JP5352099B2 - Redox catalyst using modified metal complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified metal complex excellent in acid resistance and thermal stability by accumulating metals; to provide a more stabilized metal complex compound by subjecting a metal complex suitable as a catalyst to a modification treatment; and to provide an excellently stable catalyst by using a carbon compound comprised of the modified metal complex. <P>SOLUTION: The modified metal complex is obtained by subjecting a metal complex comprising as a ligand an organic compound having in the molecule one nitrogen-containing aromatic heterocycle and at least four structures selected from the group consisting of a phenolic ring, a thiophenolic ring, an aniline ring and a nitrogen-containing aromatic heterocycle to any one treatment of a heating treatment, a radiation-irradiating treatment and an electric discharge treatment so that the mass reduction rate by the treatment is at least 1 mass% and at most 90 mass% and that the carbon content after the treatment is at least 5 mass%. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

The present invention relates Reddokkusu catalyst using a highly stable modified metal complex thereof to acid and heat.

The metal complex acts as a catalyst (redox catalyst) in a redox reaction involving electron transfer such as oxygen addition reaction, oxidative coupling reaction, dehydrogenation reaction, hydrogenation reaction, oxide decomposition reaction, etc. Used in manufacturing. Furthermore, they are also used in various applications such as additives, modifiers, batteries, and sensor materials.
In particular, it is known that, among the metal complexes, the accumulation of metal complexes provides a unique reaction space, which can increase the reaction rate of the redox reaction and control the reaction selectivity (non- Patent Document 1).
Among metal complexes, when having a transition metal atom as a central metal, it is known to have excellent reaction activity as a hydrogen peroxide decomposition catalyst or an oxidative coupling catalyst (see Non-Patent Document 2 and Non-Patent Document 3). .
However, metal complexes such as those disclosed in Non-Patent Document 2 and Non-Patent Document 3 have insufficient stability, especially when the reaction is performed in the presence of an acid or when the reaction is performed under heating. There were problems with using the catalyst. Thus, in order to apply a metal complex as a catalyst, it has been eagerly desired to improve stability against acid or heat.
Susumu Kitagawa, Ryo Kitaura, Shin-ichiro Noro, Angelwande Chemie International Edition, 43, 2334 (2004). Bulletin of Chemical Society of Japan, 68, 1105 (1995). Angelwandte Chemie International Edition, 42, 6008 (2003).

An object of the present invention is to provide a Redox catalyst using a modified metal complex having excellent stability.

  As a result of intensive studies, the present inventors have completed the present invention.

That is, the present invention provides a Reddokkusu catalyst using shown to varying metal complexes in the following (1) to (11).
(1) The ligand of an organic compound represented by the following general formula (I) and having a total number of coordination atoms of 5 or 6 is one transition metal atom belonging to the fourth to sixth periods of the periodic table, or The metal complex coordinated in two is treated by any of heat treatment, radiation irradiation treatment or discharge treatment until the mass reduction rate before and after the treatment is 1% by mass or more and 90% by mass or less. A Redox catalyst using a modified metal complex having a carbon content of 5% by mass or more.

(In the formula, R ¹ represents a hydrogen atom , a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, a halogen atom, a monovalent hydrocarbon group which may be substituted, or a substituted group. Optionally substituted hydrocarbon oxy group, optionally substituted N, N-dihydrocarbon amino group, optionally substituted hydrocarbon thio group, optionally substituted hydrocarbon carbonyl group, substituted Represents an optionally substituted hydrocarbon oxycarbonyl group, an optionally substituted N, N-dihydrocarbonaminocarbonyl group, or an optionally substituted hydrocarbon sulfonyl group , bonded to two adjacent atoms. The two R ¹ groups may be linked to each other, and a plurality of R ¹ groups may be the same or different from each other, and Q ¹ represents a pyridylene group, a pyradylene group, a pyrimidine group, Len group, pyridazylene group, pyrrolylene group, thiazolylene group, imidazolylene group, oxazolylene group, triazolylene group, indolenylene group, benzoimidazolylene group, benzofurylene group, benzothienylene group, quinolylene group, isoquinolylene group, cinnolylene group, quinazolylene group, quinazolylene group Quinoxarylene group, benzodiazylene group, 1,10-phenanthroylene group, 2,2′-bipyridylene group, 2,2′-bithiophenylene group, 2,2′-bipyrrolene group, 2,2′-bithiazolylene group, Represents a divalent organic group selected from a 2,2′-bifurylene group, a 2,2′-bipyrimidylene group, a 2,2′-bipyridazilen group and a 2,2′-biimidazolylene group, and T ¹ represents a pyridyl group, Pyrazyl group, pyrimidyl group, pyridazyl group, pyrrolyl group, pyrazolyl group Thiazolyl group, an imidazolyl group, an oxazolyl group, a triazolyl group, indolyl group, benzimidazolyl group, quinolyl group, isoquinolyl group, cinnolyl group, phthalazyl group, quinazolyl group, a monovalent organic group selected from a quinoxalyl group and Benzojiajiru group, The two T ¹ may be the same or different, and the charge is omitted.)
( 2 ) In the broad X-ray absorption fine structure (EXAFS) radial distribution function of the central metal, the catalyst is 0.58Å from the peak derived from the first adjacent atom observed in the range of 1.0Å to 2.5Å. The redox catalyst according to ( 1), further comprising one or more peaks other than the peak derived from a metal atom that is not observed in the metal complex before the heat treatment, radiation irradiation treatment, or discharge treatment .
(3) The Redox catalyst according to (1) or (2), wherein the intensity of the another peak is 2/5 or more of the peak intensity derived from the first adjacent atom.
(4) The Redox catalyst according to any one of (1) to (3), wherein the catalyst comprises the modified metal complex and graphene.
(5) In the spectrum obtained by laser Raman spectroscopy of the excitation wavelength 532 nm, and having an absorption maximum in the range of 1500～1600Cm ^-1 (1) according to any one of - (4) Reddokkusu Catalyst .
(6) the metal complex, only nitrogen atom and an oxygen atom, characterized in that a coordinating atom (1) to (5) Reddokkusu catalyst according to any one of.
(7) The redox catalyst according to any one of (1) to (6), wherein the transition metal atom is manganese, iron, cobalt, nickel, or copper.
(8) the formula characterized in that it is a polymer having a residue of a ligand represented by (I) (1) ~ Reddokkusu catalyst according to any one of (7).
( 9 ) The Redox catalyst according to ( 8 ), which is a polymer having a residue of the ligand represented by the general formula (I) as a repeating unit.
(10) Reddokkusu catalyst according to any one of, wherein said is a modified metal complex formed by heat treatment processes before the metal complex at 250 ° C. or higher 1200 ° C. or less of (1) to (9) .
(11) Any of (1) to (9), wherein the heat treatment of the metal complex before the treatment is a modified metal complex obtained by heat treatment at 250 ° C. or more and 1200 ° C. or less together with the carbon support. The Redox catalyst according to Item 1.

The modified metal complex in the catalyst of the present invention is a modified metal complex having excellent stability (for example, acid resistance and thermal stability) and usually exhibits excellent catalytic activity. The modified metal complex in the catalyst of the present invention is a complex compound that exhibits excellent metal retention in a solution. In addition, metal atoms are accumulated by either nitrogen-containing aromatic heterocycles or phenol rings, providing a reaction space suitable for catalytic reaction, and by denaturation treatment, new metal atoms are accumulated between the accumulated metal complexes. By forming such a bond, it is expected that the catalyst is not only improved in stability but also excellent in reaction selectivity.

  According to the present invention, as a catalyst for redox reactions involving electron transfer such as peroxide decomposition reaction, oxide decomposition reaction, oxygen addition reaction, oxidative coupling reaction, dehydrogenation reaction, hydrogenation reaction, electrode reaction, etc., A catalyst having high reaction activity can be obtained even in the presence or under heating, and the catalyst should be suitably used for synthesis of organic compounds and polymer compounds, and for additives, modifiers, and sensor materials. It is extremely useful industrially.

Ligand of the metal complex to be applied to the present invention is an organic compound represented by the nitrogen-containing aromatic heterocyclic ring, the formula below having a phenolic ring (I).
Here, although it is not a ligand of a metal complex applied to the present invention, any one of a nitrogen-containing aromatic heterocycle and a phenol ring, a thiophenol ring, an aniline ring, and a nitrogen-containing aromatic heterocycle Specific structures of the organic compound having four or more structures are exemplified in the following formulas (a) to (e). The charge is omitted.

  Here, the nitrogen-containing aromatic heterocyclic ring is an aromatic group as a compound structure that satisfies the minimum requirement of having an aromatic heterocyclic skeleton containing at least one nitrogen atom in the ring. The atoms constituting the ring system may contain heteroatoms such as oxygen and sulfur atoms in addition to carbon and nitrogen. Specific examples of the nitrogen-containing aromatic heterocycle include pyridine, pyrazine, pyridazine, pyrimidine, pyrrole, triazole, pyrazole, thiazole, oxazole, imidazole, indole, benzimidazole, phenanthroline, carbazole, quinoline, isoquinoline, cinnoline, phthalazine, and quinazoline. , Quinoxaline, benzodiazine and the like. Note that phenanthroline is counted as having two nitrogen-containing aromatic heterocycles.

  The phenol ring is an aromatic group as a compound structure that satisfies the minimum requirement of having a benzene ring skeleton to which at least one hydroxy group (OH) is bonded. The thiophenol ring is at least one sulfhydryl group. (SH) is an aromatic group as a compound structure that satisfies the minimum requirement of having a benzene ring skeleton bonded to it, and the aniline ring is the minimum requirement of having a benzene ring skeleton to which at least one amino group is bonded. An aromatic group as a compound structure to be filled. One or more protons may be released from a hydroxy group (OH), a sulfhydryl group (SH), and an amino group.

  Specific examples of the aromatic group as a compound structure that satisfies the minimum requirement for having a benzene ring skeleton include benzene, naphthalene, indene, biphenylene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, and ASEAN. Basically, condensed heterocyclic compounds containing oxygen and sulfur elements such as aromatic hydrocarbons such as tolylene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, pentacene, tetraphenylene, hexacene and coronene, benzothiophene, benzofuran and xanthene. Examples of the skeleton include groups. An aromatic hydrocarbon group is preferable, and a group obtained from benzene, naphthalene, indene, biphenylene, acenaphthylene, fluorene, and phenanthrene is more preferable. One or more protons may be released from a hydroxy group (OH), a sulfhydryl group (SH), and an amino group.

Incidentally, bract 1 a nitrogen-containing aromatic heterocyclic ring, a phenol ring, thiophenol ring, aniline ring, and a nitrogen-containing aromatic heterocyclic organic compound having 4 or more of any of the structures, as the ligand, More preferably, it has two or more phenol rings, three or more nitrogen-containing aromatic heterocycles, and two or more phenol rings. By using a ligand having the above structure, stability is increased. The number of preferable nitrogen-containing aromatic heterocycle is 3-8, More preferably, it is 3-5, Most preferably, it is 3 or 4. Further, the number of phenol rings is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2.

Ligand denaturing pretreatment of the metal complexes used in the present invention is an organic compound represented by the following general formula (I).

（式中、Ｒ^１は、水素原子または置換基を表し、隣合う２つの原子に結合している２つのＲ^１は、互いに連結していてもよく、複数あるＲ^１は、それぞれ同一であっても異なっていてもよい。Ｑ^１は、ピリジレン基、ピラジレン基、ピリミジレン基、ピリダジレン基、ピロリレン基、チアゾリレン基、イミダゾリレン基、オキサゾリレン基、トリアゾリレン基、インドリレン基、ベンゾイミダゾリレン基、ベンゾフリレン基、ベンゾチエニレン基、キノリレン基、イソキノリレン基、シンノリレン基、フタラジレン基、キナゾリレン基、キノキサリレン基、ベンゾジアジレン基、１，１０−フェナントロリレン基、２，２’−ビピリジレン基、２，２’−ビチオフェニレン基、２，２’−ビピローレン基、２，２’−ビチアゾリレン基、２，２’−ビフリレン基、２，２’−ビピリミジレン基、２，２’−ビピリダジレン基および２，２’−ビイミダゾリレン基から選択される２価の有機基を表し、Ｔ^１は、ピリジル基、ピラジル基、ピリミジル基、ピリダジル基、ピロリル基、ピラゾリル基、チアゾリル基、イミダゾリル基、オキサゾリル基、トリアゾリル基、インドリル基、ベンゾイミダゾリル基、キノリル基、イソキノリル基、シンノリル基、フタラジル基、キナゾリル基、キノキサリル基およびベンゾジアジル基から選択される１価の有機基を表し、２つのＴ^１は、同一でも異なっていてもよい。なお、電荷は省略してある。）

(In the formula, R ¹ represents a hydrogen atom or a substituent, and two R ¹ bonded to two adjacent atoms may be connected to each other, and a plurality of R ¹ may be the same. Q ¹ may be a pyridylene group, a pyrazylene group, a pyrimidylene group, a pyridazylene group, a pyrrolylene group, a thiazolylene group, an imidazolylene group, an oxazolylene group, a triazolylene group, an indolenylene group, a benzoimidazolylene group, a benzofurylene group, Benzothienylene group, quinolylene group, isoquinolylene group, cinnolylene group, phthalazilene group, quinazolylene group, quinoxarylene group, benzodiazylene group, 1,10-phenanthrolylene group, 2,2'-bipyridylene group, 2,2'-bithiophenylene Group, 2,2′-bipyrrolene group, 2,2′-bithiazolylene group, 2,2 ′ Bifuriren group, 2,2' Bipirimijiren group, a divalent organic radical selected from 2,2' Bipiridajiren group and 2,2' Biimidazoriren group, ^{T 1} is a pyridyl group, pyrazyl group, pyrimidyl group , Pyridazyl group, pyrrolyl group, pyrazolyl group, thiazolyl group, imidazolyl group, oxazolyl group, triazolyl group, indolyl group, benzoimidazolyl group, quinolyl group, isoquinolyl group, cinnolyl group, phthalazyl group, quinazolyl group, quinoxalyl group and benzodiazyl group It represents a monovalent organic group, two T ¹ may be the same or different. in addition, the charge is omitted.)

When R ¹ in the general formula (I) is a substituent , in the present invention, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, a halogen atom, or a substituent may be substituted. A good monovalent hydrocarbon group, an optionally substituted hydrocarbyloxy group (optionally substituted hydrocarbonoxy group), an amino group substituted with two unsubstituted or substituted monovalent hydrocarbon groups ( That is, an optionally substituted hydrocarbon disubstituted amino group , an optionally substituted N, N- dihydrocarbon amino group ), an optionally substituted hydrocarbyl mercapto group (substituted) May be a hydrocarbon mercapto group , that is, an optionally substituted hydrocarbon thio group, an optionally substituted hydrocarbylcarbonyl group (an optionally substituted hydrocarbon group). A sulfonyl group), an optionally substituted hydrocarbyloxycarbonyl group (an optionally substituted hydrocarbon oxycarbonyl group), an aminocarbonyl group substituted with two unsubstituted or substituted monovalent hydrocarbon groups (ie, a optionally substituted hydrocarbon disubstituted aminocarbonyl group, an optionally substituted N, N-di-hydrocarbon aminocarbonyl group), or an optionally substituted Hidorokarubi Angeles Ruhoniru group (substitution An optionally substituted hydrocarbon sulfonyl group), an optionally substituted monovalent hydrocarbon group, an optionally substituted hydrocarbyloxy group, two unsubstituted or substituted monovalent hydrocarbon groups. substituted amino group, an optionally substituted hydrocarbyloxy group, an optionally substituted hydrocarbyl group, and a substituted Which may have been a substituent selected from a good hydrocarbyloxy carbonyl group, it may be substituted monovalent hydrocarbon group, an optionally substituted hydrocarbyloxy group, unsubstituted or substituted monovalent hydrocarbon An amino group substituted with two hydrogen groups is more preferred, and a monovalent hydrocarbon group which may be substituted and a hydrocarbyloxy group which may be substituted are more preferred. In these groups, the nitrogen atom to which a hydrogen atom is bonded is preferably substituted with a monovalent hydrocarbon group. Moreover, when the group represented by R ¹ has a plurality of substituents, the two substituents may be linked to form a ring.

Examples of the monovalent hydrocarbon group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a nonyl group, An alkyl group having 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms such as dodecyl group, pentadecyl group, octadecyl group, docosyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group A cyclic saturated hydrocarbon group having 3 to 50 carbon atoms, preferably 3 to 20 carbon atoms such as a norbornyl group and an adamantyl group; an ethenyl group, a propenyl group, a 3-butenyl group, a 2-butenyl group, a 2-pentenyl group, 2- An alkenyl group having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms, such as a hexenyl group, a 2-nonenyl group, and a 2-dodecenyl group; a phenyl group 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl Group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group, 4-phenylphenyl group and the like, and an aryl group having 6 to 50 carbon atoms, preferably 6 to 20 carbon atoms Phenylphenyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1- 7 to 50 carbon atoms such as propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group and 6-phenyl-1-hexyl group , Preferably 7-20 aralkyl groups are mentioned.

The monovalent hydrocarbon group represented by R ¹ preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 2 to 12 carbon atoms, and 1 carbon atom. To 10 carbon atoms are more preferable, and those having 3 to 10 carbon atoms are particularly preferable.

The hydrocarbyloxy group, hydrocarbyl mercapto group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, and hydrocarbylsulfonyl group represented by R ¹ are the oxy group, mercapto group, carbonyl group, oxycarbonyl group, and sulfonyl group, respectively. This is a group formed by bonding one valent hydrocarbon group.

“Amino group substituted with two unsubstituted or substituted monovalent hydrocarbon groups” represented by R ¹ , “aminocarbonyl group substituted with two unsubstituted or substituted monovalent hydrocarbon groups” Are groups in which two hydrogen atoms in an amino group and an aminocarbonyl group (that is, —C (═O) —NH ₂ ) are substituted with the monovalent hydrocarbon group. Specific examples and preferred examples of the monovalent hydrocarbon group contained in these are the same as the monovalent hydrocarbon group represented by R ¹ described above.

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

Among R ¹ , particularly preferred are a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a phenyl group, a methylphenyl group, and a naphthyl group.

To Q ¹ the general formula (I), pin Rijiren group, pyrazylene group, a pyrimidylene group, pyridazylene group, pyrrolylene group, thiazolylene group, an imidazolylene group, an oxazolylene group, triazolylene group, an indolylene group, benzimidazolylene alkylene group, Benzofuriren group, benzothienylene Group, quinolylene group, isoquinolylene group, cinnolylene group, phthalazylene group, quinazolylene group, quinoxarylene group, benzodiazylene group, 1,10-phenanthrolylene group, 2,2'-bipyridylene group, 2,2'-bithiophenylene group , 2,2' Bipiroren group, 2,2' Bichiazoriren group, 2,2' Bifuriren group, 2,2' Bipirimijiren group, selected from 2,2' Bipiridajiren group and 2,2' Biimidazoriren group Represents a divalent organic group. Among these groups , pyridylene group, pyrazylene group, pyrimidylene group, pyridazylene group, pyrrolylene group, 1,10-phenanthrolylene group, 2,2′-bipyridylene group, 2,2′-bithiophenylene are preferable. Group, 2,2'-bipyrrolene group, 2,2'-bithiazolylene group, 2,2'-bifurylene group, 2,2'-bipyrimidylene group, 2,2'-bipyridazilene group, 2,2'-biimidazolylene group And more preferably a 1,10-phenanthrolylene group, a 2,2′-bipyridylene group, a 2,2′-bipyrrolene group, a 2,2′-bithiazolylene group, or a 2,2′-biimidazolylene group.
Further, these groups may be further substituted with R ¹ .

T ¹ is an optionally substituted nitrogen-containing aromatic heterocyclic group , and is pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, pyrrolyl group, pyrazolyl group, thiazolyl group, imidazolyl group, oxazolyl group, triazolyl group, indolyl group, a benzimidazolyl group, quinolyl group, isoquinolyl group, cinnolyl group, phthalazyl group, quinazolyl group, a group selected from a quinoxalyl group and Benzojiajiru group.
Preferably, it is a pyridyl group, pyrazyl group, pyridazyl group, pyrrolyl group, pyrazolyl group, pyridazyl group, thiazolyl group, indolyl group, benzoimidazolyl group, and more preferably a pyridyl group, pyrrolyl group, pyrazolyl group, pyridazyl group, thiazolyl group It is.
Further, these groups may be further substituted with the substituent in R ¹ .

  The ligand represented by the general formula (I) is preferably a ligand having a structure of the following formula (II).

（式中、Ｒ²は、一般式（II）のＲ¹と同義であり、隣合う２つの原子に結合している２つのＲ²は、互いに連結していてもよく、複数あるＲ²は、それぞれ同一であっても異なっていてもよい。）Ｙ¹及びＹ²は、

(In the formula, R ² has the same meaning as R ^{1 in the} general formula (II), and two R ² bonded to two adjacent atoms may be connected to each other, and a plurality of R ² are Each may be the same or different.) Y ¹ and Y ² are

（Ｒ^３は水素原子または炭素数が１〜４の炭化水素基である。）
を表す。Ｐ^１は、Ｙ^１とＹ^１の隣接位の２つの炭素原子と一体となって複素環を形成するために必要な原子群であり、Ｐ^２は、Ｙ^２とＹ^２の隣接位の２つの炭素原子と一体となって複素環を形成するために必要な原子群であり、Ｐ^１とＰ^２が互いにさらに結合して環を形成しても良い。
ただし、Ｐ ^１ 、Ｙ ^１ 、Ｐ ^２ 、Ｙ ^２ で形成される基は、前記一般式（Ｉ）におけるＱ ^１ を形成する
Ｔ^２は、一般式（Ｉ）のＴ^１と同義である。なお、電荷は省略してある。）

(R ³ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
Represents. P ¹ is an atomic group necessary for forming a heterocyclic ring together with two carbon atoms adjacent to Y ¹ and Y ¹ , and P ² is ² adjacent to Y ² and Y 2. It is an atomic group necessary for forming a heterocyclic ring integrally with one carbon atom, and P ¹ and P ² may be further bonded to each other to form a ring.
However, in the group formed by P ¹ , Y ¹ , P ² and Y ² , T ² forming Q ¹ in the general formula (I) has the same meaning as T ^{1 in the} general formula (I). The charge is omitted. )

Y ¹ and Y ² in the formula (II) are

（Ｒ^３は、水素原子または炭素数が１〜４の炭化水素基である。）
を表し、Ｐ^１は、Ｙ^１とＹ^１の隣接位の２つの炭素原子と一体となって含窒素芳香族複素環を形成するために必要な原子群が好ましく、Ｐ^２は、Ｙ^２とＹ^２の隣接位の２つの炭素原子と一体となって含窒素芳香族複素環を形成するために必要な原子群が好ましく、Ｐ^１とＰ^２が互いにさらに結合して環を形成しても良い。含窒素芳香族複素環の具体例として、ピリジン、ピラジン、ピリミジン、ピロール、Ｎ−アルキルピロール、チアゾール、イミダゾール、オキサゾール、イソキノリン、キナゾリンが挙げられ、これらは前記Ｒ^１で置換されてもよい。好ましくは、ピリジン、ピラジン、ピリミジン、ピロール、Ｎ−アルキルピロール、チアゾール、イミダゾール、オキサゾール、であり、さらに好ましくは、ピリジン、ピラジン、ピリミジン、ピロール、Ｎ−アルキルピロール、イミダゾールである。これらの基は、さらに前記Ｒ^１における置換基で置換されてもよい。Ｎ−アルキピロールのアルキル基は、メチル基、エチル基が好ましく、より好ましくはメチル基である。

(R ³ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.)
P ¹ is preferably an atomic group necessary to form a nitrogen-containing aromatic heterocyclic ring together with two carbon atoms adjacent to Y ¹ and Y ¹ , and P ² is Y ² and A group of atoms necessary for forming a nitrogen-containing aromatic heterocyclic ring integrally with two carbon atoms adjacent to Y ² is preferable , and even if P ¹ and P ² are further bonded to each other to form a ring good. Specific examples of the nitrogen-containing aromatic heterocycle include pyridine, pyrazine, pyrimidine, pyrrole, N-alkylpyrrole, thiazole, imidazole, oxazole, isoquinoline, and quinazoline, which may be substituted with R ¹ . Preferred are pyridine, pyrazine, pyrimidine, pyrrole, N-alkylpyrrole, thiazole, imidazole and oxazole, and more preferred are pyridine, pyrazine, pyrimidine, pyrrole, N-alkylpyrrole and imidazole. These groups may be further substituted with the substituent in R ¹ . The alkyl group of N-alkylpyrrole is preferably a methyl group or an ethyl group, and more preferably a methyl group.

Further, P ¹ and P ² skeletons may be bonded to each other to form a new ring, and those having the following structures (III-1) to (III-6) are preferred. More preferably, it has a structure of (III-1) to (III-3).

（式中のＲ⁴は、一般式（I）のＲ¹と同義であり、複数あるＲ⁴は、それぞれ同じでも、異なっていてもよい。Ｒ⁵は水素原子または炭素数が１〜３０で表される炭化水素基を表し、複数あるＲ⁵は、それぞれ同じでも、異なっていてもよい。

(In the formula, R ⁴ has the same meaning as R ^{1 in} formula (I), and a plurality of R ⁴ may be the same or different. R ⁵ has a hydrogen atom or a carbon number of 1 to 30. A plurality of R ^{5 s} each representing the hydrocarbon group represented may be the same or different.

R ⁵ is preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t- Examples thereof include a butyl group, a hexyl group, a phenyl group, and an octyl group.

Examples of the ligand in the metal complex, that Yusuke 5 or 6 coordination atoms capable of bonding with coordinate bonds with metal atoms. Here, the coordination atom is an electron donated to an empty orbit of the metal atom as described in Ryogo Kubo et al., “Iwanami Rikagaku Dictionary 4th Edition” (issued January 10, 1991, Iwanami Shoten), page 966. An atom having an unshared electron pair and bonded to a metal atom through a coordinate bond.
The total number of coordinating atoms in the ligand is preferably six. The coordinating atom may be electrically neutral or a charged ion.

The coordinating atom, a nitrogen atom, SansoHara Komata is selected from sulfur atom, a plurality of coordination atoms may be the same or different from each other. More preferably nitrogen atom and oxygen atom.

  Here, specific structures of the ligand having the structure of the formula (II) are exemplified in the following formulas (IV-1) to (IV-18). Of these, the formulas (IV-1) to (IV-12) are preferable, and the formulas (IV-1) to (IV-6) are particularly preferable. The charge is omitted.

  In the metal complex of the present invention, a metal atom to which a ligand atom is coordinated may be an uncharged or charged ion.

Wherein the metal atom is in the present invention, Ru Oh transition metal atom belonging to period 4 to 6 of the periodic table of the elements.
Specifically, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, lanthanum, cerium, praseodymium, neodymium, samarium, europium And a metal atom selected from the group consisting of gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold.
Among these, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, silver, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, A metal atom selected from the group consisting of dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum and tungsten, more preferably scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium And a metal atom selected from the group consisting of niobium, molybdenum, tantalum and tungsten.
Among these, a metal atom selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel and copper is preferable, and the metal atom manganese, iron, cobalt, nickel and the metal atoms exemplified above are particularly preferable. It is a metal atom selected from the group consisting of copper.

The metal complex used in the present invention, that have one or to two metal atoms.

The metal complex used in the present invention is required to have the organic compound represented by the general formula (I) as a ligand, but has other ligands in addition to the ligand. May be. The other ligand may be an ionic or electrically neutral compound, and when it has a plurality of such other ligands, these other ligands may be the same as or different from each other.

Examples of the electrically neutral compound in the other ligand include ammonia, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, pyrazole, imidazole, 1,2,3-triazole, and oxazole. , Isoxazole, 1,3,4-oxadiazole, thiazole, isothiazole, indole, indazole, quinoline, isoquinoline, phenanthridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, acridine, 2,2 '-Bipyridine, 4,4'-bipyridine, 1,10-phenanthroline, ethylenediamine, propylenediamine, phenylenediamine, cyclohexanediamine, piperazine, 1,4-diazabicyclo [2,2,2] octane, pyridine N-oxide, 2 , 2'-bipyridine N, N'-dioxide, oxamide, dimethylglyoxime, o-aminophenol and other nitrogen atom-containing compounds; water, methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, isobutyl alcohol , Sec-butyl alcohol, tert-butyl alcohol, 2-methoxyethanol, phenol, oxalic acid, catechol, salicylic acid, phthalic acid, 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione Oxygen-containing compounds such as hexafluoropentanedione, 1,3-diphenyl-1,3-propanedione, and 2,2′-binaphthol; sulfur-containing compounds such as dimethylsulfoxide and urea; 1,2-bis (dimethylphosphino ) Ethane, 1,2-phenylenebis (dimethyl) Examples include phosphorus-containing compounds such as ruphosphine).
Preferably ammonia, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, pyrazole, imidazole, 1,2,3-triazole, oxazole, isoxazole, 1,3,4-oxadiazole, indole , Indazole, quinoline, isoquinoline, phenanthridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, acridine, 2,2'-bipyridine, 4,4'-bipyridine, 1,10-phenanthroline, ethylenediamine, propylene Diamine, phenylenediamine, cyclohexanediamine, piperazine, 1,4-diazabicyclo [2,2,2] octane, pyridine N-oxide, 2,2'-bipyridine N, N'-dioxide, oxamide, dimethylglyoxime o-aminophenol, water, phenol, oxalic acid, catechol, salicylic acid, phthalic acid, 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, hexafluoropentanedione, 1,3 -Diphenyl-1,3-propanedione, 2,2'-binaphthol, more preferably ammonia, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, pyrazole, imidazole, 1,2, 3-triazole, oxazole, isoxazole, 1,3,4-oxadiazole, indole, indazole, quinoline, isoquinoline, phenanthridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, acridine, 2,2 '-Bipyridine, 4,4'-bipyri 1,10-phenanthroline, ethylenediamine, propylenediamine, phenylenediamine, cyclohexanediamine, pyridine N-oxide, 2,2'-bipyridine N, N'-dioxide, o-aminophenol, phenol, catechol, salicylic acid, phthalic acid 1,3-diphenyl-1,3-propanedione, and 2,2′-binaphthol.
Among these, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, pyrazole, imidazole, oxazole, indole, quinoline, isoquinoline, acridine, 2,2′-bipyridine, 4,4′-bipyridine, 1,10-phenanthroline, phenylenediamine Piperazine, 1,4-diazabicyclo [2,2,2] octane, pyridine N-oxide, 2,2′-bipyridine N, N′-dioxide, o-aminophenol, and phenol are more preferable.

Examples of the anionic ligand include hydroxide ions, peroxides, superoxides, cyanide ions, thiocyanate ions, fluoride ions, chloride ions, bromide ions, iodide ions, and the like, Sulfate ion, nitrate ion, carbonate ion, perchlorate ion, tetrafluoroborate ion, tetraarylborate ion such as tetraphenylborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluene Sulfonate ion, benzenesulfonate ion, phosphate ion, phosphite ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, metal oxide ion, methoxide ion, etho Side ion, 2-ethylhexanoic acid ion, and the like.
Preferably, hydroxide ion, chloride ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfone Examples include acid ions, p-toluenesulfonate ions, benzenesulfonate ions, phosphate ions, acetate ions, trifluoroacetate ions. Among these, hydroxide ions, chloride ions, sulfate ions, nitrate ions, carbonate ions Ions, tetraphenylborate ions, trifluoromethanesulfonate ions, p-toluenesulfonate ions, acetate ions, trifluoroacetate ions, and 2-ethylhexanoate ions are more preferable.

  Furthermore, the ions exemplified as the ligand having an anionic property may have as a counter ion for electrically neutralizing the metal complex itself of the present invention.

Further, the metal complex used in the present invention may have a counter ion having a cationic property that maintains electrical neutrality. Examples of the counter ion having a cationic property include alkali metal ions, alkaline earth metal ions, tetraalkylammonium ions such as tetra (n-butyl) ammonium ion and tetraethylammonium ion, and tetraarylphosphonium ions such as tetraphenylphosphonium ion. Specifically, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, magnesium ion, calcium ion, strontium ion, barium ion, tetra (n-butyl) ammonium ion, tetraethylammonium ion, tetraphenyl Phosphonium ion, more preferably tetra (n-butyl) ammonium ion, tetraethylammonium ion, tetraphenylphosphonium Ion, and the like.
Among these, tetra (n-butyl) ammonium ions and tetraethylammonium ions are preferable as the counter ion having a cationic property.

  Next, a method for synthesizing a metal complex applied to the present invention will be described. The metal complex of the present invention can be obtained by synthesizing a ligand organically and mixing with the above-mentioned reagent for imparting a metal atom (hereinafter referred to as “metal imparting agent”). As the metal imparting agent, the exemplified metal acetates, hydrochlorides, sulfates, carbonates and the like can be used.

  As described in Non-Patent Document Tetrahedron., 1999, 55, 8377., the ligand is synthesized by adding an organometallic reactant to a heterocyclic compound and oxidizing it, followed by a halogenation reaction, It can be synthesized by a cross-coupling reaction using a transition metal catalyst. Moreover, it is also possible to synthesize | combine by a cross-coupling reaction in steps using the halide of a heterocyclic ring.

As described above, the metal complex of the present invention can be obtained by mixing a ligand and a metal imparting agent in the presence of a suitable reaction solvent. Specifically, the reaction solvent includes water, acetic acid, oxalic acid, aqueous ammonia, methanol, ethanol, n-propanol, isopropyl alcohol, 2-methoxyethanol, 1-butanol, 1,1-dimethylethanol, ethylene. Glycol, diethyl ether, 1,2-dimethoxyethane, methyl ethyl ether, 1,4-dioxane, tetrahydrofuran, benzene, toluene, xylene, mesitylene, durene, decalin, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, 1,2- Examples include dichlorobenzene, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, acetone, acetonitrile, benzonitrile, triethylamine, and pyridine. It may be used by mixing two or more reaction solvent, but is preferably one ligand and the metal-providing agent is soluble. 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. It can be carried out in ~ 12 hours. The reaction temperature and reaction time can also be appropriately set depending on the type of ligand and metal imparting agent.
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.
As a preferred coordination form as the metal complex used in the present invention, any of transition metals selected from transition metals belonging to the fourth period and ligands described in the above formulas (IV-1) to (IV-12) More preferably, a transition metal selected from manganese, iron, cobalt, nickel, and copper and a ligand described in the above formulas (IV-1) to (IV-7) are used. It is a metal complex obtained by reacting either one.

The polymer having a residue of the metal complex represented by the formula (I) is an atom formed by removing part or all (usually one) of hydrogen atoms in the metal complex represented by the formula (I). This means a polymer having a group of groups, and the polymer used in this case is not particularly limited, but is a conductive polymer, dendrimer, natural polymer, solid polymer electrolyte, polyethylene, polyethylene glycol, polypropylene, etc. Can be illustrated. Among these, a conductive polymer and a solid polymer electrolyte are particularly preferable. The conductive polymer is a general term for polymer substances showing metallic or semi-metallic conductivity (Iwanami Riken Dictionary 5th edition: published in 1988). Examples of conductive polymers include polyacetylene and polyacetylene described in “Conductive Polymers” (Shinichi Yoshimura, Kyoritsu Publishing) and “Latest Applied Technologies 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, polyfluorene and derivatives thereof, polycarbazole and derivatives thereof , Polyindole and derivatives thereof, and copolymers of the conductive polymers.
Examples of the solid polymer electrolyte include perfluorosulfonic acid, polyether ether ketone, polyimide, polyphenylene, polyarylene, and a polymer obtained by sulfonating polyarylene ether sulfone.

The polymer having a residue of the metal complex represented by the formula (I) as a repeating unit removes part or all (usually two) of hydrogen atoms in the metal complex represented by the formula (I). It is produced by polymerizing a bifunctional monomer containing a macrocyclic ligand, for example.
It does not depend on the length of the molecular chain.

Next, the metal complex stabilization treatment (modification treatment) conditions in the present invention will be described in detail.
As the metal complex used for the modification treatment, only one kind of metal complex may be used, or two or more kinds of metal complexes may be used.
It is particularly preferable that the metal complex is dried for 6 hours or more at a temperature of 15 ° C. or more and 200 ° C. or less and a reduced pressure of 10 Torr or less as a pretreatment for the modification treatment. As the pretreatment, a vacuum dryer or the like can be used.

The atmosphere used for the modification treatment of the metal complex is preferably in the presence of hydrogen, helium, nitrogen, ammonia, oxygen, neon, argon, krypton, xenon, acetonitrile, and a mixed gas thereof.
Preferably it is in the presence of hydrogen, helium, nitrogen, ammonia, oxygen, neon, argon, and a mixed gas thereof, more preferably in the presence of hydrogen, nitrogen, ammonia, argon, and a mixed gas thereof.
Further, the pressure related to the modification treatment can be appropriately changed in the modification treatment to be selected. The temperature at which the metal complex is heat-treated is such that the mass reduction rate is 1% by mass or more and 90% by mass or less before and after the heat treatment, and the carbon content of the modified product after the heat treatment is 5% by mass or more. If it is temperature to become, it will not specifically limit.
The treatment temperature for the heat treatment is preferably 250 ° C. or higher, more preferably 300 ° C. or higher, further preferably 400 ° C. or higher, and particularly preferably 500 ° C. or higher. Further, the upper limit of the temperature for the baking treatment is not particularly limited as long as the carbon content of the modified product after the treatment can be 5% by mass or more, but is preferably 1200 ° C or less, more preferably 1000 ° C. It is as follows.

The atmosphere used for the heat treatment of the polynuclear complex is a reducing atmosphere such as hydrogen or carbon monoxide, an oxidizing atmosphere such as oxygen, carbon dioxide or water vapor, or an inert gas such as nitrogen, helium, neon, argon, krypton, or xenon. It is preferably in the presence of an atmosphere, a gas or vapor of a nitrogen-containing compound such as ammonia or acetonitrile, and a mixed gas thereof. More preferably, in a reducing atmosphere, hydrogen and a mixed atmosphere of hydrogen and the inert gas, in an oxidizing atmosphere, oxygen, a mixed atmosphere of oxygen and the inert gas, or an inert gas atmosphere If so, it is a mixed atmosphere of nitrogen, neon, argon, and these gases.
Moreover, the pressure which concerns on heat processing is although it does not specifically limit, It is preferable in the normal pressure vicinity of about 0.5-1.5 atmospheres.

  The processing time required for the heat treatment can be appropriately set depending on the gas used, the temperature, etc. In the sealed or vented state of the gas, the temperature is gradually raised from room temperature and the temperature is lowered immediately after reaching the target temperature. Also good. Especially, after reaching | attaining target temperature, it is preferable to heat a metal complex gradually by maintaining temperature, since durability can be improved more. The holding time after reaching the target temperature is preferably 1 to 100 hours, more preferably 1 to 40 hours, further preferably 2 hours to 10 hours, and particularly preferably 2 to 5 hours. .

  An apparatus for performing the heat treatment is not particularly limited, and examples thereof include a tubular furnace, an oven, a furnace, and an IH hot plate. The modified metal complex of the present invention causes a decrease in mass accompanied by low molecular desorption due to the heat treatment as described above, and the ligands react with each other to form a condensate, and the condensate. It is considered that the coordination structure is stabilized in this. Even in other modification treatments in place of the heat treatment, the same effects can be obtained in the treatment capable of setting the mass reduction rate within the above range.

Examples of modification treatments that can replace heat treatment include α rays, β rays, neutron rays, electron rays, γ rays, X rays, vacuum ultraviolet rays, ultraviolet rays, visible rays, infrared rays, microwaves, radio waves, electromagnetic waves such as laser beams, particle rays, etc. Can be selected from discharge treatment such as any one of irradiation treatment, corona discharge treatment, glow discharge treatment, plasma treatment (including low temperature plasma treatment).
Among these, preferable modification treatment includes radiation irradiation treatment or low-temperature plasma treatment selected from X-rays, electron beams, ultraviolet rays, visible rays, infrared rays, microwaves and lasers. More preferred is a method of irradiating radiation selected from ultraviolet rays, visible rays, infrared rays, microwaves and lasers.
These methods can be carried out in accordance with the equipment and processing methods usually used for the surface modification treatment of polymer films. For example, the literature (Journal of the Japan Adhesion Society, “Surface Analysis / Modification Chemistry”, daily publication) The method described in Kogyo Shimbun, published on December 19, 2003) can be used.

  Here, when performing the heat treatment, radiation irradiation treatment or discharge treatment, the metal complex has a mass reduction rate before and after the treatment of 1% by mass to 90% by mass, and the modified carbon after the treatment. The conditions that can be modified can be arbitrarily set so that the content can be 5% by mass or more, but the preferable treatment time is within 10 hours, more preferably within 3 hours, even more preferably within 1 hour, particularly preferably. Within 30 minutes.

The modified metal complex of the present invention is subjected to a modification treatment such as heat treatment, radiation irradiation treatment, or discharge treatment as described above, and the mass reduction rate is 1% by mass or more, preferably 2% by mass or more. can get.

Furthermore, the modified metal complex of the present invention has a carbon content of 5% by mass or more in elemental analysis.
The carbon content is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more and 98% by mass or less. A higher carbon content of the treated product is preferable because the complex structure is more stabilized and the degree of accumulation of metal atoms in the modified metal complex is easily improved. The modified metal complex of the present invention can be obtained by the above-described treatment, but after the treatment contains an unreacted metal complex, metal fine particles or metal oxides generated by decomposition of the metal complex. There is a case. In such a case, the modified metal complex is obtained by removing the metal fine particles and the metal oxide by acid treatment or the like, but can be used as a catalyst as long as the function as the modified metal complex is not hindered.
In the present invention, the “modified metal complex” means a mass reduction rate before and after treatment of 1% by mass or more and 90% by mass or less, preferably 80% by mass or less by any modification treatment of heat treatment, radiation irradiation treatment or discharge treatment. More preferably, it is a metal complex that is modified until it is 70% by mass or less, particularly preferably 60% by mass or less, and the carbon content after modification is 5% by mass or more, preferably a carbon compound is formed. More preferably, the graphene compound is formed. In addition, a carbon compound means the compound whose carbon content rate is 5 mass% or more. The catalytic activity similar to that of the metal complex before the modification treatment can be stabilized and further enhanced. Specifically, the decrease in mass is mainly caused by the desorption of low molecules from the metal complex. Such desorption of low molecules causes the gas components generated by the denaturation treatment to be removed using a mass spectrometer or the like. Can be confirmed. The metal complex structure can be confirmed from a spectrum attributed to a bond between a metal atom and a coordination atom by X-ray absorption fine structure (EXAFS) analysis, infrared spectroscopy, Raman spectroscopy, or the like.

As described above, the modified metal complex of the present invention is produced by the reaction between ligands accompanying the modification treatment, that is, the ligands condense with low molecular separation and the ligands condense. In the modified ligand, it is presumed that the metal atom maintains a spatial arrangement substantially equivalent to that of the metal complex before the modification. Here, it is preferable that the modified ligand is in a state of being condensed and connected in a graphene-like structure, since the stability to acid and the thermal stability are further increased. In addition, “graphene-like structure” means a carbon hexagonal network structure in which carbon atoms are chemically bonded by sp ² hybrid orbitals and spread in two dimensions. Some of the carbon atoms constituting the graphene-like structure are nitrogen and the like. May be replaced by a heteroatom. Moreover, you may take the graphite-like structure on which the above-mentioned graphene-like structure was laminated | stacked.
Moreover, when the modified metal complex of the present invention has a graphene-like structure, there is also an effect that conductivity is improved. The presence of the graphene-like structure in this case is confirmed by the presence of a peak (maximum) of 1550 to 1600 cm ⁻¹ representing the presence of the graphene-like structure in the spectrum obtained by laser Raman spectroscopy with an excitation wavelength of 532 nm. The observed is the lower limit of the peak (maximum), preferably 1560 cm ^-1, more preferably 1570 cm ^-1. The upper limit value observed of the peaks (maxima), preferably 1595Cm ^-1, more preferably 1590 cm ^-1.
Next, another embodiment of the modified metal complex of the present invention will be described.
A metal complex mixture comprising (a) a metal complex as described above and (b) a carbon support, an organic compound having a boiling point or melting point of 250 ° C. or higher, or an organic compound having a thermal polymerization initiation temperature of 250 ° C. or lower. Is subjected to any modification treatment of heat treatment, radiation irradiation treatment or discharge treatment, and the mass reduction rate before and after the treatment is modified to 1 mass% or more and 90 mass% or less, and the carbon content after modification is 5 mass% or more. As a modified metal complex composition. Here, the mass reduction rate is obtained with respect to the total mass of (a) and (b) in the metal complex mixture.

  The mixing ratio of (a) and (b) in the metal complex mixture should be set so that the content of (a) is 1 to 70% by mass with respect to the total mass of (a) and (b). Is preferred. The content of the base metal complex is more preferably 2 to 60% by mass, and particularly preferably 3 to 50% by mass.

  Examples of the carbon support include Norrit (manufactured by NORIT), Ketjen black (manufactured by Lion), Vulcan (manufactured by Cabot), black pearl (manufactured by Cabot), acetylene black (manufactured by Chevron) (all products) Name), fullerenes such as C60 and C70, carbon nanotubes, carbon nanohorns, and carbon fibers.

Examples of organic compounds having a boiling point or melting point of 250 ° C. or higher include perylene-3,4,9,10-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic diimide, 1,4 , 5,8-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid diimide, 1,4,5,8-naphthalenetetracarboxylic acid, pyromellitic acid, dianhydropyromellitic acid, etc. And aromatic compound carboxylic acid derivatives. Here, the boiling point or melting point can be measured using a known method, and can be selected from the measured values, but is selected using the values described in the literature. You can also.
Also, it may be a calculated value obtained by computer simulation, for example, Chemical
You can also use the calculated boiling point or melting point registered in SciFinder, which is software provided by Abstract Service. In the compounds shown below, “calc” at the boiling point (b.p.) is a calculated value registered in the SciFinder.

  Moreover, the compound which starts thermal polymerization at 250 degrees C or less is an organic compound which has a double bond or a triple bond other than an aromatic ring, for example, organic compounds, such as acenaphthylene and vinyl naphthalene, are illustrated. The numerical value described in the compound shown below is the polymerization start temperature of each organic compound. The numerical values are described in “Basics of Carbonization Engineering” (first edition, second printing, 1982, Ohmsha).

In this embodiment, in addition to the component (a) as described above, in addition to the component (b), the modification treatment method, treatment conditions, mass reduction rate due to the modification treatment (stabilization treatment), carbon of the metal complex after treatment About a content rate etc., it is the same as that of 1st Embodiment.
As a second embodiment of the present invention, there is provided a method for treating the metal complex described above with a carbon support, an organic compound having a boiling point or melting point of 250 ° C. or higher, and an organic compound having a thermal polymerization start temperature of 250 ° C. or lower. In some cases, after the treatment, metal fine particles or metal oxides generated by decomposition of the metal complex may be included. In such a case, the modified metal complex of the second embodiment is obtained by removing the metal fine particles and the metal oxide. On the other hand, in the second embodiment, the carbon carrier, the unreacted component of the organic compound, and the decomposition component of the organic compound may be mixed. In such a case, it is preferable to remove unreacted components and decomposition components by washing with a solvent, column separation, solvent extraction operation, etc., but as long as the function as a modified metal complex is not hindered, it should be used as it is as a catalyst. Can do.
Further, as a third embodiment of the present invention, the metal complex described above is reduced in mass by treatment conditions and modification treatment (stabilization treatment) except that a composition containing a carbon support and / or a conductive polymer is used. About a rate, the carbon content rate of the metal complex after a process, etc., a modified | denatured metal complex is obtained by performing the process similar to 1st Embodiment. As the carbon carrier, the carbon carrier exemplified above can be used. In addition, as the conductive polymer, as described in “conductive polymer” (Shinichi Yoshimura, Kyoritsu Publishing) and “latest applied technology of conductive polymer” (supervised by Masao Kobayashi, CMC Publishing) Polyacetylene and 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, polyfluorene and derivatives thereof, polycarbazole and Examples thereof include a derivative thereof, polyindole and a derivative thereof, and a copolymer of the conductive polymer.

In particular, when the above-described treatment is performed on a metal complex having a hetero atom as a coordination atom, a new bond is formed in addition to the bond between the central metal and the hetero atom, thereby further improving the stability. The heteroatom here is an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, an arsenic atom, or a halogen atom, more preferably an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom, more preferably Oxygen atom, nitrogen atom and sulfur atom, particularly preferably oxygen atom and nitrogen atom.
The metal atom contained in the metal complex has the same meaning as the above metal atom. The formation of a new bond to the central metal can be confirmed using a wide area X-ray absorption fine structure (EXAFS) analysis method. In the EXAFS radial distribution function of the central metal, the hetero atom coordinated to the central metal is observed as a peak derived from the first adjacent atom, and is usually observed in the range of 1.0 to 2.5 cm. The lower limit of the range in which the peak derived from the first adjacent atom is observed is more preferably 1.1 Å or more, and further preferably 1.2 Å or more. Further, the upper limit value is more preferably 2.2 mm or less, further preferably 1.8 mm or less, and particularly preferably 1.6 mm or less. The formation of the new bond is observed as another peak at a position farther from the central metal than the peak derived from the first neighboring atom. The position of the peak is within 0.58 cm, more preferably within 0.57 cm, more preferably within 0.56 cm, and particularly preferably within 0.55 cm, relative to the peak derived from the first adjacent atom. is there.
Although the number of another peak will not be specifically limited if it is 1 or more, Preferably it is 1-3, More preferably, it is 1-2, Especially preferably, it is 1. The intensity of the peak is preferably 2/5 or more of the peak intensity derived from the first adjacent atom, more preferably 1/2 or more, particularly preferably 2/3 or more. The strength is particularly preferably 3/4 or more.

  The modified metal complex of the present invention can be used in combination with various carriers, additives, etc., and can be processed in shape according to various applications. The treated metal complex of the present invention has a stable complex structure and a high degree of accumulation of metal atoms, so that it can be used as a hydrogen peroxide decomposition catalyst, a battery electrode material, a memory material for electronic devices, and a film deterioration preventing agent for fuel cells. It is particularly suitable for oxidative coupling catalysts for aromatic compounds, exhaust gas / drainage purification catalysts, oxidation-reduction catalyst layers for dye-sensitized solar cells, carbon dioxide reduction catalysts, catalysts for producing reformed hydrogen, oxygen sensors, and the like.

Moreover, when using the modified metal complex of this invention as a catalyst, it can also be used as a composition containing a carbon support | carrier and / or a conductive polymer. This is useful from the standpoint that the stability of the modified metal complex is further increased and the catalytic activity is further improved.
Examples of the conductive polymer include polyacetylene, polyaniline, and polypyrrole. Specific examples of the carbon support are the same as described above. In addition, as such a composition, a plurality of the modified metal complexes of the present invention can be mixed and used, or a plurality of carbon carriers or conductive polymers can be used. A combination of molecules can also be used.

Below, the preferable use of the modified | denatured metal complex of this invention is demonstrated.
The modified metal complex of the present invention preferably forms a carbon compound, and more preferably forms a graphene compound. The catalytic activity similar to that of the metal complex before the modification treatment can be stabilized and further enhanced. Specifically, it is more preferably used as a peroxide decomposition catalyst, particularly as a hydrogen peroxide decomposition catalyst. When used as a hydrogen peroxide decomposition catalyst, it has a feature that it can be decomposed into water and oxygen while suppressing generation of hydroxyl radicals. Specifically, it can be used for a solid polymer electrolyte fuel cell or water electrolysis ion conductive membrane deterioration preventive, medical agrochemical, food antioxidant, and the like.
Moreover, it is suitable also as an oxidative coupling catalyst of an aromatic compound, and when it is this use, it can be used, for example as a catalyst in connection with polymer manufacture, such as polyphenylene ether and a polycarbonate. Examples of usage forms include a method of directly adding the modified product to the reaction solution, and a method of supporting the modified product on zeolite or silica.

  The modified metal complex of the present invention can also be used as a desulfurization / denitration catalyst for converting sulfur oxides and nitrogen oxides contained in exhaust gases from various factories and automobiles into sulfuric acid and ammonia. Examples include a method of filling a tower in which exhaust gas from a factory is ventilated and a method of filling an automobile muffler.

Furthermore, the modified metal complex of the present invention can also be used as a catalyst for modifying CO in the reformed hydrogen. The reformed hydrogen contains CO and the like, and when the reformed hydrogen is used as a fuel cell, it is a problem that the fuel electrode is poisoned by CO, and it is desirable to reduce the CO concentration as much as possible. It is. For specific usage forms, for example, Chemical
The method described in Communication, 3385 (2005), etc. are mentioned.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail concretely based on an Example, this invention is not restrict | limited to an Example.
Synthesis example 1
A metal complex (A) was synthesized according to the following reaction formula.

In addition, the said ligand used as the raw material of a complex was synthesize | combined by the method as described in Tetrahedron, 55,8377 (1999). In a nitrogen atmosphere, a 200 ml solution of 2-methoxyethanol containing 1.388 g of ligand and 1.245 g of cobalt acetate tetrahydrate was placed in a 500 ml eggplant flask and stirred for 2 hours while heating to 80 ° C. A brown solid was formed. This solid was collected by filtration, further washed with 20 ml of 2-methoxyethanol and dried to obtain a metal complex (A) (yield 1.532 g: yield 74%). Elemental analysis _{(%): C 49 H 50} Co 2 N 4 as O _8; calcd C, 62.56; H, 5.36; N, 5.96; Co, 12.53. Found: C, 62.12; H, 5.07; N, 6.03; Co,
12.74. Further, the metal complex (A) and the carbon support (Ketjen Black EC300J (trade name), manufactured by Lion Corporation) were mixed at a mass ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then brought to room temperature. The metal complex mixture (A) was prepared by drying under reduced pressure of 1.5 Torr for 12 hours.

Synthesis example 2
A metal complex (B) was synthesized according to the following reaction formula.

In addition, the ligand synthesize | combined in Example 1 was used for the said ligand used as the raw material of a complex. 50 ml of ethanol containing 0.315 g of the ligand and 0.124 g of cobalt acetate tetrahydrate was placed in a 100 ml eggplant flask and stirred at 80 ° C. for 1 hour. The produced brown precipitate was collected by filtration, washed with ethanol, and then vacuum-dried to obtain a metal complex (B) (yield 0.270 g: yield 81%). Elemental analysis _{(%): C 42 H 40} CoN 4 as O _4; Calculated C, 69.70; H, 5.57; N, 7.74; Found: C, 70.01; H, 5 . 80; N, 7.56. Further, the metal complex (B) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a mass ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (B) was prepared by drying under reduced pressure for 12 hours.

Synthesis example 3
A metal complex (C) represented by the following reaction formula was synthesized according to the method described in Australian Journal of Chemistry, 23, 2225 (1970).

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. A solution prepared by dissolving 0.59 g of 1,3-propanediamine in 20 ml of methanol was gradually added to this solution. 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 (C) (yield 1.75 g: yield 74%). In the above reaction formula, “Cl ₂ ” indicates that 2 equivalents of chlorine ions are present as counter ions, and “2MeOH” indicates that 2 equivalents of methanol are contained. Elemental analysis value (%): C ₂₆ H ₃₄ Cl ₂ Co ₂ N ₄ O ₄ ; calculated value C, 47.65; H, 5.23; N, 8.55. Found: C, 46.64; H, 5.02; N, 8.58. Further, the metal complex (C) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a mass ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (C) was prepared by drying under reduced pressure for 12 hours.

Synthesis example 4
A metal complex (D) was synthesized according to the following reaction formula.

In addition, the ligand synthesize | combined in the synthesis example 1 was used for the said ligand used as the raw material of a complex. In a nitrogen atmosphere, 10 ml of ethanol containing 0.126 g of ligand and 5 ml of methanol containing 0.078 g of iron acetate were placed in a 50 ml eggplant flask and stirred for 3 hours while heating to 80 ° C. A brown solid precipitated out. The solid was collected by filtration, further washed with methanol and dried to obtain a metal complex (D) (yield 0.075 g: yield 41%). In the above reaction formula, “(OAc) ₂ ” indicates that 2 equivalents of acetate ion is a counter ion, and “MeOH” indicates that 2 equivalents of methanol molecules are included. Yes. Elemental analysis (%): as _{C 48 H 50 Fe 2 N 4} O 8; Calculated: C, 62.49; H, 5.46 ; N, 6.07, Found: C, 59.93; H , 5.29; N, 5.70. Further, the metal complex (D) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a mass ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (D) was prepared by drying under reduced pressure for 12 hours.

Synthesis example 5
A metal complex (E) was synthesized according to the following reaction formula.

In addition, the ligand synthesize | combined in the synthesis example 1 was used for the said ligand used as the raw material of a complex. In a nitrogen atmosphere, 2 ml of chloroform containing 0.126 g of ligand and 6 ml of ethanol containing 0.089 g of manganese chloride tetrahydrate were placed in a 25 ml eggplant flask and heated to 80 ° C. while heating. When stirred for a period of time, a yellow solid precipitated. The solid was collected by filtration, further washed with chloroform and ethanol, and dried to obtain a metal complex (E) (yield 0.092 g). 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 are contained. ing. Elemental analysis (%): as _{C 42 H 40 Mn 2 N 4} O 4; Calculated: C, 59.66; H, 4.77 ; N, 6.63, Found: C, 58.26; H 4.58; N, 6.33. Further, the metal complex (E) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (E) was prepared by drying under reduced pressure for 12 hours.

Synthesis Example 6
A metal complex (F) was synthesized by mixing and reacting a ligand and a chloroform solution containing cobalt 2-ethylhexanoate according to the following reaction formula. The following ligands as raw materials for the complex were synthesized based on Tetrahedron., 1999, 55, 8377.

In a nitrogen atmosphere, place 5 ml of chloroform containing 0.077 g of ligand and 0.239 g of cobalt 2-ethylhexanoate (65 wt% mineral oil solution) in a 25 ml eggplant flask and stir for 9 hours while heating to 60 ° C. did. This solution was added dropwise to a 50 ml Erlenmeyer flask with diethyl ether. The precipitated solid was collected by filtration, further washed with diethyl ether and dried to obtain a metal complex (F) (yield 0.146 g). ESI-MS [M +.]: 1032.2.
Elemental analysis value (%): calculated value (as C ₅₈ H ₆₆ Co ₂ N ₄ O ₆ ); C, 67.43; H, 6.44; N, 5.42. Found: C, 66.97; H, 6.21; N, 5.27. Further, the metal complex (F) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (F) was prepared by drying under reduced pressure for 12 hours.

Synthesis example 7
The metal complex (G) was synthesized according to the following reaction formula by mixing and reacting a ligand and an ethanol solution containing nickel acetate tetrahydrate. The following ligands as raw materials for the complex were synthesized based on Tetrahedron., 1999, 55, 8377.

Under a nitrogen atmosphere, 30 ml of ethanol containing 0.250 g of ligand and 0.100 g of nickel acetate tetrahydrate was placed in a 50 ml eggplant flask and stirred at 80 ° C. for 2 hours. The produced orange precipitate was collected by filtration, washed with ethanol, and then vacuum dried to obtain a metal complex (G) (yield 0.242 g). Elemental analysis (%): Calcd for C ₄₂ H ₃₆ N ₄ NiO ₂ ; C, 73.38; H, 5.28; N, 8.15. Found: C, 72.42; H, 5.27; N, 7.96. ESI-MS [M + ·]: 687.1. Further, the metal complex (G) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was mixed in ethanol. After stirring at room temperature, the metal complex mixture (G) was prepared by drying at room temperature under reduced pressure of 1.5 Torr for 12 hours.

Synthesis example 8
The metal complex (H) was synthesized by mixing and reacting an ethanol solution containing a ligand and copper acetate monohydrate according to the following reaction formula. The following ligands as raw materials for the complex were synthesized based on Tetrahedron., 1999, 55, 8377.

Under a nitrogen atmosphere, 30 ml of ethanol containing 0.315 g of ligand and 0.100 g of copper acetate monohydrate was placed in a 50 ml eggplant flask and stirred at 80 ° C. for 2 hours. The produced ocherous precipitate was collected by filtration, washed with ethanol, and then vacuum dried to obtain a metal complex (H) (yield 0.250 g). Elemental analysis _{(%): Calcd for C 42} H 36 CuN 4 O 2; C, 72.87; H, 5.24; N, 8.09. Found: C, 72.22; H, 5.37; N, 7.77. ESI-MS [M +. After stirring at room temperature, the metal complex mixture (H) was prepared by drying at room temperature under reduced pressure of 1.5 Torr for 12 hours.

Synthesis Example 9
The metal complex (I) was synthesized by mixing and reacting a ligand and an ethanol solution containing iron acetate according to the following reaction formula. The following ligands as raw materials for the complex were synthesized based on Tetrahedron., 1999, 55, 8377.

Under a nitrogen atmosphere, 30 ml of ethanol containing 0.440 g of ligand and 0.120 g of iron acetate was placed in a 50 ml eggplant flask and stirred at 80 ° C. for 2 hours. The produced orange precipitate was collected by filtration, washed with ethanol, and then vacuum-dried to obtain a metal complex (I) (yield 0.380 g). Elemental analysis _{(%): Calcd for C 42} H 36 FeN 4 O 2; C, 73.68; H, 5.30; N, 8.18. Found: C, 72.20; H, 5.42; N, 7.85. ESI-MS [M + ·]: 684.0. Further, the metal complex (I) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was mixed in ethanol. After stirring at room temperature, the metal complex mixture (I) was prepared by drying at room temperature under reduced pressure of 1.5 Torr for 12 hours.

Synthesis Example 10
A metal complex (J) was synthesized by mixing and reacting an ethanol solution containing a ligand and nickel acetate according to the following reaction formula. The following ligands as raw materials for the complex were synthesized based on Tetrahedron., 1999, 55, 8377.

In a nitrogen atmosphere, an ethanol 30 ml solution containing 0.200 g of ligand and 0.250 g of nickel acetate tetrahydrate was stirred in a 50 mL eggplant flask while heating to 100 ° C. for 2 hours. Precipitated. This solid was collected by filtration, washed with ethanol and diethyl ether, and dried to obtain a metal complex (J) (yield 0.276 g). Elemental analysis _(%): as _{C 46 H 42 N 4 Ni 2} O 6, Calculated: C, 63.93; H, 4.90 ; N, 6.07. Found: C, 63.22; H, 5.02; N, 6.43. Further, the metal complex (J) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (J) was prepared by drying under reduced pressure for 12 hours.

Synthesis Example 11
A metal complex (K) was synthesized by mixing and reacting a chloroform solution containing a ligand and a methanol solution containing cobalt nitrate hexahydrate according to the following reaction formula. The following ligands as raw materials for the complex were synthesized based on Tetrahedron., 1999, 55, 8377.

Under a nitrogen atmosphere, a mixed solution of 2 ml of chloroform and 5 ml of methanol containing 0.096 g of ligand and 0.082 g of cobalt nitrate hexahydrate was placed in a 100 ml eggplant flask and stirred for 7 hours while heating to 60 ° C. A yellow solid was formed. This solid was collected by filtration, further washed with methanol, and dried to obtain a metal complex (K) (yield 0.036 g). _{ESI-MS [M-NO 3} ] +: 808.0. Further, the metal complex (K) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (K) was prepared by drying under reduced pressure for 12 hours.

Synthesis Example 12
The metal complex (L) was synthesized according to the following reaction formula by mixing and reacting a ligand and an ethanol solution containing cobalt acetate tetrahydrate. The following ligands as raw materials for the complex were synthesized based on Tetrahedron., 1999, 55, 8377.

Under a nitrogen atmosphere, 0.303 g of ligand and 0.125 g of cobalt acetate tetrahydrate were placed in a 100 ml two-necked flask and 50 ml of ethanol was added. The solution was refluxed for 3 hours to produce an ocher solid. The precipitate was collected by filtration and dried to obtain a metal complex (L) (yield 0.242 g). ESI-MS [M + H] ⁺ : 664.2. Further, the metal complex (L) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (L) was prepared by drying under reduced pressure for 12 hours.

Synthesis Example 13
A metal complex (M) was synthesized according to the following reaction formula by mixing and reacting a ligand and an ethanol solution containing cobalt acetate tetrahydrate. The following ligands as raw materials for the complex were synthesized based on Tetrahedron., 1999, 55, 8377.

Under a nitrogen atmosphere, 0.303 g of ligand and 0.324 g of cobalt acetate tetrahydrate were placed in a 100 ml two-necked flask, and 20 ml of ethanol and 20 ml of chloroform mixed solution were added. The solution was refluxed for 3 hours to produce an ocher solid. The precipitate was collected by filtration and dried to obtain a metal complex (M) (yield 0.133 g). ESI-MS [M-OAc] ⁺ : 781.0. Further, the metal complex (M) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (M) was prepared by drying under reduced pressure for 12 hours.

  A metal complex (P) was synthesized via compound (N) and ligand (O) according to the following reaction formula.

Synthesis Example 14 [Synthesis of Compound (N)]

3.945 g 2,9-di (3'-bromo-5'-tert-butyl-2'-methoxyphenyl) -1,10-phenanthroline, 3.165 g 1-N-Boc-pyrrole- under argon atmosphere 2-boronic acid, 0.138 g tris (benzylideneacetone) dipalladium, 0.247 g 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl, 5.527 g potassium phosphate mixed with 200 mL dioxane and 20 mL water It melt | dissolved in the solvent and stirred at 60 degreeC for 6 hours. After completion of the reaction, the mixture was allowed to cool, distilled water and chloroform were added, and the organic layer was extracted. The resulting organic layer is concentrated to give a black residue. This was refine | purified using the silica gel column, and the compound (N) was obtained. ¹ H-NMR (300MHz, CDCl ₃ ) δ1.34 (s, 18H), 1.37 (s, 18H), 3.30 (s, 6H), 6.21 (m, 2H), 6.27 (m, 2H), 7.37 (m , 2H), 7.41 (s, 2H), 7.82 (s, 2H), 8.00 (s, 2H), 8.19 (d, J = 8.6Hz, 2H), 8.27 (d, J = 8.6Hz, 2H).

Synthesis Example 15 [Synthesis of Ligand (O)]

Under a nitrogen atmosphere, 0.904 g of compound (N) is dissolved in 10 mL of anhydrous dichloromethane. While cooling the dichloromethane solution to −78 ° C., 8.8 mL of boron tribromide (1.0 M dichloromethane solution) was slowly added dropwise. After dropping, the mixture was allowed to stir for 10 minutes and then allowed to stand while stirring to room temperature. After 3 hours, the reaction solution was cooled to 0 ° C., saturated aqueous NaHCO ₃ solution was added, chloroform was added for extraction, and the organic layer was concentrated. The obtained brown residue was purified with a silica gel column to obtain the ligand (O). ¹ H-NMR (300MHz, CDCl ₃ ) δ1.40 (s, 18H), 6.25 (m, 2H), 6.44 (m, 2H), 6.74 (m, 2H), 7.84 (s, 2H), 7.89 (s , 2H), 7.92 (s, 2H), 8.35 (d, J = 8.4Hz, 2H), 8.46 (d, J = 8.4Hz, 2H), 10.61 (s, 2H), 15.88 (s, 2H).

Synthesis Example 16 [Synthesis of Metal Complex (P)]

  Under a nitrogen atmosphere, a acetonitrile solution degassed with 20 ml of Ar containing 0.100 g of ligand (O) and 0.040 g of cobalt acetate tetrahydrate was placed in a 100 ml two-necked flask and stirred at room temperature. did. To this solution, 45 μl of triethylamine was added dropwise and refluxed for 3 hours. The solution was concentrated and cooled, and then filtered through a membrane filter and dried to obtain a metal complex (P) (yield 0.098 g). ESI-MS [M +.]: 663.1. Further, the metal complex (P) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (P) was prepared by drying under reduced pressure for 12 hours.

  A metal complex (S) was synthesized via compound (Q) and ligand (R) according to the following reaction formula.

Synthesis Example 17 [Synthesis of Compound (Q)]

  Under argon atmosphere, 0.132 g 2,9-di (3′-bromo-5′-tert-butyl-2′-methoxyphenyl) -1,10-phenanthroline, 0.061 g 3-pyridylboronic acid, 0.046 g Of tetrakis (triphenylphosphino) palladium and 0.111 g of potassium carbonate were dissolved in a mixed solvent of 5 mL of dioxane and 0.5 mL of water and stirred at 100 ° C. for 9 hours. After completion of the reaction, the mixture was allowed to cool, distilled water and chloroform were added, and the organic layer was extracted. The resulting organic layer is concentrated to give a black residue. This was purified using a silica gel column to obtain compound (Q).

Synthesis Example 18 [Synthesis of Ligand (R)]

Under a nitrogen atmosphere, 0.110 g of compound (Q) was dissolved in 3 mL of anhydrous dichloromethane. While the dichloromethane solution was cooled to −78 ° C. with a dry ice / acetone bath, 1.3 mL of boron tribromide (1.0 M dichloromethane solution) was slowly added dropwise. After dropping, the mixture was stirred for 10 minutes as it was, then the dry ice / acetone bath was removed, and the mixture was allowed to stand while stirring to room temperature. After 4 hours, a saturated aqueous NaHCO ₃ solution was added for neutralization, and chloroform was added for extraction three times. The obtained organic layer was concentrated, and the resulting residue was purified to obtain a ligand (R). ¹ H-NMR (300MHz, CDCl ₃ ) δ1.47 (s, 18H), 7.44 (t, J = 6.2Hz, 2H), 7.55 (s, 2H), 7.95 (s, 2H), 8.16 (s, 2H ), 8.40 (d, J = 8.3Hz, 2H), 8.53 (d, J = 8.3Hz, 2H), 8.67 (d, J = 7.5Hz, 2H), 9.47 (s, 2H), 9.79 (d, J = 2.8Hz, 2H), 15.36 (s, 2H).

Synthesis Example 19 [Synthesis of Metal Complex (S)]

  Under a nitrogen atmosphere, a mixed solution of 10 ml of chloroform and 4 ml of ethanol containing 0.096 g of ligand (R) and 0.037 g of cobalt acetate tetrahydrate was placed in a 100 ml eggplant flask and heated to 60 ° C. while heating. Stir for hours to produce a brown solid. This solid was collected by filtration, further washed with ethanol and dried to obtain a metal complex (S) (yield 0.040 g). ESI-MS [M +.]: 687.1. Further, the metal complex (S) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (S) was prepared by drying for 12 hours under reduced pressure.

  Metal complex (V) was synthesized via compound (T) and ligand (U) according to the following reaction formula.

Synthesis Example 20 [Synthesis of Compound (T)]

Under an argon atmosphere, 0.662 g 2,9-di (3'-bromo-5'-tert-butyl-2'-methoxyphenyl) -1,10-phenanthroline, 0.520 g 2-tert-butyl-5- Methoxyphenylboronic acid, 0.090 g tris (benzylideneacetone) dipalladium, 0.160 g 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl, 0.920 g potassium phosphate mixed with 30 mL dioxane and 10 mL water It melt | dissolved in the solvent and stirred at 60 degreeC for 31 hours. After completion of the reaction, the mixture was allowed to cool, distilled water and chloroform were added, and the organic layer was extracted. The resulting organic layer is concentrated to give a black residue. This was refine | purified using the silica gel column, and the compound (T) was obtained. ¹ H-NMR (300MHz, CDCl ₃ ) δ1.34 (s, 18H), 1.39 (s, 18H), 3.33 (s, 6H), 3.76 (s, 6H), 6.91 (s, 2H), 6.94 (s , 2H), 7.36 (m, 6H), 7.83 (s, 2H), 7.95 (d, J = 2.6Hz, 2H), 8.16 (d, J = 8.2Hz, 2H), 8.26 (d, J = 8.2Hz , 2H).

Synthesis Example 21 [Synthesis of Ligand (U)]

Under a nitrogen atmosphere, 0.281 g of compound (T) is dissolved in 5 mL of acetic acid. 0.573 g of 48% hydrobromic acid was added dropwise, and the mixture was stirred at 110 ° C. After 20 hours, the reaction solution was cooled to 0 ° C., water was added, chloroform was added for extraction, and the organic layer was concentrated. The obtained residue was purified with a silica gel column to obtain a ligand (U). ¹ H-NMR (300MHz, CDCl ₃ ) δ1.40 (s, 18H), 1.44 (s, 18H), 6.59 (s, 2H), 6.62 (s, 2H), 7.35 (m, 6H), 7.53 (s , 2H), 7.89 (s, 2H), 8.01 (s, 2H), 8.38 (d, J = 9.0Hz, 2H), 8.47 (d, J = 9.0Hz, 2H), 16.12 (s, 2H).

Synthesis Example 22 [Synthesis of Metal Complex (V)]

  Under a nitrogen atmosphere, a mixed solution of 10 ml of chloroform and 2 ml of ethanol containing 0.077 g of the ligand (U) and 0.050 g of cobalt acetate tetrahydrate was placed in a 25 ml eggplant flask and heated to 70 ° C. while heating. Stir for hours. This solution was added dropwise to a 50 ml Erlenmeyer flask with diethyl ether. The precipitated solid was collected by filtration, further washed with diethyl ether and dried to obtain a metal complex (V) (yield 0.018 g). ESI-MS [M +.]: 829.3. Further, the metal complex (V) and the carbon support (Ketjen Black EC300J, manufactured by Lion Corporation) were mixed at a weight ratio of 1: 4, and the mixture was stirred in ethanol at room temperature and then 1.5 Torr at room temperature. The metal complex mixture (V) was prepared by drying under reduced pressure for 12 hours.

Reference example 1
Using a thermal mass / differential thermal analyzer (Seiko Instruments EXSTAR-6300, hereinafter referred to as a thermal analyzer), a metal complex (A), a metal complex (B), a metal complex (D), and a metal complex (E) The weight change (TGA) during the heat treatment was measured. The measurement conditions were under a nitrogen atmosphere (temperature increase rate: 10 ° C./min), and an alumina dish was used for the heat treatment. An analysis result (analysis chart) is shown in FIGS.

Examples 1-20, Reference Example A
Based on the knowledge obtained from the thermal mass analysis results, the heat treatment was performed so that the mass reduction rate during the heat treatment was 1% by mass or more. That is, a metal complex or a metal complex mixture, using a tubular furnace was subjected to heat treatment for 2 hours at target temperature under nitrogen atmosphere.
The tubular furnace and heat treatment conditions used for the heat treatment are shown below.
Tubular furnace: Program-controlled open / close tubular furnace EPKRO-14R, Isuzu Manufacturing Heat treatment atmosphere: Nitrogen gas flow (200 ml / min)
Temperature increase rate and temperature decrease rate: 200 ° C / h
Table 1 shows the metal complex or metal complex mixture used, the name of the modified metal complex obtained by heat treatment, the heat treatment temperature, and the mass reduction rate after treatment. The carbon content (elemental analysis value) after the heat treatment is also shown.

Reference Example 2 [Evaluation Test of Metal Retention Capacity of Modified Metal Complex]
The modified metal complex (A-2), the modified metal complex (B-1), the modified metal complex (B-2) and the modified metal complex (E-1) are each immersed in a 0.1 mol / L hydrochloric acid aqueous solution, And sonicated for 15 minutes. The amount of metal contained in the sample was quantified by the inductively coupled plasma emission spectroscopy (ICP-AES) method, and the metal retention was calculated using the following calculation formula.
Metal retention (%) = 100− (amount of metal eluted to solution side) / (amount of metal contained in modified product) × 100

Comparative Example 1
In addition, as a comparative reference example, the metal complex mixture (C) prepared in Synthesis Example 3 was subjected to a heat treatment at 500 ° C. according to the methods described in Examples 1 to 20 and Reference Example A , whereby the metal complex composition (C )
The metal retention rate of the obtained metal complex composition (C) was calculated according to the above method. The metal complex composition (C) having no nitrogen-containing aromatic heterocycle includes a modified metal complex (A-2), a modified metal complex (B-1), a modified metal complex (B-2), and a modified metal complex. Compared with (E-1), it was inferior to metal holding ability.

Examples 21 to 25 [Measurement of laser Raman spectrum of modified metal complex]
FIG. 5 shows a laser Raman spectrum of the modified metal complex (A-1). The measurement was performed under the following conditions.
Equipment used: Microscopic laser Raman spectrometer NSR1000 (JASCO)
Excitation wavelength: 532 nm
Objective lens: 50 times Measurement range: 200-3900 cm ⁻¹
FIG. 5 shows that the modified metal complex (A-1) has a maximum peak at 1580 cm ⁻¹ . This indicates that graphene-like carbon is generated in the modified metal complex obtained by the modification treatment.
Similarly, a Raman spectroscopic measurement is performed on the modified metal complex (B-1), the modified metal complex (E-1), the modified metal complex (G-1), and the modified metal complex (L), and the laser Raman spectrum is obtained. It shows in FIG.6, FIG.7, FIG.8 and FIG. Any of the chart, ^{respectively, 1588cm -1, 1587cm -1, 1579cm} -1, has a maximum peak at 1592cm ^-1, graphene-like carbon can be shown that is generating.

Examples 26 , 27 and 28 [Measurement of wide-area X-ray absorption fine structure]
The above-mentioned modified metal complex (A-2), modified metal complex (B-2) and modified metal complex (P-2) are subjected to ultrasonic treatment in a hydrochloric acid solution and dried in a vacuum to obtain a carbon compound (A-2). ), Carbon compound (B-2) and carbon compound (P-2) were obtained. Measurement of these extended X-ray absorption fine structures (EXAFS) was performed. For the measurement of EXAFS, the beam line (BL-9A, 12C) of the synchrotron radiation research facility of the High Energy Accelerator Research Organization was used. The pelletized sample having a diameter of 10 mm was cooled to a temperature of 20 K, and measurement was performed by a transmission method. The radial distribution function was obtained by Fourier transforming the X-ray absorption spectrum obtained by the measurement. 10 and 11 show radial distribution functions of the carbon compound (A-2) and the carbon compound (B-2). The carbon compound (A-2) and the carbon compound (B-2) have a first adjacent atom [the first adjacent atom here is an atom (group) closest to the central metal to be measured in the EXAFS analysis. For example, a hetero atom such as an oxygen atom or a nitrogen atom located within a range of 1.0 to 2.5 cm from the central metal corresponds to this. From the peaks derived from the above, it can be seen that there are peaks at 0.50Å and 0.53Å respectively. The EXAFS of the cobalt metal foil was measured at room temperature using the same beam line, and in the obtained radial distribution function, a peak derived from cobalt metal was observed at 2.19 mm. The peak here refers to a peak having a half or more of the maximum intensity value. For the carbon compound (P-2), the same measurement is performed, and in the obtained radial distribution function, a peak derived from the first adjacent atom is observed at 1.35 、 and has a peak at 0.49 か ら from the peak. I understood.

Comparative Example 2 [Measurement of wide-area X-ray absorption fine structure]
As a comparative example, the weight ratio of 5,10,15,20-tetraphenyl-21H, 23H-porphine cobalt (II) (Aldrich) and carbon support (Ketjen Black EC300J, Lion) was 1: 4. The mixture was stirred in ethanol at room temperature, and dried at room temperature under a reduced pressure of 1.5 Torr for 12 hours to prepare a metal complex mixture (W). This metal complex mixture was heat-treated at 600 ° C. in the same manner as described above to prepare a modified metal complex (W). (Mass reduction rate 1.67%, carbon content rate 92.95%)
The modified metal complex (W) was subjected to ultrasonic treatment in a hydrochloric acid solution and vacuum dried to obtain a carbon compound (W). The X-ray absorption fine structure (EXAFS) was measured by the same method as described above, and the radial distribution function was obtained. As a result, a peak derived from the first adjacent atom with cobalt was observed at 1.44 cm, but no other peak was observed.

Reference Example 3 [hydrogen peroxide decomposition test of modified metal complex (E-1)]
3.6 mg (about 8 μmol (per metal atom)) of the modified metal complex (E-1) was weighed into a two-necked flask and a tartaric acid / sodium tartrate buffer solution (1.00 ml (0.20 mol / l tartaric acid) was used as a solvent. Prepared from aqueous solution and 0.10 mol / l sodium tartrate aqueous solution, pH 4.0)) and ethylene glycol (1.00 ml) were added and stirred. This was used as a catalyst mixed solution.

A septum was attached to one mouth of the two-necked flask containing the catalyst mixed solution, and the other mouth was connected to a gas burette. After stirring the flask at 80 ° C. for 5 minutes, an aqueous hydrogen peroxide solution (11.4 mol / l, 0.20 ml (2.28 mmol)) was added with a syringe, and a hydrogen peroxide decomposition reaction was performed at 80 ° C. for 20 minutes. It was. The generated oxygen was measured with a gas burette, and the decomposed hydrogen peroxide was quantified.
The amount of hydrogen peroxide decomposed was determined from the volume of gas containing oxygen generated in the hydrogen peroxide decomposition test. From the following formula, the actually generated gas volume value v was converted to a gas volume V at 0 ° C. and 101325 Pa (760 mmHg) in consideration of the water vapor pressure.
The results are shown in FIG. The modified metal complex (E-1) of the present invention has a higher generated gas volume compared to the blank test described later, and the catalytic effect related to hydrogen peroxide decomposition was confirmed.

(In the formula, P: atmospheric pressure (mmHg), p: vapor pressure of water (mmHg), t: temperature (° C), v: measured gas volume (ml), V: 0 ° C, 101325 Pa (760 mmHg) Gas volume (ml).

[Blank test]
To a two-necked flask, 1.00 ml of a tartaric acid aqueous solution / sodium tartrate buffer solution (prepared from 0.20 mol / l aqueous tartaric acid solution and 0.10 mol / l aqueous sodium tartrate solution, pH 4.0) and 1.00 ml of ethylene glycol were added as solvents. A septum was attached to one of the two-necked flasks, and the other was connected to a gas burette. After stirring the flask at 80 ° C. for 5 minutes, an aqueous hydrogen peroxide solution (11.4 mol / l, 0.200 ml (2.28 mmol)) was added, and the generated gas was quantified with a gas buret at 80 ° C. for 20 minutes. .
In this blank test, it is considered that air or the like dissolved in the solution is mainly detected.

Comparative Example 3 [Hydrogen peroxide decomposition test of metal complex (E)]
A test equivalent to that of Reference Example 3 was performed, except that the modified metal complex (E-1) of Reference Example 3 was changed to the metal complex (E). The results are shown in FIG.
From these results, it was found that the modified metal complex obtained by the modification treatment showed higher oxygen reducing ability under acidic conditions than the complex.

The thermogravimetric analysis chart of a metal complex (A) is shown. The thermogravimetric analysis chart of a metal complex (B) is shown. The thermogravimetric analysis chart of a metal complex (D) is shown. The thermogravimetric analysis chart of a metal complex (E) is shown. The laser Raman spectrum of a modified metal complex (A-1) is shown. The laser Raman spectrum of a modified metal complex (B-1) is shown. The laser Raman spectrum of a modified metal complex (E-1) is shown. The laser Raman spectrum of a modified metal complex (G-1) is shown. The laser Raman spectrum of a modified metal complex (L) is shown. Radial distribution function obtained from wide-area X-ray absorption fine structure of modified metal complex (A-2) Radial distribution function obtained from wide-area X-ray absorption fine structure of modified metal complex (B-2) Results of hydrogen peroxide decomposition test of modified metal complex (E-1) and metal complex (E)

Claims (11)

The ligand of the organic compound represented by the following general formula (I) and having the total number of coordination atoms of 5 or 6 is one or two transition metal atoms belonging to the fourth to sixth periods of the periodic table. The coordinated metal complex is treated by heat treatment, radiation irradiation treatment or discharge treatment until the mass reduction rate before and after the treatment is 1 mass% or more and 90 mass% or less, and the carbon content after the treatment Redox catalyst using a modified metal complex containing 5% by mass or more.

(In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, a halogen atom, a monovalent hydrocarbon group which may be substituted, or a substituted group. Optionally substituted hydrocarbon oxy group, optionally substituted N, N-dihydrocarbon amino group, optionally substituted hydrocarbon thio group, optionally substituted hydrocarbon carbonyl group, substituted Represents an optionally substituted hydrocarbon oxycarbonyl group, an optionally substituted N, N-dihydrocarbonaminocarbonyl group, or an optionally substituted hydrocarbon sulfonyl group, bonded to two adjacent atoms. The two R ¹ groups may be linked to each other, and a plurality of R ¹ groups may be the same or different from each other, and Q ¹ represents a pyridylene group, a pyradylene group, a pyrimidine group, Len group, pyridazylene group, pyrrolylene group, thiazolylene group, imidazolylene group, oxazolylene group, triazolylene group, indolenylene group, benzoimidazolylene group, benzofurylene group, benzothienylene group, quinolylene group, isoquinolylene group, cinnolylene group, quinazolylene group, quinazolylene group Quinoxarylene group, benzodiazylene group, 1,10-phenanthrolylene group, 2,2'-bipyridylene group, 2,2'-bithiophenylene group, 2,2'-bipyrrolene group, 2,2'-bithiazolylene group, Represents a divalent organic group selected from a 2,2′-bifurylene group, a 2,2′-bipyrimidylene group, a 2,2′-bipyridazilen group and a 2,2′-biimidazolylene group, and T ¹ represents a pyridyl group, Pyrazyl group, pyrimidyl group, pyridazyl group, pyrrolyl group, pyrazolyl group Represents a monovalent organic group selected from thiazolyl group, imidazolyl group, oxazolyl group, triazolyl group, indolyl group, benzoimidazolyl group, quinolyl group, isoquinolyl group, cinnolyl group, phthalazyl group, quinazolyl group, quinoxalyl group and benzodiazyl group; two T ¹ may be the same or different.) The catalyst is within 0.58 cm from the peak derived from the first adjacent atom observed in the range of 1.0 to 2.5 cm in the broad X-ray absorption fine structure (EXAFS) radial distribution function of the central metal . 2. The Redox catalyst according to claim 1, further comprising one or more peaks other than the peak derived from a metal atom that is not observed in the metal complex before the heat treatment, the radiation irradiation treatment, or the discharge treatment . 3. The Redox catalyst according to claim 1, wherein the intensity of the another peak is 2/5 or more of the peak intensity derived from the first adjacent atom. The Redox catalyst according to any one of claims 1 to 3, wherein the catalyst comprises the modified metal complex and graphene. In the spectrum obtained by laser Raman spectroscopy of the excitation wavelength 532 nm, Reddokkusu catalyst according to any one of claims 1-4, characterized in that it has an absorption maximum in the range of 1500~1600cm ^-1. Wherein the metal complex is Reddokkusu catalyst according to any one of claim 1 to 5, characterized in that a nitrogen atom and an oxygen atom only a coordination atom. The redox catalyst according to any one of claims 1 to 6, wherein the transition metal atom is manganese, iron, cobalt, nickel, or copper. Reddokkusu catalyst according to any one of claim 1 to 7, wherein a polymer having a residue of a ligand represented by the general formula (I). The Redox catalyst according to claim 8 , which is a polymer having a residue of a ligand represented by the general formula (I) as a repeating unit. Reddokkusu catalyst according to any one of claim 1 to 9, characterized in that said metal complex is a modified metal complex formed by heat treatment at 250 ° C. or higher 1200 ° C. or less. The heat treatment of the metal complex before the treatment is a modified metal complex obtained by heat treatment at 250 ° C. or more and 1200 ° C. or less together with the carbon support. Redox catalyst.

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