JP2013184926A - Method for producing silicon-substituted cyclopentadienyl titanium trihalide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method by which a silicon-substituted cyclopentadienyl titanium trihalide is efficiently produced.SOLUTION: A method for producing a silicon-substituted cyclopentadienyl titanium trihalide represented by general formula (1) includes a step (i), a step (ii), and a step (iii).

Description

  The present invention relates to a method for producing a silicon-substituted cyclopentadienyl titanium trihalide.

  Cyclopentadienyl titanium trihalide is usually a reaction involving the bond breakage of a carbon atom and a silicon atom of cyclopentadiene (hereinafter abbreviated as desilylation reaction) by reacting silicon-substituted cyclopentadiene with titanium halide. (See Non-Patent Document 1, for example). For this reason, in order to obtain silicon-substituted cyclopentadienyl titanium trihalide by the desilylation reaction, it is necessary to introduce two silicon substituents into cyclopentadiene (for example, Non-patent Documents 2 and 3). reference).

  In addition, as a method for obtaining silicon-substituted cyclopentadienyl titanium trihalide, a tin-substituted cyclopentadidi having a trimethyltin substituent introduced by reacting a reaction product of silicon-substituted cyclopentadiene with n-butyllithium with trimethyltin chloride. It has been reported that silicon-substituted cyclopentadienyl titanium trihalide can be obtained by synthesizing an enyl compound and then reacting with titanium halide, resulting in a reaction involving bond breakage of the carbon atom and tin atom of cyclopentadiene. However, this method requires the use of trimethyltin chloride, which is harmful to the human body.

  Synthesis of cyclopentadienyl titanium trihalide having a phenyl group-containing silicon atom as a substituent is obtained by reacting n-butyllithium with a corresponding silicon-substituted cyclopentadiene, and halogen-substituted cyclopentadienyl lithium. It is synthesized by reaction with titanium fluoride (see, for example, Non-Patent Document 6). Similarly, cyclopentadienyl titanium trihalide having a silicon atom having an aryl group as a substituent is obtained by reacting a corresponding cyclopentadiene compound with n-butyllithium in the presence of an amine, and then titanium halide. Has been reported (for example, see Patent Document 1), but the yield of the target silicon-substituted cyclopentadienyl titanium trihalide may not be good depending on the substituents on silicon. It was.

  On the other hand, as a method of synthesizing cyclopentadienyl titanium trihalide, after synthesizing cyclopentadienyl titanium trialkoxide by reaction of cyclopentadienyl lithium with titanium halide trialkoxide, silicon tetrachloride or boron trichloride is synthesized. Has been reported to be chlorinated (see, for example, Patent Document 2). This method of synthesizing cyclopentadienyl titanium trihalide has been shown to be suitable for cyclopentadiene compounds having an alkyl substituent of 1 to 6 carbon atoms. No synthesis is disclosed.

Japanese Patent Application Laid-Open No. 2011-98954 US Pat. No. 6,531,619

Organometallics 1989, 8, 105-119. J. et al. Am. Chem. Soc. 2000, 122, 5499-5509. J. et al. Mol. Catal. A: Chem. 2006, 257, 14-25. Organometallics 2004, 23, 2850-2854. J. et al. Organomet. Chem. 2007, 692, 1974-1982. 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 production method capable of efficiently producing silicon-substituted cyclopentadienyl titanium trihalide.

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７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^８）_３（３つのＲ^８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^８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、
−Ｎ（Ｒ^９）_２（２つのＲ^９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^９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、
または、一般式（２）

｛式中、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^８）_３（３つのＲ^８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^８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、
−Ｎ（Ｒ^９）_２（２つのＲ^９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^９にある炭素原子数の合計が２〜２０である。）で示される２置換アミノ基を表す。｝
Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立にハロゲン原子を表す。］
で表されるケイ素置換シクロペンタジエニルチタントリハライドの製造方法にかかるものである。
工程（ｉ）
一般式（３）

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は前記と同義であり、

で表されるケイ素置換シクロペンタジエン化合物と、アルカリ金属化合物とを反応させることにより一般式（４）

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は前記と同義であり、
Ｍ^１はアルカリ金属である。］
で表されるケイ素置換シクロペンタジエニルアルカリ金属化合物を生成させる工程
工程（ｉｉ）
前記ケイ素置換シクロペンタジエニルアルカリ金属化合物に、一般式（５）

［式中、Ｘ^４はハロゲン原子を表し、Ｙ^１、Ｙ^２及びＹ^３は、それぞれ独立に、
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のアルコキシ基を表す。］
で表される遷移金属化合物を反応させることにより一般式（６）

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｙ^１、Ｙ^２及びＹ^３は前記と同義である。］
で表されるケイ素置換シクロペンタジエニルチタントリアルコキシドを生成させる工程
工程（ｉｉｉ）
前記ケイ素置換シクロペンタジエニルチタントリアルコキシドに、一般式（７）

［式中、Ｍ^２は元素の周期律表の第３族〜第１４族の原子を表し、Ｘ^５はハロゲン原子を表し、Ｒ^１５は水素原子、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、又は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のアリール基を表し、ｎは１以上の整数であり、ｍ＋ｎはＭ^２の価数に等しい整数である。］
で表されるハロゲン化合物を反応させる工程。 That is, the first of the present invention is the general formula (1) having the following step (i), step (ii), and step (iii).

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently
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 ⁸ ) ₃ (three R ⁸ 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 ⁸ is 1 to 20; A substituted silyl group represented by:
In -N ^(R ₉₎ 2 (two ^{R 9} each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, the total number of carbon atoms in the two ^{R 9} is 2-20.) The disubstituted amino group shown,
Or general formula (2)

{Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently
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 ⁸ ) ₃ (three R ⁸ 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 ⁸ is 1 to 20; A substituted silyl group represented by:
In -N ^(R ₉₎ 2 (two ^{R 9} each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, the total number of carbon atoms in the two ^{R 9} is 2-20.) Represents the disubstituted amino group shown. }
X ¹ , X ² and X ³ each independently represent a halogen atom. ]
It relates to a method for producing a silicon-substituted cyclopentadienyl titanium trihalide represented by the formula:
Step (i)
General formula (3)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,

By reacting a silicon-substituted cyclopentadiene compound represented by the formula (4) with an alkali metal compound.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,
M ¹ is an alkali metal. ]
A step (ii) of producing a silicon-substituted cyclopentadienyl alkali metal compound represented by the formula:
The silicon-substituted cyclopentadienyl alkali metal compound is represented by the general formula (5)

[Wherein, X ⁴ represents a halogen atom, and Y ¹ , Y ² and Y ³ are each independently
The C1-C20 alkoxy group which may have a halogen atom as a substituent is represented. ]
Is reacted with a transition metal compound represented by the general formula (6)

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Y ¹ , Y ² and Y ³ are as defined above]. ]
A step (iii) of producing a silicon-substituted cyclopentadienyl titanium trialkoxide represented by
The silicon-substituted cyclopentadienyl titanium trialkoxide has the general formula (7)

[Wherein M ² represents an atom belonging to Group 3 to Group 14 of the periodic table of elements, X ⁵ represents a halogen atom, and R ¹⁵ has a hydrogen atom or a halogen atom as a substituent. A good alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, n is an integer of 1 or more, and m + n is M ² An integer equal to the valence. ]
A step of reacting a halogen compound represented by the formula:

  According to the present invention, a method for producing a silicon-substituted cyclopentadienyl titanium trihalide can be provided. In particular, a silicon-substituted cyclopentadienyl titanium trisilane having a silicon atom having an aryl group as a substituent, which is useful as a catalyst component capable of efficiently and selectively producing 1-hexene by a trimerization reaction of ethylene. Suitable for the production of halides.

In the present invention, the term “substituent” includes a halogen atom constituting a compound or group.
In the present invention, the silicon-substituted cyclopentadiene compound represented by the general formula (2) has isomers having different double bond positions on each cyclopentadienyl ring. A silicon-substituted cyclopentadienyl compound represents any of them or a mixture thereof.

<Method for producing silicon-substituted cyclopentadienyl titanium trihalide>
Hereinafter, a method for producing a silicon-substituted cyclopentadienyl titanium trihalide will be described in detail.

In the general formulas (1) to (7), the substituents 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 , R ¹⁵ , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , Y ¹ , Y ² and Y ³ are as defined 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, a preferable aryl group is an aryl group having 6 to 10 carbon atoms, more preferably a phenyl group. 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 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 ⁸ ) ₃ (three R ⁸ 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 ⁸ is 1 to 20; In the substituted silyl group represented by formula (1), each R ⁸ 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 A hydrocarbyl group such as a phenyl group; a halogenated hydrocarbyl group in which part or all of the hydrogen atoms in the hydrocarbyl group are replaced by halogen atoms; The total number of carbon atoms of one R ⁸ is in the range of 1-20. The total number of carbon atoms of the three R ⁸ 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 ⁹ ) ₂ (two R ^{9 s} each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ⁹ is 2 to 20). In the disubstituted amino group shown, each R ⁹ independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms of the two R ⁹ 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 ⁹ 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.

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. R ⁵ , R ⁶ and R ⁷ may be bonded to form a ring together with the silicon atom to which they are bonded. The ring referred to here is a saturated or unsaturated hydrocarbyl ring substituted with a hydrocarbyl group having 1 to 20 carbon atoms, saturated with a hydrocarbyl group having 1 to 20 carbon atoms. Or an unsaturated silahydrocarbyl ring. 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, anthracene ring, silacyclopropane ring, silacyclobutane ring, silacyclopentane ring, and silacyclohexane ring.

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. Group or an aralkyl group having 7 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and still more preferably a methyl group.

（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 (8)

(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.

  Methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butylcyclopentadienyl, Dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl, octa Examples include partial structures such as hydrofluorenyl.

  Of the cyclopentadienyl partial structures exemplified here, preferred cyclopentadienyl partial structures are tetramethylcyclopentadienyl, trimethylcyclopentadienyl, and the like.

（式中、Ｒ^５、Ｒ^６及びＲ^７は前記と同じ意味を表す。）
において、次のような部分構造を挙げることができる。 A preferred combination of R ⁵ , R ⁶ and R ⁷ includes a partial structural formula (9)

(Wherein R ⁵ , R ⁶ and R ⁷ represent the same meaning as described above.)
The following partial structure can be mentioned.

  Trimethylsilyl, triethylsilyl, triisopropylsilyl, tri (n-butyl) silyl, dimethylphenylsilyl, diethylphenylsilyl, diisopropylphenylsilyl, di (n-butyl) phenylsilyl, methylethylphenylsilyl, methylisopropylphenylsilyl, methyl ( n-butyl) phenylsilyl, methylcyclohexylphenylsilyl, methyl (n-octadecyl) phenylsilyl, methyldiphenylsilyl, ethyldiphenylsilyl, isopropyldiphenylsilyl, n-butyldiphenylsilyl, methylbis (3,5-dimethylphenyl) silyl, Methyldi (4-methylphenyl) silyl, methyldi (4-n-butylphenyl) silyl, triphenylsilyl, tris (3,5-dimethylphenyl) silyl, Lis (3,5-diethylphenyl) silyl, tris (3,5-di-tert-butylphenyl) silyl, tris (3,5-diphenylphenyl) silyl, tri (4-n-butylphenyl) silyl, tris ( 3-trimethylsilyl-phenyl) silyl, tris (5-methyl-3-trimethylsilyl-phenyl) silyl, (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl, (3,5- Examples thereof include a partial structure such as di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silyl.

  Among the substituted silyl partial structures exemplified here, preferred substituted silyl partial structures are dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, tris (3,5-dimethylphenyl) silyl, tris (3-trimethylsilyl-phenyl) silyl, Tris (5-methyl-3-trimethylsilyl-phenyl) silyl, (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl, (3,5-di-tert-butylphenyl) ( 3,5-dimethylphenyl) (phenyl) silyl and the like.

（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、例えば、次のような部分構造を挙げることができる。 As a preferable combination of R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ^{14 in} the general formula (2), the partial structural formula (2)

(Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ represent the same meaning as described above.)
For example, the following partial structure can be given.

  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 Examples thereof include partial structures such as aminophenyl and methyl (trimethylsilyl) phenyl.

  Among the partial structures exemplified here, more preferred partial structures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, di-tert-butylphenyl, diphenylphenyl, trimethylsilylphenyl, methyl (trimethylsilyl) phenyl, and the like.

In the general formula (1), X ¹ , X ² and X ³ are halogen atoms, more preferably chlorine atoms.

  Specific examples of the silicon-substituted cyclopentadienyl titanium trihalide (1) include the following complexes.

  [1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride Chloride, [1-phenyldi (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diisopropylphenylsilyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-di (n-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (isobutyl) phenylsilyl-2 , 3,4,5-Tetramethylcyclopentadienyl] titanium trichloride [1-di (sec-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (tert-butyl) phenylsilyl-2,3,4,5 -Tetramethylcyclopentadienyl] titanium trichloride, [1-ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (n-propyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [ 1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopen Dienyl] titanium trichloride, [1-isobutylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-sec-butylmethylphenylsilyl-2,3,4,5 -Tetramethylcyclopentadienyl] titanium trichloride, [1-tert-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-cyclohexylmethylphenylsilyl-2 , 3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (n-octadecyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-dimethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diethyl (3,5-dimethylphenyl) silyl-2,3 , 4,5-tetramethylcyclopentadienyl] titanium trichloride, [1- (3,5-dimethylphenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium trichloride, [1-diisopropyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (n-butyl) (3,5 -Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (i Butyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (sec-butyl) (3,5-dimethylphenyl) silyl- 2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (tert-butyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopenta Dienyl] titanium trichloride, [1-ethylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (3,5- Dimethylphenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloro [1-methyl (3,5-dimethylphenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-butylmethyl (3,5-dimethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isobutylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadi Enyl] titanium trichloride, [1-sec-butylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tert-butylmethyl (3,3 5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] tita Nium trichloride, [1-cyclohexylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (n-octadecyl) (3 5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-dimethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diethyl (3,5-diethylphenyl) silyl-2,3 , 4,5-tetramethylcyclopentadienyl] titanium trichloride, [1- (3,5-diethylphenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium trichloride, [1-diisopropyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (n-butyl) (3,5 -Diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (i Butyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (sec-butyl) (3,5-diethylphenyl) silyl- 2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (tert-butyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopenta Dienyl] titanium trichloride, [1-ethylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (3,5- Diethylphenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloro [1-methyl (3,5-diethylphenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-butylmethyl (3,5-diethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isobutylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadi Enyl] titanium trichloride, [1-sec-butylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tert-butylmethyl (3,3 5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] tita Nium trichloride, [1-cyclohexylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (n-octadecyl) (3 5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-dimethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diethyl (5-methyl-3-trimethylsilyl-phenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1- (5-methyl-3-trimethylsilyl-phenyl) di (n-propyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] titanium trichloride, [1-diisopropyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [ 1-di (n-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl 2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (isobutyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-di (sec-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [ 1-di (tert-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-ethylmethyl (5-methyl- 3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium trichloride, [1-methyl (5-methyl-3-trimethylsilyl-phenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (5-methyl-3-trimethylsilyl-phenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-butylmethyl (5-methyl-3-trimethylsilyl- Phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isobutylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetra Methylcyclopentadienyl] titanium trichloride, [1-sec-butylmethyl] Tyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tert-butylmethyl (5-methyl-3-trimethylsilyl-phenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-cyclohexylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-methyl (n-octadecyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-Methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-ethyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride Chloride, [1-n-propyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isopropyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadi] Enyl] titanium trichloride, [1-n-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isobutyldiphenylsilyl-2,3,4,5-tetra Methylcyclopentadienyl] titanium trichloride, [1-se -Butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tert-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride Chloride, [1-cyclohexyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-octadecyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadi] Enyl] titanium trichloride, [1-methylphenyl (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (3-methylphenyl) silyl -2,3,4,5-tetramethylcyclopenta Enyl] titanium trichloride, [1-methylphenyl (4-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (2,3-dimethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (2,4-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadi] Enyl] titanium trichloride, [1-methylphenyl (2,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (2,6- Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] tita Nium trichloride, [1-methylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (3,5-diethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium trichloride, [1-methylphenyl (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-ethylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-propylphenyl (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isopropylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium trichloride, [1-n-butylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isobutylphenyl (3,5- Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Chloride, [1-sec-butylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tert-butylphenyl (3,5- Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-cyclohexylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-n-octadecylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (2 -Methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-the Lamethylcyclopentadienyl] titanium trichloride, [1-methyl (3-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-Methyl (4-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (2,3-dimethylphenyl) ) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl ( 2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (2,6-dimethylphenyl) ( 3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylbis (3,5-dimethylphenyl) silyl-2,3,4,5- Tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (3,5-dimethylphenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium trichloride,

  [1-ethylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-propylphenyl (3,5-diethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isopropylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium trichloride, [1-n-butylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isobutylphenyl (3,5- Diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Chloride, [1-sec-butylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tert-butylphenyl (3,5- Diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-cyclohexylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-n-octadecylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (2 -Methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-te Lamethylcyclopentadienyl] titanium trichloride, [1-methyl (3-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (4-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (2,3-dimethylphenyl) ) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (2,4-dimethylphenyl) (3,5-diethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl ( 2,5-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylphenyl (2,6-dimethylphenyl) ( 3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methylbis (3,5-diethylphenyl) silyl-2,3,4,5- Tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (3,5-diethylphenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium trichloride,

  [1-ethylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-propylphenyl (5-methyl-3 -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-isopropylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-butylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride Chloride, [1-isobutylphenyl (5-methyl-3-trimethyl) Silyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-sec-butylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4 , 5-Tetramethylcyclopentadienyl] titanium trichloride, [1-tert-butylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Trichloride, [1-cyclohexylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-octadecylphenyl (5- Methyl-3-trimethylsilyl-phenyl) silyl-2 3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium trichloride, [1-methyl (3-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride [1-methyl (4-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (2, 3-Dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3 4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (2,4-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium trichloride, [1-methyl (2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Trichloride, [1-methylphenyl (2,6-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1 -Methylbis (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4 5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyl (5-methyl-3-trimethylsilyl-phenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium trichloride,

  [1-Triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyldi (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopenta Dienyl] titanium trichloride, [1-phenyldi (3-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyldi (4-methylphenyl) silyl- 2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenylbis (2,3-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Trichloride, [1-phenylbis (2,4-dimethylphenyl) silyl-2,3,4,5 Tetramethylcyclopentadienyl] titanium trichloride, [1-phenylbis (2,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenylbis] (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenylbis (3,5-dimethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenylbis (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1- Phenylbis (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4, - tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl-bis (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-diphenyl (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diphenyl (3-methylphenyl) silyl-2,3,4,5 -Tetramethylcyclopentadienyl] titanium trichloride, [1-diphenyl (4-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diphenyl (2, 3-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diphenyl (2,4-dimethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium trichloride, [1-diphenyl (2,5-dimethylphenyl) Ril-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diphenyl (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium trichloride, [1-diphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diphenyl (3,5-diethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadi Enyl] titanium trichloride, [1-diphenyl (3,4,5-trimethylphenyl) silane Le-2,3,4,5-tetramethyl-cyclopentadienyl] titanium trichloride,

  [1-phenyl (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (3-methylphenyl) ( 3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (4-methylphenyl) (3,5-dimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-phenyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5 -Tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Trichloride, [1-phenyl (3,5-dimethylphenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-di (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) ( 3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (4-methylphenyl) (3,5-dimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-bis (2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-bis (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5- Tramethylcyclopentadienyl] titanium trichloride, [1-bis (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride Chloride, [1-bis (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tris (3 5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1- (3,5-dimethylphenyl) bis (3,4,5-dimethylphenyl) silyl- 2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-phenyl (2-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (3-methylphenyl) ( 3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (4-methylphenyl) (3,5-diethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-phenyl (2,4-dimethylphenyl) (3,5-diethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (2,5-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5 -Tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (2,6-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Trichloride, [1-phenyl (3,5-diethylphenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-di (2-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (3-methylphenyl) ( 3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (4-methylphenyl) (3,5-diethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-bis (2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-bis (2,4-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5- Tramethylcyclopentadienyl] titanium trichloride, [1-bis (2,5-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride Chloride, [1-bis (2,6-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tris (3 5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1- (3,5-diethylphenyl) bis (3,4,5-dimethylphenyl) silyl- 2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride,

  [1-phenyl (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (3-methyl Phenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (4-methylphenyl) (5-methyl-3) -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (2,3-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] titanium trichloro , [1-phenyl (2,4-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl ( 2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (2,6-dimethylphenyl) ) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-phenyl (5-methyl-3-trimethylsilyl-phenyl) (3 , 4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadie Le] titanium trichloride,

  [1-di (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (3-methyl Phenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-di (4-methylphenyl) (5-methyl-3) -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-bis (2,3-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-bis (2,4 Dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-bis (2,5-dimethylphenyl) (5- Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-bis (2,6-dimethylphenyl) (5-methyl-3-trimethylsilyl- Phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium trichloride, [1- (5-methyl-3-trimethylsilyl) - phenyl) bis (3,4,5-dimethylphenyl) include silicon-substituted cyclopentadienyl titanium trichloride complex such as silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride.

  In the complexes exemplified here, “2,3,4,5-tetramethylcyclopentadienyl” is replaced with “2-methylcyclopentadienyl”, “3-methylcyclopentadienyl”, “2,3- “Dimethylcyclopentadienyl”, “2,4-dimethylcyclopentadienyl”, “2,5-dimethylcyclopentadienyl”, “2,3,5-trimethylcyclopentadienyl”, “2-ethylcyclo “Pentadienyl”, “3-ethylcyclopentadienyl”, “2-n-propylcyclopentadienyl”, “3-n-propylcyclopentadienyl”, “2-isopropylcyclopentadienyl”, “ “3-isopropylcyclopentadienyl”, “2-n-butylcyclopentadienyl”, “3-n-butylcyclopentadienyl”, “2-sec- “Tylcyclopentadienyl”, “3-sec-butylcyclopentadienyl”, “2-tert-butylcyclopentadienyl”, “3-tert-butylcyclopentadienyl”, “2-phenylcyclopentadienyl” “Enyl”, “3-phenylcyclopentadienyl”, “2-benzylcyclopentadienyl”, “3-benzylcyclopentadienyl”, “indenyl”, “2-methylindenyl”, “fluorenyl”, “ Silicon substituted cyclopentadienyl titanium trichlorides substituted with “tetrahydroindenyl”, “2-methyltetrahydroindenyl”, “octahydrofluorenyl” are also exemplified.

Further, in the silicon-substituted cyclopentadienyl titanium trihalide exemplified here, silicon-substituted cyclopentadienyl titanium tribromide in which “chloride” is replaced with “bromide”, or silicon-substituted cyclopentadienyl in which “iodide” is replaced. A titanium substituted tri-iodide, or silicon substituted cyclopentadienyl titanium trifluoride replaced with “fluoride” is also exemplified. Among these, silicon-substituted cyclopentadienyl titanium trichloride is preferable.
<Process (i)>

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は前記と同義であり、

で表されるケイ素置換シクロペンタジエン化合物と、アルカリ金属化合物とを反応させることにより一般式（４）

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は前記と同義であり、
Ｍ^１はアルカリ金属である。］
で表されるケイ素置換シクロペンタジエニルアルカリ金属化合物を生成させる工程である。 Step (i) in the method for producing a silicon-substituted cyclopentadienyl titanium trihalide is the general formula (3)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,

By reacting a silicon-substituted cyclopentadiene compound represented by the formula (4) with an alkali metal compound.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,
M ¹ is an alkali metal. ]
A silicon-substituted cyclopentadienyl alkali metal compound represented by the formula:

ケイ素置換シクロペンタジエン化合物（３）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 silicon-substituted cyclopentadiene compound (3), isomers different in the position of the double bond of the cyclopentadiene ring are the following structural isomers.

In the silicon-substituted cyclopentadiene compound (3), there are isomers having different double bond positions on each cyclopentadienyl ring, and in the present invention, any one of them or a mixture thereof is represented.

  Specific examples of the silicon-substituted cyclopentadiene compound (3) include the following compounds.

  1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyldi (n-propyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-diisopropylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (n-butyl) phenylsilyl-2,3,4,5-tetra Methylcyclopentadiene, 1-di (isobutyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (sec-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (tert-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, -Ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (isopropyl) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-isobutylmethylphenylsilyl-2,3,4, 5-tetramethylcyclopentadiene, 1-sec-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene 1-cyclohexylmethylphenylsilyl-2,3,4,5-teto Methyl cyclopentadiene, 1-methyl (n- octadecyl) phenyl silyl-2,3,4,5-tetramethyl-cyclopentadiene,

  1-dimethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadiene, 1- (3,5-dimethylphenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diisopropyl (3,5-dimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-di (n-butyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (isobutyl) (3,5 -Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (sec-butyl) (3,5-dimethylphenyl) silyl 2,3,4,5-tetramethylcyclopentadiene, 1-di (tert-butyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-ethylmethyl (3 , 5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (3,5-dimethylphenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclo Pentadiene, 1-methyl (3,5-dimethylphenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylmethyl (3,5-dimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-isobutylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadiene, 1-sec-butylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylmethyl (3,5-dimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-cyclohexylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (n-octadecyl) (3,5-dimethyl Phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-dimethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadiene, 1- (3,5-diethylphenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diisopropyl (3,5-diethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-di (n-butyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (isobutyl) (3,5 -Diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (sec-butyl) (3,5-diethylphenyl) silyl 2,3,4,5-tetramethylcyclopentadiene, 1-di (tert-butyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-ethylmethyl (3 , 5-Diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (3,5-diethylphenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclo Pentadiene, 1-methyl (3,5-diethylphenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylmethyl (3,5-diethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-isobutylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadiene, 1-sec-butylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylmethyl (3,5-diethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-cyclohexylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (n-octadecyl) (3,5-diethyl Phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-dimethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4 , 5-tetramethylcyclopentadiene, 1- (5-methyl-3-trimethylsilyl-phenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diisopropyl (5-methyl- 3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (n-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5- Tetramethylcyclopentadiene, 1-di (isobutyl) (5-methyl-3-trimethylsilyl-phenyl) silyl 2,3,4,5-tetramethylcyclopentadiene, 1-di (sec-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (Tert-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-ethylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-methyl (5-methyl-3-trimethylsilyl-phenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (5 -Methyl-3-trimethylsilyl-phenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclope Tadiene, 1-n-butylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-isobutylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl- 2,3,4,5-tetramethylcyclopentadiene, 1-sec-butylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylmethyl ( 5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-cyclohexylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5- Tetramethylcyclopentadiene, 1-methyl (n-octadecyl) ( 5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-ethyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-propyldiphenylsilyl-2,3 4,5-tetramethylcyclopentadiene, 1-isopropyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1 -Isobutyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-sec-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butyldiphenylsilyl-2,3 , 4,5-tetramethylcyclopentadiene, 1-cyclohexyldi Phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-octadecyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2-methylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (3-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (4-methylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2,3-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2,4-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2, -Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (3,4,5-trimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene,

  1-ethylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-propylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5 -Tetramethylcyclopentadiene, 1-isopropylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylphenyl (3,5-dimethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadiene, 1-isobutylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-sec-butylphenyl (3,5- Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylpheny (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-cyclohexylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-octadecylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2-methylphenyl) (3,5-dimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-methyl (3-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (4-methyl) Phenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl 2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1- Methylphenyl (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylbis (3,5-dimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-methyl (3,5-dimethylphenyl) (3,4,5-trimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene,

  1-ethylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-propylphenyl (3,5-diethylphenyl) silyl-2,3,4,5 -Tetramethylcyclopentadiene, 1-isopropylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylphenyl (3,5-diethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadiene, 1-isobutylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-sec-butylphenyl (3,5- Diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylpheny (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-cyclohexylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-octadecylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2-methylphenyl) (3,5-diethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-methyl (3-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (4-methyl) Phenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl 2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2,4-dimethylphenyl) (3,5-diethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2,5-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1- Methylphenyl (2,6-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylbis (3,5-diethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-methyl (3,5-diethylphenyl) (3,4,5-trimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene,

  1-ethylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-propylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2 , 3,4,5-tetramethylcyclopentadiene, 1-isopropylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylphenyl (5 -Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-isobutylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetra Methylcyclopentadiene, 1-sec-butylphenyl (5-methyl-3-to Methylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene 1-cyclohexylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-octadecylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl- 2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1- Methyl (3-methylphenyl) (5-methyl-3-trimethyl) Ru-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (4-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetra Methylcyclopentadiene, 1-methyl (2,3-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2,4-dimethyl) Phenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2,6-dimethylpheny L) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylbis (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4, 5-tetramethylcyclopentadiene, 1-methyl (5-methyl-3-trimethylsilyl-phenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyldi (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyldi (3-methyl Phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyldi (4-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis (2,3- Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis (2,4-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis ( 2,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis ( , 6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, Phenylbis (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5- Tetramethylcyclopentadiene, 1-phenylbis (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-diphenyl (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (3-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, Diphenyl (4-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (2,3-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1- Diphenyl (2,4-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (2,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene 1-diphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadiene, 1-diphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (3,4,5-trimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene,

  1-phenyl (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (3-methylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (4-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl ( 2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,5-dimethylphenyl) (3,5-dimethylpheny ) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (3,5-dimethylphenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-di (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (3-methylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-di (4-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-bis ( 2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-bis (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-bis (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-the Lamethylcyclopentadiene, 1-bis (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tris (3,5-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1- (3,5-dimethylphenyl) bis (3,4,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene ,

  1-phenyl (2-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (3-methylphenyl) (3,5-diethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (4-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl ( 2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,4-dimethylphenyl) (3,5-diethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,5-dimethylphenyl) (3,5-diethylpheny ) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,6-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (3,5-diethylphenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-di (2-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (3-methylphenyl) (3,5-diethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-di (4-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-bis ( 2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-bis (2,4-dimethylphenyl) (3,5-diethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-bis (2,5-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-the Lamethylcyclopentadiene, 1-bis (2,6-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tris (3,5-diethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1- (3,5-diethylphenyl) bis (3,4,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene ,

  1-phenyl (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (3-methylphenyl) (5-methyl-3 -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (4-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5- Tetramethylcyclopentadiene, 1-phenyl (2,3-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,4- Dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetra Tylcyclopentadiene, 1-phenyl (2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,6-dimethyl) Phenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (5-methyl-3-trimethylsilyl-phenyl) (3,4,5-trimethyl Phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-di (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (3-methylphenyl) (5-methyl-3 -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (4-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5- Tetramethylcyclopentadiene, 1-bis (2,3-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-bis (2,4- Dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, -Bis (2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-bis (2,6-dimethylphenyl) (5- Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclo Examples include silicon-substituted cyclopentadiene compounds such as pentadiene and 1- (5-methyl-3-trimethylsilyl-phenyl) bis (3,4,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene. .

  In the silicon-substituted cyclopentadiene compounds exemplified here, “2,3,4,5-tetramethylcyclopentadiene” is replaced with “2-methylcyclopentadiene”, “3-methylcyclopentadiene”, “2,3-dimethylcyclohexane”. "Pentadiene", "2,4-dimethylcyclopentadiene", "2,5-dimethylcyclopentadiene", "2,3,5-trimethylcyclopentadiene", "2-ethylcyclopentadiene", "3-ethylcyclopentadiene" , “2-n-propylcyclopentadiene”, “3-n-propylcyclopentadiene”, “2-isopropylcyclopentadiene”, “3-isopropylcyclopentadiene”, “2-n-butylcyclopentadiene”, “3- n-butylcyclopentadiene ”,“ 2-sec- “Tylcyclopentadiene”, “3-sec-butylcyclopentadiene”, “2-tert-butylcyclopentadiene”, “3-tert-butylcyclopentadiene”, “2-phenylcyclopentadiene”, “3-phenylcyclopentadiene” , “2-benzylcyclopentadiene”, “3-benzylcyclopentadiene”, “indene”, “2-methylindene”, “fluorene”, “tetrahydroindene”, “2-methyltetrahydroindene”, “octahydrofluorene” A silicon-substituted cyclopentadiene compound replaced with is also exemplified.

  Examples of the alkali metal compound to be reacted with the silicon-substituted cyclopentadiene compound (3) in the step (i) include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, Examples thereof include organic alkali metal compounds such as lithium acetylide, trimethylsilylmethyl lithium, vinyl lithium, phenyl lithium and allyl lithium, and alkali metal hydride compounds such as lithium hydride, sodium hydride and potassium hydride. Among these, alkali metal hydride compounds such as sodium hydride and potassium hydride are preferable, and potassium hydride is particularly preferable.

  The usage-amount of an alkali metal compound should just be the range of 0.5-5 mol per 1 mol of silicon substituted cyclopentadienyl compounds (3).

  In the step (i), the silicon-substituted cyclopentadiene compound (3) and the alkali metal compound are preferably reacted in the presence of a solvent. When a solvent is used, a solid may precipitate in the reaction mixture obtained by reacting the silicon-substituted cyclopentadiene compound (3) with an alkali metal compound in the solvent. In this case, the precipitated solid is dissolved. Until the solvent is added, or the precipitated solid may be separated once by filtration or the like and used in the next step (ii). After the solvent is added to the separated solid and dissolved or suspended, Then, the process may proceed to the next step (ii).

  As the solvent used in the step (i), 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. 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 silicon-substituted cyclopentadiene compound (3). preferable.

  The reaction temperature in process (i) should just be -100 degreeC or more and the boiling point or less of a solvent, Preferably it is the range of -80-100 degreeC.

  Thus, the produced silicon-substituted cyclopentadienyl alkali metal compound (4) can be extracted from the reaction mixture obtained through the step (i) by various known purification methods. Further, the reaction mixture of the silicon-substituted cyclopentadiene compound (3) and the alkali metal compound can be used as it is in the next step (ii).

In the silicon-substituted cyclopentadienyl alkali metal compound (4), M ¹ is an alkali metal, and examples thereof include lithium, sodium, potassium, rubidium, and cesium, and preferably lithium, sodium, and potassium.

  Specific examples of the silicon-substituted cyclopentadienyl alkali metal compound (4) include the following compounds.

  [1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -Phenyldi (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diisopropylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (n-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (isobutyl) phenylsilyl-2,3,4,5-tetramethylcyclo Pentadienyl] potassium, [1-di (sec-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium , [1-di (tert-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclo Pentadienyl] potassium, [1-methylphenyl (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methylphenyl (isopropyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] potassium, [1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isobutylmethylphenylsilyl-2,3 , 4,5-tetramethylcyclopentadienyl] potassium, [1-sec-butylmethylphenylsilyl-2,3,4,5 Tetramethylcyclopentadienyl] potassium, [1-tert-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-cyclohexylmethylphenylsilyl-2,3,4, 5-tetramethylcyclopentadienyl] potassium, [1-methyl (n-octadecyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-dimethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diethyl (3,5-dimethylphenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] potassium, [1- (3,5-dimethylphenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -Diisopropyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (n-butyl) (3,5-dimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (isobutyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Ntadienyl] potassium, [1-di (sec-butyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (tert-butyl) ( 3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-ethylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetra Methylcyclopentadienyl] potassium, [1-methyl (3,5-dimethylphenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (3 , 5-Dimethylphenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-n-butylmethyl (3,5- Methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isobutylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadi Enyl] potassium, [1-sec-butylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-tert-butylmethyl (3,5-dimethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-cyclohexylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Potassium, [1-methyl (n-octadecyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] potassium,

  [1-Dimethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-Diethyl (3,5-diethylphenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] potassium, [1- (3,5-diethylphenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -Diisopropyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (n-butyl) (3,5-diethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (isobutyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclo Ntadienyl] potassium, [1-di (sec-butyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (tert-butyl) ( 3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-ethylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetra Methylcyclopentadienyl] potassium, [1-methyl (3,5-diethylphenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (3 , 5-Diethylphenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-n-butylmethyl (3,5- Ethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isobutylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadi Enyl] potassium, [1-sec-butylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-tert-butylmethyl (3,5-diethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-cyclohexylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Potassium, [1-methyl (n-octadecyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] potassium,

  [1-dimethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diethyl (5-methyl-3-trimethylsilyl-phenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] potassium, [1- (5-methyl-3-trimethylsilyl-phenyl) di (n-propyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] potassium, [1-diisopropyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (n-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [ -Di (isobutyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (sec-butyl) (5-methyl-3 -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (tert-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3 4,5-tetramethylcyclopentadienyl] potassium, [1-ethylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -Methyl (5-methyl-3-trimethylsilyl-phenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclope Tadienyl] potassium, [1-methyl (5-methyl-3-trimethylsilyl-phenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-n-butylmethyl (5- Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isobutylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] potassium, [1-sec-butylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -Tert-butylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3 4,5-tetramethylcyclopentadienyl] potassium, [1-cyclohexylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -Methyl (n-octadecyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-ethyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -N-propyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isopropyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -N-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isobutyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -Sec-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-t rt-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-cyclohexyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1- n-octadecyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methylphenyl (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl ] Potassium, [1-methylphenyl (3-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methylphenyl (4-methylphenyl) silyl-2,3, 4,5-tetramethylcyclopentadienyl] potassium, [1-methylphenyl (2,3-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methylphenyl (2,4-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium [1-methylphenyl (2,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methylphenyl (2,6-dimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] potassium, [1-methylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1- Methylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methylphenyl] Ru (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methylphenyl (3,4,5-trimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-ethylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-n-propylphenyl (3,5-dimethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadienyl] potassium, [1-isopropylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -N-butylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isobutylphenyl (3,5-dimethylphenyl) silyl-2,3 , 4,5-tetramethylcyclopentadienyl] potassium, [1-sec-butylphenyl (3,5-dimethylphenyl) silyl-2 3,4,5-tetramethylcyclopentadienyl] potassium, [1-tert-butylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [ 1-cyclohexylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-n-octadecylphenyl (3,5-dimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Potassium, [1-methyl (3-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcycl Pentadienyl] potassium, [1-methyl (4-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (2,3- Dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetra Methylcyclopentadienyl] potassium, [1-methylphenyl (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-te Tramethylcyclopentadienyl] potassium, [1-methylbis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (3,5-dimethyl) Phenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-Ethylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-n-propylphenyl (3,5-diethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadienyl] potassium, [1-isopropylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1 -N-butylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isobutylphenyl (3,5-diethylphenyl) silyl-2,3 , 4,5-tetramethylcyclopentadienyl] potassium, [1-sec-butylphenyl (3,5-diethylphenyl) silyl-2 3,4,5-tetramethylcyclopentadienyl] potassium, [1-tert-butylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [ 1-cyclohexylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-n-octadecylphenyl (3,5-diethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (2-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Potassium [1-methyl (3-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethyl Pentadienyl] potassium, [1-methyl (4-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (2,3- Dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (2,4-dimethylphenyl) (3,5-diethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (2,5-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetra Methylcyclopentadienyl] potassium, [1-methylphenyl (2,6-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-te Tramethylcyclopentadienyl] potassium, [1-methylbis (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (3,5-diethyl) Phenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-Ethylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-n-propylphenyl (5-methyl-3-trimethylsilyl) -Phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isopropylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] potassium, [1-n-butylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-isobutylphenyl ( 5-Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclope Tadienyl] potassium, [1-sec-butylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-tert-butylphenyl (5 -Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-cyclohexylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3 4,5-tetramethylcyclopentadienyl] potassium, [1-n-octadecylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-Methyl (2-methylphenyl) (5-methyl-3-trimethylsilyl- Enyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (3-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] potassium, [1-methyl (4-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium [1-methyl (2,3-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (2, 4-Dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadieny Potassium], [1-methyl (2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl Phenyl (2,6-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methylbis (5-methyl-3- Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-methyl (5-methyl-3-trimethylsilyl-phenyl) (3,4,5-trimethylphenyl) silyl- 2,3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-Triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyldi (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl ] Potassium, [1-phenyldi (3-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyldi (4-methylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] potassium, [1-phenylbis (2,3-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenylbis (2 , 4-Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenylbis (2,5-dimethyl) Phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenylbis (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl ] Potassium, [1-phenylbis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenylbis (3,5-diethylphenyl) silyl- 2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenylbis (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Potassium, [1-phenylbis (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium Umm,

  [1-diphenyl (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diphenyl (3-methylphenyl) silyl-2,3,4,5-tetra Methylcyclopentadienyl] potassium, [1-diphenyl (4-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diphenyl (2,3-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diphenyl (2,4-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [ 1-diphenyl (2,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diphenyl Ru (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diphenyl (3,5-dimethylphenyl) silyl-2,3,4,5- Tetramethylcyclopentadienyl] potassium, [1-diphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diphenyl (5-methyl-3) -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-diphenyl (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] potassium,

  [1-phenyl (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (3-methylphenyl) (3 5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (4-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] potassium, [1-phenyl (2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-Phenyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium [1-phenyl (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (2,6- Dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (3,5-dimethylphenyl) (3,4,5-trimethyl Phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-di (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (3-methylphenyl) (3 5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (4-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] potassium, [1-bis (2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-bis (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-bis (2,5- Methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-bis (2,6-dimethylphenyl) (3,5-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1- (3,5-dimethylphenyl) bis (3,4,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-phenyl (2-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (3-methylphenyl) (3 5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (4-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] potassium, [1-phenyl (2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-Phenyl (2,4-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium [1-phenyl (2,5-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (2,6- Dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (3,5-diethylphenyl) (3,4,5-trimethyl Phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-di (2-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (3-methylphenyl) (3 5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (4-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] potassium, [1-bis (2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-bis (2,4-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-bis (2,5- Methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-bis (2,6-dimethylphenyl) (3,5-diethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-tris (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1- (3,5-diethylphenyl) bis (3,4,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium,

  [1-phenyl (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (3-methylphenyl) (5-Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (4-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (2,3-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] potassium, [1-phenyl (2,4-dimethylphenyl) (5-methyl-3- Limethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] potassium, [1-phenyl (2,6-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] potassium, [1-phenyl (5-methyl-3-trimethylsilyl-phenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium ,

  [1-di (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (3-methylphenyl) (5-Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-di (4-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-bis (2,3-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] potassium, [1-bis (2,4-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1-bis (2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] potassium, [1-bis (2,6-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl ] Potassium, [1-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium, [1- (5-methyl-3-trimethylsilyl-phenyl) ) Silicon such as bis (3,4,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] potassium Conversion cyclopentadienyl potassium compound.

  In the complexes exemplified here, “2,3,4,5-tetramethylcyclopentadienyl” is replaced with “2-methylcyclopentadienyl”, “3-methylcyclopentadienyl”, “2,3- “Dimethylcyclopentadienyl”, “2,4-dimethylcyclopentadienyl”, “2,5-dimethylcyclopentadienyl”, “2,3,5-trimethylcyclopentadienyl”, “2-ethylcyclo “Pentadienyl”, “3-ethylcyclopentadienyl”, “2-n-propylcyclopentadienyl”, “3-n-propylcyclopentadienyl”, “2-isopropylcyclopentadienyl”, “ “3-isopropylcyclopentadienyl”, “2-n-butylcyclopentadienyl”, “3-n-butylcyclopentadienyl”, “2-sec- “Tylcyclopentadienyl”, “3-sec-butylcyclopentadienyl”, “2-tert-butylcyclopentadienyl”, “3-tert-butylcyclopentadienyl”, “2-phenylcyclopentadienyl” “Enyl”, “3-phenylcyclopentadienyl”, “2-benzylcyclopentadienyl”, “3-benzylcyclopentadienyl”, “indenyl”, “2-methylindenyl”, “fluorenyl”, “ Silicon substituted cyclopentadienyl potassium compounds substituted with “tetrahydroindenyl”, “2-methyltetrahydroindenyl”, “octahydrofluorenyl” are also exemplified.

  Furthermore, in the silicon-substituted cyclopentadienyl potassium compound exemplified here, a silicon-substituted cyclopentadienyl sodium compound in which “potassium” is replaced with “sodium”, or a silicon-substituted cyclopentadienyl lithium compound in which “lithium” is replaced Are also exemplified. Among these, a silicon-substituted cyclopentadienyl potassium compound is preferable.

<Process (ii)>

［式中、Ｘ^４はハロゲン原子を表し、Ｙ^１、Ｙ^２及びＹ^３は、それぞれ独立に、
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のアルコキシ基を表す。］
で表される遷移金属化合物を反応させることにより一般式（６）

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｙ^１、Ｙ^２及びＹ^３は前記と同義である。］
で表されるケイ素置換シクロペンタジエニルチタントリアルコキシドを生成させる工程である。 Step (ii) in the method for producing a silicon-substituted cyclopentadienyl titanium trihalide includes the silicon-substituted cyclopentadienyl alkali metal compound (4) represented by the general formula (5)

[Wherein, X ⁴ represents a halogen atom, and Y ¹ , Y ² and Y ³ are each independently
The C1-C20 alkoxy group which may have a halogen atom as a substituent is represented. ]
Is reacted with a transition metal compound represented by the general formula (6)

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Y ¹ , Y ² and Y ³ are as defined above]. ]
Is a step of generating a silicon-substituted cyclopentadienyl titanium trialkoxide represented by:

  Specific examples of the transition metal compound (5) include the following compounds.

  Chlorotrimethoxytitanium, chlorotriethoxytitanium, chlorotri (n-propoxy) titanium, chlorotriisopropoxytitanium, chlorotri (n-butoxy) titanium, chlorotri (tert-butoxy) titanium, chloro (dimethoxy) (isopropoxy) titanium, Chloro (methoxy) (diisopropoxy) titanium, chloro (diethoxy) (isopropoxy) titanium, chloro (ethoxy) (diisopropoxy) titanium, chloro (isopropoxy) (di-tert-butoxy) titanium, chloro (diiso Mention may be made of chlorotrialkoxytitanium compounds such as propoxy) (tert-butoxy) titanium.

  Further, in the chlorotrialkoxytitanium compounds exemplified here, bromotrialkoxytitanium compounds in which “chloro” is replaced with “bromo”, iodotrialkoxytitanium compounds in which “iodo” is replaced, or fluorotrialkanols in which “fluoro” is replaced Alkoxytitanium compounds are also exemplified. Of these, chlorotrialkoxytitanium compounds are preferred.

  The usage-amount of a transition metal compound (5) should just be the range of 0.5-5 mol per mol of silicon substituted cyclopentadienyl alkali metal compounds (4).

  In the step (ii), the silicon-substituted cyclopentadienyl alkali metal compound (4) and the transition metal compound (5) are preferably reacted in the presence of a solvent. When a solvent is used, a solid may precipitate in the reaction mixture obtained by reacting the silicon-substituted cyclopentadienyl alkali metal compound (4) with the transition metal compound (5) in the solvent. The solvent may be added until the precipitated solid is dissolved, or the precipitated solid may be temporarily separated by filtration or the like and used in the next step (iii). The solvent is added to the separated solid and dissolved. Or after suspending, it may proceed to the next step (iii).

  As the solvent used in the step (ii), 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 per 1 part by weight of the silicon-substituted cyclopentadienyl alkali metal compound (4), and 3 to 50 Part by weight is more preferred.

  The reaction temperature in the step (ii) may be -100 ° C or higher and not higher than the boiling point of the solvent, and is preferably in the range of -80 to 100 ° C.

  Thus, the produced silicon-substituted cyclopentadienyl titanium trialkoxide (6) can be taken out from the reaction mixture obtained through the step (ii) by various known purification methods. Further, the reaction mixture of the silicon-substituted cyclopentadienyl alkali metal compound (4) and the transition metal compound (5) can be used as it is in the next step (iii).

  Specific examples of the silicon-substituted cyclopentadienyl titanium trialkoxide (6) include the following compounds.

  [1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium triisopropoxide, [1-phenyldi (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diisopropylphenylsilyl-2,3,4 , 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (n-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [ 1-di (isobutyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadie [Ru] titanium triisopropoxide, [1-di (sec-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (tert-butyl) Phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triiso Propoxide, [1-methylphenyl (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methylphenyl (isopropyl) silyl-2,3, 4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-n- Tylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-isobutylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Triisopropoxide, [1-sec-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-tert-butylmethylphenylsilyl-2,3, 4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (N-octadecyl) phenylsilyl-2,3,4,5- Tetramethylcyclopentadienyl] titanium triisopropoxide,

  [1-dimethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diethyl (3,5-dimethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1- (3,5-dimethylphenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium triisopropoxide, [1-diisopropyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di ( n-butyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium tri Sopropoxide, [1-di (isobutyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (sec-butyl) ( 3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (tert-butyl) (3,5-dimethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-ethylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium triisopropoxide, [1-methyl (3,5-dimethylphenyl) (n-propyl) silyl-2,3,4,5-te Lamethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (3,5-dimethylphenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide [1-n-butylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-isobutylmethyl (3,5-dimethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-sec-butylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium triisopropoxide, [1-tert-butylmethyl (3, 5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-cyclohexylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5 -Tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (n-octadecyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium tri Isopropoxide,

  [1-Dimethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diethyl (3,5-diethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1- (3,5-diethylphenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium triisopropoxide, [1-diisopropyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di ( n-butyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium tri Sopropoxide, [1-di (isobutyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (sec-butyl) ( 3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (tert-butyl) (3,5-diethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-ethylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium triisopropoxide, [1-methyl (3,5-diethylphenyl) (n-propyl) silyl-2,3,4,5-te Lamethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (3,5-diethylphenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide [1-n-butylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-isobutylmethyl (3,5-diethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-sec-butylmethyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium triisopropoxide, [1-tert-butylmethyl (3, 5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-cyclohexylmethyl (3,5-diethylphenyl) silyl-2,3,4,5 -Tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (n-octadecyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium tri Isopropoxide,

  [1-dimethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diethyl (5-methyl-3-trimethylsilyl) -Phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1- (5-methyl-3-trimethylsilyl-phenyl) di (n-propyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diisopropyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl ] Titanium triisopropoxide, [1-di (n-butyl) (5-methyl-3-trimethyl) Ryl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (isobutyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3 , 4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (sec-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium triisopropoxide, [1-di (tert-butyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium tri Isopropoxide, [1-ethylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (5-methyl-3-trimethylsilyl-phenyl) (n-propyl) silyl-2,3,4,5-tetra Methylcyclopentadienyl] titanium triisopropoxide, [1-methyl (5-methyl-3-trimethylsilyl-phenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triiso Propoxide, [1-n-butylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-isobutylmethyl (5 -Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethyl [Lucyclopentadienyl] titanium triisopropoxide, [1-sec-butylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxy [1-tert-butylmethyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-cyclohexylmethyl (5- Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (n-octadecyl) (5-methyl-3-trimethylsilyl-phenyl) ) Silyl-2,3,4,5-tetramethylcyclope Tajieniru] triisopropoxide,

  [1-Methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-ethyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] Titanium triisopropoxide, [1-n-propyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-isopropyldiphenylsilyl-2,3,4,5 -Tetramethylcyclopentadienyl] titanium triisopropoxide, [1-n-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-isobutyldiphenylsilyl -2,3,4,5-tetramethylcyclopentadienyl] titani Mutriisopropoxide, [1-sec-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-tert-butyldiphenylsilyl-2,3,4, 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-cyclohexyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-n-octadecyldiphenyl Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methylphenyl (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl ] Titanium triisopropoxide, [1-methylphenyl (3 Methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methylphenyl (4-methylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium triisopropoxide, [1-methylphenyl (2,3-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl Phenyl (2,4-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methylphenyl (2,5-dimethylphenyl) silyl-2,3 , 4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methylphenyl] Enyl (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methylphenyl (3,5-dimethylphenyl) silyl-2,3 , 4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium tri Isopropoxide, [1-methylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methylphenyl (3 , 4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl Triisopropoxide,

  [1-ethylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-n-propylphenyl (3,5-dimethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-isopropylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium triisopropoxide, [1-n-butylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1 -Isobutylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopen Dienyl] titanium triisopropoxide, [1-sec-butylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-tert -Butylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-cyclohexylphenyl (3,5-dimethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-n-octadecylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadi Enyl] titanium triisopropoxide, [1-methyl (2-methylphenyl) 3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (3-methylphenyl) (3,5-dimethylphenyl) silyl- 2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (4-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetra Methylcyclopentadienyl] titanium triisopropoxide, [1-methyl (2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Triisopropoxide, [1-methyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadi Enyl] titanium triisopropoxide, [1-methylphenyl (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxy [1-methylbis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (3,5-dimethylphenyl) ( 3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titani Beam triisopropoxide,

  [1-ethylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-n-propylphenyl (3,5-diethylphenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-isopropylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium triisopropoxide, [1-n-butylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1 -Isobutylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopen Dienyl] titanium triisopropoxide, [1-sec-butylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-tert -Butylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-cyclohexylphenyl (3,5-diethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-n-octadecylphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadi Enyl] titanium triisopropoxide, [1-methyl (2-methylphenyl) 3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (3-methylphenyl) (3,5-diethylphenyl) silyl- 2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (4-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetra Methylcyclopentadienyl] titanium triisopropoxide, [1-methyl (2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium Triisopropoxide, [1-methyl (2,4-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (2,5-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadi Enyl] titanium triisopropoxide, [1-methylphenyl (2,6-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxy [1-methylbis (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (3,5-diethylphenyl) ( 3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titani Beam triisopropoxide,

  [1-ethylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-n-propylphenyl (5-methyl -3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-isopropylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-n-butylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium triisopropoxide, [1-isobutylphenyl ( -Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-sec-butylphenyl (5-methyl-3-trimethylsilyl-phenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-tert-butylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5 -Tetramethylcyclopentadienyl] titanium triisopropoxide, [1-cyclohexylphenyl (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triiso Propoxide, [1-n-octadecylphenyl (5-methyl Ru-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (2-methylphenyl) (5-methyl-3-trimethylsilyl- Phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (3-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (4-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5- Tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (2,3-dimethyl) Phenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (2,4-dimethylphenyl) (5 -Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (2,5-dimethylphenyl) (5-methyl-3 -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methylphenyl (2,6-dimethylphenyl) (5-methyl-3-trimethylsilyl- Phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trii Propoxide, [1-methylbis (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-methyl (5-methyl- 3-trimethylsilyl-phenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide,

  [1-Triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyldi (2-methylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium triisopropoxide, [1-phenyldi (3-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyldi (4 -Methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenylbis (2,3-dimethylphenyl) silyl-2,3,4,5- Tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenylbis (2,4-dimethylphenyl) Nyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenylbis (2,5-dimethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium triisopropoxide, [1-phenylbis (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1- Phenylbis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenylbis (3,5-diethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenylbis (5- Til-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenylbis (3,4,5-trimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide,

  [1-diphenyl (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diphenyl (3-methylphenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diphenyl (4-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [ 1-diphenyl (2,3-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diphenyl (2,4-dimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diphenyl] (2,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diphenyl (2,6-dimethylphenyl) silyl-2,3,4 , 5-Tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide [1-diphenyl (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-diphenyl (5-methyl-3-trimethylsilyl-phenyl) ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropo Sid, [1- diphenyl (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide,

  [1-phenyl (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (3-methylphenyl ) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (4-methylphenyl) (3,5-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (2,4-dimethylphenyl) ( , 5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (3,5-dimethylphenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium triisopropoxide,

  [1-di (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (3-methylphenyl) ) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (4-methylphenyl) (3,5-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4 , 5-Tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2,4-dimethylphenyl) (3,5-dimethylphenyl) Ryl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopenta Dienyl] titanium triisopropoxide, [1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1- (3 5-dimethylphenyl) bis (3,4,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titani Beam triisopropoxide,

  [1-Phenyl (2-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (3-methylphenyl ) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (4-methylphenyl) (3,5-diethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (2,4-dimethylphenyl) ( , 5-Diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (2,5-dimethylphenyl) (3,5-diethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (2,6-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (3,5-diethylphenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium triisopropoxide,

  [1-di (2-methylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (3-methylphenyl) ) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (4-methylphenyl) (3,5-diethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2,3-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2,4-dimethylphenyl) (3,5-diethylphenyl) Ryl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2,5-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4 , 5-Tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2,6-dimethylphenyl) (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopenta Dienyl] titanium triisopropoxide, [1-tris (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1- (3 5-diethylphenyl) bis (3,4,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titani Beam triisopropoxide,

  [1-Phenyl (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (3 -Methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (4-methylphenyl) (5 -Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (2,3-dimethylphenyl) (5-methyl-3 -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] tita Umtriisopropoxide, [1-phenyl (2,4-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxy [1-phenyl (2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1 -Phenyl (2,6-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-phenyl (5 -Methyl-3-trimethylsilyl-phenyl) (3,4,5-trimethylphenyl) silyl-2 3,4,5-tetramethyl-cyclopentadienyl] titanium triisopropoxide,

  [1-di (2-methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (3 -Methylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-di (4-methylphenyl) (5 -Methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2,3-dimethylphenyl) (5-methyl-3 -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxy [1-bis (2,4-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1 -Bis (2,5-dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-bis (2 , 6-Dimethylphenyl) (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, [1-tris (5-methyl-3 -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopro Oxide, [1- (5-methyl-3-trimethylsilyl-phenyl) bis (3,4,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide, etc. And silicon-substituted cyclopentadienyl titanium triisopropoxy complex.

  In the complexes exemplified here, “2,3,4,5-tetramethylcyclopentadienyl” is replaced with “2-methylcyclopentadienyl”, “3-methylcyclopentadienyl”, “2,3- “Dimethylcyclopentadienyl”, “2,4-dimethylcyclopentadienyl”, “2,5-dimethylcyclopentadienyl”, “2,3,5-trimethylcyclopentadienyl”, “2-ethylcyclo “Pentadienyl”, “3-ethylcyclopentadienyl”, “2-n-propylcyclopentadienyl”, “3-n-propylcyclopentadienyl”, “2-isopropylcyclopentadienyl”, “ “3-isopropylcyclopentadienyl”, “2-n-butylcyclopentadienyl”, “3-n-butylcyclopentadienyl”, “2-sec- “Tylcyclopentadienyl”, “3-sec-butylcyclopentadienyl”, “2-tert-butylcyclopentadienyl”, “3-tert-butylcyclopentadienyl”, “2-phenylcyclopentadienyl” “Enyl”, “3-phenylcyclopentadienyl”, “2-benzylcyclopentadienyl”, “3-benzylcyclopentadienyl”, “indenyl”, “2-methylindenyl”, “fluorenyl”, “ Silicon substituted cyclopentadienyl titanium triisopropoxy complexes substituted with “tetrahydroindenyl”, “2-methyltetrahydroindenyl”, “octahydrofluorenyl” are also exemplified.

<Process (iii)>

［式中、Ｍ^２は元素の周期律表の第３族〜第１４族の原子を表し、Ｘ^５はハロゲン原子を表し、Ｒ^１５は水素原子、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、又は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のアリール基を表し、ｎは１以上の整数であり、ｍ＋ｎはＭ^２の価数に等しい整数である。］
で表されるハロゲン化合物を反応させる工程である。 Step (iii) in the method for producing a silicon-substituted cyclopentadienyl titanium trihalide means that the silicon-substituted cyclopentadienyl trialkoxide (6) is represented by the general formula (7)

[Wherein M ² represents an atom belonging to Group 3 to Group 14 of the periodic table of elements, X ⁵ represents a halogen atom, and R ¹⁵ has a hydrogen atom or a halogen atom as a substituent. A good alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, n is an integer of 1 or more, and m + n is M ² An integer equal to the valence. ]
Is a step of reacting a halogen compound represented by the formula:

In the halogen compound (7), M ² represents an atom of Group 3 to Group 14 of the periodic table of elements, for example, scandium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom. , Chromium atom, manganese atom, iron atom, cobalt atom, nickel atom, copper atom, zinc atom, boron atom, aluminum atom, gallium atom, indium atom, thallium atom, carbon atom, silicon atom, germanium atom, tin atom, lead An atom, preferably a titanium atom, a boron atom, an aluminum atom, a carbon atom, or a silicon atom, and more preferably a silicon atom.

In the halogen compound (7), n represents an integer of 1 or more, m + n is an integer equal to the valence of M ^2. For example, if ^{M 2} is silicon, n is an integer from 1 to 4, m + n is 4.

  Specific examples of the halogen compound (7) include the following compounds.

  Tetrachlorosilane, trichlorosilane, dichlorosilane, chlorosilane, methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, n-butyltrichlorosilane, tert-butyltrichlorosilane, phenyltrichlorosilane, dimethylchlorosilane, dimethyldi Chlorosilane, diethylchlorosilane, diethyldichlorosilane, di (n-propyl) chlorosilane, di (n-propyl) dichlorosilane, diisopropylchlorosilane, diisopropyldichlorosilane, di (n-butyl) chlorosilane, di (n-butyl) dichlorosilane, Di (tert-butyl) chlorosilane, di (tert-butyl) dichlorosilane, diphenylchlorosilane, diphenyldichlorosilane, Silicon halide compounds such as limethylchlorosilane, triethylchlorosilane, tri (n-propyl) chlorosilane, triisopropylchlorosilane, tri (n-butyl) chlorosilane, tri (tert-butyl) chlorosilane, triphenylchlorosilane, carbon tetrachloride, four Examples thereof include halogenated carbon compounds such as carbon bromide and carbon tetraiodide, and halogenated germanium compounds such as germanium tetrachloride.

  In addition, metal chlorides such as titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, boron trichloride, aluminum trichloride, gallium trichloride, indium trichloride, thallium chloride, tin tetrachloride, and lead chloride are also included. .

  The usage-amount of a halogen compound (7) should just be the range of 1-20 mol per mol of silicon substituted cyclopentadienyl titanium trialkoxide (6).

  In the step (iii), the silicon-substituted cyclopentadienyl titanium trialkoxide (6) and the halogen compound (7) are preferably reacted in the presence of a solvent.

  As the solvent used in the step (iii), an inert solvent that does not significantly disturb the progress of the reaction relating 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. These solvents can be used alone or in admixture of two or more. The amount used is preferably 1 to 200 parts by weight per 1 part by weight of the silicon-substituted cyclopentadienyl titanium trialkoxide (6), and 3 to 50 Part by weight is more preferred.

  The reaction temperature in the step (iii) may be -100 ° C or higher and not higher than the boiling point of the solvent, and is preferably in the range of -80 to 100 ° C.

  Thus, the produced silicon-substituted cyclopentadienyl titanium trihalide (1) can be extracted from the reaction mixture obtained through steps (i) to (iii) by various known purification methods. For example, after the produced precipitate is filtered off, the filtrate is concentrated to precipitate silicon-substituted cyclopentadienyl titanium trihalide (1), and then the target silicon-substituted cyclopentadienyl titanium is collected by a method of filtering it. Trihalide (1) can be obtained.

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)
Apparatus: Bruker Biospin DPX300
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, OBNUC ¹ H, PULPROG zg30, integration times 16 times or more Repeat time: ACQTM 2.7 seconds, PD 1 second Internal standard: CDCl ₃ (7.26 ppm)

(2) Carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR)
Apparatus: Bruker Biospin DPX300
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 parameter: 5 mmφ probe, OBNUC ¹³ C, PULPROG zgpg30, number of integration 256 times or more Repeat time: ACQTM 1.36 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-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride (hereinafter referred to as“ complex 1 ”)”

“Synthesis of [1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Thereafter, the obtained potassium hydride (1.04 g, 26.00 mmol) and tetrahydrofuran (103 mL) were mixed. To this mixture, a solution of 1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (9.30 g, 20.00 mmol) dissolved in tetrahydrofuran (90 mL) was added dropwise. And stirred at 50 ° C. for 7 hours. The obtained mixture was cooled to room temperature, and insoluble matters were removed by filtration. The obtained filtrate was cooled to −78 ° C., and a solution of chlorotriisopropoxytitanium (5.21 g, 20.00 mmol) dissolved in tetrahydrofuran (21 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, pentane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure to obtain [1-tris (3,5-dimethylphenyl). ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide was obtained as a pale yellow solid (12.95 g, 94.0% yield).
¹ H-NMR (CDCl ₃ , δ ppm): 1.10 (d, J = 5.9 Hz, 18H), 1.67 (s, 6H), 1.99 (s, 6H), 2.26 (s, 18H), 4.53 (sep, J = 5.9 Hz, 3H), 6.98 (s, 3H), 7.25 (s, 6H)
¹³ C-NMR (CDCl ₃ , δ ppm): 11.76, 14.94, 21.51, 26.50, 75.69, 112.65, 126.37, 130.55, 131.16, 134.59 136.18, 136.42
Mass spectrum (EI-MS, m / z): 688 (M ⁺ )

“Synthesis of Complex 1”
Toluene solution of [1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide (11.75 g, 17.06 mmol) under nitrogen atmosphere (290 mL) was added dropwise with a solution of silicon tetrachloride (28.98 g, 170.57 mmol) in toluene (145 mL) at 0 ° C., gradually warmed to room temperature, and then stirred at room temperature for 4 hours. . The solvent was concentrated under reduced pressure, and heptane was added and filtered. Heptane-insoluble matter was extracted with toluene, the solvent was concentrated under reduced pressure, and then dried under reduced pressure to obtain 4.89 g of a mixture containing Complex 1. The solvent was concentrated from the above heptane-washed filtrate under reduced pressure, washed with pentane, and dried under reduced pressure to obtain 2.94 g of a mixture containing Complex 1. The mixture containing these complexes 1 were combined, further washed with pentane, and then dried under reduced pressure to obtain complex 1 (7.52 g, yield 71.4%) as an orange solid. The yield of complex 1 was 67.1% by a two-step reaction using 1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene as a starting material.
¹ H-NMR (CDCl ₃ , δ ppm): 2.03 (s, 6H), 2.27 (s, 18H), 2.36 (s, 6H), 7.06 (s, 3H), 7.20 (S, 6H)
¹³ C-NMR (CDCl ₃ , δ ppm): 14.52, 17.83, 21.41, 131.63, 132.93, 134.60, 137.03, 142.26, 146.34
Mass spectrum (EI-MS, m / z): 616 (M ⁺ )
[Example 2]
“Synthesis of [1-tris (3,5-dimethylphenyl) silyl-2,3,5-trimethylcyclopentadienyl] titanium trichloride (hereinafter referred to as“ complex 2 ”)”

“Synthesis of 1-tris (3,5-dimethylphenyl) silyl-2,3,5-trimethylcyclopentadiene”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Then, the obtained potassium hydride (0.88 g, 21.85 mmol) and tetrahydrofuran (51 mL) were mixed. The mixture was heated to 50 ° C., and a solution of 1,3,4-trimethylcyclopenta-1,3-diene (2.00 g, 18.49 mmol) dissolved in tetrahydrofuran (13 mL) was added dropwise. For one and a half hours. To this solution, a solution of chlorotris (3,5-dimethylphenyl) silane (6.37 g, 16.81 mmol) dissolved in tetrahydrofuran (32 mL) was added dropwise, stirred at 50 ° C. for 2 hours, and then refluxed for 12 hours. Stir. The resulting mixture was added dropwise at 0 ° C. to a mixed solution of 10% sodium hydrogen carbonate (32 mL) and 10% sodium carbonate (32 mL). Toluene (32 mL) was added for liquid separation. The oil phase was dried over sodium sulfate, filtered and the solvent was concentrated under reduced pressure. After removing insolubles by adding hexane, the filtrate was concentrated under reduced pressure. By recrystallization from pentane, 1-tris (3,5-dimethylphenyl) silyl-2,3,5-trimethylcyclopentadiene was obtained (1.80 g, yield 22.4%).
¹ H-NMR (CDCl ₃ , δ ppm): 1.50 (s, 3H), 1.62 (s, 3H), 1.71 (s, 3H), 2.27 (s, 18H), 3.77 (S, 1H), 5.87 (s, 1H), 7.00 (s, 3H), 7.19 (s, 6H)
¹³ C-NMR (CDCl ₃ , δ ppm): 12.45, 14.74, 17.67, 21.47, 51.86, 130.92, 132.32, 133.52, 134.08, 134.53 135.33, 136.49, 141.90.
Mass spectrum (EI-MS, m / z): 450 (M ^<+> )

“Synthesis of [1-tris (3,5-dimethylphenyl) silyl-2,3,5-trimethylcyclopentadienyl] titanium triisopropoxide”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Then, the obtained potassium hydride (0.10 g, 2.45 mmol) and tetrahydrofuran (8.5 mL) were mixed. The mixture was heated to 50 ° C., and 1-tris (3,5-dimethylphenyl) silyl-2,3,5-trimethylcyclopentadiene (0.85 g, 1.89 mmol) was dissolved in tetrahydrofuran (4.5 mL). The solution was dropped and stirred at 50 ° C. for 3 hours. The obtained mixture was cooled to room temperature, and insoluble matters were removed by filtration. The obtained filtrate was cooled to −78 ° C., and a solution of chlorotriisopropoxytitanium (0.49 g, 1.89 mmol) dissolved in tetrahydrofuran (8.5 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, pentane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure to obtain [1-tris (3,5-dimethylphenyl). ) Silyl-2,3,5-trimethylcyclopentadienyl] titanium triisopropoxide was obtained as a pale yellow solid (1.14 g, 89.8% yield).
¹ H-NMR (CDCl ₃ , δ ppm): 1.11 (d, J = 6.2 Hz, 9H), 1.13 (d, J = 6.2 Hz, 9H), 1.62 (s, 3H), 1.72 (s, 3H), 2.02 (s, 3H), 2.26 (s, 18H), 4.57 (sep, J = 6.2 Hz, 3H), 5.98 (s, 1H) 6.98 (s, 3H), 7.28 (s, 6H)
¹³ C-NMR (CDCl ₃ , δ ppm): 12.82, 14.91, 17.17, 21.51, 26.17, 26.38, 76.62, 115.43, 117.55, 123.91 130.59, 132.12, 134.64, 135.06, 136.01, 136.18
Mass spectrum (EI-MS, m / z): 674 (M ⁺ )

“Synthesis of Complex 2”
Under a nitrogen atmosphere, [1-tris (3,5-dimethylphenyl) silyl-2,3,5-trimethylcyclopentadienyl] titanium triisopropoxide (1.05 g, 1.56 mmol) in toluene (21 mL) A solution of silicon tetrachloride (2.64 g, 15.56 mmol) in toluene (16 mL) was added dropwise at 0 ° C., and the mixture was gradually warmed to room temperature and stirred at room temperature for 1 hour. After concentrating the solvent under reduced pressure, toluene (21 mL) was added again, and a solution of silicon tetrachloride (1.32 g, 7.78 mmol) dissolved in toluene (8 mL) was added dropwise at 0 ° C., and gradually brought to room temperature. After raising the temperature, the mixture was stirred at room temperature for 1 hour. After the solvent was concentrated under reduced pressure, insoluble matters were removed by adding pentane to the residue and filtering. The solvent was concentrated from the filtrate under reduced pressure and recrystallized from pentane to obtain Complex 2 as an orange solid (0.65 g, yield 69.1%). The yield of Complex 2 was 62.1% by a two-step reaction using 1-tris (3,5-dimethylphenyl) silyl-2,3,5-trimethylcyclopentadiene as a starting material.
¹ H-NMR (CDCl ₃ , δ ppm): 2.00 (s, 3H), 2.05 (s, 3H), 2.28 (s, 18H), 2.36 (s, 3H), 6.84 (S, 1H), 7.07 (s, 3H), 7.21 (s, 6H)
¹³ C-NMR (CDCl ₃ , δ ppm): 16.06, 17.43, 20.05, 21.41, 130.07, 131.71, 132.56, 134.54, 136.39, 137.09 142.69, 146.69, 148.14.
Mass spectrum (EI-MS, m / z): 602 (M ⁺ )

[Example 3]
“[1- (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride (hereinafter“ complex ”) 3 ”))”

“Synthesis of trichloro (3,5-di-tert-butylphenyl) silane”
Under nitrogen atmosphere, 1-bromo-3,5-di-tert-butylbenzene (35.00 g, 130.00 mmol) in diethyl ether solution (175 mL) at −78 ° C. with 1.65 M hexane solution of n-butyllithium. (88.67 mL, 143.00 mmol) was added dropwise, and the temperature was gradually raised to room temperature, followed by stirring at room temperature for 2 hours. The obtained mixture was added dropwise to a solution of tetrachlorosilane (66.26 g, 390.00 mmol) dissolved in diethyl ether (58 mL) at −78 ° C., gradually warmed to room temperature, and then at room temperature for 3 hours. Stir. After the reaction, the solvent was concentrated under reduced pressure, hexane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. Purification by vacuum distillation gave trichloro (3,5-di-tert-butylphenyl) silane (24.11 g, yield 57.3%).
¹ H-NMR (CDCl ₃ , δ ppm): 1.36 (s, 18H), 7.61-7.67 (m, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): 31.51, 35.25, 127.23, 127.39, 130.75, 151.26
Mass spectrum (EI-MS, m / z): 322 (M ⁺ )

“Synthesis of Chloro (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silane”
Under a nitrogen atmosphere, a solution of trichloro (3,5-di-tert-butylphenyl) silane (12.95 g, 40.00 mmol) in diethyl ether (74 mL) at −78 ° C. with 3,5-dimethylphenyllithium (11. A solution prepared by dissolving 09 g, 98.96 mmol) in diethyl ether (95 mL) was added dropwise, gradually warmed to room temperature, and then stirred at room temperature for 2 hours. After the reaction, the solvent was concentrated under reduced pressure, hexane was added to the residue, and the insoluble matter was removed by filtration. The solvent was concentrated from the filtrate under reduced pressure to quantitatively obtain chloro (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silane.
¹ H-NMR (CDCl ₃ , δ ppm): 1.30 (s, 18H), 2.31 (s, 12H), 7.10 (s, 2H), 7.28 (s, 4H), 7.52 (S, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): 21.51, 31.57, 35.09, 124.72, 129.67, 131.88, 132.45, 133.04, 133.36, 137.46 , 150.08
Mass spectrum (EI-MS, m / z): 462 (M ⁺ )

“Synthesis of 1- (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Then, the obtained potassium hydride (1.09 g, 27.27 mmol) and tetrahydrofuran (39 mL) were mixed. The mixture was heated to 50 ° C., and a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (2.44 g, 20.00 mmol) dissolved in tetrahydrofuran (8 mL) was added dropwise. , And stirred at 50 ° C. for 3 hours. A solution prepared by dissolving chloro (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silane (8.42 g, 18.18 mmol) in tetrahydrofuran (19 mL) at 50 ° C. was added dropwise to this solution. And stirred at the same temperature for 6 hours. The resulting mixture was added dropwise at 0 ° C. to a 10% aqueous sodium carbonate solution (50 ml). Toluene (50 mL) was added for liquid separation, and the oil phase was washed twice with water (50 mL), and further with saturated brine (50 mL). The oil phase was dried over sodium sulfate, filtered and the solvent was concentrated under reduced pressure. The obtained solid was washed with a small amount of hexane and then dried under reduced pressure to give 1- (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4, 5-tetramethylcyclopentadiene was obtained (5.18 g, yield 51.9%).
¹ H-NMR (CDCl ₃ , δ ppm): 1.31 (s, 18H), 1.56 (s, 6H), 1.63 (s, 6H), 2.29 (s, 12H), 3.76 (S, 1H), 7.00 (s, 2H), 7.29 (s, 4H), 7.39-7.47 (m, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): 11.36, 15.01, 21.59, 31.63, 34.95, 51.41, 122.80, 130.47, 130.77, 131.64 133.44, 133.60, 135.45, 136.58, 136.69, 148.88
Mass spectrum (EI-MS, m / z): 548 (M ⁺ )

“Synthesis of [1- (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Thereafter, the obtained potassium hydride (0.15 g, 3.64 mmol) and tetrahydrofuran (34 mL) were mixed. To this mixture was added 1- (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (1.54 g, 2.80 mmol) at room temperature. ) In tetrahydrofuran (11 mL) was added dropwise and then stirred at 50 ° C. for 7 hours. The obtained mixture was cooled to room temperature, and insoluble matters were removed by filtration. The obtained filtrate was cooled to −78 ° C., and a solution of chlorotriisopropoxytitanium (0.73 g, 2.80 mmol) in tetrahydrofuran (7 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, and insoluble matters were removed by adding pentane to the residue and filtering, and the solvent was concentrated from the filtrate under reduced pressure. The obtained solid was washed with a small amount of pentane and then dried under reduced pressure, whereby [1- (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] titanium triisopropoxide was obtained (1.93 g, 89.4% yield).
¹ H-NMR (CDCl ₃ , δ ppm): 1.11 (d, J = 6.2 Hz, 18H), 1.24 (s, 18H), 1.68 (s, 6H), 1.99 (s, 6H), 2.26 (s, 12H), 4.55 (sep, J = 6.2 Hz, 3H), 6.96 (s, 2H), 7.21 (d, J = 1.8 Hz, 2H) 7.36 (t, J = 1.8 Hz, 1H), 7.39 (s, 4H)
¹³ C-NMR (CDCl ₃ , δ ppm): 11.61, 14.87, 21.47, 26.52, 31.38, 34.77, 75.60, 113.00, 122.10, 126.62 , 130.44, 131.39, 131.56, 134.33, 134.39, 136.12, 137.01, 148.68
Mass spectrum (EI-MS, m / z): 772 (M ⁺ )

“Synthesis of Complex 3”
[1- (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide under nitrogen atmosphere To a toluene solution (4 mL) of (0.22 g, 0.28 mmol), a solution of silicon tetrachloride (0.48 g, 2.85 mmol) in toluene (3 mL) was added dropwise at 0 ° C., and gradually brought to room temperature. After raising the temperature, the mixture was stirred at room temperature for 3 hours. After the reaction, the solvent was concentrated under reduced pressure, and insoluble matter was removed by adding heptane to the residue and filtering. The solvent was concentrated from the filtrate under reduced pressure and recrystallized from pentane to obtain Complex 3 as an orange solid (0.17 g, yield 87.3%). Complex 3 by a two-step reaction starting from 1- (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene The yield of was 78.0%.
¹ H-NMR (CDCl ₃ , δ ppm): 1.25 (s, 18H), 2.04 (s, 6H), 2.27 (s, 12H), 2.36 (s, 6H), 7.06 (S, 2H), 7.25 (s, 4H), 7.45 (s, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): 14.40, 17.65, 21.37, 31.33, 34.91, 123.39, 131.40, 131.50, 131.58, 133.11. 134.51, 136.97, 137.52, 142.38, 146.04, 149.49
Mass spectrum (EI-MS, m / z): 702 (M ⁻ )

[Example 4]
“[1- (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride (hereinafter, Synthesis of “Complex 4”)

“Synthesis of dichloro (3,5-di-tert-butylphenyl) (phenyl) silane”
1.65 M hexane solution of n-butyllithium in diethyl ether solution (106 mL) of 1-bromo-3,5-di-tert-butylbenzene (10.60 g, 39.37 mmol) at −78 ° C. under nitrogen atmosphere (23.86 mL, 39.37 mmol) was added dropwise, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 3 hours. The obtained mixture was added dropwise to a diethyl ether solution (106 mL) of trichlorophenylsilane (24.99 g, 118.12 mmol) at −78 ° C., gradually warmed to room temperature, and stirred at room temperature. After the reaction, the solvent was concentrated under reduced pressure, hexane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. Dichloro (3,5-di-tert-butylphenyl) (phenyl) silane was obtained by heating to 100 ° C. under reduced pressure to remove trichlorophenylsilane (11.77 g, yield 81.8%). .
¹ H-NMR (CDCl ₃ , δ ppm): 1.33 (s, 18H), 7.43-7.63 (m, 6H), 7.73-7.78 (m, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm): 31.37, 35.00, 125.75, 126.11, 128.10, 128.25, 130.69, 131.59, 134.09, 150.63
Mass spectrum (EI-MS, m / z): 364 (M ⁺ )

“Synthesis of Chloro (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silane”
Under a nitrogen atmosphere, dichloro (3,5-di-tert-butylphenyl) (phenyl) silane (7.00 g, 19.16 mmol) in diethyl ether solution (70 mL) at −20 ° C. with 3,5-dimethylphenyllithium A solution prepared by dissolving (2.15 g, 19.16 mmol) in diethyl ether (22 mL) was added dropwise, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature. 3,5-Dimethylphenyllithium (1.26 g, 11.24 mmol) was added, and the mixture was further stirred at room temperature. After the reaction, the solvent was concentrated under reduced pressure, hexane was added to the residue, and the insoluble matter was removed by filtration. The solvent was concentrated from the filtrate under reduced pressure, and chloro (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silane (7.21 g, yield 86.5%) was added to a yellow oil. Got as.
¹ H-NMR (CDCl ₃ , δ ppm): 1.22 (s, 18H), 2.23 (s, 6H), 7.03 (s, 1H), 7.20 (s, 2H), 7.26 -7.48 (m, 6H), 7.55-7.62 (m, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm): 21.34, 31.39, 34.92, 124.71, 125.75, 127.93, 129.40, 130.43, 131.51, 132.37 132.89, 133.69, 135.20, 137.37, 150.01
Mass spectrum (EI-MS, m / z): 434 (M ⁺ )

“Synthesis of 1- (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Thereafter, the obtained potassium hydride (0.98 g, 24.55 mmol) and tetrahydrofuran (75 mL) were mixed. The mixture was heated to 50 ° C., and a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (2.40 g, 19.64 mmol) dissolved in tetrahydrofuran (19 mL) was added dropwise. , And stirred at 50 ° C. for 1 hour. A solution of chloro (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silane (7.12 g, 16.37 mmol) dissolved in tetrahydrofuran (47 mL) at 50 ° C. in this solution. Was added dropwise and stirred under reflux for 3 hours. The resulting mixture was added dropwise at 0 ° C. to a mixed solution of 10% sodium hydrogen carbonate (47 mL) and 10% sodium carbonate (47 mL). Toluene (47 mL) was added for liquid separation, and the oil phase was washed with water (100 mL). The oil phase was dried over sodium sulfate, filtered and the solvent was concentrated under reduced pressure. The obtained solid was washed with a small amount of hexane and then dried under reduced pressure to give 1- (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silyl-2,3. 4,5-tetramethylcyclopentadiene was obtained (3.54 g, yield 41.5%).
¹ H-NMR (CDCl ₃ , δ ppm): 1.28 (s, 18H), 1.53 (s, 6H), 1.61 (s, 6H), 2.27 (s, 6H), 3.73 (S, 1H), 6.99 (s, 1H), 7.26 (s, 2H), 7.28-7.34 (m, 3H), 7.40 (s, 3H), 7.62 ( dd, J = 7.3, 2.1 Hz, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm): 11.21, 14.77, 21.43, 31.47, 34.80, 51.23, 122.83, 127.37, 128.89, 130.22 130.71, 131.53, 133.29, 133.45, 134.88, 135.67, 135.90, 136.49, 136.67, 148.93
Mass spectrum (EI-MS, m / z): 520 (M ⁺ )

“[1- (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide Synthesis ''
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Then, the obtained potassium hydride (0.26 g, 6.40 mmol) and tetrahydrofuran (20 mL) were mixed. To this mixture was added 1- (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (2.57 g, 4 at room temperature). .92 mmol) in tetrahydrofuran (28 mL) was added dropwise, followed by stirring at 50 ° C. for 7 hours. The obtained mixture was cooled to room temperature, and insoluble matters were removed by filtration. The obtained filtrate was cooled to −78 ° C., and a solution of chlorotriisopropoxytitanium (1.28 g, 4.92 mmol) in tetrahydrofuran (26 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, pentane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure to give [1- (3,5-di-tert. -Butylphenyl) (3,5-dimethylphenyl) (phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide was obtained (3.41 g, yield 92.9). %).
¹ H-NMR (CDCl ₃ , δ ppm): 1.11 (dd, J = 5.9, 1.5 Hz, 18H), 1.23 (s, 18H), 1.67 (s, 6H), 1. 99 (s, 6H), 2.45 (s, 6H), 4.55 (sep, J = 5.9 Hz, 3H), 6.96 (s, 1H), 7.20-7.44 (m, 8H), 7.46 (dd, J = 7.7, 1.8 Hz, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm): 11.59, 11.64, 14.87, 21.44, 26.46, 31.39, 34.77, 75.58, 112.70, 122.33 126.35, 126.65, 127.13, 128.56, 130.52, 131.42, 131.60, 134.32, 134.42, 136.19, 136.72, 136.81, 137 .24, 148.83
Mass spectrum (EI-MS, m / z): 744 (M ⁺ )

“Synthesis of Complex 4”
Under nitrogen atmosphere, [1- (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triiso To a toluene solution (30 mL) of propoxide (1.49 g, 2.00 mmol), a solution of silicon tetrachloride (3.40 g, 20.00 mmol) dissolved in toluene (20 mL) at 0 ° C. was dropped, and gradually After heating up to room temperature, it stirred at room temperature for 3 hours. After the reaction, the solvent was concentrated under reduced pressure, and insoluble matter was removed by adding heptane to the residue and filtering. The solvent was concentrated from the filtrate under reduced pressure and recrystallized from pentane to obtain Complex 4 as an orange solid (0.73 g, yield 54.0%). By a two-step reaction starting from 1- (3,5-di-tert-butylphenyl) (3,5-dimethylphenyl) (phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, The yield of complex 4 was 50.1%.
¹ H-NMR (CDCl ₃ , δ ppm): 1.25 (s, 18H), 2.02 (s, 3H), 2.05 (s, 3H), 2.28 (s, 6H), 2.36 (S, 6H), 7.07 (s, 1H), 7.30 (s, 2H), 7.32-7.45 (m, 3H), 7.46 (s, 3H), 7.55- 7.60 (m, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm): 14.40, 17.59, 17.67, 21.37, 31.34, 34.92, 123.58, 127.82, 129.81, 131.23 131.55, 131.59, 132.81, 133.83, 134.55, 136.76, 137.006, 142.38, 146.00, 146.06, 149.63
Mass spectrum (EI-MS, m / z): 674 (M ⁻ )

[Example 5]
“Synthesis of [1-tris (3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride (hereinafter referred to as“ complex 5 ”)”

"Synthesis of chlorotris (3-trimethylsilyl-phenyl) silane"
Diethyl ether (100 mL) was added to 1-bromo-3-trimethylsilylbenzene (20.00 g, 87.27 mmol) under a nitrogen atmosphere. The mixture was cooled to −78 ° C., a 1.65 M hexane solution of n-butyllithium (53.73 mL, 88.65 mmol) was added dropwise, the temperature was raised to 0 ° C., and the mixture was stirred at that temperature for 2 hours. The obtained mixture was sent at −78 ° C. to a solution of tetrachlorosilane (4.71 g, 27.70 mmol) dissolved in diethyl ether (33 mL). After stirring at −78 ° C. for 50 minutes, the temperature was gradually raised to room temperature. After the reaction, the solvent was concentrated under reduced pressure, hexane was added to the residue, and the insoluble matter was removed by filtration. The solvent was concentrated from the filtrate under reduced pressure to quantitatively obtain chlorotris (3-trimethylsilyl-phenyl) silane.
¹ H-NMR (CDCl ₃ , δ ppm): 0.20 (s, 27H), 7.36 (t, J = 7.3 Hz, 3H), 7.60 (d, J = 8.4 Hz, 6H), 7.79 (s, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): −1.02, 127.44, 132.25, 135.75, 135.80, 140.15, 140.22
Mass spectrum (EI-MS, m / z): 510 (M ⁺ )

“Synthesis of 1-tris (3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Thereafter, the obtained potassium hydride (1.20 g, 30.00 mmol) and tetrahydrofuran (43 mL) were mixed. The mixture was heated to 50 ° C., and a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (2.69 g, 22.00 mmol) dissolved in tetrahydrofuran (9 mL) was added dropwise. The mixture was stirred at 50 ° C. for 3.5 hours. A solution of chlorotris (3-trimethylsilyl-phenyl) silane (10.23 g, 20.00 mmol) dissolved in tetrahydrofuran (43 mL) was added dropwise to this solution, and the mixture was stirred at 50 ° C. for 8 hours. The resulting mixture was added dropwise at 0 ° C. to a 10% aqueous sodium carbonate solution (40 ml). Toluene (60 mL) was added for liquid separation, and the oil phase was washed twice with water (60 mL) and further with saturated brine (60 mL). 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-tris (3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (7.08 g, yield 59.3%).
¹ H-NMR (CDCl ₃ , δ ppm): 0.20 (s, 27H), 1.51 (s, 6H), 1.54 (s, 6H), 3.76 (s, 1H), 7.19 -7.33 (m, 3H), 7.46-7.60 (m, 6H), 7.77 (s, 3H)
Mass spectrum (EI-MS, m / z): 596 (M ⁺ )

“Synthesis of [1-tris (3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Then, the obtained potassium hydride (0.13 g, 3.25 mmol) and tetrahydrofuran (34 mL) were mixed. To this mixture was added dropwise a solution of 1-tris (3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (1.49 g, 2.50 mmol) dissolved in tetrahydrofuran (11 mL). And stirred at 50 ° C. for 6 hours. The obtained mixture was cooled to room temperature, and insoluble matters were removed by filtration. The obtained filtrate was cooled to −78 ° C., and a solution of chlorotriisopropoxytitanium (0.65 g, 2.50 mmol) dissolved in tetrahydrofuran (7 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, insolubles were removed by adding pentane to the residue and filtered, and the solvent was concentrated from the filtrate under reduced pressure to give [1-tris (3-trimethylsilyl-phenyl]. ) Silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide was obtained quantitatively as an orange oil.
¹ H-NMR (CDCl ₃ , δ ppm): 0.15 (s, 27H), 1.09 (d, J = 6.2 Hz, 18H), 1.66 (s, 6H), 1.99 (s, 6H), 4.53 (sep, J = 6.2 Hz, 3H), 7.31 (t, J = 7.3 Hz, 3H), 7.50 (d, J = 7.3 Hz, 3H), 7. 61 (s, 3H), 7.82 (d, J = 7.3 Hz, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): −1.13, 11.65, 15.01, 26.44, 75.63, 112.20, 126.60, 131.54, 133.70, 135. 54, 136.12, 137.70, 138.44, 141.38
Mass spectrum (EI-MS, m / z): 820 (M ⁺ )

“Synthesis of Complex 5”
Under a nitrogen atmosphere, a toluene solution of [1-tris (3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide (2.05 g, 2.50 mmol) 42 mL), a solution of silicon tetrachloride (4.25 g, 25.00 mmol) in toluene (21 mL) was added dropwise at 0 ° C., and the mixture was gradually warmed to room temperature and then stirred at room temperature for 3 hours. After the reaction, the solvent was concentrated under reduced pressure, and insoluble matter was removed by adding heptane to the residue and filtering. The solvent was concentrated from the filtrate under reduced pressure and recrystallized from pentane to obtain Complex 5 as an orange solid (0.30 g, yield 15.8%). The yield of Complex 5 was 15.8% by a two-step reaction using 1-tris (3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene as a starting material.
¹ H-NMR (CDCl ₃ , δ ppm): 0.21 (s, 27H), 2.01 (s, 6H), 2.35 (s, 6H), 7.34 (t, J = 7.3 Hz, 3H), 7.53 (dt, J = 7.3, 1.4 Hz, 3H), 7.59 (dt, J = 7.3, 1.4 Hz, 3H), 7.86 (s, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): −1.19, 14.32, 17.59, 127.14, 132.00, 134.89, 136.08, 137.06, 139.83, 142. 08, 142.44, 145.76
Mass spectrum (EI-MS, m / z): 750 (M ⁻ )

[Example 6]
“Synthesis of [1-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride (hereinafter referred to as“ complex 6 ”)”
"Synthesis of chlorotris (5-methyl-3-trimethylsilyl-phenyl) silane"
Under a nitrogen atmosphere, 5-methyl-3-trimethylsilyl-1-bromobenzene (20.06 g, 82.49 mmol) and diethyl ether (200 mL) were added. The mixture was cooled to −78 ° C., a 1.65 M hexane solution of n-butyllithium (50.00 mL, 82.49 mmol) was added dropwise, the temperature was raised to 0 ° C., and the mixture was stirred at that temperature for 3 hours. The obtained mixture was sent at −78 ° C. to a solution of tetrachlorosilane (4.45 g, 26.19 mmol) dissolved in diethyl ether (44 mL). After stirring at −78 ° C. for 10 minutes, the temperature was gradually raised to room temperature. After the reaction, the solvent was concentrated under reduced pressure, hexane was added to the residue and filtered to remove the hexane-insoluble portion by celite filtration, and the solvent was concentrated from the filtrate under reduced pressure to obtain chlorotris (5-methyl-3 -Trimethylsilyl-phenyl) silane (13.10 g, 90.4% yield) was obtained as a pale yellow oil.
¹ H-NMR (CDCl ₃ , δ ppm): 0.24 (s, 27H), 2.37 (s, 9H), 7.45 (s, 3H), 7.48 (s, 3H), 7.64 (S, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): −0.98, 21.72, 132.25, 136.41, 136.49, 136.62, 137.37, 139.94
Mass spectrum (EI-MS, m / z): 552 (M ⁺ )

“Synthesis of 1-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Thereafter, the obtained potassium hydride (0.88 g, 21.82 mmol) and tetrahydrofuran (38 mL) were mixed. The mixture was heated to 50 ° C., and a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (2.00 g, 16.37 mmol) dissolved in tetrahydrofuran (8 mL) was added dropwise. , And stirred at 50 ° C. for 1 hour. To this solution, a solution of chlorotris (5-methyl-3-trimethylsilyl-phenyl) silane (7.81 g, 14.11 mmol) dissolved in tetrahydrofuran (38 mL) was added dropwise and stirred at 65 ° C. for 3 hours. The resulting mixture was added dropwise at 0 ° C. to a mixed solution of 10% sodium hydrogen carbonate (38 mL) and 10% sodium carbonate (38 mL). Toluene (38 mL) was added 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-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (5.40 g, yield 59.9%). ).
¹ H-NMR (CDCl ₃ , δ ppm): 0.22 (s, 27H), 1.53 (s, 6H), 1.56 (s, 6H), 2.29 (s, 9H), 3.78 (S, 1H), 7.31 (s, 3H), 7.37 (s, 3H), 7.63 (s, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): −0.90, 11.25, 15.05, 21.77, 51.38, 133.22, 133.52, 134.83, 135.65, 136. 92, 136.99, 138.06, 138.79
Mass spectrum (EI-MS, m / z): 638 (M ⁺ )

“Synthesis of [1-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide”
Mineral oil was removed by washing potassium hydride dispersed in mineral oil with hexane under a nitrogen atmosphere. Thereafter, the obtained potassium hydride (0.29 g, 7.24 mmol) and tetrahydrofuran (36 mL) were mixed. The mixture was heated to 50 ° C., and 1-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (3.56 g, 5.57 mmol) was added to tetrahydrofuran (3.5 19 mL) was added dropwise, and the mixture was stirred at 50 ° C. for 6 hours. The obtained mixture was cooled to room temperature, and insoluble matters were removed by filtration. The obtained filtrate was cooled to −78 ° C., and a solution of chlorotriisopropoxytitanium (1.45 g, 5.57 mmol) in tetrahydrofuran (10 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, insolubles were removed by adding pentane to the residue and filtered, and the solvent was concentrated from the filtrate under reduced pressure to give [1-tris (5-methyl-3 -Trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide was quantitatively obtained as a pale yellow solid.
¹ H-NMR (CDCl ₃ , δ ppm): 0.14 (s, 27H), 1.08 (d, J = 6.2 Hz, 18H), 1.67 (s, 6H), 1.98 (s, 6H), 2.32 (s, 9H), 4.50 (quin, J = 6.2 Hz, 3H), 7.29 (s, 3H), 7.37 (s, 3H), 7.62 (s) 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): −1.12, 11.62, 15.03, 21.70, 26.52, 75.66, 112.59, 126.69, 131.28, 134. 41, 135.28, 135.52, 138.17, 138.94
Mass spectrum (EI-MS, m / z): 862 (M ⁺ )

“Synthesis of Complex 6”
[1-Tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium triisopropoxide (4.81 g, 5.57 mmol) under nitrogen atmosphere A solution prepared by dissolving silicon tetrachloride (9.47 g, 55.71 mmol) in toluene (56 mL) at 0 ° C. was added dropwise to a toluene solution (96 mL), and the temperature was gradually raised to room temperature. Stir for hours. After the reaction, the solvent was concentrated under reduced pressure, and insoluble matter was removed by adding heptane to the residue and filtering. The solvent was concentrated from the filtrate under reduced pressure and recrystallized from pentane to obtain Complex 6 as an orange solid (1.07 g, yield 24.4%). The yield of complex 6 was 24.4% by a two-step reaction starting from 1-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene. there were.
¹ H-NMR (CDCl ₃ , δ ppm): 0.19 (s, 27H), 2.02 (s, 6H), 2.30 (s, 9H), 2.35 (s, 6H), 7.38 (S, 3H), 7.41 (s, 3H), 7.59 (s, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): −1.17, 14.32, 17.63, 21.61, 131.94, 135.51, 136.11, 137.05, 137.78, 139. 21, 139.44, 142.43, 145.83
Mass spectrum (EI-MS, m / z): 792 (M ⁻ )

[Comparative Example 1]

“Synthesis of Complex 1”
Under a nitrogen atmosphere, 1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (0.93 g, 2.00 mmol), triethylamine (1.01 g, 10.00 mmol) To a toluene solution (20 mL) was added dropwise a 1.67 M hexane solution (1.32 mL, 2.20 mmol) of n-butyllithium at −78 ° C., and the mixture was gradually warmed to room temperature and then stirred at room temperature for 5 hours. . The obtained mixture was cooled to −78 ° C., and a solution of titanium tetrachloride (0.42 g, 2.20 mmol) in toluene (2 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, heptane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure to give complexes 1 and 2,2′-bis {tris ( 3,5-dimethylphenyl) silyl} -1,1 ′, 3,3 ′, 4,4 ′, 5,5′-octamethyl-5,5′-bi-1,3-cyclopentadienyl Obtained as an orange solid. Further, diethyl ether was added to the obtained mixture and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. After adding pentane and cooling to −20 ° C., the obtained solid was filtered, washed with a small amount of pentane, and then dried under reduced pressure to obtain Complex 1 (0.03 g, yield 2.7%) as an orange solid. Got as.
¹ H-NMR (CDCl ₃ , δ ppm): 2.03 (s, 6H), 2.27 (s, 18H), 2.36 (s, 6H), 7.06 (s, 3H), 7.20 (S, 6H)
¹³ C-NMR (CDCl ₃ , δ ppm): 14.52, 17.83, 21.41, 131.63, 132.93, 134.60, 137.03, 142.26, 146.34
Mass spectrum (EI-MS, m / z): 616 (M ⁺ )

[Comparative Example 2]

“Synthesis of Complex 3”
1- (3,5-Di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (2.20 g, 4.00 mmol) under nitrogen atmosphere To a toluene solution (45 mL) of triethylamine (2.02 g, 20.00 mmol), a 1.65 M hexane solution (2.91 mL, 4.80 mmol) of n-butyllithium was added dropwise at −78 ° C. and gradually brought to room temperature. After heating up, it stirred at 50 degreeC for 7 hours. The obtained mixture was cooled to −78 ° C., and a solution of titanium tetrachloride (0.83 g, 4.40 mmol) in toluene (4 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, heptane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. The obtained solid was washed with a small amount of pentane and then dried under reduced pressure to give complex 3 and 2,2′-bis {(3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl). A mixture of silyl} -1,1 ′, 3,3 ′, 4,4 ′, 5,5′-octamethyl-5,5′-bi-1,3-cyclopentadienyl was obtained as an orange solid. The content of Complex 3 determined by ¹ H-NMR using ferrocene as an internal standard substance was 60.5 wt% (0.53 g, yield 18.8%).
¹ H-NMR (CDCl ₃ , δ ppm): 1.28 (s, 18H), 2.07 (s, 6H), 2.30 (s, 12H), 2.39 (s, 6H), 7.08 (S, 2H), 7.28 (s, 4H), 7.48 (s, 3H)
Mass spectrum (EI-MS, m / z): 702 (M ⁻ )

[Comparative Example 3]

“Synthesis of Complex 5”
1-Tris (3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (0.88 g, 1.47 mmol), triethylamine (0.75 g, 7.37 mmol) in toluene under nitrogen atmosphere To the solution (20 mL), a 1.65 M hexane solution (0.98 mL, 1.62 mmol) of n-butyllithium was added dropwise at −78 ° C., the temperature was gradually raised to room temperature, and the mixture was stirred at 50 ° C. for 7 hours. . The resulting mixture was cooled to −45 ° C., and a solution of titanium tetrachloride (0.31 g, 1.62 mmol) in toluene (2 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, heptane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. The insoluble matter is removed by adding pentane to the obtained solid and filtering, and the solvent is concentrated from the filtrate under reduced pressure to give complex 5 and 2,2′-bis {tris (3-trimethylsilyl-phenyl) silyl. } -1,1 ′, 3,3 ′, 4,4 ′, 5,5′-octamethyl-5,5′-bi-1,3-cyclopentadienyl was obtained as an orange solid. The content of complex 5 determined by ¹ H-NMR using ferrocene as an internal standard was 11.7 wt% (76.4 mg, yield 6.9%).
¹ H-NMR (CDCl ₃ , δ ppm): 0.18 (s, 27H), 1.99 (s, 6H), 2.33 (s, 6H), 7.16-7.35 (m, 3H) 7.42-7.61 (m, 6H), 7.76 (s, 3H)
Mass spectrum (EI-MS, m / z): 750 (M ⁻ )

[Comparative Example 4]

“Synthesis of Complex 6”
Under a nitrogen atmosphere, 1-tris (5-methyl-3-trimethylsilyl-phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (1.84 g, 2.88 mmol), triethylamine (1.46 g, 14. 40 mmol) in a toluene solution (55 mL), a 1.63 M hexane solution (2.12 mL, 3.46 mmol) of n-butyllithium was added dropwise at −78 ° C., and the temperature was gradually raised to room temperature. Stir for 8 hours. The obtained mixture was cooled to −50 ° C., and a solution of titanium tetrachloride (0.60 g, 3.17 mmol) in toluene (6 mL) was added dropwise at the same temperature. The temperature was raised again, and the mixture was stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, heptane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. The supernatant obtained by adding pentane is concentrated under reduced pressure to give complex 6 and 2,2′-bis {tris (5-methyl-3-trimethylsilyl-phenyl) silyl} -1,1 ′, 3,3 A mixture of ', 4,4', 5,5'-octamethyl-5,5'-bi-1,3-cyclopentadienyl was obtained as an orange solid. The content of Complex 6 determined by ¹ H-NMR using ferrocene as an internal standard was 18.1 wt% (146.0 mg, yield 6.4%)
¹ H-NMR (CDCl ₃ , δ ppm): 0.19 (s, 27H), 2.02 (s, 6H), 2.30 (s, 9H), 2.35 (s, 6H), 7.38 (S, 3H), 7.41 (s, 3H), 7.59 (s, 3H)
¹³ C-NMR (CDCl ₃ , δ ppm): −1.17, 14.32, 17.63, 21.61, 131.94, 135.51, 136.11, 137.05, 137.78, 139. 21, 139.44, 142.43, 145.83
Mass spectrum (EI-MS, m / z): 792 (M ⁻ )

Claims (4)

The manufacturing method of the silicon substituted cyclopentadienyl titanium trihalide represented by General formula (1) which has the following process (i), process (ii), and process (iii).

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently
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 ⁸ ) ₃ (three R ⁸ 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 ⁸ is 1 to 20; A substituted silyl group represented by:
In -N ^(R ₉₎ 2 (two ^{R 9} each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, the total number of carbon atoms in the two ^{R 9} is 2-20.) The disubstituted amino group shown,
Or it is an aryl group represented by General formula (2).

{Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently
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 ⁸ ) ₃ (three R ⁸ 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 ⁸ is 1 to 20; A substituted silyl group represented by:
In -N ^(R ₉₎ 2 (two ^{R 9} each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, the total number of carbon atoms in the two ^{R 9} is 2-20.) Represents the disubstituted amino group shown. }
X ¹ , X ² and X ³ each independently represent a halogen atom. ]
Step (i):
General formula (3)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,

By reacting a silicon-substituted cyclopentadiene compound represented by the formula (4) with an alkali metal compound.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,
M ¹ is an alkali metal. ]
Step (ii) of producing a silicon-substituted cyclopentadienyl alkali metal compound represented by:
The silicon-substituted cyclopentadienyl alkali metal compound is represented by the general formula (5)

[Wherein, X ⁴ represents a halogen atom, and Y ¹ , Y ² and Y ³ are each independently
The C1-C20 alkoxy group which may have a halogen atom as a substituent is represented. ]
Is reacted with a transition metal compound represented by the general formula (6)

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Y ¹ , Y ² and Y ³ are as defined above]. ]
Step (iii) of producing a silicon-substituted cyclopentadienyl titanium trialkoxide represented by:
The silicon-substituted cyclopentadienyl titanium trialkoxide has the general formula (7)

[Wherein M ² represents an atom belonging to Group 3 to Group 14 of the periodic table of elements, X ⁵ represents a halogen atom, and R ¹⁵ has a hydrogen atom or a halogen atom as a substituent. A good alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, n is an integer of 1 or more, and m + n is M ² An integer equal to the valence. ]
A step of reacting a halogen compound represented by In the general formula (1), at least one of R ⁵ , R ⁶ and R ⁷ is an aryl group represented by the general formula (2). The silicon-substituted cyclopentadienyl titanium trihalide according to claim 1 Production method. In the general formula (1), R ⁵ , R ⁶ and R ⁷ are each independently an aryl group represented by the general formula (2). The silicon-substituted cyclopentadienyl titanium trihalide according to claim 1 Production method. Silicon-substituted manufacturing method of cyclopentadienyl titanium trihalide according to any one of claims 1 to 3 M ² is a silicon atom in the general formula (7).