JP7630783B2 - Complex-immobilized catalyst - Google Patents

Description

The present disclosure relates to a complex-immobilized catalyst, and more specifically to a catalyst in which a tridentate metal complex compound is immobilized on a substrate. The contents of all documents described in this specification are incorporated herein by reference.

The hydrosilylation reaction is a useful reaction for synthesizing organosilanes, and has an excellent environmental impact because it produces few by-products. A metal catalyst is required to carry out this reaction, and Pt catalysts are commonly used. In recent years, catalysts using first transition metals have been developed to solve the problem of the scarcity of Pt.

JP 2018-065103 A

V. Crosshenny, F. M. Romero, R. Ziessel, J. Org. Chem., 1997, 62, 1491-1500. M. C. Haberecht, J. M. Schnorr, E. V. Andreitchenko, C. G. Clark, Jr., M. Wagner, K. Mullen, Angew. Chem. Int. Ed., 2008, 47, 1662-1667. C. Chakraborty, R. K. Pandey, U. Rana, M. Kanao, S. Moriyama, M. Higuchi, J. Mater. Chem. C, 2016, 4, 9428-9437. X. Liu, J. Xu, Y. Lv, W. Wu, W. Liu, Y. Tang, Dalton Trans., 2013, 42, 9840-9846. D. Zych, A. Kurpanik, A. Slodek, A. Maron, M, Pajak, G. Szafraniec-Gorol, M. Matussek, S. Krompiec, E. Schab-Balcerzak, S. Kotowicz, M. Siwy, K. Smolarek, S. Mackowski, W. Danikiewicz, Chem. Eur. J., 2017, 23, 15746-15758. H. S. Mader, M. Link, D. E. Achatz, K. Uhlmann, X. Li, O. S. Wolfbeis, Chem. Eur. J., 2010, 16, 5416-5424. R. E. Ruther, M. L. Rigsby, J. B. Gerken, S. R. Hogendoorn, E. C. Landis, S. S. Stahl, R. J. Hamers, J. Am. Chem. Soc., 2011, 133, 5692-5694; J. B. Gerken, M. L. Rigsby, R. E. Ruther, R. J. Perez-Rodriguez, I. A. Guzei, R. J. Hamers, S. S. Stahl, Inorg. Chem., 2013, 52, 2790-2798. C. Arana, M. Keshavarz, K. T. Pottsb, H. D. Abruna, Inorg. Chim. Acta 1994, 225, 285-295. H. Nishiyama, A. Furuta, Chem. Commun. 2007, 760-762; D. Noda, A. Tahara, Y. Sunada, H. Nagashima, J. Am. Chem. Soc. 2016, 138, 2480-2483. S. Gutierrez-Tarrino, P. Concepcion, P. Ona-Burgos, Eur. J. Inorg. Chem., 2018, 4867-4874. J. H. Docherty, J. Peng, A. P. Dominey, S. P. Thomas, Nat. Chem. 2017, 9, 595-600

When using base metal catalysts, ligands with complex structures are required, which are more expensive than the metal at the active center. In addition, these catalysts are generally difficult to recover, so costs are high whether a precious metal or base metal catalyst is used.

Furthermore, many of the ligands used in hydrosilylation complex catalysts using first transition metals that have been reported so far are pincer-type tridentate ligands. In general, when such a type of ligand forms a complex with a first transition metal, it becomes a stable _ML2 type (L=tridentate ligand) complex, and the catalytic activity is greatly reduced (one example is shown in the formula below).

Therefore, a strategy of introducing a bulky substituent into the ligand L to prevent the formation of _ML2 is often used, but the introduction of this substituent further increases the cost of the ligand.

Therefore, the inventors conducted research with the aim of providing a relatively low-cost hydrosilylation complex catalyst that has as low a ligand cost as possible and can be used repeatedly.

The inventors discovered that by immobilizing a tridentate metal complex compound on a substrate, it is possible to provide a relatively low-cost hydrosilylation complex catalyst that can be used repeatedly, and have made further improvements.

The present disclosure includes, for example, the subject matter described in the following sections:
Item 1.
A complex-immobilized catalyst,
A method for producing a metal complex having a tridentate ligand and a substrate,
A catalyst in which a tridentate metal complex compound is immobilized on a substrate.
Item 2.
Item 2. The catalyst according to item 1, wherein the substrate is a silica compound substrate or a metal substrate having an oxide film on its surface.
Item 3.
Item 3. The catalyst according to item 1 or 2, wherein the tridentate metal complex compound and the substrate are bonded via a linker moiety.
Item 4.
Item 4. The catalyst according to item 3, wherein the bond between the linker part and the substrate is a silane coupling bond.
Item 5.
Item 5. The catalyst according to item 3 or 4, wherein the whole or part of the linker moiety is derived from an alkoxysilane.
Item 6.
6. The catalyst according to any one of Items 1 to 5, wherein the tridentate ligand is terpyridine.
Item 7.
Formula (A):
[Tridentate metal complex compound]-[Linker part]-[Substrate] (A)
A catalyst represented by the formula:
The tridentate metal complex compound has the formula:

(wherein M represents Fe, Co, Ni, Mn, or Cu; X may be the same or different and represents Cl, Br, _-OCH3 , -OC(O) ^Rx , or -OH; when there are two ^Rx'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:

(where Z is a bond or

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 each represents 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 of another linker part.

(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 part),
Item 7. The catalyst according to any one of items 1 to 6.
Item 8.
8. The catalyst according to any one of Items 1 to 7, wherein the tridentate metal complex compound is a tridentate cobalt complex compound.
Item 9.
Item 9. The catalyst according to any one of Items 1 to 8, which is a hydrosilylation catalyst.
Item 10.
Item 10. A method for producing a hydrosilylated compound, comprising carrying out a hydrosilylation reaction in the presence of the catalyst according to any one of Items 1 to 9.
Item 11.
Item 10. A method for producing a hydrosilylated compound, comprising carrying out a hydrosilylation reaction in the presence of the catalyst according to any one of Items 1 to 9 and an alkoxide salt and/or a carboxylate salt.

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), and a xylyl group (o-xylyl, m-xylyl, p-xylyl).

A complex catalyst with hydrosilylation catalytic activity that can be used repeatedly and is relatively low cost is provided.

IR spectra of Si-Co(L1)(OAc) ₂ /H ₂ O (A) and Si-Co(L1)(OAc) ₂ /THF (B) (before catalytic reaction: solid line, after catalytic reaction: dotted line). Shown is (A) a Schlenk flask (glass container catalyst) modified with a complex catalyst and (B) the results (yield) of a repeated hydrosilylation reaction test. The contents of each compound (compound 1 and compound 2) in the product obtained when flow synthesis was carried out by hydrosilylation reaction of 1-octene with diphenylsilane (Ph ₂ SiH ₂ ) are shown.

Each embodiment included in the present disclosure will be described in more detail below. The present disclosure preferably includes, but is not limited to, a complex catalyst and its uses, and the present disclosure includes everything disclosed in this specification that can be recognized by a person skilled in the art.

The complex catalyst included in the present disclosure is an immobilized complex catalyst, more specifically, a catalyst comprising a tridentate metal complex compound and a substrate, in which the tridentate metal complex compound is immobilized on the substrate. In this specification, the catalyst may be referred to as the "catalyst of the present disclosure."

Examples of tridentate ligands include 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.

In the above formulas, R ¹ is the same or different and represents a phenyl group (Ph), a 2,4,6-trimethylphenyl group (Mes), a 2,4-diisopropylphenyl group (Dipp), or a cyclohexyl group (Cy); R ² is the same or different and represents a hydrogen atom (H), a methyl group (Me), or a trifluoromethyl group (CF ₃ ); R ³ is a methyl group at the 4-, 5-, or 6-position (4'-Me, 5'-Me, or 6'-Me); and R ⁴ is the same or different and represents an isopropyl group ( ⁱ Pr), a phenyl group (Ph), or a pentafluorophenyl group (C ₆ F ₅ ).

Among the tridentate ligands, 2,2':6'2"-terpyridine (tpy) is particularly preferred.

Examples of metals 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. Among these, Fe, Co, Ni, Mn, Cu, Cr, and Mo are preferred, and Co is particularly preferred.

The substrate is preferably one on which the tridentate metal complex compound can be easily fixed. As described below, for example, when the fixing is performed by silane coupling bonding, a substrate having OH groups 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. In addition, the metal oxide film itself is also included in the substrate having a metal oxide film on the surface as referred to here. Among these, silica compound substrates are preferred.

Preferable examples of the silica compound in the silica compound substrate include silica and glass. Examples of the silica compound substrate include, but are not limited to, silica particles, glass plates, glass containers, etc.

The tridentate metal complex compound may be directly immobilized on the substrate, but it is preferable that it is immobilized via a linker. In other words, it is preferable that the tridentate metal complex compound and the substrate are bonded by a linker portion.

In this case, the structure of the catalyst of the present disclosure can be generally represented, for example, as shown in formula (A) below.
[Tridentate metal complex compound]-[Linker part]-[Substrate] (A)

The bond between the linker part and the substrate is preferably a silane coupling bond. It is also preferable that the whole or part of the linker part is derived from an alkoxysilane.

For example, the linker part and the substrate are formed by bonding a compound (hereinafter also referred to as a "linker part precursor compound"), which is entirely or at an end thereof, to the substrate through a silane coupling reaction, thereby immobilizing the linker part precursor compound on the substrate, and then bonding the part of the immobilized linker part precursor compound that is different from the substrate side to a tridentate ligand metal complex compound, thereby producing the catalyst of the present disclosure.

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

(wherein M represents Fe, Co, Ni, Mn, Cr, or Cu, and X may be the same or different and represents Cl, Br, -OCH ₃ , -OC(O)R ^X , or -OH). 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). Of these, a methyl group, a t-butyl group, or the like is preferred. When there are two R ^X in the formula, they may be the same or different.

In addition, the tridentate metal complex compound in the above formula (A) may be, for example, any of the following formulas:

(In the formula, M and X are the same as above.)
Preferred is a group represented by the formula:

(In the formula, M and X are the same as above.)
A group represented by the following formula is more preferred.

In addition, in the above formula (A), -[linker part]-* (where * indicates the substrate side) can be, for example, the following formula:

(where Z is a bond or

wherein 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 each represents 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:

(wherein Z, n, *, R ⁱ and R ⁱⁱ are as defined above) are preferable.

When Z is a bond, "-Z-" becomes "-".

In the groups represented by these formulas, the portion represented by * may be bonded to the substrate or may be bonded to a Si atom of another linker part. However, at least one * is bonded to the substrate. In other words, when both R ⁱ and R ⁱⁱ represent an alkyl group having 1 to 4 carbon atoms, only one * is present, and therefore the * is the site bonded to the substrate. In addition, when one or both of R ⁱ and R ⁱⁱ represent -O-*, two or three * are present, and at least one of these * is the 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 is Si derived from an alkoxysilane of another linker part), but at least one * is Si-O-[substrate].

Among these groups, a group in which both R ⁱ and R ⁱⁱ are -O-*, that is, a group represented by the formula:

(where Z, n, and * are the same as above) or a group represented by the formula:

(where Z, n, and * are as defined above) is preferred.

The catalyst of the present disclosure can be produced by combining known methods or methods that can be easily derived from known methods.

For example, as described above, the catalyst of the present disclosure can be produced by fixing a compound (also called a "linker precursor compound") in which alkoxysilane constitutes the entirety or end portion to a substrate by a silane coupling reaction, and then bonding a portion of the fixed linker precursor compound that is different from the substrate side to a tridentate metal complex compound. Note that in the production process, it is preferable to use only a ligand compound in which metal complex formation has not yet been performed 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.

Examples of linker precursor compounds include those of the formula:

(wherein R ^a represents an alkoxy group having 1 to 6 carbon atoms; R ^b and R ^c are the same or different and represent an alkoxy group having 1, 2, 3, 4, 5, or 6 carbon atoms, an aryloxy group, or an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, or an aryl group; R represents _NH2 or _N3 ; and m represents 1, 2, 3, 4, 5, or 6.) As the alkoxy group having 1 to 6 carbon atoms, a methoxy group or an ethoxy group is particularly preferred.

When the linker precursor compound is the above formula, R contributes to the bond 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 by 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 is preferably one having a structure in which an alkynyl group is introduced into the tridentate ligand. For example, the formula:

(wherein Z is the same as above) is preferred. When R is NH ₂ (amino group), the linker precursor compound and the tridentate metal complex compound can be bonded together by reacting with an alkyl halide, for example. In this case, the tridentate metal complex compound is preferably one having a structure in which the tridentate ligand is modified with a halo group. For example, the formula:

In the formula, ^Rd represents a halogen atom, p represents 0, 1, 2, 3, or 4, and Z is the same as defined above. As the halogen atom, F, Cl, Br, or I is preferred.

The catalyst of the present disclosure can be preferably used as a hydrosilylation catalyst. The catalyst of the present disclosure makes it possible to carry out the hydrosilylation reaction with high efficiency.

In addition, by using the catalyst of the present disclosure in combination with an alkoxide salt or a carboxylate salt, the hydrosilylation reaction can be carried out more efficiently. In other words, by including the catalyst of the present disclosure and an alkoxide salt or a carboxylate salt in a hydrosilylation reaction system, the hydrosilylation reaction can be carried out more efficiently.

Also, it can be said that alkoxide salts and carboxylate salts can be used as hydrosilylation catalytic activity enhancers for the catalysts disclosed herein.

Examples of alkoxide salts include metal alkoxide salts, more specifically, for example, sodium methoxide, sodium ethoxide, potassium t-butoxide, etc. Examples of carboxylate salts include linear or branched carboxylate salts having 1, 2, 3, 4, 5, or 6 carbon atoms, more specifically, for example, acetate salts, propionate salts, pivalate salts, etc.

The amount of alkoxide salt and/or carboxylate used is not particularly limited, but is preferably about 0.1 to 5 mol % relative to the substrate, and more preferably about 0.5 to 3 mol %.

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, or a C=N double bond. For example, unsaturated hydrocarbons are preferred, and unsaturated hydrocarbons having a double bond are particularly preferred. For example, although not particularly limited, olefinic hydrocarbons and styrene-based hydrocarbons are preferred.

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

The catalysts disclosed herein can also be preferably used for flow synthesis.

In this specification, the term "comprising" includes "consisting essentially of" and "consisting of." In addition, the present disclosure includes any combination of the constituent elements described in this specification.

Furthermore, the various characteristics (properties, structures, functions, etc.) described for each embodiment of the present disclosure above may be combined in any way to identify the subject matter encompassed by the present disclosure. In other words, the present disclosure encompasses all subject matter consisting of any combination of the combinable characteristics described in this specification.

The following provides a more detailed explanation of the embodiments of the present disclosure, but the embodiments of the present disclosure are not limited to the following examples.

The sources of the reagents and equipment used are listed below.
[reagent]
4'-Bromo-2,2':6'2"-terpyridine (Tokyo Chemical Industry), triisopropylsilylacetylene (Tokyo Chemical Industry), CuI (Wako Pure Chemical Industry), Pd(PPh ₃ ) ₂ Cl ₂ (Wako Pure Chemical Industry), diisopropylamine (Tokyo Chemical Industry), 1.0 M tetrabutylammonium fluoride THF solution (Tokyo Chemical Industry), 4-ethynylbenzaldehyde (Tokyo Chemical Industry), 2-acetylpyridine (Tokyo Chemical Industry), aqueous ammonia (Nacalai Tesque), sodium hydroxide (Nacalai Tesque), p-tolualdehyde (Wako Pure Chemical Industry), N-bromosuccinimide (Nacalai Tesque), α,α-azobisisobutyronitrile (Nacalai Tesque), 3-chloropropyltriethoxysilane (Tokyo Chemical Industry), sodium azide (Wako Pure Chemical Industry), tetrabutylammonium bromide (Wako Pure Chemical Industry), sodium EDTA (Dojin Chemical Industry), CoBr ₂ (Aldrich), Co(OAc) ₂ (Aldrich), _FeBr2 (Aldrich), Fe(OAc) ₂ (Aldrich), _NiBr2 (Wako Pure Chemical Industries), CuBr (Nacalai Tesque), _MnCl2.4H2O (Wako Pure Chemical Industries), 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 Co., Ltd.), triethoxysilane (Tokyo Chemical Industry Co., Ltd.), pentamethyldisiloxane (Shin-Etsu Chemical Co., Ltd.), 1-octene (Tokyo Chemical Industry Co., Ltd.), styrene (Tokyo Chemical Industry Co., Ltd.), allyl chloride (Wako Pure Chemical Industry Co., Ltd.), 6-chloro-1-hexene (Wako Pure Chemical Industry Co., Ltd.), vinylcyclohexane (Tokyo Chemical Industry Co., Ltd.), 5-hexen-2-one (Tokyo Chemical Industry Co., Ltd.), methyl acrylate (Tokyo Chemical Industry Co., Ltd.), allyl acetate (Wako Pure Chemical Industry Co., Ltd.), N,N-dimethylallylamine (Tokyo Chemical Industry Co., Ltd.)
[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.)

2,2':6'2"-terpyridine is sometimes referred to simply as terpyridine or tpy.

Synthesis of Compound 1 Compound 1 was synthesized with reference to Non-Patent Document 1 mentioned above. 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 37 mg (0.19 mmol) of _{CuI and 136 mg (0.19 mmol) of Pd(PPh3)2Cl2 were suspended} in the solution. Finally, 13.5 mL ₍ 96 mmol) of diisopropylamine ( ^iPr2NH ) was added to initiate the reaction. After reacting for 2 hours under reflux, the yellow suspension turned reddish purple and then brown. After removing the black precipitate by filtration, the solvent was removed by evaporation. The residue was purified using an alumina column (eluent: chloroform/hexane = 1/4). After removing the solvent, the mixture was dried in vacuum to obtain compound 1 as a pale yellow powder. Yield: 1.27 g, 96%.

Synthesis of Compound L1 The synthesis was carried out with reference to Non-Patent Document 2 mentioned above. 500 mg of Compound 1 (1.21 mmol) was dissolved in 3.0 mL of THF, and 2.4 mL of 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 chloroform (5.0 mL x 2). After removing the solvent with an evaporator, the product was purified with an alumina column (eluent: chloroform/hexane = 1/1). After distilling off the solvent, the pale yellow powder was washed with hexane. Compound L1 was obtained by vacuum drying. Yield: 173 mg, 56%.

Synthesis of Compound L2: The compound was synthesized according to the above-mentioned Non-Patent Document 3. 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 stirred at room temperature for 3 days. The resulting white precipitate was filtered and further recrystallized from chloroform-ethanol. The obtained pale yellow needle crystals were dried in vacuum to obtain compound L2. Yield: 1.7 g, 32%.

Synthesis of Compound 2 The synthesis was carried out according to the above-mentioned Non-Patent Document 4. 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 further added and stirred at 34°C for 2 days. After the reaction, the resulting white precipitate was filtered off. The obtained white solid was dissolved in hot ethanol and recrystallized by cooling on ice. The obtained needle-like crystals were filtered off, washed with 10 mL of ice-cold ethanol, and then dried in vacuum. Yield 4.35 g, 70%.

Synthesis of Compound L3 : The compound was synthesized according to the above-mentioned Non-Patent Document 4. 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 start the reaction. After reacting for 2 hours under heating and refluxing conditions, the resulting precipitate was removed by filtration. After removing the solvent with an evaporator, recrystallization was carried out from ethanol. The obtained pale yellow needle crystals were dried in vacuum to obtain Compound L3. Yield 0.63 g, 63%.

Compound (Si-C3-N ₃ Synthesis of

The synthesis was carried out with reference to the above-mentioned non-patent documents 5 and 6. 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 reacting for 24 hours under heating and reflux, the solvent was removed using an evaporator. 100 mL of ether was added to the resulting residue, and unnecessary materials were filtered off. The solvent of the filtrate was removed using an evaporator. The resulting colorless, transparent oil was purified by distillation under reduced pressure. Yield: 13 g, yield: 80%.

Overview of Click Modification Method 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.

Details of Scheme 1 are given below.

Azide-modified silica gel (5.0 g) was added to 50 mL of a toluene solution of 1.0% (v/v) compound (Si-C3-N ₃ ) 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 obtained silica gel was washed with toluene and then ether (10 mL each x 3), and finally dried in vacuum to immobilize compound (Si-C3-N ₃ ) on the silica surface. Yield: 5.0 g. The compound (Si-C3-N ₃ )-immobilized silica thus obtained may be referred to simply as Si-N ₃ in the description of this example (see Scheme 1).

Modification of Si-N ₃ with compound L1 Modification of tpy was performed with reference to Non-Patent Document 7 and Non-Patent Document 8. 20 mL of water in which 64 mg of CuSO ₄ (0.40 mmol) was dissolved was mixed with 60 mL of DMSO solution in which 21 mg of L1 (0.080 mmol) was dissolved. 2.0 g of Si-N ₃ was dispersed in the resulting solution, and 0.96 g of sodium ascorbate (4.85 mmol) was added to start the reaction. After 3 hours of reaction at room temperature, the reaction solution 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 sodium EDTA aqueous solution. The obtained pale yellow silica gel was collected by centrifugation and washed with water, methanol, acetone, and then ether (20 mL each x 3). Finally, it was dried in vacuum to obtain 1.9 g of Si-N ₃ modified with compound L1 as a pale yellow powder. The thus obtained Si- _N3 modified with the compound L1 may be simply referred to as Si-L1 in the description of this embodiment (see Scheme 1).

Modification of Si-N ₃ with compound L2 Except for using 5 g of Si-N ₃ and using compound L2 instead of compound L1, synthesis was performed in the same manner as the synthesis of Si-L1 above to obtain Si-N ₃ modified with compound L2. Yield: 4.7 g. In the description of this example, the Si-N ₃ modified with compound L2 thus obtained may be simply referred to as Si-L2.

Summary of 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.

Modification of Amino-Modified Silica Gel with Compound L3 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. When stirring was continued at room temperature, the undissolved compound L3 disappeared. After stirring for 24 hours, the silica gel was collected by centrifugation and washed with 20 mL of toluene, 20 mL of acetone, and 20 mL of ether. 1.2 g of pale yellow amino-modified silica gel modified with compound L3 was obtained by vacuum drying. The amino-modified silica gel modified with compound L3 obtained in this manner may be simply referred to as Si-L3 in the description of this embodiment.

Complexation to tridentate ligand-immobilized silica gel: Preparation of (Si-M(Ln)X ₂ /H ₂ O)
0.25 mmol of metal salt MX ₂ (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 hours, the mixture was collected by centrifugation. The obtained silica gel was washed with water, methanol, and ether (each 5.0 mL × 2) and dried in vacuum. This resulted in 470-490 mg of silica gel-immobilized metal complex (Si-M(Ln)X ₂ /H ₂ O).

Complex formation on tridentate ligand-immobilized silica gel: Preparation of (Si-M(Ln)X ₂ /THF) The same reaction as in the preparation of Si-M(Ln)X ₂ /H ₂ O was carried out in THF instead of water. The obtained silica gel was washed with THF and ether (5.0 mL each x 2), and then vacuum dried. As a result, 470-490 mg of silica gel-immobilized metal complex catalyst (Si-M(Ln)X ₂ /THF) was obtained.

Synthesis of [Co(tpy)Br2 _]
CoBr ₂ (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. When 3 mL of methanol was added, the color of the precipitate changed to emerald green. After reacting for 24 hours, the precipitate was filtered and washed with a small amount of methanol. After drying in vacuum, 170 mg of the green target product ([Co(tpy)Br ₂ ]) was obtained (yield 94%). Anal. Calcd for C ₁₅ H ₁₁ Br ₂ N ₃ Co.0.5H ₂ O (M + 0.5H ₂ O): 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 BrN ₃ Co: 370.9468; Found: 370.9479.

Synthesis of [Co(tpy) ₂ ](PF6 ₎ 2 _: The synthesis was carried out according to the above-mentioned non-patent document 8. 95 mg of _CoCl2.6H2O (0.40 mmol) and 215 mg of _2,2 ':6'2"-terpyridine (0.92 mmol) were dissolved in 15 mL of water and stirred at room temperature for 30 minutes. An excess of _{NH4PF6 aqueous} solution was added to produce a brown precipitate. The precipitate was filtered, washed with water and ether, and dried in vacuum. Yield: 0.32 g, 98%.

To investigate the hydrosilylation activity of silica gel-immobilized metal complex catalysts incorporating various metals (M) and monodentate ligands (X), the reaction shown in the following formula (1) was carried out. As the catalyst in formula (1), each silica gel-immobilized metal complex catalyst was used.

50 mg of Si-M(L1)X ₂ /H ₂ O was placed in a Schlenk and dried under vacuum for 1 hour. After that, 1.0 mL of diphenylsilane (5.4 mmol) and 0.85 mL of 1-octene (5.4 mmol) were added, and N ₂ was bubbled for about 1 minute to create a nitrogen atmosphere. After heating and stirring at 100°C for 24 hours, Si-M(L1)X ₂ /H ₂ O was removed by centrifugation to obtain a colorless, transparent liquid. The product was quantified by GC analysis. The results are shown in Table 1 (entries 1-1 to 1-5). In the following tables, N.D. means not detectable.

As a result, it was found that the hydrosilylation reaction proceeded regardless of which metal was used as the complex, and that the hydrosilylation reaction proceeded in particularly high yields when Co was used as the complex (entry 1-3).

As a control experiment, a reaction was also carried out using a silica gel modified with compound L1 that had not been introduced with a metal, and it was confirmed that the hydrosilylation reaction did not proceed (entry 1-6). This showed that the coordination of a metal was necessary for the reaction. In addition, catalytic reaction activity was confirmed using silica gel (chemical formula 26 below) in which a Ph group (phenyl group) had been introduced instead of tpy. As a result, it was found that in the case of silica gel modified with a Ph group that does not have the ability to form a complex with a metal (entry 1-7, 1-8), hydrosilylation activity was not exhibited even when treated with CoBr ₂ (entry 1-8). Therefore, it was revealed that a metal formed a complex with the tpy immobilized on the surface, and as a result, hydrosilylation activity was exhibited. In addition, although a reducing agent is generally required to induce a first transition metal complex into a catalytically active species, it was also found that catalytic activity was exhibited in this reaction without the addition of a reducing agent.

Consideration of hydrosilylation catalytic activity in the case of monodentate ligand X = OAc Generally, it is known that low-valent chemical species are active species in hydrosilylation catalysts using first transition metals, so it is necessary to isolate the low-valent species in advance using a reducing agent or add a reducing agent during the catalytic reaction. However, it has been reported that when an acyloxy ligand is used as the monodentate ligand X, the hydrosilylation reaction proceeds without a reducing agent (Non-Patent Documents 9 and 10 mentioned above). Therefore, in the same manner as above, an immobilized catalyst was prepared using M(OAc) ₂ as the metal salt for complex formation, and the catalytic activity in the reaction of the above formula (1) was evaluated. Fe or Co was used as the metal to form the complex. The results are shown in Table 2.

It was found that when Fe(OAc) ₂ was complexed in THF, the activity was slightly higher than that of _FeBr2 (entry 2-2). When Co(OAc) ₂ was used, it was found to show almost the same activity as _CoBr2 (entries 2-3 and 2-4).

IR Spectra of Monodentate Ligands
IR measurements were performed on Si-Co(L1)(OAc) ₂ /H ₂ O and Si-Co(L2)(OAc) ₂ /THF. Measurements were also performed after the catalytic reaction to confirm the state of the OAc ligand. The results are shown in Figure 1.

As a result, in Si-Co(L1)(OAc) ₂ /THF, a peak due to the carbonyl group of the acetate ligand was observed at 1570 cm ^-1 (red in Fig. 1B), but this peak was not observed in the case of Si-Co(L1)(OAc) ₂ /H ₂ O complexed in water (red in Fig. 1A). From this result, it is inferred that the monodentate ligand of Si-Co(L1)(OAc) ₂ /H ₂ O is OH, not OAc.

In addition, it was confirmed that a new peak appeared at 2147 cm ^-1 after the reaction for both catalysts. This peak is close to the reported position of the stretching vibration of Co-H (2151 cm ^-1 ) (Non-Patent Document 10). Therefore, it is possible that in this catalyst system, Co-H species are generated on the silica gel surface and act as active species to drive the reaction.

Although we do not wish to limit the interpretation, the estimated activation mechanism for X = OH and X = OAc, which is inferred from the above results, is shown in Scheme 3.

In this presumed activation mechanism, it is believed that the OAc or OH ligand is converted to a hydride species (active species in Scheme 3) through σ-bond metathesis, and the reaction proceeds. IR suggests that the structure shown as the active species in the scheme is passed through, and a similar activation mechanism has also been proposed for a system using a tpy ligand (Non-Patent Document 10, cited above).

Examination of the effect of immobilization To examine the effect of catalyst immobilization, the catalytic activity of non-immobilized metal complexes ([Co(tpy)Br ₂ ] or [Co(tpy) ₂ ](PF ₆ ) ₂ ) was examined according to the procedure described below and compared with that of silica gel-immobilized metal complexes.

1.0 mL of diphenylsilane (5.4 mmol), 0.85 mL of 1-octene (5.4 mmol), and 0.0054 mmol of the complex ([Co(tpy) _Br2 ] or [Co(tpy) ₂ ]( _PF6 ) ₂ ) were added to the Schlenk flask, followed by _N2 bubbling for 1 minute. Then, 108 mml of 1.0 M NaBHEt3 in _toluene was added to initiate the reaction. After the reaction was carried out at 100°C for 24 hours, the catalyst and salt were removed using a dry silica gel column. The resulting liquid product was quantified by GC. The results are shown in Table 3.

In an experiment using 30 mg of Si-Co(L1)(Br) ₂ /H ₂ O, the hydrosilylation reaction proceeded quantitatively even under the condition of adding a reducing agent (entry 3-1). As mentioned above, the reaction proceeded quantitatively in a 24-hour reaction using 50 mg of Si-Co(L1)(OAc) ₂ /H ₂ O or Si-Co(L1)(Br) ₂ /H ₂ O (entries 2-3, 1-3, Table 2). These reactions may have been completed with a smaller amount of catalyst and in a shorter reaction time, so they are not suitable for calculating the reaction turnover number per hour (TOF: catalyst turnover frequency). Therefore, an experiment was performed using 20 mg of Si-Co(L1)(OAc) ₂ /H ₂ O, whose catalyst loading is known, and the reaction time was limited to 2 hours. From elemental analysis and X-ray fluorescence analysis, the amount of Co supported was estimated to be 0.9 wt%, and the TOF per hour of Si-Co(L1)(OAc) ₂ /H ₂ O was calculated to be 584 (entry 3- 2 ). On the other hand, the reaction hardly proceeded with unimmobilized [Co(tpy)Br ₂ ] in the absence of a reducing agent, but it showed catalytic activity when 2.0 mol% of NaBHEt ₃ was added to reduce the catalyst (entries 3-3 and 3-4). Even when [Co(tpy) ₂ ](PF ₆ ) ₂ , in which all the coordination sites are occupied by tpy, was used as a catalyst, it was found to show the same catalytic activity and TOF as [Co(tpy)Br ₂ ] in the presence of a reducing agent. It was revealed that the TOF of Si-Co(L1)(OAc) ₂ /H ₂ O immobilized on the silica gel surface was nearly 30 times larger than that of the unimmobilized catalyst.

Repeated durability test (silica gel immobilized metal complex catalyst)
The durability of the silica gel immobilized catalyst to repeated use was examined by the reaction shown in formula 1. After the reaction, the silica gel immobilized catalyst was recovered, and the same reaction was repeated.

Specifically, the hydrosilylation activity of each catalyst was examined in the same manner as above, and after the reaction was completed, the liquid product was separated by centrifugation to recover the silica gel-immobilized catalyst. The recovered catalyst was washed with 5 mL of hexane and ether, dried, and then used again in a catalytic reaction. The results of the repeated catalytic reactions are shown in Table 4.

As a result, it was found that the hydrosilylation product could be obtained in good yield even if the catalyst was reused. In addition, the activity of Si-Co(L1)(OAc) ₂ /THF gradually decreased with repeated reactions, but this is thought to be due to the loss associated with the recovery of the powdered catalyst.

Repeated durability test (metal complex catalyst immobilized in glass container)
In order to solve the problem of loss caused by recovery of silica gel immobilized catalyst, we developed a container-immobilized catalyst in which the catalyst is immobilized inside a glass container.

To clean the Schlenk flask, the inside of the flask was treated with pyranor (concentrated sulfuric acid: hydrogen peroxide solution = 8:2, 20 mL) for 2 hours. After thorough washing with pure water, it was thoroughly dried in a dryer at 120 °C. 10 mL of a 1.0% (v/v) toluene solution of compound (Si-C3- _N3 ) was added to the dried Schlenk flask and stirred (using a mechanical stirrer) at 110 °C for 3 hours to modify the inside surface of the Schlenk flask with azide. After the reaction, the reaction solution was discarded and thoroughly washed with toluene and ether. Then, a solution was prepared by mixing 4.0 mL of water in which 13 mg of _CuSO4 was dissolved and 12 mL of DMSO solution in which 4.1 mg of compound L1 was dissolved, and added to the azide-modified Schlenk flask. 0.19 g of sodium ascorbate was added to start the reaction, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, the reaction solution was removed, and the inside of the vessel was thoroughly washed with water, methanol, acetone, and ether. An aqueous solution of 0.1 M sodium EDTA was added to the Schlenk flask and stirred overnight at room temperature (using a mechanical stirrer). The inside of the Schlenk flask was then thoroughly washed with pure water and dried. 44.3 mg of Co(OAc) ₂ was added to the Schlenk flask, and 10 mL of water was added and stirred for 24 hours. After the reaction, the Schlenk flask was washed with water, methanol, and ether, and used as a vessel catalyst after drying (Figure 2A). Si-Co(L1)(OAc) ₂ / _H2O was immobilized on the inner surface of the Schlenk flask.

After adding 1.0 mL of diphenylsilane (5.4 mmol) and 0.85 mL of 1-octene (5.4 mmol) to the Schlenk flask, _N2 was bubbled for about 1 minute to create a nitrogen atmosphere. After heating and stirring at 100°C for 24 hours using a mechanical stirrer, the colorless, transparent solution of the product was taken out. The inside of the vessel catalyst was thoroughly washed with hexane and ether and used again in a catalytic reaction. The product was quantified by GC. The results of repeated reactions are shown in Figure 2B.

Because the surface area on which the catalyst was immobilized was small, the overall amount of product was small (Figure 2B), but it was clear that the hydrosilylation reaction was progressing. From the first 10 reactions, the hydrosilylation product was confirmed to be about 15% by GC, demonstrating that this catalyst can withstand repeated use.

Examination of hydrosilylation catalytic activity (silica gel-immobilized metal complex catalyst using compound L1)
A reaction similar to that shown in formula (1) was carried out using a different substrate (olefin) (the following formula (4): R represents a phenyl group or a cyclohexane group).

Specifically, the procedure was as follows. 20 mg of Si-Co(L1)(OAc) ₂ /H ₂ O was placed in a normal Schlenk tube and vacuum dried for 1 hour. Then, 1.0 mL of diphenylsilane (5.4 mmol) and olefin (5.4 mmol) were added, and N ₂ was bubbled for about 1 minute to create a nitrogen atmosphere. After heating and stirring at 100°C for 24 hours, Si-Co(L1)(OAc) ₂ /H ₂ O was removed by centrifugation to obtain a colorless, transparent liquid. The product was quantified by GC analysis. The results are shown in Chemical formula 29.

Si-Co(L1)(OAc) ₂ /H ₂ O was found to efficiently catalyze the hydrosilylation of olefins such as styrene and vinylcyclohexane.

In addition, a reaction was carried out using Si-Co(L1)(OAc) ₂ /THF complexed in THF as a catalyst and styrene as an olefin substrate (see the following scheme).

As a result, it was confirmed that all the raw materials had been consumed, and it was found that 50% of the hydrosilylation product had been produced. The yield of the hydrosilylation product in this reaction was slightly low, but this is thought to be due to competition with the production of polystyrene and polysiloxane.

Examination of hydrosilylation catalytic activity (silica gel-immobilized metal complex catalyst using compound L2)
As described above, Si-Co(L1)(OAc) ₂ /H ₂ O and Si-Co(L1)(OAc) ₂ /THF showed relatively high activity in hydrosilylation reactions and also showed good resistance to repeated use. However, 4'-bromo-2,2':6'2"-terpyridine, the starting material for the synthesis of L1, is very expensive. Therefore, we prepared and examined an immobilized catalyst (Si-Co(L2)(OAc) ₂ /H ₂ O, M = Co, X = OAc) using compound L2, which can be synthesized more cheaply than compound L1. Complexation was performed in water using Co(OAc) ₂ .

Using the obtained silica gel-immobilized metal complex catalyst, the hydrosilylation activity of the reaction shown in the following formula was examined.

These results show that the hydrosilylation product can be obtained in good yields even when using a silica gel-immobilized metal complex catalyst with compound L2.

Furthermore, the reaction was carried out using Si-Co(L2)(OAc) ₂ /THF complexed in THF as a catalyst and styrene as an olefin substrate (see the following scheme).

As a result, it was found that 71% of the hydrosilylated product was produced.

Examination of hydrosilylation catalytic activity (silica gel-immobilized metal complex catalyst using compound L3)
The immobilized catalyst using compound L3 is expected to be prepared more inexpensively because amino-functionalized silica gel (e.g., 3-aminopropyl-functionalized silica) is commercially available. Therefore, we prepared an immobilized catalyst Si-Co(L3)(OAc) ₂ /THF by coordinating Co(OAc) ₂ to silica gel modified with compound L3 in THF, and investigated the hydrosilylation activity of the reaction shown in the following formula.

As a result, it was found that the hydrosilylation product could be obtained in very high yield (Table 5, entry 5-1). As a control experiment, the hydrosilylation reaction of the above formula was attempted using amino silica gel (commercially available amino silica gel (3-aminopropyl-functionalized silica) itself) that was not modified with compound L3 and reacted with Co(OAc) ₂ in THF as the catalyst (Co(OAc) ₂ /amino silica/THF). As a result, the product was obtained in 23% yield. This result shows that the immobilized compound L3 exerts extremely high hydrosilylation activity when complexed with Co.

Examination of the effect of adding carboxylate to a catalytic reaction systemWe examined whether it is possible to make the complex catalytically active by adding an external carboxylate to an immobilized catalytic reaction system.The immobilized complex used in the study was Si-Co(L1)(Br) ₂ /H ₂ O, which does not have a carboxylate ion.

As shown in the above formula, Si-Co(L1)(Br) ₂ /H ₂ O did not show any catalytic activity in the hydrosilylation reaction using triethoxysilane (HSi(OEt) ₃ ) and styrene as substrates. However, when a similar reaction was carried out by adding 2.5 mol% potassium pivalate (KOPv) to hydrosilane, Si-Co(L1)(Br) ₂ /H ₂ O showed catalytic activity and the reaction proceeded almost quantitatively (see formula below).

Furthermore, when a similar study was conducted using Si-Co(L2)(Br) ₂ /H ₂ O, it was found that Si-Co(L2)(Br) ₂ /H ₂ O showed some catalytic activity even without the addition of KOPv, but the catalytic activity was dramatically improved by adding a catalytic amount of KOPv (see the formula below).

Examination of the effect of adding an alkoxide salt to the catalytic reaction system As mentioned above, it was found that the activity of the immobilized catalyst in the hydrosilylation catalytic reaction using triethoxysilane (HSi(OEt) ₃ ) as a substrate was dramatically improved by adding KOPv (preferably adding a catalytic amount of KOPv). In a previous study, a first transition metal complex catalyst was activated with sodium t-butoxide (NaO ^t Bu) and a hydrosilylation reaction was performed (Non-Patent Document 11). Therefore, one possibility was that potassium pivalate (KOPv) in the above-mentioned reaction system acted as an effective base to induce the dibromocobalt complex to become a catalytically active species. Therefore, the hydrosilylation reaction of styrene with triethoxysilane (see the following formula) was examined by adding another carboxylate salt (potassium acetate (KOAc)) or an alkoxide salt (potassium t-butoxide (KO ^t Bu)). The results are shown in Table 6.

From the above, it was found that the activity of the immobilized catalyst can be significantly improved by adding not only KOPv but also other carboxylates or alkoxide salts.

Study of application to flow synthesis The immobilized complex catalyst (Si-Co(L1)(Br) ₂ /H ₂ O) was applied to flow synthesis, which can significantly improve the efficiency of post-treatment of the reaction.

The following conditions:
Column: φ5.0 mm × 100 mm
Flow rate: 0.05ml/min
Temperature: 100°C
Packing material: Si-Co(L1) _Br2 / _H2O + KOPv (5:1.9), 500 mg
Substrate: 1-octene + diphenylsilane (1:1)
Then, the hydrosilylation reaction of 1-octene with diphenylsilane (Ph ₂ SiH ₂ ) (see the following scheme) was carried out.

As a result, it was found that linear hydrosilylated product (1) and a very small amount of branched hydrosilylated product (2) were obtained. After 50 hours of flow reaction, 49 g of reaction product was obtained, with the contents of hydrosilylated products being 1: 81% and 2: 6%. Figure 4 shows the time course of the content of hydrosilylated products. The content of hydrosilylated products was low for 1 hour after the start of the reaction, but then increased, and the content of 1 became constant at about 80%, with no decrease in the content at all even after 50 hours of reaction. These results confirmed that the immobilized complex catalyst (Si-Co(L1)(Br) ₂ /H ₂ O) can be applied to flow synthesis, and suggested the possibility of it being able to withstand large-scale synthesis.

Claims (7)

Formula (A):
[Tridentate metal complex compound]-[Linker part]-[Substrate] (A)
A complex-immobilized catalyst in which a tridentate ligand metal complex compound represented by the formula :
The tridentate metal complex compound has the formula:

(wherein M represents Fe, Co, Ni, Mn, or Cu; X may be the same or different and represents Cl, Br, _-OCH3 , -OC(O) ^Rx , or -OH; when there are two ^Rx'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:

(wherein Z is a bond or

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 each represents 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 of another linker part.

(wherein Z, n, *, R ⁱ and R ⁱⁱ are the same as defined 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 portion) ,
The substrate is a silica compound substrate or a metal substrate having an oxide film on its surface, and
Used for hydrosilylation reactions,
catalyst. 2. The catalyst of claim 1 , wherein the tridentate metal complex compound is a tridentate cobalt complex compound. In formula (A), X may be the same or different and is Cl, Br, -OCH ₃ , -OC(O)R ^X or —OH, R ^X The catalyst according to claim 1 or 2, wherein, when there are two, they may be the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms. The catalyst according to any one of claims 1 to 3, wherein in formula (A), n represents 2, 3, or 4. In formula (A), R ⁱ and R ⁱⁱ are the same or different and represent an alkyl group having 1, 2, or 3 carbon atoms, or -O-* (wherein at least one * is bonded to the substrate, and the other * may be bonded to a Si atom of another linker portion), the catalyst according to any one of claims 1 to 4. A method for producing a hydrosilylated compound, comprising carrying out a hydrosilylation reaction in the presence of the catalyst according to any one of claims 1 to 5 . A method for producing a hydrosilylated compound, comprising carrying out a hydrosilylation reaction in the presence of the catalyst according to any one of claims 1 to 5 and an alkoxide salt and/or a carboxylate salt.

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