JP6501544B2 - Group 4 metal complex, method for producing the same, method for producing group 4 metal-containing thin film - Google Patents

Description

  The present invention relates to a Group 4 metal complex having a silyloxycyclopentadienyl ligand, useful as a raw material for producing a semiconductor device, a method for producing the same, and a method for producing a Group 4 metal-containing thin film using the complex. .

  Since Group 4 metal compounds exhibit remarkable electrical and optical properties, their application in the fields of electronic materials and optical materials is being studied as thin films with a thickness of several nano to several hundreds of nanometers. For example, Group 4 metal oxides such as titanium oxide, zirconium oxide and hafnium oxide themselves have high dielectric constants, and exhibit even higher dielectric constants when combined with alkaline earth metals and the like. Because of that, it attracts attention as a semiconductor element material such as DRAM. From the viewpoint of optical materials, for example, titanium oxide is known to exhibit a high refractive index, and its use as an antireflective film is expected by using it in combination with a low refractive index material such as silicon oxide.

  When forming a thin film of a Group 4 metal compound having such characteristics, a solution method such as dip coating method, spin coating method or ink jet method, chemical vapor deposition (CVD method) or atomic layer deposition method (ALD method) Chemical vapor deposition methods based on chemical reactions are used as needed. In recent years, the CVD method and the ALD method which can uniformly form thin films of several nano to several tens of nanometers thick on a three-dimensionalized substrate have attracted particular attention mainly in the semiconductor field, and new metal complexes used as the materials Development is desired. In addition, studies using a complex oxide thin film of a Group 4 metal and another metal as a semiconductor element material are also in progress. For example, since strontium titanate exhibits a very high dielectric constant, practical use as a high dielectric constant material is being studied. However, in the case of producing a composite oxide thin film such as strontium titanate, a high film forming temperature is required, and therefore, high thermal stability is also required for the Group 4 metal complex used as a film precursor material. In addition, in order to use as a material of the CVD method or the ALD method, it is also essential to have an appropriate vapor pressure.

  Patent Document 1 and Non-patent Document 1 describe substituted titanocenes and substituted zirconocenes having silyloxycyclopentadienyl ligands. Non-patent Document 2 describes (1-trimethylsilyloxy-2,3,4,5-tetramethylcyclopentadienyl) trichlorotitanium. They differ from the Group 4 metal complexes of the present invention in that they do not have an alkoxy group ligand. Further, Patent Document 1 and Non-patent Documents 1 and 2 do not describe the thermal stability of these known complexes and the method for producing a metal thin film using a vapor deposition method.

WO 01/53362 brochure

Journal of Organometallic Chemistry, 544, 133 (1997) Journal of Organometallic Chemistry, 558, 231 (1998)

  An object of the present invention is to provide a Group 4 metal complex which has excellent thermal stability and a suitable vapor pressure and is suitable as a material for producing a Group 4 metal-containing thin film.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve said subject, the present inventors find out that the said subject can be solved, and came to complete this invention.

  That is, the present invention relates to the general formula (1)

（式中、Ｍは第４族金属原子を表す。Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々独立に、水素原子又は炭素数１〜６のアルキル基を表す。Ｒ^５、Ｒ^６及びＲ^７は、各々独立に、炭素数１〜８のアルキル基を表す。Ｒ^８、Ｒ^９及びＲ^１０は、各々独立に、炭素数１〜６のアルキル基又はジ（炭素数１〜３のアルキル）アミノ基を表す。）で示される第４族金属錯体に関する。

(Wherein, M represents a group 4 metal atom. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁵ , R ⁶ And R ⁷ each independently represents an alkyl group having 1 to 8 carbon atoms, R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 6 carbon atoms or di (1 to 3 carbon atoms) And a group 4 metal complex represented by

  Further, the present invention relates to the general formula (2)

（式中、Ｘ^１はハロゲン原子を表す。Ｍ、Ｒ^５、Ｒ^６及びＲ^７は、一般式（１）のＭ、Ｒ^５、Ｒ^６及びＲ^７とそれぞれ同義である。）で示される第４族金属トリアルコキシドと、一般式（３）

(Wherein, .M ^{X 1} is representing a halogen ^atom, R 5, ^{R 6} and ^{R 7, M} in the general formula ^(1), and R 5, ^{R 6} and ^{R 7} are respectively the same.) Represented by Group 4 metal trialkoxide and the general formula (3)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^８、Ｒ^９及びＲ^１０は、一般式（１）のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^８、Ｒ^９及びＲ^１０とそれぞれ同義である。）で示されるリチウムシクロペンタジエニドを反応させることを特徴とする、
一般式（１）で示される第４族金属錯体の製造方法に関する。

^{(Wherein, R 1, R 2, R} 3, R 4, R 8, R 9 and ^{R 10, R 1, R 2, R} 3 in the general formula ^{(1), R 4, R} 8, R 9 and And lithium cyclopentadienide represented by R ¹⁰ is the same as the above.
The present invention relates to a method for producing a Group 4 metal complex represented by the general formula (1).

  Further, the present invention provides a compound represented by the general formula (5)

（式中、ＡＭ^１はアルカリ金属原子を表す。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、一般式（１）のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７とそれぞれ同義である。）で示されるアルカリ金属−チタン錯体と、一般式（４）
Ｓｉ（Ｒ^８）（Ｒ^９）（Ｒ^１０）Ｘ^２ （４）
（式中、Ｘ^２はハロゲン原子を表す。Ｒ^８、Ｒ^９及びＲ^１０は、一般式（１）のＲ^８、Ｒ^９及びＲ^１０とそれぞれ同義である。）で示される置換シリルハライドを反応させることを特徴とする、一般式（１Ｔｉ）

^(.R 1 wherein, AM ¹ is representative of an alkali metal ^{atom, R 2, R 3, R} 4, R 5, R 6 and ^{R 7, R} 1 in the general formula ^{(1), R 2, R} 3, An alkali metal-titanium complex represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ respectively, and the general formula (4)
Si (R ⁸ ) (R ⁹ ) (R ¹⁰ ) X ² (4)
(Wherein, ^.R 8, ^{R 9} and ^{R 10 X 2} is representing a halogen atom, general formula ^R 8, respectively ^{R 9} and ^{R 10} are synonymous. (1)) a substituted silyl halide represented by A general formula (1 Ti) characterized by reacting

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は一般式（１）のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０とそれぞれ同義である。）で示されるチタン錯体の製造方法に関する。

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 each} represent R ¹ , R ² , R ³ or R in the general formula (1)) ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ respectively have the same meaning.

  The present invention also relates to an alkali metal-titanium complex represented by the general formula (5).

  The present invention also relates to a method for producing a Group 4 metal-containing thin film, comprising vaporizing a Group 4 metal complex represented by the general formula (1) and decomposing the Group 4 metal complex on a substrate. .

Hereinafter, the present invention will be described in more detail. First, the definitions of M, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (1) will be described. Examples of the Group 4 metal atom represented by M include a titanium atom, a zirconium atom and a hafnium atom.

The alkyl group having 1 to 6 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ may be linear, branched or cyclic, and specifically, methyl group, ethyl group, propyl group Group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group Group, cyclopentyl group, cyclobutyl methyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethyl Butyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group Cyclohexyl group, cyclopentylmethyl group, a 1-cyclobutylethyl group, a 2-cyclobutylethyl group of can be exemplified. In the group 4 metal complex (1) of the present invention, R ¹ , R ² , R ³ and R ^{4 each} represent a hydrogen atom or a carbon number in view of having vapor pressure and thermal stability suitable as a CVD material or an ALD material. It is preferably a linear alkyl group of 1 to 3 and more preferably a hydrogen atom or a methyl group.

The alkyl group having 1 to 8 carbon atoms represented by R ⁵ , R ⁶ and R ⁷ may be linear, branched or cyclic, and more specifically, methyl, ethyl, propyl, isopropyl Group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl Group, cyclobutylmethyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclo Hexyl group, cyclopentyl methyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group, heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5- Methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 2, 2- Dimethylpentyl group, 2,3-dimethylpentyl group, 3,3-dimethylpentyl group, 4,4-dimethylpentyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2 -Methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-2-methylbutyl group, cyclo A pentyl, cyclohexyl methyl, octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl group , 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 2,2-dimethylhexyl group, 2, 3-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1,1,3-trimethylpentyl group, 1,1,3,3-tetramethyl Butyl group, 1-ethyl-1-methylpentyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, - ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, cyclooctyl group, 1-cyclohexylethyl group, a 2-cyclohexylethyl group of can be exemplified. In the group 4 metal complex (1) of the present invention, an alkyl group having 1 to 5 carbon atoms is preferable from the viewpoint of having vapor pressure and thermal stability suitable as a CVD material or an ALD material, and an isopropyl group, A sec-butyl group, a tert-butyl group or a tert-pentyl group is more preferred, and an isopropyl group or a tert-butyl group is particularly preferred.

In the group 4 metal complex (1) of the present invention, the alkyl group having 1 to 6 carbon atoms represented by R ⁸ , R ⁹ and R ¹⁰ may be linear, branched or cyclic, Specifically, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group , Isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, cyclobutylmethyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1, 1 -Dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbu Examples thereof include a chill group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group and a 2-cyclobutylethyl group. Examples of the di (C1-C3 alkyl) amino group represented by R ⁸ , R ⁹ and R ¹⁰ include dimethylamino, ethylmethylamino, diethylamino, methyl (propyl) amino, methyl (isopropyl) An amino group, a dipropylamino group, a diisopropylamino group etc. can be illustrated. In the group 4 metal complex (1) of the present invention, R ⁸ , R ⁹ and R ^{10 each} represent a methyl group, an ethyl group or a propyl group in that they have vapor pressure and thermal stability suitable as a CVD material or ALD material. , Tert-butyl or dimethylamino is preferred.

More specific examples of the substituted silyl group Si (R ⁸ ) (R ⁹ ) (R ¹⁰ ) include trimethylsilyl, ethyldimethylsilyl, dimethyl (propyl) silyl, isopropyldimethylsilyl and cyclopropyldimethylsilyl , Butyldimethylsilyl group, sec-butyldimethylsilyl group, isobutyldimethylsilyl group, tert-butyldimethylsilyl group, cyclobutyldimethylsilyl group, dimethyl (pentyl) silyl group, dimethyl (1-methylbutyl) silyl group, dimethyl (2) -Methylbutyl) silyl group, isopentyldimethylsilyl group, dimethyl (neopentyl) silyl group, dimethyl (tert-pentyl) silyl group, cyclopentyldimethylsilyl group, (cyclobutylmethyl) dimethylsilyl group, hexyldimethylsilyl group, Lohexyl dimethyl silyl group, diethyl (methyl) silyl group, dipropyl (methyl) silyl group, diisopropyl (methyl) silyl group, dibutyl (methyl) silyl group, di-sec- butyl (methyl) silyl group, diisobutyl (methyl) silyl group Group, di-tert-butyl (methyl) silyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tributylsilyl group, tri-sec-butylsilyl group, triisobutylsilyl group, tri-tert-butylsilyl group, Tripentylsilyl, trihexylsilyl, tricyclohexylsilyl, (dimethylamino) dimethylsilyl, (ethylmethylamino) dimethylsilyl, (diethylamino) dimethylsilyl, (dimethylamino) (ethyl) (methyl) silyl Group, Dimethylamino) diethylsilyl group, bis (dimethylamino) (methyl) silyl group, bis (ethyl (methyl) amino) (methyl) silyl group, bis (diethylamino) (methyl) silyl group, tris (dimethylamino) silyl group, Examples include tris (ethyl (methyl) amino) silyl and tris (diethylamino) silyl. In the group 4 metal complex (1) of the present invention, a trimethylsilyl group, an ethyldimethylsilyl group, a dimethyl (propyl) silyl group, an isopropyldimethyl group in that it has vapor pressure and thermal stability suitable as a CVD material or ALD material. Silyl group, sec-butyldimethylsilyl group, isobutyldimethylsilyl group, tert-butyldimethylsilyl group, diethyl (methyl) silyl group, triethylsilyl group, (dimethylamino) dimethylsilyl group, (ethylmethylamino) dimethylsilyl group and A (diethylamino) dimethylsilyl group is preferable, and a trimethylsilyl group, a tert-butyldimethylsilyl group, a triethylsilyl group and a (dimethylamino) dimethylsilyl group are more preferable.

Specific examples of the Group 4 metal complex (1) of the present invention include triisopropoxy (η ⁵ -1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) H ₄ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) H ₄ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) H ₄ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) H ₄ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2-ethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) EtH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2-ethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) EtH ₃ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2-ethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) EtH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2-ethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) EtH ₃ ) Ti (O ^t Pe) ₃ ), Trimethoxy (η ⁵ -2-Pentyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) PeH ₃ ) Ti (OMe) ₃ ), Triisopropoxy (η ⁵ -2-Pentyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) PeH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2-Pentyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) PeH ₃ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2-Pentyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) PeH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2-Pentyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) PeH ₃ ) Ti (O ^t Pe) ₃ ), Trimethoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (OMe) ₃ ), Triethoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (OEt) ₃ ), Tripropoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (OPr) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (O ⁱ Pr) ₃ ), Tributoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (OBu) ₃ ), Triisobutyloxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (O ⁱ Bu) ₃ ), Tri-sec-butoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Ethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) EtH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -3-Ethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) EtH ₃ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -3-Ethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) EtH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Ethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) EtH ₃ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ 3-Propyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) PrH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ 3-Propyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) PrH ₃ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ 3-Propyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) PrH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ 3-Propyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) PrH ₃ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-tert-Butyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) ^t BuH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -3-tert-Butyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) ^t BuH ₃ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -3-tert-Butyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) ^t BuH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-tert-Butyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) ^t BuH ₃ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Cyclohexyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) CyH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -3-Cyclohexyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) CyH ₃ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -3-Cyclohexyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) CyH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Cyclohexyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) CyH ₃ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2,3- Dime
Tyl-1-trimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,3-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,4-Dimethyl 1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2,4-Dimethyl 1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,4-Dimethyl 1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,4-Dimethyl 1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,5-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2,5-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,5-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,5-Dimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,4-Trimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₃ H) Ti (O ⁱ Pr) ₃ ), Tributoxy (η ⁵ -2,3,4-Trimethyl-1-trimethylsilyloxycyclopentadienyl) titanium, tri-sec-butoxy (η ⁵ -2,3,4-Trimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₃ H) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4-Trimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₃ H) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4-Trimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₃ H) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,5-Trimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₃ H) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2,3,5-Trimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₃ H) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,5-Trimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₃ H) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,5-Trimethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₃ H) Ti (O ^t Pe) ₃ ), Trimethoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (OMe) ₃ ), Triethoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (OEt) ₃ ), Tripropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (OPr) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (O ⁱ Pr) ₃ ), Tributoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (OBu) ₃ ), Triisobutyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (O ⁱ Bu) ₃ ), Tri-sec-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (O ^t Bu) ₃ ), Tri-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (OPe) ₃ ), Tri (1-methylbutyloxy) (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (OCMePrH) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (O ^t Pe) ₃ ), Tricyclopentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (O ^c Pe) ₃ ), Tricyclohexyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (OCy) ₃ ), Tris (1,1-diethylpropyloxy) (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (OCEt ₃ ) ₃ ), Tris (1,1,3,3-tetramethylbutyloxy) (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Ti (OCMe ₂ CH ₂ CMe ₃ ) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Zr (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Zr (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C
₅ (OSiMe ₃ ) MeH ₃ ) Zr (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Zr (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Zr (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Zr (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Zr (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Zr (O ^t Pe) ₃ ), Trimethoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (OMe) ₃ ), Triethoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (OEt) ₃ ), Tripropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (OPr) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (O ⁱ Pr) ₃ ), Tributoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (OBu) ₃ ), Triisobutyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (O ⁱ Bu) ₃ ), Tri-sec-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (O ^t Bu) ₃ ), Tri-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (OPe) ₃ ), Tri (1-methylbutyloxy) (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (OCMePrH) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (O ^t Pe) ₃ ), Tricyclopentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (O ^c Pe) ₃ ), Tricyclohexyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (OCy) ₃ ), Tris (1,1-diethylpropyloxy) (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (OCEt ₃ ) ₃ ), Tris (1,1,3,3-tetramethylbutyloxy) (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Zr (OCMe ₂ CH ₂ CMe ₃ ) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Hf (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Hf (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Hf (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) MeH ₃ ) Hf (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Hf (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Hf (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Hf (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3,4-Dimethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₂ H ₂ ) Hf (O ^t Pe) ₃ ), Trimethoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (OMe) ₃ ), Triethoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (OEt) ₃ ), Tripropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (OPr) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (O ⁱ Pr) ₃ ), Tributoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (OBu) ₃ ), Triisobutyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (O ⁱ Bu) ₃ ), Tri-sec-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (O ^t Bu) ₃ ), Tri-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (OPe) ₃ ), Tri (1-methylbutyloxy) (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (OCMePrH) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (O ^t Pe) ₃ ), Tricyclopentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (O ^c Pe) ₃ ), Tricyclohexyloxy (η ⁵ -2, 3
, 4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (OCy) ₃ ), Tris (1,1-diethylpropyloxy) (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (OCEt ₃ ) ₃ ), Tris (1,1,3,3-tetramethylbutyloxy) (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSiMe ₃ ) Me ₄ ) Hf (OCMe ₂ CH ₂ CMe ₃ ) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSi ^t BuMe ₂ ) MeH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSi ^t BuMe ₂ ) MeH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSi ^t BuMe ₂ ) MeH ₃ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Ti (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Ti (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1-triethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiEt ₃ ) MeH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1-triethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiEt ₃ ) MeH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1-triethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSiEt ₃ ) MeH ₃ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiEt ₃ ) Me ₄ ) Ti (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiEt ₃ ) Me ₄ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSiEt ₃ ) Me ₄ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) MeH ₃ ) Ti (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) MeH ₃ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium ((( ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) MeH ₃ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) Me ₄ ) Ti (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) Me ₄ ) Ti (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) Me ₄ ) Ti (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1-tert-butyldimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) MeH ₃ ) Zr (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1-tert-butyldimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) MeH ₃ ) Zr (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1-tert-butyldimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) MeH ₃ ) Zr (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Zr (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Zr (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Zr (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Zr (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1-triethylsilyloxycyclopentadienyl) zirconium ((( ⁵ -C ₅ (OSiEt ₃ ) MeH ₃ ) Zr (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1-triethylsilyloxycyclopentadienyl) zirconium ((( ⁵ -C ₅ (OSiEt ₃ ) MeH ₃ ) Zr (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1-triethylsilyloxycyclopentadienyl) zirconium ((( ⁵ -C ₅ (OSiEt ₃ ) MeH ₃ ) Zr (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiEt ₃ ) Me ₄ ) Zr (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiEt ₃ ) Me ₄ ) Zr (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSiEt ₃ ) Me ₄ ) Zr (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) MeH ₃ ) Zr (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) MeH ₃ ) Zr (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) MeH ₃ ) Zr (O ^t Pe) ₃ ), Torii
Sopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) Me ₄ ) Zr (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) Me ₄ ) Zr (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) zirconium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) Me ₄ ) Zr (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1-tert-butyldimethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSi ^t BuMe ₂ ) MeH ₃ ) Hf (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1-tert-butyldimethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSi ^t BuMe ₂ ) MeH ₃ ) Hf (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1-tert-butyldimethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSi ^t BuMe ₂ ) MeH ₃ ) Hf (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Hf (O ⁱ Pr) ₃ ), Tri-sec-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Hf (O ^s Bu) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Hf (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSi ^t BuMe ₂ ) Me ₄ ) Hf (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1-triethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSiEt ₃ ) MeH ₃ ) Hf (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1-triethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSiEt ₃ ) MeH ₃ ) Hf (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1-triethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSiEt ₃ ) MeH ₃ ) Hf (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSiEt ₃ ) Me ₄ ) Hf (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSiEt ₃ ) Me ₄ ) Hf (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSiEt ₃ ) Me ₄ ) Hf (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) MeH ₃ ) Hf (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) MeH ₃ ) Hf (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) hafnium ((η ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) MeH ₃ ) Hf (O ^t Pe) ₃ ), Triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) Me ₄ ) Hf (O ⁱ Pr) ₃ ), Tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) Me ₄ ) Hf (O ^t Bu) ₃ ), Tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) hafnium ((( ⁵ -C ₅ (OSi (NMe ₂ ) Me ₂ ) Me ₄ ) Hf (O ^t Pe) ₃ And the like. In the group 4 metal complex (1) of the present invention, triisopropoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium, tri-tert-butoxy (η ⁵ -3-Methyl-1-trimethylsilyloxycyclopentadienyl) titanium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium, tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium, tri-tert-butoxy (ブ ト キ シ ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) titanium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) titanium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium, tri-tert-butoxy (ブ ト キ シ ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium, tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) zirconium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) zirconium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) zirconium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) zirconium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) zirconium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) zirconium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium, tri-tert-pentyloxy (η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) hafnium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) hafnium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) hafnium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) hafnium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) hafnium, tri-tert-butoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) hafnium is preferred, and triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium, triisopropoxy
(Η ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-triethylsilyloxycyclopentadienyl) titanium, triisopropoxy (η ⁵ -2,3,4,5-Tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienyl) titanium, tri-tert-butoxy (ブ ト キ シ ⁵ -2,3,4,5-Tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium and tri-tert-butoxy (η ⁵ More preferred is -2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium.

Next, the method for producing the Group 4 metal complex (1) of the present invention will be described. The Group 4 metal complex (1) of the present invention can be produced according to production method 1 or production method 2. Production method 1 is a method for producing a Group 4 metal complex (1) by reacting the Group 4 metal trialkoxide (2) with lithium cyclopentadienide (3).
Manufacturing method 1

（式中、Ｍは第４族金属原子を表す。Ｘ^１はハロゲン原子を表す。Ｒ^５、Ｒ^６及びＲ^７は、各々独立に、炭素数１〜８のアルキル基を表す。Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々独立に、水素原子又は炭素数１〜６のアルキル基を表す。Ｒ^８、Ｒ^９及びＲ^１０は、各々独立に、炭素数１〜６のアルキル基又はジ（炭素数１〜３のアルキル）アミノ基を表す。） Ｘ^１で表されるハロゲン原子の例としては、塩素原子、臭素原子及びヨウ素原子を挙げることが出来る。製造方法１の収率が良い点で、塩素原子が好ましい。製造方法１で用いることが出来る第４族金属トリアルコキシド（２）の例としては、クロロトリメトキシチタン（Ｔｉ（ＯＭｅ）_３Ｃｌ）、クロロトリエトキシチタン（Ｔｉ（ＯＥｔ）_３Ｃｌ）、クロロトリプロポキシチタン（Ｔｉ（ＯＰｒ）_３Ｃｌ）、クロロトリイソプロポキシチタン（Ｔｉ（Ｏ^ｉＰｒ）_３Ｃｌ）、トリブトキシクロロシチタン（Ｔｉ（ＯＢｕ）_３Ｃｌ）、トリ−ｓｅｃ−ブトキシクロロチタン（Ｔｉ（Ｏ^ｓＢｕ）_３Ｃｌ）、クロロトリ（イソブチルオキシ）チタン（Ｔｉ（Ｏ^ｉＢｕ）_３Ｃｌ）、トリ−ｔｅｒｔ−ブトキシクロロチタン（Ｔｉ（Ｏ^ｔＢｕ）_３Ｃｌ）、クロロトリ（ネオペンチルオキシ）チタン（Ｔｉ（Ｏ^ｎＰｅ）_３Ｃｌ）、クロロトリ（ｔｅｒｔ−ペンチルオキシ）チタン（Ｔｉ（Ｏ^ｔＰｅ）_３Ｃｌ）、クロロトリ（シクロペンチルオキシ）チタン（Ｔｉ（Ｏ^ｃＰｅ）_３Ｃｌ）、クロロトリス（１，３−ジメチルブチルオキシ）チタン（Ｔｉ（ＯＣＨ（Ｍｅ）ＣＨ_２ＣＨＭｅ_２）_３Ｃｌ）、クロロトリ（シクロヘキシルオキシ）チタン（Ｔｉ（ＯＣｙ）_３Ｃｌ）、クロロトリス（１，１−ジエチルプロピルオキシ）チタン（Ｔｉ（ＯＣＥｔ_３）_３Ｃｌ）、クロロトリス（１，１，３，３−テトラメチルブチルオキシ）チタン（Ｔｉ（ＯＣＭｅ_２ＣＨ_２ＣＭｅ_３）_３Ｃｌ）、ジブトキシ（クロロ）（エトキシ）チタン（Ｔｉ（ＯＢｕ）_２（ＯＥｔ）Ｃｌ）、ジブトキシ（クロロ）（イソプロポキシ）チタン（Ｔｉ（ＯＢｕ）_２（Ｏ^ｉＰｒ）Ｃｌ）、ブロモトリメトキシチタン（Ｔｉ（ＯＭｅ）_３Ｂｒ）、ブロモトリエトキシチタン（Ｔｉ（ＯＥｔ）_３Ｂｒ）、ブロモトリプロポキシチタン（Ｔｉ（ＯＰｒ）_３Ｂｒ）、ブロモトリイソプロポキシチタン（Ｔｉ（Ｏ^ｉＰｒ）_３Ｂｒ）、トリブトキシブロモシチタン（Ｔｉ（ＯＢｕ）_３Ｂｒ）、トリ−ｓｅｃ−ブトキシブロモチタン（Ｔｉ（Ｏ^ｓＢｕ）_３Ｂｒ）、ブロモトリ（イソブチルオキシ）チタン（Ｔｉ（Ｏ^ｉＢｕ）_３Ｂｒ）、トリ−ｔｅｒｔ−ブトキシブロモチタン（Ｔｉ（Ｏ^ｔＢｕ）_３Ｂｒ）、ブロモトリ（ネオペンチルオキシ）チタン（Ｔｉ（Ｏ^ｎＰｅ）_３Ｂｒ）、ブロモトリ（ｔｅｒｔ−ペンチルオキシ）チタン（Ｔｉ（Ｏ^ｔＰｅ）_３Ｂｒ）、ブロモトリ（シクロペンチルオキシ）チタン（Ｔｉ（Ｏ^ｃＰｅ）_３Ｂｒ）、ブロモトリス（１，３−ジメチルブチルオキシ）チタン（Ｔｉ（ＯＣＨ（Ｍｅ）ＣＨ_２ＣＨＭｅ_２）_３Ｂｒ）、ブロモトリ（シクロヘキシルオキシ）チタン（Ｔｉ（ＯＣｙ）_３Ｂｒ）、ブロモトリス（１，１−ジエチルプロピルオキシ）チタン（Ｔｉ（ＯＣＥｔ_３）_３Ｂｒ）、ブロモトリス（１，１，３，３−テトラメチルブチルオキシ）チタン（Ｔｉ（ＯＣＭｅ_２ＣＨ_２ＣＭｅ_３）_３Ｂｒ）、ヨードトリメトキシチタン（Ｔｉ（ＯＭｅ）_３Ｉ）、ヨードトリエトキシチタン（Ｔｉ（ＯＥｔ）_３Ｉ）、ヨードトリプロポキシチタン（Ｔｉ（ＯＰｒ）_３Ｉ）、ヨードトリイソプロポキシチタン（Ｔｉ（Ｏ^ｉＰｒ）_３Ｉ）、トリブトキシヨードシチタン（Ｔｉ（ＯＢｕ）_３Ｉ）、トリ−ｓｅｃ−ブトキシヨードチタン（Ｔｉ（Ｏ^ｓＢｕ）_３Ｉ）、ヨードトリ（イソブチルオキシ）チタン（Ｔｉ（Ｏ^ｉＢｕ）_３Ｉ）、トリ−ｔｅｒｔ−ブトキシヨードチタン（Ｔｉ（Ｏ^ｔＢｕ）_３Ｉ）、ヨードトリ（ネオペンチルオキシ）チタン（Ｔｉ（Ｏ^ｎＰｅ）_３Ｉ）、ヨードトリ（ｔｅｒｔ−ペンチルオキシ）チタン（Ｔｉ（Ｏ^ｔＰｅ）_３Ｉ）、ヨードトリ（シクロペンチルオキシ）チタン（Ｔｉ（Ｏ^ｃＰｅ）_３Ｉ）、ヨードトリス（１，３−ジメチルブチルオキシ）チタン（Ｔｉ（ＯＣＨ（Ｍｅ）ＣＨ_２ＣＨＭｅ_２）_３Ｉ）、ヨードトリ（シクロヘキシルオキシ）チタン（Ｔｉ（ＯＣｙ）_３Ｉ）、ヨードトリス（１，１−ジエチルプロピルオキシ）チタン（Ｔｉ（ＯＣＥｔ_３）_３Ｉ）、ヨードトリス（１，１，３，３−テトラメチルブチルオキシ）チタン（Ｔｉ（ＯＣＭｅ_２ＣＨ_２ＣＭｅ_３）_３Ｉ）、クロロトリメトキシジルコニウム（Ｚｒ（ＯＭｅ）_３Ｃｌ）、クロロトリエトキシジルコニウム（Ｚｒ（ＯＥｔ）_３Ｃｌ）、クロロトリプロポキシジルコニウム（Ｚｒ（ＯＰｒ）_３Ｃｌ）、クロロトリイソプロポキシジルコニウム（Ｚｒ（Ｏ^ｉＰｒ）_３Ｃｌ）、トリブトキシクロロシジルコニウム（Ｚｒ（ＯＢｕ）_３Ｃｌ）、トリ−ｓｅｃ−ブトキシクロロジルコニウム（Ｚｒ（Ｏ^ｓＢｕ）_３Ｃｌ）、クロロトリ（イソブチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｉＢｕ）_３Ｃｌ）、トリ−ｔｅｒｔ−ブトキシクロロジルコニウム（Ｚｒ（Ｏ^ｔＢｕ）_３Ｃｌ）、クロロトリ（ネオペンチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｎＰｅ）_３Ｃｌ）、クロロトリ（ｔｅｒｔ−ペンチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｔＰｅ）_３Ｃｌ）、クロロトリ（シクロペンチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｃＰｅ）_３Ｃｌ）、クロロトリス（１，３−ジメチルブチルオキシ）ジルコニウム（Ｚｒ（ＯＣＨ（Ｍｅ）ＣＨ_２ＣＨＭｅ_２）_３Ｃｌ）、クロロトリ（シクロヘキシルオキシ）ジルコニウム（Ｚｒ（ＯＣｙ）_３Ｃｌ）、クロロトリス（１，１−ジエチルプロピルオキシ）ジルコニウム（Ｚｒ（ＯＣＥｔ_３）_３Ｃｌ）、クロロトリス（１，１，３，３−テトラメチルブチルオキシ）ジルコニウム（Ｚｒ（ＯＣＭｅ_２ＣＨ_２ＣＭｅ_３）_３Ｃｌ）、ブロモトリメトキシジルコニウム（Ｚｒ（ＯＭｅ）_３Ｂｒ）、ブロモトリエトキシジルコニウム（Ｚｒ（ＯＥｔ）_３Ｂｒ）、ブロモトリプロポキシジルコニウム（Ｚｒ（ＯＰｒ）_３Ｂｒ）、ブロモトリイソプロポキシジルコニウム（Ｚｒ（Ｏ^ｉＰｒ）_３Ｂｒ）、トリブトキシブロモシジルコニウム（Ｚｒ（ＯＢｕ）_３Ｂｒ）、トリ−ｓｅｃ−ブトキシブロモジルコニウム（Ｚｒ（Ｏ^ｓＢｕ）_３Ｂｒ）、ブロモトリ（イソブチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｉＢｕ）_３Ｂｒ）、トリ−ｔｅｒｔ−ブトキシブロモジルコニウム（Ｚｒ（Ｏ^ｔＢｕ）_３Ｂｒ）、ブロモトリ（ネオペンチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｎＰｅ）_３Ｂｒ）、ブロモトリ（ｔｅｒｔ−ペンチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｔＰｅ）_３Ｂｒ）、ブロモトリ（シクロペンチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｃＰｅ）_３Ｂｒ）、ブロモトリス（１，３−ジメチルブチルオキシ）ジルコニウム（Ｚｒ（ＯＣＨ（Ｍｅ）ＣＨ_２ＣＨＭｅ_２）_３Ｂｒ）、ブロモトリ（シクロヘキシルオキシ）ジルコニウム（Ｚｒ（ＯＣｙ）_３Ｂｒ）、ブロモトリス（１，１−ジエチルプロピルオキシ）ジルコニウム（Ｚｒ（ＯＣＥｔ_３）_３Ｂｒ）、ブロモトリス（１，１，３，３−テトラメチルブチルオキシ）ジルコニウム（Ｚｒ（ＯＣＭｅ_２ＣＨ_２ＣＭｅ_３）_３Ｂｒ）、ヨードトリメトキシジルコニウム（Ｚｒ（ＯＭｅ）_３Ｉ）、ヨードトリエトキシジルコニウム（Ｚｒ（ＯＥｔ）_３Ｉ）、ヨードトリプロポキシジルコニウム（Ｚｒ（ＯＰｒ）_３Ｉ）、ヨードトリイソプロポキシジルコニウム（Ｚｒ（Ｏ^ｉＰｒ）_３Ｉ）、トリブトキシヨードシジルコニウム（Ｚｒ（ＯＢｕ）_３Ｉ）、トリ−ｓｅｃ−ブトキシヨードジルコニウム（Ｚｒ（Ｏ^ｓＢｕ）_３Ｉ）、ヨードトリ（イソブチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｉＢｕ）_３Ｉ）、トリ−ｔｅｒｔ−ブトキシヨードジルコニウム（Ｚｒ（Ｏ^ｔＢｕ）_３Ｉ）、ヨードトリ（ネオペンチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｎＰｅ）_３Ｉ）、ヨードトリ（ｔｅｒｔ−ペンチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｔＰｅ）_３Ｉ）、ヨードトリ（シクロペンチルオキシ）ジルコニウム（Ｚｒ（Ｏ^ｃＰｅ）_３Ｉ）、ヨードトリス（１，３−ジメチルブチルオキシ）ジルコニウム（Ｚｒ（ＯＣＨ（Ｍｅ）ＣＨ_２ＣＨＭｅ_２）_３Ｉ）、ヨードトリ（シクロヘキシルオキシ）ジルコニウム（Ｚｒ（ＯＣｙ）_３Ｉ）、ヨードトリス（１，１−ジエチルプロピルオキシ）ジルコニウム（Ｚｒ（ＯＣＥｔ_３）_３Ｉ）、ヨードトリス（１，１，３，３−テトラメチルブチルオキシ）ジルコニウム（Ｚｒ（ＯＣＭｅ_２ＣＨ_２ＣＭｅ_３）_３Ｉ）、クロロトリメトキシハフニウム（Ｈｆ（ＯＭｅ）_３Ｃｌ）、クロロトリエトキシハフニウム（Ｈｆ（ＯＥｔ）_３Ｃｌ）、クロロトリプロポキシハフニウム（Ｈｆ（ＯＰｒ）_３Ｃｌ）、クロロトリイソプロポキシハフニウム（Ｈｆ（Ｏ^ｉＰｒ）_３Ｃｌ）、トリブトキシクロロシハフニウム（Ｈｆ（ＯＢｕ）_３Ｃｌ）、トリ−ｓｅｃ−ブトキシクロロハフニウム（Ｈｆ（Ｏ^ｓＢｕ）_３Ｃｌ）、クロロトリ（イソブチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｉＢｕ）_３Ｃｌ）、トリ−ｔｅｒｔ−ブトキシクロロハフニウム（Ｈｆ（Ｏ^ｔＢｕ）_３Ｃｌ）、クロロトリ（ネオペンチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｎＰｅ）_３Ｃｌ）、クロロトリ（ｔｅｒｔ−ペンチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｔＰｅ）_３Ｃｌ）、クロロトリ（シクロペンチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｃＰｅ）_３Ｃｌ）、クロロトリス（１，３−ジメチルブチルオキシ）ハフニウム（Ｈｆ（ＯＣＨ（Ｍｅ）ＣＨ_２ＣＨＭｅ_２）_３Ｃｌ）、クロロトリ（シクロヘキシルオキシ）ハフニウム（Ｈｆ（ＯＣｙ）_３Ｃｌ）、クロロトリス（１，１−ジエチルプロピルオキシ）ハフニウム（Ｈｆ（ＯＣＥｔ_３）_３Ｃｌ）、クロロトリス（１，１，３
，３−テトラメチルブチルオキシ）ハフニウム（Ｈｆ（ＯＣＭｅ_２ＣＨ_２ＣＭｅ_３）_３Ｃｌ）、ブロモトリメトキシハフニウム（Ｈｆ（ＯＭｅ）_３Ｂｒ）、ブロモトリエトキシハフニウム（Ｈｆ（ＯＥｔ）_３Ｂｒ）、ブロモトリプロポキシハフニウム（Ｈｆ（ＯＰｒ）_３Ｂｒ）、ブロモトリイソプロポキシハフニウム（Ｈｆ（Ｏ^ｉＰｒ）_３Ｂｒ）、トリブトキシブロモシハフニウム（Ｈｆ（ＯＢｕ）_３Ｂｒ）、トリ−ｓｅｃ−ブトキシブロモハフニウム（Ｈｆ（Ｏ^ｓＢｕ）_３Ｂｒ）、ブロモトリ（イソブチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｉＢｕ）_３Ｂｒ）、トリ−ｔｅｒｔ−ブトキシブロモハフニウム（Ｈｆ（Ｏ^ｔＢｕ）_３Ｂｒ）、ブロモトリ（ネオペンチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｎＰｅ）_３Ｂｒ）、ブロモトリ（ｔｅｒｔ−ペンチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｔＰｅ）_３Ｂｒ）、ブロモトリ（シクロペンチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｃＰｅ）_３Ｂｒ）、ブロモトリス（１，３−ジメチルブチルオキシ）ハフニウム（Ｈｆ（ＯＣＨ（Ｍｅ）ＣＨ_２ＣＨＭｅ_２）_３Ｂｒ）、ブロモトリ（シクロヘキシルオキシ）ハフニウム（Ｈｆ（ＯＣｙ）_３Ｂｒ）、ブロモトリス（１，１−ジエチルプロピルオキシ）ハフニウム（Ｈｆ（ＯＣＥｔ_３）_３Ｂｒ）、ブロモトリス（１，１，３，３−テトラメチルブチルオキシ）ハフニウム（Ｈｆ（ＯＣＭｅ_２ＣＨ_２ＣＭｅ_３）_３Ｂｒ）、ヨードトリメトキシハフニウム（Ｈｆ（ＯＭｅ）_３Ｉ）、ヨードトリエトキシハフニウム（Ｈｆ（ＯＥｔ）_３Ｉ）、ヨードトリプロポキシハフニウム（Ｈｆ（ＯＰｒ）_３Ｉ）、ヨードトリイソプロポキシハフニウム（Ｈｆ（Ｏ^ｉＰｒ）_３Ｉ）、トリブトキシヨードシハフニウム（Ｈｆ（ＯＢｕ）_３Ｉ）、トリ−ｓｅｃ−ブトキシヨードハフニウム（Ｈｆ（Ｏ^ｓＢｕ）_３Ｉ）、ヨードトリ（イソブチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｉＢｕ）_３Ｉ）、トリ−ｔｅｒｔ−ブトキシヨードハフニウム（Ｈｆ（Ｏ^ｔＢｕ）_３Ｉ）、ヨードトリ（ネオペンチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｎＰｅ）_３Ｉ）、ヨードトリ（ｔｅｒｔ−ペンチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｔＰｅ）_３Ｉ）、ヨードトリ（シクロペンチルオキシ）ハフニウム（Ｈｆ（Ｏ^ｃＰｅ）_３Ｉ）、ヨードトリス（１，３−ジメチルブチルオキシ）ハフニウム（Ｈｆ（ＯＣＨ（Ｍｅ）ＣＨ_２ＣＨＭｅ_２）_３Ｉ）、ヨードトリ（シクロヘキシルオキシ）ハフニウム（Ｈｆ（ＯＣｙ）_３Ｉ）、ヨードトリス（１，１−ジエチルプロピルオキシ）ハフニウム（Ｈｆ（ＯＣＥｔ_３）_３Ｉ）、ヨードトリス（１，１，３，３−テトラメチルブチルオキシ）ハフニウム（Ｈｆ（ＯＣＭｅ_２ＣＨ_２ＣＭｅ_３）_３Ｉ）などを挙げることが出来、その中でもクロロトリイソプロポキシチタン、トリ−ｓｅｃ−ブトキシクロロチタン、トリ−ｔｅｒｔ−ブトキシクロロチタン、クロロトリ（ｔｅｒｔ−ペンチルオキシ）チタン、クロロトリイソプロポキシジルコニウム、トリ−ｓｅｃ−ブトキシクロロジルコニウム、トリ−ｔｅｒｔ−ブトキシクロロジルコニウム、クロロトリ（ｔｅｒｔ−ペンチルオキシ）ジルコニウム、クロロトリイソプロポキシハフニウム、トリ−ｓｅｃ−ブトキシクロロハフニウム、トリ−ｔｅｒｔ−ブトキシクロロハフニウム及びクロロトリ（ｔｅｒｔ−ペンチルオキシ）ハフニウムが好ましく、クロロトリイソプロポキシチタン、トリ−ｔｅｒｔ−ブトキシクロロチタン、クロロトリイソプロポキシジルコニウム、トリ−ｔｅｒｔ−ブトキシクロロジルコニウム、クロロトリイソプロポキシハフニウム及びトリ−ｔｅｒｔ−ブトキシクロロハフニウムが更に好ましい。

(Wherein, M represents a group 4 metal atom, X ¹ represents a halogen atom, R ⁵ , R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 8 carbon atoms. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 6 carbon atoms or represents a diamino group (alkyl of 1 to 3 carbon atoms).) examples of the halogen atom represented by X ¹ can be mentioned chlorine atom, bromine atom and iodine atom. In terms of a good yield of production method 1, a chlorine atom is preferred. Examples of the Group 4 metal trialkoxide (2) which can be used in Production method 1 include chlorotrimethoxytitanium (Ti (OMe) ₃ Cl), chlorotriethoxytitanium (Ti (OEt) ₃ Cl), chlorotrimethoxytitanium (Ti (OEt) ₃ Cl) Propoxytitanium (Ti (OPr) ₃ Cl), chlorotriisopropoxytitanium (Ti (O ⁱ Pr) ₃ Cl), tributoxychlorositanium (Ti (OBu) ₃ Cl), tri-sec-butoxychlorotitanium (Ti) (O ^s Bu) ₃ Cl), chlorotri (isobutyloxy) titanium (Ti (O ⁱ Bu) ₃ Cl), tri-tert-butoxychlorotitanium (Ti (O ^t Bu) ₃ Cl), chlorotri (neopentyloxy) Titanium (Ti (O ⁿ Pe) ₃ Cl), chlorotri (tert-pentyloxy) titanium (Ti (O) ^t Pe) ₃ Cl), chlorotri (cyclopentyloxy) titanium (Ti (O ^c Pe) ₃ Cl), chlorotris (1,3-dimethylbutyloxy) titanium (Ti (OCH (Me) CH ₂ CHMe ₂ ) ₃ Cl) Chlorotri (cyclohexyloxy) titanium (Ti (OCy) ₃ Cl), chlorotris (1,1-diethylpropyloxy) titanium (Ti (OCEt ₃ ) ₃ Cl), chlorotris (1,1,3,3-tetramethylbutyl) Oxy) titanium (Ti (OCMe ₂ CH ₂ CMe ₃ ) ₃ Cl), dibutoxy (chloro) (ethoxy) titanium (Ti (OBu) ₂ (OEt) Cl), dibutoxy (chloro) (isopropoxy) titanium (Ti (OBu) ^{_{) 2 (O i Pr) Cl}} ), bromo trimethoxy titanium (Ti _(OMe) 3 Br Bromo triethoxy titanium _{(Ti (OEt) 3 Br)} , bromo tripropoxy titanium _{(Ti (OPr) 3 Br)} , bromo triisopropoxy titanium _{^{(Ti (O i Pr) 3}} Br), tributoxyethyl bromo Shi titanium (Ti _(OBu) 3 Br), tri -sec- butoxy bromo titanium _{^{(Ti (O s Bu) 3}} Br), Buromotori (isobutyl oxy) titanium _{^{(Ti (O i Bu) 3}} Br), tri -tert- butoxy bromo titanium ( Ti (O ^t Bu) ₃ Br), bromotri (neopentyloxy) titanium (Ti (O ⁿ Pe) ₃ Br), bromotri (tert-pentyloxy) titanium (Ti (O ^t Pe) ₃ Br), bromotri (cyclopentyl) oxy) titanium _{^{(Ti (O c Pe) 3}} Br), bromotris (1,3 Jimechirubu Yloxy) titanium _{(Ti (OCH (Me) CH} 2 CHMe 2) 3 Br), Buromotori (cyclohexyloxy) titanium _{(Ti (OCy) 3 Br)} , bromotris (1,1-diethyl-propyloxy) titanium (Ti (OCEt ₃ ) ₃ Br), bromotris (1,1,3,3-tetramethylbutyloxy) titanium (Ti (OCMe ₂ CH ₂ CMe ₃ ) ₃ Br), iodotrimethoxytitanium (Ti (OMe) ₃ I), iodotrit Ethoxy titanium (Ti (OEt) ₃ I), iodotripropoxy titanium (Ti (OPr) ₃ I), iodo triisopropoxy titanium (Ti (O ⁱ Pr) ₃ I), tributoxy iodocytitanium (Ti (OBu) ₃ I), tri -sec- butoxy iodo titanium _{^{(Ti (O s Bu) 3}} I), Yodoto (Iso-butyloxy) titanium _{^{(Ti (O i Bu) 3}} I), tri -tert- butoxy iodo titanium _{^{(Ti (O t Bu) 3}} I), Yodotori (neopentyloxy) titanium _{^{(Ti (O n Pe) 3}} I ), Iodotri (tert-pentyloxy) titanium (Ti (O ^t Pe) ₃ I), iodotri (cyclopentyloxy) titanium (Ti (O ^c Pe) ₃ I), iodotris (1,3-dimethylbutyloxy) titanium _{Ti (OCH (Me) CH 2} CHMe 2) 3 I), Yodotori (cyclohexyloxy) titanium _{(Ti (OCy) 3 I)} , Yodotorisu (1,1-diethyl-propyloxy) titanium _{(Ti (OCEt 3) 3 I} ) , Iodotris (1,1,3,3-tetramethylbutyloxy) titanium (Ti (OCMe ₂ CH ₂₎ CMe ₃ ) ₃ I), chlorotrimethoxyzirconium (Zr (OMe) ₃ Cl), chlorotriethoxyzirconium (Zr (OEt) ₃ Cl), chlorotripropoxyzirconium (Zr (OPr) ₃ Cl), chlorotriisopropoxy zirconium _{^{(Zr (O i Pr) 3}} Cl), tributoxyzirconium cyclo rosiglitazone zirconium (Zr _(OBu) 3 Cl), tri -sec- butoxy chloro zirconium _{^{(Zr (O s Bu) 3}} Cl), Kurorotori (isobutyloxy) zirconium (Zr (O ⁱ Bu) ₃ Cl), tri-tert-butoxychlorozirconium (Zr (O ^t Bu) ₃ Cl), chlorotri (neopentyloxy) zirconium (Zr (O ⁿ Pe) ₃ Cl), chlorotri (tert) -Pentyloxy) zirconium (Z _{^{(O t Pe) 3 Cl)}} , Kurorotori (cyclopentyloxy) zirconium _{^{(Zr (O c Pe) 3}} Cl), chlorotris (1,3-dimethyl-butyloxy) zirconium _{(Zr (OCH (Me) CH} 2 CHMe 2) 3 Cl), chlorotri (cyclohexyloxy) zirconium (Zr (OCy) ₃ Cl), chlorotris (1,1-diethylpropyloxy) zirconium (Zr (OCEt ₃ ) ₃ Cl), chlorotris (1,1,3,3-tetra) Methylbutyloxy) zirconium (Zr (OCMe ₂ CH ₂ CMe ₃ ) ₃ Cl), Bromotrimethoxyzirconium (Zr (OMe) ₃ Br), Bromotriethoxyzirconium (Zr (OEt) ₃ Br), Bromotripropoxyzirconium Zr _(OPr) 3 Br) Bromo triisopropoxy zirconium _{^{(Zr (O i Pr) 3}} Br), tributoxy bromo Shi zirconium _{(Zr (OBu) 3 Br)} , tri -sec- butoxy bromo zirconium _{^{(Zr (O s Bu) 3}} Br), Buromotori ( Isobutyloxy) zirconium (Zr (O ⁱ Bu) ₃ Br), tri-tert-butoxybromozirconium (Zr (O ^t Bu) ₃ Br), bromotri (neopentyloxy) zirconium (Zr (O ⁿ Pe) ₃ Br) , Buromotori (tert- pentyloxy) zirconium ^(Zr (O t _Pe) 3 Br), Buromotori (cyclopentyloxy) zirconium ^(Zr (O c _Pe) 3 Br), bromotris (1,3-dimethyl-butyloxy) zirconium (Zr (OCH _(Me) CH 2 CHM _{2) 3} Br), Buromotori (cyclohexyloxy) zirconium _{(Zr (OCy) 3 Br)} , bromotris (1,1-diethyl propyl oxy) zirconium _{(Zr (OCEt 3) 3 Br} ), bromotris (1,1,3, 3-tetramethylbutyl oxy) zirconium _{(Zr (OCMe 2 CH 2 CMe} 3) 3 Br), iodo trimethoxysilane zirconium _{(Zr (OMe) 3 I)} , iodine triethoxysilane zirconium _{(Zr (OEt) 3 I)} , Yodotori propoxy zirconium _{(Zr (OPr) 3 I)} , iodine triisopropoxy zirconium _{^{(Zr (O i Pr) 3}} I), tributoxy iodo Shi zirconium _{(Zr (OBu) 3 I)} , tri -sec- butoxy iodo zirconium (Zr _{^{(O s Bu) 3 I)}} , Yodoto (Iso-butyloxy) zirconium _{^{(Zr (O i Bu) 3}} I), tri -tert- butoxy iodo zirconium _{^{(Zr (O t Bu) 3}} I), Yodotori (neopentyloxy) zirconium _{^{(Zr (O n Pe) 3}} I ), Iodotri (tert-pentyloxy) zirconium (Zr (O ^t Pe) ₃ I), iodotri (cyclopentyloxy) zirconium (Zr (O ^c Pe) ₃ I), iodotris (1,3-dimethylbutyloxy) zirconium (Zr (O ^c Pe) ₃ I) _{Zr (OCH (Me) CH 2} CHMe 2) 3 I), Yodotori (cyclohexyloxy) zirconium _{(Zr (OCy) 3 I)} , Yodotorisu (1,1-diethyl propyl oxy) zirconium _{(Zr (OCEt 3) 3 I} ) , Iodotris (1,1,3,3-tetramethyl) Rubuchiruokishi) zirconium _{(Zr (OCMe 2 CH 2 CMe} 3) 3 I), chlorotrifluoroethylene methoxy hafnium _{(Hf (OMe) 3 Cl)} , chlorotrifluoroethylene ethoxy hafnium _{(Hf (OEt) 3 Cl)} , chlorotrifluoroethylene propoxy hafnium (Hf ( _OPr) 3 _Cl), chlorotrifluoroethylene-isopropoxy hafnium _{^{(Hf (O i Pr) 3}} Cl), tributoxyethyl cyclo rosiglitazone hafnium _{(Hf (OBu) 3 Cl)} , tri -sec- butoxy chloro hafnium ^(Hf (O s Bu) ₃ Cl), chlorotri (isobutyloxy) hafnium (Hf (O ⁱ Bu) ₃ Cl), tri-tert-butoxychlorohafnium (Hf (O ^t Bu) ₃ Cl), chlorotri (neopentyloxy) hafnium (Hf (O) ⁿ _Pe) 3 _Cl), Kurorotori (ter - pentyloxy) hafnium _{^{(Hf (O t Pe) 3}} Cl), Kurorotori (cyclopentyloxy) hafnium _{^{(Hf (O c Pe) 3}} Cl), chlorotris (1,3-dimethyl-butyloxy) hafnium (Hf (OCH (Me ) CH ₂ CHMe ₂ ) ₃ Cl), chlorotri (cyclohexyloxy) hafnium (Hf (OCy) ₃ Cl), chlorotris (1,1-diethylpropyloxy) hafnium (Hf (OCEt ₃ ) ₃ Cl), chlorotris (1,1) 1, 3
3, 3-Tetramethylbutyloxy) hafnium (Hf (OCMe ₂ CH ₂ CMe ₃ ) ₃ Cl), Bromotrimethoxyhafnium (Hf (OMe) ₃ Br), Bromotriethoxyhafnium (Hf (OEt) ₃ Br), Bromo tripropoxy hafnium _{(Hf (OPr) 3 Br)} , bromo triisopropoxy hafnium _{^{(Hf (O i Pr) 3}} Br), tributoxyethyl bromo Shi hafnium _{(Hf (OBu) 3 Br)} , tri -sec- butoxy bromo hafnium ( Hf (O ^s Bu) ₃ Br), bromotri (isobutyloxy) hafnium (Hf (O ⁱ Bu) ₃ Br), tri-tert-butoxybromohafnium (Hf (O ^t Bu) ₃ Br), bromotri (neopentyloxy) ) hafnium _{^{(Hf (O n Pe) 3}} Br), Breakfast Yuan Li (tert- pentyloxy) hafnium _{^{(Hf (O t Pe) 3}} Br), Buromotori (cyclopentyloxy) hafnium _{^{(Hf (O c Pe) 3}} Br), bromotris (1,3-dimethyl-butyloxy) hafnium (Hf ( _{OCH (Me) CH 2 CHMe 2} ) 3 Br), Buromotori (cyclohexyloxy) hafnium _{(Hf (OCy) 3 Br)} , bromotris (1,1-diethyl propyl oxy) hafnium _{(Hf (OCEt 3) 3 Br} ), bromotris (1,1,3,3-Tetramethylbutyloxy) hafnium (Hf (OCMe ₂ CH ₂ CMe ₃ ) ₃ Br), iodotrimethoxyhafnium (Hf (OMe) ₃ I), iodotriethoxyhafnium (Hf (OEt) ) ₃ I), iodotripropoxy hafnis Um _{(Hf (OPr) 3 I)} , iodine triisopropoxy hafnium _{^{(Hf (O i Pr) 3}} I), tributoxyethyl iodo Shi hafnium _{(Hf (OBu) 3 I)} , tri -sec- butoxy iodo hafnium (Hf ( O 2 ^s Bu) ₃ I), iodotri (isobutyloxy) hafnium (Hf (O ⁱ Bu) ₃ I), tri-tert-butoxyiodohafnium (Hf (O ^t Bu) ₃ I), iodotri (neopentyloxy) hafnium (Hf (O ⁿ Pe) ₃ I), iodotri (tert-pentyloxy) hafnium (Hf (O ^t Pe) ₃ I), iodotri (cyclopentyloxy) hafnium (Hf (O ^c Pe) ₃ I), iodotris (1) , 3-dimethyl-butyloxy) hafnium _{(Hf (OCH (Me) CH} 2 CHMe 2 ₃ I), Yodotori (cyclohexyloxy) hafnium _{(Hf (OCy) 3 I)} , Yodotorisu (1,1-diethyl propyl oxy) hafnium _{(Hf (OCEt 3) 3 I} ), Yodotorisu (1,1,3,3 And tetramethylbutyloxy) hafnium (Hf (OCMe ₂ CH ₂ CMe ₃ ) ₃ I) and the like, and among them, chlorotriisopropoxytitanium, tri-sec-butoxychlorotitanium, tri-tert-butoxychlorotitanium, Chlorotri (tert-pentyloxy) titanium, chlorotriisopropoxyzirconium, tri-sec-butoxychlorozirconium, tri-tert-butoxychlorozirconium, chlorotri (tert-pentyloxy) zirconium, chlorotriisopropoxyha Preferred are sodium, tri-sec-butoxychlorohafnium, tri-tert-butoxychlorohafnium and chlorotri (tert-pentyloxy) hafnium, and chlorotriisopropoxytitanium, tri-tert-butoxychlorotitanium, chlorotriisopropoxyzirconium, trichlorotert-butoxychlorotitanium. Preference is further given to -tert-butoxychlorozirconium, chlorotriisopropoxyhafnium and tri-tert-butoxychlorohafnium.

  Examples of lithium cyclopentadienide (3) that can be used in Production method 1 include lithium (1-trimethylsilyloxycyclopentadienide), lithium (2-methyl-1-trimethylsilyloxycyclopentadienide), lithium (2-ethyl-1-trimethylsilyloxycyclopentadienide), lithium (2-pentyl-1-trimethylsilyloxycyclopentadienide), lithium (3-methyl-1-trimethylsilyloxycyclopentadienide), lithium (3 -Ethyl-1-trimethylsilyloxycyclopentadienide), lithium (3-propyl-1-trimethylsilyloxycyclopentadienide), lithium (3-tert-butyl-1-trimethylsilyloxycyclopentadienide), lithium (3-tert-butyl-1-trimethylsilyloxycyclopentadienide) -Cyclohexyl-1-trimethylsilyloxycyclopentadienide), lithium (2,3-dimethyl-1-trimethylsilyloxycyclopentadienide), lithium (3,4-dimethyl-1-trimethylsilyloxycyclopentadienide), lithium (2,4-Dimethyl 1-trimethylsilyloxycyclopentadienide), lithium (2,5-dimethyl-1-trimethylsilyloxycyclopentadienide), lithium (2,3,4-trimethyl-1-trimethylsilyloxycyclopenta) (Dienide), lithium (2,3,5-trimethyl-1-trimethylsilyloxycyclopentadienide), lithium (2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienide), lithium (3 -Methyl-1-t rt-Butyldimethylsilyloxycyclopentadienide), lithium (2,3,4,5-tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienide), lithium (3-methyl-1-triethylsilyloxy) Cyclopentadienide), lithium (2,3,4,5-tetramethyl-1-triethylsilyloxycyclopentadienide), lithium [3-methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienide] And lithium [2,3,4,5-tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienide] etc., among which lithium (3-methyl-1-trimethylsilyloxycyclopentadi) can be mentioned. (Enide), lithium (2,3,4,5-tetramethyl-1-to) Lymethylsilyloxycyclopentadienide), lithium (3-methyl-1-tert-butyldimethylsilyloxycyclopentadienide), lithium (2,3,4,5-tetramethyl-1-tert-butyldimethylsilyl) Oxycyclopentadienide), lithium (3-methyl-1-triethylsilyloxycyclopentadienide), lithium (2,3,4,5-tetramethyl-1-triethylsilyloxycyclopentadienide), lithium [ 3-Methyl-1- (dimethylamino) dimethylsilyloxycyclopentadienide] and lithium [2,3,4,5-tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienide] are preferred.

  Production method 1 is preferably carried out in an organic solvent in terms of a good yield. The organic solvent which can be used is not particularly limited as long as it does not inhibit the reaction, and specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, benzene , Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc., diethyl ether, diisopropyl ether, dibutyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl ether (CPEE), tert-butyl methyl ether (MTBE), tetrahydrofuran (THF) And ethers such as dioxane, 1,2-dimethoxyethane and the like. Among these organic solvents, one type can be used alone, and a plurality can be used by mixing in an arbitrary ratio. From the viewpoint of good yield, as the organic solvent, ether is preferable, CPME, MTBE, diethyl ether and THF are preferable, and THF is more preferable.

  Production method 1 is preferably carried out in an inert gas atmosphere in terms of a good yield. Specific examples of the inert gas include nitrogen, helium, neon, argon, krypton, xenon and the like, and nitrogen or argon is more preferable. The reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing the organolithium compound. As a specific example, at a reaction temperature appropriately selected from a temperature range of -80 ° C. to 120 ° C., a group 4 metal complex (1 of the present invention) can be obtained by selecting a reaction time suitably selected from a range of 10 minutes to 120 hours. Can be obtained with good yield.

  The Group 4 metal complex (1) of the present invention obtained by the production method 1 can be purified by appropriately selecting and using a general purification method when a person skilled in the art refines the Group 4 metal complex It can. As a specific purification method, filtration, extraction, distillation, sublimation, crystallization and the like can be mentioned.

  Next, the method for obtaining the Group 4 metal trialkoxide (2) that can be used in Production method 1 will be described. Commercial products can be purchased and used. When prepared and obtained, Group 4 metal trialkoxide (2) is described in Journal of the American Chemical Society, Vol. 135, p. 12960, Supporting Information (2013), Inorganic Chemistry, vol. 28, p. 1768 (1989). Method of reacting a Group 4 metal tetraalkoxide with a Group 4 metal tetrahalide, as described in, eg, Organoc Synthesis, Collective Volume, Vol. 8, page 495 (1993), Journal of the Chemical Society, p. (1965), JP-B-50-7565, etc., Group 4 metal tetraalkoxides and acyl halides. Such as a method of reacting a can be obtained by reference to. Group 4 metal trialkoxides (2) having different alkoxy ligands are described, for example, in the Journal of the Indian Chemical Society, Volume 31, page 683 (1955), based on dialkoxy (dichloro) titanium and alcohol It can be obtained with reference to the method of reacting in the presence and the like.

  Lithium cyclopentadienide (3) which can be used in the production method 1 can be obtained by reacting a silyloxycyclopentadiene represented by the general formula (6) with a lithiolating agent.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^８、Ｒ^９及びＲ^１０は、一般式（１）のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^８、Ｒ^９及びＲ^１０とそれぞれ同義である。）
用いることが出来るシリルオキシシクロペンタジエン（６）の例としては、１−トリメチルシリルオキシ−１，３−シクロペンタジエン、２−トリメチルシリルオキシ−１，３−シクロペンタジエン、１−トリメチルシリルオキシ−２−メチル−１，３−シクロペンタジエン、１−トリメチルシリルオキシ−２−エチル−１，３−シクロペンタジエン、１−トリメチルシリルオキシ−２−ペンチル−１，３−シクロペンタジエン、１−メチル−３−トリメチルシリルオキシ−１，３−シクロペンタジエン、１−エチル−３−トリメチルシリルオキシ−１，３−シクロペンタジエン、１−プロピル−３−トリメチルシリルオキシ−１，３−シクロペンタジエン、１−ｔｅｒｔ−ブチル−３−トリメチルシリルオキシ−１，３−シクロペンタジエン、１−シクロヘキシル−３−トリメチルシリルオキシ−１，３−シクロペンタジエン、１，３−ジメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン、３，４−ジメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン、３，５−ジメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン、４，５−ジメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン、１，３，４−トリメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン、１，３，５−トリメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン、１，３，４，５−トリメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン、２，３，４，５−テトラメチル−１−トリメチルシリルオキシ−１，３−シクロペンタジエン、１−トリエチルシリルオキシ−１，３−シクロペンタジエン、２−トリエチルシリルオキシ−１，３−シクロペンタジエン、１−トリエチルシリルオキシ−２−メチル−１，３−シクロペンタジエン、１−トリエチルシリルオキシ−２−エチル−１，３−シクロペンタジエン、１−トリエチルシリルオキシ−２−ペンチル−１，３−シクロペンタジエン、１−メチル−３−トリエチルシリルオキシ−１，３−シクロペンタジエン、１，３，４，５−トリメチル−２−トリエチルシリルオキシ−１，３−シクロペンタジエン、２，３，４，５−テトラメチル−１−トリエチルシリルオキシ−１，３−シクロペンタジエン、１−ｔｅｒｔ−ブチルジメチルシリルオキシ−１，３−シクロペンタジエン、２−ｔｅｒｔ−ブチルジメチルシリルオキシ−１，３−シクロペンタジエン、１−ｔｅｒｔ−ブチルジメチルシリルオキシ−２−メチル−１，３−シクロペンタジエン、１−ｔｅｒｔ−ブチルジメチルシリルオキシ−２−エチル−１，３−シクロペンタジエン、１−ｔｅｒｔ−ブチルジメチルシリルオキシ−２−ペンチル−１，３−シクロペンタジエン、１−メチル−３−ｔｅｒｔ−ブチルジメチルシリルオキシ−１，３−シクロペンタジエン、１，３，４，５−トリメチル−２−ｔｅｒｔ−ブチルジメチルシリルオキシ−１，３−シクロペンタジエン、２，３，４，５−テトラメチル−１−ｔｅｒｔ−ブチルジメチルシリルオキシ−１，３−シクロペンタジエン、１−（ジメチルアミノ）ジメチルシリルオキシ−１，３−シクロペンタジエン、２−（ジメチルアミノ）ジメチルシリルオキシ−１，３−シクロペンタジエン、１−（ジメチルアミノ）ジメチルシリルオキシ−２−メチル−１，３−シクロペンタジエン、１−（ジメチルアミノ）ジメチルシリルオキシ−２−エチル−１，３−シクロペンタジエン、１−（ジメチルアミノ）ジメチルシリルオキシ−２−ペンチル−１，３−シクロペンタジエン、１−メチル−３−（ジメチルアミノ）ジメチルシリルオキシ−１，３−シクロペンタジエン、１，３，４，５−トリメチル−２−（ジメチルアミノ）ジメチルシリルオキシ−１，３−シクロペンタジエン、２，３，４，５−テトラメチル−１−（ジメチルアミノ）ジメチルシリルオキシ−１，３−シクロペンタジエンなどを挙げることが出来る。また、これらとはシクロペンタジエン環の二重結合の位置が異なっている異性体も同様に用いることが出来る。

^{(Wherein, R 1, R 2, R} 3, R 4, R 8, R 9 and ^{R 10, R 1, R 2, R} 3 in the general formula ^{(1), R 4, R} 8, R 9 and Each is synonymous with R ¹⁰ )
Examples of silyloxycyclopentadiene (6) which can be used include 1-trimethylsilyloxy-1,3-cyclopentadiene, 2-trimethylsilyloxy-1,3-cyclopentadiene, 1-trimethylsilyloxy-2-methyl-1 , 3-Cyclopentadiene, 1-trimethylsilyloxy-2-ethyl-1,3-cyclopentadiene, 1-trimethylsilyloxy-2-pentyl-1,3-cyclopentadiene, 1-methyl-3-trimethylsilyloxy-1,3 -Cyclopentadiene, 1-ethyl-3-trimethylsilyloxy-1,3-cyclopentadiene, 1-propyl-3-trimethylsilyloxy-1,3-cyclopentadiene, 1-tert-butyl-3-trimethylsilyloxy-1,3 -Cyclopentadie 1-Cyclohexyl-3-trimethylsilyloxy-1,3-cyclopentadiene, 1,3-dimethyl-2-trimethylsilyloxy-1,3-cyclopentadiene, 3,4-dimethyl-2-trimethylsilyloxy-1,3-butadiene Cyclopentadiene, 3,5-dimethyl-2-trimethylsilyloxy-1,3-cyclopentadiene, 4,5-dimethyl-2-trimethylsilyloxy-1,3-cyclopentadiene, 1,3,4-trimethyl-2-trimethylsilyl Oxy-1,3-cyclopentadiene, 1,3,5-trimethyl-2-trimethylsilyloxy-1,3-cyclopentadiene, 1,3,4,5-trimethyl-2-trimethylsilyloxy-1,3-cyclopentadiene 2,3,4,5-Tetramethyl-1-trimethylsilane Ruoxy-1,3-cyclopentadiene, 1-triethylsilyloxy-1,3-cyclopentadiene, 2-triethylsilyloxy-1,3-cyclopentadiene, 1-triethylsilyloxy-2-methyl-1,3-cyclo Pentadiene, 1-triethylsilyloxy-2-ethyl-1,3-cyclopentadiene, 1-triethylsilyloxy-2-pentyl-1,3-cyclopentadiene, 1-methyl-3-triethylsilyloxy-1,3-butadiene Cyclopentadiene, 1,3,4,5-trimethyl-2-triethylsilyloxy-1,3-cyclopentadiene, 2,3,4,5-tetramethyl-1-triethylsilyloxy-1,3-cyclopentadiene 1-tert-butyldimethylsilyloxy-1,3-cyclopentadiene, 2 -Tert-Butyldimethylsilyloxy-1,3-cyclopentadiene, 1-tert-butyldimethylsilyloxy-2-methyl-1,3-cyclopentadiene, 1-tert-butyldimethylsilyloxy-2-ethyl-1,- 3-cyclopentadiene, 1-tert-butyldimethylsilyloxy-2-pentyl-1,3-cyclopentadiene, 1-methyl-3-tert-butyldimethylsilyloxy-1,3-cyclopentadiene, 1,3,4 5-trimethyl-2-tert-butyldimethylsilyloxy-1,3-cyclopentadiene, 2,3,4,5-tetramethyl-1-tert-butyldimethylsilyloxy-1,3-cyclopentadiene, 1- (Dimethylamino) dimethylsilyloxy-1,3-cyclopentadiene 2- (Dimethylamino) dimethylsilyloxy-1,3-cyclopentadiene, 1- (dimethylamino) dimethylsilyloxy-2-methyl-1,3-cyclopentadiene, 1- (dimethylamino) dimethylsilyloxy-2- Ethyl 1,3-cyclopentadiene, 1- (dimethylamino) dimethylsilyloxy-2-pentyl-1,3-cyclopentadiene, 1-methyl-3- (dimethylamino) dimethylsilyloxy-1,3-cyclopentadiene 1,3,4,5-trimethyl-2- (dimethylamino) dimethylsilyloxy-1,3-cyclopentadiene, 2,3,4,5-tetramethyl-1- (dimethylamino) dimethylsilyloxy-1 And 3-cyclopentadiene. Also, isomers different from these in the position of double bond of cyclopentadiene ring can be used similarly.

  The method for obtaining silyloxycyclopentadiene (6) will be described. Silyloxy cyclopentadiene (6) can be obtained by silylation of a substituted or unsubstituted cyclopentenone. For example, Acta Chemica Scandinavica, Vol. 43, p. 188 (1989), Chemical Communication, p. 2123 (1996), Journal of Organometallic Chemistry, Vol. 558, p. 231 (1998), Organometallics, Vol. 16, p. 5950. (1997) and the like can be used as a reference.

  As a lithiolating agent which can be used, alkyllithiums such as methyllithium, ethyllithium, propyllithium and butyllithium, aryllithiums such as phenyllithium and tolyllithium, lithium dialkyls such as lithium dimethylamide, lithium diethylamide and lithium diisopropylamide An amide etc. can be illustrated. From the viewpoint of good yield, butyllithium, lithium diethylamide and lithium diisopropylamide are preferred, and lithium diisopropylamide is more preferred.

  The reaction of the silyloxycyclopentadiene with the lithiation agent is preferably carried out in an organic solvent in terms of a good yield. The organic solvent which can be used is not particularly limited as long as it does not inhibit the reaction, and specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, benzene , Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc., diethyl ether, diisopropyl ether, dibutyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl ether (CPEE), tert-butyl methyl ether (MTBE), tetrahydrofuran (THF) And ethers such as dioxane, 1,2-dimethoxyethane and the like. Among these organic solvents, one type can be used alone, and a plurality can be used by mixing in an arbitrary ratio. The organic solvent is preferably an ether, CPME, MTBE, diethyl ether and THF are preferable, and THF is more preferable, in that the yield of lithium cyclopentadienide (3) is good.

  The reaction of the silyloxycyclopentadiene (6) with the lithiation agent is preferably carried out in an inert gas atmosphere in terms of a good yield. Specific examples of the inert gas include nitrogen, helium, neon, argon, krypton, xenon and the like, and nitrogen or argon is more preferable. The reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing the organolithium compound. As a specific example, at a reaction temperature appropriately selected from a temperature range of -80 ° C to 120 ° C, lithium cyclopentadienide (3) is collected by selecting a reaction time appropriately selected from a range of 10 minutes to 120 hours. It can be obtained efficiently.

  The lithium cyclopentadienide (3) obtained by the reaction of the silyloxycyclopentadiene (6) and the lithiation agent can be used as a raw material for the production method 1 with or without purification. When purifying lithium cyclopentadienide (3), those skilled in the art can carry out purification by appropriately selecting and using a general purification method for purifying an organolithium compound. As a specific purification method, filtration, extraction, decantation, crystallization and the like can be mentioned.

Next, manufacturing method 2 will be described. Production method 2 is a method for producing a titanium complex (1Ti) by reacting an alkali metal-titanium complex (5) with a substituted silyl halide (4).
Manufacturing method 2

（式中、ＡＭ^１はアルカリ金属原子を表す。Ｘ^２はハロゲン原子を表す。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、一般式（１）のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０とそれぞれ同義である。）
ＡＭ^１で表されるアルカリ金属原子の例としては、リチウム原子、ナトリウム原子及びカリウム原子を挙げることが出来る。製造方法２の収率が良い点で、リチウム原子又はナトリウム原子が好ましい。

Wherein AM ¹ represents an alkali metal atom, X ² represents a halogen atom, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ Is as defined in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the general formula (1).
Examples of the alkali metal atom represented by AM ¹ include lithium atom, sodium atom and potassium atom. The lithium atom or the sodium atom is preferable in that the yield of the production method 2 is good.

As an example of the alkali metal-titanium complex (5) which can be used in the production method 2, triisopropoxy (η ⁵ -3-methyl-1-lithium oxycyclopentadienyl) titanium ((η ⁵ -C ₅ ( ^{_{OLi) MeH 3) Ti (O}} i Pr) 3), tri-isopropoxy (eta ^{5-3-methyl-1-sodium-oxy} cyclopentadienyl) titanium _{^{((η 5 -C 5 (ONa}} ) MeH 3) Ti ( O ⁱ Pr) ₃ ), triisopropoxy (η ⁵ 3-methyl-1-potassium oxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OK) MeH ₃ ) Ti (O ⁱ Pr) ₃ ), triisopropoxy (eta ^5-2-pentyl-1 lithium titanyl cyclopentadienyl) titanium _{^{((η 5 -C 5 (OLi}} ) PeH 3) Ti (O i Pr) 3), tri Isopropoxy (η ⁵ -2- pentyl 1-sodium oxycyclopentadienyl) titanium (( ^{5 5-} C ₅ (ONa) PeH ₃ ) Ti (O ⁱ Pr) ₃ ), triisopropoxy ( ⁵ 5-2) -Pentyl-1-potassium oxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OK) PeH ₃ ) Ti (O ⁱ Pr) ₃ ), triisopropoxy (η ⁵ -2, ₃ , 4, ^5- Tetramethyl-1-lithium oxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OLi) Me ₄ ) Ti (O ⁱ Pr) ₃ ), triisopropoxy (η ⁵ -2, ₃ , _4, 5-) tetramethyl-1-sodium-oxy cyclopentadienyl) titanium _{^{((η 5 -C 5 (ONa}} ) Me 4) Ti (O i Pr) 3), tri-isopropoxy (eta ^5-2,3,4,5 Te Ramechiru -1- potassium oxy cyclopentadienyl) titanium _{^{((η 5 -C 5 (OK}} ) Me 4) Ti (O i Pr) 3), tri -tert- butoxy (η ⁵ -2,3,4,5 -Tetramethyl-1-lithium oxycyclopentadienyl) titanium ((η ^5- C ₅ (OLi) Me ₄ ) Ti (O ^t Bu) ₃ ), tri-tert-butoxy (η ⁵ -2, ₃ , 4 , 5-tetramethyl-1-sodium-oxy cyclopentadienyl) titanium _{^{((η 5 -C 5 (ONa}} ) Me 4) Ti (O t Bu) 3), tri -tert- butoxy (eta ^5-2,3 And 4,5-tetramethyl-1-potassium oxycyclopentadienyl) titanium ((η ⁵ -C ₅ (OK) Me ₄ ) Ti (O ^t Bu) ₃ ) and the like. Carboxymethyl (eta ^{5-3-methyl-1-lithium} titanyl cyclopentadienyl) titanium, triisopropoxy (eta ^{5-3-methyl-1-sodium-oxy} cyclopentadienyl) titanium, triisopropoxy (eta ⁵ -2 3,4,5-Tetramethyl-1-lithium oxycyclopentadienyl) titanium and triisopropoxy (η ⁵ -2,3,4,5-tetramethyl-1-sodium oxycyclopentadienyl) titanium; preferable.

  Examples of substituted silyl halide (4) which can be used in production method 2 include chlorotrimethylsilane, chloro (ethyl) dimethylsilane, chlorodimethyl (propyl) silane, chloro (isopropyl) dimethylsilane, butyl (chloro) dimethylsilane Chloro (isobutyl) dimethylsilane, sec-butyl (chloro) dimethylsilane, tert-butyl (chloro) dimethylsilane, chlorodimethyl (tert-pentyl) silane, chloro (cyclohexyl) dimethylsilane, chlorodiethyl (methyl) silane, chloro Triethylsilane, chlorotripropylsilane, chlorotriisopropylsilane, chloro (dimethylamino) dimethylsilane, chlorobis (dimethylamino) methylsilane, chlorotris (dimethylamino) silane, chloro (Ethylmethylamino) dimethylsilane, chloro (diethylamino) dimethylsilane, bromotrimethylsilane, bromo (ethyl) dimethylsilane, bromodimethyl (propyl) silane, bromo (isopropyl) dimethylsilane, butyl (bromo) dimethylsilane, bromo (isobutyl) ) Dimethylsilane, sec-butyl (bromo) dimethylsilane, tert-butyl (bromo) dimethylsilane, bromodimethyl (tert-pentyl) silane, bromo (cyclohexyl) dimethylsilane, bromodiethyl (methyl) silane, bromotriethylsilane, bromo Tripropylsilane, Bromotriisopropylsilane, Iodotrimethylsilane, Iodo (ethyl) dimethylsilane, Iododimethyl (propyl) silane, Iodo (isopropyl) Methylsilane, butyl (iodo) dimethylsilane, iodo (isobutyl) dimethylsilane, sec-butyl (iodo) dimethylsilane, tert-butyl (iodo) dimethylsilane, iododimethyl (tert-pentyl) silane, iodo (cyclohexyl) dimethylsilane, Examples include iododiethyl (methyl) silane, iodotriethylsilane, iodotripropylsilane, iodotriisopropylsilane and the like, among which chlorotrimethylsilane, tert-butyl (chloro) dimethylsilane, chlorotriethylsilane, chlorotripropyl Silane, chlorotriisopropylsilane and chloro (dimethylamino) dimethylsilane are preferred.

  Production method 2 is preferably carried out in an organic solvent in terms of a good yield. The organic solvent which can be used is not particularly limited as long as it does not inhibit the reaction, and specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, benzene , Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc., diethyl ether, diisopropyl ether, dibutyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl ether (CPEE), tert-butyl methyl ether (MTBE), tetrahydrofuran (THF) And ethers such as dioxane, 1,2-dimethoxyethane and the like. Among these organic solvents, one type can be used alone, and a plurality can be used by mixing in an arbitrary ratio. From the viewpoint of good yield, as the organic solvent, ether is preferable, CPME, MTBE, diethyl ether and THF are preferable, and THF is more preferable.

  Production method 2 is preferably carried out in an inert gas atmosphere in terms of a good yield. Specific examples of the inert gas include nitrogen, helium, neon, argon, krypton, xenon and the like, and nitrogen or argon is more preferable. The reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a titanium complex. As a specific example, the titanium complex (1Ti) can be obtained with good yield by selecting the reaction time appropriately selected from the range of 10 minutes to 120 hours at the reaction temperature appropriately selected from the temperature range of -80 ° C to 120 ° C. I can do it.

  The titanium complex (1Ti) obtained by Production method 2 can be purified by appropriately selecting and using a general purification method when a titanium complex is purified by those skilled in the art. As a specific purification method, filtration, extraction, distillation, sublimation, crystallization and the like can be mentioned.

Next, a method of producing an alkali metal-titanium complex (5), which is a raw material of production method 2, will be described. The alkali metal-titanium complex (5) can be produced according to production method 3 or production method 4. Production method 3 is a method of producing an alkali metal-titanium complex (5) by reacting a titanium complex (1Ti) with an alkali metal alkoxide (7).
Manufacturing method 3

（式中、ＡＭ^１はアルカリ金属原子を表す。Ｒ^ａは炭素数１〜８のアルキル基を表す。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、一般式（１）のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０とそれぞれ同義である。）
まずアルカリ金属アルコキシド（７）のＲ^ａ及びＡＭ^１の定義について説明する。Ｒ^ａで表される炭素数１〜８のアルキル基は、直鎖状、分岐状及び環状のいずれでも良く、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロブチル基、ペンチル基、１−メチルブチル基、２−メチルブチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、シクロペンチル基、シクロブチルメチル基、ヘキシル基、１−メチルペンチル基、２−メチルペンチル基、３−メチルペンチル基、４−メチルペンチル基、１，１−ジメチルブチル基、１，２−ジメチルブチル基、１，３−ジメチルブチル基、２，２−ジメチルブチル基、２，３−ジメチルブチル基、３，３−ジメチルブチル基、シクロヘキシル基、シクロペンチルメチル基、１−シクロブチルエチル基、２−シクロブチルエチル基、ヘプチル基、１−メチルヘキシル基、２−メチルヘキシル基、３−メチルヘキシル基、４−メチルヘキシル基、５−メチルヘキシル基、１−エチルペンチル基、２−エチルペンチル基、３−エチルペンチル基、１，１−ジメチルペンチル基、１，２−ジメチルペンチル基、１，３−ジメチルペンチル基、２，２−ジメチルペンチル基、２，３−ジメチルペンチル基、３，３−ジメチルペンチル基、４，４−ジメチルペンチル基、１，１−ジエチルプロピル基、１−エチル−１−メチルブチル基、１−エチル−２−メチルブチル基、１−エチル−３−メチルブチル基、２−エチル−１−メチルブチル基、２−エチル−２−メチルブチル基、シクロヘプチル基、シクロヘキシルメチル基、オクチル基、１−メチルヘプチル基、２−メチルヘプチル基、３−メチルヘプチル基、４−メチルヘプチル基、５−メチルヘプチル基、６−メチルヘプチル基、１−エチルヘキシル基、２−エチルヘキシル基、３−エチルヘキシル基、４−エチルヘキシル基、１，１−ジメチルヘキシル基、１，２−ジメチルヘキシル基、１，３−ジメチルヘキシル基、２，２−ジメチルヘキシル基、２，３−ジメチルヘキシル基、３，３−ジメチルヘキシル基、４，４−ジメチルヘキシル基、５，５−ジメチルヘキシル基、１，１，３−トリメチルペンチル基、１，１，３，３−テトラメチルブチル基、１−エチル−１−メチルペンチル基、１−エチル−２−メチルペンチル基、１−エチル−３−メチルペンチル基、２−エチル−１−メチルペンチル基、２−エチル−２−メチルペンチル基、シクロオクチル基、１−シクロヘキシルエチル基、２−シクロヘキシルエチル基などを例示することが出来る。製造方法３の収率が良い点で、炭素数１〜５のアルキル基であることが好ましく、メチル基、エチル基、イソプロピル基、ｔｅｒｔ−ブチル基が更に好ましく、ｔｅｒｔ−ブチル基が殊更好ましい。

(Wherein, AM ¹ represents an alkali metal atom, R ^a represents an alkyl group having 1 to 8 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , ^{R 9} and ^{R 10, R 1, R 2, R} 3, R 4, R 5, R 6, R 7, R 8, are each synonymous with ^{R 9} and ^{R 10} in the general formula (1).)
First, the definitions of R ^a and AM ¹ of the alkali metal alkoxide (7) will be described. The alkyl group having 1 to 8 carbon atoms represented by R ^a may be linear, branched or cyclic, and specifically, methyl, ethyl, propyl, isopropyl, cyclopropyl and butyl Group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, cyclobutylmethyl group, Hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl , 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group, cyclopentene A methyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group, heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-Dimethylpentyl group, 3,3-dimethylpentyl group, 4,4-dimethylpentyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-2-methylbutyl group, cycloheptyl group, cyclohexene group Methyl group, octyl group, 1-methyl heptyl group, 2-methyl heptyl group, 3-methyl heptyl group, 4-methyl heptyl group, 5-methyl heptyl group, 6-methyl heptyl group, 1-ethylhexyl group, 2-ethylhexyl Group, 3-ethylhexyl group, 4-ethylhexyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group Group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1,1,3-trimethylpentyl group, 1,1,3,3-tetramethylbutyl group, 1 -Ethyl-1-methylpentyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 2-ethyl-1-methyl pentyl group Pentyl group, 2-ethyl-2-methylpentyl group, cyclooctyl group, 1-cyclohexylethyl group, a 2-cyclohexylethyl group of can be exemplified. From the viewpoint of good yield of production method 3, an alkyl group having 1 to 5 carbon atoms is preferable, a methyl group, an ethyl group, an isopropyl group and a tert-butyl group are more preferable, and a tert-butyl group is particularly preferable.

Examples of the alkali metal atom represented by AM ¹ include lithium atom, sodium atom and potassium atom. A lithium atom or a sodium atom is preferable, and a lithium atom is more preferable, in terms of a good yield of production method 3.

  Examples of the alkali metal alkoxide (7) which can be used in production method 3 include lithium methoxide, lithium ethoxide, lithium propoxide, lithium isopropoxide, lithium butoxide, lithium (isobutyl) oxide, lithium-sec-butoxide Lithium-tert-butoxide, lithium (tert-pentyl) oxide, lithium (hexyl) oxide, lithium (heptyl) oxide, lithium (octyl) oxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, Sodium butoxide, sodium (isobutyl) oxide, sodium-sec-butoxide, sodium-tert-butoxide, sodium (tert-pentyl) oxide, Sodium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium (isobutyl) oxide, potassium-sec-butoxide, potassium-tert-butoxide, potassium (tert-pentyl) oxide, etc. it can. Lithium-tert-butoxide, sodium-tert-butoxide and potassium-tert-butoxide are preferred, and lithium-tert-butoxide is more preferred, from the viewpoint of a good yield of production method 3.

  Production method 3 is preferably carried out in an organic solvent in terms of a good yield. The organic solvent which can be used is not particularly limited as long as it does not inhibit the reaction, and specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, benzene , Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc., diethyl ether, diisopropyl ether, dibutyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl ether (CPEE), tert-butyl methyl ether (MTBE), tetrahydrofuran (THF) And ethers such as dioxane, 1,2-dimethoxyethane and the like. Among these organic solvents, one type can be used alone, and a plurality can be used by mixing in an arbitrary ratio. From the viewpoint of good yield, as the organic solvent, ether is preferable, CPME, MTBE, diethyl ether and THF are preferable, and THF is more preferable.

  Production method 3 is preferably carried out in an inert gas atmosphere in terms of a good yield. Specific examples of the inert gas include nitrogen, helium, neon, argon, krypton, xenon and the like, and nitrogen or argon is more preferable. The reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a titanium complex. As a specific example, at a reaction temperature appropriately selected from a temperature range of -80 ° C. to 100 ° C., an alkali metal-titanium complex (5) is collected by selecting a reaction time suitably selected from a range of 10 minutes to 120 hours. It can be obtained efficiently.

  The alkali metal-titanium complex (5) obtained by production method 3 can be used as a raw material for production method 2 after purification or without purification. When purifying the alkali metal-titanium complex (5), the person skilled in the art can perform purification by appropriately selecting and using a general purification method for purifying the titanium complex. As a specific purification method, filtration, extraction, crystallization and the like can be mentioned.

Among the alkali metal-titanium complexes (5), lithium-titanium complexes (5Li) in which AM ¹ is a lithium atom can also be produced according to production method 4. Production method 4 is a method of producing lithium-titanium complex (5Li) by reacting lithium cyclopentadienide (3) with tetraalkoxytitanium (8).
Manufacturing method 4

（式中、Ｒ^ｂは同一又は相異なって、炭素数１〜８のアルキル基を表す。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^８、Ｒ^９及びＲ^１０は、一般式（１）のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^８、Ｒ^９及びＲ^１０とそれぞれ同義である。）
まずテトラアルコキシチタン（８）のＲ^ｂの定義について説明する。Ｒ^ｂで表される炭素数１〜８のアルキル基は、直鎖状、分岐状及び環状のいずれでも良く、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロブチル基、ペンチル基、１−メチルブチル基、２−メチルブチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、シクロペンチル基、シクロブチルメチル基、ヘキシル基、１−メチルペンチル基、２−メチルペンチル基、３−メチルペンチル基、４−メチルペンチル基、１，１−ジメチルブチル基、１，２−ジメチルブチル基、１，３−ジメチルブチル基、２，２−ジメチルブチル基、２，３−ジメチルブチル基、３，３−ジメチルブチル基、シクロヘキシル基、シクロペンチルメチル基、１−シクロブチルエチル基、２−シクロブチルエチル基、ヘプチル基、１−メチルヘキシル基、２−メチルヘキシル基、３−メチルヘキシル基、４−メチルヘキシル基、５−メチルヘキシル基、１−エチルペンチル基、２−エチルペンチル基、３−エチルペンチル基、１，１−ジメチルペンチル基、１，２−ジメチルペンチル基、１，３−ジメチルペンチル基、２，２−ジメチルペンチル基、２，３−ジメチルペンチル基、３，３−ジメチルペンチル基、４，４−ジメチルペンチル基、１，１−ジエチルプロピル基、１−エチル−１−メチルブチル基、１−エチル−２−メチルブチル基、１−エチル−３−メチルブチル基、２−エチル−１−メチルブチル基、２−エチル−２−メチルブチル基、シクロヘプチル基、シクロヘキシルメチル基、オクチル基、１−メチルヘプチル基、２−メチルヘプチル基、３−メチルヘプチル基、４−メチルヘプチル基、５−メチルヘプチル基、６−メチルヘプチル基、１−エチルヘキシル基、２−エチルヘキシル基、３−エチルヘキシル基、４−エチルヘキシル基、１，１−ジメチルヘキシル基、１，２−ジメチルヘキシル基、１，３−ジメチルヘキシル基、２，２−ジメチルヘキシル基、２，３−ジメチルヘキシル基、３，３−ジメチルヘキシル基、４，４−ジメチルヘキシル基、５，５−ジメチルヘキシル基、１，１，３−トリメチルペンチル基、１，１，３，３−テトラメチルブチル基、１−エチル−１−メチルペンチル基、１−エチル−２−メチルペンチル基、１−エチル−３−メチルペンチル基、２−エチル−１−メチルペンチル基、２−エチル−２−メチルペンチル基、シクロオクチル基、１−シクロヘキシルエチル基、２−シクロヘキシルエチル基などを例示することが出来る。製造方法４の収率が良い点で、イソプロピル基及びｓｅｃ−ブチル基が好ましく、イソプロピル基が更に好ましい。

(Wherein R ^b is the same or different and represents an alkyl group having 1 to 8 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ⁹ and R ¹⁰ have the general formula (1) And the same as R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ⁹ and R ¹⁰ ).
First, the definition of R ^b of tetraalkoxytitanium (8) will be described. The alkyl group having 1 to 8 carbon atoms represented by R ^b may be linear, branched or cyclic, and specifically, methyl, ethyl, propyl, isopropyl, cyclopropyl and butyl Group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, cyclobutylmethyl group, Hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl , 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group, cyclopentene A methyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group, heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-Dimethylpentyl group, 3,3-dimethylpentyl group, 4,4-dimethylpentyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-2-methylbutyl group, cycloheptyl group, cyclohexene group Methyl group, octyl group, 1-methyl heptyl group, 2-methyl heptyl group, 3-methyl heptyl group, 4-methyl heptyl group, 5-methyl heptyl group, 6-methyl heptyl group, 1-ethylhexyl group, 2-ethylhexyl Group, 3-ethylhexyl group, 4-ethylhexyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group Group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1,1,3-trimethylpentyl group, 1,1,3,3-tetramethylbutyl group, 1 -Ethyl-1-methylpentyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 2-ethyl-1-methyl pentyl group Pentyl group, 2-ethyl-2-methylpentyl group, cyclooctyl group, 1-cyclohexylethyl group, a 2-cyclohexylethyl group of can be exemplified. An isopropyl group and a sec-butyl group are preferable, and an isopropyl group is more preferable in that the yield of the production method 4 is good.

  Examples of tetraalkoxytitanium (8) that can be used in the production method 4 include tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetra (isopropoxy) titanium, tetrabutoxytitanium, tetra (isobutyloxy) titanium, tetratetra (Sec-butoxy) titanium, tetra (tert-butoxy) titanium, tetra (pentyloxy) titanium, tetra (1-ethylpropyloxy) titanium, tetra (cyclohexyloxy) titanium, tetra (1-methylhexyloxy) titanium, tetra (Octyloxy) titanium etc. can be mentioned. In terms of a good yield of the production method (4), tetra (isopropoxy) titanium and tetra (sec-butoxy) titanium are preferable, and tetra (isopropoxy) titanium is more preferable.

  Production method 4 is preferably carried out in an organic solvent in terms of a good yield. The organic solvent which can be used is not particularly limited as long as it does not inhibit the reaction, and specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, benzene , Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc., diethyl ether, diisopropyl ether, dibutyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl ether (CPEE), tert-butyl methyl ether (MTBE), tetrahydrofuran (THF) And ethers such as dioxane, 1,2-dimethoxyethane and the like. Among these organic solvents, one type can be used alone, and a plurality can be used by mixing in an arbitrary ratio. From the viewpoint of good yield, as the organic solvent, ether is preferable, CPME, MTBE, diethyl ether and THF are preferable, and THF is more preferable.

  Production method 4 is preferably carried out in an inert gas atmosphere in terms of a good yield. Specific examples of the inert gas include nitrogen, helium, neon, argon, krypton, xenon and the like, and nitrogen or argon is more preferable. The reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a titanium complex. As a specific example, at a reaction temperature appropriately selected from a temperature range of -80 ° C. to 100 ° C., a reaction time selected appropriately from a range of 10 minutes to 120 hours yields a lithium-titanium complex (5Li). You can get it well.

  The lithium-titanium complex (5Li) obtained by the production method 4 can be used as a raw material of the production method 2 after purification or without purification. By continuously carrying out Production Method 4 and Production Method 2, the Group 4 metal complex (1) of the present invention of the present invention can also be produced in one pot. When purifying lithium-titanium complex (5Li), those skilled in the art can perform purification by appropriately selecting and using a general purification method for purifying a titanium complex. As a specific purification method, filtration, extraction, crystallization and the like can be mentioned.

  Next, a method for producing a Group 4 metal-containing thin film, which comprises evaporating the Group 4 metal complex (1) of the present invention and decomposing the Group 4 metal complex on a substrate, will be described in detail. .

  As a film production condition when producing a Group 4 metal-containing thin film, a person skilled in the art can exemplify a usual technical means used to produce a metal-containing thin film. Specifically, a vapor phase deposition method based on a chemical reaction, and a solution method such as a dip coating method, a spin coating method or an inkjet method can be exemplified. In the present specification, a chemical vapor deposition method based on a chemical reaction is a method of producing a Group 4 metal-containing thin film by vaporizing the Group 4 metal complex (1) of the present invention and decomposing it on a substrate. Specifically, it includes CVD methods such as thermal CVD method, plasma CVD method, photo CVD method, ALD method and the like. From the viewpoint of easily forming a Group 4 metal-containing thin film uniformly on the surface of a substrate having a three-dimensionalized structure, a chemical vapor deposition method based on a chemical reaction is preferable, and a CVD method or an ALD method is more preferable. The CVD method is particularly preferred in terms of a good film deposition rate, and the ALD method is particularly preferred in terms of good step coverage. For example, in the case of producing a thin film containing a Group 4 metal by CVD or ALD, the Group 4 metal complex (1) is vaporized and supplied to the reaction chamber, and the Group 4 metal complex is provided on the substrate provided in the reaction chamber. By decomposing (1), a Group 4 metal-containing thin film can be produced on the substrate. As a method of decomposing Group 4 metal complex (1), those skilled in the art can cite ordinary technical means used for producing a metal-containing thin film. Specifically, a method of reacting Group 4 metal complex (1) with a reaction gas, a method of causing heat, plasma, light or the like to act on Group 4 metal complex (1) can be exemplified.

  When producing a Group 4 metal-containing thin film by a CVD method or an ALD method, a Group 4 metal-containing thin film can be produced by appropriately selecting and using these decomposition methods. A plurality of decomposition methods can be used in combination. Examples of the method for supplying the Group 4 metal complex (1) to the reaction chamber include methods commonly used by those skilled in the art, such as bubbling and liquid vaporization and supply systems, and the method is not particularly limited.

  When producing a Group 4 metal-containing thin film by a CVD method or an ALD method, as a carrier gas and a dilution gas, a rare gas such as helium, neon, argon, krypton, xenon or nitrogen is preferable, and nitrogen or More preferred is argon. The flow rates of the carrier gas and the dilution gas are appropriately adjusted according to the volume of the reaction chamber and the like. For example, when the volume of the reaction chamber is 1 to 10 L, the flow rate of the carrier gas is not particularly limited, and 1 to 10000 sccm is preferable for economic reasons. It is also possible to supply the Group 4 metal complex (1) to the reaction chamber without using a carrier gas. For example, in the case of producing a Group 4 metal-containing thin film by the ALD method, it is possible to supply the Group 4 metal complex (1) by reducing the pressure in the reaction chamber. In the present specification, “sccm” is a unit representing the flow rate of a gas, and “1 sccm” indicates that the gas moves at a rate of 2.68 mmol / h in terms of an ideal gas.

  When using a reaction gas, examples of the reaction gas that can be used include oxygen, ozone, water vapor, hydrogen peroxide, laughing gas, formic acid, acetic acid, ammonia, hydrogen, monosilane, substituted or unsubstituted hydrazine and the like. It can. In the case of producing a group 4 metal oxide thin film, oxygen, ozone, water vapor, hydrogen peroxide and the like are preferable in terms of easy handling. The flow rate of the reaction gas is appropriately adjusted according to the reactivity of the Group 4 metal complex (1) with the reaction gas and the volume of the reaction chamber. For example, when the volume of the reaction chamber is 1 to 10 L, the flow rate of the reaction gas is not particularly limited, and is preferably 1 to 10000 sccm for economic reasons.

  The substrate temperature when producing the group 4 metal-containing thin film by the CVD method or the ALD method is appropriately selected depending on the use of heat, plasma, light and the like, the type of reaction gas, and the like. For example, in the case of using oxygen as a reaction gas without using light or plasma in combination, the substrate temperature is not particularly limited, and 200 ° C. to 1000 ° C. is preferable for economic reasons. The temperature is preferably 250 ° C. to 800 ° C., particularly preferably 300 ° C. to 800 ° C., in terms of a good film deposition rate. In addition, by appropriately using light, plasma, decomposition gas or the like, it is possible to produce a Group 4 metal-containing thin film in a temperature range of 200 ° C. or less.

  Examples of the Group 4 metal-containing thin film obtained by the method for producing a Group 4 metal-containing thin film of the present invention include, for example, Group 4 metal thin films, Group 4 metal oxide thin films, Group 4 metal nitride thin films, and Group 4 A metal oxynitride thin film or the like can be obtained. In addition, metal materials containing typical elements such as strontium, barium, calcium, silicon, germanium and bismuth, transition metals such as vanadium, niobium, tantalum and tungsten, and rare earth metals such as lanthanum and neodymium, and the Group 4 metal complex of the present invention By using (1) in combination, it is also possible to obtain a Group 4 metal-containing composite film containing these metal elements. For example, a strontium titanate thin film can be obtained by using the titanium complex of the present invention and a strontium material in combination. As a strontium material, bis (dipivaloylmethanato) strontium, diethoxystrontium, bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) strontium, bis (pentamethyl) It is possible to exemplify cyclopentadienyl) strontium and the like. In addition, in the case of producing a Group 4 metal-containing composite thin film by the CVD method or the ALD method, even if the Group 4 metal complex (1) of the present invention and other metal materials are separately supplied into the reaction chamber, they are mixed. You may supply it after that.

  A high-performance semiconductor device with improved reliability and storage capacity by using the Group 4 metal-containing thin film produced by the method for producing a Group 4 metal-containing thin film of the present invention as a component, or high reflection preventing ability Can be produced, a transparent conductive film having excellent conductivity and transparency, a highly efficient photocatalyst, and the like. Examples of semiconductor devices include semiconductor storage devices such as DRAMs, FeRAMs, ReRAMs, and flash memories, and field effect transistors. As these constituent members, a high dielectric film of DRAM, a ferroelectric film of FeRAM, a gate insulating film of a transistor, etc. can be exemplified.

  The Group 4 metal complex (1) of the present invention has high thermal stability and an appropriate vapor pressure, and by using this as a material, a Group 4 containing thin film can be produced.

FIG. 2 is a view showing DSC of triisopropoxy (η ⁵ -2, 3,4,5- tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium obtained in Example 1. FIG. 2 is a graph showing a TG of triisopropoxy ( ^{5 5} -2, 3,4,5-tetramethyl-1- (dimethylamino) dimethylsilyloxycyclopentadienyl) titanium obtained in Example 1. It illustrates the DSC of triisopropoxy (eta ^{5-2,3,4,5-tetramethyl-1-trimethylsilyloxy} cyclopentadienyl) titanium obtained in Example 2. It shows a TG of triisopropoxy (eta ^{5-2,3,4,5-tetramethyl-1-trimethylsilyloxy} cyclopentadienyl) titanium obtained in Example 2. FIG. 16 is a view showing DSC of tri-tert-butoxy (η ⁵ -2, 3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienyl) zirconium obtained in Example 5. Shows a TG of tri -tert- butoxy (eta ^{5-2,3,4,5-tetramethyl-1-trimethylsilyloxy} cyclopentadienyl) zirconium obtained in Example 5. It illustrates the DSC of tri -tert- butoxy (eta ^{5-2,3,4,5-tetramethyl-1-trimethylsilyloxy} cyclopentadienyl) hafnium obtained in Example 6. Shows a TG of tri -tert- butoxy (eta ^{5-2,3,4,5-tetramethyl-1-trimethylsilyloxy} cyclopentadienyl) hafnium obtained in Example 6. It illustrates the DSC of triisopropoxy (eta ^{5-2,3,4,5-tetramethyl-1-triethylsilyloxy-cyclopentadienyl)} titanium obtained in Example 12. It shows a TG of triisopropoxy (eta ^{5-2,3,4,5-tetramethyl-1-triethylsilyloxy-cyclopentadienyl)} titanium obtained in Example 12. It is a figure which shows the CVD apparatus used in Example 14 and 15.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. All experimental procedures were performed under an argon atmosphere. In the present specification, Me, Et, Pr, ⁱ Pr, Bu, ⁱ Bu, ^s Bu, ^t Bu, Pe, ^t Pe, ⁿ Pe, ^c Pe and Cy are each a methyl group, an ethyl group and a propyl group. And an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a tert-pentyl group, a neopentyl group, a cyclopentyl group and a cyclohexyl group.

  Reference Example 1

３−メチル−２−シクロペンテノン８．１８ｇ（８５．１ｍｍｏｌ）及びトリエチルアミン９．４７ｇ（９３．６ｍｍｏｌ）をヘキサン１００ｍＬに溶かし、トリフルオロメタンスルホキシ（トリメチル）シラン１８．９１ｇ（８５．１ｍｍｏｌ）を氷冷条件下で滴下した。その後、室温で２時間撹拌した。生成した不溶物をセライトを用いてろ別した後、ろ液を減圧下で濃縮した。得られた粗生成物を減圧蒸留（留出温度５９−６０℃、背圧１．１×１０^３Ｐａ）することにより、１−メチル−３−トリメチル シリルオキシ−１，３−シクロペンタジエン１０．９７ｇを無色液体として得た。収率７７％。
^１Ｈ ＮＭＲ（５００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：６．０６（ｍ，１Ｈ），５．０９（ｍ，１Ｈ），２．６４（ｍ，２Ｈ），１．７９（ｓ，３Ｈ），０．２１（ｓ，９Ｈ）．
参考例２

8.18 g (85.1 mmol) of 3-methyl-2-cyclopentenone and 9.47 g (93.6 mmol) of triethylamine are dissolved in 100 mL of hexane, and 18.91 g (85.1 mmol) of trifluoromethanesulfoxy (trimethyl) silane is dissolved It was added dropwise under ice-cold conditions. Then, it stirred at room temperature for 2 hours. The resulting insolubles were filtered off using Celite, and the filtrate was concentrated under reduced pressure. The crude product obtained is distilled under reduced pressure (distillation temperature 59-60 ° C., back pressure 1.1 × 10 ³ Pa) to give 10.97 g of 1-methyl-3-trimethylsilyloxy-1,3-cyclopentadiene. Was obtained as a colorless liquid. 77% yield.
¹ H NMR (500 MHz, C ₆ D ₆ , δ / ppm): 6.06 (m, 1 H), 5.09 (m, 1 H), 2.64 (m, 2 H), 1.79 (s, 3 H) ), 0.21 (s, 9H).
Reference Example 2

ジイソプロピルアミン２０．０ｇ（１９８ｍｍｏｌ）をＴＨＦ６０ｍＬに溶かし、−７０℃においてＢｕＬｉヘキサン溶液（２．６５Ｍ，７３ｍＬ）を加え、室温で１時間撹拌することによりリチウムジイソプロピルアミド（ＬＤＡ）溶液を調製した。別の容器に２，３，４，５−テトラメチル−２−シクロペンテノン２６．０ｇ（１８８ｍｍｏｌ）をヘキサン１００ｍＬに溶かした溶液を調製し、該ＬＤＡ溶液を−７０℃にて投入した。投入終了後、室温で１４時間撹拌した。反応液を減圧下で濃縮した後、ヘキサン１００ｍＬ及びＴＨＦ１００ｍＬを加え、０℃に冷やしてクロロトリメチルシラン２１．１ｇ（１９４ｍｍｏｌ）を投入した。室温で１時間撹拌した後、セライトろ過により不溶物をろ別した。ろ液を減圧下で濃縮し、減圧蒸留（留出温度７２−７３℃、背圧６．０×１０^２Ｐａ）することにより、１，３，４，５−テトラメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン３５．７ｇを淡黄色液体として得た。収率９１％。
^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３，δ／ｐｐｍ）：２．４４（ｑ，Ｊ＝７．６Ｈｚ，１Ｈ），１．７９（ｓ，３Ｈ），１．７３（ｓ，３Ｈ），１．６９（ｓ，３Ｈ），１．００（ｄ，Ｊ＝７．６Ｈｚ，３Ｈ），０．２０（ｓ，９Ｈ）．
参考例３

A solution of lithium diisopropylamide (LDA) was prepared by dissolving 20.0 g (198 mmol) of diisopropylamine in 60 mL of THF, adding BuLi hexane solution (2.65 M, 73 mL) at -70 ° C and stirring at room temperature for 1 hour. In a separate container, a solution of 26.0 g (188 mmol) of 2,3,4,5-tetramethyl-2-cyclopentenone in 100 mL of hexane was prepared, and the LDA solution was charged at -70 ° C. After the addition was completed, the mixture was stirred at room temperature for 14 hours. The reaction solution was concentrated under reduced pressure, 100 mL of hexane and 100 mL of THF were added, cooled to 0 ° C., and 21.1 g (194 mmol) of chlorotrimethylsilane was added. After stirring at room temperature for 1 hour, insolubles were filtered off by Celite filtration. The filtrate is concentrated under reduced pressure and distilled under reduced pressure (distillation temperature 72-73 ° C., back pressure 6.0 × 10 ² Pa) to obtain 1,3,4,5-tetramethyl-2-trimethylsilyloxy- 35.7 g of 1,3-cyclopentadiene was obtained as a pale yellow liquid. 91% yield.
¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.44 (q, J = 7.6 Hz, 1 H), 1.79 (s, 3 H), 1.73 (s, 3 H), 1.69 (S, 3 H), 1.00 (d, J = 7.6 Hz, 3 H), 0.20 (s, 9 H).
Reference Example 3

ジイソプロピルアミン１８．９ｇ（１８７ｍｍｍｏｌ）をＴＨＦ３０ｍＬに溶かし、−７０℃においてＢｕＬｉヘキサン溶液（２．６５Ｍ，６４ｍＬ）を加え、室温で１時間撹拌することによりリチウムジイソプロピルアミド（ＬＤＡ）溶液を調製した。別の容器に２，３，４，５−テトラメチル−２−シクロペンテノン２２．６ｇ（１６４ｍｍｏｌ）をヘキサン６０ｍＬに溶かした溶液を調製し、該ＬＤＡ溶液を−７０℃にて投入した。投入終了後、室温で２４時間撹拌した。反応液を減圧下で濃縮した後、ヘキサン１００ｍＬ及びＴＨＦ５０ｍＬを加え、さらにクロロトリエチルシラン２４．９ｇ（１６５ｍｍｏｌ）を投入した。室温で２時間撹拌した後、セライトろ過により不溶物をろ別した。ろ液を減圧下で濃縮し、減圧蒸留（留出温度５７℃、背圧２．３×１０^２Ｐａ）することにより、１，３，４，５−テトラメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン３４．２ｇを無色液体として得た。収率８３％。
^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３，δ／ｐｐｍ）：２．４２（ｑ，Ｊ＝７．６Ｈｚ，１Ｈ），１．７９（ｓ，３Ｈ），１．７５（ｓ，３Ｈ），１．７１（ｓ，３Ｈ），０．９９（ｔ，Ｊ＝８．０Ｈｚ，９Ｈ），０．９８（ｄ，Ｊ＝７．６Ｈｚ，３Ｈ），０．７０（ｑ，Ｊ＝８．０Ｈｚ，６Ｈ）．
参考例４

A solution of lithium diisopropylamide (LDA) was prepared by dissolving 18.9 g (187 mmol) of diisopropylamine in 30 mL of THF, adding BuLi hexane solution (2.65 M, 64 mL) at -70 ° C and stirring at room temperature for 1 hour. In a separate container, a solution of 22.6 g (164 mmol) of 2,3,4,5-tetramethyl-2-cyclopentenone in 60 mL of hexane was prepared, and the LDA solution was charged at -70 ° C. After the addition was completed, the mixture was stirred at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, 100 mL of hexane and 50 mL of THF were added, and 24.9 g (165 mmol) of chlorotriethylsilane was further added. After stirring at room temperature for 2 hours, insolubles were filtered off by Celite filtration. The filtrate is concentrated under reduced pressure and distilled under reduced pressure (distillation temperature 57 ° C., back pressure 2.3 × 10 ² Pa) to obtain 1,3,4,5-tetramethyl-2-trimethylsilyloxy-1, 34.2 g of 3-cyclopentadiene were obtained as a colorless liquid. 83% yield.
¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.42 (q, J = 7.6 Hz, 1 H), 1.79 (s, 3 H), 1.75 (s, 3 H), 1.71 (S, 3 H), 0.99 (t, J = 8.0 Hz, 9 H), 0.98 (d, J = 7.6 Hz, 3 H), 0.70 (q, J = 8.0 Hz, 6 H) .
Reference Example 4

ジイソプロピルアミン１７．２ｇ（１７０ｍｍｏｌ）をＴＨＦ４０ｍＬに溶かし、−７０℃においてブチルリチウムのヘキサン溶液（２．６５Ｍ、６０．０ｍＬ）を加えた後、室温で１５分間撹拌することによりリチウムジイソプロピルアミド溶液を調製した。別の容器に２，３，４，５−テトラメチル−２−シクロペンテノン２１．３ｇ（１５４ｍｍｏｌ）及びＴＨＦ５０ｍＬを加えて−７０℃に冷却し、該リチウムジイソプロピルアミド溶液を加えた。室温で６時間撹拌した後、減圧濃縮した。残渣にＴＨＦ５０ｍＬ及びヘキサン５０ｍＬを加えて−７０℃に冷却後、クロロ（ｔｅｒｔ−ブチル）ジメチルシラン２６．４ｇ（１７５ｍｍｏｌ）のヘキサン（２０ｍＬ）溶液を加え、室温で２時間撹拌した。生成した不溶物をセライトを用いてろ別した後、ろ液を減圧下で濃縮した。得られた粘性液体を減圧蒸留（留出温度７２℃、背圧６．０×１０^１Ｐａ）することにより、１，３，４，５−テトラメチル−２−ｔｅｒｔ−ブチルジメチルシリルオキシ−１，３−シクロペンタジエン３０．４ｇを無色液体として得た。収率７８％。
^１Ｈ ＮＭＲ（５００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：２．３９（ｑ，Ｊ＝７．３Ｈｚ，１Ｈ），１．８１（ｓ，３Ｈ），１．８０（ｓ，３Ｈ），１．７４（ｓ，３Ｈ），１．０６（ｓ，９Ｈ），０．９８（ｄ，Ｊ＝７．３Ｈｚ，３Ｈ），０．１５（ｓ，６Ｈ）．
^１３Ｃ ＮＭＲ（１２５ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：１４９．６，１３８．０，１３１．５，１１８．０，４７．８，２６．２，１８．６，１４．８，１２．１，１０．９，１０．５，−３．６．
参考例５

Dissolve 17.2 g (170 mmol) of diisopropylamine in 40 mL of THF, add a solution of butyllithium in hexane (2.65 M, 60.0 mL) at -70 ° C, and stir at room temperature for 15 minutes to prepare a lithium diisopropylamide solution. did. In a separate container, 21.3 g (154 mmol) of 2,3,4,5-tetramethyl-2-cyclopentenone and 50 mL of THF were added and cooled to -70 ° C., and the lithium diisopropylamide solution was added. After stirring at room temperature for 6 hours, it was concentrated under reduced pressure. After 50 mL of THF and 50 mL of hexane were added to the residue and cooled to −70 ° C., a solution of 26.4 g (175 mmol) of chloro (tert-butyl) dimethylsilane in hexane (20 mL) was added and stirred at room temperature for 2 hours. The resulting insolubles were filtered off using Celite, and the filtrate was concentrated under reduced pressure. The obtained viscous liquid is distilled under reduced pressure (distillation temperature 72 ° C., back pressure 6.0 × 10 ¹ Pa) to obtain 1,3,4,5-tetramethyl-2-tert-butyldimethylsilyloxy-1 30.4 g of 3-cyclopentadiene was obtained as a colorless liquid. Yield 78%.
¹ H NMR (500 MHz, C ₆ D ₆ , δ / ppm): 2.39 (q, J = 7.3 Hz, 1 H), 1.81 (s, 3 H), 1.80 (s, 3 H), 1 .74 (s, 3 H), 1.06 (s, 9 H), 0.98 (d, J = 7.3 Hz, 3 H), 0.15 (s, 6 H).
¹³ C NMR (125 MHz, C ₆ D ₆ , δ / ppm): 149.6, 138.0, 131.5, 118.0, 47.8, 26.2, 18.6, 14.8, 12. 1, 10.9, 10.5, -3.6.
Reference Example 5

ジクロロジメチルシラン１２．６ｇ（９７．９ｍｍｏｌ）にビス（ジメチルアミノ）ジメチルシラン１４．３ｇ（９７．９ｍｍｏｌ）を加え、室温で１４時間撹拌した。生成した少量の不溶物をグラスフィルター（Ｇ４）を用いてろ別することにより、クロロ（ジメチルアミノ）ジメチルシラン２６．３ｇを無色液体として得た。収量９７％。
^１Ｈ ＮＭＲ（５００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：２．２８（ｓ，６Ｈ），０．２８（ｓ，６Ｈ）．
^１３Ｃ ＮＭＲ（１２５ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：３７．１，１．４．
ジイソプロピルアミン１９．０ｇ（１８８ｍｍｏｌ）をＴＨＦ６０ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、７０．０ｍＬ）を加えた。室温で２時間撹拌した後、減圧濃縮した。残渣にＴＨＦ５０ｍＬ及びヘキサン５０ｍＬを加えて−７０に冷却後、クロロ（ジメチルアミノ）ジメチルシラン２６．３ｇ（１９１ｍｍｏｌ）のヘキサン（２０ｍＬ）溶液を加え、室温で２時間撹拌した。生成した不溶物をセライトを用いてろ別した後、ろ液を減圧下で濃縮した。得られた粘性液体を減圧蒸留（留出温度９０−９２℃、背圧６．１×１０^２Ｐａ）することにより、１，３，４，５−テトラメチル−２−（ジメチルアミノ）ジメチルシリルオキシ−１，３−シクロペンタジエンを黄色液体として得た（収量３６．２ｇ，収率８３％）。
^１Ｈ ＮＭＲ（５００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：２．４６（ｓ，６Ｈ），２．４１（ｑ，Ｊ＝７．６Ｈｚ，１Ｈ），１．８４（ｓ，３Ｈ），１．８２（ｓ，３Ｈ），１．７６（ｓ，３Ｈ），１．００（ｄ，Ｊ＝７．６Ｈｚ，３Ｈ），０．２３（ｓ、６Ｈ）．
^１３Ｃ ＮＭＲ（１２５ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：１４９．７，１３７．７，１３１．７，１１８．０，４７．７，３７．７，１４．８，１２．１，１０．４，１０．１，−２．２．
実施例１

To 12.6 g (97.9 mmol) of dichlorodimethylsilane, 14.3 g (97.9 mmol) of bis (dimethylamino) dimethylsilane was added, and the mixture was stirred at room temperature for 14 hours. A small amount of generated insoluble matter was filtered off using a glass filter (G4) to obtain 26.3 g of chloro (dimethylamino) dimethylsilane as a colorless liquid. Yield 97%.
¹ H NMR (500 MHz, C ₆ D ₆ , δ / ppm): 2.28 (s, 6 H), 0.28 (s, 6 H).
¹³ C NMR (125 MHz, C ₆ D ₆ , δ / ppm): 37.1, 1.4.
19.0 g (188 mmol) of diisopropylamine was dissolved in 60 mL of THF, and a hexane solution (2.65 M, 70.0 mL) of butyllithium was added at -70 ° C. After stirring at room temperature for 2 hours, it was concentrated under reduced pressure. After 50 mL of THF and 50 mL of hexane were added to the residue and cooled to -70, a solution of 26.3 g (191 mmol) of chloro (dimethylamino) dimethylsilane in hexane (20 mL) was added and stirred at room temperature for 2 hours. The resulting insolubles were filtered off using Celite, and the filtrate was concentrated under reduced pressure. The obtained viscous liquid is distilled under reduced pressure (distillation temperature 90-92 ° C., back pressure 6.1 × 10 ² Pa) to obtain 1,3,4,5-tetramethyl-2- (dimethylamino) dimethylsilyl Oxy-1,3-cyclopentadiene was obtained as a yellow liquid (yield 36.2 g, 83%).
¹ H NMR (500 MHz, C ₆ D ₆ , δ / ppm): 2.46 (s, 6 H), 2.41 (q, J = 7.6 Hz, 1 H), 1.84 (s, 3 H), 1 . 82 (s, 3 H), 1. 76 (s, 3 H), 1.00 (d, J = 7.6 Hz, 3 H), 0.23 (s, 6 H).
¹³ C NMR (125 MHz, C ₆ D ₆ , δ / ppm): 149.7, 137.7, 131.7, 118.0, 47.7, 37.7, 14.8, 12.1, 10. 4, 10.1, -2.2.
Example 1

テトライソプロポキシチタン８．８８ｇ（３１．２ｍｍｏｌ）をトルエン１０ｍＬに溶かし、四塩化チタンのトルエン溶液（１．０５Ｍ）９．９ｍＬ（１０．４ｍｍｏｌ）を加えて２２時間撹拌することにより、クロロトリイソプロポキシチタン溶液を調製した。これとは別途に、ジイソプロピルアミン４．９２ｇ（４８．６ｍｍｏｌ）をＴＨＦ５ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、１６．５ｍＬ）を加えて室温で２時間撹拌することにより、ＬＤＡ溶液を調製した。参考例５で合成した１，３，４，５−テトラメチル−２−（ジメチルアミノ）ジメチルシリルオキシ−１，３−シクロペンタジエン１０．２ｇ（４２．６ｍｍｏｌ）のＴＨＦ（５ｍＬ）溶液にＬＤＡ溶液を加え、３時間加熱還流することにより、リチウム［（２，３，４，５−テトラメチル−１−（ジメチルアミノ）ジメチルシリルオキシ）シクロペンタジエニド］を調製した。これをクロロトリイソプロポキシチタン溶液に加え、室温で２時間撹拌した。減圧下で濃縮した後、ヘキサン２５ｍＬを加え、不溶物をセライトを用いてろ別した。ろ液を減圧濃縮したのち、減圧蒸留（留出温度１０５−１０８℃、背圧３．８×１０^１Ｐａ）することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−（ジメチルアミノ）ジメチルシリルオキシシクロペンタジエニル）チタンを黄色液体として得た（収量１２．２ｇ，収率６３％）。
^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３，δ／ｐｐｍ）：４．６１（ｓｅｐｔ，Ｊ＝６．１Ｈｚ，３Ｈ），２．５２（ｓ，６Ｈ），１．９４（ｓ，６Ｈ），１．８９（ｓ，６Ｈ），１．１０（ｄ，Ｊ＝６．１Ｈｚ，１８Ｈ），０．１８（ｓ，６Ｈ）．
実施例２

By dissolving 8.88 g (31.2 mmol) of tetraisopropoxy titanium in 10 mL of toluene, and adding 9.9 mL (10.4 mmol) of a toluene solution of titanium tetrachloride (1.05 M) and stirring for 22 hours, chlorotriiso A propoxy titanium solution was prepared. Separately, dissolve 4.92 g (48.6 mmol) of diisopropylamine in 5 mL of THF, add a solution of butyllithium in hexane (2.65 M, 16.5 mL) at -70 ° C, and stir at room temperature for 2 hours. Then, an LDA solution was prepared. LDA solution of a solution of 10.2 g (42.6 mmol) of 1,3,4,5-tetramethyl-2- (dimethylamino) dimethylsilyloxy-1,3-cyclopentadiene synthesized in Reference Example 5 in THF (5 mL) Then, lithium [(2,3,4,5-tetramethyl-1- (dimethylamino) dimethylsilyloxy) cyclopentadienide] was prepared by heating under reflux for 3 hours. This was added to the chlorotriisopropoxytitanium solution and stirred at room temperature for 2 hours. After concentration under reduced pressure, 25 mL of hexane was added, and the insoluble matter was filtered off using Celite. The filtrate is concentrated under reduced pressure and then distilled under reduced pressure (distillation temperature 105-108 ° C., back pressure 3.8 × 10 ¹ Pa) to obtain triisopropoxy (η ⁵ -2, ^{3, 4, 5-} tetramethyl) -1- (Dimethylamino) dimethylsilyloxycyclopentadienyl) titanium was obtained as a yellow liquid (yield 12.2 g, 63% yield).
¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 4.61 (sept, J = 6.1 Hz, 3 H), 2.52 (s, 6 H), 1.94 (s, 6 H), 1.89 (S, 6 H), 1. 10 (d, J = 6.1 Hz, 18 H), 0.18 (s, 6 H).
Example 2

ジイソプロピルアミン２．５０ｇ（２４．７ｍｍｏｌ）をＴＨＦ１０ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、９．１ｍＬ）を加えた後、室温で１５分間撹拌することによりＬＤＡ溶液を調製した。別の容器に参考例２で合成した１，３，４，５−テトラメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン４．８４ｇ（２３．０ｍｍｏｌ）及びＴＨＦ５ｍＬを加えて氷冷し、該ＬＤＡ溶液を加えた。その後４時間加熱還流することにより、リチウム（２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニド）を調製した（溶液Ａ）。更に別の容器にクロロトリイソプロポキシチタン５．９９ｇ（２３．０ｍｍｏｌ）及びヘキサン１０ｍＬ、及び溶液Ａを順次加えて室温で１４時間撹拌した。生成した不溶物をセライトろ過によりろ別し、ろ液を減圧下で濃縮した。残った粘性液体を減圧蒸留（留出温度１１３℃、背圧６．３×１０^１Ｐａ）することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニル）チタンを黄色液体として得た（収量３．１８ｇ，収率３２％）。
^１Ｈ ＮＭＲ（５００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：４．８０（ｓｅｐｔ，Ｊ＝６．４Ｈｚ，３Ｈ），２．０７（ｓ，６Ｈ），２．０３（ｓ，６Ｈ），１．２７（ｄ，Ｊ＝６．４Ｈｚ，１８Ｈ），０．１６（ｓ，９Ｈ）．
^１３Ｃ ＮＭＲ（１２５ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：１４２．９，１１６．６，１０９．６，７４．８，２６．８，１１．５，１０．３，０．７．
実施例３

Dissolve 2.50 g (24.7 mmol) of diisopropylamine in 10 mL of THF, add a solution of butyllithium in hexane (2.65 M, 9.1 mL) at -70 ° C, and stir at room temperature for 15 minutes to obtain an LDA solution. Prepared. In a separate container, 4.84 g (23.0 mmol) of 1,3,4,5-tetramethyl-2-trimethylsilyloxy-1,3-cyclopentadiene synthesized in Reference Example 2 and 5 mL of THF were added and ice cooled. LDA solution was added. Then, lithium (2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienide) was prepared by refluxing for 4 hours (solution A). In another container, 5.99 g (23.0 mmol) of chlorotriisopropoxy titanium, 10 mL of hexane, and solution A were sequentially added, and the mixture was stirred at room temperature for 14 hours. The resulting insolubles were filtered off through Celite, and the filtrate was concentrated under reduced pressure. The remaining viscous liquid is distilled under reduced pressure (distillation temperature 113 ° C., back pressure 6.3 × 10 ¹ Pa) to obtain triisopropoxy (η ⁵ -2, 3,4,5-tetramethyl-1-trimethylsilyloxy) Cyclopentadienyl) titanium was obtained as a yellow liquid (yield 3.18 g, 32%).
¹ H NMR (500 MHz, C ₆ D ₆ , δ / ppm): 4.80 (sept, J = 6.4 Hz, 3 H), 2.07 (s, 6 H), 2.03 (s, 6 H), 1 .27 (d, J = 6.4 Hz, 18 H), 0.16 (s, 9 H).
¹³ C NMR (125 MHz, C ₆ D ₆ , δ / ppm): 142.9, 116.6, 109.6, 74.8, 26.8, 11.5, 10.3, 0.7.
Example 3

ジイソプロピルアミン２．９６ｇ（２９．３ｍｍｏｌ）をＴＨＦ３ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、９．５ｍＬ）を加えた後、室温で１５分間撹拌することによりＬＤＡ溶液を調製した。別の容器に参考例４で合成した１，３，４，５−テトラメチル−２−ｔｅｒｔ−ブチルジメチルシリルオキシ−１，３−シクロペンタジエン６．３８ｇ（２５．３ｍｍｏｌ）及びＴＨＦ７ｍＬを加えて氷冷し、該ＬＤＡ溶液を加えた。その後３時間加熱還流することにより、リチウム（２，３，４，５−テトラメチル−１−ｔｅｒｔ−ブチルジメチルシリルオキシシクロペンタジエニド）を調製した（溶液Ａ）。更に別の容器にクロロトリイソプロポキシチタン６．２７ｇ（２４．１ｍｍｏｌ）及びＴＨＦ１０ｍＬ、及び溶液Ａを順次加えて室温で１４時間撹拌した。生成した不溶物をセライトろ過によりろ別し、ろ液を減圧下で濃縮した。残った粘性液体を減圧蒸留（留出温度１０４−１０７℃、背圧１．９×１０^１Ｐａ）することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−ｔｅｒｔ−ブチルジメチルシリルオキシシクロペンタジエニル）チタンを黄色液体として得た（７．１２ｇ、収率６２％）。
^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３，δ／ｐｐｍ）：４．６４（ｓｅｐｔ，Ｊ＝６．１Ｈｚ，３Ｈ），１．９４（ｓ，６Ｈ），１．９０（ｓ，６Ｈ），１．１０（ｄ，Ｊ＝６．１Ｈｚ，１８Ｈ），１．０１（ｓ，９Ｈ），０．１２（ｓ，６Ｈ）．
実施例４

Dissolve 2.96 g (29.3 mmol) of diisopropylamine in 3 mL of THF, add a solution of butyllithium in hexane (2.65 M, 9.5 mL) at -70 ° C, and stir at room temperature for 15 minutes to make the LDA solution Prepared. In a separate container, 6.38 g (25.3 mmol) of 1,3,4,5-tetramethyl-2-tert-butyldimethylsilyloxy-1,3-cyclopentadiene synthesized in Reference Example 4 and 7 mL of THF were added and ice was added. Cool and add the LDA solution. Then, lithium (2,3,4,5-tetramethyl-1-tert-butyldimethylsilyloxycyclopentadienide) was prepared by heating under reflux for 3 hours (solution A). In a further separate vessel, 6.27 g (24.1 mmol) of chlorotriisopropoxy titanium, 10 mL of THF and solution A were sequentially added and stirred at room temperature for 14 hours. The resulting insolubles were filtered off through Celite, and the filtrate was concentrated under reduced pressure. The remaining viscous liquid is distilled under reduced pressure (distillation temperature 104-107 ° C., back pressure 1.9 × 10 ¹ Pa) to obtain triisopropoxy (η ⁵ -2, ^{3, 4, 5-} tetramethyl-1-). tert-Butyldimethylsilyloxycyclopentadienyl) titanium was obtained as a yellow liquid (7.12 g, 62% yield).
¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 4.64 (sept, J = 6.1 Hz, 3 H), 1.94 (s, 6 H), 1.90 (s, 6 H), 1.10 (D, J = 6.1 Hz, 18 H), 1.01 (s, 9 H), 0.12 (s, 6 H).
Example 4

テトラ（ｔｅｒｔ−ブトキシ）チタン５．９７ｇ（１７．５ｍｍｏｌ）をトルエン１０ｍＬに溶かし、四塩化チタン１．１１ｇ（５．８５ｍｍｏｌ）を加えて２２時間撹拌することにより、クロロトリ（ｔｅｒｔ−ブトキシ）チタン溶液を調製した。これとは別途に、参考例１で合成した１−メチル−３−トリメチルシリルオキシ−１，３−シクロペンタジエン４．１０ｇ（２４．４ｍｍｏｌ）のＴＨＦ（１５ｍＬ）溶液を−７０℃に冷却し、ブチルリチウムヘキサン溶液（２．６５Ｍ、９．５ｍＬ）を滴下し、室温で２時間撹拌することにより、リチウム（３−メチル−１−トリメチルシリルオキシシクロペンタジエニド）を調製した。これをクロロトリ（ｔｅｒｔ−ブトキシ）チタン溶液に加え、室温で２時間撹拌した。減圧下で濃縮した後、トルエン１５ｍＬを加え、不溶物をセライトを用いてろ別した。ろ液を減圧濃縮したのち、減圧蒸留（留出温度１００−１０２℃、背圧８．０×１０^１Ｐａ）することにより、トリ−ｔｅｒｔ−ブトキシ（η^５−３−メチル−１−トリメチルシリルオキシシクロペンタジエニル）チタンを黄色液体として得た（収量４．６７ｇ，収率４６％）。
^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３，δ／ｐｐｍ）：５．６３（ｍ，１Ｈ），５．３４（ｍ，１Ｈ），５．３１（ｍ，１Ｈ），２．１０（ｓ，３Ｈ），１．２５（ｓ，２７Ｈ），０．２４（ｓ，９Ｈ）．
実施例５

Chlorotri (tert-butoxy) titanium solution by dissolving 5.97 g (17.5 mmol) of tetra (tert-butoxy) titanium in 10 mL of toluene, adding 1.11 g (5.85 mmol) of titanium tetrachloride and stirring for 22 hours Was prepared. Separately, a solution of 4.10 g (24.4 mmol) of 1-methyl-3-trimethylsilyloxy-1,3-cyclopentadiene synthesized in Reference Example 1 in THF (15 mL) was cooled to -70 ° C., and butyl was added thereto. Lithium (3-methyl-1-trimethylsilyloxycyclopentadienide) was prepared by adding lithium hexane solution (2.65 M, 9.5 mL) dropwise and stirring at room temperature for 2 hours. This was added to chlorotri (tert-butoxy) titanium solution and stirred at room temperature for 2 hours. After concentration under reduced pressure, 15 mL of toluene was added, and the insoluble matter was filtered off using celite. The filtrate is concentrated under reduced pressure and then distilled under reduced pressure (distillation temperature 100-102 ° C., back pressure 8.0 × 10 ¹ Pa) to give tri-tert-butoxy (η ⁵ -3-methyl-1-trimethylsilyloxy). Cyclopentadienyl) titanium was obtained as a yellow liquid (yield 4.67 g, 46%).
¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 5.63 (m, 1 H), 5. 34 (m, 1 H), 5.31 (m, 1 H), 2. 10 (s, 3 H), 1.25 (s, 27 H), 0.24 (s, 9 H).
Example 5

四塩化ジルコニウム１．４８ｇ（６．３５ｍｍｏｌ）をＴＨＦ９ｍＬに溶かし、氷冷下、テトラ（ｔｅｒｔ−ブトキシ）ジルコニウム７．３４ｇ（１９．１ｍｍｏｌ）を加えて２２時間撹拌することにより、クロロトリ（ｔｅｒｔ−ブトキシ）ジルコニウム溶液を調製した。これとは別途に、ジイソプロピルアミン３．０４ｇ（３０．０ｍｍｏｌ）をＴＨＦ３ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、１０．５ｍＬ）を加えて室温で２時間撹拌することにより、ＬＤＡ溶液を調製した。参考例２で合成した１，３，４，５−テトラメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン５．６４ｇ（２６．８ｍｍｏｌ）のＴＨＦ（６ｍＬ）溶液にＬＤＡ溶液を加え、３時間加熱還流することにより、リチウム（２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニド）を調製した。これをクロロトリ（ｔｅｒｔ−ブトキシ）ジルコニウム溶液に加え、室温で１４時間撹拌した。減圧下で濃縮した後、ヘキサン５０ｍＬを加え、不溶物をセライトを用いてろ別した。ろ液を減圧濃縮したのち、減圧蒸留（留出温度１０５℃、背圧１．８×１０^１Ｐａ）することにより、トリ−ｔｅｒｔ−ブトキシ（η^５−２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニル）ジルコニウムを淡黄色液体として得た（収量８．５３ｇ，収率６５％）。この錯体を室温で数時間静置したところ、固化した。
^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３，δ／ｐｐｍ）：１．９９（ｓ，６Ｈ），１．９３（ｓ，６Ｈ），１．２０（ｓ，２７Ｈ），０．１９（ｓ，９Ｈ）．
^１３Ｃ ＮＭＲ（１００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：１４２．３，１１３．１，１０６．４，７５．５，３３．２，１１．４，１０．２，０．８．
実施例６

By dissolving 1.48 g (6.35 mmol) of zirconium tetrachloride in 9 mL of THF, and adding 7.34 g (19.1 mmol) of tetra (tert-butoxy) zirconium under ice-cooling and stirring for 22 hours, chlorotri (tert-butoxy) is dissolved. ) A zirconium solution was prepared. Separately, dissolve 3.04 g (30.0 mmol) of diisopropylamine in 3 mL of THF, add a hexane solution (2.65 M, 10.5 mL) of butyllithium at -70 ° C, and stir at room temperature for 2 hours. Then, an LDA solution was prepared. The LDA solution was added to a solution of 5.64 g (26.8 mmol) of 1,3,4,5-tetramethyl-2-trimethylsilyloxy-1,3-cyclopentadiene synthesized in Reference Example 2 in THF (6 mL), and 3 hours Lithium (2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienide) was prepared by heating under reflux. This was added to chlorotri (tert-butoxy) zirconium solution and stirred at room temperature for 14 hours. After concentration under reduced pressure, 50 mL of hexane was added, and the insoluble matter was filtered off using Celite. The filtrate is concentrated under reduced pressure and then distilled under reduced pressure (distillation temperature 105 ° C., back pressure 1.8 × 10 ¹ Pa) to give tri-tert-butoxy (η ⁵ -2, ^{3, 4, 5-} tetramethyl) -1-trimethylsilyloxycyclopentadienyl) zirconium was obtained as a pale yellow liquid (yield 8.53 g, 65%). The complex solidified upon standing at room temperature for several hours.
¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 1.99 (s, 6 H), 1.93 (s, 6 H), 1. 20 (s, 27 H), 0.19 (s, 9 H).
¹³ C NMR (100 MHz, C ₆ D ₆ , δ / ppm): 142.3, 113.1, 106.4, 75.5, 33.2, 11.4, 10.2, 0.8.
Example 6

四塩化ジハフニウム２．１０ｇ（６．５７ｍｍｏｌ）をＴＨＦ１０ｍＬに溶かし、氷冷下、テトラ（ｔｅｒｔ−ブトキシ）ハフニウム９．６５ｇ（２０．５ｍｍｏｌ）を加えて１２時間撹拌することにより、クロロトリ（ｔｅｒｔ−ブトキシ）ハフニウム溶液を調製した。これとは別途に、ジイソプロピルアミン３．０４ｇ（３０．０ｍｍｏｌ）をＴＨＦ３ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、１０．５ｍＬ）を加えて室温で２時間撹拌することにより、ＬＤＡ溶液を調製した。参考例２で合成した１，３，４，５−テトラメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン５．７５ｇ（２７．３ｍｍｏｌ）のＴＨＦ（４ｍＬ）溶液にＬＤＡ溶液を加え、３時間加熱還流することにより、リチウム（２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニド）を調製した。これをクロロトリ（ｔｅｒｔ−ブトキシ）ジルコニウム溶液に加え、室温で１４時間撹拌した。減圧下で濃縮した後、ヘキサン５０ｍＬを加え、不溶物をセライトを用いてろ別した。ろ液を減圧濃縮したのち、減圧蒸留（留出温度１０８−１１４℃、背圧２．６×１０^１Ｐａ）することにより、トリ−ｔｅｒｔ−ブトキシ（η^５−２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニル）ハフニウムを黄色液体として得た（収量８．３１ｇ，収率５１％）。
^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３，δ／ｐｐｍ）：２．０１（ｓ，６Ｈ），１．９４（ｓ，６Ｈ），１．２０（ｓ，２７Ｈ），０．１８（ｓ，９Ｈ）．
^１３Ｃ ＮＭＲ（１００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：１４１．５，１１２．２，１０５．１，７５．３，３３．５，１１．４，１０．１，０．８．
実施例７

Chlorotri (tert-butoxy) is obtained by dissolving 2.10 g (6.57 mmol) of dihafnium tetrachloride in 10 mL of THF, adding 9.65 g (20.5 mmol) of tetra (tert-butoxy) hafnium under ice-cooling and stirring for 12 hours. ) A hafnium solution was prepared. Separately, dissolve 3.04 g (30.0 mmol) of diisopropylamine in 3 mL of THF, add a hexane solution (2.65 M, 10.5 mL) of butyllithium at -70 ° C, and stir at room temperature for 2 hours. Then, an LDA solution was prepared. The LDA solution was added to a solution of 5.75 g (27.3 mmol) of 1,3,4,5-tetramethyl-2-trimethylsilyloxy-1,3-cyclopentadiene synthesized in Reference Example 2 in THF (4 mL) for 3 hours. Lithium (2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienide) was prepared by heating under reflux. This was added to chlorotri (tert-butoxy) zirconium solution and stirred at room temperature for 14 hours. After concentration under reduced pressure, 50 mL of hexane was added, and the insoluble matter was filtered off using Celite. The filtrate is concentrated under reduced pressure and then distilled under reduced pressure (distillation temperature 108-114 ° C., back pressure 2.6 × 10 ¹ Pa) to give tri-tert-butoxy (η ⁵ -2, ^{3, 4, 5-)} Tetramethyl-1-trimethylsilyloxycyclopentadienyl) hafnium was obtained as a yellow liquid (yield 8.31 g, 51%).
¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.01 (s, 6 H), 1.94 (s, 6 H), 1. 20 (s, 27 H), 0.18 (s, 9 H).
¹³ C NMR (100 MHz, C ₆ D ₆ , δ / ppm): 141.5, 112.2, 105.1, 75.3, 33.5, 11.4, 10.1, 0.8.
Example 7

ジイソプロピルアミン２．１８ｇ（２１．５ｍｍｏｌ）をＴＨＦ５ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、７．７ｍＬ）を加えた後、室温で３０分間撹拌することによりＬＤＡ溶液を調製した。別の容器に、参考例２で合成した１，３，４，５−テトラメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン４．４０ｇ（２０．９ｍｍｏｌ）及びＴＨＦ１０ｍＬを加えて氷冷し、該ＬＤＡ溶液を加えた。その後５時間加熱還流することにより、リチウム（２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニド）を調製した（溶液Ａ）。更に別の容器にテトライソプロポキシチタン５．７７ｇ（２０．３ｍｍｏｌ）、ヘキサン１５ｍＬ、及び溶液Ａを順次加えて室温で１６時間撹拌した。溶媒を減圧下で留去することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−リチウムオキシシクロペンタジエニル）チタンを黄色固体として得た（収量７．４７ｇ、収率１００％）。
^１Ｈ ＮＭＲ（４００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：４．５７（ｓｅｐｔ，Ｊ＝６．１Ｈｚ，３Ｈ），２．２７（ｓ，６Ｈ），２．１３（ｓ，６Ｈ），１．１５（ｄ，Ｊ＝６．１Ｈｚ，１８Ｈ）．
^１３Ｃ ＮＭＲ（１００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：１６４．３，１１７．０，１１０．９，７３．１，２６．２，１２．０，９．８．
実施例８

Dissolve 2.18 g (21.5 mmol) of diisopropylamine in 5 mL of THF, add a solution of butyllithium in hexane (2.65 M, 7.7 mL) at -70 ° C, and stir at room temperature for 30 minutes to obtain an LDA solution. Prepared. In a separate container, 4.40 g (20.9 mmol) of 1,3,4,5-tetramethyl-2-trimethylsilyloxy-1,3-cyclopentadiene synthesized in Reference Example 2 and 10 mL of THF were added and ice cooled. The LDA solution was added. Then, lithium (2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienide) was prepared by heating under reflux for 5 hours (solution A). Furthermore, 5.77 g (20.3 mmol) of tetraisopropoxy titanium, 15 mL of hexane and solution A were sequentially added to another container, and the mixture was stirred at room temperature for 16 hours. The solvent was distilled off under reduced pressure to obtain triisopropoxy (η ⁵ -2, ^{3, 4, 5-} tetramethyl-1-lithium oxycyclopentadienyl) titanium as a yellow solid (yield 7.47 g , Yield 100%).
¹ H NMR (400 MHz, C ₆ D ₆ , δ / ppm): 4.57 (sept, J = 6.1 Hz, 3 H), 2.27 (s, 6 H), 2.13 (s, 6 H), 1 .15 (d, J = 6.1 Hz, 18 H).
¹³ C NMR (100 MHz, C ₆ D ₆ , δ / ppm): 164.3, 117.0, 110.9, 73.1, 26.2, 12.0, 9.8.
Example 8

イソプロピルアルコール４６２ｍｇ（７．６９ｍｍｏｌ）をヘキサン３ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、２．９ｍＬ）を加えて室温で１時間撹拌することにより、リチウムイソプロポキシド溶液を調製した。実施例２で合成したトリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニル）チタン３．２９ｇ（７．５７ｍｍｏｌ）をＴＨＦ１０ｍＬに溶かし、氷浴を用いて冷やしながら、リチウムイソプロポキシド溶液を加え、室温で１５時間撹拌した。減圧下で溶媒を留去することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−リチウムオキシシクロペンタジエニル）チタンを黄色固体として得た（収量２．７８ｇ、収率９９％）。

Lithium isopropoxide solution by dissolving 462 mg (7.69 mmol) of isopropyl alcohol in 3 mL of hexane, adding a hexane solution (2.65 M, 2.9 mL) of butyllithium at -70 ° C and stirring at room temperature for 1 hour Was prepared. Dissolved triisopropoxy synthesized in Example 2 (eta ^{5-2,3,4,5-tetramethyl-1-trimethylsilyloxy} cyclopentadienyl) titanium 3.29g of (7.57 mmol) in 10 mL of THF, the ice bath While cooling with use, lithium isopropoxide solution was added and stirred at room temperature for 15 hours. The solvent was distilled off under reduced pressure to obtain triisopropoxy (η ⁵ -2, 3,4,5- tetramethyl-1-lithium oxycyclopentadienyl) titanium as a yellow solid (yield 2.78 g , Yield 99%).

  Example 9

実施例２で合成したトリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニル）チタン３．６６ｇ（８．４２ｍｍｏｌ）をＴＨＦ１０ｍＬに溶かし、氷浴を用いて冷やしながら、ナトリウム−ｔｅｒｔ−ブトキシド８１０ｍｇ（８．４３ｍｍｏｌ）を加え、室温で１５時間撹拌した。減圧下で溶媒を留去することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−ナトリウムオキシシクロペンタジエニル）チタンを黄色固体として得た（収量３．２３ｇ、収率９９％）。
^１Ｈ ＮＭＲ（４００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：４．６６（ｓｅｐｔ，Ｊ＝６．０Ｈｚ，３Ｈ），２．２４（ｓ，６Ｈ），２．１３（ｓ，６Ｈ），１．２２（ｄ，Ｊ＝６．０Ｈｚ，１８Ｈ）．
^１３Ｃ ＮＭＲ（１００ＭＨｚ，Ｃ_６Ｄ_６，δ／ｐｐｍ）：１６４．８，１１６．７，１０８．３，７２．８，２６．８，１２．２，１１．１．
実施例１０

Dissolved triisopropoxy synthesized in Example 2 (eta ^{5-2,3,4,5-tetramethyl-1-trimethylsilyloxy} cyclopentadienyl) titanium 3.66g of (8.42 mmol) in 10 mL of THF, the ice bath While cooling with use, 810 mg (8.43 mmol) of sodium-tert-butoxide was added and stirred at room temperature for 15 hours. The solvent was distilled off under reduced pressure to obtain triisopropoxy (η ⁵ -2, 3,4,5- tetramethyl-1-sodium oxycyclopentadienyl) titanium as a yellow solid (yield: 3.23 g , Yield 99%).
¹ H NMR (400 MHz, C ₆ D ₆ , δ / ppm): 4.66 (sept, J = 6.0 Hz, 3 H), 2.24 (s, 6 H), 2.13 (s, 6 H), 1 .22 (d, J = 6.0 Hz, 18 H).
¹³ C NMR (100 MHz, C ₆ D ₆ , δ / ppm): 164.8, 116.7, 108.3, 72.8, 26.8, 12.2, 11.1.
Example 10

ヘキサン３０ｍＬとＴＨＦ１０ｍＬの混合物に、実施例８で合成したトリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−リチウムオキシシクロペンタジエニル）チタン７．４７ｇ（２０．３ｍｍｏｌ）を溶かし、クロロトリメチルシラン２．２４ｇ（２０．６ｍｍｏｌ）を加えて室温で２０時間撹拌した。溶媒を減圧乾固し、ヘキサン４０ｍＬを加え、セライトろ過により不溶物をろ別した。ろ液を減圧濃縮したのち、減圧蒸留（留出温度１１３℃、背圧６．３×１０^１Ｐａ）することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニル）チタンを黄色液体として得た（収量７．０５ｇ，収率８０％）。

Hexane 30mL and the mixture of 10 mL of THF, synthesized triisopropoxy (eta ^{5-2,3,4,5-tetramethyl-1-lithium} titanyl cyclopentadienyl) In Example 8 the titanium 7.47 g (20.3 mmol) Was dissolved, 2.24 g (20.6 mmol) of chlorotrimethylsilane was added, and the mixture was stirred at room temperature for 20 hours. The solvent was evaporated to dryness under reduced pressure, 40 mL of hexane was added, and the insoluble matter was filtered off by celite filtration. The filtrate is concentrated under reduced pressure and then distilled under reduced pressure (distillation temperature 113 ° C., back pressure 6.3 × 10 ¹ Pa) to give triisopropoxy (η ⁵ -2, ^{3, 4, 5-} tetramethyl-1). -Trimethylsilyloxycyclopentadienyl) titanium was obtained as a yellow liquid (yield 7.05 g, 80%).

  Example 11

ヘキサン１０ｍＬとＴＨＦ１０ｍＬの混合物に、実施例９で合成したトリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−ナトリウムオキシシクロペンタジエニル）チタン３．２３ｇ（８．４１ｍｍｏｌ）を溶かし、クロロトリメチルシラン９２０ｍｇ（８．４７ｍｍｏｌ）を加えて室温で６時間撹拌した。溶媒を減圧乾固し、ヘキサン２５ｍＬを加え、セライトろ過により不溶物をろ別した。ろ液を減圧濃縮したのち、減圧蒸留（留出温度１１３℃、背圧６．３×１０^１Ｐａ）することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニル）チタンを黄色液体として得た（収量２．８９ｇ，収率７９％）。

3.23 g (8.41 mmol) of triisopropoxy (η ⁵ -2, 3,4,5- tetramethyl-1-sodium oxycyclopentadienyl) titanium synthesized in Example 9 in a mixture of 10 mL of hexane and 10 mL of THF The solution was dissolved, 920 mg (8.47 mmol) of chlorotrimethylsilane was added, and the mixture was stirred at room temperature for 6 hours. The solvent was evaporated to dryness under reduced pressure, 25 mL of hexane was added, and the insoluble matter was filtered off by celite filtration. The filtrate is concentrated under reduced pressure and then distilled under reduced pressure (distillation temperature 113 ° C., back pressure 6.3 × 10 ¹ Pa) to give triisopropoxy (η ⁵ -2, ^{3, 4, 5-} tetramethyl-1). -Trimethylsilyloxycyclopentadienyl) titanium was obtained as a yellow liquid (yield 2.89 g, 79%).

  Example 12

ジイソプロピルアミン３．４９ｇ（３４．５ｍｍｏｌ）をＴＨＦ８ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、１２．５ｍＬ）を加えた後、室温で３０分間撹拌することによりＬＤＡ溶液を調製した。別の容器に参考例２で合成した１，３，４，５−テトラメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン６．８６ｇ（３２．６ｍｍｏｌ）及びＴＨＦ７ｍＬを加えて氷冷し、該ＬＤＡ溶液を加えた。その後６時間加熱還流することにより、リチウム（２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニド）を調製した（溶液Ａ）。更に別の容器にテトライソプロポキシチタン８．８５ｇ（３１．１ｍｍｏｌ）、ＴＨＦ１０ｍＬ、及び溶液Ａを順次加えて室温で１４時間撹拌した。反応溶液を一部サンプリングしてＮＭＲスペクトルを測定したところ、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−リチウムオキシシクロペンタジエニル）チタンが生成していることが確認された。反応容器を氷浴に浸して冷やしながらクロロトリエチルシラン５．１５ｇ（３４．２ｍｍｏｌ）を滴下し、室温において１時間撹拌した。溶媒を減圧乾固し、ヘキサン１００ｍＬを加え、セライトろ過により不溶物をろ別した。ろ液を減圧濃縮したのち、減圧蒸留（留出温度１１３℃、背圧６．３×１０^１Ｐａ）することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−トリエチルシリルオキシシクロペンタジエニル）チタンを黄色液体として得た（収量１０．６３ｇ，収率７２％）。
^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３，δ／ｐｐｍ）：４．６２（ｓｅｐｔ，Ｊ＝６．０Ｈｚ，３Ｈ），１．９３（ｓ，６Ｈ），１．９０（ｓ，６Ｈ），１．１０（ｄ，Ｊ＝６．０Ｈｚ，１８Ｈ），０．９６（ｔ，Ｊ＝８．０Ｈｚ，９Ｈ），０．６９（ｑ，Ｊ＝８．０Ｈｚ，６Ｈ）．
実施例１３

Dissolve 3.49 g (34.5 mmol) of diisopropylamine in 8 mL of THF, add a solution of butyllithium in hexane (2.65 M, 12.5 mL) at -70 ° C, and stir at room temperature for 30 minutes to obtain an LDA solution. Prepared. In a separate container, 6.86 g (32.6 mmol) of 1,3,4,5-tetramethyl-2-trimethylsilyloxy-1,3-cyclopentadiene synthesized in Reference Example 2 and 7 mL of THF were added and ice cooled. LDA solution was added. Then, lithium (2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienide) was prepared by heating under reflux for 6 hours (solution A). In a further separate vessel, 8.85 g (31.1 mmol) of tetraisopropoxy titanium, 10 mL of THF, and solution A were sequentially added, and the mixture was stirred at room temperature for 14 hours. The reaction solution was measured by NMR spectrum was partially sampled, that triisopropoxy (eta ^{5-2,3,4,5-tetramethyl-1-lithium} titanyl cyclopentadienyl) titanium is generated confirmed. While the reaction vessel was immersed in an ice bath to cool, 5.15 g (34.2 mmol) of chlorotriethylsilane was added dropwise, and the mixture was stirred at room temperature for 1 hour. The solvent was evaporated to dryness under reduced pressure, 100 mL of hexane was added, and the insoluble matter was filtered off by celite filtration. The filtrate is concentrated under reduced pressure and then distilled under reduced pressure (distillation temperature 113 ° C., back pressure 6.3 × 10 ¹ Pa) to give triisopropoxy (η ⁵ -2, ^{3, 4, 5-} tetramethyl-1). -Triethylsilyloxycyclopentadienyl) titanium was obtained as a yellow liquid (yield 10.63 g, 72%).
¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 4.62 (sept, J = 6.0 Hz, 3 H), 1.93 (s, 6 H), 1.90 (s, 6 H), 1.10 (D, J = 6.0 Hz, 18 H), 0.96 (t, J = 8.0 Hz, 9 H), 0.69 (q, J = 8.0 Hz, 6 H).
Example 13

ジイソプロピルアミン８．６９ｇ（８５．９ｍｍｏｌ）をＴＨＦ２５ｍＬに溶かし、−７０℃にてブチルリチウムのヘキサン溶液（２．６５Ｍ、２８．５ｍＬ）を加えた後、室温で３０分間撹拌することによりＬＤＡ溶液を調製した。別の容器に参考例２で合成した１，３，４，５−テトラメチル−２−トリメチルシリルオキシ−１，３−シクロペンタジエン１５．５ｇ（７３．４ｍｍｏｌ）及びＴＨＦ２５ｍＬを加えて氷冷し、該ＬＤＡ溶液を加えた。その後６時間加熱還流することにより、リチウム（２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニド）を調製した（溶液Ａ）。更に別の容器にテトライソプロポキシチタン２０．０ｇ（７０．４ｍｍｏｌ）、ＴＨＦ４５ｍＬ、及び溶液Ａを順次加えて室温で５時間撹拌した。反応溶液を一部サンプリングしてＮＭＲスペクトルを測定したところ、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−リチウムオキシシクロペンタジエニル）チタンが生成していることが確認された。反応容器を氷浴に浸して冷やしながらクロロトリメチルシラン８．３９ｇ（７７．２ｍｍｏｌ）を滴下し、室温において２時間撹拌した。溶媒を減圧乾固し、ヘキサン１００ｍＬを加え、セライトろ過により不溶物をろ別した。ろ液を減圧濃縮したのち、減圧蒸留（留出温度１１３℃、背圧６．３×１０^１Ｐａ）することにより、トリイソプロポキシ（η^５−２，３，４，５−テトラメチル−１−トリメチルシリルオキシシクロペンタジエニル）チタンを黄色液体として得た（収量２３．３９ｇ，収率７６％）。

Dissolve 8.69 g (85.9 mmol) of diisopropylamine in 25 mL of THF, add a solution of butyllithium in hexane (2.65 M, 28.5 mL) at -70 ° C, and stir at room temperature for 30 minutes to obtain an LDA solution. Prepared. In a separate container, 15.5 g (73.4 mmol) of 1,3,4,5-tetramethyl-2-trimethylsilyloxy-1,3-cyclopentadiene synthesized in Reference Example 2 and 25 mL of THF were added and ice cooled. LDA solution was added. Then, lithium (2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienide) was prepared by heating under reflux for 6 hours (solution A). Furthermore, 20.0 g (70.4 mmol) of tetraisopropoxy titanium, 45 mL of THF, and solution A were sequentially added to another container, and the mixture was stirred at room temperature for 5 hours. The reaction solution was measured by NMR spectrum was partially sampled, that triisopropoxy (eta ^{5-2,3,4,5-tetramethyl-1-lithium} titanyl cyclopentadienyl) titanium is generated confirmed. While the reaction vessel was immersed in an ice bath to cool, 8.39 g (77.2 mmol) of chlorotrimethylsilane was added dropwise, and the mixture was stirred at room temperature for 2 hours. The solvent was evaporated to dryness under reduced pressure, 100 mL of hexane was added, and the insoluble matter was filtered off by celite filtration. The filtrate is concentrated under reduced pressure and then distilled under reduced pressure (distillation temperature 113 ° C., back pressure 6.3 × 10 ¹ Pa) to give triisopropoxy (η ⁵ -2, ^{3, 4, 5-} tetramethyl-1). -Trimethylsilyloxycyclopentadienyl) titanium was obtained as a yellow liquid (yield 23.39 g, 76%).

Test Example In order to evaluate the thermal stability of the Group 4 metal complex obtained in Examples 1, 2, 5, 6 and 12, DSC at a temperature rising rate of 10 ° C./min in a container sealed under an argon atmosphere. Was measured. The results are shown in FIGS. 1, 3, 5, 7 and 9, respectively.

  Moreover, in order to evaluate the vaporization characteristic of the group 4 metal complex obtained in Examples 1, 2, 5, 6 and 12, the temperature rising rate is 10 ° C./min in an atmosphere in which argon is circulated at 400 mL / min. The TG was measured under the following conditions. The results are shown in Figures 2, 4, 6, 8 and 10, respectively.

Thin Film Preparation Example (Examples 14 and 15)
A Group 4 metal-containing thin film was produced by a thermal CVD method using the Group 4 metal complex of the present invention as a material. The outline of the apparatus used for thin film preparation is shown in FIG. Argon as a carrier gas and oxygen as a reaction gas were respectively introduced into the reaction chamber. The material supply rate to the reaction chamber can be determined based on a formula of (carrier gas flow rate × vapor pressure of material × total pressure in material container). The pressure in the reaction chamber was adjusted to 0.53 kPa. The substrate used is a silicon wafer with a thermal oxide film, and the film preparation time is 1 hour.

Example 14
A titanium-containing thin film was produced by a thermal CVD method using triisopropoxy (−2 ⁵ 2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium synthesized in Example 2 as a material. . The film preparation conditions are as follows. Material container temperature: 87 ° C., material vapor pressure: 13 Pa, carrier gas (argon) flow rate: 20 sccm, material container total pressure: 13 kPa, material supply rate to reaction chamber: 0.020 sccm, reaction gas (oxygen) flow rate: 60 sccm, dilution gas (argon) flow rate: 220 sccm, total pressure in reaction chamber: 0.53 kPa, substrate temperature: 400 ° C. When the produced film was confirmed by fluorescent X-ray analysis, a characteristic X-ray based on titanium was detected, and it was confirmed that the titanium-containing thin film was deposited.

Example 15
A titanium-containing thin film was produced by a thermal CVD method using triisopropoxy (−2 ⁵ 2,3,4,5-tetramethyl-1-trimethylsilyloxycyclopentadienyl) titanium synthesized in Example 2 as a material. . The film forming conditions are as shown in Example 14, except that the substrate temperature is 250 ° C. When the produced film was confirmed by fluorescent X-ray analysis, a characteristic X-ray based on titanium was detected, and it was confirmed that the titanium-containing thin film was deposited.

Reference Signs List 1 material container 2 constant temperature bath 3 reaction chamber 4 substrate 5 reaction gas 6 dilution gas 7 carrier gas 8 mass flow controller 9 mass flow controller 10 mass flow controller 11 oil rotary pump 12 exhaust

Claims (10)

General formula (1)

(Wherein, M represents a group 4 metal atom. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁵ , R ⁶ And R ⁷ each independently represents an alkyl group having 1 to 8 carbon atoms, R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 6 carbon atoms or di (1 to 3 carbon atoms) Represents an alkyl group of
Group 4 metal complex represented by The group 4 metal complex according to claim ¹ , wherein R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom or a methyl group, and R ⁵ , R ⁶ and R ⁷ are an isopropyl group or a tert-butyl group. The group 4 metal complex according to claim 1 or 2, wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent a methyl group, an ethyl group, a propyl group, a tert-butyl group or a dimethylamino group. General formula (2)

(Wherein, .M ^{X 1} is representing a halogen ^atom, R 5, ^{R 6} and ^{R 7} are ^M in the general formula ^(1), and R 5, ^{R 6} and ^{R 7} respectively the same.)
And a group 4 metal trialkoxide represented by the general formula (3)

^{(Wherein, R 1, R 2, R} 3, R 4, R 8, R 9 and ^{R 10, R 1, R 2, R} 3 in the general formula ^{(1), R 4, R} 8, R 9 and Each is synonymous with R ¹⁰ )
Reacting lithium cyclopentadienide represented by
General formula (1)

(Wherein, M represents a group 4 metal atom. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁵ , R ⁶ And R ⁷ each independently represents an alkyl group having 1 to 8 carbon atoms, R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 6 carbon atoms or di (1 to 3 carbon atoms) Represents an alkyl group of
The manufacturing method of the group 4 metal complex shown by these. General formula (5)

^(.R 1 wherein, AM ¹ is representative of an alkali metal ^{atom, R 2, R 3, R} 4, R 5, R 6 and ^{R 7, R} 1 in the general formula ^{(1), R 2, R} 3, The same as R ⁴ , R ⁵ , R ⁶ and R ⁷ respectively.)
With an alkali metal-titanium complex represented by the general formula (4)
Si (R ⁸ ) (R ⁹ ) (R ¹⁰ ) X ² (4)
(Wherein, ^.R 8, ^{R 9} and ^{R 10 X 2} is representing a halogen atom is a ^R 8, ^{R 9} and ^{R 10} in the general formula (1) the same meanings.)
And reacting a substituted silyl halide represented by the general formula (1 Ti)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently selected from the group consisting of R ¹ , R ² , R ³ , It is synonymous with R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ respectively).
The manufacturing method of the titanium complex shown by these. General formula (5)

^(.R 1 wherein, AM ¹ is representative of an alkali metal ^{atom, R 2, R 3, R} 4, R 5, R 6 and ^{R 7, R} 1 in the general formula ^{(1), R 2, R} 3, The same as R ⁴ , R ⁵ , R ⁶ and R ⁷ respectively.)
An alkali metal-titanium complex represented by General formula (1)

(Wherein, M represents a group 4 metal atom. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁵ , R ⁶ And R ⁷ each independently represents an alkyl group having 1 to 8 carbon atoms, R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 6 carbon atoms or di (1 to 3 carbon atoms) Represents an alkyl group of
A method for producing a Group 4 metal-containing thin film, characterized in that the Group 4 metal complex represented by is vaporized to decompose the Group 4 metal complex on a substrate. The production method according to claim 7, which is a method for producing a group 4 metal-containing thin film by a vapor deposition method based on a chemical reaction. The production method according to any one of claims 7 and 8, which is a method for producing a Group 4 metal-containing thin film by a chemical vapor deposition method. The method according to any one of claims 7 to 9, wherein the Group 4 metal-containing thin film is a Group 4 metal oxide thin film.

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