PL166376B1 - The method of obtaining heterogeneous complex catalysts - Google Patents

Abstract

A method for obtaining heterogenized complex catalysts of general formula 1, wherein R is -C6H4CH2 or -C8H4, M is a transition metal such as Rh, Ru, Pt, Pd, Ir, Co and Ni, L is an easily replaceable ligand such as a carboxyl, phosphine, olefin, amine group or a solvent molecule such as acetylnitrile or benzonitrile, n is an integer from 1 to 6, and Y is a polymer support such as a chloromethylated or brominated copolymer of styrene and divinylbenzene, polyvinyl chloride, copolymers of vinyl chloride with other monomers such as divinylbenzene, chlorinated polypropylene, poly(parabromostyrene), brominated polybutadiene, most preferably a chloromethylated copolymer of styrene and divinylbenzene, poly(parabromostyrene), polyvinyl chloride and brominated polybutadiene. polybutadiene, characterized in that the chelate ligand of general formula 2, wherein R has the meaning given above, is metallated with a 1: 1 complex of n-butyllithium with N,N,N,N-tetraethylenediamine, using equimolar amounts of substrates in ether solvents, most preferably tetrahydrofuran, at a temperature of 18 - 70°C for 4-8 hours, and then, after completion of the metallation reaction, with the obtained metalated ligand of general formula 3,

Description

The subject of the invention is a process for the preparation of heterogenized complex catalysts of general formula I, in which R is -C eH 4 CH 2 or -C eH 4, M is a transition metal, such as Rh, Ru, Pt, Pd, Ir, Co and Ni, L is easily exchangeable ligand like carboxyl, phosphine, olefin, amino or solvent molecule like acetyl nitrile or benzonitrile, n is an integer 1-6 and Y is a polymer support like chloromethylated or brominated styrene-divinylbenzene copolymer, polyvinyl chloride, chloride copolymers of vinyl with other monomers such as divinylbenzene, chlorinated polyethylene, chlorinated polypropylene, poly (parabromostyrene), brominated polybutadiene, most preferably chloromethylated styrene-divinylbenzene copolymer, poly (parabromostyrene), polyvinyl chloride and brominated polybutadiene.

There are known methods for the preparation of heterogenized complex catalysts, which consist, inter alia, in the exchange of ligands of the homogeneous complex into chemical ligands bound to the carrier or in the in situ reaction of the complexes from appropriate precursors, most often dimers, the bridge structure of which is broken by the action of ligands bound to the substrate. These methods are described in the monographs edited by P. Hodge and D. C. Sherrington, "Polymer-Supported Reactions in Organic Synthesis", Chichester, 1980, and F. R. Hartley, "Supported Metal Complexes," Dorchrecht, 1985.

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The described methods lead to obtaining a new generation of complex catalysts deposited on supports, which combine the best features of homogeneous catalysts, such as high activity and selectivity, and the ease of separating them from reaction products, which is characteristic of heterogeneous catalysts. The disadvantage of these systems is the low bond durability of the metal complex - polymer support, which is manifested by the detachment of the metal ion from the substrate and its loss. This disadvantage can be reduced by the use of chelate ligands, for example bis-phosphine ligands, however, it is associated with a reduction in catalytic activity.

The method of obtaining heterogenized complex catalysts of general formula I, in which all symbols have the above-mentioned meanings, according to the invention, consists in that a chelate ligand of general formula 2, in which R is as defined above, is subjected to metalation with a 1: 1 n complex. -butyllithium with N, N, N, N-tetramethylethylenediamine, using equimolar amounts of starting materials in ether solvents, most preferably tetrahydrofuran, at 18-70 ° C for 4-8 hours. After completion of the reaction, with the obtained metallated ligand of general formula 3, in which R 'is CaH 3 CH 2 or CeH 3, and M' is an alkali metal Li, Na, K, most preferably Li, the functionalization of a halogen-containing polymer support of the general formula is performed 4. The method of claim 4, wherein X is a halogen atom and Y is as defined above by treating the polymer support suspended in tetrahydrofuran twice with the halogen concentration with an excess of freshly prepared metallated ligand at 60-65 ° C for 6-8 hours. The functionalized support was then filtered off and washed several times with tetrahydrofuran, water, methanol and benzene, and then dried under reduced pressure. As a result of this reaction, a polymer-immobilized chelate ligand of the general formula 5, in which R and Y are as defined above, is obtained, and in which both donor functions are chemically linked to the substrate, to which a metal complex solution of the general formula 6 is then added dropwise. in which M, L and n are as defined above, followed by heterogenization in an organic solvent in the form of aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, ketones, ethers, alcohols or their mixtures, at a temperature of 20-80 ° C for 2-418 hours. After completion of the heterogenization reaction, the supported complex catalyst is filtered off, extracted with a suitable solvent in a Soxhlet apparatus and dried in vacuo.

In the method of the invention, the binding of the metal complex takes place using chelate ligands with mixed aminophosphine donor functions, of which the stronger phosphine holds the metal ion on the support during the catalytic cycle, while the weaker amine frees up the site for substrate coordination, which increases the stability of the metal complexes on the support without fear of elution of the metal ion into the solution and lowering the activity of the catalyst.

The catalysts obtained by the process of the invention are used in hydrogenation, hydrosilylation, hydroformylation, carbonylation, dimerization, olefin oligomerization and other reactions.

The method according to the invention is illustrated by the following limiting examples.

Example I. To 0.4 g of o- (diphenylphosphino) -N, N-dimethylbenzylamine dissolved in 5 ml of dry and freshly distilled tetrahydrofuran, trade name THF, 0.2 ml of tetramethylethylenediamine, trade name TMEDA and 1 ml of 15% were added with stirring. butyllithium in hexane. The reaction mixture turned dark red immediately, was stirred for 6 hours at room temperature and then left overnight. The metallated ligand was obtained and used directly for the next polymer support functionalization reaction, all reactions carried out under nitrogen.

To 1 g of a polymer, which is a cross-linked copolymer of styrene, chloromethylstyrene and divinylbenzene, containing 2.22% of Cl swollen in 5 ml of dry tetrahydrofuran, was added dropwise a double excess of the chlorine content of a freshly prepared lithiated ligand solution. The reaction mixture was stirred and heated for 8 hours at 65-70 ° C. After another 8 hours of stirring at room temperature, the polymer support beads were filtered and washed with tetrahydrofuran, water, methanol and benzene and dried in vacuo. A chelate ligand containing support was obtained which contained 1.79% Cl and 0.65% P.

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Subsequently, the obtained product was subjected to a heterogenization reaction, and for this purpose, a benzene solution in 40 mg of di-p-chlorotetracarbonyldyrodium was added dropwise to 1 g of the product suspended in benzene at room temperature. The mixture was refluxed for 6 hours and then left overnight at room temperature. The colorless solution was poured over the polymer beads and extracted with boiling benzene. The yellow product was filtered off and dried under reduced pressure. A complex heterogenized rhodium catalyst was obtained which contained 1.8% by weight of rhodium.

Example II. An acetone solution of 70 mg of bis (acetonitrile) dihloroplatinum was added dropwise to 1 g of the support containing the chelate ligand prepared as in Example 1, suspended in acetone. The mixture was refluxed for 4 hours, then the light yellow product was filtered off, extracted with acetone in a Soxhlet apparatus and dried under reduced pressure. A complex heterogenized platinum catalyst was obtained containing 3.2% by weight of platinum.

Example III. To 1 g of the support containing the chelate ligand, obtained as in Example 1, suspended in benzene, 77 mg of bis (benzonitrile) dichloropalladium in benzene solution was added dropwise, and the heterogenization reaction was carried out as in Example I. A complex heterogenized palladium catalyst containing 1.9 % by weight of palladium.

Example IV. To 0.7 g of o- (diftnylphosphino) -N, N-dimethylaniline dissolved in 5 ml of dry and freshly distilled tetrahydrofuran was added 0.45 ml of TMEDA and 2.4 ml of 15% butyllithium in hexane with stirring. The reaction mixture, which turned instantly dark red, was stirred for 8 hours at the reflux temperature of tetrahydrofuran, ie 65 ° C, then left overnight. After completion of the reaction, the metallated ligand was obtained and used directly for the polymer support functionalization reaction.

To 1 g of brominated polybutadiene containing 52.3% bromine in 10 ml of THF was added dropwise a 1.5-fold excess over the bromine content of a freshly prepared solution of the above-obtained metallated ligand. The mixture was heated with stirring for 10 hours and then left overnight. The precipitate was then filtered off, washed with THF, methanol, water, methanol and benzene and dried under reduced pressure. A carrier was obtained which contained 45.8% by weight of bromine and 6.1% by weight of phosphorus.

A solution of 115 mg of dicarbonylchloro-o-diphenylphosphine-N, N-dimethylaniliniride, IrCl (CO) -oP (CeHs) ₂ CH 3 H 4 N (CH 3) 2 in chloride was added dropwise to 1 g of the carrier obtained above, suspended in methylene chloride. methylene. The mixture was heated to the reflux temperature of the solvent 40 ° C for 6 hours and left to stand overnight. The product was then filtered, extracted with boiling methylene chloride in a Soxhlet apparatus and dried under reduced pressure. An iridium complex catalyst containing 3.2% iridium was obtained.

ExampleV. 53 mg of ruthenium trichloride trihydrate dissolved in an ethanol / water mixture was added dropwise to 1 g of the carrier prepared as in Example 4, suspended in ethyl alcohol. The mixture was heated at 50 ° C with constant stirring until the color of the solution disappeared completely. The product was then extracted with ethanol and dried under reduced pressure. A heterogenized ruthenium catalyst containing 1.8% of ruthenium was obtained.

Example VI. To 1 g of the carrier, obtained as in Example 4, suspended in methylene chloride, 156 mg of bis-N-dimethylanilino-dichlororutene, RuCl2 [-o-P (C6H5) 2C6H4N (CH3) 2] 2 in methylene chloride was added dropwise. The next step was as in Example 4. A heterogenized ruthenium catalyst containing 1.9% ruthenium was obtained.

Example VII. 77 mg of bis (benzonitrile) dichloropalladium dissolved in benzene were added dropwise to 1 g of the carrier prepared as in Example 1, swollen in benzene. The solution was stirred for 8 hours at room temperature and then left overnight. The further procedure was as in Example 1. A heterogenized palladium catalyst containing 1.7% Pd was obtained.

Example VIII. 68 mg of octacarbonyldicobalt dissolved in benzene was added dropwise to 1 g of the carrier prepared as in Example 1, swollen in benzene. The next step was as in Example VII. A heterogenized cobalt catalyst containing 0.9% Co was obtained.

PiCeHsh

-R “ML _n

N (CH ₃ ) ₂ formula 1

P (C ₆ H ₅ )

R

Ń (CH ₃ ) ₂ formula 2

Υ-Χ formula 4

P (C ₆ H _s ) ₂ M'-R '

Ń (CH ₃ ) ₂ formula 3

P (C ₆ H ₅ ) ₂

-R ML _n

Ń (CH ₃ ) ₂ formula 6 formula 5

Publishing Department of the UP RP. Circulation of 90 copies. Price PLN 1.00.

Claims (1)

Patent claim A method for the preparation of heterogenized complex catalysts of general formula I, in which R is -C eH 4 CH 2 or -CeH 4, M is a transition metal like Rh, Ru, Pt, Pd, Ir, Co and Ni, L is an easily exchangeable ligand, like a carboxyl, phosphine, olefin, amino group or a solvent molecule like acetyl nitrile or benzonitrile, n is an integer from 1 to 6 and Y is a polymer support like a chloromethylated or brominated copolymer of styrene and divinylbenzene, polyvinyl chloride, copolymers of vinyl chloride with other monomers such as divinylbenzene, chlorinated polypropylene, poly (parabromostyrene), brominated polybutadiene, most preferably a chloromethylated copolymer of styrene and divinylbenzene, poly (parabromostyrene), polyvinyl chloride and brominated polybutadiene, characterized in that the chelate ligand of the general formula R above is meaning, subjected to metallation with 1: 1 n-butyllithium complex with Ν, Ν, Ν, Ν-tetraethylenediamine, using equimolar amounts of substro in ethereal solvents, most preferably tetrahydrofuran, at a temperature of 18-70 ° C during 4-8 hours, then after completion of the metallation reaction, the obtained metallated ligand of general formula 3, where R 'is -C eH 3 CH 2 or -C eH 3 and M' is an alkali metal, such as Li, Na, K, most preferably Li, a functionalization reaction of the halogen-containing polymer support of the general formula IV is carried out in which X is a halogen atom and Y is as defined above by treating the polymer support suspended in tetrahydrofuran twice with an excess of the metalated ligand in relation to the halogen concentration. at 60-65 ° C for 6-8 hours, then the functionalized support is filtered off and washed several times with tetrahydrofuran, water, methanol and dried, and then the obtained polymer-immobilized chelate ligand of general formula 5, in which R and Y are as defined above, a solution of a metal complex of the general formula 6 in which M, L and n are as defined above is added dropwise and subjected to heterogenization in an organic solvent in ref. aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, ketones, ethers, alcohols or their mixtures, at a temperature of 20-80 ° C for 2-418 hours, and after the heterogenization reaction is completed, the complex catalyst deposited on the carrier is filtered off, and extracted with a suitable solvent in in a Soxhlet apparatus and dried under reduced pressure.