JP2014181212A - Method for manufacturing silicon compound and catalyst composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for obtaining, by using a transition metal complex, a silicon-silicon coupling compound based on a dehydrohalogenation reaction of a silane compound and a catalyst composition used for this method.SOLUTION: [1] In the provided method for manufacturing a silicon compound, a silicon-silicon coupling compound is obtained by reacting a hydrosilane compound (A) and a halosilane compound (B) or by reacting a hydrohalosilane compound (C) by using a transition metal complex expressed by the general formula (I) in the presence of a reductant; [2] a catalyst composition with which a transition metal complex expressed by the general formula (I) and a compound expressed by the general formula (II) are mixed is also provided.

Description

  The present invention relates to a method for producing a silicon compound and a catalyst composition to obtain a silicon-silicon coupling compound.

In order to obtain a silicon-silicon coupling compound by a conventional method, for example, a Wurtz coupling reaction in which a halosilane compound is homocoupled with metallic sodium can be mentioned. In addition, a method of dehydrocondensing a hydrosilane compound using a transition metal catalyst is known (Non-Patent Document 1).
Moreover, as a manufacturing method of the silicon-silicon coupling compound by cross coupling, the method of making a lithium silane compound react with a halosilane compound is mentioned (nonpatent literature 2).
According to these reactions, it has been necessary to use difficult-to-handle reagents such as metallic lithium or organic lithium compounds that react violently with water and oxygen. Since these reagents are dangerous and have high reactivity, there are limitations on the available organic chlorosilanes. In addition, undesired homo-coupling products are also produced as a by-product.

T.D.Tilley, Acc. Chem. Res. 26, 22, (1993). H. Gilman and G.D.Lichtenwalter, J. Am. Chem. Soc., 80, 608, (1958).

As a method using a transition metal catalyst, silicon-silicon bond formation by homo-coupling reaction between the same chlorosilane compound or hydrosilane compounds has been known, but silicon by coupling using a catalyst of a different hydrosilane compound and chlorosilane compound is known. -No silicon bond forming reaction has been reported so far.
Accordingly, an object of the present invention is to provide a method for obtaining a silicon-silicon coupling compound by a dehydrohalogenation reaction of a silane compound using a transition metal complex, and a catalyst composition.

As a result of intensive studies, the present inventor found that the coupling reaction between a hydrosilane compound and a halosilane compound proceeds by using a specific molybdenum complex in the presence of a reducing agent, and completed the present invention. It came.
That is, the present invention relates to [1] to [5].

〔一般式（Ｉ）中、Ｘは下記一般式（Ｉ−１）で表されるシリル基を示し、Ａ¹はリン、砒素、及び窒素から選ばれる少なくとも１種の原子を示し、Ｒ¹はそれぞれ同一であっても異なっていてもよい炭素数１〜９の炭化水素基を示し、Ｒ²は炭素数１〜９の炭化水素基又は炭素数１〜９の二価の炭化水素基を示し、Ｒ³は炭素数２〜４のアルカンジイル基を示し、ａは１〜３の整数である。ただしＲ²が二価の炭化水素基である場合には、Ｒ²はＸのシリル基のケイ素原子と結合を有する。〕
Ｒ⁴ _nＹ_pＨ_3-(n+p)Ｓｉ−＊ （Ｉ−１）
〔一般式（Ｉ−１）中、Ｒ⁴はそれぞれ同一であっても異なっていてもよく、１以上の水素が官能基又はハロゲン原子と置換していてもよい、炭素数１〜９の炭化水素基を示し、Ｙは、Ｒ²との結合部位を示し、＊はＭｏ原子との結合部位を示し、ｎは１〜３の整数であり、ｐは０又は１であり、ｎ＋ｐは３以下である。ただし、Ｒ²が二価の炭化水素基である場合、ｐは１であり、Ｒ²が二価の炭化水素基でない場合、ｐは０である。〕
［２］還元剤が、下記一般式（II）で表される化合物である、［１］に記載のケイ素化合物の製造方法。
Ａ²Ｈ_(v-m)Ｒ⁶ _mＭ_v-3 （II）
〔一般式（II）中、Ａ²はホウ素又はアルミニウム原子を示し、Ｒ⁶は炭素数１〜８の炭化水素基を示し、Ｍはリチウム又はナトリウム原子を示し、ｖは３又は４の整数であり、ｍは０〜３の整数であり、ｖ−ｍは１以上である。〕
［３］ヒドロシラン化合物（Ａ）が下記一般式（III）で表される化合物であり、ハロシラン化合物（Ｂ）が下記一般式（IV）で表される化合物である、［１］又は［２］に記載のケイ素化合物の製造方法。
Ｒ^a _4-eＳｉＨ_e （III）
〔一般式（III）中、Ｒ^aは、１以上の水素が官能基又はハロゲン原子と置換していてもよい、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、又は炭素数５〜２０のアリールオキシ基を示し、ｅは１〜３の整数である。〕
Ｒ^b _4-fＳｉＺ_f （IV）
〔一般式（IV）中、Ｒ^bは、１以上の水素が官能基又はハロゲン原子と置換していてもよい、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、又は炭素数５〜２０のアリールオキシ基を示し、Ｚは塩素、臭素及びヨウ素から選ばれる少なくとも１種の原子であり、ｆは１〜３の整数である。〕
［４］ヒドロハロシラン化合物（Ｃ）が、下記一般式（Ｖ）で表される化合物である、［１］〜［３］のいずれかに記載のケイ素化合物の製造方法。
Ｒ^c _4-g-hＳｉＨ_gＺ_h （Ｖ）
〔一般式（Ｖ）中、Ｒ^cは、１以上の水素が官能基又はハロゲン原子と置換していてもよい、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、又は炭素数５〜２０のアリールオキシ基を示し、Ｚは塩素、臭素及びヨウ素から選ばれる少なくとも１種の原子であり、ｇは１〜２の整数であり、ｈは１〜２の整数である。〕
［５］下記一般式（Ｉ）で表される遷移金属錯体、及び、下記一般式（II）で表される化合物を配合した触媒組成物。

〔一般式（Ｉ）中、Ｘは下記一般式（Ｉ−１）で表されるシリル基を示し、Ａ¹はリン、砒素、及び窒素から選ばれる少なくとも１種の原子を示し、Ｒ¹はそれぞれ同一であっても異なっていてもよい炭素数１〜９の炭化水素基を示し、Ｒ²は炭素数１〜９の炭化水素基又は炭素数１〜９の二価の炭化水素基を示し、Ｒ³は炭素数２〜４のアルカンジイル基を示し、ａは１〜３の整数である。ただしＲ²が二価の炭化水素基である場合には、Ｒ²はＸのシリル基のケイ素原子と結合を有する。〕
Ｒ⁴ _nＹ_pＨ_3-(n+p)Ｓｉ−＊ （Ｉ−１）
〔一般式（Ｉ−１）中、Ｒ⁴はそれぞれ同一であっても異なっていてもよく、１以上の水素が官能基又はハロゲン原子と置換していてもよい、炭素数１〜９の炭化水素基を示し、Ｙは、Ｒ²との結合部位を示し、＊はＭｏ原子との結合部位を示し、ｎは１〜３の整数であり、ｐは０又は１であり、ｎ＋ｐは３以下である。ただし、Ｒ²が二価の炭化水素基である場合、ｐは１であり、Ｒ²が二価の炭化水素基でない場合、ｐは０である。〕
Ａ²Ｈ_(v-m)Ｒ⁶ _mＭ_v-3 （II）
〔一般式（II）中、Ａ²はホウ素又はアルミニウム原子を示し、Ｒ⁶は炭素数１〜８の炭化水素基を示し、Ｍはリチウム又はナトリウム原子を示し、ｖは３又は４の整数であり、ｍは０〜３の整数であり、ｖ−ｍは１以上である。〕 [1] Using the transition metal complex represented by the following general formula (I) in the presence of a reducing agent, the hydrosilane compound (A) is reacted with the halosilane compound (B), or the hydrohalosilane compound (C ) To obtain a silicon-silicon coupling compound.

[In general formula (I), X represents a silyl group represented by the following general formula (I-1), A ¹ represents at least one atom selected from phosphorus, arsenic, and nitrogen, and R ¹ represents Each represents the same or different hydrocarbon group having 1 to 9 carbon atoms, and R ² represents a hydrocarbon group having 1 to 9 carbon atoms or a divalent hydrocarbon group having 1 to 9 carbon atoms. , R ³ represents an alkanediyl group having 2 to 4 carbon atoms, and a is an integer of 1 to 3. However, when R ² is a divalent hydrocarbon group, R ² has a bond with the silicon atom of the silyl group of X. ]
_{^{R 4 n Y p H 3- (}} n + p) Si- * (I-1)
[In General Formula (I-1), R ⁴ may be the same or different, and one or more hydrogen atoms may be substituted with a functional group or a halogen atom. Represents a hydrogen group, Y represents a bonding site to R ² , * represents a bonding site to Mo atom, n represents an integer of 1 to 3, p is 0 or 1, and n + p is 3 or less It is. However, when R ² is a divalent hydrocarbon group, p is 1, and when R ² is not a divalent hydrocarbon group, p is 0. ]
[2] The method for producing a silicon compound according to [1], wherein the reducing agent is a compound represented by the following general formula (II).
A ² H _(vm) R ⁶ _m M _v-3 (II)
[In General Formula (II), A ² represents a boron or aluminum atom, R ⁶ represents a hydrocarbon group having 1 to 8 carbon atoms, M represents a lithium or sodium atom, and v represents an integer of 3 or 4. Yes, m is an integer from 0 to 3, and vm is 1 or more. ]
[3] The hydrosilane compound (A) is a compound represented by the following general formula (III), and the halosilane compound (B) is a compound represented by the following general formula (IV) [1] or [2] The manufacturing method of the silicon compound as described in 2.
R ^a _4-e SiH _e (III)
[In General Formula (III), R ^a is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be substituted with a functional group or a halogen atom, or An aryloxy group having 5 to 20 carbon atoms is shown, and e is an integer of 1 to 3. ]
R ^b _4-f SiZ _f (IV)
[In general formula (IV), ^Rb is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or one or more hydrogen atoms optionally substituted with a functional group or a halogen atom, or An aryloxy group having 5 to 20 carbon atoms is shown, Z is at least one atom selected from chlorine, bromine and iodine, and f is an integer of 1 to 3. ]
[4] The method for producing a silicon compound according to any one of [1] to [3], wherein the hydrohalosilane compound (C) is a compound represented by the following general formula (V).
R ^c _4-gh SiH _g Z _h (V)
[In the general formula (V), R ^c is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be substituted with a functional group or a halogen atom, or A C5-C20 aryloxy group is shown, Z is at least 1 type of atom chosen from chlorine, a bromine, and an iodine, g is an integer of 1-2, h is an integer of 1-2. ]
[5] A catalyst composition comprising a transition metal complex represented by the following general formula (I) and a compound represented by the following general formula (II).

[In general formula (I), X represents a silyl group represented by the following general formula (I-1), A ¹ represents at least one atom selected from phosphorus, arsenic, and nitrogen, and R ¹ represents Each represents the same or different hydrocarbon group having 1 to 9 carbon atoms, and R ² represents a hydrocarbon group having 1 to 9 carbon atoms or a divalent hydrocarbon group having 1 to 9 carbon atoms. , R ³ represents an alkanediyl group having 2 to 4 carbon atoms, and a is an integer of 1 to 3. However, when R ² is a divalent hydrocarbon group, R ² has a bond with the silicon atom of the silyl group of X. ]
_{^{R 4 n Y p H 3- (}} n + p) Si- * (I-1)
[In General Formula (I-1), R ⁴ may be the same or different, and one or more hydrogen atoms may be substituted with a functional group or a halogen atom. Represents a hydrogen group, Y represents a bonding site to R ² , * represents a bonding site to Mo atom, n represents an integer of 1 to 3, p is 0 or 1, and n + p is 3 or less It is. However, when R ² is a divalent hydrocarbon group, p is 1, and when R ² is not a divalent hydrocarbon group, p is 0. ]
A ² H _(vm) R ⁶ _m M _v-3 (II)
[In General Formula (II), A ² represents a boron or aluminum atom, R ⁶ represents a hydrocarbon group having 1 to 8 carbon atoms, M represents a lithium or sodium atom, and v represents an integer of 3 or 4. Yes, m is an integer from 0 to 3, and vm is 1 or more. ]

  ADVANTAGE OF THE INVENTION According to this invention, the method of obtaining the silicon- silicon coupling compound by the dehydrohalogenation reaction of a silane compound using a transition metal complex, and a catalyst composition can be provided.

  In the method for producing a silicon compound of the present invention, a hydrosilane compound (A) and a halosilane compound (B) are reacted using the transition metal complex represented by the general formula (I) in the presence of a reducing agent ( Hereinafter, it is also referred to as “coupling reaction I”) or the hydrohalosilane compound (C) is reacted (hereinafter also referred to as “coupling reaction II”) to obtain a silicon-silicon coupling compound. In the present invention, by using the transition metal complex represented by the above general formula (I) in the presence of a reducing agent, a coupling compound is obtained by a dehydrohalogenation reaction between halosilane and hydrosilane.

[Transition metal complexes]
The transition metal complex used in the present invention is represented by the following general formula (I).

In general formula (I), X represents a silyl group represented by the following general formula (I-1), A ¹ represents at least one atom selected from phosphorus, arsenic, and nitrogen, and R ¹ represents R 1 represents a hydrocarbon group having 1 to 9 carbon atoms which may be the same or different, and R ² represents a hydrocarbon group having 1 to 9 carbon atoms or a divalent hydrocarbon group having 1 to 9 carbon atoms, R ³ represents an alkanediyl group having 2 to 4 carbon atoms, and a is an integer of 1 to 3. However, when R ² is a divalent hydrocarbon group, R ² has a bond with the silicon atom of the silyl group of X.
In addition, the part shown with the arrow in the general formula of this specification means a coordination bond.

^{_{R 4 n Y p H 3- (}} n + p) Si- * (I-1)
In general formula (I-1), R ⁴ may be the same or different, and one or more hydrogen atoms may be substituted with a functional group or a halogen atom. Y represents a bonding site with R ² , * represents a bonding site with Mo (molybdenum) atom, n is an integer of 1 to 3, p is 0 or 1, and n + p is 3 or less. However, when R ² is a divalent hydrocarbon group, p is 1, and when R ² is not a divalent hydrocarbon group, p is 0.
R ⁴ is, for example, phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, aminophenyl group, 4-dimethylaminophenyl group, fluorophenyl group, perfluorophenyl group, methyl group, hexyl group, octyl group. Among these, a phenyl group is preferable.
n is preferably 2.

A ¹ is preferably a phosphorus atom. R ¹ is preferably a phenyl group. R ³ is preferably an alkanediyl group having 2 carbon atoms, more preferably a dimethylene group.
a is preferably 2 or 3, and more preferably 3.
R ² is preferably a phenyl group or a divalent phenylene group, and more preferably a divalent phenylene group. The divalent phenylene group for R ² is preferably a 1,2-phenylene group.

一般式（Ｉ−３）中Ａ¹はリン、砒素、及び窒素から選ばれる少なくとも１種の原子を示し、Ｒ¹はそれぞれ同一であっても異なっていてもよい炭素数１〜９の炭化水素基を示し、Ｒ’²は炭素数１〜９の二価の炭化水素基を示し、Ｒ³は炭素数２〜４のアルカンジイル基を示す。
Ｒ’²は、フェニレン基が好ましく、１，２−フェニレン基がより好ましい。 Moreover, it is preferable that the transition metal complex used for this invention is a transition metal complex represented by the following general formula (I-3).

In general formula (I-3), A ¹ represents at least one atom selected from phosphorus, arsenic, and nitrogen, and R ¹ is a hydrocarbon having 1 to 9 carbon atoms that may be the same or different. R ′ ² represents a divalent hydrocarbon group having 1 to 9 carbon atoms, and R ³ represents an alkanediyl group having 2 to 4 carbon atoms.
R ′ ² is preferably a phenylene group, and more preferably a 1,2-phenylene group.

Specific examples of the transition metal complex used in the present invention include the following transition metal complexes (Ia) to (Id).

  Among the transition metal complexes (Ia) to (Id), the transition metal complex (Ia) is preferable.

〔一般式（Ｉ−４）中、Ａ¹、Ｒ¹、Ｒ³は一般式（Ｉ）と同様である。〕
Ｒ⁴ _nＨ_4-nＳｉ （Ｉ−５）
〔一般式（Ｉ−５）中、Ｒ⁴、ｎは一般式（Ｉ−１）と同様である。〕 The transition metal complex includes, for example, a transition metal complex represented by the following general formula (I-4) such as bis [bis (diphenylphosphino) ethane (dppe)] molybdenum tetrahydride complex, and the following general formula (I- It is obtained by reacting with the silane compound represented by 5).

[In General Formula (I-4), A ¹ , R ¹ and R ³ are the same as those in General Formula (I). ]
R ⁴ _n H _4-n Si (I-5)
[In general formula (I-5), R < ⁴ >, n is the same as that of general formula (I-1). ]

In addition, the transition metal complex represented by the general formula (I-3) includes a transition metal complex represented by the general formula (I-4) and a secondary class represented by the following general formula (I-6). It is obtained by reacting with a silane compound at 80 to 150 ° C.
R ⁴ ₂ H ₂ Si (I-6)
[In general formula (I-5), R ⁴ is the same as in general formula (I-1). ]
By the above reaction, a dehydrogenative condensation reaction between silicon on the secondary silane compound and R ¹ in the transition metal complex occurs, and a transition metal complex represented by the general formula (I-3) is obtained.
In addition, in the manufacturing method of this invention, the raw material of said transition metal complex is mixed, the transition metal complex shown by general formula (I) or (I-3) is generated, hydrosilane compound (A) and halosilane compound The coupling reaction may be carried out by adding (B) or the hydrohalosilane compound (C).

[Reducing agent]
In the production method of the present invention, the reducing agent is used for reduction of the transition metal complex. In the reaction mechanism assumed in the production method of the present invention, after a coupling reaction between a hydrosilane compound and a chlorosilane compound, a halogen atom (Z) such as a hydrogen atom (hydride) and chlorine has a covalent bond to molybdenum metal. It is thought that H- [Mo] -Z species are generated. By reacting the H- [Mo] -Z species with a reducing agent, H- [Mo] -H species that are active species are generated by applying heat, and the coupling reaction of the present invention proceeds as a catalytic reaction. I think that.

The reducing agent used in the present invention is preferably a compound represented by the following general formula (II).
A ² H _(vm) R ⁶ _m M _v-3 (II)
In the general formula (II), A ² represents a boron or aluminum atom, R ⁶ represents a hydrocarbon group having 1 to 8 carbon atoms, M represents a lithium or sodium atom, and v represents an integer of 3 or 4. , M is an integer of 0 to 3, and vm is 1 or more.

A ² is preferably boron. R ⁶ is preferably an isobutyl group, a tertiary butyl group, or an isopropyl group. v is preferably 3. From the viewpoint of using a compound having hydride reducing property, vm is 1 or more, and 3 is preferable.
Specifically, the reducing agent used in the present invention is borane (BH ₃ ), aluminum hydride (AlH ₃ ), diisobutylaluminum hydride (DIBAL-H), sodium borohydride (NaBH ₄ ), borohydride. Examples thereof include lithium (LiBH ₄ ) and lithium aluminum hydride (LiAlH ₄ ). Among these, borane and lithium borohydride are preferable.

In addition, in the manufacturing method of the present invention, it is preferable to use a copper salt in order to increase the yield of the product.
Examples of copper salts include copper (II) trifluoromethanesulfonate (Cu (OTf) ₂ ), copper (II) paratoluenesulfonate (Cu (OTs) ₂ ), and copper (II) acetate (Cu (OCOCH ₃ ) ₂ ). , Copper sulfate (II) (CuSO ₄ ), copper chloride (II), and copper iodide (II). Among these, copper (II) trifluoromethanesulfonate is preferable. In particular, the copper (II) trifluoromethanesulfonate is preferably used in the reaction of the hydrohalosilane compound (C).

[Catalyst composition]
The catalyst composition of the present invention is a composition in which a transition metal complex represented by the above general formula (I) and a compound represented by the above general formula (II) are blended. Moreover, it is suitable for the said composition to mix | blend copper salt arbitrarily.
In the catalyst composition of the present invention, the blending amount of the transition metal complex is preferably 0.01 to 20 mol%, more preferably 0.1 to 10 mol% with respect to the compound represented by the general formula (II). Preferably, 0.1 to 3 mol% is more preferable.
The compounding amount of the copper salt is preferably 1 to 10 mol times, more preferably 2 to 9 mol times, and more preferably 3 to 8 times the compounding amount of the transition metal complex.

[Coupling reaction I]
In the production method of the present invention, the silicon-silicon coupling compound (I) is obtained by reacting the hydrosilane compound (A) with the halosilane compound (B). Examples of the silicon-silicon coupling compound (I) include disilane compounds, trisilane compounds, and polysilanes.

[Hydrosilane Compound (A)]
The hydrosilane compound (A) is preferably a compound represented by the following general formula (III).
R ^a _4-e SiH _e (III)
In general formula (III), R ^a is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or carbon in which one or more hydrogen atoms may be substituted with a functional group or a halogen atom The aryloxy group of number 5-20 is shown, and e is an integer of 1-3.

Examples of the functional group for ^Ra include an amino group, a carboxy group, an aldehyde group, a cyano group, and a nitro group. Examples of the halogen atom for ^Ra include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group having 1 to 20 carbon atoms of ^Ra include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, and a hexyl group. Octyl group, cyclohexyl group, phenyl group, biphenyl group, fluorenyl group, naphthyl group and the like.
The alkoxy group having 1 to 20 carbon atoms R ^a, a methoxy group, an ethoxy group, n- propyl group, i- propyl group, n- butyloxy, i- butyloxy group, t-butyloxy group, a hexyloxy group Octyloxy group, lauryloxy group and the like.
Examples of the aryloxy group having 5 to 20 carbon atoms for ^Ra include a phenoxy group, a naphthyloxy group, and a pyridinyl group.
e is preferably 1 or 2.

  Specifically, the hydrosilane compound (A) is a monohydrosilane such as trimethylsilane, triethylsilane, triphenylsilane, methyldiphenylsilane, phenyldimethylsilane, octyldimethylsilane; dimethylsilane, diethylsilane, diphenylsilane, methylphenylsilane. And dihydrosilane such as octylmethylsilane.

[Halosilane Compound (B)]
The halosilane compound (B) is preferably a compound represented by the following general formula (IV).
R ^b _4-f SiZ _f (IV)
In general formula (IV), ^Rb is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or carbon in which one or more hydrogen atoms may be substituted with a functional group or a halogen atom An aryloxy group of 5 to 20 is shown, Z is at least one atom selected from chlorine, bromine and iodine, and f is an integer of 1 to 3.
f is preferably 1 or 2.
Functional group R ^b, a halogen atom, a hydrocarbon group, the alkoxy group, or aryloxy group may be selected from those exemplified the same type of the R ^a.

  Specifically, the halosilane compound (B) is a monochlorosilane such as trimethylchlorosilane, triethylchlorosilane, triphenylchlorosilane, methyldiphenylchlorosilane, phenyldimethylchlorosilane, octyldimethylchlorosilane; dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, Examples thereof include dichlorosilane such as methylphenyldichlorosilane and octylmethyldichlorosilane.

[Silicon-silicon coupling compound (I)]
In the production method of the present invention, the silicon-silicon coupling compound (I) obtained by reacting the hydrosilane compound (A) and the halosilane compound (B), for example, when e is 1 and f is 1, It is represented by Formula (VI-1).
R ^a ₃ Si—SiR ^b ₃ (VI-1)
[In General Formula (VI-1), R ^a and R ^b are the same as those in General Formulas (III) and (IV). ]

When e is 1 and f is 2, the silicon-silicon coupling compound (I) is represented by the general formula (VI-2).
R ^a ₃ Si—SiR ^b ₂ —SiR ^a ₃ (VI-2)
[In General Formula (VI-2), R ^a and R ^b are the same as those in General Formulas (III) and (IV). ]

When e is 2 and f is 1, the silicon-silicon coupling compound (I) is represented by the general formula (VI-3).
R ^b ₃ Si—SiR ^a ₂ —SiR ^b ₃ (VI-3)
[In General Formula (VI-3), R ^a and R ^b are the same as those in General Formulas (III) and (IV). ]

When e is 2 and f is 2, the silicon-silicon coupling compound (I) is represented by the general formula (VI-4).
-(SiR ^a ₂ -SiR ^b ₂ ) _p- (VI-4)
[In General Formula (VI-4), R ^a and R ^b are the same as those in General Formulas (III) and (IV). ]
That is, an alternating copolymer having a structural unit derived from the hydrosilane compound (A) and a structural unit derived from the halosilane compound (B) is obtained.
The mass average molecular weight of the alternating copolymer represented by the general formula (VI-4) is, for example, 1,000 to 20,000.

[Coupling reaction II]
In the production method of the present invention, the hydrohalosilane compound (C) is reacted to obtain the silicon-silicon coupling compound (II). An example of the silicon-silicon coupling compound (II) is polysilane.

[Hydrohalosilane compound (C)]
The hydrohalosilane compound (C) is preferably a compound represented by the following general formula (V).
R ^c _4-gh SiH _g Z _h (V)
In general formula (V), R ^c is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or carbon in which one or more hydrogen atoms may be substituted with a functional group or a halogen atom An aryloxy group of formula 5 to 20 is shown, Z is at least one atom selected from chlorine, bromine and iodine, g is an integer of 1 to 2, and h is an integer of 1 to 2.
g is preferably 1, and h is preferably 1. g + h is preferably 3 or less.
Functional group R ^c, halogen atom, a hydrocarbon group, the alkoxy group, or aryloxy group may be selected from those exemplified the same type of the R ^a.
Specific examples of the hydrohalosilane compound (C) include dimethylchlorosilane, diethylchlorosilane, diphenylchlorosilane, phenylmethylchlorosilane, octylmethylchlorosilane, and the like.

[Silicon-silicon coupling compound (II)]
For example, when g is 1 and h is 1, the silicon-silicon coupling compound (II) obtained by reacting the hydrohalosilane compound (C) in the production method of the present invention is represented by the general formula (VII-1). ).
-(SiR ^c ₂ ) _p- (VII-1)
[In general formula (VII-1), ^Rc is the same as that of the said general formula (V). ]
That is, a polymer having a structural unit derived from the hydrohalosilane compound (C) is obtained.
The mass average molecular weight of the polymer represented by the general formula (VII-1) is, for example, 1,000 to 20,000.

[Reaction conditions]
In the production method of the present invention, the blending amount of the transition metal complex represented by the general formula (I) is 0.01 to 20 mol% relative to the raw hydrosilane compound (A) or hydrohalosilane compound (C). Is preferable, 0.1-10 mol% is more preferable, and 0.1-3 mol% is still more preferable.
The amount of the reducing agent is preferably 0.8 to 5 molar equivalents relative to 1 mole of the raw hydrosilane compound (A) or hydrohalosilane compound (C) in order to prevent deactivation of the catalyst. A molar equivalent is more preferred.
In the coupling reaction (I), the molar ratio [A / B] of the hydrosilane compound (A) to the halosilane compound (B) is preferably 0.5 to 2, more preferably 0.8 to 1.5, and 9 to 1.1 is more preferable.

The production method of the present invention is preferably carried out in an inert gas atmosphere in order to maintain the catalytic activity of the transition metal complex. Examples of the inert gas include nitrogen, argon, helium and the like. Among these, argon is preferable because it has little effect on the transition metal complex.
The reaction temperature in the production method of the present invention is preferably 50 to 150 ° C., more preferably 60 to 110 ° C., and still more preferably 70 to 100 ° C. in order to prevent reaction activity and catalyst deactivation.

  As described above, by the production method of the present invention, the silicon-silicon coupling compound can be obtained by reacting the hydrosilane compound (A) with the halosilane compound (B) or reacting the hydrohalosilane compound (C). According to this method, the dehydrohalogenation reaction between the hydrosilane compound and the halosilane compound can be performed under mild conditions without going through the lithium salt. That is, silicon-silicon coupling compounds such as disilane compounds and polysilane compounds can be obtained by the production method of the present invention.

  Examples of the present invention will be described below, but the present invention is not limited to them.

[Production example of transition metal complex]
[Production Example 1]
Molybdenum tetrahydride complex [(MoH ₄ (dppe) ₂ ), 0.255 mmol] and diphenylsilane (Ph ₂ SiH ₂ , 1.53 mmol) are dissolved in toluene (20 ml) and heated under reflux in an argon atmosphere for 5 hours. . The reaction solution is cooled to room temperature and the solvent is removed under reduced pressure. Dissolve the residue in benzene (10 ml), add hexane (25 ml) to it and leave at room temperature overnight. The resulting yellow precipitate was filtered off, washed with hexane (5 ml × 3) and then vacuum dried to obtain the transition metal complex of formula (Ia) (0.239 g, 87%) shown above. (Reference: 1. “5th edition, Experimental Chemistry Course 21” (2004), p. 136. 2. Organometallics, (2005), 24, 3434.)

[Disilane production method]
[Example 1]
In a Schlenk flask substituted with an argon atmosphere, a transition metal complex (0.018 mmol) of the formula (Ia) obtained by Production Example 1 and a tetrahydrofuran solution (borane content: 1.87 mmol) of borane (BH ₃ ) were added. After the addition, triethylsilane (Et ₃ SiH, 1.87 mmol) and triphenylchlorosilane (Ph ₃ SiCl, 1.87 mmol) were added. After the mixture was stirred at room temperature, it was moved to a pressure-resistant tube substituted with an argon atmosphere, and heated and reacted at 80 ° C. for 24 hours. Thereafter, the mixture was cooled to room temperature, and an appropriate amount of water was added to terminate the reaction.
The reaction solution was extracted with methylene chloride using a separatory funnel, and the resulting organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure. Then, generated by column chromatography, 1,1,1-triphenyl-2,2,2-triethyl disilane (Ph ₃ Si-SiEt ₃₎ was obtained in (53% yield).

[Examples 2 to 6]
The production methods of Examples 2 to 6 were carried out in the same manner as in Example 1 except that the triethylsilane and triphenylchlorosilane used in Example 1 were changed to the compounds shown in Table 1. The results are shown in Table 1.

[Method for producing homopolymerized polysilane]
Example 7
In a Schlenk flask substituted with an argon atmosphere, a tetrahydrofuran solution (borane content 1.87 mmol, 1) of the transition metal complex of formula (Ia) obtained by Preparation Example 1 (20 mg, 0.018 mmol) and borane (BH ₃ ) was added. , 87 mL), and then diphenylchlorosilane (Ph ₂ SiHCl, 1.87 mmol) and Cu (OTf) ₂ (0.2 mmol). After the mixture was stirred at room temperature, it was moved to a pressure-resistant tube substituted with an argon atmosphere, and heated and reacted at 80 ° C. for 24 hours. After cooling to room temperature and adding an appropriate amount of tetrahydrofuran, the mixture was stirred and then filtered using Celite. The reaction solution was washed with a saturated saline solution using a separatory funnel, the organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure. Then, polydiphenylsilane was obtained by the extraction with hexane (yield 72%). The results are shown in Table 2.

Example 8
The production method of Example 8 was carried out in the same manner as in Example 7 except that diphenylchlorosilane used in Example 7 was changed to phenylmethylchlorosilane. The results are shown in Table 2.

[Production method of alternating copolymerized polysilane]
Example 9
In a Schlenk flask substituted with an argon atmosphere, a tetrahydrofuran solution (borane content: 1.87 mmol, 1) of the transition metal complex of formula (Ia) obtained in Preparation Example 1 (20 mg, 0.018 mmol) and borane (BH ₃ ) was added. , 87 mL), and diphenylsilane (Ph ₂ SiH ₂ , 1.87 mmol) and dimethyldichlorosilane (Me ₂ SiCl ₂ , 1.87 mmol) were added. After the mixture was stirred at room temperature, it was moved to a pressure-resistant tube replaced with an argon atmosphere and heated at 80 ° C. for 24 hours. After cooling to room temperature and adding an appropriate amount of tetrahydrofuran, the mixture was stirred and then filtered using Celite. The reaction solution was washed with a saturated saline solution using a separatory funnel, the organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure. Then, diphenylsilane-dimethylsilane alternating copolymer was obtained with a yield of 45% by performing extraction with hexane. The results are shown in Table 3.

  From the above Examples 1 to 9, it can be seen that the disilane compound undergoes a coupling reaction of the hydrohalosilane compound (C) by the coupling reaction of the hydrosilane compound and the halosilane compound to obtain polysilane.

  According to the present invention, a silicon-silicon coupling compound is obtained by the reaction of a hydrosilane compound and a halosilane compound. For example, disilane obtained by the present invention can obtain amorphous silicon by thermal decomposition, and polysilane has interesting physical properties such as semiconductor properties based on σ-conjugate of the main chain, high hole mobility, photoreactivity, and unique optical properties. As a new functional material, it is expected to be applied to various fields.

Claims (5)

In the presence of a reducing agent, the transition metal complex represented by the following general formula (I) is used to react the hydrosilane compound (A) with the halosilane compound (B), or the hydrohalosilane compound (C) is reacted. A method for producing a silicon compound, wherein a silicon-silicon coupling compound is obtained.

[In general formula (I), X represents a silyl group represented by the following general formula (I-1), A ¹ represents at least one atom selected from phosphorus, arsenic, and nitrogen, and R ¹ represents Each represents the same or different hydrocarbon group having 1 to 9 carbon atoms, and R ² represents a hydrocarbon group having 1 to 9 carbon atoms or a divalent hydrocarbon group having 1 to 9 carbon atoms. , R ³ represents an alkanediyl group having 2 to 4 carbon atoms, and a is an integer of 1 to 3. However, when R ² is a divalent hydrocarbon group, R ² has a bond with the silicon atom of the silyl group of X. ]
_{^{R 4 n Y p H 3- (}} n + p) Si- * (I-1)
[In General Formula (I-1), R ⁴ may be the same or different, and one or more hydrogen atoms may be substituted with a functional group or a halogen atom. Represents a hydrogen group, Y represents a bonding site to R ² , * represents a bonding site to Mo atom, n represents an integer of 1 to 3, p is 0 or 1, and n + p is 3 or less It is. However, when R ² is a divalent hydrocarbon group, p is 1, and when R ² is not a divalent hydrocarbon group, p is 0. ] The method for producing a silicon compound according to claim 1, wherein the reducing agent is a compound represented by the following general formula (II).
A ² H _(vm) R ⁶ _m M _v-3 (II)
[In General Formula (II), A ² represents a boron or aluminum atom, R ⁶ represents a hydrocarbon group having 1 to 8 carbon atoms, M represents a lithium or sodium atom, and v represents an integer of 3 or 4. Yes, m is an integer from 0 to 3, and vm is 1 or more. ] The silicon compound according to claim 1 or 2, wherein the hydrosilane compound (A) is a compound represented by the following general formula (III), and the halosilane compound (B) is a compound represented by the following general formula (IV). Manufacturing method.
R ^a _4-e SiH _e (III)
[In General Formula (III), R ^a is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be substituted with a functional group or a halogen atom, or An aryloxy group having 5 to 20 carbon atoms is shown, and e is an integer of 1 to 3. ]
R ^b _4-f SiZ _f (IV)
[In general formula (IV), ^Rb is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or one or more hydrogen atoms optionally substituted with a functional group or a halogen atom, or An aryloxy group having 5 to 20 carbon atoms is shown, Z is at least one atom selected from chlorine, bromine and iodine, and f is an integer of 1 to 3. ] The manufacturing method of the silicon compound in any one of Claims 1-3 whose hydrohalosilane compound (C) is a compound represented by the following general formula (V).
R ^c _4-gh SiH _g Z _h (V)
[In the general formula (V), R ^c is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be substituted with a functional group or a halogen atom, or A C5-C20 aryloxy group is shown, Z is at least 1 type of atom chosen from chlorine, a bromine, and an iodine, g is an integer of 1-2, h is an integer of 1-2. ] A catalyst composition comprising a transition metal complex represented by the following general formula (I) and a compound represented by the following general formula (II).

[In general formula (I), X represents a silyl group represented by the following general formula (I-1), A ¹ represents at least one atom selected from phosphorus, arsenic, and nitrogen, and R ¹ represents Each represents the same or different hydrocarbon group having 1 to 9 carbon atoms, and R ² represents a hydrocarbon group having 1 to 9 carbon atoms or a divalent hydrocarbon group having 1 to 9 carbon atoms. , R ³ represents an alkanediyl group having 2 to 4 carbon atoms, and a is an integer of 1 to 3. However, when R ² is a divalent hydrocarbon group, R ² has a bond with the silicon atom of the silyl group of X. ]
_{^{R 4 n Y p H 3- (}} n + p) Si- * (I-1)
[In General Formula (I-1), R ⁴ may be the same or different, and one or more hydrogen atoms may be substituted with a functional group or a halogen atom. Represents a hydrogen group, Y represents a bonding site to R ² , * represents a bonding site to Mo atom, n represents an integer of 1 to 3, p is 0 or 1, and n + p is 3 or less It is. However, when R ² is a divalent hydrocarbon group, p is 1, and when R ² is not a divalent hydrocarbon group, p is 0. ]
A ² H _(vm) R ⁶ _m M _v-3 (II)
[In General Formula (II), A ² represents a boron or aluminum atom, R ⁶ represents a hydrocarbon group having 1 to 8 carbon atoms, M represents a lithium or sodium atom, and v represents an integer of 3 or 4. Yes, m is an integer from 0 to 3, and vm is 1 or more. ]