JP6584150B2 - Cobalt complex and method for producing the same, cobalt-containing thin film and method for producing the same - Google Patents

Description

  The present invention relates to a cobalt complex useful as a raw material for producing a semiconductor element, a method for producing the same, a cobalt-containing thin film produced by using the cobalt complex as a material, and a method for producing the same.

Cobalt has characteristics such as high conductivity, high work function, ability to form conductive silicide, and excellent lattice matching with copper, so it can be used for gate electrodes and sources of semiconductor elements such as transistors. -It has attracted attention as a material for contacts on the diffusion layer in the drain region, copper wiring seed layer / liner layer, and the like. In the next generation semiconductor device, a highly minute and three-dimensional design is adopted for the purpose of further improving the storage capacity and responsiveness. Therefore, in order to use cobalt as a material constituting the next generation semiconductor element, it is necessary to establish a technology for uniformly forming a cobalt-containing thin film having a thickness of several nanometers to several tens of nanometers on a three-dimensional substrate. is needed. Technologies for producing metal thin films on three-dimensional substrates include the use of vapor deposition methods based on chemical reactions such as atomic layer deposition (ALD) and chemical vapor deposition (CVD). It is regarded as promising. CoSi ₂ that has been silicided after the formation of a cobalt film has been studied as a contact on the diffusion layer of the gate electrode and source / drain portion of the next-generation semiconductor device. On the other hand, when cobalt is used as the copper wiring seed layer / liner layer, titanium nitride, tantalum nitride, or the like is expected to be employed as the barrier metal for the underlayer. When silicon or a barrier metal is oxidized during the production of a cobalt-containing thin film, problems such as poor conduction with a transistor due to an increase in resistance value occur. In order to avoid these problems, a material capable of producing a cobalt-containing thin film under conditions that do not use an oxidizing gas such as oxygen or ozone is required.

Non-Patent Document 1, as a compound having a structure similar to the cobalt complex (1) of the present invention, (eta ⁵ - acetyl cyclopentadienyl) (eta ^{4-1,2,3,4-tetraphenyl} pigs - Although 1,3-diene) cobalt is described, the structure is different from the cobalt complex of the present invention. The synthesis method described in this document is based on the reaction of bis (triphenylphosphine) (η ⁵ -acetylcyclopentadienyl) cobalt and diphenylacetylene, and is different from the production method of the present invention. Further, this document does not describe any use of this complex as a material for producing a cobalt-containing thin film.

Journal of Organometallic Chemistry, Vol. 691, 1183 (2006).

  This invention makes it a subject to provide a cobalt complex useful as a material which enables preparation of a cobalt containing thin film on the conditions which do not use oxidizing gas.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the cobalt complex represented by the general formula (1) contains cobalt under conditions in which an oxidizing gas is not used as a reaction gas, particularly in a condition in which a reducing gas is used. The inventors have found that it is useful as a material for producing a thin film, and have completed the present invention.

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

(In the formula, A represents the general formula (2)

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom) or a general formula (3)

(Wherein, ^{R 1} represents the general formula (2) ^{R 1} .R represents a synonymous ² represents. Alkyl group having 1 to 4 carbon atoms) of 1-trifluoromethyl-1-silyloxy alkyl represented by Represents a group. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁸ represent a hydrogen atom or a group that forms an alkylene group having 1 to 4 carbon atoms together. ), More specifically, the general formula (1A)

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meanings as R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1), R ¹ represents ^{R 1} as defined in formula (2).) cobalt complexes represented by, and the general formula (1a)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1), ^{R 1} and ^{R 1} in formula (2) And a cobalt complex represented by the general formula (1b)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1), ^{R 1} and ^{R 1} in the general formula (2) X represents a C1-C4 alkylene group integrated in R ³ and R ⁸ in the general formula (1), and a general formula (1c).

^{(Wherein, R 3, R 4, R 5} , R 6, ^{R 7} and ^{R 8} represent ^{R 3, R 4, R 5} , R 6, same meanings as ^{R 7} and ^{R 8} in the general formula (1), R ¹ represents ^{R 1} as defined in the general formula (2), ^{R 2} relates to cobalt complex represented by represents a ^{R 2} as defined in formula (3).).

  The present invention also provides a general formula (4)

(Wherein R ¹ represents the same meaning as R ^{1 in} formula (2)),
General formula (5)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7 R 4,} R 5, ^R represents a ⁶ and ^{R 7} as defined. In formula (1)) the conjugated chain diene represented by,
Reaction in the presence of an alkali metal, general formula (1a)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1), ^{R 1} and ^{R 1} in the general formula (2) It represents the same meaning.).

  The present invention also provides a general formula (4)

(Wherein R ¹ represents the same meaning as R ^{1 in} formula (2)),
General formula (6)

(In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ are synonymous with R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (1). X represents R ³ and R in the general formula (1). represents an alkylene group having 1 to 4 carbon atoms which is integral in ^8. conjugated cyclic diene or formula represented by) (7a)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1).) Or the general formula (7b)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7 R 4,} R 5, ^R represents a ⁶ and ^{R 7} as defined. In formula (1)) the non-conjugated cyclic diene represented by,
Reaction in the presence of an alkali metal, general formula (1b)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1), ^{R 1} and ^{R 1} in the general formula (2) X is related to a method for producing a cobalt complex represented by X 1 represents an alkylene group having 1 to 4 carbon atoms integrated in R ³ and R ⁸ of the general formula (1).

  Further, the present invention provides a compound of the general formula (8)

(Wherein ^{represents R 3, R 4, R 5} , R 6, R 7 and ^{R 8 R} 3 in the general formula ^{(1), R 4, R} 5, R 6, same meanings as ^{R 7} and ^{R 8.} And a cobalt complex represented by
With alkyllithium,
After reacting in the presence of alkali metal alkoxide,
General formula (9)

(Wherein R ¹ has the same meaning as R ^{1 in} formula (2), Y represents a leaving group), and reacts with an acylating agent represented by formula (1A)

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meanings as R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1), R ¹ is a method for producing a cobalt complex represented by the representative of R ¹ as defined in formula (2).).

  Further, the present invention provides a compound represented by the general formula (1A)

^{(Wherein, R 3, R 4, R 5} , R 6, ^{R 7} and ^{R 8} represent ^{R 3, R 4, R 5} , R 6, same meanings as ^{R 7} and ^{R 8} in the general formula (1), cobalt complex represented by R ¹ in general formula. representing the ^{R 1} as defined in (2)),
CF ₃ Si ^(R ₂₎ 3 (10) (wherein, ^{R 2} is ^{R 2} represents a synonymous. Of formula (3)) is reacted with trifluoromethyl silane represented by the general formula (1c)

^{(Wherein, R 3, R 4, R 5} , R 6, ^{R 7} and ^{R 8} represent ^{R 3, R 4, R 5} , R 6, same meanings as ^{R 7} and ^{R 8} in the general formula (1), R ¹ represents ^{R 1} as defined in formula (2), ^{R 2} represents a method of manufacturing a cobalt complex represented by the representative of ^{R 2} as defined in formula (3).).

  Furthermore, the present invention relates to a general formula (1)

(In the formula, A represents the general formula (2)

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom) or a general formula (3)

(Wherein, ^{R 1} represents the general formula (2) ^{R 1} .R represents a synonymous ² represents. Alkyl group having 1 to 4 carbon atoms) of 1-trifluoromethyl-1-silyloxy alkyl represented by Represents a group. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁸ represent a hydrogen atom or a group that forms an alkylene group having 1 to 4 carbon atoms together. It is related with the preparation method of a cobalt containing thin film characterized by vaporizing the cobalt complex shown by this, and decomposing | disassembling this cobalt complex on a board | substrate.

  Furthermore, this invention relates to the cobalt containing thin film produced by vaporizing the cobalt complex shown by General formula (1), and decomposing | disassembling this cobalt complex on a board | substrate. Furthermore, the present invention provides a cobalt-containing thin film produced by vaporizing the cobalt complex represented by the general formula (1) and decomposing the cobalt complex on the substrate, and forming the cobalt-containing thin film on the gate electrode of the transistor and the diffusion layer in the source / drain region. The present invention relates to a semiconductor device used for at least one of a contact and a copper wiring seed layer / liner layer.

  The present invention is a cobalt complex represented by the general formula (1). Here, A in the general formula (1) is an acyl group represented by the general formula (2) or a 1-trifluoromethyl-1-silyloxyalkyl group represented by the general formula (3).

  Among the cobalt complexes represented by the general formula (1), the cobalt complex represented by the general formula (1A) or (1c) is preferable. Of the cobalt complexes represented by the general formula (1A), the cobalt complexes represented by the general formulas (1a) and (1b) are preferable.

The alkyl group having 1 to 6 carbon atoms represented by R ¹ of Formula (2), linear, branched and may or cyclic alkyl group, specifically a methyl group, an ethyl group, a propyl group , Isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-ethylpropyl 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, cyclohexyl group, cyclopentylmethyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group and the like.

The alkyl group having 1 to 6 carbon atoms represented by R ¹ may be substituted with a fluorine atom. Examples of the alkyl group having 1 to 6 carbon atoms substituted with a fluorine atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, and a 1,1-difluoroethyl group. 2,2,2-trifluoroethyl group, perfluoroethyl group, perfluoropropyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group, perfluorobutyl group, 1,1,2 , 3,3,3-hexafluoro-2- (trifluoromethyl) propyl group, 1,2,2,3,3,3-hexafluoro-1- (trifluoromethyl) propyl group, 2,2,2 Examples thereof include -trifluoro-1,1-bis (trifluoromethyl) ethyl group, perfluoropentyl group, perfluorohexyl group and the like.

  In terms of having a vapor pressure suitable for the CVD complex or ALD material of the cobalt complex (1) of the present invention, examples of the alkyl group having 1 to 6 carbon atoms substituted with a fluorine atom include a trifluoromethyl group and a perfluoroethyl group. A perfluoropropyl group is preferred, and a trifluoromethyl group is more preferred.

From the viewpoint that the cobalt complex (1) of the present invention has vapor pressure and thermal stability suitable for CVD materials and ALD materials, R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and an isobutyl group Or it is more preferable that it is a C1-C4 linear alkyl group, and it is still more preferable that they are a methyl group, a propyl group, or an isobutyl group.

The alkyl group having 1 to 4 carbon atoms represented by R ² in the general formula (3), linear, branched and may or cyclic alkyl group, specifically a methyl group, an ethyl group, a propyl group Isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group and the like. R ² is preferably a methyl group, an ethyl group or a propyl group, and preferably a methyl group, in that the cobalt complex (1) of the present invention has vapor pressure and thermal stability suitable as a CVD material or an ALD material. Is more preferable.

Three R ² in the general formula (3) may be the same or different.

The alkyl group having 1 to 4 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (1) may be any of linear, branched and cyclic alkyl groups, specifically Examples include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, and cyclobutyl group. R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a carbon number of 1 to 1 in that the cobalt complex (1) of the present invention has a vapor pressure and thermal stability suitable as a CVD material or an ALD material. 3 is preferable, and a hydrogen atom or a methyl group is more preferable.

The alkylene group having 1 to 4 carbon atoms R ³ and R ⁸ form together the general formula (1) may be straight-chain or branched alkyl group, a methylene group, an ethylene group, a propylene group , Butylene group, trimethylene group, tetramethylene group and the like. In terms of the vapor pressure and thermal stability suitable for the cobalt complex (1) of the present invention as a CVD material or an ALD material, R ⁸ and R ⁹ are hydrogen atoms, or a methylene group, an ethylene group, It is preferable to form a trimethylene group or a tetramethylene group, more preferably a hydrogen atom, or more preferably an ethylene group, and even more preferably a hydrogen atom.

Specific examples of the cobalt complex (1a) of the present invention include (η ⁵ -acetylcyclopentadienyl) (η ⁴ -buta-1,3-diene) cobalt (1a-1), (η ⁵ -acetylcyclopenta). Dienyl) [(1-4-η) -penta-1,3-diene] cobalt (1a-2), (η ⁵ -acetylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene ) Cobalt (1a-3), (η ⁵ -acetylcyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1a-4), (η ⁴ -buta-1, 3-diene) (η ⁵ -propionylcyclopentadienyl) cobalt (1a-5), [(1-4-η) -penta-1,3-diene] (η ⁵ -propionylcyclopentadienyl) cobalt ( ^{1a-6), (η 4} -2- methylcarbamoyl Buta-1,3-diene) (eta ⁵ - propionylamino cyclopentadienyl) cobalt (1a-7), (η 4 -2,3- dimethyl-1,3-diene) (eta ⁵ - propionylamino cyclopentadienyl Enyl) cobalt (1a-8), (η ⁴ -buta-1,3-diene) (η ⁵ -butyrylcyclopentadienyl) cobalt (1a-9), (η ⁵ -butyrylcyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1a-10), (η ⁵ -butyrylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a-11), (η ⁵ -butyrylcyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1a-12), (η ⁴ -buta-1,3 -Diene) (η ⁵ -isobutyrylcyclope Tantadienyl) cobalt (1a-13), (η ⁵ -isobutyrylcyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1a-14), (η ⁵ -iso Butyrylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a-15), (η ⁴ -2,3-dimethylbuta-1,3-diene) (η ⁵ -iso Butyrylcyclopentadienyl) cobalt (1a-16), (η ⁴ -buta-1,3-diene) (η ⁵ -valerylcyclopentadienyl) cobalt (1a-17), [(1-4- η) -penta-1,3-diene] (η ⁵ -valerylcyclopentadienyl) cobalt (1a-18), (η ⁴ -2-methylbuta-1,3-diene) (η ⁵ -valerylcyclo) Pentadienyl) cobalt (1a-19) (Eta ^{4-2,3-dimethyl-1,3-diene)} (eta ⁵ - valeryl cyclopentadienyl) cobalt (1a-20), (η 4 - buta-1,3-diene) (eta ⁵ -Isovalerylcyclopentadienyl) cobalt (1a-21), (η ⁵ -isovalerylcyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1a-22) ), (Η ⁴ -2-methylbuta-1,3-diene) (η ⁵ -isovalerylcyclopentadienyl) cobalt (1a-23), (η ⁴ -2,3-dimethylbuta-1,3- Diene) (η ⁵ -isovalerylcyclopentadienyl) cobalt (1a-24), (η ⁴ -buta-1,3-diene) [η ^5- (3-methylbutanoyl) cyclopentadienyl] cobalt (1a-25), [η 5 - (3- methyl Tanoiru) cyclopentadienyl] [(1-4-η) - penta-1,3-diene] cobalt (1a-26), (η 4 -2- methylbut-1,3-diene) [η ⁵ - ( 3-methylbutanoyl) cyclopentadienyl] cobalt (1a-27), (η ⁴ -2,3-dimethylbuta-1,3-diene) [η ^5- (3-methylbutanoyl) cyclopentadienyl ] cobalt (1a-28), (η 4 - buta-1,3-diene) (eta ⁵ - pivaloyl cyclopentadienyl) cobalt (1a-29), [( 1-4-η) - penta - 1,3-diene] (eta ⁵ - pivaloyl cyclopentadienyl) cobalt (1a-30), (η 4 -2- methylbut-1,3-diene) (eta ⁵ - pivaloyl cyclopentadienyl ) Cobalt (1a-31), (η ⁴ -2,3- Dimethylbuta-1,3-diene) (η ⁵ -pivaloylcyclopentadienyl) cobalt (1a-32), (η ⁵ -formylcyclopentadienyl) (η ⁴ -buta-1,3-diene) Cobalt (1a-33), (η ⁵ -formylcyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1a-34), (η ⁵ -formylcyclopentadienyl) ) (Η ⁴ -2methylbuta-1,3-diene) cobalt (1a-35), (η ⁵ -formylcyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1a-36), (η ^5- (fluoroacetyl) cyclopentadienyl) (η ⁴ -buta-1,3-diene) cobalt (1a-37), (η ^5- (fluoroacetyl) cyclopentadienyl ) [(1 -4-η) -penta-1,3-diene] cobalt (1a-38), (η ^5- (fluoroacetyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt ( 1a-39), (η ^5- (fluoroacetyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1a-40), (η ^5- (difluoroacetyl) Cyclopentadienyl) (η ⁴ -buta-1,3-diene) cobalt (1a-41), (η ^5- (difluoroacetyl) cyclopentadienyl) [(1-4-η) -penta-1, 3-diene] cobalt (1a-42), (η ^5- (difluoroacetyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a-43), (η ^5- ( Difluoroacetyl ) Cyclopentadienyl) (eta ^{4-2,3-dimethyl-1,3-diene)} cobalt (1a-44), (η 5 - ( trifluoroacetyl) cyclopentadienyl) (eta ⁴ - Pig - 1,3-diene) cobalt (1a-45), (η ^5- (trifluoroacetyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1a-46) , (η ⁵ - (trifluoroacetyl) cyclopentadienyl) (eta ^{4-2-methylbut-1,3-diene)} cobalt (1a-47), (η 5 - ( trifluoroacetyl) cyclopentadienyl) (Η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1a-48), (η ^5- (pentafluoropropionyl) cyclopentadienyl) (η ⁴ -buta-1,3-diene) Koval (1a-49), (η ^5- (pentafluoropropionyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1a-50), (η ^5- ( Pentafluoropropionyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a-51), (η ^5- (pentafluoropropionyl) cyclopentadienyl) (η ⁴ -2, 3-dimethylbuta-1,3-diene) cobalt (1a-52), (η ^5- (heptafluorobutyryl) cyclopentadienyl) (η ⁴ -buta-1,3-diene) cobalt (1a-53) ), (Η ^5- (heptafluorobutyryl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1a-54), (η ^5- (heptafluorobutyryl) ) Cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a-55), (η ^5- (heptafluorobutyryl) cyclopentadienyl) (η ⁴ -2,3- Examples thereof include dimethylbuta-1,3-diene) cobalt (1a-56). (1a-1), (1a-2), (1a-3), (1a-4), (1a-5), (1a-1), (1a-2), (1a-5), (1a-5) 1a-6), (1a-7), (1a-8), (1a-9), (1a-10), (1a-11), (1a-12), (1a-17), (1a- 18), (1a-19), (1a-20), (1a-21), (1a-22), (1a-23), (1a-24), (1a-33) to (1a-36) And (1a-45) to (1a-48), (1a-1), (1a-2), (1a-3), (1a-4), (1a-5), (1a-6) , (1a-7), (1a-8), (1a-9), (1a-10), (1a-11), (1a-12), (1a-23) and (1a-24) Preferably liquid Handling an easy point (1a-3) is a, (1a-4), (1a-11), (1a-12) and (1a-23) is especially preferred.

Specific examples of the cobalt complex (1b) of the present invention include (η ⁵ -acetylcyclopentadienyl) (η ⁴ -cyclopenta-1,3-diene) cobalt (1b-1), (η ⁵ -acetylcyclopenta). dienyl) (eta ⁴ - cyclohexa-1,3-diene) cobalt (1b-2), (η 5 - acetyl cyclopentadienyl) (eta ⁴ - cyclohepta-1,3-diene) cobalt (1b-3) , (Η ⁵ -acetylcyclopentadienyl) (η ⁴ -cycloocta-1,3-diene) cobalt (1b-4), (η ⁴ -cyclopenta-1,3-diene) (η ⁵ -propionylcyclopentadiene) Enyl) cobalt (1b-5), (η ⁴ -cyclohexa-1,3-diene) (η ⁵ -propionylcyclopentadienyl) cobalt (1b-6), (η ⁴ -cyclohexene) Butane-1,3-diene) (η ⁵ -propionylcyclopentadienyl) cobalt (1b-7), (η ⁴ -cycloocta-1,3-diene) (η ⁵ -propionylcyclopentadienyl) cobalt (1b -8), (η ⁵ -butyrylcyclopentadienyl) (η ⁴ -cyclopenta-1,3-diene) cobalt (1b-9), (η ⁵ -butyrylcyclopentadienyl) (η ⁴ -cyclohexa -1,3-diene) cobalt (1b-10), (η ⁵ -butyrylcyclopentadienyl) (η ⁴ -cyclohepta-1,3-diene) cobalt (1b-11), (η ⁵ -butyryl) Cyclopentadienyl) (η ⁴ -cycloocta-1,3-diene) cobalt (1b-12), (η ⁴ -cyclopenta-1,3-diene) (η ⁵ -isobutyrylcyclopentadiene) Enyl) cobalt (1b-13), (η ⁴ -cyclohexa-1,3-diene) (η ⁵ -isobutyrylcyclopentadienyl) cobalt (1b-14), (η ⁴ -cyclohepta-1,3- Diene) (η ⁵ -isobutyrylcyclopentadienyl) cobalt (1b-15), (η ⁴ -cycloocta-1,3-diene) (η ⁵ -isobutyrylcyclopentadienyl) cobalt (1b-16) ), (Η ⁴ -cyclopenta-1,3-diene) (η ⁵ -valerylcyclopentadienyl) cobalt (1b-17), (η ⁴ -cyclohexa-1,3-diene) (η ⁵ -valeryl) Cyclopentadienyl) cobalt (1b-18), (η ⁴ -cyclohepta-1,3-diene) (η ⁵ -valerylcyclopentadienyl) cobalt (1b-19), (η ⁴ -cyclo Octa-1,3-diene) (η ⁵ -valerylcyclopentadienyl) cobalt (1b-20), (η ⁴ -cyclopenta-1,3-diene) (η ⁵ -isovalerylcyclopentadienyl) Cobalt (1b-21), (η ⁴ -cyclohexa-1,3-diene) (η ⁵ -isovalerylcyclopentadienyl) cobalt (1b-22), (η ⁴ -cyclohepta-1,3-diene) (eta ⁵ - isovaleryloxy cyclopentadienyl) cobalt (1b-23), (η 4 - cycloocta-1,3-diene) (eta ⁵ - isovaleryloxy cyclopentadienyl) cobalt (1b-24), (eta ⁴ - cyclopenta-1,3-diene) [η ⁵ - (3- methylbutanoyl) cyclopentadienyl] cobalt (1b-25), (η 4 - cyclohexa-1,3-diene) [ ⁵ - (3-methyl-butanoyl) cyclopentadienyl] cobalt (1b-26), (η 4 - cyclohepta-1,3-diene) [eta ⁵ - (3-methyl-butanoyl) cyclopentadienyl] cobalt (1b-27), (η ⁴ -cycloocta-1,3-diene) [η ^5- (3-methylbutanoyl) cyclopentadienyl] cobalt (1b-28), (η ⁴ -cyclopenta-1,3 -Diene) (η ⁵ -pivaloylcyclopentadienyl) cobalt (1b-29), (η ⁴ -cyclohexa-1,3-diene) (η ⁵ -pivaloylcyclopentadienyl) cobalt (1b- 30), (η ⁴ - cyclohepta-1,3-diene) (eta ⁵ - pivaloyl cyclopentadienyl) cobalt (1b-31), (η 4 - cycloocta-1,3-diene) (eta ⁵ Pivaloyl cyclopentadienyl) cobalt (1b-32), (η 5 - formyl cyclopentadienyl) (eta ⁴ - cyclopenta-1,3-diene) cobalt (1b-33), (η 5 - Horumirushikuro pentadienyl) (eta ⁴ - cyclohexa-1,3-diene) cobalt (1b-34), (η 5 - formyl cyclopentadienyl) (eta ⁴ - cyclohepta-1,3-diene) cobalt (1b-35 ), (Η ⁵ -formylcyclopentadienyl) (η ⁴ -cycloocta-1,3-diene) cobalt (1b-36), (η ^5- (fluoroacetyl) cyclopentadienyl) (η ⁴ -cyclopenta- 1,3-diene) cobalt (1b-37), (η 5 - ( trifluoroacetyl) cyclopentadienyl) (eta ⁴ - cyclohexa-1,3-diene) Baltic (1b-38), (η 5 - ( trifluoroacetyl) cyclopentadienyl) (eta ⁴ - cyclohepta-1,3-diene) cobalt (1b-39), (η 5 - ( trifluoroacetyl) Shikuropentaji Enyl) (η ⁴ -cycloocta-1,3-diene) cobalt (1b-40), (η ^5- (difluoroacetyl) cyclopentadienyl) (η ⁴ -cyclopenta-1,3-diene) cobalt (1b- 41), (η ^5- (difluoroacetyl) cyclopentadienyl) (η ⁴ -cyclohexa-1,3-diene) cobalt (1b-42), (η ^5- (difluoroacetyl) cyclopentadienyl) (η ⁴ -cyclohepta-1,3-diene) cobalt (1b-43), (η ^5- (difluoroacetyl) cyclopentadienyl) (η ⁴ -cyclooct -1,3-diene) cobalt (1b-44), (η ^5- (trifluoroacetyl) cyclopentadienyl) (η ⁴ -cyclopenta-1,3-diene) cobalt (1b-45), (η ⁵ - (trifluoroacetyl) cyclopentadienyl) (eta ⁴ - cyclohexa-1,3-diene) cobalt (1b-46), (eta ⁵ - (trifluoroacetyl) cyclopentadienyl) (eta ⁴ - cyclohepta -1,3-diene) cobalt (1b-47), (η ^5- (trifluoroacetyl) cyclopentadienyl) (η ⁴ -cycloocta-1,3-diene) cobalt (1b-48), (η ⁵ - (pentafluoropropionyl) cyclopentadienyl) (eta ⁴ - cyclopenta-1,3-diene) cobalt (1b-49), (η 5 - ( pentafluoropropionic Onyl) cyclopentadienyl) (eta ⁴ - cyclohexa-1,3-diene) cobalt (1b-50), (η 5 - ( pentafluoropropionyl) cyclopentadienyl) (eta ⁴ - cyclohepta-1,3 Diene) cobalt (1b-51), (η ^5- (pentafluoropropionyl) cyclopentadienyl) (η ⁴ -cycloocta-1,3-diene) cobalt (1b-52), (η ^5- (heptafluorobuty) Yl) cyclopentadienyl) (η ⁴ -cyclopenta-1,3-diene) cobalt (1b-53), (η ^5- (heptafluorobutyryl) cyclopentadienyl) (η ⁴ -cyclohexa-1,3 - diene) cobalt (1b-54), (η 5 - ( heptafluorobutyryl) cyclopentadienyl) (eta ⁴ - cyclohepta-1,3 Ene) cobalt (1b-55), (η 5 - ( heptafluorobutyryl) cyclopentadienyl) (eta ⁴ - cycloocta-1,3-diene) and the like can be exemplified cobalt (1b-56). (1b-2), (1b-6), (1b-10), (1b-18), (1b-22), (1b-2), (1b-6), (1b-22), (1b-22) 1b-34) and (1b-46) are preferred, and (1b-2) is more preferred.

Specific examples of the cobalt complex (1c) of the present invention include (η ⁵ -(2,2,2-trifluoro-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-1), (η ⁵ -(2,2,2-trifluoro-1-trimethylsilyloxyethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-2), (η ⁵ -(2,2,2-trifluoro-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-3), (η ⁵ -(2,2,2-trifluoro-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-4), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-5), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-6), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-7), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-8), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-9), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-10 ), (Η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-11), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-12), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-13), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-14), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-15), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-16), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-17), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-18), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-19), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-20), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-21), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-22), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-23), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-24), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-25), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) [(1-4-η) -penta-1,3 -Diene] cobalt (1c-26), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-27), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-28), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-29), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxyethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-30), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-31), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-32), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-33), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-34), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-35), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-36), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-37), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c- 38), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-39), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-40), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-41), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-42), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-43), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-44), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-45), (η ⁵ -(2,2,3,3,3-pentafluoro-1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] Cobalt (1c-46), (η ⁵ -(2,2,3,3,3-pentafluoro-1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-47), (η ⁵ -(2,2,3,3,3-pentafluoro-1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-48), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-49), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-50), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-51), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-52), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-53), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) [(1-4-η) -penta-1, 3-diene] cobalt (1c-54), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-triethylsilyloxy-1-trifluoromethylbutyl)
Cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-55), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-56), (η ⁵ -(2,2,2-trifluoro-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-57), (η ⁵ -(2,2,2-trifluoro-1-tripropylsilyloxyethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-58), (η ⁵ -(2,2,2-trifluoro-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-59), (η ⁵ -(2,2,2-trifluoro-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-60), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-61), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-62), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-63), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-64), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-65), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c -66), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-67), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-68), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-69), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-70), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-71), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-72), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-73), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene ] Cobalt (1c-74), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-75), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-76), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-77), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene ] Cobalt (1c-78), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-79), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-80), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-81), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) [(1-4-η) -penta-1 , 3-Diene] cobalt (1c-82), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-83), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-84), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoroethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-85), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoroethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-86), (Η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoroethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-87), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoroethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-88), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-89), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-90), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-91), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-92), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoro-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-93), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoro-1-trifluoromethylethyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-94), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoro-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-95), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoro-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-96), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-97), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-98), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-99), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-100), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,3-pentafluoro-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-101), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,3-pentafluoro-1-trifluoromethylpropyl) cyclopentadienyl) [(1-4-η) -penta-1,3 -Diene] cobalt (1c-102), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,3-pentafluoro-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-103), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,3-pentafluoro-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-104), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-105), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) [(1-4-η) -penta-1,3-diene] cobalt (1c-106), (η ⁵ -(1-tert-butyldimethylsilane
(Ryloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-107), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-108), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,4,4,4-heptafluoro-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Buta-1,3-diene) cobalt (1c-109), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,4,4,4-heptafluoro-1-trifluoromethylbutyl) cyclopentadienyl) [(1-4-η) -penta -1,3-diene] cobalt (1c-110), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,4,4,4-heptafluoro-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-111), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,4,4,4-heptafluoro-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-112), (η ⁵ -(2,2,2-trifluoro-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-113), (η ⁵ -(2,2,2-trifluoro-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-114), (η ⁵ -(2,2,2-trifluoro-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-115), (η ⁵ -(2,2,2-trifluoro-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-116), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-117), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-118), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-119), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-120), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-121), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-122), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-123), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-124), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-125), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-126), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-127), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-128), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-129), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-130), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-131), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-trimethylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-132), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-133), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-134), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-135), (η ⁵ -(1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-136), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-137), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-138), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-139), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-trimethylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-140), (η ⁵ -(2,2,2-trifluoro-1-trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-141), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-142), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-143), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-144), (η ⁵ -(1-triethylsilyloxy 1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-145), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-146), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-147), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-148), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-149), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-150), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-151), (η ⁵ -(2,2,2-trifluoro-1-triethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-152), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-153), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-154), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-155), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-156), (η ⁵ -(2,2,3,3,3-pentafluoro-1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-157), (η ⁵ -(2,2,3,3,3-pentafluoro-1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-158), (η ⁵ -(2,2,3,3,3-pentafluoro-1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-159), (η ⁵ −
(2,2,3,3,3-pentafluoro-1-triethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-160), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-161), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-162), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-163), (η ⁵ -(1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-164), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-165), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-166), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-167), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-triethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-168), (η ⁵ -(2,2,2-trifluoro-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-169), (η ⁵ -(2,2,2-trifluoro-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-170), (η ⁵ -(2,2,2-trifluoro-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-171), (η ⁵ -(2,2,2-trifluoro-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-172), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-173), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-174), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-175), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-176), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-177), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-178), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-179), (η ⁵ -(2,2,2-trifluoro-1-trifluoromethyl-1-tripropylsilyloxyethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-180), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-181), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-182), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-183), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-184), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-185), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-186), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-187), (η ⁵ -(2,2,3,3,3-pentafluoro-1-trifluoromethyl-1-tripropylsilyloxypropyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-188), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-189), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-190), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-191), (η ⁵ -(1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-192), (η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-193), (η ⁵ − (Η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-194), (η ⁵ − (Η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-195), (η ⁵ − (Η ⁵ -(2,2,3,3,4,4,4-heptafluoro-1-trifluoromethyl-1-tripropylsilyloxybutyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-196), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoroethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-197), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoroethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-198), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoroethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-199), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoroethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-200), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-201), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-202), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-203), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-204), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoro-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-205), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoro-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-206), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoro-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-207), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,2-trifluoro-1-trifluoromethylethyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-208), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-209), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-210), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-211), (η
⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-212), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,3-pentafluoro-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-213), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,3-pentafluoro-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-214), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,3-pentafluoro-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-215), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,3-pentafluoro-1-trifluoromethylpropyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-216), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-217), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-218), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-219), (η ⁵ -(1-tert-butyldimethylsilyloxy-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-220), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,4,4,4-heptafluoro-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclopenta-1,3-diene) cobalt (1c-221), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,4,4,4-heptafluoro-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclohexa-1,3-diene) cobalt (1c-222), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,4,4,4-heptafluoro-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cyclohepta-1,3-diene) cobalt (1c-223), (η ⁵ -(1-tert-butyldimethylsilyloxy-2,2,3,3,4,4,4-heptafluoro-1-trifluoromethylbutyl) cyclopentadienyl) (η ⁴ -Cycloocta-1,3-diene) cobalt (1c-224) etc. can be illustrated. (1c-1) to (1c-8), (1c-114), and (1c-118) are preferable from the viewpoint of having vapor pressure and thermal stability suitable for CVD materials and ALD materials, ), (1c-3) to (1c-5), (1c-7), (1c-8) are more preferred, (1c-3), (1c-4), (1c-7), (1c- 8) is particularly preferred.

  The cobalt complex (1) of the present invention may be a mixture of stereoisomers such as a conformational isomer and a configurational isomer.

  Next, the manufacturing method of the cobalt complex (1) of this invention is demonstrated.

  First, a method for producing a cobalt complex (1A) that is preferably used among the cobalt complexes (1) will be described.

  The cobalt complex (1A) can be produced by production method 1. Of the cobalt complexes (1A), the cobalt complexes (1a) and (1b) that are preferably used can be produced by production methods 2 and 3, respectively.

  Production method 1 is a method for producing a cobalt complex (1A) by reacting a cobalt complex (8) with alkyllithium in the presence of an alkali metal alkoxide and then reacting with an acylating agent (9). is there.

  Manufacturing method 1

^{(Wherein, R 3, R 4, R 5} , R 6, ^{R 7} and ^{R 8} represent ^{R 3, R 4, R 5} , R 6, same meanings as ^{R 7} and ^{R 8} in the general formula (1), R ¹ has the same meaning as R ^{1 in} formula (2), Y represents a leaving group.)
Production method 2 is a method of producing a cobalt complex (1a) by reacting cobaltcene (4) with a conjugated chain diene (5) in the presence of an alkali metal.

  Manufacturing method 2

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1), ^{R 1} and ^{R 1} in the general formula (2) Synonymous.)
In production method 3, cobalt complex (1b) is produced by reacting cobaltcene (4) with conjugated cyclic diene (6) or non-conjugated cyclic diene (7a) or (7b) in the presence of an alkali metal. It is a method to do.

  Manufacturing method 3

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1), ^{R 1} and ^{R 1} in the general formula (2) (X represents an alkylene group having 1 to 4 carbon atoms, which is integrated in R ³ and R ⁸ in the general formula (1).)
First, the manufacturing method 1 will be described. Production method 1 includes a first step in which cobalt complex (8) and alkyllithium are reacted in the presence of an alkali metal alkoxide, and a second step in which the product of the first step is reacted with acylating agent (9). It consists of a process.

  As the leaving group represented by Y in Production Method 1, a dialkylamino group, a halogen atom, an alkoxy group, an acyloxy group, a 1-imidazolyl group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a p-toluenesulfonyloxy group Etc. can be illustrated. Dialkylamino groups include dimethylamino, ethylmethylamino, diethylamino, propylmethylamino, isopropylmethylamino, ethylpropylamino, ethylisopropylamino, dipropylamino, diisopropylamino, 1-piperidyl A group etc. can be illustrated. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy, pentyloxy, allyloxy, cyclohexyloxy, benzyloxy A group etc. can be illustrated. Acyloxy groups include acetoxy, propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, isovaleryloxy, pivaloyloxy, fluoroacetoxy, difluoroacetoxy, trifluoroacetoxy, pentafluoropropionyloxy Group, heptafluorobutyryloxy group and the like.

  Y is a dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, 1-piperidyl group, chlorine atom, bromine atom, iodine atom, acetoxy group, propionyloxy in that the yield of the cobalt complex (1A) is good. Group, butyryloxy group, valeryloxy group, trifluoroacetoxy group, pentafluoropropionyloxy group and heptafluorobutyryloxy group are preferable, and dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group and 1-piperidyl group are further included. A 1-piperidyl group is preferred, and an even more preferred one.

Examples of the cobalt complex (8) that can be used in the production method 1 include (η ⁴ -buta-1,3-diene) (η ⁵ -cyclopentadienyl) cobalt, (η ⁵ -cyclopentadienyl). [(1-4-η) -penta-1,3-diene] cobalt, (η ⁵ -cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt, (η ⁵ -cyclopenta Dienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt, (η ⁴ -cyclopenta-1,3-diene) (η ⁵ -cyclopentadienyl) cobalt, (η ⁴ -cyclohexa 1,3-diene) (eta ⁵ - cyclopentadienyl) cobalt, (η ⁴ - cyclohepta-1,3-diene) (eta ⁵ - cyclopentadienyl) cobalt, (η ⁴ - cycloocta-1,3 -Diene) (η ⁵ - can be exemplified such as cyclopentadienyl) cobalt, (eta ⁴ - buta-1,3-diene) (eta ⁵ - cyclopentadienyl) cobalt, (eta ⁵ - cyclopentadienyl) (eta ⁴ - 2-methylbuta-1,3-diene) cobalt, (η ⁵ -cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt, (η ⁴ -cyclohexa-1,3- diene) (eta ⁵ - cyclopentadienyl) cobalt are preferable, (eta ⁵ - cyclopentadienyl) (eta ^{4-2-methylbut-1,3-diene)} cobalt, (eta ⁵ - cyclopentadienyl) ( (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt and (η ⁴ -cyclohexa-1,3-diene) (η ⁵ -cyclopentadienyl) cobalt are more preferred.

The cobalt complex (8) used in production method 1 of the present invention comprises bis (η ⁵ -cyclopentadienyl) cobalt and conjugated chain diene (5) or conjugated cyclic diene (6) in the presence of an alkali metal. In addition to the synthesis, it can be synthesized according to the method described in Organometallics, Vol. 32, page 3415 (2013).

  Examples of alkyl lithium that can be used in Production Method 1 include methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, butyl lithium, sec-butyl lithium, isobutyl lithium, tert-butyl lithium, pentyl lithium, and tert-pentyl lithium. , Cyclopentyl lithium, hexyl lithium, cyclohexyl lithium and the like. Butyl lithium is preferred in terms of good yield.

  The alkyl lithium used in the production method 1 of the present invention may be a commercially available product, edited by the Chemical Society of Japan, “Experimental Chemistry Course 18 Synthesis of Organic Compounds VI”, 5th edition, Maruzen, 2004, Journal of the American Chemical. A product manufactured according to the method described in Society, vol. 108, page 7016 (1986), or the like may be used.

  Examples of the alkali metal alkoxide that can be used in Production Method 1 include lithium methoxide, lithium ethoxide, lithium propoxide, lithium isopropoxide, lithium-butoxy, lithium iso-butoxy, lithium sec-butoxy, lithium tert. -Butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, sodium butoxide, sodium isobutoxide, sodium sec-butoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium Examples include isopropoxide, potassium butoxide, potassium isobutoxide, potassium sec-butoxide, potassium tert-butoxide, etc. It can be. In terms of good yield of the cobalt complex (1A), potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium isobutoxide, potassium sec-butoxide, and potassium tert-butoxide are preferable. Tert-butoxide is more preferred.

  A commercial item can be used for the alkali metal alkoxide used by the manufacturing method 1 of this invention.

  Examples of the acylating agent (9) that can be used in Production Method 1 include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), N, N-diethylacetamide, N, N- Dimethylpropionic acid amide, N, N-diethylpropionic acid amide, N, N-dimethylbutyric acid amide, N, N-diethylbutyric acid amide, N, N-dimethylisobutyric acid amide, N, N-diethylisobutyric acid amide, N, N- Dimethylvaleric acid amide, N, N-diethylvaleric acid amide, N, N-dimethylisovaleric acid amide, N, N-diethylisovaleric acid amide, N, N-dimethylpivalic acid amide, N, N-diethylpivalic acid amide, N, N-dimethylfluoroacetamide, N, N-diethylfluoroacetamide, N, N-dimethyldifluoroacetamide N, N-diethyldifluoroacetamide, N, N-dimethyltrifluoroacetamide, N, N-diethyltrifluoroacetamide, N-methyl-bis (trifluoroacetamide), N, N-dimethylpentafluoropropionic acid amide, N , N-diethylpentafluoropropionic acid amide, N, N-dimethylheptafluorobutyric acid amide, N, N-diethylheptafluorobutyric acid amide, 1-acetylpiperidine, 1-propionylpiperidine, 1-butyrylpiperidine, 1-isobuty Rilpiperidine, 1-valerylpiperidine, 1-isovalerylpiperidine, 1-pivaloylpiperidine, 1- (fluoroacetyl) piperidine, 1- (difluoroacetyl) piperidine, 1- (trifluoroacetyl) piperidine, 1- (Penta (Luoropropionyl) piperidine, 1- (heptafluorobutyryl) piperidine and other carboxylic acid dialkylamides, acetyl chloride, acetyl bromide, acetyl iodide, propionyl chloride, propionyl bromide, propionyl iodide, butyryl chloride, butyryl bromide , Butyryl iodide, isobutyryl chloride, isobutyryl bromide, isobutyryl iodide, valeryl chloride, valeryl bromide, valeryl iodide, isovaleryl chloride, isovaleryl bromide, isovaleryl iodide, pivaloyl chloride, pivaloyl bromide, pivaloyl iodide, chloride Fluoroacetyl, fluoroacetyl bromide, fluoroacetyl iodide, difluoroacetyl chloride, difluoroacetyl bromide, difluoroacetyl iodide, trifluoroacetyl chloride, trifluoroacetyl bromide, trifluoroiodide Carboxylic acid halides such as loacetyl, pentafluoropropionyl chloride, pentafluoropropionyl bromide, pentafluoropropionyl iodide, heptafluorobutyryl chloride, heptafluorobutyryl bromide, heptafluorobutyryl iodide, methyl formate, ethyl formate Propyl formate, isopropyl formate, butyl formate, phenyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate , Phenyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, phenyl butyrate, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, isoprobutyrate Butyl isobutyrate, phenyl isobutyrate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, phenyl valerate, methyl isovalerate, ethyl isovalerate, propyl isovalerate, iso Isopropyl valerate, butyl isovalerate, phenyl isovalerate, methyl pivalate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, phenyl pivalate, methyl fluoroacetate, ethyl fluoroacetate, propyl fluoroacetate, Isopropyl fluoroacetate, butyl fluoroacetate, phenyl fluoroacetate, methyl difluoroacetate, ethyl difluoroacetate, propyl difluoroacetate, isopropyl difluoroacetate, butyl difluoroacetate, phenyl difluoroacetate, methyl trifluoroacetate, trifluoro Ethyl acetate, propyl trifluoroacetate, isopropyl trifluoroacetate, butyl trifluoroacetate, phenyl trifluoroacetate, methyl pentafluoropropionate, ethyl pentafluoropropionate, propyl pentafluoropropionate, isopropyl pentafluoropropionate, pentafluoropropion Carboxylates such as butyl acid, phenyl pentafluoropropionate, methyl heptafluorobutyrate, ethyl heptafluorobutyrate, propyl heptafluorobutyrate, isopropyl heptafluorobutyrate, butyl heptafluorobutyrate, phenyl heptafluorobutyrate, acetic anhydride, anhydrous propionic acid , Butyric anhydride, isobutyric anhydride, valeric anhydride, isovaleric anhydride, pivalic anhydride, fluoroacetic anhydride, difluoroacetic anhydride , Trifluoroacetic anhydride, pentafluoropropionic anhydride, carboxylic anhydride such as heptafluorobutyric anhydride, 1-acetylimidazole, 1-propionylimidazole, 1-butyrylimidazole, 1-isobutyrylimidazole, 1 -Valerylimidazole, 1-isovalerylimidazole, 1-pivaloylimidazole, 1- (fluoroacetyl) imidazole, 1- (difluoroacetyl) imidazole, 1- (trifluoroacetyl) imidazole, 1- (pentafluoropropionyl) ) Imidazole, imidazole compounds such as 1- (heptafluorobutyryl) imidazole, acetyl methanesulfonate, propionyl methanesulfonate, butyryl methanesulfonate, isobutyryl methanesulfonate, valeri Methane sulfonate, isovaleryl methane sulfonate, pivaloyl methane sulfonate, fluoroacetyl methane sulfonate, difluoroacetyl methane sulfonate, trifluoroacetyl methane sulfonate, pentafluoropropionyl methane sulfonate, heptafluorobutyryl methane sulfo Methane sulfonate acyl such as nate, acetyl triflate, propionyl triflate, butyryl triflate, isobutyryl triflate, valeryl triflate, isovaleryl triflate, pivaloyl triflate, fluoroacetyl triflate, difluoroacetyl triflate, trifluoroacetyl triflate, Trifluors such as pentafluoropropionyl triflate and heptafluorobutyryl triflate Acylromethanesulfonate, acetyl p-toluenesulfonate, propionyl p-toluenesulfonate, butyryl p-toluenesulfonate, isobutyryl p-toluenesulfonate, valeryl p-toluenesulfonate, isovaleryl p-toluenesulfonate, pivaloyl p- P such as toluene sulfonate, fluoroacetyl p-toluene sulfonate, difluoroacetyl p-toluene sulfonate, trifluoroacetyl p-toluene sulfonate, pentafluoropropionyl p-toluene sulfonate, heptafluorobutyryl p-toluene sulfonate -Toluene sulfonic acid acyl etc. can be mentioned. In view of the good yield of the cobalt complex (1A), carboxylic acid dialkylamides are preferable, and DMF, 1-acetylpiperidine, and 1- (trifluoroacetyl) piperidine are more preferable.

  The acylating agent (9) used in the production method 1 of the present invention may be a commercially available product, edited by the Chemical Society of Japan, “Experimental Chemistry Course 16 Synthesis of Organic Compounds IV”, 5th edition, Maruzen, 2005, Journal, Of the American Chemical Society, Vol. 134, page 640 (2012), Synthesis, Vol. 44, page 2249 (2012), and the like may be used.

  It is preferable to implement the manufacturing method 1 in inert gas atmosphere at the point with the good yield of a cobalt complex (1A). Specific examples of the inert gas include helium, neon, argon, krypton, xenon, nitrogen gas and the like, and argon or nitrogen gas is preferable from the viewpoint of low cost.

  It is preferable to implement the manufacturing method 1 in an organic solvent at the point with the good yield of a cobalt complex (1A). The type of organic solvent that can be used is not particularly limited as long as the reaction is not inhibited. Examples of usable solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, and butylbenzene. , Aromatic hydrocarbons such as isobutylbenzene, sec-butylbenzene, tert-butylbenzene, 1,3,5-trimethylbenzene (mesitylene), diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl Ethers such as ether (CPEE), tert-butyl methyl ether (MTBE), tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane It can be mentioned. One of these organic solvents can be used alone, or a plurality of them can be mixed at an arbitrary ratio. In terms of good yield of the cobalt complex (1A), the organic solvent is preferably ether, CPME, MTBE, diethyl ether or THF is more preferred, and THF is particularly preferred.

  Next, the molar ratio of the cobalt complex (8), alkyllithium, alkali metal alkoxide, and acylating agent (9) when the production method 1 is carried out will be described. Preferably, after reacting 0.9 to 1.5 mol of alkyl lithium and 0.9 to 1.5 mol of alkali metal alkoxide with respect to 1 mol of cobalt complex (8), 0.9 to 2. By reacting 0 mol of acylating agent (9), cobalt complex (1A) can be produced with good yield.

  The first step of production method 1 is preferably carried out at a reaction temperature of 0 ° C. or lower, and the reaction time is not particularly limited, and those skilled in the art can use general conditions for producing metal complexes. . As a specific example, at a reaction temperature appropriately selected from a temperature range of −80 ° C. to 0 ° C., a reaction time appropriately selected from a range of 10 minutes to 120 hours can be selected.

  In the second step of production method 1, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a metal complex. As a specific example, a cobalt complex (1A) is produced with high yield by selecting a reaction time appropriately selected from a range of 10 minutes to 120 hours at a reaction temperature appropriately selected from a temperature range of -80 ° C to 120 ° C. I can do it.

  The cobalt complex (1A) produced by the production method 1 can be purified by appropriately selecting and using a general purification method when a person skilled in the art purifies a metal complex. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography and the like.

  Next, manufacturing methods 2 and 3 will be described.

Examples of cobaltcene (4) that can be used in production methods 2 and 3 include bis (η ⁵ -acetylcyclopentadienyl) cobalt, bis (η ⁵ -propionylcyclopentadienyl) cobalt, and bis (η ⁵ -Butyrylcyclopentadienyl) cobalt, bis (η ⁵ -isobutyrylcyclopentadienyl) cobalt, bis (η ⁵ -valerylcyclopentadienyl) cobalt, bis (η ⁵ -isovalerylcyclopentadi) Enyl) cobalt, bis [η ^5- (3-methylbutanoyl) cyclopentadienyl] cobalt, bis (η ⁵ -pivaloylcyclopentadienyl) cobalt and the like, and bis (η ⁵ -acetylcyclopenta). dienyl) cobalt, bis (eta ⁵ - propionylamino cyclopentadienyl) cobalt, bis (eta ⁵ - Buchirirushikuro Ntajieniru) cobalt, bis (eta ⁵ - valeryl cyclopentadienyl) cobalt and bis (eta ⁵ - isovaleryloxy cyclopentadienyl) cobalt are preferable, bis (eta ⁵ - acetyl cyclopentadienyl) cobalt, bis ( More preferred are [eta] ⁵ -butyrylcyclopentadienyl) cobalt and bis ([eta] ⁵ -isovalerylcyclopentadienyl) cobalt.

  Cobaltene (4) that can be used in the production methods 2 and 3 is disclosed in Journal of the American Chemical Society, Vol. 102, page 1196 (1980), Journal of Macromolecular Science. Pt. A, Chemistry, A16, page 243 (1981). Specifically, a sodium acylcyclopentadienide is prepared by reacting sodium cyclopentadienide with a carboxylic acid ester, and the sodium acylcyclopentadienide and cobalt chloride are reacted to obtain cobalt cene (4). Can be manufactured.

  In production methods 2 and 3, cobaltcene (4) can be used as a raw material without purification, and cobaltcene (4) purified by a general purification method for metal complexes can be used as a raw material. Specific purification methods include filtration, extraction, centrifugation, decantation, sublimation, crystallization, column chromatography and the like.

  Examples of the conjugated chain diene (5) that can be used in Production Method 2 include buta-1,3-diene, 2-methylbuta-1,3-diene (isoprene), 2,3-dimethylbuta-1, Examples include 3-diene, penta-1,3-diene, hexa-1,3-diene, hexa-2,4-diene, hepta-2,4-diene, and the like. From the viewpoint of good yield of the cobalt complex (1a), buta-1,3-diene, isoprene, 2,3-dimethylbuta-1,3-diene and penta-1,3-diene are preferable, isoprene, 2, 3-Dimethylbuta-1,3-diene is particularly preferred.

  Specific examples of the alkali metal that can be used in the production method 2 include lithium, sodium, potassium, and the like, and lithium or sodium is preferable because it is inexpensive and easy to handle.

  It is preferable to implement the manufacturing method 2 in inert gas atmosphere at the point with the good yield of a cobalt complex (1a). Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas, which may be appropriately selected and used according to the type of alkali metal. For example, argon or nitrogen gas is more preferable when the alkali metal is sodium or potassium, and argon is more preferable when the alkali metal is lithium.

  Production method 2 is preferably carried out in an organic solvent in that the yield of cobalt complex (1a) is good. The type of organic solvent that can be used is not particularly limited as long as the reaction is not inhibited. Examples of usable solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, and butylbenzene. , Aromatic hydrocarbons such as isobutylbenzene, sec-butylbenzene, tert-butylbenzene, 1,3,5-trimethylbenzene (mesitylene), diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl Ethers such as ether (CPEE), tert-butyl methyl ether (MTBE), tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane It can be mentioned. One of these organic solvents can be used alone, or a plurality of them can be mixed at an arbitrary ratio. From the viewpoint of good yield of the cobalt complex (1a), the organic solvent is preferably ether, CPME, MTBE, diethyl ether or THF is more preferred, and THF is particularly preferred.

  Next, the molar ratio of cobaltcene (4), conjugated chain diene (5) and alkali metal when manufacturing method 2 is carried out will be described. Preferably, by using 0.9 to 5.0 moles of conjugated chain diene (5) and 0.9 to 1.3 moles of alkali metal per mole of cobaltcene (4), cobalt can be obtained with good yield. Complex (1a) can be produced.

  In Production Method 2, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a metal complex. As a specific example, a cobalt complex (1a) is produced in a high yield by selecting a reaction time appropriately selected from a range of 10 minutes to 120 hours at a reaction temperature appropriately selected from a temperature range of −80 ° C. to 120 ° C. I can do it. The cobalt complex (1a) produced by the production method 2 can be purified by appropriately selecting and using a general purification method when a person skilled in the art purifies a metal complex. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography and the like.

  Conjugated chain dienes (5) that can be used in production method 2 are described in Russian Journal of Applied Chemistry, Vol. 84, page 261 (2011), ACS Catalyst, Vol. 2, page 2173 (2012), etc. It can be synthesized according to the method. Commercially available conjugated chain diene (5) can also be used as a raw material for production method 2.

  Examples of the conjugated cyclic diene (6) that can be used in production method 3 include cyclopenta-1,3-diene, methylcyclopenta-1,3-diene, ethylcyclopenta-1,3-diene, and propylcyclopenta. -1,3-diene, isopropylcyclopenta-1,3-diene, cyclopropylcyclopenta-1,3-diene, butylcyclopenta-1,3-diene, isobutylcyclopenta-1,3-diene, sec- Butylcyclopenta-1,3-diene, tert-butylcyclopenta-1,3-diene, 1,2-dimethylcyclopenta-1,3-diene, 1,3-dimethylcyclopenta-1,3-diene, Cyclohexa-1,3-diene, 5-methylcyclohexa-1,3-diene, 5,5-dimethylcyclohexa-1,3-diene, 5 Ethyl-5-methyl-cyclohexa-1,3-diene, 1-isopropyl-4-methylcyclohexa-1,3-diene (α-terpinene), 5-isopropyl-2-methylcyclohexa-1,3-diene (Α-ferrandrene), 3-methyl-5,5-dimethylcyclohexa-1,3-diene, cyclohepta-1,3-diene, 6-methylcyclohepta-1,3-diene, 6-ethylcyclohepta -1,3-diene, 6-propylcyclohepta-1,3-diene, 6-isopropylcyclohepta-1,3-diene, 6-butylcyclohepta-1,3-diene, 6-isobutylcyclohepta-1 , 3-diene, 6-sec-butyl-cyclohepta-1,3-diene, 6-tert-butyl-cyclohepta-1,3-diene, 1,6-dimethylsilane Lohepta-1,3-diene, 2,6-dimethylcyclohepta-1,3-diene, 5,6-dimethylcyclohepta-1,3-diene, 6,6-dimethylcyclohepta-1,3-diene, Examples include cycloocta-1,3-diene, 1,6-dimethylcycloocta-1,3-diene, and 2,6-dimethylcycloocta-1,3-diene.

  Examples of non-conjugated cyclic dienes (7a) and (7b) that can be used in production method 3 include cyclohexa-1,4-diene, 1-methylcyclohexa-1,4-diene, and 1-isopropyl-4- Examples include methylcyclohexa-1,4-diene (γ-terpinene). In view of the good yield of the cobalt complex (1b), the conjugated cyclic diene (6) is preferably used, and cyclohexa-1,3-diene is more preferable.

  Specific examples of the alkali metal that can be used in the production method 3 include lithium, sodium, potassium, and the like, and lithium or sodium is preferable because it is inexpensive and easy to handle.

  Production method 3 is preferably carried out in an inert gas atmosphere in that the yield of cobalt complex (1b) is good. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas, which may be appropriately selected and used according to the type of alkali metal. For example, argon or nitrogen gas is more preferable when the alkali metal is sodium or potassium, and argon is more preferable when the alkali metal is lithium.

  Production method 3 is preferably carried out in an organic solvent in that the yield of cobalt complex (1b) is good. The type of organic solvent that can be used is not particularly limited as long as the reaction is not inhibited. Examples of usable solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, and butylbenzene. , Aromatic hydrocarbons such as isobutylbenzene, sec-butylbenzene, tert-butylbenzene, 1,3,5-trimethylbenzene (mesitylene), diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl Ethers such as ether (CPEE), tert-butyl methyl ether (MTBE), tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane It can be mentioned. One of these organic solvents can be used alone, or a plurality of them can be mixed at an arbitrary ratio. In terms of good yield of the cobalt complex (1b), the organic solvent is preferably ether, CPME, MTBE, diethyl ether or THF is more preferred, and THF is particularly preferred.

  Next, the molar ratio of cobaltcene (4), conjugated cyclic diene (6), nonconjugated cyclic diene (7a), (7b), and alkali metal when manufacturing method 3 is carried out will be described. Preferably 0.9 to 5.0 mol of conjugated cyclic diene (6) or non-conjugated cyclic diene (7a), (7b) and 0.9 to 1.3 mol of mol of cobaltcene (5) By using an alkali metal, the cobalt complex (1b) can be produced with good yield.

  In production method 3, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a metal complex. As a specific example, a cobalt complex (1b) is produced with high yield by selecting a reaction time appropriately selected from a range of 10 minutes to 120 hours at a reaction temperature appropriately selected from a temperature range of −80 ° C. to 120 ° C. I can do it. The cobalt complex (1b) produced by the production method 3 can be purified by appropriately selecting and using a general purification method when a person skilled in the art purifies a metal complex. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography and the like.

  Conjugated cyclic diene (6) and non-conjugated cyclic diene (7a), (7b) that can be used in production method 3 are described in ACS Catalysis, Vol. 2, page 2173 (2012), JP 2001-31595 A, The Journal of Organic Chemistry, Vol. 55, p. 1854 (1990), The Journal of Organic Chemistry, Vol. 56, p. 5101 (1991), Chemistry-A Europ. , Organometallics, Vol. 13, page 1020 (1994), and the like. Commercially available conjugated cyclic dienes (6) and non-conjugated cyclic dienes (7a) and (7b) can also be used as raw materials for production method 3.

  Next, the manufacturing method 4 is demonstrated.

  Production method 4 is a method for producing a cobalt complex (1c) by reacting a cobalt complex (1A) with trifluoromethylsilane (10).

  Manufacturing method 4

^{(Wherein, R 3, R 4, R 5} , R 6, ^{R 7} and ^{R 8} represent ^{R 3, R 4, R 5} , R 6, the same meaning as ^{R 7,} and ^{R 8} in the general formula (1), R ¹ represents ^{R 1} as defined in the general formula (2), ^{R 2} represents ^{R 2} as defined in formula (3).)
Examples of the cobalt complex (1A) that can be used in production method 4 include cobalt complexes (1a) and (1b).

  Examples of trifluoromethylsilane (10) that can be used in production method 4 include (trifluoromethyl) trimethylsilane, (trifluoromethyl) triethylsilane, (trifluoromethyl) tripropylsilane, and (trifluoromethyl). Examples include tri (isopropyl) silane, (trifluoromethyl) tributylsilane, tert-butyldimethyl (trifluoromethyl) silane, and the like. (Trifluoromethyl) trimethylsilane, (trifluoromethyl) triethylsilane, and (trifluoromethyl) tripropylsilane are preferred in terms of availability of trifluoromethylsilane (10) and good yield of cobalt complex (1c). (Trifluoromethyl) trimethylsilane is more preferred.

  The trifluoromethylsilane (10) used in the production method 4 of the present invention may be a commercially available product or a product produced according to the method described in Science, Vol. 338, page 1324 (2012).

  In the production method 4, cesium fluoride, tetrabutylammonium fluoride (TBAF), tetrabutylammonium difluorotriphenyl silicate (TBAT), or the like may be added.

  It is preferable to implement the manufacturing method 4 in inert gas atmosphere at the point with the good yield of a cobalt complex (1c). Specific examples of the inert gas include helium, neon, argon, krypton, xenon, nitrogen gas and the like, and argon or nitrogen gas is preferable from the viewpoint of low cost.

  It is preferable to implement the manufacturing method 4 in an organic solvent at the point with the favorable yield of a cobalt complex (1c). The type of organic solvent that can be used is not particularly limited as long as the reaction is not inhibited. Examples of usable solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, and butylbenzene. , Aromatic hydrocarbons such as isobutylbenzene, sec-butylbenzene, tert-butylbenzene, 1,3,5-trimethylbenzene (mesitylene), diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl Ethers such as ether (CPEE), tert-butyl methyl ether (MTBE), tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane It can be mentioned. One of these organic solvents can be used alone, or a plurality of them can be mixed at an arbitrary ratio. In terms of good yield of the cobalt complex (1c), the organic solvent is preferably ether, CPME, MTBE, diethyl ether or THF is more preferred, and THF is particularly preferred.

  Next, the molar ratio of the cobalt complex (1A) and the trifluoromethylsilane (10) when the production method 4 is carried out will be described. Preferably, cobalt complex (1c) can be produced with good yield by reacting 1.0 to 3.0 mol of trifluoromethylsilane (10) with respect to 1 mol of cobalt complex (1A).

  In production method 4, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a metal complex. As a specific example, a cobalt complex (1c) is produced with high yield by selecting a reaction time appropriately selected from a range of 10 minutes to 120 hours at a reaction temperature appropriately selected from a temperature range of −80 ° C. to 120 ° C. I can do it.

  The cobalt complex (1c) produced by the production method 4 can be purified by appropriately selecting and using a general purification method when a person skilled in the art purifies a metal complex. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography and the like.

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

  Examples of film formation conditions for producing the cobalt-containing thin film include normal technical means used by those skilled in the art to produce a metal-containing thin film. Specifically, a vapor deposition method based on a chemical reaction, a solution method such as a dip coating method, a spin coating method, or an ink jet method can be exemplified. In the present specification, the vapor deposition method based on a chemical reaction is a method of producing a cobalt-containing thin film by vaporizing the cobalt complex (1) of the present invention and decomposing it on a substrate. It includes CVD methods such as thermal CVD method, plasma CVD method, photo CVD method, ALD method and the like. A vapor deposition method based on a chemical reaction is preferable, and a CVD method or an ALD method is more preferable in that a cobalt-containing thin film can be easily formed uniformly on the surface of a substrate having a three-dimensional structure. The CVD method is particularly preferable from the viewpoint of good film forming speed, and the ALD method is particularly preferable from the viewpoint of good step coverage. For example, when a cobalt-containing thin film is produced by a CVD method or an ALD method, the cobalt complex (1) is vaporized and supplied to the reaction chamber, and the cobalt complex (1) is decomposed on the substrate provided in the reaction chamber, A cobalt-containing thin film can be formed on the substrate. Examples of the method for decomposing the cobalt complex (1) include normal technical means used by those skilled in the art to produce a metal-containing thin film. Specifically, a method of reacting the cobalt complex (1) with the reaction gas, a method of applying heat, plasma, light or the like to the cobalt complex (1) can be exemplified.

  In the case of using a reaction gas, examples of the reaction gas that can be used include a reducing gas and an oxidizing gas. As the reaction gas, a reducing gas is preferable in that it can prevent deterioration of the substrate when a film is formed on a substrate that is easily oxidized such as metal or metal nitride. Specific examples of the reducing gas include ammonia, hydrogen, monosilane, hydrazine, formic acid and the like. As the reducing gas, ammonia, hydrogen, or formic acid is preferable, and ammonia is more preferable because it is less restricted by the specifications of the film forming apparatus and easy to handle. When an oxidizing gas is used, specific examples thereof include oxygen, ozone, water vapor, hydrogen peroxide, laughing gas, hydrogen chloride, nitric acid gas, acetic acid and the like, and oxygen, ozone or water vapor is preferred. The flow rate of the reaction gas is appropriately adjusted according to the reactivity of the material and the capacity of the reaction chamber. For example, when the reaction chamber has a capacity of 1 to 10 L, the flow rate of the reaction gas is not particularly limited and is preferably 1 to 10,000 sccm for economic reasons. In this specification, sccm is a unit representing the gas flow rate, and 1 sccm represents that the gas is moving at a rate of 2.68 mmol / h when converted to an ideal gas.

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

  As a carrier gas and a dilution gas for producing a cobalt-containing thin film by a CVD method or an ALD method, a rare gas such as helium, neon, argon, krypton, or xenon, or a nitrogen gas is preferable. For economic reasons, nitrogen gas or argon Is more preferable. The flow rates of the carrier gas and the dilution gas are appropriately adjusted according to the capacity of the reaction chamber. For example, when the capacity of the reaction chamber is 1 to 10 L, the flow rate of the carrier gas is not particularly limited and is preferably 1 to 10,000 sccm for economical reasons.

  The substrate temperature when the cobalt-containing thin film is produced by the CVD method or the ALD method is appropriately selected depending on the use of heat, plasma, light, etc., the type of reaction gas, and the like. For example, when ammonia is used as a reaction gas without using light or plasma, the substrate temperature is not particularly limited, and is preferably 200 ° C. to 1000 ° C. for economic reasons. In view of a good film forming rate, 250 ° C to 800 ° C is preferable, and 300 ° C to 800 ° C is particularly preferable. In addition, by using light, plasma, ozone, hydrogen peroxide, or the like as appropriate, a cobalt-containing thin film can be formed in a temperature range of 200 ° C. or lower.

Examples of the cobalt-containing thin film obtained by the method for producing a cobalt-containing thin film of the present invention include a metal cobalt thin film, a cobalt oxide thin film, a cobalt nitride thin film, and a cobalt oxynitride thin film. Moreover, a cobalt containing composite film can be obtained by heat-processing a board | substrate at arbitrary temperature after producing a metal cobalt thin film. For example, after a metal cobalt thin film is formed on a silicon substrate, a cobalt silicide thin film of Co ₂ Si, CoSi, CoSi ₂ or the like can be obtained by heat treatment at 300 ° C. to 900 ° C. In addition, a cobalt-containing composite thin film can be obtained when used in combination with other metal materials. For example, a cobalt silicide thin film can be obtained by using the cobalt complex (1) of the present invention in combination with a silicon material. Examples of the silicon material include monosilane, disilane, trisilane, tetraethoxysilane, dimethyldimethoxysilane, bis (tert-butylamino) silane, bis (diethylamino) silane, and tris (dimethylamino) silane. Further, a metal material containing a typical metal such as aluminum or germanium, a transition metal such as titanium, zirconium, hafnium, niobium, tantalum or tungsten, or a rare earth metal such as lanthanum or neodymium, and the cobalt complex (1) of the present invention are used in combination. Thus, a cobalt-containing composite film containing these metal elements can also be obtained. In addition, when a cobalt-containing composite thin film is produced by CVD or ALD, the cobalt complex (1) of the present invention and another metal material may be supplied separately into the reaction chamber or after being mixed. Also good.

  By using the cobalt-containing thin film of the present invention as a constituent member, a high-performance semiconductor element with improved reliability and responsiveness can be manufactured. Examples of semiconductor elements include semiconductor memory devices such as DRAM, FeRAM, PRAM, MRAM, ReRAM, and flash memory, field effect transistors, and the like. Examples of these constituent members include a gate electrode of a transistor, a contact on a diffusion layer of a source / drain portion, a copper wiring seed layer / liner layer, and the like.

  By using the cobalt complex (1) of the present invention as a material, a cobalt-containing thin film can be produced under conditions using a reducing gas as a reaction gas.

It is a figure which shows the CVD apparatus used in Examples 5-8, 10-12, 16, and Comparative Examples 1 and 2. FIG. It is a figure which shows the X-ray-diffraction (henceforth, XRD) pattern of the film | membrane obtained in Examples 5-7. 10 is a diagram showing an XRD pattern of a film obtained in Example 8. FIG. It is a figure which shows the CVD apparatus used in Examples 20 and 21.

Hereinafter, although an example is given and the present invention is explained still in detail, the present invention is not limited to these. ¹ H and ¹³ C-NMR spectra were measured using a Varian VXR-500S NMR Spectrometer. Production of the complexes described in Reference Examples 1 to 4, Examples 1 to 4, 9, 13 to 15, 17 to 19, and 22 to 25 was all performed in an argon atmosphere.

  Reference example 1

Aldrich sodium cyclopentadienide / THF solution (2.0 M, 48.0 mL, 96 mmol) was added at 25 ° C. to 11.7 g (132 mmol) of ethyl acetate manufactured by Wako Pure Chemical Industries, Ltd., and the mixture was heated to reflux for 6 hours. . The solvent was distilled off from the resulting slurry under reduced pressure. To the remaining solid, 6.00 g (46.2 mmol) of cobalt chloride manufactured by Wako Pure Chemical Industries and 230 mL of THF were added at 25 ° C., followed by stirring at 25 ° C. for 65 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 250 mL of toluene was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. The produced suspension was filtered, and the filtrate was dried under reduced pressure to give bis (η ⁵ -acetylcyclopentadienyl) cobalt (Co (η ⁵ -C ₅ H ₄ C (O) CH ₃ ) ₂ ). Was obtained as a purple solid (4.00 g, 32% yield).

  Example 1

To a solution prepared by mixing 922 mg (3.37 mmol) of bis (η ⁵ -acetylcyclopentadienyl) cobalt prepared in Reference Example 1 and 14 mL of THF, 953 mg (14. 0 mmol) and 83 mg (3.61 mmol) of sodium were added. After stirring at 25 ° C. for 16 hours, the solvent was distilled off under reduced pressure. 20 mL of hexane was added to the remaining solid and vigorously stirred at 25 ° C. After the produced suspension was filtered, the filtrate was concentrated under reduced pressure. The remaining liquid was distilled under reduced pressure (distillation temperature 88 ° C./back pressure 36 Pa) to obtain (η ⁵ -acetylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a-3 ) As a red liquid (177 mg, 22% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
5.01 (brs, 1H), 4.94 (brs, 1H), 4.55-4.77 (br, 2H), 4.37 (brs, 1H), 2.10 (s, 3H), 1 .80 (s, 3H), 1.72 (brs, 1H), 1.63 (brs, 1H), -0.37 (brs, 1H), -0.44 (brs, 1H).
¹³ C-NMR (125 MHz, C ₆ D ₆ , δ)
194.9, 96.2, 93.7, 84.0, 83.2, 81.8, 81.2, 80.9, 35.5, 32.8, 27.1, 22.2.
Example 2

A solution prepared by mixing 1.59 g (5.82 mmol) of bis (η ⁵ -acetylcyclopentadienyl) cobalt prepared in Reference Example 1 and 24 mL of THF was added to 2,3-made by Aldrich at −78 ° C. 1.96 g (23.9 mmol) of dimethylbuta-1,3-diene and 146 mg (6.35 mmol) of sodium were added. After stirring at 25 ° C. for 16 hours, the solvent was distilled off under reduced pressure. To the remaining solid, 35 mL of hexane was added and vigorously stirred at 25 ° C. After the produced suspension was filtered, the filtrate was concentrated under reduced pressure. By purifying the remaining liquid using column chromatography (alumina, THF), (η ⁵ -acetylcyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1a -4) was obtained as a red liquid (311 mg, 22% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
4.94 (brs, 2H), 4.54 (brs, 2H), 2.06 (s, 3H), 1.81 (s, 6H), 1.67 (brs, 2H), -0.48 ( brs, 2H).
¹³ C-NMR (125 MHz, C ₆ D ₆ , δ)
194.8, 93.6, 93.3, 84.3, 81.7, 36.5, 27.2, 19.2.
Example 3

A sodium cyclopentadienide / THF solution (2.0 M, 50.0 mL, 100 mmol) manufactured by Aldrich was added to 10.8 g (122 mmol) of ethyl acetate manufactured by Wako Pure Chemical Industries, Ltd. at 25 ° C. and then heated to reflux for 6 hours. . After the solvent was distilled off from the obtained slurry under reduced pressure, the remaining solid was washed with 50 mL of hexane. To the obtained solid, 6.00 g (46.2 mmol) of cobalt chloride manufactured by Wako Pure Chemical Industries and 100 mL of THF were added at 0 ° C., and the mixture was stirred at 25 ° C. for 64 hours. To this mixture, 5.14 g (64.2 mmol) of cyclohexa-1,3-diene manufactured by Johnson Matthey and 1.07 g (46.5 mmol) of sodium were added at 0 ° C., followed by stirring at 25 ° C. for 24 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 190 mL of hexane was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. After the produced suspension was filtered, the solvent was distilled off from the filtrate under reduced pressure. By sublimating the remaining solid (heating temperature 110 ° C./back pressure 32 Pa), (η ⁵ -acetylcyclopentadienyl) (η ⁴ -cyclohexa-1,3-diene) cobalt (1b-2) was converted into a brown solid. (914 mg, 8% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
5.07-5.11 (m, 2H), 4.61-4.66 (m, 2H), 4.30-4.33 (m, 2H), 2.93-2.98 (br, 2H) ), 2.16 (s, 3H), 1.35-1.42 (m, 2H), 0.61-0.68 (m, 2H).
Example 4

To a solution prepared by mixing 2.91 g (10.7 mmol) of bis (η ⁵ -acetylcyclopentadienyl) cobalt prepared in Reference Example 1 and 40 mL of THF, cyclohexa-1 manufactured by Tokyo Chemical Industry at 0 ° C. 4-diene 4.30 g (53.7 mmol) and sodium 244 mg (10.6 mmol) were added. After stirring at 25 ° C. for 33 hours, the solvent was distilled off from the reaction mixture under reduced pressure. 190 mL of hexane was added to the remaining solid and vigorously stirred at 25 ° C. The produced suspension was filtered, and the filtrate was dried under reduced pressure to give (η ⁵ -acetylcyclopentadienyl) (η ⁴ -cyclohexa-1,3-diene) cobalt (1b-2) as a brown solid. (155 mg, 6% yield). The resulting brown solid (eta ⁵ - acetyl cyclopentadienyl) (eta ⁴ - cyclohexa-1,3-diene) that cobalt (1b-2) ^were identified on the basis of 1 H-NMR spectrum.

Examples 5 to 7, Comparative Examples 1 and 2
A cobalt-containing thin film was produced by a thermal CVD method using cobalt complex (1) or bis (ethylcyclopentadienyl) cobalt (Co (η ⁵ -C ₅ H ₄ CH ₂ CH ₃ ) ₂ ) as a material. Bis (ethylcyclopentadienyl) cobalt is produced according to the method described in the Chemical Society of Japan, “Experimental Chemistry Course 18 Organometallic Complex”, 4th edition, Maruzen, 1992. Specifically, it was synthesized by reacting sodium ethylcyclopentadienyl with cobalt chloride. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as shown in Table 1, and other conditions are as follows.

  Carrier gas flow rate: 20 sccm, ammonia flow rate: 120 sccm, dilution gas flow rate: 60 sccm, substrate: Si, deposition time: 1 hour, total reaction chamber pressure: 1.3 kPa. The total pressure in the material container was adjusted so that the material supply rate was 0.020 sccm. The material supply rate to the reaction chamber can be obtained based on the calculation formula of (carrier gas flow rate × material vapor pressure ÷ total pressure in the material container). Argon was used as the carrier gas and diluent gas.

  In the case of Examples 5 to 7 and Comparative Example 1, when the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on cobalt were detected. On the other hand, in the case of Comparative Example 2, characteristic X-rays based on cobalt were not detected. For fluorescence X-ray analysis, 3370E manufactured by Rigaku Corporation was used. The measurement conditions were X-ray source: Rh, output: 50 kV, 50 mA, and measurement diameter: 10 mm. Table 1 shows the film thickness calculated from the detected X-ray intensity. The electrical characteristics of the produced cobalt-containing thin film were measured by a four-probe method, and the obtained resistivity is shown in Table 1. For the four-point probe method, LORESTA HP MCP-T410 manufactured by Mitsubishi Oil Chemical Co., Ltd. was used.

  The thin films prepared under the conditions of Examples 5 to 7 were subjected to crystal evaluation by XRD, and it was suggested that all the thin films were β-Co having a face-centered cubic (fcc) structure. RAD-C manufactured by Rigaku Corporation was used for XRD. Measurement conditions were X-ray source: CuKα (using graphite monochromator), output: 50 kV 200 mA, 2θ continuous scan, θ = 0.4 ° (however, only the thin film produced in Example 5 was fixed at 0.7 °).

Example 8
The thin film produced under the conditions of Example 5 (however, the ammonia flow rate: 160 sccm, the dilution gas flow rate: 20 sccm) was subjected to heat treatment using MILA-3000-PN made by ULVAC-RIKO. The heating conditions were as follows: temperature: 800 ° C., atmosphere: nitrogen 2 Pa, heating rate: 26 ° C./sec, holding time: 30 sec. Was subjected to a crystallization evaluated by XRD for thin film after heat _treatment, the presence of beta-Co of CoSi 2, CoSi and fcc structure was confirmed.

The following can be understood from the above embodiments. That is, it can be seen from Examples 5 to 7 that the cobalt complex (1) is a material capable of producing a cobalt-containing thin film without using an oxidizing gas. Moreover, from Examples 5 to 7, it can be seen that by using the cobalt complex (1) as a material, a metal cobalt thin film having an fcc structure can be produced without using an oxidizing gas. Furthermore, it can be seen from Example 8 that a cobalt silicide thin film such as CoSi ₂ or CoSi can be produced by heat-treating a metal cobalt thin film produced using the cobalt complex (1) as a material.

  From the above examples, the cobalt complex (1) is a material capable of forming a cobalt-containing film at a low temperature of 400 ° C. or less without using light or plasma without using an oxidizing gas. It turns out that it is a useful material with a wide application range as a material.

  Example 9

Aldrich sodium cyclopentadienide / THF solution (2.0 M, 50.0 mL, 100 mmol) was added at 25 ° C. to 14.9 g (128 mmol) of ethyl butyrate manufactured by Wako Pure Chemical Industries, Ltd., and then heated to reflux for 7 hours. . After the solvent was distilled off from the obtained solution under reduced pressure, the remaining solid was washed with 50 mL of hexane. To the obtained solid, 5.90 g (45.4 mmol) of cobalt chloride manufactured by Wako Pure Chemical Industries and 100 mL of THF were added at 0 ° C., and the mixture was stirred at 25 ° C. for 14 hours. To the obtained mixture, 7.27 g (88.5 mmol) of 2,3-dimethylbuta-1,3-diene made by Aldrich and 1.16 g (50.4 mmol) of sodium were added at 0 ° C., and then 25 ° C. For 23 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 170 mL of hexane was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. After the produced suspension was filtered, the solvent was distilled off from the filtrate under reduced pressure. The remaining liquid column chromatography (alumina, THF) by purified using, (eta ⁵ - butyryl cyclopentadienyl) (eta ^{4-2,3-dimethyl-1,3-diene)} cobalt ( 1a-12) was obtained as a brown liquid (1.88 g, 15% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
5.00-5.03 (m, 2H), 4.48-4.54 (m, 2H), 2.45 (t, J = 7.5 Hz, 2H), 1.83 (s, 6H), 1.74-1.82 (m, 2H), 1.71 (brs, 2H), 0.93 (t, J = 7.5 Hz, 3H), -0.45 (brs, 2H).
Example 10
Obtained in Example 1 - by (eta ^{5-acetyl-cyclopentadienyl)} (eta ^{4-2-methylbut-1,3-diene)} cobalt thermal CVD cobalt-containing thin film (1a-3) with the material Produced. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

  Carrier gas flow rate: 20 sccm, ammonia flow rate: 120 sccm, dilution gas flow rate: 60 sccm, substrate: Si, film formation time: 1 hour, total reaction chamber pressure: 1.3 kPa, material container temperature: 83 ° C., vapor pressure of material: 6 7 Pa, substrate temperature: 250 ° C. The total pressure in the material container was adjusted so that the material supply rate was 0.020 sccm. Argon was used as the carrier gas and diluent gas.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on cobalt were detected.

Example 11
Using (η ⁵ -acetylcyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1a-4) obtained in Example 2 as a material, a cobalt-containing thin film was heated. It was produced by the CVD method. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

  Carrier gas flow rate: 20 sccm, ammonia flow rate: 160 sccm, dilution gas flow rate: 20 sccm, substrate: Si, film formation time: 1 hour, total reaction chamber pressure: 1.3 kPa, material container temperature: 72 ° C., vapor pressure of material: 13 3 Pa, substrate temperature: 250 ° C. The total pressure in the material container was adjusted so that the material supply rate was 0.020 sccm. Argon was used as the carrier gas and diluent gas.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on cobalt were detected.

Example 12
A cobalt-containing thin film was produced by a thermal CVD method using (η ⁵ -acetylcyclopentadienyl) (η ⁴ -cyclohexa-1,3-diene) cobalt (1b-2) obtained in Example 3 as a material. . The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

  Carrier gas flow rate: 20 sccm, ammonia flow rate: 160 sccm, dilution gas flow rate: 20 sccm, substrate: Si, film formation time: 1 hour, total reaction chamber pressure: 1.3 kPa, material container temperature: 86 ° C., vapor pressure of material: 13 3 Pa, substrate temperature: 250 ° C. The total pressure in the material container was adjusted so that the material supply rate was 0.020 sccm. Argon was used as the carrier gas and diluent gas.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on cobalt were detected.

  The following can be understood from the above embodiments. That is, it can be seen from Examples 10 to 12 that the cobalt complex (1) is a material capable of producing a cobalt-containing thin film without using an oxidizing gas.

  Reference example 2

A sodium cyclopentadienide / THF solution (2.0 M, 50.0 mL, 100 mmol) manufactured by Aldrich was added to 15.7 g (120 mmol) of ethyl isovalerate manufactured by Tokyo Chemical Industry at 25 ° C., followed by heating to reflux for 19 hours. did. The solvent was distilled off from the resulting solution under reduced pressure. To the remaining solid, 5.90 g (45.4 mmol) of cobalt chloride manufactured by Wako Pure Chemical Industries and 100 mL of THF were added at 0 ° C., followed by stirring at 25 ° C. for 30 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 130 mL of hexane was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. The produced suspension was filtered, and the filtrate was dried under reduced pressure to give bis (η ⁵ -isovalerylcyclopentadienyl) cobalt (Co (η ⁵ -C ₅ H ₄ C (O) CH ₂ CH (CH ₃ ) ₂ ) ₂ ) was obtained as a purple liquid (7.56 g, 47% yield).

  Example 13

To a solution of 13.2 g (101 mmol) of sodium acetylcyclopentadienyl synthesized according to the method described in Journal of the American Chemical Society, Vol. 102, page 1196 (1980) in THF (100 mL) at 0 ° C. 6.50 g (50.0 mmol) of cobalt chloride manufactured by Yakuhin Kogyo was added and stirred at 25 ° C. for 3 hours (solution A). A butadiene-hexane solution was prepared by putting 81 mL of hexane in another container and dissolving 6.4 g of buta-1,3-diene. Under 0 ° C., 40 mL of the butadiene-hexane solution and 1.20 g (52.2 mmol) of sodium were added to the solution A, followed by stirring at 25 ° C. for 16 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 160 mL of hexane was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. The produced suspension is filtered, and then the solvent is distilled off from the filtrate under reduced pressure to obtain (η ⁵ -acetylcyclopentadienyl) (η ⁴ -buta-1,3-diene) cobalt (1a-1). Was obtained as a red liquid (1.25 g, 11% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
4.99-5.06 (m, 2H), 4.72-4.81 (m, 2H), 4.40-4.47 (m, 2H), 2.11 (s, 3H), 1. 65-1.71 (m, 2H), -0.31 (brs, 2H).
¹³ C-NMR (125 MHz, C ₆ D ₆ , δ)
194.9, 93.8, 82.8, 81.6, 81.0, 33.7, 26.9.
Example 14

A sodium cyclopentadienide / THF solution (2.0 M, 80.0 mL, 160 mmol) manufactured by Aldrich was added to 22.1 g (190 mmol) of ethyl butyrate manufactured by Tokyo Chemical Industry Co., Ltd. at 25 ° C., followed by heating under reflux for 8 hours. After the solvent was distilled off from the obtained slurry under reduced pressure, the remaining solid was washed with 100 mL of hexane. To the obtained solid, 9.87 g (76.0 mmol) of cobalt chloride manufactured by Wako Pure Chemical Industries and 100 mL of THF were added at 0 ° C., and the mixture was stirred at 25 ° C. for 4 hours. Further, 17.4 g (256 mmol) of isoprene manufactured by Kanto Chemical Co., Ltd. and 1.87 g (81.1 mmol) of sodium were added at 0 ° C., followed by stirring at 25 ° C. for 18 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 200 mL of hexane was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. The produced suspension was filtered, and then the solvent was distilled off from the filtrate under reduced pressure to obtain (η ⁵ -butyrylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a -11) was obtained as a red liquid (9.08 g, yield 46%).
¹ H-NMR (500 MHz, CDCl ₃ , δ)
5.22-5.29 (m, 1H), 5.16-5.22 (m, 1H), 4.92-5.05 (m, 2H), 4.69-4.79 (m, 1H) ), 2.72 (t, J = 7.4 Hz, 2H), 2.05 (s, 3H), 1.88 (brs, 1H), 1.69-1.83 (m, 3H),. 99 (t, J = 7.4 Hz, 3H), -0.33 (brs, 1H), -0.42 (brs, 1H).
Example 15

To a solution prepared by mixing 7.56 g (21.2 mmol) of bis (η ⁵ -isovalerylcyclopentadienyl) cobalt prepared in Reference Example 2 and 100 mL of THF, isoprene 5 manufactured by Kanto Chemical Co., Ltd. at 0 ° C. .45 g (80.0 mmol) and 558 mg (24.3 mmol) of sodium were added. After stirring at 25 ° C. for 15 hours, the solvent was distilled off under reduced pressure. To the remaining solid, 140 mL of hexane was added and vigorously stirred at 25 ° C. After the produced suspension was filtered, the filtrate was concentrated under reduced pressure. By purifying the remaining liquid using column chromatography (alumina, THF), (η ⁵ -isovalerylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a- 23) was obtained as a red liquid (1.30 g, 22% yield).
¹ H-NMR (500 MHz, CDCl ₃ , δ)
5.24 (brs, 1H), 5.18 (brs, 1H), 4.95-5.04 (m, 1H), 4.92 (brs, 1H), 4.72 (brs, 1H), 2 .62 (d, J = 7.0 Hz, 2H), 2.26-2.42 (m, 1H), 2.06 (s, 3H), 1.90 (brs, 1H), 1.73-1 .83 (m, 1H), 1.00 (d, J = 7.0 Hz, 6H), -0.33 (brs, 1H), -0.42 (brs, 1H).
¹³ C-NMR (125 MHz, C ₆ D ₆ , δ)
197.3, 96.2, 83.9, 82.9, 81.5, 81.2, 80.9, 79.4, 48.7, 35.7, 32.9, 25.3, 23. 0, 22.4.
Example 16
Using the (η ⁵ -isovalerylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a-23) obtained in Example 15 as a material, a cobalt-containing thin film was subjected to thermal CVD. It was produced by the method. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

  Carrier gas flow rate: 20 sccm, ammonia flow rate: 160 sccm, dilution gas flow rate: 20 sccm, substrate: Si, film formation time: 1 hour, total reaction chamber pressure: 1.3 kPa, material container temperature: 69 ° C., vapor pressure of material: 13 3 Pa, substrate temperature: 300 ° C. The total pressure in the material container was adjusted so that the material supply rate was 0.020 sccm. Argon was used as the carrier gas and diluent gas.

When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on cobalt were detected.
The following can be understood from Example 16. That is, it can be seen that the cobalt complex (1) is a material capable of producing a cobalt-containing thin film without using an oxidizing gas.

  Reference example 3

To a solution prepared by mixing 1.92 g (10.1 mmol) of bis (η ⁵ -cyclopentadienyl) cobalt manufactured by Wako Pure Chemical Industries and 28 mL of THF, 3.40 g of isoprene manufactured by Kanto Chemical Co., Ltd. at −78 ° C. (50.0 mmol) and 260 mg (11.3 mmol) of sodium were added. After stirring at 25 ° C. for 25 hours, the solvent was distilled off under reduced pressure. Hexane 40mL was added to the remaining solid and it stirred violently at 25 degreeC. After the produced suspension was filtered, the filtrate was concentrated under reduced pressure. The remaining liquid was distilled under reduced pressure (distillation temperature: 45 ° C./back pressure: 27 Pa) to obtain (η ⁵ -cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt as a red liquid. (988 mg, 51% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
4.85 (brs, 1H), 4.54 (s, 5H), 1.96 (s, 3H), 1.81 (brs, 1H), 1.69 (brs, 1H), -0.35 ( brs, 1), -0.47 (brs, 1H).
¹³ C-NMR (125 MHz, C ₆ D ₆ , δ)
94.2, 80.2, 78.7, 34.0, 30.3, 23.4.
Reference example 4

A solution prepared by mixing bis (η ⁵ -cyclopentadienyl) cobalt 10.1 (53.3 mmol) manufactured by Wako Pure Chemical Industries and 100 mL of THF was added to 2,3-dimethylbutane manufactured by Aldrich at 0 ° C. -1,3-Diene 13.1g (159mmol) and sodium 1.36g (59.1mmol) were added. After stirring at 25 ° C. for 18 hours, the solvent was distilled off under reduced pressure. To the remaining solid, 100 mL of hexane was added and vigorously stirred at 25 ° C. After filtering the produced suspension, the solvent was distilled off from the filtrate under reduced pressure to obtain (η ⁵ -cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt. Obtained as a red solid (10.9 g, 99% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
4.51 (s, 5H), 1.98 (s, 6H), 1.77 (brs, 2H), -0.47 (brs, 2H).
Example 17

To the solution prepared by mixing 655 mg (3.18 mmol) of (η ⁵ -cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt prepared in Reference Example 4 and 10 mL of THF. After adding 1.30 mL (2.65 M, 3.45 mmol) of an n-butyllithium / hexane solution manufactured by Kanto Chemical and 392 mg (3.49 mmol) of potassium tert-butoxide manufactured by Kanto Chemical at −78 ° C., − The mixture was stirred for 3 hours while maintaining at 78 ° C. To this reaction solution, 472 mg (6.46 mmol) of N, N-dimethylformamide manufactured by Kanto Chemical Co. was added at −78 ° C., followed by stirring at 25 ° C. for 19 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 20 mL of hexane was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. After the produced suspension is filtered, the solvent is distilled off from the filtrate under reduced pressure to obtain (η ⁵ -formylcyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt. (1a-36) was obtained as a yellow solid (650 mg, 87% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
9.72 (s, 1H), 4.85 (brs, 2H), 4.47 (brs, 2H), 1.78 (s, 6H), 1.68 (brs, 2H), -0.45 ( brs, 2H).
Example 18

To a solution prepared by mixing 4.98 g (25.9 mmol) of (η ⁵ -cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt prepared in Reference Example 3 and 100 mL of THF, After adding 10.3 mL (2.65 M, 27.3 mmol) of n-butyllithium / hexane solution manufactured by Kanto Chemical and 3.05 g (27.2 mmol) of potassium tert-butoxide manufactured by Kanto Chemical at −78 ° C. The mixture was stirred for 3 hours while maintaining at -78 ° C. To this reaction solution was added 4.96 g (27.4 mmol) of 1- (trifluoroacetyl) piperidine manufactured by Tokyo Chemical Industry at −78 ° C., and the mixture was stirred at 25 ° C. for 30 minutes. After the solvent was distilled off from the reaction mixture under reduced pressure, 130 mL of hexane was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. The produced suspension is filtered, and then the solvent is distilled off from the filtrate under reduced pressure to obtain (η ^5- (trifluoroacetyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene). Cobalt (1a-47) was obtained as a red liquid (7.32 g, yield 98%).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
4.99-5.07 (m, 1H), 4.96 (brs, 2H), 4.74 (brs, 1H), 4.69 (brs, 1H), 2.09 (s, 3H), 1 .99 (brs, 1H), 1.92 (brs, 1H), -0.27 (brs, 1H), -0.33 (brs, 1H). ¹⁹ F-NMR (470 MHz, C ₆ D ₆ , δ)
-74.9 (s).
Example 19

Prepared by mixing 2.62 g (12.7 mmol) of (η ⁵ -cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt prepared in Reference Example 4 and 30 mL of THF. To the solution, 5.30 mL (2.65 M, 14.1 mmol) of n-butyllithium / hexane solution manufactured by Kanto Chemical Co., Ltd. and 1.57 g (14.0 mmol) of potassium tert-butoxide manufactured by Kanto Chemical Co. were added at −78 ° C. Then, the mixture was stirred for 3 hours while maintaining at -78 ° C. To this reaction solution was added 2.54 g (14.0 mmol) of 1- (trifluoroacetyl) piperidine manufactured by Tokyo Chemical Industry at −78 ° C., followed by stirring at 25 ° C. for 30 minutes. After the solvent was distilled off from the reaction mixture under reduced pressure, 35 mL of hexane was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. The produced suspension is filtered, and then the solvent is distilled off from the filtrate under reduced pressure to obtain (η ^5- (trifluoroacetyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3. -Diene) cobalt (1a-48) was obtained as a red liquid (3.72 g, 97% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
4.93 (brs, 2H), 4.72 (brs, 2H), 2.09 (s, 6H), 1.94 (brs, 2H), -0.37 (brs, 2H).
¹⁹ F-NMR (470 MHz, C ₆ D ₆ , δ)
-73.5 (s).
Example 20
Obtained in Example 1 - by (eta ^{5-acetyl-cyclopentadienyl)} (eta ^{4-2-methylbut-1,3-diene)} cobalt thermal CVD cobalt-containing thin film (1a-3) with the material Produced. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

  Material container temperature: 72 ° C., material carrier gas flow rate: 20 sccm, material container total pressure: 13.3 kPa, reaction gas container temperature: 25 ° C., reaction gas carrier gas flow rate: 10 sccm, reaction gas container total pressure: 66 0.7 kPa, dilution gas flow rate: 170 sccm, substrate: Si, film formation time: 1 hour, total reaction chamber pressure: 1.3 kPa, substrate temperature: 300 ° C. Argon was used as the carrier gas and diluent gas. Formic acid was used as the reaction gas.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on cobalt were detected.

Example 21
Using (η ⁵ -acetylcyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1a-4) obtained in Example 2 as a material, a cobalt-containing thin film was heated. It was produced by the CVD method. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

  Material container temperature: 72 ° C., material carrier gas flow rate: 40 sccm, material container total pressure: 5.3 kPa, reaction gas container temperature: 25 ° C., reaction gas carrier gas flow rate: 20 sccm, reaction gas container total pressure: 26 0.7 kPa, dilution gas flow rate: 10 sccm, substrate: Si, film formation time: 1 hour, total reaction chamber pressure: 1.3 kPa, substrate temperature: 300 ° C. Argon was used as the carrier gas and diluent gas. Formic acid was used as the reaction gas.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on cobalt were detected.

  Example 22

To a solution prepared by mixing 1.34 g (6.97 mmol) of (η ⁵ -cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt prepared in Reference Example 3 and 30 mL of THF, After adding 2.90 mL (2.65 M, 7.69 mmol) of an n-butyllithium / hexane solution manufactured by Kanto Chemical and 862 mg (7.68 mmol) of potassium tert-butoxide manufactured by Kanto Chemical at −78 ° C., −78 The mixture was stirred for 3 hours while maintaining the temperature. To this reaction solution, 566 mg (7.75 mmol) of N, N-dimethylformamide manufactured by Kanto Chemical Co. was added at −78 ° C., followed by stirring at 25 ° C. for 14 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 45 mL of hexane was added to the remaining solid, and the mixture was vigorously stirred at 25 ° C. After the produced suspension was filtered, the solvent was distilled off from the filtrate under reduced pressure to obtain (η ⁵ -formylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1a- 35) was obtained as a yellow solid (1.38 g, 90% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
9.77 (s, 1H), 4.81-4.92 (m, 2H), 4.65-4.76 (m, 1H), 4.58 (brs, 1H), 4.28 (brs, 1H), 1.76 (s, 3H), 1.73 (brs, 1H), 1.57-1.64 (m, 1H), -0.33 (brs, 1H), -0.42 (brs) , 1H).
Example 23

To the solution prepared by mixing 1.38 g (6.27 mmol) of (η ⁵ -formylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt prepared in Example 22 and 30 mL of THF. After adding 1.73 g (12.2 mmol) of (trifluoromethyl) trimethylsilane manufactured by Tokyo Chemical Industry at 0 ° C., the mixture was stirred at 25 ° C. for 1 hour. After the solvent was distilled off from the reaction mixture under reduced pressure, the remaining liquid was distilled under reduced pressure (distillation temperature 72 ° C./back pressure 19 Pa) to obtain (η ^5- (2,2,2-trifluoro-1-). Trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-3) was obtained as a red liquid (372 mg, 16% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
4.72-5.08 (m, 3H), 4.17-4.42 (m, 2H), 3.87-4.16 (m, 1H), 1.93 (brs, 3H), 1. 63-1.73 (m, 1H), 1.73-1.85 (m, 1H), 0.15 (s, 9H), -0.36 (brs, 1H), -0.47 (brs, 1H).
¹⁹ F-NMR (470 MHz, C ₆ D ₆ , δ)
-77.4 (brs).
Example 24

A solution prepared by mixing 858 mg (3.66 mmol) of (η ⁵ -formylcyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt prepared in Example 17 and 20 mL of THF. To this was added 518 mg (3.65 mmol) of (trifluoromethyl) trimethylsilane manufactured by Tokyo Chemical Industry at 0 ° C., and the mixture was stirred at 25 ° C. for 15 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, the remaining liquid was distilled under reduced pressure (distillation temperature 80 ° C./back pressure 37 Pa) to give (η ^5- (2,2,2-trifluoro-1-). Trimethylsilyloxyethyl) cyclopentadienyl) (η ⁴ -2,3-dimethylbuta-1,3-diene) cobalt (1c-4) was obtained as a red liquid (330 mg, 24% yield).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
5.01-5.15 (m, 1H), 4.26-4.72 (m, 3H), 3.83 (brs, 1H), 1.99 (brs, 3H), 1.92 (brs, 3H), 1.76-1.86 (m, 1H), 1.65-1.76 (m, 1H), 0.18 (brs, 9H), -0.44 (brs, 1H), -0 .48 (brs, 1H).
¹⁹ F-NMR (470 MHz, C ₆ D ₆ , δ)
-77.5 (brs).
Example 25

To a solution prepared by mixing 369 mg (1.58 mmol) of (η ⁵ -acetylcyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt prepared in Example 1 and 20 mL of THF, 25 After adding 221 mg (1.55 mmol) of (trifluoromethyl) trimethylsilane manufactured by Tokyo Chemical Industry and 240 mg (1.58 mmol) of cesium fluoride manufactured by Wako Pure Chemical Industries, Ltd., the mixture was stirred at 25 ° C. for 20 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, the remaining liquid was distilled under reduced pressure (distillation temperature 77 ° C./back pressure 45 Pa) to give (η ^5- (1-trifluoromethyl-1-trimethylsilyloxyethyl). ) Cyclopentadienyl) (η ⁴ -2-methylbuta-1,3-diene) cobalt (1c-7) was obtained as a red liquid (242 mg, yield 41%).
¹ H-NMR (500 MHz, C ₆ D ₆ , δ)
4.77-4.88 (m, 1H), 4.70-4.92 (m, 1H), 4.36-4.61 (m, 1H), 4.03-4.25 (m, 1H) ), 3.92-4.03 (m, 1H), 1.93 (s, 3H), 1.77-1.83 (m, 1H), 1.76 (s, 3H), 1.65 1.73 (m, 1H), 0.18 (s, 9H), -0.39 (brs, 1H), -0.50 (brs, 1H).
¹⁹ F-NMR (470 MHz, C ₆ D ₆ , δ)
-80.1 (brs).

DESCRIPTION OF SYMBOLS 1 Material container 2 Constant temperature bath 3 Reaction chamber 4 Substrate 5 Reaction gas introduction port 6 Dilution gas introduction port 7 Carrier gas introduction port 8 Mass flow controller 9 Mass flow controller 10 Mass flow controller 11 Oil rotary pump 12 Exhaust 13 Material container 14 Constant temperature for materials Tank 15 Reaction gas container 16 Constant temperature bath for reaction gas 17 Reaction chamber 18 Substrate 19 Material carrier gas introduction port 20 Dilution gas introduction port 21 Reaction gas carrier gas introduction port 22 Mass flow controller 23 Mass flow controller 24 Mass flow controller 25 Oil rotary vacuum pump 26 Exhaust

Claims (15)

General formula (1)

(In the formula, A represents the general formula (2)

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom) or a general formula (3)

(Wherein, ^{R 1} represents the general formula (2) ^{R 1} .R represents a synonymous ² represents. Alkyl group having 1 to 4 carbon atoms) of 1-trifluoromethyl-1-silyloxy alkyl represented by Represents a group. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁸ represent a hydrogen atom or a group that forms an alkylene group having 2 to 4 carbon atoms together. A cobalt complex represented by General formula (1A)

^{(Wherein, R 3, R 4, R 5} , R 6, ^{R 7} and ^{R 8} represent ^{R 3, R 4, R 5} , R 6, same meanings as ^{R 7} and ^{R 8} in the general formula (1), R ¹ represents R ¹ as defined in formula (2).) cobalt complex of claim 1 represented by. General formula (1a)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1), ^{R 1} and ^{R 1} in the general formula (2) The cobalt complex according to claim 1, which represents the same meaning. General formula (1b)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1), ^{R 1} and ^{R 1} in the general formula (2) The cobalt complex according to claim 1, wherein X represents a synonym, wherein X represents an integrated alkylene group having 2 to 4 carbon atoms in R ³ and R ⁸ of the general formula (1). General formula (1c)

^{(Wherein, R 3, R 4, R 5} , R 6, ^{R 7} and ^{R 8} represent ^{R 3, R 4, R 5} , R 6, same meanings as ^{R 7} and ^{R 8} in the general formula (1), R ¹ represents ^{R 1} as defined in formula (2), the cobalt complex according to claim 1 ^{R 2} is represented by representing the ^{R 2} as defined in formula (3).). General formula (4)

(Wherein R ¹ represents the same meaning as R ^{1 in} formula (2)),
General formula (5)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7 R 4,} R 5, ^R represents a ⁶ and ^{R 7} as defined. In formula (1)) the conjugated chain diene represented by,
The manufacturing method of the cobalt complex of Claim 3 made to react in presence of an alkali metal. General formula (4)

(Wherein R ¹ represents the same meaning as R ^{1 in} formula (2)),
General formula (6)

^{(Wherein, R 4, R 5, R} 6 and ^{R 7 R} 4 in the general formula ^{(1), R 5, R} 6 and .X general formula representing the ^{R 7} synonymous (1) of the ^R 3, R represents an alkylene group having a carbon number of 2-4, which is integral in ^8. conjugated cyclic diene or formula represented by) (7a)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7} represent ^{R 4,} R 5, the same meaning as ^{R 6} and ^{R 7} in the general formula (1).) Or the general formula (7b)

^(Wherein, R ^4, R 5, ^{R 6} and ^{R 7 R 4,} R 5, ^R represents a ⁶ and ^{R 7} as defined. In formula (1)) the non-conjugated cyclic diene represented by,
The manufacturing method of the cobalt complex of Claim 4 made to react in presence of an alkali metal. General formula (8)

(Wherein ^{represents R 3, R 4, R 5} , R 6, R 7 and ^{R 8 R} 3 in the general formula ^{(1), R 4, R} 5, R 6, same meanings as ^{R 7} and ^{R 8.} And a cobalt complex represented by
With alkyllithium,
After reacting in the presence of alkali metal alkoxide,
General formula (9)

(In the formula, R ¹ .Y representing the R ¹ as defined in formula (2) represents. A leaving group) is reacted with an acylating agent represented by the method for producing a cobalt complex according to claim 2 . The method for producing a cobalt complex according to claim 8, wherein Y is a dialkylamino group. General formula (1A)

^{(Wherein, R 3, R 4, R 5} , R 6, ^{R 7} and ^{R 8} represent ^{R 3, R 4, R 5} , R 6, same meanings as ^{R 7} and ^{R 8} in the general formula (1), cobalt complex represented by R ¹ in general formula. representing the ^{R 1} as defined in (2)),
CF ₃ Si ^(R ₂₎ 3 (10) (wherein, ^{R 2} is Formula (3). Representing the ^{R 2} and synonymous) reacting the trifluoromethyl silane represented by, according to claim 5 A method for producing a cobalt complex. A method for producing a cobalt-containing thin film, comprising vaporizing the cobalt complex according to claim 1 and decomposing the cobalt complex on a substrate. The method according to claim 11, wherein decomposition is performed using a reducing gas. The production method according to claim 11 or 12, which is a production method of a cobalt-containing thin film by a vapor deposition method based on a chemical reaction. The manufacturing method in any one of Claims 11-13 which is a manufacturing method of the cobalt containing thin film by a chemical vapor deposition method. The method according to claim 11, wherein the cobalt-containing thin film is a metallic cobalt thin film.

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