JP2009057366A - Metal complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal complex excellent in heat resistance and acid resistance, and useful for redox reaction catalysts or the like. <P>SOLUTION: The metal complex is represented by the formula or the like in the figure. The metal used for the complex includes a transition metal element, especially preferably vanadium, chromium, manganese, iron, cobalt, nickel, copper or zinc. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  The metal complex acts as a catalyst in a redox reaction involving electron transfer such as oxygen addition reaction, oxidative coupling reaction, dehydrogenation reaction, hydrogenation reaction, oxide decomposition reaction, electrode reaction, etc. to produce an organic compound or a polymer compound Is used. Recently, metal complexes have been used for various applications such as phosphorescent complexes of organic EL materials, additives, modifiers, batteries, and sensor materials.

  In particular, as a redox reaction catalyst, it is known that a metal complex having a cyclic polydentate ligand has a highly active and highly selective catalytic ability. For example, a complex having an optically active cyclic ligand is used as a catalyst. As a result of carrying out enantioselective oxidative coupling reaction of 2-naphthol, it gives a good yield and enantiomeric excess (Non-patent Document 1), and catalyzes an optically active cyclic Schiff base type complex. It has been reported that an asymmetric cyclopropanation reaction of styrene proceeds (Non-patent Document 2).

  However, when these metal complexes are used as a catalyst, the catalyst may become unstable at a high temperature or in the presence of a strong acid, and the activity may decrease.

Angew. Chem. Int. Ed. 2003, 42, 6008. Org. Biomol. Chem. 2005, 3, 2126.

  The present invention provides a metal complex useful for a redox reaction catalyst or the like that is stable (that is, excellent in heat resistance and acid resistance) even at a high temperature or in the presence of a strong acid.

The object of the present invention has been achieved by the following means [1] to [7].
[1] A metal complex represented by the following formula (1).

(In the formula, R ^{100 to} R ¹⁰⁷ each independently represent a hydrogen atom or a substituent. A and b are each independently 1 or 2. R ¹⁰⁰ and R ¹⁰¹ , R ¹⁰¹ and R ¹⁰² , R ^103. And R ¹⁰⁴ , R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰² and R ¹⁰⁶ , and R ¹⁰⁵ and R ¹⁰⁷ may be combined with each other to form a ring. Two R ^{106 s} may be the same or different, and may be bonded to each other to form a ring.When b is 2, two R ^{107 s} may be the same or different, They may be bonded to each other to form a ring, Q ¹ represents a divalent linking group, and Y ¹ and Y ² each independently represent the following formula:

(In the formula, R _α represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. P ¹ represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ¹ , P ² represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ² , and P ¹ and P ² may be connected to each other to form a ring. Z ¹ and Z ² are each independently represented by the following formula:

(In the formula, _Rβ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. M represents a transition metal element or a typical metal element described in the periodic table. m is 1 or 2. When m is 2, two M may be the same or different. X represents a counter ion or a neutral molecule. n is the number of X in the complex and represents an integer of 0 or more (usually 10 or less). When there are a plurality of X, they may be the same or different. )

[2] The metal complex according to [1], which is a metal complex represented by the following formula (2) or (3).

(In the formula, R ^{121 to} R ¹³⁰ each independently represents a hydrogen atom or a substituent. R ¹²¹ and R ¹²² , R ¹²² and R ¹²³ , R ¹²³ and R ¹²⁴ , R ¹²⁵ and R ¹²⁶ , R ¹²⁷ and R One or more selected from the group consisting of ¹²⁸ , R ¹²⁸ and R ¹²⁹ , and R ¹²⁹ and R ¹³⁰ may be bonded to each other to form a ring, and Y ³ and Y ⁴ each independently represent the following formula:

(In the formula, R _γ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. P ³ represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ³ , P ⁴ represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ⁴ , and P ³ and P ^{3 4} may be connected to each other to further form a ring. M, X, m and n have the same meaning as described above. )

（式中、Ｒ^１３１〜Ｒ^１４４は、それぞれ独立に水素原子又は置換基を表す。Ｒ^１３１とＲ^１３２、Ｒ^１３２とＲ^１３３、Ｒ^１３３とＲ^１３４、Ｒ^１３４とＲ^１３５、Ｒ^１３５とＲ^１３６、Ｒ^１３６とＲ^１３７、Ｒ^１３８とＲ^１３９、Ｒ^１３９とＲ^１４０、Ｒ^１４０とＲ^１４１、Ｒ^１４１とＲ^１４２、Ｒ^１４２とＲ^１４３、Ｒ^１４３とＲ^１４４、及びＲ^１４４とＲ^１３１からなる群から選ばれる一種以上は、互いに結合して環を形成してもよい。ｃ及びｄは、それぞれ独立に１又は２である。ｃが２の場合、２つのＲ^１３７は同一であっても異なっていてもよく、互いに結合して環を形成してもよい。ｄが２の場合、２つのＲ^１３８は同一であっても異なっていてもよく、互いに結合して環を形成してもよい。Ｑ^２は２価の連結基を表す。Ｚ^３及びＺ^４は、それぞれ独立に下記式：

(Wherein R ^{131 to} R ¹⁴⁴ each independently represent a hydrogen atom or a substituent. R ¹³¹ and R ¹³² , R ¹³² and R ¹³³ , R ¹³³ and R ¹³⁴ , R ¹³⁴ and R ¹³⁵ , R ¹³⁵ and R ¹³⁶ , ^R136 and ^R137 , ^R138 and ^R139 , ^R139 and ^R140 , ^R140 and ^R141 , ^R141 and ^R142 , ^R142 and ^R143 , ^R143 and ^R144 , and ^R144 and ^R131 One or more selected from the group consisting of may be bonded to each other to form a ring, and c and d are each independently 1 or 2. When c is 2, two R ^137s are the same. May be bonded to each other to form a ring, and when d is 2, two R ^138s may be the same or different, and are bonded to each other to form a ring. May be. Q ² represents a divalent linking group, and Z ³ and Z ⁴ each independently represent the following formula:

(Wherein R _δ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. M, X, m and n have the same meaning as described above. )

[3] The metal complex according to [1], which is a metal complex represented by the following formula (4).

(Wherein R ^{151 to} R ¹⁶⁶ each independently represent a hydrogen atom or a substituent. R ¹⁵¹ and R ¹⁵² , R ¹⁵² and R ¹⁵³ , R ¹⁵³ and R ¹⁵⁴ , R ¹⁵⁴ and R ¹⁵⁵ , R ¹⁵⁵ and R ¹⁵⁶ , R ¹⁵⁶ and R ¹⁵⁷ , R ¹⁵⁸ and R ¹⁵⁹ , R ¹⁶⁰ and R ¹⁶¹ , R ¹⁶¹ and R ¹⁶² , R ¹⁶² and R ¹⁶³ , R ¹⁶³ and R ¹⁶⁴ , R ¹⁶⁴ and R ¹⁶⁵ , R ¹⁶⁵ and R ¹⁶⁶ , And one or more selected from the group consisting of R ¹⁶⁶ and R ¹⁵¹ may combine with each other to form a ring, and M, X, m, and n have the same meaning as described above.

[4] The formula (4), wherein R ¹⁵⁵ and R ¹⁶² represent an alkyl group, and R ¹⁵⁸ and R ¹⁵⁹ , and R ¹⁵¹ and R ¹⁶⁶ are bonded to each other to form a ring. Metal complex.

[5] The metal complex according to any one of [1] to [4], wherein M is a transition metal element.

[6] The metal complex according to any one of [1] to [4], wherein M is vanadium, chromium, manganese, iron, cobalt, nickel, copper, or zinc.

[7] A catalyst comprising the metal complex according to any one of [1] to [6].

  The metal complex of the present invention is a metal complex having a novel cyclic multidentate ligand and is excellent in heat resistance and acid resistance. Accordingly, the metal complex is industrially useful because it can suppress a decrease in catalytic activity even at high temperatures or in the presence of a strong acid and can be a highly versatile catalyst.

A preferred embodiment of the present invention will be described.
The metal complex represented by the formula (1), which is the first embodiment of the present invention, will be described. In the metal complex, a metal atom M which is a transition metal element or a typical metal element forms a complex with a ligand having at least six heteroatoms. Moreover, the bond which connects the oxygen atom and metal atom of a phenol group is a coordination bond or an ionic bond, and when there are two metal atoms, it may be bridged and coordinated between the metal atoms. In the general formula (1), the coordination state of the metal atom M and the ligand of this metal complex is as follows: R ^{100 to} R ¹⁰⁷ are hydrogen atoms, Q ¹ is a phenylene group, Y ¹ , Y ² , Z ¹ and Z ² are -N =, and P ¹ and P ² form a pyridine ring together with the carbon atom adjacent to Y ¹ or Y ² , and the pyridine rings cross each other, the following formula (5) This is shown schematically.

  The “transition metal” constituting the metal complex of the present invention is described as “transition element” on page 1283 of “Chemical Dictionary” (Michinori Oki et al., Issued July 1, 2005, Tokyo Chemical Dojin). Means an element having an incomplete d or f subshell. The transition metal atom M in the present invention may be uncharged or charged ion. The same applies to the typical metal atom M, which may be uncharged or charged ions.

  Examples of the transition metal atom M are scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium. , Hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury.

  Examples of the typical metal atom M include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, gallium, germanium, indium, tin, antimony, thallium, germanium, tin, lead, Antimony and bismuth.

  The M is preferably titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tantalum, tungsten, rhenium, osmium, iridium, platinum. Gold, more preferably titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, and particularly preferably vanadium, chromium, Manganese, iron, cobalt, nickel, copper, and zinc are used, but these ions may be used.

  The metal complex represented by the formula (1) is preferably represented by the formula (2) or (3), and more preferably represented by the formula (4).

  M described in the formulas (1) to (5) is preferably a metal atom selected from the transition metal atoms described in the periodic table. When m is 2, two Ms may be different from each other but the same. It may be.

Next, the ligand of the metal complex represented by the formula (1) will be described.
R < ¹⁰⁰ > -R < ¹⁰⁷ > in the said Formula (1) represents a hydrogen atom or a substituent each independently.
Here, the substituents are specifically described as follows: halogeno group such as fluoro group, chloro group, bromo group, iodo group, hydroxyl group, carboxyl group, mercapto group, sulfonic acid group, nitro group, phosphonic acid group, carbon number Silyl group having 1 to 4 alkyl groups, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, sec-butyl group, pentyl group, hexyl group, nonyl group, dodecyl Group, pentadecyl group, octadecyl group, docosyl group, etc., linear or branched alkyl group having about 1 to 50 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbornyl group , C3-C50 cyclic alkyl group such as adamantyl group, ethenyl group, propenyl group A linear, branched or cyclic alkenyl or alkynyl group having 2 to 50 carbon atoms, such as a 3-butenyl group, a 2-butenyl group, a 2-pentenyl group, a 2-hexenyl group, a 2-nonenyl group, or a 2-dodecenyl group; A methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a cyclohexyloxy group, a norbornyloxy group, a decyloxy group, a dodecyloxy group, etc. Alkyl groups having about 6 to 60 carbon atoms such as alkoxy groups, phenyl groups, 4-methylphenyl groups, 1-naphthyl groups, 2-naphthyl groups, 9-anthryl groups, phenylmethyl groups, 1-phenylethyl groups, 2 -Phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenylpropyl group, 3-phenyl And aralkyl group having 7 to 50 carbon atoms such as a 1-propyl group and the like.
R ^{100 to} R ¹⁰⁷ are preferably a halogeno group such as a fluoro group, a chloro group, a bromo group or an iodo group, a mercapto group, a hydroxy group, a carboxyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a pentyl group. Group, tert-butyl group, cyclohexyl group, norbornyl group, linear, branched or cyclic alkyl group having about 1 to 20 carbon atoms, methoxy group, ethoxy group, propoxy group, butoxy group exemplified by adamantyl group A linear or branched alkoxy group having about 1 to 10 carbon atoms, such as a pentyloxy group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, etc. And more preferably, a chloro group, a bromo group, a hydroxy group, a carboxyl group, a methyl group, an ethyl group tert- butyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a methoxy group, an ethoxy group, a phenyl group.

R ¹⁰⁰ and ^{R 101, R 101} and ^{R 102, R 103} and ^{R 104, R 104} and ^{R 105, R 102} and ^{R 106,} and one or more selected from the group consisting of ^{R 105} and ^{R 107} are bonded to each other A ring may be formed. Here, examples of the ring include a hydrocarbon ring such as a cyclohexene ring, a benzene ring, a naphthalene ring, an anthracene ring, and an acenaphthene ring, and a heterocyclic ring such as a furan ring and a thiophene ring.
In addition, the ring formed by connecting with a combination of two substituents may further have a substituent, and these substituents are the same as described above.

When a is 2, two R ¹⁰⁶ may be the same or different and may be bonded to each other to form a ring. When b is 2, two R ¹⁰⁷ may be the same or different, and may be bonded to each other to form a ring. Here, examples of the ring include hydrocarbon rings such as cyclopropane ring, cyclopropene ring, cyclobutane ring, and cyclobutene ring; and heterocyclic rings such as pyrrolidine ring and tetrahydrofuran ring. Moreover, these rings may have a substituent. The substituent is the same as described above.

Examples of the divalent linking group represented by Q ¹ include a divalent group containing at least one selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and an alkylene group having 1 to 30 carbon atoms. , C 2-30 alkenylene group, C 2-30 alkynylene group, C 2-40 arylene group, —NH— group, —O— group, —S— group, —CO— group, —CO _It consists of _2- , -SO2- groups, etc., alone or in combination. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, and a cyclobutylene group. Examples of the alkenylene group include a vinylene group, a propenylene group, and a butadienylene group. The alkynylene group includes an ethynylene group, a propynylene group, and a butynylene group. Etc. Arylene groups include phenylene group, naphthylene group, anthracenediyl group, phenanthrene diyl group, pyridylene group, pyrazylene group, pyrimidylene group, pyridazylene group, pyrrolylene group, furylene group, thienylene group, imidazolylene group, pyrazolylene group, thiazolylene group, oxazolylene group. Groups and the like. The linking group may have a substituent. The substituent is the same as described above. The divalent linking group represented by Q ¹ is preferably an alkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an —NH— group, an —O— group, or an —S— group. A group formed by combining at least one, an alkenylene group having 2 to 20 carbon atoms, and an arylene group having 2 to 30 carbon atoms, more preferably an alkenylene group having 2 to 10 carbon atoms and an arylene group having 2 to 20 carbon atoms. It is.

Y ¹ and Y ² are each independently represented by the following formula:

(In the formula, R _α represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented.

P ¹ represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ¹ , P ² represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ² , and P ¹ and P ² may be connected to each other to form a ring.
P ¹ and P ² include pyridine, pyrazine, pyrimidine, pyridazine, pyrrole, furan, thiophene, thiazole, imidazole, oxazole, triazole, indole, benzimidazole, benzofuran, benzothiophene, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, Examples include quinoxaline and benzodiazine, preferably pyridine, pyrazine, pyrimidine, pyridazine, pyrrole, furan, and thiophene, and more preferably pyridine, pyrrole, furan, and thiophene.
In addition, P ¹ and P ² skeletons may be bonded to each other to form a new ring, and those having a structure represented by any of the following formulas (1-a) to (1-i) are preferable. A compound having a structure represented by any of the following formulas (1-a) to (1-d) is more preferable.

Here, R represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
Note that the P ¹ and P ² structures may have a substituent. The substituent is the same as the substituent for R ^{100 to} R ¹⁰⁷ described above.

The metal complex represented by the formula (1) preferably has a ligand structure made from those represented by the specific examples of P ¹ and P ² , Y ¹ and Y ² .

  Next, the metal complex of the present invention is preferably a metal complex represented by the formula (2) or (3). As described above, the ligand has at least two nitrogen atoms and at least two oxygen atoms as coordination atoms. Moreover, this ligand may have a substituent. The substituent is the same as described above.

In the metal complex represented by the formula (2), Y ³ and Y ⁴ are each independently represented by the following formula:

(In the formula, R _γ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. P ³ is an atomic group necessary for forming an aromatic heterocyclic ring together with Y ³ , and P ⁴ is an atomic group necessary for forming an aromatic heterocyclic ring together with Y ⁴ , and P ³ and P ^{3 4} may be connected to each other to further form a ring. Specific examples and preferred rings of P ³ and P ⁴ include the same rings as P ¹ and P ² . M, X, m and n have the same meaning as described above.

  The metal complex represented by the formula (2) preferably has the ligand skeleton structures (I) to (XII) shown below. In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

  In the formulas (I) to (XII), the metal atom is not shown and the charge is omitted.

In the metal complex represented by the formula (3), c and d are each independently 1 or 2. When c is 2, two R ¹³⁷ may be the same or different and may be bonded to each other to form a ring. When d is 2, two R ¹³⁸ may be the same or different and may be bonded to each other to form a ring. Q ² represents a divalent linking group. The divalent linking group represented by Q ² is the same as the divalent linking group represented by Q ¹ .

Z ³ and Z ⁴ are each independently represented by the following formula:

(Wherein R _δ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. M, X, m and n have the same meaning as described above.

  The metal complex represented by the formula (3) preferably has a ligand skeleton structure represented by any of the following formulas (XIII) to (XVIII).

  In the formulas (XIII) to (XVIII), the metal atom is not shown and the charge is omitted.

Furthermore, as a metal complex of this invention, the metal complex represented by the said Formula (4) is preferable. This ring may have a substituent. R ^{151 to} R ¹⁶⁶ in the formula (4) each independently represent a hydrogen atom or a substituent. The substituent is the same as described above.

In the formula (4), R ¹⁵⁵ and R ¹⁶² preferably represent an alkyl group, and R ¹⁵⁸ and R ¹⁵⁹ , and R ¹⁵¹ and R ¹⁶⁶ are bonded to each other to form a ring. Here, the alkyl group is a linear, branched or cyclic group having about 1 to 20 carbon atoms, and preferably a methyl group, an ethyl group or a tert-butyl group. In addition, R ¹⁵⁸ and R ¹⁵⁹ , and R ¹⁵¹ and R ¹⁶⁶ are bonded to each other, and a ring formed is a hydrocarbon ring such as a cyclohexene ring, a benzene ring, a naphthalene ring, an anthracene ring, or an acenaphthene ring, a furan ring, a thiophene ring And preferably an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring or an anthracene ring. These rings may have a substituent, and the substituent is the same as described above.

  X in the above formulas (1) to (4) is a neutral molecule or a counter ion. Examples of the neutral molecule include molecules that solvate to form solvated salts, and ligands other than the cyclic ligands in the above formulas (1) to (4). 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′-di Tylacetamide, N-methyl-2-pyrrolidone, chloroform, acetonitrile, benzonitrile, triethylamine, pyridine, pyrazine, diazabicyclo [2,2,2] octane, 4,4'-bipyridine, tetrahydrofuran, dimethoxyethane, 1,4- Dioxane. These neutral molecules may be present alone or in combination of two or more.

In addition, when X is a counter ion, the transition metal atom and the typical metal atom usually have a positive charge, so an anion that makes this electrically neutral is selected, and fluoride ion, chloride ion, Bromide ion, iodide ion, sulfide ion, oxide ion, hydroxide ion, hydride ion, sulfite ion, phosphate ion, cyanide ion, acetate ion, carbonate ion, sulfate ion, sulfate ion, nitrate ion, bicarbonate ion Trifluoroacetate 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 a neutral molecule and a counter ion coexist is also possible.
n is the number of X in the metal complex, and represents an integer of 0 or more, preferably an integer of 0 to 10, more preferably an integer of 0 to 8, particularly preferably an integer of 0 to 6.

Here, the manufacturing method of the metal complex represented by said Formula (1)-(4) is demonstrated.
The metal complex represented by the formulas (1) to (4) is a phenol compound having two carbonyl groups represented by the following formula (6a) that forms a ligand (hereinafter referred to as “phenol compound”). And a diamine derivative represented by the following formula (6b) (hereinafter referred to as “diamine compound”) in the presence of a reaction agent that imparts a transition metal atom (hereinafter referred to as “metal imparting agent”). Can be obtained.

(In the formula, R ¹⁰⁰ ′ to R ¹⁰⁷ ′ and Q ¹ ′ have the same meaning as R ^{100 to} R ¹⁰⁷ and Q ¹ described in the formula (1).)
The metal imparting agent is a compound having the above transition metal atom M, and a salt having such a transition metal as a cation is usually used.

  The metal complex represented by the formula (1) is obtained by, for example, condensing a phenol compound and a diamine compound to synthesize a ligand, and then reacting the ligand with a metal imparting agent. You can also.

  The ligand obtained by condensing the phenol compound and the diamine compound can further synthesize a reduced form using a reducing agent such as sodium borohydride. The metal complex represented by the formula (1) can also be obtained by the reaction between the reductant and the metal-imparting agent.

The reaction may be performed in the presence of a reaction solvent. As a reaction solvent, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, 2-methoxyethanol, tetrahydrofuran, ether, 1,2-dimethoxyethane, acetonitrile, benzonitrile, acetone, 1 -Methyl-2-pyrrolidinone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetic acid, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, and a reaction solvent obtained by mixing two or more of these may be used. Although it is good, what can dissolve the phenolic compound, diamine compound, and metal imparting agent to apply is preferable. 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 the synthesis reaction of the metal complexes represented by the formulas (1) to (4), the use molar ratio of the phenol compound represented by the above formula (6a) and the diamine compound represented by (6b) is 1: 1.5 is preferable, and 1: 1 is more preferable. Further, the molar ratio of the metal atom M in the metal imparting agent to the phenol compound represented by the formula (6a) is preferably 1/1 to 2.5 / 1. X is combined with the metal atom M and the compound serving as a ligand so that the metal complexes represented by the formulas (1) to (4) are electrically neutral and the coordination environment is saturated.
As a means for isolating and purifying the generated metal complex from the reaction solution after the reaction, an optimum means can be appropriately selected and used from known recrystallization methods, reprecipitation methods, or chromatography methods. May be combined.
Depending on the type of the reaction solvent, the generated metal complex may precipitate. The precipitated metal complex may be separated by filtration, etc., and the metal complex may be removed by washing or drying as necessary. It can also be isolated and purified.

Since the metal complexes represented by the formulas (1) to (4) have an aromatic structure in the basic skeleton and have a cyclic multidentate structure in which metal atoms are not easily released by a linking group, all have high heat resistance. It is expected that the complex structure is maintained relatively stably even at high temperatures or in the presence of strong acids, and the decrease in catalytic ability is small.
In particular, the metal complex is suitable for use as a redox catalyst or the like. Specifically, it is a catalyst for decomposition of hydrogen peroxide, an oxidation polymerization catalyst for aromatic compounds, a catalyst for exhaust gas / drainage purification, a dye-sensitized solar cell. Applications include oxidation-reduction catalysts, carbon dioxide reduction catalysts, catalysts for producing reformed hydrogen, oxygen sensors, and the like. Moreover, it is thought that it can be used also as organic-semiconductor materials, such as an organic electroluminescent light emitting material, an organic transistor, and a dye-sensitized solar cell, by extending conjugation.
Hereinafter, the present invention will be described specifically by way of examples. However, these are merely examples, and the scope of the present invention is not limited to these.

[Example 1] (Synthesis of metal complex (A))
The metal complex (A) was synthesized by mixing and reacting in a chloroform / ethanol mixed solution containing a phenol compound, a diamine compound, and cobalt acetate tetrahydrate according to the following reaction formula.
In addition, the following phenol compound used as a raw material of a complex in the following Examples 1-10 is Tetrahedron, 1999, 55, 8377. It was synthesized according to the description of.

Under a nitrogen atmosphere, a mixed solution of 5 ml of chloroform and 5 ml of ethanol containing 0.199 g of cobalt acetate tetrahydrate and 0.213 g of a phenol compound was placed in a 50 ml eggplant flask and stirred at 60 ° C. To this solution was slowly added a 5 ml ethanol solution containing 0.043 g o-phenylenediamine. The resulting 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 (A) (yield 0.109 g: yield 28%). Elemental analysis value (%): calculated value C ₄₅ H ₄₁ Cl ₃ Co ₂ N ₄ O ₆ ; C, 56.41; H, 4.31; N, 5.85. Found: C, 58.28; H, 4.81; N, 5.85.
_{ESI-MS: 779.0 ([M} -CH 3 COO] +)

[Example 2] (Synthesis of metal complex (B))
According to the following reaction formula, the metal complex (B) was synthesized by mixing and reacting in a chloroform / ethanol mixed solution containing a phenol compound, a diamine compound and manganese acetate tetrahydrate.

Under a nitrogen atmosphere, a mixed solution of 10 ml of chloroform and 5 ml of ethanol containing 0.221 g of manganese acetate tetrahydrate and 0.213 g of a phenol compound was placed in a 50 ml eggplant flask and stirred at 60 ° C. To this solution was slowly added a 5 ml ethanol solution containing 0.043 g o-phenylenediamine. The resulting 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 0.166 g: yield 44%).
_{ESI-MS: 771.0 ([M} -CH 3 COO] +)

[Example 3] (Synthesis of metal complex (C))
According to the following reaction formula, the metal complex (C) was synthesized by mixing and reacting in a chloroform / methanol mixed solution containing a phenol compound, a diamine compound, and copper acetate monohydrate.

Under a nitrogen atmosphere, 0.200 g of copper acetate monohydrate and 0.213 g of a phenol compound were placed in a 100 ml two-necked flask, and 30 ml of a methanol solution containing 0.065 g of o-phenylenediamine was added. The resulting mixture was refluxed for 3 hours to produce a brown solid. The resulting solution was concentrated to dryness, washed with diethyl ether and dried to obtain a binuclear metal complex (C) (yield 0.370 g).
_{ESI-MS: 789.0 ([M} -CH 3 COO] +)

[Example 4] (Synthesis of metal complex (D))
The metal complex (D) was synthesized by mixing and reacting in a chloroform / methanol mixed solution containing a phenol compound, a diamine compound and iron acetate according to the following reaction formula.

Under a nitrogen atmosphere, 0.213 g of a phenol compound and 0.174 g of iron acetate were placed in a 100 ml two-necked flask, and 10 ml of a methanol solution containing 20 ml of chloroform and 0.065 g of o-phenylenediamine was added. The solution was refluxed for 3 hours to produce a brown precipitate. The obtained suspension was concentrated to dryness, washed with diethyl ether and dried to obtain a metal complex (D) (yield 0.344 g).
ESI-MS: 690.2 ([M + MeOH] ⁺ )

[Example 5] (Synthesis of metal complex (E))
The metal complex (E) was synthesized by mixing and reacting in a chloroform / methanol mixed solution containing a phenol compound, a diamine compound, and cobalt acetate tetrahydrate according to the following reaction formula.

Under a nitrogen atmosphere, 0.249 g of cobalt acetate tetrahydrate, 0.213 g of phenolic compound and 0.079 g of 2,3-diaminonaphthalene were placed in a 100 ml two-necked flask, and 20 ml of chloroform and 10 ml of methanol were added. added. When this solution was refluxed for 3 hours, a dark brown precipitate was formed. The solution was concentrated and allowed to stand in the refrigerator overnight, and then the precipitate was collected by filtration, washed and dried to obtain a binuclear metal complex (E) (yield 0.282 g: yield 79%).
_{ESI-MS: 829.1 ([M} -CH 3 COO] +)

[Example 6] (Synthesis of metal complex (F))
According to the following reaction formula, the metal complex (F) was synthesized by mixing and reacting in a chloroform / methanol mixed solution containing a phenol compound, a diamine compound, and cobalt acetate tetrahydrate.

Under a nitrogen atmosphere, 0.213 g of a phenol compound and 0.224 g of cobalt acetate tetrahydrate were placed in a 50 ml two-necked flask. A brown precipitate was formed by adding 10 ml of a methanol solution containing 0.085 g of (1R, 2R)-(+) diphenyl-1,2-ethylenediamine and 10 ml of chloroform, and refluxing for 3 hours. The precipitate was collected by filtration and dried to obtain a metal complex (F) (yield 0.448 g).
_{ESI-MS: 883.1 ([M} -CH 3 COO] +)

[Example 7] (Synthesis of metal complex (G))
The metal complex (G) was first synthesized by reacting a phenol compound and a diamine compound to synthesize a ligand precursor, and then mixing and reacting in a methanol solution containing nickel acetate tetrahydrate. .

Under a nitrogen atmosphere, 0.270 g of K ₂ CO ₃ and 0.020 g of n-Bu ₄ NBr were added to a 200 ml three-necked flask equipped with a heating reflux tube and a dropping funnel, and then 10 ml of water, 40 ml of ethanol and 60 μl of a diamine compound. Was added. After slowly dropping 40 ml of chloroform solution containing 0.300 g of phenol compound with a dropping funnel, the mixture was stirred at 85 ° C. for 3 hours. After cooling at room temperature, 50 ml of water was added, the organic layer was separated and extracted using a separatory funnel, and the organic layer was further washed with 50 ml × 2 water. After adding Na ₂ SO ₄ to the organic layer and drying overnight, the volatile components were removed to obtain the ligand precursor as an orange glue (0.270 g).
Under a nitrogen atmosphere, 10 ml of a mixed solution of methanol containing 0.040 g of nickel acetate tetrahydrate and 0.050 g of the ligand precursor was placed in a 50 ml eggplant flask, and the mixture was stirred at 50 ° C. for 2 hours. Stir. After cooling this solution to room temperature, the solvent was distilled off to obtain a binuclear metal complex (G) as an orange powder (0.075 g: yield 87%).
_{ESI-MS: 772.1 ([M} -CH 3 COO] +)

[Example 8] (Synthesis of metal complex (H))
The metal complex (H) was first synthesized by reacting a phenol compound and a diamine compound to synthesize a ligand precursor, and then mixing and reacting in a chloroform solution containing cobalt acetate tetrahydrate. .

Under a nitrogen atmosphere, 10 ml of a mixed solution of chloroform containing 0.040 g of cobalt acetate tetrahydrate and 0.050 g of the same ligand precursor as in Example 7 was placed in a 50 ml eggplant flask, and the mixture was Refluxed for 2 hours. The solution was cooled to room temperature, and the solvent was distilled off to obtain a binuclear metal complex (H) (0.055 g: yield 80%).
_{ESI-MS: 774.1 ([M} -CH 3 COO] +)

[Example 9] (Synthesis of metal complex (I))
First, a phenol compound and a diamine compound were reacted to synthesize a ligand precursor, and then treated with sodium borohydride to obtain a reduced form thereof. The metal complex (I) was synthesized by mixing and reacting in a methanol solution containing the reduced form and nickel chloride hexahydrate.

Under a nitrogen atmosphere, 10 ml of a chloroform solution containing 0.100 g of a phenol compound and 10 ml of an ethanol solution containing 20 μl of a diamine compound were mixed and heated to reflux for 4 hours. After cooling at room temperature, volatile components were distilled off, and 10 ml of ethanol was added to the residue. The ethanol solution was kept at 0 ° C., 0.085 g of sodium borohydride was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling at room temperature, 30 ml of water was added, extraction was performed using 50 ml × 2 chloroform, and the chloroform solution was dried over Na ₂ SO ₄ , and then the volatile component was distilled off to obtain a reduced product as a pale yellow powder ( 0.070 g, yield 65%).
ESI-MS: 575.3 ([M + H] ⁺ )

In a nitrogen atmosphere, put a mixed solution of 5 ml of methanol containing 0.020 g of nickel chloride hexahydrate and 0.050 g of a reduced product into a 50 ml eggplant flask, add 10 μl of triethylamine, and add the mixture at room temperature for 3 hours. Stir. The solvent was distilled off to obtain a binuclear metal complex (I) (0.025 g: yield 79%).
ESI-MS: 344.1 ([M-2Cl] ²⁺ )

[Example 10] (Synthesis of metal complex (J))
First, a phenol compound and a diamine compound were reacted to synthesize a ligand precursor, and then treated with sodium borohydride to obtain a reduced form thereof. The metal complex (J) was synthesized by mixing and reacting in a methanol solution containing the reductant and nickel chloride hexahydrate.

窒素雰囲気下において、０．１００ｇのフェノール化合物を含んだ１０ｍｌのクロロホルム溶液と２０μｌのジアミン化合物を含んだ１０ｍｌのメタノール溶液を混合し、３時間加熱還流した。室温冷却後、揮発成分を留去し、残渣にメタノール１０ｍｌを加えた。該メタノール溶液を０℃で保持し、４０ｍｇの水素化ホウ素ナトリウムを加え、８０℃で２時間攪拌した。室温冷却後、３０ｍｌの水を加え、５０ｍｌ×２のクロロホルムを用いて抽出し、Ｎａ_２ＳＯ_４でクロロホルム溶液を乾燥後、揮発成分を留去し、還元体を薄黄色粉末として得た（８５ｍｇ、収率７５％）。
ＥＳＩ−ＭＳ：６０４．３（［Ｍ＋Ｈ］^＋）

Under a nitrogen atmosphere, 10 ml of a chloroform solution containing 0.100 g of a phenol compound and 10 ml of a methanol solution containing 20 μl of a diamine compound were mixed and heated to reflux for 3 hours. After cooling at room temperature, volatile components were distilled off, and 10 ml of methanol was added to the residue. The methanol solution was kept at 0 ° C., 40 mg of sodium borohydride was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling at room temperature, 30 ml of water was added, extraction was performed using 50 ml × 2 chloroform, the chloroform solution was dried over Na ₂ SO ₄ , volatile components were distilled off, and a reduced product was obtained as a pale yellow powder (85 mg Yield 75%).
ESI-MS: 604.3 ([M + H] ⁺ )

In a nitrogen atmosphere, put a mixed solution of 5 ml of methanol containing 0.020 g of nickel chloride hexahydrate and 0.050 g of a reduced product into a 50 ml eggplant flask, add 10 μl of triethylamine, and add the mixture at room temperature for 3 hours. Stir. The solvent was distilled off to obtain a binuclear metal complex (J) (0.030 g: yield 90%).
ESI-MS: 358.6 ([M-2Cl] ₂ ⁺ )

IR spectra of the metal complexes (A), (B), (C), (D), (E) and (H) obtained in the above examples are shown in FIGS.
[Comparative Example 1] (Synthesis of metal complex (K))
A metal complex (K) was synthesized according to the following reaction formula.

First, in a nitrogen atmosphere, a 10 ml ethanol solution containing 0.476 g of cobalt chloride hexahydrate and 0.412 g of 4-tert-butyl-2,6-diformylphenol was placed in a 50 ml eggplant flask and brought to room temperature. And stirred. 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. This precipitate was collected by filtration and dried to obtain a metal complex (K) (yield 0.465 g: yield 63%).
Elemental analysis (%): Calculated _{(as 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.

[Comparative Example 2] (Synthesis of metal complex (L))
The metal complex (L) shown in the following reaction formula was converted into Aus. J. et al. Chem. 1970, 23, 2225. Was synthesized according to the method described in 1.

First, 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 under a nitrogen atmosphere and stirred at room temperature. did. 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 metal complex (L) (yield 1.75 g: yield 74%).
Elemental analysis (%): Calculated _{(as C 26 H 34 C l2 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.

[Test Example 1] (Acid resistance test of complex)
About the metal complex (A) of Example 1, the tolerance test to the acid using a sulfuric acid was done. 7.90 mg of metal complex (A) was taken and dissolved in 36 mL of methanol. 9.0 mL of the solution was taken and 1.0 mL of 1 M aqueous sulfuric acid solution was added. After stirring rapidly, 0.3 mL was collected and a 10-fold diluted solution was placed in the cell, the lid was closed, and the mixture was heated to 60 ° C. Using a spectrophotometer (Varian, Cary 5E), the time-dependent change in ultraviolet-visible absorption of the solution was observed. Table 1 shows the absorbance at a wavelength of 445 nm and the absorbance ratio immediately after dropping.

  The metal complex (A) of Example 1 was replaced with the metal complex (H) of Example 8, and the same operation as described above was performed, and the change with time in ultraviolet-visible absorption was observed. Table 2 shows the absorbance at a wavelength of 437 nm and the absorbance ratio immediately after dropping.

  For comparison, the metal complex (A) of Example 1 was replaced with the metal complex (K) of Comparative Example 1, and the same operation as described above was performed, and the change in UV absorption over time was observed. Table 3 shows the absorbance at a wavelength of 455 nm and the absorbance ratio immediately after dropping. The metal complex (K) of Comparative Example 1 has a significantly reduced absorbance over time in the presence of an acid as compared to the metal complexes (A) and (H), indicating that the degree of decomposition is large.

  The metal complex (L) of Comparative Example 2 was similarly subjected to an acid resistance test using sulfuric acid. 2.84 mg of metal complex (L) 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 measured using an UV-visible spectrophotometer (manufactured by JASCO Corporation, V-530). Observed. Table 4 shows the absorbance at a wavelength of 371 nm. Although the metal complex (L) of Comparative Example 2 has a room temperature, the absorbance is greatly reduced compared to the metal complexes (A) and (H) in the presence of an acid at 60 ° C., and the degree of decomposition with respect to the acid is large. It is recognized.

[Test Example 2] (Heat resistance test of complex)
(1) About the metal complexes (A), (E) and (H) of Example 1, for each metal complex using a thermogravimetric / differential thermal analyzer (manufactured by Seiko Instruments Inc., EXSTAR-6300), The mass change (TGA) at the time of heat-processing in the range of 40-800 degreeC was measured, and the mass decreasing rate was calculated | required from the ratio with the initial mass used for 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 5 shows the mass reduction rate at 800 ° C.
(2) For comparison, the metal complexes (A), (E) and (H) were replaced with the metal complex (L) of Comparative Example 2, and the thermal mass / differential thermal analyzer (made by Seiko Instruments Inc. Experiments were performed using EXSTAR-6300).
Table 5 shows the mass change rate.

  From Table 5, when the metal complexes (A), (E) and (H) of the present invention are compared with the metal complex (L) of the comparative example, it is recognized that the mass reduction rate is smaller than that of the comparative example and is excellent in heat resistance. .

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

Claims (7)

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

(In the formula, R ^{100 to} R ¹⁰⁷ each independently represent a hydrogen atom or a substituent. A and b are each independently 1 or 2. R ¹⁰⁰ and R ¹⁰¹ , R ¹⁰¹ and R ¹⁰² , R ^103. And R ¹⁰⁴ , R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰² and R ¹⁰⁶ , and R ¹⁰⁵ and R ¹⁰⁷ may be combined with each other to form a ring. Two R ^{106 s} may be the same or different, and may be bonded to each other to form a ring.When b is 2, two R ^{107 s} may be the same or different, They may be bonded to each other to form a ring, Q ¹ represents a divalent linking group, and Y ¹ and Y ² each independently represent the following formula:

(In the formula, R _α represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. P ¹ represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ¹ , P ² represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ² , and P ¹ and P ² may be connected to each other to form a ring. Z ¹ and Z ² are each independently represented by the following formula:

(In the formula, _Rβ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. M represents a transition metal element or a typical metal element described in the periodic table. m is 1 or 2. When m is 2, two M may be the same or different. X represents a counter ion or a neutral molecule. n is the number of X in the complex and represents an integer of 0 or more. When there are a plurality of X, they may be the same or different. ) It is a metal complex represented by following formula (2) or (3), The metal complex of Claim 1 characterized by the above-mentioned.

(In the formula, R ^{121 to} R ¹³⁰ each independently represents a hydrogen atom or a substituent. R ¹²¹ and R ¹²² , R ¹²² and R ¹²³ , R ¹²³ and R ¹²⁴ , R ¹²⁵ and R ¹²⁶ , R ¹²⁷ and R One or more selected from the group consisting of ¹²⁸ , R ¹²⁸ and R ¹²⁹ , and R ¹²⁹ and R ¹³⁰ may be bonded to each other to form a ring, and Y ³ and Y ⁴ each independently represent the following formula:

(In the formula, R _γ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. P ³ represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ³ , P ⁴ represents an atomic group necessary for forming an aromatic heterocyclic ring together with Y ⁴ , and P ³ and P ^{3 4} may be connected to each other to further form a ring. M represents a transition metal element or a typical metal element described in the periodic table. m is 1 or 2. When m is 2, two M may be the same or different. X represents a counter ion or a neutral molecule. n is the number of X in the complex and represents an integer of 0 or more. When there are a plurality of X, they may be the same or different. )

(Wherein R ^{131 to} R ¹⁴⁴ each independently represent a hydrogen atom or a substituent. R ¹³¹ and R ¹³² , R ¹³² and R ¹³³ , R ¹³³ and R ¹³⁴ , R ¹³⁴ and R ¹³⁵ , R ¹³⁵ and R ¹³⁶ , ^R136 and ^R137 , ^R138 and ^R139 , ^R139 and ^R140 , ^R140 and ^R141 , ^R141 and ^R142 , ^R142 and ^R143 , ^R143 and ^R144 , and ^R144 and ^R131 One or more selected from the group consisting of may be bonded to each other to form a ring, and c and d are each independently 1 or 2. When c is 2, two R ^137s are the same. They may be bonded to each other to form a ring, and when d is 2, two R ^138s may be the same or different and may bond to each other to form a ring. May be. Q ² represents a divalent linking group, and Z ³ and Z ⁴ each independently represent the following formula:

(Wherein R _δ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
The group represented by either of these is represented. M represents a transition metal element or a typical metal element described in the periodic table. m is 1 or 2. When m is 2, two M may be the same or different. X represents a counter ion or a neutral molecule. n is the number of X in the complex and represents an integer of 0 or more. When there are a plurality of X, they may be the same or different. ) It is a metal complex represented by following formula (4), The metal complex of Claim 1 characterized by the above-mentioned.

(Wherein R ^{151 to} R ¹⁶⁶ each independently represent a hydrogen atom or a substituent. R ¹⁵¹ and R ¹⁵² , R ¹⁵² and R ¹⁵³ , R ¹⁵³ and R ¹⁵⁴ , R ¹⁵⁴ and R ¹⁵⁵ , R ¹⁵⁵ and R ¹⁵⁶ , R ¹⁵⁶ and R ¹⁵⁷ , R ¹⁵⁸ and R ¹⁵⁹ , R ¹⁶⁰ and R ¹⁶¹ , R ¹⁶¹ and R ¹⁶² , R ¹⁶² and R ¹⁶³ , R ¹⁶³ and R ¹⁶⁴ , R ¹⁶⁴ and R ¹⁶⁵ , R ¹⁶⁵ and R ¹⁶⁶ , And one or more selected from the group consisting of R ¹⁶⁶ and R ¹⁵¹ may be bonded to each other to form a ring, M represents a transition metal element or a typical metal element described in the periodic table, and m represents 1 or 2 When m is 2, two M's may be the same or different, X represents a counter ion or a neutral molecule, n is the number of X in the complex, and 0 Table of integers above If .X there are multiple, they may be the same or different.) 4. The metal complex according to claim 3, wherein, in the formula (4), R ¹⁵⁵ and R ¹⁶² represent an alkyl group, and R ¹⁵⁸ and R ¹⁵⁹ , and R ¹⁵¹ and R ¹⁶⁶ are bonded to each other to form a ring.   The metal complex according to claim 1, wherein M is a transition metal element.   The metal complex according to any one of claims 1 to 4, wherein the M is vanadium, chromium, manganese, iron, cobalt, nickel, copper, or zinc.   The catalyst which uses the metal complex of any one of Claims 1-6.

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