Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
  • C01C1/00—Ammonia; Compounds thereof
  • C01C1/02—Preparation, purification or separation of ammonia
  • C01C1/04—Preparation of ammonia by synthesis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
  • C07F9/576—Six-membered rings
  • C07F9/58—Pyridine rings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/60—Reduction reactions, e.g. hydrogenation
  • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
  • B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
  • B01J2531/64—Molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
  • B01J2540/20—Non-coordinating groups comprising halogens
  • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
  • B01J2540/20—Non-coordinating groups comprising halogens
  • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
  • B01J2540/225—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate comprising perfluoroalkyl groups or moieties
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present invention relates to a method for producing ammonia, a molybdenum complex used in the production method, and a ligand that is a raw material for the molybdenum complex.
• the Haber-Bosch process which is an industrial method for converting nitrogen molecules into ammonia, is an energy-intensive process that requires severe conditions of high temperature and high pressure, and consumes energy to produce hydrogen gas. As such, a few percent of the world's annual energy consumption is used for the Haber-Bosch process.
• a method for producing ammonia from nitrogen molecules at normal temperature and pressure without using hydrogen gas there is a report on the production of ammonia using a molybdenum complex as a catalyst and water as a proton source. (Non-Patent Document 1).
• Non-Patent Document 2 describes, for example, molybdenum complexes represented by formulas (A) and (B) These molybdenum complexes are phosphorus-carbon-phosphorus type pincer ligands (hereinafter referred to as PCP ligands) in which three coordinating atoms are bonded from three directions on the same plane containing molybdenum metal. It was characterized by having a phosphorus-nitrogen-phosphorus type pincer ligand (hereinafter sometimes referred to as a PNP ligand).
• PCP ligands phosphorus-carbon-phosphorus type pincer ligands
• the present inventors molecularly designed and searched molybdenum complexes having phosphorus-nitrogen-phosphorus type pincer ligands (PNP ligands), By introducing a phenyl group, or an aryl group with an electron-withdrawing substituent, it functions as a catalyst for the production of ammonia, exceeding the performance of molybdenum complexes with PNP ligands known so far. and completed the present invention.
• PNP ligands phosphorus-nitrogen-phosphorus type pincer ligands
• the present invention [1] Formula (1) (wherein R 1 and R 2 each independently represent a C 3 -C 10 alkyl group, R 3 , R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, a trifluoromethyl group, a phenyl group or an Ar 1 aryl group, and at least one of R 3 , R 4 and R 5 represents a phenyl group or an Ar 1 aryl group. ), a method for producing ammonia from nitrogen molecules in the presence of a reducing agent and a proton source, using a molybdenum complex obtained by reacting a ligand represented by ) with a molybdenum compound as a catalyst.
• Formula (2) (wherein R 1 and R 2 each independently represent a C 3 -C 10 alkyl group, R 3 and R 4 each independently represent a hydrogen atom, a fluorine atom, a trifluoromethyl group, a phenyl group, or an Ar 1 aryl group; R5 represents an Ar1 aryl group. ) molybdenum complex represented by.
• n stands for normal, "s” for secondary, “t” for tertiary, “o” for ortho, “m” for meta, and “p” for para.
• t Bu represents a tertiary butyl group and "thf” represents tetrahydrofuran.
• C a -C b alkyl group is a monovalent alkyl group produced by losing one hydrogen atom from a linear, branched or cyclic aliphatic hydrocarbon having a to b carbon atoms.
• n-octyl group represents a group such as methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1,1-dimethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, 3-ethylpentyl group, n-octyl group, 2,2,4-trimethylpentyl group, 2,5-dimethylhex
• halogen atoms in the present specification include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
• Ar 1 aryl group in this specification represents a monovalent group generated by losing one hydrogen atom from an aromatic ring of an aromatic hydrocarbon having 6 carbon atoms, for example, from 2-position to 6-position is a phenyl group having a substituent on at least one of Substituents on the aromatic ring of the Ar 1 aryl group include electron-withdrawing groups.
• the group includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or —CH ⁇ CHNO 2 .
• Substituents having electron-withdrawing mesomeric and inducing effects include a trifluoromethyl group, a trichloro A methyl group, a cyano group, a nitro group, a formyl group, and a carboxylic acid group can be mentioned, and preferred electron-withdrawing groups include a fluorine atom and a trifluoromethyl group.
• Ar 1 aryl group for example, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 3,4,5-tri fluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoromethylphenyl group, or 3,5-bis ( trifluoromethyl)phenyl group and the like.
• R 1 and R 2 in formulas (1) and (2) each independently include a C 3 -C 10 alkyl group such as isopropyl, cyclopropyl, isobutyl, s-butyl, t-butyl, cyclobutyl, isopentyl, neopentyl; group, t-pentyl group, 1,1-dimethylpropyl group, cyclopentyl group, isohexyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, cyclohexyl group and adamantyl group is preferred, and isopropyl group, t-butyl group and adamantyl group are more preferred.
• a C 3 -C 10 alkyl group such as isopropyl, cyclopropyl, isobutyl, s-butyl, t-butyl, cyclobutyl, isopent
• R 3 and R 4 in formulas (1) and (2) each independently include a hydrogen atom, a fluorine atom, a trifluoromethyl group, a phenyl group, or an Ar 1 aryl group.
• Ar 1 aryl groups include o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 3,4, 5-trifluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoromethylphenyl group, or 3,5 -Bis(trifluoromethyl)phenyl group and the like.
• R 3 and R 4 in formula (1) and formula (2) are preferably hydrogen atom, phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,6-difluoro phenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethyl A phenyl group, a p-trifluoromethylphenyl group and a 3,5-bis(trifluoromethyl)phenyl group are preferred, and a hydrogen atom is particularly preferred.
• R5 in formulas (1) and (2) will be described.
• R 5 include an Ar 1 aryl group, and specific examples of the substituents on the aromatic ring of the Ar 1 aryl group and the Ar 1 aryl group are the same as above.
• R 5 in formulas (1) and (2) more specifically, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,6-difluorophenyl group, 3,5- difluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoro Methylphenyl group, or 3,5-bis(trifluoromethyl)phenyl group and the like, m-fluorophenyl group, p-fluorophenyl group, 3,5-difluorophenyl group,
• R 1 , R 2 , R 3 and R 4 in formulas (1) and (2) are the same as above, and , R 5 includes phenyl group and Ar 1 aryl group, specifically phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,6-difluorophenyl group , 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group , p-trifluoromethylphenyl group, or 3,5-bis(trifluoromethyl)phenyl group, and the like, phenyl group, m-fluorophenyl group, p-fluorophenyl group, 3,5-difluorophenyl group, A 3,4,5
• X in the molybdenum complex represented by formula (2) will be explained.
• X includes a halogen atom, preferably X is an iodine atom, a bromine atom or a chlorine atom, and more preferably an iodine atom or a chlorine atom.
• molybdenum compounds include molybdenum(III) chloride, molybdenum(III) bromide, molybdenum(III) iodide, trichlorotris(tetrahydrofuran)molybdenum(III), tribromotris(tetrahydrofuran)molybdenum(III), triiodotris(tetrahydrofuran) ) molybdenum (III), etc.
• Preferred molybdenum compounds are trichlorotris(tetrahydrofuran)molybdenum (III) and triiodotris(tetrahydrofuran)molybdenum (III).
• the reducing agent has an energy level of the highest occupied molecular orbital of -5.0 eV or higher, that is, a reducing agent having an ionization potential of 5.0 eV or lower. be done.
• the reducing agent includes lanthanide metal halides and sandwich compounds.
• the lanthanide metals of lanthanide metal halides include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. Preferred are samarium, europium and ytterbium, which can be in a divalent state.
• Halogens of lanthanide metal halides include chlorine, bromine and iodine, with iodine being preferred.
• the lanthanide metal halide may be a complex in which ether compounds such as tetrahydrofuran, 4-methyltetrahydropyran, and diethyl ether are coordinated. It is also possible to use a complex in which tetrahydrofuran is coordinated to a metal halide.
• ether compounds such as tetrahydrofuran, 4-methyltetrahydropyran, and diethyl ether are coordinated. It is also possible to use a complex in which tetrahydrofuran is coordinated to a metal halide.
• lanthanide metal halides such as EuCl 2 , EuI 2 , SmI 2 and YbI 2 are available from Sigma-Aldrich Japan.
• Preferred lanthanide metal halides include samarium (II) halide, europium (II) halide, ytterbium (II) halide, and tetrahydrofuran-coordinated complexes of the above compounds, and samarium iodide ( II), complexes of samarium (II) iodide coordinated with tetrahydrofuran (for example, SmI 2 (thf) 2 can be mentioned, which can be obtained by dissolving SmI 2 in tetrahydrofuran and recrystallizing it). is more preferred.
• a sandwich compound is a compound consisting of a metal atom and two arene ligands.
• metal atoms in the sandwich compound include titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, iron, ruthenium, Cobalt, rhodium, iridium, nickel, palladium, platinum, samarium and the like can be mentioned, with chromium, molybdenum, tungsten, iron, ruthenium, cobalt, rhodium and iridium being preferred.
• Sandwich compounds composed of the above metal atom and two arene ligands include, for example, bis(cyclopentadienyl) metal complex, bis(pentamethylcyclopentadienyl) metal complex, bis(benzene) metal complex, Bis(cyclooctatetraenyl) metal complexes and the like are mentioned, and bis(cyclopentadienyl) metal complexes and bis(pentamethylcyclopentadienyl) metal complexes are preferred. Bis(pentamethylcyclopentadienyl) metal complexes are more preferred.
• ammonia may be produced in a solvent using nitrogen molecules as a raw material.
• the solvent is not particularly limited as long as it can dissolve or disperse the reducing agent, but cyclic ether compounds, chain ether compounds, nitrile compounds, aromatic hydrocarbon compounds, Alternatively, a saturated hydrocarbon-based compound and the like may be mentioned.
• Cyclic ether compounds include, for example, tetrahydrofuran, 4-methyltetrahydropyran, tetrahydropyran-4-methanol, and 1,4-dioxane.
• chain ether compounds include diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, and cyclopentylmethyl ether.
• nitrile compounds include acetonitrile and propionitrile.
• aromatic hydrocarbon compounds include toluene and o-xylene.
• saturated hydrocarbon compounds include hexane, heptane, petroleum ether, and the like.
• Preferred solvents in the method for producing ammonia of the present embodiment are tetrahydrofuran and 1,2-dimethoxyethane.
• the proton source may be alcohol or water.
• the alcohol to be used include glycol, R a OH (R a is a chain alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group, or a branched alkyl group in which a hydrogen atom may be substituted with a fluorine atom. ) may be used.
• Glycols include, for example, ethylene glycol, propylene glycol, diethylene glycol, and the like.
• R a OH is, for example, a chain or branched alkyl alcohol such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, s-butyl alcohol, isobutyl alcohol, or t-butyl alcohol.
• Alkyl alcohols include cyclopropanol, cyclopentanol, cyclohexanol, and the like.
• Examples of alcohols containing fluorine atoms include trifluoroethyl alcohol and tetrafluoroethyl alcohol.
• preferred proton sources are water and ethylene glycol, with water being more preferred.
• the yield of generated ammonia can be measured by a known method.
• Ammonia in the aqueous sulfuric acid solution can be quantified using, for example, the known indophenol method (Analytical Chemistry, 1967, vol. 39, pp. 971-974).
• normal pressure or pressurized nitrogen gas can be used as nitrogen molecules, and normal pressure nitrogen gas is preferably used. Since nitrogen gas is inexpensive, it may be used in large excess relative to other reagents.
• the reaction temperature is not particularly limited as long as the reaction proceeds, but is preferably -10 to 60°C, more preferably 0 to 50°C.
• the amount of catalyst used is preferably 0.00001 to 0.1 equivalents, more preferably 0.0001 to 0.01 equivalents, relative to the reducing agent.
• the amount of proton source used is preferably 0.5 to 5 equivalents, more preferably 1 to 2 equivalents, relative to the reducing agent.
• the solution A (0.5 mL) was added to a Schlenk reaction vessel under a normal pressure nitrogen atmosphere, and then the dichloromethane was distilled off under reduced pressure to add the molybdenum complex (7a) (0.2 ⁇ mol), Subsequently, after adding diiodobis(tetrahydrofuran) samarium (II) (197 mg, 0.36 mmol) and tetrahydrofuran (5.5 mL), a tetrahydrofuran solution (0.5 mL, water 6.5 mg, 0.36 mmol) was added, and the mixture was stirred at room temperature of 20 to 25° C. for 18 hours.
• an aqueous potassium hydroxide solution (30% by mass, 5 mL) was added to the reaction vessel, and the reaction vessel was distilled under reduced pressure to convert the distillate to an aqueous sulfuric acid solution (0.5 M, 10 mL).
• the amount of ammonia in the aqueous sulfuric acid solution was determined by the indophenol method. As a result, in a reaction time of 18 hours, 564 equivalents of ammonia were produced per amount of molybdenum complex used as a catalyst.
• the molybdenum complex represented by the formula (7d) can be prepared according to the non-patent document J. Phys. Am. Chem. Soc. , 2014, 136, 9719-9731, DaltonTrans. , 2019, vol. 48, pp. 3182-3186. Ammonia content results are described below. It is 542 equivalents in Experimental Example 2 using the molybdenum complex represented by Formula (7b), and 458 equivalents in Experimental Example 3 using the molybdenum complex represented by Formula (7c). It was 449 equivalents in Experimental Example 4 using the molybdenum complex.
• diiodobis(tetrahydrofuran) samarium (II) (197 mg, 0.36 mmol) and a tetrahydrofuran solution (0.5 mL, 6.5 mg as water, 0.36 mmol) adjusted to a water concentration of 0.72 mol/L were added.
• a tetrahydrofuran solution 0.5 mL, 6.5 mg as water, 0.36 mmol
• ammonia was produced in a total reaction time of 28 hours.
• the same operation as in Experimental Example 1 was performed to determine the amount of ammonia, and it was confirmed that 3160 equivalents of ammonia were produced per amount of molybdenum complex used as a catalyst.
• solution D 25 ⁇ L was added to a Schlenk reaction vessel under a nitrogen atmosphere at normal pressure, and then dichloromethane was distilled off under reduced pressure to add molybdenum complex (7d) (0.01 ⁇ mol), followed by , Diiodobis(tetrahydrofuran) samarium (II) (197 mg, 0.36 mmol) and tetrahydrofuran (2.5 mL) were added, and then a tetrahydrofuran solution (0.5 mL, water was , 6.5 mg, 0.36 mmol) was added thereto, and the mixture was stirred for 48 hours at room temperature of 25°C to produce ammonia. Thereafter, the same operation as in Experimental Example 1 was performed to determine the amount of ammonia, and it was confirmed that 4017 equivalents of ammonia were produced per amount of molybdenum complex used as a catalyst.
• the present invention can be used for a method for producing ammonia.

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