JP2008169203A - Binuclear metal complexes and uses thereof - Google Patents

Abstract

【選択図】なしDisclosed is a binuclear metal complex useful for a redox reaction catalyst or the like, in which the catalytic activity hardly decreases even in the presence of a strong acid or at a high temperature.
A binuclear metal complex synthesized by the following reaction formula or the like.

[Selection figure] None

Description

  The present invention relates to a binuclear metal complex, and more particularly to a binuclear metal complex suitable as a catalyst.

  Metal complexes act as catalysts in redox reactions involving electron transfer, such as oxygen addition reactions, oxidative coupling reactions, dehydrogenation reactions, hydrogenation reactions, oxide decomposition reactions, and electrode reactions, and produce organic or polymer compounds. Is used. Furthermore, they are also used in various applications such as additives, modifiers, batteries, and sensor materials.

  In particular, as a redox reaction catalyst, a redox reaction involving multiple electron transfer is possible by using a polynuclear metal complex having a plurality of metal atoms in a molecule and a certain amount of metal atoms accumulated in a metal complex. Therefore, the reaction rate of the oxidation-reduction reaction can be increased, and side reactions caused by radical species generated by one-electron transfer can be suppressed. In addition, in the oxidative coupling reaction, it is known that radicals of two or more molecules can be generated at the same time, and not only the reaction rate is increased but also the reaction selectivity can be controlled.

As described above, polynuclear metal complexes are capable of accumulating metal sites as reaction sites, and are regarded as important as a method for enhancing the reaction activity and selectivity of catalysts. In particular, various types of binuclear metal complexes have been studied. . For example, it has been reported that when a binuclear copper complex having a bridged oxygen atom in the form of μ-oxo or μ-hydroxo disclosed in Patent Document 1 is used, efficient four-electron reduction of oxygen can be performed. Yes.
In addition, a number of reported examples of redox catalysts can be seen from the advantage that a binuclear metal complex having a Schiff base type ligand is easier to produce. For example, Non-Patent Document 1 reports that an optically active Schiff base-type copper binuclear complex catalyst causes asymmetric oxygen oxidation of naphthol, which shows that it is effective to be binuclear.

JP-A-11-276900 (Examples 1 and 2) Angew. Chem. Int. Ed., 2003, 42, 6008.

However, as a result of studies by the present inventors, the binuclear copper complex disclosed in Non-Patent Document 1 has a problem in that the catalytic activity is significantly reduced under heating. On the other hand, the binuclear metal complex disclosed in Patent Document 1 has a problem that the catalytic activity is impaired in the presence of a strong acid, and is a catalyst whose application range is limited. As described above, the conventionally disclosed binuclear metal complexes are likely to have low catalytic activity depending on the reaction conditions.
The present invention provides a binuclear metal complex useful for a redox reaction catalyst and the like, with almost no decrease in catalytic activity even in the presence of a strong acid or at a high temperature as compared with a conventionally disclosed binuclear metal complex catalyst. It is.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention provides binuclear metal complexes, polymers and catalysts shown in the following [1] to [8].

（式中、Ｍ¹、Ｍ²は、一方が長周期型周期表の第６族〜第９族に属する遷移金属原子を表し、他方が長周期型周期表の第６族〜第１１族に属する遷移金属原子を表し、Ｍ¹とＭ²は同一でも異なっていてもよい。
Ｒ^1a〜Ｒ^1f、Ｒ^2a〜Ｒ^2d、Ｒ^3a〜Ｒ^3dは、それぞれ独立に水素原子又は置換基を表し、Ｒ^1aとＲ^1b、Ｒ^1aとＲ^1c、Ｒ^1dとＲ^1e、Ｒ^1dとＲ^1f、Ｒ^2aとＲ^2b、Ｒ^2cとＲ^2d、Ｒ^1bとＲ^3a、Ｒ^1cとＲ^3c、Ｒ^1eとＲ^3b、Ｒ^1fとＲ^3dの、それぞれの組の２つの置換基は、互いに連結して環を形成していてもよい。
Ｘは、複核金属錯体を電気的に中性とする対イオン又は中性分子であり、ｍは、錯体中にあるＸの個数であり、０〜４の整数を表し、Ｘが複数ある場合それらは同一でも異なっていてもよい。
→は、Ｍ¹又はＭ²に対する配位結合又はイオン結合を表す。）
［２］前記式（１）で表される複核金属錯体における、Ｍ¹、Ｍ²のうち、少なくともどちらかが長周期型周期表の第４周期に属する遷移金属イオンである［１］の複核金属錯体
［３］下記式(２)で表される複核金属錯体

（式中、Ｍ¹、Ｍ²は、一方が長周期型周期表の第６族〜第９族に属する遷移金属原子を表し、他方が長周期型周期表の第６族〜第１１族に属する遷移金属原子を表し、Ｍ¹とＭ²は同一でも異なっていてもよい。
Ｒ^4a〜Ｒ^4f、Ｒ^5a〜Ｒ^5h、Ｒ^6a〜Ｒ^6dは、それぞれ独立に水素原子又は置換基を表し、Ｒ^4aとＲ^4b、Ｒ^4aとＲ^4c、Ｒ^4dとＲ^4e、Ｒ^4dとＲ^4f、Ｒ^5aとＲ^5b、Ｒ^5bとＲ^5c、Ｒ^5cとＲ^5d、Ｒ^5eとＲ^5f、Ｒ^5fとＲ^5g、Ｒ^5gとＲ^5h、Ｒ^4bとＲ^6a、Ｒ^4eとＲ^6b、Ｒ^4cとＲ^6c、Ｒ^4fとＲ^6dのそれぞれの組の２つの置換基は、互いに連結して環を形成していてもよい。
Ｘは、複核金属錯体を電気的に中性とする対イオン又は中性分子であり、ｍは、錯体中にあるＸの個数であり、０〜４の整数を表し、Ｘが複数ある場合それらは同一でも異なっていてもよい。
→は、Ｍ¹又はＭ²に対する配位結合又はイオン結合を表す。）
［４］前記式（２）で表される複核金属錯体における、Ｍ¹、Ｍ²のうち、少なくともどちらかが長周期型周期表の第４周期に属する遷移金属イオンである［３］の複核金属錯体
［５］下記式(３)で表される複核金属錯体

（式中、Ｍ¹、Ｍ²は、一方が長周期型周期表の第６族〜第９族に属する遷移金属原子を表し、他方が長周期型周期表の第６族〜第１１族に属する遷移金属原子を表し、Ｍ¹とＭ²は同一でも異なっていてもよい。
Ｒ^7a、Ｒ^7b、Ｒ^8a〜Ｒ^8d、Ｒ^9a〜Ｒ^9dは、それぞれ独立に水素原子又は置換基を表し、Ｒ^8aとＲ^8b、Ｒ^8cとＲ^8dの、それぞれの組の２つの置換基は、互いに連結して環を形成していてもよい。
Ｘは、複核金属錯体を電気的に中性とする対イオンまたは中性分子であり、ｍは、錯体中にあるＸの個数であり、０〜４の整数を表し、Ｘが複数ある場合それらは同一でも異なっていてもよい。
→は、Ｍ¹又はＭ²に対する配位結合又はイオン結合を表す。）
[６]前記式（３）で表される複核金属錯体における、Ｍ¹、Ｍ²のうち、少なくともどちらかが長周期型周期表の第４周期に属する遷移金属イオンである［３］の複核金属錯体
[７]前記［１］〜［６］のいずれかに記載の複核金属錯体から水素原子または置換基を取り除いてなる部位を有する高分子。
[８]さらに、本発明は前記［１］〜［６］のいずれかの複核金属錯体および/または[７]の高分子を含む触媒を提供する。 [1] A binuclear metal complex represented by the following formula (1).

(In the formula, ^one of M ¹ and M ² represents a transition metal atom belonging to Group 6 to Group 9 of the long-period periodic table, and the other represents Group 6 to Group 11 of the long-period periodic table. It represents the transition metal atom to which it belongs, and M ¹ and M ² may be the same or different.
R ^{1a to} R ^1f , R ^{2a to} R ^2d , and R ^{3a to} R ^3d each independently represent a hydrogen atom or a substituent, and R ^1a and R ^1b , R ^1a and R ^1c , R ^1d and R ^1e , R ^1d And R ^1f , R ^2a and R ^2b , R ^2c and R ^2d , R ^1b and R ^3a , R ^1c and R ^3c , R ^1e and R ^3b , R ^1f and R ^3d , May be linked to each other to form a ring.
X is a counter ion or neutral molecule that makes the binuclear metal complex electrically neutral, m is the number of X in the complex, represents an integer of 0 to 4, and when there are a plurality of X, May be the same or different.
→ represents a coordination bond or ionic bond to M ¹ or M ² . )
[2] The binuclear metal of [1], wherein at least ^one of M ¹ and M ² in the binuclear metal complex represented by the formula (1) is a transition metal ion belonging to the fourth period of the long-period periodic table. Metal complex [3] Binuclear metal complex represented by the following formula (2)

(In the formula, ^one of M ¹ and M ² represents a transition metal atom belonging to Group 6 to Group 9 of the long-period periodic table, and the other represents Group 6 to Group 11 of the long-period periodic table. It represents the transition metal atom to which it belongs, and M ¹ and M ² may be the same or different.
R ^{4a to} R ^4f , R ^{5a to} R ^5h and R ^{6a to} R ^6d each independently represent a hydrogen atom or a substituent, and R ^4a and R ^4b , R ^4a and R ^4c , R ^4d and R ^4e , R ^4d And R ^4f , R ^5a and R ^5b , R ^5b and R ^5c , R ^5c and R ^5d , R ^5e and R ^5f , R ^5f and R ^5g , R ^5g and R ^5h , R ^4b and R ^6a , R ^4e and R Two substituents of each set of ^6b , R ^4c and R ^6c , R ^4f and R ^6d may be linked to each other to form a ring.
X is a counter ion or neutral molecule that makes the binuclear metal complex electrically neutral, m is the number of X in the complex, represents an integer of 0 to 4, and when there are a plurality of X, May be the same or different.
→ represents a coordination bond or ionic bond to M ¹ or M ² . )
[4] In the binuclear metal complex represented by the formula (2), at least ^one of M ¹ and M ² is a transition metal ion belonging to the fourth period of the long-period periodic table [3] Metal complex [5] Binuclear metal complex represented by the following formula (3)

(In the formula, ^one of M ¹ and M ² represents a transition metal atom belonging to Group 6 to Group 9 of the long-period periodic table, and the other represents Group 6 to Group 11 of the long-period periodic table. It represents the transition metal atom to which it belongs, and M ¹ and M ² may be the same or different.
R ^7a , R ^7b , R ^{8a to} R ^8d , R ^{9a to} R ^9d each independently represents a hydrogen atom or a substituent, and two substitutions in each set of R ^8a and R ^8b , R ^8c and R ^8d The groups may be connected to each other to form a ring.
X is a counter ion or a neutral molecule that makes the binuclear metal complex electrically neutral, m is the number of X in the complex, represents an integer of 0 to 4, and when there are a plurality of X, May be the same or different.
→ represents a coordination bond or ionic bond to M ¹ or M ² . )
[6] In the binuclear metal complex represented by the formula (3), at least ^one of M ¹ and M ² is a transition metal ion belonging to the fourth period of the long-period periodic table [3] Metal complex
[7] A polymer having a site obtained by removing a hydrogen atom or a substituent from the binuclear metal complex according to any one of [1] to [6].
[8] Furthermore, the present invention provides a catalyst comprising the binuclear metal complex of any one of [1] to [6] and / or the polymer of [7].

  The binuclear metal complex of the present invention is excellent in heat resistance and acid resistance. Therefore, the binuclear metal complex is industrially useful because it can be a catalyst with a wide range of applications because the decrease in catalytic activity is suppressed even in the presence of a strong acid or at a high temperature.

The binuclear metal complex represented by the formula (1), which is the first embodiment of the present invention, will be described. The binuclear metal complex is a complex in which two transition metal atoms (M ¹ , M ² ) form a complex with a ligand having four nitrogen atoms and two oxygen atoms, and the four nitrogen atoms Π electrons in a ring having a delocalization. The bond connecting the oxygen atom and the metal atom is a coordination bond or an ionic bond, and may be bridged between two transition metal atoms. Here, “transition metal” has the same meaning as “transition element” described on page 1283 of “Chemical Dictionary” (Michinori Oki et al., Issued July 1, 2005, Tokyo Kagaku Dojin). Yes, means an element with an incomplete d or f subshell. The transition metal atom in the present invention may be an uncharged or charged ion.
Here, one of M ¹ and M ² is a transition metal atom selected from transition metal atoms belonging to Groups 6 to 9 of the long-period periodic table, and the other is Group 6 of the long-period periodic table. ~ Transition metal atom selected from transition metal atoms belonging to Group 11.
Specific examples of the former transition metal atom include chromium, manganese, iron, cobalt, molybdenum, technesium, ruthenium, rhodium, tungsten, rhenium, osmium, and iridium. Preferred is chromium, manganese, iron, cobalt, molybdenum, ruthenium, rhodium, more preferred is chromium, manganese, iron, cobalt, and still more preferred is manganese, iron, cobalt belonging to the fourth period of the periodic table. It is. In the present invention, as described above, the former transition metal atom is preferably a transition metal ion belonging to the fourth period of the periodic table.

  Specific examples of the latter transition metal atoms include transition metal atoms selected from nickel, copper, palladium, silver, platinum and gold in addition to the above-described examples of the former transition metal atoms. Preferably, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, more preferably chromium, manganese, iron, cobalt, nickel, copper, and more preferably the period. Manganese, iron, cobalt, nickel, and copper belonging to the fourth period of the table. The latter transition metal atom is preferably a transition metal ion belonging to the fourth period of the periodic table.

Next, the ligand of the binuclear metal complex represented by the formula (1) will be described. As described above, the ligand has four nitrogen atoms and two oxygen atoms as coordination atoms, and the ring having the four nitrogen atoms delocalizes π electrons on the ring, that is, π-conjugated. This ring may have a substituent, and R ^{1a to} R ^1f , R ^{2a to} R ^2f , and R ^{3a to} R ^3d in formula (1) are each independently a hydrogen atom or a substituent. .
Here, as the substituent, a halogeno group such as a fluoro group, a chloro group, a bromo group, and an iodo group, a hydroxy group, a carboxyl group, a mercapto group, a sulfonic acid group, a nitro group, a phosphonic acid group, and a carbon number of 1 to 3 Silyl group having an alkyl group, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, norbornyl Straight chain having 1 to 50 carbon atoms in total, such as a group, nonyl group, cyclononyl group, decyl group, 3,7-dimethyloctyl group, adamantyl group, dodecyl group, cyclododecyl group, pentadecyl group, octadecyl group, docosyl group, Branched or cyclic saturated hydrocarbon group, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy Group, cyclohexyloxy group, norbornyloxy group, decyloxy group, dodecyloxy group, etc., straight, branched or cyclic alkoxy group having about 1 to 50 carbon atoms, phenyl group, 4-methylphenyl group, 1-naphthyl Examples include aromatic groups having 3 to 60 carbon atoms, such as a group, 2-naphthyl group, pyridyl group, furyl group, oxazolyl group, imidazolyl group, pyrazolyl group, pyrazyl group, pyrimidyl group, pyridazyl group, and benzoimidazolyl group. Is done.
R ^{1a to} R ^1f , R ^{2a to} R ^2f and R ^{3a to} R ^3d are preferably halogeno groups such as fluoro group, chloro group, bromo group and iodo group, mercapto group, hydroxy group, carboxyl group, methyl group, ethyl Group, propyl group, isopropyl group, butyl group, pentyl group, tert-butyl group, cyclohexyl group, norbornyl group, hydrocarbon group having about 1 to 20 carbon atoms exemplified by adamantyl group, methoxy group, ethoxy group , A propoxy group, a butoxy group, a pentyloxy group, a linear or branched alkoxy group having about 1 to 10 carbon atoms, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, etc. It is an aromatic group having about 6 to 30 carbon atoms.
More preferred are chloro, bromo, hydroxy, carboxyl, methyl, ethyl, tert-butyl, cyclohexyl, norbornyl, adamantyl, methoxy, ethoxy and phenyl groups.

R ^1a and R ^1b , R ^1a and R ^1c , R ^1d and R ^1e , R ^1d and R ^1f , R ^2a and R ^2b , R ^2c and R ^2d , R ^1b and R ^3a , R ^1c and R ^3c , Two substituents of each set of R ^1e and R ^3b and R ^1f and R ^3d may be connected to each other to form a ring.
Here, as the ring, cyclohexene ring, benzene ring, naphthalene ring, anthracene ring, tetracene ring, perylene ring, pentacene ring, acenaphthene ring and other hydrocarbon rings, pyran ring, furan ring, pyridine ring, pyrazine ring, pyrazolyl ring, Aromatic heterocycles such as imidazolyl ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, thiophene ring and the like can be mentioned. The ring is preferably a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring, particularly preferably a benzene ring and a naphthalene ring, and most preferably a benzene ring.
The ring formed by linking a combination of two substituents may further have a substituent, and these substituents are equivalent to the substituents exemplified above. Can be mentioned.
As the binuclear metal complex of the present invention, among the combinations of the two substituents exemplified above, it is preferable that a combination of one or more substituents forms a ring. The heat resistance of the is further improved.

  X in the above formula (1) is a neutral molecule or a counter ion that electrically neutralizes the binuclear metal complex. Examples of the neutral molecule include a molecule that solvates to form a solvated salt, and a ligand other than the cyclic ligand in formula (1). Specific examples of the neutral molecule include water, methanol, ethanol, n-propanol, isopropyl alcohol, 2-methoxyethanol, 1,1-dimethylethanol, ethylene glycol, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, acetone, chloroform, acetonitrile, benzonitrile, triethylamine, pyridine, pyrazine, diazabicyclo [2,2,2] octane, 4,4′-bipyridine , Tetrahydrofuran, diethyl ether, dimethoxyethane, methyl ethyl ether, 1,4-dioxane. Preferably, water, methanol, ethanol, isopropyl alcohol, ethylene glycol, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, chloroform, acetonitrile, benzonitrile, triethylamine, pyridine, Pyrazine, diazabicyclo [2,2,2] octane, 4,4′-bipyridine, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane.

When X is an ion, the transition metal atoms of M ¹ and M ² usually have a positive charge, so an anion that makes this electrically neutral is selected, and 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, tri Fluoroacetate ion, thiocyanide ion, trifluoromethanesulfonate ion, acetylacetonate, tetrafluoroborate ion, hexafluorophosphate ion, tetraphenylborate ion. Preferably, 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 , Tetraphenylborate ion.
When a plurality of X are present, they may be the same or different, and a form in which neutral molecules and ions coexist is also possible.

（式中、Ｒ^1a〜Ｒ^1f、Ｒ^2a〜Ｒ^2d、Ｒ^3a〜Ｒ^3dは前記式（１）と同義である。）
なお、金属供与剤とは、前記の遷移金属原子Ｍ¹、Ｍ²を有する化合物であり、通常これらの遷移金属を陽イオンとして有する塩が用いられる。 Here, the manufacturing method of the binuclear metal complex represented by Formula (1) is demonstrated.
The binuclear metal complex represented by the formula (1) is a phenol compound having two carbonyl groups represented by the following formula (4a) and / or formula (4b) that form a ligand at the 2-position and the 6-position. (Hereinafter referred to as “phenol compound”) and a diamine derivative represented by the following formula (4c) and / or formula (4d) (hereinafter referred to as “diamine compound”) to donate a transition metal atom It can be obtained by condensation in the presence of an agent (hereinafter referred to as “metal donor”).

(In formula, R < ^1a > -R <^1f> , R < ^2a > -R <^2d> , R < ^3a > -R <^3d> is synonymous with the said Formula (1).]
The metal donor is a compound having the aforementioned transition metal atoms M ¹ and M ² , and usually a salt having these transition metals as cations is used.

As described above, the binuclear metal complex of the present invention can be obtained by condensing the phenol compound, the diamine compound and the metal-imparting agent in the presence of an appropriate reaction solvent. Specifically, examples of the reaction solvent include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, 2-methoxyethanol, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, acetonitrile, Examples include benzonitrile, acetone, 1-methyl-2-pyrrolidinone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetic acid, benzene, toluene, xylene, dichloromethane, chloroform, and carbon tetrachloride. Although a reaction solvent may be used, those in which the phenol compound, diamine compound and metal imparting agent to be applied are soluble are preferred. The reaction temperature is usually −10 to 200 ° C., preferably 0 to 150 ° C., particularly preferably 0 to 100 ° C., and the reaction time is usually 1 minute to 1 week, preferably 5 minutes to 24 hours, particularly preferably 1 hour. Can be carried out in ~ 6 hours. The reaction temperature and reaction time can also be optimized as appropriate depending on the type of phenol compound, diamine compound and metal imparting agent to be applied.
In addition, the binuclear metal complex of the present invention was obtained by condensing a phenol compound and a diamine compound in the aforementioned reaction solvent in the presence of an acid such as hydrochloric acid as described in the document Journal of Organic Chemistry 1999, 64, 1442. Thereafter, it can also be produced using a method of adding a metal salt. As the metal salt, acetate, hydrochloride, sulfate, carbonate and the like can be used.
As a means for isolating and purifying the produced binuclear metal complex from the reaction solution after the reaction, an optimal means can be appropriately selected and used from known recrystallization methods, reprecipitation methods or chromatography methods. You may combine a means.
Depending on the type of the reaction solvent, the produced binuclear metal complex may be precipitated, and the precipitated binuclear metal complex may be separated by filtration or the like, and may be washed or dried as necessary. A metal complex can also be isolated and purified.

Examples of the binuclear metal complex represented by the formula (1) include those having the ligand skeleton structures (a-I) to (a-XI) shown below.
The transition metal atom is not shown and the charge is omitted. In the following examples, Me represents methyl, Et represents ethyl, and t-Bu represents tert-butyl.

Specific examples of the binuclear metal complex represented by the formula (1) include the following (I) to (XII). In the following examples, the charge and X of the binuclear metal complex are omitted, Me represents methyl, Et represents ethyl, and t-Bu represents tert-butyl.

（式中、Ｍ¹、Ｍ²は、一方が長周期型周期表の第６族〜第９族に属する遷移金属原子を表し、他方が長周期型周期表の第６族〜第１１族に属する遷移金属原子を表し、Ｍ¹とＭ²は同一でも異なっていてもよい。
Ｒ⁷、Ｒ^8a〜Ｒ^8d、Ｒ⁹は、それぞれ独立に水素原子又は置換基を表し、２つのＲ⁷、４つのＲ⁹は同一でも異なっていてもよい。Ｒ^8aとＲ^8b、Ｒ^8cとＲ^8dの、それぞれの組の２つの置換基は、互いに連結して環を形成していてもよい。
Ｘは、複核金属錯体を電気的に中性とする対イオンまたは中性分子であり、ｍは、錯体中にあるＸの個数であり、０〜４の整数を表し、Ｘが複数ある場合それらは同一でも異なっていてもよい。
→は、Ｍ¹又はＭ²に対する配位結合又はイオン結合を表す。） In the binuclear metal complex represented by the formula (1), the longer the conjugated length of the delocalized π electrons, the better the heat resistance, and specifically, the combination of the two substituents described above. Among them, in a combination of one or more substituents, a binuclear metal complex having a ligand in which a ring formed by connecting two substituents is an aromatic allocyclic ring or an aromatic heterocyclic ring is preferable. Thus, a binuclear metal complex having a ligand in which the number of aromatic homocycles and / or aromatic heterocycles formed by linking two substituents is increased tends to be higher in heat resistance.
Preferably, in the combination of the two substituents, R ^2a and R ^2b and R ^2c and R ^2d are each a binuclear metal complex having a ligand in the form of an aromatic ring linked to each other, As a second embodiment of the present invention, a binuclear metal complex represented by the following formula (2) can be exemplified.

(In the formula, ^one of M ¹ and M ² represents a transition metal atom belonging to Group 6 to Group 9 of the long-period periodic table, and the other represents Group 6 to Group 11 of the long-period periodic table. It represents the transition metal atom to which it belongs, and M ¹ and M ² may be the same or different.
R ⁷ , R ^{8a to} R ^8d and R ⁹ each independently represents a hydrogen atom or a substituent, and two R ⁷ and four R ⁹ may be the same or different. The two substituents in each set of R ^8a and R ^8b and R ^8c and R ^8d may be linked to each other to form a ring.
X is a counter ion or a neutral molecule that makes the binuclear metal complex electrically neutral, m is the number of X in the complex, represents an integer of 0 to 4, and when there are a plurality of X, May be the same or different.
→ represents a coordination bond or ionic bond to M ¹ or M ² . )

When any of R ^{4a to} R ^4f , R ^{5a to} R ^5h , and R ^{6a to} R ^{6d in} the formula (2) is a substituent, examples of the substituent include the substituent in the formula (1) The thing equivalent to the illustrated group is mentioned.
R ^4a and R ^4b , R ^4a and R ^4c , R ^4d and R ^4e , R ^4d and R ^4f , R ^5a and R ^5b , R ^5b and R ^5c , R ^5c and R ^5d , R ^5e and R ^5f , The two substituents of each group of R ^5f and R ^5g , R ^5g and R ^5h , R ^4b and R ^6a , R ^4e and R ^6b , R ^4c and R ^6c , R ^4f and R ^6d are linked together. The ring may form a hydrocarbon ring such as cyclohexene ring, benzene ring, naphthalene ring, anthracene ring, acenaphthene ring, pyran ring, furan ring, pyridine ring, pyrazine ring, pyrazolyl ring, imidazolyl. Aromatic heterocycles such as a ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, and a thiophene ring are exemplified, and among these, a monocyclic aromatic homocyclic ring or a monocyclic aromatic heterocyclic ring is preferable. Thus, when the combination of the two substituents in formula (2) forms a monocyclic aromatic homocyclic ring or monocyclic aromatic heterocyclic ring, the binuclear metal complex has the formula This corresponds to the fact that the ring formed by linking the combination of the two substituents shown in (1) is a condensed polycycle.

  Here, the illustration about the binuclear metal complex specifically represented by Formula (2) can mention (III)-(XII) in the illustration of said Formula (1).

（式中、Ｍ¹、Ｍ²は、一方が長周期型周期表の第６族〜第９族に属する遷移金属原子を表し、他方が長周期型周期表の第６族〜第１１族に属する遷移金属原子を表し、Ｍ¹とＭ²は同一でも異なっていてもよい。
Ｒ^7a、Ｒ^7b、Ｒ^8a〜Ｒ^8d、Ｒ^9a〜Ｒ^9dは、それぞれ独立に水素原子又は置換基を表し、Ｒ^8aとＲ^8b、Ｒ^8cとＲ^8dの、それぞれの組の２つの置換基は、互いに連結して環を形成していてもよい。
Ｘは、複核金属錯体を電気的に中性とする対イオンまたは中性分子であり、ｍは、錯体中にあるＸの個数であり、０〜４の整数を表し、Ｘが複数ある場合それらは同一でも異なっていてもよい。
→は、Ｍ¹又はＭ²に対する配位結合又はイオン結合を表す。） In the binuclear metal complex represented by the formula (2), R ^4b , R ^4c , R ^4e , R ^4f , R ^5a , R ^5d , R ^5e, and R ^5h are each a hydrogen atom. A binuclear metal complex that can be used can be cited as a third embodiment of the present invention.

(In the formula, ^one of M ¹ and M ² represents a transition metal atom belonging to Group 6 to Group 9 of the long-period periodic table, and the other represents Group 6 to Group 11 of the long-period periodic table. It represents the transition metal atom to which it belongs, and M ¹ and M ² may be the same or different.
R ^7a , R ^7b , R ^{8a to} R ^8d , R ^{9a to} R ^9d each independently represents a hydrogen atom or a substituent, and two substitutions in each set of R ^8a and R ^8b , R ^8c and R ^8d The groups may be connected to each other to form a ring.
X is a counter ion or a neutral molecule that makes the binuclear metal complex electrically neutral, m is the number of X in the complex, represents an integer of 0 to 4, and when there are a plurality of X, May be the same or different.
→ represents a coordination bond or ionic bond to M ¹ or M ² . )

  The binuclear metal complex represented by the formula (3) has an advantage that both a phenol compound and a diamine compound for deriving a ligand of the binuclear metal complex can use raw materials that are industrially easily available. It is preferable because the binuclear metal complex of the present invention can be obtained at low cost.

The binuclear metal complex of the present invention can also be used as a polymer having a site obtained by removing one or more hydrogen atoms or substituents from the metal complex. For example, the site constitutes the main chain as a side chain. It may be bonded to a polymer. The polymer constituting the main chain is not particularly limited, and examples thereof include conductive polymers, dendrimers, and natural polymers. Among these, a conductive polymer is particularly preferable. The conductive polymer is a general term for high-molecular substances exhibiting metallic or semiconducting conductivity (Iwanami Rikagaku Dictionary 5th edition: issued in 1998). Examples of conductive polymers include polyacetylene and polyacetylene described in “Conductive Polymers” (Shinichi Yoshimura, Kyoritsu Publishing) and “Latest Applied Technology for Conducting Polymers” (supervised by Masao Kobayashi, CMC Publishing). Derivatives thereof, polyparaphenylene and derivatives thereof, polyparaphenylene vinylene and derivatives thereof, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyfluorene and derivatives thereof, polycarbazole and derivatives thereof, polyindole and derivatives thereof And a copolymer of the conductive polymer.
Moreover, the binuclear metal complex of the present invention can also be used as a polymer containing as a repeating unit a site obtained by removing a plurality of hydrogen atoms and / or substituents from the binuclear metal complex.

All of the binuclear metal complexes of the present invention have high heat resistance and acid resistance, and the complex structure is stably maintained even at high temperatures or in the presence of strong acids, so catalysis related to two metal sites is expected. Is done.
In particular, the binuclear metal complex is suitable for use as a redox catalyst or the like, and specifically, a decomposition catalyst for hydrogen peroxide, an oxidation polymerization catalyst for aromatic compounds, a catalyst for exhaust gas / drainage purification, a dye-sensitized solar cell. Applications of the redox catalyst layer, carbon dioxide reduction catalyst, reformed hydrogen production catalyst, oxygen sensor and the like. Further, it is considered that it can be used as an organic EL light-emitting material by utilizing the fact that the conjugated skeleton is widened.

窒素雰囲気下において０．４７６ｇの塩化コバルト６水和物と０．４１２gの４―ｔｅｒｔ-ブチル−２，６−ジホルミルフェノールを含んだ１０ｍｌエタノール溶液を５０ｍｌのナスフラスコに入れ、室温にて攪拌した。この溶液に０．２１６ｇのｏ−フェニレンジアミンを含んだ５ｍｌエタノール溶液を徐々に添加した。上記混合物を２時間還流することにより茶褐色沈殿が生成した。この沈殿を濾取し、乾燥することで複核金属錯体（Ａ）を得た（収量０．４６５ｇ：収率６３％）。得られた複核金属錯体（Ａ）の赤外線（ＩＲ）吸収スペクトルを図１に示す。元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₃₆Ｈ₃₈Ｃｌ₂Ｃｏ₂Ｎ₄Ｏ₄；Ｃ，５５．４７；Ｈ，４．９１；Ｎ，７．１９．Ｆｏｕｎｄ：Ｃ，５６．３４；Ｈ，４．８３；Ｎ，７．２３．なお、上記反応式において「Ｃｌ₂」とは２当量の塩化物イオンが対イオンとしてあることを示し、「２Ｈ₂Ｏ」とは、２当量の水分子が複核金属錯体（Ａ）を構成する成分として含まれていることを示す。 Example 1 [Synthesis of Binuclear Metal Complex (A)]
The binuclear metal complex (A) was synthesized according to the following reaction formula.

In a nitrogen atmosphere, 10 ml ethanol solution containing 0.476 g cobalt chloride hexahydrate and 0.412 g 4-tert-butyl-2,6-diformylphenol was placed in a 50 ml eggplant flask and stirred at room temperature. did. To this solution was gradually added a 5 ml ethanol solution containing 0.216 g o-phenylenediamine. The mixture was refluxed for 2 hours to produce a brown precipitate. The precipitate was collected by filtration and dried to obtain a binuclear metal complex (A) (yield 0.465 g: yield 63%). The infrared (IR) absorption spectrum of the obtained binuclear metal complex (A) is shown in FIG. Elemental analysis value (%): Calcd for C ₃₆ H ₃₈ Cl ₂ Co ₂ N ₄ O ₄ ; C, 55.47; H, 4.91; N, 7.19. Found: C, 56.34; H, 4.83; N, 7.23. In the above reaction formula, “Cl ₂ ” indicates that 2 equivalents of chloride ions are present as counter ions, and “2H ₂ O” indicates that 2 equivalents of water molecules constitute the binuclear metal complex (A). Indicates that it is contained as a component.

窒素雰囲気下において０．２３８ｇの塩化コバルト６水和物と０．１９２gの４―メチル−２，６−ジアセチルフェノールを含んだ５ｍｌエタノール溶液を５０ｍｌのナスフラスコに入れ、室温にて攪拌した。この溶液に０．１０８ｇのｏ−フェニレンジアミンを含んだ１０ｍｌエタノール溶液を徐々に添加した。上記混合物を３時間還流することにより茶褐色沈殿が生成した。この沈殿を濾取し、乾燥することで複核金属錯体（Ｂ）を得た（収量０．１２９ｇ：収率３６％）。得られた複核金属錯体（Ｂ）の赤外線（ＩＲ）吸収スペクトルを図２に示す。元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₃₄Ｈ₃₄Ｃｌ₂Ｃｏ₂Ｎ₄Ｏ₄；Ｃ，５４．３４；Ｈ，４．５６；Ｎ，７．４６．Ｆｏｕｎｄ：Ｃ，５３．５７；Ｈ，４．４９；Ｎ，７．００．なお、上記反応式において「Ｃｌ₂」とは２当量の塩化物イオンが対イオンとしてあることを示し、「２Ｈ₂Ｏ」とは、２当量の水分子が複核金属錯体（Ｂ）を構成する成分として含まれていることを示す。 Example 2 [Synthesis of Binuclear Metal Complex (B)]
The binuclear metal complex (B) was synthesized according to the following reaction formula.

Under a nitrogen atmosphere, a 5 ml ethanol solution containing 0.238 g of cobalt chloride hexahydrate and 0.192 g of 4-methyl-2,6-diacetylphenol was placed in a 50 ml eggplant flask and stirred at room temperature. To this solution was slowly added a 10 ml ethanol solution containing 0.108 g o-phenylenediamine. The mixture was refluxed for 3 hours to produce a brown precipitate. The precipitate was collected by filtration and dried to obtain a binuclear metal complex (B) (yield 0.129 g: yield 36%). The infrared (IR) absorption spectrum of the obtained binuclear metal complex (B) is shown in FIG. Elemental analysis _{(%): Calcd for C 34} H 34 Cl 2 Co 2 N 4 O 4; C, 54.34; H, 4.56; N, 7.46. Found: C, 53.57; H, 4.49; N, 7.00. In the above reaction formula, “Cl ₂ ” indicates that 2 equivalents of chloride ions are present as a counter ion, and “2H ₂ O” indicates that 2 equivalents of water molecules constitute the binuclear metal complex (B). Indicates that it is contained as a component.

窒素雰囲気下において０．４７６ｇの塩化コバルト６水和物と０．３２８gの４―メチル−２，６−ジホルミルフェノールを含んだ２５ｍｌメタノール溶液を１００ｍｌのナスフラスコに入れ、室温にて攪拌した。この溶液に０．２１６ｇのｏ−フェニレンジアミンを含んだ５ｍｌメタノール溶液を徐々に添加した。上記混合物を室温で2時間攪拌することにより黒褐色沈殿が生成した。この沈殿を濾取し、乾燥することで複核金属錯体（Ｃ）を得た（収量０．３６８ｇ：収率５６％）。得られた複核金属錯体（Ｃ）の赤外線（ＩＲ）吸収スペクトルを図３に示す。元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₃₀Ｈ₂₆Ｃｌ₂Ｃｏ₂Ｎ₄Ｏ₄；Ｃ，５１．８２；Ｈ，３．７７；Ｎ，８．０６．Ｆｏｕｎｄ：Ｃ，５２．４１；Ｈ，３．９５；Ｎ，８．２０．なお、上記反応式において「Ｃｌ₂」とは２当量の塩化物イオンが対イオンとしてあることを示し、「２Ｈ₂Ｏ」とは、２当量の水分子が複核金属錯体（Ｃ）を構成する成分として含まれていることを示す。 Example 3 [Synthesis of Binuclear Metal Complex (C)]
The binuclear metal complex (C) was synthesized according to the following reaction formula.

Under a nitrogen atmosphere, a 25 ml methanol solution containing 0.476 g cobalt chloride hexahydrate and 0.328 g 4-methyl-2,6-diformylphenol was placed in a 100 ml eggplant flask and stirred at room temperature. To this solution was slowly added a 5 ml methanol solution containing 0.216 g o-phenylenediamine. The mixture was stirred at room temperature for 2 hours to produce a black brown precipitate. The precipitate was collected by filtration and dried to obtain a binuclear metal complex (C) (yield 0.368 g: yield 56%). The infrared (IR) absorption spectrum of the obtained binuclear metal complex (C) is shown in FIG. Elemental analysis _{(%): Calcd for C 30} H 26 Cl 2 Co 2 N 4 O 4; C, 51.82; H, 3.77; N, 8.06. Found: C, 52.41; H, 3.95; N, 8.20. In the above reaction formula, “Cl ₂ ” indicates that 2 equivalents of chloride ions are present as a counter ion, and “2H ₂ O” indicates that 2 equivalents of water molecules constitute the binuclear metal complex (C). Indicates that it is contained as a component.

窒素雰囲気下において０．４７６ｇの塩化コバルト６水和物と０．４１２gの４―ｔｅｒｔ-ブチル−２，６−ジホルミルフェノールを含んだ１０ｍｌエタノール溶液を５０ｍｌのナスフラスコに入れ、室温にて攪拌した。この溶液に０．２７２ｇの４、５―ジメチルー１、２―フェニレンジアミンを含んだ１０ｍｌエタノール溶液を徐々に添加した。上記混合物を２時間還流することにより茶褐色沈殿が生成した。この沈殿を濾取し、乾燥することで複核金属錯体（Ｄ）を得た（収量０．５１３ｇ：収率６４％）。得られた複核金属錯体（Ｄ）の赤外線（ＩＲ）吸収スペクトルを図３に示す。元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₃₆Ｈ₃₄Ｃｌ₂Ｃｏ₂Ｎ₄Ｏ₂；Ｃ，５７．５０；Ｈ，５．５５；Ｎ，６．７１．Ｆｏｕｎｄ：Ｃ，５３．８５；Ｈ，５．８６；Ｎ，５．７８．なお、上記反応式において「Ｃｌ₂」とは２当量の塩化物イオンが対イオンとしてあることを示し、「２Ｈ₂Ｏ」とは、２当量の水分子が複核金属錯体（Ｄ）を構成する成分として含まれていることを示す。 Example 4 [Synthesis of Binuclear Metal Complex (D)]
The binuclear metal complex (D) was synthesized according to the following reaction formula.

In a nitrogen atmosphere, 10 ml ethanol solution containing 0.476 g cobalt chloride hexahydrate and 0.412 g 4-tert-butyl-2,6-diformylphenol was placed in a 50 ml eggplant flask and stirred at room temperature. did. To this solution was gradually added 10 ml ethanol solution containing 0.272 g of 4,5-dimethyl-1,2-phenylenediamine. The mixture was refluxed for 2 hours to produce a brown precipitate. The precipitate was collected by filtration and dried to obtain a binuclear metal complex (D) (yield 0.513 g: yield 64%). The infrared (IR) absorption spectrum of the obtained binuclear metal complex (D) is shown in FIG. Elemental analysis _{(%): Calcd for C 36} H 34 Cl 2 Co 2 N 4 O 2; C, 57.50; H, 5.55; N, 6.71. Found: C, 53.85; H, 5.86; N, 5.78. In the above reaction formula, “Cl ₂ ” indicates that 2 equivalents of chloride ions are present as counter ions, and “2H ₂ O” indicates that 2 equivalents of water molecules constitute the dinuclear metal complex (D). Indicates that it is contained as a component.

窒素雰囲気下において１．９ｇの塩化コバルト６水和物と１．３１gの４―メチル−２，６−ジホルミルフェノールを含んだ５０ｍｌメタノール溶液を１００ｍｌのナスフラスコに入れ、室温にて攪拌した。この溶液に０．５９ｇの１，３−プロパンジアミンを含んだ２０ｍｌメタノールを徐々に添加した。上記混合物を３時間還流することにより茶褐色沈殿が生成した。この沈殿を濾取し、乾燥することで複核金属錯体（Ｅ）を得た（収量１．７５ｇ：収率７４％）。元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₂₆Ｈ₃₄Ｃｌ₂Ｃｏ₂Ｎ₄Ｏ₄；Ｃ，４７．６５；Ｈ，５．２３；Ｎ，８．５５．Ｆｏｕｎｄ：Ｃ，４６．６４；Ｈ，５．０２；Ｎ，８．５８．なお、上記反応式において「Ｃｌ₂」とは２当量の塩化物イオンが対イオンとしてあることを示し、「２ＭｅＯＨ」とは、２当量のメタノール分子が複核金属錯体（Ｅ）を構成する成分として含まれていることを示す。 Comparative Example 1 [Synthesis of Binuclear Metal Complex (E)]
The binuclear metal complex (E) was synthesized according to the method described in Australian Journal of Chemistry, 1970, 23, 2225 as shown in the following reaction formula.

Under a nitrogen atmosphere, a 50 ml methanol solution containing 1.9 g of cobalt chloride hexahydrate and 1.31 g of 4-methyl-2,6-diformylphenol was placed in a 100 ml eggplant flask and stirred at room temperature. To this solution was slowly added 20 ml methanol containing 0.59 g 1,3-propanediamine. The mixture was refluxed for 3 hours to produce a brown precipitate. The precipitate was collected by filtration and dried to obtain a binuclear metal complex (E) (yield 1.75 g: yield 74%). Elemental analysis _{(%): Calcd for C 26} H 34 Cl 2 Co 2 N 4 O 4; C, 47.65; H, 5.23; N, 8.55. Found: C, 46.64; H, 5.02; N, 8.58. In the above reaction formula, “Cl ₂ ” means that 2 equivalents of chloride ions are used as a counter ion, and “2MeOH” means that 2 equivalents of methanol molecules are components constituting the dinuclear metal complex (E). Indicates that it is included.

窒素雰囲気下において０．４７６ｇの塩化コバルト６水和物と０．３２８gの４―メチル−２，６−ジホルミルフェノールを含んだ１０ｍｌメタノール溶液を５０ｍｌのナスフラスコに入れ、室温にて攪拌した。この溶液に０．２２８ｇのtrans―１、２―シクロヘキサンジアミンを含んだ５ｍｌメタノール溶液を徐々に添加した。上記混合物を２時間還流することにより茶褐色沈殿が生成した。この沈殿を濾取し、乾燥することで複核金属錯体（Ｆ）を得た（収量０．１４１ｇ：収率２１％）。元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₃₀Ｈ₃₈Ｃｌ₂Ｃｏ₂Ｎ₄Ｏ₄；Ｃ，５０．９３；Ｈ，５．４１；Ｎ，７．９２．Ｆｏｕｎｄ：Ｃ，４９．６０；Ｈ，５．４７；Ｎ，８．０４．なお、上記反応式において「Ｃｌ₂」とは２当量の塩化物イオンが対イオンとしてあることを示し、「２Ｈ₂Ｏ」とは、２当量の水分子が複核金属錯体（Ｆ）を構成する成分として含まれていることを示す。 Comparative Example 2 [Synthesis of Binuclear Metal Complex (F)]
The binuclear metal complex (F) was synthesized according to the following reaction formula.

Under a nitrogen atmosphere, a 10 ml methanol solution containing 0.476 g cobalt chloride hexahydrate and 0.328 g 4-methyl-2,6-diformylphenol was placed in a 50 ml eggplant flask and stirred at room temperature. To this solution was slowly added a 5 ml methanol solution containing 0.228 g of trans-1,2-cyclohexanediamine. The mixture was refluxed for 2 hours to produce a brown precipitate. The precipitate was collected by filtration and dried to obtain a binuclear metal complex (F) (yield 0.141 g: yield 21%). Elemental analysis _{(%): Calcd for C 30} H 38 Cl 2 Co 2 N 4 O 4; C, 50.93; H, 5.41; N, 7.92. Found: C, 49.60; H, 5.47; N, 8.04. In the above reaction formula, “Cl ₂ ” indicates that 2 equivalents of chloride ions are present as a counter ion, and “2H ₂ O” indicates that 2 equivalents of water molecules constitute the dinuclear metal complex (F). Indicates that it is contained as a component.

Example 5
About the binuclear metal complex (A) and the binuclear metal complex (E), the tolerance test to the acid using a sulfuric acid was performed at room temperature (25 degreeC). 2.84 mg of the binuclear metal complex (A) was taken and dissolved in 20 ml of methanol. 9.0 ml of the solution was taken and 1.0 ml of 1M aqueous sulfuric acid solution was added. After rapidly stirring, 0.3 ml of a 10-fold diluted solution was placed in a cell, and the time-dependent change in UV-visible absorption at room temperature was observed using an UV-visible spectrophotometer (manufactured by JASCO Corporation, V-530). did. The absorbance at a wavelength of 454 nm is shown in Table 1. From this result, it was found that the binuclear metal complex (A) hardly changes in absorbance even in the presence of an acid and retains the complex structure.

Comparative Example 3
The binuclear metal complex (A) of Example 5 was replaced with the binuclear metal complex (E), the same operation as in Example 5 was performed, and the change in UV absorption over time was observed. The absorbance at a wavelength of 371 nm is shown in Table 2. The binuclear metal complex (E) was found to have a changed complex structure because the absorbance decreased with time in the presence of an acid.

Example 6
About the binuclear metal complex (C), the weight change (TGA) at the time of heat processing was measured using the thermogravimetric / differential thermal analyzer (Seiko Instruments EXSTAR-6300). The weight reduction rate at 800 ° C. was determined from the ratio to the initial weight subjected to the measurement. The measurement conditions were 40 to 800 ° C. (temperature increase rate 10 ° C./min) under a nitrogen atmosphere, and an alumina dish was used for the heat treatment. Table 3 shows the weight loss rate.

Comparative Example 4 and Comparative Example 5
The binuclear metal complex (C) of Example 6 was replaced with the binuclear metal complex (E) and the binuclear metal complex (F), and the same operation as in Example 6 was performed, and weight change (TGA) was measured. Table 3 shows the weight reduction rate of each binuclear metal complex at 800 ° C.

表３より、複核金属錯体（Ｃ）が、複核金属錯体（Ｅ）および複核金属錯体（Ｆ）と比較して重量減少率が小さく、耐熱性に優れることが判明した。

From Table 3, it was found that the binuclear metal complex (C) had a smaller weight reduction rate and excellent heat resistance compared to the binuclear metal complex (E) and the binuclear metal complex (F).

It is IR absorption spectrum of a binuclear metal complex (A). It is IR absorption spectrum of a binuclear metal complex (B). It is IR absorption spectrum of a binuclear metal complex (C). It is IR absorption spectrum of a binuclear metal complex (D).

Claims (8)

A binuclear metal complex represented by the following formula (1).

(In the formula, ^one of M ¹ and M ² represents a transition metal atom belonging to Group 6 to Group 9 of the long-period periodic table, and the other represents Group 6 to Group 11 of the long-period periodic table. It represents the transition metal atom to which it belongs, and M ¹ and M ² may be the same or different.
R ^{1a to} R ^1f , R ^{2a to} R ^2d , and R ^{3a to} R ^3d each independently represent a hydrogen atom or a substituent, and R ^1a and R ^1b , R ^1a and R ^1c , R ^1d and R ^1e , R ^1d And R ^1f , R ^2a and R ^2b , R ^2c and R ^2d , R ^1b and R ^3a , R ^1c and R ^3c , R ^1e and R ^3b , R ^1f and R ^3d , May be linked to each other to form a ring.
X is a counter ion or neutral molecule that makes the binuclear metal complex electrically neutral, m is the number of X in the complex, represents an integer of 0 to 4, and when there are a plurality of X, May be the same or different.
→ represents a coordination bond or ionic bond to M ¹ or M ² . ) 2. The binuclear metal complex according to claim ¹ , wherein at least ^one of M ¹ and M ² in the binuclear metal complex represented by the formula (1) is a transition metal ion belonging to the fourth period of the long-period periodic table. . A binuclear metal complex represented by the following formula (2).

(In the formula, ^one of M ¹ and M ² represents a transition metal atom belonging to Group 6 to Group 9 of the long-period periodic table, and the other represents Group 6 to Group 11 of the long-period periodic table. It represents the transition metal atom to which it belongs, and M ¹ and M ² may be the same or different.
R ^{4a to} R ^4f , R ^{5a to} R ^5h and R ^{6a to} R ^6d each independently represent a hydrogen atom or a substituent, and R ^4a and R ^4b , R ^4a and R ^4c , R ^4d and R ^4e , R ^4d And R ^4f , R ^5a and R ^5b , R ^5b and R ^5c , R ^5c and R ^5d , R ^5e and R ^5f , R ^5f and R ^5g , R ^5g and R ^5h , R ^4b and R ^6a , R ^4e and R Two substituents of each set of ^6b , R ^4c and R ^6c , R ^4f and R ^6d may be linked to each other to form a ring.
X is a counter ion or neutral molecule that makes the binuclear metal complex electrically neutral, m is the number of X in the complex, represents an integer of 0 to 4, and when there are a plurality of X, May be the same or different.
→ represents a coordination bond or ionic bond to M ¹ or M ² . ) 4. The binuclear metal complex according to claim 3, wherein at least ^one of M ¹ and M ² in the binuclear metal complex represented by the formula (2) is a transition metal ion belonging to the fourth period of the long-period periodic table. . A binuclear metal complex represented by the following formula (3).

(In the formula, ^one of M ¹ and M ² represents a transition metal atom belonging to Group 6 to Group 9 of the long-period periodic table, and the other represents Group 6 to Group 11 of the long-period periodic table. It represents the transition metal atom to which it belongs, and M ¹ and M ² may be the same or different.
R ^7a , R ^7b , R ^{8a to} R ^8d , R ^{9a to} R ^9d each independently represents a hydrogen atom or a substituent, and two substitutions in each set of R ^8a and R ^8b , R ^8c and R ^8d The groups may be connected to each other to form a ring.
X is a counter ion or a neutral molecule that makes the binuclear metal complex electrically neutral, m is the number of X in the complex, represents an integer of 0 to 4, and when there are a plurality of X, May be the same or different.
→ represents a coordination bond or ionic bond to M ¹ or M ² . ) 6. The binuclear metal complex according to claim 5, wherein at least ^one of M ¹ and M ² in the binuclear metal complex represented by the formula (3) is a transition metal ion belonging to the fourth period of the long-period periodic table. .   The polymer which has a site | part formed by removing a hydrogen atom or a substituent from the binuclear metal complex in any one of Claims 1-6.   A catalyst comprising the binuclear metal complex according to claim 1 and / or the polymer according to claim 7.

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