EP4267591A2 - Composés organométalliques - Google Patents

Composés organométalliques

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Publication number
EP4267591A2
EP4267591A2 EP21835767.1A EP21835767A EP4267591A2 EP 4267591 A2 EP4267591 A2 EP 4267591A2 EP 21835767 A EP21835767 A EP 21835767A EP 4267591 A2 EP4267591 A2 EP 4267591A2
Authority
EP
European Patent Office
Prior art keywords
tert
compound
radicals
phosphine
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21835767.1A
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German (de)
English (en)
Inventor
Angelino Doppiu
Ralf Karch
Eileen Woerner
Andreas RIVAS NASS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore AG and Co KG
Original Assignee
Umicore AG and Co KG
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Publication date
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Publication of EP4267591A2 publication Critical patent/EP4267591A2/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage

Definitions

  • Pd(I) dimer di- ⁇ -bromo-bis(tri-tert-butylphosphine)dipalladium( I) [Pd( ⁇ -Br)(PtBu 3 )] 2
  • pi-allylpalladium chloride complexes Homoleptic palladium(0) complexes of the [Pd(phosphine) 2 ] type are generally synthesized by reacting [Pd( ⁇ 3 -C 3 H 5 )-( ⁇ 5 -C 5 H 5 )] with the free phosphine.
  • the Pd(0) compound [(tBu 3 P)Pd(dvds)] was obtained in 66 % yield.
  • the authors state that in a solution of the Pd(0) complex [(tBu 3 P)Pd(dvds)], ligand redistribution occurs to form [Pd(PtBu 3 ) 2 ] and [Pd(dvds) 2 ].
  • the above processes for preparing heteroleptic Pd(0) complexes having the general formula [Pd(dvds)(phosphine)] are disadvantageous due to the use of relatively expensive palladium precursors and/or because an excess of the diolefin dvds is required and in some Cases as a further solvent diethyl ether is used.
  • the desired Pd(I) dimer is only obtained in low yield (18 %), making this route unsuitable for large-scale production.
  • the Schoenebeck group describes two comproportionation reactions in which the palladium(0) compound [Pd(P(iPr)(tBu) 2 ) 2 ] reacts either with PdI2 or with CuI to form the complex [Pd( ⁇ -I)(P(iPr )(tBu) 2 ] 2.
  • EP 2726202 A1 discloses a process for preparing [Pd( ⁇ -Br)(PtBu 3 )] 2 which also makes use of a comproportionation reaction.
  • the palladium(II) compound PdBr 2 and the palladium(0) compound [Pd(PtBu 3 ) 2 ] are converted into the desired target compound in an aliphatic or aromatic solvent.
  • PdBr 2 is subject to an aging process during storage over a longer period of time. Therefore, in a preferred embodiment of this method, an additional step is carried out before the above-mentioned reaction, namely the activation of PdBr 2 by treatment, z. B. dispersing in a solvent. Depending on the degree of activation of PdBr 2 , yields in the range from 70% to almost 90% are achieved. A disadvantage of this process is the additional expenditure of time, money and resources required by the activation of the starting material PdBr 2 . In addition, it cannot be ruled out that the end product contains traces of PdBr 2 .
  • the [Pd( ⁇ -Br)(PtBu 3 )] 2 complex is prepared using a mixture of [PdBr 2 (diolefin)] and PtBu 3 in a solvent in the presence of an alkali metal hydroxide.
  • NBD 2,5-norbornadiene
  • COD 1,5-cyclooctadiene
  • both [PdBr 2 (COD)] and [PdBr 2 (NBD)] are difficult to handle.
  • the compounds must be stored under an inert gas atmosphere at low temperatures.
  • Another disadvantage is that these starting materials are prepared from the respective chlorine derivative by halogen substitution with potassium bromide.
  • the target compound [Pd( ⁇ -Br)(PtBu 3 )] 2 can be contaminated by organic residues from the respective diolefin-containing starting material, which is disadvantageous in particular with regard to use as a catalyst or precatalyst.
  • Another way to prepare [Pd( ⁇ -Br)(PtBu 3 )] 2 is the autocatalytic oxidative addition of bromobenzene to [Pd(PtBu 3 ) 2 ].
  • WO 2018/073559 A1 describes, among other things, a process for the preparation of [Pd( ⁇ -Br)(PtBu 3 )] 2 which comprises reacting [Pd(diolefin)X2] or PdX2 in the absence of a base, where X is a halide.
  • ⁇ -Allylpalladium chloride complexes can be obtained both from Pd(II) and Pd(0) by reaction with an organic substance containing at least one double bond.
  • Preparation of the complexes via transmetalation can be effected via reaction of palladium(II) halides or acetates.
  • ⁇ -Allylpalladium chloride complexes can also be obtained by insertion of palladium(0) into allyl halides.
  • This reaction can generally be performed using tris(dibenzylideneacetone)dipalladium(0) ([Pd 2 (dba) 3 ]) or palladium(II) chloride together with a reducing agent such as carbon monoxide/water (Dent, WT; Long, R. ; Wilkinson, AJ, J. Chem.
  • the object of the invention is therefore to overcome these and other disadvantages of the prior art and to provide a process with which homoleptic Pd(0)-phosphine complexes can be prepared in high purity and good yield simply, reproducibly and comparatively inexpensively are.
  • the purity of these compounds should meet the requirements placed on catalyst compounds.
  • a method is to be provided with which heteroleptic Pd(0) complexes which have a phosphine ligand and a dvds ligand can be produced in high purity and good yield in a simple, reproducible and comparatively inexpensive manner.
  • the purity of these Pd(0) compounds should in particular meet the requirements placed on catalyst compounds.
  • new homoleptic Pd(0)-phosphine complexes and heteroleptic Pd(0) complexes which have a phosphine ligand and a dvds ligand are to be provided, which are suitable as catalysts, in particular for organic coupling reactions.
  • the present invention is based on the object of providing a method available with which simple, reproducible and comparatively inexpensive compounds of the general formula [Pd ( ⁇ -X) (PR A R B R C )] 2 in high purity and good yield can be produced. In particular, the purity of these compounds should meet the requirements placed on catalyst compounds.
  • new compounds of the type [Pd( ⁇ -X)(PR A R B R C )] 2 are to be made available, which are suitable as catalysts, in particular for organic coupling reactions.
  • new ⁇ -allylpalladium halide complexes are to be provided which are suitable as catalysts, in particular for organic coupling reactions.
  • the object is achieved by a process for preparing a compound of the general formula [PdZ A Z B ] (I), where the phosphine ligands ZA and Z B are independently selected from the group consisting of tri-tert-butylphosphine (PtBu 3 ), di-tert-butyl(iso-propyl)phosphine (P(iPr)tBu 2 ), tert-butyl-di-(iso-propyl)phosphine (P(iPr) 2 tBu), 1-adamantyl-di-( tert-butyl)phosphine (P(1-Ad)tBu 2 ), di(1-adamantyl)-tert-butylphosphine (P(1-Ad) 2 tBu), 1-adamantyl-di-(iso-propyl)phosphine ( P(1-Ad)iPr 2 ), di(1-adamant
  • a mononuclear or multinuclear palladium compound in particular a palladium(0) compound, where at least one palladium center carries a ligand LS which is an organosilicon compound, and ii.
  • each of a phosphine ligand Z A and Z B where Z A and Z B are independently selected from the group consisting of tri-tert-butylphosphine (PtBu 3 ), di-tert-butyl(iso-propyl)phosphine (P(iPr)tBu 2 ), tert-butyl-di- (iso-propyl)phosphine (P(iPr) 2 tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu 2 ), di(1-adamantyl)-tert-butylphosphine (P (1-Ad) 2 tBu), 1-adamantyl-di-(iso- propyl)phosphine (P(1-Ad)iPr 2 ), di(1-adamantyl)-iso-propylphosphine (P(1-Ad) 2 ),
  • organosilicon compound also called organosilicon compound, means an alkyl or aryl derivative of silicon having one or more Si-heteroatom bonds selected from the group consisting of Si-C bonds, Si-N bonds , Si-O bonds. Apart from the semi-metal silicon, the molecular formula of the organosilicon compound contains no metals or semi-metals, i.e. only non-metals.
  • the organosilicon compound can also be a mixture of several different organosilicon compounds. For example, it can be a mixture consisting of different siloxanes. Alternatively, the organosilicon compound can also comprise a siloxane and a silazane, for example, or consist of these two organosilicon compounds.
  • the palladium compound to be made available in step A. which is in particular a palladium(0) compound, can be mononuclear or multinuclear, in particular dinuclear, as a monomer or oligomer, in particular dimer, or as a solvent adduct.
  • the phosphine ligands Z A and Z B can each independently be mono- or bisphosphine ligands.
  • Solid, liquid, solution or suspension are provided, advantageously as a solution in one or more aromatic hydrocarbons, eg. B. toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures and combinations thereof.
  • aromatic hydrocarbons eg. B. toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures and combinations thereof.
  • the target compounds of the type [PdZ A Z B ] (I) are obtained in high purity, in particular in high NMR purity, advantageously free from ether, and in a satisfactory yield. In most cases, the yields achieved are at least comparable with the values given in the literature. Due to the use of a non-ethereal solvent, contamination of the end products in the form of traces of oxygen (in the ppm range), in particular from oxygen-containing solvents such as ethers, can be largely ruled out.
  • the target compounds of the type [PdZ A Z B ] (I) do not contain impurities due to palladium-containing by-products, such as [Pd(dvds)PtBu 3 )], which are difficult or impossible to separate, in particular due to their solubility behavior or contained only in traces ( ⁇ 1000 ppm).
  • the high purity of the end products according to formula I is in view of possible uses such. B. as catalysts, especially in coupling reactions, particularly advantageous.
  • palladium(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane [Pd 2 ( dvds ) 3 ]
  • Pd(dvds) Pd(vs)
  • Pd-VS palladium-VS--can be used as starting material.
  • both the provision of the palladium compound in step A. and the reaction in step B. can take place without the addition of an olefin, for example an alkene or polyene.
  • polyene means in particular a diene, for example a 1,6-diene.
  • the ligand LS is an organosilicon compound.
  • the ligand LS contains at least one terminal, in particular vinylic, double bond. It is even more advantageous if the ligand LS contains two terminal double bonds.
  • the ligand LS is a cyclic or a non-cyclic siloxane.
  • the ligand LS is a cyclic or a non-cyclic siloxane which is selected from the group consisting of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3, 3-Tetramethyl-1,3-dithien-2-yldisiloxane, 1,1,3,3-Tetramethoxy-1,3-divinyldisiloxane, 1,3-dimethyl-1,3-divinyldisiloxanediol and 2,4,6,8- Tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane.
  • the ligand LS is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane.
  • the palladium compound to be made available in step A. can then be, for example, palladium(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane ([Pd 2 (dvds) 3 ]).
  • a molar ratio of palladium: phosphine ligand Z A and a molar ratio of palladium: phosphine ligand Z B is, independently of one another, at least 1.0:1.0, for example 1.00:1.05 or 1.00: 1.10 or 1.00:1.15 or 1.00:1.20 or 1.00:1.25 or 1.00:1.30 or 1.00:1.35 or 1.00:1, 40 or 1.00:1.45 or 1.00:1.50, especially 1.0:1.0 respectively.
  • the solvent SC can also be a solvent mixture.
  • the solvent or solvent mixture SC includes or is in particular a solvent selected from the group consisting of aromatic hydrocarbons, ketones, z. acetone, and alcohols, e.g.
  • the at least one aromatic hydrocarbon can be selected, for example, from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.
  • the process can generally be carried out at reaction temperatures of 0°C to 50°C, in particular 15°C to 45°C or 20°C to 30°C.
  • the reaction times can be 10 minutes to 48 hours, in particular 1 hour to 36 hours or 2 to 24 hours or 3 to 12 hours.
  • Fu catalyst of the following formula (I.1) can usually be obtained in yields of usually more than 90%, often more than 97%, in particular more than 99%, ie practically quantitatively :
  • a molar ratio of palladium:phosphine ligand Z A is at least 1.0:2.0, for example 1.00:2.05 or 1.00:2.10 or 1.00:2.15 or 1.00:2, 20 or 1.00 : 2.25 or 1.00 : 2.30 or 1.00 : 2.35 or 1.00 : 2.40 or 1.00 : 2.45 or 1.00 : 2.50, in particular 1.0:2.0.
  • the palladium compound is prepared in step A.
  • a palladium(II) compound which consists in particular of a palladium(II) cation and two monovalent anions or a divalent anion
  • a ligand LS which is an organosilicon compound, in particular a cyclic or a non-cyclic siloxane
  • the expression "generated/prepared in situ” or “in situ generation/preparation” means that the starting materials which are required for the synthesis of a compound to be prepared in this way are present in a suitable stoichiometry in a solvent or Solvent mixture are reacted and the resulting product is not isolated.
  • reaction container and reaction vessel are used synonymously in connection with the present invention and are not limited to a volume, a material composition, an equipment or a shape.
  • Suitable reaction vessels are e.g. B. glass flasks, glass-lined reactors, stirred tank reactors, pressure vessels, tubular reactors, microreactors and flow reactors.
  • a neutral ligand such as B. COD is not provided. Consequently, inexpensive, commercially available palladium(II) compounds, such as PdCl 2 , can advantageously be used.
  • the palladium(II) compound to be used as starting material in the above-mentioned in situ preparation has two identical monovalent anions which are selected in particular from the group consisting of halides and monovalent weakly coordinating anions.
  • the term "weakly coordinating” also includes the expressions "very weakly coordinating" and "moderately strongly coordinating”.
  • Chloride, bromide or iodide can advantageously be used as halide anions, particularly advantageously chloride or bromide, in particular chloride.
  • the monovalent weakly coordinating are in particular perfluorinated anions such.
  • bases means inorganic and organic bases, in particular inorganic bases, but not organometallic bases. The bases should not decompose in water. Suitable bases are e.g. B. Salts of Bronsted acids. Carbonates, bicarbonates, acetates, formates, ascorbates, oxalates and hydroxides are advantageously used.
  • the solvent SC and the solvent SD are miscible or identical. Then there is no need to change the solvent, which is particularly advantageous from an economic and ecological point of view.
  • two solvents are referred to as miscible if they are miscible at least during the respective reaction, ie are not present as two phases.
  • a further variant of the method claimed here provides for the addition of a precipitation reagent before and/or during and/or after step B., advantageously during and/or after step B., in particular after step B.
  • the precipitating reagent is advantageously a polar solvent which is miscible with the reaction medium from step B., in particular the solvent SC.
  • the polar solvent is an alcohol, e.g. B. selected from the group consisting of methanol, ethanol and iso-propanol, and mixtures thereof.
  • a step C. is carried out, which comprises isolating the compound prepared in step B.
  • preparation means a solution, a suspension, a dispersion or a gel.
  • the preparation can therefore be in the form of a solution, suspension, dispersion or gel, in particular depending on the non-ethereal solvent present and/or the compound of the formula I present.
  • the solvent can also be a mixture of solvents.
  • the solvent comprises or is a solvent which is miscible or identical to the solvent SC used within the context of the solvent.
  • the isolation comprises a filtration step and/or decanting and/or centrifuging.
  • the aforementioned measures can also be carried out several times.
  • one or more filtrations over a cleaning medium such as. B. activated carbon, or silica, z. B. Celite ® , take place.
  • the filtrate, centrifugate or decantate or the solid can be subjected to the purification and/or isolation steps that may be provided and can be carried out quickly and without any particular preparative effort.
  • the isolation of the compound according to the general formula [PdZ A Z B ] (I) may include further process steps, such as. B.
  • the end product can still contain residues of solvents or, for example, impurities from the starting materials.
  • Isolated compounds of the type [PdZ A Z B ] (I) have a purity of at least 97%, advantageously more than 97%, in particular more than 98% or 99%.
  • the reproducible yield is usually ⁇ 50%, particularly depending on the choice of starting materials and the solvent or solvent mixture—even in the case of upscaling to an industrial scale.
  • the object is also achieved by a compound of the general formula [PdZ A Z B ] (I), obtained or obtainable by a process for preparing such compounds according to one of the exemplary embodiments described above, with the exception of the compounds [Pd(P(iPr )tBu 2 ) 2 ] and [Pd(P(1-Ad)tBu 2 ) 2 ].
  • the palladium(0) compounds of the general formula [PdZ A Z B ] (I) can also be mononuclear or multinuclear, in particular dinuclear, as a monomer or oligomer, in particular dimer, or as a solvent adduct.
  • the compound contained therein according to the general formula [PdZ A Z B ] (I) or the preparation itself is in particular obtained or obtainable by a process for preparing such a compound according to one of the exemplary embodiments described above.
  • the silicon content, which is present in particular in the form of the at least one organosilicon compound is ⁇ 100 ppm and ⁇ 1000 ppm, advantageously ⁇ 110 ppm and ⁇ 900 ppm, in particular ⁇ 120 ppm and ⁇ 800 ppm.
  • the silicon content which is present in particular in the form of the at least one organosilicon compound, can be determined using analytical methods which are known to the person skilled in the art, in particular using quantitative 1 H-NMR spectroscopy and/or atomic emission spectrometry with inductively coupled plasma Inductively Coupled Plasma-Atomic Emission Spectrometers (ICP-AES).
  • the preparation contains a, in particular non-ethereal, solvent SZ.
  • the preparation can be in the form of a solution, suspension, dispersion or gel, in particular depending on the organosilicon compound contained and/or the solvent S Z used.
  • the solvent SZ can also be a solvent mixture.
  • alkanes aromatic hydrocarbons and polar solvents selected from the group consisting of alcohols, alkanes, ketones, ethers or combinations thereof, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, aromatic hydrocarbons having 6 to 9 carbon atoms, ethers with 4 to 8 carbon atoms or ketones with 2 to 6 carbon atoms or mixtures thereof.
  • polar solvents selected from the group consisting of alcohols, alkanes, ketones, ethers or combinations thereof, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, aromatic hydrocarbons having 6 to 9 carbon atoms, ethers with 4 to 8 carbon atoms or ketones with 2 to 6 carbon atoms or mixtures thereof.
  • the solvent SZ comprises or is a solvent which is selected from the group consisting of aromatic hydrocarbons, ketones, e.g. acetone, and alcohols, e.g. B. methanol, ethanol or isopropanol, and mixtures thereof, the preparation is in the form of a solution or suspension.
  • the at least one aromatic hydrocarbon can be selected, for example, from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.
  • Another variant of the preparation provides that the solvent SZ is miscible or identical to the solvent SC, which is used in the process for preparing the compound of the formula I.
  • the at least one organosilicon compound contains at least one terminal, in particular vinylic, double bond.
  • the at least one organosilicon compound comprises or is a cyclic or a non-cyclic siloxane.
  • the preparation contains in addition to the palladium compound according to the general formula [PdZ A Z B] (I) at least one palladium compound according to the general formula [LSPdZ] (II) and/or at least one palladium compound according to the general Formula [Pd(LS) 2 ] (III), where - the ligand LS is in particular identical to the at least one organosilicon compound, in particular a cyclic or a non-cyclic siloxane, and wherein the at least one organosilicon compound contains at least one terminal double bond, and - Z is selected from the group consisting of tri-tert- butylphosphine (PtBu 3 ), di-tert-butyl(iso-propyl)phosphine (P(iPr)tBu 2 ), tert-butyl-di-(iso-propyl)phosphine (P(iPr) 2 tBu), 1-adamantyl
  • the ligand LS is identical to the organosilicon compound, the ligand LS being in particular a cyclic or a non-cyclic siloxane which has at least one terminal, in particular vinylic, double bond. Then the ligand LS is advantageously coordinated or bonded via at least one pi bond to the palladium center of the compound of the general formula [LSPdZ] (II) or [Pd(LS) 2 ] (III).
  • one of the organosilicon compounds comprises or is a cyclic or a non-cyclic siloxane and/or one of the ligands LS is a cyclic or a non-cyclic siloxane, which is selected from the group consisting of 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-Tetramethyl-1,3-dithien-2-yldisiloxane, 1,1,3,3-Tetramethoxy-1,3- divinyldisiloxane, 1,3-dimethyl-1,3-divinyldisiloxanediol and 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane.
  • one of the organosilicon compounds comprises or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds) and/or one of the ligands LS is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds ).
  • one of the organosilicon compounds and/or one of the ligands is LS dvds.
  • the object is achieved by new compounds of the general formula [PdZ A Z B ] (I), where Z A and Z B are independently selected from the group consisting of 1,2-bis (diphenylphosphino) ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp).
  • Z A and Z B are independently selected from the group consisting of 1,2-bis (diphenylphosphino) ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp).
  • These compounds can be used, for example, as catalysts, in particular as catalysts in palladium-catalyzed cross-coupling reactions.
  • L is a phosphane ligand and compounds according to the general formula IV are excluded, in which L is selected from the group consisting of tri-tert-butylphosphine (PtBu 3 ), di-tert-butyl(iso-propyl)phosphine (P(iPr )tBu 2 ), tert-butyl-di-(iso-propyl)phosphine (P(iPr 2 )tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu 2 ), Di (1-adamantyl)-tert-butylphosphine (P(1-Ad) 2 tBu), 1-adamantyl-di-(iso-propyl)phosphine (P(1-Ad)iP
  • a mononuclear or multinuclear palladium compound in particular a palladium(0) compound, where at least one palladium center carries a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane ligand, and ii.
  • phosphine ligand L a phosphine ligand L, with the exception of phosphine ligands selected from the group consisting of tri-tert-butylphosphine (PtBu 3 ), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu 2 ), tert-butyl-di- (iso-propyl)phosphine (P(iPr 2 )tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu 2 ), di(1-adamantyl)-tert-butylphosphine (P (1-Ad) 2 tBu), 1-adamantyl-di-(iso-propyl)phosphine (P(1-Ad)iPr 2 ), di(1-adamantyl)-iso-propylphosphine (P(
  • step A. Reaction of the palladium compound and the phosphine ligand L from step A. in a non-ethereal solvent SE , and C. optional isolation of the compound prepared in step B. according to the general formula [LPd(dvds)] (IV).
  • the palladium compound to be made available in step A. which is in particular a palladium(0) compound, can be mononuclear or multinuclear, in particular dinuclear, as a monomer or oligomer, in particular dimer, or as a solvent adduct.
  • the provision of the palladium compound in step A. and the reaction in step B. take place without the addition of an olefin, for example an alkene or polyene.
  • polyene means in particular a diene, for example a 1,6-diolefin.
  • the phosphane ligand may be provided as a solid, liquid, solution or suspension, particularly as a solution in one or more aromatic hydrocarbons, e.g. B. toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.
  • the phosphine ligand L - is a tertiary phosphine according to the general formula P-R10R20R30, where R10 and R20 are independently selected from the group consisting of substituted and unsubstituted straight-chain alkyl radicals, substituted and unsubstituted branched alkyl radicals, substituted and unsubstituted cycloalkyl radicals, substituted and unsubstituted aryl radicals, and substituted and unsubstituted heteroaryl radicals, wherein the heteroatoms are selected from the group consisting of sulfur, nitrogen and oxygen, and R30 is defined as R10 and R20 or is a metallocenyl radical, or - selected from the group consisting of 2-(Dicyclohexylphosphino)-2'-(N,N-dimethylamino))-1,1'-biphenyl (Dave
  • R10 and R20 can independently be substituted and unsubstituted branched or straight-chain alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec -butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl or stearyl, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or adamantyl, or aryl groups such as phenyl, naphthyl or anthracyl.
  • alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec -butyl, tert-buty
  • the alkyl groups of the tertiary phosphine according to the general formula P-R10R20R30 can be optionally substituted with one or more substituents such as halide (F, Cl, Br or I) or alkoxy groups, e.g. B. methoxy, ethoxy or propoxy.
  • the aryl groups can be optionally substituted with one or more (e.g. 1, 2, 3, 4 or 5) substituents such as halide (F, Cl, Br or I), straight-chain or branched alkyl groups (e.g.
  • C 1 -C 10 alkyl alkoxy (eg C 1 -C 10 alkoxy), straight-chain or branched (dialkyl)amino groups (eg C 1 - C 10 dialkylamino), heterocycloalkyl (eg C3 - C 10 heterocycloalkyl groups such as morpholinyl and piperadinyl) or trihalomethyl (eg trifluoromethyl).
  • Suitable substituted aryl groups include, but are not limited to, 4-dimethylaminophenyl, 4-methylphenyl, 3,5-dimethylphenyl, 4-methoxyphenyl, and 4-methoxy-3,5-dimethylphenyl.
  • R10 and R20 of the tertiary phosphane are linked together according to the general formula P-R10R20R30 and form a ring structure with the phosphorus atom, in particular a four- to seven-membered ring.
  • R10 and R20 are the same and are tert-butyl, cyclohexyl, phenyl or substituted phenyl groups.
  • R10 and R20 are tert-butyl.
  • R10 and R20 may independently be alkoxy (e.g., C 1 - C 10 alkoxy) or aryloxy (e.g., C 1 - C 10 aryloxy).
  • R30 is defined like R10 and R20, but can also be a metallocenyl radical. In the latter embodiment, R30 is a substituted or unsubstituted metallocenyl group. The metallocenyl group has a first cyclopentadienyl radical and a second cyclopentadienyl radical.
  • a number p of radicals R40 can optionally be provided on the first cyclopentadienyl radical via which the tertiary phosphine according to the general formula P-R10R20R30 is bonded or coordinated to the palladium center, and a number q of radicals R41 can optionally be provided on the second cyclopentadienyl radical be.
  • R40 and R41 are independently organic groups having 1 to 20 carbon atoms.
  • R40 and R41 can, independently of one another, be defined like R10 and R20.
  • p can have the values 0, 1, 2, 3 or 4 and q can have the values 0, 1, 2, 3, 4 or 5.
  • q 5 and R41 is methyl or phenyl.
  • p 0.
  • R10 is methyl or phenyl and R10 and R20 are tert-butyl (QPhos), or R10 and R20 are tert-butyl and R30 is 4-dimethylaminophenyl (AmPhos), or R10 and R20 are tert-butyl and R30 is phenyl.
  • R10, R20 and R30 are the same and 1-adamantyl, 2-adamantyl, phenyl, orthotolyl, cyclohexyl, tert-butyl, or R10 and R20 are 1-adamantyl or 2-adamantyl and R30 is n-butyl.
  • a large number of compounds according to the general formula IV can be prepared by means of the process described here in a relatively simple and inexpensive manner and reproducibly in high purity, in particular in high NMR purity, advantageously ether-free and in satisfactory yield.
  • the palladium(0) complex compounds [Pd(PCy 3 )(dvds)], [Pd(PiPr 3 )(dvds)], [Pd (P(1-Ad) 2 Bu)(dvds)] and [Pd(P(tBu 2 )iPr)(dvds)] in yields of ⁇ 50 %, e.g. T.
  • a molar ratio of palladium: phosphine ligand L is at least 1.0: 1.0, for example 1.00: 1.05 or 1.00: 1.10 or 1.00: 1.15 or 1.00: 1 .20 or 1.00 : 1.25 or 1.00 : 1.30 or 1.00 : 1.35 or 1.00 : 1.40 or 1.00 : 1.45 or 1.00 : 1.50 , especially 1.0:1.0.
  • the solvent SE can also be a solvent mixture.
  • the solvent or solvent mixture SE includes or is in particular a solvent selected from the group consisting of aromatic hydrocarbons, ketones, z.
  • the palladium compound in step A is selected, for example, from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.
  • the palladium compound in step A is selected, for example, from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.
  • a palladium (II) compound which in particular from a palladium (II) - cation and two anions
  • a ligand LS which is an organosilicon compound, in particular a cyclic or a non-cyclic siloxane
  • base prepared in situ in a solvent SF.
  • bases means inorganic and organic bases, in particular inorganic bases, but not organometallic bases. The bases should not decompose in water. Suitable bases are e.g. B. Salts of Bronsted acids.
  • Carbonates, bicarbonates, acetates, formates, ascorbates, oxalates and hydroxides are advantageously used. These can be used in the form of their ammonium salts (Brönsted acid)NR 4 , where R is, for example, H or alkyl, alkali metal salts, for example sodium or potassium salts, and alkaline earth metal salts.
  • R is, for example, H or alkyl
  • alkali metal salts for example sodium or potassium salts
  • alkaline earth metal salts alkaline earth metal salts.
  • the solvent SE and the solvent SF are miscible or identical. Then there is no need to change the solvent, which is particularly advantageous from an economic and ecological point of view.
  • two solvents are referred to as miscible if they are miscible at least during the respective reaction, ie are not present as two phases.
  • a step C. is carried out, which comprises isolation of the compound prepared in step B. according to the general formula [LPd(dvds)] (IV): - as a preparation, which comprises a compound according to the general formula [LPd(dvds)] (IV) and a non-ethereal solvent, or - as a substance, advantageously as a solid.
  • the preparation can be in the form of a solution, suspension, dispersion or gel, in particular depending on the non-ethereal solvent present and/or the compound of the formula [LPd(dvds)] (IV) present.
  • the solvent can also be a mixture of solvents.
  • the solvent comprises or is a solvent which is miscible or identical to the solvent SE used within the framework of the solvent.
  • the preparation is then usually in the form of a solution or suspension.
  • the isolation comprises a filtration step and/or decanting and/or centrifuging. The aforementioned measures can also be carried out several times.
  • one or more filtrations over a cleaning medium such as. B. activated carbon, or silica, z. B. Celite ® , take place.
  • the filtrate, centrifugate or decantate or the solid can be subjected to the purification and/or isolation steps that may be provided and can be carried out quickly and without any particular preparative effort.
  • the isolation of the compound according to the general formula [LPd (dvds)] (IV) may include further process steps, such as. B. reducing the volume of the mother liquor, ie concentration, z. B. by means of "bulb-to-bulb", the addition of a solvent and / or a solvent exchange to achieve a precipitation of the product from the mother liquor and / or to remove impurities and / or starting materials, crystallization, sublimation, washing, e.g. B. with an alcohol such as ethanol, methanol or iso-propanol, and mixtures thereof, and drying the product.
  • the aforementioned Steps can each be provided in different orders and frequencies.
  • the purification and/or isolation of the target compound according to the general formula [LPd(dvds)] (IV) is relatively simple and inexpensive.
  • the end product can still contain residues of solvents or, for example, impurities from the starting materials.
  • Isolated compounds of the type [LPd(dvds)] (IV) have a purity of at least 97%, advantageously more than 97%, in particular more than 98% or 99%.
  • the reproducible yield is usually ⁇ 50%, in some cases ⁇ 60%, particularly depending on the choice of starting materials and the solvent or solvent mixture—even in the case of upscaling to an industrial scale.
  • the palladium(0) compounds of the general formula [LPd(dvds)] (IV) claimed here, obtained or obtainable by a process according to one of the further Embodiments described above can be used, for example, as catalysts, in particular as catalysts in palladium-catalyzed cross-coupling reactions. They are advantageously suitable as catalysts for the reactions specified below.
  • L is a phosphine ligand and compounds according to the general formula IV are excluded, in which L is selected from the group consisting of tri-tert-butylphosphine (PtBu 3 ), tri-iso- propylphosphine (PiPr 3 ), trimethylphosphine (PMe 3 ), tricyclohexylphosphine (PCy 3 ), tris-o- tolylphosphine (P(o-tolyl) 3 ), triphenylphosphine (PPh 3 ), di-tert-butyl (iso-propyl)phosphine (P(iPr)tBu 2 ), tert-butyl-di-(iso-propyl)phosphine (P(iPr) 2 tBu), 1-adamantyl-di-(tert-butyl)phosphine (P (1-A),
  • the phosphine ligand L - is a tertiary phosphane according to the general formula P-R10R20R30, where R10 and R20 are independently selected from the group consisting of substituted and unsubstituted straight-chain alkyl, substituted and unsubstituted branched-chain alkyl, substituted and unsubstituted cycloalkyl, substituted and unsubstituted aryl, and substituted and unsubstituted heteroaryl, wherein the heteroatoms are selected from the group consisting of sulfur, nitrogen and oxygen, and R30 is defined as R10 and R20 or is a metallocenyl radical, or - selected from the group consisting of 2-(
  • the ligand L is di-(1-adamantyl)-n-butylphosphine ( cataCXium® A) and the compound has the formula
  • the object is also achieved by a preparation containing i. a compound according to the general formula [LPd(dvds)] (IV) and ii. in addition to the palladium compound according to the general formula [LPd(dvds)] (IV), the palladium(0) compound [Pd 2 (dvds) 3 ].
  • the compound according to the general formula [LPd(dvds)] (IV) or the preparation itself is in particular obtained or obtainable by a process for the preparation of such a compound according to one of the embodiments described above.
  • the preparation contains a, in particular non-ethereal, solvent SZ.
  • the preparation can be in the form of a solution, suspension, dispersion or gel, in particular depending on the solvent SZ present and/or the solvent present.
  • the solvent SZ can also be a solvent mixture.
  • alkanes aromatic hydrocarbons and polar solvents advantageously selected from the group consisting of alcohols, alkanes, ketones, ethers or combinations thereof, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, aromatic hydrocarbons having 6 to 9 carbon atoms, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, or mixtures thereof.
  • the solvent SZ comprises or is a solvent which is selected from the group consisting of aromatic hydrocarbons, ketones, e.g. acetone, and alcohols, e.g. B. methanol, ethanol or isopropanol, and mixtures thereof, the preparation is in the form of a solution or suspension.
  • the at least one aromatic hydrocarbon can be selected, for example, from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.
  • the preparation contains a compound according to the formula
  • R A , R B and R C are independently selected from the group consisting of tert-butyl, iso-propyl and 1-adamantyl and - the bridging atoms X are independently bromine (Br) or iodine (I), with the exception of Compounds [Pd ( ⁇ -Br) (PiPr 3 )] 2 and [Pd ( ⁇ -I) (PiPr 3 )] 2 , comprising a reaction of a mononuclear or multinuclear palladium compound, in particular a palladium (0) compound, wherein at least one Palladium center carries a ligand LS, which is an organosilicon compound, the ligand LS being in particular a cyclic or a non-cyclic siloxane, with i.
  • a phosphine ligand according to the general formula PR A R B R C , where R A , R B and R C are independently selected from the group consisting of tert-butyl, iso-propyl and 1-adamantyl, the phosphine ligand PiPr 3 being excluded , and ii. a transition metal-free oxidizing agent whose empirical formula contains bromine (Br) or iodine (I) in a solvent SA.
  • organosilicon compound has already been defined above.
  • the reaction scheme shown below exemplifies the sequence of the first process claimed here for the preparation of complex compounds of the type [Pd( ⁇ -X)(PR A R B R C )] 2 (VII), starting from a mononuclear or multinuclear Palladium compound in which at least one palladium center carries a ligand LS which is an organosilicon compound.
  • the palladium(0) compound [Pd 2 (dvds) 3 ] present in a dinuclear form in the solid is provided as the mononuclear or multinuclear palladium compound.
  • the Pd(0) complex [Pd 2 (dvds) 3 ] reacts with the phosphine ligand PtBu 3 to give the homoleptic palladium(0) complex [Pd(PtBu 3 ) 2 ] and [Pd 2 (dvds) 3 ] implemented.
  • the transition-metal-free oxidizing agent is added, the empirical formula of which contains bromine (Br), which reacts with the [Pd 2 (dvds) 3 ] contained in the reaction mixture to form PdBr 2 .
  • PdBr 2 is thus advantageously generated in situ.
  • the preparation of the analogous bromine compound of the following formula is also possible: It is surprisingly particularly advantageous here to add the solution of bromine to a mixture containing phosphine and [Pd 2 (dvds) 3 ] in order to obtain this complex. If phosphine becomes a mixture containing 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0) - abbreviated as [Pd 2 (dvds) 3 ], [Pd(dvds)], Pd( vs), Pd-VS or palladium-VS - and bromine are added, this complex is obtained in a slightly lower, but still satisfactory, yield.
  • the object is also achieved by a second process for preparing a compound of the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) where - R A , R B and R C are independently selected from the group consisting of tert-butyl, iso-propyl and 1-adamantyl, and - the bridging atoms X are independently bromo (Br) or iodo (I), comprising a Reaction of a palladium(II) compound, with the exception of palladium(II) halides, with i.
  • HBr Hydrogen bromide
  • HI hydrogen iodide
  • organosilicon compound has already been defined above.
  • first method and “second method” - for the preparation of complexes of the type [Pd( ⁇ -X)(PR A R B R C )] 2 (VII ) are particularly advantageous compared to the methods of the prior art described above.
  • both bromine and iodine derivatives of the formula VII can be prepared with them, in good yields and purities.
  • the methods are also based on a comproportion reaction. However, this advantageously takes place between a palladium(0) compound and sufficiently reactive PdBr 2 or PI 2 generated in situ, which is reacted completely or almost completely in each case.
  • Activation of the PdBr 2 or PdI2 can therefore be dispensed with.
  • Unreacted PdBr 2 or PI 2 can be quantitatively separated off simply by filtration, decantation and/or centrifugation and then—after a washing step that can be provided if necessary—recycled.
  • the starting materials required for the processes claimed here are easy to handle, and in particular can be stored for several months or longer without observing aging or decomposition processes.
  • the starting materials used are advantageously easy and relatively inexpensive to obtain.
  • the manufacturing processes described here are simple and can be carried out under mild conditions.
  • reaction conditions mean, for example, the choice of palladium compounds, the transition metal-free oxidizing agent, the solvent or solvent mixture, the reaction temperature and/or the reaction pressure, the palladium concentration, the batch size and the order in which the starting materials are added.
  • the solvent SA or SB can each also be a solvent mixture. It is advantageously selected from the group consisting of alkanes, aromatic hydrocarbons and polar solvents such as ketones, e.g. acetone, and alcohols, e.g. B.
  • alcohols advantageously selected from the group consisting of alcohols, alkanes, ketones, ethers or combinations thereof, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, aromatic hydrocarbons having 6 to 9 carbon atoms , ethers with 4 to 8 carbon atoms or ketones with 2 to 6 carbon atoms or mixtures thereof.
  • organosilicon compounds comprises a cyclic or a non-cyclic siloxane selected from the group consisting of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds), 1,1,3,3-tetramethyl -1,3-dithien-2-yldisiloxane, 1,1,3,3-tetramethoxy-1,3-divinyldisiloxane, 1,3-dimethyl-1,3-divinyldisiloxanediol and 2,4,6,8-tetravinyl-2 ,4,6,8-tetramethylcyclotetrasiloxane.
  • dvds 1,1,3,3-tetramethyl-1,3-divinyldisiloxane
  • dvds 1,1,3,3-tetramethyl -1,3-dithien-2-yldisiloxane
  • one of the organosilicon compounds includes or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds).
  • one of the organosilicon compounds is dvds.
  • the transition metal-free oxidizing agent whose molecular formula contains bromine (Br), selected from the group consisting of molecular bromine, hydrogen bromide, bromo-1,4-dioxane complex, bromotrichloromethane, 1,2-dibromo-1,1,2,2-tetrachloroethane, carbon tetrabromide, tetrabutylammonium tribromide, trimethylphenylammonium tribromide, benzyltrimethylammonium tribromide, pyridinium tribromide, 4 -dimethyl
  • the palladium(II) compound required as starting material is palladium(II) acetylacetonate ([Pd(acac) 2 ]).
  • Another advantageous embodiment of the second method provides for the use of a, in particular aqueous, hydrogen bromide and/or hydrogen iodide solution.
  • in situ generation of the hydrogen bromide (HBr) and/or the hydrogen iodide (HI) is provided.
  • a first step comprises a reaction of the palladium(II) compound, in particular palladium(II) acetylacetonate, with an HBr donor and/or an HI donor in the presence of water and/or an alcohol.
  • an HBr donor and/or an HI donor in the presence of water and/or an alcohol.
  • a molar ratio (HBr donor and/or HI donor): (water and/or alcohol) is at least 1:1. Based on the amount of substance of the HBr donor and/or HI donor, it can also be more than one molar equivalent Water or more than one molar equivalent of an alcohol can be provided.
  • the molar ratio (HBr donor and/or HI donor): (water and/or alcohol) can be between 1:1 and 1:5, for example 1.0:1.1 or 1.0:1.2 or 1.0 : 1.3 or 1.0 : 1.4 or 1.0 : 1.5 or 1.0 : 1.6 or 1.0 : 1.7 or 1.0 : 1.8 or 1, 0 : 1.9 or 1.0 : 2.0 or 1.0 : 2.1 or 1.0 : 2.2 or 1.0 : 2.3 or 1.0 : 2.4 or 1.0 : 2.5 or 1.0:2.6 or 1.0:2.7 or 1.0:2.8 or 1.0:2.9 or 1.0:3.0 or 1.0:3, 1 or 1.0:3.2 or 1.0:3.3 or 1.0:3.4 or 1.0:3.5 or 1.0:3.6 or 1.0:3.7 or 1.0 : 3.8 or 1.0 : 3.9 or 1.0 : 4.0 or 1.0 : 4.1 or 1.0 : 4.2 or 1.0 : 4.3 or 1, 0:4.4 or 1.0:4.5 or 1.0:4.6 or
  • the HBr donor or HI donor is a brominated or iodinated, in particular organic, compound which has at least one H-Br bond or one HI bond with the lowest possible dissociation energy and among the under the reaction conditions selected here, in particular in the presence of an at least identical amount of water and/or an alcohol, HBr or HI is eliminated.
  • HBr or HI is eliminated.
  • no elimination of HBr or HI should take place during prolonged storage of the HBr donor or HI donor.
  • the reaction mixture must contain at least traces of water and/or alcohol. This can be done, for example, simply by using a not or not completely realize dried solvent.
  • the HBr donor acetyl bromide splits off hydrogen bromide (HBr), which reacts with palladium(II) acetylacetonate to form PdBr 2 .
  • a molar ratio of HBr donor: (water and/or alcohol) must be at least 1:1.
  • the only by-products are acetylacetone and acetic acid and/or an acetic acid ester.
  • the palladium(0) compound [Pd 2 (dvds) 3 ] is added, which reacts with the PdBr 2 , which is generated in situ and is sufficiently active per se, by way of a comproportionation reaction to give the desired target compound.
  • Pd 2 (dvds) 3 the palladium(0) compound
  • An advantageous embodiment of the second process claimed here for preparing compounds of the formula VII, starting from a palladium(II) compound, provides that the HBr donor is acetyl bromide or trimethylsilyl bromide (TMS-Br) and the HI donor is acetyl iodide or is trimethylsilyl iodide (TMS-I).
  • the reaction mixture must then contain water and/or alcohol and the aforementioned acetyl halides react to form hydrogen bromide or hydrogen iodide and acetic acid and/or an acetic acid ester, while TMSBr or TMSI forms hydrogen bromide or hydrogen iodide and trimethylsilane and/or an alkoxytrimethylsilane, also referred to as alkyl trimethylsilyl ether , react.
  • acetyl halides and trimethylsilyl halides are easier to handle than the corresponding hydrogen halides.
  • a molar ratio (HBr donor and/or HI donor): (water and/or alcohol) must be at least 1:1.
  • the reaction a) comprises providing the mononuclear or multinuclear palladium compound, in particular palladium (0) compound, wherein at least one Palladium center carries a ligand LS, which is an organosilicon compound, in a solvent SA1 in a first step, adding the phosphine ligand according to the general formula PR A R B R C in a second step and adding the transition metal-free oxidizing agent whose empirical formula is bromine (Br) or contains iodine (I), in a third step or b) providing the mononuclear or multinuclear palladium compound, in particular palladium(0) compound, wherein at least one palladium center carries a ligand LS, which is an organosilicon compound, in a solvent SA1 in a first Step, addition of the transition metal-free
  • the solvent SA1 is advantageously miscible or identical, in particular identical, to the solvent SA.
  • the transition metal-free oxidizing agent and/or the phosphine ligand can be added as a substance, ie as a gas, liquid or solid, or as a solution, emulsion or suspension in a solvent which is miscible with the solvent SA.
  • the transition metal-free oxidizing agent is selected from the group consisting of Br2, NBS and acetyl bromide, and mixtures thereof.
  • the mononuclear or multinuclear palladium compound, in particular palladium(0) compound by reacting a palladium(II) compound, which consists in particular of a palladium(II) cation and two monovalent anions or a divalent anion, with a ligand LS, which is an organosilicon compound, in particular a cyclic or a non-cyclic siloxane, is prepared in situ in a solvent SQ in the presence of a base.
  • the solvents SA and the solvent SQ are miscible or identical. Then there is no need to change the solvent, which is particularly advantageous from an economic and ecological point of view.
  • a definition of the expression “miscible solvents” has already been given above.
  • the expression “generated/prepared in situ” or “in situ generation/preparation” and the term “weakly coordinating” have already been defined above.
  • the term “bases” means inorganic and organic bases, in particular inorganic bases, but not organometallic bases. The bases should not decompose in water. Suitable bases are e.g. B. Salts of Bronsted acids.
  • Carbonates, bicarbonates, acetates, formates, ascorbates, oxalates and hydroxides are advantageously used. These can be used in the form of their ammonium salts (Brönsted acid)NR 4 , where R is, for example, H or alkyl, alkali metal salts, for example sodium or potassium salts, and alkaline earth metal salts.
  • the palladium(II) compound can have two different or two identical monovalent anions or one divalent anion. A neutral ligand such as B. COD is not provided. Consequently, inexpensive, commercially available palladium(II) compounds, such as PdCl 2 , can advantageously be used.
  • the palladium(II) compound to be used as starting material in the above-mentioned in situ preparation has two identical monovalent anions which are selected in particular from the group consisting of halides and monovalent weakly coordinating anions.
  • the reaction a) comprises providing the palladium(II) compound in a solvent SB1 in a first step, adding hydrogen bromide (HBr) and/or hydrogen iodide (HI) and/or adding an HBr donor and/or an HI donor, for example selected from the group consisting of TMSBr, TMSI, acetyl bromide, Acetyl iodide, and mixtures thereof, in particular acetyl bromide and/or acetyl iodide, in a second step and adding the palladium(0) compound of the general formula [Pd(PR A R B R C ) 2 ] and/or the preparation containing a Palladium(0) compound of the general formula [Pd(PR A R B R C ) 2 ] and at least one organosilicon compound, in a third step, adding hydrogen bromide (HBr) and/or hydrogen iodide (HI) and/or adding an HBr donor and/or an HI donor, for example selected
  • the intended preparation contains a solvent SZ.
  • the preparation itself can be in the form of a solution, suspension, dispersion or gel, in particular depending on the solvent SZ present and/or the organosilicon compound present.
  • the solvent SZ can also be a solvent mixture.
  • alkanes aromatic hydrocarbons and polar solvents advantageously selected from the group consisting of alcohols, alkanes, ketones, ethers or combinations thereof, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, aromatic hydrocarbons having 6 to 9 carbon atoms, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, or mixtures thereof.
  • the solvent SZ comprises or is a solvent which is selected from the group consisting of aromatic hydrocarbons, ketones, e.g. acetone, and alcohols, e.g. B. methanol, ethanol or iso-propanol, and mixtures thereof, the preparation is as a solution or suspension before.
  • the at least one aromatic hydrocarbon can be selected, for example, from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof. It is particularly advantageous if the solvent SZ and the solvent SB used in the second method are miscible or identical.
  • a further embodiment of the second process for preparing a compound of the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) provides for a reaction of the palladium(II) compound with the preparation described above , containing a palladium(0) compound according to the general formula [Pd(PR A R B R C ) 2 ] and at least one organosilicon compound, wherein a) the at least one organosilicon compound contains at least one terminal, in particular vinylic, double bond, in particular comprises or is a cyclic or a non-cyclic siloxane, and/or b) the preparation, in addition to the palladium compound of the general formula [Pd(PR A R B R C ) 2 ], comprises at least one palladium compound of the general formula [LSPd(PR A R B R C )] (II) and/or at least one palladium compound according to the general formula [Pd(LS) 2 ] (III), where - the ligand LS in
  • the ligand LS is identical to the organosilicon compound, the ligand LS being in particular a cyclic or a non-cyclic siloxane which has at least one terminal, in particular vinylic, double bond.
  • the ligand LS is then advantageously coordinated or bonded via at least one pi bond to the palladium center of the compound of the general formula LSPd(PR A R B R C ) (II) or [Pd(LS) 2 ] (III).
  • transition metal-free oxidizing agent and / or the palladium (0) compound according to the general formula [Pd (PR A R B R C ) 2 ] can in bulk, ie as a gas, liquid or solid, or as a solution, emulsion or suspension in a be added with the solvent SB miscible solvent.
  • a further embodiment of the second method claimed here for preparing a compound of the formula VII provides that the reaction according to the second method for preparing a compound of the formula VII is an in situ preparation of the palladium(0) compound of the general formula [Pd (PR A R B R C ) 2 ] includes, in particular starting from a palladium (0) compound, wherein at least one palladium center carries a ligand LS, which is an organosilicon compound, and a phosphine ligand according to the general formula PR A R B R C in the solvent chosen for the reaction according to the second method of preparing a compound of formula VII, or a solvent miscible therewith.
  • the reaction according to the second method for preparing a compound of the formula VII is an in situ preparation of the palladium(0) compound of the general formula [Pd (PR A R B R C ) 2 ] includes, in particular starting from a palladium (0) compound, wherein at least one palladium center carries a ligand LS, which is an organ
  • the radicals R A , R B and RC are independently selected from the group consisting of tert-butyl, iso-propyl and 1-adamantyl, with the exception of the phosphine ligand PiPr 3 .
  • the preparation containing a palladium(0) compound according to the general formula [Pd(PR A R B R C ) 2 ] and at least one organosilicon compound is produced in situ, specifically in particular starting from a mononuclear or multinuclear palladium compound, in particular a palladium(0) compound, where at least one palladium center carries a ligand LS, which is an organosilicon compound, and in each case a phosphine ligand (PR A R B R C ).
  • the latter are independently selected from the group consisting of tri-tert-butylphosphine (PtBu 3 ), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu 2 ), tert-butyl-di-(iso-propyl).
  • the preparation is generated in situ in the solvent selected for the reaction according to the second method for preparing a compound of formula VII, or a solvent miscible therewith.
  • the choice or definition of the ligand LS and the organosilicon compound corresponds to that given above.
  • the expression "created/prepared in situ” or “created/prepared in situ” has already been defined above.
  • a molar ratio Pd: X is at least 1.0: 0, 5, advantageously between 1.0:0.5 and 1.0:2.0, more advantageously between 1.0:0.6 and 1.0:1.9, particularly advantageously between 1.0:0.7 and 1.0:1.8, in particular between 1.0:0.8 and 1.0:1.7, for example 1.0:0.9 or 1.0:1.0 or 1.0:1.1 or 1.0:1.2 or 1.0:1.3 or 1.0:1.4 or 1.0:1.5 or 1.0:1.6 and/or - a molar ratio of palladium(0 ) compound : PR A R B R C at least 1:1, advantageously between 1.0:1.0 and 1.0:2.5, more advantageously between 1.0:1.1 and 1.0:2, 4, particularly advantageously between 1.0:1.2 and 1.0:2.3, in particular between 1.0:1.3 and 1.0:2.2, for example 1.0:1.4 or 1.0
  • Another embodiment of the second process for preparing a compound according to the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) provides that - a molar ratio of palladium(II) compound: transition metal-free Oxidizing agent or palladium (II) compound: bromine (Br) and/or iodine (I) is at least 1:2, advantageously between 1:2 to 1:3, more advantageously between 1.0:2.1 and 1.0 : 2.9, particularly advantageously between 1.0:2.2 and 1.0:2.8, in particular between 1.0:2.3 and 1.0:2.7, for example 1.0:2.4 or 1.0:2.5 or 1.0:2.6, and/or - a molar ratio of palladium(II) compound: palladium(0) compound is between 1:2 and 2:1, advantageously between 1 0:1.9 and 1.9:1.0, more
  • the molar ratio of palladium(II) compound: transition metal-free oxidizing agent is 1:2 and the molar ratio of palladium(II) compound: palladium(0) compound is 1: is 1.
  • a further embodiment of the second method for preparing a compound according to the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) provides that the preparation contains at least one organosilicon compound, with a content of silicon , which is present in particular in the form of the at least one organosilicon compound, is ⁇ 100 ppm and ⁇ 1000 ppm, advantageously ⁇ 110 ppm and ⁇ 900 ppm, in particular ⁇ 120 ppm and ⁇ 800 ppm.
  • the silicon content which is present in particular in the form of the at least one organosilicon compound, can be determined using analytical methods which are known to the person skilled in the art, in particular using quantitative 1 H-NMR spectroscopy and/or atomic emission spectrometry with inductively coupled plasma Inductively Coupled Plasma-Atomic Emission Spectrometers (ICP-AES).
  • analytical methods which are known to the person skilled in the art, in particular using quantitative 1 H-NMR spectroscopy and/or atomic emission spectrometry with inductively coupled plasma Inductively Coupled Plasma-Atomic Emission Spectrometers (ICP-AES).
  • the organosilicon compound can be the ligand LS or the palladium compound according to the general formula [LSPd(PR A R B R C )] (II) and/or according to the general formula [Pd(LS) 2 ] (III).
  • a further step is carried out after the reaction, which comprises a Isolation of the compound produced by means of the reaction according to the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) comprises: - as preparation, which [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) and a solvent SA or a solvent SB and/or SZ, or - as a substance, advantageously as a solid.
  • the term “preparation” means a solution, a suspension, a dispersion or a gel.
  • the preparation can therefore, in particular depending on the solvent contained and/or on the compound contained according to the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII), as a solution, suspension, Dispersion or gel present.
  • the solvent can also be a mixture of solvents.
  • the solvent comprises or is a solvent which is miscible or identical to the solvent SA used in the first method or the solvent SB and/or SZ used in the second method.
  • the preparation is then usually in the form of a solution or suspension.
  • the isolation comprises a filtration step and/or decanting and /or centrifugation.
  • the aforementioned measures can also be carried out several times.
  • one or more filtrations over a cleaning medium such as. B. activated carbon, or silica, z. B. Celite ® , take place.
  • the filtrate, centrifugate or decantate or the solid can be subjected to the purification and/or isolation steps that may be provided and can be carried out quickly and without any particular preparative effort.
  • the isolation of the compound according to the general formula [Pd ( ⁇ -X) (PR A R B R C )] 2 (VII) may include further process steps, such as. B. reducing the volume of the mother liquor, ie concentration, z. B. by means of "bulb-to-bulb", the addition of a solvent and / or a solvent exchange to achieve a precipitation of the product from the mother liquor and / or to remove impurities and / or starting materials, crystallization, sublimation, washing, e.g. B. with acetone, pentane or hexane, and mixtures thereof, drying the product.
  • the aforementioned steps can each be provided in different sequences and frequencies.
  • the purification and/or isolation of the target compound according to the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) is relatively simple and inexpensive.
  • the end product can still contain residues of solvents or, for example, impurities from the starting materials.
  • Isolated compounds of the type [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) have a purity of at least 97%, advantageously more than 97%, in particular more than 98% or 99%.
  • the reproducible yield is at least 60%, usually >80%, sometimes also >90%, depending in particular on the choice of starting materials and the solvent or solvent mixture—even in the case of upscaling to an industrial scale.
  • R A , R B and R C are independently selected from the group consisting of tert-butyl, iso-propyl and 1-adamantyl, and - the bridging atoms X are independently bromine (Br) or iodine (I), with With the exception of the compounds [Pd( ⁇ -Br)(PtBu 3 )] 2 , [Pd( ⁇ -I)(P(iPr)tBu 2 )] 2 and [Pd( ⁇ -Br)(P(1-Ad)tBu 2 )] 2 .
  • the palladium(I) compounds of the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) claimed here can be prepared in particular by a process for preparing a compound of the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) according to one of the embodiments described above. They can be used, for example, as catalysts and/or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. They are advantageously suitable as precatalysts for the reactions specified below. In addition, the object is achieved by a preparation containing i.
  • the compound contained therein according to the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII) or the preparation itself is in particular obtained or obtainable by a process for the production of such Connection according to one of the embodiments described above.
  • the silicon content, which is present in particular in the form of the at least one organosilicon compound is ⁇ 100 ppm and ⁇ 1000 ppm, advantageously ⁇ 110 ppm and ⁇ 900 ppm, in particular ⁇ 120 ppm and ⁇ 800 ppm.
  • the silicon content which is present in particular in the form of the at least one organosilicon compound, can be determined using analytical methods which are known to the person skilled in the art, in particular using quantitative 1 H-NMR spectroscopy and/or atomic emission spectrometry with inductively coupled plasma Inductively Coupled Plasma-Atomic Emission Spectrometers (ICP-AES).
  • the preparation contains a solvent SZ.
  • the preparation can be in the form of a solution, suspension, dispersion or gel, in particular depending on the solvent SZ present and/or the organosilicon compound present.
  • the solvent SZ can also be a solvent mixture.
  • alkanes aromatic hydrocarbons and polar solvents advantageously selected from the group consisting of alcohols, alkanes, ketones, ethers or combinations thereof, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, aromatic hydrocarbons having 6 to 9 carbon atoms, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, or mixtures thereof.
  • the solvent SZ comprises or is a solvent which is selected from the group consisting of aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof, polar solvents such as acetone and alcohols, e.g. B. selected from the group consisting of methanol, ethanol and iso-propanol, and mixtures thereof, and ethers, e.g. B. selected from the group consisting of diethyl ether, THF, 2-methyltetrahydrofuran and 1,4-dioxane, and mixtures thereof, the preparation is in the form of a solution or suspension.
  • aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof
  • polar solvents such as acetone and alcohols, e.g.
  • the at least one organosilicon compound contains at least one terminal, in particular vinylic, double bond.
  • the at least one organosilicon compound comprises or is a cyclic or a non-cyclic siloxane.
  • the preparation in addition to the palladium compound of the general formula [Pd( ⁇ -X)(PR A R B R C )] 2 (VII), it contains a palladium compound of the general formula [LSPdZ] (II) and/ or a palladium compound represented by the general formula [Pd(LS) 2 ] (III).
  • the ligand LS is in particular identical to the at least one organosilicon compound, in particular a cyclic or a non-cyclic siloxane.
  • the at least one organosilicon compound contains at least one terminal double bond and Z is selected from the group consisting of tri-tert-butylphosphine (PtBu 3 ), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu 2 ), tert- butyl-di-(iso-propyl)phosphine (P(iPr) 2 tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu 2 ), di(1-adamantyl)-tert -butylphosphine (P(1-Ad) 2 tBu), 1-adamantyl-di-(iso-propyl)phosphine (P(1-Ad)i
  • a further variant of the preparation provides that at least one organosilicon compound comprises or is a cyclic or a non-cyclic siloxane and/or at least one ligand LS is a cyclic or a non-cyclic siloxane which is selected from the group consisting of 1, 1,3,3-Tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-Tetramethyl-1,3-dithien-2-yldisiloxane, 1,1,3,3-Tetramethoxy-1,3-divinyldisiloxane, 1,3-dimethyl-1,3-divinyldisiloxanediol and 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane.
  • one of the organosilicon compounds comprises or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds) and/or one of the ligands LS is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds ).
  • dvds 1,1,3,3-tetramethyl-1,3-divinyldisiloxane
  • dvds 1,1,3,3-tetramethyl-1,3-divinyldisiloxane
  • - X is an anionic ligand
  • - the radicals R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl radicals, branched, straight-chain and cyclic alkylene radicals, branched, straight-chain and cyclic alkynyl radicals, unsubstituted mononuclear or polynuclear aryl radicals, substituted mononuclear or polynuclear aryl radicals, unsubstituted mononuclear or polynuclear heteroaryl radicals and substituted mononuclear or polynuclear heteroaryl radicals or - two radicals of R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together one form an unsaturated or aliphatic ring or - two radicals of R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form a first radical
  • a palladium compound in particular a mononuclear or multinuclear palladium(0) compound, wherein at least one palladium center carries a ligand LS which is an organosilicon compound, wherein the ligand LS is in particular a cyclic or a non-cyclic siloxane , B. Reaction of the palladium compound from step A.
  • R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl radicals, branched, straight-chain and cyclic alkylene radicals, branched, straight-chain and cyclic alkynyl radicals, unsubstituted mononuclear or polynuclear aryl radicals, substituted mononuclear or polynuclear aryl radicals, unsubstituted mononuclear or polynuclear heteroaryl radicals and substituted mononuclear or polynuclear heteroaryl radicals or - two radicals of R1, R2, R3 and R4 together form an unsaturated or aromatic ring, advantageously R1 and R3 or R2 and R4, form or - two radicals of R1, R2, R3 and R4, advantageously R1 and R3 or R2 and
  • organosilicon compound has already been defined above.
  • a large number of palladium(II) complex compounds of type VIII can be provided simply, relatively inexpensively and reproducibly by means of the method described here.
  • the target compounds are usually obtained in high yields and good purity, especially NMR purity.
  • the compounds that can be prepared by means of the process described here contain no or only traces ( ⁇ 1000 ppm) of impurities from palladium-containing by-products that are difficult or impossible to separate, in particular because of their solubility behavior.
  • the high purity of the end products is important with a view to possible uses, e.g. B.
  • Palladium(II) dimers according to formula VIII are easy-to-use catalyst precursors with excellent catalytic performance.
  • they are easily accessible in one step from commercially available precursors and react without problems with a large number of electron donor ligands, in particular phosphine and NHC ligands, to form defined palladium(II) complexes.
  • the palladium compound to be made available in step A. which is in particular a palladium(0) compound, can be mononuclear or multinuclear, in particular dinuclear, as a monomer or oligomer, in particular dimer, and/or as a solvent adduct.
  • the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.
  • the term "weakly coordinating” also includes the expressions "very weakly coordinating" and “moderately strongly coordinating”.
  • Chloride, bromide or iodide can advantageously be used as halide anions X, particularly advantageously chloride or bromide, in particular chloride.
  • the monovalent weakly coordinating are in particular perfluorinated anions such.
  • the expression “unsaturated ring” means a non-aromatic carbocycle or heterocycle which has at least one double bond.
  • the unsaturated ring can also be part of a ring system consisting of two or more fused rings, which can include aliphatic, aromatic and other unsaturated carbo- and/or heterocycles.
  • a saturated ring is formed, for example, by the radicals R1 and R3 if, for example, an allyl halide AH derived from phenalene or indene was used as starting material for the preparation of the compound of the formula VIII.
  • a molar ratio of Pd:AH is at least 1:1, advantageously between 1.0:1.0 and 1.0:5.0, more advantageously between 1.0:1.1 and 1.
  • 0:4.0 particularly advantageously between 1.0:1.2 and 1.0:3.0, in particular between 1.0:1.3 and 1.0:2.0, for example 1.0:1.4 or 1.0:1.5 or 1.0:1.6 or 1.0:1.7 or 1.0:1.8 or 1.0:1.9 or 1.0:2.1 or 1.0:2.2 or 1.0:2.3 or 1 .0 : 2.4 or 1.0 : 2.5 or 1.0 : 2.6 or 1.0 : 2.7 or 1.0 : 2.8 or 1.0 : 2.9 or 1.0 : 3.1 or 1.0 : 3.2 or 1.0 : 3.3 or 1.0 : 3.4 or 1.0 : 3.5 or 1.0 : 3.6 or 1.0 : 3 .7 or 1.0:3.8 or 1.0:3.9 or 1.0:4.1 or 1.0:4.2 or 1.0:4.3 or 1.0:4.4 or 1.0:4.5 or 1.0:4.6 or 1.0:4.7 or 1.0:4.8 or 1.0:4.9.
  • a compound according to the general formula VIII which can be obtained by means of the process claimed here has two identical ⁇ 3 -bonded allyl ligands.
  • the allyl ligand is derived in each case from the compound AH used as starting material according to the general formula ab, where X, R1, R2, R3 and R4 are as defined above.
  • a palladium(0) compound which in particular has a ligand LS which is an organosilicon compound, in particular a cyclic or a non-cyclic siloxane, can be reacted with 1-naphthylmethyl chloride.
  • a molar ratio of Pd:AH of at least 1:1 can be provided.
  • a palladium(II) compound of the formula VIII which can be obtained in this way then has two identical, in particular ⁇ 3 -bonded, allyl ligands derived from naphthalene.
  • a complex according to formula VIII has no naphthyl ligand in the true sense. This is because the electrons involved in the complexation of the palladium center are not in conjugation with the ring electrons.
  • the aromaticity of the bicyclic naphthalene is restricted to one of the two fused six-membered rings as a result of complex formation.
  • an ⁇ 1 -bonded ligand or ⁇ 3 -bonded allyl ligand derived from naphthalene is referred to as a naphthyl ligand for the sake of simplicity.
  • the product of the above example reaction is therefore referred to as a dimeric palladium(II) 1-methylnaphthyl chloride complex, where the chlorine atoms act as bridging ligands, ie two chlorine bridges are present, or as a chloride-bridged 1-methylnaphthylpalladium(II) dimer.
  • a further variant of the claimed process for preparing a compound of the general formula VIII provides that the radicals R1, R2, R3 and R4 of the starting material AH are selected independently from the group consisting of hydrogen (H), straight-chain alkyl radicals with one to ten carbon atoms, i.e.
  • the radicals R1, R2, R3 and R4 of the starting material AH are independently selected from the group consisting of hydrogen (H), straight-chain alkyl radicals having one to eight carbon atoms, branched alkyl radicals having one to eight carbon atoms, cyclic alkyl radicals with four, five or six carbon atoms, unsubstituted mononuclear or polynuclear aryl radicals with six to fourteen carbon atoms, i.e.
  • the radicals R1, R2, R3 and R4 of the starting material AH can be selected independently from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl , cyclopentyl, cyclohexyl, benzyl, tolyl, xylyl, pyridinyl, and combinations thereof.
  • two radicals from R1 to R4 of the starting material AH can form an unsaturated or aromatic carbocyclic ring which is substituted by one or more of the aforementioned alkyl radicals.
  • a starting material AH can be provided, where the radicals R2 and R4 form a substituted, unsaturated carbocyclic five-membered ring which is fused to exactly one aromatic ring.
  • An example of such a starting material AH is 3-(tert-butyl)-1-chloro-1H-indene (starting material for 9-Cl).
  • a starting material AH can also be provided, with the radicals R2 and R4 forming an unsubstituted, unsaturated carbocyclic six-membered ring.
  • An example of such a starting material AH is 3-bromocyclohexene (starting material for 6-Br).
  • R1 and R3 of the starting material AH together form one carbocyclic unsaturated ring with five to eight carbon atoms.
  • R1 and R3 of the starting material AH together form a carbocyclic unsaturated ring or an aromatic ring with five or six carbon atoms, the carbocyclic unsaturated ring or the aromatic ring being fused with at least one aromatic ring.
  • R1 and R3 together can be part of a naphthyl, anthracenyl, phenanthrenyl, phenalenyl, tetracenyl or chrysenyl ring system.
  • the radicals R1 and R3 of the starting material AH together form the first, in particular carbocyclic, ring which is aromatic or unsaturated and is fused with at least one aromatic ring, and - the radicals R1 and R2 and/or R3 and R4 are a second, in particular carbocyclic, ring having 5 to 8 carbon atoms, which is aromatic or unsaturated and is fused to the first ring and/or to the at least one aromatic ring.
  • the second ring can be unsubstituted or optionally substituted with one or more radicals selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl , cyclohexyl, benzyl, tolyl, xylyl, pyridinyl, and combinations thereof.
  • the first ring is in particular a carbocyclic ring with five to eight carbon atoms.
  • the first and second rings are independently selected from the group consisting of a cyclopentadienyl ring, cyclohexadienyl ring, cycloheptadienyl ring, cyclooctadienyl ring and a benzene ring.
  • R2 and R4 (apart from the required halogen atom) of the starting material AH can form a substituted or unsubstituted carbocyclic, in particular unsaturated or saturated, ring having 5 to 8 carbon atoms, which can optionally be at least one aromatic ring may be fused, e.g. B.
  • This carbocyclic ring is advantageously a cyclopentenyl, cyclohexenyl, cycloheptenyl or cyclooctenyl ring.
  • this carbocyclic ring is a cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl ring.
  • R1 and R3 of the starting material AH can together form a carbocyclic ring, in particular an aromatic or unsaturated ring, which is fused to at least one aromatic ring.
  • R1 of the starting material AH is hydrogen (H), methyl or phenyl, or R1 together with R3 forms a phenyl ring which is fused to a benzene ring, so that R1 and R3 are part of a naphthyl ring.
  • R2 of the starting material AH is hydrogen (H), methyl or phenyl or, together with R4, forms a cyclohexenyl ring.
  • R3 of the starting material AH is hydrogen (H), methyl or phenyl, or R3 together with R1 forms a phenyl ring which is fused to a benzene ring, so that R1 and R3 are part of a naphthyl ring.
  • R4 of the starting material AH is hydrogen (H), methyl or phenyl, or R4 together with R2 forms a cyclohexenyl ring.
  • R1 to R4 of the starting material AH can be the following radicals. Residues marked with an asterisk * together form the indicated residue. a) The radicals R1 and R3 together form an aromatic ring, namely a phenyl ring, the aromatic ring being fused to at least one aromatic ring, namely a benzene ring. Thus, R1 and R3 are part of a naphthyl ring.
  • the educt AH can then be, for example, 1-(chloromethyl)naphthalene (educt for compound 7-Cl, see below), 2-(chloromethyl)naphthalene (educt for compound 8-Cl, see below), 1-(bromomethyl)naphthalene (educt for compound 7-Br, see below) or 2-(bromomethyl)naphthalene (educt for compound 8-Br, see below).
  • R1 and/or R2 is a methyl radical
  • R1 and/or R2 is a methyl radical
  • R1 or R2 is a methyl radical
  • an ethyl radical can be used instead of the methyl radical n-propyl radical or a n-butyl radical can be provided.
  • One embodiment of the process claimed here provides that the reaction in step B.
  • the solvent SC is selected from the group consisting of alcohols, alkanes, aromatic hydrocarbons, ketones, ethers, and their Combinations, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, aromatic hydrocarbons having 6 to 9 carbon atoms, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, and mixtures thereof.
  • a palladium(II) compound which advantageously consists of a palladium(II) cation and two monovalent anions or a divalent anion, with a ligand LS, which is an organosilicon compound, advantageously a cyclic or a non-cyclic siloxane, in the presence of a base.
  • the palladium compound to be made available in step A. can therefore advantageously be prepared in situ.
  • the palladium(II) compound can have two different or two identical monovalent anions or one divalent anion.
  • a neutral ligand such as B. COD is not provided. Consequently, inexpensive, commercially available palladium(II) compounds, such as PdCl 2 , can advantageously be used.
  • a palladium(II) compound of the type [Pd(ligand)Y 2 ] which is associated with expenditure of time and money, e.g. B. ligand COD, so can be omitted as a starting material for the in situ generation of mononuclear or multinuclear palladium compound.
  • This is particularly advantageous from a (nuclear) economic and ecological point of view.
  • the number of possible impurities in the end product according to general form VIII is reduced in this way.
  • the palladium(II) compound to be used as starting material in the above-mentioned in situ preparation has two identical monovalent anions which are selected in particular from the group consisting of halides and monovalent weakly coordinating anions.
  • the expression “generated/manufactured in situ” or “in situ generation/manufacture” and the term “weakly coordinating” have already been defined above.
  • the term “bases” means inorganic and organic bases, in particular inorganic bases, but not organometallic bases. The bases should not decompose in water. Suitable bases are e.g. B. Salts of Bronsted acids.
  • Carbonates, bicarbonates, acetates, formates, ascorbates, oxalates and hydroxides are advantageously used. These can be used in the form of their ammonium salts (Brönsted acid)NR 4 , where R is, for example, H or alkyl, alkali metal salts, for example sodium or potassium salts, and alkaline earth metal salts.
  • R is, for example, H or alkyl
  • alkali metal salts for example sodium or potassium salts
  • alkaline earth metal salts alkaline earth metal salts.
  • the reaction of the palladium(II) compound with a ligand LS, which is an organosilicon compound, in step A. usually takes place in a solvent SC1 .
  • the solvents S C1 are not particularly limited. Examples of possible solvents S C1 are polar solvents such as water, alcohols, ketones, hydrocarbons, z. B.
  • aromatic hydrocarbons such as benzene and toluene, or aliphatic hydrocarbons such as pentane, hexane and heptane, open-chain or cyclic ethers, amides and esters.
  • the solvent S C1 provided for the provision or reaction in step A. and the solvent SC provided for the reaction in step B. are miscible with one another or are identical. Then can no need to change the solvent, which is particularly advantageous from an economic and ecological point of view.
  • a definition of the expression "two miscible solvents" has already been given above.
  • one of the ligands LS is a cyclic or a non-cyclic siloxane which is selected from the group consisting of 1,1,3,3-tetramethyl-1, 3-divinyldisiloxane (dvds), 1,1,3,3-tetramethyl-1,3-dithien-2-yldisiloxane, 1,1,3,3-tetramethoxy-1,3-divinyldisiloxane, 1,3-dimethyl-1 ,3-divinyldisiloxanediol and 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane.
  • dvds 1,1,3,3-tetramethyl-1, 3-divinyldisiloxane
  • dvds 1,1,3,3-tetramethyl-1,3-dithien-2-yldisiloxane
  • One of the ligands LS is advantageously 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds).
  • one of the ligands is LS dvds.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0)—abbreviated as [Pd 2 (dvds) 3 ], [Pd(dvds)], Pd( vs), Pd-VS or palladium-VS - is an excellent starting material for the preparation of compounds of the formula VIII, for example ⁇ -allylpalladium halide complexes such as ⁇ -allylpalladium chloride complexes, which in particular by means of the method described here usually in yields of mostly more than 90%, often more than 97%, in particular more than 99%.
  • the reaction temperature in step A. and/or step B., in particular in step B. is 10°C to 60°C, in particular 15°C to 45°C or 20°C to 30°C.
  • the reaction time in step A. and/or step B., in particular in step B. is 10 minutes to 48 hours, in particular 1 hour to 36 hours or 2 to 24 hours or 3 to 12 hours.
  • - X is an anionic ligand
  • - the radicals R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl radicals, branched, straight-chain and cyclic alkylene radicals, branched, straight-chain and cyclic alkynyl radicals, unsubstituted mononuclear or polynuclear aryl radicals, substituted mononuclear or polynuclear aryl radicals, unsubstituted mononuclear or polynuclear heteroaryl radicals and substituted mononuclear or polynuclear heteroaryl radicals or - two radicals of R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form an unsaturated or aliphatic ring or - two radicals of R1, R2, R3 and R4,
  • the compounds of the formula VIII claimed here are generally obtainable in yields of usually more than 80%, often more than 85%, in particular more than 90%, in particular according to one of the exemplary embodiments of the process described above for preparing such compounds.
  • the palladium(II) compounds of the general formula VIII can be used, for example, as catalysts and/or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. They are advantageously suitable as catalysts for the reactions specified below.
  • Palladium(II) dimers according to formula VIII are easy-to-use catalyst precursors with excellent catalytic performance.
  • the expression “unsaturated ring” means a non-aromatic carbocycle or heterocycle which has at least one double bond.
  • the unsaturated ring can be part of a ring system consisting of two or more fused rings, which can include aliphatic, aromatic and other unsaturated carbo- and/or heterocycles.
  • the radicals R2 and R4 form, for example, a saturated ring if, for example, an allyl halide derived from phenalene or indene was used as starting material for the preparation of the compound of the formula VIII.
  • a compound according to the general formula VIII has two identical ⁇ 3 -bonded allyl ligands.
  • the allyl ligand is derived in each case from a compound AH used as starting material according to the general formula ab, where X, R1, R2, R3 and R4 are as defined above.
  • a palladium(0) compound which in particular has a ligand LS which is an organosilicon compound, in particular a cyclic or a non-cyclic siloxane can be reacted with 1-naphthylmethyl chloride.
  • a molar ratio of Pd:AH of at least 1:1 can be provided.
  • a palladium(II) compound of the formula VIII which can be obtained in this way then has two identical, in particular ⁇ 3 -bonded, allyl ligands derived from naphthalene.
  • a complex according to Formula VIII does not have a naphthyl ligand in the true sense.
  • the product of the above example reaction is therefore referred to as a dimeric palladium(II) 1-methylnaphthyl chloride complex, where the chlorine atoms act as bridging ligands, ie two chlorine bridges are present, or as a chloride-bridged 1-methylnaphthylpalladium(II) dimer.
  • the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.
  • the term "weakly coordinating” also includes the expressions "very weakly coordinating" and "moderately strongly coordinating”. Chloride, bromide or iodide can advantageously be used as halide anions X, particularly advantageously chloride or bromide, in particular chloride.
  • the monovalent weakly coordinating are in particular perfluorinated anions such.
  • substituted mononuclear or polynuclear aryl radicals with six to fourteen carbon atoms i.e. also with seven, eight, nine, ten, eleven, twelve or thirteen carbon atoms, unsubstituted mononuclear or polynuclear heteroaryl radicals with five to thirteen carbon atoms, i.e. also with six, seven, eight, nine, ten, eleven or twelve carbon atoms, and substituted mononuclear or polynuclear heteroaryl radicals with five to thirteen carbon atoms, ie also with six, seven, eight, nine, ten, eleven or twelve carbon atoms.
  • the radicals R1, R2, R3 and R4 of the compound according to formula VIII are independent are selected from the group consisting of hydrogen (H), straight-chain alkyl radicals having one to eight carbon atoms, branched alkyl radicals having one to eight carbon atoms, cyclic alkyl radicals having four, five or six carbon atoms, unsubstituted mononuclear or polynuclear aryl radicals having six to fourteen carbon atoms, So also with seven, eight, nine, ten, eleven, twelve or thirteen carbon atoms, substituted mononuclear or polynuclear aryl radicals having six to ten carbon atoms, unsubstituted mononuclear or polynuclear heteroaryl radicals having five to nine carbon atoms, and substituted mononuclear or polyn
  • the radicals R1, R2, R3 and R4 of the compounds according to the general formula VIII claimed here can be independently selected from the group consisting of hydrogen (H), methyl, ethyl, n -propyl, iso -propyl, n -butyl, iso -butyl, tert -butyl, cyclopentyl, cyclohexyl, benzyl, tolyl, xylyl, pyridinyl, and combinations thereof.
  • two radicals of R1 to R4 can form a saturated or unsaturated carbocyclic ring which is unsubstituted is or is substituted with one or more of the aforementioned alkyl radicals or aryl radicals.
  • R2 and R4 (apart from the required halogen atom) can be a substituted or unsubstituted carbocyclic, in particular saturated , form a ring with 5 to 8 carbon atoms.
  • the carbocyclic ring is advantageously a cyclopentenyl ring, cyclohexenyl ring, cycloheptenyl ring or cyclooctenyl ring or a cyclopentyl ring, cyclohexyl ring, cycloheptyl ring or cyclooctyl ring.
  • the groups R2 and R4 form an ⁇ 3 -bonded allyl ligand derived from a substituted cyclopentenyl ring, which for convenience is referred to as a cyclopentyl ligand.
  • radicals R2 and R4 in the compounds 6-Cl and 6-Br shown below each form a cyclohexyl ring.
  • the radicals R2 and R4 together form the first, in particular carbocyclic, ring with five to eight carbon atoms, advantageously five or six carbon atoms, the first ring being unsaturated or saturated and being fused with at least one aromatic ring.
  • R2 and R4 together can be part of an ⁇ 3 -bonded allyl ligand which is derived from a fluorenyl or indenyl system. An example of this is the compound 9-Cl.
  • R1 and R3 together form the first, in particular carbocyclic, ring with five to eight carbon atoms, which is unsaturated or saturated and is fused with at least one aromatic ring.
  • R1 and R3 of a compound according to formula VIII in particular obtained or obtainable by a process for preparing such a compound according to one of the exemplary embodiments described above, form the first, in particular carbocyclic, ring with five or six carbon atoms, which is unsaturated or saturated and is fused with at least one aromatic ring.
  • R1 and R3 together can be part of a naphthyl, anthracenyl, phenanthrenyl, phenalenyl, tetracenyl or chrysenyl ring system.
  • Examples of R1 and R3 together forming an unsaturated carbocyclic ring with six carbon atoms, the unsaturated six-membered ring being fused with at least one aromatic ring, are the compounds 7-Cl, 7-Br, 8-Cl and 8-Br.
  • the electrons involved in the complexation of the palladium center are not in conjugation with the ring electrons.
  • the aromaticity of the bicyclic naphthalene is restricted to one of the two fused six-membered rings as a result of complex formation.
  • a derived from naphthalene, in particular ⁇ 3 -bonded, allyl ligand for the sake of simplicity referred to as naphthyl ligand.
  • the aforementioned example compound 7-Cl is therefore referred to as a dimeric palladium(II) 1-methylnaphthyl chloride complex, with the chlorine atoms acting as bridging ligands, i.e. two chlorine bridges being present, or as a chloride-bridged 1-methylnaphthylpalladium(II) dimer.
  • palladium(II) compounds of the formula VIII which are obtainable using an anthracenyl, phenanthrenyl, phenalenyl, fluorenyl, indenyl, tetracenyl or chrysenyl halide.
  • the radicals R1 and R3 together form the first, in particular carbocyclic, ring which is unsaturated or is saturated and is fused with at least one aromatic ring, and - the radicals R1 and R2 and/or R3 and R4 a second, in particular carbocyclic, ring with 5 to 8 carbon atoms, which is aromatic or unsaturated and with the first ring and/ or fused to the at least one aromatic ring.
  • the second ring can be unsubstituted or optionally substituted with one or more radicals selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl , cyclohexyl, benzyl, tolyl, xylyl, pyridinyl, and combinations thereof.
  • the first ring is advantageously selected from the group consisting of a cyclopentenyl ring, cyclohexenyl ring, cycloheptenyl ring, cyclooctenyl ring, cyclopentyl ring, cyclohexyl ring, cycloheptyl ring and cyclooctyl ring.
  • the second ring is selected from the group consisting of a one cyclopentadienyl ring, cyclohexadienyl ring, cycloheptadienyl ring, cyclooctadienyl ring and a benzene ring.
  • R1 is hydrogen (H), methyl or phenyl, or R1 together with R3 forms a Cyclohexenyl ring fused with a benzene ring such that R1 and R3 are part of a naphthyl ring.
  • R2 is hydrogen (H), methyl or phenyl, or together with R4 forms a cyclohexyl ring .
  • R3 is hydrogen (H), methyl or phenyl, or R3 forms together with R1 a cyclohexenyl ring fused to a benzene ring such that R1 and R3 are part of a naphthyl ring.
  • R4 is hydrogen (H), methyl or phenyl or R4 together with R2 forms a cyclohexyl ring.
  • R1 to R4 of a compound of the formula VIII obtained or obtainable by a process for preparing such a compound according to one of the exemplary embodiments described further above can be the following radicals. Residues marked with an asterisk * together form the indicated residue. a) See e.g. B. the compounds 6-Cl and 6-Br shown below. b) R1 and R3 together form a first unsaturated ring, namely a cyclohexenyl ring, which is fused with at least one aromatic ring, namely a benzene ring.
  • R1 and R3 are part of a naphthyl-derived, in particular ⁇ 3 -bonded, allyl ligand, which for the sake of simplicity is referred to as a naphthyl ligand.
  • a naphthyl ligand examples of such compounds according to formula VIII are the compounds 7-Cl, 7-Br, 8-Cl and 8-Br shown below.
  • the following compounds can be prepared as compounds of the formula VIII:
  • this new compound can also be obtained by the process described here for the preparation of compounds according to general formula VIII, in good yield and high purity.
  • the palladium(II) compound of the formula 4-Br can be used, for example, as a catalyst and/or precatalyst be used, in particular as a precatalyst in palladium-catalyzed cross-coupling reactions.
  • R alkyl, cycloalkyl or aryl.
  • the new compounds of the formula VIII claimed here are generally obtainable in yields of usually more than 90%, often more than 97%, in particular more than 99%, in particular according to one of the exemplary embodiments of the process described above for the preparation of such compounds.
  • These palladium(II) compounds of the general formula VIII can be used, for example, as catalysts and/or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. They are advantageously suitable as precatalysts and/or catalysts for the reactions specified below.
  • the new palladium(II) dimers of the formula VIII claimed here are catalyst precursors that are easy to use and have excellent catalytic performance. Advantageously, they are easily accessible in one step from commercially available precursors and react without problems with a large number of electron donor ligands, in particular phosphine and NHC ligands, to form defined palladium(II) complexes. Starting from the new dimeric palladium(II) compounds of the formula VIII, it is therefore possible to produce, even in situ, highly active monoligated palladium(II) precatalysts and/or palladium(II) catalysts in a simple and reproducible manner.
  • the expression “unsaturated ring” means a non-aromatic carbocycle or heterocycle which has at least one double bond.
  • the unsaturated ring can be part of a ring system consisting of two or more fused rings, which can include aliphatic, aromatic and other unsaturated carbo- and/or heterocycles.
  • a saturated ring is formed, for example, by the radicals R2 and R4 if, for example, an allyl halide derived from phenale or indene was used as starting material for the preparation of the compound of the formula VIII.
  • a compound according to the general formula VIII has two identical ⁇ 3 -bonded allyl ligands. The allyl ligand is derived in each case from a compound AH used as starting material according to the general formula
  • a palladium(0) compound which in particular has a ligand LS which is an organosilicon compound, in particular a cyclic or a non-cyclic siloxane can be reacted with 1-naphthylmethyl chloride.
  • a molar ratio of Pd:AH of at least 1:1 can be provided.
  • a palladium(II) compound of the formula VIII which can be obtained in this way then has two identical, in particular ⁇ 3 -bonded, allyl ligands derived from naphthalene.
  • a complex according to formula VIII has no naphthyl ligand in the true sense. This is because the electrons involved in the complexation of the palladium center are not in conjugation with the ring electrons.
  • the aromaticity of the bicyclic naphthalene is restricted to one of the two fused six-membered rings as a result of complex formation.
  • an ⁇ 1 -bonded ligand or ⁇ 3 -bonded allyl ligand derived from naphthalene is referred to as a naphthyl ligand for the sake of simplicity.
  • the product of the above example reaction is therefore referred to as a dimeric palladium(II) 1-methylnaphthyl chloride complex, where the chlorine atoms act as bridging ligands, ie two chlorine bridges are present, or as a chloride-bridged 1-methylnaphthylpalladium(II) dimer.
  • the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.
  • the term "weakly coordinating” also includes the expressions "very weakly coordinating" and “moderately strongly coordinating”.
  • Chloride, bromide or iodide can advantageously be used as halide anions X, particularly advantageously chloride or bromide, in particular chloride.
  • the monovalent weakly coordinating are in particular perfluorinated anions such.
  • R1 and R3 together form the first, in particular carbocyclic, ring with five to eight carbon atoms, which is unsaturated or saturated and is fused with at least one aromatic ring.
  • R1 and R3 of a compound according to formula VIII form the first, in particular carbocyclic, ring with five or six carbon atoms, which is unsaturated or saturated and is fused with at least one aromatic ring.
  • R1 and R3 together can be part of a naphthyl, anthracenyl, phenanthrenyl, phenalenyl, tetracenyl or chrysenyl ring system.
  • R1 and R3 together forming an unsaturated carbocyclic ring with six carbon atoms, the unsaturated six-membered ring being fused with at least one aromatic ring are the compounds 7-Cl, 7-Br, 8-Cl and 8-Br.
  • the electrons involved in the complexation of the palladium center are not in conjugation with the ring electrons.
  • the aromaticity of the bicyclic naphthalene is restricted to one of the two fused six-membered rings as a result of complex formation.
  • a derived from naphthalene, in particular ⁇ 3 -bonded, allyl ligand for the sake of simplicity referred to as naphthyl ligand.
  • the aforementioned example compound 7-Cl is therefore referred to as a dimeric palladium(II) 1-methylnaphthyl chloride complex, with the chlorine atoms acting as bridging ligands, i.e. two chlorine bridges being present, or as a chloride-bridged 1-methylnaphthylpalladium(II) dimer.
  • palladium(II) compounds of the formula VIII which are obtainable using an anthracenyl, phenanthrenyl, phenalenyl, fluorenyl, indenyl, tetracenyl or chrysenyl halide.
  • the radicals R1 and R3 together form the first, in particular carbocyclic, ring which is unsaturated or saturated and is fused with at least one aromatic ring
  • - the radicals R1 and R2 and/or or R3 and R4 a second, in particular carbocyclic, ring with 5 to 8 carbon atoms, which is aromatic or unsaturated and is fused to the first ring and/or to the at least one aromatic ring
  • the second aromatic or unsaturated ring being unsubstituted or optional with one or more radicals selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, benzyl, tolyl, xylyl , pyridinyl, and combinations thereof, may be substituted.
  • H hydrogen
  • the first unsaturated or saturated ring is selected from the group consisting of cyclopentenyl ring, cyclohexenyl ring, cycloheptenyl ring, cyclooctenyl ring, cyclopentyl ring, cyclohexyl ring, cycloheptyl ring and cyclooctyl ring and the second unsaturated or aromatic ring is selected from the group consisting a cyclopentadienyl ring, cyclohexadienyl ring, cycloheptadienyl ring, cyclooctadienyl ring and a benzene ring.
  • the radicals R2 and R4 together form the first, in particular carbocyclic, ring with five to eight carbon atoms, advantageously five or six carbon atoms, which is unsaturated or saturated and is fused with at least one aromatic ring .
  • An example of this is the compound 9-Cl shown above, in which R2 and R4 together are part of an ⁇ 3 -bonded allyl ligand derived from an indenyl system.
  • R2 and R4 together can also be part of an ⁇ 3 -bonded allyl ligand derived from a fluorenyl system.
  • R1 together with R3 forms a cyclohexenyl ring which is fused with a benzene ring, so that R1 and R3 are part of a naphthyl ring.
  • R1 to R4 of a compound of the formula VIII claimed here can be the following radicals. Residues marked with an asterisk * together form the indicated residue. a) R1 and R3 together form a first unsaturated ring, namely a cyclohexenyl ring, which is fused with at least one aromatic ring, namely a benzene ring.
  • R1 and R3 are part of a naphthyl-derived, in particular ⁇ 3 -bonded, allyl ligand, which for the sake of simplicity is referred to as a naphthyl ligand.
  • a naphthyl ligand examples of such compounds according to formula VIII are the compounds 7-Cl, 7-Br, 8-Cl and 8-Br shown below.
  • a compound of the general formula VIII.a where - X is an anionic ligand, - R4 is selected from the group consisting of hydrogen (H) and branched, straight-chain or cyclic alkyl radicals and - a radical Ra is an aromatic radical, wherein at least one ring of the respective aromatic radical R a with the Cyclohexenyl ring is fused, and an R b , an R c , and an R d radical are independently selected from the group consisting of hydrogen (H), branched, straight-chain, and cyclic alkyl radicals, branched, straight-chain, and cyclic alkylene radicals, branched, straight-chain and cyclic alkynyl groups, unsubstituted mononuclear or polynuclear aryl groups, substituted mononuclear or polynuclear aryl groups, unsubstituted mononuclear or polynuclear heteroaryl groups, and substituted
  • the new compounds of the formula VIII.a are generally obtainable in yields of usually more than 90%, often more than 97%, in particular more than 99%, in particular according to one of the exemplary embodiments of the process described above for preparing such compounds .
  • These palladium(II) compounds of the formula VIII.a can be used, for example, as catalysts and/or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. They are advantageously suitable as precatalysts and/or catalysts for the reactions specified below.
  • the new palladium(II) dimers of the formula VIII.a claimed here are catalyst precursors that are easy to use and have excellent catalytic performance.
  • the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.
  • the term "weakly coordinating” also includes the expressions "very weakly coordinating" and "moderately strongly coordinating”.
  • Chloride, bromide or iodide can advantageously be used as halide anions X, particularly advantageously chloride or bromide, in particular chloride.
  • the monovalent weakly coordinating are in particular perfluorinated anions such.
  • the radical R4 is selected from the group consisting of hydrogen (H), straight-chain alkyl radicals with one to ten carbon atoms, ie also with two, three, four, five, six, seven , eight or nine carbon atoms, branched alkyl radicals with one to ten carbon atoms, i.e. also with two, three, four, five, six, seven, eight or nine carbon atoms, and cyclic alkyl radicals with three to eight carbon atoms, i.e. also with four, five, six or seven carbon atoms.
  • the radical R4 is selected from the group consisting of hydrogen (H), straight-chain alkyl radicals with one to eight carbon atoms, branched alkyl radicals with one to eight carbon atoms and cyclic alkyl radicals with four, five or six carbon atoms.
  • the radical R1 is selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, and combinations thereof.
  • the radical Ra is selected from the group consisting of unsubstituted or substituted mononuclear aromatics, unsubstituted or substituted mononuclear heteroaromatics, unsubstituted or substituted polynuclear aromatics and unsubstituted or substituted polynuclear heteroaromatics.
  • the radical Ra is a mononuclear aromatic or heteroaromatic which is fused to the cyclohexenyl ring in the ortho-position or in the meta-position to the tertiary carbon atom of the cyclohexenyl ring.
  • the mononuclear aromatic or heteroaromatic can be selected from the group consisting of benzene, toluene, xylene, pyrazine, pyridine, pyrimidine, pyrrole, furan, thiophene and imidazole.
  • Ra is benzene
  • a naphthalene-derived ⁇ 3 -bonded allyl ligand is present.
  • the radical Ra is a polynuclear aromatic or heteroaromatic which is fused to the cyclohexenyl ring in the ortho-position and/or in the meta-position to the tertiary carbon atom of the cyclohexenyl ring.
  • the respective ⁇ 3 -bonded allyl ligand can be an ortho-fused ring system or an ortho-peri-fused ring system.
  • the ⁇ 3 -bonded allyl ligand can exist as a linear ring system or as a bent (angular) ring system.
  • the polynuclear aromatic can be selected from the group consisting of naphthalene, anthracene and phenanthrene.
  • the radical Ra is, for example, naphthalene, then an ⁇ 3 -bonded allyl ligand derived from anthracene or from phenanthrene or from phenalene can be present.
  • the radical Ra is anthracene, then an ⁇ 3 -bonded allyl ligand derived from tetracene is present.
  • Ra is phenanthrene
  • a chrysene-derived ⁇ 3 -bonded allyl ligand may be present.
  • a further variant of the claimed compounds according to formula VIII.a provides that the radical R b , the radical R c and the radical R d are independently selected from the group consisting of hydrogen (H), straight-chain alkyl radicals with one to ten carbon atoms , i.e. also with two, three, four, five, six, seven, eight or nine carbon atoms, branched alkyl radicals with one to ten carbon atoms, i.e. also with two, three, four, five, six, seven, eight or nine carbon atoms, and cyclic alkyl radicals with three to eight carbon atoms, i.e.
  • R b , R c , and R d are independently selected from the group consisting of hydrogen (H), straight chain alkyl of one to eight carbon atoms, branched chain alkyl of one to eight carbon atoms, cyclic alkyl with four, five or six carbon atoms, unsubstituted mononuclear or polynuclear aryl radicals with six to fourteen carbon atoms, i.e.
  • the radical R b , the radical R c and the radical R d are independently selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert -butyl, cyclopentyl, cyclohexyl, benzyl, tolyl, xylyl, pyridinyl, and combinations thereof.
  • the compound is selected from the compounds shown below
  • the object is achieved by a preparation containing i. a compound according to the general formula (VIII), where X and the radicals R1, R2, R3 and R4 are as defined above, or according to the general formula VIII.a wherein X, (R) ad and R4 are as defined above, and ii. at least one organosilicon compound.
  • organosilicon compound has already been defined above.
  • the compound contained in the preparation according to the general formula VIII or VIII.a or the preparation claimed here itself is in particular obtained or obtainable by the process described above for the preparation of a compound according to formula VIII, advantageously according to one of the exemplary embodiments described above.
  • Palladium(II) dimers according to formula VIII or formula VIII.a are easy-to-use catalyst precursors with excellent catalytic performance. Advantageously, they are easily accessible in one step from commercially available precursors and readily react with a variety of electron donor ligands, especially phosphine and NHC ligands, to defined palladium(II) complexes. Consequently, starting from dimeric palladium(II) compounds of the formula VIII or formula VIII.a, it is possible to produce, even in situ, highly active monoligated palladium(II) precatalysts and/or palladium(II) catalysts in a simple and reproducible manner.
  • the silicon content, which is present in particular in the form of the at least one organosilicon compound is ⁇ 100 ppm and ⁇ 1000 ppm, advantageously ⁇ 110 ppm and ⁇ 900 ppm, in particular ⁇ 120 ppm and ⁇ 800 ppm.
  • the silicon content, which is present in particular in the form of the at least one organosilicon compound can be determined using analytical methods which are known to the person skilled in the art, in particular using quantitative 1 H-NMR spectroscopy and/or atomic emission spectrometry with inductively coupled plasma Inductively Coupled Plasma-Atomic Emission Spectrometers (ICP-AES).
  • the preparation contains a solvent SZ.
  • the preparation can be in the form of a solution, suspension, dispersion or gel, in particular depending on the organosilicon compound contained and/or the solvent SZ used.
  • the solvent SZ can also be a solvent mixture.
  • alkanes aromatic hydrocarbons and polar solvents advantageously selected from the group consisting of alcohols, alkanes, ketones, ethers or combinations thereof, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, aromatic hydrocarbons having 6 to 9 carbon atoms, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, or mixtures thereof.
  • the solvent SZ comprises or is a solvent which is selected from the group consisting of alcohols, alkanes, aromatic hydrocarbons, ketones, e.g. B.
  • acetone, ethers, and combinations thereof in particular alcohols having 2 to 6 carbon atoms, aromatic hydrocarbons having 6 to 9 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, and mixtures thereof, the preparation is in the form of a solution or suspension.
  • the solvent SZ can be selected from the group consisting of diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol and isopropanol, and mixtures thereof.
  • Another variant of the preparation provides that the solvent SZ is miscible or identical to the solvent SC, which is used in the process for preparing the compound of the formula VIII.
  • the at least one organosilicon compound contains at least one terminal, in particular vinylic, double bond.
  • the at least one organosilicon compound comprises or is a cyclic or a non-cyclic siloxane.
  • the preparation contains at least one palladium compound according to the general formula [Pd(LS) 2 ] (III) in addition to the palladium compound according to the general formula VIII.
  • the general formula [Pd(LS) 2 ] (III) also includes multinuclear complexes, in particular dinuclear complexes according to the general formula [Pd 2 (LS) 3 ].
  • the ligand LS is in particular identical to the at least one organosilicon compound, in particular a cyclic or a non-cyclic siloxane, and the at least one organosilicon compound contains at least one terminal double bond.
  • the ligand LS is identical to the organosilicon compound, the ligand LS being in particular a cyclic or a non-cyclic siloxane which has at least one terminal, in particular vinylic, double bond.
  • the ligand LS is then advantageously coordinated or bonded to the palladium center of the compound according to the general formula [Pd(LS) 2 ] (III) via at least one pi bond.
  • one of the organosilicon compounds comprises or is a cyclic or a non-cyclic siloxane and/or one of the ligands LS is a cyclic or a non-cyclic siloxane, which is selected from the group consisting of 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-Tetramethyl-1,3-dithien-2-yldisiloxane, 1,1,3,3-Tetramethoxy-1,3- divinyldisiloxane, 1,3-dimethyl-1,3-divinyldisiloxanediol and 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane.
  • one of the organosilicon compounds comprises or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds) and/or one of the ligands is LS 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds ).
  • one of the organosilicon compounds and/or one of the ligands is LS dvds.
  • the new compounds of the formula IX claimed here are, in particular according to one of the exemplary embodiments of the process described below for the preparation of such compounds, usually in yields of usually more than 90%, often more than 97%, especially more than 99% available.
  • These palladium(II) compounds of the general formula IX can be used, for example, as catalysts and/or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. They are advantageously suitable as precatalysts and/or catalysts for the reactions specified below.
  • the anionic ligand X and the radicals R1, R2, R3 and R4 are as defined in a compound of formula VIII according to one of the embodiments described above, and the neutral electron donor ligand L is a phosphine ligand or an NHC ligand.
  • the neutral electron donor ligand L - is a tertiary phosphine according to the general formula P-R10R20R30, where R10 and R20 are independently selected from the group consisting of substituted and unsubstituted straight-chain alkyl radicals, substituted and unsubstituted branched alkyl radicals, substituted and unsubstituted cycloalkyl radicals, substituted and unsubstituted aryl radicals, and substituted and unsubstituted heteroaryl radicals, where the heteroatoms are selected from the group consisting of sulfur, nitrogen and oxygen, and R30 is defined as R10 and R20 or is a metallocenyl radical, or - a phosphine ligand selected from the group consisting of 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino))-1,1'-biphenyl (
  • R10 and R20 can independently be substituted and unsubstituted branched or straight-chain alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec -butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl or stearyl, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or adamantyl, or aryl groups such as phenyl, naphthyl or anthracyl.
  • alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec -butyl, tert-buty
  • the alkyl groups of the tertiary phosphine according to the general formula P-R10R20R30 can be optionally substituted with one or more substituents such as halide (F, Cl, Br or I) or alkoxy groups, e.g. B. methoxy, ethoxy or propoxy.
  • the aryl groups can be optionally substituted with one or more (e.g. 1, 2, 3, 4 or 5) substituents such as halide (F, Cl, Br or I), straight-chain or branched alkyl groups (e.g.
  • C 1 -C 10 alkyl alkoxy (eg C 1 -C 10 alkoxy), straight-chain or branched (dialkyl)amino groups (eg C 1 - C 10 dialkylamino), heterocycloalkyl (eg C3 - C 10 heterocycloalkyl groups such as morpholinyl and piperadinyl) or trihalomethyl (eg trifluoromethyl).
  • Suitable substituted aryl groups include, but are not limited to, 4-dimethylaminophenyl, 4-methylphenyl, 3,5-dimethylphenyl, 4-methoxyphenyl, and 4-methoxy-3,5-dimethylphenyl.
  • Heteroaryl groups such as pyridyl, furanyl, thiophenyl, pyrrolyl, or quinolinyl can also be used.
  • R10 and R20 of the tertiary phosphane are linked together according to the general formula P-R10R20R30 and form a ring structure with the phosphorus atom, in particular a four- to seven-membered ring.
  • R10 and R20 are the same and are tert-butyl, cyclohexyl, phenyl or substituted phenyl groups.
  • R10 and R20 are tert-butyl.
  • R10 and R20 may independently be alkoxy (e.g., C 1 - C 10 alkoxy) or aryloxy (e.g., C 1 - C 10 aryloxy).
  • R30 is defined like R10 and R20, but can also be a metallocenyl radical. In the latter embodiment, R30 is a substituted or unsubstituted metallocenyl group. The metallocenyl group has a first cyclopentadienyl radical and a second cyclopentadienyl radical.
  • a number p of radicals R40 can optionally be provided on the first cyclopentadienyl radical via which the tertiary phosphine according to the general formula P-R10R20R30 is bonded or coordinated to the palladium center, and a number q of radicals R41 can optionally be provided on the second cyclopentadienyl radical be.
  • R40 and R41 are independently organic groups having 1 to 20 carbon atoms.
  • R40 and R41 can, independently of one another, be defined like R10 and R20.
  • p can have the values 0, 1, 2, 3 or 4 and q can have the values 0, 1, 2, 3, 4 or 5.
  • q 5 and R41 is methyl or phenyl.
  • p 0.
  • R10 is methyl or phenyl and R10 and R20 are tert-butyl (QPhos), or R10 and R20 are tert-butyl and R30 is 4-dimethylaminophenyl (AmPhos), or R10 and R20 are tert-butyl and R30 is phenyl.
  • R10, R20 and R30 are the same and 1-adamantyl, 2-adamantyl, phenyl, orthotolyl, cyclohexyl, tert-butyl, or R10 and R20 are 1-adamantyl or 2-adamantyl and R30 is n-butyl.
  • the electron donor ligand L is a phosphine ligand according to general formula YPR 1 R 2 (Va) or Y 2 PR 1 (Vb) or Y 3 P (VI), where Y is as defined above , and wherein - the alkyl groups are selected from straight-chain, branched or cyclic alkyl groups with 1 to 10 carbon atoms, advantageously from straight-chain, branched or cyclic alkyl groups with 1 to 6 carbon atoms and cycloalkyl groups with 4 to 10 carbon atoms, - the aryl groups are selected from aryl groups with 6 to 14 carbon atoms, advantageously from aryl groups with 6 to 10 carbon atoms, - the alkenyl groups are selected from monounsaturated, polyunsaturated, straight-chain, branched and cyclic alkenyl groups with 2 to 10 carbon atoms, advantageously from monounsaturated, polyunsaturated
  • the electron donor ligand L is a phosphine ligand according to the general formula where - On is a phosphonium group -PR 3 R 4 R 5 where R 3 , R 4 and R 5 are independently selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 4 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, - X is selected from the group consisting of straight-chain, branched and cyclic alkyl groups having 1 to 6 carbon atoms, aryl groups having 3 to 10 carbon atoms, mono-saturated, polyunsaturated, straight-chain, branched and cyclic alkenyl groups having 2 to 6 carbon atoms, trialkylsilyl groups -SiR 3 R 4 R 5 , arylsulfonyl groups R 12 -SO 2 R 3 and - R 1 and R 2 are ary
  • the electron donor ligand L is a phosphine ligand according to the general formula YPR 1 R 2 (Va) or Y 2 PR 1 (Vb) or Y 3 P (VI), where Y as above is defined and where R 3 , R 4 and R 5 119 a) are independently selected from the group consisting of methyl, ethyl, butyl, cyclohexyl, phenyl, and combinations thereof or b) are the same and are selected from the group consisting of methyl, ethyl, butyl, cyclohexyl, phenyl, and combinations thereof , advantageously cyclohexyl and phenyl.
  • the electron donor ligand L is a phosphine ligand according to the general formula YPR 1 R 2 (Va) or Y 2 PR 1 (Vb) or Y 3 P (VI), where Y is as defined above and where X is selected from the group consisting of methyl, ethyl, cyclohexyl, phenyl, p-tolyl, trimethylsilyl, p-tolylsulfonyl, and combinations thereof.
  • the electron donor ligand L is a phosphine ligand according to the general formula YPR 1 R 2 (Va) or Y 2 PR 1 (Vb) or Y 3 P (VI), where Y is like is defined above and wherein R 1 and R 2 are independently selected from the group consisting of phenyl, cyclohexyl, methyl, and combinations thereof.
  • the neutral electron donor ligand L is cyclohexylphosphine, triphenylphosphine, triorthotolylphosphine.
  • R13 and R14 can in particular be identical or different and independently of one another substituted or unsubstituted phenyl, or phenyl substituted with one or more substituents selected from the group consisting of C 1 - C 20 alkyl, substituted C 1 -C 20 alkyl, C 1 -C 20 heteroalkyl, substituted C 1 -C 20 heteroalkyl, C 5 -C 24 aryl, substituted C 5 -C 24 aryl, C 5 -C 24 heteroaryl, C C 6 -C 24 aralkyl, C 6 -C
  • Q can be a bridge of two or three atoms and can be saturated or unsaturated.
  • Examples of functional groups are carboxyl, C 1 -C 20 alkoxy, C 5 -C 24 aryloxy, C 2 -C 20 alkoxycarbonyl, C 5 -C 24 alkoxycarbonyl, C2-C 24 acyloxy, C 1 -C 20 alkylthio, C 5 - C 24 arylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulphinyl optionally substituted with one or more Substituents selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 5 -C 14 aryl, hydroxyl, sulfhydryl, formyl, and halogen (F, Cl, Br, I).
  • R21, R11, R23 and R24 are in particular selected from hydrogen (H), C1 -C12 alkyl, substituted C1 -C12 alkyl, C1 -C12 heteroalkyl , substituted C1 -C12 heteroalkyl , phenyl and substituted phenyl .
  • two radicals selected from R21, R22, R23 and R24 can be joined together and form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g. a C 4 -C 12 alicyclic ring or a C 5 - or C 6 -aryl group, which itself may be substituted, such as with aromatic groups or other substituents.
  • the radicals R21, R22, R23 and R24 are independently selected from the group consisting of hydrogen (H), a branched or straight-chain alkyl, alkylene or alkynyl radical having one to ten carbon atoms, a cyclic alkyl , alkylene or alkynyl radical with three to ten carbon atoms, a substituted or unsubstituted mononuclear or polynuclear aryl radical with six to fourteen carbon atoms and a substituted or unsubstituted mononuclear or polynuclear heteroaryl radical with five to thirteen carbon atoms, -O-alkyl, -OC(O)- alkyl, -O-(aryl), -OC(O)-aryl, -F, -Cl, -OH, -NO 2 , -Si(alkyl) 3 , -CF 3 , -CN, -CO 2 H, - C(H), a branche
  • alkyl, alkylene or alkynyl radicals can each be substituted, for example, with F, Cl, Br, I, alkyl, O-alkyl, phenyl, O-phenyl, OH, NH 2 and/or CF 3 ; . with F, Cl, Br, I, alkyl, O-alkyl, phenyl and/or O-phenyl.
  • N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as the neutral electron donor ligand L include, for example, the following structures:
  • R13 and R14 can independently represent, for example, DIPP, Mes, 3,5-di-tert-butylphenyl, 2-methylphenyl and combinations thereof, where DIPP or DiPP represents 2,6-diisopropylphenyl and Mes represents 2,4, 6-trimethylphenyl (mesityl).
  • R13 and R14 can independently represent, for example, DIPP, Mes, 3,5-di-tert-butylphenyl, 2-methylphenyl, and combinations thereof.
  • suitable N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as the neutral electron donor ligand L include, for example, the following structures:
  • R W1 , R W2 , R W3 , R W4 can independently be hydrogen (H), unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom-containing hydrocarbyl and where one or both R W3 and/or R W4 can be independently selected from halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio or nitroso groups.
  • N-heterocyclic carbene (NHC) ligands useful as the neutral electron donor ligand L are disclosed, for example, in US Patent Nos.
  • the neutral electron donor ligand L is selected from the group consisting of tri-tert-butylphosphine, tricyclohexylphosphine, tri-1-adamantylphosphine, tri-2-adamantylphosphine, di-(1-adamantyl )-n-butylphosphine ( cataCXium® A), 2-(dicyclohexylphosphino)-2',4',6'-tri-iso-propyl-1,1'-biphenyl (XPhos), 2-dicyclohexylphosphino-2',6 '-di-iso-propoxy-1,1'-biphenyl (RuPhos), di-1,3-bis(2,4,6-trimethylpheny
  • a compound of the general formula IX.a where - X and L are as defined in a compound according to formula IX, - R4 is selected from the group consisting of hydrogen (H) and branched, straight-chain or cyclic alkyl radicals and - a radical R a is an aromatic radical, wherein at least one ring of respective aromatic radical R a is fused to the cyclohexenyl ring, and R b , R c , and R d are independently selected from the group consisting of hydrogen (H), branched, straight-chain, and cyclic alkyl, branched, straight-chain, and cyclic alkylene, branched, straight-chain, and cyclic alkynyl, unsubstituted mononuclear or polynuclear aryl radicals, substituted mononuclear or polynuclear aryl radicals, unsubstituted mononuclear or polynuclear heteroary
  • the new compounds of formula IX.a claimed here are generally in yields of mostly more than 90%, often more than 97%, in particular according to one of the exemplary embodiments of the process described above for preparing compounds of formula IX than 99% available.
  • the palladium(II) compounds of the formula IX. can be used, for example, as catalysts and/or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. They are advantageously suitable as precatalysts and/or catalysts for the reactions specified below.
  • the radical R4 is selected from the group consisting of hydrogen (H), straight-chain alkyl radicals with one to ten carbon atoms, i.e. also with two, three, four, five, six, seven, eight or nine carbon atoms, branched alkyl radicals with one to ten carbon atoms, i.e. also with two, three, four, five, six, seven, eight or nine carbon atoms, and cyclic alkyl radicals with three to eight carbon atoms, i.e. also with four, five, six or seven carbon atoms.
  • the radical R4 is selected from the group consisting of hydrogen (H), straight-chain alkyl radicals with one to eight carbon atoms, branched alkyl radicals with one to eight carbon atoms and cyclic alkyl radicals with four, five or six carbon atoms.
  • the radical R1 is selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, and combinations thereof.
  • the radical Ra is selected from the group consisting of unsubstituted or substituted mononuclear aromatics, unsubstituted or substituted mononuclear heteroaromatics, unsubstituted or substituted polynuclear aromatics and unsubstituted or substituted polynuclear heteroaromatics.
  • the radical Ra is a mononuclear aromatic or heteroaromatic which is fused to the cyclohexenyl ring in the ortho-position or in the meta-position to the tertiary carbon atom of the cyclohexenyl ring.
  • the mononuclear aromatic or heteroaromatic can be selected from the group consisting of benzene, toluene, xylene, pyrazine, pyridine, pyrimidine, pyrrole, furan, thiophene and imidazole.
  • R2 is benzene
  • a naphthalene-derived ⁇ 3 -bonded allyl ligand is present.
  • the radical Ra is a polynuclear aromatic or heteroaromatic which is fused to the cyclohexenyl ring in the ortho-position and/or in the meta-position to the tertiary carbon atom of the cyclohexenyl ring.
  • the respective ⁇ 3 -bonded allyl ligand can be an ortho-fused ring system or an ortho-peri-fused ring system.
  • the ⁇ 3 -bonded allyl ligand can exist as a linear ring system or as a bent (angular) ring system.
  • the polynuclear aromatic can be selected from the group consisting of naphthalene, anthracene and phenanthrene.
  • the radical Ra is, for example, naphthalene, then an ⁇ 3 -bonded allyl ligand derived from anthracene or from phenanthrene or from phenalene can be present.
  • the radical Ra is anthracene, then an ⁇ 3 -bonded allyl ligand derived from tetracene is present.
  • Ra is phenanthrene
  • a chrysene-derived ⁇ 3 -bonded allyl ligand may be present.
  • a further variant of the claimed compounds according to formula IX.a provides that the radical R b , the radical R c and the radical R d are independently selected from the group consisting of hydrogen (H), straight-chain alkyl radicals with one to ten carbon atoms , i.e. also with two, three, four, five, six, seven, eight or nine carbon atoms, branched alkyl radicals with one to ten carbon atoms, i.e. also with two, three, four, five, six, seven, eight or nine carbon atoms, and cyclic alkyl radicals with three to eight carbon atoms, i.e.
  • the radical R b , the radical R c and the radical R d are independently selected from the group consisting of hydrogen (H), straight-chain alkyl radicals with one to eight carbon atoms, branched Alkyl radicals with one to eight carbon atoms, cyclic alkyl radicals with four, five or six carbon atoms, unsubstituted mononuclear or polynuclear aryl radicals with six to fourteen carbon atoms, i.e.
  • the radical R b , the radical R c and the radical R d are independently selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert -butyl, cyclopentyl, cyclohexyl, benzyl, tolyl, xylyl, pyridinyl, and combinations thereof.
  • the compound has the formula IX.b or IX.c on, where X and L are as defined in a compound according to formula IX.
  • a compound of the formula IX.c can be selected, for example, from the following compounds:
  • the object is achieved by a compound of the general formula IX.d
  • - X is an anionic ligand
  • - the radicals R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl radicals, branched, straight-chain and cyclic alkylene radicals, branched, straight-chain and cyclic alkynyl radicals, unsubstituted mononuclear or polynuclear aryl radicals, substituted mononuclear or polynuclear aryl radicals, unsubstituted mononuclear or polynuclear heteroaryl radicals and substituted mononuclear or polynuclear heteroaryl radicals or - two radicals of R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form an unsaturated or aliphatic ring or - two radicals of R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form a first radicals
  • the new compounds of formula IX.d claimed here are generally in yields of mostly more than 90%, often more than 97%, in particular according to one of the exemplary embodiments of the process described above for preparing compounds of formula IX than 99% available.
  • These palladium(II) compounds of the formula IX.d can be used, for example, as catalysts and/or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. They are advantageously suitable as precatalysts and/or catalysts for the reactions specified below.
  • the expression “unsaturated ring” means a non-aromatic carbocycle or heterocycle which has at least one double bond.
  • the unsaturated ring can be part of a ring system consisting of two or more fused rings, which can include aliphatic, aromatic and other unsaturated carbo- and/or heterocycles.
  • a saturated ring is formed, for example, by the radicals R2 and R4 if, for example, an allyl halide derived from phenalene or indene was used as starting material for the preparation of the compound of the formula IX.d.
  • the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.
  • the term "weakly coordinating" also includes the expressions "very weakly coordinating" and "moderately strongly coordinating".
  • Chloride, bromide or iodide can advantageously be used as halide anions X, particularly advantageously chloride or bromide, in particular chloride.
  • the monovalent weakly coordinating are in particular perfluorinated anions such.
  • the radicals R1, R2, R3 and R4 are as defined in a compound according to formula VIII.
  • a compound according to formula IX.d can surprisingly be a heteroleptic palladium complex of formula IX.P below.
  • the object is achieved by a compound of the formula XI
  • This compound is obtained, in particular, by reacting the compound 8-Cl with 1,3-bis-(2,6-diisopropylphenyl)imidazolin-2-ylidene (unsaturated NHC ligand, “IPr”), advantageously in an aprotic-polar Solvents, in particular in an ether, for example in diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran or 1,4-dioxane.
  • IPr unsaturated NHC ligand
  • the molar ratio 8-Cl:IPr is, for example, 1:1.
  • the reaction can advantageously be carried out at room temperature, the reaction time depending on the choice of the other reaction conditions, e.g. B. choice of solvent or solvent mixture, concentration of the starting materials, molar ratio of the starting materials, is usually between 10 minutes and 3 hours.
  • Single crystals of the compound XI ⁇ toluene suitable for a crystal structure analysis were obtained from toluene/hexane.
  • the compound of the formula XI can be used, for example, as a catalyst and/or precatalyst, in particular as a precatalyst in palladium-catalyzed cross-coupling reactions.
  • - X is an anionic ligand
  • the radicals R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl radicals, branched, straight-chain and cyclic alkylene radicals, branched, straight-chain and cyclic alkynyl radicals, unsubstituted mononuclear or polynuclear aryl radicals , substituted mononuclear or polynuclear aryl radicals, unsubstituted mononuclear or polynuclear heteroaryl radicals and substituted mononuclear or polynuclear heteroaryl radicals or two radicals of R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form an unsaturated or
  • the procedure comprises the steps: A. Making available i. a palladium compound, in particular a mononuclear or multinuclear palladium(0) compound, where at least one palladium center has a ligand LS carries, which is an organosilicon compound, wherein the ligand LS is in particular a cyclic or a non-cyclic siloxane, ii.
  • a compound AH according to the general formula where - X is an anionic ligand, - the radicals R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl radicals, branched, straight-chain and cyclic alkylene radicals, branched, straight-chain and cyclic Alkynyl radicals, unsubstituted mononuclear or polynuclear aryl radicals, substituted mononuclear or polynuclear aryl radicals, unsubstituted mononuclear or polynuclear heteroaryl radicals and substituted mononuclear or polynuclear heteroaryl radicals or - two radicals of R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together an unsaturated or form an aromatic ring or - two radicals of R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R
  • the palladium compound to be made available in step A. which is in particular a palladium(0) compound, can be mononuclear or multinuclear, in particular dinuclear, as a monomer or oligomer, in particular dimer, and/or as a solvent adduct.
  • the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.
  • weakly coordinating also includes the expressions "very weakly coordinating" and "moderately strongly coordinating".
  • Chloride, bromide or iodide can advantageously be used as halide anions X, particularly advantageously chloride or bromide, in particular chloride.
  • the monovalent weakly coordinating are in particular perfluorinated anions such.
  • the expression “unsaturated ring” means a non-aromatic carbocycle or heterocycle which has at least one double bond.
  • the unsaturated ring can also be part of a ring system consisting of two or more fused rings, which can include aliphatic, aromatic and other unsaturated carbo- and/or heterocycles.
  • the radicals R1 and R3 form, for example, a saturated ring if, for example, an allyl halide AH derived from phenalene or indene was used as starting material for the preparation of the compound of the formula IX.
  • An embodiment of the process claimed here for preparing a compound according to general formula IX provides that - R1 to R4 and X are as defined in the above-described embodiments of the process for preparing a compound according to general formula VIII and - the neutral electron donor ligand L is a phosphine ligand or an NHC ligand.
  • the neutral electron donor ligand L - is a tertiary phosphane according to the general formula P-R10R20R30, where R10 and R20 are independently selected from the group consisting of substituted and unsubstituted straight-chain alkyl radicals , substituted and unsubstituted branched alkyl radicals, substituted and unsubstituted cycloalkyl radicals, substituted and unsubstituted aryl radicals, and substituted and unsubstituted heteroaryl radicals, wherein the heteroatoms are selected from the group consisting of sulfur, nitrogen and oxygen, and R30 is defined as R10 and R20 or a metallocenyl radical is, or - a phosphine ligand selected from the group consisting of 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino))-1,
  • R13 and R14 are the same or different and are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C20 alkenyl, substituted or unsubstituted C1 to C20 heteroalkyl , substituted or unsubstituted C1 to C20 alkynyl , substituted or unsubstituted alicyclic or aromatic rings or ring systems having one to five rings, and optionally having one or more heteroatoms and/or substituents and - Q is a substituted or unsubstituted hydrocarbon bridge, which is saturated or unsaturated, or a substituted or unsubstituted heteroatom -containing hydrocarbon bridge optionally having two or more substituents on adjacent atoms connected to other cyclic structures and having a fused cyclic structure with from two to five cyclic structures.
  • R10 and R20 can independently be substituted and unsubstituted branched or straight-chain alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec -butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl or stearyl, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or adamantyl, or aryl groups such as phenyl, naphthyl or anthracyl.
  • alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec -butyl, tert-buty
  • the alkyl groups of the tertiary phosphine according to the general formula P-R10R20R30 can be optionally substituted with one or more substituents such as halide (F, Cl, Br or I) or alkoxy groups, e.g. B. methoxy, ethoxy or propoxy.
  • the aryl groups can be optionally substituted with one or more (e.g. 1, 2, 3, 4 or 5) substituents such as halide (F, Cl, Br or I), straight-chain or branched alkyl groups (e.g.
  • C 1 -C 10 alkyl alkoxy (eg C 1 -C 10 alkoxy), straight-chain or branched (dialkyl)amino groups (eg C1 - C10 dialkylamino), heterocycloalkyl (eg C3 - C10 heterocycloalkyl groups such as morpholinyl and piperadinyl) or trihalomethyl (eg trifluoromethyl).
  • Suitable substituted aryl groups include, but are not limited to, 4-dimethylaminophenyl, 4-methylphenyl, 3,5-dimethylphenyl, 4-methoxyphenyl, and 4-methoxy-3,5-dimethylphenyl.
  • R10 and R20 of the tertiary phosphane are linked together according to the general formula P-R10R20R30 and form a ring structure with the phosphorus atom, in particular a four- to seven-membered ring.
  • R10 and R20 are the same and are tert-butyl, cyclohexyl, phenyl or substituted phenyl groups.
  • R10 and R20 are tert-butyl.
  • R10 and R20 may independently be alkoxy (e.g., C 1 - C 10 alkoxy) or aryloxy (e.g., C 1 - C 10 aryloxy).
  • R30 is defined like R10 and R20, but can also be a metallocenyl radical. In the latter embodiment, R30 is a substituted or unsubstituted metallocenyl group. The metallocenyl group has a first cyclopentadienyl radical and a second cyclopentadienyl radical.
  • a number p of radicals R40 can optionally be provided on the first cyclopentadienyl radical via which the tertiary phosphine according to the general formula P-R10R20R30 is bonded or coordinated to the palladium center, and a number q of radicals R41 can optionally be provided on the second cyclopentadienyl radical be.
  • R40 and R41 are independently organic groups with 1 up to 20 carbon atoms.
  • R40 and R41 can, independently of one another, be defined like R10 and R20.
  • p can have the values 0, 1, 2, 3 or 4 and q can have the values 0, 1, 2, 3, 4 or 5.
  • q 5 and R41 is methyl or phenyl.
  • p 0.
  • R10 is methyl or phenyl and R10 and R20 are tert-butyl (QPhos), or R10 and R20 are tert-butyl and R30 is 4-dimethylaminophenyl (AmPhos), or R10 and R20 are tert-butyl and R30 is phenyl.
  • R10, R20 and R30 are the same and 1-adamantyl, 2-adamantyl, phenyl, orthotolyl, cyclohexyl, tert-butyl, or R10 and R20 are 1-adamantyl or 2-adamantyl and R30 is n-butyl.
  • the electron-donor ligand L is a phosphine ligand according to the general formula YPR 1 R 2 (Va) or Y 2 PR 1 (Vb) or Y 3 P (VI), where Y is as above is defined, and wherein - the alkyl groups are selected from straight-chain, branched or cyclic alkyl groups with 1 to 10 carbon atoms, advantageously from straight-chain, branched or cyclic alkyl groups with 1 to 6 carbon atoms and cycloalkyl groups with 4 to 10 carbon atoms, - the aryl groups are selected from aryl groups with 6 to 14 carbon atoms, advantageously from aryl groups with 6 to 10 carbon atoms, - the alkenyl groups are selected from monounsaturated, polyunsaturated, straight-chain, branched and cyclic alkenyl groups with 2 to 10 carbon atoms, advantageously from monouns
  • the electron donor ligand L is a phosphine ligand of general formula where - On is a phosphonium group -PR 3 R 4 R 5 where R 3 , R 4 and R 5 are independently selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 4 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, - X is selected from the group consisting of straight-chain, branched and cyclic alkyl groups with 1 to 6 carbon atoms, aryl groups with 3 to 10 Carbon atoms, monosaturated, polyunsaturated, straight-chain, branched and cyclic alkenyl groups with 2 to 6 carbon atoms, trialkylsilyl groups -SiR 3 R 4 R 5 , arylsulfonyl groups R 12 -SO 2 R 3 and - R 1 and R 2 ary
  • the electron donor ligand L is a phosphine ligand according to the general formula YPR 1 R 2 (Va) or Y 2 PR 1 (Vb) or Y 3 P (VI), where Y is as defined above and wherein R 3 , R 4 and R 5 are c) independently selected from the group consisting of methyl, ethyl, butyl, cyclohexyl, phenyl, and combinations thereof or d) are the same and are selected from the group consisting from methyl, ethyl, butyl, cyclohexyl, phenyl, and combinations thereof, advantageously cyclohexyl and phenyl.
  • the electron donor ligand L is a phosphine ligand according to the general formula YPR 1 R 2 (Va) or Y 2 PR 1 (Vb) or Y 3 P (VI), where Y is like is defined above and wherein X is selected from the group consisting of methyl, ethyl, cyclohexyl, phenyl, p-tolyl, trimethylsilyl, p-tolylsulfonyl, and combinations thereof.
  • the electron donor ligand L is a phosphine ligand according to the general formula YPR 1 R 2 (Va) or Y 2 PR 1 (Vb) or Y 3 P (VI), where Y is as defined above and wherein R 1 and R 2 are independently selected from the group consisting of phenyl, cyclohexyl, methyl, and combinations thereof.
  • the neutral electron donor ligand L is cyclohexylphosphine, triphenylphosphine, triorthotolylphosphine.
  • R13 and R14 can in particular be identical or different and independently of one another substituted or unsubstituted phenyl, or phenyl substituted with one or more substituents selected from the group consisting of C 1 - C 20 alkyl, substituted C 1 -C 20 alkyl, C 1 -C 20 heteroalkyl, substituted C 1 -C 20 heteroalkyl, C 5 -C 24 aryl, substituted C 5 -C 24 aryl, C 5 -C 24 heteroaryl, C C 6 -C 24 aralkyl, C 6 -C
  • Q can be a bridge of two or three atoms and can be saturated or unsaturated.
  • Examples of functional groups are carboxyl, C1-C20 alkoxy, C5-C24 aryloxy , C2- C20 alkoxycarbonyl , C5 - C24 alkoxycarbonyl , C2- C24 acyloxy , C1- C20 alkylthio , C5 -C 24 arylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulphinyl optionally substituted with one or more substituents selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 5 -C 14 aryl, hydroxyl, sulfhydryl, formyl, and halogen (F, Cl, Br, I).
  • R21, R11, R23 and R24 are in particular selected from hydrogen (H), C1 -C12 alkyl, substituted C1 -C12 alkyl, C1 -C12 heteroalkyl , substituted C1 -C12 heteroalkyl , phenyl and substituted phenyl .
  • two radicals selected from R21, R22, R23 and R24 can be joined together and form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g. a C 4 -C 12 alicyclic ring or a C 5 - or C 6 -aryl group, which itself may be substituted, such as with aromatic groups or other substituents.
  • the radicals R21, R22, R23 and R24 are independently selected from the group consisting of hydrogen (H), a branched or straight-chain alkyl, alkylene or alkynyl radical having one to ten carbon atoms, a cyclic alkyl , alkylene or alkynyl radical with three to ten carbon atoms, a substituted or unsubstituted mononuclear or polynuclear aryl radical with six to fourteen carbon atoms and a substituted or unsubstituted mononuclear or polynuclear heteroaryl radical with five to thirteen carbon atoms, -O-alkyl, -OC(O)- alkyl, -O-(aryl), -OC(O)-aryl, -F, -Cl, -OH, -NO 2 , - Si(alkyl) 3 , -CF 3 , -CN, -CO 2 H, -C(O
  • alkyl, alkylene or alkynyl radicals can each be substituted, for example, with F, Cl, Br, I, alkyl, O-alkyl, phenyl, O-phenyl, OH, NH 2 and/or CF 3 ; . with F, Cl, Br, I, alkyl, O-alkyl, phenyl and/or O-phenyl.
  • N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as the neutral electron donor ligand L include, for example, the following structures:
  • R13 and R14 can independently represent, for example, DIPP, Mes, 3,5-di-tert-butylphenyl, 2-methylphenyl and combinations thereof, where DIPP or DiPP represents 2,6-diisopropylphenyl and Mes represents 2,4, 6-trimethylphenyl (mesityl).
  • R13 and R14 can independently represent, for example, DIPP, Mes, 3,5-di-tert-butylphenyl, 2-methylphenyl, and combinations thereof.
  • N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as the neutral electron donor ligand L include, for example, the following structures: where R W1 , R W2 , R W3 , R W4 can independently be hydrogen (H), unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom-containing hydrocarbyl and where one or both R W3 and/or R W4 can be independently selected from Halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio or nitroso groups.
  • R W1 , R W2 , R W3 , R W4 can independently be hydrogen (H), unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom-containing hydrocarbyl and where one or both R W3 and/or R W4 can be independently selected from Halogen, nitro, amido, carboxyl, al
  • N-heterocyclic carbene (NHC) ligands useful as the neutral electron donor ligand L are disclosed, for example, in US Patent Nos. 7,378,528; 7,652,145; 7,294,717; 6,787,620; 6,635,768; and 6,552,139.
  • the neutral electron donor ligand L is selected from the group consisting of tri-tert-butylphosphine, tricyclohexylphosphine, Tri-1-adamantylphosphine, tri-2-adamantylphosphine, di-(1-adamantyl)-n-butylphosphine (cataCXium ® A), 2-(dicyclohexylphosphino)-2',4',6'-tri-iso-propyl- 1,1'-biphenyl (XPhos), 2-dicyclohexylphosphino-2',6'-di-iso-propoxy-1,1'-biphenyl (RuPhos), di-1,3-bis(2,4,6 - trimethylphenyl)-imidazolidin-2-ylidene ("SIMes”), 1,3-bis-(2,6-dazolidin-2-ylidene ("SIMes”), 1,3-bis-(
  • reaction in step B comprises the following steps: B.1.
  • submission of the palladium compound as a solid, solution or suspension, B.2. adding the neutral electron donor ligand L, as a solid, solution or suspension, and B.3. adding the compound AH, as a solid, solution or suspension, or B.1.
  • submission of the compound AH as a solid, solution or suspension, B.2. adding the palladium compound, as a solid, solution or suspension, and B.3. adding the neutral electron donor ligand L, as a solid, solution or suspension, or B.1.
  • a molar Pd:AH is at least 1:1, advantageously between 1.0:1.0 and 1.0:5.0, more advantageously between 1.0:1.1 and 1.0 : 4.0, particularly advantageously between 1.0:1.2 and 1.0:3.0, in particular between 1.0:1.3 and 1.0:2.0, for example 1.0:1.4 or 1.0:1.5 or 1.0:1.6 or 1.0:1.7 or 1.0:1.8 or 1.0:1.9 or 1.0:2.1 or 1 .0 : 2.2 or 1.0 : 2.3 or 1.0 : 2.4 or 1.0 : 2.5 or 1.0 : 2.6 or 1.0 : 2.7 or 1.0 : 2.8 or 1.0 : 2.9 or 1.0 : 3.1 or 1.0 : 3.2 or 1.0 : 3.3 or 1.0 : 3.4 or 1.0 : 3 .5 or 1.0 : 3.6 or 1.0 : 3.7 or 1.0 : 3.8 or 1.0:3.9 or 1.0:4.1 or 1.0:4.2 or 1.0:4.3 or 1.0
  • a molar ratio Pd:L is at least 1:1, advantageously between 1.0:1.0 and 1.0:1.5, even more advantageously between 1.00:1.01 and 1.00 : 1.49, particularly advantageously between 1.00:1.02 and 1.00:1.48, in particular between 1.00:1.03 and 1.00:1.47, for example 1.00:1.04 or 1.00 : 1.05 or 1.00 : 1.06 or 1.00 : 1.07 or 1.00 : 1.08 or 1.00 : 1.09 or 1.00 : 1.10 or 1 .00 : 1.11 or 1.00 : 1.12 or 1.00 : 1.13 or 1.00 : 1.14 or 1.00 : 1.15 or 1.00 : 1.16 or 1.00 : 1.17 or 1.00 : 1.18 or 1.00 : 1.19 or 1.00 : 1.20 or 1.00 : 1.25 or 1.00 : 1.30 or 1.00 : 1 .35 or 1.00 : 1.40 or 1.00 : 1.45.
  • the reaction in step B. is carried out in at least one solvent SL.
  • the solvent SL is selected from the group consisting of alcohols, alkanes, aromatic hydrocarbons, ketones, ethers, and combinations thereof, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as Petroleum ethers, aromatic hydrocarbons containing 6 to 9 carbon atoms, ethers containing 4 to 8 carbon atoms or ketones containing 2 to 6 carbon atoms, and mixtures thereof.
  • the provision of the palladium compound in step A. comprises a reaction of a palladium(II) compound which advantageously consists of a palladium(II) cation and two monovalent anions or a divalent anion, with a ligand LS, which is an organosilicon compound, advantageously a cyclic or a non-cyclic siloxane, in the presence of a base.
  • a palladium compound to be made available in step A. can thus advantageously be prepared in situ, advantageously in a solvent SL1.
  • the palladium(II) compound can have two different or two identical monovalent anions or one divalent anion.
  • a neutral ligand such as B. COD is not provided. Consequently, inexpensive, commercially available palladium(II) compounds, such as PdCl 2 , can advantageously be used.
  • a palladium(II) compound of the type [Pd(ligand)Y 2 ] which is associated with expenditure of time and money, e.g. B. ligand COD, so can be omitted as a starting material for the in situ generation of mononuclear or multinuclear palladium compound. This is particularly advantageous from a (nuclear) economic and ecological point of view.
  • the number of possible impurities in the end product according to general form IX is reduced in this way.
  • the palladium(II) compound to be used as starting material in the above-mentioned in situ preparation has two identical monovalent anions which are selected in particular from the group consisting of halides and monovalent weakly coordinating anions.
  • the expression “generated/manufactured in situ” or “in situ generation/manufacture” and the term “weakly coordinating” have already been defined above.
  • the term “bases” means inorganic and organic bases, in particular inorganic bases, but not organometallic bases. The bases should not decompose in water. Suitable bases are e.g. B. Salts of Bronsted acids.
  • Carbonates, bicarbonates, acetates, formates, ascorbates, oxalates and hydroxides are advantageously used. These can be used in the form of their ammonium salts (Brönsted acid)NR 4 , where R is, for example, H or alkyl, alkali metal salts, for example sodium or potassium salts, and alkaline earth metal salts.
  • R is, for example, H or alkyl
  • alkali metal salts for example sodium or potassium salts
  • alkaline earth metal salts alkaline earth metal salts.
  • the reaction of the palladium(II) compound with a ligand LS, which is an organosilicon compound, in step A. usually takes place in a solvent SL1.
  • the solvents SL1 are not particularly limited. Examples of possible solvents SL1 are polar solvents such as water, alcohols, ketones, hydrocarbons, e.g. B.
  • aromatic hydrocarbons such as benzene and toluene, or aliphatic hydrocarbons such as pentane, hexane and heptane, open-chain or cyclic ethers, amides and esters.
  • the solvent SL1 intended for the provision or reaction in step A. and the solvent SL intended for the reaction in step B. are miscible with one another or are identical. Then there is no need to change the solvent, which is particularly advantageous from an economic and ecological point of view.
  • a definition of the expression "two miscible solvents" has already been given above.
  • one of the ligands LS is a cyclic or a non-cyclic siloxane which is selected from the group consisting of 1,1,3,3-tetramethyl-1, 3-divinyldisiloxane (dvds), 1,1,3,3-tetramethyl-1,3-dithien-2-yldisiloxane, 1,1,3,3-tetramethoxy-1,3-divinyldisiloxane, 1,3-dimethyl-1 ,3-divinyldisiloxanediol and 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane.
  • dvds 1,1,3,3-tetramethyl-1, 3-divinyldisiloxane
  • dvds 1,1,3,3-tetramethyl-1,3-dithien-2-yldisiloxane
  • One of the ligands LS is advantageously 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds).
  • one of the ligands is LS dvds.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0)—abbreviated as [Pd 2 (dvds) 3 ], [Pd(dvds)], Pd( vs), Pd-VS or palladium-VS - is an excellent starting material for the preparation of compounds of the formula IX, for example ⁇ -allylpalladium halide complexes such as ⁇ -allylpalladium chloride complexes, which in particular by means of the process described here usually in yields of mostly more than 90%, often more than 97%, in particular more than 99%.
  • the reaction temperature in step A. and/or step B., in particular in step B. is 10°C to 60°C, in particular 15°C to 45°C or 20°C to 30°C.
  • the reaction time in step A. and/or step B., in particular in step B. is 10 minutes to 48 hours, in particular 1 hour to 36 hours or 2 to 24 hours or 3 up to 12 hours.
  • the object is also achieved by a compound according to the general formula
  • the compounds of formula IX claimed here are usually in high purity, especially in high NMR purity, and usually in yields of usually more than 90%, in particular according to one of the exemplary embodiments of the process described above for the preparation of such compounds more than 97%, especially more than 99% available.
  • These palladium(II) compounds of the general formula IX can be used, for example, as catalysts and/or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. They are advantageously suitable as precatalysts and/or catalysts for the reactions specified below.
  • the compound of the formula IX obtained or obtainable by a process for the preparation of such compounds according to one of the exemplary embodiments described above can—as was surprisingly found—have the following formula IX.N or IX.P exhibit.
  • the following compounds can be prepared as compounds of the formula IX:
  • the object is achieved by a preparation containing i. a compound according to the general formula IX where X, R1, R2, R3, R4 and L are as defined above, or according to the general formula IX.a wherein X, Ra, Rb , Rc , Rd , R4 and L are as defined above, and ii. at least one organosilicon compound.
  • organosilicon compound has already been defined above.
  • the silicon content which is present in particular in the form of the at least one organosilicon compound, is ⁇ 100 ppm and ⁇ 1000 ppm, advantageously ⁇ 110 ppm and ⁇ 900 ppm, in particular ⁇ 120 ppm and ⁇ 800 ppm.
  • the silicon content which is present in particular in the form of the at least one organosilicon compound, can be determined using analytical methods which are known to the person skilled in the art, in particular using quantitative 1 H-NMR spectroscopy and/or atomic emission spectrometry with inductively coupled plasma Inductively Coupled Plasma-Atomic Emission Spectrometers (ICP-AES).
  • the preparation contains a solvent SZ.
  • the preparation can be in the form of a solution, suspension, dispersion or gel, in particular depending on the organosilicon compound contained and/or the solvent SZ used.
  • the solvent SZ can also be a solvent mixture.
  • alkanes aromatic hydrocarbons and polar solvents advantageously selected from the group consisting of alcohols, alkanes, ketones, ethers or combinations thereof, in particular alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, aromatic hydrocarbons having 6 to 9 carbon atoms, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, or mixtures thereof.
  • the solvent SZ comprises or is a solvent which is selected from the group consisting of alcohols, alkanes, aromatics hydrocarbons, ketones, e.g. B.
  • acetone, ethers, and combinations thereof in particular alcohols having 2 to 6 carbon atoms, aromatic hydrocarbons having 6 to 9 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ethers, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, and mixtures thereof, the preparation is in the form of a solution or suspension.
  • the solvent SZ can be selected from the group consisting of diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, toluene, benzene, o-xylene, m-xylene, p- xylene, mesitylene, acetone, methanol and isopropanol, and mixtures thereof.
  • Another variant of the preparation provides that the solvent SZ is miscible or identical to the solvent SL, which is used in the process for preparing the compound of the formula IX.
  • the at least one organosilicon compound contains at least one terminal, in particular vinylic, double bond.
  • the at least one organosilicon compound comprises or is a cyclic or a non-cyclic siloxane.
  • the preparation contains at least one palladium compound according to the general formula [Pd(LS) 2 ] (III) in addition to the palladium compound according to the general formula VIII.
  • the general formula [Pd(LS) 2 ] (III) also includes multinuclear complexes, in particular dinuclear complexes according to the general formula [Pd 2 (LS) 3 ].
  • the ligand LS is in particular identical to the at least one organosilicon compound, in particular a cyclic or a non-cyclic siloxane, and the at least one organosilicon compound contains at least one terminal double bond.
  • the ligand LS is identical to the organosilicon compound, the ligand LS being in particular a cyclic or a non-cyclic siloxane which has at least one terminal, in particular vinylic, double bond.
  • the ligand LS is then advantageously coordinated or bonded to the palladium center of the compound according to the general formula [Pd(LS) 2 ] (III) via at least one pi bond.
  • one of the organosilicon compounds comprises or is a cyclic or a non-cyclic siloxane and/or one of the ligands LS is a cyclic or a non-cyclic siloxane, which is selected from the group consisting of 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-Tetramethyl-1,3-dithien-2-yldisiloxane, 1,1,3,3-Tetramethoxy-1,3- divinyldisiloxane, 1,3-dimethyl-1,3-divinyldisiloxanediol and 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane.
  • one of the organosilicon compounds comprises or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds) and/or one of the ligands LS is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds ).
  • one of the organosilicon compounds and/or one of the ligands is LS dvds.
  • the object is also achieved by a method for cross-coupling a first starting material and a second starting material, comprising the steps: A. providing a reaction mixture containing a first starting material, a second starting material and at least one compound or preparation according to one or more of the embodiments described above; and B.
  • the cross-coupling can be a carbon-carbon coupling reaction or a carbon-heteroatom coupling reaction.
  • the latter include carbon-nitrogen coupling reactions, ie Buchwald-Hartwig couplings, carbon-oxygen and carbon-sulfur coupling reactions.
  • the object is achieved by a method for catalyzing a reaction of a first starting material and a second starting material, the method involving contacting the first starting material with the second starting material in the presence of at least one compound or preparation according to one or more of the embodiments described above .
  • the first educt and the second educt are selected from the group consisting of: (i) the first educt is an aromatic or heteroaromatic boronic acid or its ester and the second starting material is an aromatic or heteroaromatic halide, tosylate, triflate, mesylate, sulfamate or carbamate; (ii) the first educt is an aromatic or heteroaromatic amine and the second educt is an aromatic or heteroaromatic halide, tosylate, triflate, mesylate, sulfamate or carbamate; (iii) the first educt is an aromatic or heteroaromatic zinc halide and the second educt is an aromatic, heteroaromatic or vinylic halide, tosylate, triflate, mesylate,
  • the method for cross-coupling a first starting material and a second starting material or of the method for catalyzing a reaction of a first starting material and a second starting material is a Stille coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Suzuki-Miyaura coupling, Sonogashira coupling, Hiyama coupling, Heck reaction, ⁇ -arylation of an enolizable ketone, ⁇ -arylation of an aldehyde, arylation of a primary amine, arylation of a secondary amine, arylation of a primary amide, arylation of an aliphatic alcohol , allylic substitution reaction or trifluoromethylation reaction.
  • the object is achieved by a method for catalyzing an anaerobic oxidation of a primary or secondary alcohol, the method involving contacting the primary or secondary alcohol with at least one compound or preparation according to one or more of the embodiments described above.
  • Example 1 Production of Pd complexes
  • Example 1-1 Ligand: tri-tert-butylphosphine, 2 mL ethanol as solvent. Reaction time: 4 h Yield: 92%, colorless solid.
  • 13 C NMR ( 63MHz , C6 D6 ) ⁇ 37.9, 33.7ppm .
  • Example 1-2 Ligand: tricyclohexylphosphine Reaction time: 3 h, then addition of 3 ml of methanol Yield: 163 mg (54%) colorless solid.
  • 1 H NMR (250 MHz, C 6 D 6 ) ⁇ 3.43 - 3.69 (m, 2 H), 3.12 - 3.42 (m, 4 H), 1.92 - 2.14 (m, 3 H), 1.51 - 1.92 (m, 16H), 0.94 - 1.48 (m, 15H), 0.58 (s, 6H), 0.07 (s, 6H) ppm.
  • Example 1-8 Ligand: di-tert-butylisopropylphosphine, addition of 6 mL toluene Reaction time: 3 h, after concentration addition of 15 mL methanol Yield: 153 mg (64%) colorless solid.
  • Example 1-9 Ligand: tert-butyldiphenylphosphine, addition of 2 mL toluene Reaction time: 3 h, after concentration addition of 15 mL methanol Yield: 110 mg (41%) colorless solid.
  • Example 1-11 Ligand: tris(pentafluorophenyl)phosphine, addition of 3 mL toluene
  • 3 mL of toluene were added to this suspension and the resulting solution was analyzed by 19 F-NMR.
  • Example 2 Catalytic Activity of Examples 1-4 In the following example, the catalytic activity of Examples 1-4, the compound tested.
  • Example 3-1 [Pd(Ph2P(CH 2 ) 3 PPh2) 2 ] Under argon, 213 mg 1,3-bis(diphenylphosphino)propane (0.5 mmol, 2 eq.) were dissolved in 3 mL toluene and 251 ⁇ L (244 mg , 0.25 mmol, 1 eq.) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane palladium was added. The solution was stirred for 2 hours whereupon a yellow solid precipitated. To the suspension was added 5 mL of methanol and the supernatant removed with a syringe.
  • Example 3-2 [Pd(Ph2P(CH2) 2 PPh2) 2 ] Under argon, 203 mg 1,3-bis(diphenylphosphino)ethane (0.5 mmol, 2 eq.) were dissolved in 3 mL toluene and 251 ⁇ L (244 mg, 0.25 mmol, 1 eq.) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane palladium is added.
  • Example 1-1 [Pd( ⁇ -Br)(PtBu 3 )] 2 starting of [Pd(acac) 2 ] and acetyl bromide
  • Example 1-2 [Pd( ⁇ -Br)(PtBu 3 )] 2 starting from [Pd 2 (dvds) 3 ] and acetyl bromide or N-bromosuccinimide
  • a mixture of [Pd 2 (dvds) 3 ] and acetyl bromide (2 eq. ) in methanol was stirred at room temperature for 2.5 hours.
  • PtBu 3 (2 eq.) was added and stirred at room temperature for 2.5 hours.
  • the precipitated solid was filtered off, washed and then dried in vacuo.
  • Example 1-3 [Pd( ⁇ -Br)(PtBu 3 )] 2 starting from [Pd 2 (dvds) 3 ] and Br2 in 1,4-dioxane [Pd 2 (dvds) 3 ] (868 mg , 1 mmol) followed by tri-tert-butylphosphine (413 mg, 2 mmol, 98%, 2 eq.).
  • a solution of bromine (Br 2 ) (4 mL, 0.25 M, 1 mmol, 1 eq.) in 1,4-dioxane was then added. The mixture was stirred at 40°C for 2 h. The solvent was removed under reduced pressure, the residue extracted with toluene and toluene removed under reduced pressure.
  • Example 2-1 [Pd( ⁇ -I)(PtBu 3 )] 2 starting from [Pd 2 (dvds) 3 ] and I2
  • a mixture of [Pd 2 (dvds) 3 ] (0.5 g Pd, 2.4 mmol) and PtBu 3 as a solution in toluene (1 eq.) in acetone was stirred at room temperature for 2.5 hours.
  • iodine (I2) (0.62 g, 2.4 mmol, 1 eq.) was added and stirred at room temperature for 2.5 hours.
  • the precipitated solid was filtered off, washed and then dried in vacuo. Yield: 83% dark purple solid.
  • Example 1-1 Di- ⁇ -chlorobis( ⁇ 3 -allyl)dipalladium (1-Cl) [CAS number: 12012-95-2] Yellow solid, mp: 149°C. Percentage of insoluble components in dichloromethane: ⁇ 0.1% (PTFE membrane filter (0.45 ⁇ m pore size)).
  • Example 1-6 Bis[(1,2,3- ⁇ )-2-buten-1-yl]di- ⁇ -chlorodipalladium (3-Cl) [CAS number: 12081-22-0] Yellow solid, melting point: 148 °C.
  • Example 1-16 Reaction of Pd(vs) with 1-(bromomethyl)naphthalene (production of 7-Br) 1592 mg (7.2 mmol, 1.2 equiv.) 1-(bromomethyl)naphthalene dissolved in 3 mL dried and degassed acetone were placed in a vial and 5210 mg (10.9% Pd, 6 mmol, 1 equiv.) Pd(vs) were added under anhydrous and oxygen-free conditions and stored overnight at 4-6°C. The orange precipitate was filtered off in air and washed five times with 5 mL acetone and dried in vacuo. There was obtained 1632 mg (83% yield) of 7-Br as an orange solid.
  • Example 1-17 Reaction of Pd(vs) with 2-(bromomethyl)naphthalene (preparation of 8-Br) 921 mg (4 mmol, 1 equiv.) 2-(bromomethyl)naphthalene dissolved in 3 mL dry and degassed acetone were placed in a vial and 4168 mg (10.9% Pd, 4.8 mmol, 1.2 equiv.) Pd(vs) added. The solution was stirred for 2 h. The orange precipitate was filtered off in air and washed three times with 5 mL acetone. The solid was dried in vacuo to give 540 mg (41% yield) as an orange solid.
  • Example 1-18 Reaction of Pd(vs) with 3-(tert-butyl)-1-chloro-1H-indene (production of 9-Cl) 3-(tert-butyl)-1-chloro-1H-indene (1 equiv, 30 mg, 0.145 mmol) dissolved in 0.1 mL acetone was introduced and Pd(vs) (1.2 equiv, 151 mg, 0.174 mmol) was added and shaken . The mixture was stored at 4°C overnight. The crystals that formed were carefully separated and washed with a few drops of water and acetone and dried. 29 mg (64%) of dark brown crystals were obtained.
  • 164 mg of 8-Br (1 eq., 0.25 mmol) and 224 mg of IPr (2 eq., 0.5 mmol) were placed in a crimp-top vial.
  • 20 mL of diethyl ether was added and the reaction mixture was stirred for 90 min under nitrogen atmosphere. 90% of the solvent was evaporated and 20 mL of pentane was added.
  • the sample was stored at -20°C overnight to crystallize the product.
  • the solution was concentrated to 90% volume and layered with 10 mL of hexane.
  • the vial was then stored in the freezer (-20°C) to precipitate the product.
  • the mother liquor was decanted and the remaining solid was washed with pentane (3x5 mL) and dried under high vacuum to afford 322 mg (80%) of a yellow solid.
  • 7-Br (1 eq, 82 mg, 0.125 mmol) and butyldi-1-adamantylphosphine (2 eq, 90 mg, 0.25 mmol) were placed in a 40 mL crimp-top vial.
  • the vial was capped and removed from the glove box.
  • 20 mL of dry and degassed THF was added and the reaction mixture was stirred at room temperature for 1.5 h. 90% of the solvent was removed under high vacuum and 15 mL of hexane was added.
  • the vial was capped and removed from the glove box. 20 mL of dry and degassed THF was added and the reaction mixture was stirred at room temperature for 1.5 h. The solvent was removed under reduced pressure and the remaining solid washed with small portions of pentane. After drying under high vacuum, 276 mg (78%) of a light yellow solid were obtained.
  • Example 2-11 Preparation of [Pd(cataCXium ® A)(allyl)Cl], [(di(1-adamantyl)-n-butylphosphine)( ⁇ 3 -allyl)chloro]palladium (IX.P) 22.5 mL of degassed acetone were placed in a three-necked flask rendered inert with argon and then 1.00 g of [Pd(allyl)Cl] 2 , bis( ⁇ 3 -allyl)di( ⁇ -chloro)dipalladium(II), (2nd .73 mmol, 1.0 eq) and 1.96 g cataCXium ® A, di(1-adamantyl)-n-butylphosphine, (5.47 mmol; 2.0 eq) added one after the other.
  • Example 2-12 Preparation of [Pd(cataCXium ® A)(allyl)Cl], [(di(1-adamantyl)-n-butylphosphine)( ⁇ 3 -allyl)chloro]palladium (IX.P) by means of one-pot synthesis In one 50 mL three-necked flask rendered inert with argon, 5.15 g Pd(vs), 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0), (1.21 mmol; 1 eq; CAS number: 252062-59 -2), and 0.97 g cataCXium ® A, di(1-adamantyl)-n-butylphosphine, (2.66 mmol, 2.20 eq) and rinsed the containers used with 12 mL acetone.
  • the resulting suspension was stirred at room temperature under argon for one hour, during which time a light yellow solid precipitated.
  • 0.97 g of cataCXium® A, di(1-adamantyl)-n-butylphosphine, (2.66 mmol, 2.20 eq) were then added. After a stirring time of about 10 minutes, a cream-colored solid precipitated out.
  • the reaction mixture was stirred at room temperature overnight. A cream-colored suspension was formed, which was filtered through a D4 frit blanketed with argon. The filter cake was washed three times in suspension with 5 mL methanol each time and dried overnight at room temperature in a vacuum drying cabinet.
  • Example 2-14 Preparation of [Pd( cataCXium® A)(1- t Bu-Ind)Cl], chloro[(1-tert-butyl-1H-inden-1-yl)(1-adamantyl)n-butylphosphine] palladium 1.15 g of cataCXium® A, di(1-adamantyl)-n-butylphosphine, (3.20 mmol; 2.0 eq) were placed in a three-necked flask rendered inert with argon, and 25 mL of acetone were added.
  • Example 2-15 Preparation of [(IPr)Pd(allyl)Cl)], allylchloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(II) (IX.N) by one-pot synthesis
  • 200 mL isopropanol were placed in a 500 mL reactor rendered inert with argon.
  • 100 g of Pd(vs), 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0), (24.18 mmol; 1 eq; CAS Number: 252062-59-2) were added and the used Rinse the container with 50 mL isopropanol.
  • Suzuki-Miyaura coupling of 3-chloropyridine with p-toluylboronic acid was chosen as a model reaction to to check the catalytic activity of the allylpalladium precatalysts. This reaction was reported by Colacot et al. investigated and yields of the coupling product of 91% determined after 30 minutes reaction time with the precatalyst 3-Cl-Xphos (Colacot TJ et al., Journal of Organic Chemistry, 2015, 80, 6794).
  • Allylpalladium bromide (1-Br) was less active than comparable chlorides.
  • Other precatalysts with the exception of 6-Cl and 6-Br, gave reactivities comparable to L1 with minor differences for chloride and bromide complexes.
  • the Hazari precatalyst was also tested and also showed activity.
  • a dried vial was charged with the allyl palladium halide dimer (x eq, x mmol) and Xphos (x eq, x mmol) and the air therein was removed by evacuating and flushing with argon three times. Then 1 ml of dried, degassed THF (tetrahydrofuran) was added and the mixture was stirred for 30 minutes. Then 3-chloropyridine (1 eq, 115 mg, 1 mmol) and p-toluylboronic acid (1.5 eq, 204 mg, 1.5 mmol) dissolved in 1 ml THF were added, followed by 4 ml K 3 PO 4 0.5 M solution.
  • the resulting homogeneous solution was stirred at 80°C for 11 hours. After completion of the reaction, the mixture was diluted with diethyl ether (10 mL) and washed with water (2 ⁇ 10 mL). The combined organic phases were dried over MgSO 4 and filtered, and the volatile constituents were removed at 300 mbar. The residue was purified by flash column chromatography (SiO 2 , pentane/diethyl ether gradient) to give the desired product.
  • IR (ATR): ⁇ 2965(f), 2932(fw), 2872(fw), 1580(f), 1490(m), 1454(f), 1230(m), 1185(f), 1085( w), 1025 (f), 893 (f), 819 (m), 751 (s), 747 (f), 650 (vw), 614 (f), 542 cm -1 (f).
  • Suzuki-Miyaura Cross-Coupling of Sterically Hindered Substrates The above palladium-naphthyl catalysts (7-8 Cl/Br) were also tested for activity in room-temperature Suzuki-Miyaura couplings of aryl chlorides leading to the formation of extremely crowded, tetra-ortho - substituted compounds lead.
  • General procedure for Suzuki-Miyaura cross-coupling of sterically hindered substrates A vial was filled with the respective catalyst (0.005 mol, 0.01 eq.) under exclusion of air and transferred to the glove box.4.72 mg of the ligand IPr*OMe, (0, 01 mmol, 0.02 eq.
  • Nolan's protocol is based on the electron-rich, sterically very demanding NHC ligand IPr*OMe in combination with [Pd(cinnamyl)Cl] 2 and has set new records in this context.
  • the only adjustment made here from Nolan's protocol was the use of THF instead of DME (1,2-dimethoxyethane) as the Solvents, due to the low solubility of the dimeric palladium naphthyl catalysts in DME.
  • Suzuki-Miyaura coupling of sterically hindered substrates a) 2,6-dimethoxy-2',4',6'-trimethylbiphenyl [CAS: 471290-69-4]
  • Catalyst/Pd source 0.5 mol% 7-Br
  • Aryl chloride 88.1 mg 2-Chloro-1,3-dimethoxybenzene Boronic acid: 123.0 mg 2,4,6-Trimethylboronic acid Yield: 126 mg (97%) off-white solid.
  • N-tert-butyl-2,6-dimethylaniline [CAS: 395116-77-5] was selected as a model reaction: Catalyst/Pd source: 0.5 mol% 7-Cl or 7-Br or 8-Cl or 8-Br or 0.5 mol% [Pd(tBu-indenyl)Cl] 2 * Aryl chloride: 143 mg 2,6-dimethylphenyl chloride Amine: 82.1 mg N-tert-butylamine * for comparison purposes Table B-5.
  • the vials were then capped and stirred at 120°C outside the glove box for 16 hours. After the reaction was complete, the vial was opened and the solution diluted with 3 mL of EtOAc. The reaction solution was containing with a pipette MgSO 4 and SiO 2 , filtered. The pipette was washed with more EtOAc until the filtrate became colorless. The solvent was removed under reduced pressure and the sample purified by flash column chromatography (SiO 2 , cyclohexane/EtOAc 0% ⁇ 20%) to obtain the desired product.
  • tert-butyl 3-(3-quinolinyl)acrylate [CAS: 259232-14-9] was chosen as the model reaction: Catalyst/Pd source: 1 mol% 7-Cl or 7-Br or 8-Cl or 8-Br or 1 mol% [Pd(tBu-indenyl)Cl] 2 * aryl chloride: 82.6 mg 2-chloroquinoline Yield: 110 mg (86%) yellow solid. * Table B-6 for comparison purposes.
  • the aryl chloride (0.5 mmol, 1 eq.) and 152 ⁇ L TMEDA (1 mmol, 2 eq.) were added to this solution.
  • the aryl zinc bromide solution in THF (0.75 mmol, 1.5 eq.) was added via syringe and the resulting mixture was stirred at room temperature for 16 h.
  • the solution was diluted with 3 mL EtOAc and washed with 15 mL water.
  • the aqueous layer was extracted with EtOAc (3x15 mL) and the combined organic layers were washed with brine.
  • the combined organic phases were dried over MgSO 4 and the volatiles removed under reduced pressure.
  • Negishi couplings a) 2,2'-dimethylbiphenyl [CAS: 605-39-0] Catalyst/Pd source: 1 mol% 7-Br aryl chloride: 64.6 mg 2-chlorotoluene aryl zinc bromide: 0.18 mL tolyl zinc bromide, solution in THF Yield: 112 mg (91%), colorless oil, after flash column chromatography (SiO 2 , pentane) .
  • the invention relates to new production processes for palladium complexes which allow the production of known products with high purity, in particular with high NMR purity, and with good yields.
  • novel palladium complexes which are usually not accessible or only accessible with great effort using the methods described in the prior art, can be obtained in high purity, in particular in high NMR purity, and with good yields by means of the production processes described here.
  • the compounds that can be prepared using the methods described here contain impurities from palladium-containing by-products, which are difficult or impossible to separate, in particular due to their solubility behavior, such as [Pd(dvds)PtBu 3 )] and [Pd 2 (dvds) 3 ], not or only in traces ( ⁇ 1000 ppm).
  • the high purity of the end products is important with a view to possible uses, e.g. B. as precatalysts and / or catalysts, particularly advantageous.
  • new palladium complexes are presented, which are suitable as precatalysts and/or catalysts, especially for cross-coupling reactions.

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  • Chemical & Material Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne de nouveaux procédés de production de complexes de palladium, qui permettent la production de produits connus de grande pureté et avec de bons rendements ainsi que la production de nouveaux complexes de palladium. L'invention concerne en outre de nouveaux complexes de palladium qui sont appropriés en tant que précatalyseurs et/ou catalyseurs, en particulier pour des réactions de couplage.
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US8772520B2 (en) * 2009-05-06 2014-07-08 Johnson Matthey Public Limited Company Preparation of a metal complex
US8618318B2 (en) 2009-07-30 2013-12-31 Johnson Matthey Public Limited Co. Process for the preparation of palladium (I) tri-tert-butylphosphine bromide dimer
CN101693725B (zh) * 2009-10-15 2012-12-05 浙江省冶金研究院有限公司 一种二(三叔丁基膦)钯(0)的合成工艺
EP2726202B1 (fr) 2011-06-29 2018-05-16 Umicore AG & Co. KG Procédé de préparation d'un dimère de bromure de tri-tert-butylphosphine-palladium(i)
KR102499277B1 (ko) * 2014-10-08 2023-02-13 예일 유니버시티 교차-커플링 반응을 위한 신규 전촉매 스캐폴드 및 이의 제조 및 이용
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