JPH09301986A - Production of aluminum-combined ruthenium carbonyl metal cluster-complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain the subject complex useful as an inexpensive catalyst for hydrosilylation by reacting Ru3 (CO)12 with tris-(acetylacetonato) aluminum, etc., in a specific molar ratio of Ru:Au. SOLUTION: Ru3 (CO)12 is reacted with an aluminum compound of the formula Al(X)a (Y)3-b (X is ethyl, ethoxy, propoxy or butoxy; Y is acetylacetonato or a 2-4C alkylacetonato ligand; (a) is 0, 1, 2 or 3) [e.g. tris-(acetylacetonato) aluminum] in the specific molar ratio of Ru:Au in the range of (3:1) to (3:7) to give the objective metal cluster complex having a composition formula of the formula [Ru3 (CO)12 ]x [Al(X)a (Y)3-b ]y (the ratio of x:y is (1:1) to (1:7) and is useful as a catalyst for hydrosilylation.

Description

Detailed Description of the Invention

[0001] BACKGROUND The present invention is useful as a catalyst for the hydrosilylation reaction, a novel ruthenium carbonyl metal cluster complexes, their preparation and use.

The addition reaction of a SiH group to a carbon-carbon bond is known as a hydrosilylation reaction, and is used for crosslinking and chain extension reactions of silicone elastomers or resins. JP-A-62-32156, JP-A-62-955
26, JP-A-3-95266, JP-A-3-20080
7, JP-A-3-277645, JP-A-4-68007,
See WO 90/10037 and the like.

This hydrosilylation reaction requires a homogeneous catalyst added to the reaction system. Heretofore, platinum and rhodium compounds and complexes have been exclusively used as catalysts for this reaction. However, these precious metal catalysts are expensive, and development of inexpensive non-precious metal catalysts is desired.

[0004] cluster catalyst disclosed in the field of recent catalytic chemical of the present invention, i.e. complex catalyst around the same or different metals populations connected by intermetallic bond is attracting attention. Therefore, the inventors examined the catalytic activity of the hydrosilylation reaction of commercially available Ru ₃ (CO) ₁₂ , which is a trinuclear cluster, and showed some activity, but at the target catalyst concentration of 1% or less, No activity comparable to a few ppm of platinum catalyst was obtained.

However, Ru ₃ (CO) ₁₂ and the formula 1: A
l (X) _a (Y) _3-a [wherein, X is ethyl, ethoxy,
Propoxy or butoxy, Y is acetylacetonate or an alkyl acetoacetate ligand having 2 to 4 carbon atoms,
a is 0, 1, 2 or 3. ] And an aluminum compound represented by
It was found that the aluminum composite ruthenium carbonyl metal cluster complex obtained by heating in HF) gives the target catalytic activity.

The aluminum composite ruthenium carbonyl metal cluster complex of the present invention comprises Ru ₃ (CO) ₁₂ and the compound of formula 1 in a Ru: Al molar ratio of preferably 3: 1.
To 3: 7, more preferably 3: 3 to 3: 5, and the reaction is carried out in a solvent.

As the solvent, any solvent which does not adversely influence the reaction may be used. Typical examples of such solvents include THF, methylene chloride and benzene. The reaction temperature may range from about room temperature to about 150 ° C, but if the reaction temperature is low, a long reaction time is required.
For example, at room temperature, it takes about 5 to 10 days, and when THF is used as a solvent and the reaction is carried out under reflux under normal pressure, the reaction is performed.
It takes 0.5 to 3 hours.

The formation of the complex was confirmed by measuring the infrared absorption spectrum of the product. Ru ₃ (C
O) ₁₂ has a stretching vibration of carbonyl group of 2000, 20
Absorption peaks are given at 25 and 2065 cm ^-1 , respectively. On the other hand, the substance obtained by the production method of the present invention newly gave an absorption peak near 1940 cm ⁻¹ on the low wavenumber side.
This demonstrated the formation of the complex and also showed that the metal of the complex was more reduced or more coordinately unsaturated.

The compound of formula 1 is tris- (acetylacetonato) aluminum, bis- (acetylacetonato) isopropoxyaluminum, acetylacetonato-di-isopropoxyaluminum, tris-
(Ethylacetoacetate) aluminum, bis- (ethylacetoacetate) isopropoxyaluminum,
Ethyl acetoacetate-di-isopropoxy aluminum, triisopropoxy aluminum, diisopropoxy-s-butoxy aluminum, triethoxy aluminum, and tri-s-butoxy aluminum are more preferable.

In the ruthenium carbonyl metal cluster complex thus synthesized, a part of the carbonyl ligand can be replaced with an organic ligand containing a hydrocarbon group. The thus obtained cluster complex has improved solubility in an organic solvent, and is more advantageous for use in a hydrosilylation reaction as a homogeneous catalyst.

Examples of the ligand compound which can be used for this purpose include cyclopentadiene, cyclooctadiene, cyclooctatriene, triphenylphosphine and trimethylphosphite.

The substitution can be carried out by heating and refluxing the cluster complex containing only carbonyl as a ligand and the ligand compound in, for example, an organic solvent (for example, an aliphatic or aromatic hydrocarbon solvent). .

Example 1 Ru in 500 ml of THF_Three(CO)₁₂With 6.39 g (10 mmol)
Bis- (acetylacetonato) isopropoxyaluminum
8.58g (30mmol) of Ni was mixed and reacted under reflux for 3 hours.
After cooling, it was cooled to obtain 9.35 g of crystals. Crystal this crystal
It is called A. The infrared absorption spectrum of crystal A is shown in FIG.
Ru_Three(CO)₁₂Compared with the spectrum of
1946 cm of contraction vibration^-1Has a peak in the aluminum
Confirm that the complex ruthenium carbonyl metal complex was formed.
I accepted.

Example 2 Ru in 500 ml of THF_Three(CO)₁₂With 6.39 g (10 mmol)
4.29 g (15 mmol) of triisopropoxyaluminum mixed
The reaction mixture at reflux for 0.5 hours, then at room temperature for 30 days.
Then, 9.72 g of crystals were obtained from this solution. This crystal
It is called crystal B. Measure the infrared absorption spectrum of crystal B
Was. Ru_Three(CO)₁₂C compared to the spectrum of
1940 cm of O stretching vibration^-1The peak of
Generation of um complex ruthenium carbonyl metal complex
It was confirmed.

Example 3 Ru in 500 ml of THF_Three(CO)₁₂With 6.39 g (10 mmol)
Ethyl acetoacetate-di-isopropoxyalumini
13.72 g (50 mmol) of Um was mixed in a reaction vessel equipped with a flow vessel.
After reacting under reflux for 0.5 hour, it was cooled to 11.56 g.
Crystals were obtained. This crystal is called crystal C. Infrared absorption of crystal C
The absorption spectrum was measured. Ru_Three(CO)₁₂Spect of
1935 cm of new CO stretching vibration compared to^-1The peak of
Has occurred, aluminum complex ruthenium carbonyl gold
It was confirmed that a genus complex was formed.

Determination of catalytic activity 4-vinyl-1,2-cyclohexene epoxide 5.5
g and the expression

Embedded image 3.01 g of polymethylhydrogen siloxane of Example 1 was dissolved in 77.4 g of xylene to give crystals A to C and Ru.
Add ₃ (CO) ₁₂ to each of 0.043g, 120 ℃
Was reacted. The reaction rate was traced by measuring the change in the absorbance of the SiH group near 2160 cm ⁻¹ and the change in the absorbance of the vinyl group near 1640 cm ^{−1 in the} reaction solution by FT-IR. The results are shown in Table 1.

[0017]

[Table 1]

From the above, it was revealed that the aluminum-complexed ruthenium carbonyl metal complex of the present invention has a higher catalytic activity for the hydrosilylation reaction than that of Ru ₃ (CO) ₁₂ .

Example 4 5 g of crystals of the carbonyl compound synthesized in Example 1 and 5 g of cyclopentadienyl sodium were mixed with THF500.
The mixture was heated under reflux in ml for 3 hours, cooled and filtered to give crystals. It was confirmed that this product had a part of carbonyl substituted with cyclopentadienyl.

[0020]

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum of crystal A of the present invention.

Claims (8)

[Claims] 1. Ru ₃ (CO) ₁₂ and formula 1: Al (X) _a
(Y) _3-a [wherein X is ethyl, ethoxy, propoxy or butoxy, Y is acetylacetonate or 2 carbon atoms]
To alkyl acetoacetate ligands, a is 0,
It is 1, 2 or 3. ] The compound of [] is mixed in a molar ratio of Ru: Al in the range of 3: 1 to 3: 7 and the reaction is carried out, and the method for producing a metal cluster complex. 2. The method for producing a metal cluster complex according to claim 1, wherein the reaction is carried out in a solvent. 3. The compound of formula 1 is tris- (acetylacetonato) aluminum, bis- (acetylacetonato) isopropoxyaluminum, acetylacetonato-di-isopropoxyaluminum, tris- (ethylacetoacetate) aluminum. , Bis- (ethylacetoacetate) isopropoxyaluminum, ethylacetoacetate-di-isopropoxyaluminum,
Triisopropoxy aluminum, diisopropoxy-
The method for producing a metal cluster complex according to claim 1 or 2, which is selected from the group consisting of s-butoxyaluminum, triethoxyaluminum, and tri-s-butoxyaluminum. 4. Ru ₃ (CO) ₁₂ and a compound of formula 1
The method for producing a metal cluster complex according to claim 1, wherein the reaction is carried out in a molar ratio of u: Al of 3: 3 to 3: 5. 5. [Ru ₃ (CO) ₁₂ ] _x [Al (X)
_a (Y) _3-a ] _y (In the formula, X is ethyl, ethoxy, propoxy or butoxy, Y is acetylacetonate or an alkylacetoacetate ligand having 2 to 4 carbon atoms, and a is 0, 1, 2 or Or 3), wherein the x: y ratio is 1: 1 to 1: 7.
Is a metal cluster complex. 6. The ratio of x: y is 1: 3 to 1: 5,
The metal cluster complex according to claim 5. 7. A part of the carbonyl ligand of the metal cluster complex according to claim 5 or 6 is selected from the group consisting of cyclopentadiene, cyclooctadiene, cyclooctatriene, triphenylphosphine and trimethylphosphite. A metal cluster complex substituted with at least one compound. 8. A catalyst for hydrosilylation reaction, which comprises the metal cluster complex according to any one of claims 5 to 7.