JP5291308B2 - Metal complex, and catalyst and electrode catalyst containing the metal complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal complex which is sufficiently stable even in a strong acid condition. <P>SOLUTION: This metal complex has a transition metal and a ligand (a) to be coordinated in this metal. In addition, the metal complex can be obtained by heating a raw material complex with the transition metal and a ligand (b) of an azadiene structure to be coordinated in the metal and an unsaturated compound which forms the ligand (a) by a chemical reaction with the ligand (b) in a co-existent state. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a metal complex, and a catalyst and an electrode catalyst containing the metal complex.

  The metal complex acts as a catalyst in a redox reaction involving an electron transfer such as an oxygen addition reaction, an oxidative coupling reaction, a dehydrogenation reaction, a hydrogenation reaction, an oxide decomposition reaction, or an electrode reaction, and the ligand (b) or high It is used for the synthesis of molecular compounds. Recently, it has been used as a phosphorescent complex of organic EL materials. Furthermore, they are also used in various applications such as additives, modifiers, batteries, and sensor materials.

In particular, as a redox reaction catalyst, it is known that a Schiff base type metal complex has a highly active and highly selective catalytic ability. For example, in Non-Patent Document 1, an asymmetric cyclopropanation reaction that oxidizes the double bond of styrene is performed using an optically active Schiff base type metal complex as a catalyst, and a favorable asymmetric reaction proceeds. Yes. In Non-Patent Document 2, water is generated by electrolytic reduction of oxygen using a Schiff base type metal complex.
Org. Biomol. Chem. 2005, 3, p. 2126-2128 Inorganic Chemistry. Vol. 40, no. 6, 2001, p. 1329-1333

  However, it is known that Schiff base is hydrolyzed under acidic conditions to decompose into aldehyde and amine (Reference: Chemical Dictionary, Tokyo Chemical Dojin, page 604). For this reason, the Schiff base type metal complex tends to be destabilized in the presence of a strong acid, and its application range is limited. That is, the conventionally disclosed Schiff base type metal complexes may decompose under the reaction conditions in which an acid is generated. For example, when used as a catalyst, there is a problem that the original performance cannot be exhibited. . For this reason, there is a demand for a metal complex that has performance equivalent to that of a conventional Schiff base type metal complex and excellent in acid stability.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a metal complex that is sufficiently stable even under strong acidity, a catalyst containing the metal complex, and an electrode catalyst.

  In the present invention, a metal complex comprising a transition metal and a ligand (a) coordinated to the metal, the raw material complex comprising a transition metal and a ligand (b) having an azadiene structure coordinated to the metal And an unsaturated compound that forms the ligand (a) by the reaction with the ligand (b) and a metal complex that can be obtained by heating in a coexisting state. This metal complex is sufficiently stable even under strong acidity and has excellent performance when used as a catalyst.

  The reason why such an effect is obtained is not necessarily clear, but the present inventors speculate as follows. That is, the raw material complex including the ligand (b) and the unsaturated compound generate a metal complex in which the azadiene structure of the ligand (b) is stabilized by an addition reaction or the like. For this reason, it is thought that it can suppress that the imino group etc. weak to an acid are decomposed | disassembled by an acid. Therefore, the present inventors infer that a sufficiently stable metal complex can be obtained even under strong acidity.

  Moreover, it is preferable that the metal complex of this invention is obtained by heating a raw material complex and an unsaturated compound in the range of 50 to 500 degreeC. This makes it possible to obtain a metal complex that is more sufficiently stable under strong acidity.

  The metal complex of the present invention is preferably obtained by heating the raw material complex and the unsaturated compound to near the decomposition temperature of the unsaturated compound. This makes it possible to obtain a more sufficiently stable metal complex under strong acidity.

上記一般式（１）中、Q^１は少なくとも２つのＣ＝Ｎ結合を有する２価の有機基を示し、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に水素原子又は置換基を示す。複数あるＲ^１、Ｒ^２及びＲ^３は、それぞれ同一でも異なっていてもよく、複数あるＲ^１は互いに連結していてもよく、複数あるＲ^３は互いに連結していてもよい。 Moreover, in this invention, it is preferable that the ligand (b) of a raw material complex is a compound represented by following General formula (1). By using a raw material complex comprising such a compound as a ligand, a metal complex having excellent reactivity when used as a catalyst while having excellent stability under strong acidity can be obtained.

In the general formula (1), Q ¹ represents a divalent organic group having at least two C═N bonds, and R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent. The plurality of R ¹ , R ² and R ³ may be the same or different, the plurality of R ¹ may be connected to each other, and the plurality of R ³ may be connected to each other.

上記一般式（２）中、Ａｒは置換されていてもよい２価の芳香族基を示し、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は置換基を示す。複数あるＡｒ、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ同一でも異なっていてもよく、複数あるＲ^４は互いに連結していてもよく、複数あるＲ^６は互いに連結していてもよい。 In the present invention, the ligand (b) is preferably a compound represented by the following general formula (2). By using a raw material complex having such a compound as the ligand (a), a metal complex having excellent stability when used as a catalyst while having excellent stability under strong acidity is obtained. be able to.

In the general formula (2), Ar represents a divalent aromatic group which may be substituted, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituent. A plurality of Ar, R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, a plurality of R ⁴ may be connected to each other, and a plurality of R ⁶ may be connected to each other.

上記一般式（３）中、X^１は炭素原子又は窒素原子を示し、複数あるＸ^１は同一でも異なっていてもよい。Ｒ^７は水素原子又は置換基を示し、複数あるＲ^７は同一でも異なっていてもよく、複数あるＲ^７は互いに連結していてもよい。

上記一般式（４）中、Ｒ^８は水素原子又は置換基を示し、複数あるＲ^８は同一でも異なっていてもよい。 Moreover, in this invention, it is preferable that an unsaturated compound is at least one of the compounds represented by following formula (3) and following formula (4). Since such a compound undergoes an addition reaction with the ligand (b) of the raw material complex, a sufficiently complex metal complex can be obtained under a strong acid.

In the general formula (3), X ¹ represents a carbon atom or a nitrogen atom, and a plurality of X ¹ may be the same or different. R ⁷ represents a hydrogen atom or a substituent, and the plurality of R ⁷ may be the same or different, and the plurality of R ⁷ may be linked to each other.

In the general formula (4), R ⁸ represents a hydrogen atom or a substituent, and a plurality of R ⁸ may be the same or different.

上記一般式（５）中、Ｒ^９は水素原子又は置換基を示し、複数あるＲ^９は同一でも異なっていてもよい。Ｘ^２は脱離基を示し、複数あるＸ^２は同一でも異なっていてもよく、複数あるＸ^２は互いに連結していてもよい。 In the present invention, the unsaturated compound is preferably a compound represented by the following formula (5). A compound such as the following formula (5) generates a reaction intermediate such as align by heating and reacts with the ligand (b) of the raw material complex to form a sufficiently stable metal complex under a strong acid. it can.

In the general formula (5), R ⁹ represents a hydrogen atom or a substituent, and a plurality of R ⁹ may be the same or different. X ² represents a leaving group, the plurality of X ² may be the same or different, and the plurality of X ² may be linked to each other.

In the present invention, the π _LUMO energy level of the unsaturated compound is preferably 0 eV or less. Such a compound can easily undergo an addition reaction with the ligand (b) of the starting complex, and a sufficiently stable metal complex can be obtained under a strong acid.

  The present invention also provides a catalyst containing the above metal complex. Since this catalyst contains the metal complex having the above characteristics, it is sufficiently stable even under strong acid and has excellent catalytic performance. Such a catalyst can be suitably used particularly as an electrode catalyst.

  According to the present invention, a metal complex that is sufficiently stable even under strong acidity, and a catalyst and an electrode catalyst containing the metal complex can be provided.

  Hereinafter, preferred embodiments of the present invention will be described. The metal complex according to the present embodiment is a metal complex including a transition metal and a ligand (a) coordinated to the metal, and has a transition metal and a ligand having an azadiene structure coordinated to the metal (b ) And an unsaturated compound that forms the ligand (a) by reaction with the ligand (b) can be obtained by heating in a coexisting state.

  As a ligand (b) which has an azadiene structure and coordinates to a transition metal, at least one of the structures represented by the following formulas A, B, C, D, E, F, G and H is contained in the molecule. The inclusion is preferred. The ligand (b) has a diene structure containing a nitrogen atom.

As a more suitable ligand (b) of a raw material complex, the compound represented by following General formula (1) can be mentioned.

In the general formula (1), Q ¹ represents a divalent organic group having at least two C═N bonds, and R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent. The plurality of R ¹ , R ² and R ³ may be the same or different, the plurality of R ¹ may be connected to each other, and the plurality of R ³ may be connected to each other.

Examples of the substituent represented by R ¹ , R ² and R ³ in the general formula (1) include a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, a halogen atom, and a substituted group. Substituted with 2 monovalent hydrocarbon groups which may be substituted, hydrocarbyloxy group which may be substituted (hydrocarbonoxy group which may be substituted), unsubstituted or substituted monovalent hydrocarbon group An amino group (that is, an optionally substituted hydrocarbon disubstituted amino group), an optionally substituted hydrocarbyl mercapto group (an optionally substituted hydrocarbon mercapto group), an optionally substituted hydrocarbylcarbonyl group (Optionally substituted hydrocarbon carbonyl group), optionally substituted hydrocarbyloxycarbonyl group (optionally substituted hydrocarbon) An oxycarbonyl group), an aminocarbonyl group substituted with two unsubstituted or substituted monovalent hydrocarbon groups (that is, an optionally substituted hydrocarbon disubstituted aminocarbonyl group), or an optionally substituted group. A hydrocarbyloxysulfonyl group (an optionally substituted hydrocarbon sulfonyl group) can be mentioned. In addition, said halogen atom means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  Monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, nonyl, dodecyl, pentadecyl, octadecyl, An alkyl group having about 1 to 50 carbon atoms such as docosyl group; about 3 to 50 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbornyl group, adamantyl group, etc. Cyclic saturated hydrocarbon group; having about 2 to 50 carbon atoms such as ethenyl group, propenyl group, 3-butenyl group, 2-butenyl group, 2-pentenyl group, 2-hexenyl group, 2-nonenyl group, 2-dodecenyl group, etc. Alkenyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4 Methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4- Aryl groups having about 6 to 50 carbon atoms such as adamantylphenyl group and 4-phenylphenyl group; phenylmethyl group, 1-phenyleneethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl- 2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group and the like An aralkyl group having about 7 to 50 carbon atoms can be exemplified.

  Among the monovalent hydrocarbon groups described above, from the viewpoint of improving the stability of the ligand, a hydrocarbon group having 1 to 20 carbon atoms is preferable, a hydrocarbon group having 1 to 12 carbon atoms is more preferable, and carbon A hydrocarbon group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is particularly preferable.

  As the above-mentioned hydrocarbyloxy group, hydrocarbyl mercapto group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, hydrocarbylsulfonyl group, the above-mentioned monovalent hydrocarbon is added to the oxy group, mercapto group, carbonyl group, oxycarbonyl group, sulfonyl group, respectively. A group to which any one of the groups is bonded can be exemplified.

“Amino group substituted with two unsubstituted or substituted monovalent hydrocarbon groups” and “aminocarbonyl group substituted with two unsubstituted or substituted monovalent hydrocarbon groups” include amino groups and A group in which each two hydrogen atoms in the aminocarbonyl group [group represented by —C (═O) —NH ₂ ] are substituted with the above-described monovalent hydrocarbon group can be exemplified. Specific examples and preferred examples of the monovalent hydrocarbon group are the same as the monovalent hydrocarbon group which is the substituent represented by R ¹ described above.

The monovalent hydrocarbon group represented by R ¹ , hydrocarbyloxy group, hydrocarbyl mercapto group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, hydrocarbylsulfonyl group, a part or all of the hydrogen atoms contained in these groups, Halogen atom, hydroxyl group, amino group, nitro group, cyano group, monovalent hydrocarbon group which may be substituted, hydrocarbyloxy group which may be substituted, hydrocarbyl mercapto group which may be substituted, substituted It may be substituted with an optionally substituted hydrocarbylcarbonyl group, an optionally substituted hydrocarbyloxycarbonyl group, an optionally substituted hydrocarbylsulfonyl group, and the like.

  The group that substitutes “a part or all of the hydrogen atoms” is preferably a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, or a halogen atom.

Among the substituents represented by R ¹ , R ² and R ³ described above, a monovalent hydrocarbon group which may be substituted, a hydrocarbyloxy group which may be substituted, an unsubstituted or substituted monovalent group Preferred are an amino group substituted by two hydrocarbon groups, an optionally substituted hydrocarbyl mercapto group, an optionally substituted hydrocarbylcarbonyl group, and an optionally substituted hydrocarbyloxycarbonyl group. Preferred is a monovalent hydrocarbon group, an optionally substituted hydrocarbyloxy group, an amino group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, and an optionally substituted monovalent hydrocarbon group. More preferred are hydrocarbon groups. In these groups, the nitrogen atom to which a hydrogen atom is bonded is preferably substituted with a monovalent hydrocarbon group.

Specific examples of R ¹ , R ² and R ³ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a phenyl group, a methylphenyl group, A naphthyl group and a pyridyl group are preferable, a hydrogen atom, a methyl group, a t-butyl group, and a phenyl group are more preferable, and a hydrogen atom and a methyl group are still more preferable.

Q ¹ in the general formula (1) represents a divalent organic group having at least two C═N bonds. Examples of the divalent organic group include divalent organic groups represented by the following general formula (1-a) and the following general formula (1-b).

In the general formula (1-a), a plurality of R ¹⁰ each independently represent a hydrogen atom or a substituent, and Z ¹ represents a divalent organic group. In the general formula (1-b), P ¹ and P ² each represent an aromatic heterocyclic group having one C═N bond, and P ¹ and P ² are bonded to each other to form a ring. May be. Moreover, at least one hydrogen of the aromatic heterocyclic group may be substituted with a substituent. P ¹ and P ² may be the same or different. Y ¹ represents a single bond, a double bond or a linking group.

Specific examples and preferred examples of R ¹⁰ are the same as ^{R 1} in the general formula (1).

Z ^{1 in the} general formula (1-a) is preferably an alkylene group which may be substituted or a divalent aromatic group which may be substituted. Examples of the alkylene group include methylene group, ethylene group, 1,1-propylene group, 1,2-propylene group, 1,3-propylene group, 2,4-butylene group, 2,4-dimethyl-2,4- Examples thereof include linear, branched or cyclic alkylene groups having about 1 to 20 carbon atoms such as butylene, 1,2-cyclopentylene and 1,2-cyclohexylene. In addition, the alkylene group may be substituted with the substituent mentioned in R ¹ of the general formula (1).

The “optionally substituted divalent aromatic group” represented by Z ¹ is a divalent group generated by losing two hydrogen atoms from the aromatic compound. As the aromatic compound here, aromatic compounds having about 6 to 60 total carbon atoms such as benzene, naphthalene, anthracene, tetracene, biphenyl, biphenylene, furan, dibenzofuran, thiophene, dibenzothiophene, pyridine, phenol, naphthol, and the like. It can be illustrated. This “optionally substituted divalent aromatic group” may be substituted with the substituents mentioned for R ¹ in the general formula (1).

  In addition, as a bivalent organic group represented by the said general formula (1-a), the following general formula (1-a-1), general formula (1-a-2), general formula (1-a-3) ), General formula (1-a-4), general formula (1-a-5), general formula (1-a-6), general formula (1-a-7), general formula (1-a-8) And compounds of the general formula (1-a-9). Among these, from the viewpoint of improving the chemical stability of the ligand, compounds of the following general formula (1-a-5) and general formula (1-a-6) are preferable.

General formula (1-a-1), general formula (1-a-2), general formula (1-a-3), general formula (1-a-4), general formula (1-a-5) In general formula (1-a-6), general formula (1-a-7), general formula (1-a-8), and general formula (1-a-9), R ¹¹ and R ¹² are Each independently represents a hydrogen atom or a substituent. A plurality of R ¹¹ and a plurality of R ¹² may be the same or different, and two R ¹¹ bonded to two adjacent atoms may be connected to each other.

Specific examples and preferred examples of R ¹¹ and R ¹² are the same as R ¹ in the general formula (1).

Examples of the aromatic heterocyclic ring that is the aromatic heterocyclic group represented by P ¹ and P ² in the general formula (1-b) include pyridine, pyrazine, pyrimidine, thiazole, imidazole, oxazole, benzimidazole, quinoline, and isoquinoline. And cinnoline, phthalazine, quinazoline, quinoxaline, and benzodiazine. These aromatic heterocycles may be substituted with the substituents mentioned for R ¹ in the general formula (1). Of the above aromatic heterocycles, pyridine, pyrazine, pyrimidine, thiazole, imidazole, oxazole, and benzimidazole are preferable, and pyridine, thiazole, imidazole, and oxazole are more preferable from the viewpoint of improving the heat resistance of the ligand.

P ¹ and P ² in the general formula (1-b) may be bonded to each other to form a ring. Examples of the divalent organic group represented by the general formula (1-b) include the following general formula (1-b-1), general formula (1-b-2), and general formula (1-b-3). , Those having a structure of the general formula (1-b-4), the general formula (1-b-5), or the general formula (1-b-6) are preferable. Among these, those having the structures of general formula (1-b-1) and general formula (1-b-2) are more preferable.

General formula (1-b-1), general formula (1-b-2), general formula (1-b-3), general formula (1-b-4), general formula (1-b-5) And R ¹³ in formula (1-b-6) represents a hydrogen atom or a substituent. A plurality of R ¹³ in the same structure may be the same or different.

R ^{14 in the} general formula (1-b-3) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. A plurality of R ¹⁴ may be the same or different.

  Specific examples of the structure of the ligand (b) represented by the general formula (1) include the following formula (I) and the following formula (II).

  As a more suitable ligand (b) of a raw material complex, the compound represented by following General formula (2) can be mentioned.

In the general formula (2), Ar represents a divalent aromatic group which may be substituted, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituent. A plurality of Ar, R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, a plurality of R ⁴ may be connected to each other, and a plurality of R ⁶ may be connected to each other.

Specific examples and preferred examples of R ⁴ , R ⁵ and R ⁶ in the general formula (2) are the same as R ¹ in the general formula (1). Specific examples of Ar can be the same as the specific examples of “optionally substituted divalent aromatic group” of Z ^{1 in} the general formula (1-a). Moreover, as Ar, what is represented by the following general formula (2-a), general formula (2-b) or general formula (2-c) is preferable, and what is represented by general formula (2-a) Is most preferred.

In the general formula (2-a), general formula (2-b) and general formula (2-c), R ¹⁵ represents a hydrogen atom or a substituent, and a plurality of R ¹⁵ in the same aromatic group may be the same. May be different. Specific examples and preferred examples of R ¹⁵ are the same as R ¹ in the general formula (1).

  The transition metal contained in the raw material complex and the metal complex according to the present embodiment is described as “transition element” on page 1283 of “Chemical Dictionary” (Michinori Oki et al., Issued July 1, 2005, Tokyo Kagaku Dojin). Meaning an element having an incomplete d or f subshell. The transition metal atom in the present embodiment may be uncharged or charged ion.

  Transition metals include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium , Osmium, iridium, platinum, gold, mercury and the like. Among these, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, palladium, silver, iridium, platinum, and gold are preferable from the viewpoint of production cost or a highly active catalyst, and manganese, iron Cobalt, copper, palladium, iridium, and platinum are more preferable. In the present embodiment, as described above, a cation of these transition metals may be used.

  The raw material complex and the metal complex preferably have two transition metal atoms per molecule. Thereby, a binuclear catalyst having two active centers and capable of promoting a two-electron transfer reaction can be obtained.

  In a raw material complex comprising a transition metal and a ligand (b) having an azadiene structure coordinated to the metal, the transition metal is coordinated by a neutral molecule and a counter ion in addition to the ligand (b). May be. Moreover, the form in which a neutral molecule and a counter ion coexist may be used.

  Neutral molecules include water, methanol, ethanol, n-propanol, isopropyl alcohol, 2-methoxyethanol, 1,1-dimethylethanol, ethylene glycol, N, N′-dimethylformamide, N, N′-dimethyl. Acetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, acetone, chloroform, acetonitrile, benzonitrile, triethylamine, pyridine, pyrazine, diazabicyclo [2,2,2] octane, 4,4′-bipyridine, tetrahydrofuran, diethyl ether, Examples include dimethoxyethane, methyl ethyl ether, 1,4-dioxane and the like. Among these, water, methanol, ethanol, isopropyl alcohol, ethylene glycol, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2 from the viewpoint of easy coordination to transition metals -Pyrrolidone, chloroform, acetonitrile, benzonitrile, triethylamine, pyridine, pyrazine, diazabicyclo [2,2,2] octane, 4,4'-bipyridine, tetrahydrofuran, dimethoxyethane, 1,4-dioxane are preferred.

  Counter ions include fluorine ion, chlorine ion, bromine ion, iodine ion, sulfide ion, oxide ion, hydroxide ion, hydride ion, sulfite ion, phosphate ion, cyanide ion, acetate ion, carbonate ion , Sulfate ion, nitrate ion, bicarbonate ion, trifluoroacetate ion, thiocyanide ion, trifluoromethanesulfonate ion, acetylacetonate, tetrafluoroborate ion, hexafluorophosphate ion, tetraphenylborate ion, etc. can do. Of these, from the viewpoint of production cost, chloride ion, bromide ion, iodide ion, oxide ion, hydroxide ion, hydride ion, phosphate ion, cyanide ion, acetate ion, carbonate ion, sulfate ion Nitrate ion, acetylacetonate and tetraphenylborate ion are preferred.

  As a raw material complex of this embodiment, it is preferable to use a Schiff base type complex. Examples of such Schiff base type complexes include complexes of the following formulas III, IV, and V.

  Next, an unsaturated compound having an unsaturated bond that can undergo an addition reaction with the ligand (b) of the raw material complex will be described. The unsaturated compound is an organic compound having an unsaturated bond that can undergo a cycloaddition reaction with a conjugated diene. The unsaturated bond capable of undergoing cycloaddition reaction is preferably an unsaturated bond to which an electron-withdrawing substituent is directly bonded. Here, specifically as an electron withdrawing substituent, a phenyl group, a cyano group, a carbonyl group, a nitro group, and a sulfonyl group are preferable, and a cyano group and a carbonyl group are more preferable. As an unsaturated compound concerning this embodiment, a compound denoted by the following general formula (3) and general formula (4) is preferred.

In the general formula (3), X ¹ represents a carbon atom or a nitrogen atom, and a plurality of X ¹ may be the same or different. R ⁷ represents a hydrogen atom or a substituent, and the plurality of R ⁷ may be the same or different, and the plurality of R ⁷ may be linked to each other.

Specific examples of R ⁷ are the same as R ¹ in the general formula (1). R ⁷ is preferably a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, or an optionally substituted monovalent hydrocarbon group from the viewpoint of improving the reactivity of the unsaturated compound. A cyano group, a carboxyl group, and a monovalent hydrocarbon group which may be substituted are more preferable, and a cyano group and a carboxyl group are more preferable.

In the general formula (4), R ⁸ represents a hydrogen atom or a substituent, and a plurality of R ⁸ may be the same or different. Specific examples of R ⁸ are the same as R ¹ in the general formula (1). R ⁸ is preferably a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, or an optionally substituted monovalent hydrocarbon group from the viewpoint of improving the reactivity of the unsaturated compound. A cyano group, a carboxyl group, and a monovalent hydrocarbon group which may be substituted are more preferable, and a cyano group and a carboxyl group are more preferable.

As the unsaturated compound having an unsaturated bond that can undergo an addition reaction with the raw material complex, a compound having a low energy level of π _LUMO is preferable. Such a compound can easily undergo an addition reaction with the ligand (b) of the starting complex. π _LUMO means the highest unoccupied orbit of π orbital, and the energy level of π _LUMO can be obtained by AM1 calculation. For the AM1 calculation, general-purpose package software can be used, for example, Chem3D Ultra Version 7.0 or the like can be used.

Compounds having low energy levels of π _LUMO include the following chemical formulas 4a, 4b, 4c, 4d, 4e, 4f, 4g, 4h, 4i, 4j, 4k, 4l, 4m, 4n, 4o, 4p, 4q, The compounds shown in 4r, 4s and 4t can be exemplified. These are suitable as the unsaturated compound of this embodiment.

Numerical values are described under each of the above compounds energy level is exemplified as the lower compound of [pi _LUMO (Unit: eV) represents the energy level of the [pi _LUMO of each compound. The energy level of π _LUMO is preferably 0 eV or less, more preferably −0.4 eV or less, still more preferably −0.8 eV or less, from the viewpoint of allowing the reaction between the raw material complex and the unsaturated compound to proceed more smoothly. -1.2 eV or less is particularly preferable.

  The compound such as 4i is a reaction intermediate that cannot be normally isolated because of unstable alignment, but is generated by heating an unsaturated compound (precursor) represented by the following general formula (5). Can be made. Accordingly, a reaction intermediate and a raw material complex generated from the unsaturated compound represented by the following general formula (5) by heating the unsaturated compound represented by the following general formula (5) and the raw material complex, etc. It is thought that the metal complex concerning this embodiment can be obtained by reacting with. In addition, as a preferable precursor, the organic compound which produces | generates benzyne as a reaction intermediate is mentioned.

R ^{9 in the} general formula (5) represents a hydrogen atom or a substituent, and a plurality of R ⁹ may be the same or different. X ² represents a leaving group, the plurality of X ² may be the same or different, and the plurality of X ² may be linked to each other. X ² is preferably one that generates alignment by heating.

  Examples of preferred compounds represented by the above general formula (5) include compounds of the following general formula (5-a), general formula (5-b), general formula (5-c) and general formula (5-d). can do.

In the general formula (5-a), general formula (5-b), general formula (5-c) and general formula (5-d), R ¹⁶ represents a hydrogen atom or a substituent, Certain R ¹⁶ may be the same or different and may be linked to each other. A specific example of R ¹⁶ is the same as R ¹ in the general formula (1). In the general formulas (5-b) and (5-c), Ar ¹ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group. The aromatic hydrocarbon group here is a monovalent group produced by the loss of one hydrogen atom by an aromatic hydrocarbon compound. Examples of the aromatic hydrocarbon compound include aromatic compounds having about 6 to 60 total carbon atoms, such as benzene, naphthalene, anthracene, tetracene, biphenyl, and biphenylene. In addition, the aromatic heterocyclic group is a monovalent group that is generated when an aromatic heterocyclic ring loses one hydrogen atom. Examples of the aromatic heterocycle include pyridine, pyrazine, pyrimidine, thiazole, imidazole, oxazole, benzimidazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, benzodiazine, furan, dibenzofuran, thiophene, and dibenzothiophene. it can.

  A raw material complex comprising a transition metal and a ligand (b) coordinated to the transition metal, and an unsaturated compound that forms a ligand (a) by reaction with the ligand (b) are a gas atmosphere. The reaction can be carried out under heating or in a solution, for example, by heating in the range of 50 to 500 ° C.

  In the present embodiment, the present inventors presume that the raw material complex and the unsaturated compound react to generate a metal complex, for example, as shown in the following reaction formula (6).

  In the reaction formula (6), it is considered that the metal complex (K) is generated from the raw material complex (Schiff base type metal complex) and the unsaturated compound diphenyliodonium-2-carboxylate. In this reaction, it is presumed that benzyne produced from diphenyliodonium-2-carboxylate reacts with a raw material complex (Schiff base type metal complex) and imino-Deals-Alder to form a metal complex (K). Since the metal complex (K) thus obtained also has a structure in which an imino group that is weak against acid is protected, the imino group is not decomposed even when it comes into contact with an acid. For this reason, such a metal complex (K) is considered to have excellent stability even under strong acidity.

  In view of the reaction mechanism of the above reaction formula (6), the metal complex of the present embodiment can be subjected to an addition reaction with an unsaturated compound having an unsaturated bond that can directly undergo an addition reaction with the raw material complex, or with the raw material complex. It is preferable to obtain the compound by using an unsaturated compound that forms a compound and heating and reacting them in a coexisting state.

  When the reaction as described above is performed by heating in a solution, the solvent to be used is preferably a solvent having a boiling point of 50 ° C to 300 ° C at normal pressure, and more preferably a solvent having a boiling point of 75 ° C to 250 ° C at normal pressure. Further, a solvent having a boiling point of 100 ° C. to 200 ° C. at normal pressure is more preferable.

  As the solvent, water, acetic acid, oxalic acid, aqueous ammonia, methanol, ethanol, n-propanol, isopropyl alcohol, 2-methoxyethanol, 1-butanol, 1,1-dimethylethanol, ethylene glycol, diethyl ether, 1 , 2-dimethoxyethane, methyl ethyl ether, 1,4-dioxane, tetrahydrofuran, benzene, toluene, xylene, mesitylene, durene, decalin, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, 1,2-dichlorobenzene, N, N Examples include '-dimethylformamide, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, acetone, acetonitrile, benzonitrile, triethylamine, pyridine and the like. As the solvent, those capable of dissolving the raw material complex and the unsaturated compound are preferable.

  The reaction in the solution may be performed under pressure. The reaction under pressure can be performed by, for example, putting a solution containing a raw material complex, an unsaturated compound, and a solvent in a sealed tube, and performing heat treatment or microwave treatment.

  As reaction temperature in the case of performing reaction in a solution, it is preferable to set it as 60-300 degreeC, and it is more preferable to set it as 70-200 degreeC. The reaction time can be, for example, 1 minute to 1 week, preferably 5 minutes to 24 hours, more preferably 1 hour to 12 hours. In addition, it is preferable to optimize reaction temperature and reaction time suitably according to the kind of raw material complex and unsaturated compound.

  When heat treatment is performed in a gas atmosphere, the gas is preferably hydrogen, helium, nitrogen, ammonia, oxygen, neon, argon, or a mixed gas thereof. Hydrogen, nitrogen, ammonia, argon, or a mixed gas thereof It is more preferable to use gas.

  As heating temperature in gas atmosphere, 80-450 degreeC is preferable and 100-400 degreeC is more preferable. The heating time is preferably 1 to 10 hours, and more preferably 1 to 5 hours.

  In this invention, when an unsaturated compound decomposes | disassembles in the range of 50 to 500 degreeC, it is preferable to heat the mixture of a raw material complex and an unsaturated compound to the temperature of decomposition temperature vicinity. The decomposition temperature of the unsaturated compound can be examined by thermogravimetric / differential thermal analysis. Specifically, when the measurement is performed under the measurement apparatus and measurement conditions shown below, an exothermic peak of 5 μV / mg or more is observed. It can be the detected temperature.

Measuring device: Rigaku THERMOFLEX TAS200 TG8101D
Temperature increase rate: 10 ° C / min
Amount of measurement sample: 5 mg to 15 mg
Sample container (dish): Aluminum pan Measurement atmosphere: Nitrogen atmosphere

  The upper limit of the heating temperature is preferably (T + 50) ° C., more preferably (T + 40) ° C., where T (decomposition temperature) is the temperature at which the exothermic peak of the unsaturated compound is observed. More preferably, T + 30) ° C. On the other hand, the lower limit of the heating temperature is preferably (T-50) ° C, more preferably (T-40) ° C, and even more preferably (T-30) ° C. The vicinity of the decomposition temperature means a temperature of (T-50) to (T + 50) ° C.

  The reaction between the raw material complex and the unsaturated compound is carried out at a temperature near the decomposition temperature of the unsaturated compound (hereinafter referred to as “heat treatment 1” for the sake of convenience), and then further heated at a higher temperature ( Hereinafter, for convenience, it is also referred to as “heat treatment 2”. As a result, the reaction can be allowed to proceed completely and excess unsaturated compounds can be completely decomposed. In this case, when the heating temperature of the heat treatment 2 is the heating temperature T1 of the heat treatment 1, the upper limit is preferably T1 + 400 ° C., and the upper limit is preferably T1 + 300 ° C. The heating time of the heat treatment 2 is preferably 1 to 5 hours, and more preferably 1 to 3 hours.

  The metal complex according to the present embodiment can be used in combination with various carriers, additives and the like, or can be processed in shape according to various applications. Applications include electrode catalysts and membrane degradation inhibitors for fuel cells, oxidative coupling catalysts for aromatic compounds, exhaust gas / drainage purification catalysts, carbon dioxide reduction catalysts, catalysts for reformed hydrogen production, oxygen sensors, etc. .

  Moreover, when using the metal complex which concerns on this embodiment as a catalyst, it can be used as a composition containing a carbon support | carrier and / or a conductive polymer. Such a composition is preferable because the stability of the metal complex increases and the catalytic activity tends to be improved.

  Examples of the conductive polymer contained in the composition include polyacetylene, polyaniline, and polypyrrole. Examples of the carbon carrier contained in the composition include carbon particles such as NORIT, Ketjen Black (Lion), Vulcan (Cabot), Black Pearl (Cabot), and Acetylene Black (Chevron), C60, C70, and the like. Fullerenes, carbon nanotubes, carbon nanohorns, carbon fibers, and the like.

  Further, the composition may be used by mixing a plurality of types of metal complexes according to the present embodiment, or may be used by combining a plurality of carbon carriers and conductive polymers, respectively. A combination with a polymer can also be used.

  Next, the preferable use of the metal complex of this embodiment is demonstrated. The metal complex of this embodiment is suitably used for a polymer electrolyte fuel cell. In the polymer electrolyte fuel cell, the metal complex can be contained in an electrolyte, an electrode, and an interface between the electrolyte and each electrode (electrolyte / each electrode interface). A polymer electrolyte fuel cell is usually sandwiched between a fuel electrode into which a fuel containing hydrogen or methanol is introduced, an oxygen electrode to which an oxidant gas containing oxygen is supplied, and the fuel electrode and the oxygen electrode. A plurality of electrolyte membrane electrode assemblies (MEA) composed of the electrolyte membranes are laminated via a separator. The metal complex of this embodiment is preferably contained at the oxygen electrode, the fuel electrode, or the electrolyte / each electrode interface. Various methods can be used as a method of incorporating the metal complex into an electrolyte, an electrode, or an electrolyte / electrode interface. For example, a method in which the metal complex is dispersed in an electrolyte solution such as a fluorine-based ion exchange resin [Nafion (registered trademark, manufactured by DuPont), etc.], and a film-like molded product is prepared from the dispersion and used as an electrolyte membrane. Alternatively, a method in which the dispersion is applied to an electrolyte membrane and dried, and used as an electrode. A dispersion in which the metal complex is dispersed is applied to an electrode and dried, and an electrolyte membrane is bonded thereto to form an electrolyte-electrode. Examples thereof include a method of introducing a layer containing a metal complex at the interface as a peroxide decomposition catalyst layer.

  In addition, the metal complex according to this embodiment is also suitably used as an oxidative coupling catalyst for aromatic compounds. For example, it is suitably used as a catalyst for producing a polymer such as polyphenylene ether or polycarbonate. Examples of usage forms include a method of directly adding the metal complex according to the present embodiment to the reaction solution, and a method of supporting the metal complex on zeolite or silica.

  The metal complex according to the present embodiment can also be used as a desulfurization / denitration catalyst for converting sulfur oxides and nitrogen oxides contained in exhaust gases from various factories and automobiles into sulfuric acid and ammonia. Specific use forms include a method of filling the catalyst containing the metal complex in a tower through which exhaust gas from a factory passes, a method of filling a muffler of an automobile, and the like.

  The metal complex according to the present embodiment can also be used as a catalyst for modifying CO in the reformed hydrogen. The reformed hydrogen contains CO, etc. When using the reformed hydrogen as a fuel cell, it is a problem that the fuel electrode is poisoned by CO, and the CO concentration in the reformed hydrogen is reduced as much as possible. It is desirable to do. Specific examples of usage include, for example, the method described in Chemical Communication, 3385 (2005).

  Furthermore, the metal complex according to the present embodiment can be applied to the synthesis of a polymer metal complex by using a bifunctional compound such as the above chemical formulas 4f and 4O as an unsaturated compound. In addition, by using a functional material such as a light-emitting material, a conductive material, or a conductive material as an unsaturated compound, a new function is imparted to a raw material complex composed of a ligand (b) having an azadiene structure and a transition metal. It is also possible to do.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

  First, the complex (L) was synthesized according to the following reaction formula (7). Specifically, 0.476 g of cobalt chloride hexahydrate and 0.412 g of 4-tert-butyl-2,6-diformylphenol were added to 10 ml of ethanol under a nitrogen atmosphere, and the ethanol solution was added. Prepared. While stirring this ethanol solution in a 50 ml eggplant flask and stirring at room temperature, a solution prepared by dissolving 0.216 g of o-phenylenediamine in 5 ml of ethanol was gradually added to the ethanol solution to prepare a mixed solution. The mixture was heated under normal pressure and refluxed for 2 hours to obtain a brown precipitate. The precipitate was collected by filtration and dried to obtain a complex (L) (yield 0.465 g: yield 63%).

In the above reaction formula (7), “Cl ₂ ” means that 2 equivalents of chlorine ions are present as a counter ion in the complex (L), and “2H ₂ O” means that in the complex (L) 2 equivalent water molecules are present as ligand (a).

  Elemental analysis of the synthesized complex (L) was performed using an elemental analyzer (product name: varioEL, manufactured by Elemental Co.). As a result, as shown in Table 1, it almost coincided with the calculated value obtained from the structure of the complex (L) in the reaction formula (7). From this result, it was confirmed that the complex (L) was synthesized according to the above reaction formula (7).

(Thermogravimetric / differential thermal analysis 1)
Thermogravimetric / differential thermal analysis of diphenyliodonium-2-carboxylate monohydrate (manufactured by TCI) was performed. Specifically, using a thermogravimetric / differential thermal analyzer (Rigaku THERMOFLEX TAS200 TG8101D, hereinafter referred to as “TG-DTA device” for convenience), 8.7 mg of diphenyliodonium-2-carboxylate monohydrate is used. Weight change (TG) and differential heat change (DTA) were measured. The measurement conditions were a nitrogen temperature, a heating rate of 10 ° C./min, and an aluminum dish was used for the heat treatment. As a result of the analysis, an exothermic peak attributed to the decomposition reaction was observed at 230 ° C. Accordingly, it was found that diphenyliodonium-2-carboxylate monohydrate was thermally decomposed at 230 ° C.

(Thermogravimetric / differential thermal analysis 2)
Thermogravimetric / differential thermal analysis of 4-phenyl-1,2,4-triazoline-3,5-dione (Aldrich) was performed. Specifically, using the above TG-DTA apparatus, the weight change (TG) and differential heat change of 9.4 mg of 4-phenyl-1,2,4-triazoline-3,5-dione (TG) and the differential heat change ( DTA) was measured. As a result of the analysis, an exothermic peak attributed to the decomposition reaction was observed at 120 ° C. Therefore, it was found that 4-phenyl-1,2,4-triazoline-3,5-dione was thermally decomposed at 120 ° C.

Example 1
Using the complex (L) as a raw material complex, an electrode catalyst containing a metal complex was prepared by the following procedure. Complex (L) 100 mg (0.135 mmol) prepared as above, diphenyliodonium-2-carboxylate monohydrate 219 mg (0.676 mmol, manufactured by TCI), and ketjen black (manufactured by ketjen black international) (Product name: Ketjen Black EC) 400 mg was added to a sample bottle, and well mixed with a spatula. The mixture thus obtained was heat-treated in a nitrogen atmosphere (nitrogen gas flow rate: 200 ml / min) using a tubular furnace (program-controlled open / close tubular furnace, manufactured by Isuzu Seisakusho, trade name: EPKRO-14R) to obtain a catalyst raw material. It was. The temperature setting of the tubular furnace at the time of the heat treatment was first raised to 200 ° C. over 1 hour and held at 200 ° C. for 2 hours, then raised to 400 ° C. over 1 hour and held at 400 ° C. for 2 hours, Thereafter, the temperature was lowered to room temperature over 2 hours. A temperature chart in the tubular furnace during the heat treatment is shown in FIG.

  4 mg of this catalyst raw material is placed in a sample bottle, 3 mL of 2N HCl is added, and ultrasonic treatment is performed for 2 hours and 20 minutes with ultrasonic vibration, followed by filtration and drying under a condition of 25 ° C. and 12 hours. The electrode catalyst was obtained by drying using Fisher Scientific, product name: Model285A Vacuum Oven).

  2 mg of the obtained electrode catalyst, 0.6 ml of distilled water, 0.4 ml of ethanol, and Nafion (registered trademark) solution (manufactured by Aldrich, 5% by mass solution, trade name: Nafion Perfluorinated resin solution 5 wt.% In lower aliphatic alcohols and 20 μL of water.contains15-20water) was added to the sample bottle, and ultrasonic treatment was performed for 30 minutes with ultrasonic vibration to obtain a suspension. On the other hand, a ring disk electrode was prepared in which the disk part was glassy carbon (4.0 mmφ) and the ring part was Pt (ring inner diameter 5.0 mm, ring outer diameter 7.0 mm). And 11 microliters of said suspension liquid was dripped at the disk part of this ring disk electrode, Then, it dried at room temperature overnight and the electrode for a measurement was obtained.

(Example 2)
Using the complex (L) as a raw material complex, an electrode catalyst containing a metal complex was prepared by the following procedure. Complex (L) 100 mg (0.135 mmol) prepared as described above, 4-phenyl-1,2,4-triazoline-3,5-dione 119 mg (0.678 mmol, manufactured by Aldrich), and ketjen black (ket 400 mg (trade name: Ketjen Black EC, manufactured by Chen Black International Co., Ltd.) was added to the sample bottle, and the mixture was mixed well with a spatula. The mixture thus obtained was heat-treated in the same tubular furnace and atmosphere as in Example 1 to obtain a catalyst raw material. The temperature setting of the tubular furnace during the heat treatment is as follows. First, the temperature is raised to 100 ° C. over 30 minutes and held at 100 ° C. for 2 hours, and then heated to 400 ° C. over 1.5 hours and then heated to 400 ° C. for 2 hours. Then, the temperature was lowered to room temperature over 2 hours. A temperature chart in the tubular furnace during the heat treatment is shown in FIG.

  Using the obtained catalyst raw material, an electrode catalyst was prepared in the same manner as in Example 1 to obtain a measurement electrode.

(Comparative Example 1)
100 mg (0.135 mmol) of the complex (L) prepared as described above and 400 mg of Ketjen Black (Ketjen Black International, trade name: Ketjen Black EC) were added to a sample bottle and mixed well with a spatula. . The mixture thus obtained was heat-treated in the same tubular furnace and atmosphere as in Example 1 to obtain a catalyst raw material. The temperature of the tubular furnace during the heat treatment was raised to 400 ° C. over 2 hours, held at 400 ° C. for 2 hours, and then lowered to room temperature over 2 hours.

  Using the obtained catalyst raw material, an electrode catalyst was prepared in the same manner as in Example 1 to obtain a measurement electrode.

(Measurement of current density)
Using the following measuring apparatus, the measurement electrodes prepared in Examples 1 and 2 and Comparative Example 1 were rotated, and the current value of the oxygen reduction reaction at that time was measured. The measurement was performed at room temperature under a nitrogen atmosphere and an oxygen atmosphere. Details of the measuring apparatus and measurement conditions are as follows.

<Measurement device>
RRDE-2 rotating ring disk electrode device ALS model 701C dual electrochemical analyzer manufactured by BS Co., Ltd.

<Measurement conditions>
Cell solution: 0.05 mol / L sulfuric acid aqueous solution (oxygen saturation)
Dispersion temperature: 25 ° C
Reference electrode: Silver / silver chloride electrode (saturated KCl)
Counter electrode: platinum wire Sweep speed: 5 mV / s
Electrode rotation speed: 600 rpm

  A value obtained by subtracting the current value obtained by measurement under a nitrogen atmosphere from the current value obtained by measurement under an oxygen atmosphere was defined as the current value for oxygen reduction. FIG. 3 shows the relationship between the current density obtained from the current value and the disk potential. The current density at a potential of 0.4 V was as shown in Table 2.

(Example 3)
100 mg (0.135 mmol) of the complex (L) prepared as described above and 219 mg (0.676 mmol, manufactured by TCI) of diphenyliodonium-2-carboxylate monohydrate were added to a sample bottle, and mixed well with a spatula. did. The mixture thus obtained was heat-treated in a nitrogen atmosphere (nitrogen gas flow rate: 200 ml / min) using a tubular furnace (program-controlled open / close tubular furnace, manufactured by Isuzu Seisakusho, trade name: EPKRO-14R) to obtain a metal complex. It was. The temperature setting of the tubular furnace at the time of the heat treatment was first raised to 200 ° C. over 1 hour and held at 200 ° C. for 2 hours, then raised to 400 ° C. over 1 hour and held at 400 ° C. for 2 hours, Thereafter, the temperature was lowered to room temperature over 2 hours.

  Infrared absorption spectrum measurement of the obtained metal complex was performed using FT-IR-460plus manufactured by JASCO Corporation. The IR spectrum of the metal complex is shown in FIG.

Example 4
Complex (L) 100 mg (0.135 mmol) prepared as described above, 4-phenyl-1,2,4-triazoline-3,5-dione 119 mg (0.678 mmol, manufactured by Aldrich), and ketjen black (ket 400 mg (trade name: Ketjen Black EC, manufactured by Chen Black International Co., Ltd.) was added to the sample bottle, and the mixture was mixed well with a spatula. The mixture thus obtained was heat-treated in the same tubular furnace and atmosphere as in Example 1 to obtain a metal complex. The temperature setting of the tubular furnace during the heat treatment is as follows. First, the temperature is raised to 100 ° C. over 30 minutes and held at 100 ° C. for 2 hours, and then heated to 400 ° C. over 1.5 hours and then heated to 400 ° C. for 2 hours. Then, the temperature was lowered to room temperature over 2 hours.

  Infrared absorption spectrum measurement of the obtained metal complex was performed using FT-IR-460plus manufactured by JASCO Corporation. The IR spectrum of the metal complex is shown in FIG.

2 is a temperature chart in a tubular furnace during heat treatment in Example 1. FIG. 6 is a temperature chart in a tubular furnace during heat treatment in Example 2. FIG. It is a graph which shows the relationship between a current density and disk electric potential. 3 is an IR spectrum of the metal complex obtained in Example 3. 4 is an IR spectrum of the metal complex obtained in Example 4.

Claims (8)

A metal complex comprising a transition metal and a ligand (a) coordinated to the metal,
Unsaturated compound which forms said ligand (a) by reaction of said transition metal and raw material complex comprising ligand (b) having an azadiene structure coordinated to said metal and said ligand (b) preparative can be obtained by heating in the coexistence state,
The ligand (b) is a compound represented by the following general formula (2),
The unsaturated compound is represented by the following general formula (3-1), the following general formula (3-2), or compound der Ru metal complex represented by the following general formula (4).

(In the formula, Ar represents an optionally substituted divalent aromatic group, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, Substituted by formyl group, hydroxysulfonyl group, halogen atom, monovalent hydrocarbon group which may be substituted, hydrocarbyloxy group which may be substituted, two unsubstituted or substituted monovalent hydrocarbon groups Substituted with amino group, optionally substituted hydrocarbyl mercapto group, optionally substituted hydrocarbylcarbonyl group, optionally substituted hydrocarbyloxycarbonyl group, two unsubstituted or substituted monovalent hydrocarbon groups aminocarbonyl group, or an optionally substituted hydrocarbyloxy-sulfonyl group. plurality of Ar, R ^4, R ⁵ and R ⁶ Each of which may be the same or different.)

(Wherein R ⁷ represents a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, a halogen atom, an optionally substituted monovalent hydrocarbon group, or a substituted group. An optionally substituted hydrocarbyloxy group, an amino group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, an optionally substituted hydrocarbyl mercapto group, an optionally substituted hydrocarbylcarbonyl group, a substituted An optionally substituted hydrocarbyloxycarbonyl group, an aminocarbonyl group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, or an optionally substituted hydrocarbyloxysulfonyl group, and a plurality of R ⁷ are the same. However, they may be different, and a plurality of R ⁷ may be linked to each other.)

(Wherein R ¹⁰ represents a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, a halogen atom, a monovalent hydrocarbon group which may be substituted, or a substituted group. An optionally substituted hydrocarbyloxy group, an amino group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, an optionally substituted hydrocarbyl mercapto group, an optionally substituted hydrocarbylcarbonyl group, a substituted An optionally substituted hydrocarbyloxycarbonyl group, an aminocarbonyl group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, or an optionally substituted hydrocarbyloxysulfonyl group, and a plurality of R ¹⁰ are the same. However, they may be different, and a plurality of R ¹⁰ may be linked to each other.)

(Wherein R ⁸ represents a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, a halogen atom, an optionally substituted monovalent hydrocarbon group, or a substituted group. An optionally substituted hydrocarbyloxy group, an amino group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, an optionally substituted hydrocarbyl mercapto group, an optionally substituted hydrocarbylcarbonyl group, a substituted An optionally substituted hydrocarbyloxycarbonyl group, an aminocarbonyl group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, or an optionally substituted hydrocarbyloxysulfonyl group, and a plurality of R ⁸ are the same. But it may be different.)   The metal complex according to claim 1, which can be obtained by heating the raw material complex and the unsaturated compound in a range of 50C to 500C.   The metal complex according to claim 1 or 2, which can be obtained by heating the raw material complex and the unsaturated compound near the decomposition temperature of the unsaturated compound. The said unsaturated compound is a compound represented by following formula (5), The metal complex as described in any one of Claims 1-3 .

(In the formula, R ⁹ is a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, a halogen atom, an optionally substituted monovalent hydrocarbon group, or a substituted group. An optionally substituted hydrocarbyloxy group, an amino group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, an optionally substituted hydrocarbyl mercapto group, an optionally substituted hydrocarbylcarbonyl group, a substituted An optionally substituted hydrocarbyloxycarbonyl group, an aminocarbonyl group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, or an optionally substituted hydrocarbyloxysulfonyl group, and a plurality of R ⁹ are the same. But it may be different. also, X ² represents a leaving group, a plurality of X ² may be the same or different, multiple A number of X ² may be linked to each other.) The metal complex according to any one of claims 1 to 4 , wherein the unsaturated compound has a π _LUMO energy level of 0 eV or less. The unsaturated compound is a compound represented by the following general formula (5-a), the following general formula (5-b), the following general formula (5-c), or the following general formula (5-d). Item 6. The metal complex according to any one of Items 1 to 5.

(In formula (5-a), formula (5-b), formula (5-c) and formula (5-d), R ¹⁶ Is a hydrogen atom, hydroxyl group, amino group, nitro group, cyano group, carboxyl group, formyl group, hydroxysulfonyl group, halogen atom, monovalent hydrocarbon group which may be substituted, hydrocarbyloxy group which may be substituted , An amino group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, an optionally substituted hydrocarbyl mercapto group, an optionally substituted hydrocarbylcarbonyl group, an optionally substituted hydrocarbyloxycarbonyl A group, an aminocarbonyl group substituted with two unsubstituted or substituted monovalent hydrocarbon groups, or an optionally substituted hydrocarbyloxysulfonyl group. Multiple R ¹⁶ May be the same or different. ) The catalyst containing the metal complex as described in any one of Claims 1-6 . The electrode catalyst containing the metal complex as described in any one of Claims 1-6 .

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