JP2010207759A - Heteronuclear complex, method of manufacturing the same and method of supporting the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new heteronuclear complex which contains different kinds of metals in a complex, a method of manufacturing the heteronuclear complex, and a method of supporting the heteronuclear complex. <P>SOLUTION: In the heteronuclear complex, at least one of acetato ligands of an acetato-platinum (IV) complex is substituted by a ligand having a ferrocene group. In the heteronuclear complex, at least one of the acetato ligands of the acetato-platinum (IV) complex is substituted by an amidine ligand and capped and at least a part of the other acetato ligands is substituted by the ligand having a ferrocene group. The method of manufacturing the heteronuclear complex, and the method of supporting the heteronuclear complex on a carrier are provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel heteronuclear complex, a method for producing the same, and a method for supporting the same, and more specifically, a heteronuclear complex capable of precisely controlling the arrangement of platinum and iron by a specific ligand, and the production thereof. The present invention relates to a method and a supporting method thereof.

Recent studies have shown that metal clusters with controlled sizes have different properties from bulk metals in terms of chemical properties such as catalytic activity and physical properties such as magnetism. This metal cluster is generally used as a term indicating a metal complex having a skeletal structure in which a plurality of metal atoms are gathered together by bonding directly or through a bridging ligand.
In order to utilize the unique properties of this metal cluster, there is a need for a method for simply and massively synthesizing a metal cluster with a controlled size (hereinafter sometimes abbreviated as cluster).
A currently known method for obtaining this size-controlled cluster is to evaporate a metal target in vacuum to generate clusters of various sizes, and from the clusters thus obtained, the principle of mass spectrum is obtained. There is a method of separating the cluster size by using (hereinafter also abbreviated as metal evaporation-MS method). However, this method cannot synthesize a cluster with a controlled size conveniently and in large quantities.

On the other hand, an example of using the catalytic performance of noble metal is purification of exhaust gas discharged from an internal combustion engine such as an automobile engine. In this exhaust gas purification, carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NO _x ), etc. contained in the exhaust gas are converted into catalyst components mainly composed of noble metals such as platinum, palladium and rhodium. , Converted to carbon dioxide, nitrogen, water, oxygen. In this exhaust gas purification application, a catalyst component that is a noble metal is generally supported on an oxide porous carrier such as alumina to provide a large contact area between the exhaust gas and the catalyst component.

  In general, this catalyst component is supported on a porous oxide support by impregnating the support with a noble metal nitrate or a solution of a noble metal complex having a single noble metal atom to disperse the noble metal compound on the surface of the support. Then, the carrier impregnated with the solution is dried and calcined. In such a method, a large amount of catalyst can be easily prepared, but the metal is in a single atom dispersed state or a state in which particles are grown by appropriate heating / atmosphere control, and a noble metal having an arbitrary number of constituent atoms. Clusters cannot be supported.

  For this reason, in exhaust gas purification catalysts, there is strong expectation for further improvement in exhaust gas purification performance from the demand for precious metal resource depletion and the demand for environmental improvement, and it is proposed that noble metals be supported in clusters. . However, since conventional metal clusters cannot be controlled to an arbitrary size (indicating the number of metal atoms), it is possible to synthesize a noble metal or noble metal oxide cluster with a controlled size easily and in large quantities. Studies have been started on a compound-containing compound and a method for producing a supported catalyst using such a compound-containing compound.

For example, in Japanese Patent Application Laid-Open No. 2007-230924, two or more metal complexes in which a ligand is coordinated to one or more metal atoms of the same type have two or more metal complexes. A multi-metal complex-containing compound is described which is bonded to each other via a polydentate ligand substituting part of the ligand and has a total of 2 to 1000 metal atoms. As a specific example, a compound containing a multiple metal complex in which a part of an acetic acid (acetato) ligand of an acetatotetraplatinum complex represented by the chemical formula: [Pt ₄ (CH ₃ COO) ₈ ] is substituted with a dicarboxylic acid is shown. ing.

  Japanese Patent Application Laid-Open No. 2007-229642 discloses a metal complex in which a compound having a coordinable functional group is bonded to a catalyst carrier and a ligand is coordinated with one or more of the same type of catalytic metal atom. A method for producing a supported catalyst is described in which a catalyst carrier is impregnated with a catalyst carrier, at least a part of the ligand is substituted with a coordinateable functional group, and the catalyst carrier is dried and calcined. As a specific example, a method for producing a supported catalyst in which an OH group on the surface of an oxide support is substituted with succinic acid or the like and Pt is supported using an acetate tetraplatinum complex is shown.

Furthermore, Japanese Patent Application Laid-Open No. 2008-13533 describes an amidine-carboxylic acid complex in which an amidine ligand and a carboxylic acid ligand are coordinated to one or more metal atoms of the same type. As specific examples, the amidine ligand is N, N′bis (p-methoxyphenyl) formamidine, N, N′bis (p-acetylphenyl) formamidine, or the like, and the carboxylic acid ligand is octaacetotetraplatinum. Monomers, dimers, trimers, tetramers and pentamers that are complexes [Pt ₄ (CH ₃ COO) ₈ ] are shown.

JP 2007-230924 A JP 2007-229642 A JP 2008-13533 A

According to the compound containing multiple metal complexes described in each of these publications, the number of metal atoms or metal oxide clusters contained in this compound is obtained by removing the ligand of this compound by firing or the like. Can do.
However, the multiple metal complex-containing compounds described in each of the above publications are those in which a plurality of metals are the same type of metal, for example, Pt is included, and the complex does not include different types of metals. There is a need for heteronuclear complexes containing heterogeneous noble metals in complexes that can enable precise control of metal alignment.
Accordingly, an object of the present invention is to provide a heteronuclear complex containing a heterogeneous metal in the complex, a production method thereof and a loading method thereof.

The first invention relates to a heteronuclear complex in which at least one of the acetate ligands of the acetate tetraplatinum complex is substituted with a ligand having a ferrocene group.
The second invention is a coordination in which at least one of the acetate ligands of the acetate tetraplatinum complex is capped with an amidine ligand, and at least one of the remaining acetate ligands has a ferrocene group. It relates to a heteronuclear complex substituted with a child.

Moreover, 3rd invention is related with the manufacturing method of the heteronuclear complex which substitutes the ligand which has a ferrocene group at least one of the acetate ligands of an acetato tetraplatinum complex.
Further, the fourth invention is a coordination in which at least one of the acetate ligands of the acetate tetraplatinum complex is capped with an amidine ligand, and at least one of the remaining acetate ligands has a ferrocene group. The present invention relates to a method for producing a heteronuclear complex that replaces a child.
Furthermore, the fifth invention relates to a method for supporting a heteronuclear complex, in which a heteronuclear complex in which at least one of the acetate ligands of the acetatotetraplatinum complex is substituted with a ligand having a ferrocene group is supported on a carrier.
Furthermore, the sixth invention is a coordination wherein at least one of the acetate ligands of the acetate tetraplatinum complex is capped by substitution with an amidine ligand, and at least one of the remaining acetate ligands has a ferrocene group. The present invention relates to a method for supporting a heteronuclear complex, in which a heteronuclear complex substituted with a child is supported on a carrier.

According to the first aspect of the present invention, a novel heteronuclear complex containing different kinds of noble metals of platinum and iron in the complex can be obtained.
In addition, according to the second aspect of the present invention, a novel heteronuclear complex in which different types of noble metals of platinum and iron are contained in the complex and the number of platinum and iron is controlled at the atomic level can be obtained.
In addition, according to the third invention, a novel heteronuclear complex containing different kinds of noble metals of platinum and iron can be easily obtained.
In addition, according to the fourth aspect of the present invention, a novel heteronuclear complex containing different kinds of noble metals of platinum and iron in the complex and having the number of platinum and iron controlled at the atomic level can be easily obtained.
According to the fifth aspect of the present invention, a novel heteronuclear complex containing different kinds of noble metals of platinum and iron can be supported on the carrier.
According to the sixth aspect of the present invention, a novel heteronuclear complex in which the number of platinum and iron is controlled at the atomic level can be supported on the carrier, including different noble metals of platinum and iron in the complex.

FIG. 1 is a diagram showing the reaction schemes of Example 1 and Example 2. FIG. 2 shows the reaction scheme of Example 3. 3 is a diagram showing a scheme of a method for supporting a heteronuclear complex of Example 4. FIG.

In the first invention, the heteronuclear complex is a ligand in which at least one of the acetate (acetic acid) ligands of the acetate tetraplatinum complex, for example, one to four, for example, one to two have a ferrocene group. It is necessary to be substituted, whereby a heteronuclear complex containing platinum and iron in the complex can be obtained.
In the second invention, at least one of the acetate ligands of the acetatotetraplatinum complex, for example, 1 to 3, for example 1 to 2, preferably 2 is substituted with an amidine ligand. And at least one of the remaining acetate ligands is substituted with a ligand having a ferrocene group, for example one to three, for example one to two, preferably two. Thus, at least one of the acetate ligands is capped with an amidine ligand, and the complex contains platinum and iron, and the number and arrangement positions of platinum and iron are controlled at the atomic level. A complex can be obtained.

As for the acetatotetraplatinum complex, octaacetatotetraplatinum ([Pt ₄ (CH ₃ COO) ₈ ]) (hereinafter referred to as [[Pt ₄ (OAc) ₈ ]), which is an example of an acetato tetraplatinum complex, (This may be abbreviated.)

As shown in this formula, the octaacetate tetraplatinum complex includes four platinum atoms arranged in a square shape, and has a structure in which four acetates are cross-linked in and out of the plane of the platinum. Of these, platinum in-plane cross-linked acetate is known to have high substitution activity.
In the acetate tetraplatinum complex according to the first invention, the eight acetate ligands may be contained in the complex like the octaacetato tetraplatinum complex, and any one of the eight acetate ligands is It may be substituted by any other ligand, such as a carboxylic acid ligand or an amidine ligand.
In the second invention, at least one of the eight acetate ligands of the octaacetatotetraplatinum complex, that is, at least one of the four platinum in-plane cross-linked acetates, for example, one to three, particularly One to two, two of them are substituted with amidine ligands.

  Examples of the carboxylic acid ligand include a monovalent carboxylic acid ligand having the following formula.

(R ₁ is hydrogen or a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alicyclic group, or aralkyl group.)
Moreover, as said amidine ligand, the monovalent or polyvalent amidine ligand which has a following formula is mentioned.

(R _{2 to} R ₅ are each independently hydrogen, or a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alicyclic group or aralkyl group, R ₆ is an alkylene group, an alkenylene group, An alkynylene group, an arylene group, an aralkylene group or a divalent alicyclic group, and n ₁ is an integer of 0 to 5.)
The amidine ligand in the second invention may be a monovalent or polyvalent amidine ligand having the above formula.

R ₂ and R ₅ which are substituents on carbon of the amidine ligand are each independently hydrogen or a substituted or unsubstituted C _{1 to} C ₁₀ alkyl group, alkenyl group, alkynyl group, aryl group, It may be an alicyclic group or an aralkyl group, in particular hydrogen or a substituted or unsubstituted phenyl group.
In addition, R ₃ and R ₄ which are substituents on nitrogen of the amidine ligand are each independently a substituted or unsubstituted aryl group or alicyclic group, particularly a substituted or unsubstituted C _{5 to} C ₃₀ aryl. It may be a group or an alicyclic group, more particularly a substituted or unsubstituted phenyl group. As this substituted phenyl group, a phenyl group substituted at the para-position, particularly a phenyl group substituted at the para-position with a C ₁ -C ₁₀ alkoxy group, a C ₁ -C ₁₀ acyl group or a halogen atom, especially the para-position can be mentioned C ₁ -C alkoxy group _5, a phenyl group substituted with an acyl group or a halogen atom C ₁ -C _5.

Groups in which R ₃ and R ₄ which are substituents on nitrogen of the amidine ligand are sterically bulky, for example, substituted or unsubstituted aryl groups or alicyclic groups, particularly phenyl groups substituted at the para position When the amidine-carboxylic acid complex is synthesized, the amidine ligand is placed in a selective position so that the amidine ligands are not coordinated adjacent to each other due to the steric hindrance of the substituent. It can be coordinated or only partially coordinated.

R ₆ linking the amidine ligands in the amidine ligand is a substituted or unsubstituted C _{1 to} C ₁₀ alkylene group, alkenylene group, alkynylene group, arylene group, aralkylene group or divalent group. It may be an alicyclic group, for example a C ₂ -C ₅ alkylene group, in particular a C ₃ alkylene group.

In the heteronuclear complex of the first invention, at least one of the acetate ligands of the acetatotetraplatinum complex, for example, one to four, for example, one to three, for example, one to two Substituted with a ligand having a ferrocene group.
In the heteronuclear complex of the second invention, at least one of the acetate ligands of the acetatotetraplatinum complex, for example, 1 to 3, for example 1 to 2, preferably 2 is an amidine ligand. At least one of the remaining acetate ligands is replaced with a ligand having a ferrocene group, which is capped by substitution with a ligand, for example one to three, for example one to two, preferably two Has been.

  As a ligand which has the said ferrocene group, it can have a following formula, for example.

(X is selected from the group of functional groups below:
-COO ^- (carboxyl _{group), - CR 7 R 8 -O} - ( alkoxy group), ^- NR ₇ - (amide group), - _NR 7 _{R 8} (amine _{group), - CR 7 = NR 8} ( imine group), = _{CO-R 7} (carbonyl _{group), - P (= O)} R 7 R 8 ( phosphine oxide _{group), - P (OR 7)} (OR 8) ( phosphite group), - S (= O ) ₂ R ₇ (sulfone ^{group), - S + (-O -} ) R 7 ( sulfoxide group), - SR ₇ (sulfide group), and _-CR 7 _R 8 -S ^- (thiolato group) _(R 7, R ₈ is independently hydrogen or a monovalent group)).

Said ligand having a ferrocene group may in particular be a functional group selected from the following group:
-COO ^- (carboxyl _{group), - CR 7 R 8 -O} - ( alkoxy group), ^- NR ₇ - (amide group), - _NR 7 _{R 8} (amine _{group) (R} 7, R ₈ are independently hydrogen, Or a monovalent group)).
Among them, the ligand having a ferrocene group, -COO - may be a ^(carboxyl group).

  The ligand source that gives the ligand having the ferrocene group is obtained by, for example, the method described in JP-A-2005-60282 in the presence of anhydrous aluminum chloride and magnesium in an organic solvent. It can be obtained by reacting with a source.

The heteronuclear complex according to the first invention can be obtained by the third invention in which at least one of the acetate ligands of the acetatotetraplatinum complex is replaced with a ligand having a ferrocene group.
The heteronuclear complex according to the second aspect of the invention comprises at least one of the acetate ligands of the acetate tetraplatinum complex, preferably two substituted with amidine ligands, and at least the remaining acetate ligands. One, for example, one to three, for example, one to two, preferably two, can be obtained by the fourth invention in which a ligand having a ferrocene group is substituted.

In the method of the third invention, an acetate tetraplatinum complex and a ligand source that gives a ligand having a ferrocene group (hereinafter sometimes simply referred to as a ferrocene ligand source) are mixed in a solvent. Can be done.
The ferrocene ligand source used in the method of the third invention can be used in a relatively large amount in order to promote substitution of the acetate ligand of the acetato tetraplatinum complex by the ferrocene ligand source. For example, the amount of the ferrocene ligand source used in this method is more than the amount necessary to replace all of the acetate ligands of the acetate tetraplatinum complex, for example, acetate coordinated to the acetate tetraplatinum complex. It is preferable that the amount is 1.0 times or more, for example, 1.1 times or more and 10 times or less, more preferably 5 times or less the amount necessary to replace all of the ligands.
As the solvent, any solvent that can stably maintain the heteronuclear complex of the present invention, for example, an aqueous solvent, or an organic solvent such as dichloroethane can be used.

In the method of the fourth invention, an acetate tetraplatinum complex and an amidine ligand source are mixed in a solvent to replace at least one, preferably two of the acetate ligands with an amidine ligand. If necessary, the obtained complex (hereinafter referred to as an acetato-amidine complex) is separated from the solvent, and the acetate-amidine complex and a ligand source that gives the ligand having the ferrocene group in the solvent. This can be done by mixing.
As the solvent, any solvent that can stably maintain the heteronuclear complex of the present invention, for example, an aqueous solvent, or an organic solvent such as dichloroethane can be used.

  In the above method for obtaining an acetate-amidine complex, the amidine ligand source can be used in a relatively large amount in order to promote the substitution of the acetate ligand of the acetate tetraplatinum complex by the amidine ligand. However, the amount of the amidine ligand source used in this method is coordinated to an amount less than that required to replace all of the acetato ligands of the acetatotetraplatinum complex, for example, the acetatotetraplatinum complex. It is preferable that the amount is not more than 1/2 of the amount necessary to replace all of the acetate ligand, for example, about 1/4.

  Examples of the acetato-amidine complex include an acetato-amidine complex having the following formula.

  (Ph represents a phenyl group, and Me represents a methyl group.)

  Moreover, as another example of the said acetato-amidine complex, the acetato-amidine complex which has the following formula can be mentioned, for example.

In the method of the fourth invention, the amount of the ligand source that gives the ligand having the ferrocene group to be used is more than the amount necessary to replace two of the acetato ligands of the acetato-amidine complex. It is preferable.
By mixing the acetato-amidine complex and the ligand source giving the ligand having the ferrocene group by the method of the fourth invention in a solvent, at least one of the acetate ligands of the acetatotetraplatinum complex is mixed. Preferably at least one of the remaining acetato ligands of the acetato-amidine complex in which two are substituted with amidine ligands, preferably two are substituted with ligands having a ferrocene group. The heteronuclear complex according to the fourth invention can be produced.

  Examples of the heteronuclear complex of the first invention include heteronuclear complexes having the following formula.

  Examples of the heteronuclear complex of the second invention include heteronuclear complexes having the following formula.

また、前記第２の発明の異核錯体としては例えば、下記の式を有する異核錯体を挙げることができる。

Examples of the heteronuclear complex of the second invention include heteronuclear complexes having the following formula.

  In particular, according to the fourth invention, at least one of the remaining acetate ligands of an acetate-amidine complex in which at least one of the acetate ligands, preferably two amidine ligands are bound to each other. Since a ligand having a ferrocene group can be preferably bonded to two, a cluster in which the size is controlled and the number and arrangement position of different noble metals of platinum and iron are precisely arranged is obtained. It becomes possible.

In the fifth invention, the heteronuclear complex heteronuclear complex in which at least one of the acetate ligands of the acetate tetraplatinum complex is substituted with a ligand having a ferrocene group is supported on a carrier. It is necessary to carry a nuclear complex.
In the sixth invention, at least one of the acetate ligands of the acetatotetraplatinum complex is substituted with a ligand having a ferrocene group, and at least one of the acetate ligands is an amidine ligand. It is necessary to support the heteronuclear complex by supporting the heteronuclear complex that is substituted and capped, and at least one of the remaining acetate ligands is replaced with a ligand having a ferrocene group. It is.

The carrier is pretreated with any compound having a functional group capable of substituting the ligand of the heteronuclear complex, such as diamine, dicarboxylic acid, such as succinic acid, adipic acid, etc. For example, it may be a diamine or dicarboxylic acid-treated carrier in which diamine or dicarboxylic acid is bound by an OH group.
In addition, as a solvent of the solution used in the method of supporting the heteronuclear complex on a carrier, any solvent that can stably maintain the heteronuclear complex of the present invention, for example, an aqueous solvent, or an organic solvent such as dichloroethane is used. Can do.

In particular, in any of the methods of the fifth and sixth inventions, the following method is preferable.
(1) In order to support the heteronuclear complex on the support, a porous metal oxide support, such as alumina, ceria, zirconia, silica, and titania, is dispersed in a solvent, and this support dispersion is stirred.
(2) Oxidizing agents, for example, metal nitrates such as silver nitrate, manganese nitrate or thallium nitrate, metal oxides such as manganese oxide or potassium permanganate, lead tetraacetate, sodium bismutate, periodic acid or sodium periodate The heteronuclear complex is converted into a cationic complex by oxidizing the ferrocene portion of the heteronuclear complex with periodate such as
(3) A cationic complex solution in which a predetermined amount of the obtained cationic complex is dissolved in a solvent is obtained.
(4) The cationic complex solution is added to the carrier dispersion solution and stirred to adsorb the heteronuclear complex to the carrier.
According to the above method, the heteronuclear complex can be supported on the carrier with high dispersion by utilizing the cationic charge of the ligand having a ferrocene group.

Then, the supported catalyst can be obtained by removing the ligand of the heteronuclear complex from the carrier on which the heteronuclear complex is supported.
Removal of the ligand of the heteronuclear complex can be achieved by drying and calcining the solution containing the heteronuclear complex. This drying and firing can be performed, for example, at a temperature and time sufficient to obtain a metal oxide cluster, for example, firing at a temperature of 120 to 250 ° C. for 1 to 2 hours, and thereafter 400 to 600 ° C. Firing for 1 to 3 hours can be performed.

  Hereinafter, the present invention will be described using examples. These examples are merely illustrative and do not limit the invention in any way.

In each of the following examples, the analysis was performed using the following measuring instruments and measuring methods.
NMR ( ¹ H, ¹³ C { ¹ H}, ³¹ P { ¹ H} NMR): VARIAN-MERCURY300-C / H (Varian) was used.
NMR ( ¹⁹⁵ Pt { ¹ H} NMR): JEOL-lamada 500 (107.4 MHz, manufactured by JEOL Ltd.) was used.
The chemical shifts of ¹ H and ¹³ C NMR spectra were expressed in ppm (δ) based on tetramethylsilane.
^{The 195} Pt { ¹ H} NMR) spectrum was based on K ₂ PtCl ₄ (δ-1622).
As the IR spectrum, JASCO FT / IR-230 manufactured by JASCO Corporation was used.
Elemental analysis: Parkin-Elmer 2400 (Parkin-Elmer)
RAXIS-RAPID (Rigaku) was used for X-ray single crystal structure analysis.
MP (melting point) was measured using Yanaco MP-52982 from Yanaco.

All reactions were performed under an argon atmosphere on a Schlenk or general vacuum line. The solvent used was dehydrated under an argon atmosphere. As a heavy solvent for NMR measurement, CDCl ₃ and CD ₂ Cl ₂ were used. The octaacetato tetraplatinum complex [Pt ₄ (OAc) ₈ ] was synthesized according to the Chemical Society of Japan, 4th edition, Experimental Chemistry Vol. 17, Inorganic Complex, page 452, 1991.

Example 1
In Schlenk, 48.0 mg (0.038 mmol) of [Pt ₄ (OAc) ₈ ] was weighed and dissolved in CH ₂ Cl ₂ (3 ml). To this was added 142 mg (0.62 mmol, 16 eq) of ferrocenecarboxylic acid dissolved in CH ₂ Cl ₂ (3 ml) / MeOH (3 ml), and the mixture was stirred at room temperature for 5 hours. After distilling off the solvent under reduced pressure, it was washed twice with MeOH (5 ml) and recrystallized with a CHCl ₃ / hexane bilayer system to give 38.0 mg of the reaction scheme shown in (1) of FIG. The heteronuclear complex [Pt ₄ Fe ₄ ] (1) was obtained as red crystals (yield 52%).
The measurement results for the obtained red crystals are shown below.
¹ H NMR (300 MHz, CDCl ₃ , 308 K, δ / ppm): 2.03 (s, 6 H, ^ax OAc), 4.28 (s, 20 H, CpH), 4.45 (t, ³ J _HH = 3 Hz , CpH), 5.21 (t, ³ J _HH = 3 Hz, 8H, CpH)

By oxidizing the obtained heteronuclear complex [Pt ₄ Fe ₄ ] with silver nitrate or the like, the cationic polynuclear complex (2) in FIG. 1 could be easily obtained.

Reference example 1
Synthesis of [Pt ₄ (k ⁴ -DTolBp)] (3) 172 mg (0.374 mmol, 1.5 eq.) Of H ₂ DTolBp and 40 mg (0.75 mmol, 3 eq.) Of NaOMe were dissolved in a mixed solvent of 10 ml of methylene chloride and 10 ml of methanol. It was. After stirring at room temperature for 1 hour, 0.312 g of [pt ₄ (μ-OAc) ₈ ] 0.249 mmol was added, and stirring was continued for 17 hours. After the solvent was distilled off under reduced pressure, the resulting red solid was dissolved in methylene chloride, and the insoluble precipitate was filtered off through celite. After removing the solvent under reduced pressure, it was washed 3 times with 20 ml of diethyl ether to obtain 305 mg of a brown solid (yield 77%).

The measurement result about the obtained brown solid is shown below.
Melting point 238-242 [deg.] C. ¹ H NMR (300 MHz, CDCl ₃ , δ / ppm): 1.75-1.90 (m, OAc, 2H, —CH ₂ CH ₂ CH ₂ —), 1.78 (s, 6H, ^ax O ₂ CCH ₃ ), 2.03 (s, 6H, ^ax O ₂ CCH ₃ ), 2.13 (s, 6H, —CH ₃ ), 2.22 (s, 6H, ^eq O ₂ CCH ₃ ), 2.95 ( dt, ² JHH = 13.6 Hz, ³ JHH = 5.3 Hz, 2H, = NCHN-), 3.07 (dt, ² JHH = 13.6 Hz, ³ JHH = 5.0 Hz, 2H, = NCHN-), 6.80 (dt, ³ JHH = 9.0 Hz, 4H, −C ₆ H ₄ CH ₃ ), 6.83 (d, ³ JHH = 9.0 Hz, 4H, −C ₆ H ₄ CH ₃ ), 7. 03-7.09 (m, 2H, Ph), 7.15-7.24 (m, 8H, h).
¹³ C { ¹ H} NMR (75 MHz, CDCl ₃ , δ / ppm): 21.1 (—CH ₃ ), 21.6 ( ^ax O ₂ CCH ₃ ), 21.7 ( ^ax O ₂ CCH ₃ ), 23 _{^{.3 (eq O 2 CCH 3)}} , 32.9 (-CH 2 CH 2 CH 2 -), 51.0 (= NCH 2), 127.7 (Ar-C), 127.8 (Ar-C) , 128.1 (Ar-C), 128.18 (Ar-C), 128.23 (Ar-C), 128.6 (Ar-C), 132.2 (Ar-C), 134.4 ( Ar-C), 145.0 (Ar-C), 172.3 (-NCChN-), 182.4 ( ^eq O ₂ CCH ₃ ), 191.7 ( ^ax O ₂ CCH ₃ ), 192.0 ( ^ax O ₂ CCH ₃ ).
ESI-MS _(CH 3 CN solution, m / z): 1533 ( [M-OAc] +.
Calcd for _{C 43 H 48 N 4 O 12} Pt 4: C, 32.42; H, 3.04; N, 3.52. Found: C, 32.81; H, 2.96; N, 3.49

Example 2
In Schlenk, 34.8 mg (0.022 mmol) of [cis-Pt ₄ (Me)] was weighed and dissolved in CH ₂ Cl ₂ (3 ml). To this was added 10.4 mg (0.045 mmol, 2 eq) of ferrocenecarboxylic acid dissolved in MeOH (3 ml), and the mixture was stirred at room temperature for 5 hours. After the solvent was distilled off under reduced pressure, the residue was washed twice with MeOH (5 ml) to give 22.2 mg of the complex [cis-Pt ₄ Fe ₂ (Me) represented by (4) in the reaction scheme shown in FIG. ] Was obtained as dark red crystals (52% yield).

The measurement results for the obtained deep red crystals are shown below.
¹ H NMR (300 MHz, CDCl ₃ , 308 K, δ / ppm): 1.86 (s, 8 H, ^ax OAc + —CH ₂ CH ₂ CH ₂ —), 2.10 (s, 6 H, ^ax OAc); _{25 (s, 6H, -C 6} H 4 Me), 2.96-3.18 (m, 4H, = NCH 2 -), 4.12 (s, 10H, CpH), 4.20 (t, 3 J _HH = 3 Hz, 4 H, CpH), 4.71 (m, 2 H, CpH), 4.78 (m, 2 H, CpH), 6.93 (d, 4 H, ³ J _HH = 9 Hz, −C ₆ H ₄ Me), 6.97 (d, 3J _HH = 9 Hz, 4H, -C ₆ H ₄ Me), 7.05 (Pseud d, ³ J _HH = 6 Hz, 2H, -Ph), 7.15-7. 33 (m, 8H, -Ph)

The cationic multinuclear complex (5) in FIG. 1 could be easily obtained by oxidizing the obtained heteronuclear complex [cis-Pt ₄ Fe ₂ (Me)] with silver nitrate or the like.

Reference example 2
Synthesis of HDTolF (6) In an eggplant flask, 3.29 g (31 mmol) of p-toluidine and 5.0 ml (30 mmol) of ethyl orthoformate were placed and refluxed at 140 ° C. for 5 hours. After allowing to cool, the produced yellow precipitate was dissolved in toluene and recrystallized to obtain 3.15 g of HDTolf (6) in FIG. 2 (6) as white crystals (yield 92%).

The measurement results for the obtained white crystals are shown below.
¹ H NMR (300 MHz, CDCl ₃ , 308 K, δ / ppm): 2.32 (s, ₆ H, —CH ₆ H ₄ Me), 6.94 (d, 3J _HH = 9 Hz, 4 H, —ArH), 7 .11 (d, ³ J _HH = 9 Hz, 4 H, ArH), 8.13 (s, 1 H, —NCHN—)

Reference example 3
Synthesis of [Pt ₄ (OAc) ₆ (DTolF) ₂ ] (7) [Pt ₄ (OAc) ₈ ] 107 mg (0.086 mmol) and HDTolF 38.5 mg (0.17 mmol, 2 eq) were weighed in a Schlenk, and MeOH 3 ml To give an orange suspension. After stirring for 1 hour, a dark red suspension was obtained, which was centrifuged and the precipitate was dried under reduced pressure to give 119 mg of complex [Pt ₄ (OAc) shown in (7) of the reaction scheme shown in FIG. ₆ (DTolF) ₂ ] was obtained as a red powder (yield 88%).

The measurement result about the obtained red powder is shown below.
Melting point 200-205 [deg.] C. (dec). ¹ H NMR (300 MHz, CDCl ₃ , 308 K, δ / ppm): 1.85 (s, 6 H, ^ax O ₂ CCH ₃ ), 1.91 (s, 6 H, ^ax O ₂ CCH ₃ ), 2.19 ( _{^{s, 6H, eq O 2 CCH}} 3), 2.35 (s, 12H, -C 5 H 4 CH 3), 6.89 (s, 2H, -NCHN -), 7.129 (d, 3 J HH _{= 8.1Hz, 8H, -C 6 H} 4 CH 3), 7.13 (d, 3 J HH = 8.1Hz, 8H, -C 6 H 4 CH 3).
¹³ C { ¹ H} NMR (75 MHz, CDCl ₃ , 308 K, δ / ppm): 20.9 (s, —C ₅ H ₄ CH ₃ ), 21.2 (s, ^ax O ₂ CCH ₃ ), 21. 7 (s, ^ax O ₂ CCH ₃ ), 22.8 (s, ^eq O ₂ CCH ₃ ), 124.3 (s, C ₆ H ₄ CCH ₃ ), 129.1 (s, —C ₆ H ₄ CH _{3), 132.8 (s, ipso} -C), 147.0 (s, ipso-C), 162.0 (s, -NCHN -), 186.3 (s, eq O 2 CCH 3), 191 .6 (s, ^ax O ₂ CCH ₃ ), 194.1 (s, ^ax O ₂ CCH ₃ ).
ESI-MS _(CH 3 CN solution, m / z): 1581 ( [M + H] +.
Calcd for _{C 42 H 48 N 4 O 12} Pt 4: C, 31.90; H, 3.06; N, 3.54. Found: C, 32.01; H, 3.03; N, 3.49

Example 3
According to the reaction scheme shown in FIG. 2, 48.5 mg (0.031 mmol) of [Pt ₄ (OAc) ₆ (DTolF) ₂ ] (7) was weighed into Schlenk, and MeOH (3 ml) was added to form a suspension. Thereafter, 14.6 mg (0.064 mmol, 2 eq) of ferrocenecarboxylic acid dissolved in MeOH (3 ml) was added. After stirring at room temperature for 5 hours, the pressure was reduced, and the reaction was carried out for 10 hours while adding MeOH (6 ml) frequently. The resulting solid was washed twice with MeOH (5 _ml), dissolved in CH ₂ Cl _{2 (3ml),} was added to HDTolF5.17mg was dissolved in _{CH 2 Cl 2 (3ml) (} 0.023mmol) at room temperature For 2 hours. The solvent was distilled off under reduced pressure, followed by washing twice with MeOH (5 ml), whereby 48.6 mg of the heteronuclear complex [trans-Pt ₄ Fe ₂ ( DTolF) ₂ ] was obtained as a dark red solid (yield 82).

The measurement results for the obtained deep red crystals are shown below.
¹ H NMR (300 MHz, CDCl ₃ , 308 K, δ / ppm): 1.86 (s, 6 H, ^ax OAc), 1.93 (s, 6 H, ^ax OAc), 2.43 (s, 12 H, —C ₆ H ₄ Me), 4.11 (s, 10 H, CpH), 4.30 (t, ³ J _HH = 3 Hz, 4 H, CpH), 4.74 (t, ³ J _HH = 3 Hz, 8 H, CpH) _{^{, 6.99 (s, 2H, -NCHN}} -), 7.24 (d, 3 J HH = 9Hz, 8H, -C 6 H 4 Me), 7.37 (d, 3 J HH = 9Hz, 8H, -C ₆ H ₄ Me).
¹³ C { ¹ H} NMR (75 MHz, CDCl ₃ , 308 K, δ / ppm): 21.0 (s, —C ₅ H ₄ Me), 21.4 (s, ^ax OAc), 21.9 (s, ^ax OAc), 69.8 (s, CpC), 70.6 (s, CpC), 70.8 (s, CpC), 73.2 (s, CpC), 124.7 (s, ArC), 129 0.0 (s, ArC), 132.8 (s, ArC), 147.2 (s, ArC), 161.9 (s, -NCHN-), 185.2 (s, -OCOFc), 191.5 (S, ^ax OAc), 193.9 (s, ^ax OAc).
ESI-MS _(CH 3 CN solution, m / z): 1920 ( [M +].

By oxidizing the obtained heteronuclear complex [trans-Pt ₄ Fe ₂ (DTolF) ₂ ] (8) with silver nitrate or the like, the cationic polynuclear complex (9) in FIG. 2 could be easily obtained.

Example 4
Using [cis-Pt ₄ Fe ₂ (Me)] obtained in Example 2, a heteronuclear complex can be supported on a carrier according to the scheme shown in FIG.

With the heteronuclear complex of the present invention, the arrangement of different metals can be controlled more precisely, and a high-performance supported catalyst can be provided.
Further, the heteronuclear complex containing a different kind of noble metal in a complex capable of more precisely controlling the arrangement of different kinds of metal capable of providing a high-performance supported catalyst by the method for producing a heteronuclear complex of the present invention is provided. can get.

Claims (6)

  A heteronuclear complex in which at least one of the acetate ligands of the acetate tetraplatinum complex is substituted with a ligand having a ferrocene group.   Heteronuclear in which at least one acetate ligand of the acetate tetraplatinum complex is capped by substitution with an amidine ligand and at least one of the remaining acetate ligands is substituted with a ligand having a ferrocene group Complex.   A method for producing a heteronuclear complex, wherein at least one of the acetate ligands of the acetate tetraplatinum complex is substituted with a ligand having a ferrocene group.   A heteronuclear complex in which at least one of the acetate ligands of the acetate tetraplatinum complex is capped with an amidine ligand and at least one of the remaining acetate ligands is replaced with a ligand having a ferrocene group. Production method.   A method for supporting a heteronuclear complex, wherein the heteronuclear complex according to claim 1 is supported on a carrier.   A method for supporting a heteronuclear complex, wherein the heteronuclear complex according to claim 2 is supported on a carrier.

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