JP4710334B2 - Cyclopentadiene compound and method for producing the same - Google Patents

Description

  The present invention relates to a cyclopentadiene compound and a method for producing the same.

Metallocene complexes are useful as a component of polymerization catalysts for olefin polymerization, and many reports have been made so far. Among them, a bridged half metallocene complex having a ligand in which cyclopentadiene and phenol are bridged by a group 14 atom of the periodic table of elements is a promising metal complex that can be expected to have a specific activity from its special structure (for example, Patent Document 1), development of a novel cyclopentadienyl compound serving as its ligand has been desired.
JP-A-9-87313

  The present invention is intended to provide a novel cyclopentadiene compound and a method for producing the same, which are effective for producing a metallocene complex.

  As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that a novel cyclopentadiene compound can be advantageously obtained, leading to the present invention.

（式中、Ｃｐ^１はシクロペンタジエン骨格を有する基を示し、Ａは炭素原子を除く元素の周期律表の第１４族の原子を示し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は水素原子、ハロゲン原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数１〜２０のアルコキシ基、置換もしくは無置換の炭素数６〜２０のアリール基、置換もしくは無置換の炭素数６〜２０のアリールオキシ基、置換もしくは無置換の炭素数７〜２０のアラルキル基、置換もしくは無置換の炭素数７〜２０のアラルキルオキシ基、置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたシリル基又は置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたアミノ基を表し、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４において隣接する基は、それぞれ任意に結合して環を形成していてもよく、Ｒ^５とＲ^６は結合して環を形成していてもよい。）
で示されるシクロペンタジエン化合物； That is, the present invention provides the formula (1)

(In the formula, Cp ¹ represents a group having a cyclopentadiene skeleton, A represents an atom of Group 14 of the periodic table of elements other than carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ And R ⁶ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Group, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, substituted or unsubstituted A silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms or an amino group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, R ¹ , R ² , R ³ and R ⁴ smell Adjacent groups, respectively may form a ring optionally, R ⁵ and R ⁶ may form a ring.)
A cyclopentadiene compound represented by:

（式中、Ａ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は前記と同じ意味を表し、Ｃｐ^２はシクロペンタジエン型アニオン骨格を有する基を表し、Ｍはアルカリ金属を表す。）
で示されるジアニオン金属塩、 Formula (3)

(In the formula, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above, Cp ² represents a group having a cyclopentadiene type anion skeleton, and M represents an alkali metal. To express.)
A dianionic metal salt represented by

（式中、Ａ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｃｐ^２及びＭは前記と同じ意味を表す。）
で示されるジアニオン金属塩と、式（４）

（式中、Ｒ^１１は水素原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜２０のアリール基、又は置換もしくは無置換の炭素数７〜２０のアラルキル基を表す。）
で示されるプロトン性の化合物とを反応させる式（１）で示されるシクロペンタジエン化合物の製造方法、及び Formula (3)

(In the formula, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Cp ² and M represent the same meaning as described above.)
A dianion metal salt represented by formula (4)

(In the formula, R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 7 to 20 carbon atoms. Represents an aralkyl group.)
A process for producing a cyclopentadiene compound represented by the formula (1), wherein a protic compound represented by formula (1) is reacted:

（式中、Ａ、Ｃｐ^１、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は前記と同じ意味を表し、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６はそれぞれ水素原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜２０のアリール基又は置換もしくは無置換の炭素数７〜２０のアラルキル基を表す。）
で示される保護されたシクロペンタジエン化合物と、式（６）

（式中、Ｍは前記と同じ意味を表し、Ｒ^１７は水素原子、ハロゲン原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜２０のアリール基、又は置換もしくは無置換の炭素数７〜２０のアラルキル基を表す。）
で示される金属化合物とを反応させる式（３）で示されるジアニオン金属塩の製造方法を提供するものである。 Formula (5)

(In the formula, A, Cp ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above, and R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represent And represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms.)
A protected cyclopentadiene compound represented by formula (6):

(In the formula, M represents the same meaning as described above, and R ¹⁷ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms.)
The manufacturing method of the dianion metal salt shown by Formula (3) with which the metal compound shown by this is made to react is provided.

  The cyclopentadiene compound represented by the formula (1) obtained by the present invention [hereinafter referred to as cyclopentadiene compound (1). ] Is useful as a polymerization catalyst component, and the compound (1) can be industrially advantageously obtained by the production method of the present invention.

  Hereinafter, the present invention will be described in detail.

In the cyclopentadiene compound (1), examples of the group 14 element in the periodic table of elements other than the carbon atom represented by A include a silicon atom, a germanium atom, a tin atom, and preferably a silicon atom. Is done.

（式中、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は同一又は相異なり、水素原子、ハロゲン原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜２０のアリール基、置換もしくは無置換の炭素数７〜２０のアラルキル基、置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたシリル基、置換もしくは無置換の炭素数１〜２０のアルコキシ基、置換もしくは無置換の炭素数６〜２０のアリールオキシ基、置換もしくは無置換の炭素数７〜２０のアラルキルオキシ基、置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたシリルオキシ基、置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたアミノ基、置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたホスフィノ基、及び、置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたチオ基を表し、隣接するＲ^７、Ｒ^８、Ｒ^９及びＲ^１０における隣接する基はそれぞれ任意に結合して環を形成していてもよい。）
で示される基が挙げられ、これらの基のシクロペンタジエン骨格の二重結合の位置の相違に由来する複数の異性体が存在することもあるが、本発明ではこれらの全ての異性体が包含される。 In the formula (1), examples of the group having a cyclopentadiene skeleton represented by Cp ¹ include, for example, the formula (2)

(Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number 6 to 20 aryl groups, substituted or unsubstituted aralkyl groups having 7 to 20 carbon atoms, silyl groups substituted with substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, substituted or unsubstituted 1 to 20 carbon atoms Substituted with a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms Silyloxy group, amino group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, phosphino substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms , And represent a substituted or unsubstituted hydrocarbon group substituted thio group having 1 to 20 carbon atoms, bonded to each adjacent groups optionally in R ^7, R ^8, R ⁹ and R ¹⁰ that are adjacent A ring may be formed.)
There may be a plurality of isomers derived from the difference in the position of the double bond of the cyclopentadiene skeleton of these groups, but the present invention includes all these isomers. The

Examples of the group represented by the formula (2) include cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, ethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n- Butylcyclopentadiene, sec-butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcyclopentadiene, neopentylcyclopentadiene, n-hexylcyclopentadiene, n-octylcyclopentadiene, tetrahydroindene, octahydrofluorene, Phenylcyclopentadiene, naphthylcyclopentadiene, trimethylsilylcyclopentadiene, triethylsilylcyclopentadiene , Triphenylsilyl cycloalkyl Bae Ntajien, tert- butyldimethylsilyl substituted or unsubstituted cyclopentadiene, such as cyclopropyl Bae Ntajien,

Indene, methylindene, dimethylindene, ethylindene, n-propylindene, isopropylindene, n-butylindene, sec-butylindene, tert-butylindene, n-pentylindene, neopentylindene, n-hexylindene, n- Substituted or unsubstituted indene such as octylindene, n-decylindene, phenylindene, methylphenylindene, naphthylindene,

Fluorene, 2-methylfluorene, 2,7-dimethylfluorene, 2-ethylfluorene, 2,7-diethylfluorene, 2-n-propylfluorene, 2,7-di-n-propylfluorene, 2-isopropylfluorene, 2 , 7-diisopropylfluorene, 2-n-butylfluorene, 2-sec-butylfluorene, 2-tert-butylfluorene, 2,7-di-n-butylfluorene, 2,7-di-sec-butylfluorene, 2 , 7-di-tert-butylfluorene, 3,6-di-tert-butylfluorene, 2-n-pentylfluorene, 2-neopentylfluorene, 2-n-hexylfluorene, 2-n-octylfluorene, 2- n-decylfluorene, 2-n-dodecylfluorene, 2-phenylfluorene Substituted or unsubstituted fluorene such as 2,7-di-phenylfluorene, 2-methylphenylfluorene, 2-naphthylfluorene and the like can be mentioned, and preferably cyclopentadiene, methylcyclopentadiene, tert-butylcyclopentadiene, tetramethylcyclopentadiene , Indene, fluorene, 2,7-di-tert-butylfluorene, 3,6-di-tert-butylfluorene, and the like.

In the present invention, examples of the halogen atom represented by the substituents R ^{1 to} R ¹⁰ and R ¹⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.

Examples of the substituent in the substituted alkyl group having 1 to 20 carbon atoms represented by the substituents R ^{1 to} R ¹⁷ include a halogen atom. Specific examples of the substituted or unsubstituted alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, Amyl group, n-hexyl group, heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group , Nonadecyl group, n-eicosyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, iodomethyl group, diiodomethyl Group, triiodomethyl group, fluoroethyl group, difluoroethyl Group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetra Bromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group Perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl A perbromobutyl group, a perbromopentyl group, a perbromohexyl group, a perbromooctyl group, a perbromododecyl group, a perbromopentadecyl group, a perbromoeicosyl group, and the like, preferably a methyl group, an ethyl group, Illustrative are isopropyl, tert-butyl and amyl groups.

Examples of the substituent in the substituted aralkyl group having 7 to 20 carbon atoms represented by the substituents R ^{1 to} R ¹⁷ include an alkyl group and a halogen atom. Specific examples of the substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl) Phenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl) (Phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2, 3,4,6-tetramethylphenyl) methyl group, (2,3,5,6- (Tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec- (Butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, Examples include (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like. A benzyl group is preferred. Any of these aralkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the substituent in the substituted aryl group having 6 to 20 carbon atoms represented by the substituents R ^{1 to} R ¹⁷ include an alkyl group and a halogen atom. Specific examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, and 2,4-xylyl group. Group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6 -Tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-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, etc. Preferably, a phenyl group is exemplified. Any of these aryl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The substituted silyl group represented by the substituents R ^{1 to} R ¹⁰ is a silyl group substituted with a substituted or unsubstituted hydrocarbon group. Examples of the hydrocarbon group include a methyl group and an ethyl group. N-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as n-nonyl group and n-decyl group, and aryl groups such as phenyl group. Specific examples of the substituted silyl group having 1 to 20 carbon atoms include a monosubstituted silyl group having 1 to 20 carbon atoms such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group, a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group. A disubstituted silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms, 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, triphenylsilyl group A trisubstituted silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms such as Illustrated, it is preferably exemplified by trimethylsilyl group, tert- butyldimethylsilyl group, a triphenylsilyl group. As the hydrocarbon group constituting these substituted silyl groups, in addition to the unsubstituted hydrocarbon group as described above, a substituted hydrocarbon group substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom Is exemplified.

Examples of the substituent in the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms represented by the substituents R ^{1 to} R ¹⁰ include a halogen atom. Specific examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-dodecyloxy group, n-undecyloxy group, n-dodecyloxy group Group, tridecyloxy group, tetradecyloxy group, n-pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, n-eicosyloxy group and the like, preferably methoxy Group, ethoxy group and tert-butoxy group are exemplified. Any of these alkoxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the substituent in the substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms represented by the substituents R ^{1 to} R ¹⁰ include an alkyl group and a halogen atom. Specific examples of the substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, and (4-methylphenyl) methoxy group. 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-Tetra Methylphenyl) 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-hexyl) Phenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like are preferable, and benzyloxy group is preferable. Any of these aralkyloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the substituent in the substituted aryloxy group having 6 to 20 carbon atoms represented by the substituents R ^{1 to} R ¹⁰ include an alkyl group and a halogen atom. Specific examples of the substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 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 Group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group Examples thereof include unsubstituted aryloxy groups having 6 to 20 carbon atoms such as a group, n-tetradecylphenoxy group, naphthoxy group, and anthracenoxy group. Specific examples of these substituted aryloxy groups include, for example, those in which the unsubstituted aryloxy group having 6 to 20 carbon atoms is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Is exemplified.

An amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms represented by substituents R ^{1 to} R ¹⁰ is an amino group substituted with two hydrocarbon groups, where Is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc. Examples thereof include an alkyl group having 1 to 20 carbon atoms and an aryl group such as a phenyl group, and these substituents may be bonded to each other to form a ring. Examples of the amino group substituted with the hydrocarbon group having 1 to 20 carbon atoms include, for example, 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, Examples include diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroindolyl group, dihydroisoindolyl group and the like, preferably dimethylamino Group, diethylamino group, pyrrolidinyl group, piperidinyl group Groups.

The silyloxy group substituted with a hydrocarbon group having 1 to 20 carbon atoms in the substituents R ^{7 to} R ¹⁰ is a silyloxy group substituted with three hydrocarbon groups, and as the hydrocarbon group, For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc. Examples thereof include an alkyl group having 1 to 20 carbon atoms and an aryl group such as a phenyl group, and these substituents may be bonded to each other to form a ring. Examples of the substituted silyloxy group having 1 to 20 carbon atoms include trimethylsilyloxy group, triethylsilyloxy group, tri-n-butylsilyloxy group, triphenylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyl group. Examples include an oxy group, a dimethylphenylsilyloxy group, and a methyldiphenylsilyloxy group, and a trimethylsilyloxy group, a triphenylsilyloxy group, a triisopropylsilyloxy group, and the like are preferable.

The phosphino group substituted with a hydrocarbon group having 1 to 20 carbon atoms represented by the substituents R ^{7 to} R ¹⁰ is a phosphino group substituted with two hydrocarbon groups, wherein the hydrocarbon group As, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, Heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, n-eicosyl Examples include alkyl groups having 1 to 20 carbon atoms such as aryl groups such as phenyl groups, and these substituents may be bonded to each other to form a ring. There. Specific examples of the phosphino group substituted with such a hydrocarbon group having 1 to 20 carbon atoms include dimethylphosphino group, diethylphosphino group, di-n-propylphosphino group, diisopropylphosphino group, di-n- Butylphosphino group, di-sec-butylphosphino group, di-tert-butylphosphino group, di-isobutylphosphino group, tert-butylisopropylphosphino group, di-n-hexylphosphino group, di-n -Octylphosphino group, di-n-decylphosphino group, diphenylphosphino group, bistrimethylsilylphosphino group, bis-tert-butyldimethylsilylphosphino group, etc. are exemplified, preferably dimethylphosphino group, diethylphosphino group And a diphenylphosphino group.

Examples of the hydrocarbon group in the thio group substituted with the hydrocarbon group having 1 to 20 carbon atoms in the substituents R ^{7 to} R ¹⁰ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group and other alkyl groups having 1 to 20 carbon atoms, phenyl group and other aryl groups. These substituents may be bonded to each other to form a ring or thiophene. Specific examples of the thio group substituted with the hydrocarbon group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group. Group, isobutylthio group, n-hexylthio group, n-octylthio group, n-decylthio group, phenylthio group and the like.

Two adjacent substituents of R ^{1 to} R ⁴ and two adjacent substituents of R ^{7 to} R ¹⁰ may be optionally bonded to form a ring, and R ⁵ and R ⁶ are bonded. A ring may be formed.

Examples of the ring formed by combining two adjacent substituents among R ^{7 to} R ¹⁰ include, for example, a saturated or unsaturated hydrocarbon ring, thiophene ring, thiazole ring, thiazoline ring, thiadiazo- Heterocycles such as ru ring and pyridine ring are exemplified.

The ring formed by combining two adjacent substituents among R ^{1 to} R ^{4 and} the ring formed by combining R ⁵ and R ⁶ include a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms. Examples thereof include a saturated or unsaturated hydrocarbon ring substituted with a hydrogen group. Specific examples thereof include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, benzene ring, naphthalene ring, anthracene ring and the like.

Examples of the cyclopentadiene compound (1) of the present invention include (phenol-2-yl) (cyclopentadienyl) dimethylsilane and (5,6-dimethylphenol-2-yl) (cyclopentadienyl) dimethylsilane. (6-tert-butyl-4-methylphenol-2-yl) (cyclopentadienyl) dimethylsilane, (6-tert-butyl-4-methoxyphenol-2-yl) (cyclopentadienyl) dimethylsilane (6-tert-butyl-4-dimethylaminophenol) (cyclopentadienyl) dimethylsilane, (6-tert-butylphenol-2-yl) (cyclopentadienyl) dimethylsilane, (6-tert-butyl- 4-chlorophenol-2-yl) (cyclopentadienyl) dimethylsilane (6-Phenylphenol-2-yl) (cyclopentadienyl) dimethylsilane, (6-tert-butyldimethylsilyl-4-methylphenol-2-yl) (cyclopentadienyl) dimethylsilane, (4-methyl -6-trimethylsilylphenol-2-yl) (cyclopentadienyl) dimethylsilane, (1-naphthol-2-yl) (cyclopentadienyl) dimethylsilane,

(Phenol-2-yl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane, (5,6-dimethylphenol-2-yl) (2,3,4,5-tetramethylcyclo Pentadienyl) dimethylsilane, (6-tert-butyl-4-methylphenol-2-yl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane, (6-tert-butyl-4) -Methoxyphenol-2-yl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane, (6-tert-butyl-4-dimethylaminophenol) (2,3,4,5-tetra Methylcyclopentadienyl) dimethylsilane, (6-tert-butylphenol-2-yl) (2,3,4,5-tetramethylcyclopentadienyl) Dimethylsilane, (6-tert-butyl-4-chlorophenol-2-yl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane, (6-phenylphenol-2-yl) (2 , 3,4,5-tetramethylcyclopentadienyl) dimethylsilane, (6-tert-butyldimethylsilyl-4-methylphenol-2-yl) (2,3,4,5-tetramethylcyclopentadienyl) ) Dimethylsilane, (4-methyl-6-trimethylsilylphenol-2-yl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane, (1-naphthol-2-yl) (2,3 , 4,5-tetramethylcyclopentadienyl) dimethylsilane,

(Phenol-2-yl) (indenyl) dimethylsilane, (5,6-dimethylphenol-2-yl) (indenyl) dimethylsilane, (6-tert-butyl-4-methylphenol-2-yl) (indenyl) Dimethylsilane, (6-tert-butyl-4-methoxyphenol-2-yl) (indenyl) dimethylsilane, (6-tert-butyl-4-dimethylaminophenol) (indenyl) dimethylsilane, (6-tert-butylphenol) -2-yl) (indenyl) dimethylsilane, (6-tert-butyl-4-chlorophenol-2-yl) (indenyl) dimethylsilane, (6-phenylphenol-2-yl) (indenyl) dimethylsilane, ( 6-tert-Butyldimethylsilyl-4-methylphenol 2- yl) (indenyl) dimethylsilane, (4-methyl-6-trimethylsilylphenol 2-yl) (indenyl) dimethylsilane, (1-naphthol-2-yl) (indenyl) dimethylsilane,

(Phenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) dimethylsilane, (5,6-dimethylphenol-2-yl) (2,7-di-tert-butylfluorene- 9-yl) dimethylsilane, (6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) dimethylsilane, (6-tert-butyl-4 -Methoxyphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) dimethylsilane, (6-tert-butyl-4-dimethylaminophenol) (2,7-di-tert-butyl) Fluoren-9-yl) dimethylsilane, (6-tert-butylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) Dimethylsilane, (6-tert-butyl-4-chlorophenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) dimethylsilane, (6-phenylphenol-2-yl) (2 , 7-Di-tert-butylfluoren-9-yl) dimethylsilane, (6-tert-butyldimethylsilyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) ) Dimethylsilane, (4-methyl-6-trimethylsilylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) dimethylsilane, (1-naphthol-2-yl) (2,7 -Di-tert-butylfluoren-9-yl) dimethylsilane, and the like. Dimethylsilane is diethylsilane, diphenylsilane. Those changes are also illustrated in the same manner.

（式中、Ａ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は前記と同じ意味を表し、Ｃｐ^２はシクロペンタジエン型アニオン骨格を有する基であり、Ｍはアルカリ金属を表す。）
で示されるジアニオン金属塩［以下、ジアニオン金属塩（３）と称す。］と、式（４）

（式中、Ｒ^１１は水素原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜２０のアリール基、又は置換もしくは無置換の炭素数７〜２０のアラルキル基を表す。）
で示されるプロトン性の化合物［以下、プロトン性の化合物（４）と称す。］を反応させることにより製造することができる。 Such cyclopentadiene compound (1) has the formula (3)

(In the formula, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above, Cp ² is a group having a cyclopentadiene type anion skeleton, and M is an alkali metal. To express.)
The dianion metal salt represented by [Hereinafter referred to as the dianion metal salt (3). ] And formula (4)

(In the formula, R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 7 to 20 carbon atoms. Represents an aralkyl group.)
A protic compound [hereinafter referred to as a protic compound (4). ] Can be made to react.

Examples of the cyclopentadienyl type anion represented by Cp ² include an anion of a group having a cyclopentadiene skeleton represented by Cp ¹ .

Examples of the alkali metal represented by M include lithium, sodium, potassium and the like, preferably lithium.

Examples of the dianion metal salt (3) include dimethylsilylene (2-phenoxy) (cyclopentadienyl) dilithium, dimethylsilylene (3,4-dimethylphenyl-2-phenoxy) (cyclopentadienyl) dilithium, and dimethylsilylene. (3-tert-butyl-5-methyl-2-phenoxy) (cyclopentadienyl) dilithium, dimethylsilylene (3-tert-butyl-5-methoxy-2-phenoxy) (cyclopentadienyl) dilithium, dimethylsilylene (3-tert-butyl-2-phenoxy) (cyclopentadienyl) dilithium, dimethylsilylene (3-tert-butyl-5-chloro-2-phenoxy) (cyclopentadienyl) dilithium, dimethylsilylene (3-phenyl) -2-phenoxy) Pentadienyl) dilithium, dimethylsilylene (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) (cyclopentadienyl) dilithium, dimethylsilylene (3-trimethylsilyl-5-methyl-2-phenoxy) (cyclopentadiene) Enyl) dilithium

Dimethylsilylene (2-phenoxy) (2,3,4,5-tetramethylcyclopentadienyl) dilithium, dimethylsilylene (3,4-dimethylphenyl-2-phenoxy) (2,3,4,5-tetramethyl Cyclopentadienyl) dilithium, dimethylsilylene (3-tert-butyl-5-methyl-2-phenoxy) (2,3,4,5-tetramethylcyclopentadienyl) dilithium, dimethylsilylene (3-tert-butyl) -5-methoxy-2-phenoxy) (2,3,4,5-tetramethylcyclopentadienyl) dilithium, dimethylsilylene (3-tert-butyl-2-phenoxy) (2,3,4,5-tetra Methylcyclopentadienyl) dilithium, dimethylsilylene (3-tert-butyl-5-chloro-2-phenyl) Noxy) (2,3,4,5-tetramethylcyclopentadienyl) dilithium, dimethylsilylene (3-phenyl-2-phenoxy) (2,3,4,5-tetramethylcyclopentadienyl) dilithium, dimethyl Silylene (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) (2,3,4,5-tetramethylcyclopentadienyl) dilithium, dimethylsilylene (3-trimethylsilyl-5-methyl-2-phenoxy) ) (2,3,4,5-tetramethylcyclopentadienyl) dilithium

Dimethylsilylene (2-phenoxy) (indenyl) dilithium, dimethylsilylene (3,4-dimethylphenyl-2-phenoxy) (indenyl) dilithium, dimethylsilylene (3-tert-butyl-5-methyl-2-phenoxy) (indenyl) ) Dilithium, dimethylsilylene (3-tert-butyl-5-methoxy-2-phenoxy) (indenyl) dilithium, dimethylsilylene (3-tert-butyl-2-phenoxy) (indenyl) dilithium, dimethylsilylene (3-tert- Butyl-5-chloro-2-phenoxy) (indenyl) dilithium, dimethylsilylene (3-phenyl-2-phenoxy) (indenyl) dilithium, dimethylsilylene (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) (Indenyl) dilithium, dimethylsilylene (3-trimethylsilyl-5-methyl-2-phenoxy) (indenyl) dilithium

Dimethylsilylene (2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium, dimethylsilylene (3,4-dimethylphenyl-2-phenoxy) (2,7-di-tert-butylfluorene) -9-yl) dilithium, dimethylsilylene (3-tert-butyl-5-methyl-2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium, dimethylsilylene (3-tert-butyl) -5-methoxy-2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium, dimethylsilylene (3-tert-butyl-2-phenoxy) (2,7-di-tert-butyl) Fluoren-9-yl) dilithium, dimethylsilylene (3-tert-butyl-5-chloro-2-phenyl) Noxy) (2,7-di-tert-butylfluoren-9-yl) dilithium, dimethylsilylene (3-phenyl-2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium, dimethyl Silylene (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium, dimethylsilylene (3-trimethylsilyl-5-methyl-2-phenoxy) ) (2,7-di-tert-butylfluoren-9-yl) dilithium and the like, and those obtained by changing dimethylsilylene to diethylsilylene, diphenylsilylene and the like are also exemplified.

Examples of the protic compound (4) used in the production of the cyclopentadiene compound (1) include water, methanol, ethanol, 1-propanol, 2-propanol, n-butanol, tert-butanol, sec-butanol, n -Pentanol, n-hexanol, n-octanol, n-nonanol, phenol, 2-methylphenol, 3-methylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2 , 6-dimethylphenol, pentamethylphenol, benzyl alcohol, (2-methylphenyl) methanol, (3-methylphenyl) methanol, (4-methylphenyl) methanol, pentamethylphenylmethanol, naphthylmethanol, anthracenylmeta Lumpur like are exemplified, preferably water, methanol, phenol, and more preferably water is exemplified.

  The production of the cyclopentadiene compound (1) is usually performed in a solvent inert to the reaction. Examples of such solvents include 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, hexamethylphosphine, and the like. Amide solvents such as hollic amide and dimethylformamide, polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone, and aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Etc. are exemplified. These solvents are used alone or in admixture of two or more, and the amount used is usually 1 to 200 parts by weight, preferably 3 to 50 parts by weight, per 1 part by weight of the cyclopentadiene compound (1). It is a range.

  The reaction temperature is usually from −100 ° C. to the boiling point of the solvent, preferably about −80 to 30 ° C.

  After the reaction, for example, the cyclopentadiene compound (1) can be obtained from the filtrate from which the insoluble matter is removed by removing the insoluble solid and distilling off the solvent or after concentrating the reaction mixture. If necessary, it can be purified by ordinary methods such as recrystallization and sublimation.

The cyclopentadiene compound (1) thus obtained can be used as a ligand of a metal complex. Although the method is not particularly limited, for example, a method of obtaining a metal complex by mixing a transition metal precursor and a cyclopentadiene compound (1) in a solvent, or a reaction of a cyclopentadiene compound (1) with a base. A method of obtaining a metal complex by generating an anion of compound (1) and then mixing it with a transition metal precursor. After mixing cyclopentadiene (1) and a transition metal precursor, a metal complex is obtained by adding a base. Examples are methods.

The metal complex thus prepared can be used for polymerization by reacting with an activated cocatalyst, and examples of the activated cocatalyst include compounds usually used by those skilled in the art, such as zinc compounds, aluminum compounds, and boron compounds. .

Preferable activating cocatalysts include aluminum compounds and non-aluminum compounds that form an ion pair with a transition metal, and are used for polymerization by reacting a single or combined compound with a metal complex. be able to.

A cyclopentadiene compound (1), a transition metal precursor, an aluminum compound, and a non-aluminum compound that forms an ion pair with a transition metal can be charged and used in any order during polymerization. It is also possible to use a reaction product obtained by previously contacting a combination of

（式中、Ａ、Ｃｐ^１、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は前記と同じ意味を表し、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、及びＲ^１６は水素原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜２０のアリール基、又は置換もしくは無置換の炭素数７〜２０のアラルキル基を表す。）
で示される保護されたシクロペンタジエン化合物［以下、保護されたシクロペンタジエン化合物（５）と称す。］と、式（６）

（式中Ｍは前記と同じ意味を表し、Ｒ^１７は水素原子、ハロゲン原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜２０のアリール基、又は置換もしくは無置換の炭素数７〜２０のアラルキル基を表す。）
で示される金属化合物［以下、金属化合物（６）と称す。］を反応させることにより製造することができる。 The dianion metal salt (3) has the formula (5)

(In the formula, A, Cp ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above, and R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ represent And represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms.)
A protected cyclopentadiene compound represented by the formula [hereinafter referred to as protected cyclopentadiene compound (5). ] And formula (6)

(In the formula, M represents the same meaning as described above, and R ¹⁷ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or Represents a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms.)
[Hereinafter referred to as metal compound (6). ] Can be made to react.

（式中、Ａ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、及びＲ^１６は前記と同じ意味を表し、Ｘはハロゲン原子を表す。）
で示されるハライド化合物と、一般式（８）

（式中、Ｍ及びＣｐ^１は前記と同じ意味を表す。）
で示されるシクロペンタジエニル金属塩を反応させる方法（例えば、特許文献１参照。）により入手することができる。 The protected cyclopentadiene compound (5) is, for example, represented by the general formula (7)

(In the formula, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ represent the same meanings as described above, and X is halogen. Represents an atom.)
A halide compound represented by formula (8):

(In the formula, M and Cp ¹ represent the same meaning as described above.)
It can obtain by the method (for example, refer patent document 1) with which the cyclopentadienyl metal salt shown by these is made to react.

  Examples of the metal compound (6) used for the production of the dianion metal salt (3) include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, lithium acetylide, and trimethylsilyl. Examples include organic lithium compounds such as methyllithium, vinyllithium, phenyllithium, and allyllithium, and organic alkali metal compounds in which lithium is replaced with sodium or potassium. The amount used is 1 mol of dianion metal salt (3). Usually, it is in the range of 0.5 to 5 mol.

  Moreover, an amine compound can also be used with a metal compound (6). 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, dimethyl Amine, diethylamine, di-n-propylamine, di-n-propylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane, Secondary amine compounds such as diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenyl Min, N, N- dimethylaniline, N, N, N ', N'-tetramethylethylenediamine, N- methylpyrrolidine, tertiary amine compounds such as 4-dimethylaminopyridine can be exemplified. The amount of the amine compound used is usually 10 mol or less, preferably 0.5 to 10 mol, more preferably 1 to 3 mol, per 1 mol of the metal compound (6).

  The production of the dianion metal salt (3) is usually performed in a solvent inert to the reaction. Examples of such solvents include 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, hexamethylphosphine, and the like. Amide solvents such as hollic amide and dimethylformamide, polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone, and aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Etc. are exemplified. These solvents are used alone or in admixture of two or more, and the amount used is usually 1 to 200 parts by weight, preferably 3 to 50 parts per 1 part by weight of the protected cyclopentadiene compound (5). The range is parts by weight.

  The reaction temperature is usually from −100 ° C. to the boiling point of the solvent, preferably about −80 to 30 ° C.

  After the reaction, for example, the dianion metal salt (3) can be obtained from the filtrate from which the insoluble matter has been removed by removing the insoluble solid and distilling off the solvent or concentrating the reaction mixture. If necessary, it can be purified by ordinary methods such as recrystallization and sublimation.

EXAMPLES Hereinafter, although this invention is demonstrated in more detail by an experiment example, this invention is not limited to these experiment examples.
[NMR measurement conditions]
Apparatus: JEOL EX270 type NMR or Bruker DPX-300 type NMR
Sample: 5 mmφ tube, sample concentration: 10 mg / 0.5 mL (CDCl ₃ or THF-d ₈ )
Measurement parameters: 5 mmφ probe, MENU: NON, OBNUC: ¹ H, integration count: 256 times Internal standard: CDCl ₃ (7.26 ppm)
Pulse angle: 45 °,
Temperature: Room temperature (about 25 ° C)
Repeat time (ACQTM + PD): Approximately 7 seconds

[MS measurement conditions (EI)]
Device: JEOL JMS-AX505W
Ionization voltage: 70 eV
Ion source temperature: 230 ° C
Data processing device: MS-MP8020D
MASS RANGE: m / z 35-1000

[Experimental Example 1]
“Synthesis of (6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane”
In a Schlenk tube, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane (1.00 g, 1.76 mmol), triethylamine ( To a toluene solution (18 mL) of 0.80 g, 7.94 mmol), a 1.59 M hexane solution (2.50 mL, 3.97 mmol) of n-butyllithium was added dropwise at −78 ° C., and the mixture was stirred for 10 minutes. Stir for hours. Water (0.07 g, 3.97 mmol) was added dropwise to the reaction mixture at −78 ° C., and the mixture was warmed to room temperature and stirred at room temperature for 1 hour. The solvent was concentrated and insoluble matter was removed by filtration with hexane, and the solvent was distilled off under reduced pressure to give (6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert). -Butylfluoren-9-yl) diethylsilane (0.52 g, 56% yield) was obtained as a yellow oil.
¹ H-NMR (CDCl ₃ , δ (ppm)): 0.63-0.76 (m, 6H), 0.82-0.93 (m, 4H), 1.25 (s, 18H), 1 .44 (s, 9H), 2.16 (s, 3H), 4.39 (s, 1H), 4.78 (s, 1H), 6.66 (s, 1H), 7.09 (s, 1H), 7.18 (s, 2H), 7.28 (d, J = 8.1 Hz, 2H), 7.64 (d, J = 8.1 Hz, 2H)
¹³ C-NMR (CDCl ₃ , δ (ppm)): 2.60, 7.46, 20.83, 30.38, 31.51, 33.83, 34.66, 40.25, 118.84, 121.30, 122.14, 122.43, 129.07, 129.18, 134.36, 134.80, 137.999, 145.55, 148.45, 157.13
Mass spectrum (EI, m / z): 526 (M ⁺ ), 497, 469, 412, 363, 292, 277, 249, 221, 164, 149, 121, 103, 57

[Experiment 2]
“Synthesis of diethylsilylene (3-tert-butyl-5-methyl-2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium”
In a Schlenk tube, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane (1.00 g, 1.76 mmol), triethylamine ( To a toluene solution (18 mL) of 0.80 g, 7.94 mmol), a 1.58 M hexane solution (2.51 mL, 3.97 mmol) of n-butyllithium was added dropwise at −78 ° C. and stirred for 10 minutes. Stir for hours. Concentrate the solvent, filter with pentane, and dry under reduced pressure to give diethylsilylene (3-tert-butyl-5-methyl-2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium (0.36 g, 38% yield) was obtained as a pale yellow solid.
¹ H-NMR (THF-d ₈ , δ (ppm)): 0.48-1.05 (m, 10H), 1.22 (s, 9H), 1.36 (s, 18H), 2.08 (S, 3H), 6.91 (s, 1H), 7.29 (s, 1H), 7.37 (d, J = 7.8 Hz, 2H), 7.57 (s, 2H) 7.64 (D, J = 7.8Hz, 2H)

[Example 3]
“Synthesis of diethylsilylene (3-tert-butyl-5-methyl-2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium”
In a Schlenk tube, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane (5.00 g, 8.82 mmol), triethylamine ( To a toluene solution (90 mL) of 4.02 g, 39.69 mmol), a 1.59 M hexane solution (12.48 mL, 19.84 mmol) of n-butyllithium was added dropwise at −78 ° C., and the mixture was stirred for 10 minutes. Stir for hours. Generation of heptane was observed by analyzing the solution by gas chromatography. The solvent was concentrated, filtered with hexane, and dried under reduced pressure to give diethylsilylene (3-tert-butyl-5-methyl-2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium Got.
The obtained (3-tert-butyl-5-methyl-2-phenoxy) (2,7-di-tert-butylfluoren-9-yl) dilithium was suspended in toluene, and water (0 .36 g, 19.84 mmol) was added. After raising the temperature to room temperature, the mixture was stirred at room temperature for 2 hours. The insoluble matter was removed by concentrating the solvent and filtering through hexane. The solvent was distilled off under reduced pressure to give (6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane (3.02 g, yield). 65%) was obtained as a yellow oil.

[Experimental Example 4]
“Polymerization with (6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane”
(6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane in 0.02M toluene solution, tetrakis (dimethylamino) titanium 0.02M The toluene solution was sampled 0.3 ml each in a vial and mixed at room temperature for 2 minutes to obtain a polymerization catalyst component solution.
Under nitrogen, toluene was charged with 5.0 mL of toluene and 1-hexene (60 μL) and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. Here, a hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical), triphenylmethyltetrakis (pentafluorophenyl) borate (9 μmol), the polymerization catalyst component solution described above (titanium concentration 0.01 M, 3 μmol) ) And polymerized. As a result of the polymerization, a polymer having a molecular weight (Mw) = 893,000, a molecular weight distribution (Mw / Mn) = 2.2, a melting point of 114.7 ° C., and a Me branch 20 of 4.6 × 10 4 per 1 mol of titanium per 1 mol of titanium. ⁷ g was produced.

[Experimental Example 5]
Polymerization was conducted in the same manner as in Experimental Example 4 except that the temperature was changed to 70 ° C. As a result of the polymerization, molecular weight (Mw) = 454,000, molecular weight distribution (Mw / Mn) = 2.9, melting point 118.8 ° C, Me 2.7 × 10 ⁷ g of the branched 14 polymer was produced per hour per 1 mol of titanium.

[Experimental Example 6]
Polymerization was conducted in the same manner as in Experimental Example 4 except that the temperature was 130 ° C. As a result of the polymerization, molecular weight (Mw) = 166,000, molecular weight distribution (Mw / Mn) = 2.0, melting point 116.8 ° C, Me The polymer of branch 9 was produced by 3.7 × 10 ⁷ g per hour per 1 mol of titanium.

[Experimental Example 7]
(6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane in 0.02M toluene solution, tetrakis (dimethylamino) zirconium 0.02M The toluene solution was sampled 0.3 ml each in a vial and mixed at room temperature for 2 minutes to obtain a polymerization catalyst component solution.
Under nitrogen, toluene was charged with 5.0 mL of toluene and 1-hexene (60 μL) and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. Here, a hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical), triphenylmethyltetrakis (pentafluorophenyl) borate (9 μmol), the polymerization catalyst component solution described above (zirconium concentration 0.01 M, 3 μmol) ) And polymerized. As a result of the polymerization, a polymer having a molecular weight (Mw) of 190,000, a molecular weight distribution (Mw / Mn) of 6.4, a melting point of 120.8 ° C., and a Me branched 5 polymer of 4.0 × 10 4 per hour per 1 mol of zirconium. ⁷ g was produced.

[Experimental Example 8]
Polymerization was conducted in the same manner as in Experimental Example 7 except that the temperature was changed to 70 ° C. As a result of the polymerization, molecular weight (Mw) = 82,000, molecular weight distribution (Mw / Mn) = 5.1, melting point 118.8 ° C, Me A polymer of branch 11 was produced at 1.7 × 10 ⁷ g per hour per 1 mol of zirconium.

[Experimental Example 9]
Polymerization was conducted in the same manner as in Experimental Example 7 except that the temperature was 130 ° C., and as a result of the polymerization, molecular weight (Mw) = 25,000, molecular weight distribution (Mw / Mn) = 3.1, melting point 117.2 ° C., Me The polymer of branch 13 was produced 4.4 × 10 ⁷ g per hour per 1 mol of zirconium.

[Experimental Example 10]
(6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane in 0.02M toluene solution, tetrakis (dimethylamino) titanium 0.02M The toluene solution was sampled 0.3 ml each in a vial and mixed at room temperature for 2 minutes to obtain a polymerization catalyst component solution.
Under nitrogen, toluene was charged with 5.0 mL of toluene and 1-hexene (60 μL) and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. To this, MMAO (0.25 M, 100 μmol) and the polymerization catalyst component solution described above (titanium concentration 0.01 M, 3 μmol) were added for polymerization. As a result of the polymerization, 3.0 × 10 ⁵ g of polymer was produced per hour per 1 mol of titanium.

[Experimental Example 11]
Polymerization was carried out in the same manner as in Experimental Example 10 except that the temperature was 70 ° C., and as a result of the polymerization, 1.1 × 10 ⁶ g of polymer was produced per hour per 1 mol of titanium.

[Experimental example 12]
Polymerization was carried out in the same manner as in Experimental Example 10 except that the temperature was 130 ° C., and as a result of the polymerization, 1.2 × 10 ⁶ g of polymer was produced per hour per 1 mol of titanium.

[Experimental Example 13]
(6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane in 0.02M toluene solution, tetrakis (dimethylamino) zirconium 0.02M The toluene solution was sampled 0.3 ml each in a vial and mixed at room temperature for 2 minutes to obtain a polymerization catalyst component solution.
Under nitrogen, toluene was charged with 5.0 mL of toluene and 1-hexene (60 μL) and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. MMAO (0.25 M, 100 μmol) and the polymerization catalyst component solution described above (zirconium concentration 0.01 M, 3 μmol) were added thereto for polymerization. As a result of the polymerization, 1.0 × 10 ⁵ g of polymer was produced per hour per 1 mol of zirconium.

[Experimental Example 14]
Polymerization was carried out in the same manner as in Experimental Example 13 except that the temperature was set to 70 ° C., and as a result of the polymerization, 2.0 × 10 ⁵ g of polymer was produced per hour per 1 mol of zirconium.

[Experimental Example 15]
Polymerization was carried out in the same manner as in Experimental Example 13 except that the temperature was 130 ° C. As a result of the polymerization, 1.0 × 10 ⁵ g of polymer was produced per hour per 1 mol of zirconium.

[Experimental Example 16]
(6-tert-butyl-4-methylphenol-2-yl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane in 0.02M toluene solution, tetrabenzylzirconium 0.02M toluene solution Each 0.3 ml was sampled into a vial and mixed at room temperature for 2 minutes to obtain a polymerization catalyst component solution.
In an autoclave, 5.0 mL of toluene was charged under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. MMAO (0.25 M, 100 μmol) and the polymerization catalyst component solution described above (zirconium concentration 0.01 M, 3 μmol) were added thereto for polymerization. As a result of the polymerization, 3.1 × 10 ⁶ g of polymer was produced per hour per 1 mol of zirconium.

[Experimental Example 17]
Polymerization was conducted in the same manner as in Experimental Example 16 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and triphenylmethyltetrakis (pentafluorophenyl) borate (9 μmol) were used instead of MMAO. As a result, 7.6 × 10 ⁶ g of polymer was produced per hour per 1 mol of chromium.

Claims (6)

Formula (3)

(In the formula, Cp ² is cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, ethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, sec -Butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcyclopentadiene, neopentylcyclopentadiene, n-hexylcyclopentadiene, n-octylcyclopentadiene, tetrahydroindene, octahydrofluorene, phenylcyclopentadiene, Naphthylcyclopentadiene, trimethylsilylcyclopentadiene, triethylsilylcyclopentadiene, triphenylsilyl Clopentadiene, tert-butyldimethylsilylcyclopentadiene, indene, methylindene, dimethylindene, ethylindene, n-propylindene, isopropylindene, n-butylindene, sec-butylindene, tert-butylindene, n-pentyl Indene, neopentylindene, n-hexylindene, n-octylindene, n-decylindene, phenylindene, methylphenylindene, naphthylindene, fluorene, 2-methylfluorene, 2,7-dimethylfluorene, 2-ethylfluorene, 2,7-diethylfluorene, 2-n-propylfluorene, 2,7-di-n-propylfluorene, 2-isopropylfluorene, 2,7-diisopropylfluorene, 2-n-butylfluorene Len, 2-sec-butyl fluorene, 2-tert-butyl fluorene, 2,7-di-n-butyl fluorene, 2,7-di-sec-butyl fluorene, 2,7-di-tert-butyl fluorene, 3, , 6-Di-tert-butylfluorene, 2-n-pentylfluorene, 2-neopentylfluorene, 2-n-hexylfluorene, 2-n-octylfluorene, 2-n-decylfluorene, 2-n-dodecylfluorene Represents an anion of a group having a cyclopentadiene skeleton selected from the group consisting of 2-phenylfluorene, 2,7-di-phenylfluorene, 2-methylphenylfluorene and 2-naphthylfluorene.
A represents a group 14 atom in the periodic table of elements other than carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, halogen atoms, carbon atoms of 1 to 20 An alkyl group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, A silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms or an amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and adjacent groups of R ¹ , R ² , R ³ and R ⁴ are , Each may be optionally combined to form a ring, and R ⁵ and R ⁶ may be combined to form a ring.
M represents an alkali metal. )
A dianion metal salt represented by formula (4)

(In the formula, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)
A reaction with a protic compound represented by formula (1)

(In the formula, Cp ¹ represents a group having the cyclopentadiene skeleton, and A and R ^{1 to} R ⁶ have the same meaning as described above.)
The manufacturing method of the cyclopentadiene compound shown by these. Cp ² is a group consisting of cyclopentadiene, methylcyclopentadiene, tert-butylcyclopentadiene, tetramethylcyclopentadiene, indene, fluorene, 2,7-di-tert-butylfluorene and 3,6-di-tert-butylfluorene. 2. The method for producing a cyclopentadiene compound according to claim ¹ , wherein the anion is a group having a cyclopentadiene skeleton selected from: Cp ¹ is a group having the cyclopentadiene skeleton. Formula (3)

(In the formula, Cp ² is cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, ethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, sec -Butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcyclopentadiene, neopentylcyclopentadiene, n-hexylcyclopentadiene, n-octylcyclopentadiene, tetrahydroindene, octahydrofluorene, phenylcyclopentadiene, Naphthylcyclopentadiene, trimethylsilylcyclopentadiene, triethylsilylcyclopentadiene, triphenylsilyl Clopentadiene, tert-butyldimethylsilylcyclopentadiene, indene, methylindene, dimethylindene, ethylindene, n-propylindene, isopropylindene, n-butylindene, sec-butylindene, tert-butylindene, n-pentyl Indene, neopentylindene, n-hexylindene, n-octylindene, n-decylindene, phenylindene, methylphenylindene, naphthylindene, fluorene, 2-methylfluorene, 2,7-dimethylfluorene, 2-ethylfluorene, 2,7-diethylfluorene, 2-n-propylfluorene, 2,7-di-n-propylfluorene, 2-isopropylfluorene, 2,7-diisopropylfluorene, 2-n-butylfluorene Len, 2-sec-butyl fluorene, 2-tert-butyl fluorene, 2,7-di-n-butyl fluorene, 2,7-di-sec-butyl fluorene, 2,7-di-tert-butyl fluorene, 3, , 6-Di-tert-butylfluorene, 2-n-pentylfluorene, 2-neopentylfluorene, 2-n-hexylfluorene, 2-n-octylfluorene, 2-n-decylfluorene, 2-n-dodecylfluorene Represents an anion of a group having a cyclopentadiene skeleton selected from the group consisting of 2-phenylfluorene, 2,7-di-phenylfluorene, 2-methylphenylfluorene and 2-naphthylfluorene.
A represents a group 14 atom in the periodic table of elements other than carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, halogen atoms, carbon atoms of 1 to 20 An alkyl group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, A silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms or an amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and adjacent groups of R ¹ , R ² , R ³ and R ⁴ are , Each may be optionally combined to form a ring, and R ⁵ and R ⁶ may be combined to form a ring.
M represents an alkali metal. )
A dianion metal salt represented by Formula (5)

(In the formula, Cp ¹ is cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, ethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, sec -Butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcyclopentadiene, neopentylcyclopentadiene, n-hexylcyclopentadiene, n-octylcyclopentadiene, tetrahydroindene, octahydrofluorene, phenylcyclopentadiene, Naphthylcyclopentadiene, trimethylsilylcyclopentadiene, triethylsilylcyclopentadiene, triphenylsilyl Clopentadiene, tert-butyldimethylsilylcyclopentadiene, indene, methylindene, dimethylindene, ethylindene, n-propylindene, isopropylindene, n-butylindene, sec-butylindene, tert-butylindene, n-pentyl Indene, neopentylindene, n-hexylindene, n-octylindene, n-decylindene, phenylindene, methylphenylindene, naphthylindene, fluorene, 2-methylfluorene, 2,7-dimethylfluorene, 2-ethylfluorene, 2,7-diethylfluorene, 2-n-propylfluorene, 2,7-di-n-propylfluorene, 2-isopropylfluorene, 2,7-diisopropylfluorene, 2-n-butylfluorene Len, 2-sec-butyl fluorene, 2-tert-butyl fluorene, 2,7-di-n-butyl fluorene, 2,7-di-sec-butyl fluorene, 2,7-di-tert-butyl fluorene, 3, , 6-Di-tert-butylfluorene, 2-n-pentylfluorene, 2-neopentylfluorene, 2-n-hexylfluorene, 2-n-octylfluorene, 2-n-decylfluorene, 2-n-dodecylfluorene , 2-phenylfluorene, 2,7-di-phenylfluorene, 2-methylphenylfluorene, and a group having a cyclopentadiene skeleton selected from the group consisting of 2-naphthylfluorene.
A represents a group 14 atom in the periodic table of elements other than carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, halogen atoms, carbon atoms of 1 to 20 An alkyl group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, A silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms or an amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and adjacent groups of R ¹ , R ² , R ³ and R ⁴ are , Each may be optionally combined to form a ring, and R ⁵ and R ⁶ may be combined to form a ring.
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. )
A protected cyclopentadiene compound represented by formula (6):

(In the formula, M represents an alkali metal , and R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. )
(3) characterized by reacting with a metal compound represented by formula (3)
Formula (3)

(In the formula, Cp ² represents an anion of the group having a cyclopentadiene skeleton, and A, M, and R ^{1 to} R ⁶ have the same meaning as described above.)
The manufacturing method of the dianion metal salt shown by these. The method for producing a dianion metal salt according to claim 4, wherein in the protected cyclopentadiene compound represented by the formula (5), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen atoms. Furthermore, it reacts in presence of amines, The manufacturing method of the dianion metal salt of Claim 4 or 5 characterized by the above-mentioned.