JPH02794A - Production of complex of nickel group metal having silicon-transition metal bond - Google Patents

Abstract

PURPOSE:To extremely readily obtain the subject complex by reacting a silicon compound having silicon-halogen atomic bond with a specific complex of nickel group transition metal. CONSTITUTION:(A) A silicon compound [e.g., compound expressed by the formula (R<1>-R<3> are alkyl, cycloalkyl, aryl, etc.; X is halogen), such as silicon tetrachloride or methyltrichlorosilane] having silicon-halogen atomic bond is reacted with a 0 valent complex [e.g., tetrakis(triethylphosphine)platinum or tetrakis(triphenyl-phosphine)nickel] of nickel group transition metal having at least two-molecular coordinated phosphine to provide the aimed complex.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] 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.

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 complex.

(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. . Method (2) uses an alkali metal, which poses operational risks, and method (3) in which silyl transition metal complexes having substituents that can react with alkali metals cannot be produced in principle. However, since alkali metals and highly toxic mercury are used in the production stage of silylmercury, 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 commonly 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 because the reaction is carried out in the presence of a base, silyl transition metal complexes having substituents that can react with bases are , cannot be produced in principle, and the types of substituents and ligands on silicon are also limited to specific ones.

The present inventors have conducted intensive research to solve these problems, and as a result, they have discovered the fact that halosilanes easily react 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 extensive 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 invention has been completed based on the discovery that the following can be obtained.

That is, according to the present invention, SL-M (M: A method for producing a nickel group transition metal complex having a nickel group transition metal (nickel group transition metal) bond is provided.

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

-3i-X + MLnL'n' ■ → -5iMXL2 In the above formula, a nickel group transition metal, X is a halogen atom, L is a phosphine, and L' is 2 or 4 other than phosphine.
Electron donating ligand, n is an integer of 2 or more, n' is 0, 1 or 2, L and L' are coordinate bonds, so MLn
The formal oxidation number of L'n' is O. Also, since the bond between A and X and the bond between A and Si are covalent bonds, -5iM
XL.

The formal oxidation number of is 2.

The silicon compound used in the present invention has at least one 5L-
It has an X (X: halogen atom) bond, and for example, those represented by the following general formula can be used.

1?1 In the above formula, R1, R2 and R3 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,
represents an aryloxy group, an aralkyloxy group, an alkenyloxy group, an alkynyloxy group, a silyl group or a halogen atom; X represents a halogen atom;

Examples of silicon compounds used in the method of the present invention include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, and trimethylbromosilane.

Examples include dimethylphenylbromosilane, methyldiphenylbromosilane, benzyldimethylbromosilane, trimethyliodosilane, 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 ligands constituting the complex may be only phosphines substituted with organic groups, but these phosphines In addition to the above, there may also be two- or four-electron donating ligands such as olefins, dienes, carbon oxides, etc.

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

These zero-valent nickel group transition metal complexes can be prepared not only as complexes but also by tetracarbonyl nickel, bis(
dibenzylideneacetone) palladium, bis(1,5-
A single complex of a zero-valent nickel group transition metal complex such as platinum (cyclooctadiene) and the above-mentioned phosphine ligand can be added to the reaction system.

The molar ratio of the silicon compound to the zero-valent nickel group transition metal complex to be subjected to the reaction can be arbitrarily selected;
Considering the yield for valent nickel group transition metal complexes,
1 or more is preferable.

The present invention can be carried out from -80°C to 300°C, preferably from 0°C to 2°C.
It is carried out at a reaction temperature of 0.000C.

The method of the present invention can be carried out with or without a solvent, but if a solvent is used, alcohol, primary or secondary
Commonly used solvents, i.e., hydrocarbons such as benzene, toluene, xylene, hexane, decalin, etc., except those that can react with silicon compounds or zero-valent nickel group transition metal complexes used as raw materials, such as grade amines and carboxylic acids. A solvent can be used.

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 range 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 0.43 mmol
.

4 equivalents of trimethylbromosilane in 0.9-benzene,
Trans-trimethylsilyl(bromo)bis(triethylphosphine)platinum was obtained by heating at 90°C for 4 hours. The yield was 93% based on NMR.

The reaction solution was concentrated and recrystallized from pentane to obtain pale yellow needle crystals with a yield of 39%. This is a new compound that has not been described in the literature, and its physical properties.

The spectral data was as follows.

Melting point: 58-60°C, IR: 1236.1038.8
40.768.742, 618■-1"H-NMR: δ
2.56-1.84 (12H1m), 1.45-1.0
2 (18H, m), 0.83.0.69.0.55 (1
:4:1) (9H1 each s, J(”'Pt-5i-C
-'H)=25.2Hz)ppm- Elemental analysis value C15H3iBrP2PtSi calculated value
C: 30.82%, H: 6.73% actual value
C: 30.80%, H: 6.80% Example 2 Tetrakis (triethylphosphine) platinum 0.14 mm
ol, 3.8 equivalents of trimethylbromosilane in benzene 0
．． After heating at 90° C. for 19.5 hours in Example 3-3, the sample was treated in the same manner as in Example 1. The yield of trans-trimethylsilyl(bromo)bis(triethylphosphine)platinum is 90%.
Met.

Example 3 Tris(triethylphosphine)platinum 0.17mm+o
l.

3.7 equivalents of trimethyliodosilane and 0.3 m of benzene
'H-N
In MR, trimethylsilyl (iodo) can be detected almost quantitatively.
The solid obtained by concentrating the 0 reaction solution in which bis(triethylphosphine)platinum was obtained 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 and spectral data are as follows.

Melting point near 9-80℃, IR: 1234.1038.83
8.760°720, 61111an-', ”H
-NMR: δ 2.61-1.98 (12H1
Otori), 1.47-0.97 (18H, m), 0.78
．． 0.65.0.52 (1:4:1) (9) 1, 3 each, J("'Pt-5i-C-"H) = 23.4Hz
)ppm Example 4 Tetrakis(trimethylphosphine)platinum 0.30mm
01. 3.8 equivalents of trimethylbromosilane and 0 equivalents of benzene
1 by heating at 120℃ for 18 hours in ゜4mQ
8 NMR shows that trimethylsilyl (
Bromo)bis(trimethylphosphine)platinum was obtained. 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: δ L, 41 (18H, br s), 0
．． 78.0.63.0.48 (1:4: l) (9H
1 each s, J(”'Pt-3i-C-1H) = 27
．． 0Hz) ppm Example 5 Tetrakis(trimethylphosphine)platinum 0.23mm
ol, 3.5 equivalents of trimethyliodosilane to benzene 0
．． 1H by heating at 90℃ for 1 hour in 3d
- According to NMR, trimethylsilyl(iodo)bis(trimethylphosphine)platinum was obtained with a yield of 90%.The reaction solution was concentrated, extracted with benzene, and the benzene 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: δ 1.63 (18H, br s), 0
．． 76, 0.61.0.46 (1:4:1) (9H1 each s, J ("5Pt-5L-C-18) = 27.0H
z)"P-NMR knee 15.8ppm (J("P-1g
SPt)=2791Hz) Example 6 Tetrakis(dimethylphenylphosphine)platinum 0.0
By heating 8 mmol, 3.3 equivalents of trimethyliodosilane in 0.25% of benzene at 120°C for 13 hours, trimethylsilyl(iodo)bis(dimethylphenylphosphine) was obtained with a yield of 78% according to 'H-NMR.
Obtained platinum. The reaction solution was condensed, extracted with benzene-pentane (v/v=1:1), and the extract was concentrated to obtain a pale yellow solid. This compound is a new compound that has not been described in 5 literatures, and its spectral data are as follows.

1H-NMR: δ 8.02-7.19 (IOH, m)
, 1.90 (12H1br s), 0.46.0.33
．． 0.20 (1:4:1) (9H1 each s, J(”5
Pt-5i-C-1H) = 23.4Hz) Example 7 Tris(triethylphosphine)platinum 0.19namo
1, by heating 3.0 equivalents of dimethylphenylbromosilane in 0.30 d of benzene at 90°C for 2 hours.
According to H-NMR, dimethylphenylsilyl(bromo)bis(triethylphosphine)platinum was obtained with a yield of 77%. After concentrating the reaction solution and extracting with pentane, a pale yellow solid was obtained by cooling the pentane solution. This is a new compound that has not been described in the literature, and its spectral data were as follows: 1H″NMRδ 8.1077.36 (5H, m);
2.30-1.68 (12H, m) 1.45-1.
01 (18H, m), 0.99.0.84.0.69 (
1:4:1) (6H1 each s, J("5Pt-5L-
C-18) = 27.0Hz) Example 8 Tris(triethylphosphine)platinum 0.075mmo
1, 8.5 equivalents of methyltrichlorosilane and 0.1 equivalent of benzene.
By heating at 90°C for 15 minutes in 25d, 11
(-NMR shows that dichloromethylsilyl (
A colorless, highly viscous liquid was obtained by concentrating the reaction solution from which chloro)bis(triethylphosphine)platinum 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: 62.48-1.96 (12H, m),
1.39-0.97 (18H1m) 1.47.1.38
．． 1.29 (1:4:1) (3H1 each, J(19
S pi-3i-C-1H)=16.2)1z)' 1
P-NMR: 19, Oppm (J (31P-”
'Pt)=2512Hz) Example 9 Tris(triethylphosphine)platinum 0.06 mmd.

3 equivalents of dichlorodimethylsilane, 0.2ml of benzene
1) 1-
According to NMR, chlorodimethylsilyl(chloro)bis(triethylphosphophine)platinum was obtained with a yield of 90%.

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 and spectral data are as follows.

1H-NMR82,37-1,72(12H,m),1
．． 31-0.79 (18H.

m) 1.09.0.97.0.85 (1:4:1)
(6H1 each s, J(L″5Pt-5i-C-H)=2
1.61(z)′”P-NMR19.2ppm (J(3
1P-”'Pt)=2700Hz) Example 10 Tris(triethylphosphine)platinum 0.38 mmol
, by heating 2.5 equivalents of iodopentamethyldisilane in 0.60°C of benzene at 90°C for 10 minutes.
Pentamethyldisilyl(iodo)bis(
The reaction solution yielding platinum (triethylphosphine) was concentrated, extracted with benzene-pentane (v/v=1:l), and the extract 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: δ 2.62-2.10 (12H-m)
, 1.47-0.99 (18H1m) 0.90.0.7
1.0.52 (1:4:1) (6H1 each s, J(
"5Pt-Si-C-1)1)=34.2)IZ),0
．． 45(9)1. s).

Claims (1)

[Claims] (1) S 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 an i-M (M: nickel group transition metal) bond.