JP2007091660A - Method for producing metal complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an industrially useful metal complex under simple and mild reaction conditions. <P>SOLUTION: In the method for producing a metal complex, a multidentate ligand is reacted with a metal compound in a solvent having a phosphorus atom in its molecule. The solvent having a phosphorus atom is preferably a phosphoric ester, and the multidentate ligand is preferably a quadridentate ligand. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a transition metal complex useful for agricultural chemicals, pharmaceuticals, catalysts, electronic materials and the like.

  A divalent tetracoordinate orthometalated complex of platinum and palladium having a carbon-metal bond in the molecule is obtained by lithiation of a ligand with n-butyllithium, followed by platinum chloride-diethyl sulfide complex (or palladium chloride- A method of synthesis by reacting with a diethyl sulfide complex) (for example, see Non-Patent Document 1) and a method of synthesis by a metal exchange reaction of an organic mercury compound (for example, see Non-Patent Document 2) have been reported.

The synthesis method using n-butyllithium requires handling at a low temperature (−78 ° C.) and is not preferable as an industrial production method. In addition, the synthetic method using organic mercury has been difficult to use in actual production due to its toxicity. The complexing method using benzonitrile as a solvent is not suitable for industrial production because the reaction temperature is very high. Therefore, an industrially useful method for producing a metal complex using simpler and milder reaction conditions has been desired.
Inorg. Chem. 1996, 35, 4883-4888 Organometallics, 2003, 22, 5243-5260

  An object of this invention is to provide the manufacturing method of an industrially useful metal complex using simple and gentle reaction conditions.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reacted the polydentate ligand and the metal compound in a solvent containing a phosphorus atom in the molecule, under mild reaction conditions, The present inventors have found that the complexing reaction proceeds and completed the present invention.
That is, the present invention has been achieved by the following means.

(1) A method for producing a metal complex, comprising reacting a multidentate ligand and a metal compound in a solvent containing a phosphorus atom in the molecule.
(2) The method for producing a metal complex as described in (1) above, wherein the solvent containing a phosphorus atom in the molecule is a phosphate ester.
(3) The method for producing a metal complex according to the above (1) or (2), wherein a metal salt containing palladium is used as the metal compound.
(4) The method for producing a metal complex according to any one of (1) to (3) above, wherein the multidentate ligand is a bidentate or higher and hexadentate or lower ligand.
(5) The method for producing a metal complex according to any one of (1) to (4) above, wherein the polydentate ligand is a tetradentate ligand represented by the following general formula (1): .

(In General Formula (1), Q ¹ , Q ² , Q ³ , and Q ⁴ each independently represent an atomic group coordinated to a metal. L ¹ , L ² , L ³ , and L ⁴ are Each independently represents a single bond or a linking group; n represents 0 or 1)

  According to the method of the present invention, a metal complex that has been difficult to synthesize can be produced under mild reaction conditions without using a highly toxic reagent.

  The present invention is described in detail below.

  The multidentate ligand used in the present invention is not particularly limited, but a bidentate to hexadentate ligand is preferably used, a tridentate and a tetradentate ligand are more preferred, and at least one As described above, it is more preferable to use a tetradentate ligand capable of generating a metal-carbon bond in the molecule.

  Examples of such ligands include organic ligands described in WO 04/108857, WO 05/042550, WO 05/042444, Pamphlet, and the like. . Among them, it is preferable to use a ligand capable of tetradentate coordination represented by the general formula (1).

The general formula (1) will be described. Q ¹ , Q ² , Q ³ , and Q ⁴ each represent an atomic group that coordinates to a metal (the bond formed by coordination includes, for example, a coordinate bond, a covalent bond, and an ionic bond). Q ¹ , Q ² , Q ³ , and Q ⁴ are not particularly limited as long as they are an atomic group coordinated to a metal. However, an atomic group coordinated by a carbon atom, an atomic group coordinated by a nitrogen atom, and an oxygen atom are coordinated. Atom group coordinated by sulfur atom, atom group coordinated by phosphorus atom, atom group coordinated by carbon atom, atom group coordinated by nitrogen atom, atom coordinated by oxygen atom A group is more preferable, and an atom group coordinated with a carbon atom and an atom group coordinated with a nitrogen atom are more preferable.

Examples of atomic groups coordinated by carbon atoms include aromatic hydrocarbon ring groups (benzene, naphthalene, etc.), heterocyclic groups (thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole. , Triazole, etc.) and condensed rings containing these, and tautomers thereof. These groups may further have a substituent. Examples of the substituent include groups described in the substituent group A described later.

  Examples of the atomic group coordinated with a nitrogen atom include nitrogen-containing heterocyclic groups (pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole, etc.), amino groups (preferably alkylamino groups (preferably , Having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as methylamino), arylamino groups (for example, phenylamino) and the like), acylamino groups ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino, benzoylamino and the like, and an alkoxycarbonylamino group (preferably having a carbon number). 2 to 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms). For example, phenyloxycarbonylamino, etc.), a sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, methanesulfonyl Amino, benzenesulfonylamino, etc.), and imino groups. These groups may be further substituted. Examples of the substituent include groups described in the substituent group A described later.

  As an atomic group coordinated by an oxygen atom, an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2 -Ethylhexyloxy and the like), an aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyl). Oxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, Pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyloxy group (preferably having 2 to 30 carbon atoms, more preferred) Has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), silyloxy group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, Particularly preferred are those having 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), carbonyl groups (for example, ketone groups, ester groups, amide groups, etc.), ether groups (for example, dialkyl ether groups, diaryls). Ether group, furyl group, etc.). These groups may be further substituted. Examples of the substituent include groups described in the substituent group A described later.

  As an atomic group coordinated by a sulfur atom, an alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio. ), An arylthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio), a heterocyclic thio group (preferably C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc. ), A thiocarbonyl group (for example, a thioketone group, a thioester group, etc.), a thioether group (for example, a dialkylthioe group). Ether groups, diaryl thioether, etc. thiofuryl group). These groups may be further substituted. Examples of the substituent include groups described in the substituent group A described later.

  Examples of the atomic group coordinated by the phosphorus atom include a dialkylphosphino group, a diarylphosphino group, a trialkylphosphine, a triarylphosphine, and a phosphinin group. These groups may be further substituted. Examples of the substituent include groups described in the substituent group A described later.

Q ¹ and Q ² are preferably an atom group coordinated by a nitrogen atom, an atom group coordinated by an oxygen atom, or an atom group coordinated by a phosphorus atom, more preferably an atom group coordinated by a nitrogen atom, A nitrogen-containing heterocyclic group that coordinates is more preferable, and a monocyclic nitrogen-containing heterocyclic group that coordinates with a nitrogen atom is particularly preferable. Q ¹ and Q ² may have a substituent selected from the substituent group A described later if possible.

Q ³ and Q ⁴ are preferably an atom group coordinated by a carbon atom, an atom group coordinated by a nitrogen atom, or an atom group coordinated by an oxygen atom, and is coordinated by an aryl group coordinated by a carbon atom or a carbon atom. More preferred are a heteroaryl group, a heteroaryl group coordinated with a nitrogen atom, a carboxyl group coordinated with an oxygen atom, an aryloxy group coordinated with an oxygen atom, and a heteroaryloxy group coordinated with an oxygen atom. More preferred are an aryl group to be coordinated, a heteroaryl group to be coordinated with a carbon atom, a heteroaryl group to be coordinated with a nitrogen atom, and a carboxyl group to be coordinated with an oxygen atom, an aryl group coordinated with a carbon atom, and a carbon atom A coordinating heteroaryl group is particularly preferred. Q ³ and Q ⁴ may have a substituent selected from the substituent group A shown below, if possible.

Substituent group A
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n- Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, For example, propargyl, 3-pentynyl, etc.), aryl groups (preferably having 6 to 30 carbon atoms, more preferably A prime number of 6 to 20, particularly preferably a carbon number of 6 to 12, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc., an amino group (preferably a carbon number of 0 to 30, more preferably a carbon number). 0 to 20, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), an alkoxy group (preferably 1 to 1 carbon atoms). 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like, and aryloxy groups (preferably 6 carbon atoms). -30, more preferably 6-20 carbons, particularly preferably 6-12 carbons, Phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, Ethoxycarbonyl, etc.), aryloxycarbonyl group (preferably Alternatively, it has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2-2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino). ), A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like, and an arylthio group (preferably 6 to 30 carbon atoms). , More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and a sulfonyl group (preferably having a carbon number). 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). Rufinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid. An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group ( Preferably it is C1-C30, More preferably, it is C1-C12, As a hetero atom, for example, a nitrogen atom, oxygen And a sulfur atom, and specific examples include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, and the like. Preferably they are C3-C40, More preferably, it is C3-C30, Most preferably, it is C3-C24, for example, trimethylsilyl, a triphenylsilyl etc. are mentioned, for example, A silyloxy group (Preferably C3-C3) 40, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyloxy, triphenylsilyloxy, and the like.

L ¹ , L ² , L ³ and L ⁴ each represent a single bond or a linking group. The linking group is not particularly limited, but an alkylene group (for example, a methylene group, a dimethylmethylene group, a diisopropylmethylene group, a diphenylmethylene group, an ethylene group, a tetramethylethylene group, etc.), an alkenylene group (a vinylene group, a dimethylvinylene group, etc.) , Alkynylene groups (such as ethynylene groups), arylene groups (such as phenylene groups and naphthylene groups), heteroarylene groups (such as pyridylene groups, pyrazylene groups, and quinolylene groups), oxygen linking groups, sulfur linking groups, nitrogen linking groups (methylamino linking) Group, a phenylamino linking group, a tbutylamino linking group, etc.), a silicon linking group, and a linking group combining these (for example, an oxylenmethylene group). Specific examples are shown below, but the present invention is not limited thereto.

L ¹ and L ³ are preferably a single bond, an alkylene group, an oxygen linking group or a nitrogen linking group, preferably an alkylene group or an oxygen linking group, and particularly preferably an alkylene group.

L ² and L ⁴ are preferably a single bond, an alkylene group or an oxygen linking group, more preferably a single bond or an alkylene group, and even more preferably a single bond.

  These linking groups may further have a substituent if possible, and examples of the substituent that can be introduced include those exemplified as the substituent group A in the description of the general formula (1).

n represents 0 or 1. When n is 0, there is no bond between Q ³ and Q ⁴ via L ³ .

  The metal complex represented by the general formula (2) can be obtained by reacting the ligand represented by the general formula (1) with the metal compound by the production method of the present invention.

(In General Formula (2), Q ¹ , Q ² , Q ³ and Q ⁴ represent an atomic group coordinated to a metal. L ¹ , L ² , L ³ and L ⁴ represent a single bond or a linking group. N represents 0 or 1. M represents a metal atom, and the bond between the metal atom and Q ¹ , Q ² , Q ³ , and Q ⁴ may be a covalent bond, a coordination bond, or an ionic bond. )

The general formula (2) will be described. In General Formula (2), Q ¹ , Q ² , Q ³ , Q ⁴ , L ¹ , L ² , L ³ , L ⁴ , and n are Q ¹ , Q ² , Q ³ , Q ⁴ in General Formula (1). , L ¹ , L ² , L ³ , L ⁴ , and n, and the preferred range is also the same. M represents a metal atom. Although it does not specifically limit as a metal atom, A transition metal atom is preferable. Specifically, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are preferable, rhodium, iridium, palladium, and platinum are more preferable, and palladium and platinum are more preferable.

  Specific examples of the metal complex represented by the general formula (2) that can be produced by the production method of the present invention are listed below, but the present invention is not limited to these compounds.

  The metal contained in the metal compound used in the present invention is not particularly limited, but is ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, platinum, more preferably rhodium, iridium, palladium, platinum. More preferred are palladium and platinum.

As the compound containing palladium in the metal compound used in the present invention, palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium acetylacetonate, palladium hexafluoroacetylacetonate, which contains divalent palladium, are used. , Palladium trifluoroacetate, allyl palladium chloride-dimer, (2,2′-bipyridine) dichloropalladium, bis (benzonitrile) dichloropalladium, bis (acetonitrile) dichloropalladium, (bicyclo [2.2.1] hepta-2 , 5-Diene) dichloropalladium, dichloro (1,5-cyclooctadiene) palladium, dibromobis (triphenylphosphine) palladium, dichloro (N, N, N ′, N′-tetramethylethylenediamine) Palladium, dichloro (1,10-phenanthroline) palladium, dichlorobis (triphenylphosphine palladium), ammonium tetrachloroparadate, diammine dibromopalladium, diammine dichloropalladium, diammine diiodopalladium, potassium tetrabromoparadate, potassium tetrachloro Examples of compounds containing zero-valent palladium such as paradate and sodium tetrachloroparadate include tetrakis (triphenylphosphine) palladium and tris (dibenzylideneacetone) dipalladium.

Examples of the metal compound used in the present invention and containing platinum include divalent platinum, platinum chloride, platinum bromide, platinum iodide, platinum acetylacetonate, bis (benzonitrile) dichloroplatinum, bis (Acetonitrile) dichloroplatinum, dichloro (1,5-cyclooctadiene) platinum, dibromobis (triphenylphosphine) platinum, dichloro (1,10-phenanthroline) platinum, dichlorobis (triphenylphosphine) platinum, ammonium tetrachloroparadate, Zero-valent para, such as diammine dibromopalladium, diammine dichloroplatinum, diammine diiodoplatinum, potassium tetrabromoplatinum, potassium tetrachloroplatinate, sodium tetrachloroplatinate As including um is tetrakis (triphenylphosphine) platinum, and the like.
These metal compounds may contain crystal water, a crystal solvent, and a coordination solvent. The valence of the metal is not particularly limited, but the metal is preferably divalent or zero-valent, more preferably divalent.

  The amount of the metal compound used in the present invention is usually 0.1 to 10 mol, preferably 1 to 10 mol, based on 1 mol of the ligand, when the metal compound contains one metal atom that forms a metal complex. 0.5 to 5 mol, more preferably 1 to 3 mol. When n metal atoms forming the metal complex are included in the metal compound, the amount used may be 1 / n times.

The solvent used in the present invention is not particularly limited as long as it contains a phosphorus atom in the molecule, but is preferably a solvent containing a phosphorus atom in the molecule, more preferably a phosphate ester. More preferably, trialkyl phosphite (Trikyl Phosphite: P (OR ′) ₃ ), trialkyl phosphate (Trikyl Phosphate: PO (OR ′) ₃ ), dialkyl phenyl phosphate (Dialkyl Phenylphosphate: PhPO (OR ′)) ₂ ), particularly preferably dialkyl phenyl phosphate and trialkyl phosphate, and most preferably trialkyl phosphate.

  R ′ will be described. R 'represents an alkyl group having 1 to 20 carbon atoms or an aryl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. And a cyclohexyl group. Examples of the aryl group include a phenyl group and a tolyl group. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and the aryl group is preferably a phenyl group. More preferably, they are a methyl group and an ethyl group.

The solvent containing a phosphorus atom in the molecule used in the present invention may be used alone, or may be used by mixing with a solvent not containing a phosphorus atom.
Examples of the solvent not containing a phosphorus atom in the molecule include amides such as N, N-dimethylformamide, formamide, N, N-dimethylacetamide, nitriles such as acetonitrile, propionitrile, butyronitrile, and benzonitrile, dichloromethane 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, o-dichlorobenzene and other halogenated hydrocarbons, pentane, hexane, octane, decane and other aliphatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. Aromatic hydrocarbons such as diethyl ether, diisopropyl ether, butyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, Ketones such as Louis Seo ketone, methanol, ethanol, 1-propanol, 2-propanol, tert- butyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, alcohols such as glycerin, water and the like.

  The amount of the solvent used in the present invention is not particularly limited as long as the reaction can proceed sufficiently, but is usually 1 to 200 times volume, preferably 5 to 100 times the amount of the ligand used. Volume is preferred.

  In the production method of the present invention, when an acidic substance such as hydrogen halide is produced during the complex formation reaction between the metal compound and the ligand, the reaction may be performed in the presence of a basic substance. Basic substances include tertiary amines such as triethylamine, diisopropylethylamine and pyridine, metal alkoxides such as sodium methoxide and sodium ethoxide, inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate and sodium bicarbonate Kind.

  The production method of the present invention is preferably carried out in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon.

  The reaction temperature, reaction time, and reaction pressure in the production method of the present invention vary depending on the raw materials and the solvent, but are usually in the range of 20 ° C to 300 ° C, preferably 50 ° C to 200 ° C, more preferably 80 ° C to 170 ° C. It is. The reaction time is usually 30 minutes to 24 hours, preferably 1 to 12 hours, more preferably 2 to 10 hours, and the reaction pressure is usually atmospheric pressure, but under pressure as necessary. But it can be under reduced pressure.

  In the present invention, the heating means is not particularly limited. Specifically, heating by an oil bath or a mantle heater or heating by microwave irradiation can be used.

  The metal complex which can be produced according to the present invention can be isolated by filtering the precipitated crystals after the completion of the reaction. If crystals do not precipitate, the solvent is distilled off, a solvent such as methanol is added, and the precipitated crystals are collected by filtration, or after completion of the reaction, after addition of water, after extraction with a solvent such as chloroform. It can also be isolated by concentrating the organic layer. The obtained metal complex can be further purified by using a usual purification method such as recrystallization, reprecipitation, sublimation, column chromatography, etc. to obtain a highly pure metal complex.

  Although the typical synthesis example of the metal complex by this invention is shown below, this invention is not limited to these synthesis examples. Other metal complexes of the present invention can be synthesized in the same manner.

[Example 1: Synthesis of Exemplified Compound 2]

Under a nitrogen atmosphere, a ligand flask A-1 (50 mg, 0.107 mmol), bis (acetonitrile) palladium (II) dichloride (28 mg, 0.107 mmol), and trimethyl phosphate (4 ml) were charged in an eggplant flask at 130 ° C. Heated and stirred for 4 and a half hours. After cooling to room temperature, the precipitated solid was filtered, washed with methanol, and dried under reduced pressure to obtain 18.6 mg of Exemplary Compound 2 as an off-white solid. Yield 30%.
¹ H-NMR (CDCl ₃ ): δ (ppm) = 8.02 (t, J = 8.0 Hz, 2H), 7.88 (dd, J = 0.8, 8.4 Hz, 2H), 7. 27 (dd, J = 0.4, 7.6 Hz, 2H), 6.74 (s, 2H), 2.00 (s, 6H)

[Example 2: Synthesis of Exemplified Compound 3]

Under a nitrogen atmosphere, a recovery flask was charged with ligand B-1 (3.5 g, 7.9 mmol), bis (acetonitrile) palladium (II) dichloride (2.25 g, 8.7 mmol), and trimethyl phosphate (200 ml). The mixture was heated and stirred at 90 ° C. for 1 hour and at 120 ° C. for 10 hours. After cooling to room temperature, the precipitated solid was filtered, washed with methanol, and dried under reduced pressure to obtain 1.2 g of Exemplified Compound 3 as an off-white solid. Yield 28%.
¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.84 (t, J = 8.0 Hz, 2H), 7.68 (dd, J = 0.8, 8.1 Hz, 2H), 7. 24 (dd, J = 0.8, 8.1 Hz, 2H), 6.44 (s, 3H), 1.92 (s, 6H), 1.40 (s, 18H)

[Example 3: Synthesis of Exemplified Compound 5]

Under a nitrogen atmosphere, an eggplant flask was charged with ligand C-1 (2.34 g, 4.6 mmol), bis (acetonitrile) palladium (II) dichloride (1.21 g, 4.6 mmol), and trimethyl phosphate (160 ml). The mixture was heated and stirred at 85 ° C for 5 hours and a half. After cooling to room temperature, the precipitated solid was filtered, washed with methanol, and dried under reduced pressure to obtain 1.0 g of Exemplified Compound 5 as an off-white solid. Yield 36%.
¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.14 (d, J = 2.0 Hz, 2H), 6.75 (d, J = 2.0 Hz, 2H), 6.42 (s, 2H), 4.01 (s, 6H), 1.83 (s, 6H), 1.40 (s, 18H)

[Comparative Example 1]
Under a nitrogen atmosphere, a ligand A-1 (64 mg, 0.107 mmol), palladium (II) dichloride (23 mg, 0.107 mmol), and benzonitrile (4 ml) were charged in an eggplant flask, and the oil bath temperature was 200 ° C. The mixture was heated to reflux and stirred for 4 hours. The mixture was cooled to room temperature and purified by silica gel chromatography (developing solution: chloroform) to obtain 2.2 mg of Exemplified Compound 2 as a pale yellow solid. Yield 3.6%.

  As is clear from the above Examples and Comparative Examples, by using the method of the present invention, a palladium complex having a tetradentate ligand can be produced simply and under mild reaction conditions. Further, by using the method of the present invention, other palladium complexes and metal complexes having tridentate or higher ligands can be similarly produced under simple and mild reaction conditions.

Claims (5)

  A method for producing a metal complex, comprising reacting a multidentate ligand and a metal compound in a solvent containing a phosphorus atom in the molecule.   The method for producing a metal complex according to claim 1, wherein the solvent containing a phosphorus atom in the molecule is a phosphate ester.   The method for producing a metal complex according to claim 1 or 2, wherein a metal salt containing palladium is used as the metal compound.   The method for producing a metal complex according to any one of claims 1 to 3, wherein the multidentate ligand is a bidentate to hexadentate ligand. The method for producing a metal complex according to any one of claims 1 to 4, wherein the multidentate ligand is a tetradentate ligand represented by the following general formula (1).

(In General Formula (1), Q ¹ , Q ² , Q ³ , and Q ⁴ each independently represent an atomic group coordinated to a metal. L ¹ , L ² , L ³ , and L ⁴ are Each independently represents a single bond or a linking group; n represents 0 or 1)