JPH0552840B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a nickel group transition metal complex having a silicon-transition metal bond.

Complexes having silicon-transition metal bonds are used as raw materials for producing transition metal silicides used in devices by chemical vapor phase reactions or vapor deposition.

[Prior art and its problems]

Conventionally, complexes with silicon-transition metal bonds are
It was manufactured in the following way.

(1) Reaction between halosilane and transition metal anion.

(2) Reaction between silyl alkali metal and transition metal halide.

(3) Reaction of silylmercury and transition metal complexes.

(4) Oxidative addition of hydrosilane to low-valent transition metal complexes.

(5) Dehydrohalogenation reaction between hydrosilane and transition metal halide.

However, each of the above methods has its own problems. In method (1), the transition metal component must form an anion, which limits the types and structures of the transition metal and the ligand. . In method (2), since an alkali metal is used, there are operational risks, and a silyl transition metal complex having a substituent that can react with an alkali metal cannot be produced in principle. In method (3), not only an alkali metal is used in the step of producing silylmercury, but also highly toxic mercury is used, so its industrial use is severely restricted. Substituents on silicon are also limited to methyl groups. Method (4) allows the production of various silicon-transition metal complexes, but the process is complicated because it requires reducing the usually easily available halosilane with expensive lithium aluminum hydride to form hydrosilane and then subjecting it to the reaction. It is. In addition, since method (5) uses hydrosilane, it has the same problems as (4), and also because the reaction is carried out in the presence of a base.
A silyl transition metal complex having a substituent that can react with a base cannot be produced in principle. Furthermore, the types of substituents and ligands on silicon are also limited to specific ones.

The present inventors have conducted extensive research to solve these problems, and as a result, have discovered that halosilane easily reacts with low-valent metal complexes, and have arrived at the present invention.

[Problem of invention]

The present invention seeks to develop a completely new method for producing silicon-transition metal bonds and to provide complexes having silicon-transition metal bonds.

[Means to solve the problem]

As a result of intensive research to achieve the above object, the present inventors have discovered that by reacting a specific nickel group metal complex with a silicon compound having a silicon-halogen atom bond, a compound having a silicon-transition metal bond can be produced. The present inventors have discovered that the following can be obtained, and have completed the present invention.

That is, according to the present invention, a silicon compound having a silicon-halogen atom bond has at least two
Si-M characterized by reacting a zero-valent nickel group transition metal complex coordinated with molecular phosphine
A method for producing a nickel group transition metal complex having a (M: nickel group transition metal) bond is provided.

The reaction in the present invention is represented by the following formula.

In the above formula, M is a nickel group transition metal, X is a halogen atom, L is phosphine, L' is a 2- or 4-electron-bearing ligand other than phosphine, n is an integer of 2 or more, and n' is 0, 1 or 2. shows. Since L and L' are coordinate bonds, the formal oxidation number of MLnL'n' is 0.
In addition, since the bond between M and X and the bond between M and Si are covalent bonds, The formal oxidation number of is 2.

The silicon compound used in the present invention has at least one Si-X (X: halogen atom) bond, and for example, those represented by the following general formula can be used.

In the above formula, R ¹ , R ² and R ³ are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkenyloxy group, and an alkynyloxy group. group, silyl group, or halogen atom. X represents a halogen atom.

Examples of silicon compounds used in the method of the present invention include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylbromosilane, dimethylphenylbromosilane, methyldiphenylbromosilane, benzyldimethylbromosilane, trimethyliodosilane, Examples include vinyldimethylchlorosilane and iodopentamethyldisilane.

The zero-valent nickel group transition metal complex used in the method of the present invention is a complex of nickel, palladium, and platinum, and the ligand constituting the complex may be only phosphines substituted with an organic group, but these phosphines In addition to the above, there may also be two- or four-electron donating ligands such as olefins, dienes, carbon monoxide, etc.

Examples of the phosphines include trimethylphosphine, triethylphosphine, tributylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, and triphenylphosphine. Therefore, examples of the zero-valent transition metal complexes include tetrakis(triethylphosphine)platinum, tris(triethylphosphine)platinum, tetrakis(trimethylphosphine)platinum,
Bis(triethylphosphine)dicarbonylplatinum, bis(triethylphosphine)ethyleneplatinum, tetrakis(trimethylphosphine)palladium, tetrakis(triethylphosphine)palladium, tetrakis(triphenylphosphine)
Examples include nickel.

These zero-valent nickel group transition metal complexes can be prepared not only as complexes, but also in the presence of the phosphine ligand, such as tetracarbonyl nickel, bis(dibenzylideneacetone)palladium, and bis(1,5-cyclooctane). Dien)
This reaction can also be carried out by adding a zero-valent nickel group transition metal complex such as platinum and the phosphine ligand to the reaction system.

The molar ratio of the silicon compound to be subjected to the reaction to the zero-valent nickel group transition metal complex can be arbitrarily selected, but in consideration of the yield regarding the zero-valent nickel group transition metal complex, it is preferably 1 or more.

The present invention can be carried out from -80°C to 300°C, preferably from 0°C to
It is carried out at a reaction temperature of 200°C.

The method of the present invention can be carried out with or without a solvent, but when a solvent is used, silicon compounds or zero-valent nickel group transition metals used as raw materials such as alcohols, primary or secondary amines, carboxylic acids, etc. Commonly used solvents, ie, hydrocarbon solvents such as benzene, toluene, xylene, hexane, decalin, etc., can be used, except for those that can react with the complex.

Separation and purification of the product from the reaction mixture is generally easily accomplished by distilling off excess silicon compounds and then recrystallizing the product.

〔Effect of the invention〕

According to the present invention, various complexes having a silicon-transition metal bond can be provided very easily by directly reacting a wide variety of silicon compounds having a halogen atom with a transition metal complex.

〔Example〕

The present invention will be explained in more detail with reference to Examples.

Example 1 Tris(triethylphosphine) platinum 0.43m
mol, 4 equivalents of trimethylbromosilane in benzene
Trans-trimethylsilyl(bromo)bis(triethylphosphine)platinum was obtained by heating in 0.9ml at 90°C for 4 hours. . Yield from NMR is 93
It was %. The reaction solution was concentrated and recrystallized from pentane to obtain pale yellow needle crystals with a yield of 39%. This compound is a new compound that has not been described in any literature, and its physical properties, spectrum data, etc. are as follows.

Melting point: 58-60℃, IR: 1236, 1038, 840, 768,
742, 618 cm ^-1 , ¹ H-NMR: δ2.56 ~ 1.84 (12H,
m), 1.45-1.02 (18H, m), 0.83, 0.69, 0.55
(1:4:1) (9H, respectively s, J ( ¹⁹⁵ Pt-Si-
C- ¹ H) = 25.2Hz) ppm. Elemental analysis value C ₁₅ H ₃₉ BrP ₂ PtSi Calculated value C; 30.82%, H;, 6.73% Actual value C; 30.80%, H;, 6.80% Example 2 Tetrakis ( triethylphosphine) platinum 0.14
Example 1 After heating 3.8 mmol of trimethylbromosilane in 0.3 ml of benzene at 90°C for 19.5 hours.
processed in the same way. The yield of trans-tremethylsilyl(bromo)bis(triethylphosphine)platinum was 90%.

Example 3 Tris(triethylphosphine) platinum 0.17m
mol, by heating 3.7 equivalents of trimethyliodosilane in 0.3 ml of benzene at 90°C for 1 hour.
According to ¹ H-NMR, trimethylsilyl(iodo)bis(triethylphosphine)platinum was obtained almost quantitatively. The solid obtained by concentrating the reaction solution was recrystallized from pentane to obtain pale yellow needle crystals. This compound is a new compound that has not been described in any literature, and its physical properties, spectrum data, etc. are as follows.

Melting point: 79-80℃, IR: 1234, 1038, 838, 760,
720, 618 cm ^-1 , ¹ H−NMR: δ2.61−1.98 (12H,
m), 1.47−0.97 (18H, m), 0.78, 0.65, 0.52
(1:4:1) (9H, respectively s, J ( ¹⁹⁵ Pt-Si-
C ^-1 H)=23.4Hz)ppm Example 4 Tetrakis(trimethylphosphine)platinum 0.30
mmol, by heating 3.8 equivalents of trimethylbromosilane in 0.4 ml of benzene at 120°C for 18 hours.
According to ¹ H-NMR, trimethylsilyl(bromo)bis(trimethylphosphine)platinum was obtained with a yield of 50%. The reaction solution was concentrated and extracted with benzene, and then pentane was added to the benzene solution to obtain a pale yellow solid. This compound is a new compound that has not been described in any literature, and its spectral data are as follows. ^1H -NMR: δ1.41 (18H, br s), 0.78, 0.63,
0.48 (1:4:1) (9H, respectively s, J ( ¹⁹⁵ Pt-Si
-C ^-1 H) = 27.0Hz) ppm Example 5 Tetrakis(trimethylphosphine)platinum 0.23
By heating 3.5 mmol of trimethyliodosilane in 0.3 ml of benzene at 90°C for 1 hour,
According to ¹ H-NMR, trimethylsilyl(iodo)bis(trimethylphosphine)platinum was obtained with a yield of 90%. After concentrating the reaction solution and extracting with benzene, a pale yellow solid was obtained by concentrating the benzene solution. This compound is a new compound that has not been described in any literature, and its spectral data are as follows. ^1H -NMR: δ1.63 (18H, br s), 0.76, 0.61,
0.46 (1:4:1) (9H, respectively s, J ( ¹⁹⁵ Pt-Si
-C ^-1 H) = 27.0Hz) ³¹ P-NMR: -15.8ppm (J( ³¹ P- ¹⁹⁵ Pt) = 2791
Hz) Example 6 By heating 0.08 mmol of tetrakis(dimethylphenylphosphine)platinum and 3.3 equivalents of trimethyliodosilane in 0.25 ml of benzene at 120°C for 13 hours, trimethylsilyl was produced with a yield of 78% according to ¹ H-NMR. (Iodo)bis(dimethylphenylphosphine)platinum was obtained. After concentrating the reaction solution and extracting with benzene-pentane (v/v=1:1),
A pale yellow solid was obtained by concentrating the extract.
This is a new compound that has not been described in the literature.
The spectrum data was as follows. ^1H -NMR: δ8.02-7.19 (10H, m), 1.90 (12H,
br s), 0.46, 0.33, 0.20 (1:4:1) (9H,
s, J ( ¹⁹⁵ Pt-Si-C ^-1 H) = 23.4 Hz) Example 7 Tris (triethylphosphine) platinum 0.19 m
By heating 3.0 equivalents of dimethylphenylbromosilane in 0.30 ml of benzene at 90°C for 2 hours, dimethylphenylsilyl(bromo)bis(trimethylphosphine)platinum was obtained with a yield of 77% by ¹ H-NMR. was gotten. After concentrating the reaction solution and extracting with pentane, a pale yellow solid was obtained by cooling the pentane solution. This compound is a new compound that has not been described in any literature, and its spectral data are as follows. ^1H -NMR: δ8.10-7.36 (5H, m), 2.30-1.68
(12H, m) 1.45−1.01 (18H, m), 0.99, 0.84,
0.69 (1:4:1) (6H, respectively s, J ( ¹⁹⁵ Pt-Si
-C ^-1 H) = 27.0Hz) Example 8 Tris (triethylphosphine) platinum 0.75m
¹ H by heating 8.5 mol, methyltrichlorosilane equivalents in 0.25 ml of benzene at 90 °C for 15 min.
-NMR showed that dichloromethylsilyl(chloro)bis(trimethylphosphine)platinum was obtained almost quantitatively. By concentrating the reaction solution, a colorless highly viscous liquid was obtained. This compound is a new compound that has not been described in any literature, and its physical property values, spectral data, etc. are as follows. ^1H -NMR: δ2.48-1.96 (12H, m), 1.39-0.97
(18H, m) 1.47, 1.38, 1.29 (1:4:1)
(3H, each s, J ( ¹⁹⁵ Pt-Si-C ^-1 H) = 16.2 Hz) ³¹ P-NMR: 19.0 ppm (J ( ³¹ P- ¹⁹⁵ Pt) = 2512 Hz) Example 9 Tris (triethylphosphine) Platinum 0.06m
md, 1 H by heating 3 equivalents of dichlorodimethylsilane in 0.2 ml of benzene at 120°C for ¹ hour.
-NMR showed that dichlorodimethylsilyl(chloro)bis(trimethylphosphine)platinum was obtained in a yield of 90°C. By concentrating the reaction solution, a pale yellow highly viscous liquid was obtained. This compound is a new compound that has not been described in any literature, and its physical properties, spectrum data, etc. are as follows. ^1H -NMR: δ2.37-1.72 (12H, m), 1.31-0.79
(18H, m) 1.09, 0.97, 0.85 (1:4:1)
(6H, respectively s, J ( ¹⁹⁵ Pt-Si-C ^-1 H) = 21.6 Hz) ³¹ P-NMR: 19.2 ppm (J ( ³¹ P- ¹⁹⁵ Pt) = 2700 Hz Example 10 Tris (triethylphosphine) platinum 0.38m
md, by heating 2.5 equivalents of iodopentamethyldisilane in 0.2 ml of benzene at 90°C for 10 minutes.
Pentamethyldisilyl(iodo)bis(trimethylphosphine)platinum was obtained with a yield of 90%. The reaction solution was concentrated and benzene-pentane (v/v=
After extraction with a ratio of 1:1), the extracted solution was concentrated to obtain a pale yellow solid. This compound is a new compound that has not been described in any literature, and its spectral data are as follows. ^1H -NMR: δ2.62-2.10 (12H, m), 1.47-0.99
(18H, m) 0.90, 0.71, 0.52 (1:4:1)
(6H, each s, J( ¹⁹⁵ Pt-Si-C ^-1 H) = 34.2
Hz), 0.45 (9H, s).

Claims (1)

[Claims] 1 Si-M (M: Nickel group transition metal) characterized by reacting a silicon compound having a silicon-halogen atom bond with a zero-valent Nickel group transition metal complex coordinated with at least two molecules of phosphine.
A method for producing a nickel group transition metal complex having a bond.