Hydrosilylation reaction catalyst coagent

Abstract

To provide a complex catalyst that allows repeated use and is available at relatively low cost, the complex catalyst having hydrosilylation catalysis.SOLUTION: A hydrosilylation catalyst aid contains an alkali metal salt, the alkali metal salt being a salt represented by MalORal or a salt represented by MalOCORal (Mal is an alkali metal and Ral is a C1-6 linear or branched alkyl group or aryl group), or at least one selected from the group consisting of a carbonate, hydrogencarbonate, sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, nitrate, nitrite, and halide salt of alkali metal.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a hydrosilylation reaction catalyst coagent, and more particularly to a hydrosilylation reaction catalyst coagent containing an alkali metal salt, the contents of all documents described herein are incorporated by reference. [Background technology]

[0002] The hydrosilylation reaction is a useful reaction for synthesizing organosilanes, and because it produces few by-products, it has an excellent environmental impact. A metal catalyst is required to drive this reaction, and Pt catalysts are commonly used. In recent years, catalysts using first transition metals have been developed to address the issue of Pt scarcity (Patent Documents 1 to 3, Non-Patent Documents 1 to 34). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2016 / 208554 [Patent Document 2] Japanese Patent Application Publication No. 2018-118925 [Patent Document 3] Japanese Patent Application Publication No. 2018-065103 [Non-patent literature]

[0004] [Non-Patent Document 1] AM Tondreau, CCH Atienza, KJ Weller, SA Nye, KM Lewis, JGP Delis, PJ Chirik, Science 2012, 335, 567. [Non-patent document 2] Y. Sunada, D. Noda, H. Soejima, H. Tsutsumi, H. Nagashima, Organometallics2015, 34, 2896. [Non-licensed document 3] A. Sanagawa, H. Nagashima, Organometallics 2018, 37, 2859.

Non-licensed Document 4

Non-licensed Document 5

Non-licensed Document 6

Non-licensed Document 7

Non-licensed literature 9

Non-licensed literature 10

Wood 37

Table 38

Table 39

Wood 40

Wood 41

Wood 42

[0005] Base metal catalysts require complex ligands, which are more expensive than the active metals, and are generally difficult to recover, making both precious and base metal catalysts expensive.

[0006] Furthermore, many of the ligands used in hydrosilylation complex catalysts using first transition metals reported to date are pincer-type tridentate ligands. Generally, when these types of ligands form complexes with first transition metals, they form stable ML2-type (L = tridentate) complexes, which dramatically reduce catalytic activity (an example is shown in the formula below).

[0007] [ka]

[0008] Therefore, a strategy of introducing bulky substituents into the ligand L to prevent the formation of ML2 is often used, but the introduction of these substituents further increases the cost of the ligand.

[0009] Therefore, there is a need for a low-cost, highly efficient method for enhancing the catalytic activity of hydrosilylation catalysts. [Means for solving the problem]

[0010] The present inventors have discovered that alkali metal salts may be able to improve the catalytic activity of hydrosilylation complex catalysts, and have made further improvements.

[0011] The present disclosure includes, for example, the subject matter described in the following sections: Section 1. A hydrosilylation reaction catalyst coagent containing an alkali metal salt. Section 2. The alkali metal salt has the formula (al-1): M al OR al (al-1) (In the formula, M al indicates an alkali metal, and R al represents a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group; Formula (al-2): M al OCOR al (al-2) (In the formula, M al indicates an alkali metal, and R al represents a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group; Alkali metal carbonates, bicarbonates, sulfates, phosphates, hydrogen phosphates, dihydrogen phosphates, nitrates, nitrites, and halide salts At least one selected from the group consisting of Item 1. The auxiliary agent according to Item 1, Section 3. Item 1. The auxiliary agent according to Item 1, wherein the alkali metal salt is an alkali metal carbonate. Section 4. Item 4. The auxiliary according to Item 3, wherein the alkali metal carbonate is at least one selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate. Section 5. 5. The auxiliary according to any one of items 1 to 4, wherein the alkali metal salt is a salt having an acid dissociation constant pKa in water of 2 or more. Section 6. 6. The auxiliary according to any one of Items 1 to 5, wherein the hydrosilylation reaction catalyst is a catalyst having a tridentate metal complex compound. Section 7. The tridentate metal complex compound has the formula (i):

[0012] [ka]

[0013] (In the formula, M represents Fe, Co, Ni, Mn, or Cu; X may be the same or different and represent Cl, Br, -OR X , -OC(O)R X , or -OH. X When there are two, they may be the same or different and each represents an aryl group or a linear or branched alkyl group having 1 to 6 carbon atoms, and formula (ii):

[0014] [ka]

[0015] (In the formula, M represents Fe, Co, Ni, Mn, or Cu; R represents a phenyl group (Ph), a 2,4,6-trimethylphenyl group (Mes), a 2,6-diisopropylphenyl group (Dipp), or a cyclohexyl group (Cy); X may be the same or different and represent Cl, Br, -OR X , -OC(O)R X , or -OH. X When there are two, they may be the same or different and each represents an aryl group or a linear or branched alkyl group having 1 to 6 carbon atoms. Item 7. The auxiliary according to item 6, which is at least one selected from the group consisting of: Section 8. Item 8. The auxiliary according to Item 6 or 7, wherein the tridentate ligand is terpyridine. Section 9. The catalyst having a tridentate metal complex compound is A complex-immobilized catalyst, A tridentate metal complex compound and a substrate are provided, Item 7. The auxiliary according to Item 6, wherein the tridentate metal complex compound is a catalyst immobilized on a substrate. Section 10. Item 10. The auxiliary according to Item 9, wherein the catalyst having a tridentate metal complex compound satisfies at least one of the following requirements (a) to (e): (a): The substrate is a silica compound substrate or a metal substrate having an oxide film on its surface. (b): The tridentate metal complex compound and the substrate are bonded by a linker portion. (c): The tridentate metal complex compound and the substrate are bonded by a linker moiety, and the bond between the linker moiety and the substrate is a silane coupling bond. (d): The tridentate metal complex compound and the substrate are bonded by a linker moiety, and the whole or part of the linker moiety is derived from an alkoxysilane. (e): The tridentate ligand is terpyridine Section 11. The catalyst having a tridentate metal complex compound has the formula (A): [Tridentate metal complex compound]-[Linker]-[Base material] (A) An immobilized complex catalyst represented by the formula: The tridentate metal complex compound has the formula:

[0016] [ka]

[0017] (In the formula, M represents Fe, Co, Ni, Mn, or Cu; X may be the same or different and represent Cl, Br, -OR X , -OC(O)R X, or -OH. X When there are two of them, they may be the same or different and each represents an aryl group or a linear or branched alkyl group having 1 to 6 carbon atoms; The -[linker part]-* (* indicates the substrate side) is represented by the formula:

[0018] [ka]

[0019] (wherein Z is a bond or

[0020] [ka]

[0021] where n is 1, 2, 3, 4, 5, or 6, * indicates the substrate side, and R i and R ii are the same or different and represent an aryl group, an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, or -O-*, provided that at least one * is bonded to the substrate, and the other * may be bonded to a Si atom of another linker moiety.) or a group represented by the formula:

[0022] [ka]

[0023] (where Z, n, *, R i and R ii is the same as above, except that at least one * may be bonded to the substrate, and the other * may be bonded to a Si atom of another linker moiety. The catalyst Item 9 or 10. The auxiliary agent according to item 9 or 10. Section 12. Item 12. The auxiliary according to any one of Items 1 to 11, which is a hydrosilylation reaction promoter. Section 13. 13. A method for producing a hydrosilylated compound, comprising carrying out a hydrosilylation reaction using a hydrosilylation catalyst in the presence of the auxiliary according to any one of items 1 to 12.

[0024] In this specification, the aryl group is not particularly limited, but preferred examples include a phenyl group, a benzyl group, a tolyl group (o-tolyl, m-tolyl, p-tolyl), a xylyl group (o-xylyl, m-xylyl, p-xylyl), etc. Furthermore, Me represents a methyl group. [Effects of the Invention]

[0025] A low-cost, highly efficient auxiliary agent for enhancing the catalytic activity of a hydrosilylation catalyst is provided. DETAILED DESCRIPTION OF THE INVENTION

[0026]

[0033] Each embodiment of the present disclosure will be described in more detail below. The present disclosure preferably includes, but is not limited to, a hydrosilylation reaction catalyst coagent and uses thereof, and the present disclosure encompasses all that is disclosed herein and that would be recognized by a person skilled in the art.

[0027] The coagent encompassed by the present disclosure includes an alkali metal salt. The coagent can enhance the catalytic activity of the hydrosilylation reaction catalyst. In this specification, the coagent may be referred to as the "coagent of the present disclosure."

[0028] Examples of the alkali metal of the alkali metal salt include lithium, sodium, potassium, rubidium, cesium, and fluoride. Of these, sodium and potassium are preferred.

[0029] The salts include organic salts and inorganic salts. The organic salts include those represented by the formula (al-1): M al OR al (al-1) or a salt represented by formula (al-2): M al OCOR al (al-2) In these formulas, M al indicates an alkali metal, and R al represents a linear or branched alkyl group or an aryl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6). Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), and a butyl group (n-butyl group, isobutyl group, or t-butyl group). Specific examples of the aryl group include a phenyl group. Specific examples of the salt of formula (a1-1) include potassium tert-butoxide and sodium tert-butoxide. Specific examples of the salt of formula (a1-2) include potassium pivalate, sodium pivalate, potassium acetate, and sodium acetate.

[0030] Examples of inorganic salts include carbonates, hydrogen carbonates, sulfates, phosphates, hydrogen phosphates, dihydrogen phosphates, nitrates, nitrites, halide salts (fluorides, chlorides, bromides, iodides), etc. Among these, carbonates are particularly preferred from the viewpoints of high effectiveness, low cost, and ease of handling.

[0031] The alkali metal salts can be used alone or in combination of two or more.

[0032] Examples of alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, and francium carbonate, and among these, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate are preferred, and lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate are more preferred. The alkali metal carbonates can be used alone or in combination of two or more.

[0033] The alkali metal salt is more preferably a salt having an acid dissociation constant pKa in water of 2 or more, and even more preferably a salt having an acid dissociation constant pKa of about 2 to 20. The upper or lower limit of this range may be, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19. For example, the range may be 3 to 19.

[0034] Preferred examples of hydrosilylation catalysts whose catalytic activity is enhanced by the auxiliary of the present disclosure include catalysts having a tridentate metal complex compound. The hydrosilylation catalyst whose catalytic activity is enhanced by the auxiliary of the present disclosure may be referred to as the "catalyst of the present disclosure." In other words, a catalyst having a tridentate metal complex compound is a preferred embodiment of the catalyst of the present disclosure.

[0035] Examples of the tridentate ligand metal complex compound include compounds represented by the formula (i):

[0036] [ka]

[0037] (In the formula, M represents Fe, Co, Ni, Mn, or Cu; X may be the same or different and represent Cl, Br, -OR X , -OC(O)R X , or -OH. X and when there are two, they may be the same or different and represent an aryl group or a linear or branched alkyl group having 1 to 6 carbon atoms.), and a compound represented by formula (ii):

[0038] [ka]

[0039] (wherein M and X are the same as above. That is, M represents Fe, Co, Ni, Mn, or Cu; R represents a phenyl group (Ph), a 2,4,6-trimethylphenyl group (Mes), a 2,6-diisopropylphenyl group (Dipp), or a cyclohexyl group (Cy); and X may be the same or different and represent Cl, Br, -OR X, -OC(O)R X , or -OH. X When there are two, they may be the same or different and each represents an aryl group or a linear or branched alkyl group having 1 to 6 carbon atoms.

[0040] In both formulas (i) and (ii), as described above, R X represents an aryl group or a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6). Among these, a methyl group, a t-butyl group, etc. are preferred. X When there are two of them in the formula, they may be the same or different.

[0041] Alternatively, the tridentate ligand metal complex compound may also include compounds having the following tridentate ligands. For example, NNN-type ligands such as terpyridine (particularly 2,2':6'2"-terpyridine (tpy)), iminobipyridine, and bisiminopyridine derivatives, and PNN-type ligands such as phosphine-iminopyridine, etc., may be mentioned as tridentate ligands.

[0042] [ka]

[0043] In each of the above formulas, R 1 are the same or different and represent a phenyl group (Ph), a 2,4,6-trimethylphenyl group (Mes), a 2,6-diisopropylphenyl group (Dipp), or a cyclohexyl group (Cy); R 2 are the same or different and represent a hydrogen atom (H), a methyl group (Me), or a trifluoromethyl group (CF3), and R 3 represents a methyl group at the 4th, 5th, or 6th position (4'-Me, 5'-Me, or 6'-Me), and R 4 are the same or different and each represents an isopropyl group ( i Pr), a phenyl group (Ph), or a pentafluorophenyl group (C6F5).

[0044] Among the tridentate ligands, 2,2':6'2"-terpyridine (tpy) is particularly preferred. The compound represented by the above formula (i) is a compound having tpy as the tridentate ligand.

[0045] Examples of the metal to be coordinated include Fe, Co, Ni, Mn, Zn, Cu, Cr, Mo, W, Ru, Pd, Pt, Ir, Rh, Os, Sm, Sc, Re, Au, and Ag. Of these, Fe, Co, Ni, Mn, Cu, Cr, and Mo are preferred, and Co is particularly preferred.

[0046] Such tridentate ligand metal complex compounds can be used singly or in combination of two or more.

[0047] The catalyst having a tridentate ligand metal complex compound may be a catalyst in which the tridentate ligand metal complex compound is immobilized on a substrate (immobilized catalyst). Next, the case in which the catalyst of the present disclosure is an immobilized catalyst will be described.

[0048] The substrate is preferably one that can easily immobilize a tridentate metal complex compound. As described below, for example, when the immobilization is performed by silane coupling bonding, a substrate having OH groups present on the surface is particularly preferred. Examples of such substrates include silica compound substrates and substrates having a metal oxide film on the surface (e.g., metal substrates). Examples of metal substrates include stainless steel substrates, aluminum substrates, and titanium substrates. Furthermore, the metal oxide film itself is also included in the substrate having a metal oxide film on the surface referred to here. Among these, silica compound substrates are preferred.

[0049] Preferred examples of the silica compound in the silica compound substrate include silica and glass, and examples of the silica compound substrate include, but are not limited to, silica particles, glass plates, and glass containers.

[0050] The tridentate metal complex compound may be directly immobilized on the substrate, but is preferably immobilized via a linker in between. In other words, it is preferable that the tridentate metal complex compound and the substrate are bonded by a linker moiety.

[0051] In this case, the outline of the structure of the catalyst of the present disclosure can be expressed, for example, as shown in the following formula (A). [Tridentate metal complex compound]-[Linker]-[Base material] (A)

[0052] The bond between the linker moiety and the substrate is preferably a silane coupling bond, and the entire or part of the linker moiety is preferably derived from an alkoxysilane.

[0053] For example, the linker portion and the substrate are formed by a silane coupling reaction between a compound (hereinafter also referred to as a "linker portion precursor compound") in which alkoxysilane constitutes the entirety or an end portion, and the substrate, thereby immobilizing the linker portion precursor compound on the substrate, and then bonding a portion of the immobilized linker portion precursor compound that is different from the substrate side to a tridentate ligand metal complex compound, thereby producing the catalyst of the present disclosure.

[0054] In the catalyst of the present disclosure, the tridentate ligand metal complex compound is, for example, a 2,2':6'2"-terpyridine metal complex, represented by the following formula:

[0055] [ka]

[0056] (In the formula, M represents Fe, Co, Ni, Mn, Cr, or Cu; X may be the same or different and represent Cl, Br, -OR X , -OC(O)R X or —OH. X represents an aryl group or a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6). Among these, a methyl group, a t-butyl group, etc. are preferred.X When there are two of them in the formula, they may be the same or different.

[0057] In addition, the [tridentate ligand metal complex compound] in the above formula (A) may be, for example, any of the following formulae:

[0058] [ka]

[0059] (wherein M and X are the same as above.) Preferred is a group represented by the formula:

[0060] [ka]

[0061] (wherein M and X are the same as above.) A group represented by the following formula is more preferred.

[0062] In addition, examples of -[linker part]-* (* indicates the substrate side) in the above formula (A) include the following formula:

[0063] [ka]

[0064] (wherein Z is a bond or

[0065] [ka]

[0066] where n is 1, 2, 3, 4, 5, or 6, * indicates the substrate side, and R i and R ii are the same or different and represent an aryl group, an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, or -O-*), or a group represented by the formula:

[0067] [ka]

[0068] (where Z, n, *, R i and R ii is the same as above.

[0069] When Z is a bond, "-Z-" becomes "-".

[0070] In the groups represented by these formulas, the moiety represented by * may be bonded to the substrate or to the Si atom of another linker moiety, provided that at least one * is bonded to the substrate. i and R ii When both R and R represent an alkyl group having 1 to 4 carbon atoms, there is only one *, and therefore the * is the site that is bonded to the substrate. i and R ii When one or both of the above represents -O-*, two or three * are present, and at least one * is a site bonded to the substrate, and the other * may be bonded to a Si atom of another linker part. In other words, the Si-O-* may be Si-O-[substrate] or Si-O- Si (The underlined Si may be Si derived from an alkoxysilane in another linker portion), but at least one * is Si—O—[base material].

[0071] Among these groups, R i and R ii each represents -O-*, that is, a group represented by the formula:

[0072] [ka]

[0073] (wherein Z, n, and * are as defined above), or a group represented by the formula:

[0074] [ka]

[0075] (wherein Z, n, and * are as defined above) is preferred.

[0076] The catalyst of the present disclosure can be produced by a known method or a combination of methods that can be easily derived from known methods.

[0077] When the catalyst of the present disclosure is an immobilized catalyst, for example, as described above, a compound (also referred to as a "linker precursor compound") in which alkoxysilane constitutes the entire or end portion and a substrate are immobilized by a silane coupling reaction, and a portion of the immobilized linker precursor compound that is different from the substrate side is bonded to a tridentate metal complex compound, thereby producing the catalyst of the present disclosure. Note that, in the production process, it is preferable to use only a ligand compound in which metal complex formation has not yet occurred as the tridentate metal complex compound. In other words, in the production process, it is preferable that the tridentate metal complex compound is a tridentate ligand.

[0078] Examples of the linker precursor compound include compounds of the formula:

[0079] [ka]

[0080] (In the formula, R a represents an alkoxy group having 1 to 6 carbon atoms, and R b and R c are the same or different and represent an alkoxy group or aryloxy group having 1, 2, 3, 4, 5, or 6 carbon atoms, or an alkyl group or aryl group having 1, 2, 3, 4, 5, or 6 carbon atoms, and R represents NH2 or N3. m represents 1, 2, 3, 4, 5, or 6. Preferred examples of the compound represented by the formula: are those represented by the formula: wherein R is the alkoxy group having 1 to 6 carbon atoms, and m is the alkoxy group having 1 to 6 carbon atoms. A methoxy group or an ethoxy group is particularly preferred.

[0081] When the linker precursor compound has the above formula, R contributes to bonding with the tridentate metal complex compound. When R is N3 (azide group), for example, the linker precursor compound and the tridentate metal complex compound can be bonded using a click reaction in which a triazole ring is formed by reacting an alkyne with an azide compound. In this case, the tridentate metal complex compound preferably has a structure in which an alkynyl group is introduced into the tridentate ligand. For example, the formula:

[0082] [ka]

[0083] (wherein Z is the same as above) is preferred. When R is NH2 (amino group), for example, the linker precursor compound can be reacted with an alkyl halide to bond the compound to the tridentate metal complex compound. In this case, the tridentate metal complex compound preferably has a structure in which the tridentate ligand is modified with a halo group. For example, the compound represented by the formula:

[0084] [ka]

[0085] (In the formula, R d represents a halogen atom, p represents 0, 1, 2, 3, or 4, and Z is the same as above. As the halogen atom, F, Cl, Br, or I is preferred.

[0086] The auxiliary of the present disclosure can be suitably used as an auxiliary for enhancing the catalytic ability of a hydrosilylation catalyst. The catalyst of the present disclosure can be suitably used as a hydrosilylation catalyst, and as described above, is particularly suitable for use in combination with the auxiliary of the present disclosure. The combined use of the auxiliary of the present disclosure and the catalyst of the present disclosure enables the hydrosilylation reaction to proceed with particularly high efficiency.

[0087] Furthermore, the auxiliary of the present disclosure contains an alkali metal carbonate, which is an inexpensive substance, and therefore, a highly efficient hydrosilylation reaction can be achieved at low cost.

[0088] As can be seen from this, the coagent of the present disclosure can be said to function favorably as a hydrosilylation reaction cocatalyst, and can be said to be particularly suitable as a cocatalyst for hydrosilylation reactions using the catalyst of the present disclosure.

[0089] The substrate for hydrosilylation is not particularly limited, and examples thereof include compounds having a C=C double bond, a C≡C triple bond, a C=O double bond, a C=N double bond, or a C≡N triple bond. Preferred examples include unsaturated hydrocarbons, and particularly unsaturated hydrocarbons having a double bond. Preferred examples include, but are not limited to, olefinic hydrocarbons (1-butene, 1-hexene, vinylcyclohexane, N,N-dimethylallylamine, 1,2-epoxy-5-hexene, etc.) and styrene-based hydrocarbons (4-methylstyrene, 4-methoxystyrene, 4-chlorostyrene, etc.).

[0090] The compound used for hydrosilylation is preferably a hydrosilane, specifically, for example, a mono-, di-, or trialkoxysilane, an aryloxysilane, or a mono-, di-, or tri-alkylsilane, or an arylsilane. For example, a compound represented by the formula (R)SiH, (R)SiH, or RSiH (in each formula, R may be the same or different and represents an alkoxy group, an aryloxy group, an alkyl group, an aryl group, or a halogen) is preferably used. Although not particularly limited, the alkoxy group and alkyl group preferably have 1, 2, 3, 4, 5, or 6 carbon atoms. Examples of halogens include F, Cl, Br, and I. More specifically, examples of such compounds include trimethoxysilane, dimethoxysilane, triethoxysilane, diethoxysilane, and diphenylsilane.

[0091] Furthermore, when the hydrosilylation reaction is carried out with the aid of the present disclosure using a hydrosilylation catalyst, it is preferably carried out in an inert gas (such as nitrogen gas) atmosphere, but it can also be carried out in air.

[0092] In this specification, the term "comprising" includes "consisting essentially of" and "consisting of." Furthermore, the present disclosure encompasses all arbitrary combinations of the constituent elements described in this specification.

[0093] Furthermore, the various characteristics (properties, structures, functions, etc.) described in each embodiment of the present disclosure above may be combined in any way to specify the subject matter encompassed by the present disclosure, i.e., the present disclosure encompasses all subject matter consisting of any combination of the combinable characteristics described herein. [Example]

[0094] Hereinafter, the embodiments of the present disclosure will be described more specifically with reference to examples, but the embodiments of the present disclosure are not limited to the following examples.

[0095] The sources from which the reagents and equipment used were purchased are listed below.

[0096] [reagent] 4'-Bromo-2,2':6'2"-terpyridine (Tokyo Chemical Industry), triisopropylsilylacetylene (Tokyo Chemical Industry), CuI (Wako Pure Chemical Industry), Pd(PPh3)2Cl2 (Wako Pure Chemical Industry), diisopropylamine (Tokyo Chemical Industry), 1.0 Tetrabutylammonium fluoride THF solution (Tokyo Chemical Industry), 4-ethynylbenzaldehyde (Tokyo Chemical Industry), 2-acetylpyridine (Tokyo Chemical Industry), ammonia water (Nacalai Tesque), sodium hydroxide (Nacalai Tesque), p-tolualdehyde (Wako Pure Chemical Industries), N-bromosuccinimide (Nacalai Tesque), α,α-azobisisobutyronitrile (Nacalai Tesque), 3-chloropropyltriethoxysilane (Tokyo Chemical Industry), sodium azide (Wako Pure Chemical Industries), tetrabutylammonium bromide (Wako Pure Chemical Industries), sodium EDTA (Dojindo Chemical Industries), CoBr2 (Aldrich), Co(OAc)2 (Aldrich), FeBr2 (Aldrich), Fe(OAc)2 (Aldrich), NiBr2 3H2O (Aldrich), NiBr2 (Wako Pure Chemical Industries), CuBr (Nacalai Tesque), CuBr2 (Wako Pure Chemical Industries), MnCl2·4H2O (Wako Pure Chemical Industries), MnBr2 (Aldrich), sodium ascorbate (Nacalai Tesque), copper sulfate (Wako Pure Chemical Industries), silica gel 60 (spherical) (neutral) (Nacalai Tesque), 3-aminopropyl-functionalized silica (Aldrich), diphenylsilane (Tokyo Chemical Industry), triethoxysilane (Tokyo Chemical Industry), pentamethyldisiloxane (Shin-Etsu Chemical), 1-octene (Tokyo Chemical Industry), styrene (Tokyo Chemical Industry), allyl chloride (Wako Pure Chemical Industry), 6-chloro-1-hexene (Wako Pure Chemical Industry), vinylcyclohexane (Tokyo Chemical Industry), 5-hexen-2-one (Tokyo Chemical Industry), methyl acrylate (Tokyo Chemical Industry), allyl acetate (Wako Pure Chemical Industry), N,N-dimethylallylamine (Tokyo Chemical Industry)

[0097] [Device] NMR: JEOL JMN-AL400 (JEOL Ltd.) GC: Shimadzu GC-2014 (Shimadzu Corporation), Column: Rtx-5MS (RESTEK, inner diameter: 0.25 mm, film thickness: 0.25 μm, length: 30 m) Elemental analysis: JM10 (J Science Co., Ltd.) Mass spectrometry: The MStation (JEOL Ltd.)

[0098] 2,2':6'2"-terpyridine may be simply referred to as terpyridine or tpy.

[0099] Synthesis of tridentate metal complex compounds According to the method described in the above-mentioned Non-Patent Document 34 (Organometallics 2017, 36, 1727), Fe[H,Dipp,Me]Br2 was synthesized using the method described in Non-Patent Document 35 (Inorg. Chem. 1988, 27, 2976-2981). Cu(tpy)Br2 was synthesized using the method described in Non-Patent Document 35 (Inorg. Chem. 1988, 27, 2976-2981). Mn(tpy)Br2, Ni(tpy)Br2, and Co(tpy)Br2 were synthesized as follows.

[0100] Synthesis of Mn(tpy)Br2 A solution of 2,2':6'2"-terpyridine (117 mg, 0.5 mmol) in 2.0 mL of ethanol was added to a solution of MnBr2 (107 mg, 0.5 mmol) in 2.0 mL of ethanol. A pale yellow precipitate appeared during stirring at room temperature. After 15 minutes of reaction, the precipitate was filtered and washed with 10 mL each of ethanol and ether. After vacuum drying, 207 mg of the pale yellow target product ([Mn(tpy)Br2]) was obtained (yield 92%). Anal. Calcd for C 15 H 11 Br2N3Mn: C, 40.26; H, 2.67; N, 9.19. Found: C, 40.21; H, 2.47; N, 9.38. HRMS(FAB): [M-Br] + Calcd. for C 15 H 11 BrN3Mn: 366.9517; Found: 366.9498.

[0101] Synthesis of Ni(tpy)Br2 To a solution of NiBr2·3H2O (117 mg, 0.43 mmol) dissolved in 25 mL of THF, a solution of 2,2':6'2"-terpyridine (100 mg, 0.43 mmol) dissolved in 5.0 mL of THF was added dropwise over 10 minutes. After stirring at room temperature for 24 hours, a pale green precipitate formed. The precipitate was filtered and washed with 10 mL each of THF and ether. After vacuum drying, 194 mg of the pale green target product ([Ni(tpy)Br2]) was obtained (86% yield). It is hygroscopic. Anal. Calcd for C 15 H 11 Br2N3Ni·1.5H2O: C, 37.63; H, 2.95; N, 8.87. Found: C, 37.76; H, 3.37; N, 9.33. HRMS(FAB): [M-Br] + Calcd. for C 15 H 11 BrN3Ni: 369.9190; Found: 369.9494.

[0102] Synthesis of Co(tpy)Br2 CoBr2 (87.5 mg, 0.4 mmol) and 2,2':6',2"-terpyridine (93.3 mg, 0.4 mmol) were dissolved in 15 mL of THF. A brown precipitate appeared during stirring at room temperature. 3 mL of methanol was added, and the color of the precipitate changed to emerald green. After 24 hours of reaction, the precipitate was filtered and washed with a small amount of methanol. The green target product ([Co(tpy)Br2]) was obtained in an amount of 170 mg (94% yield). Anal. Calcd for C 15 H 11 Br2N3Co·0.5H2O (M + 0.5H2O): C, 39.08; H, 2.62; N, 9.11. Found: C, 39.34; H, 2.53; N, 9.14. HRMS(FAB): [M-Br] + Calcd. for C 15 H 11 BrN3Co: 370.9468; Found: 370.9479.

[0103] Fe[H,Dipp,Me]Br2 is a compound represented by the formula (ii) above, where M represents Fe and all Xs represent Br; Cu(tpy)Br2 is a compound represented by the formula (i) above, where M represents Cu and all Xs represent Br; Mn(tpy)Br2 is a compound represented by the formula (i) above, where M represents Mn and all Xs represent Br; Ni(tpy)Br2 is a compound represented by the formula (i) above, where M represents Ni and all Xs represent Br; and Co(tpy)Br2 is a compound represented by the formula (i) above, where M represents Co and all Xs represent Br.

[0104] Examination of catalyst activation by various alkali metal salts [Consideration 1] 1-Octene (5.4 mmol), diphenylsilane (5.4 mmol, Ph2SiH2), 2.4 mg of Co(tpy)Br2 (0.0054 mmol, 0.1 mol%), and various inorganic additives (0.108 mmol, 2.0 mol%) were added to a Schlenk tube, followed by bubbling with N2 for 10 minutes. After reaction at 25 °C or 100 °C for 24 hours, the catalyst and salts were removed using a dry silica gel column. The resulting liquid products were quantified by GC.

[0105] [ka]

[0106] The yield of the hydrosilylated product and the pK of the conjugate acid of each additive added a is shown in Table 1a.

[0107] [Table 1a]

[0108] Overall, pK aIt was found that the larger the pK value, i.e., the stronger the basicity of the additive, the higher the catalytic activity. This tendency was more pronounced at a lower reaction temperature of 25°C. KOPv (potassium pivalate, entries 5 and 6) and KOAc (potassium acetate, entries 7 and 8) had almost the same pK a Nevertheless, KOPv was more active, which was thought to be due to its higher solubility in organic solvents (in this case, the mixture of 1-octene and Ph2SiH2, the substrate).

[0109] [Consideration 2] In Table 1a, various alkali metal salts were used as additives for hydrosilylation reactions. However, because the structures of the anions differ, the pK a However, the effect as an additive may differ depending on the anion structure. a We attempted hydrosilylation reactions using Co(tpy)Br2 as a catalyst with variable phosphate as an additive. Potassium phosphate salts have pK values ​​that vary depending on the number of potassium ions in the salt. a Since it is possible to change the amount of hydroxybenzoate, the hydrosilylation reaction was carried out using KH2PO4, K2HPO4, and K3PO4 as additives (see formula below). The results are shown in Table 1b.

[0110] [ka]

[0111] [Table 1b]

[0112] These results clearly demonstrate that salts with higher basicity are more suitable as additives.

[0113] [Study 3] Amines have a pK in water aThe value of α is large, indicating strong basicity. Therefore, we thought that it would be suitable as an additive for hydrosilylation reactions catalyzed by Co(tpy)Br2, and performed hydrosilylation reactions using amines as additives (see formula below). The results are shown in Table 1c.

[0114] [ka]

[0115] [Table 1c]

[0116] It was found that the catalytic activity of the hydrosilylation reaction was not very high when an amine was used as an additive. This result indicates that the addition of an amine as an additive does not significantly activate Co(tpy)Br2. This result indicates that the pK a This is thought to be due to the difference in the pK value between normal water and organic solvents. For example, the pK value of TEA (triethylamine) is a In water, the value is 10.8, which is much larger than that of KOAc (4.57), and it is thought to be a strong base, but in organic solvents (DMSO), the former is 9.0 and the latter is 12.3, which is the opposite. - The behavior of anionic bases such as amines differs between water and organic solvents, with the former acting as a weak base in organic solvents and the latter acting as a strong base in organic solvents. Because the hydrosilylation reaction is carried out in organic solvents, it was thought that the latter anionic bases would be more effective, while neutral bases such as amines would be less effective.

[0117] [Study 4] In entries 17 and 18 of Table 1a, KF showed good results as an additive. Halide salts, like carbonate salts, are easy to handle and inexpensive. Therefore, hydrosilylation reactions were performed using various halide salts as additives. The results are shown in Table 1d.

[0118] [ka]

[0119] [Table 1d]

[0120] When comparing KF and KCl, the results showed that KF was relatively more active (comparison of entries 1C and 2C with entries 3C and 4C). Therefore, the additive effects of various fluoride salts were investigated. As a result, it was found that LiF (entries 5C and 6C) and CaF2 (entries 9C and 10C) were not relatively active. On the other hand, CsF was found to be more active than KF (entries 7C and 8C). This can be explained as follows: When fluoride salts function as additives, F - is released, which is expected to act as a base. - The ease of release of F is due to the lattice energy of each fluoride salt. - It is thought that KF and CsF, which have low lattice energy, are more effective as additives.

[0121] Potassium carbonate (K 2 CO 3 ) for catalytic activation 1.0 mL of diphenylsilane (HSiPh, 5.4 mmol), 0.85 mL of 1-octene or 0.62 mL of styrene (5.4 mmol), 2.4 mg of Co(tpy)Br (0.0054 mmol, 0.1 mol%), and 15 mg of KCO (0.108 mmol, 2.0 mol%) were added to a Schlenk tube, followed by bubbling with N for 1 minute. After the reaction was run at 100 °C for 24 h, the catalyst and salts were removed using a dry silica gel column. The resulting liquid product was quantified by GC. A similar reaction was also performed using 1.0 mL of triethoxysilane (HSi(OEt), 5.4 mmol) and 0.62 mL of styrene (5.4 mmol) as substrates.

[0122] The results of examining the effect of K2CO3 on catalytic activity are shown in Table 2a.

[0123] [ka]

[0124] [Table 2a]

[0125] Co(tpy)Br2 does not exhibit hydrosilylation activity in the absence of potassium carbonate (Table 2a, Entries 1a and 2a). However, when potassium carbonate (K2CO3) was added to the reaction system, catalytic activity was observed in all cases (Table 2a, Entries 3a and 4a).

[0126] Potassium carbonate (K 2 CO 3 ) Consideration of the amount of addition The hydrosilylation reaction shown in the following reaction formula was carried out by adding various amounts of K2CO3. The results are shown in Table 2b. The experimental procedure was the same as above, and the amount of K2CO3 was examined in the range of 0.5 to 2.5 mol%.

[0127] [ka]

[0128] [Table 2b]

[0129] Table 2b shows that the product yield remains almost unchanged at around 85% when the amount of K2CO3 added is in the range of 0.5 to 2.0 mol%. Therefore, it was found that an amount of K2CO3 added of around 0.5 mol% is sufficient, and that adding an excess amount to the catalyst does not cause side reactions or anything like that, and the yield remains almost unchanged.

[0130] Consideration of reaction temperature The temperature dependence of the hydrosilylation reaction using K2CO3 as a co-catalyst was investigated. The reaction shown in the following reaction formula was investigated in the temperature range of 25 to 100°C. The results are shown in Table 3.

[0131] [ka]

[0132] [Table 3]

[0133] It was found that Co(tpy)Br2 generates low-valent active species even at room temperature in the presence of K2CO3, and catalyzes the hydrosilylation of 1-octene with diphenylsilane with high efficiency.

[0134] Next, we investigated the same temperature dependence in the hydrosilylation of styrene with triethoxysilane (reaction scheme shown below).

[0135] [ka]

[0136] [Table 4]

[0137] Similar to the results in Table 3, Co(tpy)Br2 was found to be sufficiently activated even at room temperature and to efficiently catalyze the hydrosilylation of styrene with triethoxysilane, yielding the product quantitatively. However, in this reaction, the yield tended to decrease slightly as the temperature increased. This was thought to be due to thermal polymerization of styrene.

[0138] Hydrosilylation reactions using various carbonates To investigate the effects of other carbonates, hydrosilylation reactions using various carbonates were investigated. As a model reaction, the hydrosilylation of styrene with triethoxysilane was used. Various carbonates were added at 2.0 mol% and the reaction was carried out at 100°C for 24 hours under N2 (reaction scheme shown below). The results are shown in Table 5.

[0139] [ka]

[0140] [Table 5]

[0141] As a result, catalytic activity was observed when all alkali metal carbonates examined were used, and particularly when Na2CO3, K2CO3, and Cs2CO3 were used, the catalytic activity was remarkable. On the other hand, no catalytic activity was observed when CaCO3 was used. As a result, it was found that alkali metal carbonates are effective in activating the Co(tpy)Br2 catalyst.

[0142] Catalytic activity of tpy complexes with various central metals in the presence of alkali metal carbonates Using tpy complexes with various central metals as catalysts, we investigated hydrosilylation reactions using K2CO3 as an auxiliary (particularly cocatalyst). In addition to Co, Fe and Ni were selected as central metals. However, since there are no M(tpy)Br2 complexes for Fe, we investigated the use of a tridentate iminobipyridine complex (Fe(BPI)). Dipp,Me )Br2) was used for the study.

[0143] [ka]

[0144] The hydrosilylation reaction of 1-octene with diphenylsilane (reaction formula below) was carried out, and the catalytic activity of each complex was compared. The results are shown in Table 6.

[0145] [ka]

[0146] [Table 6]

[0147] Ni and Fe complexes were also found to be activated by K2CO3 and catalyze hydrosilylation reactions, but their activity was lower than that of the Co(tpy)Br2 complex, which was found to be an extremely good hydrosilylation catalyst in the presence of K2CO3.

[0148] Preparation of immobilized catalyst complexes An immobilized complex catalyst was prepared as follows.

[0149] [ka]

[0150] Synthesis of Compound 1 The synthesis was carried out with reference to the above-mentioned Non-Patent Document 36. Under a nitrogen stream, 1.0 g (3.2 mmol) of 4'-bromo-2,2':6'2"-terpyridine and 1.8 mL (8.0 mmol) of triisopropylsilylacetylene were dissolved in 10 mL of THF, and then 37 mg (0.19 mmol) of CuI and 136 mg (0.19 mmol) of Pd(PPh3)2Cl2 were suspended. Finally, diisopropylamine ( i The reaction was initiated by adding 13.5 mL (96 mmol) of Pr2NH. After 2 hours of heating under reflux, the yellow suspension turned reddish purple and then brown. After removing the black precipitate by filtration, the solvent was removed using an evaporator. The residue was purified using an alumina column (eluent: chloroform / hexane = 1 / 4). After removing the solvent, the residue was dried in vacuo to obtain compound 1 as a pale yellow powder. Yield: 1.27 g, 96%.

[0151] Synthesis of compound L1 The synthesis was carried out with reference to Non-Patent Document 37. 500 mg of compound 1 (1.21 mmol) was dissolved in 3.0 mL of THF, and 2.4 mL of a 1.0 M THF solution of tetrabutylammonium fluoride was added. After reacting for 1 hour, 2.0 mL of water was added, and the product was extracted with 5.0 mL of chloroform x 2. The solvent was removed using an evaporator, and the product was purified using an alumina column (eluent: chloroform / hexane = 1 / 1). After the solvent was removed, the pale yellow powder was washed with hexane. The product was dried in vacuo to obtain compound L1. Yield: 173 mg, 56%.

[0152] [ka]

[0153] Synthesis of compound L2 The synthesis was carried out according to the above-mentioned Non-Patent Document 38. 0.5 g of 4-ethynylbenzaldehyde (3.84 mmol) and 0.86 mL of 2-acetylpyridine (7.68 mmol) were dissolved in 50 mL of ethanol, and 25 mL of 28% aqueous ammonia was added. Finally, 0.3 g of NaOH (7.5 mmol) was added, and the mixture was stirred at room temperature for 3 days. The resulting white precipitate was filtered and recrystallized from chloroform-ethanol. The resulting pale yellow needle-like crystals were dried in vacuo to obtain compound L2. Yield: 1.7 g, 32%.

[0154] [ka]

[0155] Synthesis of compound 2 The synthesis was carried out according to the above-mentioned Non-Patent Document 39. 4.84 g of 2-acetylpyridine (40 mmol) and 2.4 g of p-tolualdehyde (20 mmol) were dissolved in 100 mL of ethanol, and 28% aqueous ammonia and 1.6 g of NaOH (40 mmol) were added. The mixture was stirred at 34°C for 2 days. After the reaction, the resulting white precipitate was filtered off. The resulting white solid was dissolved in hot ethanol and recrystallized by ice-cooling. The resulting needle-like crystals were filtered off, washed with 10 mL of ice-cooled ethanol, and then vacuum-dried. Yield: 4.35 g, 70%.

[0156] Synthesis of compound L3 The synthesis was carried out according to the above-mentioned Non-Patent Document 39. The reaction was carried out under a nitrogen stream. 0.80 g of compound 2 (2.47 mmol) and 0.53 g of N-bromosuccinimide (NBS, 2.97 mmol) were dissolved in 10 mL of carbon tetrachloride. Then, 33 mg (0.20 mmol) of α,α-azobisisobutyronitrile was added to initiate the reaction. After the reaction was heated under reflux for 2 hours, the resulting precipitate was removed by filtration. The solvent was removed using an evaporator, and the compound was recrystallized from ethanol. The resulting pale yellow needle-like crystals were dried in vacuo to obtain compound L3. Yield: 0.63 g, 63%.

[0157] Compound (Si-C3-N 3 ) synthesis

[0158] [ka]

[0159] The synthesis was carried out with reference to Non-Patent Documents 40 and 41. The reaction was carried out under a nitrogen stream. 16 g (66 mmol) of 3-chloropropyltriethoxysilane, 6.5 g (100 mmol) of sodium azide, and 4.3 g (13 mmol) of tetrabutylammonium bromide were added to 200 mL of dehydrated acetonitrile. After 24 hours of reaction under reflux, the solvent was removed using an evaporator. 100 mL of ether was added to the resulting residue, and insoluble materials were filtered off. The solvent in the filtrate was removed using an evaporator. The resulting colorless, transparent oil was purified by vacuum distillation. Yield: 13 g, 80%.

[0160] Overview of click modification An example of a method for immobilizing a complex catalyst on a substrate by the click modification method is shown in the following scheme 1. Scheme 1 is a scheme for immobilizing compound L1 on silica gel by the click modification method.

[0161] [ka]

[0162] The details of Scheme 1 are as follows:

[0163] Azide modification of silica gel 5.0 g of silica gel was added to 50 mL of a 1.0% (v / v) toluene solution of compound (Si-C3-N3) and vigorously stirred. After reacting at 110 °C for 3 hours, the mixture was returned to room temperature and the silica gel was collected by filtration. The resulting silica gel was washed with toluene and then ether (10 mL each × 3), and finally dried under vacuum to immobilize compound (Si-C3-N3) on the silica surface. Yield: 5.0 g. The compound (Si-C3-N3)-immobilized silica thus obtained is sometimes referred to simply as Si-N3 in the description of this example (see Scheme 1).

[0164] Si-N 3 Modification of compound L1 to Modification of tpy was carried out based on the above-mentioned Non-Patent Documents 42 and 43. 20 mL of water containing 64 mg of CuSO4 (0.40 mmol) was mixed with 60 mL of DMSO containing 21 mg of L1 (0.080 mmol). 2.0 g of Si-N3 was dispersed in the resulting solution, and 0.96 g of sodium ascorbate (4.85 mmol) was added to initiate the reaction. After 3 hours of reaction at room temperature, the reaction mixture turned dark brown. The dark brown silica gel was collected by centrifugation. The collected silica gel was stirred overnight in 100 mL of 0.1 M aqueous sodium EDTA solution. The resulting pale yellow silica gel was collected by centrifugation and washed with water, methanol, acetone, and then ether (20 mL each x 3). Finally, the mixture was dried in vacuo to obtain 1.9 g of Si-N3 modified with compound L1 as a pale yellow powder. The Si-N3 modified with the compound L1 thus obtained may be simply referred to as Si-L1 in the description of this example (see Scheme 1).

[0165] Si-N 3 Modification of compound L2 to Using 5 g of Si-N3, compound L2 was used instead of compound L1, and the synthesis was carried out in the same manner as for the synthesis of Si-L1. Si-N3 modified with compound L2 was obtained. Yield: 4.7 g. In the description of this example, the Si-N3 modified with compound L2 obtained in this manner may be simply referred to as Si-L2.

[0166] Overview of the amino coupling method An example of a method for immobilizing a complex catalyst on a substrate by the amino coupling method is shown in the following scheme 2. Scheme 2 is a scheme for immobilizing compound L3 on silica gel by the amino coupling method.

[0167] [ka]

[0168] Modification of compound L3 onto amino-modified silica gel 0.25 g (0.61 mmol) of compound L3 was dissolved in 5.0 ml of toluene, and 1.0 g of amino-modified silica gel was added. Stirring was continued at room temperature until the remaining compound L3 disappeared. After 24 hours of stirring, the silica gel was recovered by centrifugation and washed with 20 mL of toluene, 20 mL of acetone, and 20 mL of ether. Vacuum drying yielded 1.2 g of pale yellow amino-modified silica gel modified with compound L3. In the following description, the amino-modified silica gel modified with compound L3 thus obtained will sometimes be referred to simply as Si-L3.

[0169] Complexation to tridentate ligand-immobilized silica gel: (Si-M(Ln)X 2 / H 2 O) Preparation 0.25 mmol of metal salt MX2 (M = Mn, Fe, Co, Ni, X = Cl, Br, OAc) or CuBr was dissolved in 10 mL of water, and 500 mg of tridentate ligand-modified silica gel (Si-Ln; i.e., Si-L1, Si-L2, or Si-L3) was added. After stirring at room temperature for 24 h, the mixture was collected by centrifugation. The resulting silica gel was washed with water, methanol, and ether (5.0 mL each × 2) and dried under vacuum. This yielded 470–490 mg of silica gel-immobilized metal complex (Si-M(Ln)X2 / HO).

[0170] Complexation to tridentate ligand-immobilized silica gel: (Si-M(Ln)X 2 Preparation of HCl (THF) The same reaction as in the preparation of Si-M(Ln)X2 / HO was carried out in THF instead of water. The obtained silica gel was washed with THF and ether (5.0 mL each × 2) and then vacuum dried. This yielded 470-490 mg of silica gel-immobilized metal complex catalyst (Si-M(Ln)X2 / THF).

[0171] [ka]

[0172] Potassium carbonate (K 2 CO 3 ) for the activation of immobilized catalysts Carbonates are essentially insoluble in organic solvents, making them easy to separate from the reaction product. This property makes them highly compatible with heterogeneous catalyst systems in which a complex catalyst is immobilized on a solid such as silica gel. In other words, the immobilized complex catalyst and carbonate can be recovered from the reaction system by filtration or centrifugation, and after separation from the reaction product, the recovered catalyst and carbonate can be reused.

[0173] Therefore, the following formula:

[0174] [ka]

[0175] We investigated the hydrosilylation reaction activated by potassium carbonate using the Co complex immobilized catalyst Si-Co(L1)Br2 / H2O (silica gel beads with Co complexes immobilized on the surface) shown in Figure 1. This reaction system is applicable to the hydrosilylation reaction of olefins and ketones. The following example shows the hydrosilylation reaction of styrene with triethoxysilane.

[0176] [ka]

[0177] The immobilized complex catalyst Si-Co(L1)Br2 / H2O does not exhibit hydrosilylation activity in this reaction under reaction conditions without potassium carbonate, but in the presence of potassium carbonate, it was found to give the hydrosilylated product almost quantitatively.

[0178] Examination of the effects of additives on catalytic reaction systems As mentioned above, in the catalytic hydrosilylation reaction using triethoxysilane (HSi(OEt)3) as a substrate, the activity of the immobilized catalyst was found to be dramatically improved by the addition of K2CO3 (preferably a catalytic amount of K2CO3). One possible explanation for this was that potassium carbonate (K2CO3) in the reaction system acted as an effective auxiliary agent, converting the dibromocobalt complex into a catalytically active species. Therefore, we next investigated the hydrosilylation reaction of styrene with triethoxysilane (see the following scheme) with various auxiliary agents added. The results are shown in Table 7.

[0179] [ka]

[0180] [Table 7]

[0181] From the above, it was found that the activity of the immobilized catalyst can be significantly improved by adding various auxiliary agents in addition to K2CO3. In addition, while favorable activity can be obtained using any auxiliary agent, the amine auxiliary agent t-butylamine ( t The addition of potassium pivalate (KOPv), potassium acetate (KOAc), potassium t-butoxide (KO BuNH2), cyclohexylamine (CyNH2), and triethylamine (TEA) had a greater effect than the addition of potassium pivalate (KOPv), potassium acetate (KOAc), and potassium t-butoxide (KO t It was found that the effect of adding auxiliary agents such as ammonium nitrate (Bu) and potassium carbonate (K2CO3) was even greater. This suggests that the activity of the immobilized catalyst can be improved even more by using auxiliary agents containing oxygen atoms. Considering the cost and ease of handling of the auxiliary agent, potassium carbonate (K2CO3) is more desirable.

[0182] Potassium carbonate (K 2 CO 3 ) Consideration of the amount of addition (immobilized catalyst) In the hydrosilylation reaction using Si-Co(L1)Br2 / HO, good results were obtained with the addition of 2.5 mol% potassium carbonate, as described above. To investigate the amount of potassium carbonate required for the substrate, similar hydrosilylation reactions were performed with various amounts of potassium carbonate added. The results are shown in Table 8.

[0183] [Table 8]

[0184] The results shown in the table indicate that the yield of the product increases slightly when the amount of K2CO3 is increased from 0.5 mol% to 2.5 mol%, but even at 0.5 mol%, the hydrosilylation reaction proceeds almost quantitatively.

[0185] Hydrosilylation reaction using various carbonates (immobilized catalysts) To investigate the catalytic activity of other carbonates, hydrosilylation reactions were attempted using various carbonates.

[0186] [ka]

[0187] The results are shown in Table 9.

[0188] [Table 9]

[0189] As with potassium carbonate (K2CO3) (Table 9, Entry 3h), the catalytic activity of Si-Co(L1)Br2 / H2O improved when sodium carbonate (Na2CO3) was added (Table 9, Entry 2h). However, the activity was slightly lower than that of K2CO3. On the other hand, no catalytic activity was observed in the system with calcium carbonate (CaCO3) added (Table 9, Entry 4h).

[0190] Carbonate-activated repeated hydrosilylation reactions The durability of an immobilized catalyst activated with potassium carbonate against repeated hydrosilylation reactions was investigated. After carrying out the reaction shown in the following formula, the immobilized catalyst and potassium carbonate were removed as solids by centrifugation, and the hydrosilylation product fraction was quantified by GC measurement of the reaction solution. The recovered immobilized catalyst and potassium carbonate were washed with toluene and ether before being used in the next reaction. The results of repeated reactions are shown in Table 10.

[0191] [ka]

[0192] [Table 10]

[0193] In the presence of a catalytic amount of potassium carbonate, Si-Co(L1)Br2 / H2O showed almost constant catalytic activity up to three reactions, demonstrating that this catalyst system can withstand repeated use.

[0194] Hydrosilylation reaction under air Hydrosilylation of styrene with triethoxysilane using Si-Co(L1)Br2 / H2O as a catalyst and K2CO3 as a carbonate was carried out under air.

[0195] [ka]

[0196] The results showed that the hydrosilylation reaction proceeded even in air. The yield was 45% when the carbonate amount was 2.5 mol%, but when the carbonate amount was increased tenfold to 25 mol%, the product yield increased to 59%.

Claims

1. a hydrosilylation reaction catalyst coagent containing an alkali metal salt, the alkali metal salt is at least one selected from the group consisting of alkali metal carbonates, hydrogen carbonates, phosphates, hydrogen phosphates, and nitrates; The hydrosilylation reaction catalyst is a catalyst having a tridentate ligand metal complex compound, and the tridentate ligand metal complex compound is represented by formula (i): 【Chemistry 1】 (wherein M represents Fe, Co, Ni, Mn, or Cu; X may be the same or different and represent Cl, Br, —OR X , —OC(O)R X , or —OH; when there are two R X s, they may be the same or different and represent an aryl group, or a linear or branched alkyl group having 1 to 6 carbon atoms).

2. 2. The auxiliary according to claim 1, wherein the alkali metal salt is an alkali metal carbonate.

3. 3. The auxiliary according to claim 1, wherein the alkali metal carbonate is at least one selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.

4. 4. The auxiliary according to claim 1, wherein the alkali metal salt is a salt having an acid dissociation constant pKa in water of 2 or more.

5. The catalyst having a tridentate metal complex compound is A complex-immobilized catalyst, A tridentate metal complex compound and a substrate are provided, A catalyst in which a tridentate metal complex compound is immobilized on a substrate, The catalyst having a tridentate metal complex compound has the formula (A): [Tridentate metal complex compound]-[linker part]-[substrate] (A) An immobilized complex catalyst represented by the formula: The tridentate metal complex compound has the formula: 【Transformation 3】 (wherein M represents Fe, Co, Ni, Mn, or Cu; X may be the same or different and represent Cl, Br, —OR X , —OC(O)R X , or —OH; when there are two R X s, they may be the same or different and represent an aryl group, or a linear or branched alkyl group having 1 to 6 carbon atoms), The -[linker part]-* (* indicates the substrate side) is represented by the formula: 【Chemistry 4】 (wherein Z is a bond or 【Transformation 5】 wherein n represents 1, 2, 3, 4, 5, or 6, * represents the substrate side, and R i and R ii are the same or different and represent an aryl group, an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, or -O-*. However, at least one * may be bonded to the substrate, and the other * may be bonded to a Si atom in another linker portion.) or a group represented by the formula: 【Transformation 6】 (wherein Z, n, *, R i and R ii are the same as above, with the proviso that at least one * is bonded to the substrate, and the other * may be bonded to a Si atom of another linker moiety), The catalyst The auxiliary according to any one of claims 1 to 4.

6. The auxiliary agent according to claim 5, wherein the substrate is a silica compound substrate or a metal substrate having an oxide film on the surface thereof.

7. The auxiliary according to any one of claims 1 to 6, which is a hydrosilylation reaction promoter.

8. A method for producing a hydrosilylated compound, comprising carrying out a hydrosilylation reaction using a hydrosilylation catalyst in the presence of the coagent according to any one of claims 1 to 7.

Images