complexes

Abstract

A compound of formula (I) wherein M is Pd(II) or Ni(II); X is a halide; R1 and R2 are independently organic radicals having 1 to 20 carbon atoms, or R1 and R2 are linked to the phosphorus atom to form a ring structure; R3 is an organic radical having 1 to 20 carbon atoms; provided that R1, R2, R3 are not all phenyl.

Description

Technical Field

[0001] This invention relates to transition metal complexes, and more particularly to metal(II) dimer complexes. The invention further relates to methods for preparing these complexes and their use in catalyzing cross-coupling reactions. Background Technology

[0002] Palladium(II) complexes containing phosphine ligands are known as active catalysts for cross-coupling reactions. For example, catalysts PdCl2(AmPhos)2, AmPhosPd(crotonyl)Cl, XPhosPd(crotonyl)Cl, RuPhosPd(crotonyl)Cl, and [BrettPhosPd(crotonyl)]OTf are commercially available from Johnson Matthey PLC.

[0003] It is also known that palladium(II) dimers can be used in certain cross-coupling reactions. For example, Naghhipour et al. (Polyhedron, Vol. 105, 2016, pp. 18-26) indicated that [Pd2Br6][Ph3PCH2C6H4CH2OC(O)CH3]2 can be used in the Stille cross-coupling reaction. Evans et al. (J. Chem. Soc., Dalton Trans., 2002, pp. 2207-2212) disclosed the in-situ formation of [Pd2I6][NEt3H]2 and its use as a pre-catalyst.

[0004] The inventors have developed alternative palladium(II) complexes with a simple preparation route using more environmentally friendly solvents. Summary of the Invention

[0005] This invention provides a compound of formula (I).

[0006]

[0007] in:

[0008] M is either Pd(II) or Ni(II);

[0009] X is a halide ion;

[0010] R1 and R2 are organic groups having 1 to 20 carbon atoms independently, or R1 and R2 are linked with phosphorus atoms to form a ring structure;

[0011] R3 is an organic group having 1 to 20 carbon atoms;

[0012] The prerequisite is that R1, R2, and R3 are not all phenyl groups.

[0013] The present invention also provides a method for preparing compounds of formula (IA).

[0014] [M2Cl6][HPR1R2R-3]2 (IA)

[0015] Where M, R1, R2, and R3 are as defined above, the method includes the step of reacting a compound of the formula H2PdCl4 with ligands PR1R2R3 or their salts.

[0016] The present invention also provides a method for preparing (IB) compounds.

[0017] [M2X'6][HPR1R2R-3]2 (IB)

[0018] Where M, R1, R2, and R3 are as defined above and X' is a bromide ion, an iodide ion, or a fluoride ion, the method includes the step of reacting a compound of the formula H2PdCl4 with ligands PR1R2R3 or their salts and compound ZX', wherein Z is hydrogen or a metal.

[0019] The present invention also provides a method for carrying out a carbon-carbon coupling reaction in the presence of a catalyst, the method comprising using a compound of formula (I) as defined above. Alternatively, the present invention provides the use of a compound of formula (I) as defined above for catalyzing a carbon-carbon coupling reaction.

[0020] The present invention also provides a method for carrying out carbon-heteroatom coupling reactions, the method comprising using a compound of formula (I) as defined above. Alternatively, the present invention provides the use of a compound of formula (I) as defined above for catalyzing carbon-heteroatom coupling reactions. Attached Figure Description

[0021] Figure 1 The crystal structure of [HSPhos]2[Pd2Br6] is shown.

[0022] Figure 2 The crystal structure of [HtBuXPhos]2[Pd2Cl6] is shown.

[0023] Figure 3 The crystal structure of [HPCy3]2[Pd2Cl6] is shown.

[0024] Figure 4 The crystal structure of [HP(2,4,6-trimethylphenyl)3]2[Pd2Cl6] is shown.

[0025] definition

[0026] The attachment point of a partial or substituent group is indicated by a "-". For example, -OH is attached via an oxygen atom.

[0027] "alkyl" refers to a straight-chain or branched saturated hydrocarbon group. In some embodiments, the alkyl group has 1 to 20 carbon atoms. In other embodiments, the alkyl group has 1 to 15 carbon atoms. In still other embodiments, the alkyl group has 1 to 8 carbon atoms. Unless otherwise stated, the alkyl group is attached at any suitable carbon atom. The alkyl group may be unsubstituted. Alternatively, the alkyl group may be substituted at any suitable carbon atom. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, etc.

[0028] "Alkoxy" refers to an optionally substituted group of the formula alkyl-O- or cycloalkyl-O-, wherein the alkyl and cycloalkyl are as defined herein.

[0029] "Alkoxyalkyl" refers to an optionally substituted group of the formula alkoxy-alkyl-, wherein the alkoxy and alkyl groups are as defined herein.

[0030] "Cycloalkyl" refers to a saturated carbocyclic hydrocarbon group. The cycloalkyl group may have a monocyclic or multiple fused rings. In some embodiments, the cycloalkyl group has 3-15 carbon atoms. In other embodiments, the cycloalkyl group has 3-10 carbon atoms. In still other embodiments, the cycloalkyl group has 6-10 carbon atoms. Unless otherwise stated, the cycloalkyl group is attached at any suitable carbon atom. The cycloalkyl group may be unsubstituted. Alternatively, the cycloalkyl group may be substituted at any suitable carbon atom. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0031] "Aryl" refers to an aromatic carbocyclic group. An aryl group can have a monocyclic or multiple fused rings. In some embodiments, the aryl group has 6-20 carbon atoms. In other embodiments, the aryl group has 6-15 carbon atoms. In still other embodiments, the aryl group has 6-12 carbon atoms. Unless otherwise stated, the aryl group is attached at any suitable carbon atom. The aryl group can be unsubstituted. Alternatively, the aryl group can be substituted at any suitable carbon atom. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracene, etc.

[0032] "Arylalkyl" refers to an optionally substituted group of the formula aryl-alkyl-, wherein the aryl and alkyl groups are as defined herein.

[0033] "Coupling" refers to a chemical reaction in which two molecules or parts of a molecule come together (Oxford Chemical Dictionary, 6th Edition, 2008).

[0034] "Halogen", "halogen", or "halogen ion" refers to –F, –Cl, –Br, and –I.

[0035] "Heteroalkyl" means an alkyl group in which one or more carbon atoms are independently replaced by one or more heteroatoms (e.g., nitrogen, oxygen, phosphorus, and / or sulfur atoms) (wherein the alkyl group is as defined herein). Unless otherwise stated, the heteroalkyl group is attached at any suitable atom. The heteroalkyl group may be unsubstituted. Alternatively, the heteroalkyl group may be substituted at any suitable atom. Examples of heteroalkyl groups include, but are not limited to, ethers, thioethers, primary amines, secondary amines, tertiary amines, etc.

[0036] "Heterocyclic alkyl" refers to a cycloalkyl group in which one or more carbon atoms are independently substituted by one or more heteroatoms (e.g., nitrogen, oxygen, phosphorus, and / or sulfur atoms) (wherein the cycloalkyl group is as defined herein). Unless otherwise stated, the heterocyclic alkyl group is attached at any suitable atom. The heterocyclic alkyl group may be unsubstituted. Alternatively, the heterocyclic alkyl group may be substituted at any suitable atom. Examples of heterocyclic alkyl groups include, but are not limited to, epoxides, morpholino, piperidinyl, piperazine, thiopropylcycloyl, pyrrolidinyl, pyrazolyl, imidazoalkyl, thiazoalkyl, thiomorpholino, etc.

[0037] "Heteroaryl" refers to an aryl group in which one or more carbon atoms are independently replaced by one or more heteroatoms (e.g., nitrogen, oxygen, phosphorus, and / or sulfur atoms) (wherein the aryl group is as defined herein). Unless otherwise stated, the heteroaryl group is attached at any suitable atom. The heteroaryl group can be unsubstituted. Alternatively, the heteroaryl group can be substituted at any suitable atom. Examples of heteroaryl groups include, but are not limited to, thiophene, furanyl, pyrrole, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, phenylthio, oxadiazolyl, pyridinyl, pyrimidinyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, quinolinyl, etc.

[0038] "Metallocene group" refers to a transition metal complex group in which a transition metal atom or ion is "sandwiched" between two atomic rings. The metallocene group can be unsubstituted or substituted. Unless otherwise specified, the metallocene group can be attached at any suitable atom and, if substituted, can be substituted at any suitable atom. Examples of transition metal atoms or ions include, but are not limited to, chromium, manganese, cobalt, ruthenium, osmium, nickel, and iron. Any example of a suitable atomic ring is a cyclopentadienyl ring. Examples of metallocene groups include, but are not limited to, ferrocene groups comprising Fe(II) ions sandwiched between two cyclopentadienyl rings, wherein each cyclopentadienyl ring can be independently unsubstituted or substituted.

[0039] "Substituted" means a group in which one or more hydrogen atoms are each independently replaced by a substituent (e.g., 1, 2, 3, 4, 5 or more), which may be the same or different. Unless the context otherwise requires, all groups defined above and mentioned below may be unsubstituted or substituted, where substitution is possible. Detailed Implementation

[0040] Preferred and / or optional features of the invention will now be described. Unless the context otherwise requires, any aspect of the invention may be combined with any other aspect of the invention. Unless the context otherwise requires, any preferred or optional feature of any aspect may be combined with any aspect of the invention, alone or in combination.

[0041] This invention provides a compound of formula (I).

[0042]

[0043] in:

[0044] M is either Pd(II) or Ni(II);

[0045] X is a halide ion;

[0046] R1 and R2 are organic groups having 1 to 20 carbon atoms independently, or R1 and R2 are linked with phosphorus atoms to form a ring structure;

[0047] R3 is an organic group having 1 to 20 carbon atoms;

[0048] The prerequisite is that R1, R2, and R3 are not all phenyl groups.

[0049] Preferably, M is Pd.

[0050] X is suitably Cl, Br, or I; more suitably Cl or Br.

[0051] In one implementation, R1 and R2 are the same.

[0052] In an alternative implementation, R1 and R2 are different.

[0053] In one embodiment of the invention, R1 and R2 are linked to the P atoms to which they are attached to form a ring structure. Suitably, the ring structure is a 4-membered to a 7-membered ring.

[0054] Suitablely, R1 and R2 are independently selected from alkyl, cycloalkyl, aryl and heteroaryl groups, wherein the heteroatom is independently selected from sulfur, nitrogen and oxygen.

[0055] More appropriately, R1 and R2 are independently selected from alkyl, cycloalkyl and aryl groups.

[0056] Examples of suitable alkyl groups for R1 or R2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (e.g., n-pentyl or neopentyl), hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or stearyl (all unsubstituted or substituted).

[0057] Examples of suitable cycloalkyl groups for R1 or R2 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or adamantyl (all unsubstituted or substituted). Examples of suitable aryl groups for R1 or R2 include phenyl, naphthyl, or anthracene (all unsubstituted or substituted).

[0058] Examples of suitable heteroaryl groups for R1 or R2 include pyridinyl (whether unsubstituted or substituted).

[0059] Any alkyl or cycloalkyl group may be independently and optionally substituted by one or more (e.g., 1, 2, 3, 4, or 5) substituents, each of which may be the same or different. Suitable substituents include, but are not limited to, halide ions (F, Cl, Br, or I) or alkoxy groups (e.g., methoxy, ethoxy, or propoxy).

[0060] Any aryl or heteroaryl group may be independently and optionally substituted by one or more (e.g., 1, 2, 3, 4, or 5) substituents, each of which may be the same or different. Suitable substituents include, but are not limited to, halide ions (F, Cl, Br, or I), straight-chain or branched alkyl groups (e.g., C1-C1). 10 ), alkoxy groups (e.g., C1-C) 10 alkoxy), straight-chain or branched (dialkyl) amino (e.g., C1-C) 10 (dialkyl)amino), heterocyclic alkyl (e.g., C14) 3-10 Heterocyclic alkyl groups, such as morpholino and piperidinyl, or tri(halo)methyl (e.g., F3C-). Suitable substituted aryl groups include, but are not limited to, 2,4,6-trimethylphenyl and 2,6-dimethoxyphenyl.

[0061] Preferably, R1 and R2 are independently selected from n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (e.g., n-pentyl or neopentyl), hexyl, cyclopentyl, cyclohexyl, or adamantyl and phenyl, wherein each group may be unsubstituted or substituted, for example, by one or more substituents as mentioned above.

[0062] More preferably, R1 and R2 are independently selected from tert-butyl, n-butyl, cyclohexyl, adamantyl, 2,4,6-trimethylphenyl and 2,6-dimethoxyphenyl.

[0063] Suitablely, R3 is selected from alkyl, cycloalkyl, aryl, heteroaryl and metallocene groups.

[0064] Suitablely, R3 is selected from alkyl, cycloalkyl, aryl, and metallocene groups.

[0065] In a first aspect of the invention, R3 is an alkyl group.

[0066] The alkyl group is optionally substituted by one or more (e.g., 1, 2, 3, 4, or 5) substituents, each of which may be the same or different. Suitable substituents include, but are not limited to, halide ions (F, Cl, Br, or I), alkoxy groups (e.g., methoxy, ethoxy, or propoxy), and aryl groups (which are optionally substituted themselves) (e.g., phenyl).

[0067] Examples of suitable alkyl groups for R3 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (e.g., n-pentyl or neopentyl), hexyl, heptyl, octyl, nonyl, decyl, dodecyl stearyl, wherein each group may be unsubstituted or substituted, for example, by one or more substituents as mentioned above.

[0068] Suitable R3 alkyl groups include tert-butyl, hexyl, and benzyl.

[0069] In a second aspect of the invention, R3 is a cycloalkyl group.

[0070] Suitablely, the cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or adamantyl.

[0071] More preferably, the cycloalkyl group is cyclohexyl or adamantyl.

[0072] In a third aspect of the invention, R3 is an aryl group.

[0073] Suitablely, the aryl group is a group of formula (II).

[0074]

[0075] in:

[0076] R4, R5, R6, R7, and R8 are independently hydrogen or organic groups having 1 to 20 carbon atoms, and are selected according to the restrictions imposed by stability and valence rules.

[0077] Suitablely, R4, R5, R6, R7, and R8 are independently selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, heteroaryl, -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), -N(cycloalkyl)2 (wherein the cycloalkyl groups may be the same or different), -N(aryl)2 (wherein the aryl groups may be the same or different), -N(heteroaryl)2 (wherein the heteroaryl groups may be the same or different), and heterocycloalkyl groups. The heteroatom in the heteroaryl group or heterocycloalkyl group may be independently selected from sulfur, nitrogen, and / or oxygen.

[0078] More preferably, R4, R5, R6, R7 and R8 are independently selected from hydrogen, alkyl, heterocyclic alkyl, alkoxy, aryl and -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups).

[0079] The alkyl group may include groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (e.g., n-pentyl or neopentyl), hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or stearyl; suitably, it is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl; more suitably, it is methyl, ethyl, n-propyl, or isopropyl; preferably, it is methyl or ethyl. The alkyl group may optionally be substituted by one or more (e.g., 1, 2, 3, 4, or 5) substituents, each of which may be the same or different, such as halide ions (F, Cl, Br, or I), or alkoxy groups, such as methoxy, ethoxy, or propoxy.

[0080] The heterocyclic alkyl group may include groups such as epoxy, morpholino, piperidinyl, piperazine, thiapropylcycloyl, pyrrolidinyl, pyrazolyl, imidazoalkyl, thiazoalkyl, and thiomorpholino. Preferably, the heterocyclic alkyl group is morpholino.

[0081] The alkoxy group may include groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, -O-pentyl, -O-hexyl, -O-heptyl, -O-octyl, -O-nonyl, -O-decyl, and -O-dodecyl. Suitably, the alkoxy group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or tert-butoxy; more suitably, it is methoxy, ethoxy, n-propoxy, or isopropoxy; preferably, it is methoxy.

[0082] The aryl group may include groups such as phenyl, naphthyl, and anthracene; suitably, it is phenyl. The aryl group may optionally be substituted by one or more (e.g., 1, 2, 3, 4, or 5) substituents, each of which may be the same or different. Suitable substituents include, but are not limited to, alkyl, cycloalkyl, alkoxy, aryl, heteroaryl, -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), -N(cycloalkyl)2 (wherein the cycloalkyl groups may be the same or different), -N(aryl)2 (wherein the aryl groups may be the same or different), -N(heteroaryl)2 (wherein the heteroaryl groups may be the same or different), and heterocyclic alkyl groups. Suitably, the substituent is selected from alkyl or alkoxy groups. Suitable substituted aryl groups include, but are not limited to, 2,6-dimethoxyphenyl, 2,6-diisopropoxyphenyl, and 2,4,6-triisopropylphenyl.

[0083] The -N(alkyl)2 group may include groups such as –NMe2, -NEt2, -N(n-Pr)2 or -N(i-Pr)2.

[0084] In one embodiment of the third aspect of the invention, R4, R5, R6 and R7 are independently selected from hydrogen, alkyl, heterocyclic alkyl, alkoxy, aryl and -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), suitably hydrogen or alkoxy, and R8 is an aryl of formula (III).

[0085]

[0086] Among them, R9, R 10 R 11 R 12 and R 13 Independently selected from hydrogen, alkyl, cycloalkyl, alkoxy, aryl, heteroaryl, -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), -N(cycloalkyl)2 (wherein the cycloalkyl groups may be the same or different), -N(aryl)2 (wherein the aryl groups may be the same or different), -N(heteroaryl)2 (wherein the heteroaryl groups may be the same or different), and heterocyclic alkyl groups. The heteroatom in the heteroaryl group or heterocyclic alkyl group may be independently selected from sulfur, nitrogen, and / or oxygen. Suitably, R9, R 10 R 11 R 12 and R 13 It is independently selected from hydrogen, alkyl and alkoxy.

[0087] In an alternative embodiment of the third aspect of the invention, R4, R5, R6, and R7 may be independently selected from hydrogen, alkyl, heterocyclic alkyl, alkoxy, aryl, and -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), suitably hydrogen or alkoxy, and R8 is an unsubstituted heterocyclic alkyl group, such as C 4-8 Heterocyclic alkyl groups, such as piperidinyl and morpholinyl, preferably morpholinyl.

[0088] In yet another embodiment of the third aspect of the invention, R4, R5, R6 and R7 may be independently selected from hydrogen, alkyl, heterocyclic alkyl, alkoxy, aryl and -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), suitably hydrogen or alkoxy, and R8 is hydrogen.

[0089] In a fourth aspect of the invention, R3 is a heteroaryl group. The heteroaryl group may optionally be substituted by one or more (e.g., 1, 2, 3, 4 or 5) substituents, such as halide ions, straight-chain or branched alkyl groups, alkoxy groups, substituted or unsubstituted aryl groups, straight-chain or branched (dialkyl)amino groups, heterocyclic alkyl groups or tri(halo)alkyl groups.

[0090] In a fifth aspect of the invention, R3 is a metallocene group. Suitably, the metallocene group is ferrocenyl, preferably in the case where the cyclopentadienyl ring is substituted.

[0091] Appropriately, PR1R2R3 is selected from:

[0092]

[0093]

[0094]

[0095] Ad = adamantyl

[0096] Cy = Cyclohexyl

[0097] Bn = benzyl

[0098] Ar = 2,6-dimethoxyphenyl

[0099] Mes = 2,4,6-trimethylphenyl.

[0100] The compound of formula (I) can be readily synthesized in high yield from H₂PdCl₄ in a single step. When X (in the compound of formula (I)) is Cl, the method includes reacting the compound of H₂PdCl₄ with the ligand PR₁R₂R₃. When X (in the compound of formula (I)) is not Cl (i.e., when X is Br, F, or I), the method includes reacting the compound of H₂PdCl₄ with the ligand PR₁R₂R₃ and the compound ZX' (where Z is hydrogen or a monovalent metal ion (such as Li or K), and X' is Br, F, or I).

[0101] Therefore, another aspect of the present invention provides a method for preparing a compound of formula (IA).

[0102] [M2Cl6][HPR1R2R-3]2 (IA)

[0103] Where M, R1, R2, and R3 are as defined above, the method includes the step of reacting a compound of the formula H2PdCl4 with ligands PR1R2R3 or salts thereof. Suitable salts include, but are not limited to, chlorides and tetrafluoroborates.

[0104] Another aspect of the present invention provides a method for preparing a compound of formula (IB).

[0105] [M2X'6][HPR1R2R-3]2 (IB)

[0106] Where M, R1, R2, and R3 are as defined above and X' is a bromide ion, iodide ion, or fluoride ion (suitably bromide ion), the method comprises reacting a compound of the formula H2PdCl4 with ligand PR1R2R3 or a salt thereof and compound ZX', wherein Z is hydrogen or a monovalent metal ion, such as Li or K. Suitable salts include, but are not limited to, chlorides and tetrafluoroborates.

[0107] The compound H2PdCl4 and the ligand PR1R2R3 are commercially available from Johnson Matthey PLC or any other commercial supplier such as Aldrich, Dalchem, or TCI Chemicals.

[0108] Compound ZX' is commercially available from sources such as Aldrich and Alfa Aesar.

[0109] The compound of formula H₂PdCl₄, the ligand PR₁R₂R₃, and the compound ZX' (when used) are combined in a solvent. In this case, the solvent is any suitable aprotic solvent or a combination of aprotic solvents. Examples of aprotic solvents are toluene, benzene, tetrahydrofuran (THF), 2-methyltetrahydrofuran, dichloromethane (DCM), dioxane, acetone, acetonitrile, dimethylformamide (DMF), N-methylpyrrolidine (NMP), dimethylacetamide (DMAc), methyl tert-butyl ether (MTBE), diethyl ether, eucalyptol, hexane, heptane, pentane, or ethyl acetate. Alternatively, protic solvents such as ethanol, methanol, or water, or a combination of protic and aprotic solvents, may be used. The selection of the solvent system is within the capabilities and knowledge of a person skilled in the art who will understand the starting materials to be used.

[0110] In one embodiment, the solvent is acetone.

[0111] The concentration of the compound of formula H2PdCl4 in the solvent is suitably from about 0.001 mol / L to about 3.00 mol / L, more preferably from about 0.03 mol / L to about 2.50 mol / L, and most preferably from about 0.1 mol / L to about 1.0 mol / L.

[0112] Any suitable amount of ligand PR1R2R3 can be used, but preferably the molar ratio of the compound of formula H2PdCl4 to ligand PR1R2R3 is from about 15:1 to about 1:15, suitably from about 10:1 to about 1:10, and preferably from about 5:1 to about 1:5. In one embodiment, the molar ratio of the compound of formula H2PdCl4 to ligand PR1R2R3 is from about 1.5:1 to about 1:1.5. If the ligand is insoluble in the solvent, it is preferable to use an excess of Pd salt.

[0113] When ZX' is added to the reaction mixture, it is suitably added in excess of the compound of formula H2PdCl4 and the ligand PR1R2R3, such as at least 5 molar equivalents, suitably at least 8 molar equivalents.

[0114] The reaction is suitably carried out under an inert atmosphere, such as nitrogen or argon; preferably, the reaction is carried out under nitrogen. Alternatively, if the ligand is stable, the reaction can be carried out in air.

[0115] The method of the present invention can be carried out at temperatures ranging from -10°C to about 100°C, suitably from about 0°C to about 60°C, preferably from about 0°C to about 35°C, and more preferably at ambient temperatures (i.e., from about 15°C to about 30°C, such as from about 18°C ​​to about 27°C). Preferably, the temperature is maintained below the decomposition temperature, and therefore the temperature should be kept below the decomposition temperature when the compound of known formula (I) decomposes within the temperature range given above.

[0116] The reaction can proceed over a period of approximately 30 minutes to approximately 24 hours. Typically, the reaction is completed within approximately 6 hours, such as within 4 hours, or even within 1 hour. Generally, the reaction is substantially instantaneous. After the reaction is complete, the resulting suspension is filtered, washed, and dried. Drying can be performed using known methods, for example, at a temperature ranging from approximately 10°C to approximately 60°C, preferably from approximately 20°C to approximately 40°C, under a vacuum of 1 mbar to 30 mbar for 1 hour to 5 days. If necessary, the compound can be recrystallized. When the compound is soluble, an antisolvent can be used.

[0117] The compounds of this invention can be used in carbon-carbon coupling reactions. Examples of carbon-carbon coupling reactions include the Heck, Suzuki, or Negishi reactions, ketone α-arylation reactions, aldehyde α-arylation reactions, allyl substitution reactions, and trifluoromethylation reactions. The catalysts of this invention can also be used in carbon-heteroatom coupling reactions, such as carbon-nitrogen coupling reactions (i.e., Buchwald-Hartwig) or carbon-oxygen or carbon-sulfur coupling reactions.

[0118] Therefore, in another aspect, the present invention provides a method for carrying out a carbon-carbon coupling reaction in the presence of a catalyst, the method comprising using a compound of formula (I) as defined above. Alternatively, the present invention provides the use of a compound of formula (I) as defined above for catalyzing a carbon-carbon coupling reaction.

[0119] In another aspect, the present invention provides a method for carrying out carbon-heteroatom coupling reactions, the method comprising using a compound of formula (I) as defined above. Alternatively, the present invention provides the use of a compound of formula (I) as defined above for catalyzing carbon-heteroatom coupling reactions.

[0120] The invention will now be described by way of the following non-limiting embodiments.

[0121] Example 1

[0122] All solvents and reagents were purchased commercially and used as is. All catalysts, ligands, or noble metal precursors were obtained from Johnson Matthey PLC or from commercial sources. All solution phases 1 H NMR, 13 C NMR, 31 P NMR and 19 F NMR spectra were recorded at ambient temperature on a Bruker Avance DRX-400 spectrometer; chemical shifts (δ) are given in ppm. 1 H and 13 CNMR spectra reference NMR solvent peaks or internal TMS. 31P NMR spectra were calibrated using external phosphoric acid standards (85% D₂O solution, provided by Sigma Aldrich). Coupling constants (J) were recorded in Hz, and distinct splitting modes were represented using the following abbreviations and appropriate combinations: s (singleton), d (doublet), t (triplet), q (quartet), m (multiplet), br (broad peak), app. (distinct). Solid state 31 P NMR at a static magnetic field intensity (ν0() at 14.1 T) 1 Acquisitions were performed on a Bruker Avance Neo console at 600 MHz (H). The probe was tuned to 242.98 MHz and referenced to 0.9 ppm ADP. A known mass of powdered sample was packed into a zirconia MAS rotor with a Kel-F cap. The rotor was rotated using compressed air purified at ambient temperature. All spectra were recorded using cross-polarization (CP), where magnetization is obtained via dipole coupling from... 1 H is passed to 31 P nuclei. During the collection process, for 31 The P experiment used a 2-millisecond contact time and applied high-power (100kHz) Spinal-64 decoupling to... 1 H channel.

[0123] Crystals of sufficient size and mass were isolated for analysis by single-crystal X-ray diffraction, and data were acquired using a Rigaku Oxford Diffraction Supernova dual-source (a four-circle diffractometer equipped with an Oxford Cryosystems Cobra cooling system). Cu Kα radiation was used for data acquisition, as described in the experimental tables. A Bruker AXS SHELXTL kit or OLEX was used. 2 Crystallography software based on F 2 The values ​​are used to analyze and refine the structure. All non-hydrogen atoms are anisotropically refined. Hydrogen atoms attached to carbon are geometrically positioned and allowed to be refined using beam-guided isotropic displacement parameters. Hydrogen atoms attached to phosphorus are located in different Fourier syntheses and are allowed to be freely refined using isotropic displacement parameters.

[0124] All GC analyses were recorded on a Varian CP-3800 gas chromatograph equipped with an Agilent DB-1 20m × 0.18mm column and a CP-8400 autosampler. All samples were run using He or N2 carrier gas in standard split injection mode. Samples were run using ethyl acetate or acetonitrile as eluent. Conversion was determined by comparing and integrating appropriate reagents, products, and impurities. Preferably, conversion was determined by the ratio of product to aryl halides.

[0125] A general procedure for synthesizing [HL]2[Pd2Cl6] dimer :

[0126] Charge the ligand or its salt and acetone into a 100 mL round-bottom flask equipped with a stir bar and condenser. Purge the flask with nitrogen, then rapidly add an acetone solution of H₂PdCl₄. Stir the mixture at ambient temperature (18°C to 27°C) for at least 0.5 hours. Filter the resulting suspension, then wash with acetone in air, followed by washing with heptane. Dry the catalyst under vacuum at ambient temperature. For reactions producing >40 g of catalyst, replace the round-bottom flask and stir bar with a 600 mL beaker or a jacketed reactor with a top stirrer.

[0127] General procedure B for synthesizing [HL]2[Pd2Br6] dimer :

[0128] Charge the ligand or its salt and acetone into a 100 mL round-bottom flask equipped with a stir bar and condenser. Purge the flask with nitrogen, then rapidly add an acetone solution of H₂PdCl₄. Stir the mixture at ambient temperature (18°C to 27°C) for at least 0.5 hours, then add dropwise a solution of MBr (M = H, Li, K) in deionized water. Stir the resulting suspension for at least 90 minutes, then filter. Wash the solid in air with acetone, then with heptane. Dry the catalyst under vacuum at ambient temperature. For reactions producing >40 g of catalyst, use a 600 mL beaker or a jacketed reactor with a top stirrer instead of a round-bottom flask and stir bar.

[0129] [HAmPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (12.0 g Pd, 0.113 mol) and AmPhos (30.0 g, 0.113 mol) were reacted in acetone (140 mL) at room temperature for 60 minutes. The resulting suspension was filtered, washed, and dried to give [HAmPhos]2[Pd2Cl6] (51.4 g, 95%) as a beige solid. 31 P solid-state CPMAS NMR spectrum: δ (ppm) 66.4. C 32 H 58 Analytical values ​​of N₂P₂Cl₆Pd₂: C 40.11; H 6.10; N 2.92. Measured values: C 39.86; H 6.12; N 2.83. Calculated Pd w / w%: 22.21. Measured value: 21.36.

[0130] [HCyAmPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (0.402 g Pd, 3.78 mmol) and CyAmPhos (1.19 g, 3.74 mmol) were reacted in acetone (15 mL) at room temperature for 60 minutes. The resulting suspension was filtered, washed, and dried to give [HCyAmPhos]2[Pd2Cl6] (1.63 g, 83%) as a beige solid. 1 H NMR (CDCl3): δ (ppm) 7.83 (m, 2H), 7.69 (m, 2H), 3.21 (s, 6H), 2.55 (m, 2H), 2.2–1.0 (m, 20H). 31 P{ 1 H} = 30.2 ppm, in CDCl3.

[0131] [HRuPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (7.89 g Pd, 74.1 mmol) and RuPhos (34.5 g, 73.9 mmol) were reacted in acetone (150 mL) at room temperature for 70 minutes. The resulting suspension was filtered, washed, and dried to give [HRuPhos]2[Pd2Cl6] (45.9 g, 91%) as a red solid. 1 H NMR (CDCl3): δ (ppm) 8.51 (dd, J = 12.0, 7.8 Hz, 1H), 7.92 (td, J = 7.7, 1.3 Hz, 1H), 7.72 (t, J = 7. 6Hz,1H),7.47(t,J=8.4Hz,1H),7.31(dd,J=7.4,1.2Hz,1H),6.77(s,J=8.4Hz,2H),6.02(dt, 1 J HP =468Hz, 3 J HH =6.7Hz,1H),4.53(heptane,J=6.1Hz,2H),3.28(m,2H),2.15(m,4H),1.9–1.6(m,10H), 1.6–1.4(m,4H),1.3–1.2(m,2H),1.24(d,J=Hz,6.1Hz,6H)1.08(d,J=6.0Hz,6H). 13 C{ 1H}NMR(CDCl3): δ(ppm)156.0,141.8,141.7,134.3,134.2,133.6,133.6,133.0,132.9,131.4,129.2,129.1,118.5,1 18.5,114.6,113.8,107.8,72.0,29.6,29.2,28.3,28.3,27.4,27.4,25.9,25.8,25.7,25.6,25.2,25.2,22.6,21.9. 31 P NMR (CDCl3): δ (ppm) 22.2 (d, 1 J HP =469Hz). C 60 H 88 Analytical values ​​for O4P2Cl6Pd2: C 52.96; H 6.62; N 0.00. Measured values: C 52.91; H 6.57; N 0.00. Calculated Pd w / w%: 15.64. Measured value: 15.56.

[0132] [HRuPhos]2[Pd2Br6]: Following general procedure B, H2PdCl4 solution (0.524 g Pd, 4.92 mmol) and RuPhos (2.26 g, 4.84 mmol) were reacted in acetone (15.0 g) at room temperature for 30 minutes. A solution of LiBr (1.80 g, 20.8 mmol) in deionized water (5.0 g) was added to the suspension. The resulting suspension was filtered, washed, and dried to give [HRuPhos]2[Pd2Br6] (3.9 g, 97%) as a red solid. 1 H NMR(CDCl3): δ(ppm)8.47(dd,J=12.0,7.8Hz,1H),7.93(m,1H),7.73(t,J=7.7Hz,1H) ,7.46(t,J=8.4Hz,1H),7.32(dd,J=7.8,4.4Hz,1H),6.75(d,J=7.9Hz,2H),6.13(dt, 1 J HP =470Hz, 3 J HH =6.7Hz,1H),4.53(heptane,J=6.1Hz,2H),4.39(m,2H),3.30(m,2H),2.18(m,4H),2.0–1.3(m,14H),1.26(d,J=6.1Hz,6H),1.08(d,J=5.9Hz,6H). 31 P NMR (CDCl3): δ (ppm) 21.7 (d,1 J HP =470Hz).

[0133] [HSPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (9.07 g Pd, 85.3 mmol) and SPhos (35.0 g, 85.2 mmol) were reacted in acetone (100 mL) at room temperature for 70 minutes. The resulting suspension was filtered, washed, and dried to give [HSPhos]2[Pd2Cl6] (49.6 g, 93%) as an orange solid. 1 H NMR (CDCl3): δ (ppm) 8.14 (m, 1H), 7.76 (m, 2H), 7.69 (t, J = 8.5Hz, 1H), 7.43 (m, 1H), 6.92 (d, J = 8.2Hz, 2H), 6.63 (d, 1 J HP =490Hz,1H),3.81(s,6H),3.1(m,2H),2.2–1.2(m,20H). 13 C{ 1 H}NMR(CDCl3): δ(ppm)156.8,141.8,141.7,134.0,134.0,133.7,133.6,133.5,133.4,132.5,128.6,12 8.4,114.5,114.5,105.0,55.8,30.9,29.9,29.5,27.7,27.7,26.8,26.7,26.2,26.0,26.0,25.9,25.2. 31 P NMR (CDCl3): δ (ppm) 18.0 (d, 1 J HP =490Hz). C 58 H 72 Analytical values ​​for O4P2Cl6Pd2: C 50.02; H 5.81; N 0.00. Measured values: C 50.30; H 5.86; N 0.00. Calculated Pd w / w%: 17.05. Measured value: 16.59.

[0134] [HSPhos]2[Pd2Br6]: Following general procedure B, H2PdCl4 solution (0.527 g Pd, 4.96 mmol) and SPhos (2.03 g, 4.95 mmol) were reacted in acetone (15.0 g) at room temperature for 30 minutes. A solution of LiBr (1.76 g, 20.3 mmol) in deionized water (5.0 g) was added to the suspension. The resulting suspension was filtered, washed, and dried to give [HSPhos]2[Pd2Br6] (3.62 g, 96%) as a red solid. 1 H NMR (CDCl3): δ (ppm) 8.11 (m, 1H), 7.77 (m, 2H), 7.70 (t, J = 8.4Hz, 1H), 7.44 (m, 1H), 6.93 (d, J = 8.5Hz, 2H), 6.54 (dt, 1 J HP =484Hz, 3 J HH =6.4Hz,1H),3.81(s,6H),3.13(m,2H),2.2–2.0(m,4H),2.0–1.2(m,16H). 31 P NMR (CDCl3): δ (ppm) 17.9 (d, 1 J HP =484Hz).

[0135] Recrystallization of [HSPhos]2[Pd2Br6] from acetone yields red, massive crystals. This asymmetric unit contains one HSPhos molecule, half of the Pd2Br6 moiety, and one acetone molecule. Empirical formula: C 58 H 84 Br6O6P2Pd2; Molecular weight: 1631.45; Temperature: 100K; Wavelength: Crystal size: 0.200mm × 0.200mm × 0.070mm; Crystal habit: deep red cut block; Crystal system: triclinic; Space group: P-1; Cell size: α=88.969(2)°, β=78.219(2)°, γ=80.045(3)°; volume: Z = 1; Density (calculated): 1.771 Mg / m³ 3Absorption coefficient μ: 10.200 mm⁻¹; F(000): 812; θ range for data collection: 3.990 to 70.283°; exponent range: -10 ≤ h ≤ 9, -13 ≤ k ≤ 13, -20 ≤ l ≤ 12; collected reflection points: 29205; independent reflection points: 5809 [R(int) = 0.0350]; coverage of independent reflection points: 100.0%; data / limits / parameters: 5809 / 0 / 342; goodness of fit on F²: 1.068; maximum Δ / σ: 0.001; final R-index: 5297 data points; I > 2σ(I) R₁ = 0.0241, wR₂ = 0.0574; all data: R₁ = 0.0276, wR₂ = 0.0598; Δρ: 0.471 and

[0136] A view of [HSPhos]2[Pd2Br6] in the crystal structure (growth fragment) is shown below. Figure 1 In the diagram, the anisotropic atomic displacement ellipsoids of non-hydrogen atoms are shown at a 50% probability level. Hydrogen atoms are shown with arbitrarily small radii.

[0137] [HXPhos]2[Pd2Cl6]: XPhos (10.3 g, 21.6 mmol) and acetone (55 mL) were packed into a 250 mL round-bottom flask equipped with a stir bar and condenser. The flask was purged with nitrogen, and then 37% w / w HCl (2.40 g, 65.9 mmol) was added dropwise until the XPhos was completely dissolved. A solution of H2PdCl4 (2.33 g, 21.9 mmol) in acetone (15 mL) was rapidly added to the round-bottom flask. The mixture was stirred at room temperature for 60 minutes. The resulting suspension was filtered, washed, and dried to give [HXPhos]2[Pd2Cl6] (2.37 g, 91%) as a pink solid. 1 H NMR (CDCl3): δ (ppm) 9.12 (dd, J = 12.4, 7.8Hz, 1H), 8.19 (m, 1H), 7.79 (m, 1H), 7.45 (dd, J = 7.7, 4.8Hz, 1H), 7.45 (s, 2H), 5.71 (d, 1 J HP =454Hz,1H),3.35(m,2H),2.99(heptane,J=6.9Hz,1H),2.4–2.2(m,4H),2.1 –1.9(m,4H),1.9–1.6(m,12H),1.5–1.2(m,14H),1.04(d,J=6.6Hz,6H). 13 C{ 1H}NMR(CDCl3): δ(ppm)150.9,146.6,145.0,144.9,136.6,136.5,134.1,134.0,132.7,132.6,132.0,132.0,130.6,130 .4,121.5,114.2,113.4,34.3,30.9,30.7,30.5,28.7,28.7,28.6,28.6,26.4,26.0,25.9,25.9,25.8,25.1,24.0,22.5. 31 P NMR (CDCl3): δ (ppm) 20.4 (d, 1 J HP =452Hz). C 66 H 100 Analytical values ​​of P₂Cl₆Pd₂: C 57.40; H 7.30; N 0.00. Measured values: C 57.68; H 7.51; N 0.00.

[0138] [HtBuXPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (8.31 g Pd, 78.5 mmol) and tBuXPhos (33.3 g, 78.3 mmol) were reacted in acetone (100 mL) at room temperature for 60 minutes. The resulting suspension was filtered, washed, and dried to give [HtBuXPhos]2[Pd2Cl6] (37.3 g, 75%) as an orange solid. The reaction supernatant and acetone washings were combined and concentrated to give orange crystals (7.61 g, 15%). 1 HNMR (CDCl3): δ (ppm) 8.51 (dd, J = 11.0, 8.0Hz, 1H), 8.30 (t, J = 7.0Hz, 1H), 7.86 (t, J = 7.6Hz, 1H), 7.54 (dd, J = 6.9, 4.9Hz, 1H), 7.13 (s, 2H), 5.58 (d, 1 J HP =446Hz, 1H), 2.98 (heptane, J = 6.9Hz, 1H), 2.37 (heptane, J = 6.7Hz, 2H), 1.77 (s, 9H), 1.7 3(s,9H),1.32(d,J=6.9Hz,6H),1.26(d,J=6.9Hz,6H),1.02(d,J=6.5Hz,6H). 13 C{ 1H}NMR(CDCl3): δ(ppm)150.9,146.7,145.8,145.7,135.1,135.0,134.2,134.2,133.9,133.8,1 31.4,131.3,130.5,130.4,121.6,115.0,114.3,35.9,35.6,34.1,31.0,29.2,26.8,23.9,22.2. 31 P NMR (CDCl3): δ (ppm) 32.5 (d, 1 J HP =463Hz). C 58 H 92 Analytical values ​​of P2Cl6Pd2: C 54.56; H 7.26; N 0.00. Measured values: C 54.14; H 7.22; N 0.00. Calculated Pd w / w%: 16.67. Measured value: 16.47.

[0139] The asymmetric unit contains two independent molecules of HtBuXPhos and one Pd2Cl6 moiety. Empirical formula: C 29 H 46 Cl3PPd; Molecular weight: 638.38; Temperature: 100(2)K; Wavelength: Crystal size: 0.180mm × 0.150mm × 0.070mm; Crystal habit: deep orange fragments; Crystal system: triclinic; Space group: P-1; Cell size: α=92.1220(10)°, β=94.6160(10)°, γ=104.303(2)°; volume: Z = 4; Density (calculated): 1.379 Mg / m³ 3 Absorption coefficient μ: 7.861 mm⁻¹; F(000): 1328; Data collection θ range: 3.455 to 70.231°; Exponential range: -10 ≤ h ≤ 10, -11 ≤ k ≤ 11, -39 ≤ l ≤ 47; Collected reflection points: 60094; Independent reflection points: 11681 [R(int) = 0.0433]; Coverage of independent reflection points: 100.0%; Data / Limitations / Parameters: 11681 / 0 / 645; Goodness-of-fit on F 2 :1.066; Δ / σ 最大值: 0.009; Final R-index: 9941 data points; I>2σ(I)R1=0.0296, wR2=0.0687; All data: R1=0.0387, wR2=0.0742; Δρ: 0.657 and

[0140] A view of the crystal structure [HtBuXPhos]2[Pd2Cl6] is shown in the figure. Figure 2 In the diagram, the anisotropic atomic displacement ellipsoids of non-hydrogen atoms are shown at a 50% probability level. Hydrogen atoms are shown with arbitrarily small radii.

[0141] [HJohnPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (0.404 g Pd, 3.79 mmol) and JohnPhos (1.12 g, 3.76 mmol) were reacted in acetone (15 mL) at room temperature for 40 minutes. The resulting suspension was filtered, washed, and dried to give [HJohnPhos]2[Pd2Cl6] (1.68 g, 87%) as an orange-brown solid. 1 H NMR (CD3CN): δ (ppm) 8.00 (m, 1H), 7.92 (tt, J = 7.7, 1.3Hz, 1H), 7.81 (m, 1H), 7.62 (m, 1H), 7.59 (m, 3H), 7.32 (m, 2H), 6.07 (d, 1 J HP =470Hz,1H),1.47(s,9H),1.43(s,9H). 13 C{ 1 H}NMR(CD3CN): δ(ppm)149.4,149.3,139.1,139.0,135.1,135.0,133.4,133.3,1 33.1,133.1,130.1,129.7,129.5,129.5,129.4,114.8,114.1,35.6,35.3,27.8. 31 P NMR (CD3CN): δ (ppm) 29.8 (m, 1 J HP =470Hz). C 46 H 56 Analytical values ​​of P₂Cl₆Pd₂: C 46.90; H 5.51; N 0.00. Measured values: C 46.89; H 5.50; N 0.00.

[0142] [HCyJohnPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (0.401 g Pd, 3.77 mmol) and CyJohnPhos (1.31 g, 3.75 mmol) were reacted in acetone (15 mL) at room temperature for 90 minutes. The resulting suspension was filtered, washed, and dried to give [HCyJohnPhos]2[Pd2Cl6] (1.77 g, 83%) as an orange-brown solid. 1 H NMR (CDCl3): δ (ppm) 8.58 (dd, J=12.8, 7.8Hz, 1H), 7.95 (t, J=7.4Hz, 1H), 7.80 (t ,J=7.6Hz,1H),7.63(m,3H),7.53(dd,J=7.2,4.6Hz,1H),7.29(m,2H),6.85(dt, 1 J HP =473Hz, 3 J HH =12.3Hz,1H),3.05(m,2H),2.00(s,2H),1.86(m,4H),1.8–1.4(m,12H),1.33(m,2H). 13 C{ 1 H}NMR(CDCl3): δ(ppm)207.0,148.0,148.0,138.6,138.6,135.7,135.6,134.4,134.4,131.8,131.7,130.0, 129.9,129.6,129.5,129.2,112.9,112.1,30.9,30.7,30.3,28.6,28.5,27.5,27.5,26.0,25.8,25.1,25.1. 31 P NMR (CDCl3): δ (ppm) 20.5 (d, 1 J HP =474Hz). C 48 H 64 Analytical values ​​of P₂Cl₆Pd₂: C 51.09; H 5.72; N 0.00. Measured values: C 51.52; H 6.00; N 0.00.

[0143] [HBrettPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (7.94 g Pd, 74.6 mmol) and BrettPhos (40.0 g, 74.5 mmol) were reacted in acetone (180 mL) at room temperature for 70 minutes. The resulting suspension was filtered, washed, and dried to give [HBrettPhos]2[Pd2Cl6] (45.2 g, 81%) as an orange solid. 1 H NMR(CDCl3): δ(ppm)7.78(m,2H),7.10(s,2H),4.96(dt 1 J HP =444Hz, 3 J HH =6.2Hz,1H),4.42(s,3H),3.77(s,3H),2.98(heptane,J=7.0Hz,2H),2.37(heptane,J=6.6Hz,1H),2.22(m,2H),1.95(m,2H),1.9–1.5(m,10H),1.59(m,2H),1.4–1.1(m,18H),1.02(d,J=6.4Hz,6H). 13 C{ 1 H}NMR(CDCl3): δ(ppm)155.5,155.4,153.2,153.1,150.4,146.8,134.8,134.7,128.0,128.0,121.3,119.9,112.9,112.8,10 4.6,103.8,58.4,55.6,34.1,31.8,31.4,30.8,30.0,30.0,28.4,28.4,26.3,26.2,26.2,26.0,25.4,25.1,25.0,23.9,23.3. 31 PNMR (CDCl3): δ (ppm) 23.0.0 (d, 1 J HP =445Hz). C 70 H 108 Analytical values ​​for O4P2Cl6Pd2: C 56.01; H 7.25; N 0.00. Measured values: C 55.83; H 7.24; N 0.00. Calculated Pd w / w%: 14.18. Measured value: 14.06.

[0144] [HtBuBrettPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (7.63 g Pd, 71.8 mmol) and tBuBrettPhos (34.8 g, 71.8 mmol) were reacted in acetone (100 mL) at room temperature for 55 minutes. The resulting suspension was filtered, washed, and dried to give [HtBuBrettPhos]2[Pd2Cl6] (46.7 g, 93%) as a red solid. The reaction supernatant and acetone washings were combined and separated by deionized water to give red crystals (2.3 g, 4%). 1 H NMR(CDCl3): δ(ppm)8.05(m,1H),7.95(m,1H),7.06(s,2H),5.11(d, 1 J HP =435Hz,1H),4.35(m,3H),3.76(s,3H),2.94(m,1H),2.37(m,2H),1.54(s,9H),1.50(s,9H),1.29(m,6H),1.22(m,6H),0.97(m,6H). 13 C{ 1 H}NMR(CDCl3): δ(ppm)155.2,155.2,155.2,153.7,153.6,150.2,147.3,147.3,147.3,135.2,135.1,127.6,127.6,12 1.2,120.5,113.4,113.3,105.5,104.8,57.6,57.6,57.5,55.4,37.1,36.8,33.9,31.1,29.6,29.6,25.8,23.8,22.9. 31 P NMR (CDCl3): δ (ppm) 44.0 (d, 1 J HP =436Hz). C 62 H 100 Analytical values ​​for O4P2Cl6Pd2: C 53.31; H 7.22; N 0.00. Measured values: C 53.34; H 7.29; N 0.00. Calculated Pd w / w%: 15.24. Measured value: 15.09.

[0145] [HMorDalPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (0.117 g Pd, 1.10 mmol) and MorDalPhos (0.500 g, 1.08 mmol) were reacted in acetone (10 mL) at room temperature for 110 min. The resulting suspension was filtered, washed, and dried to give [HMorDalPhos]2[Pd2Cl6] (0.663 g, 94%) as a brown solid. 1 H NMR (CD3CN): δ (ppm) 7.88 (t, J = 7.8 Hz, 1H), 7.82 (t, J = 8.9 Hz, 1H), 7.74 (dd, J = 8.0, 4.6 Hz, 1H), 7.56 (td, J = 7.8, 2.2 Hz, 1H), 6.78 (d, 1 J HP =482.4Hz, 1H), 3.86 (t, J = 4.5Hz, 4H), 2.90 (m, 4H), 2.20 (s, 24H), 1.81 (s, 6H). 13 C{ 1 H}NMR(CD3CN): δ(ppm)158.5,136.7,136.6,134.7,134.6,127.4,127.3,126.4,126 .3,112.6,111.8,78.8,66.9,54.4,39.4,39.1,39.0,38.9,35.6,35.6,28.4,28.3. 31 P NMR (CD3CN): δ (ppm) 16.16 (d, 1 J HP =483Hz). C 60 H 86 Analytical values ​​of O2N2P2Cl6Pd2: C 53.19; H 6.40; N 2.07. Measured values: C 52.90; H 6.31; N 1.98.

[0146] [HQPhos]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (0.301 g Pd, 2.83 mmol) and QPhos (2.00 g, 2.81 mmol) were reacted in acetone (15 mL) at room temperature for 45 minutes. The resulting suspension was filtered, washed, and dried to give [HQPhos]2[Pd2Cl6] (2.28 g, 87%) as a red solid. 1 H NMR(CD3CN): δ(ppm)7.28(m,10H),7.19(m,5H),7.13(m,10H),6.11(d, 1 JHP =467.4Hz,1H),5.31(m,2H),5.10(m,2H),1.17(s,9H),1.12(s,9H). 13 C{ 1 H}NMR (CD3CN): δ (ppm) 135.1, 133.6, 128.4, 128.2, 91.1, 80.3, 62.5, 61.7, 35.8, 28.4. 31 P NMR (CD3CN): δ (ppm) 41.1 (m, 1 J HP =467.6Hz). C 96 H 96 Analytical values ​​for Fe₂P₂Cl₆Pd₂: C 62.36; H 5.23; N 0.00. Measured values: C 61.95; H 5.47; N 0.00.

[0147] [HPCy3]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (0.404 g Pd, 3.79 mmol) and PCy3 (1.05 g, 3.75 mmol) were reacted in acetone (25 mL) at room temperature for 45 minutes. The resulting suspension was filtered, washed, and dried to give [HPCy3]2[Pd2Cl6] and (PCy3)PdCl2 in a ratio of approximately 9:1. 1 ¹H NMR (CDCl₃): δ (ppm) 7.31 (d, 1 J HP =473.9Hz,1H),2.77(m,3H),2.32(m,6H),2.1–1.2(m,24H). 31 PNMR (CDCl3): δ (ppm) 24.3 (m, 1 J HP =474.0Hz).

[0148] Recrystallization of [HPCy3]2[Pd2Cl6] from chloroform yields orange flaky crystals. This asymmetric unit contains one HPCy3 molecule, half of the Pd2Cl6 moiety, and one chloroform molecule. Empirical formula: C 19 H 35 Cl6PPd; Molecular weight: 613.54; Temperature: 100(2)K; Wavelength: Crystal size: 0.150mm × 0.150mm × 0.005mm; Crystal habit: light orange lamellar; Crystal system: monoclinic; Space group: P21 / n; Cell size: α=90°, β=93.959(2)°, γ=90°; volume: Z = 4; Density (calculated): 1.610 Mg / m³ 3 Absorption coefficient μ: 12.368 mm⁻¹; F(000): 1248; Data collection θ range: 4.251 to 70.246°; Exponential range: -13 ≤ h ≤ 13, -18 ≤ k ≤ 20, -15 ≤ l ≤ 15; Collected reflection points: 24631; Independent reflection points: 4779 [R(int) = 0.0574]; Coverage of independent reflection points: 100.0%; Data / Limits / Parameters: 4779 / 0 / 248; F 2 Goodness of fit on Δ / σ: 1.040; 最大值 : 0.001; Final R-index: 4130 data points; I>2σ(I)R1=0.0353, wR2=0.0925; All data: R1=0.0427, wR2=0.0992; Δρ: 1.213 and

[0149] A view of [HPCy3]2[Pd2Cl6] in the crystal structure (growth fragment) is shown below. Figure 3 In the diagram, the anisotropic atomic displacement ellipsoids of non-hydrogen atoms are shown at a 50% probability level. Hydrogen atoms are shown with arbitrarily small radii.

[0150] HP t Bu3]2[Pd2Cl6]: Following general procedure A, mix H2PdCl4 solution (63 mg Pd, 0.59 mmol) and P t Bu3 (12 wt% in xylene, 0.96 g, 0.57 mmol) was reacted in acetone (2 mL) at room temperature for 30 minutes. Water (2 mL) was added to the mixture, and the resulting suspension was filtered, washed, and dried to give [HP] as a red solid. t Bu3]2[Pd2Cl6]. 1 ¹H NMR (CDCl₃): δ (ppm) 7.93 (d, 1 J HP =461.0Hz,1H),1.91(d,J=15.2Hz,27H), 31 P NMR (CDCl3): δ (ppm) 48.2 (m, 1 J HP =465.8Hz).

[0151] HP t Bu2 n[Hexyl]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (35 mg Pd, 0.33 mmol) and di-tert-butyl(n-hexyl)phosphonium tetrafluoroborate (0.10 g, 0.32 mmol) were reacted in acetone (2 mL) at room temperature for 30 minutes. Water (2 mL) was added to the mixture, and the product precipitated after 15 minutes. The resulting suspension was filtered, washed, and dried to give [HP]2[Pd2Cl6]2 as an orange solid. t Bu2 n [Hexyl]2[Pd2Cl6](0.11g, 75%). 1 ¹H NMR (CDCl₃): δ (ppm) 7.70 (d, 1 J HP =471.6Hz,1H),2.45(m,2H),2.15(m,2H),1.76(d,J=16.2Hz,18H),1.61(m,2H),1.40(m,4H),0.91(t,J=7.0Hz,3H). 31 P NMR (CDCl3): δ (ppm) 40.1 (m, 1 J HP =472.7Hz).

[0152] [HPAd3]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (31 mg Pd, 0.29 mmol) and PAd3 (125 mg, 0.29 mmol) were reacted in acetone (4 mL) at room temperature for 60 minutes. The resulting suspension was filtered, washed, and dried to give [HPAd3]2[Pd2Cl6] (136 mg, 72%) as an orange solid. 1 ¹H NMR (CDCl₃): δ (ppm) 7.28 (d, 1 J HP =450.2Hz,1H),2.84(s,12H),2.3-2.1(m,13H),2.02(m,6H),1.82(m,6H),1.66(m,8H). 31 P NMR (CDCl3): δ (ppm) 25.9 (m, 1 J HP =447.7Hz).

[0153] [HCataCXiumA]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (39 mg Pd, 0.37 mmol) and CataCXiumA (133 mg, 0.37 mmol) were reacted in acetone (4 mL) at room temperature for 40 minutes. Water (1 mL) was added to the mixture and the resulting suspension was filtered, washed, and dried to give [HCataCXiumA]2[Pd2Cl6] (148 mg, 68%) as an orange solid. 1 ¹H NMR (CDCl₃): δ (ppm) 7.29 (d, 1 J HP =464.6Hz,1H),2.6–2.4(m,11H),2.25(s,4H),2.1–1.9(m,6H),1.85(m,4H),1.64(m,2H),1.29(m,6H),1.05(m,3H),0.89(m,3H). 31 P NMR (CDCl3): δ (ppm) 29.8 (m, 1 J HP =464.6Hz).

[0154] [HCataCXiumABn]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (38 mg Pd, 0.36 mmol) and CataCXiumABn (137 mg, 0.35 mmol) were reacted in acetone (2 mL) at room temperature for 40 minutes. The resulting suspension was filtered, washed, and dried to give [HCataCXiumABn]2[Pd2Cl6] (175 mg, 82%) as a beige solid. 1 H NMR(CDCl3): δ(ppm)7.5–7.3(m,5H),5.58(dt, 1 J HP =457.2Hz, 3 J HH =5.5Hz,1H),3.73(dd,J=12.7,5.5Hz,2H),2.2–2.0(m,18H),1.84(m,12H). 31 P NMR (CDCl3): δ (ppm) 37.5 (m, 1 J HP =458.0Hz).

[0155] [HP(2,6-dimethoxyphenyl)3]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (0.13 g Pd, 1.16 mmol) and tris(2,6-dimethoxyphenyl)phosphine (0.51 g, 1.16 mmol) were reacted in acetone (4 mL) at room temperature for 60 minutes. The resulting suspension was filtered, washed, and dried to give [HP(2,6-dimethoxyphenyl)3]2[Pd2Cl6] (0.667 g, 87%) as an orange solid. 1 ¹H NMR (CD₃CN): δ (ppm) 8.53 (d, 1 J HP =548.5Hz, 1H), 7.64 (t, J = 8.4Hz, 3H), 6.76 (d, J = 8.4Hz, 3H), 6.74 (d, J = 8.5Hz, 3H), 3.67 (s, 18H). 31 P NMR (CD3CN): δ (ppm) -51.1 (d, 1 J HP =548.7Hz). (Ar=2,6-dimethoxyphenyl)

[0156] [HP(2,4,6-trimethylphenyl)3]2[Pd2Cl6]: Following general procedure A, H2PdCl4 solution (0.11 g Pd, 1.07 mmol) and tris(2,4,6-trimethylphenyl)phosphine (0.41 g, 1.06 mmol) were reacted in acetone (6 mL) at room temperature for 30 minutes. Water (5 mL) was added to the mixture, and the resulting suspension was filtered, washed, and dried to give [HP(2,4,6-trimethylphenyl)3]2[Pd2Cl6] (0.52 g, 81%) as a red solid. The mother liquor and acetone washings were combined and concentrated to give orange crystals. 1 ¹H NMR (CDCl₃): δ (ppm) 8.81 (d, 1 J HP =499.3Hz,1H),7.15(m,br,6H),2.66(s,br 9H),2.41(s,9H),2.04(s,9H). 31 P NMR (CDCl3): δ (ppm) -26.4 (d, 1 J HP =499.5.7Hz).

[0157] The asymmetric unit comprises two independent molecules of HP(2,4,6-trimethylphenyl)3 and a Pd2Cl6 moiety. Empirical formula: C 27 H 34Cl3PPd; Molecular weight: 602.26; Temperature: 100(2)K; Wavelength: Crystal size: 0.180mm × 0.060mm × 0.060mm; Crystal habit: deep orange fragments; Crystal system: monoclinic; Space group: P21 / c; Cell size: α=90°, β=108.3280(13)°, γ=90°; volume: Z = 8; Density (calculated): 1.491 Mg / m³ 3 Absorption coefficient: 8.985 mm⁻¹; F(000): 2464; θ range for data collection: 3.459 to 70.251°; Exponential range: -17 ≤ h ≤ 14, -30 ≤ k ≤ 30, -18 ≤ l ≤ 18; Number of collected reflection points: 53878; Number of independent reflection points: 10155 [R(int) = 0.0521]; Coverage of independent reflection points: 99.9%; Data / Limitations / Parameters: 10155 / 0 / 603; Goodness of fit on F²: 1.051; Δ / σ 最大值 : 0.004; Final R-index: 8700 data points; I>2σ(I)R1=0.0304, wR2=0.0714; All data: R1=0.0391, wR2=0.0769; =Δρ: 0.633 and

[0158] A view of the crystal structure (asymmetric portion) of [HP(2,4,6-trimethylphenyl)3]2[Pd2Cl6] is shown in the figure. Figure 4 In the diagram, the anisotropic atomic displacement ellipsoids of non-hydrogen atoms are shown at a 50% probability level. Hydrogen atoms are shown with arbitrarily small radii.

[0159] Example 2: α-arylation of ketones

[0160]

[0161] In a glove box, a 4mL vial equipped with a stir bar and a polypropylene cap (with a silicone diaphragm with a PTFE surface) is filled with the catalyst and NaO. t Bu (2.5 mmol). On the workbench, 5-chloro-1,5-dimethylpyrazole (1.0 mmol), 1-tetrahydronaphthone (1.3 mmol), and dioxane (2 mL) were added using a needle. The vial was placed in a preheated aluminum block at 100 °C and stirred for 22 hours. After cooling to room temperature, the aliquots were diluted in ethyl acetate and filtered for GC analysis.

[0162]

[0163] *Average conversion rate after 2 runs

[0164] Example 3: Heck alkynylation of heteroaryl chlorides

[0165]

[0166] In a glove box, a 4 mL vial equipped with a stir bar and a polypropylene cap (with a PTFE-coated silicone diaphragm) was filled with the catalyst and CsCO3 (2.2 mmol). On the workbench, 5-chloro-1,5-dimethylpyrazole (1.0 mmol), 1-decyne (1.3 mmol), and acetonitrile (2 mL) were added using a needle. The vial was placed in a preheated aluminum block at 90 °C and stirred for 5 hours. After cooling to room temperature, aliquots were diluted in ethyl acetate and filtered for GC analysis.

[0167]

[0168] *Average conversion rate after 2 runs

[0169] Example 4: Suzuki-Miyaura Coupling of Heteroaryl Chlorides

[0170]

[0171] In a glove box, a 4 mL vial equipped with a stir bar and a polypropylene cap (with a PTFE-coated silicone diaphragm) was filled with the catalyst and K3PO4 (3.1 mmol) and 3-thiopheneboronic acid (2.3 mmol). On the workbench, 5-chloro-1,5-dimethylpyrazole (1.5 mmol), THF (1.0 mL), and water (2.0 mL) were added using a needle. The vial was placed in a preheated aluminum block at 40 °C and stirred for 3 hours. After cooling to room temperature, aliquots were diluted in ethyl acetate and filtered for GC analysis.

[0172]

[0173]

[0174] *Average conversion rate after 2 runs

[0175] Example 5: Amination of 4-chloroanisole

[0176]

[0177] In a glove box, a 4mL vial equipped with a stir bar and a polypropylene cap (with a silicone diaphragm with a PTFE surface) is filled with the catalyst and NaO. tBu (2.4 mmol). On the workbench, add 4-chloroanisole (2.0 mmol), morpholine (2.4 mmol), and THF (2 mL) using a needle. Place the vial in a preheated aluminum block at 80 °C and stir for 4 hours. After cooling to room temperature, dilute the aliquots in acetonitrile and filter for GC analysis.

[0178]

[0179] *Average conversion rate after 2 runs

[0180] The catalyst used in the comparative example (commercially available or purchased from Johnson Matthey PLC)

[0181] Pd-111: Palladium acetate

[0182] Pd-132: PdCl2(AmPhos)2

[0183] Pd-161: AmPhos Pd (crotonyl)Cl

[0184] Pd-170: XPhos Pd (crotonyl)Cl

[0185] Pd-171: RuPhos Pd (crotonyl)Cl

[0186] Pd-173: [BrettPhos Pd (Bard's Formula)] OTf

[0187] G3-cyclic palladium complex:

[0188]

[0189] AmPhos G3: L = AmPhos

[0190] RuPhos G3: L = RuPhos

[0191] XPhos G3: L = XPhos

[0192] BrettPhos G3: L = BrettPhos

[0193] G4-ring palladium complex:

[0194]

[0195] AmPhos G4: L = AmPhos

[0196] XPhos G4: L = XPhos

[0197] Other aspects and features of the invention are set forth in the following numbered clauses:

[0198] 1. A compound of formula (I)

[0199]

[0200] Where M is Pd(II) or Ni(II);

[0201] X is a halide ion;

[0202] R1 and R2 are organic groups having 1 to 20 carbon atoms independently, or R1 and R2 are linked with phosphorus atoms to form a ring structure;

[0203] R3 is an organic group having 1 to 20 carbon atoms;

[0204] The prerequisite is that R1, R2, and R3 are not all phenyl groups.

[0205] 2. The compound according to Clause 1, wherein M is Pd.

[0206] 3. The compound according to clause 1 or 2, wherein X is Cl, Br or I.

[0207] 4. The compound according to Clause 3, wherein X is Cl or Br.

[0208] 5. The compound according to any of the preceding clauses, wherein R1 and R2 are the same.

[0209] 6. The compound according to any one of clauses 1 to 4, wherein R1 and R2 are different.

[0210] 7. The compound according to any of the preceding clauses, wherein R1 and R2 are linked to the P atoms to which they are attached to form a ring structure.

[0211] 8. The compound according to Clause 7, wherein the ring structure is a 4-membered to a 7-membered ring.

[0212] 9. The compound according to any of the preceding clauses, wherein R1 and R2 are independently selected from alkyl, cycloalkyl, aryl and heteroaryl groups, wherein the heteroatom is independently selected from sulfur, nitrogen and oxygen.

[0213] 10. The compound according to Clause 9, wherein R1 and R2 are independently selected from alkyl, cycloalkyl and aryl groups.

[0214] 11. The compound according to clause 9 or 10, wherein the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (e.g., n-pentyl or neopentyl), hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or stearyl.

[0215] 12. The compound according to any one of clauses 9 to 11, wherein the cycloalkyl group is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or adamantyl.

[0216] 13. The compound according to any one of clauses 9 to 12, wherein the aryl group is selected from phenyl, naphthyl or anthracene.

[0217] 14. The compound according to any one of clauses 9 to 13, wherein the heteroaryl group is pyridyl.

[0218] 15. The compound according to any one of clauses 1 to 8, wherein R1 and R2 are independently selected from n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (e.g., n-pentyl or neopentyl), hexyl, cyclopentyl, cyclohexyl or adamantyl and phenyl.

[0219] 16. The compound according to Clause 15, wherein R1 and R2 are independently selected from tert-butyl, n-butyl, cyclohexyl, adamantyl, 2,4,6-trimethylphenyl and 2,6-dimethoxyphenyl.

[0220] 17. The compound according to any of the preceding clauses, wherein R3 is selected from alkyl, cycloalkyl, aryl, heteroaryl and metallocene groups.

[0221] 18. The compound according to Clause 17, wherein R3 is an alkyl group.

[0222] 19. The compound according to Clause 18, wherein R3 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (e.g., n-pentyl or neopentyl), hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or stearyl.

[0223] 20. The compound according to clause 18 or 19, wherein R3 is optionally substituted by one or more substituents that may be the same or different.

[0224] 21. The compound according to Clause 20, wherein the substituents are independently selected from halide ions, alkoxy groups (e.g., methoxy, ethoxy, or propoxy) or aryl groups (e.g., phenyl).

[0225] 22. The compound according to any one of clauses 18 to 21, wherein R3 is tert-butyl, hexyl or benzyl.

[0226] 23. The compound according to Clause 17, wherein R3 is a cycloalkyl group.

[0227] 24. The compound according to Clause 23, wherein R3 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or adamantyl.

[0228] 25. The compound according to Clause 24, wherein R3 is cyclohexyl or adamantyl.

[0229] 26. The compound according to Clause 17, wherein R3 is an aryl group.

[0230] 27. The compound according to Clause 26, wherein R3 is a group of formula (II).

[0231]

[0232] R4, R5, R6, R7 and R8 are independently hydrogen or organic groups having 1 to 20 carbon atoms, and are selected according to the restrictions imposed by the rules of stability and valence.

[0233] 28. The compound according to Clause 27, wherein R4, R5, R6, R7 and R8 are independently selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, heteroaryl, -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), -N(cycloalkyl)2 (wherein the cycloalkyl groups may be the same or different), -N(aryl)2 (wherein the aryl groups may be the same or different), -N(heteroaryl)2 (wherein the heteroaryl groups may be the same or different), and heterocycloalkyl groups.

[0234] 29. The compound according to Clause 28, wherein R4, R5, R6, R7 and R8 are independently selected from hydrogen, alkyl, heterocyclic alkyl, alkoxy, aryl and -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups).

[0235] 30. The compound according to clause 28 or 29, wherein the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (e.g., n-pentyl or neopentyl), hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or stearyl.

[0236] 31. The compound according to Clause 30, wherein the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.

[0237] 32. The compound according to Clause 31, wherein the alkyl group is selected from methyl, ethyl, n-propyl, and isopropyl.

[0238] 33. The compound according to clause 32, wherein the alkyl group is selected from methyl or ethyl.

[0239] 34. The compound according to any one of clauses 28 to 33, wherein the heterocyclic alkyl group is selected from epoxy, morpholino, piperidinyl, piperazine, thiapropylcycloyl, pyrrolidinyl, pyrazolyl, imidazoalkyl, thiazoalkyl, and thiomorpholino.

[0240] 35. The compound according to Clause 34, wherein the heterocyclic alkyl group is morpholino.

[0241] 36. The compound according to any one of clauses 28 to 35, wherein the alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, -O-pentyl, -O-hexyl, -O-heptyl, -O-octyl, -O-nonyl, -O-decyl, -O-dodecyl.

[0242] 37. The compound according to Clause 36, wherein the alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy.

[0243] 38. The compound according to Clause 37, wherein the alkoxy group is selected from methoxy, ethoxy, n-propoxy, and isopropoxy.

[0244] 39. The compound according to clause 38, wherein the alkoxy group is a methoxy group.

[0245] 40. The compound according to any one of clauses 28 to 39, wherein the aryl group is selected from phenyl, naphthyl and anthracene.

[0246] 41. The compound according to clause 40, wherein the aryl group is phenyl.

[0247] 42. The compound according to clause 40 or 41, wherein the aryl group is optionally substituted by one or more substituents, each of which may be the same or different and is selected from alkyl, cycloalkyl, alkoxy, aryl, heteroaryl, -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), -N(cycloalkyl)2 (wherein the cycloalkyl groups may be the same or different), -N(aryl)2 (wherein the aryl groups may be the same or different), -N(heteroaryl)2 (wherein the heteroaryl groups may be the same or different), and heterocyclic alkyl groups.

[0248] 43. The compound according to clause 42, wherein the substituents are independently selected from alkyl or alkoxy groups.

[0249] 44. The compound according to Clause 43, wherein the substituted aryl group is 2,6-dimethoxyphenyl, 2,6-diisopropoxyphenyl, and 2,4,6-triisopropylphenyl.

[0250] 45. The compound according to any one of clauses 28 to 44, wherein the -N(alkyl)2 group is selected from –NMe2, -NEt2, -N(n-Pr)2 or -N(i-Pr)2.

[0251] 46. ​​The compound according to Clause 27, wherein R4, R5, R6 and R7 are independently selected from hydrogen, alkyl, heterocyclic alkyl, alkoxy, aryl and -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), suitably hydrogen or alkoxy, and R8 is an aryl of formula (III),

[0252]

[0253] Among them, R9, R 10 R 11 R 12 and R 13 The group is independently selected from hydrogen, alkyl, cycloalkyl, alkoxy, aryl, heteroaryl, -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), -N(cycloalkyl)2 (wherein the cycloalkyl groups may be the same or different), -N(aryl)2 (wherein the aryl groups may be the same or different), -N(heteroaryl)2 (wherein the heteroaryl groups may be the same or different), and heterocyclic alkyl groups.

[0254] 47. The compound according to clause 46, wherein R9, R 10 R 11 R 12 and R 13 It is independently selected from hydrogen, alkyl and alkoxy.

[0255] 48. The compound according to Clause 27, wherein R4, R5, R6 and R7 are independently selected from hydrogen, alkyl, heterocyclic alkyl, alkoxy, aryl and -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), suitably hydrogen or alkoxy, and R8 is an unsubstituted heterocyclic alkyl group.

[0256] 49. The compound according to clause 48, wherein R8 is C 4-8 Heterocyclic alkyl groups.

[0257] 50. The compound according to clause 49, wherein R8 is piperidinyl or morpholinyl.

[0258] 51. The compound according to Clause 50, wherein R8 is a morpholino group.

[0259] 52. The compound according to Clause 27, wherein R4, R5, R6 and R7 are independently selected from hydrogen, alkyl, heterocyclic alkyl, alkoxy, aryl and -N(alkyl)2 (wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched groups), suitably hydrogen or alkoxy, and R8 is hydrogen.

[0260] 53. The compound according to Clause 17, wherein R3 is a heteroaryl group.

[0261] 54. The compound according to Clause 17, wherein R3 is a metallocene-based compound.

[0262] 55. The compound according to Clause 54, wherein R3 is ferrocene-based.

[0263] 56. The compound according to any one of clauses 1 to 4, wherein PR1R2R3 is selected from:

[0264]

[0265]

[0266]

[0267] Ad = adamantyl

[0268] Cy = Cyclohexyl

[0269] Bn = benzyl

[0270] Ar = 2,6-dimethoxyphenyl

[0271] Mes = 2,4,6-trimethylphenyl.

[0272] 57. A method for preparing a compound of formula (IA).

[0273] [M2Cl6][HPR1R2R-3]2 (IA)

[0274] Where M, R1, R2, and R3 are as defined above, the method includes the step of reacting a compound of the formula H2PdCl4 with ligands PR1R2R3 or their salts.

[0275] 58. A method for preparing a compound of formula (IB).

[0276] [M2X'6][HPR1R2R-3]2 (IB)

[0277] Where M, R1, R2, and R3 are as defined above and X' is a bromide ion, iodide ion, or fluoride ion (suitably bromide ion), the method includes the step of reacting a compound of the formula H2PdCl4 with ligands PR1R2R3 or their salts and compound ZX', wherein Z is hydrogen or a monovalent metal ion, such as Li or K.

[0278] 59. A method for carrying out a carbon-carbon coupling reaction in the presence of a catalyst, the method comprising using a compound according to any one of clauses 1 to 56.

[0279] 60. Use of any compound according to any one of clauses 1 to 56 for catalyzing carbon-carbon coupling reactions.

[0280] 61. A method for carrying out a carbon-heteroatom coupling reaction in the presence of a catalyst, the method comprising using a compound according to any one of clauses 1 to 56.

[0281] 62. Use of any compound according to any one of clauses 1 to 56 for catalyzing carbon-heteroatom coupling reactions.

Claims

1. A compound of formula (I) Where M is Pd(II); X is a halide ion; R1 and R2 are independently organic groups having 1 to 20 carbon atoms, said organic groups being selected from alkyl, cycloalkyl and aryl groups; R3 is an organic group having 1 to 20 carbon atoms, wherein the organic group is selected from alkyl, cycloalkyl, aryl, and metallocene groups; The prerequisite is that R1, R2, and R3 are not all phenyl groups.

2. The compound according to claim 1, wherein X is Cl, Br or I.

3. The compound according to claim 2, wherein X is Cl or Br.

4. A compound of formula (I) Where M is Pd(II); X is a halide ion; PR1R2R3 is selected from: Ad = adamantyl Cy = Cyclohexyl Bn = benzyl Ar = 2,6-dimethoxyphenyl Mes = 2,4,6-trimethylphenyl.

5. A method for preparing a compound of formula (IA). [M2Cl6][HPR1R2R3]2(IA) Where M is Pd(II); R1 and R2 are independently organic groups having 1 to 20 carbon atoms, said organic groups being selected from alkyl, cycloalkyl and aryl groups; Furthermore, R3 is an organic group having 1 to 20 carbon atoms, wherein the organic group is selected from alkyl, cycloalkyl, aryl, and metallocene groups. The prerequisite is that R1, R2, and R3 are not all phenyl groups. The method includes the step of reacting a compound of the formula H2PdCl4 with a ligand PR1R2R3 or a salt thereof.

6. A method for preparing a compound of formula (IB). [M2X'6][HPR1R2R3]2(IB) Where M is Pd(II); R1 and R2 are independently organic groups having 1 to 20 carbon atoms, said organic groups being selected from alkyl, cycloalkyl and aryl groups; R3 is an organic group having 1 to 20 carbon atoms, wherein the organic group is selected from alkyl, cycloalkyl, aryl, and metallocene groups; And X' is a bromide ion, iodide ion, or fluoride ion, the method comprising the step of reacting a compound of the formula H2PdCl4 with a ligand PR1R2R3 or a salt thereof and a compound ZX', wherein Z is a hydrogen or monovalent metal ion.

7. A method for carrying out a carbon-carbon coupling reaction in the presence of a catalyst, the method comprising using a compound according to any one of claims 1 to 4.

8. Use of the compound according to any one of claims 1 to 4 for catalyzing carbon-carbon coupling reactions.

9. A method for carrying out a carbon-heteroatom coupling reaction in the presence of a catalyst, the method comprising using a compound according to any one of claims 1 to 4.

10. Use of the compound according to any one of claims 1 to 4 for catalyzing carbon-heteroatom coupling reactions.

Images