US20200001285A1 - Catalyst for hydrosilylation reaction, hydrogenation reaction, and hydrosilane reduction reaction - Google Patents

Catalyst for hydrosilylation reaction, hydrogenation reaction, and hydrosilane reduction reaction Download PDF

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US20200001285A1
US20200001285A1 US16/489,254 US201816489254A US2020001285A1 US 20200001285 A1 US20200001285 A1 US 20200001285A1 US 201816489254 A US201816489254 A US 201816489254A US 2020001285 A1 US2020001285 A1 US 2020001285A1
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reaction
catalyst
group
mmol
compound
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Hideo Nagashima
Atsushi SANAGAWA
Shoma KAWABATA
Daisuke Noda
Koji Sakuta
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Shin Etsu Chemical Co Ltd
Kyushu University NUC
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Shin Etsu Chemical Co Ltd
Kyushu University NUC
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    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
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    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
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    • C08G77/06—Preparatory processes
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    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
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    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
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    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0222—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
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    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
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    • B01J2531/845—Cobalt
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Definitions

  • the present invention relates to a catalyst made of a prescribed metal-isocyanide complex, and relates more specifically to a catalyst having activity in at least one reaction selected from hydrosilylation reaction or hydrogenation reaction on an aliphatic unsaturated bond and hydrosilane reduction reaction on a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond.
  • Hydrosilylation reaction which is addition of a Si—H functional compound to a compound having a carbon-carbon double bond or triple bond is a useful method for the synthesis of organosilicon compounds and an industrially important synthesis reaction.
  • Pt, Pd and Rh compounds are known.
  • Pt compounds as typified by Speier's catalyst and Karstedt's catalyst are most commonly used.
  • Another problem is that the selectivity of ⁇ - and ⁇ -adducts is low depending on the type of olefin.
  • Non-Patent Document 1 reaction in the presence of iron-carbonyl complexes (Fe(CO) 5 , Fe 3 (CO) 12 ) is known from Non-Patent Document 1, although this reaction requires reaction conditions including as high a temperature as 160° C. or photo-irradiation (Non-Patent Document 2).
  • Non-Patent Document 4 and Patent Document 2 report a reaction of methylvinyldisiloxane and methylhydrogendisiloxane in the presence of an iron-carbonyl complex coordinated with a cyclopentadienyl group. Since dehydrogenative silylation reaction takes place along with the relevant reaction, the selectivity of addition reaction is low.
  • Non-Patent Document 5 refers to reaction in the presence of an iron catalyst having a terpyridine ligand. Although PhSiH 3 and Ph 2 SiH 2 add to olefins, more useful trialkylsilanes, alkoxysilanes and siloxanes have poor addition reactivity to olefins.
  • Non-Patent Document 6 reports that from reaction in the presence of an iron catalyst having a terpyridine ligand and a bistrimethylsilylmethyl group, an addition reaction product is obtained in high yields.
  • This method needs a catalyst synthesis, including first synthesizing a terpyridine-iron complex as a catalyst precursor and introducing a bistrimethylsilylmethyl group therein at a low temperature, which is not easy.
  • Non-Patent Documents 7 and 8 report iron complexes having a bisiminopyridine ligand. It is disclosed that they exhibit high reactivity to alkoxysilanes and siloxanes under mild conditions.
  • Non-Patent Document 9 shows an iron complex having a chiral iminopyridine oxazoline ligand.
  • a reducing agent NaBHEt 3
  • dihydrodiphenylsilane is not a reaction substrate having high industrial value.
  • Non-Patent Documents 10 to 15 Also an example of reaction by a cobalt-carbonyl complex (Co 2 (CO) 8 or the like) is reported (Non-Patent Documents 10 to 15); however, this is not satisfactory in terms of reaction yield or reaction molar ratio, and the complex has highly toxic carbon monoxide and the handling and storage of the complex require the conditions of being in an inert gas atmosphere and at low temperature.
  • Non-Patent Document 16 Also an example of reaction of olefin with trialkylsilane in the presence of a cobalt-carbonyl complex having a trialkylsilyl group is reported in Non-Patent Document 16, but the yield is low and the selectivity is low.
  • Non-Patent Document 17 reports reaction of olefin with trialkylsilane in the presence of a cobalt-phosphite complex coordinated with a cyclopentadienyl group
  • Non-Patent Document 18 reports reaction of olefin with trihydrophenylsilane in the presence of a cobalt complex coordinated with N-heterocyclic carbene. Because of low stability, these complex compounds require an inert gas atmosphere and a low temperature for handling and storage.
  • Non-Patent Document 19 Also an example of reaction by a cobalt catalyst having a ⁇ -diketiminate group as a ligand is reported (Non-Patent Document 19); however, when the reaction substrate is trihydrophenylsilane, the industrial utility value is low. Although also an example of reaction between 1-hexene and triethoxysilane is shown, the amount of the catalyst needs to be 2 mol %, and the catalytic activity is not high.
  • Non-Patent Document 20 Also an example of reaction by a cobalt catalyst having a pyridinediimine ligand, the precursor of which catalyst is easy to handle, is reported, and the catalyst has high catalytic activity (Non-Patent Document 20); however, in this reaction, also dehydrogenative silylation reaction progresses, and therefore minute amounts of dehydrogenative silylated compounds always coexist; consequently, the selectivity of the addition product is low.
  • Non-Patent Document 21 a hydrosilylation reaction catalyst using bis(cyclooctatetraenyl)iron and an isocyanide compound as ligands
  • Non-Patent Document 22 a hydrosilylation reaction catalyst using iron pivalate or cobalt pivalate and an isocyanide compound as ligands
  • Non-Patent Documents 23 and 24 the sulfur element acts as a catalytic poison; hence, an example using a Pt catalyst and an example using a Rh catalyst, which are only among few examples of reports, are reported (Non-Patent Documents 23 and 24).
  • the catalytic activity is lower than in other substrates, and the selectivity of the addition reaction product is low.
  • Rh catalyst reports that an addition product in which Si is bonded to carbon adjacent to the sulfur element is obtained selectively (Non-Patent Document 25); however, the catalytic activity is low, and the selectivity of the adduct is low.
  • Non-Patent Document 26 a catalyst having a phosphine ligand (Non-Patent Document 26) lacks in selectivity and requires careful handling and storage.
  • Non-Patent Document 27 With a vinylsiloxane-coordinated catalyst (Non-Patent Document 27), a product due to the dehydrogenative becomes predominant, indicating low selectivity of addition reaction.
  • Non-Patent Document 28 With an allylphosphine-coordinated catalyst (Non-Patent Document 28), the yield is low, and trihydrophenylsilane is not a reaction substrate of industrial worth.
  • Non-Patent Document 29 A metal bisamide catalyst (Non-Patent Document 29) needs careful handling and storage, and dihydrodiphenylsilane is not a reaction substrate of industrial worth.
  • Non-Patent Document 30 A catalyst having N-heterocyclocarbene ligand (Non-Patent Document 30) has low selectivity of reaction, and trihydrophenylsilane is not of industrial worth.
  • Patent Documents 3 to 6 report iron, cobalt and nickel catalysts having terpyridine, bisiminopyridine and bisiminoquinoline ligands. Like the above-cited Non-Patent Documents 6 to 8, there is an industrial difficulty of synthesis of a catalyst precursor or synthesis of the complex catalyst from the precursor.
  • Patent Document 7 discloses a method of conducting reaction in the presence of a complex catalyst having a bisiminoquinoline ligand, using Mg(butadiene).2THF or NaEt 3 BH as the catalyst activator. Likewise, the yield of the desired product is less than satisfactory.
  • the catalysts with their application to organopolysiloxanes being borne in mind include a catalyst having a phosphine ligand (Patent Document 8), a catalyst having an aryl-alkyl-triazenide group (Patent Document 9), a colloidal catalyst (Patent Document 10), a catalyst coordinated with a sulfide group (Patent Document 11), and a catalyst coordinated with an amino, phosphino or sulfide group and an organosiloxane group (Patent Document 12).
  • Patent Documents 13 and 14 only well-known platinum catalysts are demonstrated to exert a catalytic effect while the structure which is combined with another metal to exert catalytic activity is indicated nowhere.
  • Patent Documents 15 to 17 disclose catalysts coordinated with carbene. Patent Document 15 does not discuss whether or not the catalyst is effective to hydrosilylation reaction.
  • Patent Documents 16 and 17 disclose catalysts coordinated with carbene and vinylsiloxane, but describe only platinum catalysts in Examples.
  • the metal catalysts coordinated with carbene require careful handling because the complex compounds have low storage stability.
  • Patent Documents 18 to 24 disclose a method of mixing a metal salt with a compound which coordinates to the metal and using the product as a catalyst rather than the use of metal complexes as the catalyst. Although these Patent Documents describe the progress of hydrosilylation with several exemplary combinations, the yield and other data are described nowhere, and the extent to which the reaction takes place is not evident. In addition, ionic salts or hydride reducing agents are used as the activator in all examples. Nevertheless, almost all examples exhibit no catalytic activity.
  • Non-Patent Document 31 hydrogenation by thermal reaction using Fe(CO) 5 as a catalyst
  • Non-Patent Document 32 hydrogenation by photoreaction
  • thermal reaction requires conditions of high temperature and high pressure (180° C., 28 atmospheres); in contrast, photoreaction progresses at room temperature; but both have low turnover numbers (TON), which number indicates the number of revolutions of the catalyst, and cannot be said to have sufficient activity.
  • TON turnover numbers
  • Non-Patent Document 36 an iron catalyst having a phosphorus-based compound as a ligand is reported (Non-Patent Document 36); in this system, although reaction is made under conditions of room temperature and relatively low pressure (4 atmospheres), the turnover number cannot be said to be sufficient.
  • Non-Patent Document 37 Also an example of an iron catalyst having a 1,2-bis(dimethylsilyl)benzene ligand is reported (Non-Patent Document 37); in this example, although reaction progresses at room temperature under normal pressure, the synthesis of the catalyst is not easy.
  • Non-Patent Document 7 Also an example of an iron catalyst having a bis(imino)pyridine ligand is reported (Non-Patent Document 7), and this example has good reactivity, i.e., a TON of 1,814, under conditions of room temperature and relatively low pressure (4 atmospheres).
  • Non-Patent Document 38 an iron catalyst having a 2,6-bis(arylimidazol-2-ylidene)pyridine ligand is reported (Non-Patent Document 38); however, both have points at issue such as safety at the time of synthesis and the stability of the compound, similarly to the Fe complex having a bis(imino)pyridine ligand mentioned above.
  • Non-Patent Document 39 a cobalt catalyst having a phosphorus-based compound as a ligand is reported (Non-Patent Document 39); in this system, although reaction progresses at room temperature under normal pressure, the synthesis of the catalyst is not easy.
  • Non-Patent Document 40 A cobalt catalyst having a bis(mesitylbenzimidazol-2-ylidene)phenyl ligand is reported (Non-Patent Document 40); however, this has points at issue such as safety at the time of synthesis and the stability of the compound, similarly to the Fe complex having a 2,6-bis(arylimidazol-2-ylidene)pyridine ligand mentioned above, and furthermore the catalytic activity cannot be said to be sufficient, in view of the TON being 50.
  • Non-Patent Document 41 Non-Patent Document 41
  • these reducing agents are ignitable, water-sensitive substances, and are therefore less easy to handle. Further, care is required in handling also when removing aluminum or a boron compound after reaction from the desired product.
  • Non-Patent Documents 50 to 62 an iron-, cobalt-, or nickel-isocyanide complex is known in Non-Patent Documents 50 to 62; however, these literatures are mainly for the synthesis, structure analysis, and reaction of the complex, and have no example in which the complex is used as a catalyst for hydrosilylation reaction or hydrogenation reaction on an aliphatic unsaturated bond or hydrosilane reduction reaction on a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a catalyst that can exhibit excellent catalytic activity in hydrosilylation reaction or hydrogenation reaction on an aliphatic unsaturated bond or hydrosilane reduction reaction on a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond, and a method for producing various compounds using the catalyst.
  • the present inventors conducted extensive studies in order to achieve the object mentioned above, and have found out that a prescribed iron-, cobalt-, or nickel-isocyanide complex can exhibit excellent catalytic activity in hydrosilylation reaction or hydrogenation reaction on an aliphatic unsaturated bond or hydrosilane reduction reaction on a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond, and allows each of the reactions mentioned above to progress under mild conditions; thus, have completed the present invention.
  • the invention provides a catalyst and a method defined below.
  • a catalyst including a compound represented by formula (1) below, and having activity in at least one reaction selected from hydrosilylation reaction or hydrogenation reaction on an aliphatic unsaturated bond and hydrosilane reduction reaction on a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond,
  • L represents an isocyanide ligand represented by formula (2) below, n represents an integer of 1 to 8, and m represents an integer of 2 to 12,
  • R 1 represents a monovalent to trivalent organic group that has 1 to 30 carbon atoms and is optionally substituted with a halogen atom and in which one or more atoms selected from oxygen, nitrogen, sulfur, and silicon are optionally interposed, and x represents an integer of 1 to 3.
  • x represents an integer of 1 to 3.
  • R 1 in the formula (2) is a monovalent hydrocarbon group having 1 to 30 carbon atoms. 7.
  • a method for producing a product of reduction reaction by a Si—H bond-containing compound of a compound having a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond wherein the method uses the catalyst according to any one of 1 to 8. 13.
  • the method for producing a product of reduction reaction according to 12, wherein the compound having a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond is an aldehyde compound, a ketone compound, an amide compound, or a nitrile compound.
  • a catalyst for reaction made of an iron-, cobalt-, or nickel-isocyanide complex (hereinafter, simply abbreviated as an isocyanide complex) of the present invention does not have a carbonyl ligand highly toxic to human bodies, and has high thermal stability and high stability in air of the complex.
  • addition reaction can be made under conditions of room temperature to less than or equal to 100° C.
  • addition reaction with an industrially useful (poly)siloxane, a trialkoxysilane, or a dialkoxysilane progresses well.
  • the catalyst of the present invention has high catalytic activity on hydrogenation reaction of an aliphatic unsaturated bond-containing compound, and the reaction progresses under mild conditions.
  • a carbonyl compound such as an amide compound, a ketone compound, or an amide compound, or a nitrile compound, and an easy-to-handle silane or (poly)siloxane having a Si—H group are reacted together, and the desired compound can be obtained with a high yield.
  • the invention provides a catalyst including a compound represented by formula (1) below, and having activity in at least one reaction selected from hydrosilylation reaction or hydrogenation reaction on an aliphatic unsaturated bond and hydrosilane reduction reaction on a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond.
  • M represents Fe, Co, or Ni with an oxidation number of 0
  • L represents an isocyanide ligand represented by formula (2) below
  • n represents an integer of 1 to 8
  • m represents an integer of 2 to 12.
  • R 1 represents a monovalent to trivalent organic group that has 1 to 30 carbon atoms and is optionally substituted with a halogen atom and in which one or more atoms selected from oxygen, nitrogen, sulfur, and silicon are optionally interposed, and x represents an integer of 1 to 3.
  • halogen atom examples include fluorine, chlorine, bromine, and iodine.
  • the monovalent to trivalent organic group having 1 to 30 carbon atoms is not particularly limited, but is preferably a monovalent to trivalent hydrocarbon group having 1 to 30 carbon atoms.
  • the alkyl groups may be straight, branched or cyclic, is preferably 1 to 20, more preferably 1 to 10 alkyl group.
  • Examples include straight or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n
  • the alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, and examples include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, and n-1-eicosenyl.
  • the alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms, and examples include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecynyl, and n-1-eicosynyl.
  • the aryl or alkylaryl group is preferably an aryl group having 6 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms, and specific examples include phenyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, o-biphenylyl, m-biphenylyl, p-biphenylyl, tolyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, a mesityl group, and the like.
  • the aralkyl group is an arylalkyl group preferably having 7 to 30 carbon atoms and more preferably having 7 to 20 carbon atoms, and specific examples include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, a naphthylpropyl group, and the like.
  • Suitable divalent hydrocarbon groups include alkylene, arylene and aralkylene groups.
  • the alkylene groups may be straight, branched or cyclic ones, preferably alkylene groups having 1 to 20 carbon atoms.
  • Examples include straight or branched alkylene groups such as methylene, ethylene, propylene, trimethylene, n-butylene, isobutylene, s-butylene, n-octylene, 2-ethylhexylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene, n-octadecylene, n-nonadecylene, and n-eicosanylene; and cycloalkylene groups such as 1,4-cyclohexylene.
  • arylene group examples include o-phenylene, m-phenylene, p-phenylene, 1,2-naphthylene, 1,8-naphthylene, 2,3-naphthylene, and 4,4′-biphenylene.
  • Examples of the aralkylene group include —(CH 2 ) y —Ar— wherein Ar is an arylene group having 6 to 20 carbon atom and y is an integer of 1 to 10, —Ar—(CH 2 ) y — wherein Ar and y are as defined above, and —(CH 2 ) y —Ar—(CH 2 ) y — wherein Ar is as defined above and y is each independently as defined above.
  • trivalent hydrocarbon group examples include those represented by the following formulae, but are not limited to these.
  • organic groups in R 1 above include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group; aryloxy groups such as a phenoxy group; alkyl halide groups such as a trifluoromethyl group; alkylamino groups such as a dimethylamino group; ester groups such as a methyl ester and an ethyl ester; a nitro group; a nitrile group; alkyl- or arylsilyl groups such as a trimethylsilyl group and a phenyldimethylsilyl group; alkoxysilyl groups such as a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group; nitrogen-containing heterocycle-containing groups such as a pyridyl group; sulfur-containing heterocycle-containing groups such as a thiol group
  • R 1 is preferably at least one hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an alkylaryl group having 7 to 30 carbon atoms, and is more preferably a t-butyl group, a 1-adamantyl group, a mesityl group, a phenyl group, a 2,6-dimethylphenyl group, and a 2,6-diisopropylphenyl group.
  • One or more atoms selected from oxygen, nitrogen, silicon, sulfur, and phosphorus may be interposed in each of the organic groups described above, and each of the organic groups described above may be substituted with a halogen atom.
  • x in formula (2) above represents an integer of 1 to 3, and is preferably 1 or 2 and more preferably 1.
  • the isocyanide compound represented by formula (2) above may be obtained as a commercially available product, or may be synthesized by a known method. For example, it may be obtained by a method in which a formylated product is obtained from an amine compound and formic acid, and subsequently the formylated product is reacted with phosphoryl chloride in the presence of an organic amine to be turned into an isocyanide (Synthesis Method 1; see Organometallics, 2004, 23, 3976-3981); as a method for obtaining a formylated product under mild conditions, a formylated product can be obtained by forming acetic formic anhydride from acetic anhydride and formic acid, and reacting the acetic formic anhydride with an amine compound (Synthesis Method 2; see Org. Synth., 2013, 90, 358-366). The obtained formylated product can be turned into an isocyanide by the method described in Synthesis Method 1, which is the same as above.
  • the synthesis can be made also by a method in which an amine compound and dichlorocarbene are reacted together to produce an isocyanide, which is a method not involving formylation (Synthesis Method 3; see Tetrahedron Letters, 1972, 17, 1637-1640).
  • isocyanide compound examples include alkyl isocyanides such as methyl isocyanide, ethyl isocyanide, n-propyl isocyanide, cyclopropyl isocyanide, n-butyl isocyanide, isobutyl isocyanide, sec-butyl isocyanide, t-butyl isocyanide, n-pentyl isocyanide, isopentyl isocyanide, neopentyl isocyanide, n-hexyl isocyanide, cyclohexyl isocyanide, cycloheptyl isocyanide, 1,1-dimethylhexyl isocyanide, 1-adamantyl isocyanide, and 2-adamantyl isocyanide; aryl isocyanides such as phenyl isocyanide, 2-methylphenyl isocyanide, 4-methylphenyl isocyanide, 2,4-dimethylphenyl iso
  • diisocyanide compound examples include 1,2-diisocyanoethane, 1,3-diisocyanopropane, 1,4-diisocyanobutane, 1,5-diisocyanopentane, 1,6-diisocyanohexane, 1,8-diisocyanooctane, 1,12-diisocyanododecane, 1,2-diisocyanocyclohexane, 1,3-diisocyanocyclohexane, 1,4-diisocyanocyclohexane, 1,3-diisocyano-2,2-dimethylpropane, 2,5-diisocyano-2,5-dimethylhexane, 1,2-bis(diisocyanoethoxy)ethane, 1,2-diisocyanobenzene, 1,3-diisocyanobenzene, 1,4-diisocyanobenzene, 1,1′-methylenebis(
  • triisocyanide compound examples include 1,3-diisocyano-2-(isocyanomethyl)-2-methylpropane, 1,5-diisocyano-3-(2-isocyanoethyl)pentane, 1,7-diisocyano-4-(3-isocyanopropyl)heptane, and 3-isocyano-N,N′-bis(3-isocyanopropyl)propane-1-amine.
  • a catalyst made of an isocyanide complex represented by formula (1) above can be synthesized by a known method; for example, the synthesis can be made by a method in which an iron, cobalt, or nickel salt and a reducing agent are reacted together in an organic solvent in the presence of an isocyanide compound, or a method in which an iron-, cobalt-, or nickel-carbonyl complex and an isocyanide compound are reacted together in an organic solvent at high temperature under light irradiation or in the presence of a catalyst.
  • the synthesis can be made also by reacting together an iron, cobalt, or nickel complex having a substitutable ligand and an isocyanide compound in an organic solvent.
  • the synthesis can be made also by reacting together an ate-type iron-, cobalt-, or nickel-isocyanide complex and an oxidizing agent in an organic solvent.
  • the iron, cobalt, or nickel salt mentioned above is not particularly limited, but is preferably a halide of Cl, Br, I, or the like, or a carboxylate such as acetate, and is more preferably a halide of Cl, Br, I, or the like, in view of reactivity with a reducing agent.
  • iron salt examples include iron halides such as FeCl 2 , FeBr 2 , FeCl 3 , FeBr 3 , and FeI 3 ; iron carboxylates such as Fe(OAc) 2 , Fe(stearate) 2 , and Fe(stearate) 3 ; and the like.
  • cobalt salt examples include cobalt halides such as CoCl 2 , CoBr 2 , and CoI 2 ; cobalt carboxylates such as Co(OAc) 2 , Co(OBz) 2 , Co(2-ethylhexanoate) 2 , and Co(stearate) 2 ; and the like.
  • iron-, cobalt-, or nickel-carbonyl complex mentioned above include Fe(CO) 5 , Fe 3 (CO) 12 , Co 2 (CO) 8 , Ni(CO) 4 , and the like.
  • substitutable ligand olefin compounds such as 1,5-cyclooctadiene and butadienes; phosphorus ligands such as trimethylphosphine; and the like are given.
  • the reducing agent mentioned above is desirably a strong reducing agent that can reduce a metal in an iron, cobalt, or nickel salt up to zero-valence; for example, is preferably a reducing agent having an oxidation-reduction potential, with ferrocene as a standard, of less than or equal to ⁇ 2.0 V in Non-Patent Document, Chem. Rev. 1996, 96, 887-910, and is particularly preferably a reducing agent having an oxidation-reduction potential of less than or equal to ⁇ 2.3 V.
  • alkali metals such as sodium and potassium
  • alkali metal alloys such as sodium-potassium and sodium amalgam
  • alkali metal naphthalenide such as potassium naphthalenide
  • Each of these alkali metals and alkali metal alloys may be one supported by a solid substance; examples include sodium, potassium, sodium-potassium alloy, or the like supported by silica, alumina, graphite, titanium oxide, zeolite, zinc oxide, cerium oxide, or polystyrene; among these, potassium-carrying graphite (hereinafter, abbreviated as KC 8 ) is preferable from the viewpoint of reactivity, and sodium-carrying silica (Stage 1 or 2) is preferable in terms of low risk of ignitability etc. from the viewpoint of safety.
  • KC 8 potassium-carrying graphite
  • Stage 1 or 2 sodium-carrying silica
  • An alkali metal supported by any of these solid substances may be obtained as, for example, one synthesized by a conventionally known method such as a method described in JP 5048503B2, or may be obtained as a commercially available product, examples of which include KC 8 (manufactured by Strem Chemicals, Inc.), Na silica gel (manufactured by Aldrich Corporation, Stage I), Na silica gel (manufactured by Aldrich Corporation, Stage II), NaK 2 silica gel (manufactured by Aldrich Corporation, Stage I), and the like.
  • KC 8 manufactured by Strem Chemicals, Inc.
  • Na silica gel manufactured by Aldrich Corporation, Stage I
  • Na silica gel manufactured by Aldrich Corporation, Stage II
  • NaK 2 silica gel manufactured by Aldrich Corporation, Stage I
  • the ate-type iron-, cobalt-, or nickel-isocyanide complex mentioned above is generally known as an ionic complex in which an iron-, cobalt-, or nickel-isocyanide complex is further reduced, and Na[Co(2,6-dimesityl isocyanide) 4 ] described in Non-Patent Document 51 and the like are known.
  • Ferrocenium triflate or the like is given as an oxidizing agent in the case where the synthesis is made by using an ate-type iron-, cobalt-, or nickel-isocyanide complex.
  • the isocyanide complex represented by formula (1) of the present invention is not particularly limited, and examples include the following.
  • iron-isocyanide complexes include Fe(CNMe) 5 , Fe(CNEt) 5 , Fe(CN n Pr) 5 , Fe(CN i Pr) 5 , Fe(CN n Bu) 5 , Fe(CN t Bu) 5 , Fe(CNCy) 5 , Fe(CNAd) 5 , Fe(CNCF 3 ) 5 , Fe(CNPh) 5 , Fe(CNXylyl) 5 , Fe(CNMes) 5 , Fe(N 2 )[CN-(2,6-bismesitylphenyl)]4, Fe[CN-(2-methyl-6-chlorophenyl)] 5 , Fe[CN-(3,5-dimethoxyphenyl)] 5 , Fe 2 (CNEt) 9 , and the like.
  • cobalt-isocyanide complexes include Co 2 (CN t Bu) 8 , Co 2 (CNCy) 8 , Co 2 (CNAd) 8 , Co 2 (CNPh) 8 , Co 2 (CNXylyl) 8 , Co 2 (CNMes) 8 , Co 2 [CN-(2-methyl-6-chlorophenyl)] 8 , Co 2 [CN-(3,5-dimethoxyphenyl)] 8 , Co[CN-(2,6-bismesitylphenyl)] 4 , and the like.
  • nickel-isocyanide complexes include Ni(CNMe) 4 , Ni(CNEt) 4 , Ni(CN t Bu) 4 , Ni 2 (CN t Bu) 4 , Ni 3 (CN t Bu) 6 , Ni(CNCy) 4 , Ni(CNPh) 4 , Ni(CNMes) 4 , Ni(CNXylyl) 4 , Ni[CN-(4-MeOC 6 H 4 )] 4 , Ni[CN-(4-NO 2 C 6 H 4 )] 4 , Ni(CNC 6 F 5 ) 4 , Ni 4 (CN t Bu) 6 , Ni 4 (CN t Bu) 7 , Ni 4 (CNMe)(CN t Bu) 6 , Ni 4 (CNCy) 7 , Ni 8 (CN i Pr) 12 , and the like.
  • n Pr represents a n-propyl group
  • i Pr an isopropyl group
  • n Bu a n-butyl group t Bu a t-butyl group
  • Cy a cyclohexylyl group Ad an adamantyl group
  • Ph a phenyl group
  • Mes a mesityl group
  • Xylyl a 2,6-dimethylphenyl group.
  • the amount of the catalyst used is not particularly limited; however, in view of obtaining the desired product with good yield by progressing reaction under mild conditions of approximately 20 to 100° C., it is preferable that more than or equal to 0.001 mol % of the isocyanide complex be used relative to 1 mol of a compound that is a substrate, it is more preferable that more than or equal to 0.01 mol % be used, and it is even more preferable that more than or equal to 0.05 mol % be used.
  • the upper limit of the amount of the isocyanide complex used is not particularly set, but is approximately 10 mol % relative to 1 mol of the substrate and is preferably 5 mol %, from the economic point of view.
  • a known two-electron donating ligand may be used in combination to the extent that the activity etc. of the catalyst are not impaired.
  • the two-electron donating ligand is not particularly limited, but is preferably a ligand other than a carbonyl group, such as an ammonia molecule, an ether compound, an amine compound, a phosphine compound, a phosphite compound, or a sulfide compound.
  • the isocyanide compound may be further added to the extent that the activity etc. thereof are not impaired, and the addition amount in this case is preferably approximately 0.1 to 5 molar equivalents relative to the catalyst of the present invention.
  • the conditions of reaction using the catalyst of the present invention are not particularly limited; usually, the reaction temperature is approximately 10 to 100° C., and preferably 20 to 80° C., and the period of reaction is approximately 1 to 48 hours.
  • the reaction may be performed without a solvent, or may use an organic solvent as necessary.
  • examples of the kind include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylenes, and mesitylene; and the like.
  • aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane
  • ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane
  • aromatic hydrocarbons such as benzene
  • the concentration of the catalyst is preferably 0.01 to 10 M and more preferably 0.1 to 5 M as molar concentration (M), in view of catalytic activity and economical efficiency.
  • the catalyst of the present invention may be used as a catalyst for hydrosilylation reaction or hydrogenation reaction on an aliphatic unsaturated bond or hydrosilane reduction reaction on a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond.
  • all the components may be collectively added, or components may be added in units of several components.
  • the molar ratio of aliphatic unsaturated bonds/Si—H bonds is 1/10 to 10/1, preferably 1/5 to 5/1, and more preferably 1/3 to 3/1.
  • aliphatic unsaturated bond-containing compound examples include the following.
  • Alkenes such as ethylene, propylene, butylene, isobutylene, hexenes, octenes, decenes, dodecenes, n-hexadecene, isohexadecene, n-octadecene, isooctadecene, norbornene, and trifluoropropene; alkynes such as ethyne, propyne, butynes, pentynes, hexynes, octynes, decynes, dodecynes, hexadecynes, and octadecynes; and aromatic group-containing alkenes such as styrene, 2-methylstyrene, 4-chlorostyrene, 4-methoxystyrene, ⁇ -methylstyrene, 4-methyl- ⁇ -methylstyrene, and allylbenzene.
  • alkynes such as
  • Trimethylvinylsilane triethylvinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, trimethoxyallylsilane, triethoxyallylsilane, triisopropoxyvinylsilane, phenyldimethoxyvinylsilane, phenyldiethoxyvinylsilane, diphenylmethoxyvinylsilane, diphenylethoxyvinylsilane, triphenylvinylsilane, triphenylvinylsilane, and the like.
  • an unsaturated bond may exist at a molecular end or may exist in the interior, or a plurality of unsaturated bonds may exist in the molecule like in hexadienes and octadienes.
  • alkene compound having a sulfide group like those shown below may be used as the aliphatic unsaturated bond-containing compound.
  • isomerization reaction of an alkene occurs, and a silicon compound in which silicon is bonded onto carbon adjacent to the sulfur element is obtained selectively.
  • Si—H bond-containing compound examples include the following silanes and siloxanes.
  • aliphatic unsaturated bond-containing compound examples include compounds similar to those given as examples in hydrosilylation reaction mentioned above.
  • introduction may be made while gas containing hydrogen molecules is caused to flow or bubble in a reactor, or reaction may be performed in a pressure resistant vessel in which gas containing hydrogen molecules is enclosed.
  • the pressure at this time is not particularly limited, but is preferably 0.1 to 3 MPa and more preferably 0.1 to 2 MPa from the viewpoint of safety.
  • the use ratio between the compound having a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond and the Si—H bond-containing compound is not particularly limited; however, as the molar ratio, (carbon-oxygen unsaturated bonds or carbon-nitrogen unsaturated bonds)/(Si—H bonds) is preferably 1/10 to 1/1, more preferably 1/5 to 1/1, and still more preferably 1/3 to 1/1.
  • Si—H bond-containing compound used in hydrosilane reduction reaction of a compound having a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond of the present invention compounds similar to those shown as examples in hydrosilylation reaction mentioned above are given; in view of reactivity and economical efficiency, among them, aryl group-containing silanes such as phenylsilane, diphenylsilane, and dimethylphenylsilane; a siloxane containing Si—H groups adjacent via an oxygen atom, such as 1,1,3,3-tetramethyldisiloxane, trimethylsiloxy group-end-capped methyl hydrogen polysiloxane, and dimethyl hydrogen siloxy group-end-capped methyl hydrogen polysiloxane, are preferable, and 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyldisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, trimethyls
  • the compound having a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond that can be used for hydrosilane reduction reaction a compound having an aldehyde, ketone, amide, or nitrile group, and the like are given; by reacting any of these compounds with a silane or a siloxane containing a Si—H group in the presence of the catalyst of the present invention and performing known post-treatment, the compound can be turned into a respective corresponding amine or alcohol compound.
  • Specific examples of the compound having a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond include acetophenone, N,N-dimethylbenzamide, acetonitrile, and the like.
  • the catalysts obtained were stored in a nitrogen gas atmosphere at 25° C. until they were used in reaction.
  • Hydrosilylation reaction and solvent purification were always carried out in an inert gas atmosphere.
  • the solvents and other ingredients were purified, dried and deoxygenated by well-known methods before they were used in various reactions.
  • the measurement of 1 H-NMR was performed using JNM-ECA600 and JNM-LA400 manufactured by JEOL Ltd, and IR measurement was performed using FT/IR-550 manufactured by JASCO Corporation.
  • Cobalt iodide (0.31 g, 1.0 mmol), tetrahydrofuran (hereinafter, abbreviated as THF) (15 mL), t-butyl isocyanide (0.33 g, 4.0 mmol), and KC 8 (manufactured by Strem Chemicals, Inc., 0.27 g, 2.0 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 40 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to ⁇ 35° C. to perform recrystallization; thus, Co 2 (CN t Bu) 8 was obtained (0.24 g, 61%).
  • THF tetrahydrofuran
  • KC 8 manufactured by Strem Chemicals
  • Cobalt iodide 13 mg, 0.10 mmol
  • mesityl isocyanide 58 mg, 0.40 mmol
  • THF 3 mL
  • KC 8 27 mg, 0.20 mmol
  • the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure.
  • the resulting dried substance was dissolved in toluene (approximately 3 mL), and the insoluble matter was removed by celite filtration.
  • Pentane (approximately 3 mL) was slowly added from above the filtrate to perform recrystallization; thus, a cobalt isocyanide complex of Co 2 (CNMes) 8 was obtained (42 mg, 66%).
  • Iron bromide 22 mg, 0.10 mmol
  • THF 3 mL
  • t-butyl isocyanide 42 mg, 0.50 mmol
  • KC 8 27 mg, 0.20 mmol
  • the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure.
  • the resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration.
  • the filtrate was cooled to ⁇ 35° C. to perform recrystallization; thus, Fe(CN t Bu) 5 was obtained (30 mg, 63%).
  • Iron bromide (216 mg, 1.0 mmol), THF (20 mL), adamantyl isocyanide (806 mg, 5.0 mmol), and KC 8 (manufactured by Strem Chemicals, Inc., 270 mg, 2.0 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in benzene (approximately 5 mL), and the insoluble matter was removed by celite filtration. Pentane was added to the filtrate, and then cooling was performed to ⁇ 35° C. to perform recrystallization; thus, Fe(CNAd) 5 was obtained (601 mg, yield: 70%).
  • Nickel bromide (a dimethoxyethane adduct) (31 mg, 0.1 mmol), THF (3 mL), t-butyl isocyanide (0.33 g, 0.4 mmol), and KC 8 (270 mg, 2.0 mmol) were added in this order to a reactor, and stirring was performed at room temperature for 30 minutes. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in benzene (approximately 5 mL), and the insoluble matter was removed by celite filtration. Ether was added to the filtrate, and then cooling was performed to ⁇ 35° C. to perform recrystallization; thus, Ni(CN t Bu) 4 was obtained (21 mg, yield: 54%).
  • Co 2 (CNAd) 8 obtained in Synthesis Example 2 (6.4 mg, 0.0005 mmol), ⁇ -methylstyrene (1.29 mL, 10 mmol), and 1,1,1,3,3-pentamethyldisiloxane (2.54 mL, 13 mmol) were added to a reactor, and stirring was performed at 80° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.94 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 2.
  • Fe(CN t Bu) 5 obtained in Synthesis Example 4 (4.7 mg, 0.01 mmol), styrene (114 ⁇ L, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 25° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.90 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 3.
  • Co 2 (CNMes) 8 obtained in Synthesis Example 3 (6.4 mg, 0.005 mmol), 1-octene (157 ⁇ L, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 25° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.50 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 3.
  • Co 2 (CNMes) 8 obtained in Synthesis Example 3 (6.4 mg, 0.005 mmol), styrene (114 ⁇ L, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 25° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.90 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 3.
  • Co 2 (CNAd) 8 obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol), allyl glycidyl ether (118 ⁇ L, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 25° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.51 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 3.
  • Co 2 (CNAd) 8 obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol), ⁇ -methylstyrene (129 ⁇ L, 1.0 mmol), and triethoxysilane (213 mg, 1.3 mmol) were added to a reactor, and stirring was performed at 80° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A sextet at 3.00 ppm, which is a signal of protons on carbon adjacent to a phenyl group in the desired product, was observed, and the yield was found. The results are shown in Table 4.
  • Co 2 (CNAd) 8 obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol), allyl glycidyl ether (154 ⁇ L, 1.3 mmol), and polydimethylsiloxane endblocked at both terminals by dimethylhydrogensiloxy groups (degree of polymerization 18) (0.74 g, 0.50 mmol) were added to a reactor, and stirring was performed at 50° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.54 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found (yield >99%).
  • Co 2 (CNAd) 8 obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol), N-allylaniline (133 mg, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 25° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.59 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 6.
  • Co 2 (CNAd) 8 obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol), N,N-diethylallylamine (113 mg, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 50° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.46 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 6.
  • Co 2 (CNMes) 8 obtained in Synthesis Example 3 (6.4 mg, 0.005 mmol), N-methyl pyrrolidone (100 ⁇ L) as a solvent, 9-vinylcarbazole (193 mg, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 25° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 1.16 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 6.
  • Co 2 (CNAd) 8 obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol), N-vinyl-2-pyrrolidone (111 mg, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 50° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.81 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 6.
  • Co 2 (CO) 8 (1.7 mg, 0.005 mmol), N-vinyl-2-pyrrolidone (111 mg, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 50° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.81 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 6.
  • Co 2 (CNAd) 8 obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol), ⁇ -methylstyrene (1.53 mg, 13 mmol), and polydimethylsiloxane endblocked at both terminals by dimethylhydrogensiloxy groups (degree of polymerization 18) (7.4 g, 5.0 mmol) were added to a reactor, and stirring was performed at 50° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.98 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found (yield >99%).
  • Fe(CNAd) 5 obtained in Synthesis Example 5 (8.6 mg, 0.01 mmol), styrene (114 ⁇ L, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 50° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.90 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 12.
  • Fe(CNAd) 5 obtained in Synthesis Example 5 (8.6 mg, 0.01 mmol), styrene (114 ⁇ L, 1.0 mmol), and diethoxy(methyl)silane (175 mg, 1.3 mmol) were added to a reactor, and stirring was performed at 50° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.90 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 12.
  • Fe(CNAd) 5 obtained in Synthesis Example 5 (8.6 mg, 0.01 mmol), styrene (154 ⁇ L, 1.3 mmol), and polydimethylsiloxane endblocked at both terminals by dimethylhydrogensiloxy groups (degree of polymerization 18) (0.74 g, 0.50 mmol) were added to a reactor, and stirring was performed at 50° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.90 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 13.
  • Ni(CN t Bu) 4 obtained in Synthesis Example 6 (3.9 mg, 0.01 mmol), styrene (114 ⁇ L, 0.01 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 80° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 2.65 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found (yield: 39%).
  • Co 2 (CN t Bu) 8 obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol), vinyltriethoxysilane (190 mg, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 ⁇ L, 1.3 mmol) were added to a reactor, and stirring was performed at 50° C. for 24 hours. After the reaction ended, 1 H-NMR spectrum was measured to determine the structure and the yield of the product. A multiplet at 0.50 ppm, which is a signal of protons on carbon adjacent to silicon in the desired product, was observed, and the yield was found. The results are shown in Table 14.

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