Organometallic compounds

Abstract

The present invention relates to a novel process for the preparation of palladium complexes, which allows the preparation of known products with high purity and good yields, and also to a method which allows the preparation of new palladium complexes. The present invention also relates to novel palladium complexes which are particularly suitable as precatalysts and / or catalysts for coupling reactions.

Description

[Technical Field]

[0001] Palladium catalysts are used in synthetic organic chemistry to produce a wide variety of compounds. The most prominent palladium-catalyzed reactions include C-C bond-forming reactions and C-heteroatom bond-forming reactions, which are commonly referred to as cross-coupling reactions. [Background technology]

[0002] In particular, homoleptic Pd(0) complexes of the general formula [Pd(phosphine)2] and heteroleptic Pd(0) complexes of the general formula [Pd(dvds)(ligand)] have been used as cross-coupling catalysts, where dvds = 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and ligand = phosphine or NHC. One of the best third-generation cross-coupling catalysts for both carbon-carbon and carbon-heteroatom coupling reactions is the Pd(I) dimer, di-μ-bromo-bis(tri-tert-butylphosphine)-dipalladium(I) ([Pd(μ-Br)(PtBu3)]2). Among the most widely used classes of precatalysts for coupling reactions are π-allylpalladium chloride complexes.

[0003] Homoleptic palladium(0) complexes of the type [Pd(phosphine)2] are generally 3 -C3H5)-(η 5It is synthesized by reacting a phosphate group (-CH) with free phosphine (T. Yoshida, S. Otsuka, D.G. Jones, J.L. Spencer, P. Binger, A. Brinkmann, P. Wedemann, in: Inorg. Synth., John Wiley & Sons, Inc., Hoboken, NJ, USA, 2007, 101-107; S. Otsuka, T. Yoshida, M. Matsumoto, K. Nakatsu, J. Am. Chem. Soc. 1976, 98(19), 5850-5858). Various ligands have been tested for this type of reaction, including PPh(tBu)2, PCy3, P(tBu)3, P(tBu)2Me, and P(1-Ad)2Bu. (H. Urata, H. Suzuki, Y. Moro-oka, T. Ikawa, J. Organomet. Chem. 1989, 364, 235-244; A.G. Sergeev, A. Zapf, A. Spannenberg, M. Beller, Organometallics 2008, 27, 297-300). The drawbacks of this synthetic route are, in particular, the formation of [Pd(η 3 -C3H5)-(η 5 -C5H5)] is unstable and highly volatile. In 2007, Mitchell and Baird reported that the less volatile [Pd(η 3 -1-PhC3H4(η 5 reported the preparation of [Pd(phosphine)2] complexes and their use as reactants to prepare Pd(phosphine)2 complexes, where phosphine = PPh3, PMePh2, PCy3, P(tBu)2Me, and PtBu3 (E.A. Mitchell, M.C. Baird, Organometallics 2007, 26, 5230-5238). Alternatively, the palladium(II) compound [Pd(cod)(CH2SiMe3)2] (AL Chan, J. Estrada, C.E. Kefalidis, V. Lavallo, Organometallics 2016, 35(19), 3257-3260) was used as a reactant. However, this is a relatively expensive palladium(0) precursor compound.

[0004] Another approach to the synthesis of this class of compounds starts with various Pd(II) precursors, which are reduced in the presence of free phosphines to the corresponding [Pd(phosphine)2] complexes. (C.S. Wei, G.H.M. Davies, O. Soltani, J. Albrecht, Q. Gao, C. Pathirana, Y. Hsiao, S. Tummala, M.D. Eastgate, Angew. Chem. Int. Ed. 2013, 52, 5822-5826; V.V.Grushin, C. Bensimon, H. Alper, Inorg. Chem. 1994, 33, 4804-4806). An example is the reduction of (PCy3)2PdCl2 with KOH in the presence of PCy3, although other methods obviate the need for additional phosphines. A variety of reducing agents have been tested for the reduction of [(PCy3)2Pd(OAc)2], with bis(pinacolato)diboron (B2pin2) proving to be the most efficient.

[0005] A drawback of previously known methods for preparing homoleptic palladium(0) complexes of the [Pd(phosphine)2] type is that expensive and / or difficult-to-handle reactants are used or, for example, an excess of phosphines is required. Therefore, all of the methods from the prior art described here must be considered unsatisfactory from an economical (atom-wise) and / or ecological point of view.

[0006] Furthermore, the preparation of heteroleptic Pd(0) complexes with the general formula [Pd(dvds)(phosphine)], where dvds = 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, has been described in the prior art. The reaction of [(tmeda)Pd(CH3)2] (tmeda = N,N,N',N') with free phosphines in the presence of the corresponding diolefin solution, i.e., excess diolefin dvds, affords the heteroleptic Pd(0) complex [Pd(dvds)(phosphine)]. (MJ-L. Tschan, EJ Garcia-Suarez, Z. Freixa, H. Launay, H. Hagen, J. Benet-Buchholz, PWNM van Leeuwen, J. Am. Chem. Soc. 2010, 132, 6463-6473; M. G. Andreu, A. Zapf, M. Beller, Chem. Commun. 2000, 2475-2476). Various phosphine-substituted complexes of this type have been prepared using both simple phosphines such as PCy3 and more sterically demanding phosphines. A publication from 1999 (K.-R. Porschke et al., J. Am. Chem. Soc. 1999, 121, 9807-9823) describes various synthetic routes for preparing heteroleptic complexes according to the general formula [Pd(dvds)(phosphine)]. Most of the described syntheses are carried out starting from complexes with the general formula [Pd(1,6-diene)(phosphine)] or [(tmeda)Pd(CH3)2]. The authors also describe a synthesis starting from [Pd2(dvds)3], i.e., the preparation of a heteroleptic palladium(0) complex [(tBu3P)Pd(dvds)], which is unstable at least in solution, by reacting [Pd2(dvds)3] with PtBu3 at -30 °C, where the molar ratio of the reactants is 1:2. A DVDs / Et2O mixture (volume ratio 1:2) is selected as the reaction medium. The Pd(0) compound [(tBu3P)Pd(dvds)] was obtained in 66% yield. The authors state that in solution of the Pd(0) complex [(tBu3P)Pd(dvds)], a ligand redistribution occurs to form [Pd(PtBu3)2] and [Pd(dvds)2].

[0007] The above-described methods for preparing heteroleptic Pd(0) complexes with the general formula [Pd(dvds)(phosphine)] are disadvantageous due to the use of relatively expensive palladium precursors and / or because an excess of diolefin DVDs is required, and in some cases diethyl ether is used as an additional solvent. In particular, it cannot be excluded that the final product contains contaminants from DVDs and / or ether. This is particularly disadvantageous for the use of these compounds as catalysts. The use of excess diolefins is disadvantageous from both an economical (atom-wise) and an ecological point of view.

[0008] Various alternatives, particularly the comproportionation reaction, for the preparation of [Pd(μ-Br)(PtBu)] have been discussed in the prior art, notably by Mingos et al. and Vilar et al. In the first variant (R. Vilar, D.M.M.Mingos et al., J. Chem. Soc., Dalton Trans. 1996, 4313-4314), the palladium(0) complex [Pd(dba)]C H (dba = dibenzylideneacetone) serves as the Pd source and is reacted with 2 molar equivalents of PtBu and 0.5 molar equivalents of CHBr. However, the desired Pd(I) dimer is obtained in low yield (18%), which means that this route is not suitable for industrial-scale production. In the second variant (V. Dura-Vila, DM PMingos, R. Vilar et al., J. Organomet. Chem. 2000, 600, 198-205), in addition to the palladium(0) complex [Pd2(dba)3]xC6H6, the palladium(II) compound [PdBr2(cod)] (cod = 1,5-cyclooctadiene) is used as the Pd source. In this case, a higher yield (60%) is achieved. However, firstly, it requires the additional use of the reactant [PdBr2(cod)], which is expensive and difficult to handle, especially for storage. Secondly, crystallization of the reactant [Pd2(dba)3]xC6H6 and the resulting contamination of the final product can occur during the synthesis.

[0009] The Schoenebeck group described two comproportionation reactions in which the palladium(0) compound [Pd(P(iPr)(tBu))] is reacted with either PdI or CuI to give the complex [Pd(μ-I)(P(iPr)(tBu)] (F. Schoenebeck et al., Organometallics 2014, 33, 6879-6884). Both the use of PdI and CuI are disadvantageous because, first, PdI, like PdBr, is expensive and, second, it usually must first be activated before use. CuI is relatively inexpensive. However, it cannot be excluded that the desired target compound will contain traces of CuI or other copper species. This is particularly disadvantageous from the perspective of using the [Pd(μ-I)(P(iPr)(tBu)] complex as a catalyst or precatalyst.

[0010] EP 2726202 A1 discloses a method for preparing [Pd(μ-Br)(PtBu3)]2, which also utilizes a comproportionation reaction. The palladium(II) compound PdBr2 is reacted with the palladium(0) compound [Pd(PtBu3)2] in an aliphatic or aromatic solvent to obtain the desired target compound. Unfortunately, PdBr2 undergoes an aging process during relatively long storage periods. Therefore, in a preferred variant of this method, an additional work step, namely, activation of PdBr2 by treatment in a solvent, e.g., dispersion, is carried out prior to the reaction. Depending on the degree of activation of PdBr2, yields ranging from 70% to nearly 90% are achieved. A disadvantage of this method is the additional time, expense, and resources required for activation of the reactant PdBr2. Additionally, it cannot be excluded that the final product contains trace amounts of PdBr2.

[0011] According to WO 2011 / 012889, the [Pd(μ-Br](PtBu)] complex is prepared using a mixture of [PdBr(diolefin)] and PtBu in a solvent in the presence of an alkali metal hydroxide. In addition to 2,5-norbornadiene (NBD), 1,5-cyclooctadiene (COD) is mentioned as a preferred diolefin. However, both [PdBr(COD)] and [PdBr(NBD)] are difficult to handle. In particular, the compounds must be stored at low temperatures under an inert gas atmosphere. Another drawback is that these reactants are prepared from their respective chlorine derivatives by halogenation with potassium bromide. This is disadvantageous, especially for large-scale applications, due to the associated high costs and significant precious metal losses. Additionally, the target compound [Pd(μ-Br)(PtBu)] can be contaminated with organic residues from the diolefin-containing reactant, which is particularly disadvantageous for use as a catalyst or precatalyst.

[0012] Another possibility for preparing [Pd(μ-Br)(PtBu3)]2 is the autocatalytic oxidative addition of bromobenzene to [Pd(PtBu3)2]. However, in this case, the target compound is obtained in low yields of up to 16%, i.e., in a mixture with other palladium compounds such as (PtBu3)Pd(Ph)Br and (PtBu3)2Pd(H)Br (J.F. Hartwig et al., J. Am. Chem Soc. 2008, 130, 5842-5843).

[0013] WO 2018 / 073559 describes, inter alia, a method for preparing [Pd(μ-Br](PtBu)], which involves the reaction of [Pd(diolefin)X] or PdX in the absence of a base, where X is a halide.

[0014] π-Allylpalladium chloride complexes can be obtained starting from both Pd(II) and Pd(0) by reaction with organic substances containing at least one double bond.

[0015] Friesen, R.W., Science of Synthesis: Product subclass 2: palladium-allyl complexes, Lautens, M., Eds.; Thieme: Stuttgart, (2001); vol. 1, pp. 113-264, describes several general methods for preparing π-allyl palladium chloride complexes: 1) transmetalation; 2) allylic hydrogen abstraction; 3) oxidative addition.

[0016] The preparation of complexes by transmetalation can be carried out by reaction with palladium(II) halides or palladium(II) acetate. For this purpose, Itoh, K.; Fukui, M.; Kurachi, Y., J. Chem. Soc., Chem. Commun., 1977, reported 500 corresponding reactions with allylsilanes; Ogoshi, S.; Kakiuchi, K.; Kurosawa, H., J. Organomet. Chem., 1994, 481 reported 19 reactions with allylstannanes; Henc, B.; et al., J. Organomet. Chem., 1980, 191 reported 425 reactions with allyl Grignard compounds; and Nesmeyanov, A.N.; Rubezhov, A.Z., J. Organomet. Chem., 1979, 164 reported 259 reactions with allylmercury compounds.

[0017] [ka]

[0018] Several methods are known for the synthesis of complexes by allylic hydrogen abstraction from alkenes using palladium(II) salts in combination with a base (usually acetate). However, such reactions are often only applicable to a limited number of reaction partners, and stereoselectivity and regioselectivity can be problematic (see, for example, Huttel, R.; Christ, H., Chem. Ber., 1963, 96, 3101).

[0019] A more generally applicable method with broad applicability is to treat a 2:1 mixture of alkene / palladium(II) chloride with sodium chloride, sodium acetate, and the weak oxidant copper(II) chloride in glacial acetic acid (e.g., as shown in Huttel, R.; Christ, H., Chem. Ber., 1964, 97, 1439).

[0020] The use of copper(II) chloride improves stereo- and regioselectivity by favoring allylic hydrogen abstraction at the more highly substituted end of the alkene.

[0021] [ka]

[0022] π-Allylpalladium chloride complexes can also be obtained by inserting palladium (0) into allyl halides. This reaction can generally be accomplished using tris(dibenzylideneacetone)dipalladium(0) ([Pd(dba)]) or palladium(II) chloride in conjunction with a reducing agent such as carbon monoxide (Dent, W.T.; Long, R.; Wilkinson, A.J., J. Chem. Soc., 1964, 1585.), carbon monoxide / primary amine (Tsuji, J.; Iwamoto, N., Chem. Commun., 1966, 828), ethene / water (Hartley, F.R.; Jones, S.R., J. Organomet. Chem., 1974, 66, 465), or tin(II) chloride (Sakakibara, M.; Takahashi, Y.; Sakai, S.; Ishii, Y., Chem. Commun., 1969, 396).

[0023] [ka]

[0024] Several methods are available for preparing π-allylpalladium chloride complexes, but η 3 The preparation of benzylpalladium halides (Roberts, JS; Klabunde, KJ, J. Organomet. Chem., 1975, 85, C13 and Roberts, JS; Klabunde, KJ, J. Am. Chem. Soc., 1977, 99, 2509) and arylpalladium halides (Klabunde, KJ, Angew. Chem., 1975, 87, 309) has been limited to the use of palladium vapor. In addition, to date, pentafluorophenylpalladium halides have only been isolated at 25°C, whereas phenylpalladium halides decompose at temperatures above -116°C.

[0025] [ka] Summary of the Invention [Problem to be solved by the invention]

[0026] Therefore, it is an object of the present invention to overcome these and further drawbacks of the prior art and to provide a method by which homoleptic Pd(0)-phosphine complexes can be prepared in a simple, reproducible, and relatively inexpensive manner with high purity and good yield. In particular, the purity of these compounds should meet the requirements imposed on catalyst compounds. In addition, a method should be provided by which heteroleptic Pd(0) complexes having phosphine and dvds ligands can be prepared in a simple, reproducible, and relatively inexpensive manner with high purity and good yield. The purity of these Pd(0) compounds should meet the requirements imposed on catalyst compounds. In addition, new homoleptic Pd(0)-phosphine and heteroleptic Pd(0) complexes having phosphine and dvds ligands, which are particularly suitable as catalysts for organic coupling reactions, should be provided. In addition, it is an object of the present invention to provide novel homoleptic Pd(0)-phosphine and heteroleptic Pd(0) complexes having the general formula [Pd(μ-X)(PRA R B R C )]To provide a method for preparing the compounds according to 2 in a simple, reproducible and relatively inexpensive manner with high purity and good yield. In particular, the purity of these compounds should meet the requirements imposed on the catalyst compound. In addition, [Pd(μ-X)(PR A R B R C )]2-type novel compounds are provided. Further, an object of the present invention is to provide a novel and simple method for preparing π-allyl palladium halide complexes that overcomes the disadvantages of the prior art. In particular, a method with higher yield, improved product quality, and simple access to η 3 -benzyl palladium halide or aryl palladium halide is desirable. Further, novel π-allyl palladium halide complexes particularly suitable as catalysts for organic coupling reactions are provided. In particular, catalysts with higher yield, improved product quality and η 3 -benzyl palladium halide or aryl palladium halide are desirable. The present invention also relates to the use of the provided palladium complexes.

Means for Solving the Problems

[0027] The main features of the present invention are defined in the claims.

[0028] This object is achieved by the general formula [PdZ A Z B (I) [wherein the phosphine ligand Z A and Z Bis achieved by a method for preparing a compound according to the invention, wherein the compound is independently selected from the group consisting of tri-tert-butylphosphine (PtBu3), di-tert-butyl(iso-propyl)phosphine (P(iPr)tBu2), tert-butyl-di-(isopropyl)phosphine (P(iPr)tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)tBu), 1-adamantyl-di-(isopropyl)phosphine (P(1-Ad)iPr2), di(1-adamantyl)isopropylphosphine (P(1-Ad)iPr), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis(diphenylphosphino)propane (dppp), The method comprises: A. i. Mononuclear or polynuclear palladium compounds, in particular ligands L in which at least one palladium center is an organosilicon compound. S a palladium(0) compound having the formula and ii. in each case one phosphine ligand Z A and Z B providing Z A and Z B are independently selected from the group consisting of tri-tert-butylphosphine (PtBu), di-tert-butyl(iso-propyl)phosphine (P(iPr)tBu), tert-butyl-di-(isopropyl)phosphine (P(iPr)tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)tBu), 1-adamantyl-di-(isopropyl)phosphine (P(1-Ad)iPr), di(1-adamantyl)isopropylphosphine (P(1-Ad)iPr), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis(diphenylphosphino)propane (dppp), B. The palladium compound and the monophosphine and / or bisphosphine ligands from step A are reacted in a non-ethereal solvent S C reacting in and C. Optionally, a compound of the general formula [PdZA A Z B (I) isolating the compound prepared in step B. Includes. DETAILED DESCRIPTION OF THE INVENTION

[0029] According to the present invention, organosilicon compounds refer to alkyl or aryl derivatives of silicon having one or more Si-heteroatom bonds selected from the group consisting of Si-C, Si-N, and Si-O bonds. Except for metalloid silicon, the molecular formula of organosilicon compounds does not include metals or metalloids, i.e., contains only nonmetals. An organosilicon compound may be a mixture of several different organosilicon compounds. For example, it may be a mixture of different siloxanes. Alternatively, an organosilicon compound may contain, for example, a siloxane and a silazane, or may consist of these two organosilicon compounds.

[0030] The palladium compounds, in particular palladium(0) compounds, may be present in mono- or polynuclear, especially binuclear, form, as monomers or oligomers, especially dimers, or as solvent adducts. A and Z B may each independently be a monophosphine ligand or a bisphosphine ligand. In addition, they may independently be provided as a solid, liquid, solution, or suspension, advantageously as a solution in one or more aromatic hydrocarbons, such as toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures and combinations thereof.

[0031] The method described herein allows for the preparation of homoleptic palladium(0) complexes, such as [Pd(PtBu3)2] and [Pd(dppe)2] (dppe = 1,2-bis(diphenylphosphino)ethane), in a particularly simple, reproducible, and relatively inexpensive manner. This obviates the need for palladium(0) precursors provided in the prior art, some of which are expensive and / or difficult to handle. [PdZ A Z B The target compounds of type (I) are obtained in high purity, especially high NMR purity, advantageously free of ethers, and in satisfactory yields. In most cases, the yields achieved are at least comparable to those given in the literature.

[0032] The use of non-ethereal solvents makes it possible to largely eliminate contamination of the final product in the form of traces of oxygen (ppm range), especially in the form of oxygen-containing solvents such as ethers. In addition, surprisingly, [PdZ A Z B It has been found that the target compounds of type (I) are free of impurities due to palladium-containing by-products, such as [Pd(dvds)PtBu3], which are difficult or impossible to separate, especially due to their solubility behavior, or contain only trace amounts of the aforementioned impurities (≦1000 ppm). The high purity of the final products of formula I is particularly advantageous in view of their possible applications, for example as catalysts, especially in coupling reactions.

[0033] In contrast to previously known synthetic strategies, palladium(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane ([Pd2(dvds)3])—also abbreviated in the context of the present invention as [Pd(dvds)], Pd(vs), Pd-VS, or palladium-VS—is relatively easy to access and handle, relatively inexpensive, and can be used as a reactant in the context of the methods claimed herein. Additionally, in the methods described herein, both the provision of the palladium compound in step A and the reaction in step B can be carried out without the addition of an olefin, such as an alkene or a polyene. Here, polyene refers in particular to a diene, such as a 1,6-diene. The fact that the presence of an olefin, such as a 1,6-diene, can be omitted surprisingly also applies when the palladium compound provided in step A is [Pd2(dvds)3]. This is particularly advantageous, as the authors of a 1999 publication (K.-R. Porschke et al., J. Am. Chem. Soc. 1999, 121, 9807-9823) noted that even in solutions of [Pd2(dvds)3] in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, i.e., in the presence of excess DVDs, the equilibrium is in favor of the dinuclear complex [Pd2(dvds)3], i.e., only a small amount of the mononuclear complex [Pd(dvds)2] is formed. Therefore, to react [Pd2(dvds)3] with PtBu3 to obtain the heteroleptic palladium(0) complex [(tBu3P)Pd(dvds)] in a molar ratio of 1:2, the authors used a DVDs / Et2O mixture as the reaction medium (volume ratio 1:2).

[0034] The fact that the presence of olefins, such as 1,6-dienes, is not required in the processes described herein, especially when using reactants such as [Pd2(dvds)3], represents an advantage, especially from an economical (atom-wise) and ecological point of view. In addition, this reduces the number of possible impurities in the final product according to general formula I.

[0035] General formula [PdZ A Z BIn an advantageous embodiment of the method described herein for preparing a compound according to formula (I), the ligand L S is an organosilicon compound. According to an alternative or additional variant, the ligand L S contains at least one terminal double bond, in particular a vinyl double bond. S It is even more advantageous if the ligand L contains two terminal double bonds. S is a cyclic or acyclic siloxane. S It is particularly advantageous if L is a cyclic or acyclic siloxane 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. S is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane. The palladium compound provided in step A can then be, for example, palladium(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane ([Pd2(dvds)3]).

[0036] According to another embodiment of the method claimed herein, palladium: phosphine ligand Z A and the molar ratio of palladium:phosphine ligand Z B are independently 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, in particular 1.0:1.0 in each case.

[0037] Solvent S C The solvent or solvent mixture S may also be a mixture of solvents. CIn particular, the solvent comprises or is selected from the group consisting of aromatic hydrocarbons, ketones, such as acetone, and alcohols, such as methanol, ethanol, or isopropanol, and mixtures thereof. The at least one aromatic hydrocarbon may, for example, be selected from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.

[0038] The present method can generally be carried out at a reaction temperature of 0°C to 50°C, particularly 15°C to 45°C or 20°C to 30°C.

[0039] The reaction time may be from 10 minutes to 48 hours, in particular from 1 hour to 36 hours, or from 2 hours to 24 hours, or from 3 hours to 12 hours.

[0040] Surprisingly, by the process claimed herein, in particular by reacting 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0) ([Pd2(dvds)3) with tert-butylphosphine under the above-mentioned reaction conditions, the Fu catalyst of the following formula (I.1) can be obtained, usually in most cases in a yield of more than 90%, often more than 97%, in particular more than 99%, i.e. essentially quantitatively:

[0041] [ka]

[0042] Another embodiment of the method is to provide a phosphine ligand Z A and Z B In an advantageous variant, the phosphine ligands Z A and Z B are identical, i.e., Z A =Z B Then, the palladium:phosphine ligand Z Ais 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.

[0043] In a further process variant, the palladium compound in step A is preferably a palladium(II) compound consisting of a palladium(II) cation and two monovalent or divalent anions, which is preferably a palladium(II) compound, and more preferably a palladium(II) compound, which is ... S and in situ in the presence of a base in solvent S D It is prepared by reacting in

[0044] In the present invention, the phrases "prepared in situ" or "produced in situ" mean that the reactants necessary for the synthesis of the compound thus prepared are reacted in a solvent or solvent mixture with the appropriate stoichiometry, and the resulting product is not isolated. Instead, the solution or suspension containing the compound produced in situ is generally reused directly, i.e., without isolation and / or further purification. The in situ production / preparation of the compound can be carried out in the reaction vessel provided for its further use or in a different reaction vessel.

[0045] The terms "reaction vessel" and "reaction vessel" in the context of the present invention are used interchangeably and are not limited by volume, material composition, equipment, or form. Suitable reaction vessels include, for example, glass flasks, enamelled reactors, stirred tank reactors, pressure vessels, tubular reactors, microreactors, and flow reactors.

[0046] The palladium(II) compound used as a reactant for the in situ generation of the palladium compound provided in step A may have two different or two identical monovalent anions or one divalent anion. Neutral ligands, such as COD, are not provided. As a result, inexpensive, commercially available palladium(II) compounds, such as PdCl, can be advantageously used. Therefore, it is possible to avoid the time-consuming and expensive preparation of palladium(II) compounds of the type [Pd(ligand)Y] (where, for example, ligand = COD and Y = Cl) as a reactant for the in situ generation of the palladium compound provided in step A. This is particularly advantageous from an economic (atom) and ecological point of view. In addition, this reduces the number of possible impurities in the final product according to general formula I.

[0047] In a further advantageous embodiment, the palladium(II) compound used as a reactant in the context of the above-mentioned in situ preparation comprises two identical monovalent anions, in particular selected from the group consisting of halides and monovalent weakly coordinating anions.

[0048] The term "weakly coordinating" also encompasses the terms "very weakly coordinating" and "moderately strongly coordinating." Chloride, bromide or iodide can be advantageously used as the halide anion, with chloride or bromide being particularly advantageous, especially chloride. Monovalent weakly coordinating anions are especially perfluorinated anions, such as PF6. - , BF4 - , F3CSO3 - (TfO - , triflate) and [(F3CSO2)2N] - (TFSI), or non-fluorinated anions, e.g., H3CSO3 - (mesylate) or tosylate.

[0049] In the context of the reactions described herein, the term "base" refers to inorganic and organic bases, especially inorganic bases, but not organometallic bases. The base should not decompose in water. Suitable bases are, for example, salts of Bronsted acids. Carbonates, hydrogen carbonates, acetates, formates, ascorbic acids, oxalates, and hydroxides are advantageously used. These can be used in the form of ammonium salts (Bronsted acids) NR4, where R is, for example, H or alkyl, alkali metal salts, for example, sodium or potassium salts, and alkaline earth metal salts.

[0050] In particular, solvent S C and solvent S D are miscible or identical. In this case, there is no need to exchange the solvent, which is particularly advantageous from an economic and ecological point of view.

[0051] In the context of the present invention, two solvents are said to be miscible if they are miscible, ie, do not exist as two phases, at least during the respective reactions.

[0052] A further variant of the process claimed herein provides for adding a precipitating agent before and / or during and / or after step B, advantageously during and / or after step B, in particular after step B. The precipitating agent is advantageously added to the reaction medium from step B, in particular solvent S. C In particular, the polar solvent is an alcohol selected from the group consisting of methanol, ethanol and isopropanol, and mixtures thereof.

[0053] According to another embodiment of the method, after the reaction in step B, a compound of the general formula [PdZ A Z B Step C is then carried out, which comprises the isolation of the compound prepared in step B by (I): - [PdZ A Z B ](I) and a non-ethereal solvent. or - As a substance, preferably as a solid.

[0054] Here and hereinafter, the term "preparation" means a solution, a suspension, a dispersion or a gel. The preparation may therefore be in the form of a solution, a suspension, a dispersion or a gel, depending in particular on the non-ethereal solvent present and / or the compound according to formula I present. The solvent may also be a mixture of solvents. In particular, the solvent may be a mixture of solvents S used. C The preparation usually comprises or is a solvent that is miscible with or identical to the solvent. The preparation is usually in the form of a solution or suspension.

[0055] In a further variant of the method, the isolation comprises a filtration step and / or centrifugation. The above procedure can also be carried out several times. Optionally, one or more filtrations on a washing medium, such as activated carbon or silica, for example Celite®, can be carried out. Advantageously, the filtrate, centrifuged or decanted material or solid can be subjected to further purification and / or isolation steps, which can be carried out quickly and without complexity and without special preparation efforts.

[0056] General formula [PdZ A Z B Isolation of the compound according to (I) may comprise further process steps, such as reduction of the mother liquor volume, i.e., concentration of the mother liquor volume, for example "bulb-to-bulb", addition and / or solvent exchange to precipitate the product from the mother liquor and / or to remove impurities and / or reactants, crystallization, sublimation, washing with alcohols, such as ethanol, methanol or isopropanol, and mixtures thereof, and drying of the product. Each of the aforementioned steps may be provided in a different order and frequency.

[0057] Overall, the general formula [PdZ A Z B Purification and / or isolation of the target compound by (I) is relatively simple and inexpensive.

[0058] Generally, the final product may still contain residues of solvent or impurities, for example, from the reactants. A Z BThe isolated compounds of type (I) have a purity of at least 97%, advantageously greater than 97%, in particular greater than 98% or 99%. Even when scaled up to industrial scale, reproducible yields are usually 50% or higher, depending in particular on the choice of reactants and solvent or solvent mixture.

[0059] The present object is also to provide compounds of the general formula [PdZ] which are obtained or can be obtained by a method for preparing such compounds according to one of the above exemplary embodiments. A Z B ] (I), excluding the compounds [Pd(P(iPr)tBu2)2] and [Pd(P(1-Ad)tBu2)2].

[0060] General formula [Z A Z B The palladium(0) compounds of formula (I) can exist as monomers or oligomers, especially dimers, or as solvent adducts, in mono- or polynuclear, especially binuclear, form. For example, they can be used as catalysts, especially in palladium-catalyzed cross-coupling reactions.

[0061] In particular, the compounds [Pd(PtBu3)2], [Pd(PtBu3)(P(1-Ad)tBu2], [Pd(PtBu3)(P(1-Ad)iPr2)], [Pd(P(1-Ad)2tBu)2], [Pd(P(1-Ad)2iPr)2], [Pd(P(1-Ad)tBu2)(P(1-Ad)iPr2)], [Pd(P(1-Ad)iPr2)2[Pd(PiPr)2tBu)2], [Pd(dppe)2] and [Pd(dppp)2] can be obtained by the above method.

[0062] The objective of this study was to develop a compound of the general formula [PdZ A Z BThis is also achieved by new compounds represented by the formula (I), which are the compounds [PdtBu3)(P(1-Ad)tBu2], [Pd(PtBu3)(P(1-Ad)iPr2)], [Pd(P(1-Ad)2tBu)2], [Pd(P(1-Ad)2iPr)2], [Pd(P(1-Ad)tBu2)(P(1-Ad)iPr2)], [Pd(P(1-Ad)iPr2)2[Pd(PiPr)2tBu)2], [Pd(dppe)2] and [Pd(dppp)2]. These are suitable as catalysts for the following reactions:

[0063] Furthermore, the objective is to: i. General formula [pDZ A Z B ] (I) [In the formula, Z A and Z B are independently selected from the group consisting of tri-tert-butylphosphine (PtBu), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu), tert-butyl-di-(isopropyl)phosphine (P(iPr)tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)tBu), 1-adamantyl-di-(isopropyl)phosphine (P(1-Ad)iPr), di(1-adamantyl)isopropylphosphine (P(1-Ad)iPr), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis(diphenylphosphino)propane (dppp). and ii. at least one organosilicon compound This is achieved by a preparation comprising:

[0064] A definition of the term organosilicon compound has already been given above.

[0065] In one embodiment of the claimed preparation, the compound of the general formula [pDZ A Z BThe compound according to (I), or the preparation itself, is obtained or obtainable in particular by a method for preparing such a compound according to one of the exemplary embodiments described above.

[0066] According to one embodiment of the preparation, the silicon content, particularly in the form of at least one organosilicon compound, is 100 ppm to 1000 ppm, preferably 110 ppm to 900 ppm, in particular 120 ppm to 800 ppm. In particular, the silicon content, particularly in the form of at least one organosilicon compound, can be determined, in particular quantitatively, using analytical methods known to those skilled in the art. 1 It can be determined using H NMR spectroscopy and / or inductively coupled plasma atomic emission spectroscopy (ICP-AES).

[0067] In an alternative or complementary embodiment of the preparation claimed herein, the preparation is Z , especially containing non-ethereal solvents.

[0068] The preparations depend in particular on the organosilicon compounds present and / or the solvent S used. Z Depending on the solvent, it may be in the form of a solution, suspension, dispersion or gel. Z The solvent S may be a mixture of solvents. It is advantageously selected from the group consisting of alkanes, aromatic hydrocarbons and polar solvents, and is preferably 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 ether, 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. For example, diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol, ethanol, isopropanol, and mixtures or combinations thereof are suitable. In particular, solvent S isZ comprises or is a solvent selected from the group consisting of aromatic hydrocarbons, ketones, such as acetone, and alcohols, such as methanol, ethanol, or isopropanol, and mixtures thereof, in which case the at least one aromatic hydrocarbon may be selected from the group consisting of, for example, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.

[0069] Another variant of the preparation is to use solvent S Z is the solvent S used in the process for preparing the compound according to formula I C It is provided that the compound is miscible with or identical to the compound.

[0070] According to a variant of the preparation of the present invention, at least one organosilicon compound contains at least one terminal double bond, in particular a vinyl double bond.In particular, at least one organosilicon compound comprises or is a cyclic or acyclic siloxane.According to an alternative or additional embodiment of the preparation, the preparation comprises a compound of the general formula [pDZ A Z B] In addition to the palladium compounds according to (I), compounds of the general formula [L S pDZ] (II) and / or at least one palladium compound according to the general formula [Pd(L S )2] (III) wherein -ligand L S is in particular identical to at least one organosilicon compound, in particular a cyclic or acyclic siloxane, 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), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu), tert-butyl-di(isopropyl)phosphine (P(iPr)tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)tBu), di(1-adamantyl)-isopropyl)phosphine (P(1-Ad)iPr), 1-adamantyl-di(isopropylphosphine (P(1-Ad)iPr), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis-(diphenylphosphino)-propane (dppp).

[0071] In particular, the ligand L S is the same as the organosilicon compound, and the ligand L S is in particular a cyclic or acyclic siloxane having at least one terminal, in particular vinyl, double bond. In this case, the ligand L S is advantageously linked via at least one π-directed bond to a group of the general formula [L S pDZ](II) or [Pd(L S )2] (III) is coordinated or bonded to the palladium center of the compound.

[0072] A further variant of the claimed preparation is that one of the organosilicon compounds comprises or is a cyclic or acyclic siloxane, and / or the ligand L SOne of the organosilicon compounds is a cyclic or acyclic siloxane 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. Advantageously, one of the organosilicon compounds comprises or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds), and / or the ligand L S One of the compounds is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds). In particular, one of the organosilicon compounds and / or the ligand L S One of them is DVDs.

[0073] In addition, this object is achieved by providing a compound of the general formula [pDZ A Z B ] (I) is a novel compound of the formula 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). For example, these compounds can be used as catalysts, particularly in palladium-catalyzed cross-coupling reactions.

[0074] This object further provides compounds according to the general formula [LPd(dvds)] (IV)

[0075] [ka] wherein L is a phosphine ligand. with the exception of compounds of general formula IV, wherein L is selected from the group consisting of tri-tert-butylphosphine (PtBu3), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu2), tert-butyl-di-(isopropyl)phosphine (P(iPr2)tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)2tBu), 1-adamantyl-di-(isopropyl)phosphine (P(1-Ad)iPr2), di(1-adamantyl)-isopropylphosphine (P(1-Ad)2iPr), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,3-bis-(diphenylphosphino)propane (dppp), The method comprises: A. i. mononuclear or polynuclear palladium compounds, in particular palladium(0) compounds, in which at least one palladium center has a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane ligand; and ii. A phosphine ligand, L, except for a phosphine ligand selected from the group consisting of tri-tert-butylphosphine (PtBu), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu), tert-butyl-di-(isopropyl)phosphine (P(iPr)tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)tBu), 1-adamantyl-di-(isopropyl)phosphine (P(1-Ad)iPr), di(1-adamantyl)isopropylphosphine (P(1-Ad)iPr), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis(diphenylphosphino)propane (dppp). providing B. The palladium compound and the phosphine ligand L from step A are reacted in a non-ethereal solvent S E The process of reacting and C. Optionally, isolating the compound according to general formula [LPd(dvds)] (IV) prepared in step B. Includes.

[0076] The palladium compound, particularly a palladium(0) compound, may be present in mono- or polynuclear, especially dinuclear, form, as a monomer or oligomer, especially a dimer, or as a solvent adduct. The provision of the palladium compound in step A and the reaction in step B are carried out without the addition of an olefin, such as an alkene or a polyene. Here, polyene means especially a diene, such as a 1,6-diolefin. The phosphine ligand may be provided as a solid, liquid, solution, or suspension, especially as a solution in one or more aromatic hydrocarbons, such as toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.

[0077] According to one embodiment of the presently claimed method for preparing a compound according to formula IV, the phosphine ligand L is tertiary phosphines according to the general formula P-R10R20R30, in which R10 and R20 are independently selected from the group consisting of substituted and unsubstituted linear alkyl groups, substituted and unsubstituted branched alkyl groups, substituted and unsubstituted cycloalkyl groups, substituted and unsubstituted aryl groups, and substituted and unsubstituted heteroaryl groups, and the heteroatoms are selected from the group consisting of sulfur, nitrogen, and oxygen; R30 is a tertiary phosphine defined as R10 and R20 or is a metallocenyl group; or -2-(Dicyclohexylphosphino)-2'-(N,N(dimethylamino))-1,1'-biphenyl (DavePhos), 2-(Dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl (XPhos), 2-Dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl (SPhos), 2-Dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl (RuPhos), 2-(Dicyclohexylphosphino)-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl (XPhos), Isopropyl-1,1'-biphenyl (BrettPhos), [4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (Xantphos), 2-dicyclohexylphosphino-2',6'-bis(dimethylamino)-1,1'-biphenyl (CPhos), tricyclohexylphosphine (PCy3), di-(1-adamantyl)-n-butylphosphine (cataCXium® A), 2-di-tert-butylphosphine 2-(di-tert-butylphosphino)-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl (t-BuXPhos), 2-(di-tert-butylphosphino)-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl (tert-BuBrettPhos), 2-(di-tert-butylphosphino)-3-methoxy-6-methyl-2',4',6'-triisopropyl-1,1'-biphenyl (RockPhos), 2-di[3,5-bis(trifluoromethyl)phenylphosphino]-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl isopropyl-1,1'-biphenyl (JackiePhos), 2-(di-tert-butylphosphino)-biphenyl (JohnPhos), R-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-tert-butylphosphine, di-tert-butyl(n-butyl)phosphine, 2-(di-1-adamantylphosphino)-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl (AdBrettPhos), 2-diethylphosphino-2',6'-bis(dimethylamino)-1,1'-Biphenyl racemic 2-di-tert-butylphosphino-1,1'-binaphthyl (TrixiePhos), triisopropylphosphine (PiPr3), 1,3,5,7-tetramethyl-8-phenyl-2,4,6-trioxa-8-phosphaadamantane (MeCgPPh), N-[2-(di-1-adamantylphosphino)phenyl]morpholine (MorDalPhos), 4,6-bis(diphenylphosphino)phenoxazine (NiXantphos), 1,1'-bis(diphenylphosphino)ferrocene (dppf) , 2-di-tert-butylphosphino-2'-(N,N(dimethylamino))-1,1'-biphenyl (tBuDavePhos), racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP), 1,1'-bis(di-tert-butylphosphino)ferrocene (DTBPF), 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl)-1,1'-biphenyl (Me4t-BuXPhos), 2-dicyclohexylphosphino-4-(N,N- dimethylamino)-1,1'-biphenyl, trimethylphosphine (PMe3), tris-p-tolylphosphine (P(p-tolyl)3), tris-o-tolylphosphine (P(o-tolyl)3), methyldiphenylphosphine, triphenylphosphine (PPh3), tris-(pentafluorophenyl)-phosphine (P(C6F5)3), trifluorophosphine, tert-butyldiphenylphosphine (P(tBu)Ph2), phenyl-di-tert-butylphosphine, di-tert-butyl-neopentylphosphine, 1 ,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene, tris(p-methoxyphenyl)phosphine, tris(p(trifluoromethylphenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(2,4,6-trimethyl)phosphine, tris(2,6-dimethylphenyl)phosphine, benzyldi-1-adamantylphosphine, cyclohexyldi-tert-butylphosphine, cyclohexyldiphenylphosphine, 2-di-tert-butylphosphino-1,1'-Binaphthyl, 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropylbiphenyl, 2-(dicyclohexylphosphino)biphenyl (cyclohexyl-JohnPhos), 2-(dicyclohexylphosphino)-2',6'-dimethoxy-1,1'-biphenyl Nyl, 2-di-tert-cyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-cyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl, 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl, 2-di-cyclohexylphosphino-2'-methylbiphenyl, 2-diphenylphosphino-2'-(N,N(dimethylamino)biphenyl), (4-dimethylaminophenyl)(tert-butyl)2-phosphine, 1,2-bis(di 1,3-bis(di-tert-butylphosphinomethyl)benzene, 1,3-bis(di-tert-butylphosphinomethyl)propane, 1,2-bis(diphenylphosphinomethyl)benzene, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,2-bis(diphenylphosphino)butane, N-(2-methoxyphenyl)-2-(di-tert-butylphosphino)pyrrole, 1-(2-methoxyphenyl)-2-(di-cyclohexylphosphino)pyrrole, N-phenyl-2-(di-tert-butylphosphinomethyl)benzene, 1,3-bis(di-tert-butylphosphinomethyl)propane, 1,2-bis(diphenylphosphinomethyl)benzene, 1,2-bis(di- ... (S)-7,7'-bis(diphenylphosphino)-3,3',4,4'-tetrahydro-4,4'-dimethyl-8,8'-bi(2H-1,4-benzoxazine) (Solphos), is selected from the group consisting of N-phenyl-2-(di-tert-butylphosphino)indole, N-phenyl-2-(dicyclohexylphosphino)pyrrole, N-phenyl-2-(dicyclohexylphosphino)indole, N-phenyl-2-(dicyclohexylphosphino)pyrrole, 1-(2,4,6-trimethylphenyl)-2(dicyclohexylphosphino)imidazole, and (S)-7,7'-bis(diphenylphosphino)-3,3',4,4'-tetrahydro-4,4'-dimethyl-8,8'-bi(2H-1,4-benzoxazine) (Solphos).

[0078] In the tertiary phosphines of the general formula P-R10R20R30, R10 and R20 can independently be substituted and unsubstituted branched or straight chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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.

[0079] In one embodiment, the alkyl group of a tertiary phosphine according to the general formula P-R10R20R30 may be optionally substituted with one or more substituents, such as a halide (F, Cl, Br, or I) or an alkoxy group, e.g., methoxy, ethoxy, or propoxy. The aryl group may be optionally substituted with one or more (e.g., 1, 2, 3, 4, or 5) substituents, such as a halide (F, Cl, Br, or I), a linear or branched alkyl group (e.g., C1-C10 alkyl), an alkoxy (e.g., C1-C10 alkoxy), a linear or branched (dialkyl)amino group (e.g., C1-C10 dialkylamino), a heterocycloalkyl (e.g., a C3-C10 heterocycloalkyl group such as morpholinyl and piperazinyl), or a trihalomethyl (e.g., 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. Substituted and unsubstituted heteroaryl groups such as pyridyl, furanyl, thiophenyl, pyrrolyl, or quinolinyl can also be used. In an alternative embodiment, R10 and R20 of a tertiary phosphine according to the general formula P-R10R20R30 are bonded together to form a ring structure, particularly a 4- to 7-membered ring, with the phosphorus atom. In particular, R10 and R20 are the same and are tert-butyl, cyclohexyl, phenyl, or substituted phenyl groups. In particular, R10 and R20 are tert-butyl. In addition, R10 and R20 can independently be alkoxy (e.g., C1-C10 alkoxy) or aryloxy (e.g., C1-C10 aryloxy).

[0080] R30 is defined similarly to R10 and R20, but may be a metallocenyl group. In the latter embodiment, R30 is a substituted or unsubstituted metallocenyl group. In this case, the metallocenyl group has a first cyclopentadienyl group and a second cyclopentadienyl group. p groups R40 may optionally be provided on the first cyclopentadienyl group, where a tertiary phosphine of the general formula P-R10R20R30 is bonded or coordinated to the palladium center, and q groups R41 may optionally be provided on the second cyclopentadienyl group. R40 and R41 are independently an organic group having 1 to 20 carbon atoms. R40 and R41 may independently be defined similarly to R10 and R20.

[0081] p can take the value 0, 1, 2, 3 or 4, and q can take the value 0, 1, 2, 3, 4 or 5. In one possible embodiment, q=5 and R41 is methyl or phenyl. In another embodiment, p=0.

[0082] In certain embodiments, p=0, q=5, 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.

[0083] In another embodiment, R10, R20 and R30 are the same and are 1-adamantyl, 2-adamantyl, phenyl, ortho-tolyl, cyclohexyl, tert-butyl, or R10 and R20 are 1-adamantyl or 2-adamantyl and R30 is n-butyl.

[0084] Surprisingly, using the methods described herein, numerous compounds according to the general formula IV can be prepared in a relatively simple and inexpensive manner, reproducibly, with high purity, particularly high NMR purity, advantageously ether-free, and in satisfactory yields. Thus, for example, starting from the palladium(0) complex [Pd2(dvds)3], it was possible to obtain the palladium(0) complex compounds [Pd(PCy3)(dvds)], [Pd(PiPr3)(dvds)], [Pd(P(1-Ad)2Bu)(dvds)], and [Pd(P(tBu2)iPr)(dvds)] in yields of ≥ 50%, and in some cases ≥ 60%. The use of non-ethereal solvents largely eliminates contamination of the final product in the form of traces of oxygen (ppm range), especially in the form of oxygen-containing solvents such as ethers. This is advantageous for the possible use of the final product according to formula IV, for example, as a catalyst, especially in palladium-catalyzed coupling reactions.

[0085] The fact that a large number of compounds according to general formula IV can be produced by the above-described method is particularly surprising, since the method can be carried out without the addition of olefins, particularly without the addition of 1,6-dienes, such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (dvds). This is also true even when, in contrast to the synthetic route described by Krause et al., the palladium compound provided in step A is a palladium(0) complex [Pd2(dvds)3], which is present in a binuclear form, especially in solution. Eliminating the addition of olefins is particularly advantageous from an economic (atom-wise) and ecological standpoint. In addition, this further reduces the number of possible impurities in the final product according to general formula IV.

[0086] According to one embodiment, the molar ratio of palladium to 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, in particular 1.0:1.0.

[0087] Solvent S E The solvent or solvent mixture S may also be a mixture of solvents. E In particular, the solvent comprises or is selected from the group consisting of aromatic hydrocarbons, ketones, such as acetone, and alcohols, such as methanol, ethanol, or isopropanol, and mixtures thereof. The at least one aromatic hydrocarbon may, for example, be selected from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.

[0088] In one variant of the claimed method for preparing compounds of type [LPd(dvds)](IV), the palladium compound in step A is in particular a palladium(II) compound consisting of a palladium(II) cation and two anions, which is reacted with a ligand L, which is an organosilicon compound, in particular a cyclic or acyclic siloxane. S and in situ in the presence of a base in solvent S F It is prepared by reacting in

[0089] In the context of the reactions described herein, the term "base" refers to inorganic and organic bases, especially inorganic bases, but not organometallic bases. The base should not decompose in water. Suitable bases are, for example, salts of Bronsted acids. Carbonates, hydrogen carbonates, acetates, formates, ascorbic acids, oxalates, and hydroxides are advantageously used. These can be used in the form of ammonium salts (Bronsted acids) NR4, where R is, for example, H or alkyl, alkali metal salts, for example, sodium or potassium salts, and alkaline earth metal salts.

[0090] In particular, solvent S E and solvent S Fare miscible or identical. In this case, there is no need to exchange the solvent, which is particularly advantageous from an economical and ecological point of view. In the context of the present invention, two solvents are said to be miscible if they are miscible at least during the respective reactions, i.e., if they do not exist as two phases.

[0091] According to another embodiment of the method, the reaction in step B is followed by a step C which comprises isolating the compound prepared in step B according to the general formula [LPd(dvds)] (IV): as a preparation comprising a compound according to the general formula [LPd(dvds)](IV) and a non-ethereal solvent, or -As a substance, preferably as a solid.

[0092] The preparation may therefore be in the form of a solution, suspension, dispersion or gel, depending in particular on the non-ethereal solvent present and / or the compound according to [LPd(dvds)](IV) present. The solvent may also be a mixture of solvents. In particular, the solvent S used may be a mixture of solvents. E The preparation usually comprises or is a solvent that is miscible with or identical to the solvent. The preparation is usually in the form of a solution or suspension.

[0093] In a further variant of the method, the isolation comprises a filtration step and / or centrifugation. The above procedure can also be carried out several times. Optionally, one or more filtrations on a washing medium, such as activated carbon or silica, for example Celite®, can be carried out. Advantageously, the filtrate, centrifuged or decanted material or solid can be subjected to further purification and / or isolation steps, which can be carried out quickly and without complexity and without special preparation efforts.

[0094] Isolation of the compound according to general formula [LPd(dvds)] (IV) may comprise further process steps, such as reduction of the mother liquor volume, i.e., concentration of the mother liquor volume, for example "bulb-to-bulb", addition and / or solvent exchange to precipitate the product from the mother liquor and / or to remove impurities and / or reactants, crystallization, sublimation, washing with alcohols, such as ethanol, methanol or isopropanol, and mixtures thereof, and drying of the product. Each of the aforementioned steps may be provided in a different order and frequency.

[0095] Overall, the purification and / or isolation of the target compounds according to general formula [LPd(dvds)](IV) is relatively simple and inexpensive.

[0096] Generally, the final product may still contain solvent residues or impurities, for example, from the reactants. The isolated compounds of type [LPd(dvds)] (IV) have a purity of at least 97%, advantageously greater than 97%, in particular greater than 98% or 99%. Even when scaled up to industrial scale, the reproducible yields are usually greater than 50%, and in some cases greater than 60%, depending in particular on the choice of reactants and solvent or solvent mixture.

[0097] This object is also achieved by a compound according to the general formula [LPd(dvds)] (IV) which is obtained or obtainable by a method according to one of the above embodiments, in which L is as defined above and L is selected from the group consisting of tri-tert-butylphosphine (PtBu3), tri-iso-propylphosphine (PiPr3), trimethylphosphine (PMe3), tricyclohexylphosphine (PCy3), tris-o-tolylphosphine (P(o-tolyl)3), triphenylphosphine (PPh3), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu2), tert- butyl-di-(isopropyl)phosphine (P(iPr)2tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)2tBu), 1-adamantyl-di-(isopropyl)phosphine (P(1-Ad)iPr2), di(1-adamantyl)-isopropylphosphine (P(1-Ad)2iPr), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp).

[0098] The palladium(0) compounds according to the presently claimed general formula [LPd(dvds)](IV), which are obtained or obtainable by a process according to one of the above embodiments, can be used, for example, as catalysts, in particular as catalysts in palladium-catalyzed cross-coupling reactions. Advantageously, they are suitable as catalysts for the reactions shown below:

[0099] The object of the present invention is to provide a compound of general formula IV

[0100] [ka] wherein L is a phosphine ligand. This can also be achieved by compounds according to the method described above, where L is tri-tert-butylphosphine (PtBu3), tri-isopropylphosphine (PiPr3), trimethylphosphine (PMe3), tricyclohexylphosphine (PCy3), tris-o-tolylphosphine (P(o-tolyl)3), triphenylphosphine (PPh3), di-tert-butyl(isopropylphosphine (P(iPr)tBu2), tert-butyl-di-isopropylphosphine (P(iPr)2tBu), 1-adamant and 1,3-bis(diphenylphosphino)propane (dppe), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis(diphenylphosphino)propane (dppp).

[0101] The palladium(0) compounds according to the general formula [LPd(dvds)](IV) claimed herein can be used, for example, as catalysts, in particular as catalysts in palladium-catalyzed cross-coupling reactions.

[0102] In one embodiment of the presently claimed compounds according to formula IV, the phosphine ligand L is tertiary phosphines according to the general formula P-R10R20R30, in which R10 and R20 are independently selected from the group consisting of substituted and unsubstituted linear alkyl groups, substituted and unsubstituted branched alkyl groups, substituted and unsubstituted cycloalkyl groups, substituted and unsubstituted aryl groups, and substituted and unsubstituted heteroaryl groups, and the heteroatoms are selected from the group consisting of sulfur, nitrogen, and oxygen; R30 is a tertiary phosphine defined as R10 and R20 or is a metallocenyl group; or -2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)-1,1'-biphenyl (DavePhos), 2-(dicyclohexylphosphino)-2',4',6'-tri-isopropyl-1,1'-biphenyl (XPhos), 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl (SPhos), 2-dicyclohexylphosphino-2',6'-di-isopropoxy-1,1'-biphenyl (RuPhos), 2-(dicyclohexylphosphino)-3,6-dimethoxy-2',4', 6'-tri-isopropyl-1,1'-biphenyl (BrettPhos), [4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (Xantphos), 2-dicyclohexylphosphino-2',6'-bis(dimethylamino)-1,1'-biphenyl (CPhos), di-(1-adamantyl)-n-butylphosphine (cataCXium® A), 2-di-tert-butylphosphino-2',4',6'- Tri-isopropyl-1,1'-biphenyl (t-BuXPhos), 2-(di-tert-butylphosphino)-3,6-dimethoxy-2',4',6'-tri-isopropyl-1,1'-biphenyl (tert-BuBrettPhos), 2-(di-tert-butylphosphino)-3-methoxy-6-methyl-2',4',6'-tri-isopropyl-1,1'-biphenyl (RockPhos), 2-di[3,5-bis(trifluoromethyl)phenylphosphino]-3,6-dimethoxy-2',4',6'-tri-isopropyl -1,1'-biphenyl (JackirPhos), 2-(di-tert-butylphosphino)-biphenyl (JohnPhos), R-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-tert-butylphosphine, di-tert-butyl(n-butyl)phosphine, 2-(di-1-adamantylphosphino)-3,6-dimethoxy-2',4',6'-tri-isopropyl-1,1'-biphenyl (AdBrettPhos), 2-diethylphosphino-2',6'-bis(dimethylamino)-1,1'-Biphenyl racemic 2-di-tert-butylphosphino-1,1'-binaphthyl (TrixiePhos), 1,3,5,7-tetramethyl-8-phenyl-2,4,6-trioxa-8-phosphaadamantane (MeCgPPh), N-[2-(di-1-adamantylphosphino)phenyl]morpholine (MorDalPhos), 4,6-bis(diphenylphosphino)phenoxazine (NiXantphos), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 2-di-tert-butylphosphino-2'-(N,N(dimethylphosphino)) 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-tri-isopropyl)-1,1'-biphenyl (Me4t-BuXPhos), 2-dicyclohexylphosphino-4-(N,N(dimethylamino)-1,1'-biphenyl, methyldiphenylphosphine, Tris-(pentafluorophenyl)-phosphine (P(C6F5)3), trifluorophosphine tert-butyldiphenylphosphine (P(tBu)Ph2), phenyl-di-tert-butylphosphine, di-tert-butyl-neopentylphosphine, 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene, tris(p-methoxyphenyl)phosphine, tris(p(trifluoromethylphenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine ethyl)phosphine, tris(2,6-dimethylphenyl)phosphine, benzyldi-1-adamantylphosphine, cyclohexyldi-tert-butylphosphine, cyclohexyldiphenylphosphine, 2-di-tert-butylphosphino-1,1'-binaphthyl, 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-di-tert-butylphosphino-2',4',6'-tri-isopropyl-1,1'-biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-tri-isopropylbiphenyl, 2-(dicyclohexylphosphino)biphenyl (cyclohexyl-JohnPhos), 2-(dicyclohexylphosphino)-2',6'-dimethoxy-1,1'-biphenyl, 2-di-tert-cyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-cyclohexylphosphino-2',6'-di-isopropoxy-1,1'-biphenyl, 2-( (dicyclohexylphosphino)-2',4',6'-tri-isopropyl-1,1'-biphenyl, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-diphenylphosphino-2'-(N,N(dimethylamino)biphenyl, (4-dimethylaminophenyl)(tert-butyl)2-phosphine, 1,2-bis(di-tert-butylphosphinomethyl)benzene, 1,3-bis(di-tert-butylphosphinomethyl)propane, 1,2-bis(diphenylphosphinomethyl)benzene, 1,3-bis(di-tert-butylphosphinomethyl)propane, 1,2-bis(diphenylphosphinomethyl)benzene, 1,3-bis(diphenyl ... N-(2-methoxyphenyl)-2-(di-tert-butylphosphino)pyrrole, 1-(2-methoxyphenyl)-2-(di-cyclohexylphosphino)pyrrole, N-phenyl-2-(di-tert-butylphosphino)indole, N-phenyl-2-(di-tert-butylphosphinomethyl)benzene, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,2-bis(diphenylphosphino)butane, N-(2-methoxyphenyl)-2-(di-tert-butylphosphino)pyrrole, 1-(2-methoxyphenyl)-2-(di-cyclohexylphosphino)pyrrole, N-phenyl-2-(di-tert-butylphosphino)indole, N-phenyl-2-(di-tert-butylphosphino) N-phenyl-2-(dicyclohexylphosphino)pyrrole, N-phenyl-2-(dicyclohexylphosphino)indole, N-phenyl-2-(dicyclohexylphosphino)pyrrole, 1-(2,4,6-trimethylphenyl)-2(dicyclohexylphosphino)imidazole, and (S)-7,7'-bis(diphenylphosphino)-3,3',4,4'-tetrahydro-4,4'-dimethyl-8,8'-bi(2H-1,4-benzoxazine) (Solphos).

[0103] In an advantageous embodiment of the compound according to the general formula IV claimed herein, the ligand L is di-(1-adamantyl)-n-butylphosphine (cataCXium® A) and the compound has the formula

[0104] [ka] It has.

[0105] The purpose is also to: i. Compounds according to the general formula [LPd((dvds)](IV) and ii. Palladium(0) compounds [Pd2(dvds)3] in addition to palladium compounds according to the general formula [LPd((dvds)](IV) This is achieved by a preparation comprising:

[0106] In one embodiment of the preparation, the compound according to the general formula [LPd((dvds)](IV), or the preparation itself, is obtained or obtainable in particular by a method for preparing such a compound according to one of the other embodiments described above.

[0107] Another embodiment of the preparation claimed herein is that the preparation is prepared in solvent S Z , particularly containing a non-ethereal solvent.

[0108] The preparation is in particular characterized by the presence of solvent S Z and / or may be in the form of a solution, suspension, dispersion or gel, depending on the solvent present. ZThe solvent S may be a mixture of solvents. It is advantageously selected from the group consisting of alkanes, aromatic hydrocarbons and polar solvents, and is preferably 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 ether, 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. For example, diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol, ethanol, isopropanol, and mixtures or combinations thereof are suitable. In particular, solvent S is Z comprises or is a solvent selected from the group consisting of aromatic hydrocarbons, ketones, such as acetone, and alcohols, such as methanol, ethanol, or isopropanol, and mixtures thereof, in which case the at least one aromatic hydrocarbon may be selected from the group consisting of, for example, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof.

[0109] In an advantageous embodiment of the preparation described herein, the preparation comprises a compound of formula

[0110] [ka] This includes compounds according to the present invention.

[0111] One of the best third-generation cross-coupling catalysts for both carbon-carbon and carbon-heteroatom coupling reactions is the palladium(I) dimer [Pd(μ-Br)(PtBu3)]2, i.e., di-μ-bromobis(tri-tert-butylphosphine)dipalladium(I) (e.g., TJ Colacot, Platinum Metals Rev. 2009, 53(4), 183-188).

[0112] General formula [Pd(μ-X)(PR A R B R C Two methods claimed herein for preparing compounds according to the formula (VII) are described and illustrated, which represent alternatives to the previously known synthetic routes described above and / or which are used to overcome the drawbacks of methods from the prior art. For ease of description, the first described method will be referred to as the "first method" and the subsequently described method as the "second method."

[0113] This purpose is based on the general formula [Pd(μ-X)(PR A R B R C )]2(VII)

[0114] [ka] During the ceremony, -R A , R B and R C is independently selected from the group consisting of tert-butyl, isopropyl, and 1-adamantyl; and the bridging atoms X are independently bromine (Br) or iodine (I); However, except for the compounds [Pd(μ-Br)(PiPr3)]2 and [Pd(μ-I)(PiPr3)]2, The method comprises: Mononuclear or polynuclear palladium compounds, in particular palladium(0) compounds, in which at least one palladium center is an organosilicon compound, ligand L S and the ligand L S is in particular a cyclic or acyclic siloxane, i. General formula PR A R B R C A phosphine ligand according to In the formula, R A , R B and R C is independently selected from the group consisting of tert-butyl, isopropyl, and 1-adamantyl; Phosphine ligands, except for the phosphine ligand PiPr3, and ii. A transition metal-free oxidizing agent having a molecular formula containing bromine (Br) or iodine (I); Solvent S A This includes reacting in

[0115] The term organosilicon compound has already been defined above.

[0116] The reaction scheme shown below is an example of a palladium complex in which at least one palladium center is an organosilicon compound, ligand L S Starting from mononuclear or polynuclear palladium compounds having the formula [Pd(μ-X)(PR A R B R C 2(VII) ] ...

[0117] [ka]

[0118] In the first step, the Pd(0) complex [Pd2(dvds)3] is reacted with the phosphine ligand PtBu3 to yield the homoleptic palladium(0) complexes [Pd(PtBu3)2] and [Pd2(dvds)3]. In the second step, a transition-metal-free oxidizing agent with the molecular formula bromine (Br) is added, which reacts with the [Pd2(dvds)3] present in the reaction mixture to give PdBr2. Therefore, the in situ generation of PdBr2 is advantageous. This is sufficiently reactive without further processing to react with the Pd(0) compound [Pd(PtBu3)2] formed in the first step via a comproportionation reaction to give the desired target compound. The Dvds produced as a by-product can be removed under vacuum, i.e., easily and completely removed from the reaction vessel at reduced pressure and / or elevated temperature.

[0119] The definition of the expressions "generated / prepared in situ" or "generated / prepared in situ" has already been given above.

[0120] It has surprisingly been found that reaction of 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0) ([Pd2(dvds)3]) with tri-tert-butylphosphine and addition of elemental iodine under the reaction conditions described below affords a homoleptic dimeric palladium complex of the formula:

[0121] [ka]

[0122] In this case, it is immaterial whether the iodine solution is added to a mixture containing the phosphine and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane palladium(0), abbreviated in the context of this invention as [Pd2(dvds)3], [Pd(dvds)], Pd(vs), Pd-VS or palladium-VS, or whether the phosphine is added to a mixture containing [Pd2(dvds)3] and iodine.

[0123] Similarly, the production of similar bromine compounds of the following formula is also possible:

[0124] [Chemical formula]

[0125] In this case, surprisingly, in order to obtain this complex, it is particularly advantageous to add a bromine solution to a mixture containing phosphine and [Pd2(dvds)3]. When phosphine is added to a mixture containing 1,3-divinyl-1,1,3,3-tetramethyldisiloxane palladium(0) - abbreviated as [Pd2(dvds)3], [Pd(dvds)], Pd(vs), Pd-VS or palladium-VS in the context of the present invention - and bromine, this complex is obtained in a slightly lower but still satisfactory yield.

[0126] This object is also achieved by a second method for preparing a compound according to general formula [Pd(μ-X)(PR A R B R C )]2(VII),

[0127] [Chemical formula] wherein, -R A , R B and R C are independently selected from the group consisting of tert-butyl, isopropyl and 1-adamantyl, and - the bridging atom X is independently bromine (Br) or iodine (I), and the method comprises a palladium(II) compound other than palladium(II) halide, i. A palladium(0) compound according to general formula [Pd(PR A R B R C )2], wherein R A , R B and R<000015is a palladium(0) compound independently selected from the group consisting of tert-butyl, isopropyl, and 1-adamantyl; and / or 1. A preparation comprising: -General formula [Pd(PR A R B R C )2], wherein R A , R B and R C is a palladium(0) compound independently selected from the group consisting of tert-butyl, isopropyl, and 1-adamantyl; and - at least one organosilicon compound A preparation comprising and ii. Hydrogen bromide (HBr) and / or hydrogen iodide (HI) Solvent S B Inside This includes reacting.

[0128] The term organosilicon compound has already been defined above.

[0129] [Pd(μ-X)(PR A R B R CThe two methods provided in the context of the present invention for preparing complexes of type )]2(VII)—referred to above and below as “Method 1” and “Method 2”—are particularly advantageous compared to the above-mentioned prior art methods. In particular, both bromine and iodine derivatives according to formula VII can be prepared by these methods in good yield and with good purity. These methods are likewise each based on a comproportionation reaction. However, this is advantageously carried out between a palladium(0) compound and sufficiently reactive PdBr2 or PI2 generated in situ, each of which is completely or substantially completely reacted. Thus, activation of PdBr2 or PdI2 can be omitted. Unreacted PdBr2 or PI2 can be quantitatively separated simply by filtration, decantation, and / or centrifugation and then recycled after an optional washing step. The reactants required for the methods claimed herein are easy to handle and, in particular, can be stored for several months or more without any aging or decomposition processes being observed. In addition, the reactants used are advantageously readily available and relatively inexpensive. Furthermore, the preparation methods described herein are simple and can be carried out under mild conditions. In addition, an advantageous selection of reactants is possible, as the [Pd(μ-X)(PR A R B R CThis method ensures that compounds of type )]2(VII) are free of impurities caused by reactant compounds that tend to crystallize, such as [Pd2(dba)3]xC6H6, or olefins, especially diolefins, contained in the reaction mixture. Additionally, a transition-metal-free oxidizing agent is provided, thus eliminating contamination of the final product with other transition metals, such as copper. Yields of at least 60%, typically >80%, and sometimes >90%, are also achieved, depending on which of the methods described herein is used and the reaction conditions selected in each case. By reaction conditions, we mean, for example, the choice of palladium compound, the choice of transition-metal-free oxidizing agent, the choice of solvent or solvent mixture, the choice of reaction temperature and / or pressure, the choice of palladium concentration, the choice of batch size, and the choice of the order in which the reactants are added.

[0130] Solvent S A or S B It may also be a mixture of solvents in each case, which is advantageously selected from the group consisting of alkanes, aromatic hydrocarbons and polar solvents, such as ketones, for example, acetone, and alcohols, preferably 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 ether, 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. For example, diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol, ethanol, isopropanol, and mixtures or combinations thereof are suitable.

[0131] General formula [Pd(μ-X)(PR A R B R CIn one embodiment of the first or second method for preparing a compound according to formula (VII), one of the organosilicon compounds is or comprises a cyclic or acyclic 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. Advantageously, one of the organosilicon compounds comprises or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (DVDs). In particular, one of the organosilicon compounds is DVDs.

[0132] General formula [Pd(μ-X](PR A R B R C According to another variant of the first method for preparing the compound according to )]2(VII), a) Transition metal-free oxidizing agents whose molecular formula contains bromine (Br) include 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-dimethylaminopyridinium tribromide, 1-butyl-3-methylimidazolium tribromide, 1,8-diazabicyclo[5.4.0]-7-undecene hydrogen tribromide, N-bromine is selected from the group consisting of mosuccinimide (NBS), (HC(COacetyl bromide)Br), N-bromophthalimide, N-bromosaccharin, N-bromoacetamide, 2-bromo-2-cyano-N,N-dimethylacetamide, 1,3-dibromo-5,5-dimethylhydantoin, dibromoisocyanuric acid (DBI), sodium bromoisocyanurate hydrate, boron tribromide, phosphorus tribromide, bromodimethylsulfonium bromide, 5,5-dibromo-2,2-dimethyl-4,6-dioxy-1,3-dioxane, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, bis(2,4,6-trimethylpyridine)bromonium hexafluorophosphate, and trimethylsilyl bromide (TMS-Br); and b) The transition metal-free oxidizing agent having the molecular formula iodine(I) is selected from the group consisting of molecular iodine, hydrogen iodide, iodoform, carbon tetraiodide, 1-chloro-2-iodoethane, N,N-dimethyl-N-(methylsulfanylmethylene)ammonium iodide, N-iodosuccinimide (NIS), acetyl iodide (HC(CO)I) N-iodosaccharin, 1,3-diiodo-5,5-dimethylhydantoin (DIH), pyridine iodide monochloride, benzyltrimethylammonium trimethylsilyl dichloroiodate iodide, bis(pyridine)iodonium tetrafluoroborate, bis(2,4,6-trimethylpyridine)iodonium hexafluorophosphate, and (TMS-I).

[0133] According to an advantageous variant of the second method, the palladium(II) compound required as a reactant is palladium(II) acetylacetonate ([Pd(acac)2]).

[0134] Another advantageous embodiment of the second method provides in particular for the use of aqueous hydrogen bromide and / or hydrogen iodide solutions.

[0135] According to a further advantageous embodiment of the second method, in situ generation of hydrogen bromide (HBr) and / or hydrogen iodide (HI) is provided. For this purpose, a first step is provided, which comprises reacting a 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. Apart from water / alcohol mixtures, it is also possible to use mixtures of several alcohols. The molar ratio of (HBr donor and / or HI donor):(water and / or alcohol) is at least 1:1. It is also possible to provide more than one molar equivalent of water or more than one molar equivalent of alcohol relative to the amount of substance of the HBr donor and / or HI donor. The molar ratio of (HBr donor and / or HI donor):(water and / or alcohol) is 1:1 to 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 may be 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 1.0:4.7 or 1.0:4.8 or 1.0:4.9.

[0136] According to the present invention, the HBr or HI donor is a brominated or iodinated, particularly organic, compound having at least one H-Br or HI bond with the lowest possible dissociation energy, which cleaves the HBr or HI under the selected reaction conditions, particularly in the presence of at least an equal amount of water and / or alcohol. However, cleavage of the HBr or HI should not occur during long-term storage of the HBr or HI donor.

[0137] The reaction scheme shown below starts with a palladium(II) compound, excluding palladium(II) halides, and proceeds to the reaction of [Pd(μ-X)(PR A R B R C

[0023] Figure 1 shows the procedure for the second method claimed herein for preparing complex compounds of type 2(VII), providing the in situ generation of HBr as an example. The reactants used in this example are palladium(II) acetylacetonate, the HBr donor acetyl bromide, and [Pd(PtBu)2.

[0138] [ka]

[0139] In the first step, palladium(II) acetylacetonate is reacted with acetyl bromide to form PdBr2, acetylacetone, and acetic acid. The reaction mixture must contain at least trace amounts of water and / or alcohol. This can be easily achieved, for example, by using a solvent that is not dried or not completely dried. In the presence of water and / or at least one alcohol, the HBr donor, acetyl bromide, cleaves hydrogen bromide (HBr), which reacts with palladium(II) acetylacetonate to give PdBr2. Here, the molar ratio of HBr donor to (water and / or alcohol) must be at least 1:1. Advantageously, the only by-products are acetylacetone and acetic acid and / or acetate esters. In the second step, a palladium(0) compound [Pd2(dvds)3] is added, which reacts with in situ-generated, sufficiently active PdBr2 via a proportionation reaction to give the desired target compound.

[0140] The definition of the expressions "generated / prepared in situ" or "generated / prepared in situ" has already been given above.

[0141] An advantageous embodiment of the second method claimed herein for preparing a compound according to 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 trimethylsilyl iodide (TMS-I). In this case, the reaction mixture must contain water and / or alcohol. The acetyl halide reacts to give hydrogen bromide or hydrogen iodide and acetic acid and / or acetate esters, while the TMSBr or TMSI reacts to give hydrogen bromide or hydrogen iodide and trimethylsilane and / or alkoxytrimethylsilanes (also called alkyltrimethylsilyl ethers). In principle, acetyl halides and trimethylsilyl halides are easier to handle than the corresponding hydrogen halides. The molar ratio of (HBr donor and / or HI donor):(water and / or alcohol) must be at least 1:1.

[0142] General formula [Pd(μ-X)(PR A R B R C According to one embodiment of the first method for preparing a compound according to )]2(VII), the reaction comprises: a) In the first step, solvent S A1 In the present invention, at least one palladium center is an organosilicon compound. S and in a second step providing a mononuclear or polynuclear palladium compound, in particular a palladium(0) compound, of the general formula PR A R B R C and in a third step, adding a transition metal-free oxidizing agent having a molecular formula containing bromine (Br) or iodine (I). or b) In the first step, solvent S A1 In the present invention, at least one palladium center is an organosilicon compound. S and in a second step, adding a transition metal-free oxidizing agent having the molecular formula bromine (Br) or iodine (I), and in a third step, providing a mononuclear or polynuclear palladium compound, in particular a palladium(0) compound, having the general formula PR A R B R C adding a phosphine ligand according to Includes.

[0143] In this case, solvent S A1 is advantageously a solvent S A It is miscible with or identical to, in particular identical to.

[0144] The transition metal-free oxidizing agent and / or phosphine ligand may be present as a substance, i.e., as a gas, liquid, or solid, or in a solvent S A The compound may be added as a solution, emulsion or suspension in a solvent that is miscible with the compound.

[0145] In particular, the general formula [Pd(μ-Br)(PR A R B R C)]2(VII.a), for example, for preparing complexes with [Pd(μ-Br)(PtBu3)]2, [Pd(μ-Br)(P(iPr)tBu2)]2, [Pd(μ-Br)(P(1-Ad)tBu2)]2, [Pd(μ-Br)(P(1-Ad)tBu2)]2, and [Pd(μ-Br)(P(1-Ad)2iPr)]2, it is preferable to select the sequence given under a). This is particularly advantageous when the transition metal-free oxidizing agent is selected from the group consisting of Br2, NBS, and acetyl bromide, and mixtures thereof.

[0146] General formula [Pd(μ-X](PR A R B R C In another variant of the first method for preparing compounds according to )]2(VII), mononuclear or polynuclear palladium compounds, in particular palladium(0) compounds, can be prepared by reacting a palladium(II) compound, in particular a palladium(II) compound consisting of a palladium(II) cation and two monovalent or divalent anions, with a ligand L, which is an organosilicon compound, in particular a cyclic or acyclic siloxane. S and in situ in the presence of a base, in solvent S Q It is prepared by reacting in

[0147] In particular, solvent S A and solvent S Q are miscible or identical. In this case, there is no need to exchange the solvent, which is particularly advantageous from an economic and ecological point of view. The definition of the expression "miscible solvent" has already been given above.

[0148] The expressions "in situ generated / prepared" or "in situ generated / prepared" and the term "weakly coordinating" have already been defined above. In the context of the reactions described herein, the term "base" refers to inorganic and organic bases, especially inorganic bases, but not organometallic bases. The base should not decompose in water. Suitable bases are, for example, salts of Brønsted acids. Carbonates, bicarbonates, acetates, formates, ascorbates, oxalates, and hydroxides are advantageously used. These can be used in the form of ammonium salts (Brønsted acids) NR4, where R is, for example, H or alkyl, alkali metal salts, for example, sodium or potassium salts, and alkaline earth metal salts.

[0149] The palladium(II) compound may have two different or two identical monovalent anions or one divalent anion. Neutral ligands, such as COD, are not provided. As a result, inexpensive, commercially available palladium(II) compounds, such as PdCl2, can be advantageously used. Therefore, it is possible to avoid the time-consuming and expensive preparation of palladium(II) compounds of the type [Pd(ligand)Y2] [where, for example, ligand = COD] as reactants for the in situ generation of mononuclear or polynuclear palladium compounds. This is particularly advantageous from an economical (atom-wise) and ecological point of view. In addition, this reduces the number of possible impurities in the final product according to general formula VII.

[0150] In a further advantageous embodiment, the palladium(II) compound used as a reactant in the context of the above-mentioned in situ preparation comprises two identical monovalent anions, in particular selected from the group consisting of halides and monovalent weakly coordinating anions.

[0151] General formula [Pd(μ-X)(PR A R B R C According to a further embodiment of the second method for preparing a compound according to )]2(VII), the reaction comprises: a) In the first step, solvent S B1In a second step, hydrogen bromide (HBr) and / or hydrogen iodide (HI) are added, and / or 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, is added, and in a third step, a palladium(II) compound of the general formula [Pd(PR A R B R C )2] and / or palladium(0) compounds of the general formula [Pd(PR A R B R C )2] and a preparation comprising a palladium(0) compound and at least one organosilicon compound. or b) In the first step, solvent S B1 and in a second step, a palladium(II) compound of the general formula [Pd(PR A R B R C )2] and / or palladium(0) compounds of the general formula [Pd(PR A R B R C )2] and a preparation comprising at least an organosilicon compound, and in a third step, adding hydrogen bromide (HBr) and / or hydrogen iodide (HI) and / or adding an HBr donor and / or an HI donor selected from the group consisting of TMSBr, TMSI, acetyl bromide, acetyl iodide, and mixtures thereof, in particular acetyl bromide and / or acetyl iodide.

[0152] In particular, the general formula [Pd(μ-Br)(PR A R B R C )]2(VII.a), for example, when preparing complexes with [Pd(μ-Br)(PtBu3)]2, [Pd(μ-Br)(P(iPr)tBu2)]2, [Pd(μ-Br)(P(1-Ad)tBu2)]2, [Pd(μ-Br)(P(1-Ad)2tBu)]2 and [Pd(μ-Br)(P(1-Ad)2iPr)]2, it is preferable to choose the sequence given under a).

[0153] According to a variant embodiment of the second method, the preparation provided is prepared by dissolving in solvent S Z The preparation itself comprises, in particular, the solvent S present. Z and / or may be in the form of a solution, suspension, dispersion or gel, depending on the organosilicon compound present. Z The solvent S may be a mixture of solvents. It is advantageously selected from the group consisting of alkanes, aromatic hydrocarbons and polar solvents, and is preferably 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 ether, 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. For example, diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol, ethanol, isopropanol, and mixtures or combinations thereof are suitable. In particular, solvent S is Z When the solvent S used in the second method comprises or is a solvent selected from the group consisting of aromatic hydrocarbons, ketones such as acetone, and alcohols such as methanol, ethanol, or isopropanol, and mixtures thereof, the preparation is in the form of a solution or suspension. In this case, the at least one aromatic hydrocarbon can be selected from the group consisting of, for example, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, and mixtures or combinations thereof. Z and solvent S B It is particularly advantageous if the are miscible or identical.

[0154] General formula [Pd(μ-X)(PR A R B R C Another embodiment of the second method for preparing a compound according to the general formula [Pd(PRA R B R C )2] with the above preparation comprising a palladium(0) compound and at least one organosilicon compound, wherein a) at least one organosilicon compound contains at least one terminal double bond, in particular a vinyl double bond, and in particular comprises or is a cyclic or acyclic siloxane; and / or b) The preparation has the general formula [Pd(PR A R B R C ) 2], as well as palladium compounds of the general formula [L S Pd(PR A R B R C )](II) and / or at least one palladium compound according to the general formula [Pd(L S )2] (III), wherein: -ligand L S is in particular identical to at least one organosilicon compound, in particular a cyclic or acyclic siloxane, the at least one organosilicon compound containing at least one terminal double bond, and -(PR A R B R C ) is selected from the group consisting of tri-tert-butylphosphine (PtBu), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu), tert-butyl-di(isopropyl)phosphine (P(iPr)tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)tBu), di(1-adamantyl)-isopropyl)phosphine (P(1-Ad)iPr), 1-adamantyl-di(isopropylphosphine (P(1-Ad)iPr), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis-(diphenylphosphino)-propane (dppp).

[0155] In particular, the ligand L S is the same as the organosilicon compound, and the ligand L S is in particular a cyclic or acyclic siloxane having at least one terminal, in particular vinyl, double bond. In this case, the ligand L S is advantageously connected via at least one π-directed bond to a group of general formula L S Pd(PR A R B R C )(II) or [Pd(L S )2] (III) is coordinated or bonded to the palladium center of the compound.

[0156] transition metal-free oxidizing agent and / or a compound of the general formula [Pd(PR A R B R C The palladium(0) compounds according to the present invention can be prepared in a substance, i.e., as a gas, liquid or solid, or in a solvent such as S B The compound may be added as a solution, emulsion or suspension in a solvent that is miscible with the compound.

[0157] A further variant of the presently claimed second process for preparing a compound according to formula VII is that the reaction according to the second process for preparing a compound according to formula VII is carried out in a solvent selected for the reaction according to the second process for preparing a compound according to formula VII or in a solvent miscible therewith, in particular in which at least one palladium center is substituted with a ligand L which is an organosilicon compound. S and palladium(0) compounds having the general formula PR A R B R C Starting from a phosphine ligand according to the general formula [Pd(PR A R B R C )2]. A , R B and R Care independently selected from the group consisting of tert-butyl, isopropyl, and 1-adamantyl, with the exception of the phosphine ligand PiPr. According to an alternative or complementary embodiment of the method, Pd(PR A R B R C Preparations comprising a palladium(0) compound and at least one organosilicon compound according to the method of claim 2 are in particular produced in situ starting from a mononuclear or polynuclear palladium compound, in particular a palladium(0) compound, in which at least one palladium center is bound to a ligand L which is an organosilicon compound. S and in each case a phosphine ligand (PR A R B R C ), the latter being independently selected from the group consisting of tri-tert-butylphosphine (PtBu3), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu2), tert-butyl-di-(isopropyl)phosphine (P(iPr)2tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)2tBu), 1-adamantyl-di(isopropylphosphine (P(1-Ad)iPr2), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis(diphenylphosphino)propane (dppp). The in situ generation of the preparation is carried out in the solvent selected for the reaction according to the second method for preparing the compound according to formula VII or in a solvent miscible therewith. The ligand L S and the selection or definition of the organosilicon compound corresponds to that above.

[0158] The expressions "generated / prepared in situ" or "generated / prepared in situ" have already been defined above.

[0159] General formula [Pd(μ-X](PR A R B R C According to a further variant of the first method for preparing compounds according to )]2(VII), the molar ratio Pd:X is at least 1.0:0.5, advantageously from 1.0:0.5 to 1.0:2.0, more advantageously from 1.0:0.6 to 1.0:1.9, particularly advantageously from 1.0:0.7 to 1.0:1.8, in particular from 1.0:0.8 to 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 -Palladium(0) compounds: PR A R B R C is at least 1:1, advantageously from 1.0:1.0 to 1.0:2.5, more advantageously from 1.0:1.1 to 1.0:2.4, particularly advantageously from 1.0:1.2 to 1.0:2.3, in particular from 1.0:1.3 to 1.0:2.2, 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 1.0:2.0 or 1.0:2.1.

[0160] From an economical (atomic) and ecological point of view, palladium(0) compounds: A R B R C It is particularly advantageous if the molar ratio of is 1:1.

[0161] General formula: [Pd(μ-X)(PR A R B R C Another embodiment of the second method for preparing a compound according to )]2(VII) is -molar ratio Palladium(II) Compounds: Transition Metal-Free Oxidizing Agents or Palladium(II) compounds: Bromine (Br) and / or Iodine (I) is at least 1:2, advantageously 1:2 to 1:3, more advantageously 1.0:2.1 to 1.0:2.9, particularly advantageously 1.0:2.2 to 1.0:2.8, in particular 1.0:2.3 to 1.0:2.7, for example 1.0:2.4 or 1.0:2.5 or 1.0:2.6, and / or the molar ratio of palladium(II) compound to palladium(0) compound is from 1:2 to 2:1, advantageously from 1.0:1.9 to 1.9:1.0, more advantageously from 1.1:1.8 to 1.8:1.1, in particular from 1.2:1.7 to 1.7:1.2, for example 1.0:1.8 or 1.8:1.0 or 1.0:1.7 or 1.7:1.0 or 1.0:1.6 or 1.6:1.0 or 1.0:1.5 or 1.5:1.0 or 1.0:1.4 or 1.4:1.0 or 1.0:1.3 or 1.3:1.0 or 1.0:1.2 or 1.2:1.0 or 1.0:1.1 or 1.1:1.0 or 1.0:1.0 To provide.

[0162] From an economical (atom-wise) and ecological point of view, it is particularly advantageous if the molar ratio of palladium(II) compound to transition metal-free oxidizing agent is 1:2 and the molar ratio of palladium(II) compound to palladium(0) compound is 1:1.

[0163] General formula: [Pd(μ-X](PR A R B R C Another embodiment of the second method for preparing compounds according to )]2(VII) provides that the preparation comprises at least one organosilicon compound, and in particular the content of silicon present in the form of at least one organosilicon compound is 100 ppm to 1000 ppm, advantageously 110 ppm to 900 ppm, in particular 120 ppm to 800 ppm. In particular, the content of silicon present in the form of at least one organosilicon compound can be determined, in particular quantitatively, using analytical methods known to those skilled in the art. 1 It can be determined using H NMR spectroscopy and / or inductively coupled plasma atomic emission spectroscopy (ICP-AES). A R B R C In the second method for preparing compounds according to (VII), the organosilicon compound is a compound having the ligand LS or the general formula [L S Pd(PR A R B R C)](II) and / or a ligand L according to the general formula [Pd(L S )2](III) can be a palladium compound. S or a palladium compound.

[0164] According to another embodiment of the first method or the second method for preparing a compound according to the general formula [Pd(μ-X)(PR A R B R C )]2.(VII), a further step is carried out after the reaction and includes isolating the compound prepared by the reaction according to [Pd(μ-X)(PR A R B R C )]2(VII). -[Pd(μ-X)(PR A R B R C )]2(VII) and a solvent S A or a solvent S B and / or S Z as a preparation containing or - as a substance, preferably as a solid.

[0165] Here and hereinafter, the term "preparation" means a solution, suspension, dispersion or gel. Thus, the preparation can be in the form of a solution, suspension, dispersion or gel, depending particularly on the solvent present and / or the compound according to [Pd(μ-X)(PR A R B R C )]2(VII) present. The solvent can be a mixture of solvents. In particular, the solvent is a solvent that is miscible with or the same as the solvent S used in the first method A or the solvent S used in the second method B and / or S Z and contains or is that solvent. The preparation is usually in the form of a solution or suspension.

[0166] According to the general formula [Pd(μ-X)(PR A R B R CIn a further variant of the first or second method for preparing a compound according to )]2(VII), the isolation comprises a filtration step and / or decantation and / or centrifugation. The above procedure can also be carried out several times. Optionally, one or more filtrations on a washing medium, such as activated carbon or silica, for example Celite®, can be carried out. Advantageously, the filtrate, centrifuged or decanted material or solid can be subjected to further purification and / or isolation steps, which can be carried out quickly and uncomplicatedly and without particular preparation-related effort.

[0167] General formula [Pd(μ-X)(PR A R B R C Isolation of the compound according to )]2(VII) may involve further process steps, such as reduction of the mother liquor volume, i.e., concentration of the mother liquor, for example, by "bulb-to-bulb", addition and / or solvent exchange to precipitate the product from the mother liquor and / or to remove impurities and / or reactants, crystallization, sublimation, washing with, for example, acetone, pentane or hexane and mixtures thereof, and drying of the product. Each of the aforementioned steps may be provided in a different order and frequency.

[0168] Overall, the general formula [Pd(μ-X)(PR A R B R C Purification and / or isolation of the target compound via )]2(VII) is relatively simple and inexpensive.

[0169] Generally, the final product may still contain residues of solvent or impurities, for example, from the reactants. [Pd(μ-X)(PR A R B R C The isolated compound of type )]2(VII) has a purity of at least 97%, advantageously greater than 97%, in particular greater than 98% or 99%. Even when scaled up to industrial scale, the reproducible yield is at least 60%, usually >80%, and in some cases >90%, depending in particular on the choice of reactants and solvent or solvent mixture.

[0170] The present invention also provides a compound of the general formula

[0171] [ka] This is achieved by the compound During the ceremony, -R A , R B and R C is independently selected from the group consisting of tert-butyl, isopropyl, and 1-adamantyl; and the bridging atoms X are independently bromine (Br) or iodine (I); However, this does not include the compounds [Pd(μ-Br)(PtBu3)]2, [Pd(μ-I)(P(iPr)tBu2)]2, and [Pd(μ-Br)(P(1-Ad)tBu2)]2.

[0172] General formula [Pd(μ-X)(PR A R B R C The palladium(I) compounds claimed herein according to the general formula [Pd(μ-X)(PR A R B R C )]2(VII)。 For example, they can be used as catalysts and / or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. Advantageously, they are suitable as precatalysts for the following reactions:

[0173] Furthermore, the objective is to: i. General formula [Pd(μ-X)(PR A R B R C )]2(VII) During the ceremony, -R A , R B and R C is independently selected from the group consisting of tert-butyl, isopropyl, and 1-adamantyl; and the bridging atoms X are independently bromine (Br) or iodine (I); and ii. at least one organosilicon compound This is achieved by a preparation comprising:

[0174] A definition of the term organosilicon compound has already been given above.

[0175] In one embodiment of the claimed preparation, the compound of the general formula [Pd(μ-X)(PR A R B R C )]2(VII), or the preparation itself, is in particular obtained or obtainable by a method for preparing such a compound according to one of the above-mentioned embodiments.

[0176] According to another embodiment of the preparation, the silicon content, especially in the form of at least one organosilicon compound, is 100 ppm to 1000 ppm, preferably 110 ppm to 900 ppm, in particular 120 ppm to 800 ppm. In particular, the silicon content, especially in the form of at least one organosilicon compound, can be determined, in particular quantitatively, using analytical methods known to those skilled in the art. 1 It can be determined using H NMR spectroscopy and / or inductively coupled plasma atomic emission spectroscopy (ICP-AES).

[0177] In an alternative or complementary embodiment of the preparation claimed herein, the preparation is Z Contains:

[0178] The preparation is in particular characterized by the presence of solvent S Z and / or may be in the form of a solution, suspension, dispersion or gel, depending on the organosilicon compound present. ZThe solvent S may be a mixture of solvents. It is advantageously selected from the group consisting of alkanes, aromatic hydrocarbons and polar solvents, and is preferably 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 ether, 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. For example, diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol, ethanol, isopropanol, and mixtures or combinations thereof are suitable. In particular, solvent S is Z comprises or is a solvent 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, such as methanol, ethanol, and isopropanol, and mixtures thereof, and ethers, such as diethyl ether, THF, 2-methyltetrahydrofuran, and 1,4-dioxane, and mixtures thereof, the preparation is in the form of a solution or suspension.

[0179] In one embodiment of the preparation claimed herein, at least one organosilicon compound contains at least one terminal double bond, in particular a vinyl double bond. In particular, the at least one organosilicon compound comprises or is a cyclic or acyclic siloxane. According to an alternative or additional variant of the preparation, the aforementioned preparation comprises a compound of the general formula [Pd(μ-X)(PR A R B R C In addition to palladium compounds according to the general formula [L S PdZ](II) and / or palladium compounds of the general formula [Pd(L S)2] (III), in which the ligand L S is particularly identical to at least one organosilicon compound, particularly cyclic or acyclic siloxane.At least one organosilicon compound contains at least one terminal double bond, and Z is selected from the group consisting of tri-tert-butylphosphine (PtBu3), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu2), tert-butyl-di-(isopropyl)phosphine (P(iPr)2tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)2tBu), 1-adamantyl-di(isopropyl)phosphine (P(1-Ad)iPr2), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp).

[0180] A further variant of the formulation is that at least one organosilicon compound comprises or is a cyclic or acyclic siloxane, and / or at least one ligand L S is a cyclic or acyclic siloxane 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. In particular, one of the organosilicon compounds comprises or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds), and / or the ligand L S One of these is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds).

[0181] The present invention further provides a compound of the general formula

[0182] [ka] This is achieved by a method for preparing a compound according to During the ceremony, -X is an anionic ligand; and the groups R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl groups, branched, straight-chain and cyclic alkylene groups, 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 mononuclear or polynuclear heteroaryl groups; or - two groups R1, R1, R3 and R4, advantageously R1 and R3 or R2 and R4, together form an unsaturated or aliphatic ring, or - two radicals R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form a first ring which is unsaturated or saturated and which is fused to at least one aromatic ring, The method comprises: A. Palladium compounds, especially mononuclear or polynuclear palladium(0) compounds, in which at least one palladium center is an organosilicon compound, Ligand L S and the ligand L S providing a palladium compound, wherein the palladium compound is in particular a cyclic or acyclic siloxane, B. The palladium compound from step A is reacted with a compound of the general formula

[0183] [ka] with a compound AH according to During the ceremony, -X is an anionic ligand; the groups R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl groups, branched, straight-chain and cyclic alkylene groups, 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 mononuclear or polynuclear heteroaryl groups; or two groups R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form an unsaturated or aromatic ring, or or two groups R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form a first ring which is aromatic or unsaturated and which is fused to at least one aromatic ring, and C. Optionally, isolating the compound of formula VIII produced in step B. Includes.

[0184] The term organosilicon compound has already been defined above.

[0185] A large number of type VIII palladium(II) complex compounds can be easily, relatively inexpensively, and reproducibly provided by the method described herein. The target compounds are usually obtained in high yield and good purity, especially NMR purity. Surprisingly, it has been found that the compounds that can be prepared by the method described herein do not contain impurities due to palladium-containing by-products, which are difficult or impossible to separate due to their solubility behavior, or contain only trace amounts (≦1000 ppm) of the aforementioned impurities. The high purity of the final product is particularly advantageous in view of possible uses, for example, as a precatalyst and / or catalyst. In addition, the method claimed herein allows the production of η 3 -allowing simplified access to benzylpalladium halides and arylpalladium halides.

[0186] Palladium(II) dimers according to Formula VIII are easy-to-use catalyst precursors with excellent catalytic performance. Advantageously, they are readily available in one step from commercially available precursors and react smoothly with numerous electron donor ligands, particularly phosphines and NHC ligands, to give defined palladium(II) complexes. As a result, even the in situ preparation of highly active monoligated palladium(II) precatalysts and / or palladium(II) catalysts starting from dimeric palladium(II) compounds according to Formula VIII is possible in a simple and reproducible manner.

[0187] The palladium compounds, in particular palladium(0) compounds, may exist in mono- or polynuclear, especially dinuclear, form, as monomers or oligomers, especially dimers, and / or as solvent adducts.

[0188] In one embodiment of the presently claimed method for preparing compounds according to general formula VIII, the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.

[0189] The term "weakly coordinating" also encompasses the terms "very weakly coordinating" and "moderately strongly coordinating." Chloride, bromide or iodide can be advantageously used as the halide anion X, with chloride or bromide being particularly advantageous, especially chloride. Monovalent weakly coordinating anions are especially perfluorinated anions, such as PF6. - , BF4 - , F3CSO3 - (TfO - , triflate) and [(F3CSO2)2N] - (TFSI), or non-fluorinated anions, e.g., H3CSO3 - (mesylate) or tosylate.

[0190] According to the present invention, the term "unsaturated ring" refers to a non-aromatic carbocyclic or heterocyclic ring having at least one double bond. The unsaturated ring may be part of a ring system consisting of two or more fused rings, which may include aliphatic, aromatic, and other unsaturated carbocyclic and / or heterocyclic rings. A saturated ring is formed, for example, by groups R1 and R3 when an allyl halide AH derived from, for example, phenalene or indene, is used as a reactant for preparing a compound according to formula VIII.

[0191] In one embodiment of the process described herein, the molar ratio of Pd:AH is at least 1:1, advantageously from 1.0:1.0 to 1.0:5.0, more advantageously from 1.0:1.1 to 1.0:4.0, particularly advantageously from 1.0:1.2 to 1.0:3.0, in particular from 1.0:1.3 to 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.

[0192] The compounds according to general formula VIII that can be obtained by the process claimed herein contain two identical η 3 The allyl ligands are in each case of the general formula

[0193] [ka] derived from compound AH used as reactant according to wherein X, R1, R2, R3 and R4 are as defined above.

[0194] For example, to prepare a compound according to formula VIII, a ligand L which is an organosilicon compound, in particular a cyclic or acyclic siloxane, is added. S Palladium(0) compounds, in particular those having η, can be reacted with 1-naphthylmethyl chloride. For example, a molar ratio of Pd:AH of at least 1:1 can be provided. The palladium(II) compounds according to formula VIII thus obtainable contain two identical aryl ligands derived from naphthalene, in particular η. 3 The complex according to formula VIII has a bound allyl ligand. In other words, the complex according to formula VIII does not have a naphthyl ligand in the strict sense. This is because the electrons involved in the complex formation of the palladium center are not conjugated with the ring electrons. The aromaticity of the bicyclic naphthalene is limited to one of the two fused six-membered rings as a result of the complex formation. However, for simplicity in the context of this invention, the η from naphthalene is 1 Binding ligand or η 3 The bound allyl ligand is called a naphthyl ligand. Therefore, the product of the reaction in the above example is called a dimeric palladium(II) 1-methylnaphthyl chloride complex (where the chlorine atom acts as a bridging ligand, i.e., there are two chlorine bridges), or a chloride-bridged 1-methylnaphthylpalladium(II) dimer. The same applies to the names of palladium(II) compounds according to Formula VIII, which can be obtained using, for example, anthracenyl, phenanthrenyl, phenalenyl, fluorenyl, indenyl, tetracenyl, or chrysenyl halides.

[0195] A further variant of the claimed process for preparing compounds according to general formula VIII is that the groups R1, R2, R3 and R4 of the reactant AH are hydrogen (H), linear alkyl groups having 1 to 10 carbon atoms, i.e. also having 2, 3, 4, 5, 6, 7, 8 or 9 carbon atoms, branched alkyl groups having 1 to 10 carbon atoms, i.e. also having 2, 3, 4, 5, 6, 7, 8 or 9 carbon atoms, and cyclic alkyl groups having 3 to 8 carbon atoms, i.e. also having 4, 5, 6 or 7 carbon atoms, cyclic alkyl groups having 6 to 14 carbon atoms, i.e. having 7, 8, 9, 10, and substituted mononuclear or polynuclear heteroaryl groups having from 5 to 13 carbon atoms, i.e., also having 6, 7, 8, 9, 10, 11, 12, or 13 carbon atoms; unsubstituted mononuclear or polynuclear aryl groups having from 6 to 14 carbon atoms, i.e., also having 7, 8, 9, 10, 11, 12, or 13 carbon atoms; unsubstituted mononuclear or polynuclear heteroaryl groups having from 5 to 13 carbon atoms, i.e., also having 6, 7, 8, 9, 10, 11, or 12 carbon atoms; and substituted mononuclear or polynuclear heteroaryl groups having from 5 to 13 carbon atoms, i.e., also having 6, 7, 8, 9, 10, 11, or 12 carbon atoms.

[0196] According to another embodiment, the groups R1, R2, R3 and R4 of the reactant AH are independently selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 8 carbon atoms, branched alkyl groups having 1 to 8 carbon atoms, cyclic alkyl groups having 4, 5 or 6 carbon atoms, unsubstituted mononuclear or polynuclear aryl groups having 6 to 14 carbon atoms, i.e. also having 7, 8, 9, 10, 11, 12 or 13 carbon atoms, substituted mononuclear or polynuclear aryl groups having 6 to 10 carbon atoms, unsubstituted mononuclear or polynuclear heteroaryl groups having 5 to 9 carbon atoms and substituted mononuclear or polynuclear heteroaryl groups having 5 to 9 carbon atoms.

[0197] The groups R1, R2, R3, and R4 of the reactant AH can be independently 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. In an alternative or complementary embodiment of the method for preparing a compound according to Formula VIII, two groups from R1 to R4 of the reactant AH can form an unsaturated or aromatic carbocyclic ring substituted with one or more of the alkyl groups described above. For example, the reactant AH can be provided in which the groups R2 and R4 form a substituted unsaturated carbocyclic five-membered ring fused with exactly one aromatic ring. An example of such a reactant AH is 3-(tert-butyl)-1-chloro-1H-indene (the 9-Cl reactant). For example, the reactant AH can also be provided in which the groups R2 and R4 form an unsubstituted unsaturated carbocyclic six-membered ring. An example of such a reactant AH is 3-bromocyclohexene (a 6-Br reactant).

[0198] In one embodiment of the presently claimed method for preparing a compound according to Formula VIII, R1 and R3 of reactant AH together form an unsaturated carbocyclic ring having 5 to 8 carbon atoms. In another variation of the claimed method, R1 and R3 of reactant AH together form an unsaturated carbocyclic or aromatic ring having 5 or 6 carbon atoms, wherein the unsaturated carbocyclic or aromatic ring is fused to at least one aromatic ring. In this case, R1 and R3 together can be part of a naphthyl, anthracenyl, phenanthrenyl, phenalenyl, tetracenyl, or chrysenyl ring system.

[0199] In another embodiment of the presently claimed method for preparing a compound according to formula VIII, the groups R1 and R3 of the reactant AH together form a first, in particular carbocyclic, ring, which ring is aromatic or unsaturated and fused to at least one aromatic ring; and the groups R1 and R2 and / or R3 and R4 form a second ring, in particular a carbocyclic ring, having 5 to 8 carbon atoms, which ring is It is aromatic or unsaturated and is fused to the first ring and / or at least one aromatic ring.

[0200] In this case, the second ring may be unsubstituted or optionally substituted with one or more groups 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 particularly a carbocyclic ring having 5 to 8 carbon atoms. Advantageously, the first and second rings are independently selected from the group consisting of cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, and benzene rings.

[0201] In another embodiment of the method described herein for preparing a compound according to Formula VIII, R2 and R4 (apart from any required halogen atoms) of reactant AH can form a substituted or unsubstituted, particularly unsaturated or saturated, carbocyclic ring having 5 to 8 carbon atoms, which may optionally be fused with at least one aromatic ring, for example, in the case of reactant AH derived from fluorene or indene, particularly 3-(tert-butyl)-1-chloro-1H-indene. Advantageously, the carbocyclic ring is a cyclopentenyl, cyclohexenyl, cycloheptenyl, or cyclooctenyl ring. Alternatively, the carbocyclic ring is a cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl ring.

[0202] In a further embodiment of the presently claimed method for preparing a compound according to formula VIII, R1 and R3 of reactant AH can together form a carbocyclic ring, particularly an aromatic or unsaturated ring fused to at least one aromatic ring.

[0203] In a further embodiment of the methods described herein for preparing a compound according to Formula VIII, R1 of reactant AH is hydrogen (H), methyl, or phenyl, or R1 together with R3 forms a phenyl ring fused to a benzene ring, such that R1 and R3 are part of a naphthyl ring.

[0204] In another embodiment of the presently claimed method for preparing a compound according to formula VIII, R2 of reactant AH is hydrogen (H), methyl, or phenyl, or together with R4 forms a cyclohexenyl ring.

[0205] In another embodiment of the methods described herein for preparing a compound according to formula VIII, R3 of reactant AH is hydrogen (H), methyl, or phenyl, or R3 together with R1 forms a phenyl ring fused to a benzene ring, such that R1 and R3 are part of a naphthyl ring.

[0206] In yet another embodiment of the presently claimed method for preparing a compound according to formula VIII, R4 of reactant AH is hydrogen (H), methyl, or phenyl, or R4 together with R2 forms a cyclohexenyl ring.

[0207] In particular, R1 to R4 of reactant AH can be the following groups: * Groups marked with together form the indicated group.

[0208] [Table 1-1]

[0209] [Table 1-2] a) The groups R1 and R3 together form an aromatic ring, i.e., a phenyl ring, which is fused to at least one aromatic ring, i.e., a benzene ring. Thus, R1 and R3 are part of a naphthyl ring. In this case, the reactant AH can be, for example, 1-(chloromethyl)naphthalene (a reactant for compound 7-Cl, see below), 2-(chloromethyl)naphthalene (a reactant for compound 8-Cl, see below), 1-(bromomethyl)naphthalene (a reactant for compound 7-Br, see below), or 2-(bromomethyl)naphthalene (a reactant for compound 8-Br, see below).

[0210] The combinations of R1, R2, R3, and R4 listed in the above table, where R1 and / or R2 are methyl groups, can be modified as follows: if either R1 or R2 is a methyl group, an ethyl group, an n-propyl group, or an n-butyl group can be provided instead of the methyl group. According to the above table, if R1 = R2 = methyl, then instead, an ethyl group, an n-propyl group, or an n-butyl group can be provided as the group R1, and the group R2 remains a methyl group, or the group R2 is an ethyl group, an n-propyl group, or an n-butyl group, and R1 = methyl. Alternatively, according to the above table, if R1 = R2 = methyl, then instead, it can be provided that R1 and R2 are independently selected from the group consisting of an ethyl group, an n-propyl group, and an n-butyl group.

[0211] One embodiment of the method claimed herein is characterized in that the reaction in step B is carried out in the presence of at least one solvent S C In another variation of the method, the method is carried out in a solvent S Cis selected from the group consisting of alcohols, alkanes, aromatic hydrocarbons, ketones, ethers, and combinations thereof, particularly alcohols having 2 to 6 carbon atoms, alkanes or cycloalkanes having 5 to 8 carbon atoms, alkane mixtures such as petroleum ether, 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. For example, diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol, isopropanol, and mixtures thereof are well suited.

[0212] According to yet another embodiment of the method described herein for preparing a compound according to general formula VIII, providing the palladium compound in step A preferably comprises reacting a palladium(II) compound consisting of a palladium(II) cation and two monovalent or divalent anions with a ligand L, which is an organosilicon compound, preferably a cyclic or acyclic siloxane. S in the presence of a base. Thus, the palladium compound provided in step A can advantageously be prepared in situ.

[0213] The palladium(II) compound may have two different or two identical monovalent anions or one divalent anion. Neutral ligands, such as COD, are not provided. As a result, inexpensive, commercially available palladium(II) compounds, such as PdCl2, can be advantageously used. Therefore, it is possible to avoid the time-consuming and expensive preparation of palladium(II) compounds of the type [Pd(ligand)Y2] [where, for example, ligand = COD] as reactants for the in situ generation of mononuclear or polynuclear palladium compounds. This is particularly advantageous from an economical (atom-wise) and ecological point of view. In addition, this reduces the number of possible impurities in the final product according to general formula VIII.

[0214] In a further advantageous embodiment, the palladium(II) compound used as a reactant in the context of the above-mentioned in situ preparation comprises two identical monovalent anions, in particular selected from the group consisting of halides and monovalent weakly coordinating anions. The expressions "in situ generated / prepared" or "in situ generated / prepared" and the term "weakly coordinating" have already been defined above.

[0215] In the context of the reactions described herein, the term "base" refers to inorganic and organic bases, especially inorganic bases, but not organometallic bases. The base should not decompose in water. Suitable bases are, for example, salts of Bronsted acids. Carbonates, hydrogen carbonates, acetates, formates, ascorbic acids, oxalates, and hydroxides are advantageously used. These can be used in the form of ammonium salts (Bronsted acids) NR4, where R is, for example, H or alkyl, alkali metal salts, for example, sodium or potassium salts, and alkaline earth metal salts.

[0216] In step A, a palladium (II) compound and a ligand L which is an organosilicon compound are reacted. S The reaction is usually carried out in solvent S C1 Solvent S C1 There is no particular limitation on the solvent S. C1 Examples of the solvent S are polar solvents such as water, alcohols, ketones, hydrocarbons, such as aromatic hydrocarbons such as benzene and toluene, or aliphatic hydrocarbons such as pentane, hexane and heptane, open-chain or cyclic ethers, amides and esters. However, as solvents, water, alcohols such as methanol, ethanol, propanol and butanol, and mixtures thereof, ketones such as acetone, and ethers such as diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, and mixtures thereof are preferred. Mixtures of these alcohols can also be used. In particular, the solvent S provided for the preparation or reaction in step A is C1 and a solvent S provided for the reaction in step B. Care miscible with one another or are identical, in which case there is no need to exchange the solvent, which is particularly advantageous from an economic and ecological point of view.

[0217] The definition of the expression "two miscible solvents" has already been given above.

[0218] In one embodiment of the presently claimed method for preparing a compound according to general formula VIII, the ligand L S is a cyclic or acyclic 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. Advantageously, the ligand L S One of the compounds is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (DVDS). In particular, the ligand L S One of these is DVDs. Surprisingly, it has been found that 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0)—abbreviated in the context of the present invention as [Pd(dvds)], [Pd(dvds)], Pd(vs), Pd-VS, or palladium-VS—is an excellent starting material for preparing compounds according to Formula VIII from π-allylpalladium halide complexes, such as π-allylpalladium chloride complexes, which can be obtained in yields typically greater than 90%, often greater than 97%, and especially greater than 99%, particularly by the methods described herein. In addition, the methods claimed herein made it possible to synthesize compounds of this type that had not previously been obtained, i.e., not described in the prior art.

[0219] According to a further variant embodiment of the presently claimed process for preparing a compound according to general formula VIII, the reaction temperature in step A and / or step B, in particular step B, is from 10° C. to 60° C., in particular from 15° C. to 45° C. or from 20° C. to 30° C. An alternative or complementary embodiment of the process provides that the reaction time in step A and / or step B, in particular step B, is from 10 minutes to 48 hours, in particular from 1 hour to 36 hours, or from 2 to 24 hours, or from 3 to 12 hours.

[0220] The present invention also provides a compound of the general formula

[0221] [ka] some of which have not been previously obtained, During the ceremony, -X is an anionic ligand; and the groups R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl groups, branched, straight-chain and cyclic alkylene groups, 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 mononuclear or polynuclear heteroaryl groups; or - two groups R1, R1, R3 and R4, advantageously R1 and R3 or R2 and R4, together form an unsaturated or aliphatic ring, or - two radicals R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form a first ring which is unsaturated or saturated and which is fused to at least one aromatic ring, In particular, it is obtained or obtainable by a method for preparing such a compound according to one of the exemplary embodiments described above.

[0222] The compounds according to Formula VIII claimed herein, particularly according to one of the exemplary embodiments of the above-described method for preparing such compounds, can generally be obtained in yields typically greater than 80%, often greater than 85%, and particularly greater than 90%. Palladium(II) compounds according to general Formula VIII can be used, for example, as catalysts and / or precatalysts, particularly as precatalysts in palladium-catalyzed cross-coupling reactions. Advantageously, they are suitable as catalysts for the following reactions:

[0223] Palladium(II) dimers according to Formula VIII are easy-to-use catalyst precursors with excellent catalytic performance. Advantageously, they are readily available in one step from commercially available precursors and react smoothly with numerous electron donor ligands, particularly phosphines and NHC ligands, to give defined palladium(II) complexes. As a result, even the in situ preparation of highly active monoligated palladium(II) precatalysts and / or palladium(II) catalysts starting from dimeric palladium(II) compounds according to Formula VIII is possible in a simple and reproducible manner.

[0224] According to the present invention, the expression "unsaturated ring" means a non-aromatic carbocyclic or heterocyclic ring having at least one double bond, where the unsaturated ring may be part of a ring system consisting of two or more fused rings which may include aliphatic, aromatic and other unsaturated carbocyclic and / or heterocyclic rings.

[0225] A saturated ring is formed, for example, by groups R2 and R4 when an allyl halide AH, derived from, for example, phenalene or indene, is used as a reactant to prepare a compound according to formula VIII.

[0226] Compounds according to general formula VIII have two identical η 3 The allyl ligands are in each case of the general formula

[0227] [ka] derived from compound AH used as reactant according to wherein X, R1, R2, R3 and R4 are as defined above.

[0228] For example, to prepare a compound according to formula VIII, a ligand L which is an organosilicon compound, in particular a cyclic or acyclic siloxane, is added. S Palladium(0) compounds, in particular those having η, can be reacted with 1-naphthylmethyl chloride. For example, a molar ratio of Pd:AH of at least 1:1 can be provided. The palladium(II) compounds according to formula VIII thus obtainable contain two identical aryl ligands derived from naphthalene, in particular η. 3 The complex according to formula VIII has a bound allyl ligand. In other words, the complex according to formula VIII does not have a naphthyl ligand in the strict sense. This is because the electrons involved in the complex formation of the palladium center are not conjugated with the ring electrons. The aromaticity of the bicyclic naphthalene is limited to one of the two fused six-membered rings as a result of the complex formation. However, for simplicity in the context of this invention, the η from naphthalene is 1 Binding ligand or η 3 The bound allyl ligand is called a naphthyl ligand. Therefore, the product of the reaction in the above example is called a dimeric palladium(II) 1-methylnaphthyl chloride complex (where the chlorine atom acts as a bridging ligand, i.e., there are two chlorine bridges), or a chloride-bridged 1-methylnaphthylpalladium(II) dimer. The same applies to the names of palladium(II) compounds according to Formula VIII, which can be obtained using, for example, anthracenyl, phenanthrenyl, phenalenyl, fluorenyl, indenyl, tetracenyl, or chrysenyl halides.

[0229] According to one embodiment of the compounds according to Formula VIII claimed herein, in particular those obtained or obtainable by the process for preparing such compounds according to one of the exemplary embodiments above, the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.

[0230] The term "weakly coordinating" also encompasses the terms "very weakly coordinating" and "moderately strongly coordinating." Chloride, bromide or iodide can be advantageously used as the halide anion X, with chloride or bromide being particularly advantageous, especially chloride. Monovalent weakly coordinating anions are especially perfluorinated anions, such as PF6. - , BF4 - , F3CSO3 - (TfO - , triflate) and [(F3CSO2)2N] - (TFSI), or non-fluorinated anions, e.g., H3CSO3 - (mesylate) or tosylate.

[0231] Further variants of the compounds according to the general formula VIII claimed herein are obtained or can be obtained in particular by the process for preparing such compounds according to one of the above exemplary embodiments, in which the groups R1, R2, R3 and R4 of the compounds according to formula VIII are selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 10 carbon atoms, i.e. also having 2, 3, 4, 5, 6, 7, 8 or 9 carbon atoms, branched alkyl groups having 1 to 10 carbon atoms, i.e. also having 2, 3, 4, 5, 6, 7, 8 or 9 carbon atoms, and cyclic alkyl groups having 3 to 8 carbon atoms, i.e. having 4, 5, 6, 7, 8 or 9 carbon atoms. groups, unsubstituted mononuclear or polynuclear aryl groups having 6 to 14 carbon atoms, i.e., 7, 8, 9, 10, 11, 12, or 13 carbon atoms, substituted mononuclear or polynuclear aryl groups having 6 to 14 carbon atoms, i.e., 7, 8, 9, 10, 11, 12, or 13 carbon atoms, and unsubstituted mononuclear or polynuclear heteroaryl groups having 5 to 13 carbon atoms, i.e., 6, 7, 8, 9, 10, 11, or 12 carbon atoms, and substituted mononuclear or polynuclear heteroaryl groups having 5 to 13 carbon atoms, i.e., 6, 7, 8, 9, 10, 11, or 12 carbon atoms.

[0232] According to another embodiment of the compounds according to the general formula VIII claimed herein, in particular those obtained or obtainable by the process for preparing such compounds according to one of the above exemplary embodiments, the groups R1, R2, R3 and R4 of the compounds according to formula VIII are independently selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 8 carbon atoms, branched alkyl groups having 1 to 8 carbon atoms, cyclic alkyl groups having 4, 5 or 6 carbon atoms, unsubstituted mononuclear or polynuclear aryl groups having 6 to 14 carbon atoms, i.e. also having 7, 8, 9, 10, 11, 12 or 13 carbon atoms, substituted mononuclear or polynuclear aryl groups having 6 to 10 carbon atoms, unsubstituted mononuclear or polynuclear heteroaryl groups having 5 to 9 carbon atoms and substituted mononuclear or polynuclear heteroaryl groups having 5 to 9 carbon atoms.

[0233] The groups R1, R2, R3 and R4 of the compounds according to the general formula VIII claimed herein, in particular of the compounds obtained or obtainable by the process for preparing such compounds according to one of the exemplary embodiments described above, can be independently 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. In an alternative or complementary embodiment of the compounds according to formula VIII claimed herein, in particular of the compounds obtained or obtainable by the process for preparing such compounds according to one of the exemplary embodiments described above, two groups R1 to R4 can form a saturated or unsaturated carbocyclic ring that is unsubstituted or substituted with one or more of the alkyl or aryl groups described above. In another embodiment of the compounds according to the general formula VIII claimed herein, particularly those obtained or obtainable by the process for preparing such compounds according to one of the above exemplary embodiments, R2 and R4 (apart from any necessary halogen atoms) can form a substituted or unsubstituted carbocyclic, particularly saturated, ring having 5 to 8 carbon atoms. In the above embodiment, the carbocyclic ring is advantageously a cyclopentenyl, cyclohexenyl, cycloheptenyl or cyclooctenyl ring, or a cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl ring. For example, in the case of compound 9-Cl, the groups R2 and R4 can be η derived from a substituted cyclopentenyl ring. 3 The bonded aryl ligand forms a cyclopentyl ligand, which for simplicity is called a cyclopentyl ligand. Thus, the groups R2 and R4 in compounds 6-Cl and 6-Br shown below each form a cyclohexyl ring.

[0234] According to an alternative or complementary embodiment, the radicals R2 and R4 together form a first ring, in particular a carbocyclic ring, having 5 to 8 carbon atoms, preferably 5 or 6 carbon atoms, which first ring is unsaturated or saturated and is fused to at least one aromatic ring, in which case R2 and R4 together form an η-substituted ring derived from a fluorenyl or indenyl system. 3 It can be part of a bound allyl ligand. An example of this is the compound 9-Cl.

[0235] In another embodiment of the compounds according to Formula VIII claimed herein, particularly those obtained or obtainable by the process for preparing such compounds according to one of the above exemplary embodiments, R1 and R3 together form a first, particularly carbocyclic, ring having 5 to 8 carbon atoms, which is unsaturated or saturated and fused to at least one aromatic ring. In another variation, R1 and R3 together form a first, particularly carbocyclic, ring having 5 or 6 carbon atoms, which is unsaturated or saturated and fused to at least one aromatic ring, which is unsaturated or saturated. In this case, R1 and R3 together can be part of a naphthyl, anthracenyl, phenanthrenyl, phenalenyl, tetracenyl, or chrysenyl ring system. Examples of R1 and R3 that together form an unsaturated carbocyclic ring having 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. It should be noted here that in the above exemplary compounds, the electrons involved in the complexation of the palladium center are not conjugated with the ring electrons. The aromaticity of the bicyclic naphthalene is limited to one of the two fused six-membered rings as a result of the complexation. However, for the sake of simplicity in the context of the present invention, the aromatic rings derived from naphthalene, especially η 3The bound allyl ligand is called a naphthyl ligand. Thus, the above-mentioned exemplary compound 7-Cl is called a dimeric palladium(II) 1-methylnaphthyl chloride complex (where the chlorine atom acts as a bridging ligand, i.e., there are two chlorine bridges), or a chloride-bridged 1-methylnaphthylpalladium(II) dimer. In this case, the same applies to the names of palladium(II) compounds according to Formula VIII, which can be obtained using, for example, anthracenyl, phenanthrenyl, phenalenyl, fluorenyl, indenyl, tetracenyl, or chrysenyl halides.

[0236] In another embodiment of the compounds according to formula VIII claimed herein, in particular, are obtained or obtainable by a process for preparing such compounds according to one of the exemplary embodiments above, the groups R1 and R3 together form a first ring, in particular a carbocyclic ring, which is unsaturated or saturated and which is fused to at least one aromatic ring, and The groups R1 and R2 and / or R3 and R4 are aromatic or unsaturated and form a second ring, in particular a carbocyclic ring, having 5 to 8 carbon atoms which is fused to the first ring and / or at least one aromatic ring.

[0237] In this case, the second ring may be unsubstituted or optionally substituted with one or more groups 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 preferably selected from the group consisting of a cyclopentenyl ring, a cyclohexenyl ring, a cycloheptenyl ring, a cyclooctenyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctyl ring. The second ring is selected from the group consisting of a cyclopentadienyl ring, a cyclohexadienyl ring, a cycloheptadienyl ring, a cyclooctadienyl ring, and a benzene ring.

[0238] In further embodiments of the compounds according to Formula VIII claimed herein, particularly those obtained or obtainable by the method for preparing such compounds according to one of the above exemplary embodiments, R1 is hydrogen (H), methyl or phenyl, or R1 together with R3 forms a cyclohexenyl ring fused to the benzene ring, such that R1 and R3 are part of the naphthyl ring.

[0239] In another embodiment of the compounds according to formula VIII claimed herein, particularly those obtained or obtainable by the method for preparing such compounds according to one of the above exemplary embodiments, R2 is hydrogen (H), methyl or phenyl, or together with R4 forms a cyclohexyl ring.

[0240] In yet another embodiment of the compounds according to Formula VIII claimed herein, particularly those obtained or obtainable by a method for preparing such compounds according to one of the above exemplary embodiments, R3 is hydrogen (H), methyl, or phenyl, or R3 together with R1 form a cyclohexenyl ring fused to the benzene ring, such that R1 and R3 are part of the naphthyl ring.

[0241] In yet another embodiment of the compounds according to formula VIII claimed herein, particularly those obtained or obtainable by the method for preparing such compounds according to one of the above exemplary embodiments, R4 is hydrogen (H), methyl or phenyl, or R4 together with R2 form a cyclohexyl ring.

[0242] In particular, R1 to R4 of the compound according to formula VIII obtained or obtainable by the method for preparing such a compound according to one of the above exemplary embodiments can be the following groups: asterisk * Groups marked with together form the indicated group.

[0243] [Table 2-1]

[0244] [Table 2-2] a) See, for example, compounds 6-Cl and 6-Br shown below. b) R1 and R3 together form a first unsaturated ring, i.e., a cyclohexenyl ring, which is fused to at least one aromatic ring, i.e., a benzene ring. Thus, R1 and R3 are substituted with naphthalene, in particular η 3 It is part of a bound allyl ligand, which for simplicity is called a naphthyl ligand. Examples of such compounds according to formula VIII are compounds 7-Cl, 7-Br, 8-Cl, and 8-Br shown below.

[0245] In particular, the following compounds can be prepared as compounds of formula VIII:

[0246] [ka]

[0247] [ka]

[0248] The present object is also to

[0249] [ka] This can also be achieved by the compound according to

[0250] Advantageously, the novel compounds can also be obtained in good yield and high purity by the methods described herein for preparing compounds according to general formula VIII. Palladium(II) compounds according to formula 4-Br can be used, for example, as catalysts and / or precatalysts, particularly as precatalysts in palladium-catalyzed cross-coupling reactions.

[0251] The present invention further provides a compound of the general formula

[0252] [ka] This is achieved by a novel compound by During the ceremony, -X is an anionic ligand; and - two radicals R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form a first ring which is unsaturated or saturated and which is fused to at least one aromatic ring, However, the formula

[0253] [ka]

[0254] Excluding compounds of the formula: [wherein R=alkyl, cycloalkyl, or aryl].

[0255] The novel compounds according to formula VIII claimed herein can generally be obtained in yields typically greater than 90%, often greater than 97%, and particularly greater than 99%, particularly according to one of the exemplary embodiments of the above-described methods for preparing such compounds. These palladium(II) compounds according to general formula VIII can be used, for example, as catalysts and / or precatalysts, particularly as precatalysts in palladium-catalyzed cross-coupling reactions. Advantageously, they are suitable as precatalysts and / or catalysts for the reactions given below.

[0256] The novel palladium(II) dimers according to Formula VIII claimed herein are easy-to-use catalyst precursors with excellent catalytic performance. Advantageously, they are readily accessible in a single step from commercially available precursors and react smoothly with numerous electron donor ligands, particularly phosphines and NHC ligands, to give defined palladium(II) complexes. As a result, even the in situ preparation of highly active monoligated palladium(II) precatalysts and / or palladium(II) catalysts starting from the novel dimeric palladium(II) compounds according to Formula VIII is possible in a simple and reproducible manner.

[0257] The broad applicability of the novel compounds according to Formula VIII claimed herein, particularly as palladium sources in coupling reactions, was demonstrated using the examples of dimeric palladium(II)-1-methylnaphthyl halide complexes in the Buchwald-Hartwig amination, Heck vinylation, α-arylation of ketones, and the Negishi-Suzuki-Miyaura coupling. In the case of the Buchwald-Hartwig amination and Suzuki-Miyaura coupling, the effect on catalytic activity of the novel palladium(II) compounds 7-Cl, 7-Br, 8-Cl, and 8-Br, which could be prepared starting from 1-methylnaphthyl halides, was particularly striking. In the case of the Suzuki-Miyaura coupling, surprisingly, it was possible to extend the reaction to new classes of substrates. While the bromide complex 7-Br was most efficient in most cases, the best results were obtained in ketone arylation using the chloride complex 7-Cl.

[0258] According to the present invention, the expression "unsaturated ring" means a non-aromatic carbocyclic or heterocyclic ring having at least one double bond, where the unsaturated ring may be part of a ring system consisting of two or more fused rings which may include aliphatic, aromatic and other unsaturated carbocyclic and / or heterocyclic rings.

[0259] A saturated ring is formed, for example, by groups R2 and R4 when an allyl halide AH, derived from, for example, phenal or indene, is used as a reactant to prepare a compound according to formula VIII.

[0260] Compounds according to general formula VIII have two identical η 3 The allyl ligands are in each case of the general formula

[0261] [ka] derived from compound AH used as reactant according to wherein X, R1, R2, R3 and R4 are as defined above.

[0262] For example, to prepare a compound according to formula VIII, a ligand L which is an organosilicon compound, in particular a cyclic or acyclic siloxane, is added. S Palladium(0) compounds, in particular those having η, can be reacted with 1-naphthylmethyl chloride. For example, a molar ratio of Pd:AH of at least 1:1 can be provided. The palladium(II) compounds according to formula VIII thus obtainable contain two identical aryl ligands derived from naphthalene, in particular η. 3 The complex according to formula VIII has a bound allyl ligand. In other words, the complex according to formula VIII does not have a naphthyl ligand in the strict sense. This is because the electrons involved in the complex formation of the palladium center are not conjugated with the ring electrons. The aromaticity of the bicyclic naphthalene is limited to one of the two fused six-membered rings as a result of the complex formation. However, for simplicity in the context of this invention, the η from naphthalene is 1 Binding ligand or η 3 The bound allyl ligand is called a naphthyl ligand. Therefore, the product of the reaction in the above example is called a dimeric palladium(II) 1-methylnaphthyl chloride complex (where the chlorine atom acts as a bridging ligand, i.e., there are two chlorine bridges), or a chloride-bridged 1-methylnaphthylpalladium(II) dimer. The same applies to the names of palladium(II) compounds according to Formula VIII, which can be obtained using, for example, anthracenyl, phenanthrenyl, phenalenyl, fluorenyl, indenyl, tetracenyl, or chrysenyl halides.

[0263] According to one embodiment of the presently claimed compounds according to Formula VIII, the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.

[0264] The term "weakly coordinating" also encompasses the terms "very weakly coordinating" and "moderately strongly coordinating." Chloride, bromide or iodide can be advantageously used as the halide anion X, with chloride or bromide being particularly advantageous, especially chloride. Monovalent weakly coordinating anions are especially perfluorinated anions, such as PF6. - , BF4 - , F3CSO3 - (TfO - , triflate) and [(F3CSO2)2N] - (TFSI), or non-fluorinated anions, e.g., H3CSO3 - (mesylate) or tosylate.

[0265] In one embodiment of the compounds according to Formula VIII claimed herein, R1 and R3 together form a first, particularly carbocyclic, ring having 5 to 8 carbon atoms, which may be unsaturated or saturated and fused to at least one aromatic ring. In another variation, R1 and R3 of the compound according to Formula VIII together form a first, particularly carbocyclic ring having 5 or 6 carbon atoms, which may be unsaturated or saturated and fused to at least one aromatic ring. In this case, R1 and R3 together may be part of a naphthyl, anthracenyl, phenanthrenyl, phenalenyl, tetracenyl, or chrysenyl ring system. Examples of R1 and R3 together forming an unsaturated carbocyclic ring having 6 carbon atoms, where the unsaturated 6-membered ring is fused to at least one aromatic ring, are the compounds 7-Cl, 7-Br, 8-Cl, and 8-Br. It should be noted here that in the above exemplary compounds, the electrons involved in complexation of the palladium center are not conjugated with the ring electrons. The aromaticity of the bicyclic naphthalene is limited to one of the two fused six-membered rings as a result of the complex formation. However, for simplicity in the context of the present invention, the aromaticity of the naphthalene-derived rings, especially the η 3 The bound allyl ligand is called a naphthyl ligand. Thus, the above-mentioned exemplary compound 7-Cl is called a dimeric palladium(II) 1-methylnaphthyl chloride complex (where the chlorine atom acts as a bridging ligand, i.e., there are two chlorine bridges), or a chloride-bridged 1-methylnaphthylpalladium(II) dimer. In this case, the same applies to the names of palladium(II) compounds according to Formula VIII, which can be obtained using, for example, anthracenyl, phenanthrenyl, phenalenyl, fluorenyl, indenyl, tetracenyl, or chrysenyl halides.

[0266] In another embodiment of the presently claimed compounds according to Formula VIII: the groups R1 and R3 together form a first ring, in particular a carbocyclic ring, which is unsaturated or saturated and which is fused to at least one aromatic ring, and the groups R1 and R2 and / or R3 and R4 form a second ring, in particular a carbocyclic ring, having 5 to 8 carbon atoms, which ring is aromatic or unsaturated and fused to the first ring and / or at least one aromatic ring; The second aromatic or unsaturated ring can be unsubstituted or optionally substituted with one or more groups 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.

[0267] Advantageously, the first unsaturated or saturated ring is selected from the group consisting of a cyclopentenyl ring, a cyclohexenyl ring, a cycloheptenyl ring, a cyclooctenyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring and a cyclooctyl ring, and the second unsaturated or aromatic ring is selected from the group consisting of a cyclopentadienyl ring, a cyclohexadienyl ring, a cycloheptadienyl ring, a cyclooctadienyl ring and a benzene ring.

[0268] According to another embodiment of the compounds according to formula VIII claimed herein, the groups R2 and R4 together form a first, in particular carbocyclic, ring having 5 to 8 carbon atoms, preferably 5 or 6 carbon atoms, which is unsaturated or saturated and is fused with at least one aromatic ring. An example of this is when R2 and R4 together form an η-ring derived from an indenyl system. 3 The compound 9-Cl shown above forms part of the binding allyl ligand. R2 and R4 together form an η group derived from, for example, a fluorenyl system. 3 It may also be part of a bound allyl ligand.

[0269] In a further embodiment of the compounds according to Formula VIII claimed herein, R1 together with R3 form a cyclohexenyl ring fused to the benzene ring, such that R1 and R3 are part of the naphthyl ring.

[0270] In particular, R1-R4 of the compounds according to Formula VIII claimed herein can be the following groups: * Groups marked with together form the indicated group.

[0271] [Table 3] a) R1 and R3 together form a first unsaturated ring, i.e., a cyclohexenyl ring, which is fused to at least one aromatic ring, i.e., a benzene ring. Thus, R1 and R3 are substituted with naphthalene, in particular η 3 It is part of a bound allyl ligand, which for simplicity is called a naphthyl ligand. Examples of such compounds according to formula VIII are compounds 7-Cl, 7-Br, 8-Cl, and 8-Br shown below.

[0272] The present invention further provides compounds of the general formula VIII.a

[0273] [ka] This is achieved by the compound according to During the ceremony, -X is an anionic ligand; -R4 is selected from the group consisting of hydrogen (H) and a branched, straight chain, or cyclic alkyl group; and -Group R a is an aromatic group, and each aromatic group R a at least one ring of which is fused to a cyclohexenyl ring; and -Group R b , group R c and group R d are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl groups, branched, straight-chain and cyclic alkylene groups, 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 mononuclear or polynuclear heteroaryl groups.

[0274] The novel compounds according to Formula VIII can generally be obtained in yields typically greater than 90%, often greater than 97%, and particularly greater than 99%, particularly according to one of the exemplary embodiments of the above-described methods for preparing such compounds. These palladium(II) compounds according to Formula VIII can be used, for example, as catalysts and / or precatalysts, particularly as precatalysts in palladium-catalyzed cross-coupling reactions. Advantageously, they are suitable as precatalysts and / or catalysts for the reactions given below.

[0275] The novel palladium(II) dimers according to Formula VIII.a claimed herein are easy-to-use catalyst precursors with excellent catalytic performance. Advantageously, they are readily accessible in a single step from commercially available precursors and react smoothly with numerous electron donor ligands, particularly phosphines and NHC ligands, to give defined palladium(II) complexes. As a result, starting from the novel dimeric palladium(II) compounds according to Formula VIII, the in situ preparation of highly active monoligated palladium(II) precatalysts and / or even palladium(II) catalysts is possible in a simple and reproducible manner.

[0276] The broad applicability of the novel compounds according to Formula VIII.a claimed herein, particularly as palladium sources in coupling reactions, was demonstrated using the examples of dimeric palladium(II)-1-methylnaphthyl halide complexes in the Buchwald-Hartwig amination, Heck vinylation, α-arylation of ketones, and the Negishi-Suzuki-Miyaura coupling. In the case of the Buchwald-Hartwig amination and Suzuki-Miyaura coupling, the effect on catalytic activity of the novel palladium(II) compounds 7-Cl, 7-Br, 8-Cl, and 8-Br, which could be prepared starting from 1-methylnaphthyl halides, was particularly striking. In the case of the Suzuki-Miyaura coupling, surprisingly, it was possible to extend the reaction to new classes of substrates. While the bromide complex 7-Br was most efficient in most cases, the best results were obtained in ketone arylation using the chloride complex 7-Cl.

[0277] According to one embodiment of the presently claimed compounds according to formula VIII.a, the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.

[0278] The term "weakly coordinating" also encompasses the terms "very weakly coordinating" and "moderately strongly coordinating." Chloride, bromide or iodide can be advantageously used as the halide anion X, with chloride or bromide being particularly advantageous, especially chloride. Monovalent weakly coordinating anions are especially perfluorinated anions, such as PF6. - , BF4 - , F3CSO3 - (TfO - , triflate) and [(F3CSO2)2N] - (TFSI), or non-fluorinated anions, e.g., H3CSO3 - (mesylate) or tosylate.

[0279] According to another embodiment of the compounds according to formula VIII.a claimed herein, the group R4 is selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 10 carbon atoms, i.e. also having 2, 3, 4, 5, 6, 7, 8 or 9 carbon atoms, branched alkyl groups having 1 to 10 carbon atoms, i.e. also having 2, 3, 4, 5, 6, 7, 8 or 9 carbon atoms, and cyclic alkyl groups having 3 to 8 carbon atoms, i.e. also having 4, 5, 6 or 7 carbon atoms.

[0280] In another variation of the compound according to Formula VIII.a, the group R4 is selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 8 carbon atoms, branched alkyl groups having 1 to 8 carbon atoms, and cyclic alkyl groups having 4, 5, or 6 carbon atoms. For example, the group R1 is selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and combinations thereof.

[0281] In one embodiment of the compounds according to formula VIII.a described herein, the group R a 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.

[0282] According to an alternative or complementary variant of the compounds according to formula VIII.a claimed herein, the group R a is a mononuclear or polynuclear aromatic fused to the cyclohexenyl ring at the ortho or meta position relative to the tertiary carbon atom of the cyclohexenyl ring. For example, the mononuclear aromatic or heteroaromatic may be selected from the group consisting of benzene, toluene, xylene, pyrazine, pyridine, pyrimidine, pyrrole, furan, thiophene, and imidazole. For example, R a is benzene, naphthalene-derived η 3 There are bound allylic ligands.

[0283] Another embodiment of the presently claimed compounds according to formula VIII.a is a compound comprising a group R a is a polynuclear aromatic or heteroaromatic ring fused to the cyclohexenyl ring at ortho and / or meta positions relative to the tertiary carbon atom of the cyclohexenyl ring.

[0284] In other words, the group R a When is a polynuclear aromatic or heteroaromatic, the respective η 3 The bound aryl ligands may be ortho-fused or ortho-peri-fused ring systems. In the case of ortho-fused ring systems, η 3 The bound aryl ligands may exist as linear ring systems or as bent (angled) ring systems. For example, the polynuclear aromatic may be selected from the group consisting of naphthalene, anthracene, and phenanthrene. The group R a is, for example, naphthalene, anthracene-derived, phenanthrene-derived, or phenalene-derived η 3 Bound allyl ligands may be present. Group R a is anthracene, η from tetracene 3 There is a bound aryl ligand. The group Ra is phenanthrene, for example, η derived from chrysene 3 Bound allyl ligands may be present.

[0285] A further variation of the claimed compounds according to formula VIII.a is the group R b , group R c and group R d is selected from the group consisting of hydrogen (H), straight-chain alkyl groups having 1 to 10 carbon atoms, i.e., also having 2, 3, 4, 5, 6, 7, 8, or 9 carbon atoms, branched alkyl groups having 1 to 10 carbon atoms, i.e., also having 2, 3, 4, 5, 6, 7, 8, or 9 carbon atoms, and cyclic alkyl groups having 3 to 8 carbon atoms, i.e., also having 4, 5, 6, or 7 carbon atoms, unsubstituted mononuclear or polynuclear alkyl groups having 6 to 14 carbon atoms, i.e., having 7, 8, 9, 10, 11, 12, or 13 carbon atoms. and substituted mononuclear or polynuclear heteroaryl groups having from 5 to 13 carbon atoms, i.e., also having 6, 7, 8, 9, 10, 11, 12, or 13 carbon atoms; unsubstituted mononuclear or polynuclear heteroaryl groups having from 5 to 13 carbon atoms, i.e., also having 6, 7, 8, 9, 10, 11, or 12 carbon atoms; and substituted mononuclear or polynuclear heteroaryl groups having from 5 to 13 carbon atoms, i.e., also having 6, 7, 8, 9, 10, 11, or 12 carbon atoms.

[0286] According to another embodiment, the group R b , group R c and group R d are independently selected from the group consisting of hydrogen (H), a straight-chain alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 1 to 8 carbon atoms, a cyclic alkyl group having 4, 5, or 6 carbon atoms, an unsubstituted mononuclear or polynuclear aryl group having 6 to 14 carbon atoms, i.e., 7, 8, 9, 10, 11, 12, or 13 carbon atoms, a substituted mononuclear or polynuclear aryl group having 6 to 10 carbon atoms, an unsubstituted mononuclear or polynuclear heteroaryl group having 5 to 9 carbon atoms, and a substituted mononuclear or polynuclear heteroaryl group having 5 to 9 carbon atoms.

[0287] For example, the group R b , group R c and group R d are independently 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.

[0288] According to a further advantageous embodiment of the compound according to formula VIII or formula VIII.a claimed herein, the compound is selected from the compounds shown below:

[0289] [ka]

[0290] Furthermore, the objective is to: i. General formula

[0291] [ka] wherein X and the groups R1, R2, R3 and R4 are as defined above, or General formula VIII.a

[0292] [ka] [where X, R, a~d and R4 is as defined above, and ii. at least one organosilicon compound This is achieved by a preparation comprising:

[0293] The term organosilicon compound has already been defined above.

[0294] The compounds according to general formula VIII or VIII.a contained in the preparations, or the preparations claimed herein themselves, are obtained or can be obtained in particular by the above-described methods for preparing compounds according to formula VIII, advantageously according to one of the above-described exemplary embodiments.

[0295] 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 react smoothly with numerous electron donor ligands, especially phosphines and NHC ligands, to give defined palladium(II) complexes. As a result, starting from dimeric palladium(II) compounds according to formula VIII or formula VIII.a, even the in situ preparation of highly active monoligated palladium(II) precatalysts and / or palladium(II) catalysts is possible in a simple and reproducible manner.

[0296] According to one embodiment of the preparation, the silicon content, particularly in the form of at least one organosilicon compound, is 100 ppm to 1000 ppm, preferably 110 ppm to 900 ppm, in particular 120 ppm to 800 ppm. In particular, the silicon content, particularly in the form of at least one organosilicon compound, can be determined, in particular quantitatively, using analytical methods known to those skilled in the art. 1 It can be determined using H NMR spectroscopy and / or inductively coupled plasma atomic emission spectroscopy (ICP-AES).

[0297] In an alternative or complementary embodiment of the preparation claimed herein, the preparation is Z The preparations contain, in particular, the organosilicon compounds present and / or the solvent S used. Z Depending on the solvent, it may be in the form of a solution, suspension, dispersion or gel. ZThe solvent S may be a mixture of solvents. It is advantageously selected from the group consisting of alkanes, aromatic hydrocarbons and polar solvents, and is preferably 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 ether, 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. For example, diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol, ethanol, isopropanol, and mixtures or combinations thereof are suitable. In particular, solvent S is Z The preparation is in the form of a solution or suspension when the solvent S comprises or is selected from the group consisting of alcohols, alkanes, aromatic hydrocarbons, ketones, such as 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, mixtures of alkanes such as petroleum ether, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, and mixtures thereof. For example, solvent S Z may 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.

[0298] Another variation of the preparation is to use solvent S Z is the solvent S used in the process for preparing the compound according to formula VIII C It is provided that the compound is miscible with or identical to the compound.

[0299] According to a variant of the preparation of the present invention, at least one organosilicon compound contains at least one terminal double bond, in particular a vinyl double bond. In particular, the at least one organosilicon compound comprises or is a cyclic or acyclic siloxane. According to an alternative or complementary embodiment of the preparation, the preparation contains, in addition to the palladium compound according to general formula VIII, a compound of the general formula [Pd(L S )2] (III) and at least one palladium compound according to the general formula [Pd(L S )2](III) is a polynuclear complex, in particular of the general formula [Pd2(L S )3]. In this case, the ligand L S is in particular identical to at least one organosilicon compound, in particular a cyclic or acyclic siloxane, the at least one organosilicon compound containing at least one terminal double bond.

[0300] In particular, the ligand L S is the same as the organosilicon compound, and the ligand L S is in particular a cyclic or acyclic siloxane having at least one terminal, in particular vinyl, double bond. In this case, the ligand L S is advantageously linked via at least one π-directed bond to a compound of the general formula [Pd(L S )2] (III) is coordinated or bonded to the palladium center of the compound.

[0301] A further variant of the claimed preparation is that one of the organosilicon compounds comprises or is a cyclic or acyclic siloxane, and / or the ligand L SOne of the organosilicon compounds is a cyclic or acyclic siloxane 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. Advantageously, one of the organosilicon compounds comprises or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds), and / or the ligand L S One of the compounds is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds). In particular, one of the organosilicon compounds and / or the ligand L S One of them is DVDs.

[0302] The present invention also relates to compounds of the general formula IX

[0303] [ka] This is achieved by the compound During the ceremony, -X is an anionic ligand; and - two radicals R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form a first ring which is unsaturated or saturated and which is fused to at least one aromatic ring, and -L is a neutral electron donor ligand; however, formula

[0304] [ka] wherein R=Me, X=Cl and L=1,3-bis(2,6-di-isopropylphenyl)imidazolin-2-ylidene, and formula

[0305] [ka] [Wherein, R=H or methyl, X=TfO - and L = racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP), (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, or (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl.

[0306] The novel compounds according to formula IX claimed herein can generally be obtained in yields typically greater than 90%, often greater than 97%, and especially greater than 99%, particularly according to one of the exemplary embodiments of the methods for preparing such compounds described below. These palladium(II) compounds according to general formula IX can be used, for example, as catalysts and / or precatalysts, especially as precatalysts in palladium-catalyzed cross-coupling reactions. Advantageously, they are suitable as precatalysts and / or catalysts for the reactions given below.

[0307] In one embodiment of the presently claimed compounds according to formula IX, the anionic ligand X and the groups R, R, R and R are as defined in the compounds according to formula VIII according to one of the above embodiments, and the neutral electron donor ligand L is a phosphine ligand or an NHC ligand.

[0308] According to another embodiment of the presently claimed compounds according to formula IX, the neutral electron donor ligand L is:

[0309] tertiary phosphines according to the general formula P-R10R20R30, in which R10 and R20 are independently selected from the group consisting of substituted and unsubstituted linear alkyl groups, substituted and unsubstituted branched alkyl groups, substituted and unsubstituted cycloalkyl groups, substituted and unsubstituted aryl groups, and substituted and unsubstituted heteroaryl groups, and the heteroatoms are selected from the group consisting of sulfur, nitrogen, and oxygen; R30 is a tertiary phosphine defined as R10 and R20 or is a metallocenyl group; or -2-(Dicyclohexylphosphino)-2'-(N,N-dimethylamino))-1,1'-biphenyl (DavePhos), 2-(Dicyclohexylphosphino)-2',4',6'-tri-isopropyl-1,1'-biphenyl (XPhos), 2-Dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl (SPhos), 2-Dicyclohexylphosphino-2',6'-di-isopropoxy-1,1'-biphenyl (RuPhos), 2-(Dicyclohexylphosphino)-3,6-dimethoxy-2',4',6'-tri -isopropyl-1,1'-biphenyl (BrettPhos), [4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (Xantphos), 2-dicyclohexylphosphino-2',6'-bis(dimethylamino)-1,1'-biphenyl (CPhos), tricyclohexylphosphine (PCy3), di-(1-adamantyl)-n-butylphosphine (cataCXium® A), 2-di-tert-butylphosphine 2-(di-tert-butylphosphino)-3,6-dimethoxy-2',4',6'-tri-isopropyl-1,1'-biphenyl (t-BuXPhos), 2-(di-tert-butylphosphino)-3,6-dimethoxy-2',4',6'-tri-isopropyl-1,1'-biphenyl (tert-BuBrettPhos), 2-(di-tert-butylphosphino)-3-methoxy-6-methyl-2',4',6'-tri-isopropyl-1,1'-biphenyl (RockPhos), 2-di[3,5-bis(trifluoromethyl)phenylphosphino]-3,6-dimethoxy-2',4',6'-tri-isopropyl isopropyl-1,1'-biphenyl (JackiePhos), 2-(di-tert-butylphosphino)-biphenyl (JohnPhos), R-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-tert-butylphosphine, di-tert-butyl(n-butyl)phosphine, 2-(di-1-adamantylphosphino)-3,6-dimethoxy-2',4',6'-tri-isopropyl-1,1'-biphenyl (AdBrettPhos), 2-diethylphosphino-2',6'-bis(dimethylamino)-1,1'-Biphenyl racemic 2-di-tert-butylphosphino-1,1'-binaphthyl (TrixiePhos), tri-tert-butylphosphine (PtBu3), triisopropyl)phosphine (PiPr3), di-tert-butyl(isopropyl)phosphine (P(iPr)tBu2), tert-butyl-di(isopropyl)phosphine (P(iPr)2tBu), 1,3,5,7-tetramethyl-8-phenyl-2,4,6-trioxa-8-phosphaadamantane (MeCgPPh), N-[2-( Di-1-adamantylphosphino)phenyl]morpholine (MorDalPhos), 4,6-bis(diphenylphosphino)phenoxazine (NiXantphos), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 2-di-tert-butylphosphino-2'-(N,N(dimethylamino))-1,1'-biphenyl (tBuDavePhos), racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP), 1,1'-bis(di-tert-butylphosphino) phosphino)ferrocene (DTBPF), 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl)-1,1'-biphenyl (Me4t-BuXPhos), 2-dicyclohexylphosphino-4-(N,N-dimethylamino)-1,1'-biphenyl, trimethylphosphine (PMe3), tris-p-tolylphosphine (P(p-tolyl)3), tris-o-tolylphosphine (P(o-tolyl)3), methyldiphenylphosphine, triphenylphosphine ( PPh3 tris-(pentafluorophenyl)phosphine (P(C6F5)3), trifluorophosphine, 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)2tBu), 1-adamantyl-di(isopropylphosphine (P(1-Ad)iPr2), di(1-adamantyl)-isopropylphosphine (P(1-Ad)2iPr), 1,3-bis-(diphenylphosphino)propane (dppp), 1,2-Bis(diphenylphosphino)ethane (dppe), tert-butyldiphenylphosphine (P(tBu)Ph2), phenyl-di-tert-butylphosphine, di-tert-butyl-neopentylphosphine, 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene, tris(p-methoxyphenyl)phosphine, tris(p(trifluoromethylphenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(2,4,6-trimethyl)phosphine, tris(p-methylphenyl ... bis(2,6-dimethylphenyl)phosphine, benzyldi-1-adamantylphosphine, cyclohexyldi-tert-butylphosphine, cyclohexyldiphenylphosphine, 2-di-tert-butylphosphino-1,1'-binaphthyl, 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-di-tert-butylphosphino-2',4',6'-tri-isopropyl-1,1'-biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl- tetramethyl-2',4',6'-tri-iso-propylbiphenyl, 2-(dicyclohexylphosphino)biphenyl (cyclohexyl-JohnPhos), 2-(dicyclohexylphosphino)-2',6'-dimethoxy-1,1'-biphenyl, 2-di-tert-cyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-cyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl, 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1 ,1'-biphenyl, 2-di-cyclohexylphosphino-2'-methylbiphenyl, 2-diphenylphosphino-2'-(N,N(dimethylamino)biphenyl, (4-dimethylaminophenyl)(tert-butyl)2-phosphine, 1,2-bis(di-tert-butylphosphinomethyl)benzene, 1,3-bis(di-tert-butylphosphinomethyl)propane, 1,2-bis(diphenylphosphinomethyl)benzene, 1,2-bis(di-phenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,a phosphine ligand selected from the group consisting of 2-bis(diphenylphosphino)butane, N-(2-methoxyphenyl)-2-(di-tert-butylphosphino)pyrrole, 1-(2-methoxyphenyl)-2-(di-cyclohexylphosphino)pyrrole, N-phenyl-2-(di-tert-butylphosphino)indole, N-phenyl-2-(di-tert-butylphosphino)pyrrole, N-phenyl-2-(dicyclohexylphosphino)indole, N-phenyl-2-(dicyclohexylphosphino)pyrrole, 1-(2,4,6-trimethylphenyl)-2-(dicyclohexylphosphino)imidazole, and (S)-7,7'-bis(diphenylphosphino)-3,3',4,4'-tetrahydro-4,4'-dimethyl-8,8'-bi(2H-1,4-benzoxazine) (Solphos); or - is the general formula YPR 1 R 2 (Va) or Y2PR 1 (Vb) or a phosphine ligand according to Y3P(VI),

[0310] [ka] During the ceremony, -Y is an ylide substituent attached to the phosphorus atom through a carbanion center, the ylide substituent having an onium group On and an X group; -On may, independently of any onium groups in further ylide substituents, be a phosphonium group -PR 3 R 4 R 5 , ammonium group -NR 3 R 4 R 5 , sulfoxonium group -SOR 3 R 4 , and the sulfonium group -SR 3 R 4 is selected from -X, independently of the X groups in further ylide substituents, can be H, primary, secondary, or tertiary alkyl, alkenyl, and alkynyl groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, benzyl groups, mononuclear aryl groups, polynuclear aryl groups, mononuclear heteroaryl groups, polynuclear heteroaryl groups, silyl groups -SiR 3 R 4 R 5 , sulfonyl group -SO2R 3 , a phosphoryl group -P(O)R 3 R 4 -P(S)R 3 R 4 , -P(NO3)r 4 R 5 , cyano group -CN, alkoxy group -OR 3 and amino group -NR 3 R 4 and During the ceremony, R 1 , R 2 , R 3 , R 4 and R 5 are, when present, independently selected from alkyl, aryl, and heteroaryl groups, which may be unsubstituted or substituted with functional groups; or -formula

[0311] [ka] is an NHC ligand based on During the ceremony, - R13 and R14 are the same or different and independently represent a substituted or unsubstituted C1-C20 alkyl, a substituted or unsubstituted C1-C20 alkenyl, a substituted or unsubstituted C1-C20 heteroalkyl, a substituted or unsubstituted C1-C20 alkynyl, a substituted or unsubstituted alicyclic or aromatic ring, or a ring system having 1 to 5 rings, optionally having one or more heteroatoms and / or substituents; and -Q is a saturated or unsaturated, substituted or unsubstituted hydrocarbon bridge or a substituted or unsubstituted heteroatom-containing hydrocarbon bridge; Optionally, two or more substituents on adjacent atoms are linked to other ring structures, resulting in fused ring structures having from 2 to 5 ring structures.

[0312] In the tertiary phosphines according to the general formula P-R10R20R30, R10 and R20 can independently be substituted and unsubstituted branched or straight chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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.

[0313] In one embodiment, the alkyl group of a tertiary phosphine according to the general formula P-R10R20R30 may be optionally substituted with one or more substituents, such as a halide (F, Cl, Br, or I) or an alkoxy group, e.g., methoxy, ethoxy, or propoxy. The aryl group may be optionally substituted with one or more (e.g., 1, 2, 3, 4, or 5) substituents, such as a halide (F, Cl, Br, or I), a linear or branched alkyl group (e.g., C1-C10 alkyl), an alkoxy (e.g., C1-C10 alkoxy), a linear or branched (dialkyl)amino group (e.g., C1-C10 dialkylamino), a heterocycloalkyl (e.g., a C3-C10 heterocycloalkyl group such as morpholinyl and piperazinyl), or a trihalomethyl (e.g., 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. Substituted and unsubstituted heteroaryl groups such as pyridyl, furanyl, thiophenyl, pyrrolyl, or quinolinyl can also be used. In an alternative embodiment, R10 and R20 of a tertiary phosphine according to the general formula P-R10R20R30 are bonded together to form a ring structure, particularly a 4- to 7-membered ring, with the phosphorus atom. In particular, R10 and R20 are the same and are tert-butyl, cyclohexyl, phenyl, or substituted phenyl groups. In particular, R10 and R20 are tert-butyl. In addition, R10 and R20 can independently be alkoxy (e.g., C1-C10 alkoxy) or aryloxy (e.g., C1-C10 aryloxy).

[0314] R30 is defined similarly to R10 and R20, but may be a metallocenyl group. In the latter embodiment, R30 is a substituted or unsubstituted metallocenyl group. In this case, the metallocenyl group has a first cyclopentadienyl group and a second cyclopentadienyl group. p groups R40 may optionally be provided on the first cyclopentadienyl group, where a tertiary phosphine of the general formula P-R10R20R30 is bonded or coordinated to the palladium center, and q groups R41 may optionally be provided on the second cyclopentadienyl group. R40 and R41 are independently an organic group having 1 to 20 carbon atoms. R40 and R41 may independently be defined similarly to R10 and R20.

[0315] p can take the value 0, 1, 2, 3 or 4, and q can take the value 0, 1, 2, 3, 4 or 5. In one possible embodiment, q=5 and R41 is methyl or phenyl. In another embodiment, p=0.

[0316] In certain embodiments, p=0, q=5, 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.

[0317] In another embodiment, R10, R20 and R30 are the same and are 1-adamantyl, 2-adamantyl, phenyl, ortho-tolyl, cyclohexyl, tert-butyl, or R10 and R20 are 1-adamantyl or 2-adamantyl and R30 is n-butyl.

[0318] According to another variant embodiment of the claimed compounds according to the general formula IX, the electron donor ligand L has the general formula YPR 1 R 2 (Va) or Y2PR 1 (Vb) or a phosphine ligand according to YP(VI), wherein Y is as defined above; the alkyl group is selected from linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, advantageously from linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms and cycloalkyl groups having 4 to 10 carbon atoms, the aryl group is selected from aryl groups having 6 to 14 carbon atoms, advantageously from aryl groups having 6 to 10 carbon atoms, the alkenyl group is selected from monounsaturated, polyunsaturated, linear, branched and cyclic alkenyl groups having from 2 to 10 carbon atoms, advantageously from monounsaturated, polyunsaturated, linear, branched and cyclic alkenyl groups having from 2 to 6 carbon atoms, the heteroaryl group is selected from heteroaryl groups having 6 to 14 carbon atoms, advantageously from heteroaryl groups having 6 to 10 carbon atoms and having 1 to 5 heteroatoms selected from N, O and S, and / or -functional group is alkyl group -R 11 , preferably an alkyl group -R having 1 to 6 carbon atoms 11 , an aryl group -R 12 , halogen - Hal, hydroxy group - OH, cyano group - CN, alkoxy group - OR 3 , amino group -N(R 11 )2, -NHR 11 and -NH2, mercapto groups -SH and -SR 11 where R 11 is another group R 11 and are independently selected from alkyl groups having 1 to 6 carbon atoms.

[0319] Yet another embodiment of the presently claimed compounds according to general formula IX is where the electron donor ligand L is a compound of the general formula

[0320] [ka] and wherein the phosphine ligand is During the ceremony, -On is a phosphonium group -PR 3 R4 R 5 and 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, and aryl groups having 6 to 10 carbon atoms; -X is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, an aryl group having 3 to 10 carbon atoms, a mono- or poly-unsaturated linear, branched, or cyclic alkenyl group having 2 to 6 carbon atoms, or a trialkylsilyl group -SiR 3 R 4 R 5 , an arylsulfonyl group R 12 -SO2R 3 selected from the group consisting of and -R 1 and R 2 is an aryl group having 6 to 10 carbon atoms, or an alkyl or cycloalkyl group having 1 to 6 carbon atoms.

[0321] In further embodiments of the compounds according to the general formula IX claimed herein, the electron donor ligand L is of the general formula YPR 1 R 2 (Va) or Y2PR 1 (Vb) or YP(VI), where Y is as defined above and R 3 , R 4 and R 5 teeth, a) 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, preferably cyclohexyl and phenyl.

[0322] According to another variant of the claimed compounds according to formula IX, the electron donor ligand L has the general formula YPR 1R 2 (Va) or Y2PR 1 (Vb) or a phosphine ligand according to YP(VI), wherein Y is as defined above and X is selected from the group consisting of methyl, ethyl, cyclohexyl, phenyl, p-tolyl, trimethylsilyl, p-tolylsulfonyl, and combinations thereof.

[0323] In yet another embodiment of the presently claimed compounds according to general formula IX, the electron donor ligand L is of the general formula YPR 1 R 2 (Va) or Y2PR 1 (Vb) or YP(VI), where Y is as defined above and R 1 and R 2 are independently selected from the group consisting of phenyl, cyclohexyl, methyl, and combinations thereof.

[0324] In another embodiment, the neutral electron donor ligand L is cyclohexylphosphine, triphenylphosphine, tri-ortho-tolylphosphine. Also suitable are phosphines such as XPhos, JohnPhos, SPhos, Bophos, Josiphos, Taniaphos, Walphos and phosphine ligands with the structures shown below

[0325] [ka] or other ligands described in WO 2019 / 030304, or ligands according to the structure shown below:

[0326] [ka]

[0327] When the neutral electron donor ligand L is an NHC ligand according to the general formula X, R and R may in particular be the same or different and independently represent substituted or unsubstituted phenyl, or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 It may be phenyl substituted with one or more substituents selected from the group consisting of alkaryl or halogen.

[0328] For example, Q can be a bridge of two or three atoms and can be saturated or unsaturated.

[0329] In another embodiment, Q is a two atom bridge having the structure -CR21R22-CR23R24- or -CR21=CR23-, particularly -CR21R22-CR23R24-, where R21, R22, R23, and R24 are independently selected from hydrogen (H), hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of functional groups include carboxyl, C1-C 20 Alkoxy, C5-C 24 Aryloxy, C2-C 20 Alkoxycarbonyl, C5-C 24 Alkoxycarbonyl, C2-C 24 Acyloxy, C1-C 20 Alkylthio, C5-C 24 Arylthio, C1-C 20 Alkylsulfonyl and C1-C 20 Alkylsulfinyl, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14R21, R11, R23 and R24 may be optionally substituted with one or more substituents selected from aryl, hydroxyl, sulfhydryl, formyl, and halogen (F, Cl, Br, I). R21, R11, R23 and R24 may be, in particular, hydrogen (H), C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 Alternatively, two groups selected from R21, R22, R23 and R24 may be joined together to form a substituted or unsubstituted, saturated or unsaturated ring structure, such as a C4-C 12 It may form an alicyclic ring or a C5 or C6 aryl group, which may itself be substituted, for example, with aromatic groups or other substituents.

[0330] In an alternative or complementary embodiment, the groups R21, R22, R23 and R24 are selected from the group consisting of hydrogen (H), branched or linear alkyl, alkylene or alkynyl groups having 1 to 10 carbon atoms, cyclic alkyl, alkylene or alkynyl groups having 3 to 10 carbon atoms, substituted or unsubstituted mononuclear or polynuclear aryl groups having 6 to 14 carbon atoms and substituted or unsubstituted mononuclear or polynuclear heteroaryl groups having 5 to 13 carbon atoms, -O-alkyl, -OC(O)-alkyl, -O-(aryl), -OC(O)-aryl, -F, -Cl, -OH, -NO2, -Si(alkyl)3, -CF3, -CN, -CO2H, -C(O)H, -SO3H, -NH2, -NH(alkyl), -N(alkyl)2, -P(alkyl)2, - and independently selected from the group consisting of SO2(alkyl), -SO(alkyl), -SO(aryl), -SO2(aryl), -SO3(alkyl), -SO3(aryl), -S-alkyl, -S-aryl, -S-alkenyl, -NH-CO(alkyl), -CO2(alkyl), -CONH2, -CO(alkyl), -NHCOH, -NHCO2(alkyl), -CO(aryl), -CO2(aryl), -CH=CH-CO2(alkyl), -CH=CH-CO2H, -P(aryl)2, -PO(aryl)2, -PO(alkyl), -PO3H, -PO(O-alkyl)2, and any fused ring system radicals where alkyl and aryl are as defined for R21, R22, R23, and R24.

[0331] The alkyl, alkylene or alkynyl groups may each be substituted with, for example, F, Cl, Br, I, alkyl, O-alkyl, phenyl, O-phenyl, OH, NH and / or CF, and the aryl and heteroaryl groups may each be substituted with, for example, F, Cl, Br, I, alkyl, O-alkyl, phenyl and / or O-phenyl.

[0332] Examples of N-heterocyclic carbene (NHC) and acyclic diaminocarbene ligands suitable as the neutral electron donor ligand L include, for example, the following structures:

[0333] [ka]

[0334] In the above structure, R13 and R14 can independently be, for example, DIPP, Mes, 3,5-di-tert-butylphenyl, 2-methylphenyl, and combinations thereof, where DIPP or DiPP is 2,6-diisopropylphenyl and Mes is 2,4,6-trimethylphenyl (mesityl).

[0335] [ka]

[0336] In the above structure, R13 and R14 can independently be, for example, DIPP, Mes, 3,5-di-tert-butylphenyl, 2-methylphenyl, and combinations thereof.

[0337] Further examples of N-heterocyclic carbene (NHC) and acyclic diaminocarbene ligands suitable as the neutral electron donor ligand L include, for example, the following structures:

[0338] [ka] In the formula, R W1 , R W2 , R W3 , R W4 can independently be hydrogen (H), unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom-containing hydrocarbyl; R W3 and / or R W4may be independently selected from halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups. Further examples of N-heterocyclic carbene (NHC) ligands suitable as the neutral electron donor ligand L are disclosed, for example, in U.S. Pat. Nos. 7,378,528; 7,652,145; 7,294,717; 6,787,620; 6,635,768; and 6,552,139.

[0339] According to a further variant embodiment of the compound according to the general formula IX claimed herein, 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′-triisopropyl-1,1′-biphenyl (XPhos), 2-dicyclohexylphosphino-2′,6′-diisopropoxy- Selected from the group consisting of 1,1'-biphenyl (RuPhos), di-1,3-bis-(2,4,6-trimethylphenyl)-imidazolidin-2-ylidene ("SIMes"), 1,3-bis-(2,6-diisopropylphenyl)-imidazolidin-2-ylidene ("SIPr"), 1,3-bis-(2,6-diisopropylphenyl)-imidazolin-2-ylidene (unsaturated NHC ligand, "IPr"), and 1,3-bis-(2,4,6-trimethylphenyl)-imidazolin-2-ylidene (unsaturated NHC ligand, "IMes").

[0340] In particular, as has been surprisingly found, the compound according to formula IX may be a compound of formula IX.N or IX.P:

[0341] [ka]

[0342] The present invention also relates to compounds of the general formula IX.a

[0343] [ka] This is achieved by the compound During the ceremony, -X and L are as defined in the compound according to formula IX, -R4 is selected from the group consisting of hydrogen (H) and a branched, straight chain, or cyclic alkyl group; and -Group R a is an aromatic group, and each aromatic group R a at least one ring of which is fused to a cyclohexenyl ring; and base R b , group R c and group R d are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl groups, branched, straight-chain and cyclic alkylene groups, 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 mononuclear or polynuclear heteroaryl groups; however, formula

[0344] [ka] wherein R=Me, X=Cl and L=1,3-bis(2,6-di-isopropylphenyl)imidazolin-2-ylidene, and formula

[0345] [ka] [Wherein, R=H or methyl, X=TfO -and L = racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP), (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, or (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl.

[0346] The novel compounds of formula IX.a claimed herein, particularly according to one of the exemplary embodiments of the above-described method for preparing compounds of formula IX, can generally be obtained in yields usually above 90%, often above 97%, and particularly above 99%. Palladium(II) compounds of formula IX can be used, for example, as catalysts and / or precatalysts, particularly as precatalysts in palladium-catalyzed cross-coupling reactions. Advantageously, they are suitable as precatalysts and / or catalysts for the reactions given below.

[0347] According to one embodiment of the compounds according to formula IX.a claimed herein, the group R4 is selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 10 carbon atoms, i.e. also having 2, 3, 4, 5, 6, 7, 8 or 9 carbon atoms, branched alkyl groups having 1 to 10 carbon atoms, i.e. also having 2, 3, 4, 5, 6, 7, 8 or 9 carbon atoms, and cyclic alkyl groups having 3 to 8 carbon atoms, i.e. also having 4, 5, 6 or 7 carbon atoms.

[0348] In another variation of the compound according to Formula IX.a, the group R4 is selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 8 carbon atoms, branched alkyl groups having 1 to 8 carbon atoms, and cyclic alkyl groups having 4, 5, or 6 carbon atoms. For example, the group R1 is selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and combinations thereof.

[0349] In one embodiment of the compounds according to formula IX.a described herein, the group R ais 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.

[0350] According to an alternative or additional variant of the compounds according to formula IX.a claimed herein, the group R a is a mononuclear or polynuclear aromatic fused to a cyclohexenyl ring at the ortho or meta position relative to the tertiary carbon atom of the cyclohexenyl ring. For example, the mononuclear aromatic or heteroaromatic can be selected from the group consisting of benzene, toluene, xylene, pyrazine, pyridine, pyrimidine, pyrrole, furan, thiophene, and imidazole. For example, when R2 is benzene, the naphthalene-derived η 3 There are bound allylic ligands.

[0351] Another embodiment of the presently claimed compounds according to formula IX.a is a compound comprising a group R a is a polynuclear aromatic or heteroaromatic group fused to the cyclohexenyl ring at ortho and / or meta positions relative to the tertiary carbon atom of the cyclohexenyl ring. a When is a polynuclear aromatic or heteroaromatic, the respective η 3 The bound aryl ligands may be ortho-fused or ortho-peri-fused ring systems. In the case of ortho-fused ring systems, η 3 The bound aryl ligands may exist as linear ring systems or as bent (angled) ring systems. For example, the polynuclear aromatic may be selected from the group consisting of naphthalene, anthracene, and phenanthrene. The group R a is, for example, naphthalene, anthracene-derived, phenanthrene-derived, or phenalene-derived η 3 Bound allyl ligands may be present. Group R a is anthracene, η from tetracene 3 There is a bound aryl ligand. The group R a is phenanthrene, for example, η derived from chrysene 3 Bound allyl ligands may be present.

[0352] A further variation of the claimed compounds according to formula IX.a is the group R b , group R c and group R d is selected from the group consisting of hydrogen (H), straight-chain alkyl groups having 1 to 10 carbon atoms, i.e., also having 2, 3, 4, 5, 6, 7, 8, or 9 carbon atoms, branched alkyl groups having 1 to 10 carbon atoms, i.e., also having 2, 3, 4, 5, 6, 7, 8, or 9 carbon atoms, and cyclic alkyl groups having 3 to 8 carbon atoms, i.e., also having 4, 5, 6, or 7 carbon atoms, unsubstituted mononuclear or polynuclear alkyl groups having 6 to 14 carbon atoms, i.e., having 7, 8, 9, 10, 11, 12, or 13 carbon atoms. and substituted mononuclear or polynuclear heteroaryl groups having from 5 to 13 carbon atoms, i.e., also having 6, 7, 8, 9, 10, 11, 12, or 13 carbon atoms; unsubstituted mononuclear or polynuclear heteroaryl groups having from 5 to 13 carbon atoms, i.e., also having 6, 7, 8, 9, 10, 11, or 12 carbon atoms; and substituted mononuclear or polynuclear heteroaryl groups having from 5 to 13 carbon atoms, i.e., also having 6, 7, 8, 9, 10, 11, or 12 carbon atoms.

[0353] According to another embodiment of the compound according to formula IX.a, the group R b , group R c and group R d are independently selected from the group consisting of hydrogen (H), a straight-chain alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 1 to 8 carbon atoms, a cyclic alkyl group having 4, 5, or 6 carbon atoms, an unsubstituted mononuclear or polynuclear aryl group having 6 to 14 carbon atoms, i.e., 7, 8, 9, 10, 11, 12, or 13 carbon atoms, a substituted mononuclear or polynuclear aryl group having 6 to 10 carbon atoms, an unsubstituted mononuclear or polynuclear heteroaryl group having 5 to 9 carbon atoms, and a substituted mononuclear or polynuclear heteroaryl group having 5 to 9 carbon atoms.

[0354] For example, the group R b , group R c and group R dare independently 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.

[0355] According to variant embodiments of the compounds according to formula IX.a claimed herein, the compounds have formula IX.b or IX.c:

[0356] [ka] wherein X and L are as defined in the compound according to formula IX. Compounds according to formula IX.b, where R=Me, X=Cl and L=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene, and compounds according to formula IX.c, where R=H or methyl, X=TfO and L=racemic 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (rac-BINAP), (S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl or (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl are not subject of the present invention.

[0357] The compound according to formula IX.b may, for example, be selected from the following compounds:

[0358] [ka]

[0359] The compound according to formula IX.c can be selected, for example, from the following compounds:

[0360] [ka]

[0361] The present invention also relates to compounds of the general formula IX

[0362] [ka] This is also achieved by the compound During the ceremony, -X is an anionic ligand; and the groups R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl groups, branched, straight-chain and cyclic alkylene groups, 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 mononuclear or polynuclear heteroaryl groups; or - two groups R1, R1, R3 and R4, advantageously R1 and R3 or R2 and R4, together form an unsaturated or aliphatic ring, or - Two groups R1, R2, R3 and R4, preferably R1 and R3 or R2 and R4, together form a first ring which is unsaturated or saturated and which is fused to at least one aromatic ring.

[0363] The novel compounds of formula IX.d claimed herein, particularly according to one of the exemplary embodiments of the above-described method for preparing compounds of formula IX, can generally be obtained in yields usually above 90%, often above 97%, and in particular above 99%. These palladium(II) compounds of formula IX.d can be used, for example, as catalysts and / or precatalysts, in particular as precatalysts in palladium-catalyzed cross-coupling reactions. Advantageously, they are suitable as precatalysts and / or catalysts for the reactions given below.

[0364] According to the present invention, the expression "unsaturated ring" means a non-aromatic carbocyclic or heterocyclic ring having at least one double bond, where the unsaturated ring may be part of a ring system consisting of two or more fused rings which may include aliphatic, aromatic and other unsaturated carbocyclic and / or heterocyclic rings.

[0365] A saturated ring is formed, for example, by groups R2 and R4 when an allyl halide, derived for example from phenal or indene, is used as a reactant for preparing a compound according to formula IX.d.

[0366] According to one embodiment of the compounds according to formula IX.d claimed herein, the anionic ligand X is a halide anion or a monovalent weakly coordinating anion. The term "weakly coordinating" also encompasses the terms "very weakly coordinating" and "moderately strongly coordinating." Chloride, bromide or iodide can be advantageously used as the halide anion X, with chloride or bromide being particularly advantageous, in particular chloride. Monovalent weakly coordinating anions are particularly perfluorinated anions, such as PF6. - , BF4 - , F3CSO3 - (TfO - , triflate) and [(F3CSO2)2N] - (TFSI), or non-fluorinated anions, e.g., H3CSO3 - (mesylate) or tosylate.

[0367] According to one embodiment of the presently claimed compounds according to formula IX.d, the groups R1, R2, R3 and R4 are as defined in the compounds according to formula VIII.

[0368] In particular, compounds according to formula IX.d may surprisingly be heteroleptic palladium complexes of formula IX.P:

[0369] [ka]

[0370] The present invention also relates to a compound of formula XI

[0371] [ka] This can also be achieved by compounds such as

[0372] This compound can be obtained, in particular, by reacting compound 8-Cl with 1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene (unsaturated NHC ligand, "IPr"), preferably in a polar aprotic solvent, especially an ether, such as diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, or 1,4-dioxane. The molar ratio of 8-Cl:IPr is, for example, 1:1. The reaction can be advantageously carried out at room temperature, and the reaction time is typically between 10 minutes and 3 hours, depending on the choice of other reaction conditions, such as the choice of solvent or solvent mixture, the concentration of reactants, and the molar ratio of reactants. Single crystals of compound XI·toluene suitable for crystal structure analysis were obtained from toluene / hexane. The compound according to formula XI can be used, for example, as a catalyst and / or precatalyst, especially in palladium-catalyzed cross-coupling reactions. Advantageously, it is suitable as a precatalyst and / or catalyst for the reactions given below.

[0373] The present invention also provides a compound of the general formula

[0374] [ka] This is also achieved by a method for preparing a compound according to During the ceremony, -X is an anionic ligand; the groups R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl groups, branched, straight-chain and cyclic alkylene groups, 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 mononuclear or polynuclear heteroaryl groups; or two groups R1, R1, R3 and R4, preferably R1 and R3 or R2 and R4, together form an unsaturated or aliphatic ring, or two groups R1, R2, R3 and R4, preferably R1 and R3 or R2 and R4, together form a first ring which is unsaturated or saturated and which is fused to at least one aromatic ring, and -L is a neutral electron donor ligand; However, the formula

[0375] [ka] Excluding compounds of the formula: wherein R=Me, X=Cl and L=1,3-bis(2,6-di-isopropylphenyl)imidazolin-2-ylidene.

[0376] This method is A. i. Palladium compounds, in particular mononuclear or polynuclear palladium compounds (0), in which at least one palladium center is an organosilicon compound, and the ligand L S and the ligand L S is in particular a cyclic or acyclic siloxane, ii. General formula

[0377] [ka] Compound AH according to During the ceremony, -X is an anionic ligand; the groups R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl groups, branched, straight-chain and cyclic alkylene groups, 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 mononuclear or polynuclear heteroaryl groups; or - two groups R1, R1, R3 and R4, advantageously R1 and R3 or R2 and R4, together form an unsaturated or aromatic ring, or compounds AH in which two radicals R1, R2, R3 and R4, advantageously R1 and R3 or R2 and R4, together form a first ring which is aromatic or unsaturated and which is fused to at least one aromatic ring, and iii. Neutral electron donor ligand providing B. Reacting the reactants according to i., ii. and iii. provided in step A; and C. Optionally, isolating the compound of formula IX produced in step B. Includes.

[0378] A definition of the term organosilicon compound has already been given above.

[0379] The methods claimed herein allow compounds according to formula IX to be prepared, usually in high purity, especially in high NMR purity, generally in yields above 90% in most cases, often above 97%, especially above 99%.

[0380] The palladium compounds, in particular palladium(0) compounds, may exist in mono- or polynuclear, especially dinuclear, form, as monomers or oligomers, especially dimers, and / or as solvent adducts.

[0381] In one embodiment of the presently claimed method for preparing compounds according to general formula IX, the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.

[0382] The term "weakly coordinating" also encompasses the terms "very weakly coordinating" and "moderately strongly coordinating." Chloride, bromide or iodide can be advantageously used as the halide anion X, with chloride or bromide being particularly advantageous, especially chloride. Monovalent weakly coordinating anions are especially perfluorinated anions, such as PF6. - , BF4 - , F3CSO3 - (TfO - , triflate) and [(F3CSO2)2N]- (TFSI), or non-fluorinated anions, e.g., H3CSO3 - (mesylate) or tosylate.

[0383] According to the present invention, the expression "unsaturated ring" means a non-aromatic carbocyclic or heterocyclic ring having at least one double bond. The unsaturated ring may be part of a ring system consisting of two or more fused rings, which may include aliphatic, aromatic and other unsaturated carbocyclic and / or heterocyclic rings. The saturated ring is formed, for example, by groups R1 and R3 when an allyl halide AH derived from, for example, phenalene or indene, is used as a reactant for preparing a compound according to formula IX.

[0384] One embodiment of the presently claimed method for preparing a compound according to general formula IX comprises: - R1 to R4 and X are as defined in the embodiments of the process for preparing a compound according to general formula VIII above; and the neutral electron donor ligand L is a phosphine ligand or an NHC ligand; To provide.

[0385] According to another embodiment of the presently claimed method for preparing a compound according to formula IX, the neutral electron donor ligand L is tertiary phosphines according to the general formula P-R10R20R30, in which R10 and R20 are independently selected from the group consisting of substituted and unsubstituted linear alkyl groups, substituted and unsubstituted branched alkyl groups, substituted and unsubstituted cycloalkyl groups, substituted and unsubstituted aryl groups, and substituted and unsubstituted heteroaryl groups, and the heteroatoms are selected from the group consisting of sulfur, nitrogen, and oxygen; R30 is a tertiary phosphine defined as R10 and R20 or is a metallocenyl group; or -2-(Dicyclohexylphosphino)-2'-(N,N-dimethylamino)-1,1'-biphenyl (DavePhos), 2-(Dicyclohexylphosphino)-2',4',6'-tri-isopropyl-1,1'-biphenyl (XPhos), 2-Dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl (SPhos), 2-Dicyclohexylphosphino-2',6'-di-isopropoxy-1,1'-biphenyl (RuPhos), 2-(Dicyclohexylphosphino)-3,6-dimethoxy-2',4',6'-tri- Isopropyl-1,1'-biphenyl (BrettPhos), [4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (Xantphos), 2-dicyclohexylphosphino-2',6'-bis(dimethylamino)-1,1'-biphenyl (CPhos), tricyclohexylphosphine (PCy3), di-(1-adamantyl)-n-butylphosphine (cataCXium® A), 2-di-tert-butylphosphine -2',4',6'-tri-isopropyl-1,1'-biphenyl (t-BuXPhos), 2-(di-tert-butylphosphino)-3,6-dimethoxy-2',4',6'-tri-isopropyl-1,1'-biphenyl (tert-BuBrettPhos), 2-(di-tert-butylphosphino)-3-methoxy-6-methyl-2',4',6'-tri-isopropyl-1,1'-biphenyl (RockPhos), 2-di[3,5-bis(trifluoromethyl)phenylphosphino]-3,6-dimethoxy-2',4',6'-tri-isopropyl -propyl-1,1'-biphenyl (JackiePhos), 2-(di-tert-butylphosphino)-biphenyl (JohnPhos), R-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-tert-butylphosphine, di-tert-butyl(n-butyl)phosphine, 2-(di-1-adamantylphosphino)-3,6-dimethoxy-2',4',6'-tri-isopropyl-1,1'-biphenyl (AdBrettPhos), 2-diethylphosphino-2',6'-bis(dimethylamino)-1,1'-Biphenyl, racemic 2-di-tert-butylphosphino-1,1'-binaphthyl (TrixiePhos), tert-butylphosphine (PtBu3), triisopropylphosphine (PiPr3), di-tert-butyl(isopropylphosphine (P(iPr)tBu2), tert-butyl-di(isopropylphosphine (P(iPr)2tBu), 1,3,5,7-tetramethyl-8-phenyl-2,4,6-trioxa-8-phosphaadamantane (MeCgPPh), N-[2-(di-1- Adamantylphosphino)phenyl]morpholine (MorDalPhos), 4,6-bis(diphenylphosphino)phenoxazine (NiXantphos), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 2-di-tert-butylphosphino-2'-(N,N(dimethylamino))-1,1'-biphenyl (tBuDavePhos), racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP), 1,1'-bis(di-tert-butylphosphino ) ferrocene (DTBPF), 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl)-1,1'-biphenyl (Me4t-BuXPhos), 2-dicyclohexylphosphino-4-(N,N-dimethylamino)-1,1'-biphenyl, trimethylphosphine (PMe3), tris-p-tolylphosphine (P(p-tolyl)3), tris-o-tolylphosphine (P(o-tolyl)3), methyldiphenylphosphine, triphenylphosphine (PPh 3), tris-(pentafluorophenyl)phosphine (P(C6F5)3), trifluorophosphine, 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad)2tBu), 1-adamantyl-di(isopropylphosphine (P(1-Ad)iPr2), di(1-adamantyl)-isopropylphosphine (P(1-Ad)2iPr), 1,3-bis-(diphenylphosphino)propane (dppp), 1,2-Bis(diphenylphosphino)ethane (dppe), tert-butyldiphenylphosphine (P(tBu)Ph2), phenyl-di-tert-butylphosphine, di-tert-butyl-neopentylphosphine, 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene, tris(p-methoxyphenyl)phosphine, tris(p(trifluoromethylphenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(2,4,6-trimethyl)phosphine, tris(p-methylphenyl ... bis(2,6-dimethylphenyl)phosphine, benzyldi-1-adamantylphosphine, cyclohexyldi-tert-butylphosphine, cyclohexyldiphenylphosphine, 2-di-tert-butylphosphino-1,1'-binaphthyl, 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-di-tert-butylphosphino-2',4',6'-tri-isopropyl-1,1'-biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl- tetramethyl-2',4',6'-tri-isopropylbiphenyl, 2-(dicyclohexylphosphino)biphenyl (cyclohexyl-JohnPhos), 2-(dicyclohexylphosphino)-2',6'-dimethoxy-1,1'-biphenyl, 2-di-tert-cyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-cyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl, 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1 '-biphenyl, 2-di-cyclohexylphosphino-2'-methylbiphenyl, 2-diphenylphosphino-2'-(N,N(4-dimethylamino)biphenyl), (4-dimethylaminophenyl)(tert-butyl)2-phosphine, 1,2-bis(di-tert-butylphosphinomethyl)benzene, 1,3-bis(di-tert-butylphosphinomethyl)propane, 1,2-bis(diphenylphosphinomethyl)benzene, 1,2-bis(di-phenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,2-Bis(diphenylphosphino)butane, N-(2-methoxyphenyl)-2-(di-tert-butylphosphino)pyrrole, 1-(2-methoxyphenyl)-2-(di-cyclohexylphosphino)pyrrole, N-phenyl-2-(di-tert-butylphosphino)indole, N-phenyl-2-(di-tert-butylphosphino)pyrrole, N-phenyl-2-(dicyclohexylphosphino)in a phosphine ligand selected from the group consisting of benzophenone, N-phenyl-2-(dicyclohexylphosphino)pyrrole, 1-(2,4,6-trimethylphenyl)-2-(dicyclohexylphosphino)imidazole, and (S)-7,7'-bis(diphenylphosphino)-3,3',4,4'-tetrahydro-4,4'-dimethyl-8,8'-bi(2H-1,4-benzoxazine) (Solphos), or -General formula YPR 1 R 2 (Va) or Y2PR 1 (Vb) or Y3P(VI),

[0386] [ka] During the ceremony, -Y is an ylide substituent attached to the phosphorus atom through a carbanion center, the ylide substituent having an onium group On and an X group; -On may, independently of any onium groups in further ylide substituents, be a phosphonium group -PR 3 R 4 R 5 , ammonium group -NR 3 R 4 R 5 , sulfoxonium group -SOR 3 R 4 , and the sulfonium group -SR 3 R 4 is selected from -X, independently of the X groups in further ylide substituents, can be H, primary, secondary, or tertiary alkyl, alkenyl, and alkynyl groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, benzyl groups, mononuclear aryl groups, polynuclear aryl groups, mononuclear heteroaryl groups, polynuclear heteroaryl groups, silyl groups -SiR 3 R 4 R 5 , sulfonyl group -SO2R 3 , a phosphoryl group -P(O)R 3 R 4 -P(S)R 3 R 4 , -P(NO3)r 4 R 5 , cyano group -CN, alkoxy group -OR 3 and amino group -NR 3 R 4 and During the ceremony, R 1 , R 2 , R 3 , R 4 and R 5 are, when present, independently selected from alkyl, aryl, and heteroaryl groups, which may be unsubstituted or substituted with functional groups; or -formula

[0387] [ka] is an NHC ligand based on During the ceremony, - R13 and R14 are the same or different and independently represent a substituted or unsubstituted C1-C20 alkyl, a substituted or unsubstituted C1-C20 alkenyl, a substituted or unsubstituted C1-C20 heteroalkyl, a substituted or unsubstituted C1-C20 alkynyl, a substituted or unsubstituted alicyclic or aromatic ring, or a ring system having 1 to 5 rings, optionally having one or more heteroatoms and / or substituents; and -Q is a saturated or unsaturated, substituted or unsubstituted hydrocarbon bridge or a substituted or unsubstituted heteroatom-containing hydrocarbon bridge; Optionally, two or more substituents on adjacent atoms are linked to other ring structures, resulting in fused ring structures having from 2 to 5 ring structures.

[0388] In the tertiary phosphines according to the general formula P-R10R20R30, R10 and R20 can independently be substituted and unsubstituted branched or straight chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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.

[0389] In one embodiment, the alkyl group of a tertiary phosphine according to the general formula P-R10R20R30 may be optionally substituted with one or more substituents, such as a halide (F, Cl, Br, or I) or an alkoxy group, e.g., methoxy, ethoxy, or propoxy. The aryl group may be optionally substituted with one or more (e.g., 1, 2, 3, 4, or 5) substituents, such as a halide (F, Cl, Br, or I), a linear or branched alkyl group (e.g., C1-C10 alkyl), an alkoxy (e.g., C1-C10 alkoxy), a linear or branched (dialkyl)amino group (e.g., C1-C10 dialkylamino), a heterocycloalkyl (e.g., a C3-C10 heterocycloalkyl group such as morpholinyl and piperazinyl), or a trihalomethyl (e.g., 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. Substituted and unsubstituted heteroaryl groups such as pyridyl, furanyl, thiophenyl, pyrrolyl, or quinolinyl can also be used. In an alternative embodiment, R10 and R20 of a tertiary phosphine according to the general formula P-R10R20R30 are bonded together to form a ring structure, particularly a 4- to 7-membered ring, with the phosphorus atom. In particular, R10 and R20 are the same and are tert-butyl, cyclohexyl, phenyl, or substituted phenyl groups. In particular, R10 and R20 are tert-butyl. In addition, R10 and R20 can independently be alkoxy (e.g., C1-C10 alkoxy) or aryloxy (e.g., C1-C10 aryloxy).

[0390] R30 is defined similarly to R10 and R20, but may be a metallocenyl group. In the latter embodiment, R30 is a substituted or unsubstituted metallocenyl group. In this case, the metallocenyl group has a first cyclopentadienyl group and a second cyclopentadienyl group. p groups R40 may optionally be provided on the first cyclopentadienyl group, where a tertiary phosphine of the general formula P-R10R20R30 is bonded or coordinated to the palladium center, and q groups R41 may optionally be provided on the second cyclopentadienyl group. R40 and R41 are independently an organic group having 1 to 20 carbon atoms. R40 and R41 may independently be defined similarly to R10 and R20.

[0391] p can take the value 0, 1, 2, 3 or 4, and q can take the value 0, 1, 2, 3, 4 or 5. In one possible embodiment, q=5 and R41 is methyl or phenyl. In another embodiment, p=0.

[0392] In certain embodiments, p=0, q=5, 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.

[0393] In another embodiment, R10, R20 and R30 are the same and are 1-adamantyl, 2-adamantyl, phenyl, ortho-tolyl, cyclohexyl, tert-butyl, or R10 and R20 are 1-adamantyl or 2-adamantyl and R30 is n-butyl.

[0394] According to another variant of the process for preparing a compound according to formula IX, the electron donor ligand L has the general formula YPR 1 R 2 (Va) or Y2PR 1 (Vb) or a phosphine ligand according to YP(VI), wherein Y is as defined above, the alkyl group is selected from linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, advantageously from linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms and cycloalkyl groups having 4 to 10 carbon atoms, the aryl group is selected from aryl groups having 6 to 14 carbon atoms, advantageously from aryl groups having 6 to 10 carbon atoms, the alkenyl group is selected from monounsaturated, polyunsaturated, linear, branched and cyclic alkenyl groups having from 2 to 10 carbon atoms, advantageously from monounsaturated, polyunsaturated, linear, branched and cyclic alkenyl groups having from 2 to 6 carbon atoms, the heteroaryl group is selected from heteroaryl groups having 6 to 14 carbon atoms, advantageously from heteroaryl groups having 6 to 10 carbon atoms and having 1 to 5 heteroatoms selected from N, O and S, and / or -functional group is alkyl group -R 11 , preferably an alkyl group -R having 1 to 6 carbon atoms 11 , an aryl group -R 12 , halogen - Hal, hydroxy group - OH, cyano group - CN, alkoxy group - OR 3 , amino group -N(R 11 )2, -NHR 11 and -NH2, mercapto groups -SH and -SR 11 where R 11 is another group R 11 and are independently selected from alkyl groups having 1 to 6 carbon atoms.

[0395] Yet another embodiment of the presently claimed method for preparing a compound according to formula IX is where the electron donor ligand L is of the general formula

[0396] [ka] and wherein the phosphine ligand is During the ceremony, -On is a phosphonium group -PR 3 R4 R 5 and 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, and aryl groups having 6 to 10 carbon atoms; -X is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, an aryl group having 3 to 10 carbon atoms, a mono- or poly-unsaturated linear, branched, or cyclic alkenyl group having 2 to 6 carbon atoms, or a trialkylsilyl group -SiR 3 R 4 R 5 , an arylsulfonyl group R 12 -SO2R 3 selected from the group consisting of and -R 1 and R 2 is an aryl group having 6 to 10 carbon atoms, or an alkyl or cycloalkyl group having 1 to 6 carbon atoms.

[0397] In a further embodiment of the presently claimed method for preparing a compound according to formula IX, the electron donor ligand L is of the general formula YPR 1 R 2 (Va) or Y2PR 1 (Vb) or YP(VI), where Y is as defined above and R 3 , R 4 and R 5 teeth, 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 of methyl, ethyl, butyl, cyclohexyl, phenyl, and combinations thereof, preferably cyclohexyl and phenyl.

[0398] According to another variant of the presently claimed method for preparing compounds according to formula IX, the electron donor ligand L has the general formula YPR 1 R 2 (Va) or Y2PR 1 (Vb) or a phosphine ligand according to YP(VI), wherein Y is as defined above and X is selected from the group consisting of methyl, ethyl, cyclohexyl, phenyl, p-tolyl, trimethylsilyl, p-tolylsulfonyl, and combinations thereof.

[0399] In yet another embodiment of the methods described herein for preparing compounds according to formula IX, the electron donor ligand L has the general formula YPR 1 R 2 (Va) or Y2PR 1 (Vb) or YP(VI), where Y is as defined above and R 1 and R 2 are independently selected from the group consisting of phenyl, cyclohexyl, methyl, and combinations thereof.

[0400] In another embodiment, the neutral electron donor ligand L is cyclohexylphosphine, triphenylphosphine, tri-ortho-tolylphosphine. Also suitable are phosphines such as XPhos, JohnPhos, SPhos, Bophos, Josiphos, Taniaphos, Walphos and phosphine ligands with the structures shown below

[0401] [ka] or other ligands described in WO 2019 / 030304, or ligands according to the structure shown below:

[0402] [ka]

[0403] When the neutral electron donor ligand L is an NHC ligand according to the general formula X, R and R may in particular be the same or different and independently represent substituted or unsubstituted phenyl, or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 It may be phenyl substituted with one or more substituents selected from the group consisting of alkaryl or halogen.

[0404] For example, Q can be a bridge of two or three atoms and can be saturated or unsaturated.

[0405] In another embodiment, Q is a two atom bridge having the structure -CR21R22-CR23R24- or -CR21=CR23-, particularly -CR21R22-CR23R24-, where R21, R22, R23, and R24 are independently selected from hydrogen (H), hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of functional groups include carboxyl, C1-C 20 Alkoxy, C5-C 24 Aryloxy, C2-C 20 Alkoxycarbonyl, C5-C 24 Alkoxycarbonyl, C2-C 24 Acyloxy, C1-C 20 Alkylthio, C5-C 24 Arylthio, C1-C 20 Alkylsulfonyl and C1-C 20 Alkylsulfinyl, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14R21, R11, R23 and R24 may be optionally substituted with one or more substituents selected from aryl, hydroxyl, sulfhydryl, formyl, and halogen (F, Cl, Br, I). R21, R11, R23 and R24 may be, in particular, hydrogen (H), C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 Alternatively, two groups selected from R21, R22, R23 and R24 may be joined together to form a substituted or unsubstituted, saturated or unsaturated ring structure, such as a C4-C 12 It may form an alicyclic ring or a C5 or c6 aryl group, which may itself be substituted, for example, with aromatic groups or other substituents.

[0406] In an alternative or complementary embodiment, the groups R21, R22, R23 and R24 are selected from the group consisting of hydrogen (H), branched or linear alkyl, alkylene or alkynyl groups having 1 to 10 carbon atoms, cyclic alkyl, alkylene or alkynyl groups having 3 to 10 carbon atoms, substituted or unsubstituted mononuclear or polynuclear aryl groups having 6 to 14 carbon atoms and substituted or unsubstituted mononuclear or polynuclear heteroaryl groups having 5 to 13 carbon atoms, -O-alkyl, -OC(O)-alkyl, -O-(aryl), -OC(O)-aryl, -F, -Cl, -OH, -NO2, -Si(alkyl)3, -CF3, -CN, -CO2H, -C(O)H, -SO3H, -NH2, -NH(alkyl), -N(alkyl)2, -P(alkyl)2, - and independently selected from the group consisting of SO2(alkyl), -SO(alkyl), -SO(aryl), -SO2(aryl), -SO3(alkyl), -SO3(aryl), -S-alkyl, -S-aryl, -S-alkenyl, -NH-CO(alkyl), -CO2(alkyl), -CONH2, -CO(alkyl), -NHCOH, -NHCO2(alkyl), -CO(aryl), -CO2(aryl), -CH=CH-CO2(alkyl), -CH=CH-CO2H, -P(aryl)2, -PO(aryl)2, -PO(alkyl), -PO3H, -PO(O-alkyl)2, and any fused ring system radicals where alkyl and aryl are as defined for R21, R22, R23, and R24.

[0407] The alkyl, alkylene or alkynyl groups may each be substituted with, for example, F, Cl, Br, I, alkyl, O-alkyl, phenyl, O-phenyl, OH, NH and / or CF, and the aryl and heteroaryl groups may each be substituted with, for example, F, Cl, Br, I, alkyl, O-alkyl, phenyl and / or O-phenyl.

[0408] Examples of N-heterocyclic carbene (NHC) and acyclic diaminocarbene ligands suitable as the neutral electron donor ligand L include, for example, the following structures:

[0409] [ka]

[0410] In the above structure, R13 and R14 can independently be, for example, DIPP, Mes, 3,5-di-tert-butylphenyl, 2-methylphenyl, and combinations thereof, where DIPP or DiPP is 2,6-diisopropylphenyl and Mes is 2,4,6-trimethylphenyl (mesityl).

[0411] [ka]

[0412] In the above structure, R13 and R14 can independently be, for example, DIPP, Mes, 3,5-di-tert-butylphenyl, 2-methylphenyl, and combinations thereof.

[0413] Further examples of N-heterocyclic carbene (NHC) and acyclic diaminocarbene ligands suitable as the neutral electron donor ligand L include, for example, the following structures:

[0414] [ka] In the formula, R W1 , R W2 , R W3 , R W4 can independently be hydrogen (H), unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom-containing hydrocarbyl; R W3 and / or R W4may be independently selected from halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups. Further examples of N-heterocyclic carbene (NHC) ligands suitable as the neutral electron donor ligand L are disclosed, for example, in U.S. Pat. Nos. 7,378,528; 7,652,145; 7,294,717; 6,787,620; 6,635,768; and 6,552,139.

[0415] According to a further variant of the presently claimed method for preparing a compound according to formula IX, 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′-triisopropyl-1,1′-biphenyl (XPhos), 2-dicyclohexylphosphino-2′,6′-diisopropyl-1,1′-biphenyl (XPhos), and 2-dicyclohexylphosphino-2′,6′-diisopropyl-1,1′-biphenyl (XPhos). and 1,3-bis-(2,4,6-trimethylphenyl)-imidazolin-2-ylidene ("SIMes"), 1,3-bis-(2,6-diisopropylphenyl)-imidazolin-2-ylidene ("SIPr"), 1,3-bis-(2,6-diisopropylphenyl)-imidazolin-2-ylidene (unsaturated NHC ligand, "IPr"), and 1,3-bis-(2,4,6-trimethylphenyl)-imidazolin-2-ylidene (unsaturated NHC ligand, "IMes").

[0416] The order in which the reaction vessel is charged with the reactants, i.e., the palladium compound, the compound AH, and the neutral electron donor ligand L, can be freely selected. This also includes the possibility of carrying out steps A and B, as well as optional step C, i.e., all steps related to the preparation of the respective target compound, in a single step, i.e., introducing all reactants and solvents into the reaction vessel simultaneously or substantially simultaneously. The definition of the term "reaction vessel" has already been given above.

[0417] According to one embodiment of the presently claimed method for preparing a compound according to general formula IX, the reaction in step B comprises the following steps: B.1. Initially charging the palladium compound as a solid, solution or suspension; B.2. Adding Compound AH as a solid, solution or suspension; B.3. Adding the neutral electron donor ligand L as a solid, solution or suspension; or B.1. Initially charging the palladium compound as a solid, solution or suspension; B.2. Adding the neutral electron donor ligand L as a solid, solution or suspension; B.3. Adding Compound AH as a solid, solution or suspension; or B.1. Initially charging compound AH as a solid, solution or suspension; B.2. Adding a palladium compound as a solid, solution or suspension; B.3. Adding the neutral electron donor ligand L as a solid, solution or suspension; or B.1. Initially charging compound AH as a solid, solution or suspension; B.2. Adding the neutral electron donor ligand L as a solid, solution or suspension; B.3. Adding a palladium compound as a solid, solution or suspension; or B.1. Initially charging the neutral electron donor ligand L as a solid, solution or suspension; B.2. Adding a palladium compound as a solid, solution or suspension; B.3. Adding Compound AH as a solid, solution or suspension; or B.1. Initially charging the neutral electron donor ligand L as a solid, solution or suspension; B.2. Adding Compound AH as a solid, solution or suspension; B.3. Adding the palladium compound as a solid, solution or suspension.

[0418] In one embodiment of the process described herein, the molar ratio of Pd:AH is at least 1:1, advantageously from 1.0:1.0 to 1.0:5.0, more advantageously from 1.0:1.1 to 1.0:4.0, particularly advantageously from 1.0:1.2 to 1.0:3.0, in particular from 1.0:1.3 to 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.

[0419] According to an alternative or additional variant embodiment, the molar ratio of Pd:L is at least 1:1, preferably 1.0:1.0 to 1.0:1.5, more preferably 1.00:1.01 to 1.00:1.49, particularly preferably 1.00:1.02 to 1.00:1.48, in particular 1.00:1.03 to 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.

[0420] Another embodiment of the presently claimed method is characterized in that the reaction in step B is carried out in the presence of at least one solvent S L In another variation of the method, the method is carried out in a solvent S L 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 ether, 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. For example, diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol, isopropanol, and mixtures thereof are well suited. When the palladium compound and / or compound AH and / or neutral electron donor ligand L are initially charged or introduced as a solution or suspension, the solvent for said solution or suspension is, in particular, the solvent S described above. L is identical to or miscible with

[0421] According to yet another embodiment of the method described herein for preparing a compound according to general formula IX, providing the palladium compound in step A preferably comprises reacting a palladium(II) compound consisting of a palladium(II) cation and two monovalent or divalent anions with a ligand L, which is an organosilicon compound, preferably a cyclic or acyclic siloxane. S The palladium compound provided in step A is thus advantageously reacted in situ, advantageously in a solvent S L1 It can be prepared in

[0422] The palladium(II) compound may have two different or two identical monovalent anions or one divalent anion. Neutral ligands, such as COD, are not provided. As a result, inexpensive, commercially available palladium(II) compounds, such as PdCl2, can be advantageously used. Therefore, it is possible to avoid the time-consuming and expensive preparation of palladium(II) compounds of the type [Pd(ligand)Y2] [where, for example, ligand = COD] as reactants for the in situ generation of mononuclear or polynuclear palladium compounds. This is particularly advantageous from an economical (atom-wise) and ecological point of view. In addition, this reduces the number of possible impurities in the final product according to general formula IX.

[0423] In a further advantageous embodiment, the palladium(II) compound used as a reactant in the context of the above-mentioned in situ preparation comprises two identical monovalent anions, in particular selected from the group consisting of halides and monovalent weakly coordinating anions. The expressions "in situ generated / prepared" or "in situ generated / prepared" and the term "weakly coordinating" have already been defined above.

[0424] In the context of the reactions described herein, the term "base" refers to inorganic and organic bases, especially inorganic bases, but not organometallic bases. The base should not decompose in water. Suitable bases are, for example, salts of Bronsted acids. Carbonates, hydrogen carbonates, acetates, formates, ascorbic acids, oxalates, and hydroxides are advantageously used. These can be used in the form of ammonium salts (Bronsted acids) NR4, where R is, for example, H or alkyl, alkali metal salts, for example, sodium or potassium salts, and alkaline earth metal salts.

[0425] In step A, a palladium (II) compound and a ligand L which is an organosilicon compound are reacted. S The reaction is usually carried out in solvent S L1 Solvent S L1 There is no particular limitation on the solvent S. L1 Examples of the solvent S are polar solvents such as water, alcohols, ketones, hydrocarbons, such as aromatic hydrocarbons such as benzene and toluene, or aliphatic hydrocarbons such as pentane, hexane and heptane, open-chain or cyclic ethers, amides and esters. However, as solvents, water, alcohols such as methanol, ethanol, propanol and butanol, and mixtures thereof, ketones such as acetone, and ethers such as diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, and mixtures thereof are preferred. Mixtures of these alcohols can also be used. In particular, the solvent S provided for the preparation or reaction in step A is L1 and a solvent S provided for the reaction in step B. L are miscible with one another or are identical, in which case there is no need to exchange the solvent, which is particularly advantageous from an economic and ecological point of view.

[0426] The definition of the expression "two miscible solvents" has already been given above.

[0427] In one embodiment of the presently claimed method for preparing a compound according to general formula IX, the ligand L S is a cyclic or acyclic 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. Advantageously, the ligand L S One of the compounds is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (DVDS). In particular, the ligand L S One of these is DVDs. Surprisingly, it has been found that 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0)—abbreviated in the context of the present invention as [Pd(dvds)], [Pd(dvds)], Pd(VS), Pd-VS, or palladium-VS—is an excellent starting material for preparing compounds according to formula IX from π-allylpalladium halide complexes, such as π-allylpalladium chloride complexes, which can be obtained in yields typically greater than 90%, often greater than 97%, and especially greater than 99%, particularly by the methods described herein. In addition, the methods claimed herein made it possible to synthesize compounds of this type that had not previously been obtained, i.e., not described in the prior art.

[0428] According to a further variant embodiment of the presently claimed process for preparing a compound according to general formula IX, the reaction temperature in step A and / or step B, in particular step B, is from 10° C. to 60° C., in particular from 15° C. to 45° C. or from 20° C. to 30° C. An alternative or complementary embodiment of the process provides that the reaction time in step A and / or step B, in particular step B, is from 10 minutes to 48 hours, in particular from 1 hour to 36 hours, or from 2 to 24 hours, or from 3 to 12 hours.

[0429] The present invention further provides a compound of the general formula

[0430] [ka] This is achieved by the compound wherein R1 to R4, X and L are as defined above, and in particular a compound obtained or obtainable by a method for preparing such a compound according to one of the exemplary embodiments described above. however, formula

[0431] [ka] wherein R=Me, X=Cl and L=1,3-bis(2,6-di-isopropylphenyl)imidazolin-2-ylidene, and formula

[0432] [ka] [Wherein, R=H or methyl, X=TfO - and L = racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP), (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, or (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl.

[0433] The compounds according to formula IX claimed herein, particularly compounds according to one of the exemplary embodiments of the above-described methods for preparing such compounds, can generally be obtained in high purity, particularly high NMR purity, generally in yields typically greater than 90%, often greater than 97%, and particularly greater than 99%. These palladium(II) compounds according to general formula IX can be used, for example, as catalysts and / or precatalysts, particularly as precatalysts in palladium-catalyzed cross-coupling reactions. Advantageously, they are suitable as precatalysts and / or catalysts for the reactions given below.

[0434] In particular, as has been surprisingly found, a compound according to formula IX, which is obtained or obtainable by a method for preparing such a compound according to one of the above exemplary embodiments, can have the following formula IX.N or IX.P:

[0435] [ka]

[0436] In particular, the following compounds can be prepared as compounds of formula IX:

[0437] [ka]

[0438] Furthermore, the objective is to: i. General formula IX

[0439] [ka] wherein X, R1, R2, R3, R4 and L are as defined above. or General formula IX.a

[0440] [ka] [where X, R a , R b , R c , R d , R4 and L are as defined above, and ii. at least one organosilicon compound This is achieved by a preparation comprising:

[0441] The term organosilicon compound has already been defined above.

[0442] The compounds according to general formula IX or IX.a contained in the preparations, or the preparations claimed herein themselves, are obtained or can be obtained in particular by the above-described methods for preparing compounds according to formula IX, advantageously according to one of the above-described exemplary embodiments.

[0443] According to one embodiment of the preparation, the silicon content, particularly in the form of at least one organosilicon compound, is 100 ppm to 1000 ppm, preferably 110 ppm to 900 ppm, in particular 120 ppm to 800 ppm. In particular, the silicon content, particularly in the form of at least one organosilicon compound, can be determined, in particular quantitatively, using analytical methods known to those skilled in the art. 1 It can be determined using H NMR spectroscopy and / or inductively coupled plasma atomic emission spectroscopy (ICP-AES).

[0444] In an alternative or complementary embodiment of the preparation claimed herein, the preparation is Z The preparations contain, in particular, the organosilicon compounds present and / or the solvent S used. Z Depending on the solvent, it may be in the form of a solution, suspension, dispersion or gel. Z The solvent S may be a mixture of solvents. It is advantageously selected from the group consisting of alkanes, aromatic hydrocarbons and polar solvents, and is preferably 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 ether, 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. For example, diethyl ether, MTBE (methyl tert-butyl ether), THF, 2-methyltetrahydrofuran, 1,4-dioxane, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, acetone, methanol, ethanol, isopropanol, and mixtures or combinations thereof are suitable. In particular, solvent S is ZThe preparation is in the form of a solution or suspension when the solvent S comprises or is selected from the group consisting of alcohols, alkanes, aromatic hydrocarbons, ketones, such as 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, mixtures of alkanes such as petroleum ether, ethers having 4 to 8 carbon atoms or ketones having 2 to 6 carbon atoms, and mixtures thereof. For example, solvent S Z may 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.

[0445] Another variant of the preparation is to use solvent S Z is the solvent S used in the process for preparing the compound according to formula IX L It is provided that the compound is miscible with or identical to the compound.

[0446] According to a variant of the preparation of the present invention, at least one organosilicon compound contains at least one terminal double bond, in particular a vinyl double bond. In particular, the at least one organosilicon compound comprises or is a cyclic or acyclic siloxane. According to an alternative or complementary embodiment of the preparation, the preparation contains, in addition to the palladium compound according to general formula VIII, a compound of the general formula [Pd(L S )2] (III) and at least one palladium compound according to the general formula [Pd(L S )2](III) is a polynuclear complex, in particular of the general formula [Pd2(L S )3]. In this case, the ligand L S is in particular identical in each case to at least one organosilicon compound, in particular a cyclic or acyclic siloxane, the at least one organosilicon compound containing at least one terminal double bond.

[0447] In particular, the ligand L S is the same as the organosilicon compound, and the ligand L S is in particular a cyclic or acyclic siloxane having at least one terminal, in particular vinyl, double bond. In this case, the ligand L S is advantageously linked via at least one π-directed bond to a compound of the general formula [Pd(L S )2] (III) is coordinated or bonded to the palladium center of the compound.

[0448] A further variant of the claimed preparation is that one of the organosilicon compounds comprises or is a cyclic or acyclic siloxane, and / or the ligand L S One of the organosilicon compounds is a cyclic or acyclic siloxane 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. Advantageously, one of the organosilicon compounds comprises or is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds), and / or the ligand L S One of the compounds is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (dvds). In particular, one of the organosilicon compounds and / or the ligand L S One of them is DVDs.

[0449] The object is also a method for cross-coupling a first reactant with a second reactant, the method comprising: A. Providing a reaction mixture comprising a first reactant, a second reactant, and at least one compound or preparation according to one or more of the above embodiments; and B. Reacting a first reactant with a second reactant in the presence of at least one compound or preparation according to one or more of the above embodiments to produce a reaction product. Includes.

[0450] The cross-coupling may be a carbon-carbon coupling reaction or a carbon-heteroatom coupling reaction, the latter including carbon-nitrogen coupling reactions, i.e., Buchwald-Hartwig coupling, carbon-oxygen and carbon-sulfur coupling reactions.

[0451] Furthermore, this object is achieved by a method for catalyzing a reaction between a first reactant and a second reactant, the method comprising contacting the first reactant with the second reactant in the presence of at least one compound or preparation according to one or more of the above embodiments.

[0452] In one embodiment of the method for cross-coupling a first reactant and a second reactant or for catalyzing a reaction between a first reactant and a second reactant, the first reactant and the second reactant are selected from the group consisting of: (i) the first reactant is an aromatic or heteroaromatic boronic acid or ester thereof, and the second reactant is an aromatic or heteroaromatic halide, tosylate, triflate, mesylate, sulfamate, or carbamate; (ii) the first reactant is an aromatic or heteroaromatic amine and the second reactant is an aromatic or heteroaromatic halide, tosylate, triflate, mesylate, sulfamate, or carbamate; (iii) the first reactant is an aromatic or heteroaromatic zinc halide and the second reactant is an aromatic, heteroaromatic, or vinyl halide, tosylate, triflate, mesylate, sulfamate, or carbamate; (iv) the first reactant is an aromatic or heteroaromatic Grignard compound and the second reactant is an aromatic, heteroaromatic, or vinyl halide, tosylate, triflate, mesylate, sulfamate, or carbamate; (v) The first reactant is an aromatic or heteroaromatic tin halide and the second reactant is an aromatic, heteroaromatic or vinyl halide, tosylate, triflate, mesylate, sulfamate or carbamate: (vi) the first reactant is a ketone, aldehyde, imine, amide, or ester and the second reactant is an aromatic, heteroaromatic, or vinyl halide, tosylate, triflate, mesylate, sulfamate, or carbamate; (vii) the first reactant is an alcohol or a thiol and the second reactant is an aromatic, heteroaromatic, or vinyl halide, tosylate, triflate, mesylate, sulfamate, or carbamate; (viii) The first reactant is an aromatic or heteroaromatic silanol, siloxane, or silane, and the second reactant is an aromatic, heteroaromatic, or vinyl halide, tosylate, triflate, mesylate, sulfamate, or carbamate.

[0453] According to another variant of the method for cross-coupling a first reactant with a second reactant or for catalyzing the reaction of a first reactant with a second reactant, it is a Stille coupling, a Kumada coupling, a Negishi coupling, a Suzuki coupling, a Suzuki-Miyaura coupling, a Sonogashira coupling, a Hiyama coupling, a Heck reaction, an α-arylation of an enolizable ketone, an α-arylation of an aldehyde, an arylation of a primary amine, an arylation of a secondary amine, an arylation of a primary amide, an arylation of an aliphatic alcohol, an allylic substitution reaction or a trifluoromethylation reaction.

[0454] Additionally, the object is achieved by a method for catalyzing the anaerobic oxidation of a primary or secondary alcohol, the method comprising contacting a primary or secondary alcohol with at least one compound or preparation according to one or more of the above embodiments.

[0455] Other features, details and advantages of the invention emerge from the claims and from the following description of exemplary embodiments.

[0456] Illustrative Embodiments A. Pd(0) complexes [Pd(phosphine)2] and [Pd(dvds)(phosphine)] where dvds = 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

[0457] Example 1: Preparation of Pd complexes

[0458] [ka]

[0459] [Table 4]

[0460] General steps: 422 μl (434 mg, 0.5 mmol, 1 equiv.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane palladium (Pd-VS or palladium-VS) was first charged to an inert Schlenk tube (heated three times while evacuating and backfilling with argon), followed by 2 equiv. (1 mmol) of the corresponding phosphine (unless otherwise noted) dissolved in a sufficient amount (usually about 3-4 mL) of toluene. After the specified reaction time at room temperature, the volume was reduced by half, and the formed precipitate was filtered off, washed with 3 × 2 mL of methanol, and dried under vacuum.

[0461] Example 1-1 Ligand: tri-tert-butylphosphine, 2 mL of ethanol as solvent. Reaction time: 4 hours Yield: 92% colorless solid 1 H NMR(250MHz,C6D6)δ=1.52(t,J=5.5Hz,54H)ppm. 13 C NMR(63MHz,C6D6)δ=37.9,33.7ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=85.14(s)ppm. Silicon content by ICP-AES = 340 ppm.

[0462] Examples 1-2 Ligand: Tricyclohexylphosphine Reaction time: 3 hours, followed by addition of 3 mL of methanol. Yield: 163 mg (54%) of a colorless solid. 1 H NMR(250MHz,C6D6)δ=3.43-3.69(m,2H),3.12-3.42(m,4H),1.92-2.14(m, 3H), 1.51-1.92(m, 16H), 0.94-1.48(m, 15H), 0.58(s, 6H), 0.07(s, 6H)ppm. 13 C NMR(63MHz,C6D6)δ=64.4,63.2,37.0,31.3,28.4,27.4,2.4,-0.3ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=34.85(s)ppm.

[0463] Examples 1-3 Ligand: triisopropylphosphine (1.2 equivalents) Reaction time: 16 hours Yield: 246 mg (51%) colorless solid 1H NMR (250MHz, C6D6) δ=3.48-3.60(m,2H),3.18-3.29(m,4H),1.96(spt,J=14.4Hz,3H),0.99(dd,J=13.0,7.1Hz,18H),0.56(s,6H),0.04(s,6H)ppm. 13 C NMR (63MHz, C6D6) δ = 64.3, 63.0, 26.8, 20.5, 2.4, -0.2ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=47.79(s)ppm.

[0464] Example 1-4 Coordinating seat: ブチルジ-1-アダマンチルホスフィン Reaction time: 3 hours, Torrent Yield: 193 mg (55%) colorless solid; solvent としてのアセトン>80% 1 H NMR(250MHz,C6D6)δ=3.76(ddd,J=12.2,5.1,1.7Hz,2H),3.14-3.53(m,4H),1.97-2.12(m,12H),1.86(br.s. ,8H),1.55-1.75(m,14H),1.42-1.55(m,2H),0.97(t,J=7.2Hz,3H),0.58(br.s.,6H),-0.12-0.31(m,6H)ppm. 13 C NMR (63MHz, C6D6) δ = 64.5, 64.0, 41.1, 40.0, 37.6, 31.1, 29.6, 26.8, 21.9, 14.8, 0.9ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=49.78(s)ppm.

[0465] Observation: reaction products

[0466]

change

[0467] Example 1-5 Ligand: 2-(dicyclohexylphosphino)biphenyl Reaction time: 16 hours, 3 mL of methanol was added after the reaction time. Yield: 91 mg (45%) colorless solid 1 H NMR (250 MHz, CD6D6) δ = 7.57 (t, J = 7.1 Hz, 1H), 7.17-7.24 (m, due to overlap with 6H solvent signal), 7.03-7.09 (m, 2H), 6.94-7.03 (m, 3H), 3.12-3.39 (m, 4H), 2.90-3.10 (m, 2H), 1.81-2.08 (m, 6H), 1.51-1.78 (m, 6H), 1.23-1.51 (m, 4H), 0.97-1.23 (m, 6H), 0.57 (br.s., 6H), 0.12 (br.s., 6H) ppm. 13 C NMR(63MHz,C6D6)δ=146.8,142.3,133.5,132.6,132.2,129.3,127.2,12 7.1,126.4,65.2,64.3,39.1,30.9,30.7,27.8,27.5,26.5,1.7,-1.2ppm. 31 P{ 1 H}NMR (101MHz, C6D6)δ=32.83ppm.

[0468] Comparative Examples 1-6 Ligand: YPhos 1 Reaction time: 3 hours Yield: 45 mg (56%) of a colorless solid 31 P NMR (101MHz, C6D6) δ = 30.96 (d, J = 78.0 Hz), 15.76 (d, J = 79.0 Hz) ppm.

[0469] Examples 1-7 Ligand: Di-tert-butylphenylphosphine Reaction time: 3 hours After concentration, 15 mL of methanol was added. Yield: 123 mg (48%) of a colorless solid 1H NMR(250MHz,C6D6)δ=7.52-7.69(m,2H),7.05-7.14(m,3H),3.65(s,2H),3.27-3.46(m,4H),1.20(d,J=12.6Hz,18H),0.19(br.s.,12H)ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=69.85ppm.

[0470] Examples 1-8 Ligand: Di-tert-butylisopropylphosphine, add 6 mL of toluene Reaction time: 3 hours After concentration, 15 mL of methanol was added. Yield: 153 mg (64%) of a colorless solid 1 H NMR(250MHz,C6D6)δ=3.45-3.68(m,2H),3.14-3.39(m,4H),2.42-2.70(m,1H),1.05-1.37(m,24H),0.53(br.s.,6H),-0.19-0.24(br.s.,6H)ppm 13 C NMR(63MHz,C6D6)δ=66.2,65.9,37.2,31.8,31.0,22.2,1.8ppm. 31 P{ 1 H}NMR (101MHz, C6D6)δ=71.27ppm.

[0471] Examples 1-9 Ligand: tert-butyldiphenylphosphine, add 2 mL of toluene Reaction time: 3 hours; after concentration, 15 mL of methanol was added. Yield: 110 mg (41%) colorless solid 1 H NMR(400MHz,C6D6)δ=7.51-7.73(m,4H),6.95-7.13(m,6H),3.38-3.67(m,4 H),3.15-3.31(m,2H),1.19(d,J=13.6Hz,9H),0.50(s,6H),0.03(s,6H)ppm. 13C NMR(101MHz,C6D6)δ=137.2(d,J=21.60Hz)134.8(d,J=13.30Hz)129.6(s)69.0(d,J =3.32Hz)68.1(d,J=8.29)34.2(d,J=9.90Hz)29.3(d,J=8.29Hz)2.2(s)-0.4(s)ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=64.01ppm.

[0472] Examples 1-10 Ligand: Tri-o-tolylphosphine, add 3 mL of toluene 63 mg of tri-o-tolylphosphine (0.2 mmol, 2 equiv.) was added to an oven-dried vial, followed by 95 μL (98 mg, 0.1 mmol, 1 equiv.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane-palladium. 3 mL of toluene was added to the suspension, and the resulting solution was 31 P{ 1 The solid was analyzed by H NMR. 31 P{ 1 H}NMR(101MHz,C6D6)δ=21.6ppm.

[0473] Examples 1-11 Ligand: Tris(pentafluorophenyl)phosphine, add 3 mL of toluene 110 mg of tris(pentafluorophenyl)phosphine (0.2 mmol, 2 equiv.) was added to an oven-dried vial, followed by 95 μL (98 mg, 0.1 mmol, 1 equiv.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane-palladium. 3 mL of toluene was added to this suspension, and the resulting solution was 19 F-NMR analysis was performed.

[0474] Example 2: Catalytic activity of Examples 1-4 The following examples illustrate the catalytic activity of compound examples 1-4.

[0475] [ka] This was done in part by comparison with other similar compounds. Activity was tested in the Suzuki-Miyaura cross-coupling using p-chlorotoluene and phenylboronic acid as reactants.

[0476] [ka] A: Examples 1-5 B: Examples 1-3 C: Examples 1-2 D: Examples 1-4

[0477] [ka]

[0478] [Table 5]

[0479] The reaction was carried out on a 1.5 mmol scale. 2 mmol of phenylboronic acid, 1.5 mmol of K3PO4, and 1.5 mmol of potassium fluoride were initially charged to an injection vial, and 0.0075 mmol of catalyst was added in a nitrogen-filled glove box. Solvent: 4 mL of THF. 1.5 mmol of p-chlorotoluene was added via syringe. The reaction time was 22 hours, and the temperature was 100 °C. The yield was determined by gas chromatography using tetradecane as an internal standard.

[0480] Solvent resistance was performed in the same manner as in step 2-1 using 3 mL of a particular solvent.

[0481] [Table 6]

[0482] Furthermore, different bases were tested in suitable solvents. 1 mmol of base was used in each case.

[0483] [Table 7]

[0484] The suitability of different reaction temperatures was tested in the same manner as in 2-1. 3 mmol of lithium carbonate was used as the base, and THF was used as the solvent. No reaction product was observed at temperatures below 80 °C, and the yield at 80 °C was only 25%.

[0485] Example 3-1 [Pd Ph2P(CH2)3PPh2]2] Under argon, 213 mg of 1,3-bis(diphenylphosphino)propane (0.5 mmol, 2 equiv.) was dissolved in 3 mL of toluene, and 251 μl (244 mg, 0.25 mmol, 1 equiv.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane-palladium was added. The solution was stirred for 2 h, resulting in the precipitation of a yellow solid. 5 mL of methanol was added to the suspension, and the supernatant was removed with a syringe. The solid was washed with methanol (2 × 10 mL) and dried under vacuum. Yield: 230 mg (99%) 31 P{ 1 H}NMR(101MHz,C6D6)δ=3.97ppm.

[0486] Example 3-2 [Pd PhP(CH)PPh] Under argon, 203 mg of 1,3-bis(diphenylphosphino)ethane (0.5 mmol, 2 equiv.) was dissolved in 3 mL of toluene, and 251 μl (244 mg, 0.25 mmol, 1 equiv.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane-palladium was added. The solution was stirred for 2 h, causing a solid to precipitate. 5 mL of methanol was added to the suspension, and the supernatant was removed with a syringe. The solid was washed with methanol (2 × 10 mL) and dried under vacuum. Yield: 215 mg (95%) 31 P{ 1 H}NMR(101MHz,C6D6)δ=29.59ppm. B. Pd(I) dimer [Pd(μ-X)(PR A R B R C )]2, where X=Br, I

[0487] Example 1-1 Starting from [Pd(acac)2] and acetyl bromide [Pd(μ-Br)(PtBu3)]2 A mixture of [Pd(acac)2] (31 g, 100 mmol) and acetyl bromide (25 g, 200 mmol) in 500 mL of acetone was stirred at room temperature for 2.5 h. Then, [Pd(PtBu3)2] (55 g, 105 mmol, 1.05 equiv.) and 400 mL of acetone were added, and the reaction mixture was stirred at room temperature for 2 h. The precipitated solid was filtered off, washed, and then dried under vacuum. Yield: 71.58 g (92%) dark green-blue solid 1 H NMR (400MHz, C6D6) δ=1.32ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=86.3ppm. Pd content: 28.1% Reversing the order of addition of acetyl bromide and [Pd(PtBu3)2] affords the product in approximately 60% yield.

[0488] Example 1-2 Starting from [Pd2(dvds)3] and acetyl bromide or N-bromosuccinimide, [Pd(μ-Br)(PtBu3)]2 A mixture of [Pd2(dvds)3] and acetyl bromide (2 equivalents) in methanol was stirred at room temperature for 2.5 hours. Then, PtBu3 (2 equivalents) was added and stirred at room temperature for 2.5 hours. The precipitated solid was filtered off, washed, and then dried under vacuum. Yield: 32% dark green-blue solid 1 H NMR (400MHz, C6D6) δ=1.32ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=86.3ppm. The reaction was carried out similarly except that N-bromosuccinimide was used as the Br donor and acetone was used as the solvent to give the product in 16% yield.

[0489] Example 1-3 [Pd(μ-Br)(PtBu)]2 starting from [Pd2(dvds)3] and Br2 in 1,4-dioxane [Pd2(dvds)3] (868 mg, 1 mmol) was added to a Schlenk tube, followed by tri-tert-butylphosphine (413 mg, 2 mmol, 98%, 2 equiv.). A solution of bromine (Br2) (4 mL, 0.25 M, 1 mmol, 1 equiv.) in 1,4-dioxane was then added. The mixture was stirred at 40 °C for 2 h. The solvent was removed under reduced pressure, and the residue was extracted with toluene, which was then removed under reduced pressure. The resulting solid was dissolved in acetone. The solution was stored at -20 °C, yielding dark green crystals, which were separated from the solution, washed with a small amount of acetone, and dried under reduced pressure. Yield: 55% dark green crystals 1 H NMR (400MHz, C6D6) δ=1.32ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=86.3ppm.

[0490] Example 2-1 Starting from [Pd2(dvds)3] and I2, [Pd(μ-I)(PtBu3)]2 A mixture of [Pd2(dvds)3] (0.5 g Pd, 2.4 mmol) as a toluene solution in acetone (1 equiv.) and PtBu3 was stirred at room temperature for 2.5 h. Iodine (I2) (0.62 g, 2.4 mmol, 1 equiv.) was then added and stirred at room temperature for 2.5 h. The precipitated solid was filtered off, washed, and then dried under vacuum. Yield: 83% dark purple solid 1 H NMR (400MHz, C6D6) δ=1.29ppm. 31 P{ 1 H}NMR(101MHz,C6D6)δ=102.3ppm.

[0491] C. π-Allylpalladium Halide Complexes C.1 General procedure for preparing dimeric allylic palladium halides according to general formula VIII An allyl halide (1.2 equiv., 0.6 mmol; or 5 equiv., 2.5 mmol; or 10 equiv., 5 mmol) was added to a solution of Pd(vs) in a Schlenk flask under an argon atmosphere (1 equiv., palladium content 5.35%, 993 mg, 0.5 mmol; or palladium content 10.9%, 488 mg, 0.5 mmol). A yellow solid rapidly formed. The mixture was stirred for 1 h, and hexane (3 mL) was added. The liquid supernatant was decanted, and the solid was washed twice with 3 mL of hexane. The solid was dried under vacuum.

[0492] Example 1-1: Di-μ-chlorobis(η 3 -allyl)dipalladium(1-Cl) [CAS number: 12012-95-2]

[0493] [ka]

[0494] Yellow solid, melting point: 149°C. Proportion of insoluble components in dichloromethane: <0.1% (PTFE membrane filter (pore size 0.45 μm)).

[0495] [Table 8] 1 H NMR (CDCl3,400MHz): δ=5.46(tt,J=12.1,6.7Hz,2H),4.12(d,J=6.6Hz,4H),3.05(d,J=12.1Hz,4H). 13 C NMR(CDCl3,101MHz)δ=111.1,62.9.

[0496] Example 1-2: Di-μ-bromobis(η 3-アリル)ジパラジウム(1-Br)[CAS number: 12077-82-6].

[0497]

change

[0498] Yellow solid, melting point: 158℃.

[0499]

Table 9

[0500] Example 1-3: ジ-μ-ヨードビス(η 3 -アリル)ジパラジウム(1-I)[CAS number: 12013-04-6]

[0501]

change

[0502] Orange solid, melting point: 180℃.

[0503]

Table 10

[0504] Example 1-4: Di-μ-chlorobis[η 3 -2-methylallyl]dipalladium(2-Cl) [CAS number: 12081-18-4].

[0505] [ka]

[0506] Yellow solid, melting point: 145°C.

[0507] [Table 11] 1 H NMR (CDCl3, 400MHz): δ = 3.86 (s, 4H), 2.89 (s, 4H), 2.15 (s, 6H). 13 C NMR (CDCl3, 101MHz): δ=127.0,61.8,22.7.

[0508] Example 1-5: Di-μ-bromobis[η 3 -2-Methylallyl]dipalladium(2-Br) [CAS number: 12080-98-7]

[0509] [ka]

[0510] Yellow solid, melting point: 153-154°C.

[0511] [Table 12] 1 H NMR (CDCl3, 400MHz): δ = 3.94 (s, 4H), 2.92 (s, 4H), 2.09 (s, 6H). 13 C NMR (CDCl3, 101MHz): δ=126.2,63.9,22.9.

[0512] Example 1-6: Bis[(1,2,3-η)-2-buten-1-yl]di-μ-chlorodipalladium(3-Cl) [CAS number: 12081-22-0]

[0513] [ka]

[0514] Yellow solid, melting point: 148°C.

[0515] [Table 13]

[0516] Syn / anti isomer ratio 97:3 syn isomer: 1 H NMR (CDCl3,400MHz): δ=5.30(td,J=11.6,6.7Hz,2H),3.78-4.01(m,4H),2.82(d,J=11.9Hz,2H),1.34(d,J=6.3Hz,6H). 13 C NMR (CDCl3, 101MHz): δ=111.4,79.0,59.2,15.8. Anti-isomer: 1 H NMR (CDCl, 400 MHz): δ = 4.86 (quin, J = 6.8 Hz, 2H), 4.10 (d, J = 7.3 Hz, 2H), 3.37 (d, J = 12.9 Hz, 2H), 1.13 ppm (d, J = 6.6 Hz, 6H). Proton overlaps with the syn isomer. 13 C NMR (CDCl3, 101MHz): δ=106.4,81.5,58.3,18.0.

[0517] Example 1-7: Bis[(1,2,3-η)-2-buten-1-yl]di-μ-chlorodipalladium(3-Br) [CAS number: 12081-43-5]

[0518] [ka]

[0519] Yellow solid, melting point: 169°C.

[0520]

Table 14

[0521] Example 1-8: ジ-μ-クロロビス[(1,2,3-η)-3-メチル-2-ブテニル]ジパラジウム(4-Cl) [CAS number: 12288-41-4]

[0522]

change

[0523] Yellow solid, melting point: 116~117℃

[0524]

Table 15

[0525] Example 1-9: Di-μ-bromobis[(1,2,3-η)-3-methyl-2-butenyl]dipalladium(4-Br)

[0526] [ka]

[0527] Yellow solid, melting point: 119-120°C

[0528] [Table 16] 1 H NMR (CDCl3,300MHz): δ=5.08(dd,J=12.7,7.3Hz,2H),3.92(dd,J=7.3,1.5Hz,2H),3.14(dd,J=12.7,1.5Hz,2H),1.60(s,6H),1.29(s,6H). 13 C NMR (CDCl3, 101MHz): δ=106.4,97.7,57.1,27.7,22.1.

[0529] Example 1-10: Di-μ-chlorobis[(1,2,3-η)-1-phenyl-2-propen-1-yl]dipalladium(5-Cl) [CAS number: 12131-44-1]

[0530] [ka]

[0531] Yellow solid, melting point: 201°C

[0532] [Table 17] 1H NMR (CDCl3, 400MHz): δ=7.44-7.56(m,4H),7.31-7.40(m,2H),7.22-7.31(m,4H),5.80(td,ddd,J=11. 9,11.4,6.7Hz,2H),4.62(d,J=11.4Hz,2H),3.97(dd,J=6.7,0.6Hz,2H),3.04(dt,J=11.9,0.9Hz,2H). 13 C NMR (CDCl3, 101MHz): δ=136.9,129.0,128.5,127.9,105.9,81.8,59.4.

[0533] Example 1-11: ジ-μ-ブロモビス[(1,2,3-η)-1-フェニル-2-プロペン-1-イル]ジパラジウム(5-Br)[CAS number: 32876-05-4]

[0534]

change

[0535] Orange solid, melting point: 173℃

[0536]

Table 18

[0537] Example 1-12: ジ-μ-クロロビス[(1,2,3-η)-2-シクロヘキセン-1-イル]ジパラジウム(6-Cl) [CAS number: 12090-09-4]

[0538] [ka]

[0539] Yellow solid, melting point: 108℃

[0540] [Table 19] 1 H NMR (CDCl3, 250MHz): δ=5.48(t,J=6.3Hz,2H),5.18(t,J=5.3Hz,4H),1.63-1.95(m,10H),0.91-1.17(m,2H). 13 C NMR (CDCl3, 63MHz): δ=101.7,78.8,28.7,19.4.

[0541] Example 1-13: Di-μ-bromobis[(1,2,3-η)-2-cyclohexen-1-yl]dipalladium(6-Br) [CAS number: 35284-31-2]

[0542] [ka]

[0543] Yellow solid, melting point: 129℃

[0544] [Table 20] 1 H NMR (CDCl3,400MHz): δ=5.47(t,J=6.5Hz,2H),5.30(t,J=5.1Hz,4H),1.70-1.99(m,10H),1.02-1.20(m,2H). 13 C NMR (CDCl3, 101MHz): δ=101.7,81.1,28.7,19.5.

[0545] Example 1-14: Reaction of Pd(vs) with 1-(chloromethyl)naphthalene (preparation of 7-Cl).

[0546] [ka]

[0547] A solution of Pd(vs) (palladium content 10.9%, 1945 mg, 2 mmol) was added to a solution of 1-(chloromethyl)naphthalene (446 mg, 2.4 mmol, 1.2 equiv.) in 3 mL of dry, degassed acetone in an injection vial under an argon atmosphere. After 1 h, a yellow solution began to form, which was kept stirring for 24 h, and 3 mL of hexane was added to it. The supernatant liquid was decanted, and the resulting solid was washed three times with 5 mL of acetone and dried under vacuum. 196 mg (yield: 34.6%) of a yellow solid was isolated. 1 H NMR(400MHz,DMSO-d6)δ=8.47(d,J=8.1Hz,2H),7.91(dd,J=19.0,8.1Hz,2H),7.53-7.73 (m,2H),7.36(t,J=7.6Hz,1H),7.05(d,J=5.5Hz,1H),3.88-3.88(m,1H),3.90(s,2H)ppm. 13 C NMR (101MHz, DMSO-d6) δ=133.99,130.03,128.27,128.20,127.47,127.45,126.35,125.34ppm. mp:>160℃(decomposition) IR(ATR):950(vw),876(vw),795(vw),772(w),753(w),709(vw),644(vw),571(vw),509(vw)cm -1 . EA Anal.Calcd for C 22 H 18 Cl2Pd2:C,46.68,H,3.20;N,0.00 Found:C,46.99H,3.171N,0.00.

[0548] Example 1-15: Reaction of Pd(vs) with 2-(chloromethyl)naphthalene (Preparation of 8-Cl)

[0549] [ka]

[0550] 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane palladium Pd(vs) (1 equiv., 1945 mg, 2 mmol, 10.9% Pd) was dissolved in 3 mL of dry, degassed acetone in an injection vial containing 2-(chloromethyl)naphthalene (1.2 equiv., 437 mg, 2.4 mmol, 97%). The mixture was stirred for 16 h. The orange precipitate was filtered off, and the solid was washed three times with 6 mL of acetone. 135 mg of product was isolated. 1 H NMR (400MHz, DMSO-d6) δ = 7.88 (s, 2H), 7.78 (t, J = 6.9Hz, 4H), 7.60-7.73 (m, 4H), 7.37-7.49 (m, 4H), 3.56 (s, 4H) ppm. 13 C NMR (101MHz, DMSO-d6) δ=125.00,126.31,127.20,127.79,127.94,131.19,134.01ppm. mp:>179℃(decomposition) IR(ATR):855(vw),816(w),746(w),648(vw),614(vw),544(vw),501(vw),571(vw),509(vw)cm -1 . EA Anal.Calcd for C 22 H 18 Cl2Pd2:C,46.68,H,3.20;N,0.00 Found:C,46.96H,3.380 N,0.00.

[0551] Example 1-16: Reaction of Pd(vs) with 1-(bromomethyl)naphthalene (Preparation of 7-Br)

[0552] [ka]

[0553] 1592 mg (7.2 mmol, 1.2 equiv.) of 1-(bromomethyl)naphthalene dissolved in 3 mL of dry, degassed acetone was initially placed in an injection vial, and 5210 mg (10.9% Pd, 6 mmol, 1 equiv.) of Pd(vs) was added under anhydrous and oxygen-free conditions. The mixture was then stored at 4-6 °C overnight. The orange precipitate was filtered in air, washed five times with 5 mL of acetone, and dried under vacuum. 1632 mg (83% yield) of 7-Br was obtained as an orange solid. 1 H NMR (400MHz, DMSO-d6)δ=8.32-8.40(m,2H),7.87-8.02(m,4H),7.64-7.77(m,4H),7.47(dd,J=8.7,6.4Hz,2H),6.44(d,J=6.2Hz,2H),4.12(s,4H)ppm. 13 C NMR (101MHz, DMSO-d6) δ=124.80,127.58,128.57,128.69,129.02,129.18,130.31,134.04ppm. Mp:>147℃(decomposition) IR(ATR):1504(vw),1329(vw),1235(vw),951(vw),876(vw),794(w),772(w),754(vw),643(vw),571(vw),510(vw)cm -1 .

[0554] Example 1-17: Reaction of Pd(vs) with 2-(bromomethyl)naphthalene (Preparation of 8-Br)

[0555] [ka]

[0556] 921 mg (4 mmol, 1 equiv.) of 2-(bromomethyl)naphthalene dissolved in 3 mL of dry, degassed acetone was initially placed in an injection vial, and 4168 mg (10.9% Pd, 4.8 mmol, 1 equiv.) of Pd(vs) was added under anhydrous and oxygen-free conditions. The solution was stirred for 2 h. The orange precipitate was filtered in air and washed three times with 5 mL of acetone. The solid was dried under vacuum, yielding 540 mg (41% yield) as an orange solid. 1 H NMR (400MHz, DMSO-d6) δ=7.85(d,J=7.9Hz,2H),7.80(d,J=7.8Hz,2H),7.74(d,J=8.7Hz,2H),7.56-7.67(m,4H),7.42-7.55(m,4H),3.71(s,4H)ppm. 13 C NMR (101MHz, DMSO-d6) δ = 125.71, 126.70, 127.05, 127.83, 127.98, 129.05, 131.41, 134.50ppm. mp:>171℃(decomposition) IR(ATR):855(vw),813(vw),766(w),747(w),650(vw),614(w),542(w)cm -1 . EA Anal.Calcd for C 22 H 18 Br2Pd2:C,40.34,H,2.77;N,0.00 Found:C,40.35H,2.652N,0.00.

[0557] Example 1-18: Reaction of Pd(vs) with 3-(tert-butyl)-1-chloro-1H-indene (Preparation of 9-Cl)

[0558] [ka]

[0559] 3-(tert-Butyl)-1-chloro-1H-indene (1 equiv., 30 mg, 0.145 mmol) dissolved in 0.1 mL of acetone was initially charged, and Pd(vs) (1.2 equiv., 151 mg, 0.174 mmol) was added and shaken. The mixture was stored at 4 °C overnight. The formed crystals were carefully separated, washed with a few drops of water and acetone, and dried. 29 mg (64%) of dark brown crystals were obtained. 1 H NMR (400MHz, CDCl3) δ=7.09-7.19(m,2H),6.83(d,J=4.3Hz,8H),5.53(d,J=2.9Hz,2H),1.32(s,18H)ppm. 13 C NMR(101MHz, CDCl3)δ=141.91,140.70,127.45,127.15,120.08,120.05,118.64,118.56,107.43,107.37,73.01,34.19,28.65ppm.

[0560] C.2 Preparation of palladium(II) compounds according to formula IX, formula IX.a or IX.b and IX.c, formula IX.d or formula IX.P and formula IX.N Example 2-1 1-Methylnaphthyl[tris(tert-butyl)phosphine]bromopalladium(II)(10-Br)

[0561] [ka]

[0562] 7-Br (1 equiv., 164 mg, 0.25 mmol) was added to the vial, and the air was purged with argon. The solid was dissolved in 20 mL of dry, degassed THF, and the vial was transferred to a glovebox. Tri-tert-butylphosphine (2 equiv., 103 mg, 0.5 mmol, 98%) was then added, and the reaction mixture was stirred at room temperature for 30 min. The suspension was filtered through a syringe filter, and the filtrate was reduced to 90% of its volume. Hexane was then added, and the sample was stored in a freezer (-20 °C) to precipitate the product. The crude reaction mixture was washed with pentane, and the remaining solid was dissolved in toluene and filtered through Celite®. The solvent was removed under reduced pressure to give 216 mg (82%) of an orange solid. 1 H NMR(400MHz,C6D6)δ=7.73(s,2H),7.57(t,J=7.6Hz,1H),7.41(d,J=7.8Hz,1H),7.31(t,J=7.1Hz ,1H),7.23(t,J=8.1Hz,1H),6.32(t,J=5.4Hz,1H),3.35(br.s,2H),1.31(d,J=12.5Hz,27H)ppm. 13 C NMR(101MHz,CD2Cl2)δ=131.85(d,J=3.70Hz),130.77(d,J=4.40Hz),129.55,128. 72,127.96,123.63,109.58(d,J=13.91Hz),40.24(d,J=5.80Hz),37.87,33.11ppm. 31 P NMR(162MHz,C6D6)δ=99.92ppm; Elemental analysiscalculated C 23 H 36 BrPPd:C,52.14,H,6.85,N,0.00;found:C,51.86H,6.28N,0.00.

[0563] Example 2-2 1-Methylnaphthyl[tris(cyclohexyl)phosphine]bromopalladium(II)(11-Br)

[0564] [ka]

[0565] 7-Br (1 equiv., 164 mg, 0.25 mmol) was added to the vial, the air was purged with argon, and the vial was transferred to a glovebox. Tricyclohexylphosphine (2 equiv., 140 mg, 0.5 mmol) was then added, followed by 20 mL of THF. The reaction mixture was stirred at room temperature for 90 minutes. 90% of the solvent was evaporated, and 10 mL of pentane was added. The sample was stored at -20 °C overnight to allow the product to crystallize. The mother liquor was decanted, and the solid was dried under high vacuum to yield 192 mg (63%) of a yellow solid. 1 H NMR(400MHz,CD2Cl2)δ=7.87(d,J=7.8Hz,1H),7.78(d,J=7.6Hz,1H),7.71(d,J=7.3Hz,1H),7.40-7.61(m,3H),6.12(t,J=5 .6Hz,1H),3.71-4.05(br.s,1H),2.54(br.s,J=1.2Hz,1H),2.00-2.18(m,3H),1.53-1.96(m,15H),1.02-1.44(m,15H)ppm. 13 C NMR(101MHz,CD2Cl2)δ=135.3(d,J=2.9Hz),131.0(d,J=5.1Hz),129.6(s),129.1(s),129.0(s),127.5(s),124.0(s),120.5 (dJ=3.7Hz),100.3(s),100.2(s),37.5(d,J=4.4Hz),35.7(d,J=19.8Hz),30.8(d,J=25.7Hz),28.1(d,J=11Hz),26.9(s)ppm. 31 P NMR (162MHz, CD2Cl2)δ=53.91ppm. Elemental analysiscalculated C 29 H 42 BrPPd * THF(C4H 8th O):C,58.28,H,7.41,N,0.00;found:C,58.65H,6.32 N,0.00.

[0566] Example 2-3 1-Methylnaphthyl[tris(cyclohexyl)phosphine]chloropalladium(II)(11-Cl)

[0567] [ka]

[0568] 7-Cl (1 equiv., 142 mg, 0.25 mmol) was added to the vial, the air was purged with argon, and the vial was transferred to a glovebox. Tricyclohexylphosphine (2 equiv., 140 mg, 0.5 mmol) was then added, followed by 20 mL of THF. The reaction mixture was stirred at room temperature for 90 min. 90% of the solvent was evaporated, and 10 mL of pentane was added. The sample was stored at -20 °C overnight to precipitate the product. The solution was decanted from the solid, and the remaining solid was washed with pentane (3 × 5 mL) and dried under high vacuum to give 91 mg (32%) of a yellow solid. 1 H NMR(400MHz,CD2Cl2):δ=7.96(d,J=7.6Hz,1H),7.88(d,J=7.3Hz,1H),7.84(dd,J=8.8,3.2Hz,1H),7.57-7.68(m,2H),7.53(t,J= 7.6Hz,1H),6.26(t,J=5.7Hz,1H),3.82(br.s.,1H),2.57(br.s.,1H),2.05-2.21(m,3H),1.65-1.97(m,15H),1.16-1.51(m,15H). 13 C NMR (101MHz, CD2Cl2): δ=135.43(d, J=2.93Hz), 130.4, 130.4, 129.5, 129.1, 129.0, 127.5, 124.1, 1 20.81(d, J=3.67Hz), 100.67(d, J=19.07Hz), 35.35, 35.16, 28.13, 28.02, 26.93(d, J=1.50Hz)ppm. 31 P NMR (162MHz, C6D6): δ=53.53ppm. HRMS(TOF-EI):m / z calculated for C 14 H18 O3:562.1747[M] + ;found 562.1772.

[0569] Example 2-4 1-Methylnaphthyl[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]bromopalladium(II)(12-Br)

[0570] [ka]

[0571] In a nitrogen-filled glovebox, 164 mg of 7-Br (1 equiv., 0.25 mmol) and 224 mg of IPr (2 equiv., 0.5 mmol) were added to a crimp-cap vial. 20 mL of diethyl ether was then added, and the reaction mixture was stirred under a nitrogen atmosphere for 90 minutes. 90% of the solvent was evaporated, and 20 mL of pentane was added. The sample was stored at -20 °C overnight to allow the product to crystallize. The mother liquor was decanted, and the remaining solid was washed with pentane (3 × 2 mL) and dried under high vacuum to give 325 mg (91%) of a yellow solid. 1 H NMR (400MHz,C6D6;283K)δ=7.32-7.43(m,2H),7.21-7.32(m,4H),7.07-7.21(m,3H,overlapping with solvent signal),6.99(br.s,2H),6.86(d,J=8.1Hz,1H),6.55(s,2H), 5.40(d,J=6.5Hz,1H),3.52-3.64(m,2H),3.38(br.s.,1H),1.88(br.s.,1 H),1.44-1.64(m,6H),1.39(dt,J=6.6,3.3Hz,2H),0.78-1.25(m,18H)ppm. 13 C NMR(101MHz,C6D6;283K)δ=184.63,146.76,136.94,135.42,132.92,130.49,130.04,1 28.97,127.21,124.79,124.41,119.00,91.88,68.14,33.85,26.38,23.09,14.59ppm. HRMS (TOF-EI) m / z calculated C 38 H 45 BrN2Pd[M] + 714.1800,found 714.1786.

[0572] Example 2-5 2-Methylnaphthyl[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]bromopalladium(II)(13-Br)

[0573] [ka]

[0574] In a nitrogen-filled glovebox, 164 mg of 8-Br (1 equiv., 0.25 mmol) and 224 mg of iPr (2 equiv., 0.5 mmol) were added to a crimp-cap vial. 20 mL of diethyl ether was then added, and the reaction mixture was stirred under a nitrogen atmosphere for 90 minutes. 90% of the solvent was evaporated, and 20 mL of pentane was added. The sample was stored at -20 °C overnight to allow the product to crystallize. The mother liquor was decanted, and the remaining solid was washed with pentane (3 × 2 mL) and dried under high vacuum to give 344 mg (96%) of a yellow solid. 1 H NMR (300 MHz, CD) δ = 7.69 (d, J = 7.9 Hz, 1H), 7.18-7.30 (m, 4H), 7.08-7.17 (m, 6H, overlapped with solvent signal), 6.63 (s, 2H), 6.11 (dd, J = 8.8, 1.7 Hz, 1H), 5.59 (s, 1H), 3.22 (spt, J = 7.0 Hz, 4H), 2.52 (br.s., 2H), 1.30-1.50 (m, 12H, overlapped with THF signal), 1.01 (d, J = 7.0 Hz, 12H) ppm. 13C NMR(75MHz,THF-d8)δ=184.19,147.37,138.61,137.78,132.66,132.54,130.53,130.48,128.48 ,127.51,126.45,126.09,124.75,124.26,119.41,91.88,40.14,29.50,27.93,26.50,23.54ppm. Elemental analysiscalculated for C 38 H 45 BrN2Pd:C,63.74,H,6.33,N,3.76 found:C,64.14H,6.46,N,3.91. HRMS(TOF-EI)m / z calculated for C 38 H 45 BrN2Pd[M] + 714.1800,found 714.1802.

[0575] Example 2-6 1-Methylnaphthyl[2-(dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl]bromopalladium(II)(14-Br)

[0576] [ka]

[0577] 7-Br (1 equiv., 164 mg, 0.25 mmol) and 2-(dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl (2 equiv., 246 mg, 0.5 mmol, 97%) were added to the vial, and the air was replaced with argon. 10 mL of THF was then added. The reaction mixture was stirred at room temperature for 90 min. The solution was concentrated to 90% by volume and covered with 10 mL of hexane. The vial was then stored in a freezer (-20 °C) to allow the product to precipitate. The mother liquor was decanted, and the remaining solid was washed with pentane (3 × 5 mL) and dried under high vacuum to give 322 mg (80%) of a yellow solid. 1H NMR(400MHz,CD2Cl2)δ=7.77-7.97(m,4H),7.51-7.70(m,3H),7.33-7.47(m,2H),7.08-7.28(m,3H),6.1 9(t,J=5.7Hz,1H),2.96(spt,J=6.8Hz,1H),2.66(br.s.,2H),2.04-2.17(m,2H),0.63-1.79(m,40H)ppm. 13 C NMR (101 MHz, CD2Cl2) δ = 149.6, 147.0, 142.3, 138.4, 138.2, 136.8, 135.2, 134.4 (two peaks), 130.8 (two peaks), 129.4, 128.7-129.2 (m, complex coupling pattern), 127.4, 126.0, 125.9, 124.1, 121.6, 120.9 (two peaks), 34.8, 31.2, 27.6 (two peaks), 27.2 (two peaks), 26.2, 26.1, 24.2, 22.8 (br.s.) ppm. 31 P NMR (162MHz, CD2Cl2)δ=63.74(br.s)ppm. Elemental analysiscalculated for C 44 H 58 BrPPd:C,65.71,H,7.27,N,0.00,found:C,65.73H,7.384,N,0.62.

[0578] Example 2-7 1-Methylnaphthyl[2-dicyclohexylphosphino-2',6'-di-i-propoxy-1,1'-biphenyl]bromopalladium(II)(15-Br)

[0579] [ka]

[0580] 7-Br (1 equiv., 164 mg, 0.25 mmol) was added to the vial, the air was purged with argon, and the vial was transferred to a glovebox. 2-Dicyclohexylphosphino-2',6'-di-i-propoxy-1,1'-biphenyl (2 equiv., 238 mg, 0.5 mmol, 98%) was then added, followed by 20 mL of THF. The reaction mixture was stirred at room temperature for 90 min. 90% of the solvent was evaporated, and 10 mL of pentane was added. The sample was stored at -20 °C overnight to allow the product to crystallize. The mother liquor was decanted, and the remaining solid was washed with pentane (3 × 5 mL) and dried under high vacuum to yield 315 mg (79%) of a yellow solid. 1 H NMR(400MHz,CD2Cl2)δ=7.86(d,J=7.8Hz,1H),7.78(d,J=8.1Hz,2H),7.60-7 .72(m,2H),7.48-7.60(m,2H),7.37-7.47(m,1H),7.24-7.35(m,2H),6.95(d, J=6.1Hz,1H),6.64(d,J=8.3Hz,2H),6.07(br.s.,1H),4.36-4.66(m,2H),3. 27(br.s,2H),2.00-2.17(m,2H),1.39-1.97(m,10H),0.67-1.37(m,22H)ppm. 13 C NMR (101 MHz, CD2Cl2) δ = 157.5, 139.6, 137.8, 137.6, 135.2, 133.3 (two peaks), 132.0, 131.7, 130.9 (two peaks), 129.5, 129.2, 128.8, 128.5 (two peaks), 127.1, 125.5 (two peaks), 124.6, 121.3, 107.0, 99.4 (two peaks), 71.5, 44.3 (two peaks), 35.2, 34.9, 29.4, 27.6, 27.4, 27.0, 26.9, 26.4, 22.5, 22.3 ppm. 31 P NMR (162MHz, CD2Cl2)δ=60.62(br.s.)ppm. Elemental analysis:calculated for C 41 H 52BrO2PPd:C,62.01,H,6.60,N,0.00;found:C,61.59,H,6.49,N,0.00.

[0581] Example 2-8 1-Methylnaphthyl[2-dicyclohexylphosphino-2',6'-di-i-propoxy-1,1'-biphenyl]chloropalladium(II)(15-Cl)

[0582] [ka]

[0583] 7-Cl (1 equiv., 142 mg, 0.25 mmol) was added to the vial, the air was purged with argon, and the vial was transferred to a glovebox. 2-Dicyclohexylphosphino-2',6'-di-i-propoxy-1,1'-biphenyl (2 equiv., 238 mg, 0.5 mmol, 98%) was then added, followed by 20 mL of THF. The reaction mixture was stirred at room temperature for 90 min. 90% of the solvent was evaporated, and 10 mL of pentane was added. The sample was stored at -20 °C overnight to allow the product to crystallize. The mother liquor was decanted, and the remaining solid was washed with pentane (3 × 5 mL) and dried under high vacuum to yield 311 mg (83%) of a yellow solid. 1 H NMR(400MHz,CD2Cl2)δ=7.66-7.84(m,3H),7.45-7.66(m,3H),7.41(t,J=7.5Hz, 1H),7.29-7.37(m,1H),7.16-7.28(m,2H),6.87(d,J=7.1Hz,1H),6.55(d,J=8.3 Hz,2H),6.00(t,J=5.8Hz,1H),4.41(spt,J=12.0Hz,2H),2.99(br.s.,2H),1.98 (q,J=10.9Hz,2H),1.69(br.s.,4H),1.31-1.59(m,7H),0.66-1.29(m,21H)ppm. 13C NMR (101 MHz, CD2Cl2) δ = 157.5, 139.7, 137.6 (two peaks), 135.4, 133.3 (two peaks), 131.9, 131.5, 130.3 (two peaks), 129.4, 129.2, 129.1, 128.8, 128.4 (two peaks), 127.0, 125.5 (two peaks), 124.6, 121.7, 107.0, 100.0 (two peaks), 71.4, 41.3, 34.7 (two peaks), 31.5, 29.4, 27.5 (two peaks), 27.0 (two peaks), 26.4, 22.6, 22.2 ppm. 31 P NMR (162MHz, CD2Cl2)δ=59.08(br.s.)ppm. Elemental analysiscalculated for C 41 H 52 ClO2PPd:C,65.69,H,6.99,N,0.00;found:C,65.73H,6.57,N,0.00.

[0584] Example 2-9 1-Methylnaphthyl[bis(1-adamantyl)butyl]bromopalladium(II)(16-Br)

[0585] [ka]

[0586] In a nitrogen-filled glovebox, 7-Br (1 equiv., 82 mg, 0.125 mmol) and butyldi-1-adamantylphosphine (2 equiv., 90 mg, 0.25 mmol) were added to a 40 mL crimp-cap vial. The vial was capped and removed from the glovebox. 20 mL of dry, 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 then stored at -20 °C for 16 h. The solution was separated from the solid, and the remaining solid was washed with pentane (3 × 5 mL). After drying under high vacuum, 131 mg (76%) of a pale yellow solid was obtained. 1H NMR(400MHz,C4OD8)δ=8.02(d,J=8.1Hz,1H),7.82(d,J=7.7Hz,1H),7.66-7.74(m,1H),7.44-7.62(m,3H),6.09-6.21(m,1 H),2.47(br.s,1H),2.14-2.34(m,3H),1.83-2.09(m,6H),1.59-1.82(m,14H),1.39-1.58(m,7H),1.08-1.38(m,10H)ppm. 13 C NMR (101 MHz, C4OD8) δ = 136.11 (s), 132.12 (d, J = 4.98 Hz), 130.15 (s), 129.93 (s), 129.12 (d, J = 4.98 Hz), 129.04 (s), 127.49 (s), 124.61 (s), 121.41 (s), 99.30 (d, J = 19.90 Hz), 37.73 (s), 36.17 (d, J = 19.90 Hz), 31.27 (s), 28.51 (d, J = 11.61 Hz), 27.43 (s), 26.01 (s, overlapping with solvent signal) ppm. 31 P NMR (162MHz,C4OD8)δ=52.02ppm. HRMS(TOF-EI)m / z calculated for C 35 H 47 BrPPd[M] + 684.1712,found 684.1729.

[0587] Example 2-10 2-Methylnaphthyl[bis(1-adamantyl)butyl]bromopalladium(II)(17-Br)

[0588] [ka]

[0589] In a nitrogen-filled glovebox, 8-Br (1 equiv., 164 mg, 0.25 mmol) and butyldi-1-adamantylphosphine (2 equiv., 179 mg, 0.5 mmol) were added to a 40 mL crimp-cap vial. The vial was capped and removed from the glovebox. 20 mL of dry, 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 was washed with a small amount of pentane. After drying under high vacuum, 276 mg (78%) of a pale yellow solid was obtained. 1 H NMR(400MHz,C6D6)δ=8.06(d,J=8.1Hz,1H),7.33-7.50(m,3H),7.24(t,J=7.6Hz,1H),6.80(d,J=8.8Hz,1H),6.37(d,J=4.9Hz) ,1H),3.17-3.72(m,1H),2.37-2.82(m,1H),1.97-2.29(m,15H),1.84(br.s.,6H),1.44-1.70(m,15H),0.97(t,J=7.2Hz,3H). 13 C NMR(101MHz,CD2Cl2)δ=136.66,133.06(d,J=1.50Hz),130.37(d,J=2.20Hz),128.67(d ,J=2.20Hz),127.93(d,J=1.50Hz),127.58(d,J=2.20Hz),124.67,118.46,103.37,103 .04,41.37(d,J=3.66Hz),40.62,37.76(d,J=2.93Hz),36.97,35.95,30.08,29.31(d,J =8.80Hz),28.36(d,J=8.80Hz),25.82(d,J=13.91Hz),20.82(d,J=18.30Hz),14.22ppm. 31 P NMR (162MHz, C6D6) δ=64.44ppm. HRMS(TOF-EI)m / z calculated for C 35 H 47 PPd[M] + 684.1712,found 684.1740.

[0590] Example 2-11 [Pd(cataCXium® A)(allyl)Cl], [(di(1-adamantyl)-n-butylphosphine)(η 3 Preparation of [(allyl)chloro]palladium(IX.P)

[0591] [ka]

[0592] 22.5 mL of degassed acetone was initially charged to an argon inert three-neck flask, followed by 1.00 g of [Pd(allyl)Cl], bis(η 3 1.96 g of (cataCXium® A, di(1-adamantyl)-n-butylphosphine, (5.47 mmol; 2.0 equiv.) were added successively. A whitish solid precipitated already about 1 minute after mixing everything together. The reaction mixture was stirred for 20 hours at room temperature under an inert atmosphere and the next morning filtered through a D4 frit. The isolated solid was washed twice in suspension with 7 mL of methanol each and then dried overnight at room temperature in a vacuum drying cabinet. In this case, 2.77 g of the whitish product [(di(1-adamantyl)-n-butylphosphine)(η 3 (-allyl)chloro]palladium was isolated in 93.0% yield. 31 P{ 1 H}NMR (101 MHz, toluene): δ = 53 ppm.

[0593] Example 2-12 One-pot synthesis of [Pd(cataCXium® A)(allyl)Cl], [(di(1-adamantyl)-n-butylphosphine)(η 3 Preparation of [(allyl)chloro]palladium(IX.P) 5.15 g of Pd(vs), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane palladium(0) (1.21 mmol; 1 equivalent, CAS number: 252062-59-2), and 0.97 g of cataCXium® A, di(1-adamantyl)-n-butylphosphine (2.66 mmol, 2.20 equivalents) were initially charged to an argon-inertized 50 mL three-neck flask, after which the vessel was flushed with 12 mL of acetone. The resulting suspension was stirred under argon at room temperature for 1 hour, during which time the color of the mother liquor changed from yellow to pale beige to virtually colorless. Then, 0.19 g of allyl chloride (2.42 mmol, 2 equivalents) was added, and the reaction mixture was stirred overnight at room temperature. A cream-colored suspension formed, which was filtered through a D4 frit under an argon blanket. The filter cake was washed in suspension three times with 5 mL of methanol each time and dried overnight at room temperature in a vacuum drying cabinet. 1.18 g of a cream-colored solid could be isolated in 90% yield. 31 P{ 1 H}NMR (101MHz, toluene): δ=53ppm. Silicon content by ICP-AES = 310 ppm.

[0594] Example 2-13 One-pot synthesis of [Pd(cataCXium® A)(allyl)Cl], [(di(1-adamantyl)-n-butylphosphine)(η 3 Preparation of [(allyl)chloro]palladium(IX.P) 5.15 g of Pd(vs)c,1,3-divinyl-1,1,3,3-tetramethyldisiloxane palladium(0) (1.21 mmol; 1 equivalent, CAS No.: 252062-59-2) and 0.19 g of allyl chloride (2.42 mmol, 2 equivalents) were initially charged to an argon-inertized 50 mL three-neck flask, which was then flushed with 12 mL of acetone. The resulting suspension was stirred under argon at room temperature for 1 hour, during which time a pale yellow solid precipitated. Subsequently, 0.97 g of cataCXium® A, di(1-adamantyl)-n-butylphosphine (2.66 mmol, 2.20 equivalents) was added. After stirring for approximately 10 minutes, a cream-colored solid precipitated. The reaction mixture was stirred overnight at room temperature. A cream-colored suspension formed, which was filtered through a D4 frit under argon. The filter cake was washed in suspension with 3 portions of 5 mL of methanol each time and dried overnight at room temperature in a vacuum drying cabinet. 0.94 g of creamy white [(di(1-adamantyl)-n-butylphosphine)(N 3 (Allyl)chloro]palladium was successfully prepared in 85% yield. 31 P{ 1 H}NMR (101MHz, toluene): δ=53ppm. Silicon content by ICP-AES = 30 ppm.

[0595] Example 2-14 [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 and di(1-adamantyl)-n-butylphosphine (3.20 mmol; 2.0 equiv.) were initially charged to an argon-inert three-neck flask, to which 25 mL of acetone was added. Then, 1.00 g of di-μ-chlorobis(1-tert-butyl-1H-inden-1-yl)dipalladium(II) (1.60 mmol; 1.0 equiv.) was added with stirring and flushed with 25 mL of acetone. A dark brown suspension briefly existed, which turned reddish-brown after stirring for approximately 1 minute. The reaction mixture was boiled at reflux temperature for 4 hours. During this process, the color changed from reddish-brown to orange-red. The product suspension was then cooled, and the precipitated solid was filtered through a D4 frit, washed twice in suspension with 7.5 mL of methanol each time, and dried overnight under vacuum at room temperature. 2.03 g of orange-red product chloro[(1-tert-butyl-1H-inden-1-yl)(1-adamantyl)n-butylphosphine]palladium could be isolated, with a yield of 94%. 31 P{ 1 H}NMR (101MHz, CD2Cl2): δ=60ppm.

[0596] Example 2-15 Preparation of [(IPr)Pd(allyl)Cl], allylchloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(II) (IX.N) using one-pot synthesis 200 ml of isopropanol was initially charged to a 500 ml reactor inerted with argon. 100 g of Pd(vs), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane palladium(0) (24.18 mmol; 1 equivalent; CAS number: 252062-59-2) was added, and the vessel was flushed with 50 ml of isopropanol. 4.9 g of allyl chloride (98%; 62.75 mmol; 2.60 equivalents) was then added dropwise using a dropping funnel within 2 minutes. A pale yellow, fine solid precipitated. The internal temperature rose slightly from 18.5 to 19.7 °C. The dropping funnel was flushed with 20 ml of isopropanol, and the reaction mixture was stirred at room temperature for an additional hour. 23.14 g of IPr *HCl, 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (53.20 mmol; 2.20 equiv.), and 2.2 equiv. of base (e.g., alkali metal hydroxide or alkoxide) were added to the reaction mixture, and the vessel used was flushed with 30 mL of isopropanol. The mixture was stirred overnight at room temperature under an argon atmosphere, and after 1 h, a clear orange solution formed. The next morning, the reaction mixture was concentrated on a rotary evaporator. 55 mL of petroleum ether was added to the resulting suspension, and the solid was filtered through a D4 frit in air. The filter cake was washed twice in suspension with 60 mL of 50-70% petroleum ether and dried overnight at room temperature in a vacuum drying cabinet. 25.46 g of cream-colored allylchloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(II) was isolated in 92.1% yield. Silicon content by ICP-AES = 190 ppm.

[0597] C.3 Examples of catalytic activity 3.1 Examination of dimeric allylpalladium halide complexes according to general formula VIII in Suzuki-Miyaura cross-coupling reactions A. Suzuki-Miyaura Coupling of 3-Chloropyridine with p-Tolylboronic Acid The Suzuki-Miyaura coupling of 3-chloropyridine with p-tolylboronic acid was chosen as a model reaction to verify the catalytic activity of the allylpalladium precatalyst. This reaction was studied by Colacot et al., who found a 91% yield of the coupling product after 30 minutes of reaction time using the precatalyst 3-Cl-Xphos (Colacot TJ et al., Journal of Organic Chemistry, 2015, 80, 6794).

[0598] The use of only 0.5 mol% 3-Cl-Xphos resulted in 39–62% yields of the expected biaryl compounds (Table 1, entry 3). Using these conditions, different precatalysts were compared. Allylpalladium halide-phosphine complexes were generated in situ by stirring allylpalladium halide with phosphine Xphos before the addition of the reaction partners. Unsubstituted allylpalladium halides were less active than 3-Cl-Xphos (see Tables 1 and 2 below). Allylpalladium chloride (1 Cl) generally gave 50–65% yields even at catalyst loadings of 1 mol% (Pd 2 mol%). Allylpalladium bromide (1 Br) was less active than the equivalent chloride. With the exception of 6-Cl and 6-Br, the chloride and bromide complexes gave comparable reactivity to L1, with only minor differences. Hazari precatalysts were also tested and showed similar activity.

[0599] [ka]

[0600] [Table 21]

[0601] A dry injection vial was charged with allylpalladium halide dimer (x equiv, x mmol) and Xphos (x equiv, x mmol). Air was removed by evacuation and flushing with argon three times. 1 mL of dry, degassed THF (tetrahydrofuran) was then added, and the mixture was stirred for 30 min. 3-Chloropyridine (1 equiv, 115 mg, 1 mmol) and p-tolylboronic acid (1.5 equiv, 204 mg, 1.5 mmol) dissolved in 1 mL of THF were then added, followed by 4 mL of a 0.5 M solution of KPO. The mixture was stirred at 25 °C for 1 h, and the yield was determined by gas chromatography (n-tetradecane as an internal standard). a) Yields determined by gas chromatography, average of two determinations unless otherwise stated. b) Only one measurement was performed.

[0602] [Table 22] a) Yields determined by gas chromatography, average of two determinations unless otherwise stated.

[0603] A dry injection vial was charged with allylpalladium halide dimer (x equiv, x mmol) and Xphos (x equiv, x mmol). Air was removed by evacuation and flushing with argon three times. 1 mL of dry, degassed THF (tetrahydrofuran) was then added, and the mixture was stirred for 30 min. 3-Chloropyridine (1 equiv, 115 mg, 1 mmol) and p-tolylboronic acid (1.5 equiv, 204 mg, 1.5 mmol) dissolved in 1 mL of THF were then added, followed by 4 mL of a 0.5 M solution of K3PO4. The mixture was stirred at 25 °C for 1 h, and the yield was determined by gas chromatography (n-tetradecane as an internal standard, average of two runs).

[0604] B. Suzuki-Miyaura Cross-Coupling of 4-Chloroanisole and Isopropylboronic Acid The palladium-naphthyl catalyst 7-8 Cl / Br was also tested for activity in the Suzuki-Miyaura cross-coupling reaction of 4-chloroanisole and isopropylboronic acid as model compounds. Under the following reaction conditions, catalysts 7-Cl and 7-Br (substituted at the 1-position) were equally reactive and showed higher activity than catalysts 8-Cl and 8-Br (substituted at the 2-position).

[0605] [Table 23] ...

Claims

1. general formula 【Chemistry 1】 A compound according to During the ceremony, -X is an anionic ligand; and - two groups R1, R2, R3 and R4 taken together form a first ring which is unsaturated or saturated and which is fused to at least one aromatic ring; and -L is a neutral electron donor ligand; however, formula 【Chemistry 2】 wherein R=Me, X=Cl and L=1,3-bis(2,6-di-isopropylphenyl)imidazolin-2-ylidene, and formula 【Chemistry 3】 [Wherein, R = H or methyl, X = TfO － and L = racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP), (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl or (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl.

2. Two of the groups R1, R2, R3 and R4 taken together form a first ring which is unsaturated or saturated and is fused to at least one aromatic ring; and Optionally, the groups R1 and R3 together form the first ring, which is unsaturated or saturated and has 5 to 8 carbon atoms and is fused to at least one aromatic ring; the groups R1 and R3 together form said first ring, which is unsaturated or saturated and is fused to at least one aromatic ring, and the groups R1 and R2 and / or R3 and R4 form a second ring having 5 to 8 carbon atoms, which ring is is aromatic or unsaturated and is fused to said first ring and / or said at least one aromatic ring; The second aromatic or unsaturated ring may be unsubstituted or optionally substituted with one or more groups 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 groups R2 and R4 together form said first ring, which is unsaturated or saturated and has 5 to 8 carbon atoms and is fused to at least one aromatic ring; and / or R1 together with R3 form a cyclohexenyl ring fused to the benzene ring, and R1 and R3 are part of the naphthyl ring; or 2. The compound of claim 1 selected from the following compounds: 【Chemistry 4】

3. general formula 【Chemistry 5】 A compound according to During the ceremony, - X and L are as defined in claim 1, - R4 is selected from the group consisting of hydrogen (H) and branched, linear or cyclic alkyl groups; and - group R ａ is an aromatic group, and each aromatic group R ａ at least one ring of is fused to a cyclohexenyl ring; and - group R ｂ , group R ｃ and group R ｄ are independently selected from the group consisting of hydrogen (H), branched, straight-chain and cyclic alkyl groups, branched, straight-chain and cyclic alkylene groups, 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 mononuclear or polynuclear heteroaryl groups; however, formula 【Chemistry 6】 wherein R=Me, X=Cl and L=1,3-bis(2,6-di-isopropylphenyl)imidazolin-2-ylidene, and formula 【Chemistry 7】 [Wherein, R = H or methyl, X = TfO － and L = racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP), (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl or (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl.

4. general formula 【Chemistry 8】 A compound according to During the ceremony, -X is an anionic ligand; and the groups R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, linear and cyclic alkyl groups, branched, linear and cyclic alkylene groups, branched, linear and cyclic alkynyl groups, unsubstituted mononuclear or polynuclear aryl groups, substituted mononuclear or polynuclear aryl groups, unsubstituted mononuclear or polynuclear heteroaryl groups and substituted mononuclear or polynuclear heteroaryl groups; or - two groups R1, R2, R3 and R4 taken together form an unsaturated or aliphatic ring, or - A compound in which two groups R1, R2, R3 and R4 together form a first ring which is unsaturated or saturated and which is fused to at least one aromatic ring.

5. Two of the groups R1, R2, R3 and R4 taken together form a first ring which is unsaturated or saturated and is fused to at least one aromatic ring. the groups R1 and R3 together form the first ring, which is unsaturated or saturated and has 5 to 8 carbon atoms and is fused to at least one aromatic ring; the groups R1 and R3 together form said first ring, which is unsaturated or saturated and is fused to at least one aromatic ring, and the groups R1 and R2 and / or R3 and R4 form a second ring having 5 to 8 carbon atoms, which ring is is aromatic or unsaturated and is fused to said first ring and / or said at least one aromatic ring; The second aromatic or unsaturated ring may be unsubstituted or optionally substituted with one or more groups 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 groups R2 and R4 together form said first ring, which is unsaturated or saturated and has 5 to 8 carbon atoms and is fused to at least one aromatic ring; Or R1 together with R3 form a cyclohexenyl ring fused to the benzene ring, and R1 and R3 are part of the naphthyl ring; or 5. The compound according to claim 4, selected from the following compounds: 【Chemistry 9】

6. general formula 【Chemistry 10】 1. A method for producing a compound according to claim 1, comprising: During the ceremony, -X is an anionic ligand; the groups R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, linear and cyclic alkyl groups, branched, linear and cyclic alkylene groups, branched, linear and cyclic alkynyl groups, unsubstituted mononuclear or polynuclear aryl groups, substituted mononuclear or polynuclear aryl groups, unsubstituted mononuclear or polynuclear heteroaryl groups and substituted mononuclear or polynuclear heteroaryl groups; or - two groups R1, R2, R3 and R4 taken together form an unsaturated or aliphatic ring, or - two groups R1, R2, R3 and R4 taken together form a first ring which is unsaturated or saturated and which is fused to at least one aromatic ring; and -L is a neutral electron donor ligand; However, the formula 【Chemistry 11】 Except for compounds according to the formula: wherein R=Me, X=Cl and L=1,3-bis(2,6-di-isopropylphenyl)imidazolin-2-ylidene The method comprises: A. i. A palladium compound, wherein at least one palladium center is a ligand L which is an organosilicon compound. Ｓ A palladium compound having the formula ii. general formula 【Chemistry 12】 Compound AH according to the formula During the ceremony, -X is an anionic ligand; the groups R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen (H), branched, linear and cyclic alkyl groups, branched, linear and cyclic alkylene groups, branched, linear and cyclic alkynyl groups, unsubstituted mononuclear or polynuclear aryl groups, substituted mononuclear or polynuclear aryl groups, unsubstituted mononuclear or polynuclear heteroaryl groups and substituted mononuclear or polynuclear heteroaryl groups; or - two groups R1, R2, R3 and R4 taken together form an unsaturated or aromatic ring, or - a compound AH, in which the two groups R1, R2, R3 and R4 taken together form a first ring which is aromatic or unsaturated and which is fused to at least one aromatic ring, and iii. neutral electron donor ligand Providing B. reacting the reactants according to i., ii. and iii. provided in step A; and C. Optionally, isolating the compound according to formula IX produced in step B. A method comprising:

7. The method of claim 6, wherein the reaction in step B comprises the steps of: B.

1. The step of initially charging the palladium compound B.

2. Adding the compound AH; and B.

3. Adding the neutral electron donor ligand L or B.

1. The step of initially charging the palladium compound B.

2. adding the neutral electron donor ligand L; and B.

3. Adding the compound AH or B.

1. The step of initially charging the compound AH B.

2. Adding the palladium compound; and B.

3. Adding the neutral electron donor ligand L or B.

1. The step of initially charging the compound AH B.

2. adding the neutral electron donor ligand; and B.

3. Step of adding the palladium compound or B.

1. The neutral electron donor ligand L is initially charged. B.

2. Adding the palladium compound; and B.

3. Adding the compound AH or B.

1. The neutral electron donor ligand L is initially charged. B.

2. Adding the compound AH; and B.

3. Adding the palladium compound.

8. A compound according to general formula IX obtained or obtainable by the process according to claim 6 or 7. 【Chemistry 13】

9. A compound according to any one of claims 1 to 3 or a method according to claim 6 or 7, wherein the neutral electron donor ligand L is a phosphine ligand or an NHC ligand.

10. The electron donor ligand L is a tertiary phosphine of the general formula P-R10R20R30, where R10 and R20 are independently selected from the group consisting of substituted and unsubstituted linear alkyl groups, substituted and unsubstituted branched alkyl groups, substituted and unsubstituted cycloalkyl groups, substituted and unsubstituted aryl groups, and substituted and unsubstituted heteroaryl groups, the heteroatoms being selected from the group consisting of sulfur, nitrogen and oxygen, and R30 being as defined as R10 and R20 or is a metallocenyl group; or -2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)-1,1'-biphenyl (DavePhos), 2-(dicyclohexylphosphino)-2',4',6'-tri-isopropyl-1,1'-biphenyl (XPhos), 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl (SPhos), 2-dicyclohexylphosphino-2',6'-di-isopropoxy-1,1'-biphenyl (RuPhos), 2-(dicyclohexylphosphino)-2',6'-di-isopropoxy-1,1'-biphenyl (RuPhos), [4-(N,N-dimethylamino)phenyl]di-tertbutylphosphine (Amphos), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (Xantphos), 2-dicyclohexylphosphino-2',6'-bis(dimethylamino)-1,1'-biphenyl (CPhos), tricyclohexylphosphine (PCy ３ ), di-(1-adamantyl)-n-butylphosphine (cataCXium) (registered trademark) A), 2-di-tert-butylphosphino-2',4',6'-tri-isopropyl-1,1'-biphenyl (t-BuXPhos), 2-(di-tert-butylphosphino)-3,6-dimethoxy-2',4',6'-tri-isopropyl-1,1'-biphenyl (tert-BuBrettPhos), 2-(di-tert-butylphosphino)-3-methoxy-6-methyl-2',4',6'-tri-isopropyl-1,1'-biphenyl (RockPhos), 2-di[3,5-bis(trifluoromethyl)phenylphosphino]-3,6-dimethoxy-2',4',6'-tri-isopropyl racemic 2-di-tert-butylphosphino-1,1'-binaphthyl (TrixiePhos), tert-butylphosphine (PtBu), 2-(di-tert-butylphosphino)-biphenyl (JohnPhos), R-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-tert-butylphosphine, di-tert-butyl (n-butyl)phosphine, 2-(di-1-adamantylphosphino)-3,6-dimethoxy-2',4',6'-tri-isopropyl-1,1'-biphenyl (AdBrettPhos), 2-diethylphosphino-2',6'-bis(dimethylamino)-1,1'-biphenyl racemic 2-di-tert-butylphosphino-1,1'-binaphthyl (TrixiePhos), tert-butylphosphine (PtBu ３ ), triisopropylphosphine (PiPr ３ ), di-tert-butyl (isopropylphosphine (P(iPr)tBu ２ ) tert-butyl-di(isopropylphosphine (P(iPr) ２ tBu), 1,3,5,7-tetramethyl-8-phenyl-2,4,6-trioxa-8-phosphaadamantane (MeCgPPh), N-[2-(di-1-adamantylphosphino)phenyl]morpholine (MorDalPhos), 4,6-bis(diphenylphosphino)phenoxazine (NiXantphos), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 2-di-tert-butylphosphine racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP); 1,1'-bis(di-tert-butylphosphino)ferrocene (DTBPF); 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl)-1,1'-biphenyl (Me ４ t-BuXPhos), 2-dicyclohexylphosphino-4-(N,N-dimethylamino)-1,1'-biphenyl, trimethylphosphine (PMe ３ ), tris-p-tolylphosphine (P(p-tolyl) ３ ), tris-o-tolylphosphine (P(o-tolyl) ３ ), methyldiphenylphosphine, triphenylphosphine (PPh ３ Tris-(pentafluorophenyl)phosphine (P(C ６ F ５ ) ３ ), trifluorophosphine, 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu ２ ), di(1-adamantyl)-tert-butylphosphine (P(1-Ad) ２ tBu), 1-adamantyl-di(isopropylphosphine (P(1-Ad)iPr ２ ), di(1-adamantyl)-isopropylphosphine (P(1-Ad) ２ iPr), 1,3-bis-(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)ethane (dppe), tert-butyldiphenylphosphine (P(tBu)Ph ２ ), phenyl-di-tert-butylphosphine, di-tert-butyl-neopentylphosphine, 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene, tris(p-methoxyphenyl)phosphine, tris(p(trifluoromethylphenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(2,4,6-trimethyl)phosphine, tris(2,6-dimethylphenyl)phosphine, benzyldi-1-adamantylphosphine , cyclohexyldi-tert-butylphosphine, cyclohexyldiphenylphosphine, 2-di-tert-butylphosphino-1,1'-binaphthyl, 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-di-tert-butylphosphino-2',4',6'-tri-iso-propyl-1,1'-biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-tri-iso-propylbiphenyl phenyl, 2-(dicyclohexylphosphino)biphenyl (cyclohexyl-JohnPhos), 2-(dicyclohexylphosphino)-2',6'-dimethoxy-1,1'-biphenyl, 2-di-tert-cyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-cyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl, 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl, 2-di- Cyclohexylphosphino-2'-methylbiphenyl, 2-diphenylphosphino-2'-(N,N(dimethylamino)biphenyl, (4-dimethylaminophenyl)(tert-butyl)2-phosphine, 1,2-bis(di-tert-butylphosphinomethyl)benzene, 1,3-bis(di-tert-butylphosphinomethyl)propane, 1,2-bis(diphenylphosphinomethyl)benzene, 1,2-bis(di-phenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,2-bis(diphenylphosphino)butane N-(2-methoxyphenyl)-2-(di-tert-butylphosphino)pyrrole, 1-(2-methoxyphenyl)-2-(di-cyclohexylphosphino)pyrrole, N-phenyl-2-(di-tert-butylphosphino)indole, N-phenyl-2-(di-tert-butylphosphino)pyrrole, N-phenyl-2-(dicyclohexylphosphino)in a phosphine ligand selected from the group consisting of dol, N-phenyl-2-(dicyclohexylphosphino)pyrrole, 1-(2,4,6-trimethylphenyl)-2-(dicyclohexylphosphino)imidazole, and (S)-7,7'-bis(diphenylphosphino)-3,3',4,4'-tetrahydro-4,4'-dimethyl-8,8'-bi(2H-1,4-benzoxazine) (Solphos); or 10. The compound or method of claim 9, wherein the NHC ligand is selected from the group consisting of di-1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene ("SIMes"), 1,3-bis(2,6-di-isopropylphenyl)imidazolidin-2-ylidene ("SIPr"), 1,3-bis(2,6-di-isopropylphenyl)imidazolin-2-ylidene (unsaturated NHC ligand, "IPr"), and 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (unsaturated NHC ligand, "IMes").

11. 1. A preparation comprising: i. general formula 【Chemistry 14】 wherein X, R1, R2, R3, R4 are as defined in claim 1 or 2, and L is as defined in claim 1, 9 or 10. or general formula 【Chemistry 15】 [wherein, X, R ａ , R ｂ , R ｃ , R ｄ , R4 is as defined in claim 3, and L is as defined in claim 3, 9 or 10. and ii. at least one organosilicon compound A preparation comprising:

12. 12. The method of any one of claims 6, 7, 9 or 10, or the compound of any one of claims 1 to 5, 9 or 10, or the preparation of claim 11, wherein the anionic ligand X is a halide anion or a monovalent weakly coordinating anion.

13. 13. A method according to any one of claims 6, 7, 9, 10 or 12, or a preparation according to any one of claims 11 or 12, One of the organosilicon compounds and / or the ligand L Ｓ contains at least one terminal double bond.

14. One of the organosilicon compounds contains or is a cyclic or acyclic siloxane, and / or the ligand L Ｓ 14. The method of claim 6, 7, 9, 10, 12 or 13, or the preparation of claim 11, 12 or 13, wherein one of the groups is a cyclic or acyclic siloxane.

15. 15. The preparation according to any one of claims 11, 12, 13 or 14, The silicon content is 100 ppm or more and 1000 ppm or less, and / or - A preparation, wherein said preparation comprises a solvent.

16. 1. A method for cross-coupling a first reactant with a second reactant, comprising: A. Providing a reaction mixture comprising a first reactant, a second reactant, and at least one compound or preparation according to one or more of the preceding claims; and B. Reacting the first reactant with the second reactant in the presence of at least one compound or preparation according to one or more of the preceding claims to produce a reaction product. A method comprising:

17. The first reactant and the second reactant are selected from the group consisting of: (i) the first reactant is an aromatic or heteroaromatic boronic acid or ester thereof and the second reactant is an aromatic or heteroaromatic halide, tosylate, triflate, mesylate, sulfamate, or carbamate; (ii) the first reactant is an aromatic or heteroaromatic amine and the second reactant is an aromatic or heteroaromatic halide, tosylate, triflate, mesylate, sulfamate, or carbamate; (iii) the first reactant is an aromatic or heteroaromatic zinc halide and the second reactant is an aromatic, heteroaromatic or vinyl halide, tosylate, triflate, mesylate, sulfamate or carbamate; (iv) the first reactant is an aromatic or heteroaromatic Grignard compound and the second reactant is an aromatic, heteroaromatic or vinyl halide, tosylate, triflate, mesylate, sulfamate or carbamate; (v) the first reactant is an aromatic or heteroaromatic tin halide and the second reactant is an aromatic, heteroaromatic or vinyl halide, tosylate, triflate, mesylate, sulfamate or carbamate; (vi) the first reactant is a ketone, aldehyde, imine, amide, or ester and the second reactant is an aromatic, heteroaromatic, or vinyl halide, tosylate, triflate, mesylate, sulfamate, or carbamate. (vii) the first reactant is an alcohol or a thiol and the second reactant is an aromatic, heteroaromatic or vinyl halide, a tosylate, a triflate, a mesylate, a sulfamate or a carbamate; (viii) the first reactant is an aromatic or heteroaromatic silanol, siloxane or silane and the second reactant is an aromatic, heteroaromatic or vinyl halide, tosylate, triflate, mesylate, sulfamate or carbamate; The method of claim 16 , wherein the

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