JP6249733B2 - Ruthenium complex and production method thereof, ruthenium-containing thin film and production method thereof - Google Patents

Description

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

  Ruthenium has features such as high conductivity, the ability to form a conductive oxide, high work function, excellent etching characteristics, and excellent lattice matching with copper. It attracts attention as a material for memory electrodes such as DRAM, gate electrodes, copper wiring seed layers / adhesion layers, and the like. In the next generation semiconductor device, a highly minute and highly three-dimensional design is adopted for the purpose of further improving the storage capacity and responsiveness. Therefore, in order to use ruthenium as a material constituting the next-generation semiconductor device, it is necessary to establish a technique for uniformly forming a ruthenium-containing thin film having a thickness of several nanometers to several tens of nanometers on a three-dimensional substrate. is necessary. Technologies for producing metal thin films on three-dimensional substrates include the use of vapor deposition methods based on chemical reactions, such as atomic layer deposition (ALD) and chemical vapor deposition (CVD). It is regarded as promising. When ruthenium is used as a next generation DRAM lower electrode or copper wiring seed layer / adhesion layer, titanium nitride, tantalum nitride, or the like is expected to be used as a barrier metal for the underlayer. When barrier metal is oxidized when ruthenium-containing thin films are produced, problems such as deterioration in barrier performance, poor conduction with transistors due to increased resistance, and reduced responsiveness due to increased capacitance between wires Occurs. In order to avoid these problems, a material that can produce a ruthenium-containing thin film even under conditions in which an oxidizing gas such as oxygen or ozone is not used is required.

Non-Patent Document 1 and Non-Patent Document 2 include (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) as a compound having a structure similar to the ruthenium complex (1a) of the present invention. η ⁵ -1,2,3,4,5-pentamethylcyclopentadienyl) ruthenium and (η ⁵ -2,4-di-tert-butyl-1-oxa-2,4-pentadienyl) (η ⁵ − 1,2,3,4,5-pentamethylcyclopentadienyl) ruthenium is described. However, what is described in the literature is limited to complexes with η ⁵ -1,2,3,4,5- pentamethylcyclopentadienyl ligand. The method of synthesis described in the literature, chloro (η ⁵ -1,2,3,4,5- pentamethylcyclopentadienyl) reaction of the ruthenium and lithium Enola DOO, and chloro (eta ⁵ -1, 2 , 3,4,5-pentamethylcyclopentadienyl) ruthenium, an enone derivative and potassium carbonate, and is different from the production method of the present invention. Furthermore, the document does not describe any use of these complexes as materials for producing ruthenium-containing thin films.

Cationic ruthenium complex [(η ⁵ -cyclopentadienyl) tris (nitrile) ruthenium] ⁺ is useful as a raw material for synthesizing various ruthenium complexes including various ruthenium complexes of the present invention. Non-Patent Document 3 discloses that [Ru (η ⁵ -C ₅ H ₅ ) (η ⁶ -C ₆ H ₆ )] [PF ₆ ] is irradiated with light in acetonitrile to produce [Ru (η ⁵ -C ₅ H _5). ) (MeCN) ₃ ] [PF ₆ ] is described. In Non-Patent Document 4, ruthenocene is reacted with aluminum chloride, aluminum, titanium chloride, naphthalene and potassium borofluoride to prepare an η ⁶ -naphthalene complex, and further reacted with acetonitrile to react with [Ru (η ⁵ -C ₅ H ₅ ) (MeCN) ₃ ] [PF ₆ ] is described.

  However, the method for synthesizing the cationic tris (nitrile) complex described in Non-Patent Document 3 and Non-Patent Document 4 requires a facility for irradiating powerful ultraviolet rays, and uses expensive raw materials and a large amount of reactants. Therefore, it is difficult to say that it is a practical manufacturing method with excellent cost merit.

Non-patent document 5 describes [(η ⁵ -methylcyclopentadienyl) tris (acetonitrile) ruthenium] ⁺ as a cationic tris (nitrile) ruthenium complex having a monosubstituted cyclopentadienyl ligand. In addition, as a cationic ruthenium complex having a pentasubstituted cyclopentadienyl ligand, [(η ⁵ -1,2,3,4,5-pentamethylcyclopentadienyl) tris (acetonitrile) ruthenium] ⁺ is non- It is described in Patent Document 6. However, there is no report of a cationic tris (nitrile) ruthenium complex having a monosubstituted cyclopentadienyl ligand having an alkyl group having 2 to 6 carbon atoms.

Organometallics, Volume 11, page 1686 (1992).

Organometallics, Vol. 21, page 592 (2002). Organometallics, 21, 21544 (2002).

Advanced Synthesis & Catalysis, 346, 901 (2004).

Dalton Transactions, 449 pages (2003).

Inorganic Chemistry, 25, 3501 (1986).

  The present invention relates to a production method capable of producing a ruthenium-containing thin film under non-oxidizing gas conditions in addition to oxidizing gas conditions, a ruthenium complex useful as a material for the production method, and a method for producing the ruthenium complex It is an issue to provide. Further, the cationic tris (nitrile) complex represented by the general formula (2) is useful as a raw material for the synthesis of the ruthenium complex represented by the general formulas (1) and (1a).

As a result of intensive studies to solve the above problems, the present inventors have found that the ruthenium complexes represented by the general formulas (1) and (1a) contain ruthenium even under non-oxidizing gas conditions in addition to oxidizing gas conditions. A cationic tris (nitrile) complex represented by the general formula (2), which is useful as a material for producing a thin film and is useful as a raw material for the synthesis of ruthenium complexes (1) and (1a), is converted into a ruthenocene derivative. It has been found that a good yield can be produced by reacting nitrile with a protonic acid, and the present invention has been completed.
That is, the present invention relates to the general formula (1a)

(In formula, R ^<1a> , R ^<2a> , R ^<3a> , R ^<4a> and R ^<5a> respectively independently represent a hydrogen atom or a C1-C6 alkyl group. However, R ^<1a> , R ^<2a> , R ^<3a> , R ^<4a> and Except for the case where all R ^5a are simultaneously methyl groups, R ^6a and R ^7a each independently represents an alkyl group having 1 to 6 carbon atoms. The present invention also provides
General formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ²¹ represents an alkyl group having 1 to 4 carbon atoms. Z ⁻ represents a counter anion) and a tris (nitrile) complex represented by the general formula (3)

(Wherein R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms), and the enone derivative represented by the general formula (1) is reacted in the presence of a base.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). It relates to a manufacturing method. Furthermore, the present invention provides
General formula (2b)

(Wherein R ^1b represents an alkyl group having 2 to 6 carbon atoms, R ^21b represents an alkyl group having 1 to 4 carbon atoms, and Zb ⁻ represents a counter anion). Concerning the complex. Furthermore, the present invention provides
General formula (4)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents the general formula (5).

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above) η ^5- (unsubstituted or substituted) cyclopentadienyl ligand, or η ⁵ -2,4-dimethyl-2,4-pentadienyl ligand is represented. ), A nitrile represented by the general formula R ²¹ CN (R ²¹ is as defined above), a general formula H ⁺ Z ⁻ , wherein Z ⁻ is as defined above. .), Which is reacted with a protonic acid represented by the general formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ²¹ and Z ⁻ represent the same meaning as described above). Furthermore, the present invention relates to a general formula (4)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents the general formula (5).

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above) η ^5- (unsubstituted or substituted) cyclopentadienyl ligand, or η ⁵ -2,4-dimethyl-2,4-pentadienyl ligand is represented. ) And ruthenocene derivative represented by a nitrile of the formula ^{R 21} CN ^(R 21 represents the same meanings as defined above), the general formula ^H + Z ^-. (Wherein, Z ^- in represents a counter anion) By reacting with the indicated protonic acid, general formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^21, and Z ⁻ represent the same meaning as described above), a cationic tris (nitrile) complex represented by Tris (nitrile) complex and general formula (3)

(Wherein R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms), and the enone derivative represented by the general formula (1) is reacted in the presence of a base. The present invention relates to a method for producing the indicated ruthenium complex. Furthermore, the present invention relates to a method for producing a ruthenium-containing thin film characterized by using a ruthenium complex represented by the general formula (1) as a material. Furthermore, the present invention relates to a ruthenium-containing thin film produced using a ruthenium complex represented by the general formula (1) as a material. Furthermore, the present invention relates to a semiconductor device characterized in that a ruthenium-containing thin film produced using a ruthenium complex represented by the general formula (1) as a material is used for an electrode portion and / or a wiring portion.

Hereinafter, the present invention will be described in more detail. The ruthenium complex represented by the general formula (1a) corresponds to a subordinate concept of the ruthenium complex represented by the general formula (1). The ruthenium complex represented by the general formula (1a) does not include the case where R ^1a , R ^2a , R ^3a , R ^4a and R ^5a are all methyl groups at the same time. On the other hand, the ruthenium complex represented by the general formula (1) includes a case where R ¹ , R ² , R ³ , R ⁴ and R ⁵ are all methyl groups at the same time.

Next, the definitions of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a and R ^7a in general formula (1a) will be described. The alkyl group having 1 to 6 carbon atoms represented by R ^1a , R ^2a , R ^3a , R ^4a and R ^5a may be linear, branched or cyclic, and specifically includes a methyl group, ethyl Group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, cyclobutylmethyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1, 2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3 Dimethylbutyl group, cyclohexyl group, cyclopentylmethyl group, a 1-cyclobutylethyl group, a 2-cyclobutylethyl group of can be exemplified. R ^1a is an alkyl group having 1 to 6 carbon atoms in that the ruthenium complex (1a) of the present invention has vapor pressure and thermal stability suitable as a CVD material or an ALD material, and R ^2a , R ^3a , R ^4a And R ^5a is preferably a hydrogen atom, R ^1a is a methyl group or an ethyl group, and R ^2a , R ^3a , R ^4a and R ^5a are more preferably a hydrogen atom.

The alkyl group having 1 to 6 carbon atoms represented by R ^6a and R ^7a may be linear, branched or cyclic, and specifically includes methyl, ethyl, propyl, isopropyl, cyclo Propyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclo Butylmethyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3 -Dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexane Sill group, cyclopentylmethyl group, a 1-cyclobutylethyl group, a 2-cyclobutylethyl group of can be exemplified. R ^6a and R ^7a are preferably methyl groups in that the ruthenium complex (1a) of the present invention has vapor pressure and thermal stability suitable for CVD materials and ALD materials.

Specific examples of the ruthenium complex (1a) of the present invention are shown in Tables 1-1 to 1-6. ^{Incidentally, Me, Et, Pr, i} Pr, Bu, i Bu, s Bu, t Bu, Pe, c Pe and Hx are each a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec -A butyl group, a tert-butyl group, a pentyl group, a cyclopentyl group and a hexyl group are shown.

Among the examples listed in Tables 1-1 to 1-6, (η ⁵ -cyclopentadienyl) (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) ruthenium (1a-1) , (Η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ⁵ -methylcyclopentadienyl) ruthenium (1a-2), (η ⁵ -2,4-dimethyl-1- Oxa-2,4-pentadienyl) (η ⁵ -ethylcyclopentadienyl) ruthenium (1a-3), (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ⁵ -propyl Cyclopentadienyl) ruthenium (1a-4), (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ⁵ -isopropylcyclopentadienyl) ruthenium (1a-5), ( η ⁵ - , 4-dimethyl-1-oxa-2,4-pentadienyl) (eta ⁵ - butylcyclopentadienyl) ruthenium (1a-6), (η 5 -2,4- dimethyl-1-oxa-2,4 Pentadienyl) (η ⁵ -isobutylcyclopentadienyl) ruthenium (1a-7), (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ^5- (sec-butyl) cyclopenta Dienyl) ruthenium (1a-8), (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ^5- (tert-butyl) cyclopentadienyl) ruthenium (1a-9) , (eta ^{5-2,4-dimethyl-1-oxa-2,4-pentadienyl)} (eta ⁵ - pentyl cyclopentadienyl) ruthenium (1a-10), (η 5 - ( cyclopentyl Cyclopentadienyl) (eta ^{5-2,4-dimethyl-1-oxa-2,4-pentadienyl)} ruthenium (1a-11) and (eta ^{5-2,4-dimethyl-1-oxa-2,4} Pentadienyl) (η ⁵ -hexylcyclopentadienyl) ruthenium (1a-12) is preferred, and 1a-2 and 1a-3 are more preferred.

  Next, the manufacturing method of the ruthenium complex (1a) of this invention is demonstrated. The ruthenium complex (1a) can be produced according to the following production method 1 of the ruthenium complex (1). Production method 1 is a method for producing ruthenium complex (1) by reacting cationic tris (nitrile) complex (2) with enone derivative (3) in the presence of a base.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ²¹ and Z ⁻ are as defined above.)
Next, definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 in} the general formula (1) will be described. The alkyl group having 1 to 6 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be linear, branched or cyclic, and specifically includes a methyl group, ethyl Group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, cyclobutylmethyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1, 2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethyl Butyl group, a cyclohexyl group, cyclopentylmethyl group, a 1-cyclobutylethyl group, 2-cyclobutyl ethyl group etc. can be exemplified. In terms of good yield, R ¹ is preferably an alkyl group having 1 to 6 carbon atoms, R ² , R ³ , R ⁴ and R ⁵ are preferably hydrogen atoms, and R ¹ is a methyl group or an ethyl group. More preferably, R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms.

The alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ⁷ may be linear, branched or cyclic, and specifically includes methyl, ethyl, propyl, isopropyl, cyclo Propyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclo Butylmethyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3 -Dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl Group, cyclopentylmethyl group, a 1-cyclobutylethyl group, 2-cyclobutyl ethyl group etc. can be exemplified. R ⁶ and R ⁷ are preferably methyl groups from the viewpoint of good yield.

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

  Among the examples listed 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 1-12 are preferable in terms of vapor pressure and thermal stability suitable as a CVD material or an ALD material, and 1a-2 and 1a-3 are more preferable.

The alkyl group having 1 to 4 carbon atoms represented by R ²¹ in the cationic tris (nitrile) complex (2) may be linear, branched or cyclic, and specifically, a methyl group or an ethyl group. Propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group and the like. From the viewpoint of good yield of the ruthenium complex (1), R ²¹ is preferably a methyl group.

As a specific example of the cation moiety of the cationic tris (nitrile) complex (2), [tris (acetonitrile) (η ⁵ -cyclopentadienyl) ruthenium (II)] ([Ru (η ⁵ -C ₅ H ₅ ) _(MeCN) 3]), [tris (acetonitrile) (eta ⁵ - cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 MeH 4) (MeCN) 3]), [ tris (acetonitrile ) (Η ⁵ -ethylcyclopentadienyl) ruthenium (II)] ([Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ]), [Tris (acetonitrile) (η ⁵ -propylcyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 PrH 4) (MeCN) 3]), [ tris (acetonitrile) (eta ⁵ - isopropylcyclopentadienyl Bae Tajieniru) ruthenium (II)] ([Ru ( η 5 -C 5 i PrH 4) (MeCN) 3]), [ tris (acetonitrile) (eta ⁵ - butylcyclopentadienyl) ruthenium (II)] ([Ru _{^{(η 5 -C 5 BuH 4)}} (MeCN) 3]), [ tris (acetonitrile) (eta ⁵ - isobutyl cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 i BuH 4) ( _MeCN) 3]), [tris (acetonitrile) (eta ⁵ - (sec-butyl) cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 s BuH 4) (MeCN) 3]), [Tris (acetonitrile) (η ^5- (tert-butyl) cyclopentadienyl) ruthenium (II)] ([Ru (η ⁵ -C ₅ ^t BuH ₄ ) (MeCN ) _3]), [tris (acetonitrile) (eta ⁵ - pentyl cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 PeH 4) (MeCN) 3]), [ tris (acetonitrile) ( η ^5- (cyclopentyl) cyclopentadienyl) ruthenium (II)] ([Ru (η ⁵ -C ₅ ^c PeH ₄ ) (MeCN) ₃ ]), [tris (acetonitrile) (η ⁵ -hexylcyclopentadienyl ) ruthenium (II)] ([Ru ( η 5 -C 5 HxH 4) (MeCN) 3]), [ tris (acetonitrile) (η ⁵ -1,2,3,4,5- pentamethylcyclopentadienyl ) ruthenium (II)] ([Ru ( η 5 -C 5 Me 5) (MeCN) 3]), [(η 5 - cyclopentadienyl) tris (propionitrile) ruthenate Um (II)] ([Ru ( η 5 -C 5 H 5) (EtCN) 3]), [(η 5 - cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η ⁵ -C ₅ MeH ₄ ) (EtCN) ₃ ]), [(η ⁵ -ethylcyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru (η ⁵ -C ₅ EtH ₄ ) ( _EtCN) 3]), [tris (propionitrile) (eta ⁵ - propyl cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 PrH 4) (EtCN) 3]), [(η ⁵ -Isopropylcyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru (η ⁵ -C ₅ ⁱ PrH ₄ ) (EtCN) ₃ ]), [(η ⁵ -butylcyclopentadiene Nyl) tris (propionitrile) ruthenium (II)] ([Ru (η ⁵ -C ₅ BuH ₄ ) (EtCN) ₃ ]), [(η ⁵ -isobutylcyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η 5 -C 5 i BuH 4) (EtCN) 3]), [(η 5 - (sec- butyl) cyclopentadienyl) tris (propionitrile) ruthenium (II)] _{^{([Ru (η 5 -C 5}} s BuH 4) (EtCN) 3]), [(η 5 - (tert- butyl) cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( _{^{η 5 -C 5 t BuH 4)}} (EtCN) 3]), [(η 5 - pentyl cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η 5 - _{5 PeH 4) (EtCN) 3} ]), [(η 5 - ( cyclopentyl) cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η 5 -C 5 c PeH 4) (EtCN _{) 3]), [(η} 5 - hexyl cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η 5 -C 5 HxH 4) (EtCN) 3]), [(η 5 - cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 H 5) (t BuCN) 3]), [(η 5 - cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 MeH 4) (t BuCN) 3]), [(η 5 - ethyl cyclopentadienyl) tris (pivalonitrile) Ruthenium (II)] ([Ru (η ⁵ -C ₅ EtH ₄ ) ( ^t BuCN) ₃ ]), [Tris (pivalonitrile) (η ⁵ -propylcyclopentadienyl) ruthenium (II)] ([Ru (η _{^{5 -C 5 PrH 4) (t}} BuCN) 3]), [(η 5 - isopropyl-cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 i PrH 4) (t _{BuCN) 3]), [(} η 5 - butylcyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 BuH 4) (t BuCN) 3]), [(η 5 - isobutyl cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 i BuH 4) (t BuCN) 3]), [(η 5 - (sec-butyl) cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 s BuH 4) (t BuCN) 3]), [(η 5 - (tert- butyl ) cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 t BuH 4) (t BuCN) 3]), [(η 5 - pentyl cyclopentadienyl) tris (pivalonitrile ) Ruthenium (II)] ([Ru (η ⁵ -C ₅ PeH ₄ ) ( ^t BuCN) ₃ ]), [(η ^5- (cyclopentyl) cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([ _{^{ru (η 5 -C 5 c PeH}} 4) (t BuCN) 3]), [(η 5 - hexyl cyclopentadienyl) tris (pivalonitrile) Ruthenium (II)] ([Ru ( η 5 -C 5 HxH 4) (t BuCN) 3]) can be exemplified a.

Examples of the counter anion Z ⁻ in the general formula (2) include those generally used as the counter anion of the cationic metal complex. Specifically, fluoro such as tetrafluoroborate ion (BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), tetrafluoroaluminate ion (AlF ₄ ⁻ ) and the like. Complex anions, trifluoromethanesulfonate ions (CF ₃ SO ₃ ⁻ ), methanesulfonate ions (MeSO ₃ ⁻ ), monosulfate ions such as methyl sulfate ions (MeSO ₄ ⁻ ), nitrate ions (NO ₃ ⁻ ), Counter anion of monobasic acid such as perchlorate ion (ClO ₄ ⁻ ), tetrachloroaluminate ion (AlCl ₄ ⁻ ), bis (trifluoromethanesulfonyl) amide ion ((CF ₃ SO ₂ ) ₂ N ⁻ ), sulfuric acid Ions (SO ₄ ²⁻ ), hydrogen sulfate ions (HSO ₄ ⁻ ), phosphate ions (P O ₄ ³⁻ ), monohydrogen phosphate ion (HPO ₄ ²⁻ ), dihydrogen phosphate ion (H ₂ PO ₄ ⁻ ), dimethyl phosphate ion ((MeO) ₂ PO ₄ ⁻ ), diethyl phosphate ion ( A counter anion of a polybasic acid such as (EtO) ₂ PO ₄ ⁻ ) or a derivative thereof can be exemplified. In terms of a good yield of ruthenium complex (1), the counter anion Z ^- The _BF ⁴ -, PF ₆ ^- fluoro complex anion such ^{_{as, CF 3 SO 3 -, MeSO}} 3 - is a monovalent acid ions such as preferred .

As a more preferable example of the specific cationic tris (nitrile) complex (2), [tris (acetonitrile) (η ⁵ -cyclopentadienyl) ruthenium (II)] [tetrafluoroborato] ([Ru (η ^5- C ₅ H ₅ ) (MeCN) ₃ ] [BF ₄ ]), [Tris (acetonitrile) (η ⁵ -methylcyclopentadienyl) ruthenium (II)] [tetrafluoroborato] ([Ru (η ⁵ _{-C 5 MeH 4) (MeCN)} 3] [BF 4]), [ tris (acetonitrile) (eta ⁵ - ethyl cyclopentadienyl) ruthenium (II)] [tetrafluoro Bora preparative] ([Ru (η ⁵ - _{C 5 EtH 4) (MeCN)} 3] [BF 4]), [ tris (acetonitrile) (η ⁵ -1,2,3,4,5- pentamethylcyclopentadienyl ) Ruthenium (II)] [tetrafluoro Bora ^{preparative] ([Ru (η 5 -C} 5 Me 5) (MeCN) 3] [BF 4]), [ tris (acetonitrile) (eta ⁵ - cyclopentadienyl) ruthenium (II)] [Hexafluorophosphato] ([Ru (η ⁵ -C ₅ H ₅ ) (MeCN) ₃ ] [PF ₆ ]), [Tris (acetonitrile) (η ⁵ -methylcyclopentadienyl) ruthenium ( II)] [hexafluorophosphato] ([Ru (η ⁵ -C ₅ MeH ₄ ) (MeCN) ₃ ] [PF ₆ ]), [Tris (acetonitrile) (η ⁵ -ethylcyclopentadienyl) ruthenium (II )] [Hexafluorophosphato] ([Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [PF ₆ ]), [Tris (acetonitrile) (η ⁵ -1 , 2,3,4,5-pentamethylcyclopentadienyl) ruthenium (II)] [hexafluorophosphato] ([Ru (η ⁵ -C ₅ Me ₅ ) (MeCN) ₃ ] [PF ₆ ]), [Tris (acetonitrile) (η ⁵ -cyclopentadienyl) ruthenium (II)] [trifluoromethanesulfonate] ([Ru (η ⁵ -C ₅ H ₅ ) (MeCN) ₃ ] [CF ₃ SO ₃ ]), [Tris (acetonitrile) (η ⁵ -methylcyclopentadienyl) ruthenium (II)] [trifluoromethanesulfonate] ([Ru (η ⁵ -C ₅ MeH ₄ ) (MeCN) ₃ ] [CF ₃ SO ₃ ]) , [Tris (acetonitrile) (η ⁵ -ethylcyclopentadienyl) ruthenium (II)] [trifluoromethanesulfonate] ([Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [CF ₃ SO ₃ ]), [Tris (acetonitrile) (η ⁵ -1,2,3,4,5-pentamethylcyclopentadienyl) ruthenium (II)] [trifluoromethane ^{sulfonato] ([Ru (η 5 -C} 5 Me 5) (MeCN) 3] [CF 3 SO 3]), [ tris (acetonitrile) (eta ⁵ - cyclopentadienyl) ruthenium (II)] [methanesulfonate Nato] ([Ru (η ⁵ -C ₅ H ₅ ) (MeCN) ₃ ] [MeSO ₃ ]), [Tris (acetonitrile) (η ⁵ -methylcyclopentadienyl) ruthenium (II)] [methanesulfonate] _{^{([Ru (η 5 -C 5}} MeH 4) (MeCN) 3] [MeSO 3]), [ tris (acetonitrile) (eta ⁵ - ethyl cyclopentadienyl) ruthenate Um (II)] [methane ^{sulfonato] ([Ru (η 5 -C} 5 EtH 4) (MeCN) 3] [MeSO 3]), [ tris (acetonitrile) (η ⁵ -1,2,3,4, 5-pentamethylcyclopentadienyl) ruthenium (II)] [methanesulfonate] ([Ru (η ⁵ -C ₅ Me ₅ ) (MeCN) ₃ ] [MeSO ₃ ]) and the like.

The alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ⁷ in the general formula (3) may be linear, branched or cyclic, and specifically includes a methyl group, an ethyl group, and a propyl group. Group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group Group, cyclopentyl group, cyclobutylmethyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethyl group Butyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group Group, cyclohexyl group, cyclopentylmethyl group, a 1-cyclobutylethyl group, a 2-cyclobutylethyl group of can be exemplified.

  Specific examples of the enone derivative (3) include 4-methylpent-3-en-2-one (mesityl oxide), 5-methylhex-4-en-3-one, 2-methylhept-2-ene-4- ON, 2,5-dimethylhex-4-en-3-one, 2-methyloct-2-en-4-one, 2,6-dimethylhept-2-en-4-one, 2,5-dimethylhepta -2-ene-4-one, 2,2,5-trimethylhex-4-en-3-one, 2-methylnon-2-en-4-one, 2,5,5-trimethylhept-2-ene -4-one, 2-methyldec-2-en-4-one, 1-cyclohexyl-3-methylbut-2-en-1-one, 4-methylhex-3-en-2-one, 4-methylhepta-3 -En-2-one, 4,5-dimethylhexa 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-ene- 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, 3,3,6,7,7-pentamethylnon-5-en-4-one, and the like. Mesityl oxide or 2,2,5,6,6-pentamethylhept-4-en-3-one is preferable, and mesityl oxide is more preferable in terms of good yield of the ruthenium complex (1).

  Examples of the base that can be used in Production Method 1 include inorganic bases and organic bases. Examples of the inorganic base include alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; magnesium carbonate, calcium carbonate and strontium carbonate. Group 2 metal carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and other typical metal hydroxides, lithium hydride, sodium hydride, potassium hydride, Typical metal hydrides such as magnesium hydride, calcium hydride and aluminum hydride, typical metal hydride complex compounds such as sodium borohydride and lithium aluminum hydride, alkali metals such as lithium amide, sodium amide and lithium dialkylamide It can be exemplified such as bromide. Examples of the organic base include alkylamines such as diethylamine, triethylamine, diethylisopropylamine and tributylamine, cyclic amines such as pyrrolidine, piperidine, piperazine and 1,4-diazabicyclooctane, and pyridine. In terms of good yield of the ruthenium complex (1), the base is preferably an alkali metal carbonate or alkylamine, more preferably lithium carbonate, sodium carbonate, potassium carbonate or triethylamine, and particularly preferably lithium carbonate or triethylamine.

  The production method 1 is preferably carried out in an inert gas in that the yield of the ruthenium complex (1) is good. Specific examples of the inert gas include helium, neon, argon, krypton, xenon and nitrogen gas, and argon or nitrogen gas is more preferable.

  It is preferable to implement the manufacturing method 1 in an organic solvent at the point with the sufficient yield of a ruthenium complex (1). When the production method 1 is carried out in an organic solvent, specific examples of the organic solvent include pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether and other aliphatic hydrocarbons, diethyl ether, diisopropyl Ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane and other ethers, acetone, methyl ethyl ketone, 3-pentanone, cyclopentanone, cyclohexanone and other ketones, methanol, ethanol, propanol, Examples include alcohols such as isopropanol, tert-butanol, and ethylene glycol. One of these organic solvents can be used alone, or a plurality of them can be mixed at an arbitrary ratio. As the organic solvent, diethyl ether, tetrahydrofuran, acetone, methanol and hexane are preferable because the yield of the ruthenium complex (1) is good.

  Next, a method for obtaining the cationic tris (nitrile) complex (2) and the enone derivative (3) will be described. Examples of the method for obtaining the cationic tris (nitrile) complex (2) include the production method described in Non-Patent Document 3 or Non-Patent Document 4 in addition to the production method 2 of the present invention described later. As a method for obtaining the enone derivative (3), in addition to obtaining a commercially available product, the production method described in Journal of Organometallic Chemistry, Vol. 402, page 17 (1991) and Japanese Patent No. 3649441 can be exemplified. .

  Next, the molar ratio of the cationic tris (nitrile) complex (2), the enone derivative (3) and the base when the production method 1 is carried out will be described. Preferably, the ruthenium complex (1) can be produced with good yield by using equimolar or more of the enone derivative (3) and the base with respect to 1 mol of the cationic tris (nitrile) complex (2).

  Moreover, in the manufacturing method 1, there is no restriction | limiting in particular in reaction temperature and reaction time, The general conditions when a person skilled in the art manufactures a metal complex can be used. As a specific example, the ruthenium complex (1) is produced in a high yield by selecting a reaction time appropriately selected from a range of 10 minutes to 120 hours at a reaction temperature appropriately selected from a temperature range of −80 ° C. to 120 ° C. I can do it.

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

Next, the cationic tris (nitrile) complex (2b) of the present invention will be described. The alkyl group having 2 to 6 carbon atoms represented by R ^1b in the general formula (2b) may be linear, branched or cyclic, and specifically, an ethyl group, a propyl group, an isopropyl group, a cyclo Propyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclo Butylmethyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3 -Dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexane Examples include xyl group, cyclopentylmethyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group and the like. R ^1b is preferably an alkyl group having 2 to 4 carbon atoms in terms of being a raw material for the synthesis of a ruthenium complex (1) having particularly suitable vapor pressure and thermal stability as a CVD material or an ALD material. More preferably it is.

The alkyl group having 1 to 4 carbon atoms represented by R ^21b in the general formula (2b) may be linear, branched or cyclic, and specifically includes a methyl group, an ethyl group, a propyl group, and isopropyl. Examples thereof include a group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclobutyl group. R ²¹ is preferably a methyl group in terms of good yield when used as a raw material for synthesis of the ruthenium complex (1).

Specific examples of the cationic portion of the cationic tris (nitrile) complex (2b), [tris (acetonitrile) (eta ⁵ - ethyl cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 EtH 4 ) _(MeCN) 3]), [tris (acetonitrile) (eta ⁵ - propyl cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 PrH 4) (MeCN) 3]), [ tris ( Acetonitrile) (η ⁵ -Isopropylcyclopentadienyl) ruthenium (II)] ([Ru (η ⁵ -C ₅ ⁱ PrH ₄ ) (MeCN) ₃ ]), [Tris (acetonitrile) (η ⁵ -butylcyclopentadiene) Enyl) ruthenium (II)] ([Ru (η ⁵ -C ₅ BuH ₄ ) (MeCN) ₃ ]), [Tris (acetonitrile) (η ⁵ − Isobutyl cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 i BuH 4) (MeCN) 3]), [ tris (acetonitrile) (eta ⁵ - (sec-butyl) cyclopentadienyl) Ruthenium (II)] ([Ru (η ⁵ -C ₅ ^s BuH ₄ ) (MeCN) ₃ ]), [Tris (acetonitrile) (η ^5- (tert-butyl) cyclopentadienyl) ruthenium (II)] ( _{^{[Ru (η 5 -C 5 t}} BuH 4) (MeCN) 3]), [ tris (acetonitrile) (eta ⁵ - pentyl cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 PeH 4 ) _(MeCN) 3]), [tris (acetonitrile) (eta ⁵ - (cyclopentyl) cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 - _{^{5 c PeH 4) (MeCN)}} 3]), [ tris (acetonitrile) (eta ⁵ - hexyl cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 HxH 4) (MeCN) 3]) , [(Η ⁵ -ethylcyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru (η ⁵ -C ₅ EtH ₄ ) (EtCN) ₃ ]), [Tris (propionitrile) ( eta ⁵ - propyl cyclopentadienyl) ruthenium (II)] ([Ru ( η 5 -C 5 PrH 4) (EtCN) 3]), [(η 5 - isopropyl-cyclopentadienyl) tris (propionitrile) Ruthenium (II)] ([Ru (η ⁵ -C ₅ ⁱ PrH ₄ ) (EtCN) ₃ ]), [(η ⁵ -butylcyclopentadienyl) tris (propionite Ryl) ruthenium (II)] ([Ru (η ⁵ -C ₅ BuH ₄ ) (EtCN) ₃ ]), [(η ⁵ -isobutylcyclopentadienyl) tris (propionitrile) ruthenium (II)] ([ _{^{Ru (η 5 -C 5 i BuH}} 4) (EtCN) 3]), [(η 5 - (sec- butyl) cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η 5 _{^{-C 5 s BuH 4) (EtCN}} ) 3]), [(η 5 - (tert- butyl) cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η 5 -C 5 t _{BuH 4) (EtCN) 3]} ), [(η 5 - pentyl cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η 5 -C 5 PeH 4) (EtCN _{) 3]), [(η} 5 - ( cyclopentyl) cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η 5 -C 5 c PeH 4) (EtCN) 3]), [ (eta ⁵ - hexyl cyclopentadienyl) tris (propionitrile) ruthenium (II)] ([Ru ( η 5 -C 5 HxH 4) (EtCN) 3]), [(η 5 - ethylcyclopentadienyl ) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 EtH 4) (t BuCN) 3]), [ tris (pivalonitrile) (eta ⁵ - propyl cyclopentadienyl) ruthenium (II)] _{^{([Ru (η 5 -C 5}} PrH 4) (t BuCN) 3]), [(η 5 - isopropyl-cyclopentadienyl) tris (pivalonitrile) ruthenium Beam (II)] ([Ru ( η 5 -C 5 i PrH 4) (t BuCN) 3]), [(η 5 - butylcyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( _{^{η 5 -C 5 BuH 4) (}} t BuCN) 3]), [(η 5 - isobutyl cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 i BuH 4) ( _{^{t BuCN) 3]), [}} (η 5 - (sec- butyl) cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 s BuH 4) (t BuCN) 3] ), [(Η ^5- (tert-butyl) cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru (η ⁵ -C ₅ ^t BuH ₄ ) ( ^t BuCN) ₃ ]), [(Η ⁵ - pentyl cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 PeH 4) (t BuCN) 3]), [(η 5 - ( cyclopentyl ) cyclopentadienyl) tris (pivalonitrile) ruthenium (II)] ([Ru ( η 5 -C 5 c PeH 4) (t BuCN) 3]), [(η 5 - hexyl cyclopentadienyl) tris (pivalonitrile ) ruthenium (II)] ([Ru ( η 5 -C 5 HxH 4) (t BuCN) 3]) can be exemplified _{^{a, [Ru (η 5 -C 5}} EtH 4) (MeCN) 3], _{^{[Ru (η 5 -C 5 PrH}} 4) (MeCN) 3], [Ru (η 5 -C 5 i PrH 4) (MeCN) 3], [Ru (η 5 -C 5 BuH 4) (MeC _{) 3], [Ru (η} 5 -C 5 i BuH 4) (MeCN) 3], [Ru (η 5 -C 5 s BuH 4) (MeCN) 3], [Ru (η 5 -C 5 t BuH ₄ ) (MeCN) ₃ ] and the like are preferred, and [Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] is particularly preferred.

Examples of the counter anion Z ⁻ in the general formula (2b) include those generally used as the counter anion of the cationic metal complex. Specifically, fluoro such as tetrafluoroborate ion (BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), tetrafluoroaluminate ion (AlF ₄ ⁻ ) and the like. Complex anions, trifluoromethanesulfonate ions (CF ₃ SO ₃ ⁻ ), methanesulfonate ions (MeSO ₃ ⁻ ), monosulfate ions such as methyl sulfate ions (MeSO ₄ ⁻ ), nitrate ions (NO ₃ ⁻ ), Counter anion of monobasic acid such as perchlorate ion (ClO ₄ ⁻ ), tetrachloroaluminate ion (AlCl ₄ ⁻ ), bis (trifluoromethanesulfonyl) amide ion ((CF ₃ SO ₂ ) ₂ N ⁻ ), sulfuric acid Ions (SO ₄ ²⁻ ), hydrogen sulfate ions (HSO ₄ ⁻ ), phosphate ions (P O ₄ ³⁻ ), monohydrogen phosphate ion (HPO ₄ ²⁻ ), dihydrogen phosphate ion (H ₂ PO ₄ ⁻ ), dimethyl phosphate ion ((MeO) ₂ PO ₄ ⁻ ), diethyl phosphate ion ( A counter anion of a polybasic acid such as (EtO) ₂ PO ₄ ⁻ ) or a derivative thereof can be exemplified. In terms of a good yield of ruthenium complex (1), the counter anion Z ^- The _BF ⁴ -, PF ₆ ^- fluoro complex anion such ^{_{as, CF 3 SO 3 -, MeSO}} 3 - is a monovalent acid ions such as preferred .

Further, as a preferable example of a specific cationic tris (nitrile) complex (2b), [tris (acetonitrile) (η ⁵ -ethylcyclopentadienyl) ruthenium (II)] [tetrafluoroborato] ([Ru ( _{^{η 5 -C 5 EtH 4) (}} MeCN) 3] [BF 4]), [ tris (acetonitrile) (eta ⁵ - ethyl cyclopentadienyl) ruthenium (II)] [hexafluoro phosphato] ([Ru (eta _{^{5 -C 5 EtH 4) (MeCN}} ) 3] [PF 6]), [ tris (acetonitrile) (eta ⁵ - ethyl cyclopentadienyl) ruthenium (II)] [trifluoromethanesulfonate] ([Ru (eta ⁵ _{-C 5 EtH 4) (MeCN)} 3] [CF 3 SO 3]), [ tris (acetonitrile) (eta ⁵ - propylcyclopentadienyl ) Ruthenium (II)] [tetrafluoro Bora ^{preparative] ([Ru (η 5 -C} 5 PrH 4) (MeCN) 3] [BF 4]), [ tris (acetonitrile) (eta ⁵ - propyl cyclopentadienyl ) Ruthenium (II)] [hexafluorophosphato] ([Ru (η ⁵ -C ₅ PrH ₄ ) (MeCN) ₃ ] [PF ₆ ]), [Tris (acetonitrile) (η ⁵ -propylcyclopentadienyl) Ruthenium (II)] [trifluoromethanesulfonate] ([Ru (η ⁵ -C ₅ PrH ₄ ) (MeCN) ₃ ] [CF ₃ SO ₃ ]), [Tris (acetonitrile) (η ⁵ -isopropylcyclopentadienyl ) ruthenium (II)] [tetrafluoro Bora ^{preparative] ([Ru (η 5 -C} 5 i PrH 4) (MeCN) 3] [BF 4] , [Tris (acetonitrile) (eta ⁵ - isopropyl cyclopentadienyl) ruthenium (II)] [hexafluoro ^{phosphato] ([Ru (η 5 -C} 5 i PrH 4) (MeCN) 3] [PF 6]) , [tris (acetonitrile) (eta ⁵ - isopropyl cyclopentadienyl) ruthenium (II)] ^{[trifluoromethanesulfonate] ([Ru (η 5 -C} 5 i PrH 4) (MeCN) 3] [CF 3 SO 3 ]), [tris (acetonitrile) (eta ⁵ - butylcyclopentadienyl) ruthenium (II)] [tetrafluoro Bora ^{preparative] ([Ru (η 5 -C} 5 BuH 4) (MeCN) 3] [BF 4] ), [tris (acetonitrile) (eta ⁵ - butylcyclopentadienyl) ruthenium (II)] [hexafluoro phosphato _{^{([Ru (η 5 -C 5}} BuH 4) (MeCN) 3] [PF 6]), [ tris (acetonitrile) (eta ⁵ - butylcyclopentadienyl) ruthenium (II)] [trifluoromethanesulfonate ( _{^{[Ru (η 5 -C 5 BuH}} 4) (MeCN) 3] [CF 3 SO 3]), [ tris (acetonitrile) (eta ⁵ - isobutyl cyclopentadienyl) ruthenium (II)] [tetrafluoro Bora preparative] _{^{([Ru (η 5 -C 5}} i BuH 4) (MeCN) 3] [BF 4]), [ tris (acetonitrile) (eta ⁵ - isobutyl cyclopentadienyl) ruthenium (II)] [hexafluoro phosphato] _{^{([Ru (η 5 -C 5}} i BuH 4) (MeCN) 3] [PF 6]), [ tris (acetonitrile) (eta ⁵ - Isobuchirushiku Ropentajieniru) ruthenium (II)] ^{[trifluoromethanesulfonate] ([Ru (η 5 -C} 5 i BuH 4) (MeCN) 3] [CF 3 SO 3]), [ tris (acetonitrile) (eta ⁵ - (sec - butyl) cyclopentadienyl) ruthenium (II)] [tetrafluoro Bora ^{preparative] ([Ru (η 5 -C} 5 s BuH 4) (MeCN) 3] [BF 4]), [ tris (acetonitrile) (eta ^5- (sec-butyl) cyclopentadienyl) ruthenium (II)] [hexafluorophosphato] ([Ru (η ⁵ -C ₅ ^s BuH ₄ ) (MeCN) ₃ ] [PF ₆ ]), [Tris ( acetonitrile) (η ⁵ - (sec- butyl) cyclopentadienyl) ruthenium (II)] [trifluoromethanesulfonate] ([Ru (η ^{5 _{C 5 s BuH 4) (MeCN}} ) 3] [CF 3 SO 3]), [ tris (acetonitrile) (eta ⁵ - (tert-butyl) cyclopentadienyl) ruthenium (II)] [tetrafluoro Bora Doo ( _{^{[Ru (η 5 -C 5 t}} BuH 4) (MeCN) 3] [BF 4]), [ tris (acetonitrile) (eta ⁵ - (tert-butyl) cyclopentadienyl) ruthenium (II)] [hexafluoro ^{phosphato] ([Ru (η 5 -C} 5 t BuH 4) (MeCN) 3] [PF 6]), [ tris (acetonitrile) (eta ⁵ - (tert-butyl) cyclopentadienyl) ruthenium (II) ] ^{[trifluoromethanesulfonate] ([Ru (η 5 -C} 5 t BuH 4) (MeCN) 3] [CF 3 SO 3]) out and the like , [Tris (acetonitrile) (eta ⁵ - ethyl cyclopentadienyl) ruthenium (II)] [tetrafluoro Bora ^{preparative] ([Ru (η 5 -C} 5 EtH 4) (MeCN) 3] [BF 4]), [Tris (acetonitrile) (η ⁵ -ethylcyclopentadienyl) ruthenium (II)] [hexafluorophosphato] ([Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [PF ₆ ]), [ Tris (acetonitrile) (η ⁵ -ethylcyclopentadienyl) ruthenium (II)] [trifluoromethanesulfonate] ([Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [CF ₃ SO ₃ ]), etc. Is more preferable.

Next, the manufacturing method of the cationic tris (nitrile) complex (2b) of this invention is demonstrated. The cationic tris (nitrile) complex (2b) can be produced according to the following production method 2 of the cationic tris (nitrile) complex (2). Production method 2 is a method of producing a cationic tris (nitrile) complex (2) by reacting a ruthenocene derivative (4), a nitrile R ²¹ CN and a protonic acid H ⁺ Z ⁻ .

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X, R ²¹ and Z ⁻ represent the same meaning as described above.)
The alkyl group having 1 to 4 carbon atoms represented by R ²¹ may be linear, branched or cyclic, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, Examples include a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclobutyl group. From the viewpoint of good yield, R ²¹ is preferably a methyl group. More specifically, nitriles include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyclopropanecarbonitrile, pentonitrile, isopentyronitrile, 3-methylbutanenitrile, 2-methylbutanenitrile, pivalonitrile, cyclobutanecarboro. Nitrile and the like can be exemplified, and acetonitrile is preferable in terms of a good yield.
X in the general formula (4) is the general formula (5).

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above) η ^5- (unsubstituted or substituted) cyclopentadienyl ligand, or η ⁵ -2,4-dimethyl-2,4-pentadienyl ligand is represented. Specific examples of the η ^5- (unsubstituted or substituted) cyclopentadienyl ligand include η ⁵ -cyclopentadienyl ligand, η ⁵ -methylcyclopentadienyl ligand, η ^5- Ethylcyclopentadienyl ligand, η ⁵ -propylcyclopentadienyl ligand, η ⁵ -isopropylcyclopentadienyl ligand, η ⁵ -butylcyclopentadienyl ligand, η ⁵ -isobutylcyclo Pentadienyl ligand, η ^5- (sec-butyl) cyclopentadienyl ligand, η ^5- (tert-butyl) cyclopentadienyl ligand, η ⁵ -pentylcyclopentadienyl ligand , η ⁵ - (cyclopentyl) cyclopentadienyl ligand, eta ⁵ - hexyl cyclopentadienyl ligand, eta ^{5-1,2-dimethyl-cyclopentadienyl} ligand, eta ⁵ - , 3-dimethyl-cyclopentadienyl ligand, eta ^5-1,3-di (isopropyl) cyclopentadienyl ligand, eta ^5-1,2,4-tri (isopropyl) cyclopentadienyl coordination And η ⁵ -1,3-di (tert-butyl) cyclopentadienyl ligand, η ⁵ -1,2,3,4,5-pentamethylcyclopentadienyl ligand, and the like. I can do it. Ruthenocene derivative (4) is in terms of easy availability, as the X eta ⁵ - is preferably a (unsubstituted or substituted) cyclopentadienyl ligands, eta ⁵ - cyclopentadienyl ligand, eta ⁵ More preferred are -methylcyclopentadienyl ligand and η ⁵ -ethylcyclopentadienyl ligand.

More specific examples of the ruthenocene derivative (4) include bis (η ⁵ -cyclopentadienyl) ruthenium ((η ⁵ -C ₅ H ₅ ) ₂ Ru), bis (η ⁵ -methylcyclopentadienyl) ruthenium ( _{^{(η 5 -C 5 MeH 4)}} 2 Ru), bis (eta ⁵ - ethyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 EtH 4}} ) 2 Ru), bis (eta ⁵ - propyl cyclopentadienyl) Ruthenium ((η ⁵ -C ₅ PrH ₄ ) ₂ Ru), bis (η ⁵ -isopropylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ ⁱ PrH ₄ ) ₂ Ru), bis (η ⁵ -butylcyclopenta dienyl) ruthenium _{^{((η 5 -C 5 BuH 4}} ) 2 Ru), bis (eta ⁵ - isobutyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 i BuH}} 4) Ru), bis (η ⁵ - (sec- butyl) cyclopentadienyl) ruthenium _{^{((η 5 -C 5 s BuH}} 4) 2 Ru), bis (η ⁵ - (tert- butyl) cyclopentadienyl) ruthenium _{^{((η 5 -C 5 t BuH}} 4) 2 Ru), bis (eta ⁵ - pentyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 PeH 4}} ) 2 Ru), bis (η ⁵ - (cyclopentyl) cyclo pentadienyl) ruthenium _{^{((η 5 -C 5 c PeH}} 4) 2 Ru), bis (eta ⁵ - hexyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 HxH 4}} ) 2 Ru), bis (eta ⁵ 1,2-dimethyl-cyclopentadienyl) ruthenium _{^{((η 5 -C 5 Me 2}} H 3) 2 Ru), bis (eta ^{5-1,3-dimethyl-cyclopentadienyl)} Ruteni Beam _{^{((η 5 -C 5 Me 2}} H 3) 2 Ru), bis (eta ^5-1,3-di (isopropyl) cyclopentadienyl) ruthenium _{^{((η 5 -C 5 (i}} Pr) 2 H 3 ) ₂ Ru), bis (eta ^5-1,2,4-tri (isopropyl) cyclopentadienyl) ruthenium _{^{((η 5 -C 5 (i}} Pr) 3 H 2) 2 Ru), bis (eta ⁵ - 1,3-di (tert-butyl) cyclopentadienyl) ruthenium ((η ⁵ -C ₅ ( ^t Bu) ₂ H ₃ ) ₂ Ru), bis (η ⁵ -1,2,3,4,5- Pentamethylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ Me ₅ ) ₂ Ru), (η ⁵ -cyclopentadienyl) (η ⁵ -1,2,3,4,5-pentamethylcyclopentadiene Enyl) ruthenium ((η ⁵ -C ₅ H ₅ ) (η ⁵ -C _{5 Me 5) Ru), (} η 5 - cyclopentadienyl) (eta ^{5-2,4-dimethyl-2,4-pentadienyl)} ruthenium _{^{(Ru (η 5 -C 5 H}} 5) (η 5 -CH 2 C (Me) CHC (Me) CH ₂ )), (η ⁵ -2,4-dimethyl-2,4-pentadienyl) (η ⁵ -methylcyclopentadienyl) ruthenium (Ru (η ⁵ -C ₅ MeH ₄ ) (Η ⁵ —CH ₂ C (Me) CHC (Me) CH ₂ )), (η ⁵ -2,4-dimethyl-2,4-pentadienyl) (η ⁵ -ethylcyclopentadienyl) ruthenium (Ru ( η ⁵ -C ₅ EtH ₄ ) (η ⁵ -CH ₂ C (Me) CHC (Me) CH ₂ )), (η ⁵ -2,4-dimethyl-2,4-pentadienyl) (η ⁵ -propylcyclopenta dienyl) ruthenium (Ru (η ^{_{-C 5 PrH 4) (η 5}} -CH 2 C (Me) CHC (Me) CH 2)), (η 5 -2,4- dimethyl-2,4-pentadienyl) (eta ⁵ - isopropylcyclopentadienyl ) Ruthenium (Ru (η ⁵ -C ₅ ⁱ PrH ₄ ) (η ⁵ -CH ₂ C (Me) CHC (Me) CH ₂ )), (η ⁵ -2,4-dimethyl-2,4-pentadienyl) ( η ⁵ -butylcyclopentadienyl) ruthenium (Ru (η ⁵ -C ₅ BuH ₄ ) (η ⁵ -CH ₂ C (Me) CHC (Me) CH ₂ )), (η ⁵ -2,4-dimethyl- 2,4-pentadienyl) (eta ⁵ - isobutyl cyclopentadienyl) ruthenium _{^{(Ru (η 5 -C 5 i}} BuH 4) (η 5 -CH 2 C (Me) CHC (Me) CH 2)), (η ^{5-2,4-dimethyl-2,} - pentadienyl) (eta ⁵ - (sec-butyl) cyclopentadienyl) ruthenium _{^{(Ru (η 5 -C 5 s}} BuH 4) (η 5 -CH 2 C (Me) CHC (Me) CH 2)), ( η ⁵ -2,4-dimethyl-2,4-pentadienyl) (η ^5- (tert-butyl) cyclopentadienyl) ruthenium (Ru (η ⁵ -C ₅ ^t BuH ₄ ) (η ⁵ -CH ₂ C ( _{Me) CHC (Me) CH 2} )), (η 5 -2,4- dimethyl-2,4-pentadienyl) (eta ⁵ - pentyl cyclopentadienyl) ruthenium _{^{(Ru (η 5 -C 5 PeH}} 4) ( η ⁵ —CH ₂ C (Me) CHC (Me) CH ₂ )), (η ⁵ -2,4-dimethyl-2,4-pentadienyl) (η ^5- (cyclopentyl) cyclopentadienyl) ruthenium (Ru ( η _{^{5 -C 5 c PeH 4) (}} η 5 -CH 2 C (Me) CHC (Me) CH 2)), (η 5 -2,4- dimethyl-2,4-pentadienyl) (eta ⁵ - hexyl cyclopentanone dienyl) ruthenium _{^{(Ru (η 5 -C 5 HxH}} 4) (η 5 -CH 2 C (Me) CHC (Me) CH 2)), (η 5 -2,4- dimethyl-2,4-pentadienyl) (η ⁵ -1,2,3,4,5- pentamethylcyclopentadienyl) ruthenium _{^{(Ru (η 5 -C 5 Me}} 5) (η 5 -CH 2 C (Me) CHC (Me) CH 2) ) And the like, and bis (η ⁵ -cyclopentadienyl) ruthenium ((η ⁵ -C ₅ H ₅ ) ₂ Ru), bis (η ⁵ -methylcyclopentadienyl) ruthenium ((η ⁵ _{-C 5 MeH 4) 2 Ru)} , bis ( ⁵ - ethyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 EtH 4}} ) 2 Ru), bis (eta ⁵ - propyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 PrH 4}} ) 2 Ru), bis (eta ⁵ - isopropyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 i PrH}} 4) 2 Ru), bis (eta ⁵ - butylcyclopentadienyl) ruthenium _{^{((η 5 -C 5 BuH 4}} ) 2 Ru ), Bis (η ⁵ -isobutylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ ⁱ BuH ₄ ) ₂ Ru), bis (η ^5- (sec-butyl) cyclopentadienyl) ruthenium ((η ⁵ − _{^{C 5 s BuH 4) 2 Ru}} ), bis (η ⁵ - (tert- butyl) cyclopentadienyl) ruthenium _{^{((η 5 -C 5 t BuH}} 4) 2 Ru) Bis (eta ⁵ - pentyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 PeH 4}} ) 2 Ru), bis (η ⁵ - (cyclopentyl) cyclopentadienyl) ruthenium _{^{((η 5 -C 5 c PeH}} 4 ) ₂ Ru), bis (η ⁵ -hexylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ HxH ₄ ) ₂ Ru), bis (η ⁵ -1,2-dimethylcyclopentadienyl) ruthenium ((η ^5- C ₅ Me ₂ H ₃ ) ₂ Ru), bis (η ⁵ -1,3-dimethylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ Me ₂ H ₃ ) ₂ Ru), bis (η ⁵ − 1,3-di (isopropyl) cyclopentadienyl) ruthenium _{^{((η 5 -C 5 (i}} Pr) 2 H 3) 2 Ru), bis (eta ^5-1,2,4-tri (isopropyl) cyclopentyl Tajieniru) ruthenium _{^{((η 5 -C 5 (i}} Pr) 3 H 2) 2 Ru), bis (eta ^5-1,3-di (tert- butyl) cyclopentadienyl) ruthenium ((η _⁵ -C ^{5 _{(t Bu) 2 H 3)}} 2 Ru), bis (η ⁵ -1,2,3,4,5- pentamethylcyclopentadienyl) ruthenium _{^{((η 5 -C 5 Me 5}} ) 2 Ru) , etc. preferably, bis (eta ⁵ - cyclopentadienyl) ruthenium _{^{((η 5 -C 5 H 5}} ) 2 Ru), bis (eta ⁵ - cyclopentadienyl) ruthenium _{^{((η 5 -C 5 MeH 4}} ) 2 Ru), bis (eta ⁵ - ethyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 EtH 4}} ) 2 Ru), bis (eta ⁵ - propyl cyclopentadienyl) ruthenium ((η _⁵ -C ⁵ PrH ₄ ) ₂ R u), bis (η ⁵ -isopropylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ ⁱ PrH ₄ ) ₂
Ru), bis (η ⁵ -butylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ BuH ₄ ) ₂ Ru), bis (η ⁵ -isobutylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ ⁱ BuH) ₄ ) ₂ Ru), bis (η ^5- (sec-butyl) cyclopentadienyl) ruthenium ((η ⁵ -C ₅ ^s BuH ₄ ) ₂ Ru), bis (η ^5- (tert-butyl) cyclopentadi ) ruthenium _{^{((η 5 -C 5 t BuH}} 4) 2 Ru), bis (eta ⁵ - pentyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 PeH 4}} ) 2 Ru), bis (η ⁵ - ( Cyclopentyl) cyclopentadienyl) ruthenium ((η ⁵ -C ₅ ^c PeH ₄ ) ₂ Ru), bis (η ⁵ -hexylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ HxH _{4) 2} Ru) is more preferable, and bis (eta ⁵ - cyclopentadienyl) ruthenium _{^{((η 5 -C 5 H 5}} ) 2 Ru), bis (eta ⁵ - cyclopentadienyl) ruthenium (( _{^{η 5 -C 5 MeH 4) 2}} Ru), bis (eta ⁵ - ethyl cyclopentadienyl) ruthenium _{^{((η 5 -C 5 EtH 4}} ) 2 Ru) is especially preferred.

  As the ruthenocene derivative (4) that can be used as a raw material for the production method 2, a commercially available product can be used as it is, and Organic Synthesis, Vol. 41, page 96 (1961), Japanese Patent Application Laid-Open No. 2003-342286. What was synthesize | combined according to the well-known method as described in gazette, Organometallics, Vol. 5, page 2321 (1986) etc. can also be used.

Examples of Z ⁻ in the protonic acid H ⁺ Z ⁻ that can be used in Production Method 2 include fluoro complex anions such as tetrafluoroborate ion (BF ₄ ⁻ ) and hexafluorophosphate ion (PF ₆ ⁻ ), trifluoro Examples include sulfonate ions such as romethanesulfonate ion (CF ₃ SO ₃ ⁻ ), sulfate ion (SO ₄ ²⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), halide ions such as chloride ion and bromide ion, and the like. Specific examples of the protonic acid include fluorocomplex acids such as tetrafluoroboric acid and hexafluorophosphoric acid; sulfonic acids such as sulfuric acid and trifluoromethanesulfonic acid; and hydrogen halides such as hydrogen chloride. . The protonic acid may form a complex with an ether such as dimethyl ether or diethyl ether. Examples of the protonic acid forming the complex include a tetrafluoroboric acid dimethyl ether complex, a tetrafluoroboric acid diethyl ether complex, and a hexafluorophosphoric acid diethyl ether complex.

  From the viewpoint of a good yield of the cationic tris (nitrile) complex (2), tetrafluoroboric acid diethyl ether complex or trifluoromethanesulfonic acid is preferable.

  Further, as the protonic acid used in Production Method 2, a fluorocomplex acid generated in the reaction system by reacting a fluorocomplex anion-containing salt with a strong acid can also be used. Examples of the fluoro complex anion-containing salt that can be used in this case include ammonium tetrafluoroborate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, hexafluorophosphorus. Examples include lithium acid, sodium hexafluorophosphate, and potassium hexafluorophosphate. Examples of strong acids 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 generated in the reaction system include tetrafluoroboric acid and hexafluorophosphoric acid. It is preferable to use either ammonium tetrafluoroborate, sodium tetrafluoroborate or ammonium hexafluorophosphate mixed with sulfuric acid in terms of high cost merit and good yield.

  Next, the molar ratio of ruthenocene derivative (4), nitrile and protonic acid used in Production Method 2 will be described. From the viewpoint of good yield of the cationic tris (nitrile) complex (2), it is preferable to use 3 moles or more of nitrile per mole of ruthenocene derivative. It is more preferable to use a nitrile having a solvent amount from the viewpoint of good yield. Specifically, it is particularly preferable to use an amount appropriately selected from the range of 5 mol to 1000 mol per mol of ruthenocene derivative. Moreover, the preferable usage-amount of a proton acid changes with kinds of proton acid. For example, when the protonic acid is a monobasic acid, it is preferable to use 1 mol or more of a protonic acid per mole of ruthenocene derivative in terms of a good yield. It is preferable to use the above protonic acid. When a mixture of a fluoro complex anion-containing salt and a strong acid is used as the protonic acid, by appropriately using 1 mol or more of the fluoro complex anion-containing salt and 0.5 mol to 2.0 mol of a strong acid per 1 mol of the ruthenocene derivative, The cationic tris (nitrile) complex (2) can be obtained with good yield.

  The production method 2 is preferably carried out in an inert gas in that the yield of the cationic tris (nitrile) complex (2) is good. Specific examples of the inert gas include helium, neon, argon, krypton, xenon and nitrogen gas, and argon or nitrogen gas is more preferable.

  Production method 2 is preferably carried out under conditions using an excess amount of nitrile as a solvent in terms of good yield of the cationic tris (nitrile) complex (2). Moreover, the manufacturing method 2 can also be implemented in an organic solvent. Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether. , Ethers such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane, ketones such as acetone, methyl ethyl ketone, 3-pentanone, cyclopentanone, cyclohexanone, alcohols such as methanol, ethanol, propanol, isopropanol, tert-butanol, ethylene glycol, etc. Can be illustrated. One of these organic solvents can be used alone, or a plurality of them can be mixed at an arbitrary ratio. As the organic solvent, diethyl ether, tetrahydrofuran, acetone, and methanol are preferable because the yield of the cationic tris (nitrile) complex (2) is good.

  In production method 2, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a metal complex. As a specific example, a cationic tris (nitrile) complex (2) is selected by selecting a reaction time appropriately selected from a range of 10 minutes to 120 hours at a reaction temperature appropriately selected from a temperature range of −80 ° C. to 150 ° C. Can be produced with good yield.

  The cationic tris (nitrile) complex (2) produced by the production method 2 can be purified by a person skilled in the art appropriately selecting and using a general purification method for purifying a metal complex. Specific purification methods include filtration, extraction, centrifugation, decantation, crystallization and the like.

The ruthenium complex (1) can also be produced by continuously carrying out production method 2 and production method 1. In this case, the cationic tris (nitrile) complex (2) produced by the production method 2 can be used as a production raw material for the production method 1 without purification, and is generally used when a person skilled in the art purifies a metal complex. A cationic tris (nitrile) complex (2) purified by appropriately selecting and using a suitable purification method can also be used as a production raw material of 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 carrying out the production method 2 and the production method 1.

  Next, a method for producing a ruthenium-containing thin film characterized by using the ruthenium complex (1) as a material will be described in detail. A method for producing the ruthenium-containing thin film of the present invention is a method in which the ruthenium complex represented by the general formula (1) is vaporized and decomposed on the substrate. The usual technical means used for producing the containing thin film can be mentioned. Specific examples include a vapor deposition method based on a chemical reaction such as a CVD method and an ALD method, and a solution method such as a dip coating method, a spin coating method, and an ink jet method. In the present specification, the vapor deposition method based on chemical reaction includes technical means commonly used by those skilled in the art, such as a CVD method such as a thermal CVD method, a plasma CVD method, and a photo CVD method, and an ALD method. When a ruthenium-containing thin film is produced by a vapor deposition method based on a chemical reaction, a chemical vapor deposition method is preferable because a thin film can be uniformly formed on the surface of a substrate having a three-dimensional structure. Or the ALD method is more preferable. The CVD method is more preferable from the viewpoint of good film forming speed, and the ALD method is more preferable from the viewpoint of good step coverage. For example, when a ruthenium-containing thin film is produced by a CVD method or an ALD method, the ruthenium complex (1) is vaporized and supplied to the reaction chamber, and the ruthenium complex (1) is decomposed on the substrate provided in the reaction chamber, A ruthenium-containing thin film can be formed on the substrate. Examples of the method for decomposing the ruthenium complex (1) include ordinary technical means used by those skilled in the art to produce a metal-containing thin film. Specifically, a method of reacting the ruthenium complex (1) with the reactive gas, a method of applying heat, plasma, light, or the like to the ruthenium complex (1) can be exemplified. A ruthenium-containing thin film can be produced by appropriately selecting and using these decomposition methods. A plurality of decomposition methods can also be used in combination. Examples of the method for supplying the ruthenium complex (1) to the reaction chamber include bubbling and a liquid vaporization supply system, and are not particularly limited.

  As a carrier gas and a dilution gas for producing a ruthenium-containing thin film by a CVD method or an ALD method, a rare gas such as helium, neon, argon, krypton, or xenon or a nitrogen gas is preferable. For economic reasons, nitrogen gas, helium Neon and argon are particularly preferred. The flow rates of the carrier gas and the dilution gas are appropriately adjusted according to the capacity of the reaction chamber. For example, when the capacity of the reaction chamber is 1 to 10 L, the flow rate of the carrier gas is not particularly limited and is preferably 1 to 10,000 sccm for economical reasons. Note that sccm is a unit representing a gas flow rate, and 1 sccm represents that the gas is moving at a rate of 2.68 mmol / h when converted to an ideal gas.

  Examples of the reaction gas for producing a ruthenium-containing thin film by the CVD method or the ALD method include non-oxidizing gases such as ammonia, hydrogen, monosilane, and hydrazine, oxygen, ozone, water vapor, hydrogen peroxide, laughing gas, and hydrogen chloride. And oxidizing gases such as nitric acid gas, formic acid, and acetic acid. Ammonia, hydrogen, oxygen, ozone, and water vapor are preferred because they are less restricted by the specifications of the film forming apparatus and are easy to handle. In the case where a ruthenium-containing thin film is produced under the condition that a non-oxidizing gas is used without using an oxidizing gas as a reaction gas, ammonia is preferable in that the deposition rate of the ruthenium-containing thin film is good. The flow rate of the reaction gas is appropriately adjusted according to the reactivity of the material and the capacity of the reaction chamber. For example, when the reaction chamber has a capacity of 1 to 10 L, the flow rate of the reaction gas is not particularly limited, and is preferably 1 to 10,000 sccm for economical reasons.

  The substrate temperature at the time of producing a ruthenium-containing thin film by the CVD method or the ALD method is appropriately selected depending on the use of heat, plasma, light, etc., the type of reaction gas, and the like. For example, when ammonia is used as a reactive gas without using light or plasma, the substrate temperature is not particularly limited, and is preferably 200 ° C. to 1000 ° C. for economic reasons. 300 to 750 degreeC is preferable at the point with a favorable film-forming rate, and 350 to 700 degreeC is especially preferable. Further, a ruthenium-containing thin film can be produced in a temperature range of 200 ° C. or lower by appropriately using light, plasma, ozone, hydrogen peroxide, or the like.

As the ruthenium-containing thin film obtained by the production method of the present invention, for example, when a ruthenium complex is used alone, a metal ruthenium thin film, a ruthenium oxide thin film, a ruthenium nitride thin film, a ruthenium oxynitride thin film, and the like can be obtained. When used in combination with materials, a ruthenium-containing composite thin film is obtained. For example, when used in combination with a strontium material, a SrRuO ₃ thin film can be obtained. Examples of the strontium material include bis (dipivaloylmethanato) strontium, diethoxystrontium, bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) strontium, and the like. It is done. In the case of producing a ruthenium-containing composite thin film by a CVD method or an ALD method, the ruthenium complex (1) and another metal material may be separately supplied into the reaction chamber or may be supplied after being mixed. .

  The ruthenium complex (1a) can also be a ruthenium-containing thin film in the same manner as the ruthenium complex (1).

  By using the ruthenium-containing thin film of the present invention as a constituent member, a high-performance semiconductor device with improved storage capacity and responsiveness can be manufactured. Examples of semiconductor devices include semiconductor memory devices such as DRAM, FeRAM, and ReRAM, field effect transistors, and the like. Examples of these constituent members include capacitor electrodes, gate electrodes, copper wiring liners, and the like.

  By using the novel ruthenium complex (1a) and ruthenium complex (1) of the present invention as materials, a ruthenium-containing thin film can be produced even under conditions where no oxidizing gas is used. Further, by reacting a ruthenocene derivative, a nitrile, and a protonic acid, a cationic tris (nitrile) complex represented by the general formula (2) that is useful as a raw material for the synthesis of the ruthenium complex (1) can be produced.

It is a figure which shows the CVD apparatus used in Examples 14-37 and Comparative Examples 1-6. 16 is an atomic force microscope (hereinafter, AFM) image of the film obtained in Example 15. FIG. FIG. 10 is a diagram showing an AFM image of the film obtained in Example 27. FIG. 10 is a view showing an AFM image of the film obtained in Example 28. FIG. 10 is a diagram showing an AFM image of the film obtained in Example 29. 6 is a diagram showing an AFM image of the film obtained in Example 31. FIG. FIG. 16 is a diagram showing an AFM image of the film obtained in Example 33. 6 is a view showing a cross-sectional FE-SEM image of the film obtained in Example 39. FIG. 6 is a view showing a cross-sectional FE-SEM image of the film obtained in Example 40. FIG.

Hereinafter, although an example is given and the present invention is explained still in detail, the present invention is not limited to these. Note that Me, Et, and ^t Bu represent a methyl group, an ethyl group, and a tert-butyl group, respectively. ¹ H and ¹³ C NMR spectra were measured using a Varian VXR-500S NMR Spectrometer.

  Example 1

Suspension prepared by mixing 3.15 g (13.6 mmol) of bis (η ⁵ -cyclopentadienyl) ruthenium ((η ⁵ -C ₅ H ₅ ) ₂ Ru) and 30 mL of acetonitrile under an argon atmosphere. To the solution, 2.35 g (14.5 mmol) of tetrafluoroboric acid diethyl ether complex was added at 0 ° C. After the mixture was stirred at room temperature for 20 hours, the solvent was distilled off under reduced pressure. The remaining solid was washed with a mixture of dichloromethane and diethyl ether (dichloromethane: diethyl ether = 1: 13 (vol%)) to give [tris (acetonitrile) (η ⁵ -cyclopentadienyl) ruthenium (II)] [ Tetrafluoroborato] ([Ru (η ⁵ -C ₅ H ₅ ) (MeCN) ₃ ] [BF ₄ ]) was obtained as a yellow solid (4.30 g, 84% yield).
¹ H-NMR (500 MHz, CDCl ₃ , δ)
4.21 (s, 5H), 2.43 (s, 9H).
¹³ C-NMR (125 MHz, CDCl ₃ , δ)
125.5, 68.8, 4.05.
Example 2

To a solution prepared by mixing 6.52 g (25.1 mmol) of bis (η ⁵ -methylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ MeH ₄ ) ₂ Ru) and 50 mL of acetonitrile under an argon atmosphere. 4.28 g (26.4 mmol) of tetrafluoroboric acid diethyl ether complex was added at 0 ° C. After the mixture was stirred at room temperature for 20 hours, the solvent was distilled off under reduced pressure. The remaining solid was washed with a mixture of dichloromethane and diethyl ether (dichloromethane: diethyl ether = 1: 10 (vol%)) to give [tris (acetonitrile) (η ⁵ -methylcyclopentadienyl) ruthenium (II)] [Tetrafluoroborato] ([Ru (η ⁵ -C ₅ MeH ₄ ) (MeCN) ₃ ] [BF ₄ ]) was obtained as a tan solid (8.61 g, yield 88%).
¹ H-NMR (500 MHz, CDCl ₃ , δ)
4.13-4.16 (brs, 2H), 3.88-3.91 (brs, 2H), 2.42 (s, 9H), 1.70 (s, 3H).
¹³ C-NMR (125 MHz, CDCl ₃ , δ)
124.9, 92.2, 70.6, 63.5, 12.9, 4.0.
Example 3

To a solution prepared by mixing 4.31 g (15.0 mmol) of bis (η ⁵ -ethylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ EtH ₄ ) ₂ Ru) and 40 mL of acetonitrile under an argon atmosphere. Then, 2.55 g (15.7 mmol) of tetrafluoroboric acid diethyl ether complex was added at 0 ° C. After the mixture was stirred at room temperature for 20 hours, the solvent was distilled off under reduced pressure. The remaining solid was washed with a mixture of dichloromethane and diethyl ether (dichloromethane: diethyl ether = 1: 10 (vol%)) to give [tris (acetonitrile) (η ⁵ -ethylcyclopentadienyl) ruthenium (II)] [Tetrafluoroborato] ([Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [BF ₄ ]) was obtained as a tan solid (5.93 g, yield 98%).
¹ H-NMR (500 MHz, CDCl ₃ , 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).
¹³ C-NMR (125 MHz, CDCl ₃ , δ)
124.9, 96.7, 70.0, 63.4, 20.3, 13.6, 3.7.
Example 4

Under an argon atmosphere, (η ⁵ -2,4-dimethyl-2,4-pentadienyl) (η ⁵ -ethylcyclopentadienyl) ruthenium (Ru (η ⁵ -C ₅ EtH ₄ ) (η ⁵ -CH ₂ C (Me) CHC (Me) CH ₂ )) 10.98 g (36.9 mmol) of tetrafluoroboric acid diethyl ether complex at 0 ° C. to a solution prepared by mixing 10.2 g (35.2 mmol) and 40 mL of acetonitrile. ) Was added. After the mixture was stirred at room temperature for 20 hours, the solvent was distilled off under reduced pressure. The remaining solid was washed with a mixture of dichloromethane and diethyl ether (dichloromethane: diethyl ether = 1: 10 (vol%)) to give [tris (acetonitrile) (η ⁵ -ethylcyclopentadienyl) ruthenium (II)] [Tetrafluoroborato] ([Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [BF ₄ ]) was obtained as a tan solid (14.1 g, 99% yield). The ¹ H and ¹³ C-NMR spectra of [Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [BF ₄ ] thus obtained were measured. These spectra were obtained in Example 3. Consistent with the spectrum of the thing.

  Example 5

To a solution prepared by dissolving 1.10 g (3.81 mmol) of bis (η ⁵ -ethylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ EtH ₄ ) ₂ Ru) in 5 mL of acetonitrile under an argon atmosphere, At 0 ° C., 603 mg (4.02 mmol) of trifluoromethanesulfonic acid was added. After the mixture was stirred at room temperature for 20 hours, the solvent was distilled off under reduced pressure. By remaining solid was washed with diethyl ether, [tris (acetonitrile) (eta ⁵ - ethyl cyclopentadienyl) ruthenium (II)] ^{[trifluoromethanesulfonate] ([Ru (η 5 -C} 5 EtH 4) (MeCN) ₃ ] [CF ₃ SO ₃ ]) was obtained as a tan solid (1.61 g, 90% yield).
¹ H-NMR (500 MHz, CDCl ₃ , 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).
¹³ C-NMR (125 MHz, CDCl ₃ , δ)
124.9, 120.8 (q, J _CF = 318 Hz), 96.9, 70.2, 63.6, 20.4, 13.7, 4.04.
Example 6

To a solution prepared by dissolving 1.53 g (5.32 mmol) of bis (η ⁵ -ethylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ EtH ₄ ) ₂ Ru) in 10 mL of pivalonitrile under an argon atmosphere, Tetrafluoroboric acid diethyl ether complex 903 mg (5.58 mmol) was added at 0 ° C. After the mixture was stirred at room temperature for 20 hours, the solvent was distilled off under reduced pressure. The remaining solid was washed with a mixed solvent of tetrahydrofuran and hexane (tetrahydrofuran: hexane = 1: 10) to obtain [tris (pivalonitrile) (η ⁵ -ethylcyclopentadienyl) ruthenium (II)] [tetrafluoroborato ^{] ([Ru (η 5 -C} 5 EtH 4) (t BuCN) 3] [BF 4]) was obtained as a red-brown oil (2.46 g, 87% yield).
¹ H-NMR (500 MHz, CDCl ₃ , 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).
¹³ C-NMR (125 MHz, CDCl ₃ , δ)
133.5, 97.8, 71.2, 63.7, 30.2, 28.3, 20.3, 13.6.
Example 7

In a suspension prepared by mixing 4.30 g (11.4 mmol) of [Ru (η ⁵ -C ₅ H ₅ ) (MeCN) ₃ ] [BF ₄ ] and 50 mL of hexane under an argon atmosphere, 13.0 g (132 mmol) of oxide and 4.22 g (41.7 mmol) of triethylamine were added. The mixture was stirred at room temperature for 20 minutes, and further stirred at 50 ° C. for 10 hours. After filtering the reaction mixture, the solvent was distilled off from the filtrate under reduced pressure. The remaining yellow solid was sublimated (heating temperature 110 ° C./back pressure 10 Pa) to give (η ⁵ -cyclopentadienyl) (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) ruthenium. (Ru (η ⁵ -C ₅ H ₅ ) (η ⁵ -CH ₂ C (Me) CHC (Me) O)) was obtained as a yellow solid (1.27 g, yield 42%).
¹ H-NMR (500 MHz, CDCl ₃ , 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).
¹³ C-NMR (125 MHz, CDCl ₃ , δ)
134.4, 101.1, 84.0, 75.6, 51.9, 26.9, 24.3.
Example 8

Under an argon atmosphere, 8.61 g (22.1 mmol) of [Ru (η ⁵ -C ₅ MeH ₄ ) (MeCN) ₃ ] [BF ₄ ] was dissolved in 69.0 g (700 mmol) of mesityl oxide for 24 hours at room temperature. Stir. Next, 8.95 g (88.4 mmol) of triethylamine was added at 0 ° C., and the mixture was stirred at 50 ° C. for 8 hours. After the solvent was distilled off under reduced pressure, 60 mL of hexane was added to the residue and stirred vigorously at room temperature. After the produced suspension was filtered, the solvent was distilled off from the filtrate under reduced pressure. The remaining solid was sublimated (heating temperature: 135 ° C./back pressure: 10 Pa) to obtain (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ⁵ -methylcyclopentadienyl) ruthenium. _{^{(Ru (η 5 -C 5 MeH}} 4) (η 5 -CH 2 C (Me) CHC (Me) O)) as an orange solid (3.73 g, 61% yield).
¹ H-NMR (500 MHz, CDCl ₃ , 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).
¹³ C-NMR (125 MHz, CDCl ₃ , 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

Under an argon atmosphere, [Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [BF ₄ ] 1.49 g (3.68 mmol) was dissolved in 13.0 g (132 mmol) of mesityl oxide, and then lithium carbonate. 1.36 g (18.4 mmol) was added and stirred at 50 ° C. for 8 hours. After the solvent was distilled off under reduced pressure, 60 mL of hexane was added to the residue and stirred vigorously at room temperature. After the produced suspension was filtered, the solvent was distilled off from the filtrate under reduced pressure. The remaining liquid was distilled under reduced pressure (distillation temperature 88 ° C./back pressure 5 Pa) to obtain (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ⁵ -ethylcyclopentadienyl). ) Ruthenium (Ru (η ⁵ —C ₅ EtH ₄ ) (η ⁵ —CH ₂ C (Me) CHC (Me) O)) was obtained as an orange liquid (0.93 g, 86% yield).
¹ H-NMR (500 MHz, CDCl ₃ , 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).
¹³ C-NMR (125 MHz, CDCl ₃ , 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

Under an argon atmosphere, 2.60 g of lithium carbonate was added to a solution prepared by dissolving 2.84 g (7.03 mmol) of [Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [BF ₄ ] in 20 mL of tetrahydrofuran. (35.2 mmol) and 1,2,5,6,6-pentamethylhept-4-en-3-one 11.0 g (60.6 mmol) were added. The mixture was stirred at room temperature for 20 minutes, and further stirred at 50 ° C. for 17 hours. After the solvent was distilled off under reduced pressure, 150 mL of hexane was added to the residue and stirred vigorously at room temperature. After the produced suspension was filtered, the solvent was distilled off from the filtrate under reduced pressure to obtain (η ⁵ -2,4-di-tert-butyl-1-oxa-2,4-pentadienyl) (η ⁵ − ethyl cyclopentadienyl) ruthenium _{^{(Ru (η 5 -C 5 EtH}} 4) (η 5 -CH 2 C (t Bu) CHC (t Bu) O)) as an orange liquid (1.41 g, yield: 53%).
¹ H-NMR (500 MHz, CDCl ₃ , 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).
¹³ C-NMR (125 MHz, CDCl ₃ , 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

In an argon atmosphere, mesityl was added to a suspension prepared by mixing 2.69 g (5.91 mmol) of [Ru (η ⁵ -C ₅ Me ₅ ) (MeCN) ₃ ] [MeSO ₃ ] and 30 mL of hexane. 5.81 g (59.2 mmol) of oxide and 1.82 g (18.0 mmol) of triethylamine were added. The mixture was stirred at room temperature for 20 minutes, and further stirred at 50 ° C. for 23 hours. After the solvent was distilled off under reduced pressure, 150 mL of hexane was added to the residue and stirred vigorously at room temperature. After the produced suspension was filtered, the solvent was distilled off from the filtrate under reduced pressure. The remaining yellow solid was purified using column chromatography (alumina, tetrahydrofuran) to obtain (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ⁵ -1,2,3 , 4,5-pentamethylcyclopentadienyl) ruthenium (Ru (η ⁵ -C ₅ Me ₅ ) (η ⁵ —CH ₂ C (Me) CHC (Me) O)) was obtained as a yellow solid (1. 97 g, yield 100%).
¹ H-NMR (500 MHz, C ₆ D ₆ , 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).
¹³ C-NMR (125 MHz, C ₆ D ₆ , δ)
133.2, 101.7, 87.5, 84.6, 55.0, 25.2, 23.2, 10.7.
Example 12

Under an argon atmosphere, 2.88 g (10.0 mmol) of bis (η ⁵ -ethylcyclopentadienyl) ruthenium ((η ⁵ -C ₅ EtH ₄ ) ₂ Ru) was dissolved in 30 mL of acetonitrile, and tetrafluoro at 0 ° C. After adding 1.70 g (10.5 mmol) of diethyl borate complex, the mixture was stirred at room temperature for 8 hours. When a part of the reaction mixture at this time was sampled and analyzed using ¹ H-NMR, it was found that [Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [BF ₄ ] was produced. confirmed. After evaporating the solvent from the reaction mixture under reduced pressure, the remaining solid was dissolved in 30 mL of acetone, 9.84 g (100 mmol) of mesityl oxide was added at room temperature, and the mixture was stirred at room temperature for 8 hours. Subsequently, after adding 5.31 g (50.1 mmol) of sodium carbonate, it stirred at 50 degreeC for 8 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 60 mL of hexane was added, and the mixture was vigorously stirred at room temperature. After the produced suspension was filtered, the solvent was distilled off from the filtrate under reduced pressure. The remaining liquid was distilled under reduced pressure (distillation temperature 88 ° C./back pressure 5 Pa) to obtain (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ⁵ -ethylcyclopentadienyl). ) Ruthenium (Ru (η ⁵ —C ₅ EtH ₄ ) (η ⁵ —CH ₂ C (Me) CHC (Me) O)) was obtained as an orange liquid (2.06 g, 70% yield). When ¹ H and ¹³ C-NMR spectra of Ru (η ⁵ -C ₅ EtH ₄ ) (η ⁵ -CH ₂ C (Me) CHC (Me) O) thus obtained were measured, these spectra were The spectrum agreed with that obtained in Example 9.

  Example 13

Under an argon atmosphere, (η ⁵ -2,4-dimethyl-2,4-pentadienyl) (η ⁵ -ethylcyclopentadienyl) ruthenium (Ru (η ⁵ -C ₅ EtH ₄ ) (η ⁵ -CH ₂ C (Me) CHC (Me) CH ₂ )) 3.25 g (11.2 mmol) was dissolved in acetonitrile 20 mL, and tetrafluoroboric acid diethyl ether complex 2.00 g (12.4 mmol) was added at 0 ° C. For 8 hours. When a part of the reaction mixture at this time was sampled and analyzed using ¹ H-NMR, it was found that [Ru (η ⁵ -C ₅ EtH ₄ ) (MeCN) ₃ ] [BF ₄ ] was produced. confirmed. After the solvent was distilled off from the reaction mixture under reduced pressure, the obtained residue was dissolved 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. Next, 1.25 g (12.4 mmol) of triethylamine was added at 0 ° C., followed by stirring at room temperature for 8 hours. After the solvent was distilled off from the reaction mixture under reduced pressure, 60 mL of hexane was added, and the mixture was vigorously stirred at room temperature. After the produced suspension was filtered, the solvent was distilled off from the filtrate under reduced pressure. The remaining liquid was distilled under reduced pressure (distillation temperature 88 ° C./back pressure 5 Pa) to obtain (η ⁵ -2,4-dimethyl-1-oxa-2,4-pentadienyl) (η ⁵ -ethylcyclopentadienyl). ) Ruthenium ([Ru (η ⁵ -C ₅ EtH ₄ ) (η ⁵ -CH ₂ C (Me) CHC (Me) O)]) was obtained as an orange liquid (1.90 g, yield 58%). When ¹ H and ¹³ C-NMR spectra of Ru (η ⁵ -C ₅ EtH ₄ ) (η ⁵ -CH ₂ C (Me) CHC (Me) O) thus obtained were measured, these spectra were The spectrum agreed with that obtained in Example 9.

Preparation examples of ruthenium-containing thin films using ammonia as a reaction gas (Examples 14 to 17, Comparative Examples 1 and 2)
A ruthenium-containing thin film was produced by a thermal CVD method using ruthenium complex (1) or (η ⁵ -C ₅ EtH ₄ ) ₂ Ru as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as shown in Table 3, and other conditions are as follows.

Total pressure in material container: 13.3 kPa, carrier gas flow rate: 30 sccm, material supply rate: 0.012 sccm, ammonia flow rate: 100 sccm, dilution gas flow rate: 70 sccm, substrate: SiO ₂ / Si, film formation time: 1 hour. Argon was used as the carrier gas and diluent gas. The material supply rate to the reaction chamber can be obtained based on a calculation formula of (carrier gas flow rate × material vapor pressure / total pressure in the material container).

  In any of Examples 14 to 17, when the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. For fluorescence X-ray analysis, 3370E manufactured by Rigaku Corporation was used. The measurement conditions were X-ray source: Rh, output: 50 kV, 50 mA, and measurement diameter: 10 mm. Table 3 shows the film thickness calculated from the detected X-ray intensity. The electrical characteristics of the produced ruthenium-containing thin film were measured by a four-probe method, and the obtained resistivity is shown in Table 3. For the four-point probe method, LORESTA HP MCP-T410 manufactured by Mitsubishi Oil Chemical Co., Ltd. was used.

Impurities contained in the film produced under the conditions of Example 15 (however, the film formation time was 2.5 hours) were quantified by secondary ion mass spectrometry. Secondary ion mass spectrometry used ADEPT1010 made by PHI. The measurement conditions were as follows: primary ion species: Cs ⁺ , primary ion acceleration voltage: 2 kV, secondary ion polarity: positive, charge compensation: E-gun.
C: 0.13 atm%, N: 0.08 atm%, O: 0.13 atm%.
When the surface smoothness of the film produced under the conditions of Example 15 was evaluated by AFM, the arithmetic average roughness (Ra) of the film was 2.1 nm, and the root mean square roughness (Rms) was 2.7 nm ( Figure 2). AFM used was NanoScope IIIa manufactured by Bruker AXS. Measurement conditions were tapping mode.

  When the thin films produced in Comparative Examples 1 and 2 were confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. Table 3 shows the film thickness calculated from the detected X-ray intensity. When the electric characteristics of the produced ruthenium-containing thin film were evaluated by the four-probe method, it was an insulating film.

Examples of producing ruthenium-containing thin films using oxygen as a reaction gas (Examples 18 to 26, Comparative Examples 3 and 4)
A ruthenium-containing thin film was produced by a thermal CVD method using ruthenium complex (1) or (η ⁵ -C ₅ EtH ₄ ) ₂ Ru as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as shown in Table 4, and the other conditions are as follows.

Total pressure in material container: 13.3 kPa, carrier gas flow rate: 30 sccm, material supply rate: 0.012 sccm, oxygen flow rate: 0.16 sccm, dilution gas flow rate: 169 sccm, substrate: SiO ₂ / Si, film formation time: 1 hour . Argon was used as the carrier gas and diluent gas. In any of Examples 18 to 26, when the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. Table 4 shows the film thickness calculated from the detected X-ray intensity. The electrical characteristics of the prepared ruthenium-containing thin film were measured by a four-probe method, and the obtained resistivity is shown in Table 4.

  When the thin film produced in Comparative Examples 3 and 4 was confirmed by fluorescent X-ray analysis, the thin film produced in Comparative Example 3 detected characteristic X-rays based on ruthenium, and the thin film produced in Comparative Example 4 exhibited characteristic X based on ruthenium. Lines were not detected. Table 4 shows the film thickness calculated from the detected X-ray intensity. The electrical characteristics of the prepared ruthenium-containing thin film were measured by a four-probe method, and the obtained resistivity is shown in Table 4.

Example 27
A ruthenium-containing thin film was produced by a thermal CVD method using the ruthenium complex (1) obtained in Example 9 as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

Material container temperature: 64 ° C., material vapor pressure: 5.3 Pa, total pressure in material container: 3.3 kPa, substrate temperature: 350 ° C., carrier gas flow rate: 30 sccm, material supply rate: 0.048 sccm, ammonia flow rate: 30 sccm Substrate: SiO ₂ / Si, film formation time: 5 hours. Argon was used as the carrier gas, and no dilution gas was used.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. It was 14 nm as calculated from the detected X-ray intensity. When the surface smoothness of the obtained film was evaluated by AFM, 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 a thermal CVD method using (η ⁵ -C ₅ EtH ₄ ) ₂ Ru as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

Material container temperature: 62 ° C., material vapor pressure: 5.3 Pa, total pressure in material container: 3.3 kPa, substrate temperature: 350 ° C., carrier gas flow rate: 30 sccm, material supply rate: 0.048 sccm, ammonia flow rate: 30 sccm Substrate: SiO ₂ / Si, film formation time: 5 hours. Argon was used as the carrier gas, and no dilution gas was used.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were not detected.

Example 28
A ruthenium-containing thin film was produced by a thermal CVD method using the ruthenium complex (1) obtained in Example 9 as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

  Material container temperature: 100 ° C., material vapor pressure: 69 Pa, total pressure in material container: 6.7 kPa, substrate temperature: 300 ° C., carrier gas flow rate: 20 sccm, material supply rate: 0.21 sccm, ammonia flow rate: 20 sccm, substrate : TaN / Ti / Si, film formation time: 6 hours. Argon was used as the carrier gas, and no dilution gas was used.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. It was 8 nm when calculated from the detected X-ray intensity. When the surface smoothness of the obtained film was evaluated by AFM, Ra of the film was 1.1 nm and Rms was 1.4 nm (FIG. 4).

Comparative Example 6
A ruthenium-containing thin film was produced by a thermal CVD method using (η ⁵ -C ₅ EtH ₄ ) ₂ Ru as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

  Material container temperature: 88 ° C., material vapor pressure: 69 Pa, total pressure in material container: 6.7 kPa, substrate temperature: 300 ° C., carrier gas flow rate: 20 sccm, material supply rate: 0.21 sccm, ammonia flow rate: 20 sccm, substrate : TaN / Ti / Si, film formation time: 6 hours. Argon was used as the carrier gas, and no dilution gas was used.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were not detected.

Example of production of ruthenium-containing thin film using ammonia as reaction gas (Examples 29 to 33)
A ruthenium-containing thin film was produced by a thermal CVD method using the ruthenium complex (1) obtained in Example 9 as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as shown in Table 5, and the other conditions are as follows.

Total pressure in material container: 6.7 kPa, carrier gas flow rate: 30 sccm, material supply rate: 0.024 sccm, ammonia flow rate: 50 sccm, dilution gas flow rate: 20 sccm, substrate: SiO ₂ / Si, film formation time: 2 hours (however, Examples 29 and 30 are 1 hour). Argon was used as the carrier gas and diluent gas.

  In any of Examples 29 to 33, when the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. Table 5 shows the film thickness calculated from the detected X-ray intensity. The electrical properties of the produced ruthenium-containing thin film were measured by a four-probe method, and the obtained resistivity is shown in Table 5.

When the surface smoothness of the film produced under the conditions of Example 29 was evaluated by AFM, Ra of the film was 3.6 nm and Rms was 4.5 nm (FIG. 5). Furthermore, impurities contained in the film produced under the conditions of Example 29 were quantified by secondary ion mass spectrometry.
C: 0.13 atm%, N: 0.01 atm%, O: 0.13 atm%.
When the surface smoothness of the film produced under the conditions of Example 31 was evaluated by AFM, Ra was 0.9 nm and Rms was 1.2 nm (FIG. 6). Furthermore, impurities contained in the film produced under the conditions of Example 31 were quantified by secondary ion mass spectrometry.
C: 0.67 atm%, N: 0.07 atm%, O: 0.07 atm%.
When the surface smoothness of the film produced under the conditions of Example 33 was evaluated by AFM, Ra of the film was 0.4 nm and Rms was 0.5 nm (FIG. 7).

Examples of production of ruthenium-containing thin films using hydrogen as a reaction gas (Examples 34 to 37)
A ruthenium-containing thin film was produced by a thermal CVD method using the ruthenium complex (1) obtained in Example 9 as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as shown in Table 6, and the other conditions are as follows.

Total pressure in material container: 6.7 kPa, carrier gas flow rate: 30 sccm, material supply rate: 0.024 sccm, hydrogen flow rate: 2 sccm, dilution gas flow rate: 68 sccm, substrate: SiO ₂ / Si, film formation time: 1 hour. Argon was used as the carrier gas and diluent gas.

  In any of Examples 34 to 37, when the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. Table 6 shows the film thickness calculated from the detected X-ray intensity. The electrical characteristics of the prepared ruthenium-containing thin film were measured by a four-probe method, and the obtained resistivity is shown in Table 6.

  The following can be understood from the above embodiments. That is, it can be seen from Examples 14 to 17 and 27 to 37 that the ruthenium complex (1) is a material capable of producing a ruthenium-containing thin film without using an oxidizing gas. It can also be seen that by using ruthenium complex (1) as a material, a metal ruthenium film with few impurities can be produced without using an oxidizing gas. Furthermore, it can be seen that the ruthenium-containing thin film produced using the ruthenium complex (1) as a material has good electrical conduction characteristics. From Examples 15, 27 and 28, it can be seen that by using ruthenium complex (1) as a material, a metal ruthenium film having excellent surface smoothness can be produced without using an oxidizing gas.

  From Examples 18 to 26, it can be seen that the ruthenium complex (1) can produce a ruthenium-containing thin film using an oxidizing gas. Further, from the comparison with Comparative Example 4, it can be seen that the ruthenium complex (1) is a material capable of producing 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 thin film forming material.

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

  Example 38

(Η ⁵ -C ₅ H ₅ ) (η ⁵ -C ₅ Me ₅ ) Ru 4.49 g (14.9 mmol) synthesized by the method described in Organometallics, Vol. 5, page 2321 (1986) under an argon atmosphere. Then, to a suspension prepared by mixing 60 mL of acetonitrile, 3.21 g (19.8 mmol) of tetrafluoroboric acid diethyl ether complex was added at 0 ° C. After the mixture was stirred at room temperature for 21 hours, the solvent was distilled off under reduced pressure. The remaining solid mixture of dichloromethane and diethyl ether by washing with (dichloromethane: diethyl ether = 1 13 (vol%)) , [ tris (acetonitrile) (η ⁵ -1,2,3,4,5- Penta Methylcyclopentadienyl) ruthenium (II)] [tetrafluoroborato] ([Ru (η ⁵ -C ₅ Me ₅ ) (MeCN) ₃ ] [BF ₄ ]) was obtained as a yellow solid (6.62 g, Yield 99%).
¹ H-NMR (500 MHz, CDCl ₃ , δ)
2.30-2.46 (br, 9H), 1.58 (s, 15H).
Example 39
A ruthenium-containing thin film was produced by a thermal CVD method using the ruthenium complex (1) obtained in Example 9 as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

Material container temperature: 64 ° C., material vapor pressure: 5.3 Pa, total pressure in material container: 6.7 kPa, substrate temperature: 400 ° C., carrier gas flow rate: 30 sccm, material supply rate: 0.024 sccm, ammonia flow rate: 100 sccm Dilution gas flow rate: 70 sccm, hole substrate: SiO ₂ / Si (hole diameter 400 nm, hole depth 1000 nm), film formation time: 5 hours. Argon was used as a carrier gas.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. It was 8 nm when calculated from the detected X-ray intensity. It was 123 microhm * cm when the electrical property of the produced ruthenium containing thin film was measured by the four probe method. When the cross section of the film was observed with an FE-SEM (field emission electron microscope), the film thickness of the hole opening and the hole bottom was equal (FIG. 8). JSM-7600F manufactured by JEOL Ltd. was used as the FE-SEM. Measurement conditions were acceleration voltage: 5 kV, observation magnification: 100,000 times, sample pretreatment: sample cutting → resin embedding → cross-sectional ion milling.

Example 40
A ruthenium-containing thin film was produced by a thermal CVD method using the ruthenium complex (1) obtained in Example 9 as a material. The outline of the apparatus used for thin film preparation is shown in FIG. The film forming conditions are as follows.

Material container temperature: 64 ° C., material vapor pressure: 5.3 Pa, total pressure in material container: 6.7 kPa, substrate temperature: 400 ° C., carrier gas flow rate: 30 sccm, material supply rate: 0.024 sccm, ammonia flow rate: 50 sccm Dilution gas flow rate: 20 sccm, hole substrate: SiO ₂ / Si (hole diameter 400 nm, hole depth 800 nm), film formation time: 5 hours. Argon was used as a carrier gas.

  When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. It was 7 nm when calculated from the detected X-ray intensity. It was 712 microhm * cm when the electrical property of the produced ruthenium containing thin film was measured by the four-point probe method. When the cross section of the film was observed by FE-SEM, the film thickness of the hole opening and the hole bottom was the same (FIG. 9). From Examples 39 and 40, it can be seen that the ruthenium complex (1) of the present invention can produce a uniform film on a stepped substrate at a low temperature of 400 ° C. or lower without using an oxidizing gas.

DESCRIPTION OF SYMBOLS 1 Material container 2 Constant temperature bath 3 Reaction chamber 4 Substrate 5 Reaction gas 6 Dilution gas 7 Carrier gas 8 Mass flow controller 9 Mass flow controller 10 Mass flow controller 11 Oil rotary pump 12 Exhaust

Claims (20)

General formula (1a)

(In formula, R ^<1a> , R ^<2a> , R ^<3a> , R ^<4a> and R ^<5a> respectively independently represent a hydrogen atom or a C1-C6 alkyl group. However, R ^<1a> , R ^<2a> , R ^<3a> , R ^<4a> and Except for the case where all of R ^5a are simultaneously methyl groups, wherein R ^6a and R ^7a each independently represents an alkyl group having 1 to 6 carbon atoms. The ruthenium complex according to claim 1, wherein R ^1a is an alkyl group having 1 to 6 carbon atoms, R ^2a , R ^3a , R ^4a and R ^5a are hydrogen atoms, and R ^6a and R ^7a are methyl groups. The ruthenium complex according to claim 1 or 2, wherein R ^1a is a methyl group or an ethyl group, R ^2a , R ^3a , R ^4a and R ^5a are hydrogen atoms, and R ^6a and R ^7a are methyl groups. General formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ²¹ represents an alkyl group having 1 to 4 carbon atoms. Z ⁻ represents a counter anion) and a tris (nitrile) complex represented by the general formula (3)

(Wherein R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms), and the enone derivative represented by the general formula (1) is reacted in the presence of a base.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). Production method. The production method according to claim 4, wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms, and R ⁶ and R ⁷ are methyl groups. The production method according to claim 4 or 5, wherein R ¹ is a methyl group or an ethyl group, R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms, and R ⁶ and R ⁷ are methyl groups. The production method according to claim 4, wherein the base is an alkali metal carbonate or an alkylamine. General formula (2b)

(Wherein R ^1b represents an alkyl group having 2 to 6 carbon atoms, R ^21b represents an alkyl group having 1 to 4 carbon atoms, and Zb ⁻ represents a counter anion). Complex. The cationic tris (nitrile) complex according to claim 8, wherein R ^21b is a methyl group. The cationic tris (nitrile) complex according to claim 8 or 9, wherein R ^1b is an ethyl group and R ^21b is a methyl group. General formula (4)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents the general formula (5).

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above) η ^5- (unsubstituted or substituted) cyclopentadienyl ligand, or η ⁵ -2,4-dimethyl-2,4-pentadienyl ligand is represented. ) A ruthenocene derivative, a general formula R ²¹ CN (R ²¹ represents an alkyl group having 1 to 4 carbon atoms), a general formula H ⁺ Z ⁻ (wherein Z ⁻ is a counter anion) And a protonic acid represented by the general formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ²¹ and Z ⁻ represent the same meaning as described above), and a method for producing a cationic tris (nitrile) complex. X is the general formula (5)

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) η ^5- (unsubstituted or substituted) The production method according to claim 11, which is a cyclopentadienyl ligand. The method according to claim 11 or 12, wherein R ²¹ is a methyl group. General formula (4)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents the general formula (5).

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above) η ^5- (unsubstituted or substituted) cyclopentadienyl ligand, or η ⁵ -2,4-dimethyl-2,4-pentadienyl ligand is represented. ) A ruthenocene derivative, a general formula R ²¹ CN (R ²¹ represents an alkyl group having 1 to 4 carbon atoms), a general formula H ⁺ Z ⁻ (wherein Z ⁻ is a counter anion) Is reacted with a protonic acid represented by the general formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^21, and Z ⁻ represent the same meaning as described above), a cationic tris (nitrile) complex represented by Tris (nitrile) complex and general formula (3)

(Wherein R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms), and the enone derivative represented by the general formula (1) is reacted in the presence of a base.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent the same meaning as described above). X is the general formula (5)

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) η ^5- (unsubstituted or substituted) The production method according to claim 14, which is a cyclopentadienyl ligand. The production method according to claim 14 or 15, wherein R ²¹ is a methyl group. General formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁶ and R ⁷ each independently represent 1 to 1 carbon atoms. A ruthenium complex represented by 6 is vaporized and decomposed on a substrate. The production method according to claim 17, which is a production method of a ruthenium-containing thin film by a chemical vapor deposition method. The manufacturing method according to claim 17 or 18, wherein an oxidizing gas is not used. The production method according to claim 17, wherein the ruthenium-containing thin film is a metal ruthenium thin film.

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