JP2022110295A - Transition metal complex-silicon complex and catalyst - Google Patents

Abstract

To provide a material that can be used as a reaction catalyst for hydrosilylation and the like.SOLUTION: A complex includes a transition metal complex, and a carrier carrying the transition metal complex, the carrier composed of a silicon material having an Si-H group, and the silicon material being selected from the group consisting of a silicon polymer, silicon ceramic, and metal silicon. A complex includes a transition metal, and a carrier carrying the transition metal, the carrier composed of a silicon material having an Si-H group, and the silicon material being selected from the group consisting of a silicon polymer, silicon ceramic, and metal silicon.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a composite of a transition metal complex and a carrier made of a silicon-based material and its use as a catalyst, particularly in reactions such as hydrosilylation.

A hydrosilylation reaction in which an Si—H functional compound is added to an unsaturated compound such as alkenes or alkynes is an industrially useful synthetic reaction that is widely used for the purpose of synthesizing organosilicides. The resulting organosilicon compounds (alkylsilanes or alkenylsilanes) are used in various fields as raw materials for producing silane coupling agents, silicone rubbers, silicone resins, and silicone oils.
Hydrosilylation reactions are typically carried out in the presence of a platinum catalyst. As typical platinum catalysts, Speier's catalyst, Karstedt's catalyst, (COD)PtCl ₂ catalyst and the like are often used in terms of catalytic activity and availability. However, platinum catalysts are very expensive because they contain platinum (Pt), which is an expensive noble metal element. There is a demand for metal compound catalysts that can be used at a lower cost, and many studies are being conducted.

As a noble metal-free metal catalyst, for example, an iron complex catalyst having a bisiminopyridine ligand has been reported (Non-Patent Document 1). However, this catalyst requires a special nitrogen tridentate ligand, is unstable against air and water and has poor handling properties, and is difficult to reuse because it is a homogeneous catalyst. There are problems such as
An iron or cobalt complex catalyst having an isocyanide ligand has also been reported (Non-Patent Document 2). However, since this catalyst is also a homogeneous catalyst, there is a problem that it is difficult to reuse.
In addition, various metal catalysts have been proposed (Non-Patent Documents 3 to 5). Since these catalysts are also homogeneous catalysts, they are difficult to reuse, and there is room for improvement in terms of catalytic activity, handleability, and the like.

Chirik, P.J., et al., Science, 2012, 335, 567-570 Nagashima, H., et al., J. Am. Chem. Soc. 2016, 138, 2480-2483 Deng, L., et al., ACS Catal. 2016, 6, 290-300 Hu, X, et al., Angew. Chem. Int. Ed. 2016, 55, 12295-12299 Holland, P. L., et al., J. Am. Chem. Soc. 2015, 137, 13244-13247

Under such circumstances, there is still a demand for novel catalysts that can be used for reactions such as hydrosilylation.

For example, the present invention is as follows.
[1] A transition metal complex and a carrier supporting the transition metal complex, the carrier being made of a silicon-based material having a Si—H group, the silicon-based material being a silicon-based polymer, silicon-based ceramics, and A composite selected from the group consisting of metallic silicon.
[2] A transition metal and a carrier supporting the transition metal, the carrier being made of a silicon-based material having a Si—H group, and the silicon-based material being a silicon-based polymer, silicon-based ceramics, and metallic silicon A complex selected from the group consisting of
[2a] to [1] or [2], wherein the transition metal complex or the transition metal contains at least one transition metal atom selected from the group consisting of transition metal atoms belonging to groups 7 to 11 of the periodic table; Described complex.
[3] The transition metal complex or the transition metal atom of the transition metal is at least selected from the group consisting of manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu) The complex according to [1] or [2], which is one species.
[4] The silicon-based polymer is selected from polysilane-based polymers, polysiloxane-based polymers, polysilazane-based polymers, polycarbosilane-based polymers, polymetallocarbosilane-based polymers and derivatives thereof, and polymers having SiH groups in side chains. The complex according to any one of [1] to [3] and [2a], comprising at least one selected.
[5] The complex according to any one of [1] to [4] and [2a], wherein the carrier is in the form of particles or plates.
[6] The composite according to any one of [1] to [5] and [2a], wherein the carrier is silicon particles having Si—H groups.
[7] The transition metal complex includes alkenes, alkynes, halogen atoms, organic acids, hydroxy, carbonyls, isocyanides, amines, imines, nitrogen-containing heterocycles, phosphines, arsines, alcohols, thiols, ethers, sulfides, nitriles, molecular The complex according to any one of [1] to [6] and [2a], comprising at least one ligand selected from hydrogen, molecular nitrogen, aldehydes, ketones and carbenes.
[8] The complex according to any one of [1] to [7] and [2a], wherein the transition metal atom of the transition metal complex and the silicon atom of the carrier are bonded.
[8a] The molar ratio (Si:M) between the silicon atoms (Si) contained in the complex and the transition metal atoms (M) in the transition metal complex is in the range of 100:1 to 1:10 (preferably 100 : 1 to 1:5, more preferably 50:1 to 1:2, still more preferably 20:1 to 1:1, particularly preferably 10:1 to 2:1). , [1] to [7], the complex according to any one of [2a].

[9] A catalyst comprising the composite according to any one of [1] to [8], [2a], and [8a].
[10] A catalyst used in a hydrosilylation reaction, a hydroboration reaction, or a coupling reaction, comprising the complex according to any one of [1] to [8], [2a], and [8a], catalyst.
[10a] The catalyst according to [9], wherein the coupling reaction is a Kumada-Tamao-Corriu coupling reaction.
[11] The catalyst according to any one of [9], [10] and [10a], which is a heterogeneous catalyst.

[12] In the presence of the catalyst according to any one of [9] to [11] and [9a], an aliphatic unsaturated bond-containing compound and/or a carbonyl group-containing compound and a Si—H group-containing compound, A method for producing a hydrosilylated product, comprising a hydrosilylation reaction.
[13] The hydrosilylated product is at least one selected from organosilicon reactants, silicone raw materials, silane coupling agents, silicone oils, silicone rubbers, silicone resins, alcohols, ethers, amines, thiols, and thioethers. The method according to [12].
[13a] In the presence of the catalyst according to any one of [9] to [11] and [9a], an unsaturated bond-containing compound and a B—H group-containing compound are subjected to a hydroboration reaction, A method for producing a hydroboride.
[14] The unsaturated bond-containing compound is an alkene, alkyne, imine, aldehyde, ketone, ester, amide, carboxylic acid, carboxylic anhydride, carboxylic acid halide, urea, thioaldehyde, thioketone, thioester, thioamide, thiocarboxylic acid , thiocarboxylic anhydride, thiocarboxylic acid halide, and thiourea.

[15] [1] to [8], [2a], [7a], including mixing a transition metal complex or its precursor with a silicon-based material having a Si—H group to form a composite A method for producing a composite according to any one of .
[15a] The composite according to any one of [1] to [8], [2a], and [8a], wherein the composite is obtained by mixing a transition metal complex and a silicon-based material having an Si—H group. A composite manufactured by a manufacturing method comprising forming a
[15b] A catalyst comprising the composite according to [15a].
[16] A catalytic reaction method, wherein the reaction is carried out using the catalyst according to any one of [9] to [11] and [9a].
[16a] The method of [16], wherein the catalytic reaction is a hydrosilylation reaction, a hydroboration reaction, or a coupling reaction.

The present invention has one or more of the following effects. (1) A transition metal complex or a novel composite of a transition metal and a carrier made of a silicon-based material is provided. The complex has catalytic activity in various reactions such as hydrosilylation, hydroboration, and coupling reactions. In some embodiments, methods are provided for performing reactions such as hydrosilylation, hydroboration reactions, coupling reactions, etc. using the complexes as catalysts.
(2) The catalyst is a heterogeneous catalyst and can be reused.
(3) A transition metal complex or a composite of a transition metal and a carrier made of a silicon-based material can be synthesized from inexpensive materials by a simple method. By using the catalyst, a product such as an organosilicon compound can be produced inexpensively and efficiently.

1A to 1D are schematic diagrams of composites in which a transition metal complex (ML _m ) is supported on polysilane, which is a silicon-based polymer, as a carrier according to one embodiment of the present invention. 2A to 2C are schematic diagrams of composites in which a transition metal complex (ML _m ) is supported on silicon particles made of metal silicon as a carrier according to one embodiment of the present invention. Hydrosilylation reaction of α-methylstyrene with silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) at reaction temperature of 60°C, 80°C, or 100°C for 1st run, 2nd run (2nd run) and 3rd (3rd run) hydrosilylate yields (yield/%) are shown.

Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the scope of the invention.
The upper and lower limits of the numerical ranges described herein can be arbitrarily combined. For example, when "A to B" and "C to D" are described, the ranges of "A to D" and "C to B" are also included in the present invention as numerical ranges.

The meanings of the terms and the like described in this specification are explained below.
"Hydrocarbon group" means a group obtained by removing one or more hydrogen atoms from a linear, cyclic or branched saturated or unsaturated hydrocarbon having a designated number of carbon atoms. Specific examples include alkyl groups, alkenyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkylene groups, alkenylene groups, and the like.
"Alkyl group" means a linear, branched, or cyclic monovalent saturated aliphatic hydrocarbon group having the specified number of carbon atoms.
"Alkenyl group" means a straight, branched, or cyclic monovalent hydrocarbon group having the specified number of carbon atoms and at least one carbon-carbon double bond. "Alkenylene group" means a straight or branched divalent hydrocarbon group having the specified number of carbon atoms and at least one carbon-carbon double bond. Examples of "alkenyl" and "alkenylene" include, but are not limited to, monoene, diene, triene and tetraene.
"Alkynyl group" means a linear, branched or cyclic monovalent hydrocarbon group having the indicated number of carbon atoms and at least one carbon-carbon triple bond.
An "aryl group" means an aromatic hydrocarbon cyclic group.
An "aralkyl group" means a group in which one of the hydrogen atoms of an alkyl group has been replaced with an aryl group.
The "halogen atom" specifically includes a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), and an iodine atom (I).

1. Composite One aspect of the present invention is a composite (hereinafter referred to as "composite (1 )”). Another aspect of the present invention is a composite (hereinafter "composite (2)") comprising a transition metal and a carrier that supports the transition metal, and the carrier is made of a silicon-based material having a Si—H group. Also called). Hereinafter, complex (1) and complex (2) are also collectively referred to as "complex". The complex of this form has catalytic activity in various reactions such as hydrosilylation reactions on aliphatic unsaturated bonds. Also, the catalyst is a heterogeneous catalyst and can be reused.

As used herein, the term "supported" refers to a state in which a transition metal complex or transition metal is attached or bound to a silicon-based material by chemical and/or physical means. Representative examples of the chemical means include chemical bonding. Specific examples of chemical bonds include covalent bonds, metallic bonds, coordinate bonds, ionic bonds, hydrogen bonds, and intermolecular forces (van der Waals forces). In some embodiments, the chemical bond is covalent, coordinate, or ionic. In some embodiments, chemical bonds are covalent bonds. Any appropriate fixing means other than chemical means can be employed as the physical means. Adsorption etc. are mentioned as a specific example.
Whether the silicon-based material carries a transition metal complex or a transition metal can be confirmed using infrared absorption spectrum, X-ray fluorescence analysis, XPS (X-ray photoelectron spectroscopy), and/or XAFS (X-ray absorption fine structure) analysis. can be confirmed.

In some embodiments, the composite has a chemical bond formed between a silicon atom (Si) of the silicon-based material and a transition metal atom. In this embodiment, the bond between the silicon atom and the transition metal atom is formed by reaction between the Si—H group (hydrosilyl group) of the silicon-based material and the transition metal complex, and the presence of such a bond causes the transition A metal complex can be stably supported on a carrier made of a silicon-based material.

式（Ｉ）中、Ｍは遷移金属原子を表し、Ｌは配位子を表し、ｍは、遷移金属原子に配位する配位子の数を表す。ｍは遷移金属原子の酸化数や配位子の種類により決定される。ｍは０以上の整数を表す。
幾つかの実施形態において、ｍは１以上の整数を表し、通常、１～６の整数を表す。ｍが１以上の整数である場合、複合体は、遷移金属錯体と、前記遷移金属錯体を担持する担体とを含み、前記担体はＳｉ－Ｈ基を有するケイ素系材料からなる（上記複合体（１）の形態）。
幾つかの実施形態において、ｍは０の整数を表す。ｍが０である場合、複合体は、遷移金属と、前記遷移金属を担持する担体とを含み、前記担体はＳｉ－Ｈ基を有するケイ素系材料からなる（上記複合体（２）の形態）。本発明の実施形態に係る複合体は、遷移金属錯体とケイ素系材料からなる担体とから形成されるが、複合体の形成過程において、遷移金属錯体の配位子が解離し、複合体形成後に複合体を構成する遷移金属錯体に配位子が含まれない場合（すなわち、上記式（I）中のｍが０である場合）がある。このような構造（例えば上記式（I）中のｍが０である構造）も本発明の複合体に包含される。また、一部の実施形態において、複合体を構成する遷移金属は、配位子が配位しているものと配位子が配位していないものとの組合せである場合がある。すなわち、複合体に含まれる遷移金属原子の一部は配位子を含む遷移金属錯体(例えば上記式（I）中のｍ≧１）の形態で担体に担持され、一部は配位子を含まない遷移金属の形態（例えば上記式（Ｉ）中のｍ＝０）で担体に担持されてもよい。 In the composite according to some embodiments, the transition metal atom (M) of the transition metal complex or transition metal forms a chemical bond with two adjacent silicon atoms in the silicon-based material (silicon polymer and silicon particles) as a support. is doing. Such a form of composite has advantages such as stabilization of the catalyst structure, improvement of catalyst performance, and improvement of reusability.
In certain embodiments, the conjugate has a structure represented by formula (I) below. In this specification, the types of chemical bonds such as covalent bonds, coordinate bonds and ionic bonds are represented by solid lines without particular distinction.

In formula (I), M represents a transition metal atom, L represents a ligand, and m represents the number of ligands coordinated to the transition metal atom. m is determined by the oxidation number of the transition metal atom and the type of ligand. m represents an integer of 0 or more.
In some embodiments, m represents an integer of 1 or greater, typically 1-6. When m is an integer of 1 or more, the composite includes a transition metal complex and a carrier that supports the transition metal complex, and the carrier is made of a silicon-based material having a Si—H group (the composite ( 1) form).
In some embodiments, m represents an integer of 0. When m is 0, the composite contains a transition metal and a carrier that supports the transition metal, and the carrier is made of a silicon-based material having a Si—H group (the form of the composite (2) above). . The composite according to the embodiment of the present invention is formed from a transition metal complex and a carrier made of a silicon-based material. In the process of forming the composite, the ligand of the transition metal complex is dissociated, There is a case where the transition metal complex that constitutes the complex does not contain a ligand (that is, the case where m in the above formula (I) is 0). Such structures (for example, structures in which m is 0 in formula (I) above) are also included in the complexes of the present invention. Also, in some embodiments, the transition metals that make up the complex may be a combination of ligand-coordinated and unliganded ones. That is, some of the transition metal atoms contained in the complex are supported on the carrier in the form of a transition metal complex containing ligands (for example, m≧1 in the above formula (I)), and some of the transition metal atoms contain ligands. It may be carried on the carrier in the form of a transition metal that does not contain it (for example, m=0 in the above formula (I)).

式（ＩＩ）におけるＭ、Ｌ、およびｍの定義は式（Ｉ）と同様である。 In the present invention, the composite form of the transition metal complex and silicon-based material is not limited to the above form. For example, the transition metal atom (M) may form a bond with one silicon atom, or may form a bond with two silicon atoms that are not adjacent to each other.
In some embodiments, the conjugate has a structure represented by formula (II) below.

The definitions of M, L, and m in formula (II) are the same as in formula (I).

式（ＩＩＩ）におけるＭ、Ｌ、およびｍの定義は式（Ｉ）と同様である。
式（ＩＩＩ）中、Ｙは、－Ｏ－、－ＣＲ^ＡＲ^Ｂ－、または－ＮＲ^Ａ－を示す。Ｒ^ＡおよびＲ^Ｂは各々独立して、水素原子又は炭素原子数１～３０のアルキル基および炭素原子数６～３０のアリール基である。
複合体における遷移金属原子と担体との間の結合の形態は単一のもの（例えば、上記式（I）、式（II）、式（III）のいずれか）であっても、複数種類の組合せ（例えば、上記式（I）、式（II）、および式（III）の２種以上の組合せ）であってもよい。 In some embodiments, the conjugate contains a structure represented by Formula (III) below.

The definitions of M, L, and m in formula (III) are the same as in formula (I).
In formula (III), Y represents -O-, -CR ^A R ^B -, or -NR ^A -. R ^A and R ^B are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms.
Even if the form of the bond between the transition metal atom and the carrier in the complex is a single one (for example, any of the formulas (I), (II), and (III) above), multiple types of It may be a combination (for example, a combination of two or more of formula (I), formula (II), and formula (III) above).

(Transition metal complex)
A transition metal complex has a structure in which one or more ligands (L) are coordinated to a transition metal atom (M).
As used herein, a "coordination bond" is an interaction between an electron pair donor and a coordination site on a metal (M) resulting in refers to an interaction in which an attractive force is generated between In some embodiments, a coordinate bond is formed between the silicon atom (Si) and the transition metal atom (M) in formulas (I)-(III) above.

The transition metal complex is not particularly limited as long as it can interact with the silicon atoms (Si) of the silicon-based material to form a complex. The ligand contained in the transition metal complex may be composed of one type, or may be a combination of two or more types. The transition metal atoms contained in the transition metal complex may consist of one type, or may be a combination of two or more types. Moreover, the complex may contain one type of transition metal complex, or may contain two or more types of transition metal complexes.

The transition metal atom contained in the transition metal complex is not particularly limited, and may be at least one transition metal atom selected from the group consisting of transition metal atoms belonging to groups 3 to 11 of the periodic table. Preferably, it is at least one transition metal atom that is a non-noble metal selected from the group consisting of transition metal atoms belonging to groups 7 to 11 of the periodic table. Among them, from the viewpoint of price and availability, manganese (Mn) , iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and at least one transition metal atom selected from the group consisting of zinc (Zn), from the viewpoint of catalytic activity and selectivity , manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu). These transition metal atoms can react with hydrosilyl groups (Si—H) of silicon-based materials to form bonds between silicon atoms (Si), thereby resulting in composites of transition metal complexes and silicon-based materials. can form bodies.

The ligand that constitutes the transition metal complex is not particularly limited as long as it is an organic group capable of coordinating with the transition metal atom. Examples thereof include two-electron ligands in which two electrons contained in the ligand coordinate to a transition metal atom. The two-electron ligand is not particularly limited, and any ligand conventionally used as a two-electron ligand for metal complexes can be used. Examples include ligands with lone pairs of electrons and/or π electrons. Typically, alkenes, alkynes, halogen atoms, organic acids, hydroxy, carbonyl (CO), isocyanides, amines, imines, nitrogen-containing heterocycles, phosphines, arsines, alcohols, thiols, ethers, sulfides, nitriles, molecular hydrogen , aldehydes, ketones and carbenes.

Although the isocyanide is not particularly limited, for example, those represented by Y--NC are suitable.
Here, Y may be substituted and is interposed by one or more atoms selected from an oxygen atom (O), a nitrogen atom (N), a sulfur atom (S) and a phosphorus atom (P). represents a monovalent organic group having 1 to 30 carbon atoms which may be substituted.
The monovalent organic group having 1 to 30 carbon atoms is not particularly limited, but a monovalent hydrocarbon group having 1 to 30 carbon atoms is preferable. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups and aralkyl groups.

The alkyl group may be linear, branched or cyclic, preferably an alkyl group having 1 to 10 carbon atoms, specific examples of which include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, Linear or branched alkyl groups such as n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosanyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl , norbornyl, and cycloalkyl groups such as adamantyl groups.

The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, and specific examples thereof include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2- butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, Examples include n-1-decenyl and n-1-eicosenyl groups.
The alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms, and specific examples thereof include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n- 3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n- butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecynyl, n-1-eicosinyl groups and the like.

The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and specific examples thereof include phenyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl and o-biphenylyl. , m-biphenylyl, and p-biphenylyl groups.

The aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and specific examples thereof include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl and naphthylpropyl groups. etc.

In addition, the monovalent organic group having 1 to 30 carbon atoms as Y may have a substituent, and may have a plurality of identical or different substituents at arbitrary positions. Specific examples of substituents include halogen atoms, alkoxy groups, amino groups such as dialkylamino groups, and the like.
Although the number of carbon atoms of the alkoxy group is not particularly limited, it preferably has 1 to 10 carbon atoms, and specific examples thereof include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, Examples include i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy and n-decyloxy groups.

Specific examples of isocyanide compounds include methyl isocyanide, ethyl isocyanide, n-propyl isocyanide, cyclopropyl isocyanide, n-butyl isocyanide, isobutyl isocyanide, sec-butyl isocyanide, t-butyl isocyanide, n-pentyl isocyanide, isopentyl isocyanide, Alkyl isocyanides such as neopentyl isocyanide, n-hexyl isocyanide, cyclohexyl isocyanide, cycloheptyl isocyanide, 1,1-dimethylhexyl isocyanide, 1-adamantyl isocyanide, 2-adamantyl isocyanide; phenyl isocyanide, 2-methylphenyl isocyanide, 4-methyl phenyl isocyanide, 2,4-dimethylphenyl isocyanide, 2,5-dimethylphenyl isocyanide, 2,6-dimethylphenyl isocyanide, 2,4,6-trimethylphenyl isocyanide, 2,4,6-tri-t-butylphenyl isocyanide, aryl isocyanide such as 2,6-diisopropylphenyl isocyanide, 1-naphthyl isocyanide, 2-naphthyl isocyanide, 2-methyl-1-naphthyl isocyanide; aralkyl isocyanide such as benzyl isocyanide and phenylethyl isocyanide; not to be

Amines include tertiary amines represented by R ₃ N.
Here, each R independently represents an alkyl group, an aryl group, or an aralkyl group optionally substituted with a halogen atom, a hydroxyl group (OH), or an alkoxy group.
Specific examples of a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, and an alkoxy group are the same as the organic groups or substituents exemplified above for Y.

Examples of imines include those represented by RC(=NR)R (wherein each R independently represents the same meaning as above). Among them, diimine (e.g., N,N'-bis(2,6-diisopropylphenyl)butane-2,3-diimine, N,N'-bis(2,4,6 -trimethylphenyl)ethane-1,2-diimine), bisiminopyridines, diamines, triamines are preferred.

Phosphines include, for example, those represented by R ₃ P (where each R independently represents the same meaning as above). Among them, tertiary alkylphosphine, tertiary arylphosphine (e.g., tri-tert-butylphosphine, triphenylphosphine, etc.), tertiary alkylphosphite, tertiary arylphosphite (tri methylolpropane phosphite, etc.) are preferred.

Arsines include, for example, those represented by R ₃ As (Rs independently represent the same meanings as above).

Examples of alcohols include those represented by ROH (R has the same meaning as above).

Thiols include those obtained by substituting a sulfur atom for the oxygen atom of the above alcohol.

Ethers include, for example, those represented by ROR (where each R independently represents the same meaning as above).

Sulfides include those obtained by substituting the oxygen atom of the above ether with a sulfur atom.

Nitriles include, for example, those represented by RCN (Rs independently represent the same meanings as above).

Examples of aldehydes include those represented by RCHO (R has the same meaning as above).

Ketones include, for example, those represented by RCOR (Rs independently represent the same meanings as above).

上記式（ｉ）において、Ｚは、炭素原子、窒素原子または酸素原子を表し、Ｚが炭素原子のとき、ｂは３であり、Ｚが窒素原子のとき、ｂは２であり、Ｚが酸素原子のとき、ｂは１である。
Ｒ¹およびＲ²は、互いに独立して、ハロゲン原子またはアルコキシ基で置換されていてもよい、炭素数１～３０のアルキル基、アリール基またはアラルキル基を表すが、Ｒ¹のいずれか１つと、Ｒ²のいずれか１つが結合して２価の有機基を構成して環状構造をとっていてもよく、この場合、環状構造内に窒素原子および／または不飽和結合を含んでいてもよい。
ハロゲン原子、炭素数１～３０のアルキル基、アリール基、およびアラルキル基、ならびにアルコキシ基の具体例はＹとしての有機基または置換基として上記で例示した基と同様のものが挙げられる。 Examples of carbenes include, but are not particularly limited to, those represented by the following formula (i).

In the above formula (i), Z represents a carbon atom, a nitrogen atom or an oxygen atom; when Z is a carbon atom, b is 3; when Z is a nitrogen atom, b is 2; When an atom, b is 1.
R ¹ and R ² independently represent an alkyl group, aryl group or aralkyl group having 1 to 30 carbon atoms and optionally substituted with a halogen atom or an alkoxy group, and any one of R ¹ and , R ² may combine to form a divalent organic group to form a cyclic structure, in which case the cyclic structure may contain a nitrogen atom and/or an unsaturated bond. .
Specific examples of a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, and an alkoxy group are the same as the organic groups or substituents exemplified above for Y.

Among them, as the carbene, a cyclic carbene compound is preferable. Specific examples of the cyclic carbene compound include, but are not limited to, the following compounds.

上記式（ｉｉ）および（ｉｉｉ）において、Ｒ¹⁰は、互いに独立して、水素原子または置換されていてもよい炭素数１～１０のアルキル基であり、アルキル基の具体例としては上記で例示した基と同様のものが挙げられる。
ビスイミノピリジン化合物の具体例としては、２，６－ビス［１－（２，６－ジメチルフェニルイミノ）エチル］ピリジン、２，６－ビス［１－（２，６－ジエチルフェニルイミノ）エチル］ピリジン、２，６－ビス［１－（２，６－ジイソプロピルフェニルイミノ）エチル］ピリジン等が挙げられる。
ターピリジン化合物の具体例としては、２，２’：６’，２”－テルピリジン等が挙げられる。 Examples of nitrogen-containing heterocycles include pyrrole, imidazole, pyridine, terpyridine, bisiminopyridine, pyrimidine, oxazoline, isoxazoline and derivatives thereof. Among them, a bisiminopyridine compound represented by the following formula (ii) and a terpyridine compound represented by the following formula (iii) are preferable.

In the above formulas (ii) and (iii), each R ¹⁰ is independently a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group are exemplified above. and the same groups as those described above.
Specific examples of the bisiminopyridine compounds include 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine and 2,6-bis[1-(2,6-diethylphenylimino)ethyl] pyridine, 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine and the like.
Specific examples of terpyridine compounds include 2,2′:6′,2″-terpyridine and the like.

Alkenes may be linear, branched or cyclic. Linear and branched alkenes include, for example, straight and branched alkenes having 2 to 30 carbon atoms, more preferably 2 to 16 carbon atoms. The cyclic alkene (cycloalkene) is, for example, a cycloalkene having 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and specific examples include cyclooctadiene, cyclooctatetraene, and the like.
Alkynes may be linear, branched or cyclic alkynes. Linear and branched alkynes include, for example, straight and branched alkynes having 2 to 30 carbon atoms, more preferably 2 to 14 carbon atoms.
The organic acid is not particularly limited, and any one conventionally known as a transition metal ligand can be used. Examples include carboxylic acids such as acetic acid, alcohols, phenols, and sulfonic acids.

In addition, the ligand constituting the transition metal complex may be a ligand (chelate) having multiple coordination sites.

Among them, carbonyl (CO), isocyanide, nitrogen-containing ligands (imine such as diimine, bisiminopyridine , amines such as trialkylamines), alkenes (e.g., ethylene and cyclooctadiene), phosphorus-containing ligands (tertiary phosphines such as alkylphosphines).
In one embodiment, the transition metal complex is a transition metal carbonyl (M(CO) _m [wherein M represents a transition metal atom and m represents an integer greater than or equal to 1, such as an integer from 1 to 6]), isocyanide Coordinated transition metal (ML _m [wherein M represents a transition metal atom, m represents an integer of 1 or more, for example, an integer of 1 to 6, and L represents an isocyanide]), transition metal-nitrogen-containing ligand complex (ML _m [wherein M represents a transition metal atom, m represents an integer of 1 or more, for example, an integer of 1 to 6, L represents a nitrogen-containing ligand]), alkene Coordination transition metal (ML _m [wherein M represents a transition metal atom, m represents an integer of 1 or more, such as an integer of 1 to 6, and L represents an alkene molecule]), phosphine coordination transition at least one selected from metals (ML _m [wherein M represents a transition metal atom, m represents an integer of 1 or more, for example, an integer of 1 to 6, and L represents a phosphine]) .

A specific example of the transition metal complex when the transition metal atom is manganese (Mn) is Mn ₂ (CO) ₁₀ .
Specific examples of transition metal complexes in which the transition metal atom is iron (Fe) include Fe(CO) ₅ , biiminopyridine-coordinated iron, and bis(phosphine)-coordinated iron.
A specific example of the transition metal complex in which the transition metal atom is cobalt (Co) is Co ₂ (CO) ₈ .
Specific examples of transition metal complexes where the transition metal atom is cobalt (Ni) include alkene-coordinated nickel such as biscyclooctadiene nickel.
Specific examples of transition metal complexes are described, for example, in Jikken Kagaku Koza <21> Organic Transition Metal Compounds, Supramolecular Complexes, and Comprehensive Organometallic Chemistry III, and the transition metal complexes disclosed therein are also suitably used in the present invention. can be used.

(Carrier)
The carrier consists of a silicon-based material having Si—H groups. Silicon-based materials are selected from the group consisting of silicon-based polymers, silicon-based ceramics, and metallic silicon.

In one embodiment, the support is a silicon-based polymer with Si—H groups.
As used herein, a silicon-based polymer refers to a polymer containing constitutional units containing silicon atoms. The silicon-based polymer of the present invention has Si—H groups, which may be introduced into the main chain of the polymer or into side chains of the polymer. Specifically, the silicon-based polymer includes (i) a polymer containing a silicon atom in the main skeleton (main chain), at least one of the silicon atoms in the main skeleton bonding to a hydrogen atom, and having a Si—H group; and (ii) polymers having Si—H groups in side chains.

(i) Examples of polymers containing silicon atoms (Si) in their main skeleton (main chain) include polysilane-based polymers, polysiloxane-based polymers, polysilazane-based polymers, polycarbosilane-based polymers, polymetallocarbosilane-based polymers, and these derivatives of The main chain skeleton of these silicon-based polymers can be linear, ladder-like, branched, cage-like, brush-like, star-like, cyclic, dendritic, etc. In the present invention, any skeleton can be used. Available.

A polysilane-based polymer refers to a polymer having a structure (polysilane structure) having a plurality of Si—Si bonds in its main skeleton (main chain).
A polysiloxane-based polymer refers to a polymer having a structure (polysiloxane structure) having a plurality of Si—O—Si bonds (siloxane bonds) in its main skeleton (main chain).
A polysilazane-based polymer refers to a polymer having a structure (polysilazane structure) having a plurality of Si—N bonds in its main skeleton (main chain).
A polycarbosilane-based polymer refers to a polymer having a structure (polycarbosilane structure) having a plurality of Si—C bonds (carbosilane bonds) in its main skeleton (main chain).
A polymetallocarbosilane-based polymer has a carbosilane bond and one or more metalloxane (-MO-, M: metal element such as Ti, Zr) bond in the main skeleton (main chain), and the carbosilane and metalloxane bonds are randomly bonded in the main chain skeleton and/or at least part of the silicon atoms of the carboxysilane bonds are bonded to each element of the metalloxane bonds via oxygen atoms, thereby Refers to a polymer in which the carbosilane moieties are crosslinked.
In addition to these, in the present invention, a polymer having two or more main chain skeletons containing silicon atoms in one molecule, such as a polysilane structure, a polysiloxane structure, and a polysiloxane structure, can be used.
Among these polymers, polymers having one or more Si—H groups may be used.

1A-1D are schematic diagrams of a composite 11 in which the carrier is polysilane, which is a silicon-based polymer, according to one embodiment of the present invention. 1A to 1D, M represents a transition metal atom, L represents a ligand, and polymer represents a polymer chain of polysilane. m represents the number of ligands coordinated to the transition metal atom. m represents an integer of 0 or more. m is selected according to the valence of the transition metal atom (M) and the type of ligand (charge of the ligand). When m is 0, the composite 11 is obtained by supporting the transition metal (M) on polysilane, which is a silicon-based polymer, as a carrier (in the form of the above composite (2)). m can be an integer greater than or equal to 1 (eg, an integer from 1 to 6). When m is an integer of 1 or more, the composite 11 is formed by supporting a transition metal complex (ML _m ) on polysilane, which is a silicon-based polymer, as a carrier (in the form of composite (1) above). n indicates the repeating number of the polymer, and is an integer from 10 to 1,000,000, for example.

The composite 11 shown in FIGS. 1A-1D is a chemical bond (—Si (-M(L _m ))- or -Si-M(L _m )-Si-) has a structural unit formed. The bond is formed by reaction of one or two hydrosilyl groups (Si—H) of the polysilane with a transition metal complex or precursor thereof. In some embodiments, the composite 11 forms a chemical bond (—Si—M(L _m )) between the transition metal atom (M) and two adjacent silicon atoms (Si) of the silicon-based polymer (polysilane). -Si-) (Fig. 1A). In some embodiments, the composite 11 has a chemical bond (-Si(-M(L _m )) between the transition metal atom (M) and one silicon atom (Si) of the silicon-based polymer (polysilane). -) (Fig. 1B). In some embodiments, composite 11 has both of its chemical bonds (—Si(—M(L _m ))— and —Si—M(L _m )—Si—) (FIG. 1C). In some embodiments, the composite 11 forms a chemical bond (-Si-M( L _m )—Si—) (FIG. 1D). In the composite 11 of some embodiments, two silicon atoms (Si) in the same polymer chain that are separated on the polymer chain of the silicon-based polymer are located close to each other due to folding of the polymer chain or the like. , may form a chemical bond with the transition metal atom (M) (not shown).
When the carrier is a silicon-based polymer, some of the _Si —H groups contained in the silicon-based polymer have a structure ( That is, the transition metal complex or the structure in which the Si—H groups to which the transition metal (ML _m ) is not bonded remain in the silicon-based polymer), or the Si—H groups contained in the silicon-based polymer A structure in which all of them form a chemical bond with the transition metal atom (M) of the transition metal complex or transition metal (ML _m ) (that is, there are Si—H groups to which no transition metal complex or transition metal (ML _m ) is bonded) structure).

(ii) A polymer having a Si—H group in a side chain is, for example, a structure having a Si—H group in the side chain of a polymer having a main chain structure such as a vinyl polymer such as polyvinyl alcohol or polystyrene. A polymer having a structure of Structures having a Si—H group include, for example, —Si(R) ₂ H such as a dimethylhydrosilyl group and a methylhydrosilyl group (wherein R is independently a hydrogen atom (H) or a 30 alkyl groups).
A specific example is polydimethylhydrosilylvinyl.

The shape of the silicon-based polymer is not particularly limited. For example, the silicon-based polymer may be particulate (powder), plate-like, film-sheet-like, or needle-like. In some embodiments, the carrier is a particulate or platy silicon-based polymer. In one embodiment, the carrier is particles (powder) of a silicon-based polymer.
The shape of the composite is not particularly limited when the carrier is a silicon-based polymer. For example, the composite may be particulate (powder), plate-like, film-sheet-like, or needle-like. In one embodiment, the composite is particulate (powdered).

In one embodiment, the support is a silicon-based ceramic with Si—H groups. As used herein, silicon-based ceramics refer to sintered bodies of inorganic compounds containing silicon atoms, such as oxides, carbides, nitrides and borides. Specific examples include silica ceramics, silicon nitride ceramics, silicon carbide ceramics, and silicon boride ceramics.
Silica ceramics refer to ceramics whose main component is silicon dioxide (SiO ₂ ).
Silicon nitride ceramics refers to ceramics whose main component is silicon nitride (Si ₃ N ₄ ).
Silicon carbide ceramics refers to non-oxide ceramics in which silicon carbide powder is sintered.
Silicon boride ceramics refer to ceramics whose main component is silicon boride (SiB, SiB ₃ , SiB ₄ , SiB ₆ or the like).
Among these silicon-based ceramics, materials having Si—H groups can be used. When the silicon-based ceramics do not contain Si—H groups, methods for introducing Si—H groups into the silicon-based ceramics include, for example, surface treatment such as treatment with hydrogen gas.

The shape of the silicon-based ceramics is not particularly limited. For example, silicon-based ceramics may be particulate (powder), plate-like, sheet-like, or needle-like. In some embodiments, the carrier is a particulate or platy silicon-based ceramic. In one embodiment, the carrier is silicon-based ceramic particles (powder).
The shape of the composite when the carrier is silicon-based ceramics is not particularly limited, and may be particulate (powder), plate-like, sheet-like, or It may be needle-like. In one embodiment, the composite is particulate (powdered).

In one embodiment, the support is metallic silicon with Si—H groups. As used herein, metallic silicon refers to metallic silicon, including elemental silicon and amorphous silicon. Any metal silicon can be used as long as it is composed of silicon atoms, mainly composed of Si--Si bonds, and has an Si--H group. In some embodiments, the metallic silicon having Si—H groups has a structure in which Si—H groups are partially introduced into metallic silicon (Si _n ) having only Si as a composition. In some embodiments, the metallic silicon having Si—H groups has a structure in which Si—H groups are partially introduced to the surface of metallic silicon (Si _n ) having only Si as a composition.
The shape of metal silicon is not particularly limited. For example, silicon-based ceramics may be particulate (powder), plate-like, sheet-like, or needle-like. In some embodiments, the carrier is particulate or platelet metallic silicon. In certain embodiments, the carrier is particles (powder) of metallic silicon (eg, silicon particles).
When the carrier is metallic silicon, the shape of the composite is not particularly limited, and may be particulate (powder), plate-like, sheet-like, or needle-like. .

2A-2C are schematic representations of composites where the carrier is metallic silicon according to one aspect of the present invention. 2A to 2C show a composite 12 in which a transition metal complex (ML _m ) is supported on hydrogen-terminated silicon particles (Si _n ), which are metallic silicon as a carrier. M, L, and m in FIGS. 2A-2C have the same meanings as in FIGS. 1A-1D. As shown in FIGS. 2A-2C, the composite 12 consists of a transition metal atom (M) of a transition metal complex (ML _m ) and one or two adjacent silicon atoms on the surface of a silicon particle (Si _n ). It has a structure in which a chemical bond (-Si(-M(L _m ))- or -Si-M(L _m )-Si-) is formed with (Si). The bond is formed by reaction of one or two adjacent hydrosilyl groups (Si—H) on the surface of hydrogen-terminated silicon particles (Si _n ) with transition metal complexes (ML _m ). In some embodiments, the complex 12 is formed between a transition metal atom (M) of a transition metal complex (ML _m ) and two adjacent silicon atoms (Si) on the surface of a silicon particle (Si _n ). It has a chemical bond (-Si-M(L _m )-Si-) (Fig. 2A). In some embodiments, the complex 12 forms a chemical bond between the transition metal atom (M) of the transition metal complex (ML _m ) and one silicon atom (Si) on the surface of the silicon particle (Si _n ). (-Si(-M(L _m ))-) (Fig. 2B). In some embodiments, composite 12 has both of its chemical bonds (-Si(-M(L _m ))- and -Si-M(L _m )-Si-) (Fig. 2C). In addition, in FIGS. 2A to 2C, in order to emphasize the bond between the silicon atom ( _Si ) and the transition metal atom (M), one or two transition metal complexes ( ML _m ) supported structure. However, the present invention is not limited to such a form. In some embodiments, multiple transition metal complexes (ML _m ) are supported via chemical bonds to silicon particles (Si _n ). In some embodiments, the composite 12 has a portion of the Si—H groups of the silicon particles (Si _n ) forming chemical bonds with the transition metal atoms (M) of the transition metal complex (ML _m ). In some embodiments, the composite 12 has all of the Si—H groups of the silicon particles (Si _n ) forming chemical bonds with the transition metal atoms (M) of the transition metal complexes (ML _m ).
The form of bonding between transition metal atoms (M) and silicon atoms (Si) (for example, any one of FIGS. 2A to 2C) can be controlled by adjusting the amount ratio of transition metal species and silicon.

In some embodiments, the carrier is particulate (or powdered).

The amount of the transition metal complex supported on the carrier (the weight ratio of the transition metal complex in the composite) may be appropriately set according to desired properties such as catalytic efficiency and selectivity. For example, when the composite is used as a catalyst, the molar ratio (Si:M) between silicon atoms (Si) and transition metal atoms (M) contained in the composite is in the range of 100: 1 to 1:10, preferably 100:1 to 1:5, more preferably 50:1 to 1:2, still more preferably 20:1 to 1:1, particularly preferably 10:1 to 2:1. It is preferred that a transition metal atom (M) is included as follows. The proportion of the transition metal complex supported on the carrier (ratio (molar ratio) between silicon atoms (Si) and transition metal atoms (M) in the complex) can be measured by fluorescent X-ray analysis.

Methods for introducing Si—H groups into metallic silicon include, for example, surface treatment such as cleaning with hydrofluoric acid.

2. Method for Producing Composite One aspect of the present invention relates to a method for producing the above-described composite. One form of composite manufacturing method includes mixing a transition metal complex or precursor thereof with a silicon-based material having Si—H groups to form a composite. In some aspects, the present invention provides a composite manufactured by a manufacturing method comprising mixing a transition metal complex or a precursor thereof with a silicon-based material having Si—H groups to form a composite. offer.
The composite of the present invention can be synthesized from a transition metal complex or its precursor and a silicon-based material by a very simple and mild method. This method does not require any special operation and can be synthesized from readily available and inexpensive raw materials, which is industrially very advantageous.

As the transition metal complex and the silicon-based material, those exemplified above can be used. A commercially available product may be used, or a synthetic product may be used.

式（Ｉ）中、Ｍは遷移金属原子を表し、Ｌは配位子を表し、ｍおよびｍ’は、遷移金属原子に配位する配位子の数を表す。ｍ’は１以上の整数を表し、通常、１～６の整数を表す。ｍは０以上の整数を表す。ｍおよびｍ’は遷移金属原子の酸化数や配位子の種類により決定される。
幾つかの実施形態において、ｍは０の整数である。当該実施形態では、複合体の形成過程において、遷移金属錯体の配位子が解離し、複合体形成後に複合体に配位子が含まれない。
幾つかの実施形態においてｍは１以上の整数を表し、通常、１～６の整数を表す。すなわち、上記スキーム１で表される反応式により得られる式（I）の複合体は、１以上（例えば１～６）の配位子を有する。 For example, when producing a composite of a transition metal complex containing, for example, alkenes, alkynes, carbonyl (CO), isocyanide, etc. as ligands and a silicon-based material, the transition metal complex and silicon having a Si—H group By mixing with the material, the transition metal atom (M) of the transition metal complex and the Si—H group of the silicon-based material react to form a bond between the silicon atom (Si) of the silicon-based material and the transition metal atom. , and the transition metal complex can be stably supported on the carrier made of a silicon-based material.
For example, the complex having the structure represented by the above formula (I) is a transition metal complex (ML _m' ) having a structure in which m' ligands (L) are coordinated to a transition metal atom (M). and a silicon-based material having two adjacent Si—H groups as shown in Scheme 1 below. In the scheme, some (for example, two) ligands (L) in the transition metal complex (ML _m′ ) are dissociated, and instead a bond is formed between the transition metal atom (M) and the silicon atom. obtain.

In formula (I), M represents a transition metal atom, L represents a ligand, and m and m' represent the number of ligands coordinated to the transition metal atom. m' represents an integer of 1 or more, usually an integer of 1-6. m represents an integer of 0 or more. m and m' are determined by the oxidation number of the transition metal atom and the type of ligand.
In some embodiments, m is an integer of 0. In this embodiment, the ligand of the transition metal complex is dissociated during the formation process of the complex, and the complex does not contain the ligand after the complex formation.
In some embodiments m represents an integer greater than or equal to 1, typically an integer from 1-6. That is, the complex of formula (I) obtained by the reaction formula represented by Scheme 1 above has one or more (eg, 1 to 6) ligands.

前記スキーム２中、Ｍは遷移金属原子を表し、Ｌは配位子を表し、ｍ、ｍ’およびｎは、遷移金属原子に配位する配位子の数を表す。ｍ’は１以上の整数を表し、通常、１～６の整数を表す。ｍは０以上の整数を表す。ｎは例えば１以上の整数を表し、通常、１～６の整数を表す。ｍ、ｍ’およびｎは遷移金属原子の酸化数や配位子の種類により決定される。ｎ’は１以上の整数（例えば、２）を表す。
幾つかの実施形態において、ｍは０の整数である。当該実施形態では、複合体の形成過程において、遷移金属錯体の配位子が解離し、複合体形成後に複合体に配位子が含まれない。
幾つかの実施形態においてｍは１以上の整数を表し、通常、１～６の整数を表す。すなわち、上記スキーム２で表される反応式により得られる式（I）の複合体は、１以上（例えば１～６）の配位子を有する。
遷移金属前駆体（Ｍ－Ｘ_ｎ）のＸ（例えば、ハロゲン原子や有機酸分子）は形成された複合体には通常残存しないが、場合によっては、複合体において一部のＸが残存し、遷移金属原子に配位した構造をとることもあり得る。 Examples of ligands include phosphorus-containing ligands (tertiary alkylphosphines such as 1,2-bis(diphenylphosphino)ethane) and nitrogen-containing ligands (imines such as diimine, bisiminopyridines such as In the case of producing a composite of a transition metal complex containing a nitrogen-containing heterocycle, a tertiary amine such as a trialkylamine, and a silicon-based material, a precursor of the transition metal complex and a Si—H group are combined. A method comprising mixing with a silicon-based material having
In some embodiments, the transition metal complex precursor comprises a transition metal precursor and a ligand molecule.
In some embodiments, a transition metal complex precursor comprising a transition metal precursor and a ligand molecule is mixed with a silicon-based material having Si—H groups in the presence of a reducing agent. In this embodiment, the transition metal precursor is reduced with a reducing agent to form a transition metal complex in which the ligand molecule is coordinated to the transition metal, and the transition metal atom (M) of this transition metal complex and the silicon-based material of the silicon-based material reacts with the Si—H group to form a bond between the silicon atom (Si) of the silicon-based material and the transition metal atom, and the transition metal complex can be stably supported on the carrier made of the silicon-based material. Examples of transition metal precursors include transition metal halides (MX _n [wherein M represents a transition metal atom, X represents F, Cl, Br, or I, and n represents an integer of 1 or more]), transition Complexes of organic acids of metals (MX _n [wherein M represents a transition metal atom, X represents an organic acid, and n represents an integer of 1 or more (eg, an integer of 1 to 6)]), a transition metal Hydroxide (M(OH) _n [In the formula, n represents an integer of 1 or more (eg, an integer of 1 to 6)]). Specific examples of transition metal halides include MnX ₂ , FeX ₂ , CoX ₂ , NiX ₂ (wherein X represents F, Cl, Br, or I). Specific examples of transition metal organic acids include manganese acetate, iron acetate, cobalt acetate, and nickel acetate. Specific examples of transition metal hydroxides include manganese hydroxide, iron hydroxide, cobalt hydroxide, and nickel hydroxide. The reducing agent may be appropriately selected according to the type of _{transition metal precursor} . aluminum (AlEt ₃ ), dibutyl aluminum hydride (Al[(CH ₃ ) ₂ CHCH ₂ ] ₂ H) and the like.
For example, the composite having the structure represented by the above formula (I) is formed by combining the transition metal precursor (M—X _n ) and the ligand molecule (L) with two adjacent Si—H It can be produced as shown in Scheme 2 below by mixing with a silicon-based material having a group. In Scheme 2, a transition metal precursor (M−X _n ) is reduced to dissociate X, a ligand molecule (L) is supported to form a transition metal complex (ML _m′ ), and then a transition A bond can be formed between the metal atom (M) and the silicon atom.

In Scheme 2, M represents a transition metal atom, L represents a ligand, and m, m' and n represent the number of ligands coordinated to the transition metal atom. m' represents an integer of 1 or more, usually an integer of 1-6. m represents an integer of 0 or more. n represents, for example, an integer of 1 or more, and usually represents an integer of 1-6. m, m' and n are determined by the oxidation number of the transition metal atom and the type of ligand. n' represents an integer of 1 or more (eg, 2).
In some embodiments, m is an integer of 0. In this embodiment, the ligand of the transition metal complex is dissociated during the formation process of the complex, and the complex does not contain the ligand after the complex formation.
In some embodiments m represents an integer greater than or equal to 1, typically an integer from 1-6. That is, the complex of formula (I) obtained by the reaction scheme represented by Scheme 2 above has one or more (eg, 1 to 6) ligands.
X (e.g., halogen atoms and organic acid molecules) of the transition metal precursor (M−X _n ) usually does not remain in the formed complex, but in some cases, some X remains in the complex, It may take a structure coordinated to a transition metal atom.

Mixing is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not affect the reaction. Examples include aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentylmethyl ether, tetrahydrofuran, 1,4-dioxane, and the like.
Although the temperature during mixing is not particularly limited, it can be carried out, for example, in the range of 0 to 300°C. In terms of reaction efficiency and ease of catalyst adjustment, the temperature is preferably in the range of 20 to 150°C, more preferably in the range of 20 to 80°C.
The mixing time is not particularly limited, but is about 1 to 48 hours, preferably 12 to 24 hours.
The mixing ratio of the transition metal complex or its precursor and the silicon-based material is appropriately set according to the reaction efficiency, catalytic activity and selectivity. For example, the molar ratio (Si:M) between the silicon atoms (Si) contained in the silicon material and the transition metal atoms (M) contained in the transition metal complex or its precursor is, for example, in the range of 100:1 to 1:10. , preferably in the range of 100:1 to 1:5, more preferably in the range of 50:1 to 1:2, still more preferably in the range of 20:1 to 1:1, particularly preferably in the range of 10:1 to 2:1 It is preferable to mix so that

The method of mixing the transition metal complex or its precursor and the silicon-based material is not particularly limited. Generally, both components are added to a solvent and stirred.
After mixing, purification treatment such as washing and filtration may be performed.
The complex obtained by the above method may be used after isolation, or may be used for the catalytic reaction described below without isolation. That is, the catalytic reaction can be carried out in the system without preparing the composite catalyst in the system and isolating it.

3. Catalyst One aspect of the present invention relates to a catalyst comprising a composite of the form described above. The above composites exhibit reactivity and selectivity as catalysts for various reactions and are widely applicable. Specific examples of applicable reactions include hydrosilylation reactions, hydroboration reactions, and coupling reactions (eg, Kumada-Tamao-Corriu coupling; also known as Grignard coupling).

Some embodiments of the present invention provide a catalytic reaction method characterized by carrying out a reaction using a catalyst containing the composite. The composite is a heterogeneous catalyst and is reusable. According to the method, a product such as an organosilicon compound can be produced inexpensively and efficiently.

The conditions for the reaction using the catalyst of the present embodiment are not particularly limited.
Although the reaction temperature varies depending on the type of reaction and reactants, it is preferably 0 to 200°C, more preferably 20 to 150°C, and even more preferably 20 to 80°C from the viewpoint of reaction efficiency.
The reaction time also varies depending on the type of reaction and reactants, but from the viewpoint of reaction efficiency, it is preferably 1 to 48 hours, more preferably 1 to 24 hours.

Although the reaction can be carried out without a solvent, an organic solvent may be used as necessary. The organic solvent is not particularly limited as long as it does not affect the reaction. Examples include aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentylmethyl ether, tetrahydrofuran, 1,4-dioxane, and the like.
When an organic solvent is used, the concentration of the catalyst is preferably 0.01 to 10 M, more preferably 0.1 to 5 M, as the molar concentration (M; mol/liter) of the catalyst, in consideration of catalytic activity and economy. .

The amount of the catalyst used is preferably 0.001 mol or more, more preferably 0.01 mol or more, and even more preferably 0.05 mol or more, per 1 mol of the compound that is the substrate. On the other hand, the amount of the catalyst to be used is not particularly limited, but is 10 mol or less, preferably 5 mol or less per 1 mol of the substrate, from an economical point of view.
In the reaction using the catalyst of the present invention, all of the components of the reactants and catalyst may be added all at once, or may be added in portions.
In some embodiments, the catalyst is particulate or powdered. That is, the particulate (powder) composite in the form described above can be used as a catalyst.

The catalyst of the present invention can have a high catalyst turnover number (TON). As used herein, catalyst turnover number (TON) refers to the number of moles of substrate that can be converted before one mole of catalyst becomes inactive. For example, in some embodiments, the catalyst of the present invention has a rpm greater than about 50, greater than about 100, greater than about 200, greater than about 400, greater than about 1,000, greater than about 5,000. (TON).
Various reactions using the composites described above as catalysts are described below.

(Hydrosilylation reaction)
Some forms of the present invention include hydrosilylation of an unsaturated bond-containing compound and a Si—H group-containing compound in the presence of at least one catalyst selected from the complexes described above. It is a method for producing compounds.
The complex can be used as a reaction catalyst for hydrosilylation reactions on aliphatic unsaturated bonds.

The unsaturated bond-containing compound is not particularly limited, and any compound conventionally used as a reactant in hydrosilylation reaction can be used. In the unsaturated bond-containing compound, the unsaturated bond may be present at the end of the molecule or inside the molecule, and multiple unsaturated bonds may be present in the molecule such as hexadiene and octadiene. As unsaturated bonds, carbon-carbon double bond (-C=C-), carbon-carbon triple bond (-C≡C-), carbonyl group (-C (=O)-), carbon-nitrogen double bond bond (-C(=NR)-), carbon-sulfur double bond (-C(=S)-) and the like.
Specific examples of unsaturated bond-containing compounds include alkenes, alkynes, imines, aldehydes, ketones, esters, amides, carboxylic acids, carboxylic acid anhydrides, carboxylic acid halides, urea, thioaldehydes, thioketones, thioesters, thioamides, and thiocarboxylic acids. , thiocarboxylic acid anhydrides, thiocarboxylic acid halides, allyl compounds, thioureas, and derivatives thereof.

The Si—H group-containing compound is not particularly limited, and any compound having an Si—H group conventionally used as a reactant in hydrosilylation reaction can be used. Examples include silanes and siloxanes.
(1) Silanes trimethoxysilane, triethoxysilane, triisopropoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, diethoxyphenylsilane, methoxydimethylsilane, ethoxydimethylsilane, triphenylsilane, diphenyldisilane , phenyltrisilane, diphenylmethylsilane, phenyldimethylsilane, diphenylmethoxysilane, diphenylethoxysilane, etc. (2) Siloxanes
Pentamethyldisiloxane, tetramethyldisiloxane, heptamethyltrisiloxane, octamethyltetrasiloxane, dimethylhydrogensiloxy end-blocked dimethylpolysiloxane, dimethylhydrogensiloxy end-blocked methylhydrogenpolysiloxane, trimethylsiloxy end-blocked methyl Hydrogen polysiloxane, dimethylhydrogensiloxy end-blocked (dimethylsiloxane/diphenylsiloxane) copolymer, trimethylsiloxy end-blocked (dimethylsiloxane/methylhydrosiloxane) copolymer, trimethylsiloxy end-blocked (dimethylsiloxane/diphenyl siloxane, methylhydrogensiloxane) copolymer, dimethylhydrogensiloxy group end-blocked (dimethylsiloxane/methylhydrogensiloxane) copolymer, dimethylhydrogensiloxy group end-blocked (dimethylsiloxane, methylhydrogensiloxane, diphenylsiloxane) Copolymers, terminal hydroxy group-blocked (dimethylsiloxane/methylhydrogensiloxane) copolymers, one-terminal dimethylhydrogensiloxy group-blocked dimethylpolysiloxanes, etc.

In the hydrosilylation reaction, the unsaturated bond-containing compound and the Si—H group-containing compound are used at a molar ratio of aliphatic unsaturated bond/Si—H bond, preferably 1/10 to 10/1, more preferably , 1/5 to 5/1, more preferably 1/3 to 3/1.

A hydrosilylation product of the unsaturated bond-containing compound and the Si—H group-containing compound is obtained by the hydrosilylation reaction. In some embodiments, the hydrosilylate is at least one selected from organosilicon reactants, silicone raw materials, silane coupling agents, silicone oils, silicone rubbers, silicone resins, alcohols, ethers, amines, thiols, and thioethers. is.

(Hydroboration reaction)
Some forms of the present invention include hydroboration reaction of an unsaturated bond-containing compound and a BH group-containing compound in the presence of at least one catalyst selected from the above complexes, A method for producing a hydroboride.
The complex can be used as a reaction catalyst for hydroboration reactions on aliphatic unsaturation.

Specific examples of the unsaturated bond-containing compound include the same compounds as exemplified in the hydrosilylation reaction above.
As the BH group-containing compound, any compound containing a BH group used in a conventional hydroboration reaction can be used without particular limitation. For example, BH3, _{H2BX (} where X is a halogen atom), _HBX2 (where X is a halogen atom), disiamylborane ((Sia) _2BH ), thexylborane (( _Thx )BH2 ), dicyclohexylborane (Cy ₂ BH), 9-borabicyclo[3.3.1]nonane (9-BBN), catecholborane (CatBH), pinacolborane (PinBH), diisopinocampheylborane (Ipc ₂ BH) etc.

When an alkene is used as the unsaturated bond-containing compound, an alkylborane is obtained as a hydroboride. This can be subsequently treated with hydrogen peroxide and a base (eg sodium hydroxide) to give the alcohol.

(Coupling reaction)
The conjugates of the above forms can be used as reaction catalysts in coupling reactions such as the Kumada-Tamao-Corriu coupling reaction.
Some forms of the present invention involve reacting an aromatic halide (Ar—X) with a Grignard reagent (R—MgX) in the presence of at least one catalyst selected from the above complexes. Methods for making cross-coupling products (Ar-R), including: Here, X is a halogen atom, Ar is an aryl group, and R is a hydrocarbon group.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified without departing from the gist of the present invention.
As used herein, "room temperature" generally indicates about 10°C to about 35°C.
As used herein, "%" indicates percent by weight unless otherwise specified.
As used herein, the term "about" can mean ±10%.

The abbreviations used in the examples are conventional abbreviations well known to those skilled in the art. Some abbreviations are listed below.
equiv. : equivalent rt: room temperature MeOH: methanol cod: 1,5-cyclooctadiene dppe: 1,2-bis(diphenylphosphino)ethane Me: methyl Et: ethyl Ph: phenyl TMS: trimethylsilyl Schlenk: Schlenk THF: tetrahydrofuran M: Molarity (mol/liter)
h: hours d: days IS: internal standard NMR: nuclear magnetic resonance conv. : conversion rate neat: no solvent dilution

The physical properties of the compounds and reaction products obtained in Synthesis Examples, Examples and Comparative Examples were measured using the following equipment.
¹ H NMR measurement: JNM-ECS400 spectrometer manufactured by JEOL and JNM-ECP600 spectrometer manufactured by JEOL
¹³ C NMR measurement: JNM-ECS400 spectrometer manufactured by JEOL and JNM-ECP600 spectrometer manufactured by JEOL
Infrared spectroscopy (IR) measurement: Spectrum Two manufactured by PerkinElmer
X-ray fluorescence analysis: JCX-1000S manufactured by JEOL

窒素雰囲気下で、攪拌子を入れた１００ｍＬのシュレンクフラスコに金属リチウム（８３０ｍｇ， １２０ｍｍｏｌ）とテトラヒドロフラン（３０ｍＬ）を混合した。このフラスコを０℃の氷浴につけ、窒素流下でトリクロロシラン（３．０ｍＬ， ３０ｍｍｏｌ）を滴下した。滴下終了後、室温下で２４時間激しく撹拌した。反応終了後、金属リチウム片を取り除き、黄土色懸濁液を得た。この黄土色懸濁液から遠心分離によって黄土色粉末を単離し、テトラヒドロフランで２回洗浄した。この粉末を十分乾燥後に１００ｍＬのシュレンクフラスコに移し、０℃の氷浴につけ、窒素流下でメタノール（２０ｍＬ）を滴下した。滴下終了後、室温下で終夜撹拌した。この黄土色懸濁液から遠心分離によって黄土色粉末を単離し、メタノールで２回洗浄し、十分乾燥することでケイ素系ポリマー１（８０２ｍｇ， １３．８ｍｍｏｌ， ９２％）を得た。 1. Transition metal complex-silicon-based polymer composite (1) Synthesis of silicon-based polymer [Synthesis Example 1: Synthesis of silicon-based polymer 1 (Si_polymer)]

Metallic lithium (830 mg, 120 mmol) and tetrahydrofuran (30 mL) were mixed in a 100 mL Schlenk flask containing a stir bar under a nitrogen atmosphere. The flask was placed in an ice bath at 0° C. and trichlorosilane (3.0 mL, 30 mmol) was added dropwise under a stream of nitrogen. After completion of dropping, the mixture was vigorously stirred at room temperature for 24 hours. After completion of the reaction, metal lithium pieces were removed to obtain an ocher suspension. An ocher powder was isolated from this ocher suspension by centrifugation and washed twice with tetrahydrofuran. After drying the powder thoroughly, it was transferred to a 100 mL Schlenk flask, immersed in an ice bath at 0° C., and methanol (20 mL) was added dropwise under a stream of nitrogen. After the dropwise addition was completed, the mixture was stirred overnight at room temperature. An ocher-colored powder was isolated from this ocher-colored suspension by centrifugation, washed with methanol twice, and sufficiently dried to obtain silicon-based polymer 1 (802 mg, 13.8 mmol, 92%).

窒素雰囲気下で、攪拌子を入れた１００ｍＬのシュレンクフラスコに金属リチウム（５２１ｍｇ， ７５ｍｍｏｌ）とテトラヒドロフラン（３０ｍＬ）を混合した。このフラスコを０℃の氷浴につけ、窒素流下でジクロロメチルシラン（３．１ｍＬ， ３０ｍｍｏｌ）を滴下した。滴下終了後、室温下で２４時間激しく撹拌した。反応終了後、金属リチウム片を取り除き、黄土色懸濁液を得た。この黄土色懸濁液から遠心分離によって薄黄色粉末を単離し、テトラヒドロフランで２回洗浄した。この粉末を十分乾燥後に１００ｍＬのシュレンクフラスコに移し、０℃の氷浴につけ、窒素流下でメタノール（２０ｍＬ）を滴下した。滴下終了後、室温下で終夜撹拌した。この薄茶色懸濁液から遠心分離によって薄茶色粉末を単離し、メタノールで２回洗浄し、十分乾燥することでメチル基置換ケイ素系ポリマー２（５４６ｍｇ， ６．１９ｍｍｏｌ， ４１％）を得た。 [Synthesis Example 2: Synthesis of methyl group-substituted silicon-based polymer 2 ( ^SiMe_polymer )]

Lithium metal (521 mg, 75 mmol) and tetrahydrofuran (30 mL) were mixed in a 100 mL Schlenk flask containing a stir bar under a nitrogen atmosphere. The flask was placed in an ice bath at 0° C. and dichloromethylsilane (3.1 mL, 30 mmol) was added dropwise under a stream of nitrogen. After the dropwise addition was completed, the mixture was vigorously stirred at room temperature for 24 hours. After completion of the reaction, metal lithium pieces were removed to obtain an ocher suspension. A pale yellow powder was isolated from this ocher suspension by centrifugation and washed twice with tetrahydrofuran. After drying the powder thoroughly, it was transferred to a 100 mL Schlenk flask, immersed in an ice bath at 0° C., and methanol (20 mL) was added dropwise under a stream of nitrogen. After completion of dropping, the mixture was stirred overnight at room temperature. A light brown powder was isolated from this light brown suspension by centrifugation, washed with methanol twice, and dried sufficiently to obtain a methyl group-substituted silicon-based polymer 2 (546 mg, 6.19 mmol, 41%).

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコにデカカルボニル二マンガン（９７ｍｇ， ０．２５ｍｍｏｌ）とメシチレン（５ｍＬ）を混合し、続けてケイ素系ポリマー１（２９ｍｇ， ０．５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１５０℃で２４時間撹拌した。反応終了後の黄色懸濁液から遠心分離によって黄土色粉末を単離し、テトラヒドロフランで４回洗浄した。その後、十分乾燥することでケイ素系ポリマー担持カルボニル配位マンガン触媒（３２ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｍｎ＝１６：１の組成比（シリコン原子とマンガン原子とのモル比）であることが確認された。 (2) Synthesis of composite [Example A-1: Synthesis of silicon-based polymer-supported carbonyl-coordinated manganese catalyst (Mn@Si_polymer)]

Under a nitrogen atmosphere, decacarbonyldimanganese (97 mg, 0.25 mmol) and mesitylene (5 mL) were mixed in a 50 mL Schlenk flask containing a stirrer, followed by addition of silicon-based polymer 1 (29 mg, 0.5 mmol). rice field. The flask was sealed with a glass stopper and stirred at 150° C. for 24 hours. An ocher powder was isolated from the yellow suspension after completion of the reaction by centrifugation and washed four times with tetrahydrofuran. Then, it was sufficiently dried to obtain a silicon-based polymer-supported carbonyl-coordinated manganese catalyst (32 mg). Fluorescent X-ray analysis confirmed that the composition ratio was Si:Mn=16:1 (molar ratio between silicon atoms and manganese atoms).

In the above chemical formula, as the structure of Mn@Si_polymer, for convenience, a structure in which Mn, which is a transition metal, is bonded to all Si—H groups of Si_polymer is shown. There may be those shown in A to D of 1. In addition, part of the Si—H groups of Si_polymer can remain without bonding to Mn, which is a transition metal. In other words, some of the Si—H groups of Si_polymer form bonds with the transition metal complex (carbonyl-coordinated manganese), and the remaining Si—H groups that do not form bonds remain as they are. Mn@Si_polymer can be a polymer containing (-Si(H)-Si(H)-) and (-Si(MnL _n )-Si-) units. The transition metal complex-silicon polymer composite in the following examples also shows a structure in which the transition metal is bonded to all of the Si—H groups for the sake of convenience.

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコにノナカルボニル二鉄（９１ｍｇ， ０．２５ｍｍｏｌ）とメシチレン（５ｍＬ）を混合し、続けてケイ素系ポリマー１（２９ｍｇ， ０．５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１５０℃で２４時間撹拌した。反応終了後の黒色懸濁液から遠心分離によって黒色粉末を単離し、テトラヒドロフランで４回洗浄した。その後、十分乾燥することでケイ素系ポリマー担持カルボニル配位鉄触媒（５０ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｆｅ＝５：１の組成比（シリコン原子と鉄原子とのモル比）であることが確認された。 [Example A-2: Synthesis of silicon-based polymer-supported carbonyl-coordinated iron catalyst (Fe@Si_polymer)]

Under a nitrogen atmosphere, nonacarbonyldiiron (91 mg, 0.25 mmol) and mesitylene (5 mL) were mixed in a 50 mL Schlenk flask containing a stirrer, followed by addition of silicon-based polymer 1 (29 mg, 0.5 mmol). rice field. The flask was sealed with a glass stopper and stirred at 150° C. for 24 hours. A black powder was isolated from the black suspension after completion of the reaction by centrifugation and washed four times with tetrahydrofuran. After that, it was sufficiently dried to obtain a silicon-based polymer-supported carbonyl-coordinated iron catalyst (50 mg). Fluorescent X-ray analysis confirmed that the composition ratio was Si:Fe=5:1 (molar ratio between silicon atoms and iron atoms).

窒素雰囲気下で、攪拌子を入れた１００ｍＬのシュレンクフラスコにオクタカルボニル二コバルト（３４２ｍｇ， １．０ｍｍｏｌ）とトルエン（２０ｍＬ）を混合し、続けてケイ素系ポリマー１（１１７ｍｇ， ２．０ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、６０℃で２４時間撹拌した。反応終了後のこげ茶色懸濁液から遠心分離によってこげ茶色粉末を単離し、テトラヒドロフランで４回洗浄した。その後、十分乾燥することでケイ素系ポリマー担持カルボニル配位コバルト触媒（２２０ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｃｏ＝２．４：１の組成比（シリコン原子とコバルト原子とのモル比）であることが確認された。 [Example A-3: Synthesis of silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]

Octacarbonyl dicobalt (342 mg, 1.0 mmol) and toluene (20 mL) were mixed in a 100 mL Schlenk flask containing a stirrer under a nitrogen atmosphere, followed by addition of silicon-based polymer 1 (117 mg, 2.0 mmol). rice field. The flask was sealed with a glass stopper and stirred at 60° C. for 24 hours. A dark brown powder was isolated from the dark brown suspension after completion of the reaction by centrifugation and washed four times with tetrahydrofuran. After that, it was sufficiently dried to obtain a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (220 mg). Fluorescent X-ray analysis confirmed that the composition ratio of Si:Co=2.4:1 (molar ratio between silicon atoms and cobalt atoms).

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコにビス（１，５－シクロオクタジエン）ニッケル（１３８ｍｇ， ０．５ｍｍｏｌ）とトルエン（５ｍＬ）を混合し、続けてケイ素系ポリマー１（２９ｍｇ， ０．５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１００℃で４８時間撹拌した。反応終了後の黒色懸濁液から遠心分離によって黒色粉末を単離し、テトラヒドロフランで４回洗浄した。その後、十分乾燥することでケイ素系ポリマー担持ニッケル触媒（５０ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｎｉ＝１：１の組成比（シリコン原子とニッケル原子とのモル比）であることが確認された。 [Example A-4: Synthesis of silicon-based polymer-supported nickel catalyst (Ni@Si_polymer)]

Bis(1,5-cyclooctadiene)nickel (138 mg, 0.5 mmol) and toluene (5 mL) were mixed in a 50 mL Schlenk flask containing a stirrer under a nitrogen atmosphere, followed by silicon-based polymer 1 (29 mg , 0.5 mmol) was added. The flask was sealed with a glass stopper and stirred at 100° C. for 48 hours. A black powder was isolated from the black suspension after completion of the reaction by centrifugation and washed four times with tetrahydrofuran. Then, it was sufficiently dried to obtain a silicon-based polymer-supported nickel catalyst (50 mg). Fluorescent X-ray analysis confirmed that the composition ratio was Si:Ni=1:1 (molar ratio between silicon atoms and nickel atoms).

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコにノナカルボニル二鉄（９１ｍｇ， ０．２５ｍｍｏｌ）とメシチレン（５ｍＬ）を混合し、続けてメチル基置換ケイ素系ポリマー２（４４ｍｇ， ０．５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１５０℃で２４時間撹拌した。反応終了後の茶色懸濁液から遠心分離によって茶色粉末を単離し、テトラヒドロフランで４回洗浄した。その後、十分乾燥することでメチル基置換ケイ素系ポリマー担持カルボニル配位鉄触媒（５５ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｆｅ＝３：１の組成比（シリコン原子と鉄原子とのモル比）であることが確認された。 [Example A-5: Synthesis of methyl group-substituted silicon-based polymer-supported carbonyl-coordinated iron catalyst (Fe@Si ^Me _polymer)]

Under a nitrogen atmosphere, nonacarbonyldiiron (91 mg, 0.25 mmol) and mesitylene (5 mL) were mixed in a 50 mL Schlenk flask containing a stirrer, followed by methyl group-substituted silicon-based polymer 2 (44 mg, 0.5 mmol). ) was added. The flask was sealed with a glass stopper and stirred at 150° C. for 24 hours. A brown powder was isolated from the brown suspension after completion of the reaction by centrifugation and washed four times with tetrahydrofuran. Then, by sufficiently drying, a methyl group-substituted silicon-based polymer-supported carbonyl-coordinated iron catalyst (55 mg) was obtained. Fluorescent X-ray analysis confirmed that the composition ratio was Si:Fe=3:1 (molar ratio between silicon atoms and iron atoms).

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコにオクタカルボニル二コバルト（８５ｍｇ， ０．２５ｍｍｏｌ）とトルエン（５ｍＬ）を混合し、続けてメチル基置換ケイ素系ポリマー２（４４ｍｇ， ０．５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１００℃で２４時間撹拌した。反応終了後の茶色懸濁液から遠心分離によって茶色粉末を単離し、テトラヒドロフランで４回洗浄した。その後、十分乾燥することでメチル基置換ケイ素系ポリマー担持カルボニル配位コバルト触媒（４７ｍｇ）を得た。 [Example A-6: Synthesis of methyl group-substituted silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si ^Me _polymer)]

Octacarbonyl dicobalt (85 mg, 0.25 mmol) and toluene (5 mL) were mixed in a 50 mL Schlenk flask containing a stirrer under a nitrogen atmosphere, followed by methyl group-substituted silicon-based polymer 2 (44 mg, 0.5 mmol). ) was added. The flask was sealed with a glass stopper and stirred at 100° C. for 24 hours. A brown powder was isolated from the brown suspension after completion of the reaction by centrifugation and washed four times with tetrahydrofuran. Then, it was sufficiently dried to obtain a carbonyl-coordinated cobalt catalyst (47 mg) supported on a methyl group-substituted silicon-based polymer.

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコに臭化鉄（ＩＩ）（１０８ｍｇ， ０．５ｍｍｏｌ）と１，２－ビス（ジフェニルホスフィノ）エタン（１９９ｍｇ， ０．５ｍｍｏｌ）とトルエン（５ｍＬ）を混合し、続けて水素化トリエチルホウ素リチウムのテトラヒドロフラン溶液（１．０１Ｍ， １．０ｍＬ， １ｍｍｏｌ）を滴下した。滴下後、ケイ素系ポリマー１（２９ｍｇ， ０．５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１００℃で２４時間撹拌した。反応終了後のこげ茶色懸濁液から遠心分離によって黄土色粉末を単離し、テトラヒドロフランで３回洗浄した。その後、十分乾燥することでケイ素系ポリマー担持ビス（ホスフィン）配位鉄触媒（２４ｍｇ）を得た。 [Example A-7: Synthesis of silicon-based polymer-supported bis(phosphine)-coordinated iron catalyst (Fe _dppe @Si_polymer)]

Under a nitrogen atmosphere, iron (II) bromide (108 mg, 0.5 mmol), 1,2-bis(diphenylphosphino)ethane (199 mg, 0.5 mmol) and toluene ( 5 mL) were mixed, and subsequently a solution of lithium triethylborohydride in tetrahydrofuran (1.01 M, 1.0 mL, 1 mmol) was added dropwise. After dropping, silicon-based polymer 1 (29 mg, 0.5 mmol) was added. The flask was sealed with a glass stopper and stirred at 100° C. for 24 hours. An ocher powder was isolated from the dark brown suspension after completion of the reaction by centrifugation and washed three times with tetrahydrofuran. After that, it was sufficiently dried to obtain a silicon-based polymer-supported bis(phosphine)-coordinated iron catalyst (24 mg).

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコに臭化鉄（ＩＩ）（１０８ｍｇ， ０．５ｍｍｏｌ）とピリジンジイミン配位子（ＰＤＩ^Ｍｅｓ）（１９９ｍｇ， ０．５ｍｍｏｌ）とトルエン（５ｍＬ）を混合し、続けて水素化トリエチルホウ素リチウムのテトラヒドロフラン溶液（１．０１Ｍ， １．０ｍＬ， １ｍｍｏｌ）を滴下した。滴下後、ケイ素系ポリマー１（２９ｍｇ， ０．５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１００℃で２４時間撹拌した。反応終了後の黒色懸濁液から遠心分離によって黒色粉末を単離し、テトラヒドロフランで３回洗浄した。その後、十分乾燥することでケイ素系ポリマー担持ピリジンジイミン配位鉄触媒（３１ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｆｅ＝１：２の組成比（シリコン原子と鉄原子とのモル比）であることが確認された。 [Example A-8: Synthesis of silicon-based polymer-supported pyridinediimine-coordinated iron catalyst (Fe _PDI ^Mes @Si_polymer)]

Under a nitrogen atmosphere, iron (II) bromide (108 mg, 0.5 mmol), pyridinediimine ligand (PDI ^Mes ) (199 mg, 0.5 mmol) and toluene (5 mL) were added to a 50 mL Schlenk flask containing a stir bar. ) were mixed, followed by dropwise addition of a tetrahydrofuran solution of lithium triethylborohydride (1.01 M, 1.0 mL, 1 mmol). After dropping, silicon-based polymer 1 (29 mg, 0.5 mmol) was added. The flask was sealed with a glass stopper and stirred at 100° C. for 24 hours. A black powder was isolated from the black suspension after completion of the reaction by centrifugation and washed three times with tetrahydrofuran. After that, it was sufficiently dried to obtain a silicon-based polymer-supported pyridinediimine-coordinated iron catalyst (31 mg). Fluorescent X-ray analysis confirmed that the composition ratio was Si:Fe=1:2 (molar ratio between silicon atoms and iron atoms).

(3) Reaction using a composite (catalyst) [Example B-1: Hydrosilylation reaction of α-methylstyrene using a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]

(first time)
Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (2.3 mg, 0.01 mmol) and α-methylstyrene (130 μL, 1 mmol) were added in a 20-mL Schlenk flask equipped with a stirrer. Mixed followed by the addition of 1,1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol). The flask was sealed with a glass stopper and stirred at 60° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and ¹ H NMR spectroscopy using dechloroform indicated a yield of >99% of the hydrosilylated product.

(Second time)
The reaction mixture was diluted with tetrahydrofuran and a black powder was isolated by centrifugation and washed twice with tetrahydrofuran. After sufficiently drying the black powder, it was transferred to a 20 mL Schlenk flask, and again α-methylstyrene (130 μL, 1 mmol) and 1,1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol) were added. C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard, and ¹ H NMR spectroscopy using deuterated chloroform indicated a 95% yield of the hydrosilylated product.

(3rd time)
As before, the reaction mixture was diluted with tetrahydrofuran and a black powder was isolated by centrifugation and washed twice with tetrahydrofuran. After sufficiently drying the black powder, it was transferred to a 20 mL Schlenk flask, and again α-methylstyrene (130 μL, 1 mmol) and 1,1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol) were added. C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard, and analysis by ¹ H NMR spectroscopy using deuterated chloroform indicated a yield of hydrosilylated product of 81%.

(Change of reaction temperature)
The above 1st to 3rd reactions were carried out by changing the reaction temperature from 60° C. to 80° C. or 100° C., and the yield of the hydrosilylated product in each reaction was measured by analysis by ¹ H NMR spectroscopy. The results are shown in FIG.
From FIG. 3, it is confirmed that the silicon-based polymer-supported carbonyl-coordinated cobalt catalyst of the present invention can be reused. Furthermore, it is confirmed that the reaction can be carried out at a temperature of 80° C. or lower (especially at a temperature of 60° C.) so that the catalyst can be reused without significantly impairing the catalytic efficiency.

窒素雰囲気下で、攪拌子を入れた１００ｍＬのシュレンクフラスコにてケイ素系ポリマー担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（１．２ｍｇ， ０．００５ｍｍｏｌ）とα－メチルスチレン（６．５ｍＬ， ５０ｍｍｏｌ）を混合し、続けて１，１，１，３，３－ペンタメチルジシロキサン（１１．７ｍＬ， ６０ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２１日間撹拌した。反応終了後、減圧蒸留（４８－５０℃／６Ｐａ）により精製することでヒドロシリル化生成物を無色液体として９．４６ｇ（３５．５ｍｍｏｌ， 収率７１％， 触媒回転数７１００）得た。
本発明のケイ素系ポリマー担持カルボニル配位コバルト触媒は、高い触媒回転数（ＴＯＮ）を示し、高効率な触媒であることが確認される。 [Example B-2: Hydrosilylation reaction of α-methylstyrene using a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (scale-up)]

Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (1.2 mg, 0.005 mmol) and α-methylstyrene (6.5 mL, 50 mmol) were added in a 100 mL Schlenk flask equipped with a stirrer. ) was mixed followed by the addition of 1,1,1,3,3-pentamethyldisiloxane (11.7 mL, 60 mmol). The flask was sealed with a glass stopper and stirred at 80° C. for 21 days. After completion of the reaction, the product was purified by distillation under reduced pressure (48-50° C./6 Pa) to obtain 9.46 g (35.5 mmol, yield 71%, catalyst turnover number 7100) of a hydrosilylation product as a colorless liquid.
The silicon-based polymer-supported carbonyl-coordinated cobalt catalyst of the present invention exhibits a high catalyst turnover number (TON), confirming that it is a highly efficient catalyst.

[Example B-3: Hydrosilylation reaction of various alkenes using silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]
Using a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) as a catalyst, hydrosilylation reactions (entries 1-7) were carried out with various combinations of alkenes and silane compounds shown in Table 1.

¹H NMR (600 MHz, CDCl₃) δ = 7.27 (t, J = 7.7 Hz, 2H), 7.21 (dd, J = 6.6, 1.6 Hz, 2H), 7.16 (tt, J = 7.4, 1.4 Hz, 1H), 2.91 (sextet, J = 7.0 Hz, 1H), 1.28 (d, J = 7.2 Hz, 3H), 0.98-0.90 (m, 2H), 0.05 (s, 9H), -0.06 (s, 3H), -0.07 (s, 3H);
¹³C NMR (150 MHz, CDCl₃) δ = 149.9, 128.3, 126.6, 125.7, 35.7, 28.5, 25.9, 2.0, 1.3, 0.9;
これらスペクトルデータは文献値と良い一致をした。（後述の文献Ｓ１） (entry 1)
Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (1.2 mg, 0.005 mmol) and α-methylstyrene (650 μL, 5 mmol) were placed in a 20-mL Schlenk flask equipped with a stirrer. Mixed followed by the addition of 1,1,1,3,3-pentamethyldisiloxane (1170 μL, 6 mmol). The flask was sealed with a glass stopper and stirred at 60° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard, and analysis by ¹ H NMR spectroscopy using deuterated chloroform indicated a 98% yield of the hydrosilylated product. Purification by vacuum distillation (60-65° C./6 Pa) gave 1.042 g (3.91 mmol, 78% yield) of the hydrosilylated product as a colorless liquid.

¹ H NMR (600 MHz, CDCl ₃ ) δ = 7.27 (t, J = 7.7 Hz, 2H), 7.21 (dd, J = 6.6, 1.6 Hz, 2H), 7.16 (tt, J = 7.4, 1.4 Hz, 1H ), 2.91 (sextet, J = 7.0 Hz, 1H), 1.28 (d, J = 7.2 Hz, 3H), 0.98-0.90 (m, 2H), 0.05 (s, 9H), -0.06 (s, 3H), -0.07 (s, 3H);
^13C NMR (150 MHz, _CDCl3 ) δ = 149.9, 128.3, 126.6, 125.7, 35.7, 28.5, 25.9, 2.0, 1.3, 0.9;
These spectral data are in good agreement with literature values. (Document S1 to be described later)

¹H NMR (600 MHz, CDCl₃) δ = 1.32-1.22 (m, 16H), 0.88 (t, J = 6.9 Hz, 3H), 0.50 (t, J= 8.0 Hz, 2H), 0.06 (s, 9H), 0.03 (s, 6H);
¹³C NMR (150 MHz, CDCl₃) δ = 33.4, 31.9, 29.7, 29.6, 29.41, 29.38, 23.3, 22.7, 18.4, 14.1, 2.0, 0.3;
これらスペクトルデータは文献値と良い一致をした。（後述の文献Ｓ２） (entry 2)
Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (1.2 mg, 0.005 mmol) and 1-decene (950 μL, 5 mmol) were mixed in a 20-mL Schlenk flask equipped with a stirrer. followed by the addition of 1,1,1,3,3-pentamethyldisiloxane (1170 μL, 6 mmol). The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to quantitatively show hydrosilylation products. Purification by vacuum distillation (70° C./8 Pa) gave 1.241 g (4.30 mmol, 86% yield) of the hydrosilylated product as a colorless liquid.

¹ H NMR (600 MHz, CDCl ₃ ) δ = 1.32-1.22 (m, 16H), 0.88 (t, J = 6.9 Hz, 3H), 0.50 (t, J = 8.0 Hz, 2H), 0.06 (s, 9H ), 0.03 (s, 6H);
^13C NMR (150 MHz, _CDCl3 ) δ = 33.4, 31.9, 29.7, 29.6, 29.41, 29.38, 23.3, 22.7, 18.4, 14.1, 2.0, 0.3;
These spectral data are in good agreement with literature values. (Document S2 to be described later)

¹H NMR (600 MHz, CDCl₃) δ = 7.28 (t, J = 7.7 Hz, 2H), 7.21 (d, J = 7.7 Hz, 2H), 7.16 (t, J = 7.1 Hz, 1H), 2.68-2.62 (m, 2H), 0.92-0.87 (m, 2H), 0.09 (s, 9H), 0.07 (s, 6H);
¹³C NMR (150 MHz, CDCl₃) δ = 145.2, 128.3, 127.8, 125.5, 29.4, 20.4, 2.0, 0.3;
これらスペクトルデータは文献値と良い一致をした。（後述の文献Ｓ１） (entry 3)
Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (2.3 mg, 0.01 mmol) and styrene (115 μL, 1 mmol) were mixed in a 20 mL Schlenk flask equipped with a stirrer, 1,1,1,3,3-Pentamethyldisiloxane (235 μL, 1.2 mmol) was subsequently added. The flask was sealed with a glass stopper and stirred at 60° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard, and analysis by ¹ H NMR spectroscopy using deuterated chloroform indicated a yield of hydrosilylated product of 89%. Purification by vacuum distillation (42° C./6 Pa) gave 190 mg (0.752 mmol, 75% yield) of the hydrosilylated product as a colorless liquid.

¹ H NMR (600 MHz, CDCl ₃ ) δ = 7.28 (t, J = 7.7 Hz, 2H), 7.21 (d, J = 7.7 Hz, 2H), 7.16 (t, J = 7.1 Hz, 1H), 2.68- 2.62 (m, 2H), 0.92-0.87 (m, 2H), 0.09 (s, 9H), 0.07 (s, 6H);
^13C NMR (150 MHz, _CDCl3 ) δ = 145.2, 128.3, 127.8, 125.5, 29.4, 20.4, 2.0, 0.3;
These spectral data are in good agreement with literature values. (Document S1 to be described later)

¹H NMR (600 MHz, CDCl₃) δ = 7.55-7.52 (m, 2H), 7.38-7.36 (m, 3H), 7.28-7.24 (overlap with solvent, 2H), 7.19-7.14 (m, 3H), 2.66-2.61 (m, 2H), 1.15-1.10 (m, 2H), 0.29 (s, 6H);
¹³C NMR (150 MHz, CDCl₃) δ = 145.0, 139.0, 133.6, 128.9, 128.3, 127.8, 127.7, 125.5, 29.9, 17.7, -3.1;
これらスペクトルデータは文献値と良い一致をした。（後述の文献Ｓ１） (entry 4)
Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (2.3 mg, 0.01 mmol) and styrene (115 μL, 1 mmol) were mixed in a 20 mL Schlenk flask equipped with a stirrer, Dimethylphenylsilane (185 μL, 1.2 mmol) was subsequently added. The flask was sealed with a glass stopper and stirred at 60° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to quantitatively show hydrosilylation products. Purification by silica gel column chromatography (eluent: hexane, R _f =0.40) gave 219 mg (0.911 mmol, yield 91%) of the hydrosilylated product as a colorless liquid.

¹ H NMR (600 MHz, CDCl ₃ ) δ = 7.55-7.52 (m, 2H), 7.38-7.36 (m, 3H), 7.28-7.24 (overlap with solvent, 2H), 7.19-7.14 (m, 3H), 2.66-2.61 (m, 2H), 1.15-1.10 (m, 2H), 0.29 (s, 6H);
^13C NMR (150 MHz, _CDCl3 ) δ = 145.0, 139.0, 133.6, 128.9, 128.3, 127.8, 127.7, 125.5, 29.9, 17.7, -3.1;
These spectral data are in good agreement with literature values. (Document S1 to be described later)

¹H NMR (600 MHz, CDCl₃) δ = 3.71 (dd, J = 11.5, 3.3 Hz, 1H), 3.50-3.41 (m, 2H), 3.39 (dd, J= 11.5, 6.1 Hz, 1H), 3.18-3.14 (m, 1H), 2.80 (t, J = 4.9 Hz, 1H), 2.62 (dd, J = 4.9, 2.8 Hz, 1H), 1.64-1.57 (m, 2H), 0.53-0.48 (m, 2H), 0.06 (s, 9H), 0.05 (s, 6H);
¹³C NMR (150 MHz, CDCl₃) δ = 74.3, 71.4, 50.9, 44.3, 23.5, 14.2, 1.9, 0.2;
これらスペクトルデータは文献値と良い一致をした（後述の文献Ｓ１）。 (entry 5)
Under a nitrogen atmosphere, silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (2.3 mg, 0.01 mmol) and allyl glycidyl ether (118 μL, 1 mmol) were mixed in a 20-mL Schlenk flask equipped with a stirrer. followed by the addition of 1,1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol). The flask was sealed with a glass stopper and stirred at 60° C. for 24 hours. After completion of the reaction, dibromomethane (70 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to quantitatively show hydrosilylation products. Purification by vacuum distillation (48° C./8 Pa) gave 213 mg (0.811 mmol, 81% yield) of the hydrosilylated product as a colorless liquid.

¹ H NMR (600 MHz, CDCl ₃ ) δ = 3.71 (dd, J = 11.5, 3.3 Hz, 1H), 3.50-3.41 (m, 2H), 3.39 (dd, J = 11.5, 6.1 Hz, 1H), 3.18 -3.14 (m, 1H), 2.80 (t, J = 4.9 Hz, 1H), 2.62 (dd, J = 4.9, 2.8 Hz, 1H), 1.64-1.57 (m, 2H), 0.53-0.48 (m, 2H ), 0.06 (s, 9H), 0.05 (s, 6H);
¹³ C NMR (150 MHz, CDCl ₃ ) δ = 74.3, 71.4, 50.9, 44.3, 23.5, 14.2, 1.9, 0.2;
These spectral data agreed well with literature values (Literature S1 described later).

¹H NMR (600 MHz, CDCl₃) δ = 3.70 (dd, J = 11.6, 3.3 Hz, 1H), 3.49-3.37 (m, 3H), 3.17-3.15 (m, 1H), 2.80 (t, J = 4.7 Hz, 1H), 2.62 (dd, J = 5.5, 2.8 Hz, 1H), 1.64-1.57 (m, 2H), 0.47-0.43 (m, 2H), 0.08 (s, 18H), 0.01 (s, 3H);
¹³C NMR (150 MHz, CDCl₃) δ = 74.2, 71.4, 50.9, 44.4, 23.3, 13.5, 1.8, -0.4;
これらスペクトルデータは文献値と良い一致をした（後述の文献Ｓ３）。 (entry 6)
Under a nitrogen atmosphere, silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (2.3 mg, 0.01 mmol) and allyl glycidyl ether (118 μL, 1 mmol) were mixed in a 20-mL Schlenk flask equipped with a stirrer. followed by the addition of 1,1,1,3,5,5,5-heptamethyltrisiloxane (325 μL, 1.2 mmol). The flask was sealed with a glass stopper and stirred at 60° C. for 24 hours. After completion of the reaction, dibromomethane (70 μL, 1 mmol) was added as an internal standard, and ¹ H NMR spectroscopy using deuterated chloroform indicated a 95% yield of the hydrosilylated product. Purification by vacuum distillation (60° C./8 Pa) gave 267 mg (0.793 mmol, 79% yield) of the hydrosilylated product as a colorless liquid.

¹ H NMR (600 MHz, CDCl ₃ ) δ = 3.70 (dd, J = 11.6, 3.3 Hz, 1H), 3.49-3.37 (m, 3H), 3.17-3.15 (m, 1H), 2.80 (t, J = 4.7 Hz, 1H), 2.62 (dd, J = 5.5, 2.8 Hz, 1H), 1.64-1.57 (m, 2H), 0.47-0.43 (m, 2H), 0.08 (s, 18H), 0.01 (s, 3H) );
^13C NMR (150 MHz, _CDCl3 ) δ = 74.2, 71.4, 50.9, 44.4, 23.3, 13.5, 1.8, -0.4;
These spectral data were in good agreement with literature values (literature S3 described later).

¹H NMR (600 MHz, CDCl₃) δ = 0.43-0.38 (m, 2H), 0.37-0.31 (m, 2H), 0.09 (s, 18H), 0.06 (s, 9H), 0.03 (s, 6H), 0.002 (s, 3H);
¹³C NMR (150 MHz, CDCl₃) δ = 9.5, 8.9, 2.0, 1.9, -0.4, -1.2;
これらスペクトルデータは文献値と良い一致をした（後述の文献Ｓ１）。 (entry 7)
Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (2.3 mg, 0.01 mmol) and vinylmethylbis(trimethylsiloxy)silane (290 μL) were placed in a 20-mL Schlenk flask equipped with a stir bar. , 1 mmol) was mixed followed by the addition of 1,1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol). The flask was sealed with a glass stopper and stirred at 60° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to quantitatively show hydrosilylation products. Purification by vacuum distillation (49° C./10 Pa) gave 328 mg (0.826 mmol, 83% yield) of the hydrosilylated product as a colorless liquid.

¹ H NMR (600 MHz, CDCl ₃ ) δ = 0.43-0.38 (m, 2H), 0.37-0.31 (m, 2H), 0.09 (s, 18H), 0.06 (s, 9H), 0.03 (s, 6H) , 0.002 (s, 3H);
^13C NMR (150 MHz, _CDCl3 ) δ = 9.5, 8.9, 2.0, 1.9, -0.4, -1.2;
These spectral data agreed well with literature values (Literature S1 described later).

窒素雰囲気下で、攪拌子を入れた20 mLのシュレンクフラスコにケイ素ポリマー担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（２．３ｍｇ， ０．０１ｍｍｏｌ）とイソシアヌル酸トリアリル（８２ｍｇ， ０．３３ｍｍｏｌ）を混合し、続けて１，１，１，３，３－ペンタメチルジシロキサン（３２０μＬ， １．６５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、１，４－ジオキサン（８５μＬ， １ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することで収率９０％のヒドロシリル化生成物が示された。濃縮後、アルミナカラム（溶離液：酢酸エチル）により触媒を取り除き、ゲル浸透クロマトグラフィーで精製することでヒドロシリル化生成物を無色液体として１６５ｍｇ （０．２３８ｍｍｏｌ， 収率７２％）得た。

¹H NMR (600 MHz, CDCl₃) δ =3.84 (t, J = 7.7 Hz, 6H), 1.67-1.60 (m, 6H), 0.54-0.50 (m, 6H), 0.05 (s, 45H);
¹³C NMR (150 MHz, CDCl₃) δ = 149.0, 45.6, 21.8, 15.3, 1.9, 0.2; [Example B-4: Hydrosilylation of triallyl isocyanurate using a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]

Under a nitrogen atmosphere, silicon polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (2.3 mg, 0.01 mmol) and triallyl isocyanurate (82 mg, 0.33 mmol) were placed in a 20 mL Schlenk flask equipped with a stir bar. Mixed followed by the addition of 1,1,1,3,3-pentamethyldisiloxane (320 μL, 1.65 mmol). The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added and ¹ H NMR spectroscopy using dechloroform indicated a 90% yield of the hydrosilylated product. After concentration, the catalyst was removed by an alumina column (eluent: ethyl acetate) and purification by gel permeation chromatography gave 165 mg (0.238 mmol, yield 72%) of a hydrosilylated product as a colorless liquid.

¹ H NMR (600 MHz, CDCl ₃ ) δ =3.84 (t, J = 7.7 Hz, 6H), 1.67-1.60 (m, 6H), 0.54-0.50 (m, 6H), 0.05 (s, 45H);
^13C NMR (150 MHz, _CDCl3 ) δ = 149.0, 45.6, 21.8, 15.3, 1.9, 0.2;

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにてケイ素系ポリマー担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（２．３ｍｇ， ０．０１ｍｍｏｌ）とアリルグリシジルエーテル（２３５μＬ， ２ｍｍｏｌ）を混合し、続けて重合度が６の水素末端ポリ（ジメチルシロキサン）（３１０μＬ， ０．５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、減圧下（８Ｐａ）室温で揮発成分を取り除き、こげ茶色油状粗生成物を得た。これを酢酸エチルで希釈し、アルミナカラムにより精製することでヒドロシリル化生成物を無色液体として３８０ｍｇ （０．４７０ｍｍｏｌ， 収率９４％）得た。

¹H NMR (600 MHz, CDCl₃) δ = 3.7 (dd, J = 11.5, 3.3 Hz, 2H), 3.50-3.41 (m, 4H), 3.39 (dd, J= 11.5, 6.0 Hz, 2H), 3.17-3.13 (m, 2H), 2.80 (t, J = 4.7 Hz, 2H), 2.61 (dd, J = 4.9, 2.7 Hz, 2H), 1.65-1.58 (m, 4H), 0.55-0.50 (m, 4H), 0.08 (s, 12H), 0.07 (s, 12H), 0.06 (s, 12H), 0.04 (s, 12H);
¹³C NMR (150 MHz, CDCl₃) δ = 74.3, 71.4, 50.8, 44.2, 23.4, 14.1, 1.1, 1.0, 0.03; [Example B-5: Modification of silicone oil by hydrosilylation using a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]

Under a nitrogen atmosphere, silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (2.3 mg, 0.01 mmol) and allyl glycidyl ether (235 μL, 2 mmol) were mixed in a 20-mL Schlenk flask equipped with a stirrer. followed by the addition of hydrogen-terminated poly(dimethylsiloxane) with a degree of polymerization of 6 (310 μL, 0.5 mmol). The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, volatile components were removed at room temperature under reduced pressure (8 Pa) to obtain a dark brown oily crude product. This was diluted with ethyl acetate and purified by an alumina column to obtain 380 mg (0.470 mmol, yield 94%) of a hydrosilylated product as a colorless liquid.

¹ H NMR (600 MHz, CDCl ₃ ) δ = 3.7 (dd, J = 11.5, 3.3 Hz, 2H), 3.50-3.41 (m, 4H), 3.39 (dd, J = 11.5, 6.0 Hz, 2H), 3.17 -3.13 (m, 2H), 2.80 (t, J = 4.7 Hz, 2H), 2.61 (dd, J = 4.9, 2.7 Hz, 2H), 1.65-1.58 (m, 4H), 0.55-0.50 (m, 4H ), 0.08 (s, 12H), 0.07 (s, 12H), 0.06 (s, 12H), 0.04 (s, 12H);
^13C NMR (150 MHz, _CDCl3 ) δ = 74.3, 71.4, 50.8, 44.2, 23.4, 14.1, 1.1, 1.0, 0.03;

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにてケイ素系ポリマー担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（２．３ｍｇ， ０．０１ｍｍｏｌ）とスチレン（４６０μＬ， ４ｍｍｏｌ）を混合し、続けて重合度が約３０のトリメチルシリル末端ポリ（メチルヒドロシロキサン）（１２５μＬ， ０．０６６ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、内部標準として１，４－ジオキサン（８５μＬ， １ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することで定量的にヒドロシリル化生成物が示された。

¹H NMR (600 MHz, CDCl₃) δ = 7.20-6.90 (m, 150H), 2.64 (br, 60 H), 0.88 (br, 60 H), 0.08 (br, 90H), 0.06 (s, 18H); [Example B-6: Modification of poly(methylhydrosiloxane) by hydrosilylation using a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]

Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (2.3 mg, 0.01 mmol) and styrene (460 μL, 4 mmol) were mixed in a 20 mL Schlenk flask equipped with a stirrer, Trimethylsilyl-terminated poly(methylhydrosiloxane) with a degree of polymerization of about 30 (125 μL, 0.066 mmol) was then added. The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to quantitatively show hydrosilylation products.

¹ H NMR (600 MHz, CDCl ₃ ) δ = 7.20-6.90 (m, 150H), 2.64 (br, 60 H), 0.88 (br, 60 H), 0.08 (br, 90H), 0.06 (s, 18H) ;

窒素雰囲気下で、攪拌子を入れた２０ｍＬのスクリューバイヤルにてケイ素系ポリマー担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（１．１ｍｇ， ０．００５ｍｍｏｌ）と重合度が約７８のビニル末端ポリ（ジメチルシロキサン）（３．００ｇ， ０．５ｍｍｏｌ）を混合し、続けて重合度が約３０のトリメチルシリル末端ポリ（メチルヒドロシロキサン）（６２μＬ， ０．０３３ｍｍｏｌ）を加えた。スクリューバイヤルを封し、８０℃で２４時間撹拌することで、シリコーンゲルを得た。赤外分光法によりケイ素－水素結合伸縮振動に由来する２１００ｃｍ^－１付近のケイ素－水素結合伸縮振動に由来するシグナルの消失を確認した。 [Example B-7: Synthesis of cross-linked silicone gel using silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]

Under a nitrogen atmosphere, silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (1.1 mg, 0.005 mmol) and vinyl-terminated poly( Dimethylsiloxane) (3.00 g, 0.5 mmol) was mixed followed by the addition of trimethylsilyl terminated poly(methylhydrosiloxane) with a degree of polymerization of about 30 (62 μL, 0.033 mmol). A silicone gel was obtained by sealing the screw vial and stirring at 80° C. for 24 hours. Infrared spectroscopy confirmed the disappearance of the signal derived from the silicon-hydrogen bond stretching vibration around 2100 cm ⁻¹ derived from the silicon-hydrogen bond stretching vibration.

By reacting polysiloxanes having alkene or silane moieties, cross-linking reactions due to silylation reactions occurred, and silicone gels were obtained.

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにてメチル基置換ケイ素系ポリマー担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ^Ｍｅ＿ｐｏｌｙｍｅｒ）（２．５ｍｇ， ０．０１ｍｍｏｌ）とα－メチルスチレン（１３０μＬ， １ｍｍｏｌ）を混合し、続けて１，１，１，３，３－ペンタメチルジシロキサン（２３５μＬ， １．２ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、内部標準として１，４－ジオキサン（８５μＬ， １ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することでヒドロシリル化生成物（７１％）とα－メチルスチレン原料（２３％）が示された。 [Example B-8: Hydrosilylation reaction of α-methylstyrene using a methyl group-substituted silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si ^Me _polymer)]

Under a nitrogen atmosphere, a methyl group-substituted silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@ ^SiMe_polymer ) (2.5 mg, 0.01 mmol) and α-methylstyrene ( 130 μL, 1 mmol) were mixed followed by the addition of 1,1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol). The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to identify the hydrosilylated product (71%) and α-methylstyrene starting material (23 %)It has been shown.

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにてケイ素系ポリマー担持カルボニル配位マンガン触媒（Ｍｎ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（２．０ｍｇ， ０．０１ｍｍｏｌ）とスチレン（１１５μＬ， １ｍｍｏｌ）を混合し、続けて１，１，１，３，３－ペンタメチルジシロキサン（２３５μＬ， １．２ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、内部標準として１，４－ジオキサン（８５μＬ， １ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することでヒドロシリル化生成物（６１％）、脱水素シリル化生成物（７％）、水素化生成物（７％）が示された。 [Example B-9: Hydrosilylation reaction of styrene using silicon-based polymer-supported carbonyl-coordinated manganese catalyst (Mn@Si_polymer)]

Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated manganese catalyst (Mn@Si_polymer) (2.0 mg, 0.01 mmol) and styrene (115 μL, 1 mmol) were mixed in a 20 mL Schlenk flask equipped with a stirrer, 1,1,1,3,3-Pentamethyldisiloxane (235 μL, 1.2 mmol) was subsequently added. The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to identify hydrosilylation products (61%), dehydrosilylation products ( 7%) and the hydrogenated product (7%).

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにてケイ素系ポリマー担持ピリジンジイミン配位鉄触媒（Ｆｅ_ＰＤＩ ^Ｍｅｓ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（２．５ｍｇ）と１－デセン（１９０μＬ， １ｍｍｏｌ）を混合し、続けて１，１，１，３，３－ペンタメチルジシロキサン（２３５μＬ， １．２ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、内部標準として１，４－ジオキサン（８５μＬ， １ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することでヒドロシリル化生成物（７７％）と１－デセン原料（７％）、アルケン異性化混合物（１５％）が示された。 [Example B-10: Hydrosilylation reaction of 1-decene using silicon-based polymer-supported pyridinediimine-coordinated iron catalyst (Fe _PDI ^Mes @Si_polymer)]

Under a nitrogen atmosphere, silicon-based polymer-supported pyridinediimine-coordinated iron catalyst (Fe _PDI ^Mes @Si_polymer) (2.5 mg) and 1-decene (190 μL, 1 mmol) were mixed in a 20-mL Schlenk flask equipped with a stirrer. followed by the addition of 1,1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol). The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to identify the hydrosilylated product (77%) and 1-decene starting material (7%). ), an alkene isomerization mixture (15%).

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにケイ素系ポリマー担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（１．２ｍｇ， ０．００５ｍｍｏｌ）とベンズアルデヒド（５１μＬ， ０．５ｍｍｏｌ）を混合し、続けて１，１，１，３，３－ペンタメチルジシロキサン（１４５μＬ， ０．７５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、内部標準として１，１，２，２－テトラクロロエタン（５２μＬ， ０．５ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することで定量的にヒドロシリル化生成物が示された。

¹H NMR (400 MHz, CDCl₃) δ = 7.34 (d, J = 4.0 Hz, 4H), 7.28-7,22 (overlap with solvent, 1H), 4.76 (s, 2H), 0.12 (s, 6H), 0.10 (s, 9H); [Example B-11: Hydrosilylation reaction of benzaldehyde using a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]

Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (1.2 mg, 0.005 mmol) and benzaldehyde (51 μL, 0.5 mmol) were mixed in a 20-mL Schlenk flask containing a stirrer. was added followed by 1,1,1,3,3-pentamethyldisiloxane (145 μL, 0.75 mmol). The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,1,2,2-tetrachloroethane (52 μL, 0.5 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to quantitatively show hydrosilylation products. was done.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.34 (d, J = 4.0 Hz, 4H), 7.28-7,22 (overlap with solvent, 1H), 4.76 (s, 2H), 0.12 (s, 6H) , 0.10 (s, 9H);

It was confirmed that the catalyst of the present invention can also catalyze the hydrosilylation of carbonyl compounds in addition to alkenes.

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにケイ素系ポリマー担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（１．２ｍｇ， ０．００５ｍｍｏｌ）とベンズアルデヒド（５１μＬ， ０．５ｍｍｏｌ）を混合し、続けてピナコールボラン（１１０μＬ， ０．７５ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。その後ジエチルエーテル（５ｍＬ）で希釈し、水酸化ナトリウム水溶液（１ Ｍ， ５ｍＬ）を加え、室温で２時間撹拌した。反応終了後塩酸で中和し、ジエチルエーテルで３回抽出した。合わせた有機相を硫酸マグネシウムで乾燥後、減圧下で溶媒留去した。内部標準として１，１，２，２－テトラクロロエタン（５２μＬ， ０．５ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することで収率９３％でベンジルアルコールが示された。

¹H NMR (400 MHz, CDCl₃) δ = 7.37 (d, J = 4.4 Hz, 4H), 7.33-7,27 (m, 1H), 4.71 (s, 2H), 1.91 (s, 1H); [Example B-12: Hydroboration reaction of benzaldehyde using a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]

Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (1.2 mg, 0.005 mmol) and benzaldehyde (51 μL, 0.5 mmol) were mixed in a 20-mL Schlenk flask containing a stirrer. was added followed by pinacolborane (110 μL, 0.75 mmol). The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After that, it was diluted with diethyl ether (5 mL), an aqueous sodium hydroxide solution (1 M, 5 mL) was added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the mixture was neutralized with hydrochloric acid and extracted three times with diethyl ether. The combined organic phases were dried over magnesium sulfate and then evaporated under reduced pressure. 1,1,2,2-Tetrachloroethane (52 μL, 0.5 mmol) was added as an internal standard and ¹ H NMR spectroscopy using deuterated chloroform indicated benzyl alcohol in 93% yield.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.37 (d, J = 4.4 Hz, 4H), 7.33-7,27 (m, 1H), 4.71 (s, 2H), 1.91 (s, 1H);

It has been determined that the catalysts of the present invention are also capable of catalyzing hydroboration reactions.

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにケイ素系ポリマー担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐｏｌｙｍｅｒ）（１．２ｍｇ， ０．００５ｍｍｏｌ）と２－ブロモピリジン（４８μＬ， ０．５ｍｍｏｌ）を混合し、続けて臭化フェニルマグネシウムのテトラヒドロフラン溶液（１．０５Ｍ， ０．７２μＬ， ０．７５ｍｍｏｌ）を加えた。室温で２４時間撹拌した後、水で反応停止した。ジエチルエーテルで３回抽出し、合わせた有機相を硫酸マグネシウムで乾燥後、減圧下で溶媒留去した。内部標準として１，４－ジオキサン（４２μＬ， ０．５ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することで収率３９％で２－フェニルピリジンが示された。

¹H NMR (400 MHz, CDCl₃) δ = 8.70 (d, J = 4.8 Hz, 1H), 7.99 (dd, J = 8.8, 1.6 Hz, 2H), 7.79-7.71 (m, 2H), 7.52-7.40 (m, 3H), 7.26-7.22 (m, 1H); [Example B-13: Coupling reaction of aromatic halide and Grignard reagent using silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer)]

Under a nitrogen atmosphere, a silicon-based polymer-supported carbonyl-coordinated cobalt catalyst (Co@Si_polymer) (1.2 mg, 0.005 mmol) and 2-bromopyridine (48 μL, 0.5 mmol) were placed in a 20-mL Schlenk flask equipped with a stir bar. was mixed, followed by the addition of a tetrahydrofuran solution of phenylmagnesium bromide (1.05 M, 0.72 μL, 0.75 mmol). After stirring at room temperature for 24 hours, the reaction was quenched with water. It was extracted three times with diethyl ether, and the combined organic phases were dried over magnesium sulfate and evaporated under reduced pressure. 1,4-Dioxane (42 μL, 0.5 mmol) was added as an internal standard and ¹ H NMR spectroscopy using deuterated chloroform indicated 2-phenylpyridine in 39% yield.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 8.70 (d, J = 4.8 Hz, 1H), 7.99 (dd, J = 8.8, 1.6 Hz, 2H), 7.79-7.71 (m, 2H), 7.52-7.40 (m, 3H), 7.26-7.22 (m, 1H);

It has been confirmed that the catalysts of the present invention are also capable of catalyzing coupling reactions.

2. Transition metal complex-metal silicon composite (1) Synthesis of composite Hydrogen-terminated silicon fine particles (manufactured by Kojundo Chemical Co., Ltd., hydrogen-terminated Si powder (metal silicon (composed of Si—Si bonds) surface A catalyst of silicon microparticles supporting a transition metal complex (transition metal complex-metal silicon composite) was synthesized using the particles into which —Si—H was introduced.

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコにてデカカルボニル二マンガン（９７ｍｇ， ０．２５ｍｍｏｌ）とメシチレン（５ｍＬ）を混合し、続けて水素終端処理ケイ素微粒子（２８ｍｇ， １ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１５０℃で２４時間撹拌した。反応終了後の黄色懸濁液から遠心分離によって暗灰色粉末を単離し、テトラヒドロフランで３回洗浄した。その後、十分乾燥することでケイ素微粒子担持カルボニル配位マンガン触媒（Ｍｎ＠Ｓｉ＿ｐａｒｔｉｃｌｅ）（１８ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｍｎ＝４９：１の組成比（シリコン原子とマンガン原子とのモル比）であることが確認された。 [Example C-1: Synthesis of silicon fine particle-supported carbonyl-coordinated manganese catalyst (Mn@Si_particle)]

Under a nitrogen atmosphere, decacarbonyldimanganese (97 mg, 0.25 mmol) and mesitylene (5 mL) were mixed in a 50 mL Schlenk flask equipped with a stirrer, and then hydrogen-terminated silicon fine particles (28 mg, 1 mmol) were added. rice field. The flask was sealed with a glass stopper and stirred at 150° C. for 24 hours. A dark gray powder was isolated from the yellow suspension after completion of the reaction by centrifugation and washed three times with tetrahydrofuran. Then, it was sufficiently dried to obtain a silicon fine particle-supported carbonyl-coordinated manganese catalyst (Mn@Si_particle) (18 mg). Fluorescent X-ray analysis confirmed that the composition ratio was Si:Mn=49:1 (molar ratio between silicon atoms and manganese atoms).

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコにてノナカルボニル二鉄（９１ｍｇ， ０．２５ｍｍｏｌ）とトルエン（５ｍＬ）を混合し、続けて水素終端処理ケイ素微粒子（２８ｍｇ， １ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１００℃で２４時間撹拌した。反応終了後の薄黄緑色懸濁液から遠心分離によって暗灰色粉末を単離し、テトラヒドロフランで３回洗浄した。その後、十分乾燥することでケイ素微粒子担持カルボニル配位鉄触媒（Ｆｅ＠Ｓｉ＿ｐａｒｔｉｃｌｅ）（２８ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｆｅ＝５：１の組成比（シリコン原子と鉄原子とのモル比）であることが確認された。 [Example C-2: Synthesis of silicon fine particle-supported carbonyl-coordinated iron catalyst (Fe@Si_particle)]

Under a nitrogen atmosphere, nonacarbonyldiiron (91 mg, 0.25 mmol) and toluene (5 mL) were mixed in a 50 mL Schlenk flask equipped with a stirrer, and then hydrogen-terminated silicon fine particles (28 mg, 1 mmol) were added. rice field. The flask was sealed with a glass stopper and stirred at 100° C. for 24 hours. A dark gray powder was isolated by centrifugation from the pale yellow-green suspension after completion of the reaction, and washed three times with tetrahydrofuran. Then, by sufficiently drying, a carbonyl-coordinated iron catalyst supported on fine silicon particles (Fe@Si_particle) (28 mg) was obtained. Fluorescent X-ray analysis confirmed that the composition ratio was Si:Fe=5:1 (molar ratio between silicon atoms and iron atoms).

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコにてオクタカルボニル二コバルト（８５ｍｇ， ０．２５ｍｍｏｌ）とトルエン（５ｍＬ）を混合し、続けて水素終端処理ケイ素微粒子（２８ｍｇ， １ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１００℃で２４時間撹拌した。反応終了後の茶色懸濁液から遠心分離によって暗灰色粉末を単離し、テトラヒドロフランで３回洗浄した。その後、十分乾燥することでケイ素微粒子担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐａｒｔｉｃｌｅ）（３０ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｃｏ＝３：１の組成比（シリコン原子とコバルト原子とのモル比）であることが確認された。 [Example C-3: Synthesis of silicon fine particle-supported carbonyl-coordinated cobalt catalyst (Co@Si_particle)]

Octacarbonyl dicobalt (85 mg, 0.25 mmol) and toluene (5 mL) were mixed in a 50 mL Schlenk flask equipped with a stirrer under a nitrogen atmosphere, and then hydrogen-terminated silicon fine particles (28 mg, 1 mmol) were added. rice field. The flask was sealed with a glass stopper and stirred at 100° C. for 24 hours. A dark gray powder was isolated from the brown suspension after the reaction by centrifugation and washed three times with tetrahydrofuran. Then, by sufficiently drying, a carbonyl-coordinated cobalt catalyst (Co@Si_particle) (30 mg) supported on fine silicon particles was obtained. A fluorescent X-ray analysis confirmed that the composition ratio was Si:Co=3:1 (molar ratio between silicon atoms and cobalt atoms).

窒素雰囲気下で、攪拌子を入れた５０ｍＬのシュレンクフラスコにてビス（１，５－シクロオクタジエン）ニッケル（１３８ｍｇ， ０．５ｍｍｏｌ）とトルエン（５ｍＬ）を混合し、続けて水素終端処理ケイ素微粒子（２８ｍｇ， １ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、１００℃で２４時間撹拌した。反応終了後の黄色懸濁液から遠心分離によって暗灰色粉末を単離し、テトラヒドロフランで３回洗浄した。その後、十分乾燥することでケイ素微粒子担持ニッケル触媒（Ｎｉ＠Ｓｉ＿ｐａｒｔｉｃｌｅ）（３０ｍｇ）を得た。蛍光Ｘ線分析からＳｉ：Ｎｉ＝５：１の組成比（シリコン原子とニッケル原子とのモル比）であることが確認された。 [Example C-4: Synthesis of silicon microparticle-supported nickel catalyst (Ni@Si_particle)]

Under a nitrogen atmosphere, bis(1,5-cyclooctadiene)nickel (138 mg, 0.5 mmol) and toluene (5 mL) were mixed in a 50 mL Schlenk flask equipped with a stir bar, followed by hydrogen-terminated silicon microparticles. (28 mg, 1 mmol) was added. The flask was sealed with a glass stopper and stirred at 100° C. for 24 hours. A dark gray powder was isolated from the yellow suspension after completion of the reaction by centrifugation and washed three times with tetrahydrofuran. After that, it was sufficiently dried to obtain a silicon fine particle-supported nickel catalyst (Ni@Si_particle) (30 mg). Fluorescent X-ray analysis confirmed that the composition ratio was Si:Ni=5:1 (molar ratio between silicon atoms and nickel atoms).

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにてケイ素微粒子担持カルボニル配位鉄触媒（Ｆｅ＠Ｓｉ＿ｐａｒｔｉｃｌｅ）（２．３ｍｇ）とスチレン（１１５μＬ， １ｍｍｏｌ）を混合し、続けて１，１，１，３，３－ペンタメチルジシロキサン（２３５μＬ， １．２ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、内部標準として１，４－ジオキサン（８５μＬ， １ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することでヒドロシリル化生成物（８９％）が反マルコフニコフ付加体とマルコフニコフ付加体の混合物（７５：２５）として示された。 (2) Reaction using a composite (catalyst) [Example D-1: Hydrosilylation reaction of styrene using a silicon fine particle-supported carbonyl-coordinated iron catalyst (Fe@Si_particle)]

Under a nitrogen atmosphere, silicon fine particle-supported carbonyl-coordinated iron catalyst (Fe@Si_particle) (2.3 mg) and styrene (115 μL, 1 mmol) were mixed in a 20 mL Schlenk flask containing a stirrer, followed by 1,1 , 1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol) was added. The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform. It was shown as a mixture of Nikov adducts (75:25).

（１回目）
窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにてケイ素微粒子担持カルボニル配位鉄触媒（Ｆｅ＠Ｓｉ＿ｐａｒｔｉｃｌｅ）（２．３ｍｇ）と１－デセン（１９０μＬ， １ｍｍｏｌ）を混合し、続けて１，１，１，３，３－ペンタメチルジシロキサン（２３５μＬ， １．２ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、内部標準として１，４－ジオキサン（８５μＬ， １ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することでヒドロシリル化生成物（４１％）と１－デセン原料（５８％）が示された。 [Example D-2: Hydrosilylation reaction of 1-decene using silicon fine particle-supported carbonyl-coordinated iron catalyst (Fe@Si_particle)]

(first time)
Under a nitrogen atmosphere, silicon fine particle-supported carbonyl-coordinated iron catalyst (Fe@Si_particle) (2.3 mg) and 1-decene (190 μL, 1 mmol) were mixed in a 20 mL Schlenk flask containing a stirrer, followed by 1 , 1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol) was added. The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform. )It has been shown.

(Second time)
The reaction mixture was diluted with tetrahydrofuran and a black powder was isolated by centrifugation and washed twice with tetrahydrofuran. After sufficiently drying this powder, it was transferred to a 20 mL Schlenk flask, 1-decene (190 μL, 1 mmol) and 1,1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol) were added again, and the mixture was heated at 80°C. Stirred for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform. )It has been shown.

It was confirmed that the silicon fine particle-supported carbonyl-coordinated iron catalyst of the present invention can be reused.

窒素雰囲気下で、攪拌子を入れた２０ｍＬのシュレンクフラスコにてケイ素微粒子担持カルボニル配位コバルト触媒（Ｃｏ＠Ｓｉ＿ｐａｒｔｉｃｌｅ）（２．３ｍｇ）と１－デセン（１９０μＬ， １ｍｍｏｌ）を混合し、続けて１，１，１，３，３－ペンタメチルジシロキサン（２３５μＬ， １．２ｍｍｏｌ）を加えた。フラスコをガラス栓で封し、８０℃で２４時間撹拌した。反応終了後、内部標準として１，４－ジオキサン（８５μＬ， １ｍｍｏｌ）を加え、重クロロホルムを用い^１Ｈ ＮＭＲ分光法で分析することでヒドロシリル化生成物（１６％）と１－デセン原料（７９％）が示された。 [Example D-3: Hydrosilylation reaction of 1-decene using silicon fine particle-supported carbonyl-coordinated cobalt catalyst (Co@Si_particle)]

Under a nitrogen atmosphere, silicon fine particle-supported carbonyl-coordinated cobalt catalyst (Co@Si_particle) (2.3 mg) and 1-decene (190 μL, 1 mmol) were mixed in a 20 mL Schlenk flask containing a stirrer, followed by 1 , 1,1,3,3-pentamethyldisiloxane (235 μL, 1.2 mmol) was added. The flask was sealed with a glass stopper and stirred at 80° C. for 24 hours. After completion of the reaction, 1,4-dioxane (85 μL, 1 mmol) was added as an internal standard and analyzed by ¹ H NMR spectroscopy using deuterated chloroform to identify the hydrosilylated product (16%) and 1-decene starting material (79%). )It has been shown.

(Literature)
Literature S1) Noda, D.; Tahara, A.; Sunda, Y.; Nagashima, HJ Am. Chem. Soc.2016, 138, 2480-2483.
Literature S2) Buslov, I.; Song, F.; Hu, X. Angew. Chem. Int. Ed. 2016, 55, 12295-12299.
Literature S3) Dierick, S.; Vercruysse, E.; Berthon-Gelloz, G.; Marko, IE Chem. Eur. J. 2015, 21, 17073-17078.

The above results show that the composite of the transition metal complex of the present invention and a carrier made of a silicon-based material (silicon-based polymer, silicon particles) having an Si—H group undergoes various reactions such as hydrosilylation, hydroboration, and coupling reactions. This demonstrates that it can be used as a heterogeneous catalyst in reactions.

The scope of the present invention is not limited to the above description, and other than the above examples can be appropriately modified and implemented without impairing the gist of the present invention. All documents and publications mentioned herein are hereby incorporated by reference in their entirety regardless of their purpose.

The composite according to the embodiment of the present invention can be used as a heterogeneous reaction catalyst in various reactions, and can be synthesized or obtained at low cost, so it is excellent in practicality and usefulness. .

11, 12 complex M transition metal atom L ligand m number of ligands coordinated to transition metal atom Polymer silicon-based polymer

Claims (15)

A transition metal complex and a carrier supporting the transition metal complex, wherein the carrier comprises a silicon-based material having a Si—H group, and the silicon-based material comprises a silicon-based polymer, silicon-based ceramics, and metallic silicon. A complex selected from the group consisting of: A group comprising a transition metal and a carrier supporting the transition metal, wherein the carrier comprises a silicon-based material having a Si—H group, and the silicon-based material comprises a silicon-based polymer, a silicon-based ceramic, and metallic silicon. A complex, selected from: The transition metal complex or the transition metal atom of the transition metal is at least one selected from the group consisting of manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu). 3. The conjugate of claim 1 or 2, wherein a The silicon-based polymer is selected from polysilane-based polymers, polysiloxane-based polymers, polysilazane-based polymers, polycarbosilane-based polymers, polymetallocarbosilane-based polymers and derivatives thereof, and polymers having SiH groups in side chains. The conjugate according to any one of claims 1 to 3, comprising at least one. The composite according to any one of claims 1 to 4, wherein the carrier is particulate or plate-like. The composite according to any one of claims 1 to 5, wherein said support is a silicon particle having Si—H groups. The transition metal complexes include alkenes, alkynes, carbonyls, halogen atoms, organic acids, hydroxy, isocyanides, amines, imines, nitrogen-containing heterocycles, phosphines, arsines, alcohols, thiols, ethers, sulfides, nitriles, molecular hydrogen, and aldehydes. , ketones and carbenes. The composite according to any one of claims 1 to 7, wherein a transition metal atom of said transition metal complex or said transition metal and a silicon atom of said support are bonded. A catalyst comprising a composite according to any one of claims 1-8. A catalyst for hydrosilylation, hydroboration or coupling reactions, comprising the complex of any one of claims 1-8. Catalyst according to claim 9 or 10, which is a heterogeneous catalyst. A method for producing a hydrosilylate, comprising hydrosilylating an unsaturated bond-containing compound and a Si—H group-containing compound in the presence of the catalyst according to any one of claims 9 to 11. 12. The hydrosilylate is at least one selected from organosilicon reactants, silicone raw materials, silane coupling agents, silicone oils, silicone rubbers, silicone resins, alcohols, ethers, amines, thiols, and thioethers. The method described in . The unsaturated bond-containing compound is an alkene, alkyne, imine, aldehyde, ketone, ester, amide, carboxylic acid, carboxylic acid anhydride, carboxylic acid halide, urea, thioaldehyde, thioketone, thioester, thioamide, thiocarboxylic acid, thiocarboxylic acid 14. The method according to claim 12 or 13, which is at least one selected from anhydrides, thiocarboxylic acid halides, allyl compounds, and thiourea, and derivatives thereof. A method for producing a composite according to any one of claims 1 to 8, comprising mixing a transition metal complex or a precursor thereof with a silicon-based material having a Si—H group to form a composite. .

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