RUTHENIUM COMPLEX, METHOD FOR PRODUCING SAME, AND METHOD FOR PRODUCING RUTHENIUM-CONTAINING THIN FILM

TECHNICAL FIELD

The present invention relates to a ruthenium complex useful as a raw material for the production of a semiconductor element, a production method thereof, and a method for producing a ruthenium-containing thin film using the ruthenium complex.

BACKGROUND ART

Ruthenium has features, e.g., exhibiting high electrical conductivity, permitting the formation of an electrically conductive oxide, having a high work function, and ensuring excellent etching characteristics and excellent lattice matching with copper and therefore, is attracting attention as a material for a memory electrode such as DRAM, a gate electrode, a copper-wiring seed layer/adhesion layer, etc. In the next-generation semiconductor device, a highly miniaturized and highly three-dimensional design is employed for the purpose of more enhancing the memory capacity or responsiveness. Accordingly, in order to use ruthenium as a material constituting the next-generation semiconductor device, it is required to establish a technique of uniformly forming a ruthenium-containing thin film with a thickness of approximately from a few nanometers to a few tens of nanometers on a three-dimensioned substrate. As the technique for producing a metal thin film on a three-dimensioned substrate, use of a vapor deposition method based on a chemical reaction, such as atomic layer deposition method (ALD method) and chemical vapor deposition method (CVD method), is believed promising. For example, in the case of depositing metallic ruthenium as a next-generation DRAM upper electrode by using this vapor deposition method, a metal oxide such as ZrO₂is used as a capacitor insulating film for the underlying base and therefore, the deposition may be performed under the conditions using an oxidizing gas. In the case of using ruthenium as a next-generation DRAM lower electrode or a copper-wiring seed layer/adhesion layer, titanium nitride, tantalum nitride, etc. is expected to be employed as a barrier metal for the underlying base. When a barrier metal is oxidized at the time of production of a ruthenium-containing thin film, there arises a problem such as deterioration of the barrier performance, defective conduction to a transistor due to rise in the resistance value, and reduction in the responsiveness resulting from an increased interconnection capacity. For the purpose of avoiding such a problem, a material enabling the production of a ruthenium-containing thin film even under the conditions without using an oxidizing gas such as oxygen and ozone is demanded.

In Non-Patent Document 1 and Non-Patent Document 2, (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium and (η⁵-2,4-di-tert-butyl-1-oxa-2,4-pentadienyl)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium are described as a compound having a structure similar to that of the ruthenium complex (1a) of the present invention. However, the compounds described in those documents are limited to a complex having an η⁵-1,2,3,4,5-pentamethylcyclopentadienyl ligand. In addition, the synthesis methods described in those documents are based on a reaction of chloro(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium with lithium enolate or a reaction of chloro(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium with an enone derivative and potassium carbonate and are different from the production method of the present invention.

Furthermore, those documents are absolutely silent as to using such a complex as a material for the production of a ruthenium-containing thin film.

A cationic ruthenium complex [(η⁵-cyclopentadienyl)tris(nitrile)ruthenium]⁺ is useful as a raw material for synthesis of various ruthenium complexes including the ruthenium complex of the present invention. Non-Patent Document 3 describes a method for producing [Ru(η⁵-C₅H₅)(MeCN)₃][PF₆] by irradiating [Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][PF₆] with light in acetonitrile. In addition, Non-Patent Document 4 describes a method for producing [Ru(η⁵-C₅H₅)(MeCN)₃][PF₆] by reacting ruthenocene with aluminum chloride, aluminum, titanium chloride, naphthalene and potassium borofluoride to prepare an η⁶-naphthalene complex and further reacting acetonitrile therewith.

However, the synthesis methods of a cationic tris(nitrile) complex described in Non-Patent Document 3 and Non-Patent Document 4 have a problem, for example, that equipment for intense ultraviolet irradiation is necessary or an expensive raw material or a large amount of a reactive agent is used, and these methods can hardly be a practical production method excellent in the cost benefit.

As a cationic tris(nitrile)ruthenium complex having a monosubstituted cyclopentadienyl ligand, [(η⁵-methylcyclopentadienyl)tris(acetonitrile)ruthenium]⁺ is described in Non-Patent Document 5. In addition, as a cationic ruthenium complex having a pentasubstituted cyclopentadienyl ligand, [(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)tris(acetonitrile)ruthenium]⁺ is described in Non-Patent Document 6. However, there is no report on a cationic tris(nitrile)ruthenium complex having a monosubstituted cyclopentadienyl ligand containing an alkyl group having a carbon number of 2 to 6.

In Non-Patent Document 7, tricarbonyl(η⁴-1,3,5,7-cyclooctatetraene)ruthenium (Ru(η⁴-C₈H₈)(CO)₃), tricarbonyl(η⁴-methyl-1,3,5,7-cyclooctatetraene)ruthenium (Ru(η⁴-C₈H₇Me)(CO)₃), and tricarbonyl(η⁴-ethyl-1,3,5,7-cyclooctatetraene)ruthenium (Ru(η⁴-C₈H₇Et)(CO)₃) are described as a compound capable of producing a metallic ruthenium thin film under the conditions using a reducing gas as the reaction gas. However, the metallic ruthenium thin films produced using these compounds have a high resistivity of 93, 152 and 125 μΩ·cm, respectively, and can be hardly a practical material.

In Non-Patent Document 8, (1-3:5-6-η⁵-cyclooctadienyl)(η⁵-2,3,4,5-tetramethylpyrrolyl)ruthenium (Ru(1-3:5-6-η⁵-C₈H₁₁)(η⁵-NC₄Me₄)) is described as a compound having a structure similar to that of the ruthenium complex (2) of the present invention. However, the compound described in this document is limited to a complex having a 1-3:5-6-η⁵-cyclooctadienyl ligand. In addition, the synthesis method described in the document is based on a reaction of di-μ-chloro-(η⁴-1,5-cyclooctadiene)ruthenium ([Ru(η⁴-C₈H₁₂)Cl₂]_x) with 2,3,4,5-tetramethylpyrrolyl-lithium and is different from the production method of the present invention. Furthermore, the document is absolutely silent as to using this complex as a material for the production of a ruthenium-containing thin film.

In Non-Patent Document 9, (η⁵-6-exo-methylcyclohexadienyl)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium is described as a compound having a structure similar to that of the ruthenium complex (3) of the present invention, but the compound described in this document is limited to a complex having an η⁵-1,2,3,4,5-pentamethylcyclopentadienyl ligand. Furthermore, the document is absolutely silent as to using this complex as a material for the production of a ruthenium-containing thin film.

BACKGROUND ART DOCUMENT
Non-Patent Document

Non-Patent Document 1: Organometallics, Vol. 11, page 1686 (1992)

Non-Patent Document 2: Organometallics, Vol. 21, page 592 (2002)

Non-Patent Document 3: Organometallics, Vol. 21, page 2544 (2002)

Non-Patent Document 4: Advanced Synthesis & Catalysis, Vol. 346, page 901 (2004)

Non-Patent Document 5: Dalton Transactions, page 449 (2003)

Non-Patent Document 6: Inorganic Chemistry, Vol. 25, page 3501 (1986)

Non-Patent Document 7: Dalton Transactions, Vol. 41, page 1678 (2012)

Non-Patent Document 8: Organometallics, Vol. 19, page 2853 (2000)

Non-Patent Document 9: Journal of the American Chemical Society, Vol. 122, page 2784 (2000)

SUMMARY OF INVENTION
Problem that Invention is to Solve

An object of the present invention is to provide a production method capable of producing a ruthenium-containing thin film both under the conditions using an oxidizing gas as the reaction gas and under the conditions using a reducing gas as the reaction gas, a ruthenium complex useful as a material for the production method, and a method for producing the ruthenium complex.

Means for Solving Problem

As a result of intensive studies to attain the above-described object, the present inventors have found that a specific ruthenium complex is useful as a material for producing a ruthenium-containing thin film both under the conditions using an oxidizing gas as the reaction gas and under the conditions using a reducing gas as the reaction gas. The present invention has been accomplished based on this finding.

That is, the present invention relates to a ruthenium complex represented by formula (A), more specifically, ruthenium complexes represented by formulae (1a), (2) and (3), a production method of the ruthenium complex, a method for producing a ruthenium-containing thin film using the ruthenium complex, and a semiconductor device using the ruthenium-containing thin film:

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(wherein T represents CR^Aor a nitrogen atom; U represents an oxygen atom or CH; each of R^A, R^B, R^C, R^D, R^E, R^F, R^G, R^Hand R^Iindependently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 6; m represents any one integer of 0, 1 and 3; and the pentahaptodienyl ligand β has a cyclic structure when m is 1 or 3, and has a non-cyclic structure when m is 0, provided that when m is 0, T is CR^A, U is an oxygen atom, R^Fand R^Gare an alkyl group having a carbon number of 1 to 6, and R^Hand R^Iare a hydrogen atom, excluding a case where all of R^A, R^B, R^C, R^Dand R^Eare a methyl group at the same time, that when m is 1, T is CR^A, U is CH and R^Iis an alkyl group having a carbon number of 1 to 6, excluding a case where all of R^F, R^Gand R^Hare a hydrogen atom at the same time and all of R^A, R^B, R^C, R^D, R^Eand R^Iare a methyl group at the same time, and that when m is 3, T is a nitrogen atom, U is CH, R^Band R^Care an alkyl group having a carbon number of 1 to 6, R^D, R^E, R^Fand R^Gare a hydrogen atom, and R^Hand R^Iare a hydrogen atom or a methyl group):

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(wherein each of R^1a, R^2a, R^3a, R^4aand R^5aindependently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 6, excluding a case where all of R^1a, R^2a, R^3a, R^4aand R^5aare a methyl group at the same time; and each of R^6aand R^7aindependently represents an alkyl group having a carbon number of 1 to 6):

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(wherein each of R⁸and R⁹independently represents an alkyl group having a carbon number of 1 to 6; and n represents an integer of 0 to 2):

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(wherein each of R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶and R¹⁷independently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 6; and R¹⁸represents an alkyl group having a carbon number of 1 to 6, excluding a case where all of R¹⁵, R¹⁶and R¹⁷are a hydrogen atom at the same time and all of R¹⁰, R¹¹, R¹², R¹³, R¹⁴and R¹⁸are a methyl group at the same time).

Another aspect of the present invention relates to a method for producing a ruthenium complex, involving reacting a cationic tris(nitrile) complex represented by formula (4):

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(wherein each of R¹, R², R³, R⁴and R⁵independently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 6; R¹⁹represents an alkyl group having a carbon number of 1 to 4; and Z⁻represents a counter anion) with an enone derivative represented by formula (5):

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(wherein each of R²⁰and R²¹independently represents an alkyl group having a carbon number of 1 to 6) in the presence of a base to produce a ruthenium complex represented by formula (1):

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(wherein each of R¹, R², R³, R⁴and R⁵independently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 6; and each of R⁶and R⁷independently represents an alkyl group having a carbon number of 1 to 6).

Effects of Invention

By virtue of using a novel ruthenium complex represented by formula (A) of the present invention, more specifically, a ruthenium complex represented by each of formulae (1a), (2) and (3) or a ruthenium complex represented by each of formulae (1) and (3a) as a material, a ruthenium-containing thin film can be produced both under the conditions using an oxidizing gas and under the conditions using a reducing gas.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a view showing a CVD apparatus used in Examples 14 to 37, 40 to 45 and 55 to 65, Evaluation Examples 1 and 2 and Comparative Examples 1 to 10.

FIG. 2 is a view showing an atomic force microscope (hereinafter, AFM) image of the film obtained in Example 15.

FIG. 3 is a view showing an AFM image of the film obtained in Example 27.

FIG. 4 is a view showing an AFM image of the film obtained in Example 28.

FIG. 5 is a view showing an AFM image of the film obtained in Example 29.

FIG. 6 is a view showing an AFM image of the film obtained in Example 31.

FIG. 7 is a view showing an AFM image of the film obtained in Example 33.

FIG. 8 is a view showing an atomic force microscope (hereinafter, AFM) image of the film obtained in Example 41.

FIG. 9 is a view showing a cross-sectional FE-SEM image of the film obtained in Evaluation Example 1.

FIG. 10 is a view showing a cross-sectional FE-SEM image of the film obtained in Example 2.

MODE FOR CARRYING OUT INVENTION

The present invention is described in more detail below.

The ruthenium complex of the present invention is a ruthenium complex represented by formula (A), and among others, ruthenium complexes represented by formulae (1a), (2) and (3) are preferred.

The ruthenium complex represented by formula (1a) corresponds to a subordinate concept of the ruthenium complex represented by formula (1). The ruthenium complex represented by formula (1a) does not encompass a case where all of R^1a, R^2a, R^3a, R^4aand R^5aare a methyl group at the same time. On the other hand, the ruthenium complex represented by formula (1) encompasses a case where all of R¹, R², R³, R⁴and R⁵are a methyl group at the same time.

Definitions of R^1a, R^2a, R^3a, R^4a, R^5a, R^6aand R^7ain formula (1a) are described below. The alkyl group having a carbon number of 1 to 6 represented by R^1a, R^2a, R^3a, R^4aand R^5amay be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a cyclobutylmethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group, and a 2-cyclobutylethyl group. From the standpoint that the ruthenium complex (1a) of the present invention has vapor pressure and thermal stability suitable as a CVD material or an ALD material, preferably, R^1ais an alkyl group having a carbon number of 1 to 6 and R^2a, R^3a, R^4aand R^5aare a hydrogen atom; and more preferably, R^1ais a methyl group or an ethyl group and R^2a, R^3a, R^4aand R^5aare a hydrogen atom.

The alkyl group having a carbon number of 1 to 6 represented by R^6aand R^7amay be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a cyclobutylmethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group, and a 2-cyclobutylethyl group. From the standpoint that the ruthenium complex (1a) of the present invention has vapor pressure and thermal stability suitable as a CVD material or an ALD material, R^6aand R^7aare preferably a methyl group.

Specific examples of the ruthenium complex (1a) of the present invention are shown in Tables 1-1 to 1-6. Here, Me, Et, Pr, ⁱPr, Bu, ⁱBu, ^sBu, ^tBu, Pe, ^cPe and Hx stand for a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclopentyl group and a hexyl group, respectively.

[Table 1]

TABLE 1-1

(1a)

Compound

No.
R^1a
R^2a
R^3a
R^4a
R^5a
R^6a
R^7a

1a-1
H
H
H
H
H
Me
Me

1a-2
Me
H
H
H
H
Me
Me

1a-3
Et
H
H
H
H
Me
Me

1a-4
Pr
H
H
H
H
Me
Me

1a-5

ⁱPr
H
H
H
H
Me
Me

1a-6
Bu
H
H
H
H
Me
Me

1a-7

ⁱBu
H
H
H
H
Me
Me

1a-8

^sBu
H
H
H
H
Me
Me

1a-9

^tBu
H
H
H
H
Me
Me

1a-10
Pe
H
H
H
H
Me
Me

1a-11

^cPe
H
H
H
H
Me
Me

1a-12
Hx
H
H
H
H
Me
Me

1a-13
Me
Me
H
H
H
Me
Me

1a-14
Me
H
Me
H
H
Me
Me

1a-15

^tBu
H

^tBu
H
H
Me
Me

1a-16
Me
Me
Me
H
H
Me
Me

1a-17
Me
Me
H
Me
H
Me
Me

1a-18

ⁱPr

ⁱPr
H

ⁱPr
H
Me
Me

1a-19
Me
Me
Me
Me
H
Me
Me

1a-20
Et
Me
Me
Me
Me
Me
Me

1a-21
Pr
Me
Me
Me
Me
Me
Me

1a-22
H
H
H
H
H
Me
Et

1a-23
Me
H
H
H
H
Me
Et

1a-24
Et
H
H
H
H
Me
Et

1a-25
Pr
H
H
H
H
Me
Et

1a-26

ⁱPr
H
H
H
H
Me
Et

1a-27
Bu
H
H
H
H
Me
Et

1a-28

ⁱBu
H
H
H
H
Me
Et

1a-29

^sBu
H
H
H
H
Me
Et

1a-30

^tBu
H
H
H
H
Me
Et

1a-31
Pe
H
H
H
H
Me
Et

1a-32

^cPe
H
H
H
H
Me
Et

1a-33
Hx
H
H
H
H
Me
Et

1a-34
Me
Me
H
H
H
Me
Et

1a-35
Me
H
Me
H
H
Me
Et

1a-36

^tBu
H

^tBu
H
H
Me
Et

1a-37
Me
Me
Me
H
H
Me
Et

1a-38
Me
Me
H
Me
H
Me
Et

[Table 2]

TABLE 1-2

(1a)

Compound

No.
R^1a
R^2a
R^3a
R^4a
R^5a
R^6a
R^7a

1a-39

ⁱPr
H

ⁱPr
H

ⁱPr
Me
Et

1a-40
Me
Me
Me
Me
H
Me
Et

1a-41
Et
Me
Me
Me
Me
Me
Et

1a-42
Pr
Me
Me
Me
Me
Me
Et

1a-43
H
H
H
H
H
Et
Me

1a-44
Me
H
H
H
H
Et
Me

1a-45
Et
H
H
H
H
Et
Me

1a-46
Pr
H
H
H
H
Et
Me

1a-47

ⁱPr
H
H
H
H
Et
Me

1a-48
Bu
H
H
H
H
Et
Me

1a-49

ⁱBu
H
H
H
H
Et
Me

1a-50

^sBu
H
H
H
H
Et
Me

1a-51

^tBu
H
H
H
H
Et
Me

1a-52
Pe
H
H
H
H
Et
Me

1a-53

^cPe
H
H
H
H
Et
Me

1a-54
Hx
H
H
H
H
Et
Me

1a-55
Me
Me
H
H
H
Et
Me

1a-56
Me
H
Me
H
H
Et
Me

1a-57

^tBu
H

^tBu
H
H
Et
Me

1a-58
Me
Me
Me
H
H
Et
Me

1a-59
Me
Me
H
Me
H
Et
Me

1a-60

ⁱPr
H

ⁱPr
H

ⁱPr
Et
Me

1a-61
Me
Me
Me
Me
H
Et
Me

1a-62
Et
Me
Me
Me
Me
Et
Me

1a-63
Pr
Me
Me
Me
Me
Et
Me

1a-64
H
H
H
H
H
Me

ⁱPr

1a-65
Me
H
H
H
H
Me

ⁱPr

1a-66
Et
H
H
H
H
Me

ⁱPr

1a-67
Pr
H
H
H
H
Me

ⁱPr

1a-68

ⁱPr
H
H
H
H
Me

ⁱPr

1a-69
Bu
H
H
H
H
Me

ⁱPr

1a-70

ⁱBu
H
H
H
H
Me

ⁱPr

1a-71

^sBu
H
H
H
H
Me

ⁱPr

1a-72

^tBu
H
H
H
H
Me

ⁱPr

1a-73
Pe
H
H
H
H
Me

ⁱPr

1a-74

^cPe
H
H
H
H
Me

ⁱPr

1a-75
Hx
H
H
H
H
Me

ⁱPr

1a-76
Me
Me
H
H
H
Me

ⁱPr

[Table 3]

TABLE 1-3

(1a)

Compound

No.
R^1a
R^2a
R^3a
R^4a
R^5a
R^6a
R^7a

1a-77
Me
H
Me
H
H
Me

ⁱPr

1a-78

^tBu
H

^tBu
H
H
Me

ⁱPr

1a-79
Me
Me
Me
H
H
Me

ⁱPr

1a-80
Me
Me
H
Me
H
Me

ⁱPr

1a-81

ⁱPr
H

ⁱPr
H

ⁱPr
Me

ⁱPr

1a-82
Me
Me
Me
Me
H
Me

ⁱPr

1a-83
Et
Me
Me
Me
Me
Me

ⁱPr

1a-84
Pr
Me
Me
Me
Me
Me

ⁱPr

1a-85
H
H
H
H
H

ⁱPr
Me

1a-86
Me
H
H
H
H

ⁱPr
Me

1a-87
Et
H
H
H
H

ⁱPr
Me

1a-88
Pr
H
H
H
H

ⁱPr
Me

1a-89

ⁱPr
H
H
H
H

ⁱPr
Me

1a-90
Bu
H
H
H
H

ⁱPr
Me

1a-91

ⁱBu
H
H
H
H

ⁱPr
Me

1a-92

^sBu
H
H
H
H

ⁱPr
Me

1a-93

^tBu
H
H
H
H

ⁱPr
Me

1a-94
Pe
H
H
H
H

ⁱPr
Me

1a-95

^cPe
H
H
H
H

ⁱPr
Me

1a-96
Hx
H
H
H
H

ⁱPr
Me

1a-97
Me
Me
H
H
H

ⁱPr
Me

1a-98
Me
H
Me
H
H

ⁱPr
Me

1a-99

^tBu
H

^tBu
H
H

ⁱPr
Me

1a-100
Me
Me
Me
H
H

ⁱPr
Me

1a-101
Me
Me
H
Me
H

ⁱPr
Me

1a-102

ⁱPr
H

ⁱPr
H

ⁱPr

ⁱPr
Me

1a-103
Me
Me
Me
Me
H

ⁱPr
Me

1a-104
Et
Me
Me
Me
Me

ⁱPr
Me

1a-105
Pr
Me
Me
Me
Me

ⁱPr
Me

1a-106
H
H
H
H
H
Me

^tBu

1a-107
Me
H
H
H
H
Me

^tBu

1a-108
Et
H
H
H
H
Me

^tBu

1a-109
Pr
H
H
H
H
Me

^tBu

1a-110

ⁱPr
H
H
H
H
Me

^tBu

1a-111
Bu
H
H
H
H
Me

^tBu

1a-112

ⁱBu
H
H
H
H
Me

^tBu

1a-113

^sBu
H
H
H
H
Me

^tBu

1a-114

^tBu
H
H
H
H
Me

^tBu

[Table 4]

TABLE 1-4

(1a)

Compound

No.
R^1a
R^2a
R^3a
R^4a
R^5a
R^6a
R^7a

1a-115
Pe
H
H
H
H
Me

^tBu

1a-116

^cPe
H
H
H
H
Me

^tBu

1a-117
Hx
H
H
H
H
Me

^tBu

1a-118
Me
Me
H
H
H
Me

^tBu

1a-119
Me
H
Me
H
H
Me

^tBu

1a-120

^tBu
H

^tBu
H
H
Me

^tBu

1a-121
Me
Me
Me
H
H
Me

^tBu

1a-122
Me
Me
H
Me
H
Me

^tBu

1a-123

ⁱPr
H

ⁱPr
H

ⁱPr
Me

^tBu

1a-124
Me
Me
Me
Me
H
Me

^tBu

1a-125
Et
Me
Me
Me
Me
Me

^tBu

1a-126
Pr
Me
Me
Me
Me
Me

^tBu

1a-127
H
H
H
H
H

^tBu
Me

1a-128
Me
H
H
H
H

^tBu
Me

1a-129
Et
H
H
H
H

^tBu
Me

1a-130
Pr
H
H
H
H

^tBu
Me

1a-131

ⁱPr
H
H
H
H

^tBu
Me

1a-132
Bu
H
H
H
H

^tBu
Me

1a-133

ⁱBu
H
H
H
H

^tBu
Me

1a-134

^sBu
H
H
H
H

^tBu
Me

1a-135

^tBu
H
H
H
H

^tBu
Me

1a-136
Pe
H
H
H
H

^tBu
Me

1a-137

^cPe
H
H
H
H

^tBu
Me

1a-138
Hx
H
H
H
H

^tBu
Me

1a-139
Me
Me
H
H
H

^tBu
Me

1a-140
Me
H
Me
H
H

^tBu
Me

1a-141

^tBu
H

^tBu
H
H

^tBu
Me

1a-142
Me
Me
Me
H
H

^tBu
Me

1a-143
Me
Me
H
Me
H

^tBu
Me

1a-144

ⁱPr
H

ⁱPr
H

ⁱPr

^tBu
Me

1a-145
Me
Me
Me
Me
H

^tBu
Me

1a-146
Et
Me
Me
Me
Me

^tBu
Me

1a-147
Pr
Me
Me
Me
Me

^tBu
Me

1a-148
H
H
H
H
H
Et
Et

1a-149
Me
H
H
H
H
Et
Et

1a-150
Et
H
H
H
H
Et
Et

1a-151
Pr
H
H
H
H
Et
Et

1a-152

ⁱPr
H
H
H
H
Et
Et

[Table 5]

TABLE 1-5

(1a)

Compound

No.
R^1a
R^2a
R^3a
R^4a
R^5a
R^6a
R^7a

1a-153
Bu
H
H
H
H
Et
Et

1a-154

ⁱBu
H
H
H
H
Et
Et

1a-155

^sBu
H
H
H
H
Et
Et

1a-156

^tBu
H
H
H
H
Et
Et

1a-157
Pe
H
H
H
H
Et
Et

1a-158

^cPe
H
H
H
H
Et
Et

1a-159
Hx
H
H
H
H
Et
Et

1a-160
Me
Me
H
H
H
Et
Et

1a-161
Me
H
Me
H
H
Et
Et

1a-162

^tBu
H

^tBu
H
H
Et
Et

1a-163
Me
Me
Me
H
H
Et
Et

1a-164
Me
Me
H
Me
H
Et
Et

1a-165

ⁱPr
H

ⁱPr
H

ⁱPr
Et
Et

1a-166
Me
Me
Me
Me
H
Et
Et

1a-167
Et
Me
Me
Me
Me
Et
Et

1a-168
Pr
Me
Me
Me
Me
Et
Et

1a-169
H
H
H
H
H

ⁱPr

ⁱPr

1a-170
Me
H
H
H
H

ⁱPr

ⁱPr

1a-171
Et
H
H
H
H

ⁱPr

ⁱPr

1a-172
Pr
H
H
H
H

ⁱPr

ⁱPr

1a-173

ⁱPr
H
H
H
H

ⁱPr

ⁱPr

1a-174
Bu
H
H
H
H

ⁱPr

ⁱPr

1a-175

ⁱBu
H
H
H
H

ⁱPr

ⁱPr

1a-176

^sBu
H
H
H
H

ⁱPr

ⁱPr

1a-177

^tBu
H
H
H
H

ⁱPr

ⁱPr

1a-178
Pe
H
H
H
H

ⁱPr

ⁱPr

1a-179

^cPe
H
H
H
H

ⁱPr

ⁱPr

1a-180
Hx
H
H
H
H

ⁱPr

ⁱPr

1a-181
Me
Me
H
H
H

ⁱPr

ⁱPr

1a-182
Me
H
Me
H
H

ⁱPr

ⁱPr

1a-183

^tBu
H

^tBu
H
H

ⁱPr

ⁱPr

1a-184
Me
Me
Me
H
H

ⁱPr

ⁱPr

1a-185
Me
Me
H
Me
H

ⁱPr

ⁱPr

1a-186

ⁱPr
H

ⁱPr
H

ⁱPr

ⁱPr

ⁱPr

1a-187
Me
Me
Me
Me
H

ⁱPr

ⁱPr

1a-188
Et
Me
Me
Me
Me

ⁱPr

ⁱPr

1a-189
Pr
Me
Me
Me
Me

ⁱPr

ⁱPr

1a-190
H
H
H
H
H

^tBu

^tBu

[Table 6]

TABLE 1-6

(1a)

Compound

No.
R^1a
R^2a
R^3a
R^4a
R^5a
R^6a
R^7a

1a-191
Me
H
H
H
H

^tBu

^tBu

1a-192
Et
H
H
H
H

^tBu

^tBu

1a-193
Pr
H
H
H
H

^tBu

^tBu

1a-194

ⁱPr
H
H
H
H

^tBu

^tBu

1a-195
Bu
H
H
H
H

^tBu

^tBu

1a-196

ⁱBu
H
H
H
H

^tBu

^tBu

1a-197

^sBu
H
H
H
H

^tBu

^tBu

1a-198

^tBu
H
H
H
H

^tBu

^tBu

1a-199
Pe
H
H
H
H

^tBu

^tBu

1a-200

^cPe
H
H
H
H

^tBu

^tBu

1a-201
Hx
H
H
H
H

^tBu

^tBu

1a-202
Me
Me
H
H
H

^tBu

^tBu

1a-203
Me
H
Me
H
H

^tBu

^tBu

1a-204

^tBu
H

^tBu
H
H

^tBu

^tBu

1a-205
Me
Me
Me
H
H

^tBu

^tBu

1a-206
Me
Me
H
Me
H

^tBu

^tBu

1a-207

ⁱPr
H

ⁱPr
H

ⁱPr

^tBu

^tBu

1a-208
Me
Me
Me
Me
H

^tBu

^tBu

1a-209
Et
Me
Me
Me
Me

^tBu

^tBu

1a-210
Pr
Me
Me
Me
Me

^tBu

^tBu

Among those exemplified in Tables 1-1 to 1-6, (η⁵-cyclopentadienyl)(η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)ruthenium (1a-1), (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-methylcyclopentadienyl)ruthenium (1a-2), (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (1a-3), (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-propylcyclopentadienyl)ruthenium (1a-4), (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-isopropylcyclopentadienyl)ruthenium (1a-5), (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-butylcyclopentadienyl)ruthenium (1a-6), (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-isobutylcyclopentadienyl)ruthenium (1a-7), (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-(sec-butyl)cyclopentadienyl)ruthenium (1a-8), (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-(tert-butyl)cyclopentadienyl)ruthenium (1a-9), (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-pentylcyclopentadienyl)ruthenium (1a-10), (η⁵-(cyclopentyl)cyclopentadienyl)(η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)ruthenium (1a-11) and (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-hexylcyclopentadienyl)ruthenium (1a-12) are preferred, and 1a-2 and 1a-3 are more preferred.

The production method of the ruthenium complex (1a) of the present invention is described below. The ruthenium complex (1a) can be produced according to the following production method 1 of a ruthenium complex (1). Production method 1 is a method of reacting a cationic tris(nitrile) complex (4) with an enone derivative (5) in the presence of a base to produce a ruthenium complex (1).

embedded image

(wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁹, R²⁰, R²¹and Z⁻have the same meanings as above.)

Definitions of R¹, R², R³, R⁴, R⁵, R⁶and R⁷in formula (1) are described below. The alkyl group having a carbon number of 1 to 6 represented by R¹, R², R³, R⁴and R⁵may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a cyclobutylmethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group, and a 2-cyclobutylethyl group. In view of a high yield, preferably, R¹is an alkyl group having a carbon number of 1 to 6 and R², R³, R⁴and R⁵are a hydrogen atom; and more preferably, R¹is a methyl group or an ethyl group and R², R³, R⁴and R⁵are a hydrogen atom.

The alkyl group having a carbon number of 1 to 6 represented by R⁶and R⁷may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a cyclobutylmethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group, and a 2-cyclobutylethyl group. In view of a high yield, R⁶and R⁷are preferably a methyl group.

Specific examples of the ruthenium complex (1) include the compounds shown in Table 2, in addition to 1a-1 to 1a-210 shown in Tables 1-1 to 1-6.

[Table 7]

TABLE 2

(1)

Compound

No.
R¹
R²
R³
R⁴
R⁵
R⁶
R⁷

1-211
Me
Me
Me
Me
Me
Me
Me

1-212
Me
Me
Me
Me
Me
Me
Et

1-213
Me
Me
Me
Me
Me
Et
Me

1-214
Me
Me
Me
Me
Me
Me

ⁱPr

1-215
Me
Me
Me
Me
Me

ⁱPr
Me

1-216
Me
Me
Me
Me
Me
Me

^tBu

1-217
Me
Me
Me
Me
Me

^tBu
Me

1-218
Me
Me
Me
Me
Me
Et
Et

1-219
Me
Me
Me
Me
Me

ⁱPr

ⁱPr

1-220
Me
Me
Me
Me
Me

^tBu

^tBu

Among those exemplified in Tables 1-1 to 1-6 and Table 2, 1a-1, 1a-2, 1a-3, 1a-4, 1a-5, 1a-6, 1a-7, 1a-8, 1a-9, 1a-10, 1a-11 and 1a-12 are preferred by virtue of having vapor pressure and heat stability suitable as a CVD material or an ALD material, and 1a-2 and 1a-3 are more preferred.

The alkyl group having a carbon number of 1 to 4 represented by R¹⁹in the cationic tris(nitrile) complex (4) may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclobutyl group. In view of a high yield of the ruthenium complex (1), R¹⁹is preferably a methyl group.

Specific examples of the cation moiety of the cationic tris(nitrile) complex (4) include [tris(acetonitrile)(η⁵-cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅H₅)(MeCN)₃]), [tris(acetonitrile)(η⁵-methylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-propylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-isopropylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-butylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-isobutylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-(sec-butyl)cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-(tert-butyl)cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-pentylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-(cyclopentyl)cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-hexylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅Me₅)(MeCN)₃]),

[(η⁵-cyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅H₅)(EtCN)₃]), [(η⁵-methylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(EtCN)₃]), [(η⁵-ethylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(EtCN)₃]), [tris(propionitrile)(η⁵-propylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(EtCN)₃]), [(η⁵-isopropylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(EtCN)₃]), [(η⁵-butylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(EtCN)₃]), [(η⁵-isobutylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(EtCN)₃]), [(η⁵-(sec-butyl)cyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(EtCN)₃]), [(η⁵-(tert-butyl)cyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(EtCN)₃]), [(η⁵-pentylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(EtCN)₃]), [(η⁵-(cyclopentyl)cyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(EtCN)₃]), [(η⁵-hexylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(EtCN)₃]), [(η⁵-cyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅H₅)(^tBuCN)₃]), [(η⁵-methylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(^tBuCN)₃]), [(η⁵-ethylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(^tBuCN)₃]), [tris(pivalonitrile)(η⁵-propylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(^tBuCN)₃]), [(η⁵-isopropylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(^tBuCN)₃]), [(η⁵-butylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(^tBuCN)₃]), [(η⁵-isobutylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(^tBuCN)₃]), [(η⁵-(sec-butyl)cyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(^tBuCN)₃]), [(η⁵-(tert-butyl)cyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(^tBuCN)₃]), [(η⁵-pentylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(^tBuCN)₃]), [(η⁵-(cyclopentyl)cyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(^tBuCN)₃]), and [(η⁵-hexylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(^tBuCN)₃]).

Examples of the counter anion Z⁻in formula (4) include those generally used as a counter anion of a cationic metal complex. Specific examples thereof include a fluoro complex anion such as tetrafluoroborate ion (BF₄⁻), hexafluorophosphate ion (PF₆⁻), hexafluoroantimonate ion (SbF₆⁻) and tetrafluoroaluminate ion (AlF₄⁻), a monovalent sulfonate ion such as trifluoromethanesulfonate ion (CF₃SO₃⁻), methanesulfonate ion (MeSO₃⁻) and methylsulfate ion (MeSO₄⁻), a counter anion of a monobasic acid, such as nitrate ion (NO₃⁻), perchlorate ion (ClO₄⁻), tetrachloroaluminate ion (AlCl₄⁻) and bis(trifluoromethanesulfonyl)amide ion ((CF₃SO₂)₂N⁻), a counter anion of a polybasic acid, such as sulfate ion (SO₄²⁻), hydrogen sulfate ion (HSO₄⁻), phosphate ion (PO₄³⁻), monohydrogen phosphate ion (HPO₄²⁻), dihydrogen phosphate ion (H₂PO₄⁻), dimethylphosphate ion ((MeO)₂PO₄⁻) and diethylphosphate ion ((EtO)₂PO₄⁻), and a derivative thereof. In view of a high yield of the ruthenium complex (1), the counter anion Z⁻is preferably a fluoro complex anion such as BF₄⁻and PF₆⁻, or a monovalent sulfonate ion such as CF₃SO₃⁻and MeSO₃⁻.

More preferred specific examples of the cationic tris(nitrile) complex (4) include [tris(acetonitrile)(η⁵-cyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅H₅)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-methylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅MeH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅Me₅)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-cyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅H₅)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-methylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅MeH₄)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅Me₅)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-cyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅H₅)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-methylcyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅MeH₄)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-ethylcyclo-pentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-1,2,3,4,5-pentamethylcyclo-pentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅Me₅)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-cyclopentadienyl)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅H₅)(MeCN)₃][MeSO₃]), [tris(acetonitrile)(η⁵-methylcyclopentadienyl)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅MeH₄)(MeCN)₃][MeSO₃]), [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][MeSO₃]), and [tris(acetonitrile)(η⁵-1,2,3,4,5-pentamethylcyclo-pentadienyl)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅Me₅)(MeCN)₃][MeSO₃]).

The alkyl group having a carbon number of 1 to 6 represented by R²⁰and R²¹in formula (5) may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a cyclobutylmethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group, and a 2-cyclobutylethyl group.

Specific examples of the enone derivative (5) include 4-methylpent-3-en-2-one (mesityl oxide), 5-methylhex-4-en-3-one, 2-methylhept-2-en-4-one, 2,5-dimethylhex-4-en-3-one, 2-methyloct-2-en-4-one, 2,6-dimethylhept-2-en-4-one, 2,5-dimethylhept-2-en-4-one, 2,2,5-trimethylhex-4-en-3-one, 2-methylnon-2-en-4-one, 2,5,5-trimethylhept-2-en-4-one, 2-methyldec-2-en-4-one, 1-cyclohexyl-3-methylbut-2-en-1-one, 4-methylhex-3-en-2-one, 4-methylhept-3-en-2-one, 4,5-dimethylhex-3-en-2-one, 4-methyloct-3-en-2-one, 4,6-dimethylhept-3-en-2-one, 4,5-dimethylhept-3-en-2-one, 4,5,5-trimethylhex-3-en-2-one, 4-methylnon-3-en-2-one, 4-methyldec-3-en-2-one, 4-cyclohexylpent-3-en-2-one, 5-methylhept-4-en-3-one, 6-methylnon-5-en-4-one, 2,5,6-trimethylhept-4-en-3-one, 2,2,5,6,6-pentamethylhept-4-en-3-one, and 3,3,6,7,7-pentamethylnon-5-en-4-one. In view of a high yield of the ruthenium complex (1), mesityl oxide or 2,2,5,6,6-pentamethylhept-4-en-3-one are preferred, and mesityl oxide is more preferred.

The base that can be used in production method 1 includes an inorganic base and an organic base. Examples of the inorganic base include an alkali metal carbonate such as lithium carbonate, sodium carbonate and potassium carbonate, an alkali metal bicarbonate salt such as lithium bicarbonate, sodium bicarbonate and potassium bicarbonate, a Group 2 metal carbonate such as magnesium carbonate, calcium carbonate and strontium carbonate, a typical metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide, a typical metal hydride such as lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride and aluminum hydride, a typical metal hydride complex compound such as sodium borohydride and aluminum lithium hydride, and an alkali metal amide such as lithium amide, sodium amide and lithium dialkylamide. Examples of the organic base include an alkylamine such as diethylamine, triethylamine, diethylisopropylamine and tributylamine, a cyclic amine such as pyrrolidine, piperidine, piperazine and 1,4-diazabicyclooctane, and pyridine. In view of a high yield of the ruthenium complex (1), the base is preferably an alkali metal carbonate or an alkyl amine, more preferably lithium carbonate, sodium carbonate, potassium carbonate or triethylamine, still more preferably lithium carbonate or triethylamine.

For the reason that the yield of the ruthenium complex (1) is high, production method 1 is preferably performed in an inert gas. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas, with argon or nitrogen gas being preferred.

For the reason that the yield of the ruthenium complex (1) is high, production method 1 is preferably performed in an organic solvent. In the case of performing production method 1 in an organic solvent, specific examples of the organic solvent include an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane and petroleum ether, an ether such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane, a ketone such as acetone, methyl ethyl ketone, 3-pentanone, cyclopentanone and cyclohexanone, and an alcohol such as methanol, ethanol, propanol, isopropanol, tert-butanol and ethylene glycol. Of these organic solvents, one kind may be used alone, or a plurality of kinds may be mixed in an arbitrary ratio and used. In view of a high yield of the ruthenium complex (1), diethyl ether, tetrahydrofuran, acetone, methanol and hexane are preferred as the organic solvent.

Methods for obtaining the cationic tris(nitrile) complex (4) and the enone derivative (5) are described below. The method for obtaining the cationic tris(nitrile) complex (4) includes the production methods described, for example, in Non-Patent Document 3 and Non-Patent Document 4, other than the later-described production method 2 of the present invention. The method for obtaining the enone derivative (5) includes the methods described, for example, in Journal of Organometallic Chemistry, Vol. 402, page 17 (1991), and Japanese Patent 3,649,441, other than the purchase of a commercial product.

The molar ratio between the cationic tris(nitrile) complex (4) and the enone derivative (5) when performing production method 1 is described below. Preferably, an equimolar or greater amount of an enone derivative (5) per mol of a cationic tris(nitrile) complex (4), and a base are used, whereby the ruthenium complex (1) can be efficiently produced.

In production method 1, the reaction temperature and the reaction time are not particularly limited, and general conditions employed by one skilled in the art when producing a metal complex may be used. As a specific example, a reaction temperature appropriately selected from a temperature range of −80° C. to 120° C. and a reaction time appropriately selected from the range of 10 minutes to 120 hours are employed, whereby the ruthenium complex (1) can be efficiently produced.

The ruthenium complex (1) produced by production method 1 may be purified by appropriately selecting and using a general purification method employed by one skilled in the art when purifying a metal complex. The purification method specifically includes filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, etc.

The cationic tris(nitrile) complex (4b) of the present invention is described below. The alkyl group having a carbon number of 2 to 6 represented by R^1bin formula (4b) may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a cyclobutylmethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group, and a 2-cyclobutylethyl group. From the standpoint of producing a raw material for synthesis of a ruthenium complex (1) having vapor pressure and thermal stability suitable particularly as a CVD material or an ALD material, R^1bis preferably an alkyl group having a carbon number of 2 to 4, more preferably an ethyl group.

The alkyl group having a carbon number of 1 to 4 represented by R^19bin formula (4b) may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclobutyl group. In view of a high yield when used as a raw material for synthesis of the ruthenium complex (1), R^19bis preferably a methyl group.

Specific examples of the cation moiety of the cationic tris(nitrile) complex (4b) include [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-propylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-isopropylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-butylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-isobutylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-(sec-butyl)cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-(tert-butyl)cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-pentylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-(cyclopentyl)cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(MeCN)₃]), [tris(acetonitrile)(η⁵-hexylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(MeCN)₃]), [(η⁵-ethylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(EtCN)₃]), [tris(propionitrile)(η⁵-propylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(EtCN)₃]), [(η⁵-isopropylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(EtCN)₃]), [(η⁵-butylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(EtCN)₃]), [(η⁵-isobutylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(EtCN)₃]), [(η⁵-(sec-butyl)cyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(EtCN)₃]), [(η⁵-(tert-butyl)cyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(EtCN)₃]), [(η⁵-pentylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(EtCN)₃]), [(η⁵-(cyclopentyl)cyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(EtCN)₃]), [(η⁵-hexylcyclopentadienyl)tris(propionitrile)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(EtCN)₃]), [(η⁵-ethylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(^tBuCN)₃]), [tris(pivalonitrile)(η⁵-propylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(^tBuCN)₃]), [(η⁵-isopropylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(^tBuCN)₃]), [(η⁵-butylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(^tBuCN)₃]), [(η⁵-isobutylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(^tBuCN)₃]), [(η⁵-(sec-butyl)cyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(^tBuCN)₃]), [(η⁵-(tert-butyl)cyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(^tBuCN)₃]), [(η⁵-pentylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(^tBuCN)₃]), [(η⁵-(cyclopentyl)cyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(^tBuCN)₃]), and [(η⁵-hexylcyclopentadienyl)tris(pivalonitrile)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(^tBuCN)₃]). Among others, [Ru(η⁵-C₅EtH₄)(MeCN)₃], [Ru(η⁵-C₅PrH₄)(MeCN)₃], [Ru(η⁵-C₅ⁱPrH₄)(MeCN)₃], [Ru(η⁵-C₅BuH₄)(MeCN)₃], [Ru(η⁵-C₅ⁱBuH₄)(MeCN)₃], [Ru(η⁵-C₅^sBuH₄)(MeCN)₃], [Ru(η⁵-C₅^tBuH₄)(MeCN)₃], etc. are preferred, and [Ru(η⁵-C₅EtH₄)(MeCN)₃] is more preferred.

Examples of the counter anion Zb⁻in formula (4b) include those generally used as a counter anion of a cationic metal complex. Specific examples thereof include a fluoro complex anion such as tetrafluoroborate ion (BF₄⁻), hexafluorophosphate ion (PF₆⁻), hexafluoroantimonate ion (SbF₆⁻) and tetrafluoroaluminate ion (AlF₄⁻), a monovalent sulfonate ion such as trifluoromethanesulfonate ion (CF₃SO₃⁻), methanesulfonate ion (MeSO₃⁻) and methylsulfate ion (MeSO₄⁻), a counter anion of a monobasic acid, such as nitrate ion (NO₃⁻), perchlorate ion (ClO₄⁻), tetrachloroaluminate ion (AlCl₄⁻) and bis(trifluoromethanesulfonyl)amide ion ((CF₃SO₂)₂N⁻), a counter anion of a polybasic acid, such as sulfate ion (SO₄²⁻), hydrogen sulfate ion (HSO₄⁻), phosphate ion (PO₄³⁻), monohydrogen phosphate ion (HPO₄²⁻), dihydrogen phosphate ion (H₂PO₄⁻), dimethylphosphate ion ((MeO)₂PO₄⁻) and diethylphosphate ion ((EtO)₂PO₄⁻), and a derivative thereof. In view of a high yield of the ruthenium complex (1), the counter anion Zb⁻is preferably a fluoro complex anion such as BF₄⁻and PF₆⁻, or a monovalent sulfonate ion such as CF₃SO₃⁻and MeSO₃⁻.

More specifically, preferred examples of the cationic tris(nitrile) complex (4b) include [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-propylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅PrH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-propylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅PrH₄)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-propylcyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅PrH₄)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-isopropylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅ⁱPrH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-isopropylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅ⁱPrH₄)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-isopropylcyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅ⁱPrH₄)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-butylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅BuH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-butylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅BuH₄)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-butylcyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅BuH₄)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-isobutylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅ⁱBuH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-isobutylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅ⁱBuH₄)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-isobutylcyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅ⁱBuH₄)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-(sec-butyl)cyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅^sBuH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-(sec-butyl)cyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅^sBuH₄)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-(sec-butyl)cyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅^sBuH₄)(MeCN)₃][CF₃SO₃]), [tris(acetonitrile)(η⁵-(tert-butyl)cyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅^tBuH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-(tert-butyl)cyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅^tBuH₄)(MeCN)₃][PF₆]), and [tris(acetonitrile)(η⁵-(tert-butyl)cyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅^tBuH₄)(MeCN)₃][CF₃SO₃]).

Of these, [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄]), [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][PF₆]), [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][CF₃SO₃]), etc. are more preferred.

The production method of the cationic tris(nitrile) complex (4b) of the present invention is described below. The cationic tris(nitrile) complex (4b) can be produced according to production method 2 of a ruthenium cationic tris(nitrile) complex (4) shown below. Production method 2 is a method of reacting a ruthenocene derivative (6), nitrile R¹⁹CN with a protonic acid H⁺Z⁻ to produce a cationic tris(nitrile) complex (4).

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(wherein R¹, R², R³, R⁴, R⁵, X, R¹⁹and Z⁻have the same meanings as above.)

The alkyl group having a carbon number of 1 to 4 represented by R¹⁹may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclobutyl group. In view of a high yield, R²¹is preferably a methyl group. Specific examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyclopropanecarbonitrile, pentylonitrile, isopentylonitrile, 3-methylbutanenitrile, 2-methylbutanenitrile, pivalonitrile, and cyclobutanecarbonitrile, and in view of a high yield, acetonitrile is preferred.

X in formula (6) represents an η⁵-(unsubstituted or substituted)cyclopentadienyl ligand represented by formula (7):

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(wherein R¹, R², R³, R⁴and R⁵have the same meanings as above) or an η⁵-2,4-dimethyl-2,4-pentadienyl ligand. Specific examples of the η⁵-(unsubstituted or substituted)cyclopentadienyl ligand include an η⁵-cyclopentadienyl ligand, an η⁵-methylcyclopentadienyl ligand, an η⁵-ethylcyclopentadienyl ligand, an η⁵-propylcyclopentadienyl ligand, an η⁵-isopropylcyclopentadienyl ligand, an η⁵-butylcyclopentadienyl ligand, an η⁵-isobutylcyclopentadienyl ligand, an η⁵-(sec-butyl)cyclopentadienyl ligand, an η⁵-(tert-butyl)cyclopentadienyl ligand, an η⁵-pentylcyclopentadienyl ligand, an η⁵-(cyclopentyl)cyclopentadienyl ligand, an η⁵-hexylcyclopentadienyl ligand, an η⁵-1,2-dimethylcyclopentadienyl ligand, an η⁵-1,3-dimethylcyclopentadienyl ligand, an η⁵-1,3-di(isopropyl)cyclopentadienyl ligand, an η⁵-1,2,4-tri(isopropyl)cyclopentadienyl ligand, an η⁵-1,3-di(tert-butyl)cyclopentadienyl ligand, and an η⁵-1,2,3,4,5-pentamethylcyclopentadienyl ligand. For the reason that the ruthenocene derivative (6) is easily obtained, X is preferably an η⁵-(unsubstituted or substituted)cyclopentadienyl ligand, more preferably an η⁵-cyclopentadienyl ligand, an η⁵-methylcyclopentadienyl ligand, or an η⁵-ethylcyclopentadienyl ligand.

More specifically, examples of the ruthenocene derivative (6) include bis(η⁵-cyclopentadienyl)ruthenium ((η⁵-C₅H₅)₂Ru), bis(η⁵-methylcyclopentadienyl)ruthenium ((η⁵-C₅MeH₄)₂Ru), bis(η⁵-ethylcyclopentadienyl)ruthenium ((η⁵-C₅EtH₄)₂Ru), bis(η⁵-propylcyclopentadienyl)ruthenium ((η⁵-C₅PrH₄)₂Ru), bis(η⁵-isopropylcyclopentadienyl)ruthenium ((η⁵-C₅ⁱPrH₄)₂Ru), bis(η⁵-butylcyclopentadienyl)ruthenium ((η⁵-C₅BuH₄)₂Ru), bis(η⁵-isobutylcyclopentadienyl)ruthenium ((η⁵-C₅ⁱBuH₄)₂Ru), bis(η⁵-(sec-butyl)cyclopentadienyl)ruthenium ((η⁵-C₅^sBuH₄)₂Ru), bis(η⁵-(tert-butyl)cyclopentadienyl)ruthenium ((η⁵-C₅^tBuH₄)₂Ru), bis(η⁵-pentylcyclopentadienyl)ruthenium ((η⁵-C₅PeH₄)₂Ru), bis(η⁵-(cyclopentyl)cyclopentadienyl)ruthenium ((η⁵-C₅^cPeH₄)₂Ru), bis(η⁵-hexylcyclopentadienyl)ruthenium ((η⁵-C₅HxH₄)₂Ru), bis(η⁵-1,2-dimethylcyclopentadienyl)ruthenium ((η⁵-C₅Me₂H₃)₂Ru), bis(η⁵-1,3-dimethylcyclopentadienyl)ruthenium ((η⁵-C₅Me₂H₃)₂Ru), bis(η⁵-1,3-di(isopropyl)cyclopentadienyl)ruthenium ((η⁵-C₅(ⁱPr)₂H₃)₂Ru), bis(η⁵-1,2,4-tri(isopropyl)cyclopentadienyl)ruthenium ((η⁵-C₅(ⁱPr)₃H₂)₂Ru), bis(η⁵-1,3-di(tert-butyl)cyclopentadienyl)ruthenium ((η⁵-C₅(^tBu)₂H₃)₂Ru), bis(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium ((η⁵-C₅Me₅)₂Ru), (η⁵-cyclopentadienyl)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium ((η⁵-C₅H₅)(η⁵-C₅Me₅)Ru), (η⁵-cyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅H₅)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-methylcyclopentadienyl)ruthenium (Ru(η⁵-C₅MeH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-propylcyclopentadienyl)ruthenium (Ru(η⁵-C₅PrH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-isopropylcyclopentadienyl)ruthenium (Ru(η⁵-C₅ⁱPrH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-butylcyclopentadienyl)ruthenium (Ru(η⁵-C₅BuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-isobutylcyclopentadienyl)ruthenium (Ru(η⁵-C₅ⁱBuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-(sec-butyl)cyclopentadienyl)ruthenium (Ru(η⁵-C₅^sBuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-(tert-butyl)cyclopentadienyl)ruthenium (Ru(η⁵-C₅^tBuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-pentylcyclopentadienyl)ruthenium (Ru(η⁵-C₅PeH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-(cyclopentyl)cyclopentadienyl)ruthenium (Ru(η⁵-C₅^cPeH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-hexylcyclopentadienyl)ruthenium (Ru(η⁵-C₅HxH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), and (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅Me₅)(η⁵-CH₂C(Me)CHC(Me)CH₂)).

Of these, bis(η⁵-cyclopentadienyl)ruthenium (η⁵-C₅H₅)₂Ru), bis(η⁵-methylcyclopentadienyl)ruthenium (η⁵-C₅MeH₄)₂Ru), bis(η⁵-ethylcyclopentadienyl)ruthenium (η⁵-C₅EtH₄)₂Ru), bis(η⁵-propylcyclopentadienyl)ruthenium (η⁵-C₅PrH₄)₂Ru), bis(η⁵-isopropylcyclopentadienyl)ruthenium (η⁵-C₅ⁱPrH₄)₂Ru), bis(η⁵-butylcyclopentadienyl)ruthenium (η⁵-C₅BuH₄)₂Ru), bis(η⁵-isobutylcyclopentadienyl)ruthenium (η⁵-C₅ⁱBuH₄)₂Ru), bis(η⁵-(sec-butyl)cyclopentadienyl)ruthenium ((η⁵-C₅^sBuH₄)₂Ru), bis(η⁵-(tert-butyl)cyclopentadienyl)ruthenium (η⁵-C₅^tBuH₄)₂Ru), bis(η⁵-pentylcyclopentadienyl)ruthenium (η⁵-C₅PeH₄)₂Ru), bis(η⁵-(cyclopentyl)cyclopentadienyl)ruthenium ((η⁵-C₅^cPeH₄)₂Ru), bis(η⁵-hexylcyclopentadienyl)ruthenium ((η⁵-C₅HxH₄)₂Ru), bis(η⁵-1,2-dimethylcyclopentadienyl)ruthenium ((η⁵-C₅Me₂H₃)₂Ru), bis(η⁵-1,3-dimethylcyclopentadienyl)ruthenium ((η⁵-C₅Me₂H₃)₂Ru), bis(η⁵-1,3-di(isopropyl)cyclopentadienyl)ruthenium ((η⁵-C₅(ⁱPr)₂H₃)₂Ru), bis(η⁵-1,2,4-tri(isopropyl)cyclopentadienyl)ruthenium ((η⁵-C₅(ⁱPr)₃H₂)₂Ru), bis(η⁵-1,3-di(tert-butyl)cyclopentadienyl)ruthenium ((η⁵-C₅(^tBu)₂H₃)₂Ru) and bis(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium (η⁵-C₅Me₅)₂Ru) are preferred; bis(η⁵-cyclopentadienyl)ruthenium (η⁵-C₅H₅)₂Ru), bis(η⁵-methylcyclopentadienyl)ruthenium ((η⁵-C₅MeH₄)₂Ru), bis(η⁵-ethylcyclopentadienyl)ruthenium (η⁵-C₅EtH₄)₂Ru), bis(η⁵-propylcyclopentadienyl)ruthenium (η⁵-C₅PrH₄)₂Ru), bis(η⁵-isopropylcyclopentadienyl)ruthenium (η⁵-C₅ⁱPrH₄)₂Ru), bis(η⁵-butylcyclopentadienyl)ruthenium ((η⁵-C₅BuH₄)₂Ru), bis(η⁵-isobutylcyclopentadienyl)ruthenium ((η⁵-C₅ⁱBuH₄)₂Ru), bis(η⁵-(sec-butyl)cyclopentadienyl)ruthenium ((η⁵-C₅^sBuH₄)₂Ru), bis(η⁵-(tert-butyl)cyclopentadienyl)ruthenium ((η⁵-C₅^tBuH₄)₂Ru), bis(η⁵-pentylcyclopentadienyl)ruthenium ((η⁵-C₅PeH₄)₂Ru), bis(η⁵-(cyclopentyl)cyclopentadienyl)ruthenium ((η⁵-C₅^cPeH₄)₂Ru) and bis(η⁵-hexylcyclopentadienyl)ruthenium ((η⁵-C₅HxH₄)₂Ru) are more preferred; and bis(η⁵-cyclopentadienyl)ruthenium ((η⁵-C₅H₅)₂Ru), bis(η⁵-methylcyclopentadienyl)ruthenium ((η⁵-C₅MeH₄)₂Ru) and bis(η⁵-ethylcyclopentadienyl)ruthenium ((η⁵-C₅EtH₄)₂Ru) are still more preferred.

As the ruthenocene derivative (6) that can be used as a raw material for synthesis in production method 2, a commercially available product may be used as it is, or a compound synthesized according to a known method described, for example, in Organic Syntheses, Vol. 41, page 96 (1961), JP-A-2003-342286 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”), and Organometallics, Vol. 5, page 2321 (1986) may also be used.

Z⁻in the protonic acid H⁺Z⁻that can be used in production method 2 includes, for example, a fluoro complex anion such as tetrafluoroborate ion (BF₄⁻) and hexafluorophosphate ion (PF₆⁻), a sulfonate ion such as trifluoromethanesulfonate ion (CF₃SO₃⁻), sulfate ion (SO₄²⁻) and bisulfate ion (HSO₄⁻), and a halide ion such as chloride ion and bromide ion. Specific examples of the protonic acid include a fluoro complex acid such as tetrafluoroboric acid and hexafluorophosphoric acid; a sulfonic acid such as sulfuric acid and trifluoromethanesulfonic acid; and a hydrogen halide such as hydrogen chloride. The protonic acid may form a complex with an ether such as dimethyl ether and diethyl ether. Examples of the protonic acid in the form of a complex include a tetrafluoroboric acid-dimethyl ether complex, a tetrafluoroboric acid-diethyl ether complex, and a hexafluorophosphoric acid-diethyl ether complex.

In view of a high yield of the cationic tris(nitrile) complex (4), a tetrafluoroboric acid-diethyl ether complex or a trifluoromethanesulfonic acid is preferred.

As the protonic acid for use in production method 2, a fluoro complex acid produced in a reaction system by reacting a fluoro complex anion-containing salt with a strong acid may also be used. In this case, examples of the fluoro complex anion-containing salt that can be used include ammonium tetrafluoroborate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, lithium hexafluorophosphate, sodium hexafluorophosphate, and potassium hexafluorophosphate. Examples of the strong acid that can be used include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, hydrogen chloride, and hydrogen bromide. Specific examples of the fluoro complex acid that can be produced in a reaction system include tetrafluoroboric acid and hexaluorophosphoric acid. In view of a high cost benefit and a high yield, any one of ammonium tetrafluoroborate, sodium tetrafluoroborate and ammonium hexafluorophosphate is preferably mixed with sulfuric acid and used.

The molar ratio among the ruthenocene derivative (6), the nitrile and the protonic acid used in production method 2 is described below. In view of a high yield of the cationic tris(nitrile) complex (4), 3 mol or more of the nitrile is preferably used per mol of the ruthenocene derivative. In view of a high yield, the nitrile is more preferably used in a solvent amount and, specifically, the nitrile is sill more preferably used in an amount appropriately selected from the range of 5 to 1,000 mol per mol of the ruthenocene derivative. The preferable amount of the protonic acid used varies depending on the kind of the protonic acid. For example, in the case where the protonic acid is a monobasic acid, in view of a high yield, 1 mol or more of the protonic acid is preferably used per mol of the ruthenocene derivative, and in the case of a dibasic acid, 0.5 mol or more of the protonic acid is preferably used per mol of the ruthenocene derivative. In the case where a mixture of a fluoro complex anion-containing salt and a strong acid is used as the protonic acid, 1 mol or more of the fluoro complex anion-containing salt and from 0.5 to 2.0 mol of the strong acid are appropriately used per mol of the ruthenocene derivative, whereby the cationic tris(nitrile) complex (4) can be efficiently obtained.

For the reason that the yield of the cationic tris(nitrile) complex (4) is high, production method 2 is preferably performed in an inert gas. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas, with argon or nitrogen gas being preferred.

For the reason that the yield of the cationic tris(nitrile) complex (4) is high, production method 2 is preferably performed under the conditions using an excessive amount of nitrile as a solvent. In addition, production method 2 can also be performed in an organic solvent. Specific examples of the organic solvent include an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane and petroleum ether, an ether such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane, a ketone such as acetone, methyl ethyl ketone, 3-pentanone, cyclopentanone and cyclohexanone, and an alcohol such as methanol, ethanol, propanol, isopropanol, tert-butanol and ethylene glycol. Of these organic solvents, one kind may be used alone, or a plurality of kinds may be mixed in an arbitrary ratio and used. In view of a high yield of the cationic tris(nitrile) complex (4), diethyl ether, tetrahydrofuran, acetone and methanol are preferred as the organic solvent.

In production method 2, the reaction temperature and the reaction time are not particularly limited, and general conditions employed by one skilled in the art when producing a metal complex may be used. As a specific example, a reaction temperature appropriately selected from a temperature range of −80° C. to 150° C. and a reaction time appropriately selected from the range of 10 minutes to 120 hours are employed, whereby the cationic tris(nitrile) complex (4) can be efficiently produced.

The cationic tris(nitrile) complex (4) produced by production method 2 may be purified by appropriately selecting and using a general purification method employed by one skilled in the art when purifying a metal complex. The purification method specifically includes filtration, extraction, centrifugation, decantation, crystallization, etc.

The ruthenium complex (1) can also be produced by continuously performing production method 2 and production method 1. In this case, the cationic tris(nitrile) complex (4) produced by production method 2 may be used as a raw material for production in production method 1 without purifying it, or the cationic tris(nitrile) complex (4) that is purified by appropriately selecting and using a general purification method employed by one skilled in the art when purifying a metal complex may be used as a raw material for production in production method 1.

In addition, the ruthenium complex (1a) of the present invention can also be produced in the same manner as the ruthenium complex (1) by continuously performing production method 2 and production method 1.

Definitions of R⁸, R⁹and n in formula (2) are described.

The alkyl group having a carbon number of 1 to 6 represented by R⁸and R⁹may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a cyclobutylmethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group, and a 2-cyclobutylethyl group. From the standpoint that the ruthenium complex (2) of the present invention has vapor pressure and thermal stability suitable as a CVD material or an ALD material, those members are preferably an alkyl group having a carbon number of 1 to 4, more preferably a methyl group.

n is an integer of 0 to 2 and from the standpoint that the ruthenium complex (2) of the present invention has vapor pressure suitable as a CVD material or an ALD material, n is preferably 0.

Specific examples of the ruthenium complex (2) of the present invention are shown in Tables 3 and 4. Here, Me, Et, Pr, ⁱPr, Bu, ^tBu, Pe and Hx stand for a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group and a hexyl group, respectively.

[Table 8]

TABLE 3

(2)

Compound No.
R⁸
R⁹
n

2-1
Me
Me
0

2-2
Me
Et
0

2-3
Et
Et
0

2-4
Et
Pr
0

2-5
Pr
Pr
0

2-6
Pr
Bu
0

2-7
Bu
Bu
0

2-8
Bu
Pe
0

2-9
Pe
Pe
0

2-10
Pe
Hx
0

2-11
Hx
Hx
0

2-12
Me

ⁱPr
0

2-13
Me

^tBu
0

2-14
Et

ⁱPr
0

2-15

ⁱPr

ⁱPr
0

2-16

ⁱPr

^tBu
0

2-17

^tBu

^tBu
0

2-18
Me
Me
1

2-19
Me
Et
1

2-20
Et
Et
1

2-21
Et
Pr
1

2-22
Pr
Pr
1

2-23
Pr
Bu
1

2-24
Bu
Bu
1

2-25
Bu
Pe
1

2-26
Pe
Pe
1

2-27
Pe
Hx
1

2-28
Hx
Hx
1

2-29
Me

ⁱPr
1

2-30
Me

^tBu
1

2-31
Et

ⁱPr
1

2-32

ⁱPr

ⁱPr
1

2-33

ⁱPr

^tBu
1

2-34

^tBu

^tBu
1

2-35
Me
Me
2

2-36
Me
Et
2

2-37
Et
Et
2

[Table 9]

TABLE 4

(2)

Compound No.
R⁸
R⁹
n

2-38
Et
Pr
2

2-39
Pr
Pr
2

2-40
Pr
Bu
2

2-41
Bu
Bu
2

2-42
Bu
Pe
2

2-43
Pe
Pe
2

2-44
Pe
Hx
2

2-45
Hx
Hx
2

2-46
Me

ⁱPr
2

2-47
Me

^tBu
2

2-48
Et

ⁱPr
2

2-49

ⁱPr

ⁱPr
2

2-50

ⁱPr

^tBu
2

2-51

^tBu

^tBu
2

Among those exemplified in Tables 3 and 4, in view of having vapor pressure and thermal stability suitable as a CVD material or an ALD material, (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dimethylpyrrolyl)ruthenium (2-1), (1-5-η⁵-cyclooctadienyl)(η⁵-2-ethyl-5-methylpyrrolyl)ruthenium (2-2), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-diethylpyrrolyl)ruthenium (2-3), (1-5-η⁵-cyclooctadienyl)(η⁵-2-ethyl-5-propylpyrrolyl)ruthenium (2-4), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dipropylpyrrolyl)ruthenium (2-5), (1-5-η⁵-cyclooctadienyl)(η⁵-2-butyl-5-propylpyrrolyl)ruthenium (2-6), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dibutylpyrrolyl)ruthenium (2-7), (1-5-η⁵-cyclooctadienyl)(η⁵-2-butyl-5-pentylpyrrolyl)ruthenium (2-8), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dipentylpyrrolyl)ruthenium (2-9), (1-5-η⁵-cyclooctadienyl)(η⁵-2-hexyl-5-pentylpyrrolyl)ruthenium (2-10), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dihexylpyrrolyl)ruthenium (2-11), (1-5-η⁵-cyclooctadienyl)(η⁵-2-methyl-5-isopropylpyrrolyl)ruthenium (2-12), (1-5-η⁵-cyclooctadienyl)(η⁵-2-tert-butyl-5-methyl)ruthenium (2-13), (1-5-η⁵-cyclooctadienyl)(η⁵-2-ethyl-5-isopropylpyrrolyl)ruthenium (2-14), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-di(isopropyl)pyrrolyl)ruthenium (2-15), (1-5-η⁵-cyclooctadienyl)(η⁵-2-tert-butyl-5-isopropylpyrrolyl)ruthenium (2-16) and (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-di(tert-butyl)pyrrolyl)ruthenium (2-17) are preferred; (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dimethylpyrrolyl)ruthenium (2-1), (1-5-η⁵-cyclooctadienyl)(η⁵-2-ethyl-5-methylpyrrolyl)ruthenium (2-2), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-diethylpyrrolyl)ruthenium (2-3), (1-5-η⁵-cyclooctadienyl)(η⁵-2-ethyl-5-propylpyrrolyl)ruthenium (2-4), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dipropylpyrrolyl)ruthenium (2-5), (1-5-η⁵-cyclooctadienyl)(η⁵-2-butyl-5-propylpyrrolyl)ruthenium (2-6), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dibutylpyrrolyl)ruthenium (2-7), (1-5-η⁵-cyclooctadienyl)(η⁵-2-methyl-5-isopropylpyrrolyl)ruthenium (2-12), (1-5-η⁵-cyclooctadienyl)(η⁵-2-tert-butyl-5-methyl)ruthenium (2-13), (1-5-η⁵-cyclooctadienyl)(η⁵-2-ethyl-5-isopropylpyrrolyl)ruthenium (2-14), (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-di(isopropyl)pyrrolyl)ruthenium (2-15), (1-5-η⁵-cyclooctadienyl)(η⁵-2-tert-butyl-5-isopropylpyrrolyl)ruthenium (2-16) and (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-di(tert-butyl)pyrrolyl)ruthenium (2-17) are more preferred; and (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dimethylpyrrolyl)ruthenium (2-1) is still more preferred.

The production method of the ruthenium complex (2) of the present invention is described below.

The ruthenium complex (2) of the present invention can be produced by the following production method 3 or production method 5.

Production method 3 is a method of reacting a cationic bis(cyclooctadienyl) complex (8) with a substituted pyrrole (9) in the presence of a base to produce the ruthenium complex (2) of the present invention.

Production Method 3:

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(wherein each of R⁸and R⁹independently represents an alkyl group having a carbon number of 1 to 6, Y⁻represents a counter anion, and n represents an integer of 0 to 2.)

Specific examples of the cation moiety of the cationic bis(cyclooctadienyl) complex (8) are shown in (8-1) to (8-12) below.

embedded image

Among those exemplified in (8-1) to (8-12), in view of having vapor pressure suitable as a CVD material or an ALD material, [bis(1-5-η⁵-cyclooctadienyl)(hydride)ruthenium(IV)] ([RuH(η⁵-C₈H₁₁)₂]) (8-1) is preferred.

Examples of the counter anion Y⁻in formula (8) include those generally used as a counter anion of a cationic metal complex. Specific examples thereof include a fluoro complex anion such as tetrafluoroborate ion (BF₄⁻), hexafluorophosphate ion (PF₆⁻), hexafluoroantimonate ion (SbF₆⁻) and tetrafluoroaluminate ion (AlF₄⁻), a monovalent sulfonate ion such as trifluoromethanesulfonate ion (CF₃SO₃⁻), methanesulfonate ion (MeSO₃⁻) and methylsulfate ion (MeSO₄⁻), a halide ion such as chloride ion and bromide ion, a counter anion of a monobasic acid, such as nitrate ion (NO₃⁻), perchlorate ion (ClO₄⁻), tetrachloroaluminate ion (AlCl₄⁻) and bis(trifluoromethanesulfonyl)amide ion ((CF₃SO₂)₂N⁻), a counter anion of a polybasic acid, such as sulfate ion (SO₄²⁻), hydrogen sulfate ion (HSO₄⁻), phosphate ion (PO₄³⁻), monohydrogen phosphate ion (HPO₄²⁻), dihydrogen phosphate ion (H₂PO₄⁻), dimethylphosphate ion ((MeO)₂PO₄⁻) and diethylphosphate ion ((EtO)₂PO₄⁻), and a derivative thereof. In view of a high yield of the ruthenium complex (2), the counter anion Y⁻is preferably a fluoro complex anion such as BF₄⁻and PF₆⁻, or a monovalent sulfonate ion such as CF₃SO₃⁻and MeSO₃⁻, more preferably BF₄⁻.

Specific preferred examples of the cationic bis(cyclooctadienyl) complex (8) include [bis(1-5-η⁵-cyclooctadienyl)(hydride)ruthenium(IV)][tetrafluoroborate] ([RuH(η⁵-C₈H₁₁)₂][BF₄]), [(bis(1-5-η⁵-cyclo-octadienyl)(hydride)ruthenium(IV))][hexafluorophosphate] ([RuH(η⁵-C₈H₁₁)₂][PF₆]), [(bis(1-5-η⁵-cyclooctadienyl)(hydride)ruthenium(IV))][trifluoromethanesulfonate] ([RuH(η⁵-C₈H₁₁)₂][CF₃SO₃]), and [(bis(1-5-η⁵-cyclooctadienyl)(hydride)ruthenium(IV))][methanesulfonate] ([RuH(η⁵-C₈H₁₁)₂][MeSO₃]). In view of a high yield of the ruthenium complex (2), [bis(1-5-η⁵-cyclooctadienyl)(hydride)ruthenium(IV)][tetrafluoroborate] ([RuH(η⁵-C₈H₁₁)₂][BF₄]), etc. are preferred.

Specific examples of the substituted pyrrole (9) include 2,5-dimethylpyrrole, 2-ethyl-5-methylpyrrole, 2,5-diethylpyrrole, 2-ethyl-5-propylpyrrole, 2,5-dipropylpyrrole, 2-butyl-5-propylpyrrole, 2,5-dibutylpyrrole, 2-butyl-5-pentylpyrrole, 2,5-dipentylpyrrole, 2-hexyl-5-pentylpyrrole, 2,5-dihexylpyrrole, 2-methyl-5-isopropylpyrrole, 2-tert-butyl-5-methylpyrrole, 2-ethyl-5-isopropylpyrrole, 2,5-di(isopropyl)pyrrole, 2-tert-butyl-5-isopropylpyrrole, and 2,5-di(tert-butyl)pyrrole. From the standpoint that the ruthenium complex (2) has vapor pressure suitable as a CVD material or an ALD material, 2,5-dimethylpyrrole, 2-ethyl-5-methylpyrrole, 2,5-diethylpyrrole, 2-ethyl-5-propylpyrrole, 2,5-dipropylpyrrole, 2-butyl-5-propylpyrrole, 2,5-dibutylpyrrole, 2-methyl-5-isopropylpyrrole, 2-tert-butyl-5-methylpyrrole, 2-ethyl-5-isopropylpyrrole, 2,5-di(isopropyl)pyrrole, 2-tert-butyl-5-isopropylpyrrole and 2,5-di(tert-butyl)pyrrole are preferred, and 2,5-dimethylpyrrole is more preferred.

The base that can be used in production method 3 includes an inorganic base and an organic base. Examples of the inorganic base include an alkali metal carbonate such as lithium carbonate, sodium carbonate and potassium carbonate, an alkali metal bicarbonate such as lithium bicarbonate, sodium bicarbonate and potassium bicarbonate, a Group 2 metal carbonate such as magnesium carbonate, calcium carbonate and strontium carbonate, a typical metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide, a typical metal hydride such as lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride and aluminum hydride, a typical metal hydride complex compound such as sodium borohydride and aluminum lithium hydride, and an alkali metal amide such as lithium amide, sodium amide and lithium dialkylamide. Examples of the organic base include a secondary or tertiary amine such as diethylamine, triethylamine, diethylisopropylamine and tributylamine, a cyclic aliphatic amine such as pyrrolidine, piperidine, piperazine and 1,4-diazabicyclooctane, and an aromatic amine such as pyridine. In view of a high yield of the ruthenium complex (2), the base is preferably a secondary or tertiary amine or pyridine, more preferably a secondary or tertiary amine, still more preferably triethylamine.

For the reason that the yield of the ruthenium complex (2) is high, production method 3 is preferably performed in an inert gas. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas, with argon or nitrogen gas being preferred.

For the reason that the yield of the ruthenium complex (2) is high, production method 3 is preferably performed in an organic solvent. In the case of performing production method 3 in an organic solvent, specific examples of the organic solvent include an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane and petroleum ether, a halogen-based aliphatic hydrocarbon such as chloroform, dichloromethane, dibromomethane, 1,1-dichloroethane, 1,2-dichloroethane and 1,1,1-trichloroethane, an ether such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, methyl-tert-butyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane, a ketone such as acetone, methyl ethyl ketone, 3-pentanone, cyclopentanone and cyclohexanone, and an alcohol such as methanol, ethanol, propanol, isopropanol, tert-butanol and ethylene glycol. Of these organic solvents, one kind may be used alone, or a plurality of kinds may be mixed in an arbitrary ratio and used. In view of a high yield of the ruthenium complex (2), as the organic solvent, chloroform, dichloromethane, cyclopentyl methyl ether, methyl-tert-butyl ether, diethyl ether, tetrahydrofuran, acetone, methanol and hexane are preferred, and chloroform, dichloromethane, cyclopentyl methyl ether, methyl-tert-butyl ether, diethyl ether and tetrahydrofuran are more preferred.

The method for obtaining the substituted pyrrole (9) includes the production methods described, for example, in Journal of the American Chemical Society, Vol. 77, page 3340 (1955), and Organic Letters, Vol. 15, page 1436 (2013), other than the purchase of a commercial product.

The molar ratio among the cationic bis(cyclooctadienyl) complex (8), the substituted pyrrole (9) and the base when performing production method 3 is described below. Preferably, 1 mol or more of the substituted pyrrole (9) and the base are used per mol of the cationic bis(cyclooctadienyl) complex (8), whereby the ruthenium complex (2) can be efficiently produced.

In production method 3, the reaction temperature and the reaction time are not particularly limited, and general conditions employed by one skilled in the art when producing a metal complex may be used. As a specific example, a reaction temperature appropriately selected from a temperature range of −80° C. to 120° C. and a reaction time appropriately selected from the range of 10 minutes to 120 hours are employed, whereby the ruthenium complex (2) can be efficiently produced. The ruthenium complex (2) produced by production method 3 may be purified by appropriately selecting and using a general purification method employed by one skilled in the art when purifying a metal complex. The purification method specifically includes filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography, etc.

The cationic bis(cyclooctadienyl) complex (8) as a raw material of production method 3 can be produced according to production method 4 described in Organometallics, Vol. 10, page 455 (1991). Production method 4 is a method of reacting a (cyclooctadiene)(cyclooctatriene) complex (15) with a protonic acid H⁺Y⁻to produce a cationic bis(cyclooctadienyl) complex (8).

Production Method 4:

embedded image

(wherein n represents an integer of 0 to 2, and Y⁻represents a counter anion.)

The (cyclooctadiene)(cyclooctatriene) complex (15) can be produced according to the method described in Journal of Organometallic Chemistry, Vol. 272, page 179 (1984). Specifically, this is a method of reacting ruthenium chloride with cyclooctadiene in the presence of zinc to produce a (cyclooctadiene)(cyclooctatriene) complex (15).

Specific examples of the cyclooctadiene include 1,5-cyclooctadiene, 1-methyl-1,5-cyclooctadiene, 1,2-dimethyl-1,5-cyclooctadiene, 1,4-dimethyl-1,5-cyclooctadiene, 1,5-dimethyl-1,5-cyclooctadiene, 2,4-dimethyl-1,5-cyclooctadiene, 1,6-dimethyl-1,5-cyclooctadiene, and 3,7-dimethyl-1,5-cyclooctadiene. In view of availability, 1,5-cyclooctadiene and 1,5-dimethyl-1,5-cyclooctadiene are preferred, and 1,5-cyclooctadiene is more preferred.

The method for obtaining the cyclooctadiene include the methods described, for example, in Journal of the American Chemical Society, Vol. 116, page 2889 (1994), Heterocycles, Vol. 77, page 927 (2009), and JP-A-11-209314, other than the purchase of a commercial product.

Specific preferred examples of the (cyclooctadiene)(cyclooctatriene) complex (15) include (η⁴-1,5-cyclooctadiene)(η⁶-1,3,5-cyclooctatriene)ruthenium (Ru(η⁴-C₈H₁₂)(η⁶-C₈H₁₀)).

Examples of the counter anion Y⁻of the protonic acid that can be used in production method 4 include those generally used as a counter anion of a cationic metal complex. Specific examples thereof include a fluoro complex anion such as tetrafluoroborate ion (BF₄⁻), hexafluorophosphate ion (PF₆⁻), hexafluoroantimonate ion (SbF₆⁻) and tetrafluoroaluminate ion (AlF₄⁻), a monovalent sulfonate ion such as trifluoromethanesulfonate ion (CF₃SO₃⁻), methanesulfonate ion (MeSO₃⁻) and methylsulfate ion (MeSO₄⁻), a halide ion such as chloride ion and bromide ion, a counter anion of a monobasic acid, such as nitrate ion (NO₃⁻), perchlorate ion (ClO₄⁻), tetrachloroaluminate ion (AlCl₄⁻) and bis(trifluoromethanesulfonyl)amide ion ((CF₃SO₂)₂N), a counter anion of a polybasic acid, such as sulfate ion (SO₄²⁻), hydrogen sulfate ion (HSO₄⁻), phosphate ion (PO₄³⁻), monohydrogen phosphate ion (HPO₄²⁻), dihydrogen phosphate ion (H₂PO₄⁻), dimethylphosphate ion ((MeO)₂PO₄⁻) and diethylphosphate ion ((EtO)₂PO₄⁻), and a derivative thereof. In view of a high yield of the cationic bis(cyclooctadienyl) complex (8), the counter anion Y⁻is preferably a fluoro complex anion such as BF₄⁻and PF₆⁻, or a monovalent sulfonate ion such as CF₃SO₃⁻and MeSO₃⁻, more preferably BF₄⁻.

Specific examples of the protonic acid include a fluoro complex acid such as tetrafluoroboric acid and hexafluorophosphoric acid; a sulfonic acid such as sulfuric acid and trifluoromethanesulfonic acid; and a hydrogen halide such as hydrogen chloride. The protonic acid may form a complex with an ether such as dimethyl ether and diethyl ether. Examples of the protonic acid in the form of a complex include a tetrafluoroboric acid-dimethyl ether complex, a tetrafluoroboric acid-diethyl ether complex, and a hexafluorophosphoric acid-diethyl ether complex. In view of a high yield of the cationic bis(cyclooctadienyl) complex (8), a tetrafluoroboric acid-diethyl ether complex, etc. are preferred.

As the protonic acid for use in production method 4, a fluoro complex acid produced in a reaction system by reacting a fluoro complex anion-containing salt with a strong acid may also be used. In this case, examples of the fluoro complex anion-containing salt that can be used include ammonium tetrafluoroborate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, lithium hexafluorophosphate, sodium hexafluorophosphate, and potassium hexafluorophosphate. Examples of the strong acid that can be used include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, hydrogen chloride, and hydrogen bromide. Specific examples of the fluoro complex acid that can be produced in a reaction system include tetrafluoroboric acid and hexaluorophosphoric acid. In view of a high cost benefit and a high yield, any one of ammonium tetrafluoroborate, sodium tetrafluoroborate and ammonium hexafluorophosphate is preferably mixed with sulfuric acid and used.

Furthermore, as the protonic acid for use in production method 4, a fluoro complex acid produced in a reaction system by reacting boron trifluoride with a strong acid may also be used. In this case, examples of the strong acid that can be used include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, hydrogen chloride, and hydrogen bromide.

The molar ratio between the (cyclooctadiene)(cyclooctatriene) complex (15) and the protonic acid used in production method 4 is described below. The preferable amount of the protonic acid used varies depending on the kind of the protonic acid. For example, in the case where the protonic acid is a monobasic acid, in view of a high yield, 1 mol or more of the protonic acid is preferably used per mol of the (cyclooctadiene)(cyclooctatriene) complex (15), and in the case of a dibasic acid, 0.5 mol or more of the protonic acid is preferably used per mol of the (cyclooctadiene)(cyclooctatriene) complex (15). In the case where a mixture of a fluoro complex anion-containing salt and a strong acid is used as the protonic acid, 1 mol or more of the fluoro complex anion-containing salt and from 0.5 to 2.0 mol of the strong acid are appropriately used per mol of the (cyclooctadiene)(cyclooctatriene) complex (15), whereby the cationic bis(cyclooctadienyl) complex (8) can be efficiently obtained.

For the reason that the yield of the cationic bis(cyclooctadienyl) complex (8) is high, production method 4 is preferably performed in an inert gas. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas, with argon or nitrogen gas being preferred.

For the reason that the yield of the cationic bis(cyclooctadienyl) complex (8) is high, production method 4 is preferably performed in an organic solvent. In the case of performing production method 4 in an organic solvent, specific examples of the organic solvent include an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane and petroleum ether, a halogen-based aliphatic hydrocarbon such as chloroform, dichloromethane, dibromomethane, 1,1-dichloroethane, 1,2-dichloroethane and 1,1,1-trichloroethane, an ether such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, methyl-tert-butyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane, a ketone such as acetone, methyl ethyl ketone, 3-pentanone, cyclopentanone and cyclohexanone, and an alcohol such as methanol, ethanol, propanol, isopropanol, tert-butanol and ethylene glycol. Of these organic solvents, one kind may be used alone, or a plurality of kinds may be mixed in an arbitrary ratio and used. In view of a high yield of the cationic bis(cyclooctadienyl) complex (8), chloroform, dichloromethane, cyclopentyl methyl ether, methyl-tert-butyl ether, diethyl ether, tetrahydrofuran, etc. are preferred. In production method 4, the reaction temperature and the reaction time are not particularly limited, and general conditions employed by one skilled in the art when producing a metal complex may be used. As a specific example, a reaction temperature appropriately selected from a temperature range of −80° C. to 150° C. and a reaction time appropriately selected from the range of 10 minutes to 120 hours are employed, whereby the cationic bis(cyclooctadienyl) complex (8) can be efficiently produced.

The cationic bis(cyclooctadienyl) complex (8) produced by production method 4 may be purified by appropriately selecting and using a general purification method employed by one skilled in the art when purifying a metal complex. The purification method specifically includes filtration, extraction, centrifugation, decantation, distillation, crystallization, etc.

The ruthenium complex (2) can also be produced by production method 5 of continuously performing production method 4 and production method 3. In this case, the cationic bis(cyclooctadienyl) complex (8) produced by production method 4 may be used as a raw material for production in production method 3 without purifying it, or the cationic bis(cyclooctadienyl) complex (8) that is purified by appropriately selecting and using a general purification method employed by one skilled in the art when purifying a metal complex may be used as a raw material for production in production method 3. Examples of the purification method include filtration, extraction, centrifugation, decantation, and crystallization.

Definitions of R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and R¹⁸in formula (3) are described below.

The alkyl group having a carbon number of 1 to 6 represented by R¹⁰, R¹¹, R¹², R¹³and R¹⁴may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a cyclobutylmethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group, and a 2-cyclobutylethyl group. From the standpoint that the ruthenium complex (3) of the present invention has vapor pressure and thermal stability suitable as a CVD material or an ALD material, preferably, R¹⁰is an alkyl group having a carbon number of 1 to 6 and R¹¹, R¹², R¹³and R¹⁴are a hydrogen atom; more preferably, R¹⁰is a methyl group or an ethyl group; and still more preferably, R¹⁰is an ethyl group.

The alkyl group having a carbon number of 1 to 6 represented by R¹⁵, R¹⁶, R¹⁷and R¹⁸may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a cyclobutylmethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a cyclohexyl group, a cyclopentylmethyl group, a 1-cyclobutylethyl group, and a 2-cyclobutylethyl group. From the standpoint that the ruthenium complex (3) of the present invention has vapor pressure and thermal stability suitable as a CVD material or an ALD material, R¹⁵, R¹⁶, R¹⁷and R¹⁸are preferably a methyl group.

Specific examples of the ruthenium complex (3) of the present invention are shown in Tables 5-1 to 5-10. Here, Me, Et, Pr, ⁱPr, Bu, ⁱBu, ^sBu, ^tBu, Pe, ^cPe and Hx stand for a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclopentyl group and a hexyl group, respectively.

[Table 10]

TABLE 5-1

(3)

Com-

pound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-1
H
H
H
H
H
H
H
H
Me

3-2
Me
H
H
H
H
H
H
H
Me

3-3
Et
H
H
H
H
H
H
H
Me

3-4
Pr
H
H
H
H
H
H
H
Me

3-5

ⁱPr
H
H
H
H
H
H
H
Me

3-6
Bu
H
H
H
H
H
H
H
Me

3-7

ⁱBu
H
H
H
H
H
H
H
Me

3-8

^sBu
H
H
H
H
H
H
H
Me

3-9

^tBu
H
H
H
H
H
H
H
Me

3-10
Pe
H
H
H
H
H
H
H
Me

3-11

^cPe
H
H
H
H
H
H
H
Me

3-12
Hx
H
H
H
H
H
H
H
Me

3-13
Me
Me
H
H
H
H
H
H
Me

3-14
Me
H
Me
H
H
H
H
H
Me

3-15

^tBu
H

^tBu
H
H
H
H
H
Me

3-16
Me
Me
Me
H
H
H
H
H
Me

3-17
Me
Me
H
Me
H
H
H
H
Me

3-18

ⁱPr

ⁱPr
H

ⁱPr
H
H
H
H
Me

3-19
Me
Me
Me
Me
H
H
H
H
Me

3-20
Et
Me
Me
Me
Me
H
H
H
Me

3-21
Pr
Me
Me
Me
Me
H
H
H
Me

3-22
H
H
H
H
H
H
H
H
Bu

3-23
Me
H
H
H
H
H
H
H
Bu

3-24
Et
H
H
H
H
H
H
H
Bu

3-25
Pr
H
H
H
H
H
H
H
Bu

3-26

ⁱPr
H
H
H
H
H
H
H
Bu

3-27
Bu
H
H
H
H
H
H
H
Bu

3-28

ⁱBu
H
H
H
H
H
H
H
Bu

3-29

^sBu
H
H
H
H
H
H
H
Bu

3-30

^tBu
H
H
H
H
H
H
H
Bu

3-31
Pe
H
H
H
H
H
H
H
Bu

3-32

^cPe
H
H
H
H
H
H
H
Bu

3-33
Hx
H
H
H
H
H
H
H
Bu

3-34
Me
Me
H
H
H
H
H
H
Bu

3-35
Me
H
Me
H
H
H
H
H
Bu

3-36

^tBu
H

^tBu
H
H
H
H
H
Bu

3-37
Me
Me
Me
H
H
H
H
H
Bu

3-38
Me
Me
H
Me
H
H
H
H
Bu

[Table 11]

TABLE 5-2

(3)

Compound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-39

ⁱPr
H

ⁱPr
H

ⁱPr
H
H
H
Bu

3-40
Me
Me
Me
Me
H
H
H
H
Bu

3-41
Me
Me
Me
Me
Me
H
H
H
Bu

3-42
Et
Me
Me
Me
Me
H
H
H
Bu

3-43
Pr
Me
Me
Me
Me
H
H
H
Bu

3-44
H
H
H
H
H
Me
Me
Me
Me

3-45
Me
H
H
H
H
Me
Me
Me
Me

3-46
Et
H
H
H
H
Me
Me
Me
Me

3-47
Pr
H
H
H
H
Me
Me
Me
Me

3-48

ⁱPr
H
H
H
H
Me
Me
Me
Me

3-49
Bu
H
H
H
H
Me
Me
Me
Me

3-50

ⁱBu
H
H
H
H
Me
Me
Me
Me

3-51

^sBu
H
H
H
H
Me
Me
Me
Me

3-52

^tBu
H
H
H
H
Me
Me
Me
Me

3-53
Pe
H
H
H
H
Me
Me
Me
Me

3-54

^cPe
H
H
H
H
Me
Me
Me
Me

3-55
Hx
H
H
H
H
Me
Me
Me
Me

3-56
Me
Me
H
H
H
Me
Me
Me
Me

3-57
Me
H
Me
H
H
Me
Me
Me
Me

3-58

^tBu
H

^tBu
H
H
Me
Me
Me
Me

3-59
Me
Me
Me
H
H
Me
Me
Me
Me

3-60
Me
Me
H
Me
H
Me
Me
Me
Me

3-61

ⁱPr
H

ⁱPr
H

ⁱPr
Me
Me
Me
Me

3-62
Me
Me
Me
Me
H
Me
Me
Me
Me

3-63
Et
Me
Me
Me
Me
Me
Me
Me
Me

3-64
Pr
Me
Me
Me
Me
Me
Me
Me
Me

3-65
H
H
H
H
H
Me
Me
Me
Bu

3-66
Me
H
H
H
H
Me
Me
Me
Bu

3-67
Et
H
H
H
H
Me
Me
Me
Bu

3-68
Pr
H
H
H
H
Me
Me
Me
Bu

3-69

ⁱPr
H
H
H
H
Me
Me
Me
Bu

3-70
Bu
H
H
H
H
Me
Me
Me
Bu

3-71

ⁱBu
H
H
H
H
Me
Me
Me
Bu

3-72

^sBu
H
H
H
H
Me
Me
Me
Bu

3-73

^tBu
H
H
H
H
Me
Me
Me
Bu

3-74
Pe
H
H
H
H
Me
Me
Me
Bu

3-75

^cPe
H
H
H
H
Me
Me
Me
Bu

3-76
Hx
H
H
H
H
Me
Me
Me
Bu

[Table 12]

TABLE 5-3

(3)

Compound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-77
Me
Me
H
H
H
Me
Me
Me
Bu

3-78
Me
H
Me
H
H
Me
Me
Me
Bu

3-79

^tBu
H

^tBu
H
H
Me
Me
Me
Bu

3-80
Me
Me
Me
H
H
Me
Me
Me
Bu

3-81
Me
Me
H
Me
H
Me
Me
Me
Bu

3-82

ⁱPr
H

ⁱPr
H

ⁱPr
Me
Me
Me
Bu

3-83
Me
Me
Me
Me
H
Me
Me
Me
Bu

3-84
Me
Me
Me
Me
Me
Me
Me
Me
Bu

3-85
Et
Me
Me
Me
Me
Me
Me
Me
Bu

3-86
Pr
Me
Me
Me
Me
Me
Me
Me
Bu

3-87
H
H
H
H
H
Et
Et
Et
Me

3-88
Me
H
H
H
H
Et
Et
Et
Me

3-89
Et
H
H
H
H
Et
Et
Et
Me

3-90
Pr
H
H
H
H
Et
Et
Et
Me

3-91

ⁱPr
H
H
H
H
Et
Et
Et
Me

3-92
Bu
H
H
H
H
Et
Et
Et
Me

3-93

ⁱBu
H
H
H
H
Et
Et
Et
Me

3-94

^sBu
H
H
H
H
Et
Et
Et
Me

3-95

^tBu
H
H
H
H
Et
Et
Et
Me

3-96
Pe
H
H
H
H
Et
Et
Et
Me

3-97

^cPe
H
H
H
H
Et
Et
Et
Me

3-98
Hx
H
H
H
H
Et
Et
Et
Me

3-99
Me
Me
H
H
H
Et
Et
Et
Me

3-100
Me
H
Me
H
H
Et
Et
Et
Me

3-101

^tBu
H

^tBu
H
H
Et
Et
Et
Me

3-102
Me
Me
Me
H
H
Et
Et
Et
Me

3-103
Me
Me
H
Me
H
Et
Et
Et
Me

3-104

ⁱPr
H

ⁱPr
H

ⁱPr
Et
Et
Et
Me

3-105
Me
Me
Me
Me
H
Et
Et
Et
Me

3-106
Et
Me
Me
Me
Me
Et
Et
Et
Me

3-107
Pr
Me
Me
Me
Me
Et
Et
Et
Me

3-108
H
H
H
H
H
Et
Et
Et
Bu

3-109
Me
H
H
H
H
Et
Et
Et
Bu

3-110
Et
H
H
H
H
Et
Et
Et
Bu

3-111
Pr
H
H
H
H
Et
Et
Et
Bu

3-112

ⁱPr
H
H
H
H
Et
Et
Et
Bu

3-113
Bu
H
H
H
H
Et
Et
Et
Bu

3-114

ⁱBu
H
H
H
H
Et
Et
Et
Bu

[Table 13]

TABLE 5-4

(3)

Compound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-115

^sBu
H
H
H
H
Et
Et
Et
Bu

3-116

^tBu
H
H
H
H
Et
Et
Et
Bu

3-117
Pe
H
H
H
H
Et
Et
Et
Bu

3-118

^cPe
H
H
H
H
Et
Et
Et
Bu

3-119
Hx
H
H
H
H
Et
Et
Et
Bu

3-120
Me
Me
H
H
H
Et
Et
Et
Bu

3-121
Me
H
Me
H
H
Et
Et
Et
Bu

3-122

^tBu
H

^tBu
H
H
Et
Et
Et
Bu

3-123
Me
Me
Me
H
H
Et
Et
Et
Bu

3-124
Me
Me
H
Me
H
Et
Et
Et
Bu

3-125

ⁱPr
H

ⁱPr
H

ⁱPr
Et
Et
Et
Bu

3-126
Me
Me
Me
Me
H
Et
Et
Et
Bu

3-127
Me
Me
Me
Me
Me
Et
Et
Et
Bu

3-128
Et
Me
Me
Me
Me
Et
Et
Et
Bu

3-129
Pr
Me
Me
Me
Me
Et
Et
Et
Bu

3-130
H
H
H
H
H
Pr
Pr
Pr
Me

3-131
Me
H
H
H
H
Pr
Pr
Pr
Me

3-132
Et
H
H
H
H
Pr
Pr
Pr
Me

3-133
Pr
H
H
H
H
Pr
Pr
Pr
Me

3-134

ⁱPr
H
H
H
H
Pr
Pr
Pr
Me

3-135
Bu
H
H
H
H
Pr
Pr
Pr
Me

3-136

ⁱBu
H
H
H
H
Pr
Pr
Pr
Me

3-137

^sBu
H
H
H
H
Pr
Pr
Pr
Me

3-138

^tBu
H
H
H
H
Pr
Pr
Pr
Me

3-139
Pe
H
H
H
H
Pr
Pr
Pr
Me

3-140

^cPe
H
H
H
H
Pr
Pr
Pr
Me

3-141
Hx
H
H
H
H
Pr
Pr
Pr
Me

3-142
Me
Me
H
H
H
Pr
Pr
Pr
Me

3-143
Me
H
Me
H
H
Pr
Pr
Pr
Me

3-144

^tBu
H

^tBu
H
H
Pr
Pr
Pr
Me

3-145
Me
Me
Me
H
H
Pr
Pr
Pr
Me

3-146
Me
Me
H
Me
H
Pr
Pr
Pr
Me

3-147

ⁱPr
H

ⁱPr
H

ⁱPr
Pr
Pr
Pr
Me

3-148
Me
Me
Me
Me
H
Pr
Pr
Pr
Me

3-149
Et
Me
Me
Me
Me
Pr
Pr
Pr
Me

3-150
Pr
Me
Me
Me
Me
Pr
Pr
Pr
Me

3-151
H
H
H
H
H
Pr
Pr
Pr
Bu

3-152
Me
H
H
H
H
Pr
Pr
Pr
Bu

[Table 14]

TABLE 5-5

(3)

Compound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-153
Et
H
H
H
H
Pr
Pr
Pr
Bu

3-154
Pr
H
H
H
H
Pr
Pr
Pr
Bu

3-155

ⁱPr
H
H
H
H
Pr
Pr
Pr
Bu

3-156
Bu
H
H
H
H
Pr
Pr
Pr
Bu

3-157

ⁱBu
H
H
H
H
Pr
Pr
Pr
Bu

3-158

^sBu
H
H
H
H
Pr
Pr
Pr
Bu

3-159

^tBu
H
H
H
H
Pr
Pr
Pr
Bu

3-160
Pe
H
H
H
H
Pr
Pr
Pr
Bu

3-161

^cPe
H
H
H
H
Pr
Pr
Pr
Bu

3-162
Hx
H
H
H
H
Pr
Pr
Pr
Bu

3-163
Me
Me
H
H
H
Pr
Pr
Pr
Bu

3-164
Me
H
Me
H
H
Pr
Pr
Pr
Bu

3-165

^tBu
Me

^tBu
H
H
Pr
Pr
Pr
Bu

3-166
Me
Me
Me
H
H
Pr
Pr
Pr
Bu

3-167
Me
Me
H
Me
H
Pr
Pr
Pr
Bu

3-168

ⁱPr
H

ⁱPr
H

ⁱPr
Pr
Pr
Pr
Bu

3-169
Me
Me
Me
Me
H
Pr
Pr
Pr
Bu

3-170
Me
Me
Me
Me
Me
Pr
Pr
Pr
Bu

3-171
Et
Me
Me
Me
Me
Pr
Pr
Pr
Bu

3-172
Pr
Me
Me
Me
Me
Pr
Pr
Pr
Bu

3-173
H
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-174
Me
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-175
Et
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-176
Pr
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-177

ⁱPr
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-178
Bu
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-179

ⁱBu
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-180

^sBu
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-181

^tBu
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-182
Pe
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-183

^cPe
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-184
Hx
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-185
Me
Me
H
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-186
Me
H
Me
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-187

^tBu
H

^tBu
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-188
Me
Me
Me
H
H

ⁱPr

ⁱPr

ⁱPr
Me

3-189
Me
Me
H
Me
H

ⁱPr

ⁱPr

ⁱPr
Me

3-190

ⁱPr
H

ⁱPr
H

ⁱPr

ⁱPr

ⁱPr

ⁱPr
Me

[Table 15]

TABLE 5-6

(3)

Compound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-191
Me
Me
Me
Me
H

ⁱPr

ⁱPr

ⁱPr
Me

3-192
Et
Me
Me
Me
Me

ⁱPr

ⁱPr

ⁱPr
Me

3-193
Pr
Me
Me
Me
Me

ⁱPr

ⁱPr

ⁱPr
Me

3-194
H
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-195
Me
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-196
Et
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-197
Pr
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-198

ⁱPr
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-199
Bu
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-200

ⁱBu
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-201

^sBu
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-202

^tBu
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-203
Pe
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-204

^cPe
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-205
Hx
H
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-206
Me
Me
H
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-207
Me
H
Me
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-208

^tBu
H

^tBu
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-209
Me
Me
Me
H
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-210
Me
Me
H
Me
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-211

ⁱPr
H

ⁱPr
H

ⁱPr

ⁱPr

ⁱPr

ⁱPr
Bu

3-212
Me
Me
Me
Me
H

ⁱPr

ⁱPr

ⁱPr
Bu

3-213
Me
Me
Me
Me
Me

ⁱPr

ⁱPr

ⁱPr
Bu

3-214
Et
Me
Me
Me
Me

ⁱPr

ⁱPr

ⁱPr
Bu

3-215
Pr
Me
Me
Me
Me

ⁱPr

ⁱPr

ⁱPr
Bu

3-216
H
H
H
H
H
Bu
Bu
Bu
Me

3-217
Me
H
H
H
H
Bu
Bu
Bu
Me

3-218
Et
H
H
H
H
Bu
Bu
Bu
Me

3-219
Pr
H
H
H
H
Bu
Bu
Bu
Me

3-220

ⁱPr
H
H
H
H
Bu
Bu
Bu
Me

3-221
Bu
H
H
H
H
Bu
Bu
Bu
Me

3-222

ⁱBu
H
H
H
H
Bu
Bu
Bu
Me

3-223

^sBu
H
H
H
H
Bu
Bu
Bu
Me

3-224

^tBu
H
H
H
H
Bu
Bu
Bu
Me

3-225
Pe
H
H
H
H
Bu
Bu
Bu
Me

3-226

^cPe
H
H
H
H
Bu
Bu
Bu
Me

3-227
Hx
H
H
H
H
Bu
Bu
Bu
Me

3-228
Me
Me
H
H
H
Bu
Bu
Bu
Me

[Table 16]

TABLE 5-7

(3)

Compound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-229
Me
H
Me
H
H
Bu
Bu
Bu
Me

3-230

^tBu
H

^tBu
H
H
Bu
Bu
Bu
Me

3-231
Me
Me
Me
H
H
Bu
Bu
Bu
Me

3-232
Me
Me
H
Me
H
Bu
Bu
Bu
Me

3-233

ⁱPr
H

ⁱPr
H

ⁱPr
Bu
Bu
Bu
Me

3-234
Me
Me
Me
Me
H
Bu
Bu
Bu
Me

3-235
Et
Me
Me
Me
Me
Bu
Bu
Bu
Me

3-236
Pr
Me
Me
Me
Me
Bu
Bu
Bu
Me

3-237
H
H
H
H
H
Bu
Bu
Bu
Bu

3-238
Me
H
H
H
H
Bu
Bu
Bu
Bu

3-239
Et
H
H
H
H
Bu
Bu
Bu
Bu

3-240
Pr
H
H
H
H
Bu
Bu
Bu
Bu

3-241

ⁱPr
H
H
H
H
Bu
Bu
Bu
Bu

3-242
Bu
H
H
H
H
Bu
Bu
Bu
Bu

3-243

ⁱBu
H
H
H
H
Bu
Bu
Bu
Bu

3-244

^sBu
H
H
H
H
Bu
Bu
Bu
Bu

3-245

^tBu
H
H
H
H
Bu
Bu
Bu
Bu

3-246
Pe
H
H
H
H
Bu
Bu
Bu
Bu

3-247

^cPe
H
H
H
H
Bu
Bu
Bu
Bu

3-248
Hx
H
H
H
H
Bu
Bu
Bu
Bu

3-249
Me
Me
H
H
H
Bu
Bu
Bu
Bu

3-250
Me
H
Me
H
H
Bu
Bu
Bu
Bu

3-251

^tBu
H

^tBu
H
H
Bu
Bu
Bu
Bu

3-252
Me
Me
Me
H
H
Bu
Bu
Bu
Bu

3-253
Me
Me
H
Me
H
Bu
Bu
Bu
Bu

3-254

ⁱPr
H

ⁱPr
H

ⁱPr
Bu
Bu
Bu
Bu

3-255
Me
Me
Me
Me
H
Bu
Bu
Bu
Bu

3-256
Me
Me
Me
Me
Me
Bu
Bu
Bu
Bu

3-257
Et
Me
Me
Me
Me
Bu
Bu
Bu
Bu

3-258
Pr
Me
Me
Me
Me
Bu
Bu
Bu
Bu

3-259
H
H
H
H
H

^tBu

^tBu

^tBu
Me

3-260
Me
H
H
H
H

^tBu

^tBu

^tBu
Me

3-261
Et
H
H
H
H

^tBu

^tBu

^tBu
Me

3-262
Pr
H
H
H
H

^tBu

^tBu

^tBu
Me

3-263

ⁱPr
H
H
H
H

^tBu

^tBu

^tBu
Me

3-264
Bu
H
H
H
H

^tBu

^tBu

^tBu
Me

3-265

ⁱBu
H
H
H
H

^tBu

^tBu

^tBu
Me

3-266

^sBu
H
H
H
H

^tBu

^tBu

^tBu
Me

[Table 17]

TABLE 5-8

(3)

Compound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-267

^tBu
H
H
H
H

^tBu

^tBu

^tBu
Me

3-268
Pe
H
H
H
H

^tBu

^tBu

^tBu
Me

3-269

^cPe
H
H
H
H

^tBu

^tBu

^tBu
Me

3-270
Hx
H
H
H
H

^tBu

^tBu

^tBu
Me

3-271
Me
Me
H
H
H

^tBu

^tBu

^tBu
Me

3-272
Me
H
Me
H
H

^tBu

^tBu

^tBu
Me

3-273

^tBu
H

^tBu
H
H

^tBu

^tBu

^tBu
Me

3-274
Me
Me
Me
H
H

^tBu

^tBu

^tBu
Me

3-275
Me
Me
H
Me
H

^tBu

^tBu

^tBu
Me

3-276

ⁱPr
H

ⁱPr
H

ⁱPr

^tBu

^tBu

^tBu
Me

3-277
Me
Me
Me
Me
H

^tBu

^tBu

^tBu
Me

3-278
Et
Me
Me
Me
Me

^tBu

^tBu

^tBu
Me

3-279
Pr
Me
Me
Me
Me

^tBu

^tBu

^tBu
Me

3-280
H
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-281
Me
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-282
Et
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-283
Pr
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-284

ⁱPr
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-285
Bu
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-286

ⁱBu
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-287

^sBu
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-288

^tBu
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-289
Pe
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-290

^cPe
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-291
Hx
H
H
H
H

^tBu

^tBu

^tBu
Bu

3-292
Me
Me
H
H
H

^tBu

^tBu

^tBu
Bu

3-293
Me
H
Me
H
H

^tBu

^tBu

^tBu
Bu

3-294

^tBu
H

^tBu
H
H

^tBu

^tBu

^tBu
Bu

3-295
Me
Me
Me
H
H

^tBu

^tBu

^tBu
Bu

3-296
Me
Me
H
Me
H

^tBu

^tBu

^tBu
Bu

3-297

ⁱPr
H

ⁱPr
H

ⁱPr

^tBu

^tBu

^tBu
Bu

3-298
Me
Me
Me
Me
H

^tBu

^tBu

^tBu
Bu

3-299
Me
Me
Me
Me
Me

^tBu

^tBu

^tBu
Bu

3-300
Et
Me
Me
Me
Me

^tBu

^tBu

^tBu
Bu

3-301
Pr
Me
Me
Me
Me

^tBu

^tBu

^tBu
Bu

3-302
H
H
H
H
H
Me

^tBu

ⁱPr
Me

3-303
Me
H
H
H
H
Me

^tBu

ⁱPr
Me

3-304
Et
H
H
H
H
Me

^tBu

ⁱPr
Me

[Table 18]

TABLE 5-9

(3)

Compound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-305
Pr
H
H
H
H
Me

^tBu

ⁱPr
Me

3-306

ⁱPr
H
H
H
H
Me

^tBu

ⁱPr
Me

3-307
Bu
H
H
H
H
Me

^tBu

ⁱPr
Me

3-308

ⁱBu
H
H
H
H
Me

^tBu

ⁱPr
Me

3-309

^sBu
H
H
H
H
Me

^tBu

ⁱPr
Me

3-310

^tBu
H
H
H
H
Me

^tBu

ⁱPr
Me

3-311
Pe
H
H
H
H
Me

^tBu

ⁱPr
Me

3-312

^cPe
H
H
H
H
Me

^tBu

ⁱPr
Me

3-313
Hx
H
H
H
H
Me

^tBu

ⁱPr
Me

3-314
Me
Me
H
H
H
Me

^tBu

ⁱPr
Me

3-315
Me
H
Me
H
H
Me

^tBu

ⁱPr
Me

3-316

^tBu
H

^tBu
H
H
Me

^tBu

ⁱPr
Me

3-317
Me
Me
Me
H
H
Me

^tBu

ⁱPr
Me

3-318
Me
Me
H
Me
H
Me

^tBu

ⁱPr
Me

3-319

ⁱPr
H

ⁱPr
H

ⁱPr
Me

^tBu

ⁱPr
Me

3-320
Me
Me
Me
Me
H
Me

^tBu

ⁱPr
Me

3-321
Me
Me
Me
Me
Me
Me

^tBu

ⁱPr
Me

3-322
Et
Me
Me
Me
Me
Me

^tBu

ⁱPr
Me

3-323
Pr
Me
Me
Me
Me
Me

^tBu

ⁱPr
Me

3-324
H
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-325
Me
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-326
Et
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-328
Pr
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-329

ⁱPr
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-330
Bu
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-331

ⁱBu
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-332

^sBu
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-333

^tBu
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-334
Pe
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-335

^cPe
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-336
Hx
H
H
H
H
Me

^tBu

ⁱPr
Bu

3-337
Me
Me
H
H
H
Me

^tBu

ⁱPr
Bu

3-338
Me
H
Me
H
H
Me

^tBu

ⁱPr
Bu

3-339

^tBu
H

^tBu
H
H
Me

^tBu

ⁱPr
Bu

3-340
Me
Me
Me
H
H
Me

^tBu

ⁱPr
Bu

3-341
Me
Me
H
Me
H
Me

^tBu

ⁱPr
Bu

3-342

ⁱPr
H

ⁱPr
H

ⁱPr
Me

^tBu

ⁱPr
Bu

3-343
Me
Me
Me
Me
H
Me

^tBu

ⁱPr
Bu

[Table 19]

TABLE 5-10

(3)

Compound

No.
R¹⁰
R¹¹
R¹²
R¹³
R¹⁴
R¹⁵
R¹⁶
R¹⁷
R¹⁸

3-344
Me
Me
Me
Me
Me
Me

^tBu

ⁱPr
Bu

3-345
Et
Me
Me
Me
Me
Me

^tBu

ⁱPr
Bu

3-346
Pr
Me
Me
Me
Me
Me

^tBu

ⁱPr
Bu

Among those exemplified in Tables 5-1 to 5-10, in view of having vapor pressure and thermal stability suitable as a CVD material or an ALD material, (η⁵-cyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-1), (η⁵-methylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-2), (η⁵-ethylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-3), (η⁵-propylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-4), (η⁵-isopropylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-5), (η⁵-butylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-6), (η⁵-isobutylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-7), (η⁵-sec-butylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-8), (η⁵-tert-butylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-9), (η⁵-pentylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-10), (η⁵-cyclopentylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-11), (η⁵-hexylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-12), (η⁵-cyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-44), (η⁵-methylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-45), (η⁵-ethylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-46), (η⁵-propylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-47), (η⁵-isopropylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-48), (η⁵-butylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-49), (η⁵-isobutylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-50), (η⁵-sec-butylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-51), (η⁵-tert-butylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-52), (η⁵-pentylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-53), (η⁵-cyclopentylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-54) and (η⁵-hexylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-55) are preferred; and (η⁵-ethylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (3-3) and (η⁵-ethylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (3-46) are more preferred.

The production method of the ruthenium complex (3) of the present invention is described below.

The ruthenium complex (3) of the present invention can be produced by the following production method 6 or production method 8.

Production method 6 is a method of reacting a cationic arene complex (10) with an alkyllithium (11) to produce a ruthenium complex (3) of the present invention.

Production Method 6:

embedded image

(wherein R¹⁰to R¹⁸have the same meanings as R¹⁰to R¹⁸in formula (3), and P⁻represents a counter anion.)

Specific examples of the cation moiety of the cationic arene complex (10) include

[(η⁶-benzene)(η⁵-cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅H₅)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-methylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-ethylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-propylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-isopropylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-butylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-isobutylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-sec-butylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-tert-butylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-pentylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-cyclopentylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-hexylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(η⁶-C₆H₆)]),
[(η⁶-benzene)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅Me₅)(η⁶-C₆H₆)]),
[(η⁵-cyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅H₅)(η⁶-C₆Me₃H₃)]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-propylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-isopropylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-butylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-isobutylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-sec-butylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-tert-butylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-pentylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-cyclopentylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-hexylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(η⁶-C₆Me₃H₃)]),
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅Me₅)(η⁶-C₆Me₃H₃)]),
[(η⁵-cyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅H₅)(η⁶-C₆Et₃H₃)]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-propylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-isopropylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-butylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-isobutylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-sec-butylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-tert-butylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-pentylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-cyclopentylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-hexylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(η⁶-C₆Et₃H₃)]),
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-triethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅Me₅)(η⁶-C₆Et₃H₃)]),
[(η⁵-cyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅H₅)(η⁶-C₆Pr₃H₃)]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-propylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-isopropylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-butylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-isobutylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-sec-butylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-tert-butylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-pentylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-cyclopentylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-hexylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(η⁶-C₆Pr₃H₃)]),
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-tripropylbenzene)ruthenium(II)] ([Ru(η⁵-C₅Me₅)(η⁶-C₆Pr₃H₃)]),
[(η⁵-cyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅H₅)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-propylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-isopropylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-butylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-isobutylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-sec-butylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-tert-butylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-pentylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-cyclopentylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-hexylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-tri(isopropyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅Me₅)(η⁶-C₆(ⁱPr)₃H₃)]),
[(η⁵-cyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅H₅)(η⁶-C₆Bu₃H₃)]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-propylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-isopropylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-butylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-isobutylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-sec-butylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-tert-butylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-pentylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-cyclopentylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-hexylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(η⁶-C₆Bu₃H₃)]),
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-tributylbenzene)ruthenium(II)] ([Ru(η⁵-C₅Me₅)(η⁶-C₆Bu₃H₃)]),
[(η⁶-1,3,5-tri(tert-butyl)benzene)(η⁵-cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅H₅)(η⁵-C₆(^tBu)₃H₃)]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-propylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-isopropylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-butylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-isobutylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-sec-butylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-tert-butylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-pentylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅PeH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-cyclopentylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅^cPeH₄)(η⁶-C₆(^tBu)₃H₃)]),
[(η⁵-hexylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅HxH₄)(η⁶-C₆(^tBu)₃H₃)]), and
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-tri(tert-butyl)benzene)ruthenium(II)] ([Ru(η⁵-C₅Me₅)(η⁶-C₆(^tBu)₃H₃)]).

For the reason that the ruthenium complex (3) has vapor pressure suitable as a CVD material or an ALD material, [(η⁶-benzene)(η⁵-cyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅H₅)(η⁶-C₆H₆)]), [(η⁶-benzene)(η⁵-methylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆H₆)]), [(η⁶-benzene)(η⁵-ethylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)]), [(η⁶-benzene)(η⁵-propylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(η⁶-C₆H₆)]), [(η⁶-benzene)(η⁵-isopropylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(η⁶-C₆H₆)]), [(η⁶-benzene)(η⁵-butylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆H₆)]), [(η⁶-benzene)(η⁵-isobutylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(η⁶-C₆H₆)]), [(η⁶-benzene)(η⁵-sec-butylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(η⁶-C₆H₆)]), [(η⁶-benzene)(η⁵-tert-butylcyclopentadienyl)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(η⁶-C₆H₆)]), [(η⁵-cyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅H₅)(η⁶-C₆Me₃H₃)]), [(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Me₃H₃)]), [(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)]), [(η⁵-propylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅PrH₄)(η⁶-C₆Me₃H₃)]), [(η⁵-isopropylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱPrH₄)(η⁶-C₆Me₃H₃)]), [(η⁵-butylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅BuH₄)(η⁶-C₆Me₃H₃)]), [(η⁵-isobutylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅ⁱBuH₄)(η⁶-C₆Me₃H₃)]), [(η⁵-sec-butylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^sBuH₄)(η⁶-C₆Me₃H₃)]), [(η⁵-tert-butylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)] ([Ru(η⁵-C₅^tBuH₄)(η⁶-C₆Me₃H₃)]), etc. are preferred.

Examples of the counter anion P⁻in formula (10) include those generally used as a counter anion of a cationic metal complex. Specific examples thereof include a fluoro complex anion such as tetrafluoroborate ion (BF₄⁻), hexafluorophosphate ion (PF₆⁻), hexafluoroantimonate ion (SbF₆⁻) and tetrafluoroaluminate ion (AlF₄⁻), a monovalent sulfonate ion such as trifluoromethanesulfonate ion (CF₃SO₃⁻), methanesulfonate ion (MeSO₃⁻) and methylsulfate ion (MeSO₄⁻), a counter anion of a monobasic acid, such as nitrate ion (NO₃⁻), perchlorate ion (ClO₄⁻), tetrachloroaluminate ion (AlCl₄⁻) and bis(trifluoromethanesulfonyl)amide ion ((CF₃SO₂)₂N⁻), a counter anion of a polybasic acid, such as sulfate ion (SO₄²⁻), hydrogen sulfate ion (HSO₄⁻), phosphate ion (PO₄³⁻), monohydrogen phosphate ion (HPO₄²⁻), dihydrogen phosphate ion (H₂PO₄⁻), dimethylphosphate ion ((MeO)₂PO₄⁻) and diethylphosphate ion ((EtO)₂PO₄⁻), and a derivative thereof. In view of a high yield of the ruthenium complex (3), the counter anion P⁻is preferably a fluoro complex anion such as BF₄⁻and PF₆⁻, or a monovalent sulfonate ion such as CF₃SO₃⁻and MeSO₃⁻.

Specific preferred examples of the cationic arene complex (10) include [(η⁶-benzene)(η⁵-cyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][BF₄]), [(η⁶-benzene)(η⁵-methylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆H₆)][BF₄]), [(η⁶-benzene)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][BF₄]), [(η⁶-benzene)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅Me₅)(η⁶-C₆H₆)][BF₄]), [(η⁶-benzene)(η⁵-cyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][PF₆]), [(η⁶-benzene)(η⁵-methylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆H₆)][PF₆]), [(η⁶-benzene)(η⁵-ethylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][PF₆]), [(η⁶-benzene)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅Me₅)(η⁶-C₆H₆)][PF₆]), [(η⁶-benzene)(η⁵-cyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][CF₃SO₃]), [(η⁶-benzene)(η⁵-methylcyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆H₆)][CF₃SO₃]), [(η⁶-benzene)(η⁵-ethylcyclopentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][CF₃SO₃]), [(η⁶-benzene)(η⁵-1,2,3,4,5-pentamethylcyclo-pentadienyl)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅Me₅)(η⁶-C₆H₆)][CF₃SO₃]), [(η⁶-benzene)(η⁵-cyclopentadienyl)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][MeSO₃]), [(η⁶-benzene)(η⁵-methylcyclopentadienyl)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆H₆)][MeSO₃]), [(η⁶-benzene)(η⁵-ethylcyclopentadienyl)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][MeSO₃]), [(η⁶-benzene)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅Me₅)(η⁶-C₆H₆)][MeSO₃]), [(η⁵-cyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅H₅)(η⁶-C₆Me₃H₃)][BF₄]),

[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Me₃H₃)][BF₄]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)][BF₄]),
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅Me₅)(η⁶-C₆Me₃H₃)][BF₄]),
[(η⁵-cyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅H₅)(η⁵-C₆Me₃H₃)][PF₆]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Me₃H₃)][PF₆]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)][PF₆]),
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][hexafluorophosphate] ([Ru(η⁵-C₅Me₅)(η⁶-C₆Me₃H₃)][PF₆]),
[(η⁵-cyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅H₅)(η⁶-C₆Me₃H₃)][CF₃SO₃]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Me₃H₃)][CF₃SO₃]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)][CF₃SO₃]),
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][trifluoromethanesulfonate] ([Ru(η⁵-C₅Me₅)(η⁶-C₆Me₃H₃)][CF₃SO₃]),
[(η⁵-cyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅H₅)(η⁶-C₆Me₃H₃)][MeSO₃]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Me₃H₃)][MeSO₃]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][methanesulfonate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)][MeSO₃]), and
[(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][methanesulfonate]([Ru(η⁵-C₅Me₅)(η⁶-C₆Me₃H₃)][MeSO₃]).

For the reason that the yield of the ruthenium complex (3) is high,

[(η⁶-benzene)(η⁵-cyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][BF₄]),
[(η⁶-benzene)(η⁵-methylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆H₆)][BF₄]),
[(η⁶-benzene)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][BF₄]),
[(η⁵-cyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅H₅)(η⁶-C₆Me₃H₃)][BF₄]),
[(η⁵-methylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆Me₃H₃)][BF₄]),
[(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)][BF₄]), etc. are preferred.

Specific examples of the alkyllithium (11) include methyllithium, ethyllithium, propyllithium, isopropyllithium, butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, tert-pentyllithium, cyclopentyllithium, hexyllithium, and cyclohexyllithium. From the standpoint that the ruthenium complex (3) has vapor pressure suitable as a CVD material or an ALD material, methyllithium, ethyllithium, propyllithium, isopropyllithium, butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, etc. are preferred.

For the reason that the yield of the ruthenium complex (3) is high, production method 6 is preferably performed in an inert gas. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas, with argon or nitrogen gas being preferred.

For the reason that the yield of the ruthenium complex (3) is high, production method 6 is preferably performed in an organic solvent. In the case of performing production method 6 in an organic solvent, specific examples of the organic solvent include an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane and petroleum ether, and an ether such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane. Of these organic solvents, one kind may be used alone, or a plurality of kinds may be mixed in an arbitrary ratio and used. In view of a high yield of the ruthenium complex (3), as the organic solvent, an ether is preferred, and diethyl ether and tetrahydrofuran are more preferred.

The method for obtaining the alkyllithium (11) includes the production methods described, for example, in Journal of the American Chemical Society, Vol. 108, page 7016 (1986), other than the purchase of a commercial product.

The molar ratio between the cationic arene complex (10) and the alkyllithium (11) when performing production method 6 is described below. Preferably, 1 mol or more of the alkyllithium (11) is used per mol of the cationic arene complex (10), whereby the ruthenium complex (3) can be efficiently produced.

In production method 6, the reaction temperature and the reaction time are not particularly limited, and general conditions employed by one skilled in the art when producing a metal complex may be used. As a specific example, a reaction temperature appropriately selected from a temperature range of −80° C. to 120° C. and a reaction time appropriately selected from the range of 10 minutes to 120 hours are employed, whereby the ruthenium complex (3) can be efficiently produced.

The ruthenium complex (3) produced by production method 6 may be purified by appropriately selecting and using a general purification method employed by one skilled in the art when purifying a metal complex. The purification method specifically includes filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography, etc.

The cationic arene complex (10) as a raw material of production method 6 can be produced according to the method described in Non-Patent Document 3, Angewandte Chemie International Edition, Vol. 46, page 4976, Supporting Information (2007), or Journal of the American Chemical Society, Vol. 111, page 1698 (1989), or the following production method 7. From the standpoint that the amount of the reaction agent used is small and the yield of the cationic arene complex (10) is high, the complex is preferably produced according to production method 7. Production method 7 is a method of reacting a ruthenocene derivative (12) and a benzene derivative (14) with a protonic acid H⁺P⁻to produce a cationic arene complex (10).

Production Method 7:

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(wherein R¹⁰to R¹⁷have the same meanings as R¹⁰to R¹⁷in formula (3), and P⁻represents a counter anion.)

In formula (12), Q represents an η⁵-2,4-dimethyl-2,4-pentadienyl ligand or an η⁵-(unsubstituted or substituted)cyclopentadienyl ligand represented by formula (13):

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(wherein R¹⁰to R¹⁴have the same meanings as R¹⁰to R¹⁴in formula (3).)

Specific examples of the η⁵-(unsubstituted or substituted)cyclopentadienyl ligand (13) include an η⁵-cyclopentadienyl ligand, an η⁵-methylcyclopentadienyl ligand, an η⁵-ethylcyclopentadienyl ligand, an η⁵-propylcyclopentadienyl ligand, an η⁵-isopropylcyclopentadienyl ligand, an η⁵-butylcyclopentadienyl ligand, an η⁵-isobutylcyclopentadienyl ligand, an η⁵-sec-butylcyclopentadienyl ligand, an η⁵-tert-butylcyclopentadienyl ligand, an η⁵-pentylcyclopentadienyl ligand, an η⁵-cyclopentylcyclopentadienyl ligand, an η⁵-hexylcyclopentadienyl ligand, an η⁵-1,2-dimethylcyclopentadienyl ligand, an η⁵-1,3-dimethylcyclopentadienyl ligand, an η⁵-1,3-di(isopropyl)cyclopentadienyl ligand, an η⁵-1,2,4-tri(isopropyl)cyclopentadienyl ligand, an η⁵-1,3-di(tert-butyl)cyclopentadienyl ligand, and an η⁵-1,2,3,4,5-pentamethylcyclopentadienyl ligand.

In view of availability of the ruthenocene derivative (12), Q is preferably an η⁵-2,4-dimethyl-2,4-pentadienyl ligand, an η⁵-cyclopentadienyl ligand, an η⁵-methylcyclopentadienyl ligand, an η⁵-ethylcyclopentadienyl ligand, an η⁵-propylcyclopentadienyl ligand, an η⁵-isopropylcyclopentadienyl ligand, an η⁵-butylcyclopentadienyl ligand, an η⁵-isobutylcyclopentadienyl ligand, an η⁵-sec-butylcyclopentadienyl ligand or an η⁵-tert-butylcyclopentadienyl ligand, more preferably an η⁵-cyclopentadienyl ligand, an η⁵-methylcyclopentadienyl ligand or an η⁵-ethylcyclopentadienyl ligand.

Specific examples of the ruthenocene derivative (12) include bis(η⁵-cyclopentadienyl)ruthenium ((η⁵-C₅H₅)₂Ru), bis(η⁵-methylcyclopentadienyl)ruthenium ((η⁵-C₅MeH₄)₂Ru), bis(η⁵-ethylcyclopentadienyl)ruthenium ((η⁵-C₅EtH₄)₂Ru), bis(η⁵-propylcyclopentadienyl)ruthenium ((η⁵-C₅PrH₄)₂Ru), bis(η⁵-isopropylcyclopentadienyl)ruthenium ((η⁵-C₅ⁱPrH₄)₂Ru), bis(η⁵-butylcyclopentadienyl)ruthenium ((η⁵-C₅BuH₄)₂Ru), bis(η⁵-isobutylcyclopentadienyl)ruthenium ((η⁵-C₅ⁱBuH₄)₂Ru), bis(η⁵-sec-butylcyclopentadienyl)ruthenium ((η⁵-C₅^sBuH₄)₂Ru), bis(η⁵-tert-butylcyclopentadienyl)ruthenium ((η⁵-C₅^tBuH₄)₂Ru), bis(η⁵-pentylcyclopentadienyl)ruthenium ((η⁵-C₅PeH₄)₂Ru), bis(η⁵-cyclopentylcyclopentadienyl)ruthenium ((η⁵-C₅^cPeH₄)₂Ru), bis(η⁵-hexylcyclopentadienyl)ruthenium ((η⁵-C₅HxH₄)₂Ru), bis(η⁵-1,2-dimethylcyclopentadienyl)ruthenium ((η⁵-C₅Me₂H₃)₂Ru), bis(η⁵-1,3-dimethylcyclopentadienyl)ruthenium ((η⁵-C₅Me₂H₃)₂Ru), bis(η⁵-1,3-di(isopropyl)cyclopentadienyl)ruthenium ((η⁵-C₅(ⁱPr)₂H₃)₂Ru), bis(η⁵-1,2,4-tri(isopropyl)cyclopentadienyl)ruthenium ((η⁵-C₅(ⁱPr)₃H₂)₂Ru), bis(η⁵-1,3-di(tert-butyl)cyclopentadienyl)ruthenium ((η⁵-C₅(^tBu)₂H₃)₂Ru), bis(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium ((η⁵-C₅Me₅)₂Ru),

(η⁵-cyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅H₅)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-methylcyclopentadienyl)ruthenium (Ru(η⁵-C₅MeH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-propylcyclopentadienyl)ruthenium (Ru(η⁵-C₅PrH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-isopropylcyclopentadienyl)ruthenium (Ru(η⁵-C₅ⁱPrH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-butylcyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅BuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-isobutylcyclopentadienyl)ruthenium (Ru(η⁵-C₅ⁱBuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-sec-butylcyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅^sBuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-tert-butylcyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅^tBuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-pentylcyclopentadienyl)ruthenium (Ru(η⁵-C₅PeH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-cyclopentylcyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅^cPeH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-hexylcyclopentadienyl)ruthenium (Ru(η⁵-C₅HxH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-1,2-dimethylcyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅Me₂H₃)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-1,3-dimethylcyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅Me₂H₃)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-1,3-di(isopropyl)cyclopentadienyl)ruthenium (Ru(η⁵-C₅(ⁱPr)₂H₃)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-1,2,4-tri(isopropyl)cyclopentadienyl)ruthenium (Ru(η⁵-C₅(ⁱPr)₃H₂)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-1,3-di(tert-butyl)cyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅(^tBu)₂H₃)(η⁵-CH₂C(Me)CHC(Me)CH₂)), and
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅Me₅)(η⁵-CH₂C(Me)CHC(Me)CH₂)).

Of these, bis(η⁵-cyclopentadienyl)ruthenium ((η⁵-C₅H₅)₂Ru),

bis(η⁵-methylcyclopentadienyl)ruthenium ((η⁵-C₅MeH₄)₂Ru),
bis(η⁵-ethylcyclopentadienyl)ruthenium ((η⁵-C₅EtH₄)₂Ru),
bis(η⁵-propylcyclopentadienyl)ruthenium ((η⁵-C₅PrH₄)₂Ru),
bis(η⁵-isopropylcyclopentadienyl)ruthenium ((η⁵-C₅ⁱPrH₄)₂Ru),
bis(η⁵-butylcyclopentadienyl)ruthenium ((η⁵-C₅BuH₄)₂Ru),
bis(η⁵-isobutylcyclopentadienyl)ruthenium ((η⁵-C₅ⁱBuH₄)₂Ru),
bis(η⁵-sec-butylcyclopentadienyl)ruthenium ((η⁵-C₅^sBuH₄)₂Ru),
bis(η⁵-tert-butylcyclopentadienyl)ruthenium ((η⁵-C₅^tBuH₄)₂Ru),
(η⁵-cyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅H₅)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-methylcyclopentadienyl)ruthenium (Ru(η⁵-C₅MeH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-propylcyclopentadienyl)ruthenium (Ru(η⁵-C₅PrH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-isopropylcyclopentadienyl)ruthenium (Ru(η⁵-C₅ⁱPrH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-butylcyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅BuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-isobutylcyclopentadienyl)ruthenium (Ru(η⁵-C₅ⁱBuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-sec-butylcyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅^sBuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)),
(η⁵-tert-butylcyclopentadienyl)(η⁵-2,4-dimethyl-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅^tBuH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)), etc. are preferred;

bis(η⁵-cyclopentadienyl)ruthenium (η⁵-C₅H₅)₂Ru), bis(η⁵-methylcyclopentadienyl)ruthenium (η⁵-C₅MeH₄)₂Ru), bis(η⁵-ethylcyclopentadienyl)ruthenium (η⁵-C₅EtH₄)₂Ru), bis(η⁵-propylcyclopentadienyl)ruthenium (η⁵-C₅PrH₄)₂Ru), bis(η⁵-isopropylcyclopentadienyl)ruthenium (η⁵-C₅ⁱPrH₄)₂Ru), bis(η⁵-butylcyclopentadienyl)ruthenium (η⁵-C₅BuH₄)₂Ru), bis(η⁵-isobutylcyclopentadienyl)ruthenium (η⁵-C₅ⁱBuH₄)₂Ru), bis(η⁵-sec-butylcyclopentadienyl)ruthenium (η⁵-C₅^sBuH₄)₂Ru), bis(η⁵-tert-butylcyclopentadienyl)ruthenium (η⁵-C₅^tBuH₄)₂Ru), etc. are more preferred; and bis(η⁵-cyclopentadienyl)ruthenium (η⁵-C₅H₅)₂Ru), bis(η⁵-methylcyclopentadienyl)ruthenium (η⁵-C₅MeH₄)₂Ru) and bis(η⁵-ethylcyclopentadienyl)ruthenium (η⁵-C₅EtH₄)₂Ru) are still more preferred.

Specific examples of the benzene derivative (14) include benzene, 1,3,5-trimethylbenzene, 1,3,5-triethylbenzene, 1,3,5-tripropylbenzene, 1,3,5-tri(isopropyl)benzene, 1,3,5-butylbenzene, 1,3,5-tri(isobutyl)benzene, 1,3,5-tri(sec-butyl)benzene, and 1,3,5-tri(tert-butyl)benzene. In view of a high yield of the cationic arene complex (10), benzene or 1,3,5-trimethylbenzene is preferred.

The counter anion P⁻of the protonic acid that can be used in production method 7 includes, for example, a fluoro complex anion such as tetrafluoroborate ion (BF₄⁻) and hexafluorophosphate ion (PF₆⁻), a sulfonate ion such as trifluoromethanesulfonate ion (CF₃SO₃⁻), sulfate ion (SO₄²⁻) and hydrogen sulfate ion (HSO₄⁻), and a halide ion such as chloride ion and bromide ion.

Specific examples of the protonic acid include a fluoro complex acid such as tetrafluoroboric acid and hexafluorophosphoric acid; a sulfonic acid such as sulfuric acid and trifluoromethanesulfonic acid; and a hydrogen halide such as hydrogen chloride. The protonic acid may form a complex with an ether such as dimethyl ether and diethyl ether. Examples of the protonic acid in the form of a complex include a tetrafluoroboric acid-dimethyl ether complex, a tetrafluoroboric acid-diethyl ether complex, and a hexafluorophosphoric acid-diethyl ether complex. In view of a high yield of the cationic arene complex (10), a tetrafluoroboric acid-diethyl ether complex, tetrafluoroboric acid, or trifluoromethanesulfonic acid is preferred.

As the protonic acid for use in production method 7, a fluoro complex acid produced in a reaction system by reacting a fluoro complex anion-containing salt with a strong acid may also be used. In this case, examples of the fluoro complex anion-containing salt that can be used include ammonium tetrafluoroborate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, lithium hexafluorophosphate, sodium hexafluorophosphate, and potassium hexafluorophosphate. Examples of the strong acid that can be used include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, hydrogen chloride, and hydrogen bromide. Specific examples of the fluoro complex acid that can be produced in a reaction system include tetrafluoroboric acid and hexaluorophosphoric acid. In view of a high cost benefit and a high yield, any one of ammonium tetrafluoroborate, sodium tetrafluoroborate and ammonium hexafluorophosphate is preferably mixed with sulfuric acid and used.

Furthermore, as the protonic acid for use in production method 7, a fluoro complex acid produced in a reaction system by reacting boron trifluoride with a strong acid may also be used. In this case, examples of the strong acid that can be used include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, hydrogen chloride, and hydrogen bromide.

The methods for obtaining the ruthenocene derivative (12) and the benzene derivative (14) are described below. The method for obtaining the ruthenocene derivative (12) includes the methods described, for example, in Organic Syntheses, Vol. 41, page 96 (1961), Organometallics, Vol. 8, page 298 (1989), and JP-A-2003-342286, other than the purchase of a commercial product. The method for obtaining the benzene derivative (14) includes the methods described, for example, in Tetrahedron, Vol. 68, page 6535 (2012), other than the purchase of a commercial product.

The molar ratio among the ruthenocene derivative (12), the benzene derivative (14) and the protonic acid used in production method 7 is described below. In view of a high yield of the cationic arene complex (10), 1 mol or more of the benzene derivative is preferably used per mol of the ruthenocene derivative. The preferable amount of the protonic acid used varies depending on the kind of the protonic acid. For example, in the case where the protonic acid is a monobasic acid, in view of a high yield, 1 mol or more of the protonic acid is preferably used per mol of the ruthenocene derivative, and in the case of a dibasic acid, 0.5 mol or more of the protonic acid is preferably used per mol of the ruthenocene derivative. In the case where a mixture of a fluoro complex anion-containing salt and a strong acid is used as the protonic acid, 1 mol or more of the fluoro complex anion-containing salt and from 0.5 to 2.0 mol of the strong acid are appropriately used per mol of the ruthenocene derivative, whereby the cationic arene complex (10) can be efficiently obtained.

For the reason that the yield of the cationic arene complex (10) is high, production method 7 is preferably performed in an inert gas. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas, with argon or nitrogen gas being preferred.

For the reason that the yield of the cationic arene complex (10) is high, production method 7 is preferably performed in an organic solvent. In the case of performing production method 7 in an organic solvent, specific examples of the organic solvent include an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane and petroleum ether, an ether such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane, a ketone such as acetone, methyl ethyl ketone, 3-pentanone, cyclopentanone and cyclohexanone, an alcohol such as methanol, ethanol, propanol, isopropanol, tert-butanol and ethylene glycol, and a nitrile such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyclopropanecarbonitrile, pentylonitrile isopentylonitrile, 3-methylbutanenitrile, 2-methylbutanenitrile, pivalonitrile and cyclobutanecarbonitrile. Of these organic solvents, one kind may be used alone, or a plurality of kinds may be mixed in an arbitrary ratio and used. In view of a high yield of the cationic arene complex (10), as the organic solvent, diethyl ether, tetrahydrofuran, acetone, methanol and acetonitrile are preferred.

In production method 7, the reaction temperature and the reaction time are not particularly limited, and general conditions employed by one skilled in the art when producing a metal complex may be used. As a specific example, a reaction temperature appropriately selected from a temperature range of −80° C. to 150° C. and a reaction time appropriately selected from the range of 10 minutes to 120 hours are employed, whereby the cationic arene complex (10) can be efficiently produced.

The cationic arene complex (10) produced by production method 7 may be purified by appropriately selecting and using a general purification method employed by one skilled in the art when purifying a metal complex. The purification method specifically includes filtration, extraction, centrifugation, decantation, crystallization, etc.

The ruthenium complex (3) can also be produced by production method 8 of continuously performing production method 7 and production method 6. In this case, the cationic arene complex (10) produced by production method 7 may be used as a raw material for production in production method 6 without purifying it, or the cationic arene complex (10) that is purified by appropriately selecting and using a general purification method employed by one skilled in the art when purifying a metal complex may be used as a raw material for production in production method 6. Examples of the purification method include filtration, extraction, centrifugation, decantation, and crystallization.

The production method of a ruthenium-containing thin film characterized by using a ruthenium complex (1), (2) or (3a) is described in detail below.

The method for producing a ruthenium-containing thin film of the present invention is a method of vaporizing a ruthenium complex represented by formula (1), (2) or (3a) and decomposing the ruthenium complex on a substrate and includes normal technical means employed by one skilled in the art when producing a metal-containing thin film. Specific examples thereof include a vapor deposition method based on a chemical reaction, such as CVD method and ALD method, and a solution method such as dip coating method, spin coating method and inkjet method. In the description of the present invention, the vapor deposition method based on a chemical reaction encompasses technical means usually employed by one skilled in the art, for example, a CVD method such as thermal CVD method, plasma CVD method and optical CVD method, and an ALD method. In the case of producing a ruthenium-containing thin film by a vapor deposition method based on a chemical reaction, for the reason that a thin film is likely to be uniformly formed even on a substrate surface having a three-dimensioned structure, a chemical vapor deposition method is preferred, and a CVD method or an ALD method is more preferred. The CVD method is more preferred in that the deposition rate is high, and the ALD method is more preferred in that the step coverage is good. For example, in the case of producing a ruthenium-containing thin film by a CVD method or an ALD method, the ruthenium complex (1), (2) or (3a) is vaporized and supplied to a reaction chamber, and the ruthenium complex (1) is decomposed on a substrate provided in the reaction chamber, whereby a ruthenium-containing thin film can be produced on the substrate. The method for decomposing the ruthenium complex (1), (2) or (3a) include normal technical means employed by one skilled in the art when producing a metal-containing thin film. Specifically, examples thereof include a method of reacting the ruthenium complex (1), (2) or (3a) with a reaction gas, and a method of causing heat, plasma, light, etc. to act on the ruthenium complex (1), (2) or (3a). By appropriately selecting and using such a decomposition method, a ruthenium-containing thin film can be produced. It is also possible to use a plurality of decomposition methods in combination. The method for supplying the ruthenium complex (1), (2) or (3a) to a reaction chamber includes, for example, bubbling and a liquid vaporization supply system but is not particularly limited.

The carrier gas and diluent gas when producing a ruthenium-containing thin film by a CVD method or an ALD method are preferably a rare gas such as helium, neon, argon, krypton and xenon, or a nitrogen gas, and among others, a nitrogen gas, helium, neon or argon is preferred for the economical reason. The flow rate of the carrier gas and diluent gas is appropriately adjusted according to the capacity of the reaction chamber, and the like. For example, in the case where the capacity of the reaction chamber is from 1 to 10 L, the flow rate of the carrier gas is not particularly limited and is preferably from 1 to 10,000 sccm for the economical reason. Here, sccm is a unit representing the flow rate of a gas, and in terms of an ideal gas, 1 sccm indicates that the gas is moving at a speed of 2.68 mmol/h.

The reaction gas when producing a ruthenium-containing thin film by a CVD method or an ALD method includes, for example, a reducing gas such as ammonia, hydrogen, monosilane and hydrazine, and an oxidizing gas such as oxygen, ozone, water vapor, hydrogen peroxide, laughter gas, hydrogen chloride, nitric acid gas, formic acid and acetic acid. From the standpoint that the restriction on the specification of a deposition apparatus is little and handling is easy, ammonia, hydrogen, oxygen, ozone and water vapor are preferred. In the case of producing a ruthenium-containing thin film under the conditions using, as the reaction gas, a reducing gas but not an oxidizing gas, ammonia is preferred in that the deposition rate of the ruthenium-containing thin film is high. The flow rate of the reaction gas is appropriately adjusted according to the reactivity of the material and the volume of the reaction chamber. For example, when the volume of the reaction chamber is from 1 to 10 L, the flow rate of the reaction gas is not particularly limited and is preferably from 1 to 10,000 sccm for the economical reason.

The substrate temperature when producing a ruthenium-containing thin film by a CVD method or an ALD method is appropriately selected according to use or non-use of heat, plasma, light, etc., the kind of the reaction gas, or the like. For example, in the case of using ammonia as the reaction gas without using light or plasma in combination, the substrate temperature is not particularly limited and is preferably from 200 to 1,000° C. for the economical reason. In view of a high deposition rate, the substrate temperature is preferably from 300 to 750° C., more preferably from 350 to 700° C. In addition, by appropriately using light, plasma, ozone, hydrogen peroxide, etc., the ruthenium-containing thin film can be produced in a temperature region of 200° C. or less.

As the ruthenium-containing thin film obtained by the production method of the present invention, for example, in the case of the ruthenium complex alone, a metallic ruthenium thin film, a ruthenium oxide thin film, a ruthenium nitride thin film, a ruthenium oxynitride thin film, etc. are obtained, and in the case of using the ruthenium complex in combination with other metallic materials, a ruthenium-containing composite thin film is obtained. For example, when the ruthenium complex is used in combination with a strontium material, an SrRuO₃thin film is obtained. The strontium material includes, for example, strontium bis(dipivaloylmethanate), diethoxystrontium, strontium bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate). In addition, when producing a ruthenium-containing composite thin oxide by a CVD method or an ALD method, the ruthenium complex (1), (2) or (3a) and other metallic materials may be supplied separately to the reaction chamber or may be mixed and then supplied.

The ruthenium complex (1a) may be formed into a ruthenium-containing thin film, similarly to the ruthenium complex (1).

By using the ruthenium-containing thin film of the present invention as a constituent member, a high-performance semiconductor device enhanced in the memory capacity or responsiveness can be produced. Examples of the semiconductor device includes a semiconductor memory device such as DRAM, FeRAM and ReRAM, and a field-effect transistor. Examples of the constituent member thereof include a capacitor electrode, a gate electrode, and copper wiring liner.

EXAMPLES

The present invention is described in greater detail below by referring to Examples, but the present invention is not limited thereto. Here, Me, Et, Bu and ^tBu stand for a methyl group, an ethyl group, a butyl group, and a tert-butyl group, respectively. The ¹H and ¹³C NMR spectra were measured using VXR-500S NMR Spectrometer manufactured by Varian.

Example 1

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In an argon atmosphere, 2.35 g (14.5 mmol) of a tetrafluoroboric acid-diethyl ether complex was added at 0° C. to a suspension prepared by mixing 3.15 g (13.6 mmol) of bis(η⁵-cyclopentadienyl)ruthenium ((η⁵-C₅H₅)₂Ru) and 30 mL of acetonitrile. The resulting mixture was stirred at room temperature for 20 hours, and the solvent was then removed by distillation under reduced pressure. The remaining solid was washed with a mixture of dichloromethane and diethyl ether (dichloromethane:diethyl ether=1:13 (vol %)) to obtain [tris(acetonitrile)(η⁵-cyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅H₅)(MeCN)₃][BF₄]) as a yellow solid (4.30 g, yield: 84%).

¹H-NMR (500 MHz, CDCl₃, δ):

4.21 (s, 5H), 2.43 (s, 9H).

¹³C-NMR (125 MHz, CDCl₃, δ):

125.5, 68.8, 4.05.

Example 2

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In an argon atmosphere, 4.28 g (26.4 mmol) of a tetrafluoroboric acid-diethyl ether complex was added at 0° C. to a solution prepared by mixing 6.52 g (25.1 mmol) of bis(η⁵-methylcyclopentadienyl)ruthenium ((η⁵-C₅MeH₄)₂Ru) and 50 mL of acetonitrile. The resulting mixture was stirred at room temperature for 20 hours, and the solvent was then removed by distillation under reduced pressure. The remaining solid was washed with a mixture of dichloromethane and diethyl ether (dichloromethane:diethyl ether=1:10 (vol %)) to obtain [tris(acetonitrile)(η⁵-methylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅MeH₄)(MeCN)₃][BF₄]) as a yellow-brown solid (8.61 g, yield: 88%).

¹H-NMR (500 MHz, CDCl₃, δ):

4.13-4.16 (brs, 2H), 3.88-3.91 (brs, 2H), 2.42 (s, 9H), 1.70 (s, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

124.9, 92.2, 70.6, 63.5, 12.9, 4.0.

Example 3

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In an argon atmosphere, 2.55 g (15.7 mmol) of a tetrafluoroboric acid-diethyl ether complex was added at 0° C. to a solution prepared by mixing 4.31 g (15.0 mmol) of bis(η⁵-ethylcyclopentadienyl)ruthenium ((η⁵-C₅EtH₄)₂Ru) and 40 mL of acetonitrile. The resulting mixture was stirred at room temperature for 20 hours, and the solvent was then removed by distillation under reduced pressure. The remaining solid was washed with a mixture of dichloromethane and diethyl ether (dichloromethane:diethyl ether=1:10 (vol %)) to obtain [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄]) as a yellow-brown solid (5.93 g, yield: 98%).

¹H-NMR (500 MHz, CDCl₃, δ):

4.10-4.15 (m, 2H), 3.89-3.94 (m, 2H), 2.40 (s, 9H), 2.03 (q, J=7.0 Hz, 2H), 1.07 (t, J=7.0 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

124.9, 96.7, 70.0, 63.4, 20.3, 13.6, 3.7.

Example 4

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In an argon atmosphere, 5.98 g (36.9 mmol) of a tetrafluoroboric acid-diethyl ether complex was added at 0° C. to a solution prepared by mixing 10.2 g (35.2 mmol) of (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)) and 40 mL of acetonitrile. The resulting mixture was stirred at room temperature for 20 hours, and the solvent was then removed by distillation under reduced pressure. The remaining solid was washed with a mixture of dichloromethane and diethyl ether (dichloromethane:diethyl ether=1:10 (vol %)) to obtain [tris(acetonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄]) as a yellow-brown solid (14.1 g, yield: 99%). The thus-obtained [Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄] was measured for the ¹H and ¹³C-NMR spectra, as a result, these spectra agreed with the spectra obtained in Example 3.

Example 5

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In an argon atmosphere, 603 mg (4.02 mmol) of trifluoromethanesulfonic acid was added at 0° C. to a solution prepared by dissolving 1.10 g (3.81 mmol) of bis(η⁵-ethylcyclopentadienyl)ruthenium ((η⁵-C₅EtH₄)₂Ru) in 5 mL of acetonitrile. The resulting mixture was stirred at room temperature for 20 hours, and the solvent was then removed by distillation under reduced pressure. The remaining solid was washed with diethyl ether to obtain [tris(acetonitrile)(η⁵-ethylcyclo-pentadienyl)ruthenium(II)] [trifluoromethanesulfonate] ([Ru(η⁵-C₅EtH₄)(MeCN)₃][CF₃SO₃]) as a yellow-brown solid (1.61 g, yield: 90%).

¹H-NMR (500 MHz, CDCl₃, δ):

4.13-4.15 (m, 2H), 3.93-3.95 (m, 2H), 2.41 (s, 9H), 2.03 (q, J=7.0 Hz, 2H), 1.07 (t, J=7.0 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

124.9, 120.8 (q, J_C-F=318 Hz), 96.9, 70.2, 63.6, 20.4, 13.7, 4.04.

Example 6

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In an argon atmosphere, 903 mg (5.58 mmol) of a tetrafluoroboric acid-diethyl ether complex was added at 0° C. to a solution prepared by dissolving 1.53 g (5.32 mmol) of bis(η⁵-ethylcyclopentadienyl)ruthenium ((η⁵-C₅EtH₄)₂Ru) in 10 mL of pivalonitrile. The resulting mixture was stirred at room temperature for 20 hours, and the solvent was then removed by distillation under reduced pressure. The remaining solid was washed with a mixed solvent of tetrahydrofuran and hexane (tetrahydrofuran:hexane=1:10) to obtain [tris(pivalonitrile)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(^tBuCN)₃][BF₄]) as a red-brown oily matter (2.46 g, yield: 87%).

¹H-NMR (500 MHz, CDCl₃, δ):

4.16-4.18 (m, 2H), 3.94-3.96 (m, 2H), 2.05 (q, J=7.5 Hz, 2H), 1.45 (s, 27H), 1.10 (t, J=7.5 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

133.5, 97.8, 71.2, 63.7, 30.2, 28.3, 20.3, 13.6.

Example 7

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In an argon atmosphere, 13.0 g (132 mmol) of mesityl oxide and 4.22 g (41.7 mmol) of triethylamine were added to a suspension prepared by mixing 4.30 g (11.4 mmol) of [Ru(η⁵-C₅H₅)(MeCN)₃][BF₄] and 50 mL of hexane. The resulting mixture was stirred at room temperature for 20 minutes and then stirred at 50° C. for 10 hours. The reaction mixture was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining yellow solid was sublimated (heating temperature: 110° C./back pressure: 10 Pa) to obtain (η⁵-cyclopentadienyl)(η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)ruthenium (Ru(η⁵-C₅H₅)(η⁵-CH₂C(Me)CHC(Me)O)) as a yellow solid (1.27 g, yield: 42%).

¹H-NMR (500 MHz, CDCl₃, δ):

5.55 (s, 1H), 4.65 (s, 5H), 3.93 (s, 1H), 2.28 (s, 3H), 1.72 (s, 3H), 1.48 (s, 1H).

¹³C-NMR (125 MHz, CDCl₃, δ):

134.4, 101.1, 84.0, 75.6, 51.9, 26.9, 24.3.

Example 8

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In an argon atmosphere, 8.61 g (22.1 mmol) of [Ru(η⁵-C₅MeH₄)(MeCN)₃][BF₄] was dissolved in 69.0 g (700 mmol) of mesityl oxide and the mixture was stirred at room temperature for 24 hours. Subsequently, 8.95 g (88.4 mmol) of triethylamine was added to the mixture at 0° C. and then the mixture was stirred at 50° C. for 8 hours. After removing the solvent by distillation under reduced pressure, the residue was added with 60 mL of hexane and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining solid was sublimated (heating temperature: 135° C./back pressure: 10 Pa) to obtain (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-methylcyclopentadienyl)ruthenium (Ru(η⁵-C₅MeH₄)(η⁵-CH₂C(Me)CHC(Me)O)) as an orange solid (3.73 g, yield: 61%).

¹H-NMR (500 MHz, CDCl₃, δ):

5.43 (s, 1H), 4.56-4.61 (m, 2H), 4.49-4.52 (m, 2H), 3.79 (s, 1H), 2.25 (s, 3H), 1.80 (s, 3H), 1.72 (s, 3H), 1.55 (s, 1H).

¹³C-NMR (125 MHz, CDCl₃, δ)

134.2, 101.4, 92.3, 84.3, 76.2, 76.1, 75.8, 74.6, 52.5, 26.6, 24.2, 13.5.

Example 9

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In an argon atmosphere, 1.49 g (3.68 mmol) of [Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄] was dissolved in 13.0 g (132 mmol) of mesityl oxide and after adding to the mixture 1.36 g (18.4 mmol) of lithium carbonate, the mixture was stirred at 50° C. for 8 hours. The solvent was removed by distillation under reduced pressure and thereafter, the residue was added with 60 mL of hexane and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining liquid was distilled under reduced pressure (distillation temperature: 88° C./back pressure: 5 Pa) to obtain (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)O)) as an orange liquid (0.93 g, yield: 86%).

¹H-NMR (500 MHz, CDCl₃, δ):

5.44 (s, 1H), 4.59-4.63 (m, 1H), 4.51-4.55 (m, 1H), 4.48-4.51 (m, 1H), 4.37-4.40 (m, 1H), 3.80 (s, 1H), 2.24 (s, 3H), 2.13 (q, J=7.5 Hz, 2H), 1.70 (s, 3H), 1.53 (s, 1H), 1.12 (t, J=7.5 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

134.2, 101.1, 100.3, 84.2, 75.7, 74.5, 74.4, 73.9, 52.3, 26.7, 24.1, 21.2, 14.8.

Example 10

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In an argon atmosphere, 2.60 g (35.2 mmol) of lithium carbonate and 11.0 g (60.6 mmol) of 2,2,5,6,6-pentamethylhept-4-en-3-one were added to a solution prepared by dissolving 2.84 g (7.03 mmol) of [Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄] in 20 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 20 minutes and then stirred at 50° C. for 17 hours. After removing the solvent by distillation under reduced pressure, the residue was added with 150 mL of hexane and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure to obtain (η⁵-2,4-di-tert-butyl-1-oxa-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(^tBu)CHC(^tBu)O)) as an orange liquid (1.41 g, yield: 53%).

¹H-NMR (500 MHz, CDCl₃, δ):

5.68 (s, 1H), 4.74-4.78 (brs, 1H), 4.70-4.74 (brs, 1H), 4.36-4.40 (m, 1H), 4.07-4.10 (m, 1H), 4.01 (s, 1H), 2.34 (q, J=7.5 Hz, 2H), 1.40 (s, 1H), 1.26 (s, 9H), 1.23 (t, J=7.5 Hz, 3H), 1.03 (s, 9H).

¹³C-NMR (125 MHz, CDCl₃, δ):

147.3, 116.0, 103.6, 76.5, 74.3, 72.5, 72.4, 71.4, 46.9, 37.4, 36.0, 31.0, 29.6, 21.9, 15.2.

Example 11

embedded image

In an argon atmosphere, 5.81 g (59.2 mmol) of mesityl oxide and 1.82 g (18.0 mmol) of triethylamine were added to a suspension prepared by mixing 2.69 g (5.91 mmol) of [Ru(η⁵-C₅Me₅)(MeCN)₃][MeSO₃] and 30 mL of hexane. The resulting mixture was stirred at room temperature for 20 minutes and then stirred at 50° C. for 23 hours. After removing the solvent by distillation under reduced pressure, the residue was added with 150 mL of hexane and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining yellow solid was purified using column chromatography (alumina, tetrahydrofuran) to obtain (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅Me₅)(η⁵-CH₂C(Me)CHC(Me)O)) as a yellow solid (1.97 g, yield: 100%).

¹H-NMR (500 MHz, C₆D₆, δ):

4.88 (s, 1H), 3.17 (s, 1H), 2.04 (s, 3H), 1.75 (s, 15H), 1.64 (s, 1H), 1.61 (s, 3H).

¹³C-NMR (125 MHz, C₆D₆, δ):

133.2, 101.7, 87.5, 84.6, 55.0, 25.2, 23.2, 10.7.

Example 12

embedded image

In an argon atmosphere, 2.88 g (10.0 mmol) of bis(η⁵-ethylcyclopentadienyl)ruthenium ((η⁵-C₅EtH₄)₂Ru) was dissolved in 30 mL of acetonitrile and after adding 1.70 g (10.5 mmol) of a tetrafluoroboric acid-diethyl ether complex to the mixture at 0° C., the mixture was stirred at room temperature for 8 hours. At this point, a part of the reaction mixture was sampled and analyzed using ¹H-NMR, as a result, it was confirmed that [Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄] was produced. The solvent was removed from the reaction mixture by distillation under reduced pressure and after dissolving the remaining solid in 30 mL of acetone, 9.84 g (100 mmol) of mesityl oxide was added to the mixture at room temperature and the mixture was stirred at room temperature for 8 hours. Subsequently, 5.31 g (50.1 mmol) of sodium carbonate was added to the mixture and the mixture was stirred at 50° C. for 8 hours. After removing the solvent from the reaction mixture by distillation under reduced pressure, the residue was added with 60 mL of hexane and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining liquid was distilled under reduced pressure (distillation temperature: 88° C./back pressure: 5 Pa) to obtain (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)O)) as an orange liquid (2.06 g, yield: 70%). The thus-obtained Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)O) was measured for ¹H and ¹³C-NMR spectra, as a result, these spectra agreed with the spectra obtained in Example 9.

Example 13

embedded image

In an argon atmosphere, 3.25 g (11.2 mmol) of (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)) was dissolved in 20 mL of acetonitrile and after adding 2.00 g (12.4 mmol) of a tetrafluoroboric acid-diethyl ether complex to the mixture at 0° C., the mixture was stirred at room temperature for 8 hours. At this point, a part of the reaction mixture was sampled and analyzed using ¹H-NMR, as a result, it was confirmed that [Ru(η⁵-C₅EtH₄)(MeCN)₃][BF₄] was produced. The solvent was removed from the reaction mixture by distillation under reduced pressure and after dissolving the obtained residue in 20 mL of dichloromethane, 11.0 g (112 mmol) of mesityl oxide was added at room temperature and the mixture was stirred at room temperature for 8 hours. Subsequently, 1.25 g (12.4 mmol) of triethylamine was added to the mixture at 0° C. and the mixture was stirred at room temperature for 8 hours. After removing the solvent from the reaction mixture by distillation under reduced pressure, the residue was added with 60 mL of hexane and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining liquid was distilled under reduced pressure (distillation temperature: 88° C./back pressure: 5 Pa) to obtain (η⁵-2,4-dimethyl-1-oxa-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium ([Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)O)]) as an orange liquid (1.90 g, yield: 58%). The thus-obtained Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)O) was measured for ¹H and ¹³C-NMR spectra, as a result, these spectra agreed with the spectra obtained in Example 9.

Production Example of Ruthenium-Containing Thin Film Using Ammonia as Reaction Gas (Examples 14 to 17 and Comparative Examples 1 and 2):

Ruthenium-containing thin films were produced by the thermal CVD method using the ruthenium complex (1) or (η⁵-C₅EtH₄)₂Ru for the material. The apparatus used for the thin film production is sketched in FIG. 1. The deposition conditions are as shown in Table 6, and other conditions are as follows.

Total pressure in material container: 13.3 kPa, flow rate of carrier gas: 30 sccm, material feed rate: 0.012 sccm, flow rate of ammonia: 100 sccm, flow rate of diluent gas: 70 sccm, substrate: SiO₂/Si, and deposition time: 1 hour. As the carrier gas and diluent gas, argon was used. Here, the material feed rate to the reaction chamber can be determined based on the calculation formula: (flow rate of carrier gas×vapor pressure of material÷total pressure in material container).

In all of Examples 14 to 17, when the produced thin film was confirmed by X-ray fluorescence analysis, a characteristic X-ray based on ruthenium was detected. For the X-ray fluorescence 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. The film thickness computed from the intensity of X-ray detected is shown in Table 6. The electrical properties of the ruthenium-containing thin film produced were measured by the four probe method, and the resistivity obtained is shown in Table 6. For the four probe method, LORESTA HP MCP-T410 manufactured by Mitsubishi Petrochemical Co., Ltd. was used.

The impurities contained in the film produced under the conditions of Example 15 (however, the deposition time was set to 2.5 hours) were quantitatively determined by the secondary ion mass spectrometry. For the secondary ion mass spectrometry, ADEPT1010 manufactured by PHI was used. The measurement conditions were primary ion species: Cs⁺, primary ion acceleration voltage: 2 kV, secondary ion polarity: Positive, and charge compensation: E-gun.

C: 0.13 atm %, N: 0.08 atm %, O: 0.13 atm %.

The surface smoothness of the film produced under the conditions of Example 15 was evaluated by AFM, as a result, the arithmetic average roughness (Ra) of the film was 2.1 nm and the root-mean-square roughness (Rms) was 2.7 nm (FIG. 2). As the AFM, NanoScope Ma manufactured by Bruker•AXS was used. The measurement conditions were in tapping mode. The thin films produced in Comparative Examples 1 and 2 were confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was detected. The film thickness computed from the intensity of X-ray detected is shown in Table 6. The ruthenium-containing thin film produced was measured for electrical properties by the four probe method and found to be an insulating film.

[Table 20]

TABLE 6

A
B
C
D
E
F

Example 14
1a-3 (Example 9)
64
5.3
500
33
15

Example 15
1a-3 (Example 9)
64
5.3
450
29
15

Example 16
1a-2 (Example 8)
65
5.3
500
43
14

Example 17
1a-2 (Example 8)
65
5.3
450
17
38

Comparative
(η⁵-C₅EtH₄)₂Ru
62
5.3
500
47
unmeasurable

Example 1

Comparative
(η⁵-C₅EtH₄)₂Ru
62
5.3
450
55
unmeasurable

Example 2

A: Material,

B: material container temperature [° C.],

C: vapor pressure of material [Pa],

D: substrate temperature [° C.],

E: film thickness [nm],

F: resistivity [μΩ · cm].

Production Example of Ruthenium-Containing Thin Film Using Oxygen as Reaction Gas (Examples 18 to 26 and Comparative Examples 3 and 4):

Total pressure in material container: 13.3 kPa, flow rate of carrier gas: 30 sccm, material feed rate: 0.012 sccm, flow rate of oxygen: 0.16 sccm, flow rate of diluent gas: 169 sccm, substrate: SiO₂/Si, and deposition time: 1 hour. As the carrier gas and diluent gas, argon was used. In all of Examples 18 to 26, when the produced thin film was confirmed by X-ray fluorescence analysis, a characteristic X-ray based on ruthenium was detected. The film thickness computed from the intensity of X-ray detected is shown in Table 7. The electrical properties of the ruthenium-containing thin film produced were measured by the four probe method, and the resistivity obtained is shown in Table 7.

The thin films produced in Comparative Examples 3 and 4 were confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was detected in case of the thin film produced in Comparative Example 3, and a characteristic X-ray based on ruthenium was not detected in case of the thin film produced in Comparative Example 4. The film thickness computed from the intensity of X-ray detected is shown in Table 7. The ruthenium-containing thin film produced was measured for electrical properties by the four probe method, and the resistivity obtained is shown in Table 7.

[Table 21]

TABLE 7

A
B
C
D
E
F

Example 18
1a-3 (Example 9)
64
5.3
400
18
14

Example 19
1a-3 (Example 9)
64
5.3
300
17
321

Example 20
1a-3 (Example 9)
64
5.3
250
15
324

Example 21
1a-3 (Example 9)
64
5.3
225
7
568

Example 22
1a-2 (Example 8)
65
5.3
400
28
10

Example 23
1a-2 (Example 8)
65
5.3
300
27
17

Example 24
1a-2 (Example 8)
65
5.3
250
23
31

Example 25
1a-2 (Example 8)
65
5.3
225
19
59

Example 26
1a-2 (Example 8)
65
5.3
200
6
296

Comparative
(η⁵-C₅EtH₄)₂Ru
62
5.3
400
26
unmeasurable

Example 3

Comparative
(η⁵-C₅EtH₄)₂Ru
62
5.3
250
0
unmeasurable

Example 4

A: Material,

B: material container temperature [° C.],

C: vapor pressure of material [Pa],

D: substrate temperature [° C.],

E: film thickness [nm],

F: resistivity [μΩ · cm].

Example 27

A ruthenium-containing thin film was produced by the thermal CVD method using the ruthenium complex (1) obtained in Example 9. The apparatus used for the thin film production is sketched in FIG. 1. The deposition conditions are as follows.

Material container temperature: 64° C., vapor pressure of material: 5.3 Pa, total pressure in material container: 3.3 kPa, substrate temperature: 350° C., flow rate of carrier gas: 30 sccm, material feed rate: 0.048 sccm, flow rate of ammonia: 30 sccm, substrate: SiO₂/Si, and deposition time: 5 hours. Argon was used as the carrier gas, and a diluent gas was not used.

The produced thin film was confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was detected. The film thickness was computed from the intensity of X-ray detected and found to be 14 nm. The surface smoothness of the film obtained was evaluated by AFM, as a result, Ra of the film was 0.5 nm, and Rms was 0.6 nm (FIG. 3).

Comparative Example 5

A ruthenium-containing thin film was produced by the thermal CVD method using (η⁵-C₅EtH₄)₂Ru for the material. The apparatus used for the thin film production is sketched in FIG. 1. The deposition conditions are as follows.

Material container temperature: 62° C., vapor pressure of material: 5.3 Pa, total pressure in material container: 3.3 kPa, substrate temperature: 350° C., flow rate of carrier gas: 30 sccm, material feed rate: 0.048 sccm, flow rate of ammonia: 30 sccm, substrate: SiO₂/Si, and deposition time: 5 hours. Argon was used as the carrier gas, and a diluent gas was not used.

The produced thin film was confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was not detected.

Example 28

Material container temperature: 100° C., vapor pressure of material: 69 Pa, total pressure in material container: 6.7 kPa, substrate temperature: 300° C., flow rate of carrier gas: 20 sccm, material feed rate: 0.21 sccm, flow rate of ammonia: 20 sccm, substrate: TaN/Ti/Si, and deposition time: 6 hours. Argon was used as the carrier gas, and a diluent gas was not used.

The produced thin film was confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was detected. The film thickness was computed from the intensity of X-ray detected and found to be 8 nm. The surface smoothness of the film obtained was evaluated by AFM, as a result, Ra of the film was 1.1 nm, and Rms was 1.4 nm (FIG. 4).

Comparative Example 6

Material container temperature: 88° C., vapor pressure of material: 69 Pa, total pressure in material container: 6.7 kPa, substrate temperature: 300° C., flow rate of carrier gas: 20 sccm, material feed rate: 0.21 sccm, flow rate of ammonia: 20 sccm, substrate: TaN/Ti/Si, and deposition time: 6 hours. Argon was used as the carrier gas, and a diluent gas was not used.

The produced thin film was confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was not detected.

Examples 29 to 33

Ruthenium-containing thin films were produced by the thermal CVD method using the ruthenium complex (1) obtained in Example 9. The apparatus used for the thin film production is sketched in FIG. 1. The deposition conditions are as shown in Table 8, and other conditions are as follows.

Total pressure in material container: 6.7 kPa, flow rate of carrier gas: 30 sccm, material feed rate: 0.024 sccm, flow rate of ammonia: 50 sccm, flow rate of diluent gas: 20 sccm, substrate: SiO₂/Si, and deposition time: 2 hours (however, in Examples 29 and 30, 1 hour). As the carrier gas and diluent gas, argon was used.

In all of Examples 29 to 33, when the produced thin film was confirmed by X-ray fluorescence analysis, a characteristic X-ray based on ruthenium was detected. The film thickness computed from the intensity of X-ray detected is shown in Table 8. The electrical properties of the ruthenium-containing thin film produced were measured by the four probe method, and the resistivity obtained is shown in Table 8.

The surface smoothness of the film produced under the conditions of Example 29 was evaluated by AFM, as a result, Ra of the film was 3.6 nm, and Rms was 4.5 nm (FIG. 5). Furthermore, the impurities contained in the film produced under the conditions of Example 29 were quantitatively determined by the secondary ion mass spectrometry.

C: 0.13 atm %, N: 0.01 atm %, O: 0.13 atm %.

The surface smoothness of the film produced under the conditions of Example 31 was evaluated by AFM, as a result, Ra was 0.9 nm, and Rms was 1.2 nm (FIG. 6). Furthermore, the impurities contained in the film produced under the conditions of Example 31 were quantitatively determined by the secondary ion mass spectrometry.

C: 0.67 atm %, N: 0.07 atm %, O: 0.07 atm %.

The surface smoothness of the film produced under the conditions of Example 33 was evaluated by AFM, as a result, Ra of the film was 0.4 nm, and Rms was 0.5 nm (FIG. 7).

[Table 22]

TABLE 8

A
B
C
D
E
F

Example 29
1a-3 (Example 9)
64
5.3
500
53
12

Example 30
1a-3 (Example 9)
64
5.3
450
55
11

Example 31
1a-3 (Example 9)
64
5.3
400
25
18

Example 32
1a-3 (Example 9)
64
5.3
375
12
68

Example 33
1a-3 (Example 9)
64
5.3
350
4
453

A: Material,

B: material container temperature [° C.],

C: vapor pressure of material [Pa],

D: substrate temperature [° C.],

E: film thickness [nm],

F: resistivity [μΩ · cm].

Examples 34 to 37

Total pressure in material container: 6.7 kPa, flow rate of carrier gas: 30 sccm, material feed rate: 0.024 sccm, flow rate of hydrogen: 2 sccm, flow rate of diluent gas: 68 sccm, substrate: SiO₂/Si, and deposition time: 1 hour. As the carrier gas and diluent gas, argon was used.

In all of Examples 34 to 37, when the produced thin film was confirmed by X-ray fluorescence analysis, a characteristic X-ray based on ruthenium was detected. The film thickness computed from the intensity of X-ray detected is shown in Table 9. The electrical properties of the ruthenium-containing thin film produced were measured by the four probe method, and the resistivity obtained is shown in Table 9.

[Table 23]

TABLE 9

A
B
C
D
E
F

Example 34
1a-3 (Example 9)
64
5.3
500
20
313

Example 35
1a-3 (Example 9)
64
5.3
450
18
509

Example 36
1a-3 (Example 9)
64
5.3
400
13
1112

Example 37
1a-3 (Example 9)
64
5.3
375
3
633

A: Material,

B: material container temperature [° C.],

C: vapor pressure of material [Pa],

D: substrate temperature [° C.],

E: film thickness [nm],

F: resistivity [μΩ · cm].

The followings can be understood from these Examples. That is, as seen from Examples 14 to 17 and 27 to 37, the ruthenium complex (1) can produce a ruthenium-containing thin film even without using an oxidizing gas. It is also seen that by using the ruthenium complex (1) as the material, a metallic ruthenium film reduced in impurities can be produced even without using an oxidizing gas. Furthermore, it is seen that the ruthenium-containing thin film produced using the ruthenium complex (1) as the material has good electrical conductive properties. As seen from Examples 15, 27 and 28, by using the ruthenium complex (1) as the material, a metallic ruthenium film excellent in the surface smoothness can be produced even without using an oxidizing gas.

As seen from Examples 18 to 26, the ruthenium complex (1) can produce a ruthenium-containing thin film also when an oxidizing gas is used. Furthermore, comparison with Comparative Example 4 reveals that the ruthenium complex (1) can produce a ruthenium-containing thin film at a low temperature. Therefore, the ruthenium complex (1) is a useful material having a wide application range as a material for the thin film formation.

It is seen from comparison between Example 27 and Comparative Example 5 and comparison between Example 28 and Comparative Example 6 that the ruthenium complex (1) can produce a film excellent in the surface smoothness at a low temperature of 350° C. or less even without using an oxidizing gas.

Example 38

embedded image

In an argon atmosphere, 3.21 g (19.8 mmol) of a tetrafluoroboric acid-diethyl ether complex was added at 0° C. to a suspension prepared by mixing 4.49 g (14.9 mmol) of (η⁵-C₅H₅)(η⁵-C₅Me₅)Ru that was synthesized by the method described in Organometallics, Vol. 5, page 2321 (1986), and 60 mL of acetonitrile. The resulting mixture was stirred at room temperature for 21 hours, and the solvent was then removed by distillation under reduced pressure. The remaining solid was washed with a mixture of dichloromethane and diethyl ether (dichloromethane:diethyl ether=1:13 (vol %)) to obtain [tris(acetonitrile)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅Me₅)(MeCN)₃][BF₄]) as a yellow solid (6.62 g, yield: 99%).

¹H-NMR (500 MHz, CDCl₃, δ):

2.30-2.46 (br, 9H), 1.58 (s, 15H).

Example 39

embedded image

In an argon atmosphere, 6.39 g (39.5 mmol) of a tetrafluoroboric acid-diethyl ether complex was added at −78° C. to a solution prepared by mixing 11.8 g (37.6 mmol) of (η⁴-1,5-cyclooctadiene)(η⁶-1,3,5-cyclooctatriene)ruthenium (Ru(η⁴-C₄H₁₂)(η⁶-C₈H₁₀)) that was synthesized according to the method described in Journal of Organometallic Chemistry, Vol. 272, page 179 (1984), and 120 mL of dichloromethane, and the mixture was stirred at 25° C. for 1 hour. At this point, a part of the reaction mixture was sampled and analyzed using ¹H-NMR, as a result, it was confirmed that [RuH(η⁵-C₈H₁₁)₂][BF₄] was produced. Subsequently, 5.36 g (56.4 mmol) of 2,5-dimethylpyrrole was added at 25° C. and after stirring for 20 hours, 15.2 g (150.3 mmol) of triethylamine was added at 25° C. The resulting mixture was stirred for 22 hours, and the solvent was then removed by distillation under reduced pressure. The remaining liquid was distilled under reduced pressure (distillation temperature: 99° C./back pressure: 15 Pa) to obtain (1-5-η⁵-cyclooctadienyl)(η⁵-2,5-dimethylpyrrolyl)ruthenium (Ru(η⁵-C₈H₁₁)(η⁵-NC₄Me₂H₂)) as a yellow-brown liquid (7.5 g, yield: 66%).

¹H-NMR (500 MHz, CDCl₃, δ):

5.76 (t, J=6.0 Hz, 1H), 5.09 (s, 2H), 4.00-4.10 (m, 2H), 3.43-3.55 (m, 2H), 2.02 (s, 6H), 1.69-1.76 (m, 2H), 1.25-1.36 (m, 2H), 1.03-1.12 (m, 1H), −0.21-−0.097 (m, 1H).

¹³C-NMR (125 MHz, CDCl₃, δ):

114.8, 102.1, 82.1, 75.3, 46.5, 29.3, 20.7, 15.1.

Examples 40 and 41 and Comparative Examples 7 and 8
Production Example of Ruthenium-Containing Thin Film Using Ammonia as Reaction Gas

Ruthenium-containing thin films were produced by the thermal CVD method using the ruthenium complex (2) or Ru(η⁵-C₅EtH₄)₂for the material. The apparatus used for the thin film production is sketched in FIG. 1. The deposition conditions are as shown in Table 10, and other conditions are as follows.

In both of Examples 40 and 41, when the produced thin film was confirmed by X-ray fluorescence analysis, a characteristic X-ray based on ruthenium was detected. For the X-ray fluorescence 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. The film thickness computed from the intensity of X-ray detected is shown in Table 10. The electrical properties of the ruthenium-containing thin film produced were measured by the four probe method, and the resistivity obtained is shown in Table 10. For the four probe method, LORESTA HP MCP-T410 manufactured by Mitsubishi Petrochemical Co., Ltd. was used.

The impurities contained in the film produced under the conditions of Example 41 (however, the deposition time was set to 1.5 hours) were quantitatively determined by the secondary ion mass spectrometry. For the secondary ion mass spectrometry, ADEPT1010 manufactured by PHI was used. The measurement conditions were primary ion species: Cs⁺, primary ion acceleration voltage: 2 kV, secondary ion polarity: Positive, and charge compensation: E-gun.

C: 0.13 atm %, N: 0.27 atm %, O: 0.53 atm %.

The surface smoothness of the film produced obtained in Example 41 was evaluated by AFM, as a result, the arithmetic average roughness (Ra) of the film was 2.0 nm and the root-mean-square roughness (Rms) was 2.7 nm (FIG. 8). As the AFM, NanoScope Ma manufactured by Bruker•AXS was used. The measurement conditions were in tapping mode.

The thin films produced in Comparative Examples 7 and 8 were confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was detected. The film thickness computed from the intensity of X-ray detected is shown in Table 10. The ruthenium-containing thin film produced was measured for electrical properties by the four probe method and found to be an insulating film.

[Table 24]

TABLE 10

A
B
C
D
E
F

Example 40
2-1 (Example 39)
83
5.3
500
49
46

Example 41
2-1 (Example 39)
83
5.3
450
39
22

Comparative
Ru(η⁵-C₅EtH₄)₂
62
5.3
500
47
10⁶or more

Example 7

Comparative
Ru(η⁵-C₅EtH₄)₂
62
5.3
450
55
10⁶or more

Example 8

A: Material,

B: material container temperature [° C.],

C: vapor pressure of material [Pa],

D: substrate temperature [° C.],

E: film thickness [nm],

F: resistivity [μΩ · cm].

Examples 42 to 45 and Comparative Examples 9 and 10
Production Example of Ruthenium-Containing Thin Film Using Oxygen as Reaction Gas

Total pressure in material container: 13.3 kPa, flow rate of carrier gas: 30 sccm, material feed rate: 0.012 sccm, flow rate of oxygen: 0.16 sccm, flow rate of diluent gas: 169 sccm, substrate: SiO₂/Si, and deposition time: 1 hour. As the carrier gas and diluent gas, argon was used. In all of Examples 42 to 45, when the produced thin film was confirmed by X-ray fluorescence analysis, a characteristic X-ray based on ruthenium was detected. The film thickness computed from the intensity of X-ray detected is shown in Table 11. The electrical properties of the ruthenium-containing thin film produced were measured by the four probe method, and the resistivity obtained is shown in Table 11.

The thin films produced in Comparative Examples 9 and 10 were confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was detected in case of the thin film produced in Comparative Example 9 and a characteristic X-ray based on ruthenium was not detected in case of the thin film produced in Comparative Example 10. The film thickness computed from the intensity of X-ray detected is shown in Table 11. The electrical properties of the ruthenium-containing thin film produced were measured by the four probe method, and the resistivity obtained is shown in Table 11.

[Table 25]

TABLE 11

A
B
C
D
E
F

Example 42
2-1 (Example 39)
83
5.3
400
27
13

Example 43
2-1 (Example 39)
83
5.3
300
27
17

Example 44
2-1 (Example 39)
83
5.3
250
24
56

Example 45
2-1 (Example 39)
83
5.3
225
25
91

Comparative
Ru(η⁵-C₅EtH₄)₂
262
5.3
400
26
10⁶or more

Example 9

Comparative
Ru(η⁵-C₅EtH₄)₂
262
5.3
250
0
unmeasurable

Example 10

A: Material,

B: material container temperature [° C.],

C: vapor pressure of material [Pa],

D: substrate temperature [° C.],

E: film thickness [nm],

F: resistivity [μΩ · cm].

The followings can be understood from these Examples. That is, as seen from Examples 40 and 41, the ruthenium complex (2) is a material capable of producing a ruthenium-containing thin film even without using an oxidizing gas. It is also seen that a ruthenium-containing thin film producing using the ruthenium complex (2) as the material has good electrical conductive properties. As seen from Example 41, by using the ruthenium complex (2) as the material, a metallic ruthenium film reduced in impurities can be produced even without using an oxidizing gas. In addition, as seen from Example 41, by using the ruthenium complex (2) as the material, a metallic ruthenium film excellent in the surface smoothness can be produced even without using an oxidizing gas.

As seen from Examples 42 to 45, the ruthenium complex (2) can produce a ruthenium-containing thin film also when an oxidizing gas is used. Furthermore, comparison with Comparative Examples 9 and 10 reveals that the ruthenium complex (2) is a material capable of producing a ruthenium-containing thin film at a low temperature and is a useful material having a wide application range as a material for the thin film formation.

Reference Example 1

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In an argon atmosphere, 1.84 g (23.6 mmol) of benzene was added to a solution prepared by mixing 5.98 g (15.9 mmol) of [tris(acetonitrile)(η⁵-cyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅H₅)(MeCN)₃][BF₄]) and 40 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 20 hours and then cooled to −78° C., and the produced solid was filtered to obtain [(η⁶-benzene)(η⁵-cyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][BF₄]) as a yellow solid (3.27 g, yield: 62%).

¹H-NMR (500 MHz, CDCl₃, δ):

6.21 (s, 6H), 5.46 (s, 5H).

¹³C-NMR (125 MHz, CDCl₃, δ):

86.1, 80.8.

Reference Example 2

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In an argon atmosphere, 2.19 g (28.1 mmol) of benzene was added to a solution prepared by mixing 9.01 g (23.1 mmol) of [tris(acetonitrile)(η⁵-methylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅MeH₄)(MeCN)₃][BF₄]) and 40 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 20 hours and then cooled to −78° C., and the produced solid was filtered to obtain [(η⁶-benzene)(η⁵-methylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅MeH₄)(η⁶-C₆H₆)][BF₄]) as a brown solid (4.94 g, yield: 62%).

¹H-NMR (500 MHz, CDCl₃, δ):

6.15 (s, 6H), 5.40-5.43 (m, 2H), 5.30-5.33 (m, 2H), 2.08 (s, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

100.2, 86.4, 81.9, 80.2, 13.9.

Example 46

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In an argon atmosphere, 9.8 mL (1.11 mol/L, 10.9 mmol) of a diethyl ether solution of methyllithium was added at −78° C. to a solution prepared by dissolving 3.27 g (9.88 mmol) of [Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][BF₄] obtained in Reference Example 1 in 30 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 20 hours and after removing the solvent by distillation under reduced pressure, the residue was added with 125 mL of hexane and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining solid was purified using column chromatography (alumina, hexane) to obtain (η⁵-cyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (Ru(η⁵-C₅H₅)(η⁵-C₆H₆Me)) as a yellow solid (850 mg, yield: 33%).

¹H-NMR (500 MHz, CDCl₃, δ):

5.64-5.72 (m, 1H), 4.73 (s, 5H), 4.28-4.38 (m, 2H), 2.83-2.92 (m, 2H), 2.28 (sext, J=6.4 Hz, 1H), 0.21 (d, J=6.5 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

79.5, 76.1, 74.9, 34.7, 32.5, 28.5.

Example 47

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In an argon atmosphere, 14 mL (1.10 mol/L, 15.4 mmol) of a diethyl ether solution of methyllithium was added at −78° C. to a solution prepared by dissolving 4.94 g (14.3 mmol) of [Ru(η⁵-C₅MeH₄)(η⁶-C₆H₆)][BF₄] obtained in Reference Example 2 in 40 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 21 hours and after removing the solvent by distillation under reduced pressure, the residue was added with 300 mL of hexane and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining liquid was purified using column chromatography (alumina, hexane) to obtain (η⁵-6-exo-methylcyclohexadienyl)(η⁵-methylcyclopentadienyl)ruthenium (Ru(η⁵-C₅MeH₄)(η⁵-C₆H₆Me)) as a yellow liquid (860 mg, yield: 22%).

¹H-NMR (500 MHz, CDCl₃, δ):

5.59-5.62 (m, 1H), 4.74-4.77 (m, 2H), 4.51-4.54 (m, 2H), 4.24-4.29 (m, 2H), 2.71-2.76 (m, 2H), 2.30 (sext, J=6.4 Hz, 1H), 1.94 (s, 3H), 0.21 (d, J=6.5 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

92.0, 79.5, 76.7, 76.5, 74.2, 34.8, 33.8, 28.4, 14.6.

Example 48

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In an argon atmosphere, 2.63 g (33.7 mmol) of benzene was added to a solution prepared by mixing 835 mg (2.91 mmol) of bis(η⁵-ethylcyclopentadienyl)ruthenium ((η⁵-C₅EtH₄)₂Ru) produced by Aldrich and 7 mL of acetonitrile. To this solution, 516 mg (3.19 mmol) of a tetrafluoroboric acid-diethyl ether complex was added at 0° C. The resulting mixture was stirred at room temperature for 20 minutes and then stirred at 80° C. for 8 hours. The solvent was removed from the reaction mixture by distillation under reduced pressure, and the remaining solid was washed with a mixture of tetrahydrofuran and hexane (tetrahydrofuran:hexane=1:3) to obtain [(η⁶-benzene)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][BF₄]) as a yellow-brown solid (1.02 g, yield: 98%).

¹H-NMR (500 MHz, CDCl₃, δ):

6.15 (s, 6H), 5.36-5.40 (m, 2H), 5.30-5.34 (m, 2H), 2.33 (q, J=7.5 Hz, 2H), 1.09 (t, J=7.5 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

106.9, 86.2, 80.3, 80.0, 21.0, 14.5.

Example 49

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In an argon atmosphere, 7.5 g (96.0 mmol) of benzene was added to a solution prepared by mixing 20.2 g (69.6 mmol) of (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)) that was synthesized according to the method described in JP-A-2003-342286, and 80 mL of tetrahydrofuran. To this solution, 15 mL (42%, 99.0 mmol) of an aqueous tetrafluoroboric acid solution was added at −78° C. The resulting mixture was stirred at room temperature for 20 hours and then cooled to −78° C., and the produced solid was filtered to obtain [(η⁶-benzene)(η⁵-ethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][BF₄]) as a white solid (19.4 g, yield: 78%). The [Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][BF₄] obtained was measured for the ¹H and ¹³C-NMR spectra, as a result, these spectra agreed with the spectra obtained in Example 48.

Example 50

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In an argon atmosphere, 47 mL (1.10 mol/L, 51.7 mmol) of a diethyl ether solution of methyllithium was added at −78° C. to a solution prepared by dissolving 16.4 g (45.7 mmol) of [Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][BF₄] obtained in Example 49 in 140 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 20 hours and after removing the solvent by distillation under reduced pressure, the residue was added with 200 mL of hexane and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining liquid was purified using column chromatography (alumina, hexane) and then distilled under reduced pressure (distillation temperature: 80° C./back pressure: 1.5 Pa) to obtain (η⁵-ethylcyclopentadienyl)(η⁵-6-exo-methylcyclohexadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-C₆H₆Me)) as a yellow liquid (5.33 g, yield: 41%).

¹H-NMR (500 MHz, CDCl₃, δ):

5.60-5.65 (m, 1H), 4.70-4.73 (m, 2H), 4.55-4.58 (m, 2H), 4.26-4.31 (m, 2H), 2.74-2.79 (m, 2H), 2.30 (sext, J=6.5 Hz, 1H), 2.25 (q, J=7.5 Hz, 2H), 1.09 (t, J=7.5 Hz, 3H), 0.20 (d, J=6.5 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

99.8, 79.4, 76.6, 74.8, 73.9, 34.8, 33.4, 28.4, 22.0, 15.0.

Example 51

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In an argon atmosphere, 7.0 mL (2.69 mol/L, 18.8 mmol) of a hexane solution of n-butyllithium was added at −78° C. to a solution prepared by dissolving 6.16 g (17.2 mmol) of [Ru(η⁵-C₅EtH₄)(η⁶-C₆H₆)][BF₄] obtained in Example 49 in 50 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 20 hours and after removing the solvent by distillation under reduced pressure, the residue was added with 125 mL of hexane and vigorously stirred at room temperature The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining liquid was purified using column chromatography (alumina, hexane) and then distilled under reduced pressure (distillation temperature: 112° C./back pressure: 37 Pa) to obtain (η⁵-ethylcyclopentadienyl)(η⁵-6-exo-butylcyclohexadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-C₆H₆Bu)) as a yellow liquid (3.66 g, yield: 65%).

¹H-NMR (500 MHz, CDCl₃, δ):

5.57-5.68 (m, 1H), 4.72 (brs, 2H), 4.57 (brs, 2H), 4.24-4.37 (m, 2H), 2.73-2.83 (m, 2H), 2.25 (q, J=7.5 Hz, 2H), 2.14-2.21 (m, 1H), 1.04-1.16 (m, 5H), 0.92-1.01 (m, 2H), 0.78 (t, J=7.5 Hz, 3H), 0.45-0.54 (m, 2H).

¹³C-NMR (125 MHz, CDCl₃, δ):

99.8, 79.6, 76.7, 74.9, 73.9, 42.3, 40.1, 32.2, 26.3, 22.7, 22.0, 15.0, 14.3.

Example 52

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In an argon atmosphere, 515 mg (4.28 mmol) of 1,3,5-trimethylbenzene was added to a solution prepared by mixing 1.01 g (3.50 mmol) of (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)) that was synthesized according to the method described in JP-A-2003-342286, and 10 mL of tetrahydrofuran. To this solution, 0.6 mL (42%, 3.96 mmol) of an aqueous tetrahydrofluoroboric acid solution was added at −78° C. The resulting mixture was stirred at room temperature for 3 days and then cooled to −78° C., and the produced solid was filtered to obtain [(η⁵-ethylcyclopentadienyl)(η⁶-1,3,5-trimethylbenzene)ruthenium(II)][tetrafluoroborate] ([Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)][BF₄]) as a white solid (717 mg, yield: 51%).

¹H-NMR (500 MHz, CDCl₃, δ):

6.00 (s, 3H), 5.11-5.20 (m, 4H), 2.31 (s, 9H), 2.23 (q, J=7.5 Hz, 2H), 1.12 (t, J=7.5 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

104.8, 101.1, 87.5, 80.9, 80.4, 20.5, 20.0, 14.7.

Example 53

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In an argon atmosphere, 1.8 mL (1.10 mol/L, 1.98 mmol) of a diethyl ether solution of methyllithium was added at −78° C. to a solution prepared by dissolving 717 mg (1.79 mmol) of [Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)][BF₄] obtained in Example 52 in 10 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 16 hours and after removing the solvent by distillation under reduced pressure, the residue was added with 20 mL of tetrahydofuran and vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining liquid was purified using column chromatography (alumina, tetrahydrofuran) and then distilled under reduced pressure (distillation temperature: 97° C./back pressure: 29 Pa) to obtain (η⁵-ethylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-C₆H₃Me₄)) as a yellow liquid (382 mg, yield: 65%).

¹H-NMR (500 MHz, CDCl₃, δ):

4.38-4.41 (m, 2H), 4.36-4.38 (m, 2H), 4.13 (s, 2H), 2.34 (q, J=6.5 Hz, 1H), 2.22 (s, 3H), 2.17 (q, J=7.5 Hz, 2H), 1.48 (s, 6H), 1.09 (t, J=7.5 Hz, 3H), 0.25 (d, J=6.5 Hz, 3H).

¹³C-NMR (125 MHz, CDCl₃, δ):

98.6, 90.3, 78.4, 76.6, 76.0, 46.9, 43.7, 24.1, 21.2, 21.1, 21.0, 15.1.

Example 54

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In an argon atmosphere, 20.0 g (166 mmol) of 1,3,5-trimethylbenzene was added to a solution prepared by dissolving 38.7 g (134 mmol) of (η⁵-2,4-dimethyl-2,4-pentadienyl)(η⁵-ethylcyclopentadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-CH₂C(Me)CHC(Me)CH₂)) that was synthesized according to the method described in JP-A-2003-342286, in 200 mL of tetrahydrofuran. To this solution, 25 mL (42%, 165 mmol) of an aqueous tetrahydrofluoroboric acid solution was added at −78° C., and the mixture was stirred at room temperature for 3 days. At this point, a part of the reaction mixture was sampled and analyzed using ¹H-NMR, as a result, it was confirmed that [Ru(η⁵-C₅EtH₄)(η⁶-C₆Me₃H₃)][BF₄] was produced. The solvent was removed from the reaction mixture by distillation under reduced pressure, and the residue was washed with 100 mL of hexane and dissolved in 150 mL of tetrahydrofuran. Subsequently, 90 mL (1.10 mol/L, 99.0 mmol) of a diethyl ether solution of methyllithium was added thereto at −78° C. and the mixture was stirred at room temperature for 20 hours. After removing the solvent from the reaction mixture by distillation under reduced pressure, 250 mL of hexane was added to the residue and the mixture was vigorously stirred at room temperature. The produced suspension was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The remaining liquid was purified using column chromatography (alumina, hexane) and then distilled under reduced pressure (distillation temperature: 97° C./back pressure: 29 Pa) to obtain (η⁵-ethylcyclopentadienyl)(η⁵-1,3,5,6-exo-tetramethylcyclohexadienyl)ruthenium (Ru(η⁵-C₅EtH₄)(η⁵-C₆H₃Me₄)) as a yellow liquid (20.0 g, yield: 61%). The obtained Ru(η⁵-C₅EtH₄)(η⁵-C₆H₃Me₄) was measured for ¹H and ¹³C-NMR spectra, as a result, these spectra agreed with the spectra obtained in Example 53.

Production Example of Ruthenium-Containing Thin Film Using Ammonia as Reaction Gas (Examples 55 to 57):

Ruthenium-containing thin films were produced by the thermal CVD method using the ruthenium complex (3a) of the present invention for the material. The apparatus used for the thin film production is sketched in FIG. 1. The deposition conditions are as shown in Table 12, and other conditions are as follows.

In all of Examples 55 to 57, when the produced thin film was confirmed by X-ray fluorescence analysis, a characteristic X-ray based on ruthenium was detected. The film thickness computed from the intensity of X-ray detected is shown in Table 12. [Table 26]

TABLE 12

A
B
C
D
E

Example 55
3-3 (Example 50)
68
5.3
500
8

Example 56
3-3 (Example 50)
68
5.3
450
3

Example 57
3-46 (Example 54)
67
5.3
500
2

A: Material, B: material container temperature [° C.], C: vapor pressure of material [Pa], D: substrate temperature [° C.], E: film thickness [nm].

Production Example of Ruthenium-Containing Thin Film Using Oxygen as Reaction Gas (Examples 58 to 65):

Ruthenium-containing thin films were produced by the thermal CVD method using the ruthenium complex (3a) for the material. The apparatus used for the thin film production is sketched in FIG. 1. The deposition conditions are as shown in Table 13, and other conditions are as follows.

Total pressure in material container: 13.3 kPa, flow rate of carrier gas: 30 sccm, material feed rate: 0.012 sccm, flow rate of oxygen: 0.16 sccm, flow rate of diluent gas: 169 sccm, substrate: SiO₂/Si, and deposition time: 1 hour. As the carrier gas and diluent gas, argon was used. In all of Examples 13 to 20, when the produced thin film was confirmed by X-ray fluorescence analysis, a characteristic X-ray based on ruthenium was detected. The film thickness computed from the intensity of X-ray detected is shown in Table 13.

[Table 27]

TABLE 13

A
B
C
D
E

Example 58
3-3 (Example 50)
68
5.3
400
3

Example 59
3-3 (Example 50)
68
5.3
300
2

Example 60
3-3 (Example 50)
68
5.3
250
37

Example 61
3-3 (Example 50)
68
5.3
225
19

Example 62
3-46 (Example 54)
67
5.3
400
1

Example 63
3-46 (Example 54)
67
5.3
300
46

Example 64
3-46 (Example 54)
67
5.3
250
32

Example 65
3-46 (Example 54)
67
5.3
225
7

A: Material, B: material container temperature [° C.], C: vapor pressure of material [Pa], D: substrate temperature [° C.], E: film thickness [nm].

The followings can be understood from these Examples. That is, as seen from Examples 55 to 57, the ruthenium complex (3a) is a material capable of producing a ruthenium-containing thin film even without using an oxidizing gas. In addition as seen from Examples 58 to 65, the ruthenium complex (3a) can produce a ruthenium-containing thin film also when an oxidizing gas is used.

Evaluation Example 1

Material container temperature: 64° C., vapor pressure of material: 5.3 Pa, total pressure in material container: 6.7 kPa, substrate temperature: 400° C., flow rate of carrier gas: 30 sccm, material feed rate: 0.024 sccm, flow rate of ammonia: 100 sccm, flow rate of diluent gas: 70 sccm, hole substrate: SiO₂/Si (hole diameter: 400 nm, hole depth: 1,000 nm), and deposition time: 5 hours. Argon was used as the carrier gas.

The produced thin film was confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was detected. The film thickness was computed from the intensity of X-ray detected and found to be 8 nm. The electrical properties of the ruthenium-containing thin film produced were measured by the four probe method, and the resistivity was found to be 123 μΩ·cm. When the cross-section of the film was observed by FE-SEM (field-emission scanning electron microscope), the film thickness was the same between the hole opening and the hole bottom (FIG. 9). As FE-SEM, JSM-7600F manufactured by JEOL Ltd. was used. The measurement conditions were acceleration voltage: 5 kV, observation magnitude: 100,000 times, and sample pretreatment: cutting of sample→resin embedding→ion milling processing of cross-section.

Evaluation Example 2

Material container temperature: 64° C., vapor pressure of material: 5.3 Pa, total pressure in material container: 6.7 kPa, substrate temperature: 400° C., flow rate of carrier gas: 30 sccm, material feed rate: 0.024 sccm, flow rate of ammonia: 50 sccm, flow rate of diluent gas: 20 sccm, hole substrate: SiO₂/Si (hole diameter: 400 nm, hole depth: 800 nm), and deposition time: 5 hours. Argon was used as the carrier gas.

The produced thin film was confirmed by X-ray fluorescence analysis, as a result, a characteristic X-ray based on ruthenium was detected. The film thickness was computed from the intensity of X-ray detected and found to be 7 nm. The electrical properties of the ruthenium-containing thin film produced were measured by the four probe method, and the resistivity was found to be 712 μΩ·cm. When the cross-section of the film was observed by FE-SEM, the film thickness was the same between the hole opening and the hole bottom (FIG. 10). It is understood from Evaluation Examples 1 and 2 that the ruthenium complex of the present invention can produce a uniform film on an uneven surface at a low temperature of 400° C. or less even without using an oxidizing gas.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

This application is based on Japanese Patent Application (Patent Application No. 2012-268396) filed on Dec. 7, 2012, Japanese Patent Application (Patent Application No. 2013-133480) filed on Jun. 26, 2013, and Japanese Patent Application (Patent Application No. 2013-156294) filed on Jul. 29, 2013, the entirety of which is incorporated herein by way of reference. All references cited herein are incorporated in their entirety.

INDUSTRIAL APPLICABILITY

The novel ruthenium complex of the present invention is useful for the production of a ruthenium-containing thin film.

EXPLANATIONS OF REFERENCE SIGNS

1 denotes a material container.

2 denotes a constant-temperature bath.

3 denotes a reaction chamber.

4 denotes a substrate.

5 denotes reaction gas.

6 denotes diluent gas.

7 denotes carrier gas.

8 denotes a mass flow controller.

9 denotes a mass flow controller.

10 denotes a mass flow controller.

11 denotes an oil rotary pump.

12 denotes an exhaust.

RUTHENIUM COMPLEX, METHOD FOR PRODUCING SAME, AND METHOD FOR PRODUCING RUTHENIUM-CONTAINING THIN FILM

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PCT Information

Number	Date	Country	Kind
2012-268396	Dec 2012	JP	national
2013-133480	Jun 2013	JP	national
2013-156294	Jul 2013	JP	national