JP2011101862A - Dissimilar-metal polynuclear complex and method for manufacturing catalyst using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-soluble metal complex which has a plurality of types of metal atoms and is capable of forming a dissimilar-metal cluster and method for manufacturing catalyst using the same. <P>SOLUTION: The metal complex is a dissimilar-metal polynuclear complex of ionicity having a plurality of types of dissimilar metal atoms, and the method for manufacturing catalyst impregnates a porous carrier in an aqueous solution including a dissimilar polynuclear complex of ionicity having a plurality of types of metal atoms. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ionic heterometallic multinuclear complex and a method for producing a catalyst using the same, and more particularly to an ionic heterometallic multinuclear complex having a plurality of types of metal atoms and a method for producing a catalyst using the same. It is.

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.
In order to utilize the unique properties of this metal cluster, there is a need for a method for simply and massively synthesizing a size-controlled cluster.
On the other hand, a currently known method for obtaining a cluster having a controlled size is to evaporate a metal target in a vacuum to generate clusters of various sizes. From the clusters thus obtained, There is a method of separating the cluster size using the principle. However, this method cannot synthesize a metal cluster with a controlled size easily and in large quantities.

As an example of using the catalytic performance of the noble metal, there can be mentioned 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.

Supporting a noble metal oxide support as a catalyst component is generally performed by impregnating a noble metal nitrate or a noble metal complex solution having a single noble metal atom into the support and dispersing the noble metal compound on the surface of the support. Then, the carrier impregnated with the solution is dried and fired. 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.
Even in such exhaust gas purification catalysts, there is a strong expectation for further improvement in exhaust gas purification performance from the demands for precious metal resource depletion and environmental improvement, and it has been proposed to support precious metals in a cluster state.

  For example, Patent Document 1 discloses a noble metal cluster-supported catalyst by precipitating a multinuclear complex composed of a plurality of organic polydentate ligands and a plurality of noble metal atoms on a support, and then removing the organic polydentate ligand. A method for producing a noble metal cluster supported catalyst to be produced is described. Then, the hydroxyl group on the surface of the oxide support is reacted with the organic polydentate ligand to bind the organic polydentate ligand to the oxide support, and the organic multidentate ligand is bonded to the noble metal atom and other organic polydentate ligands. A method is disclosed that includes reacting with a bidentate ligand to form a polynuclear complex bonded on an oxide support, and then burning off the organic polydentate ligand of the polyhedral complex, for example, by heating in an atmospheric atmosphere. ing.

  On the other hand, a complex containing a plurality of metals is known as a metal complex. For example, Non-Patent Document 1 discloses a binuclear complex having two palladium in a molecule and an amide as a bridging ligand, four palladium. Including amide-bridged tetranuclear complexes, binuclear rhodium amide complexes or binuclear imide complexes have been proposed.

JP 2006-55807 A

Abstracts of Coordination Chemistry Conference, 2007.9.9, Vol. 57, Page 8, Lecture No. 1Aa-07 “Synthesis of Amide-Bridged Palladium Clusters”

However, it is impossible to synthesize in a large amount with a conventionally known metal cluster, or when a noble metal complex is supported, the metal atom contained in the complex is limited to one type of metal atom. In addition, since the water solubility described in Patent Document 1 is not intended, an organic solvent is required at the time of catalyst preparation, and the organic solvent solution does not have good wettability with the support surface. It requires a complicated process, and since it contains organic ligands, firing in an oxygen atmosphere is required to decompose the organic ligands. If the firing temperature is too high, the size of the noble metal cluster may be affected and obtained. The catalyst is susceptible to the calcination conditions in terms of performance.
Accordingly, an object of the present invention is to produce a metal complex having a plurality of types of metal atoms and capable of forming heterogeneous metal clusters and being water-soluble, and a catalyst using such a metal complex. Is to provide a method.

The present invention relates to an ionic dissimilar metal polynuclear complex having plural kinds of dissimilar metal atoms.
Furthermore, the present invention relates to a method for producing a catalyst in which a porous carrier is impregnated with an aqueous solution containing an ionic heterometallic multinuclear complex having a plurality of types of metal atoms.

According to the present invention, it is possible to obtain a metal complex that has a plurality of types of metal atoms and can form different types of metal clusters and is water-soluble.
Moreover, according to the present invention, since the heterogeneous metal polynuclear complex having a plurality of types of metal atoms is water-soluble, a catalyst containing heterogeneous metal clusters can be prepared using water as a solvent.

FIG. 1 is a diagram showing the results of single crystal structure analysis of the complex 4 obtained in Example 3. FIG. 2 is an MS spectrum diagram of the complex obtained in Example 4. FIG. 3 is an NMR spectrum diagram of the complex obtained in Example 4.

According to the embodiment of the present invention, the ionic heterometallic multinuclear complex having plural kinds of heterometallic atoms is water-soluble because the heterometallic multinuclear complex is ionic.
Further, according to the embodiment of the present invention, the metal complex is ionic by the ionic heterogeneous metal multinuclear complex having a plurality of types of metal atoms, so that it is water soluble and can be prepared using water as a solvent. In particular, since a plurality of metal atoms are cross-linked with a nitrogen-containing group, the nitrogen-containing compound can be removed by heating.

According to the conventional technology, when attention is paid to a certain element, chemical characteristics such as catalytic activity and physical characteristics such as magnetism can change depending on the size of the cluster (a collection of atoms).
In order to utilize the specific properties of this cluster, a method for synthesizing a cluster with a controlled size easily and in large quantities is desired. However, as a currently attempted method for generating a cluster with a controlled size, It is a method that separates the cluster size using the principle of MASS (sometimes abbreviated as MS) spectrum after generating various size clusters by evaporating the metal target in vacuum. Is possible. In addition, in the method using a complex used as a method for preparing a catalyst, a large amount of catalyst can be easily prepared. However, since metal grows particles in a single atom dispersion state or by appropriate heating / atmosphere control, It cannot carry a metal atom composed of a metal or a cluster having a composition.

As described above, in the cluster preparation according to the conventional technique, it is impossible to synthesize clusters in a large amount at a low cost because of apparatus limitations. For example, in a method of supporting a conventionally known complex such as tetraammine Pd or nitric acid Pd, the number of metal atoms contained in the complex is one atom, so that it cannot be a cluster. Moreover, even if two types of complexes are mixed using a conventionally known complex, it is difficult to form an alloy cluster because chemical bonds between complex metals cannot be formed.
In addition, even if the complex contains multiple metals, the complex compound contains an organic ligand in the molecule, so the complex is difficult to dissolve in water and must be fired in the presence of oxygen to decompose the ligand. If the temperature is too high, the cluster size can be adversely affected.

  On the other hand, the different metal polymetallic complex of the present invention has a plurality of types of different metal atoms and is ionic, by selecting a counter ion which is an anion (hereinafter simply abbreviated as a counter ion). It can be a water-soluble compound. Also, according to the dissimilar metal multi-metal complex of the present invention, an alloy cluster in which multiple kinds of metal elements are complexed can be chemically synthesized, so that the characteristics of the material obtained by the prior art are greatly exceeded. It may be possible to create a material with unique properties.

Hereinafter, the present invention will be described using different metal polymetallic complexes represented by the following chemical formula, which is an embodiment of the present invention.
As an example of the heterogeneous metal polymetallic complex which is an embodiment of the present invention, the following chemical formula:

The two types of different metal polynuclear complexes shown by these are mentioned.
The heterogeneous metal polymetallic complex according to the embodiment of the present invention is a noble metal multinuclear complex in which different metal atoms are bridged with different noble metal elements and Pd and Pt are NH ₂ groups, and a noble metal cluster having a plurality of noble metal atoms is chemically Can be synthesized. Further, it may be possible to chemically synthesize a metal cluster in which a plurality of types of metal elements are combined.

Further, when the heterogeneous metal multimetal complex is used for the preparation of the catalyst, it can be made a compound that is soluble in water by selecting a counter ion, and water can be used as a solvent for the preparation of the catalyst. In addition, the complex can be adsorbed as a cation on the surface of the metal oxide which is a carrier of the catalyst, and further, the NH ₂ group is used as a ligand to bond the noble metals to each other, so that this complex is supported on the carrier. The ligand can be easily removed by simply heating without the need for subsequent firing in the presence of oxygen. Furthermore, since the ligand is an NH ₂ group, it is excellent in terms of cost in consideration of utilization on an industrial basis.

The compounds of different metals multinuclear complex of the present invention have the _{formula: [M1 p M2 q A a} B b] n + X n n- (M1, M2 are each different metal atom, A is a divalent ligand B is a monovalent ligand, X _n ^n- is a counter ion, p and q are integers of 1 or more, a and b are even numbers, and n is an integer of 1 to 3. ).

  The dissimilar metal constituting the ionic dissimilar metal polynuclear complex is not particularly limited as long as it is a transition metal. For example, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zirconium, niobium, molybdenum, technetium, It may be at least two metals selected from ruthenium, rhodium (Rh), palladium (Pd), silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum (Pt) and gold, in particular Pd, Pt and Two types selected from Rh are preferred.

The heterogeneous metal atom is a divalent ligand (represented by A in the above general formula), such as a divalent nitrogen-containing group, preferably an NR ₂ group (R is H or an alkyl group such as methyl A plurality of metals are monovalent ligands (represented by B in the above general formula), for example, monovalent nitrogen-containing groups. , Preferably NR ′ ₃ [R ′ is H or an alkyl group such as a methyl group, an ethyl group, a propyl group or the like, or a pyridine group (indicated by Py in the chemical formula)]. Examples of the divalent ligand include NH ₂ group, and examples of the monovalent ligand include NH ₃ group and pyridine group.
The total number of metal atoms in the ionic heterometallic multinuclear complex is 2 or more, preferably 2 to 100, particularly 2 to 10.

As counter ions of the heterometallic multinuclear complex compound in the present invention, B [C ₆ H ₃ (CF ₃ ) ₂ ] ₄ ⁻ , [B [C ₆ F ₅ ) ₄ ⁻ , C ⁻ (C is a halogen atom. ), OH ⁻ , AlCl ₄ ⁻ , AlBr ₄ ⁻ , GaCl ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , SbF ₆ ^{− and the} like. To B [C ₆ H ₃ (CF ₅ ) ₂ ] ₄ ⁻ and [B (C ₆ F ₅ ) ₄ ⁻ are preferable.

  The ionic dissimilar metal multinuclear complex of the present invention is an ionic complex having two or more dissimilar metal atoms in the molecule, is water-soluble, and can be adsorbed by the surface of a porous carrier that is a ceramic substrate. It is possible to adsorb the ionic dissimilar metal multinuclear complex on the surface of the support without special treatment on the surface, for example, pretreatment with OH, and remove the ligand only by heating to form a dissimilar metal cluster. From the viewpoint of improving the catalytic activity. However, it is natural that the adhesion with the ionic heterometallic multinuclear complex of the present invention may be improved by pretreating the surface of the porous carrier in advance.

The ionic heterometallic multinuclear complex compound in the present invention is, for example, a first metal having a first metal such as Pt, a monovalent ligand, a divalent ligand, lithium and a counter ion in an organic solvent. The two metal compounds by contacting the second metal compound with a second metal such as Pd, a second metal compound having a pyridine group and a counter ion, and removing the counter ion compound of pyridine and lithium. By doing so, it can be obtained as an ionic heterometallic multinuclear complex compound having a first metal, a second metal, a monovalent ligand, a divalent ligand, and a counter ion. By continuing this reaction sequence, or by selecting a combination of the first metal compound and the second metal compound, wherein the _{formula: [M1 p M2 q A a} B b] n + X n optionally in ^n- It is possible to obtain an ionic heterometallic multinuclear complex having the following p and q.

The organic solvent is not particularly limited, and examples thereof include ethers such as tetrahydrofuran (THF) and diethyl ether, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, chlorobenzene and dichlorobenzene, N-methyl 2-pyrrolidone, N , N-dimethylacetamide and the like, or a mixed solvent of at least one of them and a hydrocarbon such as n-hexane (simply abbreviated as hexane).
The reaction can be carried out at a temperature not lower than the freezing point of the solvent and not higher than 25 ° C., preferably at −95 to 25 ° C. with stirring for 2 to 24 hours.
After completion of the reaction, solids that are insoluble in the solvent are removed, and the crystals can be obtained by distilling off the solvent or by recrystallization.

The chemical structure of the ionic dissimilar metal polynuclear complex of the present invention is a ¹ H chart by nuclear magnetic resonance (hereinafter abbreviated as NMR) analysis described in detail for the measurement method in the column of Examples described later. From the mass spectrometry (hereinafter abbreviated as MS) analysis and elemental analysis described in detail in the column of Examples, the molecular weight and each ligand are described in detail in the column of Examples described later. that a single crystal of a cation comprising the ORTEP diagram based on X-ray structural analysis a plurality of different metal atoms (e.g., the _{formula: [M1 p M2 q a a} B b] n + X n from ^{_n-X n n-is} taken _{formula: [M1 p M2 q A a} B b] cation represented by ^{n +)} is identified.
Further, the MS chart, monovalent cation (wherein n number of counter ions _X ^{n n-1} pieces of D of the ionic complex is _{eliminated: [M1 p M2 q A a} B b] n + X n (n ^-1)- ) m / z (m represents the mass number of the ion and z represents the valence of the ion).
From these analysis results, the chemical structure of the ionic heterometallic polynuclear complex becomes clear.

  For example, according to the MS chart of the ionic heterometallic multinuclear complex compound obtained in Example 1, which is one embodiment of the present invention, the binuclear ionic heterometallic multinuclear complex compound is one of two counter ions. The monovalent cation m / z = 1203 of the detached monovalent cation, and the heteronuclear multinuclear of the trinuclear ion of the ionic heterometallic multinuclear complex compound obtained in Example 2 which is one embodiment of the present invention In the complex compound, m / z = 1307 of a monovalent cation from which one of two counter ions is eliminated.

FIG. 1 shows an ORTEP as an example of the above-mentioned trinuclear ionic heterometallic multinuclear complex (formula in which X ⁿ⁻ is taken from the formula: [M1 _p M2 _q A _a B _b ] ^{n +} ) It can be seen that in the ionic heterometallic multinuclear complex, one Pd atom and two Pt atoms are arranged in the same plane.
From these results, it can be confirmed that the ionic heterometallic multinuclear complex which is an embodiment of the present invention has the above-mentioned chemical structure.

  As a method for producing a catalyst for impregnating a porous carrier with an aqueous solution containing an ionic heterogeneous metal multinuclear complex of the present invention, particularly a method for producing an exhaust gas purification catalyst, each of the (p + q) nuclear ion heterometallic multinuclear complexes of the present invention An example is a method in which an oxide carrier is impregnated with an aqueous solution, and then heated in an inert atmosphere, dried and fired, and metal clusters are supported on the porous carrier.

  The porous carrier is not particularly limited, and for example, a honeycomb substrate made of a heat-resistant ceramic material such as cordierite, alumina, zirconia, silicon carbide, etc. having a large number of fine pores in the substrate. It is preferable to use a cordierite honeycomb having excellent heat resistance and a low thermal expansion coefficient. This honeycomb substrate preferably has a large number of cells open at both ends. The pores present in the cell walls of the honeycomb substrate are preferably substantially non-through holes, and it is preferable to use the cell walls having a porosity of 40 to 75% and a pore diameter of 10 to 50 μm. .

  The porous carrier has many active sites on its surface, for example, functional groups such as OH groups and O groups and defects such as protrusions, and is treated with an aqueous solution containing the ionic heterometallic multinuclear complex of the present invention. By doing so, the cation of the ionic heterometallic multinuclear complex is chemically or physically adsorbed at the active site, and a metal cluster can be formed by a drying / firing step in an inert atmosphere of post-treatment.

  The ionic heterometallic multinuclear complex having the number of p + q nuclei that gives good catalytic activity is, for example, the number of metal clusters on the support obtained separately by forming various numbers of metal clusters by the above-described metal evaporation-MS method. By obtaining in advance the number of metal clusters that give good catalytic activity obtained from the graph showing the relationship between the catalyst activity and the number of metal clusters, the relationship between the number of p + q nuclei and the number of metal clusters in the ionic heterometallic multinuclear complex is obtained. An ionic p + q nucleus heterogeneous multinuclear complex with p + q nuclei that gives good catalytic activity can be determined.

Examples of the present invention will be described below.
The following examples are for illustrative purposes only and are not intended to limit the invention.
In each of the following examples, the analysis was performed with the following measuring instruments.
NMR: VARIAN-MERCURY300-C / H (Varian)
MS: JEOL SX-203 (JEOL)
Elemental analysis: Parkin-Elmer 2400 (Parkin-Elmer)
X-ray crystal structure analysis: PAXIS-RAID (Rigaku)
ORTEP: IR measurement based on X-ray crystal structure analysis by PAXIS-RAID (Rigaku) for single crystal: JASCO FT-IR4100 (JASCO Corporation)

Reference example 1
Synthesis of [Pt (NH ₃ ) ₄ ] [B (C ₆ F ₅ ) ₄ ] ₂ (1) [Pt (NH ₃ ) ₄ ] Cl ₂ .H ₂ O (991 mg, 2.82 mmol) in water (30 mL) Was added with an aqueous solution (60 mL) of Li [B (C ₆ F ₅ ) ₄ ] (5.53 g, 5.63 mmol) at room temperature (25 ° C.) and stirred for 1 hour. The resulting solid was filtered off, washed with THF (30 mL), and dried over magnesium sulfate. By filtering again and vacuum drying, 1.4.3 THF (a substance obtained by solvating 4.3 THF on average in the substance of the following chemical formula 1) was obtained as a colorless crystalline solid. The yield was 2.48 g (88% yield).

The NMR, MS, and IR measurement results of Compound 1 are shown below.
¹ H NMR (CD ₃ CN): d3.36 (br, 12H, NH ₃ )
MS (FAB): m / z 942 {(1- [B (C ₆ F ₅ ) ₄ ]} ⁺
IR (nujol): 3356 (br), 1516 (s), 1274 (m), 1084 (m), 979 (s) cm ⁻¹
The reaction of Reference Example 1 is shown in the following chemical formula.

Reference example 2
[Pd (C ₆ H ₅ N) ₄ ] [B (C ₆ F ₅ ) ₄ ] ₂ (2) Synthesis [Pd (NH ₃ ) ₄ ] [B (C ₆ F ₅ ) ₄ ] ₂ · 4.6THF ( (2.00 g, 1.07 mmol) was dissolved in pyridine (10 mL) and stirred at 80 ° C. for 10 hours. The solvent was distilled off, and the remaining solid was recrystallized with THF / hexane (10 mL / 40 mL) to obtain 2.THF (one THF solvated in the following chemical formula 2) as colorless crystals. It was. The yield was 1.51 g (76% yield).

The MS, NMR and IR measurement results of Compound 2 are shown below.
_{C 72 H 28 B 2 F 40} N 4 Calculated as OPd: C, 46.67; H, 1.52; N, 3.02 measured values: C, 46.69; H, 1.33 ; N, 2.87
¹ H NMR (CD ₃ CN): d7.52 (m, 8H, py), 7.98 (m, 4H, py), 8.73 (m, 8H, py)
MS (FAB): m / z 1101 {(2- [B (C ₆ F ₅ ) ₄ ]} ⁺
IR (nujol): 1644 (m), 1610 (w), 1515 (s), 1275 (m), 1090 (m), 1090 (m), 1058 (w), 977 (s), 757 (m) cm ^-1
The reaction of Reference Example 2 is shown in the following chemical formula.

Example 1
Synthesis of [(NH ₃ ) ₂ Pt (m ₂ —NH ₂ ) ₂ Pd (C ₆ H ₅ N) ₂ ] [B (C ₆ F ₅ ) ₄ ] ₂ (3) 1.4.3THF (100 mg, 0 .052 mmol) in THF (5 mL) was cooled to −95 ° C., n-BuLi (2.64 M hexane solution, 41 μL, 0.11 mmol) was added, and then gradually stirred to room temperature over 3 hours with vigorous stirring. Returned. The reaction solution was cooled again to −95 ° C., a THF solution (5 mL) of 2 · THF (96 mg, 0.052 mmol) was added, and the mixture was returned to room temperature over 12 hours with vigorous stirring. The reaction solution, which was colorless, turned yellow. The solvent was distilled off, and the remaining solid was washed with water (30 mL), dissolved in THF (10 mL), and dried over magnesium sulfate. The solid was filtered off and the solvent was distilled off to obtain 3.THF.0.5 pyridine as a light yellow crystalline solid. The yield was 89 mg (yield 89%).

The NMR, MS, and IR measurement results of Compound 3 are shown below.
^{_{1 H NMR (CD 3 CN)}} : d-0.70 (br, 4H, m 2 -NH 2), 2.84 (br, 6H, NH 3), 7.45 (m, 4H, py), 7 .91 (m, 2H, py), 8.48 (m, 4H, py)
MS (FAB): m / z 1203 {(3- [B (C ₆ F ₅ ) ₄ ]} ⁺
IR (nujol): 3635 (br), 3292 (w), 1644 (m), 1515 (s), 1276 (m), 1087 (m), 977 (s) cm ⁻¹
The reaction of Example 1 is shown in the following chemical formula.

Example 2
Synthesis of [(NH ₃ ) ₂ Pt (m ₂ -NH ₂ ) ₂ Pd (m ₂ -NH ₂ ) ₂ Pt (NH ₃ ) ₂ ] [B (C ₆ F ₅ ) ₄ ] ₂ (4) (3 and Synthesis from 1)
1.4.3 THF (72 mg, 0.037 mmol) in THF (5 mL) was cooled to −95 ° C. and n-BuLi (2.64 M hexane solution, 30 μL, 0.079 mmol) was added, followed by vigorous stirring. The temperature was gradually returned to room temperature over 3 hours. The reaction solution was cooled again to −95 ° C., a THF solution (5 mL) of 3 · THF · 0.5 pyridine (80 mg, 0.037 mmol) was added, and the mixture was returned to room temperature over 12 hours with vigorous stirring. The solvent was distilled off, and the remaining solid was washed with water (30 mL), dissolved in THF (10 mL), and dried over magnesium sulfate. By filtering off the solid and then distilling off the solvent, 4.3.7THF was obtained as a light yellow crystalline solid. The yield was 72 mg (86% yield).

The MS, NMR and IR measurement results of Compound 4 are shown below.
_{C 52 H 28 B 2 F 40} N 8 calculated for _{OPdPt 2: C, 30.33; H} , 1.37; N, 5.44 measured values: C, 30.31; H, 1.32 ; N , 5.17
¹ H NMR (CD ₃ CN): d-1.61 (br, 8H, m ₂ —NH ₂ ), 2.69 (br, 12H, NH ₃ )
MS (FAB): m / z 1307 (4- [B (C ₆ F ₅ ) ₄ ]} ⁺
IR (nujol): 3680 (w), 3623 (w), 3369 (br), 3289 (w), 3174 (br), 1645 (m), 1515 (s), 1275 (m), 1084 (m), 977 (s) cm ⁻¹
The reaction of Example 2 is shown in the following chemical formula.

Example 3
Synthesis of [(NH ₃ ) ₂ Pt (m ₂ —NH ₂ ) ₂ Pd (m ₂ —NH ₂ ) ₂ Pt (NH ₃ ) ₂ ] [B (C ₆ F ₅ ) ₄ ] ₂ (4) (1 and 1 pot synthesis from 2)
1.4.3 THF (1.01 g, 0.52 mmol) in THF (10 mL) was cooled to −95 ° C., n-BuLi (2.64 M hexane solution, 417 μL, 1.10 mmol) was added, and then vigorously While stirring, the temperature was gradually returned to room temperature over 3 hours. The reaction solution was cooled again to −95 ° C., a THF solution (10 mL) of 2 · THF (485 mg, 0.262 mmol) was added, and the mixture was returned to room temperature over 12 hours with vigorous stirring. The solvent was distilled off, and the remaining solid was washed with water (50 mL) and recrystallized from THF / hexane (10 mL / 40 mL) to obtain 4 as yellow needle crystals. The yield was 500 mg (yield 96%).
The single crystal structure analysis result of the obtained complex compound 4 is shown in FIG.
The reaction of Example 3 is shown in the following chemical formula.

Example 4
Synthesis of [Pt ₃ Pd ₂ (NH ₂ ) ₈ NH ₃ ) ₄ ] [B (C ₆ F ₅ ) ₄ ] ₂ (5) Pt complex compound 1 (279 mg, 0.150 mmol) was dissolved in 5 mL of THF and −95. Cooled to ° C. 159 μL of n-BuLi solution (2.64 M hexane solution, 0.420 mmol) was added dropwise and stirred for 2.5 hours. During this time, the temperature rose to room temperature, and the reaction solution became cloudy. The mixture was cooled again to −95 ° C., and a THF solution (2.5 mL) of Pd complex compound 2 (191 mg, 0.100 mmol) was added dropwise. The solution became a yellow solution. While stirring, the temperature was returned to room temperature over about 2 hours. The solution was then stirred overnight. A part of the reaction solution was collected, and ¹ H NMR was measured. As a result, a 5-nuclear complex compound: [Pt ₃ Pd ₂ (NH ₂ ) ₈ (NH ₃ ) ₄ ] [B (C ₆ F ₅ ) ₄ ] ₂ A signal of trinuclear complex compound: [Pt ₂ Pd (NH ₂ ) ₄ (NH ₃ ) ₄ ] [B (C ₆ F ₅ ) ₄ ] ₂ was observed. The production ratio of both products was 5 nuclei: 3 nuclei = 8: 3. From this, the obtained reaction solution contains a mixture of a pentaheteronuclear complex compound and a triheteronuclear complex compound, but there is no other component and the molecular weight is greatly different, so that the liquid carmato It was estimated that it was easy to obtain 5 as a single product, easily separable by chromatography.

The NMR and MS measurement results of the product (5 nuclei: 3 nuclei = 8: 3) are shown below.
¹ H NMR (500 MHz, CD ₃ CN) for [Pt ₃ Pd ₂ (NH ₂ ) ₈ NH ₃ ) ₄ ] [B (C ₆ F ₅ ) ₄ ] ₂ : d2.69 (br, 12H, NH ₃ ), _{-1.64 (br, 8H, m 2} -NH 2), - 2.04 (br, 8H, m 2 -NH 2)
FAB-MS (in 2-nitrophenyl Octyl ether) for [Pt ₃ Pd ₂ (NH ₂ ) ₈ NH ₃ ) ₄ ] [B (C ₆ F ₅ ) ₄ ] ₂ : m / z 1673 ({[Pt ₃ Pd ₂ ( (NH ₂ ) ₈ NH ₃ ) ₄ ] [B (C ₆ F ₅ ) ₄ ]} ⁺
The reaction of Example 4 is shown in the following chemical formula.

(Wherein [B] represents [B (C ₆ F ₅ ) ₄ ])
Further, FIG. 2 shows an MS spectrum of the product obtained in Example 4, and FIG. 3 shows an NMR spectrum of the product.
In FIG. 2, the peak at 942 m / z indicates the following metal complex.

  In FIG. 2, the peak at 1307 m / z indicates the following metal complex.

  In FIG. 2, the peak at 1673 m / z indicates the following metal complex.

According to the ionic dissimilar metal multinuclear complex of the present invention, it is possible to prepare a catalyst using water as a solvent. In particular, when a dissimilar metal atom is crosslinked with NH ₂ , the dissimilar metal multinuclear complex is subjected to an inert atmosphere. And can be removed by heating, and a high-performance catalyst can be obtained.

Claims (6)

  An ionic dissimilar metal polynuclear complex having plural kinds of dissimilar metal atoms.   The heterogeneous metal multinuclear complex according to claim 1, wherein a plurality of metal atoms are crosslinked with a divalent nitrogen-containing group. The heterometallic multinuclear complex according to claim ₂ , wherein the nitrogen-containing group is an NH ₂ group, an N (CH ₃ ) ₂ group, or a pyridine group.   The heterometallic multinuclear complex according to any one of claims 1 to 3, wherein the number of metal atoms is 2 to 100. Counterions dissimilar metals multinuclear complex is ^{_{B (C 6 F 5) 4}} -, C - (C is a halogen atom.) Or OH ^- dissimilar metals according to claim 1, represented by Multinuclear complex.   A method for producing a catalyst comprising impregnating a porous carrier with an aqueous solution containing an ionic heterometallic multinuclear complex having a plurality of types of metal atoms.

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