JP2009235032A - Method for producing ruthenium complex compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for safely and economically advantageously obtaining a ruthenium complex having a low impurity content efficiently. <P>SOLUTION: The method for producing a ruthenium complex compound represented by general formula (1) (wherein X and Y are each an anionic ligand; L<SP>1</SP>-L<SP>3</SP>are each a neutral ligand; R<SP>1</SP>-R<SP>5</SP>are each hydrogen, a halogen atom or an organic group; R<SP>6</SP>and R<SP>7</SP>are each hydrogen or an organic group; and n and m are each an integer of 0-2) comprises a process for bringing a compound (2) into contact with a Y hydride (HY) and a compound (3) and then a process for bringing the resulting substance into contact with a compound (4). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a ruthenium complex compound. More specifically, the present invention relates to a method for producing a highly active and stable ruthenium carbene complex compound.

The metathesis catalyst is used for an olefin metathesis reaction (disproportionation reaction), and recently, it has been awarded as a catalyst for ring-opening polymerization of cyclic olefins.
Recently, many transition metal metathesis catalysts, especially ruthenium catalysts, have been developed. However, many of these ruthenium catalysts have problems such as a multi-step synthesis and a slow reaction initiation rate.

  Patent Document 1 discloses ruthenium and osmium carbene compounds represented by the following general formula, which are stable in the presence of various functional groups, and are suitable as catalysts for olefin metathesis reactions on unstrained cyclic and acyclic olefins. It is disclosed.

（上記式において、Ｍは、Ｏｓ又はＲｕであり；Ｒ^Ａは水素であり；Ｘ及びＸ^Ａは、異なっていても同じであってもよく、且ついずれのアニオン配位子であってもよく；Ｌ及びＬ^Ａは、異なっていても同じであってもよく、且ついずれの中性電子供与体であってもよく；Ｒは、水素、置換若しくは未置換アルキル、又は置換若しくは未置換アリールである）。
この化合物は、例えば、Ｘ＝Ｘ^Ａ＝Ｃｌ、Ｌ＝Ｌ^Ａ＝ＰＰｈ_３、Ｒ^Ａ＝Ｈ、Ｒ＝フェニル又はｐ−置換フェニルである場合、下記経路に示すように、ＲｕＣｌ_２（ＰＰｈ_３）_３と、ジアゾエタン、ジアゾプロパン又はｐ−置換アリールジアゾアルカン（ｐ−Ｃ_６Ｈ_４ＸＣＨＮ_２）との迅速反応によるＲｕＣｌ_２（＝ＣＨ−ｐ−Ｃ_６Ｈ_４Ｘ）（ＰＰｈ_３）_３の合成を経て、得られている。
しかし、この合成方法で使用するジアゾ化合物は、有毒で爆発性であり、安全性の確保に費用を要する。

(In the above formula, M is Os or Ru; R ^A is hydrogen; X and X ^A may be different or the same and may be any anionic ligand. ; L and L ^a may be the same or different, and may be any neutral electron donor; R is hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl is there).
For example, when X = X ^A = Cl, L = L ^A = PPh ₃ , R ^A = H, R = phenyl or p-substituted phenyl, this compound is represented by RuCl ₂ (PPh ₃ ) ₃ and a rapid reaction of diazoethane, diazopropane or p-substituted aryldiazoalkanes (p-C ₆ H ₄ XCHN ₂ ) with RuCl ₂ (= CH-p-C ₆ H ₄ X) (PPh ₃ ) ₃ It is obtained through synthesis.
However, the diazo compound used in this synthesis method is toxic and explosive, and costs are required to ensure safety.

On the other hand, in Patent Document 2, the metal salt represented by the general formula (D1) is reacted with a tertiary phosphine or phosphite or a ditertiary diphosphine or diphosphite in the presence of a base and a secondary or tertiary alcohol. And after that, it is reacted with an alkyne of formula (D2) in the presence of an acid to obtain a complex compound obtained by formula (D3), and then this alkene of formula (D4) is reacted with this complex compound (D3). A method for obtaining a complex compound represented by the formula (D5) is disclosed.
Examples include a reaction solution containing RuCl ₂ (cis, cis-1,5-cyclooctadiene), 1,8-diazabicyclo [5.4.0] undec-7-ene and tri (cyclohexyl) phosphine. 1-hexyne (or 1-pentyne) and styrene were added to give Cl ₂ (P (C ₆ H ₁₁ ) ₃ ) ₂ Ru═CH—C ₆ H ₅ .

In the above formulas (D1) to (D5), Me is a ruthenium atom or osmium atom; X ⁰¹ and X ⁰² are each independently a halogen atom; T ¹ and T ² are each independently a third phosphine or phosphite Or T ¹ and T ² are taken together to form a di-tertiary diphosphine or diphosphite; and T ³ is a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group, heterocycloalkyl A group, an aryl group or a heteroaryl group.
However, this method requires the use of a large amount of styrene, which is 10 to 20 times the mole of the Ru compound, which remains as an impurity in the product and has a problem in cost. Moreover, when the usage-amount of styrene is less than 10 times mole, there exists a problem that the ruthenium carbene complex to produce | generate becomes a mixture of multiple types, and control of catalyst activity becomes difficult.

Japanese National Patent Publication No. 11-510807 JP-A-10-180114

  Accordingly, an object of the present invention is to provide a method for efficiently and efficiently obtaining a ruthenium complex having a low impurity content, in a safe and economical manner.

  As a result of intensive studies to achieve the above object, the present inventor has found that the target compound can be obtained with high selectivity by interposing a specific compound, and the present invention has been completed based on this finding. It came to do.

  Thus, according to the present invention, the step of contacting the compound (2) represented by the general formula (2) with the hydride of Y (HY) and the compound (3) represented by the general formula (3) [1] And the manufacturing method of the ruthenium complex compound represented by General formula (1) including the process [2] which contacts the compound (4) represented by General formula (4) after that is provided.

（式（１）中、Ｘ及びＹは、それぞれ、アニオン性配位子；Ｌ^１及びＬ^２は、それぞれ、中性配位子；Ｒ^１〜Ｒ^５は、それぞれ、水素、ハロゲン原子又は有機基である。）

(In Formula (1), X and Y are respectively anionic ligands; L ¹ and L ² are respectively neutral ligands; and R ^{1 to} R ⁵ are each a hydrogen atom, a halogen atom or an organic compound. Group.)

（式（２）中、Ｘ、Ｌ^１及びＬ^２は、式（１）における定義と同じ；Ｌ^３は中性配位子；ｎ及びｍは、それぞれ、０〜２の整数である。）
Ｒ^６―Ｃ≡Ｃ―ＣＯＯＲ^７ （３）
（式（３）中、Ｒ^６及びＲ^７は、それぞれ、水素又は有機基を表す。）

(In formula (2), X, L ¹ and L ² are the same as defined in formula (1); L ³ is a neutral ligand; n and m are each an integer of 0 to 2.)
R ⁶ -C≡C-COOR ⁷ (3)
(In formula (3), R ⁶ and R ⁷ each represent hydrogen or an organic group.)

（式（４）中、Ｒ^１〜Ｒ^５は、式（１）における定義と同じである。）

(In formula (4), R ^{1 to} R ⁵ are the same as defined in formula (1).)

In the method for producing a ruthenium complex compound of the present invention, the compound (3) is preferably H—C≡C—COOR ⁷ (R ⁷ represents hydrogen or an organic group).
In the method for producing a ruthenium complex compound of the present invention, the compound (3) is preferably R ⁶ —C≡C—COOH (R ⁶ represents hydrogen or an organic group).
Furthermore, in the method for producing a ruthenium complex compound of the present invention, it is particularly preferable that the compound (3) is H—C≡C—COOH.

Furthermore, in the method for producing a ruthenium complex compound of the present invention, it is preferable that the compound (5) represented by the general formula (5) is present in the step [1].
R ⁸ -CN (5)
(In formula (5), R ⁸ is a monovalent organic group.)

  According to the present invention, a ruthenium complex having a low impurity content can be obtained efficiently and safely and advantageously. The ruthenium catalyst obtained by the method of the present invention has high activity and is useful as a catalyst for metathesis polymerization and the like.

The method for producing a ruthenium complex of the present invention is a method for producing a ruthenium complex represented by the formula (1).

In the formula (1), X and Y are anionic ligands, which may be the same or different.
The anionic ligand is not particularly limited, and specific examples thereof include halogen, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and 3 carbon atoms. -20 alkyl diketonate group, aryl diketonate group, C1-C20 carboxylate group, aryl sulfonate group, C1-C20 alkyl sulfonate group, C1-C20 alkylthio group, carbon number A 1-20 alkylsulfonyl group and a C1-C20 alkylsulfinyl group can be shown. These groups may be substituted with an alkyl group having 1 to 5 carbon atoms, halogen, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group. The phenyl group is further substituted with halogen, 1 to 5 carbon atoms. It may be substituted with an alkyl group or an alkoxy group having 1 to 5 carbon atoms.

The anionic ligand is preferably chlorine, bromine, iodine, hydrogen, benzoate group, carboxylate group having 1 to 5 carbon atoms, alkyl group having 1 to 5 carbon atoms, phenoxy group, or alkoxy having 1 to 5 carbon atoms. Group, an alkylthio group having 1 to 5 carbon atoms, an aryl group, or an alkyl sulfonate group having 1 to 5 carbon atoms. These groups may be substituted with an alkyl group having 1 to 5 carbon atoms or a phenyl group, and this phenyl group is further halogen, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. May be substituted.
More preferably, the anionic ligand is Cl, Br, I, CF ₃ CO ₂ , CH ₃ CO ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, (CF ₃ ) (CH ₃ ) ₂ CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate.
The anionic ligand is particularly preferably chlorine, and most preferably X and Y are both chlorine.

L ¹ and L ² are each a neutral ligand and may be the same or different.
The neutral ligand is not particularly limited, and specific examples thereof include phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine and thioether. Can be mentioned.
The neutral ligand is preferably a phosphine, more preferably one secondary alkyl group or cycloalkyl group, aryl, a primary alkyl group having 1 to 10 carbon atoms, and a secondary alkyl group. And a phosphine having two groups independently selected from the group consisting of cycloalkyl groups, particularly preferably tri (cyclohexyl) phosphine, tri (cyclopentyl) phosphine, tri (isopropyl) phosphine and tri (phenyl) phosphine It is.

R ^{1 to} R ⁵ each may have an amino group, a nitro group, an alkyl group, or an aryl group that may have hydrogen, halogen, a hydroxy group, a hydroxycarbonyl group, an alkyl group, or an aryl group. A silyl group, an acyl group having 1 to 10 carbon atoms, a sulfonyl group optionally having an alkyl group or an aryl group, an alkylthio group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and 1 to 10 carbon atoms Or an alkyl group or an aryl group having 1 to 20 carbon atoms which may have a substituent. Examples of the substituent that the alkyl group or aryl group may have include a halogen, a hydroxy group, an amino group that may have an alkyl group or an aryl group, a nitro group, and an alkoxy group having 1 to 5 carbon atoms. And an acyloxy group having 1 to 10 carbon atoms.
The present invention is particularly, as R ¹ to R ^5, can be suitably used for the preparation of a ruthenium complex compound having a halogen-substituted alkyl group or an acyloxy group.

  In the method for producing the ruthenium complex compound represented by the formula (1), the compound (2) represented by the general formula (2) is used.

In the formula (2), X, L ¹ and L ² are the same as those defined in the formula (1).
L ³ is a neutral ligand, and specific examples thereof include the same ones as given as specific examples of L ¹ and L ² .
n and m are each an integer of 0-2.

The compound represented by the formula (2) can be synthesized, for example, according to the following literature.
M.M. L. Christ, S.M. Sabo-Etienne, B.M. Chaudret, Organometallics, 1994, Vol. 13, p. 3800.
J. et al. Wolf, W.M. Stuer, C.I. Grunwald, O .; Gevert, M.M. Laubender, H.M. Werner, Eur. J. et al. Inorg. Chem. 1998, p. 1827
P. A. van der Schaaf, R.A. Kolly, A.M. Hafner, Chem. Commun. 2000, p. 1045.
Japanese translation of PCT publication No. 2001-503434 N. Coalter III, K.M. G. Culton, New J .; Chem. 2001, Vol. 25, p. 679.
S. Jung, C.I. D. Brandt, J.M. Wolf, H.M. Werner, Dalton Trans. 2004, p. 375.
W. Stuer, B.B. Weberndorf, J.A. Wolf, H.M. Werner, Dalton Trans. 2005, p. 1796.

Examples of the Y hydride (HY) used in the step [1] include hydrogen halide, hydrogen, alcohol, phenols, carboxylic acid, ketone, diketone, alkyl sulfonic acid and aryl sulfonic acid.
Of these, hydrogen acid is preferred, and specific examples thereof include hydrogen chloride, hydrogen bromide, hydrogen iodide, acetic acid, propionic acid, acrylic acid, methacrylic acid, crotonic acid, propiolic acid, benzoic acid, trichloroacetic acid. Trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like.

In the step [1], a compound represented by the general formula (3) is used.
R ⁶ -C≡C-COOR ⁷ (3)
In formula (3), R ⁶ and R ⁷ each represent hydrogen or an organic group.
Specific examples of the organic group represented by R ⁶ and R ⁷ include an alkyl group having 1 to 20 carbon atoms and an aryl group. More specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group Cyclohexyl group, benzyl group, phenyl group, toluyl group and the like.
The compound (3) represented by the general formula (3) is preferably H—C≡C—COOR ⁷ and particularly preferably H—C≡C—COOH.

In the step [1], the hydride of Y (HY) and the compound (3) represented by the general formula (3) are brought into contact with the compound represented by the general formula (2).
The ratio of the compound (2) represented by the general formula (2) and the compound (3) represented by the general formula (3) is usually from 0.5 to 0.5 per 1 mol of the compound (2). The range is 5 moles.
Moreover, the usage-amount of the hydride (HY) of Y is the range of 0.5-3 mol normally with respect to 1 mol of compounds (2).

  The method of bringing these compounds into contact with each other is not particularly limited, but after reacting compound (2) and compound (3), the reaction mixture is isolated without any reaction product being isolated. ) To be reacted.

In the step [1], it is preferable that the compound (5) represented by the general formula (5) is present.
R ⁸ -CN (5)
In formula (5), R ⁸ is a monovalent organic group.
Specific examples of the monovalent organic group represented by R ⁸ include an alkyl group having 1 to 20 carbon atoms and an aryl group. More specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group Cyclohexyl group, benzyl group, phenyl group, toluyl group and the like.
The monovalent organic group represented by R ⁸ is preferably an alkyl group, and more preferably a methyl group.
The amount of the compound (5) represented by the general formula (5) is in the range of 0.5 to 30 parts by weight, preferably 3 to 10 parts per 100 parts by weight of the compound represented by the general formula (2). is there.

In step [1], the reaction is usually carried out in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. Specific examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 2-methyltetrahydrofuran, and ethylene glycol dimethyl ether; pentane, hexane, Hydrocarbon solvents such as petroleum ether, heptane, octane, cyclopentane, cyclohexane; aromatic solvents such as benzene, toluene, xylene; methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, i- And alcohol solvents such as butanol, t-butanol, benzyl alcohol, ethylene glycol, and propylene glycol;
The reaction is preferably performed in an inert gas atmosphere, and specific examples of the inert gas may include a rare gas such as argon, nitrogen gas, and the like.
The reaction temperature is not particularly limited, but the reaction is preferably performed in the range of −90 to 10 ° C., more preferably in the range of −50 to −10 ° C.
The reaction time is not particularly limited, but is usually about 1 minute to 12 hours.

式中、Ｘ、Ｙ、Ｌ^１及びＬ^２は、式（１）における定義と同じであり、Ｒ^６及びＲ^７は、式（３）における定義と同じである。 By the step [1], a reaction product having a structure represented by the following formula is obtained.

In the formula, X, Y, L ¹ and L ² are the same as defined in formula (1), and R ⁶ and R ⁷ are the same as defined in formula (3).

This reaction product (5) is subjected to the next step [2] without isolation.
In the step [2], the reaction product (5) is brought into contact with the compound (4) represented by the general formula (4).
The reaction conditions may be the same as those in step [1].
After completion of the reaction, the temperature is gradually raised to room temperature, and then the target compound (1) is isolated.
Isolation of compound (1) may be carried out according to a conventional method. Usually, the solvent is removed under reduced pressure, and after washing with alcohol or the like, if necessary, drying is carried out under reduced pressure.

Specific examples of the ruthenium complex compound (1) obtained by the production method of the present invention include bis ((tricyclohexyl) phosphine) (p-acetoxybenzylidene) ruthenium (IV) dichloride [L ¹ = L ² = (tricyclohexyl). Phosphine, X = Y = chlorine, R ¹ = R ² = R ⁴ = R ⁵ = H, R ³ = acetoxy compound], bis ((tricyclohexyl) phosphine) (p-chloromethylbenzylidene) ruthenium (IV) dichloride [L ¹ = L ² = (tricyclohexyl) phosphine, X = Y = chlorine, R ¹ = R ² = R ⁴ = R ⁵ = H, R ³ = chloromethyl compound] bis ((tricyclohexyl) phosphine) ( benzylidene) ruthenium (IV) dichloride ^[L 1 ^{= L} 2 ⁼ (tricyclohexylphosphine) phosphine, X = Y = Containing ^a compound of ^{R 1 = R 2 = R 3} = R 4 = R 5 = H ], bis ((tricyclohexylphosphine) phosphine) ⁼ (p-chlorobenzylidene) ruthenium (IV) dichloride ^[L 1 ^L 2 = (tri Cyclohexyl) phosphine, X = Y = chlorine, R ¹ = R ² = R ⁴ = R ⁵ = H, R ³ = chloro compound], bis ((tricyclohexyl) phosphine) (p-bromobenzylidene) ruthenium (IV) Dichloride [L ¹ = L ² = (tricyclohexyl) phosphine, X = Y = chlorine, R ¹ = R ² = R ⁴ = R ⁵ = H, R ³ = bromo compound], bis ((tricyclohexyl) phosphine) (p- methylbenzylidene) ruthenium (IV) dichloride ^[L 1 ^{= L} 2 ⁼ (tricyclohexylphosphine) phosphine, X = Y = ^{chlorine, R} 1 ⁼ R 2 ⁼ R = ^R 5 = H, the compound of ^{R 3} = methyl], bis ((tricyclohexylphosphine) phosphine) (p-methoxy benzylidene) ruthenium (IV) dichloride ^[L 1 ^{= L} 2 ⁼ (tricyclohexylphosphine) phosphine, X = Y = Chlorine, R ¹ = R ² = R ⁴ = R ⁵ = H, R ³ = methoxy compound], bis ((tricyclohexyl) phosphine) (p-acetoxybenzylidene) ruthenium (IV) dibromide [L ¹ = L ² = (Tricyclohexyl) phosphine, X = Y = bromine, R ¹ = R ² = R ⁴ = R ⁵ = H, R ³ = acetoxy compound], bis ((tricyclohexyl) phosphine) (p-acetoxybenzylidene) ruthenium ( IV) Bromide chloride [L ¹ = L ² = (tricyclohexyl) phosphine, X = chlorine, Y = bromine, R ¹ = R ² = R ⁴ = R ⁵ = H, R ³ = Acetoxy compound] and the like.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples and examples. In addition, the part and% in each example are mass references | standards unless there is particular notice.

The purity of the complex was measured by ¹ H-NMR and ³¹ P-NMR.
The ratio of each component in the total carbene was determined by a peak integration ratio of 19 ppm to 21 ppm in ¹ H-NMR (standard substance tetramethylsilane: 0 ppm).

[Example 1]
Synthesis of bis (tri (cyclohexyl) phosphine) (p-acetoxybenzylidene) ruthenium (IV) dichloride (complex a) 0.77 parts of bis (tri (cyclohexyl) phosphine) (dihydrogen) hydridoruthenium (II) chloride was schlenk The tube was replaced with argon. Thereto, 9 parts of tetrahydrofuran substituted with argon was added and dissolved, and cooled to -30 ° C. Thereto was added 0.08 part of propiolic acid while stirring. The color of the solution changed to reddish brown. Thereafter, the mixture was stirred for 10 minutes, and 0.78 part of a 1 mol / l HCl / diethyl ether solution was added, followed by 0.18 part of p-acetoxystyrene. After stirring at −30 ° C. for 10 minutes, the temperature was raised to 20 ° C. over 3 hours, and then the solvent was removed under reduced pressure to obtain 1.06 parts of dark pink powder.
^{As a} result of analysis by ¹ H-NMR, the ratio of complex a in all carbenes was 81%. The obtained powder was washed three times with 20 parts of methanol and dried under reduced pressure to obtain 0.48 parts of complex a as a pink powder. When this powder was analyzed by ¹ H-NMR, the proportion of complex a in all carbene was 100%. Moreover, when analyzed by ³¹ P-NMR, it showed a single peak.

The NMR spectrum data of the obtained complex a is shown below.
¹ H-NMR (CDCl ₃ , 25 ° C.) δ ppm: 19.90 (s, 1H), 8.49 (d, 2H), 7.04 (d, 2H), 2.61 (brs, 6H), 2 .30 (s, 3H), 1.90-1.02 (m, 60H)
³¹ P-NMR (CDCl ₃ , 25 ° C.) δ ppm: 36.4 (s)

[Example 2]
The reaction was conducted in the same manner as in Example 1 except that the amount of p-acetoxystyrene charged was changed from 0.18 parts to 1.80 parts to obtain 2.75 parts of a red-violet viscous liquid. ^{As a} result of analysis by ¹ H-NMR, the ratio of complex a in all carbenes was 90%. The obtained liquid was washed 3 times with 20 parts of methanol and dried under reduced pressure to obtain 0.51 part of complex a as a pink powder. ^{As a} result of analysis by ¹ H-NMR, the ratio of complex a in all carbenes was 100%.

Example 3
The same operation as in Example 1 was carried out except that 0.10 parts of acetonitrile was added immediately before the addition of propiolic acid to obtain 1.19 parts of dark pink powder.
^{As a} result of analysis by ¹ H-NMR, the ratio of complex a in all carbenes was 81%. The obtained powder was washed 3 times with 20 parts of methanol and dried under reduced pressure to obtain 0.59 parts of complex a as a pink powder. ^{As a} result of analysis by ¹ H-NMR, the ratio of complex a in all carbenes was 100%.

Example 4
The reaction was conducted in the same manner as in Example 3 except that the addition amount of p-acetoxystyrene was changed from 0.18 part to 0.90 part to obtain 1.69 parts of a red-violet viscous liquid.
^{As a} result of analysis by ¹ H-NMR, the ratio of the complex a in the total carbene was 95%. The obtained liquid was washed 3 times with 20 parts of methanol and dried under reduced pressure to obtain Complex a as 0.69 parts of pink powder. ^{As a} result of analysis by ¹ H-NMR, the ratio of complex a in all carbenes was 100%.

Example 5
Synthesis of bis (tri (cyclohexyl) phosphine) (p-chloromethylbenzylidene) ruthenium (IV) dichloride (complex b) Instead of 0.18 part of p-acetoxystyrene, 0.17 part of p-chloromethylstyrene was used. The reaction was conducted in the same manner as in Example 3 except that 1.10 parts of dark pink powder was obtained.
^{As a} result of analysis by ¹ H-NMR, the ratio of the complex b in the total carbene was 75%. The obtained powder was washed three times with 20 parts of methanol and dried under reduced pressure to obtain 0.51 part of complex b as a pink powder. When this powder was analyzed by ¹ H-NMR, the ratio of the complex b in the total carbene was 100%. Moreover, when analyzed by ³¹ P-NMR, it showed a single peak.

The NMR spectrum data of the obtained complex b are shown below.
¹ H-NMR (CDCl ₃ , 25 ° C.) δ ppm: 20.04 (s, 1H), 8.44 (d, 2H), 7.34 (d, 2H), 4.41 (s, 2H), 2 .61 (brs, 6H), 1.90-1.05 (m, 60H)
³¹ P-NMR (CDCl ₃ , 25 ° C.) δ ppm: 36.6 (s)

[Comparative Example 1]
The reaction was conducted in the same manner as in Example 1 except that 0.22 part of phenylacetylene was used instead of 0.08 part of propiolic acid to obtain 1.20 parts of a reddish brown powder.
^{As a} result of analysis by ¹ H-NMR, the ratio of complex a in all carbenes was 81%. In addition, 12% of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride (complex c) and 7% of bis (tricyclohexylphosphine) (2-phenylethylidene) ruthenium (IV) dichloride (complex d) were observed. Moreover, when analyzed by ³¹ P-NMR, three peaks were confirmed. Although 20 parts of methanol was added to the obtained powder and washed three times, complex c and complex d could not be removed.

[Comparative Example 2]
The reaction was conducted in the same manner as in Example 3 except that 0.11 part of phenylacetylene was used instead of 0.08 part of propiolic acid to obtain 1.25 parts of a reddish brown powder. ^{As a} result of analysis by ¹ H-NMR, the ratio of complex a in all carbenes was 80%. In addition, 11% of complex c and 9% of complex d were observed. Moreover, when analyzed by ³¹ P-NMR, three peaks were confirmed. Although 20 parts of n-hexane was added to the obtained powder and washed three times, the complex c and the complex d could not be removed.

Claims (4)

The step [1] of contacting the compound (2) represented by the general formula (2) with the hydride of Y (HY) and the compound (3) represented by the general formula (3), and then the general formula The manufacturing method of the ruthenium complex compound represented by General formula (1) including the process [2] which contacts the compound (4) represented by (4).

(In Formula (1), X and Y are respectively anionic ligands; L ¹ and L ² are respectively neutral ligands; and R ^{1 to} R ⁵ are each a hydrogen atom, a halogen atom or an organic compound. Group.)

(In formula (2), X, L ¹ and L ² are the same as defined in formula (1); L ³ is a neutral ligand; n and m are each an integer of 0 to 2.)
R ⁶ -C≡C-COOR ⁷ (3)
(In formula (3), R ⁶ and R ⁷ each represent hydrogen or an organic group.)

(In formula (4), R ^{1 to} R ⁵ are the same as defined in formula (1).) The method for producing a ruthenium complex compound according to claim 1, wherein R ⁶ is hydrogen. The method for producing a ruthenium complex compound according to claim 1 or 2, wherein R ⁷ is hydrogen. The method for producing a ruthenium complex compound according to any one of claims 1 to 3, wherein the compound (5) represented by the general formula (5) is present in the step [1].
R ⁸ -CN (5)
(In formula (5), R ⁸ is a monovalent organic group.)