JP2001348395A - Method for purifying half-metallocene metal complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially and economically purifying method for a half-metallocene metal complex in a few processes. SOLUTION: This method for purifying a transition metal complex comprises synthesizing a transition metal complex represented by general formula (1), filtering insoluble material after the synthesis, removing a part of the reaction solvent by distillation, and cooling the resultant solution while stirring the solution to precipitate the transition metal complex.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for purifying a half metallocene type metal complex.

[0002]

BACKGROUND OF THE INVENTION The half metallocene type metal complex of the present invention has been disclosed in Japanese Unexamined Patent Publication No. 9-87313, which is a complex which is highly active and soluble in a saturated hydrocarbon solvent at an efficient reaction temperature in an olefin polymerization industrial process. It has been reported as. For the purification method, for example, after completion of the synthesis reaction, the generated precipitate is separated by filtration, and then the filtrate is concentrated to precipitate a solid. After washing with a poor solvent, a method of recrystallization using an appropriate solvent and the like have been reported. However, these methods have many steps and require complicated operations, and thus a more advantageous purification method of the half metallocene-type metal complex of the present invention has been demanded.

[0003]

The object of the present invention is to provide an industrially advantageous purification method in which the number of steps of the above half metallocene type metal complex is short.

[0004]

That is, the present invention provides a compound represented by the following general formula (1): (Wherein, M ¹ represents a transition metal atom of Group 4 of the periodic table, A represents an atom of Group 16 of the periodic table, and B represents an atom of Group 14 of the periodic table. Cp ¹ is a group having a cyclopentadienyl skeleton, and the above transition metal atom and π
Has a bond. R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or a carbon atom which may be substituted with a halogen atom. An aralkyl group having 7 to 20 atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, a substituted silyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom An alkoxy group having 1 to 20 carbon atoms which may be substituted by an aralkyloxy group having 1 to 20 carbon atoms which may be substituted by a halogen atom; a carbon atom having 1 carbon atom which may be substituted by a halogen atom And R ⁵ and R ⁶ each independently represent a hydrogen atom or a carbon atom which may be substituted with a halogen atom. An alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom A substituted silyl group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms optionally substituted with a halogen atom, and 1 to 20 carbon atoms optionally substituted with a halogen atom An aralkyloxy group having 1 carbon atom which may be substituted with a halogen atom
Represents an aryloxy group of from 20 to 20 or a disubstituted amino group of from 2 to 20 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ may be arbitrarily bonded to form a ring,
X ¹ and X ^{2 each} represent a halogen atom. After synthesizing the transition metal complex represented by the formula (1), insolubles are filtered, a part of the reaction solvent is distilled off, and the mixture is cooled with stirring to precipitate the transition metal complex. It is intended to provide a method for purifying a metal complex.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION [Transition Metal Complex] In the transition metal compound represented by the general formula (1), the transition metal atom represented by M1 is defined as a periodic table of elements (IUPAC revised version of inorganic chemical nomenclature 1989). Group 4 transition metal atom of
For example, a titanium atom, a zirconium atom, a hafnium atom and the like can be mentioned.

The sixteenth element of the periodic table of the element represented by A
Examples of group atoms include an oxygen atom, a sulfur atom, and a selenium atom, and an oxygen atom is preferable.

The fourteenth element of the periodic table of the element represented by B
Examples of group atoms include a carbon atom, a silicon atom, and a germanium atom.

Examples of the group having a cyclopentadiene type anion skeleton represented by the substituent Cp1 include, for example, η5
-Cyclopentadienyl group, η5-methylcyclopentadienyl group, η5-dimethylcyclopentadienyl group,
η5-trimethylcyclopentadienyl group, η5-tetramethylcyclopentadienyl group, η5-ethylcyclopentadienyl group, η5-n-propylcyclopentadienyl group, η5-isopropylcyclopentadienyl group, η5-n- Butylcyclopentadienyl group, η5-
sec-butylcyclopentadienyl group, η5-ter
t-butylcyclopentadienyl group, η5-n-pentylcyclopentadienyl group, η5-neopentylcyclopentadienyl group, η5-n-hexylcyclopentadienyl group, η5-n-octylcyclopentadienyl group, η5-phenylcyclo Pentadienyl group, η5-naphthylcyclopentadienyl group, η5-trimethylsilylcyclopentadienyl group, η5-triethylsilylcyclopentadienyl group, η5-tert-butyldimethylsilylcyclopentadienyl group, η5-indenyl group, η5-methylindene Nyl group, η5-dimethylindenyl group, η5-ethylindenyl group, η5-n-propylindenyl group, η5-isopropylindenyl group, η
5-n-butylindenyl group, η5-sec-butylindenyl group, η5-tert-butylindenyl group, η
5-n-pentylindenyl group, η5-neopentylindenyl group, η5-n-hexylindenyl group, η5-
n-octylindenyl group, η5-n-decylindenyl group, η5-phenylindenyl group, η5-methylphenylindenyl group, η5-naphthylindenyl group, η5
-Trimethylsilylindenyl group, η5-triethylsilylindenyl group, η5-tert-butyldimethylsilylindenyl group, η5-tetrahydroindenyl group,
η5-fluorenyl group, η5-methylfluorenyl group,
η5-dimethylfluorenyl group, η5-ethylfluorenyl group, η5-diethylfluorenyl group, η5-n-propylfluorenyl group, η5-di-n-propylfluorenyl group, η5-isopropylfluorene Olenyl group, η5-
Diisopropylfluorenyl group, η5-n-butylfluorenyl group, η5-sec-butylfluorenyl group, η
5-tert-butylfluorenyl group, η5-di-n-
Butylfluorenyl group, η5-di-sec-butylfluorenyl group, η5-di-tert-butylfluorenyl group, η5-n-pentylfluorenyl group, η5-neopentylfluorenyl group, η5 -N-hexylfluorenyl group, η5-n-octylfluorenyl group, η5-n-
Decylfluorenyl group, η5-n-dodecylfluorenyl group, η5-phenylfluorenyl group, η5-di-phenylfluorenyl group, η5-methylphenylfluorenyl group, η5-naphthylfluorenyl group , Η5-trimethylsilylfluorenyl group, η5-bis-trimethylsilylfluorenyl group, η5-triethylsilylfluorenyl group, η5-tert-butyldimethylsilylfluorenyl group, and the like. Dienyl group, η5-methylcyclopentadienyl group, η
5-tert-butylcyclopentadienyl group, η5-
Examples include a tetramethylcyclopentadienyl group, an η5-indenyl group, and an η5-fluorenyl group.

The substituents X1, X2, R1, R2, R3, R
Examples of the halogen atom in 4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituents R1, R2, R3, R4, R5, R
As the alkyl group having 1 to 20 carbon atoms in 6,
For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-
Butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group,
Examples thereof include an n-dodecyl group, an n-pentadecyl group, an n-eicosyl group and the like, preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group and an amyl group.

All of these alkyl groups may be substituted with halogen atoms such as fluorine, chlorine, bromine and iodine. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, perbromoeicosyl and the like.

The substituents R1, R2, R3, R4, R5, R
Examples of the aralkyl group having 7 to 20 carbon atoms in 6 include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, a (4-methylphenyl) methyl group, a (2,3- (Dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,4-
5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group,
(2,3,4-trimethylphenyl) methyl group, (2,3
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-propyl Phenyl) 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-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. And preferably a benzyl group. Any of these aralkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituents R1, R2, R3, R4, R5, R
6 as the aryl group having 6 to 20 carbon atoms,
For example, phenyl, 2-tolyl, 3-tolyl, 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
A tetramethylphenyl group, a pentamethylphenyl group,
Ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n -Octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like, and a phenyl group is preferable. Any of these aryl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituents R1, R2, R3, R4, R5, R
The substituted silyl group in 6 is a silyl group substituted with a hydrocarbon group, wherein the hydrocarbon group includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group,
Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a cyclohexyl group and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group and the like. Di-substituted silyl group having 2 to 20 carbon atoms, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-ter
t-butylsilyl group, tri-isobutylsilyl group, te
Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as an rt-butyl-dimethylsilyl group, a tri-n-pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilyl group, and a triphenylsilyl group. And preferably a trimethylsilyl group, a tert-butyldimethylsilyl group and a triphenylsilyl group. In any of these substituted silyl groups, the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituents R1, R2, R3, R4, R5, R
As the alkoxy group having 1 to 20 carbon atoms in 6, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, Examples thereof include a neopentoxy group, an n-hexoxy group, an n-octoxy group, an n-dodesoxy group, an n-pentadeoxy group, and an n-icosoxy group, and a methoxy group, an ethoxy group, and a tert-butoxy group are preferable. All of these alkoxy groups are a fluorine atom, a chlorine atom, a bromine atom,
It may be substituted by a halogen atom such as an iodine atom.

The substituents R1, R2, R3, R4, R5, R
Examples of the aralkyloxy group having 7 to 20 carbon atoms in 6 include a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group,
(4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) 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, (2,4,6-trimethylphenyl)
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, (n-tetradecylphenyl) methoxy And a naphthylmethoxy group, an anthracenylmethoxy group and the like, preferably a benzyloxy group. Any of these aralkyloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituents R1, R2, R3, R4, R5, R
Examples of the aryloxy group in 6 include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,5- Dimethylphenoxy group, 2,6-dimethylphenoxy group,
3,4-dimethylphenoxy 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, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethyl Phenoxy group,
n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecyl Examples thereof include an aryloxy group having 6 to 20 carbon atoms such as a phenoxy group, a naphthoxy group, and an anthracenoxy group. Any of these aryloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituents R1, R2, R3, R4, R5, R
6 is a disubstituted amino group having 2 to 20 carbon atoms.
An amino group substituted with two hydrocarbon groups, wherein the hydrocarbon group is, for example, a methyl group, an ethyl group, an n-
Propyl group, isopropyl group, n-butyl group, sec-
Examples thereof include an alkyl group having 2 to 20 carbon atoms such as a butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group and a cyclohexyl group, and an aryl group such as a phenyl group. Examples of such a disubstituted amino group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-sec
-Butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenyl Amino group, bistrimethylsilylamino group, bis-tert
-Butyldimethylsilylamino group and the like, and preferably a dimethylamino group and a diethylamino group.

Substituents R1, R2, R3, R4, R5, R
6 may be optionally bonded to form a ring.

The substituents X 1 and X 2 are preferably chlorine atoms. R1 is preferably an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an aralkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, or a group which may be substituted with a halogen atom. Preferred are an aryl group having 6 to 20 carbon atoms and a substituted silyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom.

Examples of the transition metal compound represented by the general formula (1) include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride and methylene (cyclopentadienyl) (3
-Tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl)
(3-phenyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2- Phenoxy) titanium dichloride,

Methylene (methylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Phenyl-2-phenoxy)
Titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride,

Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Methylene (tert
-Butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tert) -Butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadiene) Enil) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy)
Titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride , Methylene (tetramethylcyclopentadienyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-
2-phenoxy) titanium dichloride,

Methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) ) (3-tert-butyldimethylsilyl-5
Methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert
-Butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene Riden (methylcyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Isopropylidene (methylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-
Phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (t
tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-
Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2)
-Phenoxy) titanium dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl- 2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2
-Phenoxy) titanium dichloride,

Isopropylidene (fluorenyl) (3,
5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methoxy-2
-Phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl- 2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenyl Methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (ter
t-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopenta Dienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (fluorenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride and the like, compounds obtained by changing titanium to zirconium and hafnium, compounds obtained by changing chloride to bromide and iodide, and (cyclopentadienyl) to (dimethyl) (Cyclopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), a compound changed to (indenyl), 3,5-dimethyl- 2-phenoxy is 2-phenoxy, 3-methyl-2-phenoxy, 3,5
-Di-tert-butyl-2-phenoxy, 3-phenyl-5-methyl-2-phenoxy, 3-tert-butyldimethylsilyl-2-phenoxy, a compound changed to 3-trimethylsilyl-2-phenoxy, methylene being replaced by diethyl A transition metal complex in which B in the general formula (1) is a carbon atom, such as a compound changed to methylene; and

Dimethylsilyl (cyclopentadienyl)
(2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5
-Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert -Butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-
Dimethyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (methylcyclopentadienyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3 5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ( 3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethyi Silyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl)
(3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n- Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n- Butylcyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) ) (5-Methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium Dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert- Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (te
rt-butylcyclopentadienyl) (3,5-di-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (ter
t-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopenta Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) ) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5- Di-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (indenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5
-Dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (indenyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) ) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-
Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-
Phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5)
-Chloro-2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (3,5-diamyl-
(2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride and the like, and (cyclopentadienyl) of these compounds are (dimethylcyclopentadienyl), (Trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl), (isobutylcyclopentadienyl) ), (Ter
t-butyldimethylsilylcyclopentadienyl),
(Phenylcyclopentadienyl), (methylindenyl), a compound changed to (phenylindenyl), 2-
Compounds in which phenoxy is changed to 3-phenyl 2-phenoxy, 3-trimethylsilyl-2-phenoxy, 3-tert-butyldimethylsilyl-2-phenoxy, compounds in which dimethylsilyl is changed to diethylsilyl, diphenylsilyl, dimethoxysilyl, titanium A transition metal complex in which B in the general formula (1) is an atom belonging to Group 14 of the periodic table of an element other than a carbon atom, such as a compound in which is changed to zirconium or hafnium, and a compound in which chloride is changed to bromide or iodide. .

The transition metal compound represented by the general formula (1) can be synthesized by the method described in JP-A-9-87313.

For example, it can be manufactured as follows. General formula (2) (Wherein Cp2 represents a group having a cyclopentadiene skeleton, R7 represents a hydrocarbon group optionally substituted by a halogen atom or a trisubstituted silyl group. A, B, R1, R
2, R3, R4, R5 and R6 each have the same meaning as described above. )) (Hereinafter referred to as compound [2]) and a base, and then reacted with a compound represented by the general formula (3): (Wherein X 3 and X 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, Group, an aralkyloxy group or an aryloxy group, or a disubstituted amino group having 2 to 20 carbon atoms.
Has the same meaning as described above. ) (Hereinafter referred to as compound [3]) can be reacted to produce a transition metal complex represented by the general formula (1).

Examples of the group having a cyclopentadiene skeleton represented by the substituent Cp2 in the compound [2] include, for example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, Tetramethylcyclopentadienyl group, ethylcyclopentadienyl group, n-propylcyclopentadienyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group, sec
-Butylcyclopentadienyl group, tert-butylcyclopentadienyl group, n-pentylcyclopentadienyl group, neopentylcyclopentadienyl group, n-hexylcyclopentadienyl group, n-octylcyclopentadienyl group, phenylcyclopentadienyl Group, naphthylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, triethylsilylcyclopentadienyl group, tert-butyldimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, dimethylindenyl group, ethylindenyl group, n -Propylindenyl group, isopropylindenyl group, n-butylindenyl group, sec-butylindenyl group, ter
t-butylindenyl group, n-pentylindenyl group,
Neopentylindenyl group, n-hexylindenyl group, n-octylindenyl group, n-decylindenyl group, phenylindenyl group, methylphenylindenyl group, naphthylindenyl group, trimethylsilylindenyl group, triethylsilylindenyl Group, tert-butyldimethylsilylindenyl group, tetrahydroindenyl group, fluorenyl group, methylfluorenyl group, dimethylfluorenyl group, ethylfluorenyl group, diethylfluorenyl group, n-propylfluorenyl group , Di-n-
Propylfluorenyl group, isopropylfluorenyl group, diisopropylfluorenyl group, n-butylfluorenyl group, sec-butylfluorenyl group, tert-
Butylfluorenyl group, di-n-butylfluorenyl group, di-sec-butylfluorenyl group, di-tert
-Butylfluorenyl group, n-pentylfluorenyl group, neopentylfluorenyl group, n-hexylfluorenyl group, n-octylfluorenyl group, n-decylfluorenyl group, n-dodecylfuryl Oleynyl, phenylfluorenyl, di-phenylfluorenyl, methylphenylfluorenyl, naphthylfluorenyl, trimethylsilylfluorenyl, bis-trimethylsilylfluorenyl, triethylsilylfluorenyl Group,
tert-butyldimethylsilylfluorenyl group and the like, preferably cyclopentadienyl group, methylcyclopentadienyl group, tert-butylcyclopentadienyl group, tetramethylcyclopentadienyl group,
Fluorenyl group, indenyl group and the like.

Examples of the hydrocarbon group represented by the substituent R7 include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group and a decyl group, a vinyl group, an allyl group, a propenyl group, -Alkenyl groups having 2 to 10 carbon atoms such as -methyl-2-propenyl group, homoallyl group, hexenyl group, decenyl group, etc., alkoxyalkyl groups such as methoxymethyl group, methoxyethoxymethyl group, benzyl group, (4-methylphenyl ) Methyl group,
An aralkyl group having 7 to 12 carbon atoms such as a (2,4,6-trimethylphenyl) methyl group is exemplified. Any of these hydrocarbon groups may be substituted with a halogen atom, and examples of the hydrocarbon group substituted with a halogen atom include a 2-chloro-2-propenyl group. Tri-substituted silyl groups such as trimethylsilyl group,
Triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group,
Tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, tricyclohexylsilyl group Examples include a phenylsilyl group. Among these substituents R7, an alkenyl group, particularly an allyl group, is preferable from the viewpoint that the compound [1] can be produced with high yield.

As the compound [2], for example, 2-
[(Cyclopenta-1,4-dienyl) methyl] -1-
Methoxybenzene, 2-[(cyclopenta-1,4-dienyl) methyl] -1-methoxy-4,6-dimethylbenzene, 2-tert-butyl-6-[(cyclopenta-1,4-dienyl) methyl]- 1-methoxy-4-methylbenzene, 6-[(cyclopenta-1,4-dienyl) methyl] -1-methoxy-2-phenylbenzene,
1-tert-butyldimethylsilyl-3-[(cyclopenta-1,4-dienyl) methyl] -2-methoxy-
5-methylbenzene, 3-[(cyclopenta-1,4-
Dienyl) methyl] -2-methoxy-5-methyl-1-
Trimethylsilylbenzene, 2-tert-butyl-6
-[(Cyclopenta-1,4-dienyl) methyl]-
1,4-dimethoxybenzene, 3-tert-butyl-
1-chloro-5-[(cyclopenta-1,4-dienyl) methyl] -4-methoxybenzene, 2-tert-
Butyl-6-[(cyclopenta-1,4-dienyl) methyl] -1-methoxybenzene,

2- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxybenzene, 2- [1- (cyclopenta-1,4-dienyl)-
1-methyl-ethyl] -1-methoxy-4,6-dimethylbenzene, 6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl]
-1-methoxy-4-methylbenzene, 6- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxy-2-phenylbenzene, 1-te
rt-butyldimethylsilyl-3- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2-
Methoxy-5-methylbenzene, 3- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2
-Methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1,4
-Dimethoxybenzene, 5-tert-butyl-1-chloro-3- [1- (cyclopenta-1,4-dienyl)
-1-methyl-ethyl] -4-methoxybenzene, 6-
tert-butyl-2- [1- (cyclopenta-1,4
-Dienyl) -1-methyl-ethyl] -1-methoxybenzene,

1-methoxy-2- [1- (4-methyl-
Cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-methoxy-4,6-dimethyl-2-
[1- (4-Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-
Butyl-1-methoxy-4-methyl-2- [1- (4-
Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-methoxy-6- [1- (4
-Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2-phenylbenzene, 1-tert
-Butyldimethylsilyl-2-methoxy-5-methyl-
3- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-methoxy-5-methyl-3- [1- (4-methyl-cyclopenta-1,4 -Dienyl) -1-methyl-ethyl] -1-trimethylsilylbenzene, 6-tert-butyl-1,
4-dimethoxy-2- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 5-tert-butyl-1-chloro-4-methoxy-3- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-ter
t-butyl-1-methoxy-2- [1- (4-methyl-
Cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene,

2- [1- (4-tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl]
-1-methoxybenzene, 2- [1- (4-tert-
Butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxy-4,6-dimethylbenzene, 6-tert-butyl-2- [1- (4-tert)
-Butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxy-4-methylbenzene,
6- [1- (4-tert-butyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] -1-methoxy-2-phenylbenzene, 1-tert-butyldimethylsilyl-3- [1- (4-tert-butyl-cyclopenta-1,4-dienyl) ) -1-Methyl-ethyl] -2-methoxy-5-methylbenzene, 3- [1-
(4-tert-butylcyclopenta-1,4-dienyl) -1-methyl-ethyl] -2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl-2- [1- (4- tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1,
4-dimethoxybenzene, 5-tert-butyl-1-
Chloro-3- [1- (4-tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -4
-Methoxybenzene, 6-tert-butyl-2- [1
-(4-tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxybenzene,

1-methoxy-2- [1- (2,3,4,
5-tetramethyl-cyclopenta-1,4-dienyl)
-1-methyl-ethyl] benzene, 1-methoxy-4,
6-dimethyl-2- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-butyl-1-methoxy-4- Methyl-2- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-methoxy-2-phenyl-6- [1- ( 2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3- [1- ( 2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 2-methoxy-5-methyl-3- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl]-
1-trimethylsilylbenzene, 6-tert-butyl-1,4-dimethoxy-2- [1- (2,3,4,5-
Tetramethyl-cyclopenta-1,4-dienyl) -1
-Methyl-ethyl] benzene, 5-tert-butyl-
1-chloro-4-methoxy-3- [1- (2,3,4,
5-tetramethyl-cyclopenta-1,4-dienyl)
-1-methyl-ethyl] benzene, 6-tert-butyl-1-methoxy-2- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl ]benzene,

1-methoxy-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-methoxy-4,6-dimethyl-2- [1- ( 3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-butyl-1-methoxy-4-methyl-2- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
1-methoxy-2-phenyl-6- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3- [1-
(3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3- [1- (3
-Trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-
Butyl-1,4-dimethoxy-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 5-tert-butyl-1
-Chloro-4-methoxy-3- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-butyl-1-methoxy-2- [1- ( 3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene,

2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -1-methoxybenzene, 2- [1- (cyclopenta-1,4-dienyl)-
1-ethyl-propyl] -1-methoxy-4,6-dimethylbenzene, 6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -1-methoxy- 4-methylbenzene, 6- [1-
(Cyclopenta-1,4-dienyl) -1-ethyl-propyl] -1-methoxy-2-phenylbenzene, 1-
tert-butyldimethylsilyl-3- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl]
-2-methoxy-5-methylbenzene, 3- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl -2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -1,4-dimethoxybenzene, 5-tert-butyl-1-chloro-3- [1- (cyclopenta-1, 4
-Dienyl) -1-ethyl-propyl] -4-methoxybenzene, 6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl]
-1-methoxybenzene,

2- [1- (cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -1-methoxybenzene, 2- [1- (cyclopenta-1,4-dienyl) -1,1- Diphenylmethyl] -1-methoxy-
4,6-dimethylbenzene, 6-tert-butyl-2
-[1- (cyclopenta-1,4-dienyl) -1,1
-Diphenylmethyl] -1-methoxy-4-methylbenzene, 2- [1- (cyclopenta-1,4-dienyl)
-1,1-diphenylmethyl] -1-methoxy-6-phenylbenzene, 1-tert-butyldimethylsilyl-3- [1- (cyclopenta-1,4-dienyl)-
1,1-diphenylmethyl] -2-methoxy-5-methylbenzene, 3-[(cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -2-methoxy-5
-Methyl-1-trimethylsilylbenzene, 6-ter
t-butyl-2-[(cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -1,4-dimethoxybenzene, 5-tert-butyl-1-chloro-3-
[(Cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -4-methoxybenzene, 6-tert
-Butyl-2-[(cyclopenta-1,4-dienyl)
-1,1-diphenylmethyl] -1-methoxybenzene,

1-allyloxy-2-[(cyclopenta-
1,4-dienyl) methyl] benzene, 1-allyloxy-2-[(cyclopenta-1,4-dienyl) methyl]
-4,6-dimethylbenzene, 1-allyloxy-2-t
tert-butyl-6-[(cyclopenta-1,4-dienyl) methyl] -4-methylbenzene, 1-allyloxy-6-[(cyclopenta-1,4-dienyl) methyl]
-2-phenylbenzene, 2-allyloxy-1-ter
t-butyldimethylsilyl-3-[(cyclopenta-
1,4-dienyl) methyl] -5-methylbenzene, 2
-Allyloxy-3-[(cyclopenta-1,4-dienyl) methyl] -5-methyl-1-trimethylsilylbenzene, 1-allyloxy-2-tert-butyl-6-
[(Cyclopenta-1,4-dienyl) methyl] -4-
Methoxybenzene, 4-allyloxy-3-tert-butyl-1-chloro-5-[(cyclopenta-1,4-dienyl) methyl] benzene, 1-allyloxy-2-te
rt-butyl-6-[(cyclopenta-1,4-dienyl) methyl] benzene,

1-allyloxy-2- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-2- [1- (cyclopenta-1,
4-dienyl) -1-methyl-ethyl] -4,6-dimethylbenzene, 1-allyloxy-6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1
-Methyl-ethyl] -4-methylbenzene, 1-allyloxy-6- [1- (cyclopenta-1,4-dienyl)
-1-methyl-ethyl] -2-phenylbenzene, 2-
Allyloxy-1-tert-butyldimethylsilyl-3
-[1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -5-methylbenzene, 2-allyloxy-3- [1- (cyclopenta-1,4-dienyl) -1
-Methyl-ethyl] -5-methyl-1-trimethylsilylbenzene, 1-allyloxy-6-tert-butyl-
2- [1- (cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] -4-methoxybenzene, 4-allyloxy-5-tert-butyl-1-chloro-3- [1-
(Cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl)-
1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-4,6-dimethyl-
2- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-tert-butyl-4-methyl-2- [1-
(4-methyl-cyclopenta-1,4-dienyl) -1
-Methyl-ethyl] benzene, 1-allyloxy-6-
[1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2-phenylbenzene,
2-allyloxy-1-tert-butyldimethylsilyl-5-methyl-3- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-allyloxy-5-methyl -3- [1- (4-Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-trimethylsilylbenzene, 1-allyloxy-6-tert-butyl-4-methoxy-2-
[1- (4-Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 4-allyloxy-5-tert-butyl-1-chloro-3- [1- (4
-Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-ter
t-butyl-2- [1- (4-methyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (4-ter)
t-butyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 1-allyloxy-2- [1
-(4-tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -4,6-dimethylbenzene, 1-allyloxy-6-tert-butyl-2-
[1- (4-tert-butyl-cyclopenta-1,4
-Dienyl) -1-methyl-ethyl] -4-methylbenzene, 1-allyloxy-6- [1- (4-tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2- Phenylbenzene, 2-allyloxy-
1-tert-butyldimethylsilyl-3- [1- (4
-Tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -5-methylbenzene, 2
-Allyloxy-3- [1- (4-tert-butylcyclopenta-1,4-dienyl) -1-methyl-ethyl]
-5-methyl-1-trimethylsilylbenzene, 1-allyloxy-6-tert-butyl-2- [1- (4-t
tert-butyl-cyclopenta-1,4-dienyl)-
1-methyl-ethyl] -4-methoxybenzene, 4-allyloxy-5-tert-butyl-1-chloro-3-
[1- (4-tert-butyl-cyclopenta-1,4
-Dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-tert-butyl-2- [1- (4-t
tert-butyl-cyclopenta-1,4-dienyl)-
1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (2,3,
4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-4,6-dimethyl-2- [1- (2,3,4,5-tetramethyl) -Cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 1-allyloxy-6-te
rt-butyl-4-methyl-2- [1- (2,3,4,
5-tetramethyl-cyclopenta-1,4-dienyl)
-1-methyl-ethyl] benzene, 1-allyloxy-2
-Phenyl-6- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-
Ethyl] benzene, 2-allyloxy-1-tert-butyldimethylsilyl-5-methyl-3- [1- (2,
3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-allyloxy-5-methyl-3- [1- (2,3,4,5-tetramethyl) -Cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-trimethylsilylbenzene, 1-
Allyloxy-6-tert-butyl-4-methoxy-2
-[1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 4-allyloxy-5-tert-butyl-1-chloro-3- [ 1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl]
Benzene, 1-allyloxy-6-tert-butyl-2
-[1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 1-allyloxy-4,6-
Dimethyl-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-tert-butyl-4-
Methyl-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-2-phenyl-6- [1- (3
-Trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-allyloxy-1-tert-butyldimethylsilyl-5-methyl-
3- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
2-allyloxy-5-methyl-1-trimethylsilyl-
3- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
1-allyloxy-6-tert-butyl-4-methoxy-2- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
4-allyloxy-5-tert-butyl-1-chloro-
3- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
1-allyloxy-6-tert-butyl-2- [1-
(3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] benzene, 1-allyloxy-2- [1- (cyclopenta-
1,4-dienyl) -1-ethyl-propyl] -4,6
-Dimethylbenzene, 1-allyloxy-6-tert-
Butyl-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -4-methylbenzene,
1-allyloxy-6- [1- (cyclopenta-1,4-
Dienyl) -1-ethyl-propyl] -2-phenylbenzene, 2-allyloxy-1-tert-butyldimethylsilyl-3- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -5 -Methylbenzene,
2-allyloxy-3- [1- (cyclopenta-1,4-
Dienyl) -1-ethyl-propyl] -5-methyl-1
-Trimethylsilylbenzene, 1-allyloxy-6-t
ert-butyl-2- [1- (cyclopenta-1,4-
Dienyl) -1-ethyl-propyl] -4-methoxybenzene, 4-allyloxy-5-tert-butyl-1-
Chloro-3- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -benzene, 1-allyloxy-6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] benzene,

1-allyloxy-2- [1- (cyclopenta-1,4-dienyl) -1,1-diphenylmethyl]
Benzene, 1-allyloxy-2- [1- (cyclopenta-1,4-dienyl) -1,1-diphenylmethyl]-
4,6-dimethylbenzene, 1-allyloxy-6-te
rt-butyl-2- [1- (cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -4-methylbenzene, 1-allyloxy-2- [1- (cyclopenta-
1,4-dienyl) -1,1-diphenylmethyl] -6
-Phenylbenzene, 2-allyloxy-1-tert-
Butyldimethylsilyl-3- [1- (cyclopenta-
1,4-dienyl) -1,1-diphenylmethyl] -5
-Methylbenzene, 2-allyloxy-3-[(cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -5-methyl-1-trimethylsilylbenzene, 1
-Allyloxy-6-tert-butyl-2-[(cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -4-methoxybenzene, 4-allyloxy-5-t
tert-butyl-1-chloro-3-[(cyclopenta-
1,4-dienyl) -1,1-diphenylmethyl] benzene, 1-allyloxy-6-tert-butyl-2-
[(Cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] benzene and the methoxy or allyloxy of these compounds are changed to ethoxy, benzyloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, methoxymethoxy Compound,
Cyclopenta-1,4-dienyl is converted to dimethylcyclopenta-1,4-dienyl, trimethylcyclopenta-1,
4-dienyl, n-butylcyclopenta-1,4-dienyl, tert-butyldimethylsilylcyclopenta-
1,4-dienyl, indenyl, a compound changed to fluorenyl, 1-methoxybenzene is converted to 1-methoxy-6-
Methylbenzene, 1-methoxy-4,6-di-tert
General formula (2a) such as -butylbenzene, 1-methoxy-4-methyl-6-phenylbenzene, 1-tert-butyldimethylsilyl-2-methoxybenzene, a compound modified to 2-methoxy-1-trimethylsilylbenzene, and the like. Wherein Cp2, A, R1, R2, R3, R4, R5,
R6 and R7 each have the same meaning as described above. ) (Hereinafter, referred to as compound [2a]);

(Cyclopenta-1,3-dienyl) (2
-Methoxyphenyl) dimethylsilane, (cyclopenta-1,3-dienyl) (2-methoxy-3-methylphenyl) dimethylsilane, (cyclopenta-1,3-dienyl) (2-methoxy-3,5-dimethylphenyl) Dimethylsilane, (3-tert-butyl-2-methoxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyl-2-methoxy-5)
-Methylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (3,5-di-tert-butyl-2-methoxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (cyclopenta-1,3 -Dienyl) (2-methoxy-5-methyl-3-phenylphenyl) dimethylsilane, (cyclopenta-1,3-dienyl) (2-methoxy-5-methyl-3-trimethylsilylphenyl) dimethylsilane, (3-tert -Butyldimethylsilyl-2-methoxy-5-methylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (3
-Tert-butyl-2,5-dimethoxyphenyl)
(Cyclopenta-1,3-dienyl) dimethylsilane,
(5-tert-butyl-3-chloro-6-methoxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-methoxyphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane,

(2-methoxy-3-methylphenyl)
(Methylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-3,5-dimethylphenyl)
(Methylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyl-2-methoxyphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyl-2-methoxy) -5
-Methylphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (3,5-di-tert-butyl-2-methoxyphenyl) (methylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-methoxy-
5-methyl-3-phenylphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-5-methyl-3-trimethylsilylphenyl)
(Methylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyldimethylsilyl-2-methoxy-5-methylphenyl) (methylcyclopenta-
(1,3-dienyl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (methylcyclopenta-
(1,3-dienyl) dimethylsilane, (3-tert-
Butyl-2,5-dimethoxyphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (5-t
tert-butyl-3-chloro-6-methoxyphenyl)
(Methylcyclopenta-1,3-dienyl) dimethylsilane,

(2-methoxyphenyl) (2, 3, 4,
5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-3-methylphenyl)
(2,3,4,5-tetramethylcyclopenta-1,3
-Dienyl) dimethylsilane, (2-methoxy-3,5
-Dimethylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane,
(3-tert-butyl-2-methoxyphenyl)
(2,3,4,5-tetramethylcyclopenta-1,3
-Dienyl) dimethylsilane, (3-tert-butyl-2-methoxy-5-methylphenyl) (2,3,4,
5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (3,5-di-tert-butyl-2-)
Methoxyphenyl) (2,3,4,5-tetramethylcyclpenta-1,3-dienyl) dimethylsilane, (2-
Methoxy-5-methyl-3-phenylphenyl) (2,
3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-5-methyl-
3-trimethylsilylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyldimethylsilyl-2-
Methoxy-5-methylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl)
(2,3,4,5-tetramethylcyclopenta-1,3
-Dienyl) dimethylsilane, (3-tert-butyl-2,5-dimethoxyphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (5-tert-butyl- 3-chloro-6-methoxyphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane,

(Tert-Butylcyclopenta-1,3
-Dienyl) (2-methoxyphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (2-methoxy-3-methylphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) ) (2-methoxy-3,5-dimethylphenyl) dimethylsilane, (tert-butylcyclopenta-1,
3-dienyl) (3-tert-butyl-2-methoxyphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (3-tert-butyl-
2-methoxy-5-methylphenyl) dimethylsilane,
(Tert-butylcyclopenta-1,3-dienyl)
(3,5-di-tert-butyl-2-methoxyphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (2-methoxy-5-methyl-3
-Phenylphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (2-methoxy-5-methyl-3-trimethylsilylphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-
Dienyl) (3-tert-butyldimethylsilyl-2
-Methoxy-5-methylphenyl) dimethylsilane,
(3,5-diamyl-2-methoxyphenyl) (ter
t-butylcyclopenta-1,3-dienyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (3-tert-butyl-2,5-dimethoxyphenyl) dimethylsilane, (5-tert- Butyl-
3-chloro-6-methoxyphenyl) (tert-butylcyclopenta-1,3-dienyl) dimethylsilane,

(2-methoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-3-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2- Methoxy-3,5-dimethylphenyl)
(Trimethylsilylcyclopenta-1,3-dienyl)
Dimethylsilane, (3-tert-butyl-2-methoxyphenyl) (trimethylsilylcyclopenta-1,3
-Dienyl) dimethylsilane, (3-tert-butyl-2-methoxy-5-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane,

(3,5-di-tert-butyl-2-methoxyphenyl) (trimethylsilylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-methoxy-
5-methyl-3-phenylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane,
(2-methoxy-5-methyl-3-trimethylsilylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyldimethylsilyl-2-methoxy-5-methylphenyl) (trimethylsilylcyclopenta -1,3-dienyl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyl-2,5
-Dimethoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (5-ter
t-butyl-3-chloro-6-methoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane,

(Inden-1-yl) (2-methoxyphenyl) dimethylsilane, (inden-2-yl) (2
-Methoxyphenyl) dimethylsilane, (indene-1)
-Yl) (2-methoxy-3-methylphenyl) dimethylsilane, (inden-2-yl) (2-methoxy-3
-Methylphenyl) dimethylsilane, (indene-1-
Yl) (2-methoxy-3,5-dimethylphenyl) dimethylsilane, (inden-2-yl) (2-methoxy-3,5-dimethylphenyl) dimethylsilane, (3-
tert-butyl-2-methoxyphenyl) (inden-1-yl) dimethylsilane, (3-tert-butyl-2-methoxyphenyl) (inden-2-yl) dimethylsilane, (3-tert-butyl-2- Methoxy-
5-methylphenyl) (inden-1-yl) dimethylsilane, (3-tert-butyl-2-methoxy-5-)
Methylphenyl) (inden-2-yl) dimethylsilane, (3,5-di-tert-butyl-2-methoxyphenyl) (inden-1-yl) dimethylsilane,
(3,5-di-tert-butyl-2-methoxyphenyl) (inden-2-yl) dimethylsilane, (inden-1-yl) (2-methoxy-5-methyl-3-phenylphenyl) dimethylsilane , (Inden-2-yl) (2-methoxy-5-methyl-3-phenylphenyl) dimethylsilane, (Inden-1-yl) (2-methoxy-5-methyl-3-trimethylsilylphenyl)
Dimethylsilane, (inden-2-yl) (2-methoxy-5-methyl-3-trimethylsilylphenyl) dimethylsilane, (3-tert-butyldimethylsilyl-
2-methoxy-5-methylphenyl) (indene-1-
Yl) dimethylsilane, (3-tert-butyldimethylsilyl-2-methoxy-5-methylphenyl) (inden-2-yl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (indene-1- Yl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (inden-2-yl) dimethylsilane, (3-t
tert-butyl-2,5-dimethoxyphenyl) (inden-1-yl) dimethylsilane, (3-tert-butyl-2,5-dimethoxyphenyl) (indene-2-
Yl) dimethylsilane, (5-tert-butyl-3-
Chloro-6-methoxyphenyl) (inden-1-yl) dimethylsilane, (5-tert-butyl-3-chloro-6-methoxyphenyl) (inden-2-yl)
Dimethylsilane,

(9H-Fluoren-9-yl) (2-methoxyphenyl) dimethylsilane, (9H-fluoren-9-yl) (2-methoxy-3-methylphenyl) dimethylsilane, (9H-fluoren-9-yl) Il) (2-
Methoxy-3,5-dimethylphenyl) dimethylsilane, (3-tert-butyl-2-methoxyphenyl)
(9H-fluoren-9-yl) dimethylsilane, (3
-Tert-butyl-2-methoxy-5-methylphenyl) (9H-fluoren-9-yl) dimethylsilane,
(3,5-di-tert-butyl-2-methoxyphenyl) (9H-fluoren-9-yl) dimethylsilane,
(9H-fluoren-9-yl) (2-methoxy-5-
Methyl-3-phenylphenyl) dimethylsilane, (9
H-fluoren-9-yl) (2-methoxy-5-methyl-3-trimethylsilylphenyl) dimethylsilane,
(3-tert-butyldimethylsilyl-2-methoxy-5-methylphenyl) (9H-fluoren-9-yl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (9H-fluoren-9-yl) ) Dimethylsilane, (3-tert-butyl-2,5-dimethoxyphenyl) (9H-fluoren-9-yl) dimethylsilane, (5-tert-butyl-3-chloro-6-methoxyphenyl) (9H-fluorene) -9-yl) dimethylsilane,

(2-Allyloxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (cyclopenta-1,3-diphenyl)
(Dienyl) dimethylsilane, (2-allyloxy-3,5)
-Dimethylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert)
-Butylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert)
-Butyl-5-methylphenyl) (cyclopenta-1,
(3-dienyl) dimethylsilane, (2-allyloxy-
3,5-di-tert-butylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, ( 2-allyloxy-5-methyl-3-trimethylsilylphenyl)
(Cyclopenta-1,3-dienyl) dimethylsilane,
(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-
Diamylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert)
-Butyl-5-methoxyphenyl) (cyclopenta-
(1,3-dienyl) dimethylsilane, (6-allyloxy-5-tert-butyl-3-chlorophenyl) (cyclopenta-1,3-dienyl) dimethylsilane,

(2-allyloxyphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy) -3,5-dimethylphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane, (2-allyloxy -3-tert-butyl-5-methylphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane,
(2-allyloxy-3,5-di-tert-butylphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (methylcyclopenta1,3 -Dienyl)
Dimethylsilane, (2-allyloxy-5-methyl-3-
Trimethylsilylphenyl) (methylcyclopenta1,
(3-dienyl) dimethylsilane, (2-allyloxy-3)
-Tert-butyldimethylsilyl-5-methylphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane , (2-allyloxy-3-tert-butyl-5
-Methoxyphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (6-allyloxy-5-te
rt-butyl-3-chlorophenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane,

(2-Allyloxyphenyl) (2,3,
4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane , (2-allyloxy-3,5-dimethylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (2 , 3,4,5-tetramethylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2
3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (2,3,4,5-tetramethylcyclopenta- (1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy -5-methyl-3-trimethylsilylphenyl)
(2,3,4,5-tetramethylcyclopenta-1,3
-Dienyl) dimethylsilane, (2-allyloxy-3-
tert-butyldimethylsilyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy- 3-tert-butyl-5-
(Methoxyphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (6
-Allyloxy-5-tert-butyl-3-chlorophenyl) (2,3,4,5-tetramethylcyclopenta-
1,3-dienyl) dimethylsilane,

(2-Allyloxyphenyl) (tert-
Butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (ter
t-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-dimethylphenyl) (tert-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3- tert
-Butylphenyl) (tert-butylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (te
rt-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-di-tert-
Butylphenyl) (tert-butylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (tert-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3- Trimethylsilylphenyl) (tert-butylcyclopenta-1,
(3-dienyl) dimethylsilane, (2-allyloxy-3)
-Tert-butyldimethylsilyl-5-methylphenyl) (tert-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (tert-butylcyclopenta-1,
(3-dienyl) dimethylsilane, (2-allyloxy-3)
-Tert-butyl-5-methoxyphenyl) (ter
t-butylcyclopenta-1,3-dienyl) dimethylsilane, (6-allyloxy-5-tert-butyl-3)
-Chlorophenyl) (tert-butylcyclopenta-
1,3-dienyl) dimethylsilane,

(2-allyloxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2 -Allyloxy-3,5-dimethylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert)
-Butylphenyl) (trimethylsilylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-di- tert-
Butylphenyl) (trimethylsilylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl ) (Trimethylsilylcyclopenta-1,
(3-dienyl) dimethylsilane, (2-allyloxy-3)
-Tert-butyldimethylsilyl-5-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (trimethylsilylcyclopenta-1,
(3-dienyl) dimethylsilane, (2-allyloxy-3)
-Tert-butyl-5-methoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (6-allyloxy-5-tert-butyl-3)
-Chlorophenyl) (trimethylsilylcyclopenta-
1,3-dienyl) dimethylsilane,

(2-Allyloxyphenyl) (indene-
1-yl) dimethylsilane, (2-allyloxyphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-3-methylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-3) -Methylphenyl) (inden-2-yl) dimethylsilane, (2
-Allyloxy-3,5-dimethylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-3,
5-dimethylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (inden-1-yl) dimethylsilane, (2
-Allyloxy-3-tert-butylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-
3-tert-butyl-5-methylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-3)
-Tert-butyl-5-methylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-3,
5-di-tert-butylphenyl) (indene-1-
Yl) dimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (inden-2-yl)
Dimethylsilane, (2-allyloxy-5-methyl-3-
Phenylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (inden-2-yl) dimethylsilane, (2
-Allyloxy-5-methyl-3-trimethylsilylphenyl) (inden-1-yl) dimethylsilane, (2-
Allyloxy-5-methyl-3-trimethylsilylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-
Methylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (inden-2-yl)
Dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (inden-1-yl) dimethylsilane,
(2-allyloxy-3,5-diamylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-
3-tert-butyl-5-methoxyphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-
3-tert-butyl-5-methoxyphenyl) (inden-2-yl) dimethylsilane, (6-allyloxy-
5-tert-butyl-3-chlorophenyl) (inden-1-yl) dimethylsilane, (6-allyloxy-5)
-Tert-butyl-3-chlorophenyl) (inden-2-yl) dimethylsilane,

(2-allyloxyphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3-methylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3) , 5-Dimethylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3-tert) -Butyl-5-methylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3,5-di-tert-
(Butylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-5-methyl- 3-trimethylsilylphenyl) (9H-fluoren-9-yl)
Dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (9H-fluorene −
9-yl) dimethylsilane, (2-allyloxy-3-t)
tert-butyl-5-methoxyphenyl) (9H-fluoren-9-yl) dimethylsilane, (6-allyloxy-5-tert-butyl-3-chlorophenyl) (9H
-Fluoren-9-yl) dimethylsilane, (1-allyloxynaphthalen-2-yl) dimethyl (1,2,3,3)
4 tetramethylcyclopentadienyl) silane,
The methoxy or allyloxy of these compounds is replaced by benzyloxy, ethoxy, trimethylsilyloxy, tert.
-Butyldimethylsilyloxy, a compound changed to methoxymethoxy, dimethylsilane to diethylsilane, diphenylsilane, a compound changed to dimethoxysilane, cyclopentadienyl to dimethylcyclopentadienyl,
Trimethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl,
n-butylcyclopentadienyl, isobutylcyclopentadienyl, sec-butylcyclopentadienyl,
tert-butyldimethylsilylcyclopentadienyl, phenylcyclopentadienyl, a compound obtained by changing to methylindenyl, 2-methoxyphenyl to 3-phenyl-2-methoxyphenyl, 3-trimethylsilyl-2
General formula (2b) such as a compound changed to -methoxyphenyl or 3-tert-butyldimethylsilyl-2-methoxyphenyl (wherein B 'is the 14th of the periodic table of elements other than carbon atoms)
A, Cp2, R1, R2, R3, R4
, R5, R6, and R7 each have the same meaning as described above. ) (Hereinafter, referred to as compound [2b]).

These compounds [2] have the substituent C
There may be a plurality of isomers derived from differences in the positions of the substituents of the cyclopentadiene skeleton and the positions of the double bonds in p2, but the compound [2] in the present invention includes all of these isomers .

In the compound [3], a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom or a halogen atom, which may be substituted by X 3 or X 4, may be substituted. 7 carbon atoms
To 20 aralkyl groups, aryl groups having 6 to 20 carbon atoms which may be substituted with halogen atoms, substituted silyl groups having 1 to 20 carbon atoms which may be substituted with halogen atoms, substituted with halogen atoms An alkoxy group having 1 to 20 carbon atoms which may be substituted, an aralkyloxy group having 1 to 20 carbon atoms which may be substituted by a halogen atom, 1 to 20 carbon atoms which may be substituted by a halogen atom
The aryloxy group and the disubstituted amino group having 2 to 20 carbon atoms include the substituents X 1 and X 2 in the compound [1].
Are the same as those described above.

Examples of the compound [3] include titanium halides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, tetrakis (dimethylamino) titanium, dichlorobis (dimethylamino) titanium, trichloro (dimethylamino) Titanium, amide titanium such as tetrakis (diethylamino) titanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium, alkoxytitanium such as trichloroisopropoxytitanium, etc. The amount of the compound is usually 0.5 to 3 with respect to the compound [2].
The molar ratio is preferably in the range of 0.7 to 1.5 molar times.

Examples of the base include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, lithium acetylide, trimethyl silyl methyl lithium, vinyl lithium, phenyl lithium, allyl lithium, and the like. Organic alkali metal compounds such as organic lithium compounds and the like can be mentioned, and the amount of use is usually in the range of 0.5 to 5 moles per mole of the compound [2].

Further, an amine compound can be used together with the base. Examples of such amine compounds include primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline, and ethylenediamine; , Diethylamine, di-n-propylamine, di-n-propylamine, di-n-butylamine,
Secondary amine compounds such as di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane, diphenylamine, trimethylamine, triethylamine, tri-n-
Propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-
Tertiary amine compounds such as n-decylamine, triphenylamine, N, N-dimethylaniline, N, N, N ′, N′-tetramethylethylenediamine, N-methylpyrrolidine, and 4-dimethylaminopyridine.
The amount of the amine compound to be used is generally 10 mol times or less, preferably 0.5 to 10 mol times, more preferably 1 to 3 mol times with respect to the base.

The reaction is usually performed in a solvent inert to the reaction. Such solvents include, for example, aromatic hydrocarbon solvents such as benzene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane, and hexamethylphosphoric acid. Amide solvents such as amides and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; aprotic solvents such as dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; Is mentioned. Each of these solvents is used alone or in combination of two or more. The amount of the solvent to be used is generally 1 to 200 times by weight, preferably 3 to 200 parts by weight, relative to compound [2].
The range is 50 times by weight.

This step can be usually carried out by adding compound [2] and a base to a solvent and then adding compound [3]. A solid may be precipitated after adding the compound [2] and the base. In this case, the solid taken out of the reaction system may be added to the same solvent as described above, and then the compound [3] may be added. . Further, the compound [2], the base and the compound [3] may be simultaneously added to the solvent. The reaction temperature is usually from -100 ° C to the boiling point of the solvent, preferably from -80 to 100 ° C. The reaction system is preferably shielded from light in terms of the yield of compound [1].

After synthesizing the transition metal complex represented by the general formula (1), the formed precipitate is separated from the obtained reaction mixture by filtration, a part of the reaction solvent is distilled off, and the mixture is cooled with stirring. Thus, the intended transition metal complex represented by the general formula (1) can be obtained with high purity and without scaling by precipitating the transition metal complex.

The reaction is usually performed in a solvent inert to the reaction. Such solvents include, for example, aromatic hydrocarbon solvents such as benzene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane, and hexamethylphosphoric acid. Amide solvents such as amides and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; aprotic solvents such as dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; Is mentioned. Such solvents are used alone or in combination of two or more. Preferably, it is an aromatic hydrocarbon solvent, and more preferably, toluene.

The solvent is distilled off under reduced pressure or normal pressure, and the temperature is not particularly limited. The amount of the solvent to be distilled off is 1/100 to 1/100 of the amount required for the solvent amount at the start of crystallization to become a saturated solution of the transition metal compound represented by the general formula (1) at the crystallization end temperature. The amount is 80/100,
Preferably, the amount is 20/100 to 30/100. The crystallization start temperature is not particularly limited as long as it is lower than the boiling point of the solvent used. The cooling rate is from 1 ° C / h to 30 ° C / h, preferably from 1 ° C / h to 10 ° C / h. By cooling while stirring from the crystallization start temperature, the transition metal compound represented by the general formula (1) precipitates without scaling. At this time, a small amount of the transition metal complex may be added to the system in order to promote the precipitation of the transition metal compound represented by the general formula (1). The transition metal compound represented by the general formula (1) can be obtained by filtering the generated crystals. Further, the crystals collected by filtration can be further purified by washing with a solvent, but as a washing solvent, aliphatic solvents such as n-pentane, n-hexane, and n-heptane are preferable in terms of yield. Preferred, but more preferred is n-hexane.

[0092]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 Dimethylsilyl (tetramethylcyclopentadienyl)
Synthesis of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (3-tert-butyl-2-allyloxy-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadi A solution of (enyl) silane (11.8 g) and triethylamine (15.1 g) in toluene (72.1 g)
Then, a 1.60 M hexane solution (31.9 g) of n-butyllithium was added dropwise at −10 ° C., and the mixture was heated to 20 ° C. and further stirred for 1 hour. The reaction solution was cooled to −10 ° C., and titanium tetrachloride (9.46 g) in toluene (37.8 g) was used.
The solution was added dropwise, and the mixture was stirred at −10 ° C. for 1 hour, heated to 90 ° C., and further stirred for 3 hours. The reaction mixture was filtered and the solid was washed with toluene (68.0 g). After combining the obtained filtrate and the washing liquid, dimethylsilyl (tetramethylcyclopentadienyl) in the reaction solution at 90 ° C. under reduced pressure.
The mixture was concentrated until (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride became 19.5 wt%, and cooled to 70 ° C. At this temperature, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.05 g) is added, and up to 20 ° C at a rate of 5 ° C / h. Cool. Dark red-brown crystals precipitated, no scaling was observed at this time. The wet cake was collected by filtration to give dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (8.48 g, 78).
% Purity, 47% yield). 0.882g
Was sampled, washed twice with hexane (1.04 ml), and dried under reduced pressure to give dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride. (0.674 g, 95% purity, 94% recovery, 4 yield)
4%).

Example 2 Dimethylsilyl (tetramethylcyclopentadienyl)
Synthesis of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride In Example 1, the sampling amount was 0.921 g, and the washing solvent was hexane (1.04 ml × 2) to toluene (0.28 ml ×). Except having changed to 3), the same operation was performed. Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.634 g, 9
8% purity, recovery rate 87%, yield 41%).

Comparative Example 1 Dimethylsilyl (tetramethylcyclopentadienyl)
Synthesis of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (3-tert-butyl-2-allyloxy-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadi A toluene solution (22.0 ml) of (enyl) silane (2.00 g, 73.5% purity) and triethylamine (2.00 g) was added at −15 ° C. to a 15.3 wt% hexane solution of n-butyllithium (4. 13 g) was added dropwise, and the mixture was stirred at -15 ° C for 1 hour, and then heated to 25 ° C and further stirred for 2 hours. The reaction solution was cooled to −15 ° C., and titanium tetrachloride (1.31 g) in toluene (6.1 m) was added.
l) The solution was added dropwise, and the mixture was stirred at -15 ° C for 1 hour, heated to 90 ° C, and further stirred for 3 hours. The reaction mixture was filtered and the solid was washed with toluene (10ml). The obtained filtrate and washing solution were combined, concentrated under reduced pressure, and the obtained orange-brown tar was washed with hexane (4.3 ml). The remaining orange-brown solid was washed with toluene (3.0 ml) and hexane (3.0 ml). 12m
Recrystallized from 1). Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.74
g, yield 48%) was obtained as dark reddish-brown needle-like crystals in the state of being attached to the wall of the flask.

[0096]

As described in detail above, according to the present invention,
The above half metallocene type metal complex can be easily purified in a short number of steps.

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[Procedure amendment]

[Submission date] June 9, 2000 (200.6.9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

[0004]

That is, the present invention provides one aspect of the present invention.
General formula (1)(Where M¹ Indicates a transition metal atom of Group 4 of the periodic table
A represents an atom belonging to Group 16 of the periodic table, and B represents a periodic rule.
The atoms of group 14 of the table are shown. Cp¹ Is cyclopentadie
A group having a phenyl skeleton, wherein the transition metal atom and π
Has a bond. R¹ , R^Two , R^Three , R^FourIs German
Is replaced by a hydrogen atom, halogen atom, halogen atom
An alkyl group having 1 to 20 carbon atoms which may be
AtomOr an alkyl groupA carbon source optionally substituted with
Aralkyl group having 7 to 20 atoms, halogen atomOr al
Kill groupHaving 6 to 20 carbon atoms which may be substituted
Reel group, carbon atom optionally substituted by halogen atom
A substituted silyl group having 1 to 20 children, substituted with a halogen atom
An alkoxy group having 1 to 20 carbon atoms which may be substituted, halo
Gen atomOr an alkyl groupOptionally substituted carbon
An aralkyloxy group having 1 to 20 atoms, a halogen atomMa
Or alkyl group1 to 1 carbon atoms which may be substituted
20 aryloxy groups or 2-20 carbon atoms
R represents a substituted amino group;^Five , R⁶ Are each independently hydrogen
Atoms, number of carbon atoms which may be substituted with halogen atoms
1-20 alkyl groups, halogen atomsOr an alkyl group
Aralkyl having 7 to 20 carbon atoms which may be substituted with
Group, halogen atomOr an alkyl groupHas been replaced by
C6-20 aryl group, halogen atom
A substituted silyl having 1 to 20 carbon atoms which may be substituted
Number of carbon atoms which may be substituted with
1 to 20 alkoxy groups, halogen atomsOr alkyl
BaseAral having 1 to 20 carbon atoms which may be substituted with
Killoxy group, halogen atomOr an alkyl groupReplaced by
An aryloxy group having 1 to 20 carbon atoms which may be
Or a disubstituted amino group having 2 to 20 carbon atoms;
¹ , R^Two , R ^Three , R^Four , R^Five , R⁶ Is optionally bonded to a ring
X may be formed.¹ , X^Two, Represents a halogen atom
Show. After the synthesis of the transition metal complex represented by
After filtration, a part of the reaction solvent is distilled off, and then cooled while stirring.
Thereby depositing the transition metal complex.
And a method for purifying the transition metal complex.
You.

Continuation of the front page F term (reference) 4H049 VN01 VN05 VP02 VQ19 VQ91 VQ92 VR24 VR31 VR41 VS09 4H050 AB40 AC90 AD15 AD17 BB11 WA15 WA26

Claims (6)

[Claims] 1. The general formula (1) (Wherein, M ¹ represents a transition metal atom of Group 4 of the periodic table, A represents an atom of Group 16 of the periodic table, and B represents an atom of Group 14 of the periodic table. Cp ¹ is a group having a cyclopentadienyl skeleton, and the above transition metal atom and π
Has a bond. R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or a carbon atom which may be substituted with a halogen atom. An aralkyl group having 7 to 20 atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, a substituted silyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom An alkoxy group having 1 to 20 carbon atoms which may be substituted by an aralkyloxy group having 1 to 20 carbon atoms which may be substituted by a halogen atom; a carbon atom having 1 carbon atom which may be substituted by a halogen atom And R ⁵ and R ⁶ each independently represent a hydrogen atom or a carbon atom which may be substituted with a halogen atom. An alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom A substituted silyl group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms optionally substituted with a halogen atom, and 1 to 20 carbon atoms optionally substituted with a halogen atom An aralkyloxy group having 1 carbon atom which may be substituted with a halogen atom
Represents an aryloxy group of from 20 to 20 or a disubstituted amino group of from 2 to 20 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ may be arbitrarily bonded to form a ring,
X ¹ and X ^{2 each} represent a halogen atom. After synthesizing the transition metal complex represented by the formula (1), insolubles are filtered, a part of the reaction solvent is distilled off, and the mixture is cooled with stirring to precipitate the transition metal complex. A method for purifying a metal complex. 2. The purification method according to claim 1, wherein the reaction solvent is an aromatic solvent. 3. The purification method according to claim 1, wherein the cooling rate is 1 ° C./h to 30 ° C./h. 4. The amount of the solvent at the start of crystallization is 1/100 to 80/80 of the amount required to become a saturated solution of the transition metal compound represented by the general formula (1) at the crystallization end temperature. The purification method according to claim 1, 2 or 3, wherein the purification method is 100. 5. The purification method according to claim 1, wherein the precipitate is further washed with an aliphatic solvent. 6. The method of claim 1, wherein B is a silicon atom.
The purification method according to 3, 4, or 5.