JP2009023897A - Heteropolyoxometallate compound and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heteropolyoxometallate compound wherein at least one element (B) chosen from the group consisting of early-transition metals comprising Sc, Y, Zr, Hf, V, Nb, Ta and Cr is introduced into vacancy structure(s) of a heteropolyoxometallate anion (A) containing two vacancy structures so as to yield a molar ratio satisfying the relation: element (B)/hetero atom>1. <P>SOLUTION: In the heteropolyoxomethalate compound, at least one element (B) chosen from the group consisting of early-transition metals comprising Sc, Y, Zr, Hf, V, Nb, Ta and Cr is introduced into the vacancy structure(s) of the heteropolyoxomethalate anion (A) containing two vacancy structures so as to yield a molar ratio satisfying the relation: element (B)/hetero atom>1. The heteropolyoxomethalate anion (A) comprises a hetero atom chosen from silicon, phosphorus and germanium and a poly atom which is at least one atom chosen from molybdenum, tungsten and vanadium. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a heteropolyoxometalate compound and a method for producing the same. More specifically, at least one element (B) selected from Sc, Y, Zr, Hf, V, Nb, Ta, and Cr, which are the first transition metals, is substituted with a deficient structure site-containing heteropolyoxometalate anion (A ) And a method for producing the heteropolyoxometalate compound introduced at a molar ratio satisfying the element (B) / heteroatom> 1.

It is widely known that heteropolyoxometalate compounds having a structure in which a polyatom is centered on a heteroatom and coordinated to the heteroatom via oxygen can be used as a catalyst for organic reactions such as oxidation reactions and acid-base reactions. . In particular, it has a deficient structure in which two atoms that should be in the structure of Keggin type heteropolyoxometalate are lacking, and the deficient site contains two or more kinds of metal elements, that is, poly atoms are Disubstituted heteropolyoxometalates that are disubstituted with one or more other metal elements are more specific oxidation catalysts than monosubstituted heteropolyoxometalates and trisubstituted heteropolyoxometalates It is known to show activity (see Non-Patent Document 1). However, it is necessary to obtain a heteropolyoxometalate compound substituted with a forward transition metal element expected as a higher oxidation catalyst property, a Lewis acid catalyst, and a new functional material, and further to establish a production method thereof. There was room for ingenuity.

A disubstituted polyoxometalate is disclosed in which Ti is introduced into a two-deficient structure site of a heteropolyoxometalate in which the hetero element is silicon, and the compound contains two Ti atoms in the two-deficient polyoxometalate. An X-ray crystal structure analysis reveals that the structure is dimerized via one oxygen atom (see Non-Patent Document 2). However, there is no disclosure of a heteropolyoxometalate compound multimer in which at least one element selected from Sc, Y, Zr, Hf, Nb, Ta, and Cr is incorporated in the defect site, and the establishment of the production method and the compound There was room for ingenuity in clarifying the structure.

Heteropolyoxometalate anion having two- and / or three-defect structural sites, vanadium, tantalum, niobium, antimony, bismuth, chromium, molybdenum, selenium, tellurium, rhenium, cobalt, nickel, ruthenium, rhodium, palladium, osmium Platinum, iridium, silver, gold, zinc, aluminum, gallium, indium, scandium, yttrium, titanium, zirconium, hafnium, germanium, tin and a catalyst containing at least one element selected from the group consisting of lanthanoids, It is disclosed that a target epoxy compound is obtained by oxidizing a heavy bond with an oxidizing agent (see Patent Document 1). However, in the catalyst in which at least one element selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, and Cr is introduced into the defect site, the yield of the product in the epoxidation reaction is as high as that of the prepared catalyst. Therefore, it was thought that there was some difference in the structure of the heteropolyoxometalate compound. Therefore, the manufacturing method was established and the structure of the compound was clarified. There was room for improvement in further improving the catalytic activity by changing from germanium to germanium.

An element selected from the group consisting of nickel, palladium, iridium and platinum of rare earth, group 4, group 5, group 6, group 7, group 9, and group 10 is introduced into the defect site in the two-deficient polyoxometalate. In addition, it is disclosed that an objective epoxy compound is obtained by oxidizing an ethylenic double bond with oxygen (see Patent Document 2). However, a heteropolyoxometalate compound in which the hetero element is phosphorus or germanium is not disclosed, and the yield and selectivity of the target epoxy compound are extremely low, so that the epoxy compound can be produced at an industrial level. Therefore, it has been found that there is room for improvement in the improvement of the heteropolyoxometalate compound that is a catalyst, and in some cases, the disclosed method for producing a heteropolyoxometalate compound cannot introduce a desired element into a defect site.

Y. Nishiyama, Y. et al. Nakagawa, N .; Mizuno, “Ange. Chem. Int. Ed.” (Germany), 2001, vol. 40, p. 3639.

Y. Goto, K.K. Kamata, K .; Yamaguchi, K .; Uehara, S .; Hikichi, N .; Mizuno, “Inorg. Chem.” (USA), 2006, 45, p. 2347.

International Publication No. 02/072257 Specification As described above, it is widely known that a transition metal element can be introduced into a deficient site of a two-deficient heteropolyoxometalate compound as described above. In particular, a method for synthesizing a heteropolyoxometalate compound in which at least one element selected from Sc, Y, Zr, Hf, Nb, Ta, and Cr is introduced has not yet been established due to its difficulty, and the structure is clearly identified. Was not. In addition, a heteropolyoxometalate compound in which V is introduced into a deficient site of a two-deficient heteropolyoxometalate compound in which the hetero element is germanium, or a V deficient site in a two-deficient heteropolyoxometalate compound in which the hetero element is phosphorus. Heteropolyoxometalate compounds in which a cation is introduced, and in particular, V disubstituted heteropolyoxometalate compounds whose counter cation is a cation of an alkylammonium salt and exhibit high activity without being decomposed in an oxidation reaction in an organic solvent have been heretofore There was no synthesis example, and its oxidation catalytic activity was not clarified.

The present invention has been made in view of the above situation. As a compound that can be suitably applied to an organic reaction such as an oxidation reaction or an acid-base reaction, a functional material, or the like, a heteropolyoxometa containing a two-deficient structure site is provided. At least one element (B) selected from Sc, Y, Zr, Hf, V, Nb, Ta, and Cr, which are the transition metals in the rate anion (A), is element (B) / hetero. It is an object of the present invention to provide a heteropolyoxometalate compound which is introduced at a molar ratio satisfying an atom> 1.

As a result of intensive investigations focusing on industrially useful heteropolyoxometalate compounds as organic materials and functional materials such as oxidation reactions and acid-base reactions, the present inventors have found that The above-mentioned element (B) charged with the prepared compound is not completely introduced into the deficient structure part of the heteropolyoxometalate anion (A) containing the two deficient structure part, that is, element (B) / heteroatom ≦ 1 It became clear that there was. At the same time, the inventors have found a compound having a novel structure in which the element (B) is introduced at a molar ratio satisfying the element (B) / heteroatom> 1, and a method for producing the compound, and have devised that the above problems can be solved brilliantly.
In addition, as a result of further studies on the heteropolyoxometalate compounds, the present inventors have found that a novel heteropolyoxometalate compound having a structure in which a defect element of a heteropolyoxometalate anion containing a two-deletion structure moiety is substituted with a V element. The present inventors have found a rate compound and a novel heteropolyoxometalate compound in which the heteroatom is phosphorus and have reached the present invention.

That is, the present invention provides a heteropolyoxometalate containing a two-deficient structure site in which the heteroatom is silicon, phosphorus or germanium and the polyatom is at least one element selected from the group consisting of molybdenum, tungsten and vanadium. At least one element (B) selected from Sc, Y, Zr, Hf, V, Nb, Ta, and Cr at the deficient structure site of the anion (A), the molar ratio satisfying the element (B) / heteroatom> 1 It is a heteropolyoxometalate compound that is introduced in

The present invention is also a heteropolyoxometalate compound having a structure in which a polyatom is coordinated via an oxygen atom to a heteroatom, wherein the heteropolyoxometalate compound has a heteroatom of phosphorus or germanium, In addition, the deficient structure site of the heteropolyoxometalate anion (A) containing at least one element selected from the group consisting of molybdenum, tungsten and vanadium is a deficient structure site, and is a forward transition metal It is also a heteropolyoxometalate compound characterized by having a heteropolyoxometalate structure in which V element (B) is introduced.

The present invention also provides a heteropolyoxometalate compound having a structure in which a polyatom is coordinated to an heteroatom via an oxygen atom, the heteropolyoxometalate compound having a heteroatom of phosphorus, and V, which is a transition metal in the preceding period, in the deficient structure site of the heteropolyoxometalate anion (A) containing at least one element selected from the group consisting of molybdenum, tungsten and vanadium, It is also a heteropolyoxometalate compound having a heteropolyoxometalate structure into which at least one element (B) selected from Sc, Y, Zr, Hf, Nb, Ta and Cr is introduced.

Further, the present invention is preferably a heteropolyoxometalate compound wherein the heteropolyoxometalate anion (A) is a γ-type Keggin-type heteropolyoxometalate anion. .

The present invention is a method for producing the heteropolyoxometalate compound, comprising a step of reacting a compound having a heteropolyoxometalate anion (A) with a compound having an element (B). This is also a method for producing a heteropolyoxometalate compound.

The present invention is also a method of using the heteropolyoxometalate compound as a catalyst, wherein the heteropolyoxometalate compound is used as an oxidation reaction catalyst and / or an acid-base reaction catalyst. But there is.

The heteropolyoxometalate compound of the present invention is a heteropolyoxometalate compound having the above-described structure and which could not be synthesized by the conventional production method. (1) Redox property, (2) Electronegativity, (3 Performances that could not be achieved with conventional heteropolyoxometalate compounds in terms of physical properties, properties, structure, catalytic activity, such as :) magnetism, (4) dipole moment, (5) acid basicity, and (6) structure As a result, it can be applied to catalysts for organic reactions such as acid-base reactions using Lewis acidity, which are expressed by the introduction of oxidation reactions and metal elements, and functional materials using unique structures. There is sex.

The heteropolyoxometalate compound of the present invention contains Sc, Y, Zr, Hf, V, Nb, Ta, which are transition metals in the deficient structure site of the heteropolyoxometalate anion (A) containing a deficient structure site. Wherein at least one element (B) selected from Cr is introduced at a molar ratio satisfying the element (B) / heteroatom> 1 (hereinafter referred to as heteropolyoxometalate compound of the first form) .)
The form of the element (B) and the heteropolyoxometalate anion (A) in the heteropolyoxometalate compound of the first aspect of the present invention is as follows. The element (B) is a heteropolyoxometalate anion (A). It will be introduced into the defect site. The term “introduced into the two deficient sites” may be a form in which the element (B) is incorporated into the deficient site, that is, a form in which a desired poly atom is replaced by the element (B), and in particular, the element (B). When the ionic radius of is large, the element (B) may be coordinated without being incorporated into the two-deficient site. Preferably, the element (B) is incorporated into two deficient sites. In this case, it is preferable that the elements (B) are adjacent to each other. The isomers in which the element (B) is adjacent to each other include α, β, γ, δ, ε isomers, etc., but the α, β isomers are isomers sharing a corner, and the γ, δ, ε isomers are It is an isomer with shared ridges. More preferred is a form in which the element (B) is incorporated into the skeleton of the β- and / or γ-type two-deficient Keggin-type polyoxometalate anion, and among these, the γ-type two-deficient Keggin-type poly is most preferred. It is a form incorporated into an oxometalate anion. The heteropolyoxometalate compound may be a monomer or a multimer. A monomer means that one heteropolyoxometalate anion site is contained in the unit structure, and a multimer means that a plurality of heteropolyoxometalate anion sites are contained in the unit structure. The structure of such a heteropolyoxometalate compound is determined or estimated from X-ray crystal structure analysis, elemental analysis, UV or FT-IR spectroscopy, and the like.

The heteropolyoxometalate compound of the first aspect of the present invention generally forms a salt, and the cation source in producing the salt may be an inorganic salt or an organic salt, and among them, acetate, nitrate, halogen Suitable examples include chloride salts, alkali metal salts, alkaline earth salts, proton salts, ammonium salts, and organic ammonium salts. For example, a liquid in which the heteropolyoxometalate anion (A) and the element (B) coexist. The salt is added as a powder or as a solution to produce the heteropolyoxometalate compound. The cation originally possessed by the heteropolyoxometalate anion (A) or the element (B) may be used.

The total content of the element (B) in the heteropolyoxometalate compound of the first aspect of the present invention is preferably more than one for one heteroatom in the compound. More preferably, it is 1.2 or more, and still more preferably 1.5 or more. Moreover, it is preferable that it is 5 or less. More preferably, it is 3 or less, and more preferably 2.5 or less.
The heteropolyoxometalate anion (A) is a heteropolyoxometalate anion having a two-deficient structure site lacking two poly atoms that should be present in the crystal structure, wherein the hetero atom is silicon, phosphorus, or germanium. And at least one poly atom selected from the group consisting of molybdenum, tungsten, and vanadium. Such a heteropolyoxometalate anion (A) has a crystal structure called Keggin type in which 10 polyatoms are coordinated to heteroatoms via oxygen.

The heteropolyoxometalate anion (A) in the heteropolyoxometalate compound of the first aspect of the present invention is preferably a Keggin type heteropolyoxometalate anion represented by the following general formula (1).
General formula (1)
[QM ₁₀ O _j ] ^k- (1)
Here, in General formula (1), Q represents a silicon, phosphorus, or germanium atom which is a hetero atom. M represents a poly atom. j and k are positive numbers, and k is determined by the valences of Q and M. More preferably, it is a Keggin type heteropolyoxometalate anion in which M is tungsten. More preferably, it is a Keggin type heteropolyoxometalate anion in which Q is silicon and M is tungsten.
Further, the Keggin heteropolyoxometalate anion preferably has a β-isomer and / or a γ-isomer structure. More preferably, [β-SiW ₁₀ O ₃₆ ] ⁸⁻ and / or [γ-SiW ₁₀ O ₃₆ ] ⁸⁻ , or [β-GeW ₁₀ O ₃₆ ] ⁸⁻ and / or Q is silicon or germanium. [Γ-GeW ₁₀ O ₃₆ ] ⁸⁻ .
More preferably, _{[γ-SiW 10 O} ^{36] 8-} or _{[γ-GeW 10 O} ^36] is ^8, and most preferably, Q is a silicon _{[γ-SiW 10 O} ^{36] 8-.}

The heteropolyoxometalate anion used in the heteropolyoxometalate compound of the first aspect of the present invention is a two-deficient type, but includes one-deficient or three-deficient types as long as it has the effects of the present invention. Also good.
Examples of counter cations that form salts of heteropolyoxometalate anions include protons, alkali metal cations, alkaline earth cations, zinc ions, lanthanide ions, aluminum ions, indium ions, tin ions, lead ions, and iron ions. Transition metal ions and quaternary ammonium salts (ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tributylmethylammonium salt, trioctylmethylammonium salt, trilaurylmethylammonium salt, Benzyltrimethylammonium salt, benzyltriethylammonium salt, benzyltributylammonium salt, cetylpyridinium salt), quaternary phosphonium salt (tetramethylphosphonate) Umushio, tetraethyl phosphonium salt, tetrabutyl phosphonium salt, tetraphenylphosphonium salt, ethyltriphenylphosphonium salts, and organic cation such as benzyl triphenyl phosphonium salt) are preferred. One kind or two or more kinds of cations can be used.
The element (B) is at least one element selected from Sc, Y, Zr, V, Hf, Nb, Ta, and Cr, and can be appropriately selected depending on the intended use. More preferred are Zr, V, Hf, Nb, and Cr, and still more preferred are Zr, V, and Hf. In addition, when synthesizing a mixture of heteropolyoxometalate compounds into which element (B) is introduced or heteropolyoxometalate compounds into which heterogeneous elements are introduced, two or more elements selected from the above elements (B) are used. May be.

The form used when introducing the element (B) may be a salt form or an oxide form. The salt may be an inorganic salt or an organic salt, but among them, acetate salt, nitrate salt, halide salt, sodium salt, potassium salt, proton salt, ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetra Butyl ammonium salt and the like are preferred. It is also possible to use a complex salt such as a polynuclear complex containing the element (B) to be introduced.
The molar amount of the salt containing the element (B) used in the synthesis is preferably more than 1 mol with respect to 1 mol of the heteropolyoxometalate anion (A). More preferably, it is 1.1 mol or more, More preferably, it is 1.5 mol or more. Moreover, it is preferable that it is 8 mol or less. More preferably, it is 3 mol or less, More preferably, it is 2.5 mol or less.
The heteropolyoxometalate anion (A) and the element (B) containing the two-deficient structure site are introduced in a molar ratio satisfying the element (B) / heteroatom> 1, but have the effects of the present invention. As long as the element (B) / heteroatom ≦ 1, it may be included. The heteropolyoxometalate compound contains at least 10% or more of a compound having a molar ratio satisfying the element (B) / hetero atom> 1, preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. It is a waste.

The present invention is also a heteropolyoxometalate compound having a structure in which a polyatom is coordinated to an heteroatom via an oxygen atom, the heteropolyoxometalate compound having a heteroatom of phosphorus or germanium, In addition, the deficient structure site of the heteropolyoxometalate anion (A) containing at least one element selected from the group consisting of molybdenum, tungsten and vanadium is a deficient structure site, and is a forward transition metal It is also a heteropolyoxometalate compound having a heteropolyoxometalate structure into which element V (B) has been introduced (hereinafter referred to as a second form of heteropolyoxometalate compound).

In the heteropolyoxometalate compound of the second aspect of the present invention, the molar ratio between the V element (B), which is the transition metal of the first period, and the heteroatom (A) is not particularly limited, but the element (B) / heteroatom> It is preferable that the V element is introduced at a molar ratio satisfying the relationship of 1. When the molar ratio is satisfied, a V-disubstituted heteropolyoxometalate compound via an oxygen atom can be realized, and two V elements and a bridging oxygen atom act cooperatively and specifically. It becomes possible.
In this case, the element (B) / heteroatom ≦ 1 may be included as long as it has the effect of the present invention. The heteropolyoxometalate compound preferably contains at least 10% of a molar ratio of the compound satisfying the element (B) / hetero atom> 1. More preferably 30% or more, still more preferably 50% or more. Most preferably, it contains 70% or more.

The form of the element (B) and the heteropolyoxometalate anion (A) in the heteropolyoxometalate compound of the second form is the same as the heteropolyoxometalate compound of the first form described above. Therefore, as long as the element (B) is to be introduced into the two deficient sites of the heteropolyoxometalate anion (A), a form in which the desired poly atom is substituted with the element (B) may be used. The element (B) may be coordinated without incorporating the element (B) into the defect site, but the element (B) is preferably incorporated into the two defect sites. In this case, the element (B) is It is preferable that they are adjacent to each other. More preferably, it is a form in which the element (B) is incorporated into the skeleton of the two-deficient Keggin-type polyoxometalate anion of β-form and / or γ-form, and most preferably the two-deficient Keggin-type polyoxometalate of γ-form. It is a form incorporated in the rate anion.
Further, the heteropolyoxometalate compound may be a monomer or a multimer.

The heteropolyoxometalate anion (A) in the heteropolyoxometalate compound of the second form is preferably a Keggin type heteropolyoxometalate anion represented by the general formula (1). Q in the general formula (1) is preferably germanium. That is, in the heteropolyoxometalate compound of the second form, the heteroatom is preferably germanium. The poly atom M in the general formula (1) is preferably tungsten or molybdenum. More preferably, it is tungsten.
The heteropolyoxometalate compound of the second form is particularly preferably [β-GeW ₁₀ O ₃₆ ] ^8- and / or [γ-GeW ₁₀ O ₃₆ , whose isomer structure is β-form and / or γ-form. ] ^8- . Most preferred is [γ-GeW ₁₀ O ₃₆ ] ⁸⁻ .

A heteropolyoxometalate structure in which the heteroatom is germanium and a V-element (B), which is a transition metal in the preceding period, is introduced into a deficient structure site of a heteropolyoxometalate anion (A) containing a deficient structure site. The heteropolyoxometalate compound has high activity as a catalyst for reactions that have been difficult to achieve in the past, such as alkane oxidation reactions, and can be suitably used as an oxidation reaction catalyst. It will be a thing.
Such an oxidation reaction catalyst which essentially requires the heteropolyoxometalate compound of the second aspect of the present invention, in which the hetero atom is germanium, is also one aspect of the present invention.

For the type of counter cation serving as a cation source in the heteropolyoxometalate compound of the second form of the present invention, the total content of element (B) in the heteropolyoxometalate compound, and the form and synthesis when element (B) is introduced The molar amount of the salt containing the element (B) used is the same as that of the heteropolyoxometalate compound of the first form described above.

The present invention also provides a heteropolyoxometalate compound having a structure in which a polyatom is coordinated to a heteroatom via an oxygen atom, the heteropolyoxometalate compound having a heteroatom of phosphorus, and V, which is a transition metal in the preceding period, in the deficient structure site of the heteropolyoxometalate anion (A) containing at least one element selected from the group consisting of molybdenum, tungsten and vanadium, It is also a heteropolyoxometalate compound having a heteropolyoxometalate structure into which at least one element (B) selected from Sc, Y, Zr, Hf, Nb, Ta and Cr is introduced (hereinafter referred to as a third form of heteropolyoxometalate compound). This is referred to as an oxometalate compound.)

In the heteropolyoxometalate compound of the third aspect of the present invention, the molar ratio between the element (B) which is the transition metal of the first period and the heteroatom (A) is not particularly limited, but the element (B) / heteroatom> 1 It is preferable that the element (B) is introduced at a molar ratio satisfying the above relationship. When such a molar ratio is satisfied, an element (B) disubstituted heteropolyoxometalate compound via an oxygen atom can be realized, and the two elements (B) and the bridging oxygen atom are cooperative and It becomes possible to act specifically.
In this case, the element (B) / heteroatom ≦ 1 may be included as long as it has the effect of the present invention. The heteropolyoxometalate compound preferably contains at least 10% of a molar ratio of the compound satisfying the element (B) / hetero atom> 1. More preferably, it is 30% or more, More preferably, it is 50% or more. Most preferably, it contains 70% or more.

In the heteropolyoxometalate compound of the third form, the element (B) is preferably at least one element selected from V, Zr, Hf, Nb, Ta and Cr. More preferred are V, Zr, Nb and Cr. More preferably, it is V.
The total content of the element (B) in the heteropolyoxometalate compound, the form used when the element (B) is introduced, and the molar amount of the salt containing the element (B) used in the synthesis are as described above. It is the same as the heteropolyoxometalate compound of the form.
Moreover, the kind of the counter cation used as the cation source in the heteropolyoxometalate compound of the third form is the same as that of the heteropolyoxometalate compound of the first form described above.

The form of the element (B) and the heteropolyoxometalate anion (A) in the heteropolyoxometalate compound of the third form is the same as the heteropolyoxometalate compound of the first form described above. Therefore, as long as the element (B) is to be introduced into the two deficient sites of the heteropolyoxometalate anion (A), a form in which the desired poly atom is substituted with the element (B) may be used. The element (B) may be coordinated without incorporating the element (B) into the defect site, but the element (B) is preferably incorporated into the two defect sites. In this case, the element (B) is It is preferable that they are adjacent to each other. More preferably, it is a form in which the element (B) is incorporated into the skeleton of the two-deficient Keggin-type polyoxometalate anion of β-form and / or γ-form, and most preferably the two-deficient Keggin-type polyoxometalate of γ-form. It is a form incorporated in the rate anion.

The heteropolyoxometalate anion (A) in the heteropolyoxometalate compound of the third form is preferably a Keggin type heteropolyoxometalate anion represented by the general formula (1). In this case, Q in the general formula (1) is phosphorus. The poly atom M in the general formula (1) is preferably tungsten or molybdenum. More preferably, it is tungsten.
The heteropolyoxometalate compound of the third form is particularly preferably [β-PW ₁₀ O ₃₆ ] ^7- and / or [γ-PW ₁₀ O ₃₆ whose isomer structure is β-form and / or γ-form. ] ^7- . Most preferred is [γ-PW ₁₀ O ₃₆ ] ^7- .

In the heteropolyoxometalate compounds of the first, second and third aspects of the present invention, the counter cation with respect to the heteropolyoxometalate anion (A) is preferably a cation of an alkyl ammonium salt. The alkyl ammonium salt is preferably one having 4 to 48 carbon atoms. More preferably, it is 4-40.
Examples of alkylammonium salts include tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tributylmethylammonium salt, trioctylmethylammonium salt, trilaurylmethylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt Salt, benzyltributylammonium salt, cetylpyridinium salt and the like. Among these, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tributylmethylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, and benzyltributylammonium salt are preferable. More preferred are tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, tributylmethylammonium salt, and benzyltriethylammonium salt.

In the heteropolyoxometalate compound of the third form, when a cation of an alkylammonium salt is used as a counter cation, unlike a conventional phosphorus-centered polyoxometalate compound that decomposes with hydrogen peroxide, it does not decompose with hydrogen peroxide. A stable phosphorus-centered polyoxometalate compound is obtained. Further, since the compound can be dissolved in an organic solvent, the compound can be suitably used as a catalyst exhibiting high activity in an oxidation reaction such as an epoxidation reaction. Furthermore, even when it is not dissolved in an organic solvent, it can be suitably used as a catalyst exhibiting high activity in an oxidation reaction such as an epoxidation reaction without being decomposed as a heterogeneous catalyst. When a heterogeneous catalyst is used using a cation of an earth metal salt, its activity is very different from that of a very low activity. This is thought to be because the heteropolyoxometalate compound using a cation of an alkylammonium salt forms a channel structure, the surface area is dramatically improved, and a substrate, a solvent, or the like can enter into the channel structure. It can be confirmed by line crystal structure analysis or the like. In addition, [(C ₄ H ₉ ) ₄ N] ₄ [γ-SiW ₁₂ O ₄₀ ] etc., which are inert to the reaction, can coexist in the system for the purpose of constructing and maintaining the channel structure.
Such a catalyst for an oxidation reaction which essentially comprises the heteropolyoxometalate compound of the third form, wherein the counter cation is a cation of an alkylammonium salt, is also one aspect of the present invention.
Hereinafter, the heteropolyoxometalate compounds of the first, second, and third aspects of the present invention are collectively referred to as the heteropolyoxometalate compound of the present invention.

In the method for producing a heteropolyoxometalate compound of the present invention, when the element (B) is introduced into the heteropolyoxometalate anion (A), the pH of the liquid in which (A) and (B) coexist is adjusted. It includes a step of setting to 0.1 to 7.5, and further includes a step of allowing (A) and (B) to coexist in a liquid for 7 minutes or more. If it does not coexist for 7 minutes or more, the element (B) may not be completely introduced into the defect site of the heteropolyoxometalate anion (A).
The addition of the element (B) is performed by adding the salt or compound of the element (B) as a powder or as a solution to the solution or mixed solution containing the heteropolyoxometalate anion (A). However, it may be added at the same time as (A) or may be carried out in the state of being dissolved in a solvent first. The element (B) salt or compound may be added all at once or gradually. The production of the heteropolyoxometalate compound may be carried out in one step or in several steps. For example, a method may be used in which a product is once taken out while leaving a part of a predetermined amount of (B), the product is redissolved in a solvent, and then the remaining (B) is added.

As pH, the range of 0.1-7.5 is good, Preferably it is 0.15-6.0, More preferably, it is 0.2-3.5, More preferably, it is 0.25- 2.9. The setting of the pH is one of the important factors that determine the structure of the heteropolyoxometalate compound, and may be appropriately selected within the above range depending on the type of the element (B). When pH changes with the addition of the element (B), it can be appropriately set to an optimum value with an acid or a base.

Although it does not specifically limit as a solvent used at the time of heteropolyoxometalate compound manufacture, Water, a water-containing organic solvent, and an organic solvent can be used. The organic solvent may be either soluble or insoluble in water, but acetone, acetonitrile, methanol, ethanol, propanol, t-butanol, chloroform and the like are suitable. More preferably, it is water.

The volume of the solvent is preferably 0.5 mL or more with respect to 1 mmol of the heteropolyoxometalate anion (A). More preferably, it is 1 mL or more, More preferably, it is 1.5 mL or more. Moreover, it is preferable that it is 300 mL or less. More preferably, it is 200 mL or less, More preferably, it is 180 mL or less.
The liquid temperature of the solvent is preferably 0 ° C. or higher and 120 ° C. or lower. More preferably, it is 5 degreeC or more and 75 degrees C or less, More preferably, it is 10 degreeC or more and 50 degrees C or less.
The introduction of the two types of the element (B) into the heteropolyoxometalate anion (A) causes the (A) and the (B) to coexist for 7 minutes or longer. More preferably, it is 10 minutes or more, More preferably, it is 20 minutes or more. Also, it is preferably within 48 hours. More preferably, it is within 24 hours. Coexisting for 7 minutes or more means a time for coexisting with the element (B) mainly in a homogeneous solution when 0.34 mmol of the heteropolyoxometalate anion (A) is used. When the salt or compound containing the element (B) is completely added to the solution or mixture containing the anion (A), the heteropolyoxometalate compound is added by addition of the inorganic salt or organic salt. It refers to the time between deposition. Depending on the number of millimoles of the heteropolyoxometalate anion (A) used (0.34 x n millimoles) (n is a positive number), for example, when coexisting for 14 minutes when using 0.68 millimoles, the coexistence time is appropriately multiplied by n Is more preferable. If precipitation of impurities or the like occurs during coexistence, it can be removed as necessary. The setting of the coexistence time is one of the important elements for determining the structure of the heteropolyoxometalate compound, and may be appropriately selected within the above range depending on the type of the element (B). Heteropolyoxometalate compounds can be purified by recrystallization or the like. However, this is not the case when the element (B) is V, and it may be present for 7 minutes or more regardless of the number of millimoles of the heteropolyoxometalate anion (A) used.

When the heteropolyoxometalate compound of the present invention is used, for example, as a catalyst, it can be used in any reaction field such as a gas phase, a liquid phase, and a supercritical phase. As a usage form, when used in a gas phase reaction, a form in which the reaction is carried out with the catalyst itself as a solid or a form in which the reaction is carried by supporting the catalyst on a carrier is possible. As the catalyst carrier, carriers generally used for gas-solid reactions such as various ion exchange resins, silica, alumina, titania, sirconia, tin oxide and other oxides can be used.

When the catalyst itself is used as a solid, when the heteropolyoxometalate compound of the first or second form described above is used, preferred counter cations are proton, potassium ion, sodium ion, cesium ion, magnesium ion, calcium. Ion, barium ion, zinc ion, aluminum ion, lanthanide ion, iron ion, tin ion, copper ion, palladium ion, platinum ion, cobalt ion, nickel ion, titanium ion, zirconium ion, vanadium ion, niobium ion, chromium ion, Manganese ion, ruthenium ion, rhodium ion, iridium ion, indium ion, and alkylammonium ion. When the heteropolyoxometalate compound of the third form described above is used, it is preferable to use an alkylammonium ion as a counter cation.

When used in a liquid phase reaction, a form in which the catalyst is dissolved and reacted in a homogeneous system, and a form in which the reaction is carried out by suspending the catalyst in the liquid phase without dissolving it in the solvent are mentioned. It is also possible to carry out the reaction using the catalyst as a solid phase. At this time, by changing the counter cation, the catalyst itself can be used as a solid, and the catalyst and the product after the reaction can be easily separated.

Further, the catalyst can be used as a solid phase by supporting the catalyst on a carrier. As the catalyst carrier, carriers generally used for heterogeneous reactions such as various ion exchange resins, silica, alumina, titania, zirconia, tin oxide and other oxides can be used. In carrying out the reaction in a homogeneous system and / or a heterogeneous system, preferred counter cations are protons, ammonium ions, potassium ions, sodium ions when the heteropolyoxometalate compound of the first or second form described above is used. , Cesium ion, magnesium ion, calcium ion, barium ion, zinc ion, aluminum ion, lanthanide ion, iron ion, tin ion, copper ion, palladium ion, platinum ion, cobalt ion, nickel ion, titanium ion, zirconium ion, vanadium Ion, niobium ion, chromium ion, manganese ion, ruthenium ion, rhodium ion, iridium ion, indium ion, tetrabutylammonium salt, tetraoctylammonium salt, trioctyl Ammonium salts, cetyl trimethyl ammonium salts, methyl tri cetyl ammonium salt, an ion of the alkyl ammonium salts such as cetyl pyridinium salts, can be used one kind or two or more kinds. When the heteropolyoxometalate compound of the third form described above is used, alkylammonium such as tetrabutylammonium salt, tetraoctylammonium salt, trioctylammonium salt, cetyltrimethylammonium salt, methyltricetylammonium salt, etc. as a counter cation It is preferred to use salt ions.

The heteropolyoxometalate compound of the present invention can be applied as a catalyst for organic reactions such as various oxidation reactions and acid-base reactions, and is particularly suitable for conducting oxidation reactions and acid-base reactions in the liquid phase. It can be applied to.

Specific examples of the oxidation reaction are not particularly limited. For example, (1) oxidation of unsaturated bond (oxidation of unsaturated double bond or unsaturated triple bond of alkene or alkyne), (2) oxidation of hydroxyl group, ( 3) Oxidation of hetero atoms (oxidation of sulfur atoms, nitrogen atoms, etc.), (4) Oxidation of saturated hydrocarbon sites, (5) Oxidation of aromatic rings, (6) Oxidation cups other than these (1) to (5) Examples thereof include an oxidation reaction such as a ring reaction. By such an oxidation reaction, the oxidizable functional group is oxidized, and an oxidized organic compound is produced.

Among the above-described heteropolyoxometalate compounds of the present invention, the heteropolyoxometalate compound is suitable as an oxidation catalyst for unsaturated bonds in the liquid phase and saturated hydrocarbon moieties. Hereinafter, a reaction substrate, an oxidizing agent, manufacturing conditions, and the like in the case of producing an oxygen-containing organic compound by oxidizing with an oxidizing agent using the catalyst as a preferred embodiment of the present invention will be described.

The reaction substrate used in the present invention may be acyclic or a cyclic organic compound. Specifically, methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, Alkanes such as decane, undecane, dodecane, tridecane, tetradecane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, adamantane; propylene, 1-butene, 1-hexene, 1-pentene, Isoprene, diisobutylene, 1-heptene, 1-octene, 1-nonene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1 -Eicosene, propylene Trimers and tetramers, alkenes having an ethylenic double bond at the terminal, such as 1,3-butadiene; 2-butene, 2-octene, 2-methyl-1-hexene, 2,3-dimethyl-2-butene, etc. Alkenes having an ethylenic double bond inside the molecule; cyclopentene, cyclohexene, 1-phenyl-1-cyclohexene, 1-methyl-1-cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclodecatriene, cyclooctadiene, Cyclic alkenes such as dicyclopentadiene, methylenecyclopropane, methylenecyclopentane, methylenecyclohexane, vinylcyclohexane, norbornene; toluene, ethyltoluene, diethyltoluene, ethylbenzene, diethylbenzene, isopropylbenzene Zen, isopropylethylbenzene, diisopropylbenzene, propylbenzene, 4,4′-dimethylbiphenyl, 4-t-butyl-1-methylbenzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene , 1,2,4,5-tetramethylbenzene and other aromatic compounds having side chains; benzene and the like.

Among these, methane, ethane, propane, butane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, cyclooctane, adamantane, C3-C12 alkene, ethylbenzene, isopropylbenzene, toluene, o-xylene , P-xylene and benzene are preferred. One type or two or more types of substrates can be used.

The reaction substrate may also be a functional group such as, for example, —CHO, —COOH, —CN, —COOR, —OR (where R represents a hydrogen, alkyl, cycloalkyl, aryl, or allylalkyl substituent), or an aryl group. An allylalkyl group, a halogen group, a nitro group, a sulfonic acid group, a carbonyl group, a hydroxyl group, and the like.

Examples of such compounds include allyl methyl ether, allyl vinyl ether, diallyl ether, o-toluic acid, m-toluic acid, p-toluic acid, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, o -Cresol, m-cresol, p-cresol, 2,4-dimethylbenzaldehyde, allyl alcohol, homoallyl alcohol, cinnamon alcohol, crotyl alcohol, pentenol, hexenol, cyclohexenol, heptenol, octenol, acrolein, cinnamic aldehyde, Examples include crotyl aldehyde, pentenal, hexenal, octenal and the like.

As the oxidizing agent in the oxidation reaction, for example, those capable of generating oxygen ions, oxygen radicals, peroxides and superperoxides can be used, for example, molecular oxygen, hydrogen peroxide, cumene hydroperoxide, t-butyl. Examples thereof include organic peroxides such as hydroperoxide and peracetic acid, a mixed gas of oxygen and hydrogen, a mixed gas of oxygen, hydrogen and nitrogen, dinitrogen monoxide, and iodosylbenzene. Among these, molecular oxygen and hydrogen peroxide are preferable.

When molecular oxygen is used as the oxidizing agent, the oxygen pressure is preferably 0.0001 atm or more and 150 atm or less. More preferably, it is 0.01 atm or more and 50 atm or less. When hydrogen peroxide is used as an oxidizing agent, a practical use form of hydrogen peroxide is preferably an aqueous solution of 0.01 to 70% by mass or a solution of alcohols. Can also be used. The amount used is preferably such that the molar ratio of the reaction substrate to hydrogen peroxide (number of moles of reaction substrate / number of moles of hydrogen peroxide) is 1000/1 or less, more preferably 100/1 or less. is there. Moreover, it is preferable to set it as 1/1000 or more, More preferably, it is 1/500 or more.

The amount of the heteropolyoxometalate catalyst used is preferably 0.000000001 mol or more, and preferably 10,000 mol or less, per 1 mol of the reaction substrate. More preferably, it is 0.0000001 mol or more and 5000 mol or less. Moreover, as a kind of catalyst, it can use 1 type or 2 types or more.

As the reaction method, it is preferable to carry out the reaction by bringing an oxidation reaction catalyst into contact with the reaction substrate and the oxidizing agent. The oxidation reaction catalyst of the present invention can be used for any reaction method of gas phase reaction or liquid phase reaction, but the reaction is carried out in the liquid phase by dissolving the substrate and the oxidizing agent in a solvent. Is more preferable in terms of reaction activity.

When performing the said reaction in a liquid phase, as a solvent to be used, it is water and / or an organic solvent, and can use 1 type, or 2 or more types as an organic solvent. Examples of such an organic solvent include primary, secondary, and tertiary monohydric alcohols having 1 to 6 carbon atoms such as methanol, ethanol, normal or isopropanol, and tertiary butanol, ethylene glycol, propylene glycol, and glycerin. Polyhydric alcohols, ethylene oxides such as diethylene glycol and triethylene glycol, oligomers with ring-opened propylene oxide, ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetyl acetone , Nitrogen compounds such as dimethylformamide, nitromethane, acetonitrile and benzonitrile, phosphorus compounds such as phosphate esters such as triethyl phosphate and diethylhexyl phosphate, Holm, halogenated hydrocarbons such as dichloromethane, n-hexane, aliphatic hydrocarbons n-heptane, toluene, xylene and like aromatic hydrocarbons, cyclohexane, alicyclic hydrocarbons such as cyclopentane and the like.

Among the above solvents, it is preferable to use water, alcohols having 1 to 6 carbon atoms, dichloromethane, heptane, acetonitrile, benzonitrile, dimethyl sulfoxide, dimethylformamide, nitromethane, toluene, xylene, cyclohexane, or a mixture thereof. In addition, when the reaction substrate compound is a liquid under the reaction conditions, it is possible to perform the reaction neat without using the solvent.

The reaction system in the above reaction is preferably neutral to acidic, and an acidic substance may be added to the reaction system. Examples of the acidic substance include Bronsted acid, Lewis acid and the like, and one kind or two or more kinds can be used. Examples of Bronsted acids include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid, and organic acids such as acetic acid, benzoic acid, formic acid, and trifluoromethanesulfonic acid, and inorganic materials such as zeolites and mixed oxides. Acids are preferred, and Lewis acid is preferably aluminum chloride, ferric chloride, boron chloride compounds, stannic chloride, antimony fluoride, zinc chloride, titanium compounds, zeolites, mixed oxides, and the like. Furthermore, inorganic and organic acid salts can also be used.

When water is present in the reaction system in the above reaction, a phase transfer catalyst or a surfactant can coexist depending on the case. It is also possible to carry out the reaction under light irradiation.

As the reaction conditions in the above reaction, for example, in the case of a liquid phase reaction, the reaction temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher. Moreover, 250 degrees C or less is preferable, More preferably, it is 180 degrees C or less. The reaction time is preferably several minutes or longer, and is preferably within 150 hours. More preferably, it is within 48 hours. The reaction pressure is preferably normal pressure or higher, and is preferably 150 atm or lower. More preferably, it is 50 atm or less. The reaction can also be performed under reduced pressure. In the case of a gas phase reaction, 100 ° C. or higher is preferable, and 150 ° C. or higher is more preferable. Moreover, 600 degrees C or less is preferable, More preferably, it is 500 degrees C or less. The reaction time is preferably several minutes or longer, and is preferably within 1000 hours. More preferably, it is within 800 hours. The reaction pressure is preferably normal pressure or higher, and is preferably 150 atm or lower. More preferably, it is 100 atm or less.

In the above reaction, by using the heteropolyoxometalate compound of the present invention as a catalyst, an oxygen-containing organic compound can be produced, and these compounds are useful compounds as intermediates and raw materials used in the production of various industrial products. It can apply suitably as a manufacturing method for supplying.

Specific examples of the acid-base reaction are not particularly limited. For example, (1) esterification reaction, (2) carbon skeleton isomerization reaction, (3) polymerization reaction, (4) addition reaction, and (5) ring-opening reaction. (6) elimination reaction (7) acetalization reaction (8) ketalization reaction (9) aromatic electrophilic substitution reaction (10) aromatic nucleophilic substitution reaction (11) aldol reaction (12) pinacol transfer reaction (13 ) Beckmann rearrangement reaction (14) Cannizzaro reaction (15) Claisen condensation reaction (16) Darzens condensation reaction (17) Diels-Alder reaction (18) Friedel-Crafts reaction (19) Friesch rearrangement reaction (20) Guttermann-Koch reaction (21) ) Mannich reaction (22) Michael reaction (23) Prince reaction (24) Glycosylation reaction (25) Solvolysis reaction (26) 1,3-dipolar cycloaddition reaction 27) ene reaction or carbonyl - ene reaction (28) (1) to (27) acid-base reaction or the like other than the like. By such an acid-base reaction, it is possible to produce an organic compound in which a functional group or a skeleton is newly constructed.

The heteropolyoxometalate compounds of the present invention are particularly suitable as acid-base catalysts for sigmatropy reactions such as ene reactions of unsaturated bonds and carbonyl-ene reactions in the liquid phase. Hereinafter, a reaction substrate, production conditions, and the like in the case of performing the reaction using the catalyst as a preferred embodiment of the present invention will be described.

The reaction substrate used in the present invention may be acyclic or a cyclic organic compound, and may cause an intermolecular reaction or an intramolecular reaction. Specific examples include alkenes having an ethylenic double bond or an acetylenic triple bond, carbonyl group-containing compounds, and compounds having both functional groups. Among these, C3-C24 alkene, formaldehyde, carbon monoxide, citronellals, etc. are mentioned.

The amount of the heteropolyoxometalate catalyst used is preferably 0.000000001 mol or more, and preferably 10,000 mol or less, per 1 mol of the reaction substrate. More preferably, it is 0.0000001 mol or more and 5000 mol or less. Moreover, as a kind of catalyst, it can use 1 type or 2 types or more.

As the above reaction method, the acid-base reaction catalyst of the present invention can be used in any of the gas phase reaction and liquid phase reaction, but the reaction is preferably carried out in the liquid phase.
When the reaction is carried out in the liquid phase, one or two or more kinds of solvents can be used. For example, methanol, ethanol, normal or isopropanol, tertiary butanol and the like having 1 to 6 carbon atoms, Secondary and tertiary monohydric alcohols, polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, ethylene oxides such as diethylene glycol and triethylene glycol, oligomers with ring-opened propylene oxide, ethyl ether, isopropyl ether, dioxane, tetrahydrofuran, etc. Ethers, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, nitrogen compounds such as dimethylformamide, nitromethane, acetonitrile, benzonitrile, triethyl phosphate, phosphorus Phosphorus compounds such as phosphate esters such as diethylhexyl, halogenated hydrocarbons such as chloroform and dichloromethane, aliphatic hydrocarbons such as normal hexane and normal heptane, aromatic hydrocarbons such as toluene and xylene, cyclohexane, cyclopentane, etc. An alicyclic hydrocarbon etc. are mentioned.

Among the above solvents, it is preferable to use dichloromethane, chloroform, hexane, heptane, acetonitrile, benzonitrile, dimethyl sulfoxide, dimethylformamide, nitromethane, toluene, xylene, cyclohexane, or a mixture thereof. In addition, when the reaction substrate compound is a liquid under the reaction conditions, it is possible to perform the reaction neat without using the solvent.

As the reaction conditions in the above reaction, for example, in the case of a liquid phase reaction, the reaction temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher. Moreover, 250 degrees C or less is preferable, More preferably, it is 180 degrees C or less. The reaction time is preferably several minutes or longer, and is preferably within 150 hours. More preferably, it is within 48 hours. The reaction atmosphere is not particularly limited, but an atmosphere of air, oxygen, nitrogen, argon or the like is preferable. The reaction pressure is preferably normal pressure or higher, and is preferably 150 atm or lower. More preferably, it is 50 atm or less. The reaction can also be performed under reduced pressure. In the case of a gas phase reaction, 100 ° C. or higher is preferable, and 150 ° C. or higher is more preferable. Moreover, 600 degrees C or less is preferable, More preferably, it is 500 degrees C or less. The reaction time is preferably several minutes or longer, and is preferably within 1000 hours. More preferably, it is within 800 hours. The reaction pressure is preferably normal pressure or higher, and is preferably 150 atm or lower. More preferably, it is 100 atm or less.

In the above reaction, by using the heteropolyoxometalate compound of the present invention as a catalyst, an oxygen-containing organic compound or the like can be produced, and these are compounds useful as intermediates and raw materials used in the production of various industrial products. It can apply suitably as a manufacturing method for supplying a compound.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited only to these Examples. For the measurement of pH, a HORIBA pH meter F-22 and a HORIBA electrode 6366-10D were used. The pH is a value when the liquid temperature is 25 ° C. when water or a water-containing organic solvent is used as a solvent, and when the organic solvent is used as a solvent, the heteropolyoxometalate anion (A) This is a value when the temperature of a liquid obtained by adding 1 mL of water to a prepared organic solvent in which 1 mmol is present is 25 ° C. For X-ray crystal structure analysis, SHELXH-97 was used. JASCO FT / IR-460 was used for IR measurement, RIGAKU AFC-10 Saturn 70 CCD Detector was used for X-ray measurement, and SHIMADZU gas chromatograph GC-2014 was used for yield measurement. Silicon center two-deficient Keggin type polyoxometalate K ₈ [γ-SiW ₁₀ O ₃₆ ] · 12H ₂ O, phosphorus center two-deficient Keggin type polyoxometalate Cs ₅ [γ-HPV ₂ W ₁₀ O ₄₀ ]. 6H ₂ O, silicon-centered-deficient Keggin-type polyoxometalate [(C ₄ H ₉ ) ₄ N] ₄ [γ-SiW ₁₂ O ₄₀ ] was synthesized according to the following literature.
A. Tze, G.M. Herve, “Inorg. Synth.” (USA), 1990, 27, p. 85.
Germanium-centered two-deficient Keggin-type polyoxometalate K ₈ [γ-GeW ₁₀ O ₃₆ ] · 6H ₂ O was synthesized according to the following literature.
N. H. NSouli, B.M. S. Bassil, M.M. H. Dickman, U.D. Kortz, B.M. Keita, L .; Nadjo, “Inorg. Chem.” (USA), 2006, 45, p. 3858.
[(C ₄ H ₉ ) ₄ N] ₄ [H ₂ SiV ₂ W ₁₀ O ₄₀ ] · H ₂ O was synthesized according to the following literature.
Y. Nakagawa, K .; Kamata, M .; Kotani, K .; Yamaguchi, N .; Mizuno, “Angevant. Chem. Int. Ed.” (Germany), 2005, vol. 44, p. 5136.
“%” Means “mol%” unless otherwise specified.

Example 1 Synthesis of H ₁₂ O _46.5 Cs _4.5 SiW ₁₀ Zr ₂ K ₈ [γ-SiW ₁₀ O ₃₆ ] .12H ₂ O 1.0 g (0.34 mmol) was added to 15 mL of water. A solution prepared by dissolving 0.23 g (0.67 mmol) of ZrCl2O.8H2O in 5 mL of water was added thereto, followed by stirring at 25 ° C. for 30 minutes. The pH of the solution at this time was 2.3. After removing the insoluble matter, 0.56 g (3.3 mmol) of CsCl was added, stirred for 30 minutes, and suction filtered to collect the precipitate. Yield: 0.50g. The results of X-ray crystal structure analysis are shown in FIG.

Example 2 Synthesis of H ₁₂ O _46.5 Cs _4.5 SiW ₁₀ Hf ₂ 1.0 g (0.34 mmol) of K ₈ [γ-SiW ₁₀ O ₃₆ ] .12H ₂ O was added to 15 mL of water. A solution prepared by dissolving 0.26 g (0.67 mmol) of HfCl2O.8H2O in 5 mL of water was added thereto, followed by stirring at 25 ° C. for 30 minutes. The pH of the solution at this time was 2.6. After removing the insoluble matter, 0.56 g (3.3 mmol) of CsCl was added, stirred for 30 minutes, and suction filtered to collect the precipitate. Yield: 0.50g. The results of X-ray crystal structure analysis are shown in FIG. 2 and Tables 3-4.

And (Comparative Example _{1) H 4 O 39 SiW 10} Cs 5 Zr synthetic _{K 8 [γ-SiW 10 O} 36] · 12H 2 O 1.0g of (0.34 mmol) was added to the water 15 mL. A solution prepared by dissolving 0.23 g (0.67 mmol) of ZrCl2O.8H2O in 5 mL of water was added thereto, followed by stirring at 25 ° C. for 2-3 minutes. The pH of the solution at this time was 2.3. 0.56 g (3.3 mmol) of CsCl was added and stirred for 20 minutes, followed by suction filtration to collect a precipitate. Yield: 0.89g. FT-IR analysis results: (KBr) / cm ⁻¹ : 3441, 1624, 1032, 999, 950, 919, 892, 868, 800, 736, 633, 570, 540, 484, 383, 362, 321, 290. The results of X-ray crystal structure analysis are shown in FIG. 3 and Tables 5-6.

Comparative Example 2 Synthesis of H ₁₁ O ₄₃ Cs ₅ SiW ₁₀ Hf K ₈ [γ-SiW ₁₀ O ₃₆ ] .12H ₂ O 1.0 g (0.34 mmol) was added to 15 mL of water. A solution prepared by dissolving 0.26 g (0.67 mmol) of HfCl 2 O.8H 2 O in 5 mL of water was added thereto, and the mixture was stirred at 25 ° C. for 2 to 3 minutes. The pH of the solution at this time was 2.6. 0.56 g (3.3 mmol) of CsCl was added, stirred for 30 minutes, and suction filtered to collect the precipitate. Yield: 0.62g. FT-IR analysis results: (KBr) / cm ⁻¹ : 3441, 1623, 1027, 999, 952, 915, 899, 871, 801, 737, 633, 563, 542, 485, 399, 381, 362, 325. The results of X-ray crystal structure analysis are shown in FIG. 4 and Tables 7-8.

Example 3 Synthesis of [(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ GeV ₂ W ₁₀ O ₄₀ ] · 2H ₂ O K ₈ [γ-GeW ₁₀ O ₃₆ ] · 6H ₂ O 15 g ( 5.1 mmol) was quickly dissolved in 53 mL of 1M aqueous HCl. 0.5 M NaVO ₃ aqueous solution (20.3 mL, 10.2 mmol) was added thereto, and the mixture was stirred at 25 ° C. for 7 minutes. The pH of the solution at this time was 0.4. After removing insolubles, 7.5 g (62 mmol) of RbCl was added. The precipitate was collected by suction filtration and washed with cold water (10 mL). Yield: 8.3g. The obtained compound (4.0 g) was dissolved in 250 mL of 0.05 M aqueous HCl, and 3.75 g (11.6 mmol) of tetrabutylammonium bromide was added and stirred for 30 minutes. The yellow precipitate was collected by suction filtration, reprecipitated with an acetonitrile (50 mL) / water (1 L) solution, recrystallized with acetone (250 mL), and dried under reduced pressure. Yield: 2.45g. ⁵¹ V-NMR analysis _{(CD 3 CN): - 545ppm} . ¹ H-NMR analysis result (CD ₃ CN): 5.02 (2H), 3,14 (32H), 1.63 (32H), 1.39 (32H), 0.98 (48H) ppm. Elemental analysis :( calc) Ge: 1.98, V: 2.78 , W: 50.2 ( measured value) Ge: 1.94, V: 2.75 , W: 49.7, H 2 O : 0.98.

Example 4 Synthesis of [(CH ₃ ) ₄ N] ₅ [γ-H ₂ GeV ₂ W ₁₀ O ₄₀ ] K ₈ [γ-GeW ₁₀ O ₃₆ ] · 6H ₂ O 3.0 g (1.0 mmol) Was quickly dissolved in 10.5 mL of 1 M aqueous HCl. A 0.5 M NaVO ₃ aqueous solution (4.05 mL, 2.03 mmol) was added thereto, and the mixture was stirred at 25 ° C. for 7 minutes. The pH of the solution at this time was 0.4. After removing insoluble matter, 1.5 g (12 mmol) of RbCl was added, and suction filtration was performed to collect a precipitate. Yield: 1.2g. The obtained compound (1.0 g) was dissolved in 30 mL of a 0.1 M HCl aqueous solution, 1.0 g (6.5 mmol) of tetramethylammonium bromide was added, and the mixture was stirred for 30 minutes. The yellow precipitate was collected by suction filtration and washed with a small amount of cold water. This compound (20 mg) was dissolved in nitromethane (2.0 mL), 1,4-dioxane (3.0 mL) was slowly added thereto, and the mixture was allowed to stand for 7 days to obtain a single crystal. ⁵¹ V-NMR analysis _{(CD 3 CN): - 546ppm} . CSI-MS analysis result (MeCN): m / z 3024 {[(CH ₃ ) ₄ N] ₅ [γ-H ₂ GeV ₂ W ₁₀ O ₄₀ ]} ⁺ . The results of X-ray crystal structure analysis are shown in FIG. 5 and Tables 9-10.

(Example 5)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ GeV ₂ W ₁₀ O ₄₀ ] · 2H ₂ O (5.0 μmol) was dissolved in MeCN / t-BuOH = 0.8 mL / 1.2 mL, Cyclohexane (1 mL, 9.3 mmol) and a 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, and the mixture was stirred at 60 ° C. for 30 minutes. Yields (based on hydrogen peroxide) were cyclohexanol (89%) and cyclohexanone (2.8%).

(Example 6)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ GeV ₂ W ₁₀ O ₄₀ ] · 2H ₂ O (0.50 μmol) was dissolved in MeCN / t-BuOH = 1.25 mL / 0.75 mL, Cyclohexane (1 mL, 9.3 mmol) and a 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, and the mixture was stirred at 60 ° C. for 30 minutes. Yields (based on hydrogen peroxide) were cyclohexanol (49%) and cyclohexanone (2.0%).

(Example 7)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ GeV ₂ W ₁₀ O ₄₀ ] · 2H ₂ O (0.50 μmol) was dissolved in MeCN / t-BuOH = 1.0 mL / 1.0 mL, Cyclohexane (1 mL, 9.3 mmol) and 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, and the mixture was stirred at 40 ° C. for 6 hours. Yields (based on hydrogen peroxide) were cyclohexanol (73%) and cyclohexanone (2.0%).

(Example 8)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ GeV ₂ W ₁₀ O ₄₀ ] · 2H ₂ O (5.0 μmol) was dissolved in MeCN / t-BuOH = 0.8 mL / 1.2 mL, Adamantane (0.37 mmol) and 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto and stirred at 60 ° C. for 1 hour. Yield (based on hydrogen peroxide) is 1-adamantanol (82%), 2-adamantanol (13%), 2-adamantanone (1.0%), 1,3-adamantanediol (3.0%) Met.

Example 9
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ GeV ₂ W ₁₀ O ₄₀ ] · 2H ₂ O (5.0 μmol) was dissolved in MeCN / t-BuOH = 0.8 mL / 1.2 mL, 1-octane (6.2 mmol) and 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, and the mixture was stirred at 60 ° C. for 3 hours. Yields (based on hydrogen peroxide) are 1-octanol (2.0%), 2-octanol (54%), 3-octanol (22%), 4-octanol (18%), 1-octanol (4.0). %)Met.

(Example 10)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ GeV ₂ W ₁₀ O ₄₀ ] · 2H ₂ O (5.0 μmol) is dissolved in MeCN / t-BuOH = 1.5 mL / 1.5 mL, 7-octen-1-ol (0.10 mmol) and a 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, followed by stirring at 20 ° C. for 24 hours. The yield of the epoxy compound (based on hydrogen peroxide) was 85%. At this time, the hydroxyl group was not oxidized, and the selectivity of the epoxy compound was 100%.

(Comparative Example 3)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ SiV ₂ W ₁₀ O ₄₀ ] · H ₂ O (5.0 μmol) is dissolved in MeCN / t-BuOH = 1.0 mL / 1.0 mL, Cyclohexane (1 mL, 9.3 mmol) and 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, and the mixture was stirred at 40 ° C. for 24 hours. Yields (based on hydrogen peroxide) were cyclohexanol (59%) and cyclohexanone (2.0%).

(Comparative Example 4)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ SiV ₂ W ₁₀ O ₄₀ ] · H ₂ O (5.0 μmol) is dissolved in MeCN / t-BuOH = 1.5 mL / 1.5 mL, 7-octen-1-ol (0.10 mmol) and a 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, followed by stirring at 20 ° C. for 24 hours. The yield of the epoxy compound (based on hydrogen peroxide) was 79%.

Example 11 Synthesis of [(C ₄ H ₉ ) ₄ N] ₄ [γ-HPV ₂ W ₁₀ O ₄₀ ] · H ₂ O 3M HCl was added to 120 mL (1.2 mmol) of 0.01 M NaVO ₃ aqueous solution to adjust the pH. Was adjusted to 2, and then 3.8 g (1.1 mmol) of Cs ₅ [γ-HPV ₂ W ₁₀ O ₄₀ ] · 6H ₂ O was added and dissolved. The turbidity was removed by filtration, and 1.8 g (5.6 mmol) of tetrabutylammonium bromide was added to form a yellow precipitate. This precipitate was taken out on a glass filter, washed with 400 mL of water, and dried under vacuum for 1 hour. The crude production amount was 4.7 g. 150 mg of this crude product was dissolved in 15 mL of acetone, filtered through a membrane filter, put into a screw bottle, and allowed to stand in a diethyl ether atmosphere for 3 days. Yellow columnar crystals were formed, and the crystals were collected and air-dried. Yield: 83 mg (60% yield from Cs salt). ⁵¹ V-NMR analysis result (MeCN): -581 ppm.

Example 12 Synthesis of [(C ₂ H ₅ ) ₄ N] ₃ [γ-H ₂ PV ₂ W ₁₀ O ₄₀ ] · 2H ₂ O · 2C ₄ H ₈ O ₂ [(C ₄ H ₉ ) ₄ N ] ₄ [γ-HPV ₂ W ₁₀ O ₄₀ ] · H ₂ O (216 mg, 60 μmol) was dissolved in 10 mL of acetonitrile, and then 0.2 M HClO ₄ (0.5 mL) prepared by diluting 70% perchloric acid with acetonitrile. , 100 μmol). When tetraethylammonium bromide (76 mg, 360 μmol) was added thereto and 20 mL of diethyl ether was added, a yellow precipitate was formed. The supernatant was removed by decantation and the precipitate was washed with ether. This precipitate was dissolved in 10 mL of acetonitrile, and after adding 20 mL of dioxane, the turbidity was removed by filtration, and acetonitrile was slowly volatilized under air until the amount of the solution reached about 20 mL. Yellow needle crystals were formed, and the crystals were collected and air-dried. Yield: 120 mg (63% yield). ⁵¹ V-NMR analysis result (MeCN): -578 ppm.
The result of X-ray crystal structure analysis is shown in FIG. X-ray crystal structure analysis results: Pnma, a = 28.8724 (6) Å, b = 14.2261 (2) Å, c = 16.3470 (4) Å, R = 0.059. V-V: 3.144 (7) Å. VVS of V—O—V bridging oxygen: 1.37 (two are equivalent).

(Example 13)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-HPV ₂ W ₁₀ O ₄₀ ] · H ₂ O (5.0 μmol) was dissolved in MeCN / t-BuOH = 0.8 mL / 1.2 mL, and Cyclohexane (1 mL, 9.3 mmol) and 30% aqueous hydrogen peroxide solution (0.10 mmol) were added, and the mixture was stirred at 60 ° C. for 60 minutes. The yield (based on hydrogen peroxide) was cyclohexanol (92%) and cyclohexanone (2.0%).

(Comparative Example 5)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ SiV ₂ W ₁₀ O ₄₀ ] · H ₂ O (5.0 μmol) was dissolved in MeCN / t-BuOH = 0.8 mL / 1.2 mL, Cyclohexane (1 mL, 9.3 mmol) and a 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, and the mixture was stirred at 60 ° C. for 4 hours. Yields (based on hydrogen peroxide) were cyclohexanol (73%) and cyclohexanone (2.0%).

(Example 14)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-HPV ₂ W ₁₀ O ₄₀ ] · H ₂ O (5.0 μmol) was dissolved in MeCN / t-BuOH = 1.5 mL / 1.5 mL, and 7-octenal (0.10 mmol) and 30% aqueous hydrogen peroxide solution (0.10 mmol) were added, and the mixture was stirred at 20 ° C. for 4 hours. The yield of the epoxy compound (based on hydrogen peroxide) was 90%. At this time, the aldehyde group was not oxidized and the selectivity of the epoxy compound was 97%.

(Comparative Example 6)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ SiV ₂ W ₁₀ O ₄₀ ] · H ₂ O (5.0 μmol) is dissolved in MeCN / t-BuOH = 1.5 mL / 1.5 mL, 7-octenal (0.10 mmol) and 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, and the mixture was stirred at 20 ° C. for 24 hours. The yield of epoxy compound (based on hydrogen peroxide) was 80%.

(Example 15)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-HPV ₂ W ₁₀ O ₄₀ ] · H ₂ O (5.0 μmol) was dissolved in MeCN / t-BuOH = 1.5 mL / 1.5 mL, and 1-octene (0.10 mmol) and 30% aqueous hydrogen peroxide (0.10 mmol) were added, and the mixture was stirred at 20 ° C. for 24 hours. The production rate of the epoxy compound was 0.72 mM / min, and the yield of the epoxy compound (based on hydrogen peroxide) was 96%.

(Comparative Example 7)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-H ₂ SiV ₂ W ₁₀ O ₄₀ ] · H ₂ O (5.0 μmol) is dissolved in MeCN / t-BuOH = 1.5 mL / 1.5 mL, 1-octene (0.10 mmol) and 30% aqueous hydrogen peroxide solution (0.10 mmol) were added thereto, and the mixture was stirred at 20 ° C. for 24 hours. The production rate of the epoxy compound was 0.39 mM / min, and the yield of the epoxy compound (based on hydrogen peroxide) was 93%.

(Example 16)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-HPV ₂ W ₁₀ O ₄₀ ] .H ₂ O ( _4.0 μmol) was dissolved in 3.0 mL of ethyl acetate, and 1-octene (0.50 mmol) was added thereto. 50% aqueous hydrogen peroxide solution (0.50 mmol) was added and stirred at 32 ° C. for 24 hours. At this time, the catalyst was not dissolved in the solvent and the system was heterogeneous. The yield of the epoxy compound (based on hydrogen peroxide) was 31%.

(Example 17)
[(C ₄ H ₉ ) ₄ N] ₄ [γ-HPV ₂ W ₁₀ O ₄₀ ] · H ₂ O (4.0 μmol) and [(C ₄ H ₉ ) ₄ N] ₄ [γ-SiW ₁₂ O ₄₀ ] (20 μmol) was dissolved in 3.0 mL of ethyl acetate, 1-octene (0.50 mmol) and 50% aqueous hydrogen peroxide solution (0.50 mmol) were added thereto, and the mixture was stirred at 32 ° C. for 24 hours. At this time, the catalyst was not dissolved in the solvent and the system was heterogeneous. The yield of the epoxy compound (based on hydrogen peroxide) was 65%.

Example 18 Synthesis of (C ₁₂ H ₂₄ O ₆ ) ₉ Cs ₈ [(SiW ₁₀ O ₃₆ ) ₂ {Hf (H ₂ O)} ₄ O (OH) ₆ ] · 7H ₂ O 18-Crown-6 -0.85 g (0.32 mmol) of ether was dissolved in 10.0 mL of water. 0.42 g (0.058 mmol) of H ₁₂ O _46.5 Cs _4.5 SiW ₁₀ Hf ₂ synthesized in Example 2 was added and stirred at 50 ° C. for 30 minutes, and then water was distilled off under reduced pressure. The compound was thoroughly washed with diethyl ether to obtain the target compound. Yield: 0.49g. Elemental analysis result: (calculated value) C: 13.86, H: 2.63, Si: 0.60, W: 39.29, Hf: 7.63 (actual value) C: 13.56, H: 2 .67, Si: 0.58, W: 38.30, Hf: 7.69.

Example 19
To 1.0 mL of nitromethane, (C ₁₂ H ₂₄ O ₆ ) ₉ Cs ₈ [(SiW ₁₀ O ₃₆ ) ₂ {Hf (H ₂ O)} ₄ O (OH) ₆ ] · 7H ₂ O (12.5 μmol), 3 -Methylcitronellal (0.50 mmol) was added and stirred at 75 ° C. under an argon atmosphere. The intramolecular carbonyl-ene reaction proceeded, and a trans cyclization product was obtained in a yield of 91% and a cis cyclization product in a yield of 6%.

From the above-mentioned Examples and Comparative Examples, it was found that the following can be said. That is, in the production of the above heteropolyoxometalate using zirconium or hafnium as one of the elements (B), in the conventional method, as shown in the comparative example, only one element (B) is one heteropolyoxometalate. On the other hand, in the method of the present invention, one element (B) is one dimerized after being introduced into the two-deficient structure site of the rate anion (A) (element (B) / hetero atom = 1). The heteropolyoxometalate anion (A) was introduced into the two-deficient structure site and then dimerized (element (B) / heteroatom> 1). It is clear that the selection of the time for coexisting pH and (A) and (B) is important. In addition, heteropolyoxometalate compounds in which two V atoms as element (B) are introduced into germanium-centered two-deficient heteropoloxometalate anions (A) are used under mild conditions for alkane oxidation and alkene epoxidation reactions. It is clarified that the catalyst can be a very good oxidation catalyst, and the catalytic activity of the silicon-centered two-deficient heteropoloxometalate anion (A) is V as an element (B). It was found to be higher than the heteropolyoxometalate compound catalyst introduced two. Further, heteropolyoxometalates having two counter-cations, alkyl ammonium salt cations, in which two Vs are introduced as the element (B) into the phosphorus center two-deficient heteropolyoxometalate anion (A), which has been difficult to prepare so far. The preparation method of the compound was established. The compound has been shown to be an excellent oxidation catalyst that proceeds alkane oxidation reaction and alkene epoxidation reaction under mild conditions. It was found to be higher than the heteropolyoxometalate compound catalyst in which two V atoms were introduced as the element (B) into the deficient heteropolyoxometalate anion (A).

The heteropolyoxometalate compound of the present invention is a novel compound having the above structure and having a new structure in which the element (B) is introduced into the deficient structure site of the two-deficient heteropolyoxometalate anion (A).

The heteropolyoxometalate compound of the present invention has a structure that is introduced at a molar ratio satisfying the element (B) / heteroatom> 1 into the deficient structure part of the heteropolyoxometalate anion (A) containing the two deficient structure part. Therefore, it can be expected to be effectively used as a catalyst for organic reactions such as oxidation reactions and acid-base reactions, and as a functional material.

X-ray of an anion portion obtained by dimerizing a heteropolyoxometalate anion in which two zirconium elements are incorporated in a defect structure site of a silicon-centered γ-deficient heteropolyoxometalate anion and zirconium is incorporated It is a crystal structure analysis figure. X-ray crystal structure of the anion portion in which two hafnium elements are incorporated into the defect structure site of the silicon-centered γ-deficient heteropolyoxometalate anion and the heteropolyoxometalate anion incorporating hafnium is dimerized FIG. In the X-ray crystal structure analysis diagram of the anion portion in which one zirconium element is incorporated into the deficient structure site of the silicon-centered γ-deficient heteropolyoxometalate anion and the heteropolyoxometalate anion is dimerized is there. In this case, one zirconium element is incorporated in each of the deficient structure sites of two different γ-two deficient heteropolyoxometalate anions. X-ray crystal structure analysis diagram of an anion portion in which a single hafnium element is incorporated into a deficient structure site of a silicon-centered γ-deficient heteropolyoxometalate anion and the heteropolyoxometalate anion is dimerized. is there. In this case, one hafnium element is incorporated into each of the deficient structure sites of two different γ-two deficient heteropolyoxometalate anions. FIG. 3 is an X-ray crystal structure analysis diagram of an anion portion in which two vanadium elements are incorporated in a defect structure site of a germanium center γ-two-deficient heteropolyoxometalate anion. FIG. 3 is an X-ray crystal structure analysis diagram of an anion portion in which two vanadium elements are incorporated into a defect structure site of a phosphorus center γ-deficient heteropolyoxometalate anion.

Claims (8)

A heteropolyoxometalate compound having a structure in which a poly atom is coordinated to an hetero atom via an oxygen atom,
The heteropolyoxometallate compound is a heteropolyoxometalate compound containing a two-deficient structure site wherein the heteroatom is silicon, phosphorus or germanium and the polyatom is at least one element selected from the group consisting of molybdenum, tungsten and vanadium. At least one element (B) selected from Sc, Y, Zr, Hf, V, Nb, Ta and Cr, which are the transition metals of the oxometalate anion (A), is present in the element (B). / A heteropolyoxometalate compound having a heteropolyoxometalate structure introduced at a molar ratio satisfying the relationship of>heteroatom> 1. A heteropolyoxometalate compound having a structure in which a poly atom is coordinated to an hetero atom via an oxygen atom,
The heteropolyoxometalate compound is a heteropolyoxometalate containing a two-deficient structure site in which the heteroatom is phosphorus or germanium and the polyatom is at least one element selected from the group consisting of molybdenum, tungsten and vanadium. A heteropolyoxometalate compound having a heteropolyoxometalate structure in which a V element (B), which is a transition metal in the preceding period, is introduced into a defective structure site of a rate anion (A). A heteropolyoxometalate compound having a structure in which a poly atom is coordinated to an hetero atom via an oxygen atom,
The heteropolyoxometalate compound is a heteropolyoxometalate anion containing a two-deficient structure site wherein the heteroatom is phosphorus and the polyatom is at least one element selected from the group consisting of molybdenum, tungsten and vanadium A heteropolyoxometalate structure in which at least one element (B) selected from V, Sc, Y, Zr, Hf, Nb, Ta, and Cr, which are the transition metals of the preceding period, is introduced into the defect structure portion of (A). Heteropolyoxometalate compound characterized by having. The heteropolyoxometalate compound according to claim 1 or 2, wherein the heteropolyoxometalate compound is a germanium hetero atom. The heteropolyoxometalate compound according to any one of claims 1 to 4, wherein the heteropolyoxometalate compound is a cation of an alkyl ammonium salt as a counter cation for the heteropolyoxometalate anion (A). . 6. The heteropolyoxometalate compound according to claim 1, wherein the heteropolyoxometalate anion (A) is a γ-type Keggin-type heteropolyoxometalate anion. Oxometallate compounds. A process for producing a heteropolyoxometalate compound according to any one of claims 1 to 6, wherein a compound having a heteropolyoxometalate anion (A) and a compound having an element (B) are reacted. A process for producing a heteropolyoxometalate compound, comprising: A method of using the heteropolyoxometalate compound according to any one of claims 1 to 6 as a catalyst, wherein the heteropolyoxometalate compound is used as an oxidation reaction catalyst and / or an acid-base reaction catalyst. How to use rate compounds.

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