WO2021251750A1 - MODIFIED μ-OXO CENTERED-MULTINUCLEAR METAL COMPLEX AND USE THEREOF - Google Patents

Abstract

The present invention relates to a modified μ-oxo centered-multinuclear metal complex compound, in which Si and/or Al is bound via a ligand containing an organic functional group having a non-covalent electron pair capable of binding to a coordinatively unsaturated site (CUSs) of a metal in a μ-oxo centered-multinuclear metal complex, to a preparation method therefor, and to use thereof. The modified μ-oxo centered-multinuclear metal complex compound according to the present invention can be used as a precursor for forming a molecular sieve, such as zeolite, or a raw material for preparing a composite metal oxide. A molecular sieve and a metal oxide crystalline body, prepared according to the present invention, enable the arbitrary control of the kind of metal to be introduced and the size and dispersion degree of metal particles, and thus can be expected to, as an absorbent and a catalyst, have increased activity and selectivity to a target substance.

Description

Modified μ-oxo-centered multinuclear metal complex and uses thereof

The present invention relates to modified μ-oxo centered multinuclear metal complexes and uses thereof, and more particularly, to a metal at sites of coordinating unsaturation formed in μ-oxo centered-multinuclear metal complexes. It relates to a complex compound bound through a ligand, a method for preparing the same, and a use thereof.

Molecular sieves are a powerful material that enables efficient use of limited resources due to their large specific surface area and adsorption capacity derived from a porous structure. continuously being tried.

Efforts have been made to improve the adsorption capacity of gases and the catalytic activity of metals by introducing metals into these molecular sieves. Representative methods for supporting metals in such molecular sieves include an impregnation method and an ion exchange method. In the impregnation method, a molecular sieve (zeolite, etc.) is added to a solution containing a precursor of a metal to be supported, and then the metal is precipitated to support the metal in the molecular sieve. On the other hand, the ion exchange method uses the principle that metal ions are exchanged with ions in the molecular sieve when the molecular sieve is put into a solution containing a metal to be replaced, and the metal is replaced by the molecular sieve.

However, the method of supporting metal in a molecular sieve through the impregnation method has problems in that it is relatively difficult to achieve uniform dispersion and it is not easy to control the size of the metal. In addition, the metal supporting method through the ion exchange method has a problem in that the type of metal capable of ion exchange is limited.

On the other hand, as another attempt to introduce a metal to a molecular sieve, a method for improving catalytic activity or stability by fixing in the form of an organic complex containing a metal rather than being supported in the form of metal on the molecular sieve has been reported. As one of the types of organic complexes, μ-oxo centered-multinuclear metal complexes including a μ-oxo centered metal trimer have recently attracted attention. have. The μ-oxo center-multinuclear metal complex is a compound in which 2 to 6 metals are bonded to a μ-oxo group, and exists as a three-dimensionally crystalline aggregate bonded together with crystal water in an ionic bond form. Attempts have been made to improve the activity of the catalyst or the performance of the adsorbent by fixing and dispersing the μ-oxo core-multinuclear metal complex present in the form of aggregates on the surface of the support.

According to Non-Patent Document 1, a selective alcohol oxidation catalyst in which a pyridine-based compound is attached to a silica surface to be functionalized, and then a trinuclear Ru cluster is coordinated to the pyridine-based compound is disclosed, Non-Patent Document 2 disclosed a 2-naphthol oxidation catalyst in which homo and heterometallic trinuclear acetate clusters of homo and heterometallic trinuclear acetate clusters were immobilized on zeolite-Y using an ion exchange method.

In addition, Patent Document 1 relates to a complex including a metal-organic trimer, and more particularly, a complex in which a metal-organic trimer and a support are covalently bonded using a linker having two or more functional groups is disclosed.

However, there is still a need to develop a technology capable of uniformly dispersing a metal in a molecular sieve in a uniform size.

In the present application, metals such as B, Al, Ga, Si, Ge, P, Ti, Zr, Sn, and other metals are bonded to the coordinating unsaturated site formed in the μ-oxo center-multinuclear metal complex through a ligand, modified By using the μ-oxo core-multinuclear metal complex compound, the present invention has been developed by developing a technology capable of evenly dispersing not only the molecular sieve, but also the active metal that acts as an active site of a catalyst or adsorbent in metal oxide crystals and polymers, etc. has been completed

In order to achieve the above object, the present invention is to provide a μ-oxo center-multinuclear metal complex compound in which Si, Al, etc. are coordinated through a ligand containing an organic functional group having a lone pair of electrons.

Another object of the present invention is to provide the composite compound as a raw material for synthesizing a molecular sieve or metal oxide, and to provide a molecular sieve or metal oxide composite having a new structure prepared from the raw material.

In order to solve the above problem, from the viewpoint of a method for introducing metal into a molecular sieve structure, the modified μ-oxo core-multinuclear metal complex according to the present invention is used as a raw material for a building unit constituting a molecular sieve, An object of the present invention is to provide a technique in which metal can be uniformly and uniformly dispersed during synthesis.

In addition, according to the present invention, a technique for preparing a polymer composite uniformly dispersed in a nano size in a polymer resin using a μ-oxo center-multinuclear metal complex to which a metal compound is coordinated, and a metal compound prepared therefrom is coordinated An object of the present invention is to provide a μ-oxo core-multinuclear metal complex-polymer complex.

In order to solve the above problems, the present invention provides a ligand including an organic functional group having a lone pair of electrons capable of binding to a coordinating unsaturated site (CUS) of a metal of μ-oxo centered-multinuclear metal complexes. At least one selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn is bonded as a medium, μ-oxo core-to provide a multinuclear metal complex compound.

The organic functional group is a hydroxyl group (-OH), an alkoxide group (-OR), a carboxyl group (-COOH), a carboxylate anion group (-COO ^- ), an amino group (-NH2), an imino group (-NH), a nitrile group ( -CN), nitro group (-NO ₂ ), thiol group (-SH), halogen group (-X) and sulfonic acid group (-SO ₃ H), sulfonic acid anion group (-SO ₃ ^- ), methanedithioic acid group ( -CS ₂ H), a methanedithioic acid anion group (-CS ₂ ^- ), a phosphate group (-PO ₄ ^3- ), may be a hydrocarbon having at least one selected from the group consisting of a pyridine group and a pyrazine group.

In one embodiment of the present invention, the μ-oxo center-multinuclear metal complex compound may be characterized by being represented by the following formula (1).

[Formula 1]

[(μ ₃ -O)M ^a M ^b M ^c (R ^a COO) ₆ E ^a E ^b E ^c ] D _f

In Formula 1, M ^a, M ^b, M ^c is the respective centers μ- oxo-center and connected to the same metal as or different and each independently represent a transition metal, since the former metals, alkaline earth metals, semi-metals, lanthanide, Ill platinum group It is one selected from, and the R ^a is a phosphine containing an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms, an amine containing carbon monoxide, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms or 6 to carbon atoms At least one selected from the group consisting of the same or different neutral ligands selected from nitrile containing an aryl group of 50, aromatic heterocyclic compounds having 2 to 50 carbon atoms having O, N, P or S as a hetero atom, E ^a , E ^b , E ^c is a coordination material independently bonded to the metal connected to the μ-oxo center, each the same or different, pyridine, nitrogen-containing organic base, H ₂ O, organic solvent, substituted or unsubstituted C1 to C10 alcohols , phosphine including a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C50 aryl group, carbon monoxide, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted carbon number Amine containing 6 to 50 aryl group, nitrile containing a substituted or unsubstituted C 1 to C 30 alkyl group or substituted or unsubstituted C 6 to C 50 aryl group, substituted or unsubstituted and heteroatoms O, N, Or any one of the same or different neutral ligands selected from aromatic heterocyclic compounds having 2 to 50 carbon atoms having S, and compounds represented by the following Chemical Formula 2, provided that E ^a , E ^b , E ^c Any one or more is necessarily a metal compound represented by the following formula (2),

[Formula 2]

M ^d R ^b _i R ^c _j R ^d _k R ^e _l

In Formula 2, M ^d is selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn, wherein R ^b , R ^c , R ^d _{, and} R ^e are the same or different from each other, and each is independent of x It may be a -type ligand or R ^L. A detailed example of the X-type ligand is described in detail in Organometallic Chemistry (publisher: Prentice Hall) p46 by Gary O. Spessard and Gary L. Miessler. Non-limiting examples of the x-type ligand include a halogen group, a hydroxyl group, an alkoxy group, an amide group, a thiol group, a carboxyl group, a saturated or unsaturated straight-chain, branched, cyclic, and two or more of them are linked to each other Examples of the hydrocarbon group include a hydrocarbon group having 1 to 20 carbon atoms, an alkyl halide having 1 to 10 carbon atoms, and the like. In Formula 2 of the present invention, at least one ^{of R b} , R ^c , R ^d _{, and} R ^{e must be R L} , wherein i, j, k, and l are 0 to 3, and R ^L is B, Al, A hydroxyl group (-OH), an alkoxide group (-OR), a carboxyl group (-COOH), a carboxylate anion group (-COO-), Amino group (-NH ₂ ), imino group (-NH), nitrile group (-CN), nitro group (-NO ₂ ), thiol group (-SH), halogen group (-X) and sulfonic acid group (-SO ₃ H ), a sulfonic acid anion group (-SO ^3- ), a methanedithioic acid group (-CS ₂ H), a methanedithioic acid anion group (-CS ₂ ^- ), a phosphate group (-PO ₄ ^3- ), a pyridine group and a pyrazine group a hydrocarbon group-having any one or more features selected from the group consisting of, at this time, the hydrocarbon constituting the R ^L is a saturated or unsaturated straight-chain, of the cyclic hydrocarbons, and as they are associated with each other two or more carbon atoms is a hydrocarbon of from 1 to 20 , where D is a counter anion for maintaining the neutral charge of the complex represented by Formula 1, and f may be any one rational number selected from 0 to 3.

In an embodiment of the present invention, D is NO ₃ ^- , SO ₄ ^2- , Cl ^- , CH ₃ COO-, C ₅ H ₇ O ^2- , HPO ₄ ^2- , PO ₄ ^3- , HCOO ^- , Br ^- , It may be one or more selected from ^{F -.}

In another embodiment of the present invention, one or more selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn according to the present invention is bonded μ-oxo center-including a multinuclear metal complex compound It provides a raw material for zeolite synthesis and a synthetic zeolite prepared using the raw material.

In addition, the present invention comprises the steps of: a) removing one or more coordination materials coordinated to the μ-oxo core-polynuclear metal complex to form a coordinating unsaturated site; and b) preparing a compound in which one or more selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn is bonded to the other end of the ligand having an organic functional group having an unshared electron pair; c) coordinating the compound of step (b) to the coordination unsaturated site of the μ-oxo center-multinuclear metal complex of step (a): B, Al, Ga, Si comprising: , Ge, P, Ti, Zr and at least one selected from Sn bonded μ-oxo center-provides a method for preparing a multinuclear metal complex compound.

Step a) may be performed at a temperature of 0 to 300 °C and a pressure of 0.001 to 1 atmosphere.

In addition, the present invention is 1) a transition metal or post-transition metal, alkaline earth metal, metalloid, lanthanum, and at least one metal selected from the actinium group, μ-oxo center-polynuclear metal through a ligand having an organic functional group having a lone pair of electrons preparing a modified μ-oxo core-polynuclear metal complex compound bound to a site of coordinating unsaturation of the complex; 2) sintering the modified μ-oxo center-multinuclear metal composite compound to remove organic matter to form a composite metal oxide; provides a method for producing a composite metal oxide comprising: a.

In one embodiment of the present invention, in step 1), the coordination material coordinated to the μ-oxo center-multinuclear metal complex is removed by exposing the oxo center-multinuclear metal complex to high temperature and/or reduced pressure reaction conditions for a predetermined time. At the site of coordinating unsaturation formed by One or more selected from linear, branched, and cyclic hydrocarbons has an organic functional group having a lone pair at one end of a hydrocarbon having 1 to 20 carbon atoms bonded to each other, and a transition metal or post-transition metal, alkaline earth metal, The compound to which one or more metals selected from metalloid, lanthanum, and actinium is bonded may be characterized in that it is carried out by coordination bonding through the lone pair of electrons.

In step 1), the compound bound to the coordinating unsaturated site of the μ-oxo center-polynuclear metal complex through a ligand is the same as or different from the μ-oxo center-polynuclear metal complex of the μ-oxo center-polynuclear metal complex It may be a complex.

In synthesizing a molecular sieve, the present invention uses a μ-oxo center-multinuclear metal complex compound to which Al, Si, etc. are bound via a ligand containing an organic functional group having a lone pair of electrons as a precursor for forming a molecular sieve. By doing so, it is possible to synthesize a uniformly dispersed molecular sieve by simply adding only a metal-containing complex in the raw material input step without performing a separate metal introduction step following the molecular sieve synthesis step.

In particular, in the production of molecular sieves such as zeolite, silicate, silica, etc., in the raw material input step, at least one selected from B, Al, Ga, Si, Ge, P, Ti, Zr, or Sn is selected from μ-oxo through a ligand. By injecting the complex compound bound to the central-multinuclear metal complex as a raw material, the complex containing the metal can be uniformly dispersed in a predetermined position inside the molecular sieve, and the number and ratio of metals contained in the complex are constant. Therefore, the size of the metal, the ratio between the introduced metals, etc. can be equally controlled.

In addition, in the modified μ-oxo core-multinuclear metal complex in which one or more selected from B, Al, Ga, Si, Ge, P, Ti, Zr, or Sn is bonded via a ligand, μ-oxo core-polynuclear It is possible to change the pore size of the synthesized molecular sieve by adjusting the length of the ligand including the organic functional group mediating the bonding between the metal complex and B, Al, Ga, Si, Ge, P, Ti, Zr, or Sn. .

In addition, the molecular sieve and metal oxide prepared according to the present invention can arbitrarily control the type of metal introduced into the molecular sieve and the metal oxide, the size of metal particles, and the degree of dispersion, and thus can be used as an adsorbent for selective separation of gas, and selectively It can be used as a raw material for organic/inorganic membranes, and by further accelerating the reaction to a desired target product, it is possible to increase the activity as a catalyst and improve the selectivity to a target material, and there is an effect that can be applied to a sensor or the like.

1 is a schematic diagram of a method for preparing a μ-oxo center-metal trimer to which Si is bonded according to the present invention as an example of the μ-oxo center-multinuclear metal complex compound of the present invention.

2 is a schematic diagram showing the structure of a synthetic zeolite prepared by using the Si-bonded μ-oxo center-metal trimer composite as an example of the present invention as a raw material according to the present invention.

3 is a schematic diagram showing the predicted structure of a synthetic zeolite prepared by using the Si-bonded μ-oxo center-metal trimer complex as an example of the present invention as a raw material after firing as an example of the present invention.

4 is an XRD result of a synthetic zeolite prepared using the Si-bonded μ-oxo center-metal trimer composite according to the present invention as a raw material.

5 is an SEM/EDS image of a synthetic zeolite prepared according to a comparative example of the present invention.

6 is a SEM/EDS image of a synthetic zeolite prepared according to an embodiment of the present invention.

7 is a TGA result of synthetic zeolites of some comparative examples and some examples according to the present invention.

8 is an Ar physisorption isotherm of a synthetic zeolite prepared using the Si-bonded μ-oxo center-metal trimer complex according to the present invention as a raw material.

9 is a pore size distribution graph of a synthetic zeolite prepared using the Si-bonded μ-oxo center-metal trimer composite according to the present invention as a raw material.

10 is an XRD analysis result of a sample prepared in Preparation Example of the present invention.

11 is an FT-IR analysis result of a sample prepared in Preparation Example of the present invention.

Hereinafter, with reference to the accompanying drawings, it will be described in detail the configuration of the present invention including preferred embodiments in which those of ordinary skill in the art can easily practice the present invention. In the detailed description of the principle of the preferred embodiment of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, the 'metal' described in the present specification is to be defined as a term including a transition metal, a typical element metal, a metalloid, and a lanthanide element.

The present invention mediates a ligand containing an organic functional group having at least one lone pair of electrons selected from B, Al, Ga, Si, Ge, P, Ti, Zr, or Sn at the site of coordinating unsaturation of the μ-oxo center-polynuclear metal complex. It relates to a modified μ-oxo core-multinuclear metal complex bound to

Specifically, the μ-oxo core-multinuclear metal complex of the present invention can generate one or more coordinating unsaturated sites by artificial treatment, and B, Al, Ga, Si through a ligand that is coordinated to the coordinating unsaturated site , Ge, P, Ti, Zr, and provides a composite to which at least one selected from Sn is bonded.

The μ-oxo center-multinuclear metal complex of the present invention _{is defined as a form in which a μ-oxo group (μ 3} -O) is located at the center, and 2 to 6 central metals are bonded to the μ-oxo group.

In the specification of the present invention, in some cases, the μ-oxo center-multinuclear metal complex is described as a μ-oxo center-metal trimer, μ-oxo center-metal tetramer, etc. depending on the number of metals bonded to the μ-oxo center. However, it goes without saying that all of them belong to the μ-oxo core-multinuclear metal complex.

The μ-oxo center-polynuclear metal complex may include one or more coordinating unsaturated sites formed by removing the bound coordination material, and may be bound to the coordinating unsaturated site with a hydroxyl group (-OH) at one end. ), alkoxide group (-OR), carboxyl group (-COOH), carboxylate anion group (-COO-), amino group (-NH ₂ ), imino group (-NH), nitrile group (-CN), nitro group ( -NO ₂ ), thiol group (-SH), halogen group (-X) and sulfonic acid group (-SO ₃ H), sulfonic acid anion group (-SO ^3- ), methanedithioic acid group (-CS ₂ H), methane Modified μ-oxo center to which a metal is bonded through a ligand having at least one functional group selected from dithioic acid anion group (-CS ₂ ^- ), phosphate group (-PO ₄ ^{3- ), pyridine group and pyrazine group-} A multinuclear metal complex compound can be prepared. Preferably, the metal bound to the modified μ-oxo center-multinuclear metal complex compound according to the present invention via a ligand is at least one selected from B, Al, Ga, Si, Ge, P, Ti, Zr, or Sn.

In addition, as an embodiment of the present invention, the modified μ-oxo core-multinuclear metal complex may be a μ-oxo core-metal trimer represented by the following formula (1).

[Formula 1]

[(μ ₃ -O)M ^a M ^b M ^c (R ^a COO) ₆ E _a E _b E _c ] D _f

In Formula 1,

M ^a, M ^b, M ^c can be a one of each of the center and the center μ- oxo-bonded by the same metal or different and each independently represent a transition metal, since the former metals, alkaline earth metals, semi-metals, lanthanide, Ill platinum group Examples include Ru, Co, Mn, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Re, Fe, Os, Rh, Ir, Ni, Pd, Pt, Cu , Al, Ga, In, Bi, Sn, Pb, B, Si, Ge, As, Sb, Zn, Tc, Ag, Cd, Au, Hg, La, Lu, Mg, Ca, Sr, from the group consisting of Ce It may be a selected one.

said R ^a is a phosphine containing an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms, an amine containing carbon monoxide, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms or 6 to carbon atoms At least one selected from the group consisting of the same or different neutral ligands selected from nitrile containing an aryl group of 50 and aromatic heterocyclic compounds having 2 to 50 carbon atoms having O, N, P or S as a hetero atom.

Wherein E ^a , E ^b , E ^c are coordinate materials independently binding to the metal of the μ-oxo center-metal trimer, and are the same or different from each other, and pyridine, nitrogen-containing organic base, H ₂ O, organic solvent, Phosphine containing a substituted or unsubstituted C1 to C10 alcohol, a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C50 aryl group, carbon monoxide, a substituted or unsubstituted carbon number An amine containing a 1 to 30 alkyl group or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a nitrile containing a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms , substituted or unsubstituted, and one of the same or different neutral ligands selected from aromatic heterocyclic compounds having 2 to 50 carbon atoms, having O, N, or S as a hetero atom, may be selected from compounds represented by the following formula (2) However, ^{at least one of E a} , E ^b , and E ^c must be a compound represented by the following formula (2).

[Formula 2]

M ^d R ^b _i R ^c _j R ^d _k R ^e _l

In Formula 2, M ^d is a transition metal, but may be one selected from a transition metal, a metalloid, a lanthanum group, and an actinium group, for example, Si, Al, Ga, In, Sn, Pb, Bi, Sb, Ti, One selected from the group consisting of Zr, Hf, Ta, Nb, W, Mo, Ir, Pd, Pt, Au, Zn, V, Cr, Fe, Co, Ni, La, Ce. Preferably, the M ^d is at least one selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn.

The R ^b , R ^c , R ^d _{, and} R ^e may be the same or different from each other, and may be an ^{independent x-type ligand or R L .} A detailed example of the X-type ligand is described in detail in Organometallic Chemistry (publisher: Prentice Hall) p46 by Gary O. Spessard and Gary L. Miessler. Non-limiting examples of the x-type ligand include a halogen group, a hydroxyl group, an alkoxy group, an amide group, a thiol group, a carboxyl group, a saturated or unsaturated straight-chain, branched, cyclic, and two or more of them are linked to each other Examples of the hydrocarbon group include a hydrocarbon group having 1 to 20 carbon atoms, an alkyl halide having 1 to 10 carbon atoms, and the like.

In Formula 2 of the present invention, at least one ^{of R b} , R ^c , R ^d _{, and} R ^{e must be R L} , i, j, k, and l are 0 to 3, and R ^L is M ^d and A hydroxyl group (-OH), an alkoxide group (-OR), a carboxyl group (-COOH), a carboxylate anion group (-COO-), an amino group (-NH ₂ ), an imino group (-NH), Nitrile group (-CN), nitro group (-NO ₂ ), thiol group (-SH), halogen group (-X) and sulfonic acid group (-SO ₃ H), sulfonic acid anion group (-SO ^3- ), methanadity Pentate group (-CS ₂ H), methanedithioic acid anion group (-CS ₂ ^- ), phosphate group (-PO ₄ ^3- ), a hydrocarbon having at least one functional group selected from the group consisting of a pyridine group and a pyrazine group, In this case, ^{the hydrocarbon constituting R L} is a saturated or unsaturated linear, branched, cyclic hydrocarbon, and two or more of them are linked to each other and has 1 to 20 carbon atoms, and D is the charge of the complex represented by the formula (1). It is a counter anion for maintaining neutrality, and f may be any one rational number selected from 0 to 3.

_{When f is 0, [(μ 3} -O)M ^a M ^b M ^c (R ^a COO) ₆ E ^a E ^b E ^c ] in the μ-oxo center-metal trimer complex structure is electrically neutral. , means that it does not have a counter anion.

The coordinating unsaturation site of the μ-oxo center-polynuclear metal complex, including the μ-oxo center-metal trimer, removes one or more of the coordination materials independently binding to the metal of the μ-oxo center-polynuclear metal complex It can be formed by performing the steps. A modified μ-oxo core-multinuclear metal complex in which one or more metals are bound to the thus formed coordinating unsaturation site via a ligand may be formed.

In addition, the modified μ-oxo center-multinuclear metal complex according to the present invention can be formed by directly bonding by removing and replacing the coordination material by the functional group included in the metal compound without separately performing the step of artificially removing the coordination material. have.

On the other hand, the present invention is a molecular sieve or metal oxide, for example, a single metal oxide or complex metal oxide such as zeolite, silica, zirconia, ceria, titania, tin oxide, indium oxide, etc. It is provided as a raw material for manufacturing, etc.

In addition, the present invention may provide a molecular sieve or a metal oxide prepared by using the raw material for synthesizing the molecular sieve. The molecular sieve may be, for example, zeolite.

In addition, the μ-oxo core-multinuclear metal complex modified according to the present invention is mixed with the polymer and uniformly dispersed in the polymer, thereby providing a mixed complex of the μ-oxo core-multinuclear metal composite and the polymer.

The μ-oxo core-multinuclear metal complex-polymer mixed complex is prepared by dispersing the μ-oxo core-multinuclear metal complex modified according to the present invention in a nano-sized polymer resin. The μ-oxo core-multinuclear metal complex and the polymer mixed complex may be prepared by putting a monomer for preparing a polymer resin and then allowing the monomer to polymerize, and the polymer resin and μ-oxo modified according to the present invention It may be prepared by dissolving the core-multinuclear metal complex in a solvent, or it may be prepared by introducing the μ-oxo core-multinuclear metal composite modified according to the present invention in a state in which the polymer resin is melted.

On the other hand, in the zeolite, which is an example of the molecular sieve provided by the present invention, the metal derived from the μ-oxo center-multinuclear metal complex may be uniformly dispersed in predetermined positions of the zeolite. That is, as the technical characteristics of the internal structure other than the surface of the zeolite structure in which the metal is incorporated into the present invention, conventional silicon (Si) as including raw TEOS, Na ₂ SiO _3, Ludox colloidal silca or SiO _2, only the input prepared It is distinguished not only from commercial zeolites, but also from silica or zeolites immobilized on the surface by the μ-oxo core-multinuclear metal complex in the preceding literature.

The μ-oxo core-multinuclear metal composite modified according to the present invention is _{introduced together with TEOS or Na 2} SiO ₃ as a raw material containing metal and undergoes reaction and firing. As a result, since the structure of the composite is regularly or irregularly included between the structure in which silicon (Si) and oxygen (O) are repeatedly bonded, a structure different from that of commercial zeolite as well as zeolite in which the composite is immobilized on the surface can be seen

In addition, the μ-oxo core-multinuclear metal complex modified according to the present invention can partially replace the use of conventional molecular sieve synthesis raw materials such as _{TEOS and SiO 2 , sodium aluminate, and thus a molecular sieve having a new structure} can be synthesized, and improved physical properties can be expected from the synthesized molecular sieve compared to the conventional one.

The present invention provides a method comprising the steps of: a) removing one or more coordination materials coordinated to a μ-oxo core-multinuclear metal complex to form a coordinating unsaturated site; and

b) preparing a compound in which one or more selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn is bonded to the other end of the ligand including an organic functional group having an unshared electron pair;

c) coordinating the compound of step (b) to the coordination unsaturated site of the μ-oxo center-polynuclear metal complex of step (a):

B, Al, Ga, Si, Ge, P, Ti, Zr or Sn, characterized in that it comprises a μ-oxo center-a method of preparing a multinuclear metal complex compound in which one or more selected from the ligand-mediated binding can provide

1 is a schematic diagram of a method for preparing a µ-oxo center-metal trimer complex to which Si is bonded according to the present invention as an example of the μ-oxo center-multinuclear metal complex compound of the present invention.

Referring to FIG. 1, in step a), the coordination material coordinated to the μ-oxo core-multinuclear metal complex is removed by exposing the μ-oxo core-multinuclear metal complex to high temperature and/or reduced pressure reaction conditions for a certain period of time. This is a step in which coordinating unsaturation sites can be formed. Specifically, the reaction may be carried out for 10 minutes to 72 hours at a temperature of 0 to 300 °C and a pressure of 0.001 to 1 atm in order to remove the coordinating unsaturated site in step a). When the temperature exceeds 300 °C, the μ-oxo core-multinuclear metal complex may be decomposed.

Step b) is a step of preparing a compound in which one or more selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn is bonded to the other end of the ligand including an organic functional group having an unshared electron pair. The organic functional group is the same as described above, and the organic functional group usually includes saturated or unsaturated linear, branched, cyclic hydrocarbons and two or more of them bonded to each other, and a hydrocarbon having 1 to 20 carbon atoms is bonded, and the organic functional group is positioned B, Al, Ga, Si, Ge, or P is bonded to the other end of the hydrocarbon.

Step c) is a step of coordinating the compound prepared in step (b) to the coordination unsaturated site of the μ-oxo center-polynuclear metal complex in which the coordination unsaturated site is formed in step a). Specifically, the µ-oxo center-polynuclear metal complex having a coordinating unsaturated site and the compound prepared in step b) are added to and mixed in a solvent to be dispersed in the solvent, and then the solution is heated at a temperature of 0 to 200 °C and a pressure of 0.001. By the reflux reaction at a pressure of 1 to 1 atmosphere, B, Al, Ga, Si, Ge, P, Ti, Zr, or Sn, at least one selected from the bonded μ-oxo center-multinuclear metal complex compound can be prepared. In the above step, steps a) and b) may be performed independently of each other, and a) may be performed first, b) may be performed first, or may be performed simultaneously.

2 is a schematic diagram showing the structure of a synthetic zeolite prepared by using the Si-bonded μ-oxo center-metal trimer composite as a raw material according to the present invention as an example of the present invention, wherein the trimer and the metal contained therein It is included in the zeolite structure, and since it is possible to control the length of the ligand according to the number of carbon atoms of the ligand in the complex, the pore size of the synthesized molecular sieve may be changed.

The present invention also provides a method for preparing a molecular sieve using the μ-oxo center-multinuclear metal complex compound to which one or more selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn according to the present invention is bonded. provide a way

In the method for producing the molecular sieve, μ-oxo center-polynuclear metal to which one or more selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn is bonded as a raw material for the molecular sieve according to the present invention It is characterized in that the molecular sieve is prepared by hydrothermal synthesis after mixing the raw materials for the molecular preparation including the complex compound.

3 is a schematic diagram showing the structure of another molecular sieve prepared using the μ-oxo center-metal trimer complex modified according to the present invention as an example of the present invention as a raw material. As the prepared molecular sieve is fired, organic components are lost, and the metal may be present in a dispersed form in the crystal lattice structure (Fe ₃ Ox or Fe ₂ M ₁ O _x , where M is a metal other than Fe).

The present invention also provides a composite metal oxide using a µ-oxo center-multinuclear metal complex compound to which a transition metal or the like is bound.

The method for manufacturing a composite metal oxide according to the present invention is 1) at least one selected from transition metal or post-transition metal, alkaline earth metal, metalloid, lanthanum group, and actinium group through a ligand having an organic functional group having a lone pair of electrons. -Preparing a modified μ-oxo center-polynuclear metal complex compound bonded to the coordinating unsaturation site of the oxo center-polynuclear metal complex, 2) calcining the modified μ-oxo center-polynuclear metal complex compound to obtain an organic material and removing to form a composite metal oxide.

In step 1), the coordinating unsaturated site formed by removing the coordination material coordinated to the μ-oxo center-multinuclear metal complex by exposing the oxo center-multinuclear metal complex to high temperature and/or reduced pressure reaction conditions for a certain period of time, usually One or more selected from saturated or unsaturated linear, branched, and cyclic hydrocarbons having 1 to 20 carbon atoms bonded to each other has an organic functional group having an unshared electron pair at one end, and a transition metal or after transition at one end It may be carried out by coordinating a compound to which one or more metals selected from a metal, an alkaline earth metal, a metalloid, a lanthanum, and an actinium group are bonded through the lone pair.

Step 2) is a step of forming a composite metal oxide by removing the organic material formed in step 1). In step 2), 0 to 300 ℃, the pressure may be carried out at 0.001 to 1 atmosphere.

The composite metal oxide prepared according to the method of the present invention has the effect of adjusting the ratio of the composite metal oxide and the distance of each metal particle as needed. Among the above effects, the control of the ratio of each complex metal is the number of metals included in the multinuclear metal complex and/or the µ-oxo center-polynuclear metal complex and the ligand when preparing the µ-oxo center-multinuclear metal complex, and It can be controlled by adjusting the number of metals present.

The metal of the μ-oxo core-multinuclear metal complex may be one metal type or may be two or more types. In addition, since the number of metals in the μ-oxo center-multinuclear metal complex is structurally limited to 2 to 6, etc., by using a composite metal rather than a single metal when manufacturing the μ-oxo center-multinuclear metal complex if necessary, The ratio may be adjusted according to the type of the metal. In addition, in each μ-oxo center-polynuclear metal complex, the ratio between metal types can be controlled at the molecular level through the process of controlling the number of metals bonded to one or more coordinating unsaturation sites.

In addition, the distance between the metal particles in the metal catalyst can be an important factor in controlling the selectivity of the catalyst. The distance between the metal particles is also adjustable by controlling the length of the hydrocarbon constituting the ligand, so that the distance between the metal particles can also be adjusted.

In addition, the present invention provides that the compound bound to the μ-oxo center-multinuclear metal complex via the ligand is another μ instead of the transition metal or post-transition metal, alkaline earth metal, metalloid, lanthanum, and an element selected from the actinium group. -oxo core-multinuclear metal complexes may be bound.

That is, by having both ends of the ligand have organic functional groups having a lone pair of electrons, the μ-oxo center-polynuclear metal complex can be bonded to each other at both ends of the ligand, and in the case of the branched hydrocarbon, three or more Of course, it is possible to cause the μ-oxo core-multinuclear metal complexes to bind to each other.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for illustrating the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited thereby.

<Preparation Example: Preparation of modified μ-oxo center-metal trimer complex>

<Preparation Examples 1 to 5: Preparation of μ-oxo center-metal trimer complex in which organosilane is coordinated with a metal compound>

0.3g of a µ-oxo center-metal trimer complex in which a coordinating unsaturated site is formed by heating 0.337 g of a µ-oxo center-metal trimer as a reactant shown in Table 1 below at a temperature of 150° C. and a pressure of 1 atm for 12 hours was obtained.

Then, the coordinating unsaturation site is formed μ-oxo center-metal trimer complex Disperse 0.3 g and 0.3 mL of aminopropyltriethoxysilane (APTES) in 100 mL absolute ethanol. After the mixture was refluxed for 12 hours, the mixture was cooled to room temperature and rotary evaporated. The obtained powder was purified with diethyl ether to prepare a µ-oxo center-metal trimer complex in which Si was bonded through a ligand to the coordinating unsaturation site of the µ-oxo center-metal trimer as the final product shown in Table 1 below. did

division	μ-oxo center-metal trimer type	End product notation
Preparation Example 1	Fe 3 (μ 3 -O)(CH 3 COO) 6 (H 2 O) 3 ]Cl 6H 2 O	Fe 3 -APTES complex
Preparation 2	[Fe 2 Ni(μ 3 -O)(CH 3 COO) 6 (H 2 O) 3 ] 3 H 2 O	Fe 2 Ni-APTES Composite
Preparation 3	[Fe 2 Co(μ 3 -O)(CH 3 COO) 6 (H 2 O) 3 ] 3 H 2 O	Fe 2 Co-APTES complex
Preparation 4	[Ru 2 Co(μ 3 -O)(CH 3 COO)6(H 2 O) 3 ]	Ru 2 Co-APTES complex
Preparation 5	[Ru 2 Ni(μ 3 -O)(CH 3 COO)6(H 2 O) 3 ]	Ru 2 Ni-APTES Composite

The structures of the complexes prepared in Examples 1 to 5 were subjected to XRD and FT-IR analysis, and the results are shown in FIGS. 10 and 11 . Referring to FIGS. 10 and 11 , in the APTES complexes prepared in the above preparation examples, it can be confirmed that APTES was coordinated to the coordinating unsaturated site while maintaining the structure of the organometallic cluster.

<Preparation of a synthetic zeolite comprising a metal compound and an organosilane coordinated μ-oxo center-metal trimer complex as a raw material>

<Examples 1 to 10: Preparation of pre-calcination product and post-calcination product of synthetic zeolite containing trimer complex as a raw material>

As a reactant listed in Table 2 below, 0.112 g of a μ-oxo center-metal trimer complex coordinated with an organosilane (APTES) as a metal compound, 20 mL of water, 10.65 g of ethanol, 9.42 g of TPAOH, 6.028 g of TEOS, 18.5 of NaOH mg was reacted at 120 °C for 48 hours. The obtained powder was purified by centrifugation and dried at 100 degrees for 12 hours to obtain a synthetic zeolite pre-calcination product containing the metal trimer complex shown in Table 2 below as a raw material (Examples 1, 3, 5, 7, 9), a product after calcination of synthetic zeolite containing a metal trimer complex as a raw material was obtained by heat-treating the product before calcining the synthetic zeolite at 500° C. for 5 hours (Examples 2,4,6,8,10).

<Comparative Examples 1 and 2: Preparation of pre-calcination product and post-calcination product of synthetic zeolite>

As a raw material used in the preparation of the synthetic zeolite of Examples 1 to 10 described in Table 2 below, the μ-oxo center-metal trimer to which Si prepared in Preparation Examples 1-5 is bonded is carried out in the same manner as the synthetic zeolite. A product before calcination was obtained (Comparative Example 1), and a product after calcination of the synthetic zeolite was obtained by heat-treating the synthetic zeolite pre-calcination product at 500° C. for 5 hours (Comparative Example 2).

<Comparative Example 3: Preparation of Fe3-ZSM-5>

_{In the synthetic zeolite production method of Examples 1 to 10, the same amount of Fe 3} (μ ₃ -O)(CH ₃ COO) ₆ instead of the μ-oxo center-metal trimer complex coordinated with organosilane (APTES) as a raw material. (H ₂ O) ₃ ]Cl·6H ₂ O Fe3-ZSM-5 was prepared in the same manner except that it was used.

<Comparative Example 4: Commercial ZSM-5>

ZSM-5 was purchased from the market and used.

In the table below, indicated as Fe3 complexes are all three metals of the μ-oxo center-metal trimer are Fe, and the μ-oxo center-metal trimer is [Fe ₃ (μ ₃ -O)(CH ₃ COO) ₆ ( H ₂ O) ₃ ]Cl·6H ₂ O means, and the Fe3-APTES complex means that APTES is bonded to the coordinating unsaturated site of the Fe3 complex. In addition, Fe2Ni represents that two of the metals are Fe and one is Ni, and the μ-oxo center-metal trimer is [Fe ₂ Ni(μ ₃ -O)(CH ₃ COO) ₆ (H ₂ O) ₃ ]Cl· 3 H ₂ O means. Others are also represented in this way.

division	raw material	product
	Si-bonded μ-oxo core-multinuclear metal complex	synthetic zeolite
Example 1	Fe3-APTES complex (Production Example 1)	Fe3-APTES-ZSM-5 before firing
Example 2		Fe3-APTES-ZSM-5 after firing
Example 3	Fe2Ni-APTES complex (Production Example 2)	Fe2Ni-APTES-ZSM-5 before firing
Example 4		After firing Fe2Ni-APTES-ZSM-5
Example 5	Fe2Co-APTES complex (Production Example 3)	Fe2Co-APTES-ZSM-5 before firing
Example 6		Fe2Co-APTES-ZSM-5 after firing
Example 7	Ru2Co-APTES complex (Production Example 4)	Ru2Co-APTES-ZSM-5 before firing
Example 8		After firing Ru2Co-APTES-ZSM-5
Example 9	Ru2Ni-APTES complex (Preparation Example 5)	Ru2Ni-APTES-ZSM-5 before firing
Example 10		After firing Ru2Ni-APTES-ZSM-5
Comparative Example 1	TEOS	ZSM-5 before firing
Comparative Example 2		ZSM-5 after firing
Comparative Example 3	Fe3 complex	Fe3-ZSM-5 after firing
Comparative Example 4	-	Commercial ZSM-5

<Experimental Example 1: XRD analysis of zeolite synthesized in Examples and Comparative Examples>

XRD analysis was performed on the zeolite synthesized in Examples and Comparative Examples, and a graph of the results is shown in FIG. 4 .

4 , in Examples 1 and 2, compared to Comparative Examples 2 to 4, the XRD peaks in the entire 2theta (2θ) region appear at the same positions, so even through the Examples according to the present invention, the same structure It can be seen that the zeolite was synthesized.

Although not shown, it was confirmed that the zeolite was well synthesized in the XRD analysis of Examples 3 to 10.

<Experimental Example 2: SEM / EDS image analysis and TGA analysis of Examples 1 and 2 synthetic zeolite>

SEM/EDS image analysis was performed on the synthetic zeolite after calcination of Comparative Examples 3 and 2, and the results are shown in FIGS. 5 (Comparative Example 3) and 6 (Example 2), respectively.

5 and 6 (b) is an EDS image in which Si is labeled in red, (d) is in green with respect to Fe metal, and (e) is an image in which Si and Fe metal are simultaneously labeled. 5 and 6 (a) and (c) are images obtained by overlapping the EDS image of (b) or (d).

Referring to FIGS. 5 and 6 (a) and (c), it can be seen that the element dispersibility of Fe is better in the case of Example 2 in which APTES is combined according to the present invention.

TGA analysis was performed on the synthetic zeolites of Examples and Comparative Examples, and a graph of the results is shown in FIG. 7 .

<Experimental Example 3: Ar physical adsorption/desorption isotherm and pore distribution analysis of synthetic zeolite of Examples and Comparative Examples>

Figs. 8 and 9 show Ar physisorption and desorption isotherms and pore distribution graphs for the synthetic zeolites of Examples and Comparative Examples.

Referring to FIGS. 8 and 9 , it was confirmed that in both the synthetic zeolite of Example 2 and Comparative Example 3, micropores having a size of 5 Å were mainly formed.

In particular, referring to FIG. 9, in the case of Example 2 using the μ-oxo center-multinuclear metal composite modified by bonding Si according to the present invention, the average pore size of about 7.5 Å shown in Comparative Example 3 disappeared, the present invention It can be confirmed that the pore characteristics of the zeolite are changed when it is prepared by the synthetic zeolite manufacturing method according to

<Experimental Example 4: Analysis of Olefin Selectivity of Example 2 and Comparative Example 3 Synthetic Zeolites Used as Fischer-Tropsch Reaction Catalysts>

After charging the synthetic zeolite of Example 2 and Comparative Example 3 as a reaction catalyst in the Fischer-Tropsch reactor, H ₂ , CO and Ar were included in a molar ratio of 64:32:4 under a pressure of 2.0 MPa and a temperature of 300 ° C. the syngas introduced for two hours to Fischer-activation was the composite of zeolite Tropsch synthesis catalyst, the pressure 2.0 MPa, temperature of synthesis gas 330 ℃ h ₂ / CO molar ratio of 2.0, under conditions 1,000 mL g _cat ^-1 h Table 3 below shows the results of the Fischer-Tropsch reaction by input with a space velocity of ^{-1 for 30 hours.}

FT reaction catalyst	Temperature (℃)	Selectivity (C-mol%)			Olefin/ (Olefin + Paraffin)
		C1	C2-C4	C5+
after firing Fe3-APTES-ZSM-5 (Example 2)	330	28.45	20.22	51.33	51.61
after firing Fe3-ZSM-5 (Comparative Example 3)		35.14	17.64	47.22	40.38

Referring to Table 3 above, when the synthetic zeolite of Example 2 synthesized using Fe3 composite (Fe3-APTES) to which APTES is bonded according to the present invention was used as a catalyst, the olefin/(olefin+paraffin) value was 51.61. appear. For comparison, in the case of Comparative Example 3 synthesized using a Fe3 complex to which APTES is not bound according to the present invention, this value is 40.38, and the synthetic zeolite catalyst according to the present invention has higher olefin selectivity and lower methane selectivity. , which showed the possibility of using it as a catalyst for more efficient FT reaction.

As described above, the present invention has been described with reference to the accompanying drawings and examples, but this is merely exemplary, and it is understood that various modifications and equivalent other embodiments are possible by those skilled in the art. will understand Accordingly, the technical protection scope of the present invention should be defined by the following claims.

Claims (10)

1. B, Al, Ga, Si via a ligand containing an organic functional group having a lone pair of electrons capable of binding to the coordinating unsaturation site (CUS) of the metal of μ-oxo centered-multinuclear metal complexes , Ge, P, Ti, Zr, or at least one selected from Sn bonded, μ-oxo center-multinuclear metal complex compound.
2. According to claim 1,

   The organic functional group is a hydroxyl group (-OH), an alkoxide group (-OR), a carboxyl group (-COOH), a carboxylate anion group (-COO ^- ), an amino group (-NH2), an imino group (-NH), a nitrile group ( -CN), nitro group (-NO ₂ ), thiol group (-SH), halogen group (-X) and sulfonic acid group (-SO ₃ H), sulfonic acid anion group (-SO ₃ ^- ), methanedithioic acid group ( -CS ₂ H), methanedithioic acid anion group (-CS ₂ ^- ), phosphate group (-PO ₄ ^3- ), characterized in that the hydrocarbon having at least one selected from the group consisting of a pyridine group and a pyrazine group, B, Al, Ga, Si, Ge, P, Ti, Zr or at least one selected from Sn bonded, μ-oxo center-multinuclear metal complex compound.
3. According to claim 1,

   The μ-oxo center-multinuclear metal complex compound is a μ-oxo center to which one or more selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn, characterized in that it is represented by the following Chemical Formula 1 - Multinuclear metal complex compounds.

   [Formula 1]

   [(μ ₃ -O)M ^a M ^b M ^c (R ^a COO) ₆ E ^a E ^b E ^c ] D _f

   In Formula 1,

   And M ^a, M ^b, M ^c is the center of one of the μ- oxo-center and connected to the same metal as or different and each independently represent a transition metal, since the former metals, alkaline earth metals, semi-metals, lanthanide, Ill platinum group,

   said R ^a is a phosphine containing an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms, an amine containing carbon monoxide, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms or 6 to carbon atoms At least one selected from the group consisting of the same or different neutral ligands selected from nitrile containing an aryl group of 50, aromatic heterocyclic compounds having 2 to 50 carbon atoms having O, N, P or S as a hetero atom,

   said E ^a , E ^b , E ^c is a coordination material independently bonded to the metal linked to the μ-oxo center, each the same or different, pyridine, nitrogen-containing organic base, H ₂ O, organic solvent, substituted or unsubstituted C1 to C10 alcohols , phosphine including a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C50 aryl group, carbon monoxide, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted carbon number An amine containing 6 to 50 aryl group, a nitrile containing a substituted or unsubstituted C 1 to C 30 alkyl group or a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted and heteroatom O, N, Or any one of the same or different neutral ligands selected from aromatic heterocyclic compounds having 2 to 50 carbon atoms having S, and compounds represented by the following Chemical Formula 2, provided that E ^a , E ^b , E ^c Any one or more is necessarily a metal compound represented by the following formula (2),

   [Formula 2]

   M ^d R ^b _i R ^c _j R ^d _k R ^e _l

   In Formula 2, M ^d is at least one selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn,

   Wherein R ^b , R ^c , R ^d _, R ^e are the same or different, and each independently may be an ^{X-type ligand, or R L , and R b} , R ^c , R ^d _, R Any one or more of ^{e is necessarily R L} and i, j, k, and l are 0 to 3,

   Wherein R ^L is a hydroxy group (-OH), the alkoxide group (-OR), carboxyl group (-COOH), a carboxylic acid anion group (-COO-), an amino group (-NH ₂₎ on one side of the terminal that is not connected to the M ^d, imino group (-NH), nitrile group (-CN), nitro group (-NO ₂ ), thiol group (-SH), halogen group (-X) and sulfonic acid group (-SO ₃ H), sulfonic acid anion group (- SO ^3- ), a methanedithioic acid group (-CS ₂ H), a methanedithioic acid anion group (-CS ₂ ^- ), a phosphate group (-PO ₄ ^3- ), any one selected from the group consisting of a pyridine group and a pyrazine group A hydrocarbon having more than one functional group, ^{wherein the hydrocarbon constituting R L} is a saturated or unsaturated linear, branched, or cyclic hydrocarbon, and two or more of these hydrocarbons linked to each other and having 1 to 20 carbon atoms.

   D is a counter anion for maintaining the neutral charge of the complex represented by Formula 1, and f is any one rational number selected from 0 to 3.
4. Claims 1 to 3, wherein at least one selected from B, Al, Ga, Si, Ge, P, Ti, Zr, or Sn of any one of claims 1 to 3 is bonded μ-oxo center- comprising a multinuclear metal complex compound Raw material for the synthesis of molecular sieves.
5. A synthetic molecular sieve, characterized in that it is prepared using the raw material of claim 4.
6. a) removing one or more coordination materials coordinated to the μ-oxo core-multinuclear metal complex to form a coordinating unsaturation site; and

   b) preparing a compound in which one or more selected from B, Al, Ga, Si, Ge, P, Ti, Zr or Sn is bonded to the other end of the ligand including an organic functional group having an unshared electron pair;

   c) coordinating the compound of step (b) to the coordination unsaturated site of the μ-oxo center-polynuclear metal complex of step (a):

   It characterized in that it comprises, B, Al, Ga, Si, Ge, P, Ti, Zr or Sn or at least one selected from the bonded μ-oxo center- a method for producing a multinuclear metal complex compound.
7. 7. The method of claim 6,

   The step a) is 0 to 300 ℃, characterized in that the pressure is carried out at 0.001 to 1 atm, B, Al, Ga, Si, Ge, P, Ti, Zr or Sn at least one selected from bonded μ- A method for preparing an oxo core-multinuclear metal complex compound.
8. 1) One or more metals selected from transition metals or post-transition metals, alkaline earth metals, metalloids, lanthanum, and actinium group, through a ligand having an organic functional group having a lone pair of electrons as a mediator of μ-oxo center-polynuclear metal complex coordination Preparing a modified μ-oxo core-polynuclear metal complex compound bonded to an unsaturation site;

   2) sintering the modified μ-oxo center-multinuclear metal composite compound to remove organic matter to form a composite metal oxide;
9. 9. The method of claim 8,

   In the step 1), the coordination material coordinated to the μ-oxo center-multinuclear metal complex is removed by exposing the oxo center-multinuclear metal complex to high temperature and/or reduced pressure reaction conditions for a certain period of time at the coordinating unsaturated site formed,

   One or more selected from saturated or unsaturated linear, branched, and cyclic hydrocarbons has an organic functional group having a lone pair at one end of a hydrocarbon having 1 to 20 carbon atoms bonded to each other, and a transition metal or post-transition metal at the other end , alkaline earth metal, metalloid, lanthanum, and a compound to which one or more metals selected from the group consisting of actinium are bonded to each other through the lone pair of electrons.
10. 9. The method of claim 8,

    In step 1), the compound bound to the coordinating unsaturated site of the μ-oxo center-polynuclear metal complex through a ligand is the same as or different from the μ-oxo center-polynuclear metal complex of the μ-oxo center-polynuclear metal complex Method for producing a composite metal oxide, characterized in that the composite.

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