DE10028540A1 - Re-usable transition metal-phosphine complex catalysts for carbon-carbon (especially Suzuki) bond-forming reactions, are obtained by fixing water-soluble chiral and achiral phosphine-metal complexes on mesoporous carriers - Google Patents

Abstract

Transition metal-phosphine complex catalysts comprise a novel mesoporous carrier on which is fixed a water-soluble chiral and achiral phosphine-Group 8 transition metal complexes. Transition metal-phosphine complex catalysts comprise: (A) a variously substituted large-pore mesoporous silicate carrier of Si(OH)y and Al(OH)x units and of incompletely anchored SiO4 tetrahedrons. The inner surfaces of the pores are partly covered with terminal silanol (SiOH) groups. The Si/Al ratio is 1-1,000, the pore wall thickness is 6-30 Angstroms and the pore radius is 30-500 Angstroms in a relatively ordered arrangement of the mesopores without the presence of an intermediate particle volume while the surface is 30-1,300m<2>/g and the pore volume 0.5-2.1ml/g; and (B) fixed to (A) is a water-soluble chiral and achiral phosphine-Group 8 transition metal complexes, the precursors of the catalytically-active components being: (i) a water-soluble Pd compound; (ii) a water-soluble Pd compound and water-soluble phosphines; (iii) a Pd species and water-soluble phosphines; or (iv) a water-soluble phosphine-Pd complex. An Independent claim is also included for the preparation of the catalyst.

Description

The invention relates to a new transition metal-phosphine complex catalyst a mesoporous support, a process for its preparation and its use for the Suzuki C-C couplings in water and multiphase systems.

Mesoporous materials are used as supports for catalysts in liquid phase reactions be used of particular interest. By using such heterogeneous Catalysts have several advantages over homogeneous catalysts. This lie in the simple separation of the catalyst from the starting material or Product phase through z. B. Filtration. In homogeneously catalyzed reactions, one closes e.g. T. elaborate workup to completely remove the catalyst from the surrounding phase to be able to separate. The recovery of a solid catalyst may be a possible one Connect the catalyst to be re-usable if it is not in the reaction was deactivated and cannot be reactivated by post-treatment.

Mesoporous structured materials, whereby in the broader sense here inorganic materials with inner pores are to be understood by hydrothermal synthesis Made using different templates. The templates probably act as Spacers have a space-filling function around which the inorganic framework condenses. After removing the template z. B. by burning out or extraction, is the inner mesoporous system accessible. Such mesoporous materials are e.g. Not at the moment commercially available.

The discovery of a new family of mesoporous silicate materials known as M41S and FSM-16 and related structured mesoporous materials has opened up new opportunities for the support of homogeneous catalysts. They are characterized by a few special features that set them apart from the SiO ₂ carriers that have been used up to now and make them interesting in terms of application. These new properties result from the internal structuring of these materials. The synthesis and application of mesoporous materials made with supramolecular templates was developed by JY Ying, CP Mehnert and MS Wong, Angew. Chem. 1999, 38, 59.

Three ways have been described in the literature for the binding of transition metal-phosphine complexes to silicate materials. One method is also known as SAPC (Surface Aqueous Phase Catalysis) (KT Wan, ME Davis, Nature, 1994, 370, 449). The possibility of anchoring is that the water-soluble phosphine-transition metal complexes are physically adsorbed on the hydrophilic surfaces with -Si (OH) _y species. The transition metal may interact with the OH groups (-Si (OH) _x PdCl ₂ L ₂ ), the phosphine groups with the OH groups or / and the OH groups with the anions of the complex (-Si (OH ) _x [Cl ^- -PdClL ₂ ]).

The second method is to anchor the water-soluble Transition metal-phosphine complexes via a chemical bond. Typical  Anchor groups are e.g. B. phosphines, amines, halides, benzyl halides, formates, Carboxylates, sulfonates, hydroxides, oxides etc.

The third variant is that amphiphilic compounds on the silicate carriers be anchored that are able to aggregate and surface active units to train (N. Flach, Diss. Uni. Rostock, 1996). In these amphiphilized surfaces transition metal-phosphine complexes can be embedded and used in catalytic reactions Multi-phase systems can be used.

The applications of transition metal complex Catalysts known on different support materials. Inorganic carriers such as Oxides, hydroxides, zeolites and silica gels swell in a wide variety of solvents not and are therefore different in a wide range of variations Solvent systems without changing their texture properties and Mass transfer properties applied.

Both inorganic and organic carriers were used for the hydroformylations used [e.g. E.g. R.H. Grubbs, CHEMTECH 1977, 512; C.U. Pittman, Chem. Eng. News 1970, 48, 36; M. Capka, P. Svobota, M. Kraus, J. Hetflejs, Chem. Ind. (London) 1972, 650; P. Panster, S. Wieland in B. Cornils, W.A. Herrmann (Eds.) Applied Homogeneous Catalysis with Organometallic Compounds, VCH, 1997, p. 605].

Publications on the Suzuki Catalytic Reaction Using Supported Palladium Complexes are not known.

Some disadvantages can be seen from the prior art, in particular none satisfactory activity of the complex catalyst present. The selectivity is also often inadequate, whereby by-products result in cleaning steps need to connect. Due to the low catalyst activity, it is also often necessary to high catalyst concentrations can be worked. All of this leads to higher costs.

The object of the present invention is therefore to create a new one To develop a complex catalyst on a mesoporous support, with the help of which the above mentioned disadvantages can be largely overcome, the relatively easy to manufacture and can be used advantageously for the Suzuki reaction and after carrying out the catalysis can be recovered and reused.

This object is achieved according to the invention by a new transition metal-phosphine complex catalyst on a mesoporous support, consisting of a differently substituted large-pore mesoporous silicate support made of Si (OH) _y and Al (OH) _x species, the framework of which is not complete anchored SiO ₄ tetrahedra, the inner surface of the pores is partially covered with terminal silanol groups (SiOH), with an Si / Al ratio of 1 to 1000 and a pore wall thickness between 6 and 30 Å and pore radii between 30 and 500 Å in a relatively ordered arrangement of the mesopores without the presence of an intermediate grain volume at surfaces of 30 to 1300 m ² / g and a pore volume of 0.5 to 2.1 ml / g, on which water-soluble chiral and achiral phosphine-transition metal complexes with metals of eighth subgroup of the periodic table of the elements are fixed, the preliminary stages of the actually catalytically active component duck consists of a water-soluble palladium compound, a water-soluble palladium compound and a water-soluble phosphine, a palladium species and a water-soluble phosphine or directly from a water-soluble phosphine-palladium complex.

Water-soluble phosphines for the catalytic conversion can all chiral and achiral water-soluble phosphines and diphosphines known from the relevant literature, especially sulfoaryl, arylalkyl and alkyl phosphines such as TPPMS, TPPTS, Ph ₂ P (CH ₂ ) ₃ SO ₃ M, Ph ₂ P (CH ₂ ) ₄ SO ₃ M, Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₃ SO ₃ M, Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ M, Men * ₂ P (CH ₂ ) ₄ SO ₃ Li, Ph ₂ P (CH ₂ ) ₂ NHC * H (COOH) CH ₂ SO ₃ H, PhP [(CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ M] ₂ , PhP [ (CH ₂ ) ₂ S (CH ₂ ) ₃ SO ₃ M] ₂ , P [(CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ M] ₃ , P [(CH ₂ ) ₂ S (CH ₂ ) ₃ SO _{3 s} ] ₃ . Ph ₂ PCH ₂ CH [S (CH ₂ ) ₃ SO ₃ Na] ₂ , Ph ₂ PCH ₂ C ₆ H ₄ SO ₃ M (o), where M = H, Li, Na, K.

Palladium compounds are PdCl ₂ (CH ₃ CN) ₂ , PdCl ₂ (C ₆ H ₅ CN) ₂ , [PdCl (COD)] ₂ , Pd ₂ (dba) ₃ and [Pd (Oac) ₂ ] ₂ . The starting materials for rhodium complexes are [Rh (COD) Cl] ₂ , [Rh (Oac) ₂ ] ₂ , Rh (Oac) ₃ , Rh (COD) (acac), RhCl ₃ × n H ₂ O, RhCl (CO) L ₂ and Rh (CO) ₂ (Oac) ₂ . Ni (COD) Cl and Co (acac) ₂ are inexpensive starting compounds for the respective transition metal complexes with the above-mentioned water-soluble phosphines.

According to the invention, the transition metal-phosphine complex is produced catalyst in three steps by first the mesoporous support material prepared, which is then modified, the inner surface of the carrier is functionalized, and then the water-soluble catalytic precursor is anchored active component on the carrier thus treated.

These novel supported complex compounds according to the invention are advantageous for Coupling reactions, especially Suzuki couplings in water and in Multi-phase systems can be used.

Generally speaking, the invention relates to the catalytic action of water-soluble chiral and achiral phosphines fixed in transition metal complexes various substituted mesoporous molecular sieves. Cobalt, nickel, Platinum, rhodium, palladium and ruthenium transition metal complexes. The catalytic Effect is under cocatalysis of surfactants to increase activity and selectivity in C-C formation reactions in water and in multi-phase reactions achieved. The mesoporous molecular sieves are in terms of Si / Al ratio and Pore radii vary between 30 and 500 Å. Particularly large-volume carriers with large ones Pore radii are characterized by the use of polymerized micelles and vesicles Obtain template during carrier manufacture after calcination. The Heterogenization of the complex catalysts is done according to three different Preparation variants made. The catalytic reactions take place in Batch reactors. Preferred coupling reactions are hydroformylations, Suzuki and Heck reactions in the presence of the heterogenized complex catalysts carried out.

Mesoporous materials are used as supports for catalysts that are in liquid phase reaction be used of particular interest. The size range of the pore radii of the Mesopores according to the invention is between 20 and 500 Å. It is therefore significantly larger than that Diameter of larger molecules, even if they are solvated in the liquid phase. Diffusion problems, i. i.e., a hindrance to the delivery and / or removal of the Reactants and reaction products to and from the catalytically active centers, such as them small-pore molecular sieves are not dominant. In addition, relieved  the presence of mesopores also the application of spatially more demanding catalytically active complexes.

The silicate materials according to the invention are distinguished by a relatively orderly arrangement of the mesopores; they are in the particles and do not represent an intermediate grain volume. The wall thicknesses of the pores are 6-30 Å depending on the chosen synthetic route and ensure high thermal stability up to a temperature of 800-900 ° C. It follows from this that both the small-pore and the large-pore mesoporous structured materials have large surfaces of 300 to 1300 m ² / g and large pore volumes of 0.5-2.1 cm ³ / g. The structure of this structured Silkate consists of not fully cross-linked SiO ₄ tetrahedra. The inner surface of the pores is therefore z. T. covered with terminal silanol groups (SiOH). They impart hydrophilic properties to the base material, but also enable active centers to be firmly anchored by way of bond formation through silylation. The Si atoms in the pore walls can also be substituted by other trivalent and tetravalent elements such as Al or Ti. The partial substitution of Si by Al leads to a negative scaffold charge and thus gives the material ion exchange properties and Brønsted acidity.

For the preparation of the mesoporous catalyst matrices, surfactants, polymerized amphiphiles (polysoaps), amphiphatic polymers and hydrophobized water-soluble polymers used. Educts were amphiphilic monomers, both in the contain hydrophilic head and polymerizable groups in the hydrophobic chain and by polymerization to polymeric micellar aggregates with a hydrodynamic Diameter of several hundred Å. The ones made with these templates Support materials have both a particularly high pore volume and large ones Pore diameter. The pore volume and radius were determined by nitrogen adsorption, TEM and XRD images determined.

Polymeric amphiphiles (polysoaps) can be cationic, anionic and nonionic Connections. Poly (methacryloyloxyundecyl trimethyl-ammonium salts) with different anions z. B. halides, carboxylates, Sulfonates or sulfates with molecular weights between 1800 and 6500 g / mol are used. Poly (sodium methacryloyloxydodecanoate) -, Poly (sodium methacryloyloxyoctadecanoate) and poly (sodium undecenyl sulfate) with Molecular weights between 1500 and 3200 g / mol used. Examples of polymers nonionic amphiphiles are poly (undecenyloxy) (polyethylene glycol) monomethyl ether with Molecular weights between 7,500 and 45,000 g / mol, poly (dodecyloxy polyethylene glycol) methacrylic acid ester) with molecular weights between 18,000 and 30,000 g / mol and poly (allyloxy polyethylene glycol) monomethyl ether with molecular weights between 5,600 and 9,000 g / mol. The amphiphatic polymers and hydrophobized water-soluble Polymers can be divided into cationic, anionic, nonionic and zwitterionic Divide connections. As nonionic amphiphatic polymers, poly (N- vinylpyrrolidone) copoly (dodecyl methacrylate) with molecular weights between 30,000 and 45,000 g / mol used. Zwitterionic amphiphatic polymers are in the sense of Invention, for example, poly (methacrylic acid) -co- (dodecyldimethylethyl-ammonium) methacrylate) (molecular weights between 50,000 and 110,000 g / mol) and poly (diallylmethyl-ethoxycarbonylmethyl-ammonium-methylsulfate) -co- (N-alkylmaleinamide acid) sodium salt with molecular weights between 25,000 and 40,000 g / mol. As Anionic amphiphatic polymers were poly (methacrylic acid) -co (sodium methacrylic oyloxydodecanoate) with molecular weights between 70,000 and 150,000 g / mol, poly  (Acrylamide) -co- (N-alkylmaleinamic acid sodium salt) with molecular weights between 30,000 and 70,000 g / mol, poly (N-vinylpyrrolidone) -co- (2-acrylamido-2-methyl-1- sodium propane sulfonic acid) (molecular weights between 20,000 and 30,000 g / mol) and Poly (N-vinyl pyrrolidone) -co- (N-alkyl maleic acid sodium salt) with molecular weights between 15,000 and 25,000 g / mol used. Cationic amphiphatic polymers are quaternized poly (ethyleneimine) (molecular weight of 27,000 g / mol), poly (acrylamide) - co- (diallyldodecylmethyl-ammonium bromide) or hydrogen sulfate) (molecular weights between 20,000 and 40,000 g / mol), poly (acrylamide) -co- (methacryloylundecenyl-trimethyl ammonium salts) (molecular weights between 20,000 and 80,000 g / mol), poly (acrylamide copoly- (N-vinyl-pyridinium) salts (molecular weights between 30,000 and 100,000 g / mol) and poly (acrylamide) -copoly- (ephidrinium methacrylate) (molecular weights between 20,000 and 45,000 g / mol).

The mesoporous supports produced with the aid of the templates used according to the invention have a high pore volume of up to 2.10 ml / g with inner surfaces of up to 1300 m ² / g and average pore radii of 30 to 500 Å, which are determined by known nitrogen adsorption measurements were on. In TEM images, the pores were seen as elongated channels that have sufficient side stabilization.

Several advantages are achieved by the invention. So is the heterogenization of Complex catalysts a simple separation of the catalysts from the starting materials and Products by filtration after the reaction and reuse of the Catalysts have become possible in a new catalytic cycle. Another advantage of Recycling of catalysts is that possible catalyst precursors occur during the reaction can be converted into the actually active catalyst. The so obtained Recycled species can therefore be a more active form. At the same time they are Educt / product mixtures catalyst-free, which simplifies the workup represents and is therefore cheaper.

Another advantage of the invention lies u. a. also in that due to the negative scaffold charge of the carrier, achieved by partial substitution of silicon by aluminum or titanium the possibilities of anchoring the catalytic component also for cationic components Complex is given.

The following examples serve to illustrate the invention, but are not intended to be so restrict.

Embodiments A) Vehicle preparation example 1 Preparation of carrier No. 1

90.1 g of H ₂ O are introduced and 1.24 g of NaOH are dissolved therein. 7.45 g of template (hexadecyltrimethylammonium bromide) are added in portions. 11.65 g of tetraethyl orthosilicate are slowly added dropwise to this batch with rapid stirring, and then 0.55 g of KAl (SO ₄ ) 2 × 12 H ₂ O is added. After stirring for 1 h, the gel is placed in an autoclave for 4 days in a drying cabinet at 100 ° C. After cooling, it is washed several times with H ₂ O until neutral. The product is dried in air and then calcined at 600 ° C for 3 days. The Si / Al ratio is 48.3.

Example 2 Preparation of carrier No. 2

1.4 g of KOH are dissolved in 58.5 g of H ₂ O with stirring. Then 10 g of tetraethyl orthosilicate solution are added dropwise with rapid stirring. Then 11,845 g of template (hexadecyltrimethylammonium bromide) are added and, after stirring for 20 minutes in an autoclave, placed in a drying cabinet at 110 ° C. for 2 days. After cooling, the mixture is washed with H ₂ O until neutral and dried in air.

Example 3 Preparation of carrier No. 3

6.36 g of template (hexadecyltrimethylammonium bromide) are added to 262 g of H ₂ O, with 76.52 g of HCl being added. After stirring for 5 minutes, 1.08 g of AlCl ₃ . 6 H ₂ O dissolved and after stirring for a further 10 min, 27.91 g of tetraethyl orthosilicate were added. After stirring for 2 h, the mixture is rinsed with H ₂ O until the supernatant solution is neutral. The product is dried in air.

Example 4 Preparation of carrier No. 4

21 g of ethanol and 4.2 g of i-propanol are added to 15 g of tetraethyl orthosilicate. 39 mg VOSO ₄ × 3 H ₂ O are dissolved in 10 g H ₂ O and pipetted in quickly. The solution is stirred for 30 minutes. 36 g of H ₂ O and 1.4 ml of 1 M HCl are added to 3.5 g of dodecylamine and stirred for 10 minutes. This solution is added to the batch and stirred for one day. After centrifugation, rinsing is carried out until the solution is neutral and dried in air and calcined at 600 ° C. for 5 hours.

Example 5 Preparation of carrier No. 5

4 g Brij 76 are stirred in 234 g H ₂ O and 24 g HCl _conc. With gentle warming until the solution is homogeneous. 5 g of tetraethyl orthosilicate are added to the cooled solution with stirring and the mixture is stirred at room temperature for 20 h. The product is suctioned off, washed and air-dried. It is then calcined at 550 ° C for 24 h.

Example 6 Preparation of carrier No. 6

8 g EO ₂₀ PO ₇₀ EO ₂₀ , (Pluronic 123), 210 g H ₂ O and 48 g HCl _conc. Are stirred with gentle warming. Then 17.05 g of tetraethyl orthosilicate are added and the mixture is stirred at 35 ° C. for 20 h. Then it is suctioned off and washed until neutral. The product is dried in a drying cabinet at 60-80 ° C. The product is then calcined at 600 ° C.

Example 7 Preparation of carrier No. 7

8.4 g of KOH is dissolved in 351 g of H ₂ O with stirring. 60 g of tetraethyl orthosilicate are added dropwise with rapid stirring and then 71.07 g of template (hexadecyltrimethylammonium bromide) are added in portions. After stirring for 20 minutes, the mixture is placed in the drying cabinet at 110 ° C. for 2 days. After cooling, wash until neutral. Drying takes place in air.

Example 8 Preparation of carrier No. 8

Solution I: 11.6 g of Pluronic 123 are dissolved in 9.0 g of i-butanol while warm. 43 mg of hydrated La (NO ₃

) ₃

added. After dissolution, 2.5 g of aluminum tri-sec butoxide are added and the mixture is stirred at 20 ° C. for 1 h.
Solution II: 0.54 g H ₂

O and 2.5 g of i-butanol are mixed and 0.5 g of ethanol is added. Solution II is added dropwise to solution I with vigorous stirring, with granular Al (OH) ₃

fails and is dissolved by stirring. Then at 45 ° C for 20 h touched. After suction, the product is washed and in the oven for 12 h at 550 ° C calcined.

Example 9 Preparation of carrier No. 9

Solution I: 11.6 g Pluronic 123 are dissolved in 9.0 g 2-butanol while warm. 43.3 mg of hydrated La (NO ₃

) ₃

added. After dissolution, 2.5 g of aluminum tri-sec butoxide are added and the mixture is stirred at 20 ° C. for 1 h.
Solution II: 0.54 g H ₂

O and 2.5 g of i-butanol are mixed and 0.5 g of ethanol is added. Solution II is added dropwise to solution I with vigorous stirring, with granular Al (OH) ₃

fails and is dissolved by stirring. Then at 45 ° C. Stirred for 20 h. After suction, the product is washed and in the oven for 12 h at 550 ° C calcined.

Example 10 Preparation of carrier No. 10

Solution I: Dissolve 1.0 g Pluronic 123 in 9.0 g 2-butanol while warm. 43.3 mg of hydrated La (NO ₃

) ₃

added. After dissolution, 2.5 g of aluminum tri-sec hutylate are added and the mixture is stirred at 20 ° C. for 1 h.
Solution II: 0.54 g H ₂

O and 2.5 g of i-butanol are mixed and 0.5 g of ethanol is added. Solution II is added dropwise to solution I with vigorous stirring, with granular Al (OH) ₃

fails and is dissolved by stirring. Then at 45 ° C for 20 h touched. After suction, the product is washed and in the oven for 12 h at 550 ° C calcined.

Example 11 Preparation of carrier No. 11

4.92 g of 25% tetramethylammonium hydroxide solution (in water) and 2.86 g of Na silicate solution (Fluka) are added to 4.32 g of 100% hexadecyltrimethylammonium chloride and stirred. A total of 2,014 g of Aerosil are added in portions and stirred. Then 10 g H ₂

O added and stirred. The mixture is left to stand at room temperature for 24 h and then with H ₂

O to neutrality washed. The product is dried in air.

Example 12 Preparation of carrier No. 12

12.8 g of a freshly prepared Na aluminate solution are slowly added to 73.6 g of tetraethylammonium hydroxide. 97.92 g of silica sol (30% SiO ₂ ) are introduced and the aluminate solution is added dropwise with rapid stirring. Aluminate solution, aluminum trichloride or aluminum isopropoxide serve as aluminum additive in order to set the desired Si / Al ratios between 5 and 200. After stirring for 5 minutes, 88 g of hexadecyltrimethylammonium chloride solution (in water) are slowly added dropwise and stirring is continued. The batch is placed in the drying cabinet at 116 ° C. for 3 days. The mixture is washed until neutral and dried in air and calcined at 600 ° C for 5 h.

Example 13 Preparation of carrier No. 13

1 g of support No. 12 is stirred three times for 20 min each with 0.6 acetic acid on 200 g of H ₂ O. It is then centrifuged off, washed, dried for one day and then baked at 300 ° C. for 2 hours.

Example 14 Preparation of carrier no.14

0.97 g of support No. 12 are stirred with 0.97 g of HNO ₃ (65%) on 200 ml of H ₂ O in three times for 20 minutes each, centrifuged off, washed and dried for one day and then baked at 300 ° C. for 2 hours.

Example 15 Preparation of carrier no.15

Carrier No. 12 is converted into the NH ₄ ⁺ form, dried and then baked at 450 ° C. for 2 h. The Si / Al ratio is 14.7

Example 16 Preparation of carrier No. 16

1 g of the template poly-ω-undecyl-polyethylene glycol are placed in 50 ml of H ₂ O and stirred at RT until a clear solution is formed. 5 g of tetraethyl orthosilicate are slowly added dropwise and then 0.5 g of Al (NO ₃ ) ₃ × 9 H ₂ O are added. It is stirred for an hour. The solution is placed in a petri dish and placed in a closed container with a dish of NH ₄ Cl solution for 24 h. It is then suctioned off and washed with ethanol. The product is dried in air overnight on absorbent paper.

Example 17 Preparation of carrier no.17

0.96 g of poly-ω-undecyl polyethylene glycol are stirred in 10 g of H ₂ O with gentle heating. 8.8 g of tetraethyl orthosilicate are added to this solution. The mixture is stirred at room temperature overnight and then 20 g of HCl are added and stirring is continued. The product is centrifuged off and washed until neutral. It is dried at 100 ° C. and then left to stand in air for 3 days.

Example 18 Preparation of carrier No. 18

1 g of carrier no. 17 is treated with 30 g of H ₂ O in an autoclave for 3 days at 100 ° C.

B) Modification / functionalization of the inner surface of the carrier Example 19 Silylation with 3-mercaptopropyltriethoxysilane

The calcined carrier is dried in an oven at 200 ° C. for 60 min and cooled to room temperature in a desiccator. 6 g of a 3-mercaptopropyltriethoxsilane / n-heptane solution (concentration: 4 g of 3-mercaptopropyl triethoxsilane in 30 ml of n-heptane or 6 g of 3-mercaptopropyltriethoxsilane in 30 ml of n-heptane) are then added to 2 g of the dried material added to a Teflon autoclave and irradiated in the microwave for 10 min. After cooling, the suspension was washed several times with n-hexane using a frit (pore 3). The powder thus obtained is stirred with excess 30% H ₂ O _{2 for} 24 hours at room temperature. After filtering, the silylated sample is washed with distilled water and ethanol and suction filtered. The residue is hydrolyzed with 5% H ₂ SO ₄ and left to stand for some time. The residue is then washed with distilled water, suction filtered and dried in a drying cabinet at 90 ° C. for 2 h.

Example 20 Silylation with 3-mercaptopropyltriethoxysilane

The calcined carrier is dried in an oven at 200 ° C. for 60 min and cooled to room temperature in a desiccator. 6 g of a 3-mercaptopropyltriethoxsilane / n-heptane solution (concentration: 4 g of 3-mercaptopropyl triethoxsilane in 30 ml of n-heptane or 6 g of 3-mercaptopropyltriethoxsilane in 30 ml of n-heptane) are then added to 2 g of the dried material added to a glass flask and stirred for 120 min at 80 ° C under a helium atmosphere. After cooling, the suspension was washed several times with n-hexane using a frit (pore 3). The powder thus obtained is stirred with excess 30% H ₂ O _{2 for} 24 hours at room temperature. After filtering, the silylated sample is washed with distilled water and ethanol and suction filtered. The residue is hydrolyzed with 5% H ₂ SO ₄ and left to stand for some time. The residue is then washed with distilled water, suction filtered and dried in a drying cabinet at 90 ° C. for 2 h.

Example 21 Silylation with trimethylchlorosilane and 3-mercaptopropyltriethoxysilane

The calcined carrier is dried in an oven at 200 ° C. for 60 min and cooled to room temperature in a desiccator. 5 g of a trimethylchlorosilane / n-heptane solution (concentration: 5 g trimethylchlorosilane in 100 ml n-heptane) and 5 g of a 3-mercaptopropyltriethoxsilane / n-heptane solution (concentration: 4 g 3 -Mercaptopropyltriethoxsilan in 30 ml n-heptane or 6 g 3-mercaptopropyltriethoxsilane in 30 ml n-heptane) added in a Teflon autoclave and irradiated in the microwave for 10 min. After cooling, the suspension was washed several times with n-hexane using a frit (pore 3). The powder thus obtained is stirred with excess 30% H ₂ O _{2 for} 24 hours at room temperature. After filtering, the silylated sample is washed with distilled water and ethanol and suction filtered. The residue is hydrolyzed with 5% H ₂ SO ₄ and left to stand for some time. The residue is then washed with distilled water, suction filtered and dried in a drying cabinet at 90 ° C. for 2 h.

Example 22 Silylation with dimethyldichlorosilane and 3-mercaptopropyltriethoxysilane

The calcined carrier is dried in an oven at 200 ° C. for 60 min and cooled to room temperature in a desiccator. 5 g of a dimethyldichlorosilane / n-heptane solution (concentration: 5 g of dimethyldichlorosilane in 100 ml of n-heptane) and 5 g of a 3-mercaptopropyltriethoxsilane / n-heptane solution (concentration: 4 g of 3 -Mercaptopropyltriethoxsilan in 30 ml n-heptane or 6 g 3- Mercaptopropyltriethoxsilan in 30 ml n-heptane) added in a Teflon autoclave and irradiated in the microwave for 10 min. After cooling, the suspension was washed several times with n-hexane using a frit (pore 3). The powder thus obtained is stirred with excess 30% H ₂ O _{2 for} 24 hours at room temperature. After filtering, the silylated sample is washed with distilled water and ethanol and suction filtered. The residue is hydrolyzed with 5% H ₂ SO ₄ and left to stand for some time. The residue is then washed with distilled water, suction filtered and dried in a drying cabinet at 90 ° C. for 2 h.

Example 23 Silylation with methyltrichlorosilane and 3-mercaptopropyltriethoxysilane

The calcined carrier is dried in an oven at 200 ° C. for 60 min and cooled to room temperature in a desiccator. 5 g of a methyltrichlorosilane / n-heptane solution (concentration: 5 g of methyltrichlorosilane in 100 ml of n-heptane) and 5 g of a 3-mercaptopropyltriethoxsilane / n-heptane solution (concentration: 4 g of 3 -Mercaptopropyltriethoxsilan in 30 ml n-heptane or 6 g 3-mercaptopropyltriethoxsilane in 30 ml n-heptane) added in a Teflon autoclave and irradiated in the microwave for 10 min. After cooling, the suspension was washed several times with n-hexane using a frit (pore 3). The powder thus obtained is stirred with excess 30% H ₂ O _{2 for} 24 hours at room temperature. After filtering, the silylated sample is washed with distilled water and ethanol and suction filtered. The residue is hydrolyzed with 5% H ₂ SO ₄ and left to stand for some time. The residue is then washed with distilled water, suction filtered and dried in a drying cabinet at 90 ° C. for 2 h.

Example. 24th Silylation with 3-aminopropyltrimethoxysilane

The calcined carrier is dried in an oven at 200 ° C. for 60 min and opened in a desiccator Cooled to room temperature. 5 g are then added to 0.5 g of the dried material a 3-aminopropyltrimethoxysilane / n-heptane solution (concentration: 5 g 3- Aminopropyltrimethoxysilane in 100 ml n-heptane) added in a Teflon autoclave and irradiated in the microwave for 10 min. After cooling, the suspension was passed through Using a frit (pore 3) washed several times with n-hexane. The powder thus obtained is dried at 90 ° C for one hour.  

C) Anchoring the catalytically active component All work was done under argon. Example 25

An aqueous solution consisting of 22 mg (0.10 mmol) of Pd (OAc) ₂ and 145 mg (0.357 mmol) was added to dried 1.0 g of carrier, prepared as in Example 12, with an Si / Al ratio of 10.7 ) Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₃ SO ₃ Na in 5.0 ml of water, and magnetically stirred for three hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 26

An aqueous solution consisting of 22 mg (0.10 mmol) of Pd (OAc) ₂ and 196 mg (0.50 mmol) was added to dried 1.0 g of carrier, prepared as in Example 12, with an Si / Al ratio of 118 ) Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ Na in 10 ml of water, and magnetically stirred for three hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 27

An aqueous solution consisting of 99 mg (0.10 mmol) of PdCl ₂ [Ph ₂ P (CH ₂ ) ₂ S () was added to dried 1.0 g of carrier, prepared as in Example 12, with an Si / Al ratio of 59. CH ₂ ) ₂ SO ₃ Na] ₂ in 5.0 ml of water, and magnetically stirred for three hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 28

An aqueous solution consisting of 90 mg (0.10 mmol) of PdCl ₂ [Ph ₂ P (CH ₂ ) _4. Was added to dried 1.0 g of carrier, prepared as in Example 12, with an Si / Al ratio of 14.7 SO ₃ K] ₂ in 10.0 ml of water, and magnetically stirred for three hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 29

An aqueous solution consisting of 22.4 mg (0.10 mmol) of Pd (OAc) ₂ and 72 mg () was added to dried 1.0 g of carrier, prepared as in Example 12, with an Si / Al ratio of 10.7. 0.20 mmol) of Ph ₂ P (CH ₂ ) ₄ SO ₃ K in 5.0 ml of water, and magnetically stirred for three hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 30

An aqueous solution consisting of 326 mg (1.0 mmol) of K ₂ PdCl ₄ and 376 mg (1.0 mmol.) Was added to dried 2.0 g of carrier, prepared as in Example 12, with an Si / Al ratio of 118 ) Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ Na in 10.0 ml of water, and magnetically stirred for three hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 31

1 g of carrier, prepared according to Example 5 and modified according to Example 23, with a pore radius of 20 Å and a sulfonic acid concentration of 0.23 mmol / g, became an aqueous solution consisting of 32.6 mg (0.10 mmol) K ₂ PdCl ₄ and 376 mg (1.0 mmol) of Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ Na in 10.0 ml of water, added and stirred magnetically for 16 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 32

1 g of carrier, produced according to Example 15 and modified according to Example 20, with an Si / Al ratio of 14.7 and a sulfonic acid concentration of 0.50 mmol / g, was converted into an aqueous solution consisting of mg 90 mg (0, 10 mmol) of PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 10.0 ml of water and magnetically stirred for 16 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example No. 33

1 g of carrier, prepared according to Example 15 and modified according to Example 20, with an Si / Al ratio of 14.7 and a sulfonic acid concentration of 0.50 mmol / g, became an aqueous solution consisting of 9.0 mg (0.010 mmol ) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ O ₃ K] ₂ in 5.0 ml of water, and magnetically stirred for 2 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 34

1 g of carrier, prepared according to Example 6 and modified according to Example 24, a pore radius of 40 Å and a sulfonic acid concentration of 0.19 mmol / g, was converted into an aqueous solution consisting of 29.7 mg (0.033 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 5.0 ml of water, and magnetically stirred for 2 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 35

1 g of carrier, prepared according to Example 6 and modified according to Example 24, a pore radius of 40 Å and a sulfonic acid concentration of 0.19 mmol / g, was converted into an aqueous solution consisting of 29.7 mg (0.033 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 5.0 ml of water, and magnetically stirred for 8 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 36

1 g of carrier, prepared according to Example 16 and modified according to Example 24, an average pore radius of 100 Å and a sulfonic acid concentration of 0.17 mmol / g, was converted into an aqueous solution consisting of 29.7 mg (0.033 mmol) PdCl ₂ [ Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 5.0 ml of water, and magnetically stirred for 6 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in vacuo at 80 ° C. for 12 hours.

Example 37

1 g of carrier, prepared according to Example 15 and modified according to Example 20, with an Si / Al ratio of 14.7 and a sulfonic acid concentration of 0.49 mmol / g, became an aqueous solution consisting of 10 mg (0.011 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] in 5.0 ml of water, added and stirred magnetically for 1 hour at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 38

1 g of carrier, prepared according to Example 15 and modified according to Example 20, with an Si / Al ratio of 14.7 and a sulfonic acid concentration of 0.49 mmol / g, became an aqueous solution consisting of 22 mg (0.10 mmol) of Pd (OAc) ₂ and 60 mg (0.15 mmol) of Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ Na in 10.0 ml of water, and magnetically stirred for 16 hours at room temperature. The solvent was removed on a rotary evaporator, dried several times with toluene and then dried in vacuo at 80 ° C. for 12 hours.

Example 39

1 g of carrier, prepared according to Example 3 and modified according to Example 20, with an Si / Al ratio of 118 and a sulfonic acid concentration of 0.60 mmol / g, became an aqueous solution consisting of 10 mg (0.011 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 5.0 ml of water, and magnetically stirred for 1 hour at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 40

1 g of carrier, prepared according to Example 3 and modified according to Example 20, with an Si / Al ratio of 118 and a sulfonic acid concentration of 0.60 mmol / g, became an aqueous solution consisting of 90 mg (0.10 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 10.0 ml of water, added and stirred magnetically for 18 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 41

1 g of carrier, prepared according to Example 1 and modified according to Example 24, with an Si / Al ratio of 59 and a sulfonic acid concentration of 0.58 mmol / g, became an aqueous solution consisting of 10 mg (0.010 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 5.0 ml of water, and magnetically stirred for 3 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in vacuo at 80 ° C. for 16 hours.

Example 42

1 g of carrier, prepared according to Example I and modified according to Example 24, with an Si / Al ratio of 59 and a sulfonic acid concentration of 0.58 mmol / g, became an aqueous solution consisting of 90 mg (0.10 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 10.0 ml of water, and magnetically stirred for 12 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in vacuo at 80 ° C. for 24 hours.

Example 43

1 g of carrier, produced according to Example 1 and modified according to Example 22, with an Si / Al ratio of 59 and a sulfonic acid concentration of 0.83 mmol / g, became an aqueous solution consisting of 10 mg (0.011 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₃ SO ₃ K] ₂ in 5.0 ml of water, and magnetically stirred for 3 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in vacuo at 80 ° C. for 24 hours.

Example 44

1 g of carrier, prepared according to Example I and modified according to Example 22, with an Si / Al ratio of 59 and a sulfonic acid concentration of 0.83 mmol / g, became an aqueous solution consisting of 90 mg (0.10 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] in 10.0 ml of water, and magnetically stirred for 16 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in a vacuum at 80 ° C. for 12 hours.

Example 45

1 g of carrier, prepared according to Example 1 and modified according to Example 21, with an Si / Al ratio of 59 and a sulfonic acid concentration of 1.11 mmol / g, became an aqueous solution consisting of 10 mg (0.011 mmol) of PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] in 5.0 ml of water, and stirred for 3 hours at room temperature magnetically. The yellow solution becomes discolored. It was washed several times with water and then dried in vacuo at 80 ° C. for 24 hours.

Example 46

1 g of carrier, prepared according to Example 1 and modified according to Example 21, with an Si / Al ratio of 59 and a sulfonic acid concentration of 1.11 mmol / g, became an aqueous solution consisting of 90 mg (0.10 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 10.0 ml of water, and magnetically stirred for 16 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in vacuo at 80 ° C. for 16 hours.

Example 47

1 g of carrier, prepared according to Example 1 and modified according to Example 19, with an Si / Al ratio of 59, a pore radius of 30 Å and a sulfonic acid concentration of 0.56 mmol / g, became an aqueous solution consisting of 250 mg (0.70 mmol) cetyltrimethylammonium bromide (CTAB) in 5.0 ml water and then with 90 mg (0.10 mmol) PdCl ₂ [Ph ₂ P (CH ₂ ) ₄ SO ₃ K] ₂ in 5.0 ml water, given and stirred magnetically for 16 hours at room temperature. The yellow solution becomes discolored. It was washed several times with water and then dried in vacuo at 80 ° C. for 48 hours.

D) catalysis Use of the supported transition metal complexes Example 48 General way of working All work was done under argon

3.20 g (13.5 mmol) of p-iodanisole in 15 ml of toluene and 1.83 were placed in a Schlenck flask g (15 mmol) phenylboronic acid or 2.03 g (15 mmol) tolylboronic acid in 15 ml ethanol solved. 11.6 g (45 mmol) were placed in an approximately 100 ml thermostated hydrogenation vessel Sodium carbonate x 10 water and 1.27 g (3.38 mmol) CTAB [p-iodanisole / CTAB = 4] weighed, secured and suspended in 15 ml of water. The p-iodanisole solution and the Phenylboronic acid solution are added, stirred briefly and an initial sample is taken. 100 mg of catalyst, prepared according to Example No. 25 with 0.86% Pd, is added and at 78 ° C intensely magnetically stirred (<1000 rpm). At certain times, if not different after 10, 20, 30, 45, 60, 90, 120, 180, 240, 360, 480, 600 and 1440 min  0.20 ml samples of the organic phase were taken and diluted with 0.80 ml of toluene Dried sodium sulfate and analyzed by gas chromatography (device: HP 68/90; HP 1 Temp.prog: 50 ° C 2 min. 10 ° / min. -260 °).

After the reaction has ended / terminated, the mixture is cooled to RT, if appropriate, the aqueous phase is extracted with toluene or dichloromethane, dried over sodium sulfate, concentrated, the residue is taken up in hexane and concentrated. After the starting material / product mixture has been worked up by column chromatography, analyzes are carried out (GC, MS, GC-MS, NMR, IR).
Yield after 8 hours: 34.5%, after 24 hours: <99% (of which 4.1% 4,4'-dimethylbiphenyl).

Example 49

Use of 100 mg of catalyst, prepared according to Example 38, procedure as in Example 48.
Yield after 1 hour: 13.6%, after 6 hours: <99% (thereof 3.3% 4,4'-dimethylbiphenyl)

Example 50

Reproduction attempt from Example 49
Yield after 1 hour: 12.9%, after 6 hours: <99% (thereof 3.8% 4,4'-dimethylbiphenyl)

Example 51

The supported catalyst was recovered and subjected to a new Suzuki reaction.
Yield after 1 hour: 80.1%, after 6 hours: <99% (no 4,4'-dimethylbiphenyl).

Example 52

Use of 100 mg of catalyst, prepared according to Example 33 with 1.94% palladium, procedure as in Example 48.
Yield after 1 hour: 90.5%, after 8 hours: <99%

Example 53

Use of 100 mg of catalyst, prepared according to Example 32, procedure as in Example 48.
Yield after 1 hour: 51%, after 24 hours: <99%

Example 54

Use of 100 mg of catalyst, prepared according to Example 32 and 0.033 mmol palladium / g, procedure as in Example 48.
Yield after 2 hours: 29.2%, after 24 hours: 55.8%

Example 55

Use of 100 mg of catalyst, prepared according to Example 31 and 0.033 mmol palladium / g, an average pore diameter of 40 Å, procedure as in Example 48.
Yield after 2 hours: 24.8%, after 24 hours: 93%

Example 56

Use of 100 mg of catalyst, prepared according to Example 36 and 0.033 mmol palladium / g, an average pore diameter of 120-200 Å, procedure as in Example 48.
Yield after 24 hours: 23.6%

Example 57

Use of 100 mg of catalyst, prepared according to Example 34 and 0.033 mmol palladium / g, an average pore diameter of 80 Å, procedure as in Example 48.
Yield after 8 hours: 40.5%

Example 58

Use of 100 mg of catalyst, prepared according to Example 43 with 0.28% palladium, procedure as in Example 48.
Yield after 2 hours: 51.8%, after 24 hours: 92%

Example 59

Use of 100 mg of catalyst, prepared according to Example 42 with 1.17% palladium, procedure as in Example 48.
Yield after 2 hours: <99%

Example 60

Use of 100 mg of catalyst, prepared according to Example 40 with 0.48% palladium, procedure as in Example 48.
Yield after 2 hours: <99%

Example 61

Use of 100 mg of catalyst, prepared according to Example 40 with 0.92% palladium, procedure as in Example 48.
Yield after 0.5 hours: 93.9%, after 6 hours: <99%

Example 62

Use of 100 mg of catalyst, prepared according to Example 47 with 0.86% palladium, procedure as in Example 48.
Yield after 1.5 hours: 92.9%, after 8 hours: <99%

Claims (21)

1. transition metal-phosphine complex calyser on a mesoporous support, characterized by a differently substituted large-pore mesoporous silicatic support made of Si (OH) _y and Al (OH) _x species, the framework of which is composed of incompletely anchored SiO ₄ tetrahedra and wherein the inner surface of the pores is partially covered with terminal silanol groups (SiOH), with an Si / Al ratio of 1 to 1000 and a pore wall thickness between 6 and 30 Å and pore radii between 30 and 500 Å in a relatively ordered arrangement of the mesopores without the presence of an intermediate grain volume on surfaces 30 to 1300 m ² / g and a pore volume of 0.5 to 2.1 ml / g, on which water-soluble chiral and achiral phosphine-transition metal complexes are fixed with metals of the eighth subgroup of the periodic table of the elements , the precursors of the actually catalytically active component being composed of a water-soluble palladium compound, e consists in a water-soluble palladium compound and water-soluble phosphines, a palladium species and water-soluble phosphines or directly from a water-soluble phosphine-palladium complex. 2. Process for the preparation of the transition metal-phosphine complex calyser Mesoporous support according to claim 1, characterized in that a first large-volume carrier with large pore radii through the use of polymerized Micelles and vesicles prepared as templates during carrier production and after Calcination is removed, this carrier thus prepared for the functionalization of its inner Surface is modified by means of silylation, and then a water-soluble precursor of catalytically active component in the form of a chiral or achiral phosphine Transition metal complex of metals of the eighth subgroup of the periodic table Elements is fixed. 3. The method according to claim 2, characterized in that polymerized as a template Amphiphiles (polysoaps) are used, the cationic, anionic and nonionic Connections can be. 4. The method according to claim 2 and 3, characterized in that as polymerized Amphiphilic (polysoaps) cationic compounds such as poly (methacryloyloxyundecyl trimethyl-ammonium salts) with various anions such as halides, carboxylates, Sulfonates or sulfates can be used. 5. The method according to claim 2 and 3, characterized in that as polymerized Amphiphilic (polysoaps) anionic compounds such as poly (methacryloyloxydodecanoate) sodium salt), poly (methacryloyloxyoctadecanoate sodium salt) and poly (undecenyl sulfate) sodium salt) can be used. 6. The method according to claim 2 and 3, characterized in that as polymerized Amphiphilic (polysoaps) amphiphatic polymers and hydrophobized water-soluble Polymers as nonionic amphiphatic polymers such as poly (N-vinylpyrrolidone) copoly (dodecyl methacrylate), zwitterionic amphiphatic polymers poly (methacrylic acid) -co- (dodecyldimethylethylammonium methacrylate) and poly (diallylmethylethoxycarbonyl methyl-ammonium-methylsulfate-co-N-alkylmaleinamic acid sodium salt), as anionic amphiphatic polymers poly (methacrylic acid) -co- (methacryloyloxydodecanoate-sodium) and poly (acrylamide) -co- (N-alkylmaleinamic acid sodium salt), poly (N-vinylpyrrolidone) -co- (2-acrylamido-2-methyl-propane sulfonic acid sodium salt) and poly (N-vinylpyrrolidone) -co-  (N-alkylmaleinamic acid sodium salt) as cationic amphiphatic polymers quaternized poly (ethyleneimine), poly (acrylamide) -co- (diallyldodecylmethyl-ammonium) - bromide or bisulfate, poly (acrylamide) -co- (methacryloylundecenyl-trimethyl) ammonium salts), poly (acrylamide) copoly (N-vinyl pyridinium salts) and poly (acrylamide) copoly (ephidrinium methacrylate) can be used. 7. The method according to claim 2 and 6, characterized in that the polymerized Amphiphilic molecular weights between 500 and 200,000, especially between 1000 and 100,000. 8. The method according to claim 2, characterized in that silicon atoms in the Carriers are substituted by trivalent and tetravalent elements such as aluminum or titanium and that Si / Al ratio between 1 and 1000, in particular between 5 and 200. 9. The method according to claim 2 and 8, characterized in that the modification of mesoporous carrier material by silylation such that the inner surface of the Pores are partially covered with terminal silanol groups (SiOH). 10. The method according to claim 2, characterized in that water-soluble phosphine transition metal complexes of the eighth subgroup of the periodic table of the elements are bound by physical adsorption on the Si (OH) _y species. 11. The method according to claim 2, characterized in that water-soluble Transition metal complexes of the eighth subgroup of the Periodic Table of the Elements through the formation of a real chemical bond via anchor groups, such as. B. Phosphines, amines, halides, benzyl halides, formates, carboxylates, sulfonates, Hydroxides. Oxides, preferably sulfonic acids, are fixed. 12. The method according to claim 2, characterized in that anchor groups on the carriers are applied, to which amphiphilic compounds are bound, which aggregate and form surface-active units in which water-soluble phosphine Transition metal complexes are embedded. 13. The method according to claim 2 and 10 to 12, characterized in that water-soluble Transition metal complex compounds directly or after formation from a Transition metal compound of the eighth subgroup of the periodic table of the elements and a water-soluble phosphine can be used as catalyst precursors. 14. The method according to claim 2 and 13, characterized in that water-soluble transition metal complex compounds directly or after formation from a transition metal compound of the eighth subgroup of the Periodic Table of the Elements and a water-soluble phosphine such as TPPMS, TPPTS, Ph ₂ P (CH ₂ ) ₃ SO ₃ M, Ph ₂ P (CH ₂ ) ₄ SO ₃ M, Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₃ SO ₃ M, Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ M, Men. ₂ P (CH ₂ ) ₄ SO ₃ Li, Ph ₂ P (CH ₂ ) ₂ NHC.H (COOH) CH ₂ SO ₃ H, PhP [(CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ M] ₂ , PhP [(CH ₂ ) ₂ S (CH ₂ ) ₃ SO ₃ Na] ₂ , P [(CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ M] ₃ , P [(CH ₂ ) ₂ S (CH ₂ ) ₃ SO ₃ M] ₃ , Ph ₂ PCH ₂ CH [S (CH ₂ ) ₃ SO ₃ Na] ₂ , Ph ₂ PCH ₂ C ₆ H ₄ SO ₃ M (o), where M = H, Li, Na, K are, can be and the transition metal / phosphine ratios should be 1/1 and 1/100, preferably between 1/2 and 1/20. 15. The method according to claim 2 and 13 characterized in that as Transition metal complex compounds of the eighth subgroup of the periodic table of the Elements mainly compounds of nickel, palladium and rhodium for Catalyst precursors are used. 16. The method according to claim 2 and 10 to 14, characterized in that water-soluble Phosphines with various hydrophilic substituents can be used, the one Cause water solubility of the complex compound of more than 1 g / l. 17. The method according to claim 2 and 15, characterized in that water-soluble Phosphines, in which the hydrophilicity by different groups such as hydroxide, phosphate, Phosphonate, sulfate, sulfonate, formate and carboxylate groups, poly (ethoxy) compounds Ammonium compounds, preferably phosphonates, sulfonates and poly (ethoxy) compounds are used, which cause the water solubility of the complex compound. 18. Use of the new transition metal-phosphine complex catalysts according to claim 1 as catalyst precursors for C-C formation reactions. 19. Use according to claim 17, in which the heterogenized complex compounds as Catalyst precursors for the Suzuki reaction in water or in multiphase systems with and can be used without detergents. 20. Use according to claim 17 and 18, in which the heterogenized Complex compounds as catalyst precursors for Suzuki reactions in Multi-phase systems with detergents are used, being surface-active substances cationic, anionic or nonionic compounds can be used. 21. transition metal-phosphine complex catalyst according to claim 1, characterized characterized in that the highly active complex catalyst after carrying out the catalysis is recycled and reused.