JP2018123073A - Production method of hydrosilane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of hydrosilane capable of producing hydrosilane efficiently.SOLUTION: Silane having a structure shown by formula (a) is reacted with hydrogen in the presence of iridium complex shown by formula (I) and organic base, to thereby produce hydrosilane efficiently.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing hydrosilane, and more particularly to a method for producing hydrosilane by hydrogenolysis of halosilanes in the presence of an iridium complex.

Hydrosilanes are important compounds used as raw materials for organosilicon compounds. However, the number of reports on its catalytic synthesis is limited. For example, hydrosilane synthesis by hydrogenolysis of silyl enol ether using a ruthenium molecular hydrogen complex as a catalyst has been reported (see Non-Patent Documents 1 and 2).
In addition, hydrogenolysis of halogenated silanes and derivatives thereof using an iridium complex as a catalyst has also been reported (see Patent Document 1). This reaction proceeds when an iridium hydride species generated from a reaction of an iridium complex having a dialkylbenzimidazol-2-ylidene ligand and a phosphine ligand with hydrogen gas reacts with a halogenated silane.

JP 2006-17071 A

M.M. Hidai, et al. Angew. Chem. Int. Ed. 1999, 38, 3047-3050. I. Takai, et al. J. et al. Organomet. Chem. 2003, 679, 32-42.

  An object of this invention is to provide the manufacturing method of hydrosilane which can manufacture hydrosilane efficiently.

As a result of intensive studies to solve the above problems, the present inventors have found that hydrosilane can be efficiently produced by reacting hydrogen with halosilane or the like in the presence of a specific iridium complex and an organic base, The present invention has been completed.
That is, the present invention is as follows.

<1> A structure represented by the following formula (b) by reacting a silane having a structure represented by the following formula (a) with hydrogen in the presence of an iridium complex represented by the following formula (I) and an organic base. A method for producing hydrosilane, comprising a hydrogenation step for producing hydrosilane having a hydrofluoric acid.
(Formula (in I), R ¹ each independently carbon atoms which may contain a hetero atom 1-1
A hydrocarbon group of 0, R ² may be a divalent or trivalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, and R ³ may independently contain a hetero atom. R 1 is a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, or a carbonyl group, R ⁵ is A hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, or a hydrogen atom, m is an integer of 0 to 5, n is 1 or 2, and a double line of a solid line and a broken line is a single bond Or a double bond and the broken line between Ir-N represent a coordination bond. However, when m is 2 or more, two or more hydrocarbon groups of R ¹ may be connected to each other to form a cyclic structure. When n is 1, the double line of the solid line and the broken line is double a bond, if n is 2, a solid line and a dashed double line is a single bond, may form a cyclic structure linked hydrocarbon group of R ² and R ³ together, R ⁴ is When it is a hydrocarbon group, the hydrocarbon groups of R ⁴ and R ⁵ may be linked to each other to form a cyclic structure. )
(In the formula (a), L represents a chlorine atom, a bromine atom, an iodine atom, or a group represented by the following formula (s).)
(In formula (s), R represents a C1-C10 hydrocarbon group which may contain a nitrogen atom, an oxygen atom, and a halogen atom.)
<2> The organic base is a compound represented by the following formula (II-1), a compound having a structure represented by the following formula (ii-1), and a structure represented by the following formula (ii-2). <1> The method for producing hydrosilane according to <1>, which is at least one selected from the group consisting of compounds having:
(In formula (II-1), each R ⁶ independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

  According to the present invention, hydrosilane can be produced efficiently.

  The details of the present invention will be described with specific examples. However, the present invention is not limited to the following contents without departing from the gist of the present invention, and can be implemented with appropriate modifications.

<Method for producing hydrosilane>
In a method for producing hydrosilane which is one embodiment of the present invention, a silane having a structure represented by the following formula (a) is reacted with hydrogen in the presence of an iridium complex represented by the following formula (I) and an organic base. It includes a hydrogenation step for producing hydrosilane having a structure represented by the following formula (b) (hereinafter sometimes abbreviated as “hydrogenation step”).
(Formula (in I), R ¹ each independently carbon atoms which may contain a hetero atom 1-1
A hydrocarbon group of 0, R ² may be a divalent or trivalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, and R ³ may independently contain a hetero atom. R 1 is a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, or a carbonyl group, R ⁵ is A hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, or a hydrogen atom, m is an integer of 0 to 5, n is 1 or 2, and a double line of a solid line and a broken line is a single bond Or a double bond and the broken line between Ir-N represent a coordination bond. However, when m is 2 or more, two or more hydrocarbon groups of R ¹ may be connected to each other to form a cyclic structure. When n is 1, the double line of the solid line and the broken line is double a bond, if n is 2, a solid line and a dashed double line is a single bond, may form a cyclic structure linked hydrocarbon group of R ² and R ³ together, R ⁴ is When it is a hydrocarbon group, the hydrocarbon groups of R ⁴ and R ⁵ may be linked to each other to form a cyclic structure. )
(In the formula (a), L represents a chlorine atom, a bromine atom, an iodine atom, or a group represented by the following formula (s).)
(In formula (s), R represents a C1-C10 hydrocarbon group which may contain a nitrogen atom, an oxygen atom, and a halogen atom.)
As mentioned above, examples of hydrocracking using ruthenium molecular hydrogen complexes or specific iridium complexes as catalysts have been reported as hydrosilane synthesis methods, but in these reaction systems, reactivity such as bromosilane and chlorosilane is reported. However, it was difficult to synthesize hydrosilane from a low halogenated silane.
The present inventors have reacted hydrosilane with “silane having a structure represented by formula (a)” and hydrogen in the presence of “iridium complex represented by formula (I)” and “organic base”. Was found to generate efficiently. In this reaction, “organic base” means HL (L = OTf, I, Br, Cl, etc.) generated by hydrogenolysis of halogenated silane or the like.
Is considered to play a role in prolonging the life of the catalyst.
The “organic base” means an organic compound having Bronsted basicity.
“Hydrogen” means a hydrogen molecule (H ₂ ).
Furthermore, the wavy line in formula (a) and formula (b) means that the structure ahead is arbitrary. Accordingly, the “silane having the structure represented by the formula (a)” may have two or more −L, and the “hydrogenation step” is a reaction for substituting all of two or more of −L. Even if it exists, the reaction which substitutes a part of -L shall be sufficient (refer following formula).
Hereinafter, the “hydrogenation step” will be described in detail.

In the hydrogenation step, a silane having a structure represented by the formula (a) is reacted with hydrogen in the presence of an iridium complex represented by the formula (I) and an organic base to form a structure represented by the formula (b). Specific types of “iridium complex represented by formula (I)”, “organic base”, and “silane having a structure represented by formula (a)” Should be selected as appropriate. Hereinafter, “iridium complex represented by formula (I)”, “organic base”, and “silane having a structure represented by formula (a)” will be described with specific examples.
R ¹ in the formula (I) is independently represented by “the number of carbon atoms which may contain a hetero atom 1
-10 hydrocarbon groups ", the" hydrocarbon group "may have a branched structure, a cyclic structure, and a carbon-carbon unsaturated bond, respectively, a saturated hydrocarbon group, an unsaturated group. Any of a hydrocarbon group, an aromatic hydrocarbon group, etc. shall be sufficient. Further, “may contain a hetero atom” means that a hydrogen atom of a hydrocarbon group is substituted with a hetero atom, that is, a monovalent functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, or the like. In addition, the carbon atom inside the carbon skeleton of the hydrocarbon group may be substituted with a divalent or higher functional group (linking group) containing a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom or the like. To do.
Examples of the functional group or linking group contained in R ¹ include a fluoro group (—F), a chloro group (—Cl),
Bromo group (—Br), iodo group (—I), phosphino group (—PR ″ ₂ ), alkoxy group (
—OR ″), trialkylsilyl group (—SiR ″ ₃ ), phosphine oxide group (—P (=
O) R ″ ₂ ) and the like.
The number of carbon atoms of the hydrocarbon group for R ¹ is preferably 9 or less, more preferably 8 or less,
More preferably, it is 7 or less, and the number of carbon atoms when R ¹ is an aromatic hydrocarbon group is usually 6 or more.
R ¹ includes a methyl group (—CH ₃ , —Me), an ethyl group (—C ₂ H ₅ , —Et), an n-propyl group ( ^—n C ₃ H ₇ , ^—n Pr), and an i-propyl group. _{^{(- i C 3 H 7,}} - i Pr), n- butyl _{^{(- n C 4 H 9,}} - n Bu), t- butyl _{^{(- t C 4 H 9,}} - t Bu), n- pentyl group _{^{(- n C 5 H 11)}} , n- hexyl group _{^{(- n C 6 H 13,}} - n Hex), cyclohexyl _{^{(- c C 6 H 11,}} -Cy), phenyl group (-C ₆ H _5, -Ph), benzyl group _{(-CH 2 C 6 H 5,} -Bn) , and the like. Among these, a methyl group is preferable.
"When m is 2 or more, two or more hydrocarbon groups of R ¹ may be linked to each other to form a cyclic structure". Indenyl anion, octahydrofluorenyl anion, and fluorenyl anion represented by
The ligand (cyclopentadienyl anion) of the iridium complex represented by the formula (I) is preferably a pentamethylcyclopentadienyl anion represented by the following formula.

R ² in the formula (I) represents “a divalent or trivalent hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom”, but “a heteroatom may be contained”. “Good” and “hydrocarbon group” have the same meaning as in R ¹ . In addition, since “when n is 1, the solid and broken double lines are double bonds, and when n is 2, the solid and broken double lines are single bonds”. The hydrogen group becomes a hydrocarbon group having two bonding sites by a single bond, and the “trivalent” hydrocarbon group becomes a hydrocarbon group having two bonding sites by one double bond and one single bond. .
Examples of functional groups and linking groups contained in R ² include ether groups (oxa groups, —O—), thioether groups (sulfide groups, —S—), fluoro groups (—F), chloro groups (—Cl), bromo groups. Group (—Br), iodo group (—I) and the like.
R ² includes methylene group (—CH ₂ —), ethylene group (—CH ₂ CH ₂ —), n-propylene group (—CH ₂ CH ₂ CH ₂ —), i-propylene group (—CH (CH _3). ) CH ₂ —), methylidyne group (methine group, ═CH—), ethylidin group (═C (CH ₃ ) —) and the like.
R ³ in the formula (I) each independently represents “a carbon atom which may contain a hetero atom 1
-10 hydrocarbon group "or" hydrogen atom "," may contain a hetero atom "and" hydrocarbon group "have the same meaning as in R ¹ .
The functional group and linking group contained when R ³ is a hydrocarbon group include a primary amino group (—
NH ₂ ), secondary amino group (—NH—), imino group (═N—), ether group (oxa group,
-O-), thioether group (sulfide group, -S-), fluoro group (-F), chloro group (-Cl), bromo group (-Br), iodo group (-I) and the like.
R ³ includes a methyl group (—CH ₃ , —Me), an ethyl group (—C ₂ H ₅ , —Et), an n-propyl group ( ^—n C ₃ H ₇ , ^—n Pr), and an i-propyl group. _{^{(- i C 3 H 7,}} - i Pr), n- butyl _{^{(- n C 4 H 9,}} - n Bu), t- butyl _{^{(- t C 4 H 9,}} - t Bu), n- pentyl group _{^{(- n C 5 H 11)}} , n- hexyl group _{^{(- n C 6 H 13,}} - n Hex), cyclohexyl _{^{(- c C 6 H 11,}} -Cy), phenyl group (-C ₆ H _5, -Ph), benzyl group _{(-CH 2 C 6 H 5,} -Bn), such as a hydrogen atom.
In addition, “the hydrocarbon groups of R ² and R ³ may be linked to each other to form a cyclic structure”, but as a case where a cyclic structure is formed, a structure represented by the following formula is exemplified.

R ⁴ in formula (I) represents “a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom” or “carbonyl group”. And “hydrocarbon group” have the same meaning as in R ¹ . Further, the “divalent hydrocarbon group” means a hydrocarbon group having two bonding sites with a single bond.
Functional groups and linking groups included when R ⁴ is a hydrocarbon group include ether groups (oxa groups, —O—), thioether groups (sulfide groups, —S—), fluoro groups (—F), chloro Examples include a group (—Cl), a bromo group (—Br), an iodo group (—I) and the like.
R ⁴ includes carbonyl group (—C (═O) —), methylene group (—CH ₂ —), ethylene group (—CH ₂ CH ₂ —), n-propylene group (—CH ₂ CH ₂ CH ₂ —). ), I-propylene group (—CH (CH ₃ ) CH ₂ —), methylidine group (methine group, ═CH—), ethylidine group (═C (CH ₃ ) —) and the like.
R ⁵ in formula (I) represents a “hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom” or “hydrogen atom”. “Good” and “hydrocarbon group” have the same meaning as in R ¹ .
The functional group and linking group contained when R ⁵ is a hydrocarbon group include a primary amino group (—
NH ₂ ), secondary amino group (—NH—), imino group (═N—), ether group (oxa group,
-O-), thioether group (sulfide group, -S-), fluoro group (-F), chloro group (-Cl), bromo group (-Br), iodo group (-I) and the like.
R ⁵ includes a methyl group (—CH ₃ , —Me), an ethyl group (—C ₂ H ₅ , —Et), an n-propyl group ( ^—n C ₃ H ₇ , ^—n Pr), and an i-propyl group. _{^{(- i C 3 H 7,}} - i Pr), n- butyl _{^{(- n C 4 H 9,}} - n Bu), t- butyl _{^{(- t C 4 H 9,}} - t Bu), n- pentyl group _{^{(- n C 5 H 11)}} , n- hexyl group _{^{(- n C 6 H 13,}} - n Hex), cyclohexyl _{^{(- c C 6 H 11,}} -Cy), phenyl group (-C ₆ H _5, -Ph), benzyl group _{(-CH 2 C 6 H 5,} -Bn), p- dimethylaminophenyl group, such as a hydrogen atom.
In addition, “when R ⁴ is a hydrocarbon group, the hydrocarbon groups of R ⁴ and R ⁵ may be linked to each other to form a cyclic structure”, Examples include a structure represented by the formula.

As the ligand (diamine anion) of the iridium complex represented by the formula (I), those represented by the following formula are preferred.

Examples of the iridium complex represented by the formula (I) include those represented by the following formula.

The iridium complex represented by the formula (I) is a complex ion having an iridium atom (Ir) having an oxidation number of +3 as a central metal, whereas the iridium complex represented by the formula (I) is represented by the formula (I). In addition to directly adding a complex salt containing an iridium complex to the reactor, the iridium complex precursor represented by the formula (I) is reacted with this precursor, for example, as in the reaction represented by the following formula: A salt that forms an iridium complex represented by the formula (I) (for example, silver trifluoromethanesulfonate) is charged into the reactor to form an iridium complex represented by the formula (I) in the reactor. Also good.

Examples of the counter ion (anion) of the iridium complex represented by the formula (I) include a triflate anion (TfO ⁻ ).
Examples of the precursor of the iridium complex represented by the formula (I) include an iridium complex represented by the following formula (I ′).
(In the formula (I ′), R ¹ , R ² , R, R ⁴ , R ⁵ , m and n are the same as those described above, and X represents a halogen atom.)
Examples of the salt for forming the iridium complex represented by the formula (I) include trifluoromethanesulfonate, and examples of the cation of the trifluoromethanesulfonate include lithium ion (Li ⁺ ) and sodium ion (Na ⁺ ), Alkali metals such as potassium ions (K ⁺ ), alkaline earth metal ions such as magnesium ions (Mg ²⁺ ) and calcium ions (Ca ²⁺ ), and silver ions (Ag ⁺ ). Among these, lithium is preferable.
Examples of the trifluoromethanesulfonate include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, and silver trifluoromethanesulfonate. Among these, lithium trifluoromethanesulfonate is preferable.

When the iridium complex represented by the formula (I) is formed in the reactor, the amount of salt used (formation amount) for forming the iridium complex represented by the formula (I) is represented by the formula (a). The amount is usually 3 mol% or more, preferably 5 mol% or more, particularly preferably 10 mol% or more, and usually 30 mol% or less in terms of the amount of the substance with respect to the silane having the structure.
When the iridium complex represented by the formula (I) is formed in the reactor, the amount of salt used (formation amount) for forming the iridium complex represented by the formula (I) is represented by the formula (I). The amount of the iridium complex precursor is usually 0.1 equivalents or more, preferably 0.5 equivalents or more, particularly preferably 1.0 equivalents or more, usually 3.0 equivalents or less, more preferably in terms of the amount of substance. Is 1.5 equivalents or less.
Within the above range, hydrosilane can be produced with higher yield.

The amount of use of the iridium complex represented by the formula (I) in the hydrogenation step (charge amount) is usually 3 mol% or more, preferably 3 mol% or more in terms of the amount of the silane having the structure represented by the formula (a), preferably It is 5 mol% or more, particularly preferably 10 mol% or more, and is usually 40 mol% or less, preferably 20 mol% or less. Within the above range, hydrosilane can be produced with higher yield.

Examples of the organic base include an amine represented by the following formula (II-1), a compound having a structure represented by the following formula (ii-1), and a compound having a structure represented by the following formula (ii-2). Can be mentioned. In addition, although the wavy line in formula (ii-1) and formula (ii-2) means that the structure ahead is arbitrary, you may form the cyclic structure specifically. Examples thereof include hydrocarbon groups having 1 to 20 carbon atoms.
(In formula (II-1), each R ⁶ independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

Specific examples of the organic base include those represented by the following formula (triethylamine, tri-n-propylamine, N, N-diisopropylamine, 1,5-diazabicyclo [4.3.0].
Non-5-ene (DBN), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 7-methyl-1,5,7-triazabicyclo [4,4,0] Deca-5-ene (MTBD), 1,5,7-triazabicyclo [4,4,0] dec-5-ene (TBD) and the like).

The amount of organic base used (charged amount) in the hydrogenation step is usually 0.1 equivalents or more, preferably 1.0 equivalents or more, usually 5 equivalents or more with respect to the silane having the structure represented by formula (a). 0.0 equivalents or less, preferably 2.5 equivalents or less, more preferably 2 equivalents or less, particularly preferably 1.5 equivalents or less.
It is below the equivalent. Within the above range, hydrosilane can be produced with higher yield.

L in the formula (a) is “chlorine atom”, “bromine atom”, “iodine atom” or “group represented by the formula (s)”, and R in the formula (s) is “nitrogen atom” Represents a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and a halogen atom, and the “hydrocarbon group” has the same meaning as in R ¹ . Further, “may contain a nitrogen atom, an oxygen atom, and a halogen atom” means that a hydrogen atom of a hydrocarbon group is substituted with a monovalent functional group containing a nitrogen atom, an oxygen atom, a halogen atom, or the like. In addition, it means that the carbon atom in the carbon skeleton of the hydrocarbon group may be substituted with a divalent or higher functional group (linking group) containing a nitrogen atom, an oxygen atom, a halogen atom, or the like.
Examples of the functional group and linking group contained in R include a fluoro group (—F), a chloro group (—Cl), a bromo group (—Br), an iodo group (—I), and a nitro group (—NO ₂ ). It is done.
R includes a methyl group (—CH ₃ , —Me), an ethyl group (—C ₂ H ₅ , —Et), an n-propyl group ( ^—n C ₃ H ₇ , ^—n Pr), an i-propyl group ( _{^{- i C 3 H 7, -}} i Pr), n- butyl _{^{(- n C 4 H 9,}} - n Bu), t- butyl _{^{(- t C 4 H 9,}} - t Bu), n- pentyl group _{^{(- n C 5 H 11)}} , n- hexyl group _{^{(- n C 6 H 13,}} - n Hex), cyclohexyl _{^{(- c C 6 H 11,}} -Cy), phenyl group (-C ₆ H _5, - Ph), benzyl _{(-CH 2 C 6 H 5,} -Bn), trifluoromethyl group (-CF _3), tolyl group _{(-C 6 H 4 CH 3,} o-, m-, or p-), 2-nitrophenyl group (-C ₆ H ₄ NO _2), and the like.
As L, a chlorine atom, a bromine atom, an iodine atom, a structure represented by the following formula (methanesulfonyloxy group, trifluoromethanesulfonyloxy group (-OTf), p-toluenesulfonyloxy group (-OTs), 2-nitrobenzene A sulfonyloxy group (-ONs)). Among these, an iodine atom and a trifluoromethanesulfonyloxy group are particularly preferable.

Examples of the silane having a structure represented by the formula (a) include silanes represented by any of the following formulas (A-1) to (A-4).
(In formulas (A-1) to (A-3), R ′ is independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a hydrogen atom, and L is independently A chlorine atom, a bromine atom, an iodine atom, or a group represented by the formula (s).
In formulas (A-1) to (A-3), R ′ each independently represents a “hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom” or “hydrogen atom”. However, “may contain a heteroatom” and “hydrocarbon group” have the same meaning as in R ¹ .
Functional groups and linking groups included when R ′ is a hydrocarbon group include ether groups (oxa groups, —O—), thioether groups (sulfide groups, —S—), fluoro groups (—F), chloro Examples include a group (—Cl), a bromo group (—Br), an iodo group (—I) and the like.
R ′ includes a methyl group (—CH ₃ , —Me), an ethyl group (—C ₂ H ₅ , —Et), n—
Propyl _{^{(- n C 3 H 7,}} - n Pr), i- propyl _{^{(- i C 3 H 7,}} - i Pr), n- butyl _{^{(- n C 4 H 9,}} - n Bu), t - butyl _{^{(- t C 4 H 9,}} - t Bu), n- pentyl _{^{(- n C 5 H 11)}} , n- hexyl group _{^{(- n C 6 H 13,}} - n Hex), cyclohexyl group (- ^c C ₆
H _11, -Cy), phenyl group _{(-C 6 H 5, -Ph)} , benzyl group _{(-CH 2 C 6 H 5,} -B
n), hydrogen atoms and the like.
Examples of the silane represented by any one of formulas (A-1) to (A-4) include compounds represented by the following formula.

  Hydrogen is usually charged as hydrogen gas into the gas phase in the system. The hydrogen partial pressure in the hydrogenation step is usually 1 atmosphere or more, preferably 4 atmospheres or more, and usually 50 atmospheres or less, preferably 10 atmospheres or less. Within the above range, hydrosilane can be produced with higher yield.

  In the hydrogenation step, it is preferable to use a solvent. The type of the solvent is not particularly limited and can be appropriately selected according to the purpose. Specifically, it is a hydrocarbon solvent such as hexane, benzene, and toluene, and an ether type such as diethyl ether and tetrahydrofuran (THF). A solvent, N-methylpyrrolidone, etc. are mentioned.

The reaction temperature in the hydrogenation step is usually 25 ° C. or higher, preferably 40 ° C. or higher, particularly preferably 60 ° C. or higher, and is usually 180 ° C. or lower, preferably 150 ° C. or lower, more preferably 120 ° C. or lower, particularly preferably 90 ° C. Less than or equal to degrees.
The reaction time of the hydrogenation step is usually 1 hour or longer, preferably 12 hours or longer, more preferably 24 hours or longer, and usually 72 hours or shorter.
Within the above range, hydrosilane can be produced with higher yield.

The specific kind of hydrosilane having a structure represented by the formula (b) generated by the hydrogenation step is not particularly limited and can be appropriately selected depending on the production purpose. Hydrosilane represented by any of (B-10) is mentioned.
(In the formulas (B-1) to (B-10), R ′ each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, L represents a chlorine atom, a bromine atom, Represents an iodine atom or a group represented by the formula (s).)
R ′ and L are the same as in the case of silane represented by any one of formulas (A-1) to (A-4).

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention can be modified as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Examples 1-6>
J. et al. Chloro [N- [4- (dimethylamino) phenyl] -2-pyridinecarboxamidato] (pentamethylcyclopentadienyl) iri represented by the following formula in an NMR sample tube with a Young valve.
A heavy benzene solution of dium (3.6 mg, 0.006 mmol), lithium trifluoromethanesulfonate (0.9 mg, 0.006 mmol), and 1,4-bis (trimethylsilyl) benzene (6.7 mg, 0.03 mmol) ( 0.5 mL) was prepared, and 0.060 mmol of diisopropylethylamine (8.5 mg, 11.5 μL, 0.066 mmol) and the silane described in Table 1 below were added. After freezing and degassing the NMR tube, hydrogen (4 atm) was introduced, and the reaction was performed at a temperature of 60 ° C. for 48 hours. ^{From the 1} H, ²⁹ Si NMR measurement, it was confirmed that the corresponding hydrosilane compound was formed. The respective yields are shown in Table 1.

<Examples 7 to 10>
J. et al. An NMR sample tube equipped with a Young valve was charged with Chloro [N- [4- (dimethylamino) phenyl] -2-pyridinecarboxamidato] (pentamethylcyclopentadienyl) iridium (3.6 mg, 0.006 mmol), lithium trifluoromethanesulfonate (0.9 mg, 0.9 mg). .006 mmol) and 1,4-bis (trimethylsilyl) benzene (6.7 mg, 0.03 mmol) in a heavy benzene solution (0.5 mL) were prepared, and 1,8-diazabicyclo [5.4.0] undeca- 7-ene (DBU) (10 mg, 10 μL, 0.066 mmol) and 0.060 mmol of silane described in Table 2 below were added. After freezing and degassing the NMR tube, hydrogen (4 atm) was introduced, and the reaction was performed at a temperature of 60 ° C. for 48 hours. ^{From the 1} H, ²⁹ Si NMR measurement, it was confirmed that the corresponding hydrosilane compound was formed. The respective yields are shown in Table 2.

<Example 11>
Trimethylchlorosilane (0.060 mmol) was added to a suspension of sodium iodide (0.66 mmol) in deuterated benzene-THF [0.5 mL (3: 2)] and stirred at room temperature for 2 hours. Separately, J.H. An NMR sample tube equipped with a Young valve was charged with Chloro [N- [4- (dimethylamino) phenyl] -2-pyridinecarboxamidato] (pentamethylcyclopentadienyl) iridium (3.6 mg, 0.006 mmol), lithium trifluoromethanesulfonate (0.9 mg, 0.9 mg). .006 mmol), 1,4-bis (trimethylsilyl) benzene (6.7 mg, 0.03 mmol), and diisopropylethylamine (8.5 mg, 11.5 μL, 0.066 mmol), and trimethylchlorosilane prepared above was measured. The suspension containing was added. After freezing and degassing the NMR tube, hydrogen (4 atm) was introduced, and the reaction was carried out at a reaction temperature of 60 ° C. for 48 hours. ^{From 1} H, ²⁹ Si NMR measurement, it was confirmed that trimethylhydrosilane was produced in a yield of 71%.
Pretreatment with sodium iodide improved the reaction yield in the hydrogenation of chlorosilane.

<Synthesis Example: Preparation of Iridium Complex Represented by Formula (I)>
The Schlenk tube has Chloro [N- [4- (dimethylamino) phenyl] -2-pyridinecarboxamito] (pentamethyl).
Cyclopentadienyl) iridium (250 mg, 0.37 mmol) and silver trifluoromethanesulfonate (95.1 mg, 0.37 mmol) were added, and the mixture was stirred at room temperature for 1 hour in a dichloromethane-acetonitrile (17 mL, 15: 2) mixed solvent. It was. At this time, generation of white precipitate was confirmed. This suspension was filtered through Celite, and the filtrate was dried under reduced pressure. This yellow powder was dissolved in a mixed solvent of dichloromethane-hexane (20 mL, 5: 1), and celite filtration was performed again. By drying this under reduced pressure for 3 hours, [N- [4- (dimethylamino) phenyl] -2-pyridinecarboxamidate] (pentamethylcyclopentadienyl) iridium trifluorometasulfonate is 226.1 mg,
The yield was 88%.
¹ H NMR (600MHz, C ₆ D ₆ -CH ₂ Cl ₂ ) δ 8.89 (dd, 1H, J = 6.2 Hz, 3.2 Hz, pyridyl), 7.93 (dd, 1H, J = 6.2 Hz, 3.2 Hz, pyridyl) , 7.36 (dd, 2H, J = 8.2 Hz, 1.8 Hz, phenyl), 7.30-7.26 (m, 2H, pyridyl), 6.66 (dd, 2H, J = 8.2 Hz, 1.6 Hz, phenyl), 2.67 (s,
6H, -NMe ₂ ), 1.09 (s, 15H, C ₅ Me ₅ ) ppm.

<Examples 12 to 16>
J. et al. [N- [4- (dimethylamino) phenyl] -2-pyridinecarboxamidate] (pentamethylcyclopentadienyl) iridium t represented by the following formula on an NMR sample tube with a Young valve.
A benzene solution (0.5 mL) of rifluorometanesulfonate (4.3 mg, 0.006 mmol) and 1,4-bis (trimethylsilyl) benzene (6.7 mg, 0.03 mmol) was prepared, and diisopropylethylamine (8.5 mg, 11.5 μL, 0.066 mmol) and 0.060 mmol of silane described in Table 3 below were added. After freezing and degassing the NMR tube, hydrogen (4 atm) was introduced, and the reaction was performed at a temperature of 60 ° C. for 48 hours. ^{From the 1} H, ²⁹ Si NMR measurement, it was confirmed that the corresponding hydrosilane compound was formed. The respective yields are shown in Table 3.

<Examples 17-18>
[N- [4- (dimethylamino) phenyl] -2-pyridinecarbboxamito] (pentamethylcyclopentadienyl) iridium trifluoroethanesulfonate (4.3 mg, 0.006 mmol), 1,4-bis (trimethylsilyl), 0.03 A heavy benzene solution (0.5 mL) was prepared, and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) (10 mg, 10 μL, 0.066 mmol) and the silane described in Table 4 below were prepared. 0.060 mmol was added. After freezing and degassing the NMR tube, hydrogen (4 atm) was introduced, and the reaction was performed at a temperature of 60 ° C. for 48 hours. ¹ H, ²⁹ Si NMR
From the measurement, it was confirmed that the corresponding hydrosilane compound was produced. Table 4 shows the yield of each.
Shown in

<Example 19>
Trimethylchlorosilane (0.060 mmol) was added to a suspension of sodium iodide (0.66 mmol) in deuterated benzene-THF [0.5 mL (3: 2)] and stirred at room temperature for 2 hours. Separately, J.H. In a NMR sample tube with a Young valve, [N- [4- (dimethylamino) phenyl] -2-pyridinecarboxamidato] (pentamethylcyclopentadienyl) iridium trifluorethansulfonate (2.2 mg, 0.003 mmol, benzene, trimethyl (trifluoroacetate), 2.2 mg, 0.003 mmol) 0.7 mg, 0.03 mmol) and diisopropylethylamine (8.5 mg, 11.5 μL, 0.066 mmol) were weighed and the suspension containing trimethylchlorosilane prepared above was added. After freezing and degassing the NMR tube, hydrogen (4 atm) was introduced, and the reaction was carried out at a reaction temperature of 60 ° C. for 48 hours. ¹ H, ²⁹ Si NMR
From the measurement, it was confirmed that trimethylhydrosilane was produced with a yield of 67%.
Pretreatment with sodium iodide improved the reaction yield in the hydrogenation of chlorosilane.

  The hydrosilane produced by the production method of the present invention can be used for producing organic / inorganic hybrid materials, functional organic molecules, and the like.

Claims (2)

Hydrosilane having a structure represented by the following formula (b) by reacting a silane having a structure represented by the following formula (a) with hydrogen in the presence of an iridium complex represented by the following formula (I) and an organic base. A method for producing hydrosilane, comprising a hydrogenation step of producing
(Formula (in I), R ¹ each independently carbon atoms which may contain a hetero atom 1-1
A hydrocarbon group of 0, R ² may be a divalent or trivalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, and R ³ may independently contain a hetero atom. R 1 is a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, or a carbonyl group, R ⁵ is A hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, or a hydrogen atom, m is an integer of 0 to 5, n is 1 or 2, and a double line of a solid line and a broken line is a single bond Or a double bond and the broken line between Ir-N represent a coordination bond. However, when m is 2 or more, two or more hydrocarbon groups of R ¹ may be connected to each other to form a cyclic structure. When n is 1, the double line of the solid line and the broken line is double a bond, if n is 2, a solid line and a dashed double line is a single bond, may form a cyclic structure linked hydrocarbon group of R ² and R ³ together, R ⁴ is When it is a hydrocarbon group, the hydrocarbon groups of R ⁴ and R ⁵ may be linked to each other to form a cyclic structure. )
(In the formula (a), L represents a chlorine atom, a bromine atom, an iodine atom, or a group represented by the following formula (s).)
(In formula (s), R represents a C1-C10 hydrocarbon group which may contain a nitrogen atom, an oxygen atom, and a halogen atom.) The organic base is an amine represented by the following formula (II-1), a compound having a structure represented by the following formula (ii-1), and a compound having a structure represented by the following formula (ii-2) The method for producing hydrosilane according to claim 1, which is at least one selected from the group consisting of:
(In formula (II-1), each R ⁶ independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)