piperidinyl group, and a group in which some or all of the hydrogen atoms in these groups are replaced with halogen atoms.

In the transition metal complex (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ^At least one of ¹⁵ is a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, or 1 to 1 carbon atoms which may have a halogen atom as a substituent. 20 alkoxy groups, an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or -N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). The disubstituted amino group shown by these is represented.

Among R ¹ , R ² , R ³ and R ⁴ , groups bonded to two adjacent carbon atoms are bonded to each other, and may form a ring together with the carbon atoms to which they are bonded. Well, among R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , groups bonded to two adjacent carbon atoms are bonded to each other, and together with the carbon atom to which they are bonded, a ring is formed. R ¹⁰ , R ¹¹ , R ¹² , R ^13, and R ¹⁴ may be formed by bonding groups adjacent to two adjacent carbon atoms together with the carbon atom to which they are bonded. To form a ring. The ring here is a saturated or unsaturated hydrocarbyl ring substituted with a hydrocarbyl group having 1 to 20 carbon atoms. Specific examples thereof include cyclopropane ring, cyclopropene ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclopentene ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cycloheptene ring, cyclooctane ring, cyclooctene ring, benzene ring. , Naphthalene ring and anthracene ring.

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は前記と同じ意味を表す。）
において、例えば、次のような部分構造を挙げることができる。 Specific examples of R ¹ , R ² , R ³ and R ⁴ include the partial structural formula (5)

(In the formula, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above.)
For example, the following partial structure can be given.

  Cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butyl Cyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyl Tetrahydroindenyl, octahydrofluorenyl,

  Of the cyclopentadienyl partial structures exemplified herein, a preferred cyclopentadienyl partial structure is tetramethylcyclopentadienyl and the like.

（式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は前記と同じ意味を表す。） A preferred combination of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is a partial structural formula (6)

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ represent the same meaning as described above.)

（式中、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は前記と同じ意味を表す。）
において、それぞれ独立に、例えば、次のような部分構造を挙げることができる。 And a preferred combination of R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ includes a partial structural formula (7)

(Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ represent the same meaning as described above.)
In the above, for example, the following partial structures can be exemplified.

  Phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, diisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, tert-butylmethylphenyl, di (Tert-Butyl) methylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl, bis (trifluoromethyl) phenyl, biphenyl, benzylphenyl, methoxyphenyl, phenoxyphenyl, benzyloxyphenyl, trimethylsilylphenyl, dimethyl Aminophenyl

  Of the partial structures exemplified here, more preferred partial structures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, trimethylsilylphenyl, and the like.

R ¹⁵ is preferably an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, Examples include n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and n-eicosyl group. Among these, preferable alkyl groups are those having 1 to 10 carbon atoms, and more preferable examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and an amyl group.

  Specific examples of the transition metal complex (1) include the following complexes.

  [1-Diphenylmethyl-2-methyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-3-methyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-2,3-dimethyl- Cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-2,4-dimethyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-3,4-dimethyl-cyclopentadienyl] titanium trichloride [1-diphenylmethyl-2,3,4-trimethyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-2,3,5-trimethyl-cyclopentadienyl] titanium trichloride, [1- Diphenylmethyl-2,3,4, -Tetramethyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-2-ethyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-3-ethyl-cyclopentadienyl] titanium trichloride [1-diphenylmethyl-2-n-propyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-3-n-propyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-2 -Isopropyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-3-isopropyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-2-n-butyl-cyclopentadienyl] titanium Lichloride, [1-diphenylmethyl-3-n-butyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-2-sec-butyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl -3-sec-butyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-2-tert-butyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-3-tert-butyl-cyclo Pentadienyl] titanium trichloride, [1-diphenylmethyl-2-phenyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-3-phenyl-cyclopentadienyl] titanium trichloride, [1-diphenyl] Mechi Ru-2-benzyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-3-benzyl-cyclopentadienyl] titanium trichloride, [1-diphenylmethyl-indenyl] titanium trichloride, [1-diphenyl Methyl-2-methylindenyl] titanium trichloride, [1-diphenylmethyl-tetrahydroindenyl] titanium trichloride, [9-diphenylmethyl-fluorenyl] titanium trichloride, [1-diphenylmethyl-2-methyltetrahydroindenyl] ] Titanium trichloride, [9-diphenylmethyl-octahydrofluorenyl] titanium trichloride, [3-diphenylmethyl-1-trimethylsilyl-cyclopentadienyl] titanium trichloride Roraido,

  [1-di (3-methylphenyl) methyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-2-methyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-3-methyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-2,3-dimethyl-cyclopentadienyl] titanium trichloride, [1 -Di (3-methylphenyl) methyl-2,4-dimethyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-3,4-dimethyl-cyclopentadienyl] titanium trichloride Chloride, [1-di (3-methylphenyl) methyl-2,3,4-trimethyl-cyclopent Dienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-2,3,5-trimethyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-2,3 , 4,5-tetramethyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-2-ethyl-cyclopentadienyl] titanium trichloride, [1-di (3-methyl) Phenyl) methyl-3-ethyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-2-n-propyl-cyclopentadienyl] titanium trichloride, [1-di (3 -Methylphenyl) methyl-3-n-propyl-cyclopentadienyl] titanium trichloride [1-di (3-methylphenyl) methyl-2-isopropyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-3-isopropyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-2-n-butyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-3-n-butyl-cyclopentadienyl] Titanium trichloride, [1-di (3-methylphenyl) methyl-2-sec-butyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-3-sec-butyl-cyclo Pentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-2- tert-butyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-3-tert-butyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) Methyl-2-phenyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-3-phenyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) Methyl-2-benzyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) methyl-3-benzyl-cyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) Methyl-indenyl] titanium trichloride, [1-di (3-methyl) Ruphenyl) methyl-2-methylindenyl] titanium trichloride, [9-di (3-methylphenyl) methyl-fluorenyl] titanium trichloride, [1-di (3-methylphenyl) methyl-tetrahydroindenyl] titanium trichloride Chloride, [1-di (3-methylphenyl) methyl-2-methyltetrahydroindenyl] titanium trichloride, [9-di (3-methylphenyl) methyl-octahydrofluorenyl] titanium trichloride, [3- Di (3-methylphenyl) methyl-1-trimethylsilyl-cyclopentadienyl] titanium trichloride,

  [1-bis (3,5-dimethylphenyl) methyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2-methyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-3-methyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2,3-dimethyl-cyclopentadi Enyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2,4-dimethyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-3 , 4-Dimethyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethyl) Ruphenyl) methyl-2,3,4-trimethyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2,3,5-trimethyl-cyclopentadienyl] titanium trichloride Chloride, [1-bis (3,5-dimethylphenyl) methyl-2,3,4,5-tetramethyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl- 2-ethyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-3-ethyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethyl) Phenyl) methyl-2-n-propyl-cyclopentadienyl] titanium trichloride, [1- (3,5-dimethylphenyl) methyl-3-n-propyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2-isopropyl-cyclopentadienyl] titanium Trichloride, [1-bis (3,5-dimethylphenyl) methyl-3-isopropyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2-n-butyl- Cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-3-n-butyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) Methyl-2-sec-butyl-cyclopentadienyl] titanium trichloride, [1 -Bis (3,5-dimethylphenyl) methyl-3-sec-butyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2-tert-butyl-cyclopentadi Enyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-3-tert-butyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2 -Phenyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-3-phenyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) ) Methyl-2-benzyl-cyclopentadienyl] titanium trichloride, 1-bis (3,5-dimethylphenyl) methyl-3-benzyl-cyclopentadienyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-indenyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2-methylindenyl] titanium trichloride, [9-bis (3,5-dimethylphenyl) methyl-fluorenyl] titanium trichloride, [1-bis (3,5-dimethyl) Phenyl) methyl-tetrahydroindenyl] titanium trichloride, [1-bis (3,5-dimethylphenyl) methyl-2-methyltetrahydroindenyl] titanium trichloride, [9-bis (3,5-dimethylphenyl) methyl -Octahydrofluorenyl] titanium trichlora De, [1,3-bis (3,5-dimethylphenyl) methyl-1-trimethylsilyl - cyclopentadienyl] titanium trichloride,

  [1- (1,1-diphenyl-ethyl) -cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -2-methyl-cyclopentadienyl] titanium trichloride, [1 -(1,1-diphenyl-ethyl) -3-methyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -2,3-dimethyl-cyclopentadienyl] titanium trichloride Chloride, [1- (1,1-diphenyl-ethyl) -2,4-dimethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -3,4-dimethyl-cyclo Pentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -2,3,4-trimethyl-cyclopent Dienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -2,3,5-trimethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -2 , 3,4,5-Tetramethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -2-ethyl-cyclopentadienyl] titanium trichloride, [1- (1 , 1-diphenyl-ethyl) -3-ethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -2-n-propyl-cyclopentadienyl] titanium trichloride, [ 1- (1,1-Diphenyl-ethyl) -3-n-propyl-cyclopentadienyl] titanium trichloride [1- (1,1-diphenyl-ethyl) -2-isopropyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -3-isopropyl-cyclopentadienyl] titanium trichloride Chloride, [1- (1,1-diphenyl-ethyl) -2-n-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -3-n-butyl-cyclo Pentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -2-sec-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -3 -Sec-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -2- tert-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -3-tert-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl) -Ethyl) -2-phenyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -3-phenyl-cyclopentadienyl] titanium trichloride, [1- (1,1 -Diphenyl-ethyl) -2-benzyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -3-benzyl-cyclopentadienyl] titanium trichloride, [1- (1 , 1-diphenyl-ethyl) -indenyl] titanium trichloride, [1- (1,1- Phenyl-ethyl) -2-methylindenyl] titanium trichloride, [1- (1,1-diphenyl-ethyl) -tetrahydroindenyl] titanium trichloride, [9- (1,1-diphenyl-ethyl) -fluorenyl ] Titanium trichloride, [1- (1,1-diphenyl-ethyl) -2-methyltetrahydroindenyl] titanium trichloride, [9- (1,1-diphenyl-ethyl) -octahydrofluorenyl] titanium trichloride Chloride, [3- (1,1-diphenyl-ethyl) -1-trimethylsilyl-cyclopentadienyl] titanium trichloride,

  [1- (1,1-diphenyl-pentyl) -cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-methyl-cyclopentadienyl] titanium trichloride, [1 -(1,1-diphenyl-pentyl) -3-methyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2,3-dimethyl-cyclopentadienyl] titanium trichloride Chloride, [1- (1,1-diphenyl-pentyl) -2,4-dimethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -3,4-dimethyl-cyclo Pentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2,3,4-trimethyl -Cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2,3,5-trimethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl- Pentyl) -2,3,4,5-tetramethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-ethyl-cyclopentadienyl] titanium trichloride, [ 1- (1,1-diphenyl-pentyl) -3-ethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-n-propyl-cyclopentadienyl] titanium Trichloride, [1- (1,1-diphenyl-pentyl) -3-n-propyl-cyclopentadienyl Titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-isopropyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -3-isopropyl-cyclopentadi Enyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-n-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -3-n -Butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-sec-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl- Pentyl) -3-sec-butyl-cyclopentadienyl] titanium trichloride, [1 -(1,1-diphenyl-pentyl) -2-tert-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -3-tert-butyl-cyclopentadienyl] Titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-phenyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -3-phenyl-cyclopentadi Enyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-benzyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -3-benzyl-cyclo Pentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -i [Denyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-methylindenyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -tetrahydroindenyl] titanium trichloride, [9- (1,1-diphenyl-pentyl) -fluorenyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -2-methyltetrahydroindenyl] titanium trichloride, [9- (1,1 -Diphenyl-pentyl) -octahydrofluorenyl] titanium trichloride, [3- (1,1-diphenyl-pentyl) -1-trimethylsilyl-cyclopentadienyl] titanium trichloride,

  [1- (1,1-diphenyl-1-tert-butyl-methyl) -cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2-methyl -Cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -3-methyl-cyclopentadienyl] titanium trichloride, [1- (1,1- Diphenyl-1-tert-butyl-methyl) -2,3-dimethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2,4-dimethyl -Cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -3,4 Dimethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2,3,4-trimethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2,3,5-trimethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) ) -2,3,4,5-tetramethyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2-ethyl-cyclopentadienyl] Titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -3-ethyl-cyclopenta Enyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2-n-propyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl- 1-tert-butyl-methyl) -3-n-propyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2-isopropyl-cyclopentadi Enyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -3-isopropyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1- tert-butyl-methyl) -2-n-butyl-cyclopentadienyl] titanium trichloride, [1 -(1,1-diphenyl-1-tert-butyl-methyl) -3-n-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) 2-sec-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -3-sec-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2-tert-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl- Methyl) -3-tert-butyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1 tert-butyl-methyl) -2-phenyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -3-phenyl-cyclopentadienyl] titanium trichloride Chloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2-benzyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl- Methyl) -3-benzyl-cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -indenyl] titanium trichloride, [1- (1,1-diphenyl) -1-tert-butyl-methyl) -2-methylindenyl] titanium trichloride, [ -(1,1-diphenyl-1-tert-butyl-methyl) -tetrahydroindenyl] titanium trichloride, [9- (1,1-diphenyl-1-tert-butyl-methyl) -fluorenyl] titanium trichloride, [1- (1,1-diphenyl-1-tert-butyl-methyl) -2-methyltetrahydroindenyl] titanium trichloride, [9- (1,1-diphenyl-1-tert-butyl-methyl) -octa Hydrofluorenyl] titanium trichloride, [3- (1,1-diphenyl-1-tert-butyl-methyl) -1-trimethylsilyl-cyclopentadienyl] titanium trichloride

  And chlorinated titanium complexes. In addition, in the complexes exemplified here, chlorinated transition metal complexes such as chlorinated zirconium complexes in which “titanium” is replaced with “zirconium”, or chlorinated hafnium complexes in which “hafnium” is replaced, “chloride” is “fluoride” Fluorinated titanium complexes replaced with “bromide”, brominated titanium complexes replaced with “bromide”, titanium iodide complexes replaced with “iodide”, titanium hydride complexes replaced with “hydride”, “methyl” Alkylated titanium complexes such as methylated titanium complexes replaced with phenoxy, arylated titanium complexes such as phenylated titanium complexes replaced with “phenyl”, aralkylated titanium complexes such as benzylated titanium complexes replaced with “benzyl”, “methoxides” ”Replaced with a methoxylated titanium complex, Aryloxygenated titanium complexes such as n-butoxylated titanium complexes replaced with “n-butoxide”, alkoxylated titanium complexes such as isopropoxylated titanium complexes replaced with “isopropoxide”, and phenoxylated titanium complexes replaced with “phenoxide” Complexes, aralkyloxytitanium complexes such as benzyloxylated titanium complexes replaced with “benzyloxide”, dimethylamidated titanium complexes replaced with “dimethylamide”, and amidated titanium complexes such as diethylamidated titanium complexes replaced with “diethylamide” It is illustrated as well.

  The transition metal complex of formula (1) is preferably [3-diphenylmethyl-1-trimethylsilyl-cyclopentadienyl] titanium trichloride, [3-di (3-methylphenyl) methyl-1-trimethylsilyl-cyclopenta Dienyl] titanium trichloride, [3-bis (3,5-dimethylphenyl) methyl-1-trimethylsilyl-cyclopentadienyl] titanium trichloride, [3- (1,1-diphenyl-ethyl) -1-trimethylsilyl -Cyclopentadienyl] titanium trichloride, [1- (1,1-diphenyl-pentyl) -cyclopentadienyl] titanium trichloride, [3- (1,1-diphenyl-pentyl) -1-trimethylsilyl-cyclo Pentadienyl] titanium trichloride, 3- (1,1-diphenyl -1-tert-butyl - methyl) -1-trimethylsilyl - such as cyclopentadienyl] titanium trichloride and the like.

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は前記と同義であり

は

を表す。］
で示される置換シクロペンタジエン化合物（以下、置換シクロペンタジエン化合物（２）と略す）と、塩基とを反応させる工程；および
前記置換シクロペンタジエン化合物（２）と塩基との反応物に、
以下の一般式（３）

（式中、Ｍ、Ｘ^１、Ｘ^２及びＸ^３は前記と同義であり、Ｘ^４は、水素原子、ハロゲン原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基、
−Ｓｉ（Ｒ^１６）_３（３つのＲ^１６はそれぞれ独立に、水素原子、ハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、３つのＲ^１６にある炭素原子数の合計が１〜２０である。）で示される置換シリル基、
または−Ｎ（Ｒ^１７）_２（２つのＲ^１７はそれぞれ独立にハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、２つのＲ^１７にある炭素原子数の合計が２〜２０である。）で示される２置換アミノ基を表し、ｍは０または１を表す。）
で示される遷移金属化合物を反応させる工程を有する製造方法により製造することができる。以下、前記置換シクロペンタジエン化合物（２）と塩基とを反応させる工程を「第１反応工程」、前記置換シクロペンタジエン化合物（２）と塩基との反応物に、遷移金属化合物（３）を反応させる工程を「第２反応工程」ということがある。 <Method for producing transition metal complex (1)>
The transition metal complex (1) is represented by, for example, the formula (2)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are Is synonymous with

Is

Represents. ]
A step of reacting a substituted cyclopentadiene compound (hereinafter abbreviated as a substituted cyclopentadiene compound (2)) represented by the following: and a reaction product of the substituted cyclopentadiene compound (2) and the base,
The following general formula (3)

(Wherein, M, X ¹ , X ² and X ³ are as defined above, and X ⁴ is a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or -N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). In which m represents 0 or 1; )
It can manufacture with the manufacturing method which has the process of making the transition metal compound shown by these react. Hereinafter, the step of reacting the substituted cyclopentadiene compound (2) with the base is referred to as “first reaction step”, and the reaction product of the substituted cyclopentadiene compound (2) and the base is reacted with the transition metal compound (3). The process may be referred to as a “second reaction process”.

置換シクロペンタジエニル化合物（２）には、各シクロペンタジエニル環の二重結合位置がそれぞれ異なる異性体が存在するが、本発明においてはそれらのうちのいずれか、またはそれらの混合物を表わす。 In the substituted cyclopentadiene compound (2), isomers different in the position of the double bond of the cyclopentadiene ring are the following structural isomers.

In the substituted cyclopentadienyl compound (2), there are isomers having different double bond positions on each cyclopentadienyl ring. In the present invention, any one of them or a mixture thereof is represented. .

  Examples of the substituted cyclopentadiene compound (2) include the following compounds.

  1-diphenylmethyl-2-methyl-cyclopentadiene, 1-diphenylmethyl-3-methyl-cyclopentadiene, 1-diphenylmethyl-2,3-dimethyl-cyclopentadiene, 1-diphenylmethyl-2,4-dimethyl-cyclo Pentadiene, 1-diphenylmethyl-3,4-dimethyl-cyclopentadiene, 1-diphenylmethyl-2,3,4-trimethyl-cyclopentadiene, 1-diphenylmethyl-2,3,5-trimethyl-cyclopentadiene, 1- Diphenylmethyl-2,3,4,5-tetramethyl-cyclopentadiene, 1-diphenylmethyl-2-ethyl-cyclopentadiene, 1-diphenylmethyl-3-ethyl-cyclopentadiene, 1-diphenylmethyl-2-n- Propyl-cyclopentadiene, 1-di Enylmethyl-3-n-propyl-cyclopentadiene, 1-diphenylmethyl-2-isopropyl-cyclopentadiene, 1-diphenylmethyl-3-isopropyl-cyclopentadiene, 1-diphenylmethyl-2-n-butyl-cyclopentadiene, 1 -Diphenylmethyl-3-n-butyl-cyclopentadiene, 1-diphenylmethyl-2-sec-butyl-cyclopentadiene, 1-diphenylmethyl-3-sec-butyl-cyclopentadiene, 1-diphenylmethyl-2-tert- Butyl-cyclopentadiene, 1-diphenylmethyl-3-tert-butyl-cyclopentadiene, 1-diphenylmethyl-2-phenyl-cyclopentadiene, 1-diphenylmethyl-3-phenyl-cyclopentadiene, 1-dipheni Methyl-2-benzyl-cyclopentadiene, 1-diphenylmethyl-3-benzyl-cyclopentadiene, 1-diphenylmethyl-indene, 1-diphenylmethyl-2-methylindene, 1-diphenylmethyl-tetrahydroindene, 9-diphenylmethyl -Fluorene, 1-diphenylmethyl-2-methyltetrahydroindene, 9-diphenylmethyl-octahydrofluorene

  1-di (3-methylphenyl) methyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2-methyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-methyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2,3-dimethyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2,4-dimethyl-cyclopentadiene, 1-di (3-methylphenyl) methyl -3,4-dimethyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2,3,4-trimethyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2,3,5-trimethyl -Cyclopentadiene, 1-di (3-methylphenyl) methyl-2,3,4,5-tetramethyl-cyclopentadiene, 1-di 3-methylphenyl) methyl-2-ethyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-ethyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2-n-propyl-cyclo Pentadiene, 1-di (3-methylphenyl) methyl-3-n-propyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2-isopropyl-cyclopentadiene, 1-di (3-methylphenyl) methyl -3-isopropyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2-n-butyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-n-butyl-cyclopentadiene, 1- Di (3-methylphenyl) methyl-2-sec-butyl-cyclopentadiene, 1-di (3-methylphenyl) Nyl) methyl-3-sec-butyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2-tert-butyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-tert-butyl- Cyclopentadiene, 1-di (3-methylphenyl) methyl-2-phenyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-phenyl-cyclopentadiene, 1-di (3-methylphenyl) methyl- 2-benzyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-benzyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-indene, 1-di (3-methylphenyl) methyl-2 -Methylindene, 9-di (3-methylphenyl) methyl-fluorene, 1-di (3-methylphenyl) ) Methyl-tetrahydroindene, 1-di (3-methylphenyl) methyl-2-methyltetrahydroindene, 9-di (3-methylphenyl) methyl-octahydrofluorene

  1-bis (3,5-dimethylphenyl) methyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-methyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3 -Methyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2,3-dimethyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2,4-dimethyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3,4-dimethyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2,3,4-trimethyl-cyclopentadiene, 1-bis ( 3,5-dimethylphenyl) methyl-2,3,5-trimethyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) Nyl) methyl-2,3,4,5-tetramethyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-ethyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl -3-ethyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-n-propyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-n-propyl-cyclo Pentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-isopropyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-isopropyl-cyclopentadiene, 1-bis (3,5- Dimethylphenyl) methyl-2-n-butyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl -3-n-butyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-sec-butyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-sec-butyl -Cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-tert-butyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-tert-butyl-cyclopentadiene, 1- Bis (3,5-dimethylphenyl) methyl-2-phenyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-phenyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl 2-benzyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-benzi Ru-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-indene, 1-bis (3,5-dimethylphenyl) methyl-2-methylindene, 9-bis (3,5-dimethylphenyl) methyl -Fluorene, 1-bis (3,5-dimethylphenyl) methyl-tetrahydroindene, 1-bis (3,5-dimethylphenyl) methyl-2-methyltetrahydroindene, 9-bis (3,5-dimethylphenyl) methyl -Octahydrofluorene

  1- (1,1-diphenyl-ethyl) -cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-methyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-methyl- Cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2,3-dimethyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2,4-dimethyl-cyclopentadiene, 1- (1, 1-diphenyl-ethyl) -3,4-dimethyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2,3,4-trimethyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2,3,5-trimethyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2,3,4,5-tetramethyl-cyclopentadiene, 1- ( , 1-diphenyl-ethyl) -2-ethyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-ethyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-n- Propyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-n-propyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-isopropyl-cyclopentadiene, 1- (1, 1-diphenyl-ethyl) -3-isopropyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-n-butyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-n -Butyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-sec-butyl-cyclopentadiene, 1- (1,1-diphe Ru-ethyl) -3-sec-butyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-tert-butyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-tert -Butyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-phenyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-phenyl-cyclopentadiene, 1- (1,1 -Diphenyl-ethyl) -2-benzyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-benzyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -indene, 1- (1 , 1-Diphenyl-ethyl) -2-methylindene, 1- (1,1-diphenyl-ethyl) -tetrahydroindene, 9- (1,1-di Phenyl-ethyl) -fluorene, 1- (1,1-diphenyl-ethyl) -2-methyltetrahydroindene, 9- (1,1-diphenyl-ethyl) -octahydrofluorene

  1- (1,1-diphenyl-pentyl) -cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-methyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-methyl- Cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2,3-dimethyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2,4-dimethyl-cyclopentadiene, 1- (1, 1-diphenyl-pentyl) -3,4-dimethyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2,3,4-trimethyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2,3,5-trimethyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2,3,4,5-tetramethyl-cyclope Tadiene, 1- (1,1-diphenyl-pentyl) -2-ethyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-ethyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl ) -2-n-propyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-n-propyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-isopropyl-cyclopentadiene 1- (1,1-diphenyl-pentyl) -3-isopropyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-n-butyl-cyclopentadiene, 1- (1,1-diphenyl- Pentyl) -3-n-butyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-sec-butyl-cycl Pentadiene, 1- (1,1-diphenyl-pentyl) -3-sec-butyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-tert-butyl-cyclopentadiene, 1- (1,1 -Diphenyl-pentyl) -3-tert-butyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-phenyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-phenyl- Cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-benzyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-benzyl-cyclopentadiene, 1- (1,1-diphenyl- Pentyl) -indene, 1- (1,1-diphenyl-pentyl) -2-methylindene, 1- (1,1-diphe Nyl-pentyl) -tetrahydroindene, 9- (1,1-diphenyl-pentyl) -fluorene, 1- (1,1-diphenyl-pentyl) -2-methyltetrahydroindene, [9- (1,1-diphenyl- Pentyl) -octahydrofluorene

  1- (1,1-diphenyl-1-tert-butyl-methyl) -cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-methyl-cyclopentadiene, 1- (1 , 1-diphenyl-1-tert-butyl-methyl) -3-methyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2,3-dimethyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2,4-dimethyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3,4-dimethyl-cyclo Pentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2,3,4-trimethyl-cyclopentadiene, 1- (1,1-diph Nyl-1-tert-butyl-methyl) -2,3,5-trimethyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2,3,4,5-tetramethyl -Cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-ethyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-ethyl -Cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-n-propyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3 -N-propyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-isopropyl-cyclopentadiene, 1- ( , 1-diphenyl-1-tert-butyl-methyl) -3-isopropyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-n-butyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-n-butyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-sec-butyl-cyclo Pentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-sec-butyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-tert -Butyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-tert-butyl-cyclopentadiene Ene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-phenyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-phenyl-cyclo Pentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-benzyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-benzyl-cyclo Pentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -indene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-methylindene, 1- (1, 1-diphenyl-1-tert-butyl-methyl) -tetrahydroindene, 9- (1,1-diphenyl-1-tert-butyl-methyl) -fluore 1- (1,1-diphenyl -1-tert-butyl - methyl) -2-methyl-tetrahydroindene, 9- (1,1-diphenyl -1-tert-butyl - methyl) - octahydro fluorene

In the transition metal compound (3), the substituent X ⁴ has the same definition as described above, and specific examples thereof include those similar to those described for X ¹ , X ² and X ³ .

  Examples of the transition metal compound (3) include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tetraiodide; tetrakis (dimethylamino) titanium, dichlorobis (dimethylamino) titanium, trichloro. Amido titanium such as (dimethylamino) titanium and tetrakis (diethylamino) titanium; alkoxytitanium such as tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium and trichloroisopropoxytitanium. Moreover, the compound etc. which replaced "titanium" of each of these compounds with "zirconium" or "hafnium" are mentioned. Of these, the preferred transition metal compound (3) is titanium tetrachloride.

  Examples of the base to be reacted with the substituted cyclopentadiene compound (2) in the first reaction step include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, lithium acetylide. Organic alkali metal compounds represented by organic lithium compounds such as trimethylsilylmethyl lithium, vinyl lithium, phenyl lithium and allyl lithium.

  The usage-amount of a base should just be the range of 0.5-5 mol per 1 mol of substituted cyclopentadienyl compounds (2).

  In the reaction of the substituted cyclopentadiene compound (2) and the base in the first reaction step, an amine compound may be used together with the organic alkali metal compound. Examples of such amine compounds include primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline, and ethylenediamine; Amine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane, diphenylamine, etc. Secondary amine compounds; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenylamine Emissions, N, N- dimethylaniline, N, N, N ', N'-tetramethylethylenediamine, N- methylpyrrolidine, 4-tertiary amine compounds such as dimethylaminopyridine; and the like. The amount of the amine compound used is preferably 10 mol or less, more preferably 0.5 to 10 mol, and even more preferably 1 to 5 mol per mol of the organic alkali metal compound. .

  In the first reaction step, when the substituted cyclopentadiene compound (2) is reacted with a base, it is preferably reacted in the presence of a solvent. When a solvent is used, after reacting the substituted cyclopentadiene compound (2) and the base in the solvent, the transition metal compound (3) is added to the reaction mixture, whereby the substituted cyclopentadiene compound (2) and The transition metal compound (3) can be further reacted with the base reactant. A solid may precipitate in the reaction mixture obtained by reacting the substituted cyclopentadiene compound (2) and the base. In this case, a solvent is added until the precipitated solid is dissolved, or the precipitated solid is removed. It may be separated once by filtration or the like, and a transition metal compound (3) may be added after a solvent is added to the separated solid to be dissolved or suspended. When a solvent is used, the first reaction step and the second reaction step can be carried out substantially simultaneously by simultaneously adding the substituted cyclopentadiene compound (2), the base and the transition metal compound (3) to the solvent. .

  As the solvent used in the first reaction step or the first reaction step and the second reaction step, an inert solvent that does not significantly disturb the progress of the reaction related to these steps is used. Examples of such solvents include aromatic hydrocarbyl solvents such as benzene and toluene; aliphatic hydrocarbyl solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; hexa Amide solvents such as methylphosphoric amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; non-protons such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Examples of the solvent are exemplified. Such solvents can be used alone or in admixture of two or more, and the amount used is preferably 1 to 200 parts by weight, more preferably 3 to 50 parts by weight per 1 part by weight of the substituted cyclopentadiene compound (2). .

  The amount of the transition metal compound (3) used is preferably in the range of 0.5 to 3 mol, more preferably in the range of 0.7 to 1.5 mol, per mol of the substituted cyclopentadiene compound (2).

  The reaction temperature in the first reaction step and the second reaction step may be −100 ° C. or more and not more than the boiling point of the solvent, and is preferably in the range of −80 to 100 ° C.

  Thus, the produced transition metal complex (1) can be taken out from the reaction mixture obtained through the first reaction step and the second reaction step by various known purification methods. For example, after the first reaction step and the second reaction step, after the generated precipitate is filtered, the filtrate is concentrated to precipitate a transition metal complex, and then the target transition metal complex ( 1) can be obtained.

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は前記と同義であり、Ｄは、ケイ素原子またはスズ原子であり、
Ｒ^１８、Ｒ^１９及びＲ^２０は、
それぞれ独立に、水素原子、ハロゲン原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基、
−Ｓｉ（Ｒ^１６）_３（３つのＲ^１６はそれぞれ独立に、水素原子、ハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、３つのＲ^１６にある炭素原子数の合計が１〜２０である。）で示される置換シリル基、
または−Ｎ（Ｒ^１７）_２（２つのＲ^１７はそれぞれ独立にハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、２つのＲ^１７にある炭素原子数の合計が２〜２０であり、

は

を表す。］
で示される置換シクロペンタジエン化合物（以下、置換シクロペンタジエン化合物（４）と略す）
以下の一般式（３）

（式中、Ｍ、Ｘ^１、Ｘ^２及びＸ^３は前記と同義であり、Ｘ^４は、水素原子、ハロゲン原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基、
−Ｓｉ（Ｒ^１６）_３（３つのＲ^１６はそれぞれ独立に、水素原子、ハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、３つのＲ^１６にある炭素原子数の合計が１〜２０である。）で示される置換シリル基、
または−Ｎ（Ｒ^１７）_２（２つのＲ^１７はそれぞれ独立にハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、２つのＲ^１７にある炭素原子数の合計が２〜２０である。）で示される２置換アミノ基を表し、ｍは０または１を表す。）
で示される遷移金属化合物を反応させる工程を有する製造方法により製造することができる。 <Method for producing transition metal complex (1)>
The transition metal complex (1) is, for example, the formula (4)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are D is a silicon atom or a tin atom,
R ¹⁸ , R ¹⁹ and R ²⁰ are
Each independently a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or —N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20,

Is

Represents. ]
A substituted cyclopentadiene compound represented by the following (hereinafter abbreviated as a substituted cyclopentadiene compound (4))
The following general formula (3)

(Wherein, M, X ¹ , X ² and X ³ are as defined above, and X ⁴ is a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or -N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). In which m represents 0 or 1; )
It can manufacture with the manufacturing method which has the process of making the transition metal compound shown by these react.

置換シクロペンタジエン化合物（４）には、各シクロペンタジエニル環の二重結合位置がそぞれ異なる異性体が存在するが、本発明においてはそれらのうちのいずれか、またはそれらの混合物を表わす。 In the substituted cyclopentadiene compound (4), isomers different in the position of the double bond of the cyclopentadiene ring are the following structural isomers.

In the substituted cyclopentadiene compound (4), there are isomers each having a different double bond position on each cyclopentadienyl ring. In the present invention, any one of them or a mixture thereof is represented. .

  In the substituted cyclopentadiene compound (4), D is a silicon atom or a tin atom. Among these, a silicon atom is preferable.

  Examples of the substituted cyclopentadiene compound (4) include the following compounds.

  1-diphenylmethyl-2-methyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3-methyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2,3-dimethyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2,3,4-trimethyl-3 -Trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2,3,5-trimethyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2,3,4,5-tetramethyl-3-trimethylsilyl-cyclopentadiene 1-diphenylmethyl-2-ethyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3-ethyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2-n-propyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3-n-propyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2-isopropyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3-isopropyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2-n-butyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3-n-butyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2 sec-butyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3-sec-butyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2-tert-butyl-3-trimethylsilyl-cyclopentadiene, 1-diphenyl Methyl-3-tert-butyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-2-phenyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3-phenyl-3-trimethylsilyl-cyclopentadiene, 1-diphenyl Methyl-2-benzyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3-benzyl-3-trimethylsilyl-cyclopentadiene, 1-diphenylmethyl-3-trimethylsilyl Ru-indene, 1-diphenylmethyl-2-methyl-3-trimethylsilyl-indene, 1-diphenylmethyl-3-trimethylsilyl-tetrahydroindene, 9-diphenylmethyl-9-trimethylsilyl-fluorene, 1-diphenylmethyl-2-methyl -3-trimethylsilyl-tetrahydroindene, 9-diphenylmethyl-9-trimethylsilyl-octahydrofluorene

  1-di (3-methylphenyl) methyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2-methyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl -3-methyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2,3-dimethyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2,4 -Dimethyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2,3,4 -Trimethyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methyl Enyl) methyl-2,3,5-trimethyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2,3,4,5-tetramethyl-3-trimethylsilyl-cyclopentadiene, 1- Di (3-methylphenyl) methyl-2-ethyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-ethyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) ) Methyl-2-n-propyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-n-propyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl 2-Isopropyl-3-trimethylsilyl-cyclopentadiene, 1-di 3-methylphenyl) methyl-3-isopropyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2-n-butyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) ) Methyl-3-n-butyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2-sec-butyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl -3-sec-butyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-2-tert-butyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3 -Tert-butyl-3-trimethylsilyl-cyclopentadi 1-di (3-methylphenyl) methyl-2-phenyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-phenyl-3-trimethylsilyl-cyclopentadiene, 1-di ( 3-methylphenyl) methyl-2-benzyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl-3-benzyl-3-trimethylsilyl-cyclopentadiene, 1-di (3-methylphenyl) methyl -3-trimethylsilyl-indene, 1-di (3-methylphenyl) methyl-2-methyl-3-trimethylsilyl-indene, 9-di (3-methylphenyl) methyl-9-trimethylsilyl-fluorene, 1-di (3 -Methylphenyl) methyl-3-trimethylsilyl-tetrahydroin Emissions, 1- di (3-methylphenyl) methyl-2-methyl-3-trimethylsilyl - tetrahydroindene, 9- di (3-methylphenyl) methyl-9-trimethylsilyl - octahydro fluorene

  1-bis (3,5-dimethylphenyl) methyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-methyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3 5-dimethylphenyl) methyl-3-methyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2,3-dimethyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3 5-dimethylphenyl) methyl-2,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1-bis ( 3,5-dimethylphenyl) methyl-2,3,4-trimethyl-3- Limethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2,3,5-trimethyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2,3 4,5-tetramethyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-ethyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl -3-ethyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-n-propyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl -3-n-propyl-3-trimethylsilyl-cyclopentadiene 1-bis (3,5-dimethylphenyl) methyl-2-isopropyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-isopropyl-3-trimethylsilyl-cyclopentadiene, 1- Bis (3,5-dimethylphenyl) methyl-2-n-butyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-n-butyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-2-sec-butyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-sec-butyl-3-trimethylsilyl-cyclo Pentadiene, 1-bis (3,5-dimethylphenyl) methyl 2-tert-butyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-tert-butyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) ) Methyl-2-phenyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-phenyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl 2-benzyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3-benzyl-3-trimethylsilyl-cyclopentadiene, 1-bis (3,5-dimethylphenyl) methyl-3 -Trimethylsilyl-indene, 1-bis (3,5 Dimethylphenyl) methyl-2-methyl-3-trimethylsilyl-indene, 9-bis (3,5-dimethylphenyl) methyl-9-trimethylsilyl-fluorene, 1-bis (3,5-dimethylphenyl) methyl-3-trimethylsilyl -Tetrahydroindene, 1-bis (3,5-dimethylphenyl) methyl-2-methyl-3-trimethylsilyl-tetrahydroindene, 9-bis (3,5-dimethylphenyl) methyl-9-trimethylsilyl-octahydrofluorene

  1- (1,1-diphenyl-ethyl) -3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-methyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl) -Ethyl) -3-methyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2,3-dimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl ) -2,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) ) -2,3,4-trimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diph) Nyl-ethyl) -2,3,5-trimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2,3,4,5-tetramethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-ethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-ethyl-3-trimethylsilyl-cyclopentadiene, 1- (1 , 1-diphenyl-ethyl) -2-n-propyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-n-propyl-3-trimethylsilyl-cyclopentadiene, 1- (1 , 1-diphenyl-ethyl) -2-isopropyl-3-trimethylsilyl-cyclopentadiene, 1- ( , 1-diphenyl-ethyl) -3-isopropyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-n-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1 -Diphenyl-ethyl) -3-n-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-sec-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1 -Diphenyl-ethyl) -3-sec-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -2-tert-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1 -Diphenyl-ethyl) -3-tert-butyl-3-trimethylsilyl-cyclopentadi 1- (1,1-diphenyl-ethyl) -2-phenyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-phenyl-3-trimethylsilyl-cyclopentadiene, (1,1-diphenyl-ethyl) -2-benzyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-ethyl) -3-benzyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1 -Diphenyl-ethyl) -3-trimethylsilyl-indene, 1- (1,1-diphenyl-ethyl) -2-methyl-3-trimethylsilyl-indene, 1- (1,1-diphenyl-ethyl) -3-trimethylsilyl- Tetrahydroindene, 9- (1,1-diphenyl-ethyl) -9-trimethylsilyl-fluor Emissions, 1- (1,1-diphenyl-ethyl) - 2-methyl-3-trimethylsilyl - tetrahydroindene, 9- (1,1-diphenyl-ethyl) - 9-trimethylsilyl - octahydro fluorene

  1- (1,1-diphenyl-pentyl) -3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-methyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl) -Pentyl) -3-methyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2,3-dimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) ) -2,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) ) -2,3,4-trimethyl-3-trimethylsilyl-cyclopentadiene, 1- 1,1-diphenyl-pentyl) -2,3,5-trimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2,3,4,5-tetramethyl-3-trimethylsilyl -Cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-ethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-ethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-n-propyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-n-propyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-isopropyl-3-trimethylsilyl Cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-isopropyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-n-butyl-3-trimethylsilyl-cyclopentadiene 1- (1,1-diphenyl-pentyl) -3-n-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-sec-butyl-3-trimethylsilyl-cyclopentadiene 1- (1,1-diphenyl-pentyl) -3-sec-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-tert-butyl-3-trimethylsilyl-cyclopentadiene 1- (1,1-diphenyl-pentyl) -3-tert-butyl Tyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-phenyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-phenyl-3- Trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -2-benzyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-pentyl) -3-benzyl-3-trimethylsilyl-cyclopentadiene 1- (1,1-diphenyl-pentyl) -3-trimethylsilyl-indene, 1- (1,1-diphenyl-pentyl) -2-methyl-3-trimethylsilyl-indene, 1- (1,1-diphenyl- Pentyl) -3-trimethylsilyl-tetrahydroindene, 9- (1 1-diphenyl-pentyl) -9-trimethylsilyl-fluorene, 1- (1,1-diphenyl-pentyl) -2-methyl-3-trimethylsilyl-tetrahydroindene, [9- (1,1-diphenyl-pentyl) -9 -Trimethylsilyl-octahydrofluorene

  1- (1,1-diphenyl-1-tert-butyl-methyl) -3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-methyl-3-trimethylsilyl -Cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-methyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2,3-dimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2,4-dimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1, 1-diphenyl-1-tert-butyl-methyl) -3,4-dimethyl-3-trimethylsilyl-cyclope Tadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2,3,4-trimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl- Methyl) -2,3,5-trimethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2,3,4,5-tetramethyl-3-trimethylsilyl -Cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-ethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-ethyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl ) -2-n-propyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-n-propyl-3-trimethylsilyl-cyclopentadiene, 1- (1 , 1-Diphenyl-1-tert-butyl-methyl) -2-isopropyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-isopropyl-3-trimethylsilyl -Cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-n-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl- Methyl) -3-n-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-di) Phenyl-1-tert-butyl-methyl) -2-sec-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-sec-butyl-3- Trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-tert-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl -Methyl) -3-tert-butyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-phenyl-3-trimethylsilyl-cyclopentadiene, 1- (1 , 1-Diphenyl-1-tert-butyl-methyl) -3-phenyl-3-trimethyl Silyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -2-benzyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl ) -3-Benzyl-3-trimethylsilyl-cyclopentadiene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-trimethylsilyl-indene, 1- (1,1-diphenyl-1-tert- Butyl-methyl) -2-methyl-3-trimethylsilyl-indene, 1- (1,1-diphenyl-1-tert-butyl-methyl) -3-trimethylsilyl-tetrahydroindene, 9- (1,1-diphenyl-1 -Tert-butyl-methyl) -9-trimethylsilyl-fluorene, 1- (1,1-diphenyl) -1-tert-butyl - methyl) -2-methyl-3-trimethylsilyl - tetrahydroindene, 9- (1,1-diphenyl -1-tert-butyl - methyl) -9-trimethylsilyl - octahydro fluorene

  And trimethylsilyl-substituted cyclopentadiene compounds. Further, in the complexes exemplified here, a triethylsilyl-substituted cyclopentadiene compound in which “trimethylsilyl” is replaced with “triethylsilyl”, or a tert-butyldimethylsilyl-substituted cyclopentadiene compound in which “tert-butyldimethylsilyl” is replaced, Triisopropylsilyl-substituted cyclopentadiene compound replaced with “isopropylsilyl”, chlorodimethylsilyl-substituted cyclopentadiene compound replaced with “chlorodimethylsilyl”, dichloromethylsilyl-substituted cyclopentadiene compound replaced with “dichloromethylsilyl”, “trichlorosilyl” The trichlorosilyl-substituted cyclopentadiene compound replaced with “trimethyltin”, the trimethyltin-substituted cyclopentadiene compound replaced with “trimethyltin”, “tri- - tri -n- butyltin substituted cyclopentadiene compound is replaced with butyltin "it is also illustrated in the same manner.

  When the substituted cyclopentadiene compound (4) and the transition metal complex (3) are reacted, it is preferably reacted in the presence of a solvent. Moreover, when using a solvent, it can be made to react by adding a transition metal compound (3) to a substituted cyclopentadiene compound (4) in this solvent. Moreover, when using a solvent, a substituted cyclopentadiene compound (4) and a transition metal compound (3) can also be simultaneously added to this solvent.

  As the solvent to be used, an inert solvent that does not significantly impede the progress of the reaction related to these steps is used. Examples of such solvents include aromatic hydrocarbyl solvents such as benzene and toluene; aliphatic hydrocarbyl solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; hexa Amide solvents such as methylphosphoric amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; non-protons such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Examples of the solvent are exemplified. Such solvents can be used alone or in admixture of two or more, and the amount used is preferably 1 to 200 parts by weight, more preferably 3 to 50 parts by weight per 1 part by weight of the substituted cyclopentadiene compound (4). .

  The amount of the transition metal compound (3) used is preferably in the range of 0.5 to 3 mol, more preferably in the range of 0.7 to 1.5 mol, per mol of the substituted cyclopentadiene compound (4).

  The reaction temperature should just be -100 degreeC or more and below the boiling point of a solvent, Preferably it is the range of -80-100 degreeC.

  From the reaction mixture thus obtained, the produced transition metal complex (1) can be taken out by various known purification methods. For example, after the produced precipitate is filtered off, the filtrate is concentrated to precipitate a transition metal complex, and then the desired transition metal complex (1) can be obtained by, for example, filtering it.

<Activation promoter component>
Examples of the activation promoter component include the following compound (A) and compound (B). Compound (A) and compound (B) may be used in combination.
Compound (A): One or more aluminum compounds selected from the group consisting of the following compounds (A1), (A2) and (A3) (A1): General formula (E ¹ ) _a Al (G) _3-a organoaluminum compounds represented (A2): the general formula ^{-Al (E 2) _-O-} cyclic aluminoxane (A3) having the structure represented by _b: formula ^{E 3 {-Al (E 3)} - A linear aluminoxane having a structure represented by O—} _c Al (E ³ ) ₂ (wherein E ¹ , E ² and E ³ represent a hydrocarbyl group having 1 to 8 carbon atoms; represents a hydrogen atom or a halogen atom, a is an integer of 1 to 3, b represents an integer of 2 or more, when c have a plurality .E ¹ is representing an integer of 1 or more, a plurality of E ¹ is May be the same or different from each other. , A plurality of G may be each the same or different. A plurality of E ² may be different from one another the same. Plurality of E ³ may be different be the same as each other .)
Compound (B): at least one boron compound selected from the group consisting of the following compounds (B1), (B2) and (B3) (B1): a boron compound represented by the general formula BQ ¹ Q ² Q ³ B2): Borate compound represented by general formula T ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (B3): General formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ Borate compounds (wherein B represents a boron atom in a trivalent valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ are the same or different and are each substituted with a halogen atom or a halogen atom) A C1-C20 hydrocarbyl group, a C1-C20 hydrocarbylsilyl group, a C1-C20 alkoxy group or a C2-C20 dihydrocarbylamino group the stands, ^{T +} is It represents machine or organic cation, represents the (L-H) ⁺ is a Bronsted acid.)

In the compounds (A1) to (A3), examples of the hydrocarbyl group having 1 to 8 carbon atoms in E ¹ , E ² and E ³ include alkyl having 1 to 8 carbon atoms, Examples of the alkyl group having 1 to 8 include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group, and a neopentyl group.

Examples of the organoaluminum compound (A1) represented by the general formula (E ¹ ) _a Al (G) _3-a include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Examples of the alkylaluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum. Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, Examples include diisobutylaluminum chloride and dihexylaluminum chloride. Examples of the nium dichloride include methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride. Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, and dipropylaluminum. Examples include hydride, diisobutylaluminum hydride, and dihexylaluminum hydride.

(A2): a cyclic aluminoxane having a structure represented by the formula {—Al (E ² ) —O—} _b or (A3) formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ Examples of E ² and E ³ in the linear aluminoxane having the structure represented include alkyl such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, and neopentyl group. Group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are each independently a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

  The above aluminoxane can be made by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to make according to a well-known method. For example, a solution obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (benzene, aliphatic hydrocarbyl, etc.) is made to contact with water. Moreover, the method of making a trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.

In the compounds (B1) to (B3), Q ¹ , Q ² , Q ³ and Q ⁴ are preferably a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom. is there. Examples of the inorganic cation for T ⁺ include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation. Examples of the organic cation include a triphenylmethyl cation. (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ includes, for example, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5- Tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5 -Bistrifluoromethylphenyl) borate and the like. Examples of (L—H) ⁺ that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.

Examples of the boron compound (B1) represented by the general formula BQ ¹ Q ² Q ³ include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2, 3,4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, etc. Can be mentioned.

Examples of the borate compound (B2) represented by the general formula T ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include ferrocenium tetrakis (pentafluorophenyl) borate and 1,1′-bis-trimethylsilylferrocete. Examples thereof include nium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (pentafluorophenyl) borate, and triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate.

Examples of the borate compound (B3) represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluoro). Phenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) Borate, N, N-bis-trimethylsilylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4 -Pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-bis-trimethylsilylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (penta Fluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (bis-trimethylsilylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate and the like.

<Trimerization catalyst>
The trimerization catalyst of the present invention is a trimerization catalyst obtained by bringing the transition metal complex (1) and the activation promoter component into contact with each other. Ethylene is trimerized to produce 1-hexene. It is a catalyst that can.

  Examples of the activation promoter component include the compounds (A) and (B). Moreover, you may use a compound (A) and a compound (B) together.

  The amount of each catalyst component used is the molar ratio of the compound (A) (in terms of aluminum atoms) to the transition metal complex (1) used as the catalyst component (compound (A) (in terms of aluminum atoms) / transition metal complex (1). ) Is usually from 0.01 to 10,000, preferably from 5 to 5,000. The molar ratio of the compound (B) and the transition metal complex (1) used as the catalyst component (compound (B) / transition metal complex (1)) is usually 0.01-100, preferably 0.5-10. It is.

  When each catalyst component is used in a solution state, the concentration of the transition metal complex (1) used as the catalyst component is usually 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter. is there. The concentration of the compound (A) is usually 0.01 to 500 mmol / liter, preferably 0.1 to 100 mmol / liter, in terms of aluminum atoms. The concentration of the compound (B) is usually 0.0001 to 5 mmol / liter, and preferably 0.001 to 1 mmol / liter.

  The method for contacting each catalyst component is not particularly limited. The transition metal complex (1) and the activation promoter component may be contacted in advance to prepare a trimerization catalyst, and the trimerization catalyst may be supplied to the reactor. Alternatively, the catalyst components may be supplied to the reactor in an arbitrary order, and contact treatment may be performed in the reactor.

<Method for producing 1-hexene>
The method for producing 1-hexene of the present invention is a method for producing 1-hexene by trimerizing ethylene in the presence of a trimerization catalyst.

  The trimerization reaction is not particularly limited. For example, aliphatic hydrocarbyl such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbyl such as benzene and toluene, or methylene dichloride and chlorobenzene. A trimerization reaction using a hydrocarbyl halide as a solvent, a trimerization reaction in a slurry state, a trimerization reaction in gaseous ethylene, or the like is possible.

  The trimerization reaction can be carried out in any of batch, semi-continuous and continuous methods.

  The pressure of ethylene is usually from normal pressure to 10 MPa, preferably from normal pressure to 5 MPa.

  The temperature of the trimerization reaction can usually range from -50 ° C to 220 ° C. Preferably it is the range of 0 degreeC-170 degreeC.

  The time for the trimerization reaction is generally appropriately determined depending on the intended reaction apparatus, but can be in the range of 1 minute to 20 hours.

Hereinafter, the present invention will be described by way of examples.
<Production of transition metal complex>
The physical properties were measured by the following method.
(1) Proton nuclear magnetic resonance spectrum ( ¹ H-NMR)
Device: DPX300 manufactured by BRUKER
Sample cell: 5 mmφ tube Measurement solvent: CDCl ₃
Sample concentration: about 10 mg / 0.5 mL
Measurement temperature: room temperature (about 25 ° C)
Measurement parameters: 5 mmφ probe, EXMOD NON, OBNUC ¹ H, integration number 16 times or more Repeat time: ACQTM 6 seconds, PD 1 second Internal standard: CDCl ₃ (7.26 ppm)
(2) Carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR)
Device: DPX300 manufactured by BRUKER
Sample cell: 5 mmφ tube Measurement solvent: CDCl ₃
Sample concentration: about 10 mg / 0.5 mL
Measurement temperature: room temperature (about 25 ° C)
Measurement parameters: 5 mmφ probe, EXMOD zgpg30, OBNUC ¹³ C, integration number 256 times or more Repeat time: ACQTM 1.4 seconds, PD 2 seconds Internal standard: CDCl ₃ (77.0 ppm)
(3) Electron ionization mass spectrometry (EI-MS)
Device: JMS-T100GC manufactured by JEOL Ltd.
Ionization voltage: 70 eV
Ion source temperature: 230 ° C
Acceleration voltage: 7 kV
MASS RANGE: m / z 35-1200
(4) Field desorption mass spectrometry (FD-MS)
Device: JMS-700 manufactured by JEOL Ltd.
Acceleration voltage: 8 kV
Cathode: 0 kV
Carbon emitter MASS RANGE: m / z 10-2000

[Example 1]
“Synthesis of [1- (1,1-diphenyl-pentyl) -cyclopentadienyl] titanium trichloride (hereinafter referred to as“ complex 1 ”)”

Synthesis of “1-trimethylsilyl-3- (1,1-diphenyl-pentyl) -cyclopentadiene” Under a nitrogen atmosphere, a 1.65 M hexane solution of n-butyllithium (27.37 mL, 45.16 mmol), diethyl ether (40 mL) ) Was added. The mixture was cooled to 0 ° C., and a solution of 6,6-diphenylfulvene (8.00 g, 34.74 mmol) dissolved in diethyl ether (160 mL) was added dropwise. After raising the temperature to room temperature, the mixture was stirred at that temperature for 2 hours. Chlorotrimethylsilane (7.55 g, 69.47 mmol) was added dropwise to the obtained mixture at 0 ° C., and then the mixture was heated to room temperature. After the reaction, the solvent was concentrated under reduced pressure, and toluene and a saturated aqueous sodium hydrogen carbonate solution were added to the residue for liquid separation. The oil phase was dried over sodium sulfate, filtered and the solvent was concentrated under reduced pressure. Purification by silica gel column chromatography gave 1-trimethylsilyl-3- (1,1-diphenyl-pentyl) -cyclopentadiene (2.27 g, yield 18.1%).
¹ H-NMR (CDCl ₃ , δ ppm): −0.05 (s, 9H), 0.88 (t, J = 7.3 Hz, 3H), 1.08-1.20 (m, 2H), 1 .34 (quant, J = 7.3 Hz, 2H), 2.38-2.50 (m, 2H), 3.27 (s, 1H), 6.16 (brs, 1H), 6.40- 6.44 (m, 1H), 6.47-6.51 (m, 1H), 7.10-7.32 (m, 10H)
Mass spectrum (EI-MS, m / z): 360 (M ⁺ )

“Synthesis of Complex 1”
To a toluene solution (30 mL) of 1-trimethylsilyl-3- (1,1-diphenylpentyl) -cyclopentadiene (1.12 g, 3.10 mmol) in a nitrogen atmosphere at −30 ° C., titanium tetrachloride (0.65 g, A solution in which 3.41 mmol) was dissolved in toluene (8 mL) was added dropwise. The temperature was raised and the mixture was stirred at room temperature for 6 days. After the reaction, the solvent was concentrated under reduced pressure, and then the solid obtained by adding pentane to the residue was filtered, washed with a small amount of pentane, and dried under reduced pressure to give complex 1 (0.92 g, yield 66). 0.9%) as a yellow solid.
¹ H-NMR (CDCl ₃ , δ ppm): 0.88 (t, J = 7.3 Hz, 3H), 1.11-1.24 (m, 2H), 1.37 (quint, J = 7.3 Hz) 2H), 2.73-2.82 (m, 2H), 6.91 (t, J = 2.9 Hz, 2H), 7.01-7.11 (m, 4H), 7.09 (t , J = 2.9 Hz, 2H), 7.19-7.34 (m, 6H)
¹³ C-NMR (CDCl ₃ , δ ppm): 13.99, 23.23, 27.43, 38.54, 54.23, 122.87, 123.17, 126.90, 128.05, 129.45 144.89, 152.65
Mass spectrum (EI-MS, m / z): 440 (M ⁻ )

<Production of 1-hexene>
(1) The analysis was performed using 1-hexene active gas chromatography (Shimadzu GC-2010, DB-1 column).

[Example 2]
After drying under reduced pressure, in a 0.4 liter autoclave with a stirrer substituted with argon, 60 mL of toluene and a toluene solution of methylaluminoxane having an Al concentration of 9.0 wt% (3.5 mmol / mL) (TMAO- manufactured by Tosoh Finechem) s) After charging 0.88 mL and raising the temperature in the system to 40 ° C., ethylene was introduced to 0.5 MPa to stabilize the system. To this, 0.60 mL of a toluene solution of Complex 1 (1 μmol / mL) was added. During the reaction, while continuously supplying ethylene gas so as to keep the total pressure constant, the reaction was performed at 40 ° C. for 30 minutes, and 1.0 mL of ethanol was added to stop the reaction. Thereafter, ethylene was purged, and the contents in the autoclave were deashed with ethanol-hydrochloric acid and filtered. 1-hexene was obtained with an activity of 5.1 × 10 ⁵ g / mol complex / h, and 21 mg of polymer was obtained.

Claims (10)

A transition metal complex represented by the following general formula (1).
General formula (1)

(In the formula, M represents a transition metal atom of Group 4 of the periodic table of elements,
X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ Are independent of each other
Hydrogen atom, halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or -N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). Represents a disubstituted amino group represented by:
R ¹⁵ is
Hydrogen atom, halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or -N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). Represents a disubstituted amino group represented by:
At least ^{one of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is A halogen atom, the alkyl group, the alkoxy group, the aryloxy group, the aralkyl group, the aralkyloxy group, the substituted silyl group, or the disubstituted amino group,
Of R ¹ , R ² , R ³ and R ⁴ , two groups bonded to two adjacent carbon atoms are bonded to form a ring together with the two carbon atoms to which the two groups are bonded. Of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , two groups bonded to two adjacent carbon atoms are bonded to each other, and the two groups are bonded to each other. May form a ring together with two carbon atoms present, and two groups bonded to two adjacent carbon atoms among R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are bonded. Then, the two carbon atoms to which the two groups are bonded may form a ring. )   The transition metal complex according to claim 1, wherein M in the general formula (1) is a titanium atom. The transition metal complex according to claim 1 or 2, wherein R ¹⁵ in the general formula (1) is an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent.   A trimerization catalyst component comprising the transition metal complex according to claim 1.   The trimerization catalyst obtained by making the transition metal complex in any one of Claims 1-3 and an activation promoter component contact. The trimerization catalyst according to claim 5, wherein the activation promoter component contains the following compound (A).
Compound (A): One or more aluminum compounds selected from the group consisting of the following compounds (A1), (A2) and (A3) (A1): General formula (E ¹ ) _a Al (G) _3-a organoaluminum compounds represented (A2): the general formula ^{-Al (E 2) _-O-} cyclic aluminoxane (A3) having the structure represented by _b: formula ^{E 3 {-Al (E 3)} - A linear aluminoxane having a structure represented by O—} _c Al (E ³ ) ₂ (wherein E ¹ , E ² and E ³ represent a hydrocarbyl group having 1 to 8 carbon atoms; represents a hydrogen atom or a halogen atom, a is an integer of 1 to 3, b represents an integer of 2 or more, when c have a plurality .E ¹ is representing an integer of 1 or more, a plurality of E ¹ is May be the same or different from each other. , A plurality of G may be each the same or different. A plurality of E ² may be different from one another the same. Plurality of E ³ may be different be the same as each other .) The trimerization catalyst according to claim 5 or 6, wherein the activation promoter component contains the following compound (B).
Compound (B): at least one boron compound selected from the group consisting of the following compounds (B1), (B2) and (B3) (B1): a boron compound represented by the general formula BQ ¹ Q ² Q ³ B2): Borate compound represented by general formula T ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (B3): General formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ Borate compounds (wherein B represents a boron atom in a trivalent valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ are the same or different and are each substituted with a halogen atom or a halogen atom) A C1-C20 hydrocarbyl group, a C1-C20 hydrocarbylsilyl group, a C1-C20 alkoxy group or a C2-C20 dihydrocarbylamino group the stands, ^{T +} is It represents machine or organic cation, represents the (L-H) ⁺ is a Bronsted acid.)   A process for producing 1-hexene, wherein ethylene is trimerized in the presence of the trimerization catalyst according to any one of claims 5 to 7. General formula (2)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are Is synonymous with

Is

Represents. ]
A step of reacting a substituted cyclopentadiene compound represented by the following: with a base; and a reaction product of the substituted cyclopentadiene compound (2) with a base,
The following general formula (3)

(Wherein, M, X ¹ , X ² and X ³ are as defined above, and X ⁴ is a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or -N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). In which m represents 0 or 1; )
The manufacturing method of the transition metal complex represented by General formula (1) of Claim 1 which has the process with which the transition metal compound shown by these is made to react. General formula (4)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are D is a silicon atom or a tin atom,
R ¹⁸ , R ¹⁹ and R ²⁰ are
Each independently a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or —N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20,

Is

Represents. ]
A substituted cyclopentadiene compound represented by the following general formula (3)

(Wherein, M, X ¹ , X ² and X ³ are as defined above, and X ⁴ each independently represents a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹⁶ ) ₃ (three R ¹⁶ each independently represents a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ¹⁶ is 1 to 20; A substituted silyl group represented by:
Or -N (R ¹⁷ ) ₂ (two R ¹⁷ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ¹⁷ is 2 to 20). In which m represents 0 or 1; )
The manufacturing method of the transition metal complex represented by General formula (1) of Claim 1 which has the process with which the transition metal compound shown by these is made to react.