WO2022210567A1 - Method for producing ammonia, molybdenum complex used in said production method, and ligand that is raw material of said molybdenum complex - Google Patents

Method for producing ammonia, molybdenum complex used in said production method, and ligand that is raw material of said molybdenum complex Download PDF

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WO2022210567A1
WO2022210567A1 PCT/JP2022/015084 JP2022015084W WO2022210567A1 WO 2022210567 A1 WO2022210567 A1 WO 2022210567A1 JP 2022015084 W JP2022015084 W JP 2022015084W WO 2022210567 A1 WO2022210567 A1 WO 2022210567A1
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group
hydrogen atom
alkyl
aryl
alkyl group
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仁昭 西林
和也 荒芝
章一 近藤
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国立大学法人東京大学
日産化学株式会社
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    • 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
    • B01J31/22—Organic complexes
    • 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 in the gas phase
    • 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
    • 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 an industrial method for converting nitrogen molecules into ammonia, requires severe conditions of high temperature and high pressure, and consumes energy to produce hydrogen gas. is used in the Haber-Bosch process, which is an energy-intensive process.
  • 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 newly synthesized a molybdenum complex having a carbon-nitrogen-carbon ligand (hereinafter sometimes referred to as a CNC ligand).
  • the inventors created a molybdenum complex having a CNC ligand and discovered that it functions as a catalyst for the production of ammonia, thereby completing the present invention.
  • R 1 represents a hydrogen atom or an electron-withdrawing group
  • R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group
  • R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group
  • R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group
  • R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group
  • Z represents an anion.
  • Equation (3) and Equation (4) (Wherein, R 1 represents a hydrogen atom or an electron-withdrawing group, R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group; R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group; R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group; R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group; X represents a halogen atom.
  • R 1 represents a hydrogen atom or an electron-withdrawing group
  • R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group
  • R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group
  • R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group
  • R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group
  • Z represents an anion.
  • R 1 represents a hydrogen atom or an electron-withdrawing group
  • R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group
  • R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group
  • R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group
  • R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group
  • X represents a halogen atom.
  • a molybdenum complex represented by any one of
  • n represents normal, “i” iso, “c” cyclo, “s” secondary, “t” tertiary, “o” ortho, “m ' stands for meta and 'p' for para.
  • Me represents a methyl group
  • Et represents an ethyl group
  • t Bu represents a tertiary butyl group
  • thf represents tetrahydrofuran.
  • C a -C b alkyl group means monovalent 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-tri
  • a C a -C b alkoxy group represents a monovalent group in which the above-described alkyl group having a to b carbon atoms is bonded to oxygen, for example, a methoxy group , ethoxy group, n-propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, cyclobutoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, t-pentoxy group, 1,1-dimethylpropoxy group, cyclopentoxy group, n-hexythoxy group, isohexyxy group, 3-methylpentoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, cyclohexy Toxy group, n-heptoxy group, 2-methylhexyoxy group, 3-ethylpentoxy group,
  • a halogen atom in the present specification includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • Ar 1 aryl group in this specification represents a monovalent group obtained by removing one hydrogen atom from an aromatic ring of an aromatic hydrocarbon having 6 carbon atoms, such as a phenyl group, 2 to 6 Examples include a phenyl group having a substituent at at least one of the positions.
  • the substituents on the aromatic ring of Ar 1 aryl include halogen atoms such as fluoro, chloro, bromo and iodo groups, as well as methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n- Examples include butyl, isobutyl, s-butyl and t-butyl groups.
  • Ar 1 aryl groups include a phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluorophenyl group, fluoromethylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl group, p- tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-(t-butyl)phenyl group, m-(t-butyl)phenyl group, m-
  • Substituents having electron-withdrawing mesomeric and inductive effects include quaternary ammonium groups, trifluoromethyl groups, perfluoroalkyl groups, trichloromethyl groups, cyano groups, nitro groups, and formyl groups, each having an anion as a counter ion.
  • each C 1 -C 6 alkyl independently represents an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms includes, for example, methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t -butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, cyclohexyl group and the like.
  • C 1 -C 6 alkoxy represents a monovalent group in which the above C 1 -C 6 alkyl is bonded to oxygen.
  • the alkoxy group having 1 to 6 carbon atoms includes, for example, methoxy group, trifluoromethoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, t-pentoxy group, 1,1-dimethylpropoxy group, n-hexytoxy group, isohetoxy group, cyclohexytoxy group and the like.
  • each Ar 2 aryl independently represents an aryl group having 6 to 10 carbon atoms.
  • the alkyl group having 6 to 10 carbon atoms includes, for example, phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-trifluoromethylphenyl group, m-trifluoro methylphenyl group, p-trifluoromethylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group,
  • examples of the anion that is the counterion of the quaternary ammonium group include hexafluorophosphate ion, hexachloroantimonate ion, trifluoromethanesulfonate ion, tetrafluoroborate ion, phosphate ion, sulfonate ion, chloride, bromide, iodide, hydroxide and the like.
  • examples of the ammonium cation of the quaternary ammonium group include —NH 3 cation, —N mono(C 1 -C 12 alkyl)H 2 cation, —N di(C 1 - C 12 alkyl)H cation, —N tri(C 1 -C 12 alkyl) cation, —N mono(Ar 2 aryl)H 2 cation, —N di(Ar 2 aryl)H cation, —N tri(Ar 2 aryl ) cation, —N(C 1 -C 12 alkyl)(Ar 2 aryl)H cation, —N di(C 1 -C 12 alkyl)mono(Ar 2 aryl) cation, or —N mono(C 1 -C 12 Alkyl)di(Ar 2 aryl) cations are included, where the "-" above represents a bond.
  • each C 1 -C 12 alkyl in the ammonium cation of the quaternary ammonium group independently represents an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group having 1 to 12 carbon atoms includes, for example, methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t -butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, cyclohexyl group, 1-methylhexyl group, n-heptyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 1-methylhept
  • the above Ar 2 aryl in the ammonium cation of the quaternary ammonium group includes the same ones as described above, phenyl group, o-trifluoromethylphenyl group, m-trifluoro A methylphenyl group, p-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 3,4,5-trifluorophenyl group, 1-naphthyl group and 2-naphthyl group are preferred.
  • the ammonium cation of the quaternary ammonium group is preferably -NH3 cation, -N trimethyl cation, -N triethyl cation, or -N dimethylphenyl cation, for example.
  • Examples of the perfluoroalkyl group in the electron withdrawing group of the present embodiment include -CF 2 CF 3 , -(CF 2 ) 2 CF 3 , -(CF 2 ) 3 CF 3 , -(CF 2 ) 4 CF 3 , - ( CF2) 5CF3 , -(CF2) 6CF3 , -( CF2 ) 7CF3 , - ( CF2 ) 8CF3 , - ( CF2 ) 9CF3 , - ( CF 2 ) 10 CF 3 , -(CF 2 ) 11 CF 3 and the like, -CF 2 CF 3 , -(CF 2 ) 2 CF 3 , -(CF 2 ) 3 CF 3 , -(CF 2 ) 4 CF 3 , -(CF 2 ) 5 CF 3 , -(CF 2 ) 9 CF 3 and -(CF 2 ) 11 CF 3 are preferred.
  • the C 1 -C 6 alkyl in the carbonyl (C 1 -C 6 alkyl) group includes the same ones as described above, a carbonylmethyl group, a carbonyltrifluoromethyl group, a carbonylethyl group , carbonyl n-propyl group, carbonyl isopropyl group, carbonyl n-butyl group, carbonyl isobutyl group, carbonyl s-butyl group and carbonyl t-butyl group are preferred.
  • the C 1 -C 6 alkoxy in the carbonyl (C 1 -C 6 alkoxy) group includes the same ones as described above, a carbonylmethoxy group, a carbonyltrifluoromethoxy group, a carbonylethoxy group , carbonyl n-propoxy group, carbonyl isopropoxy group, carbonyl n-butoxy group, carbonyl isobutoxy group, carbonyl s-butoxy group and carbonyl t-butoxy group are preferred.
  • Ar 2aryl in the carbonyl (Ar 2aryl ) group is the same as those described above, and includes a carbonylphenyl group, a carbonyl o-trifluoromethylphenyl group, a carbonyl m-trifluoromethyl A phenyl group, a carbonyl p-trifluoromethylphenyl group, a carbonyl 3,5-bistrifluoromethylphenyl group, a carbonyl 3,4,5-trifluorophenyl group, a carbonyl 1-naphthyl group and a carbonyl 2-naphthyl group are preferred.
  • the C 1 -C 6 alkyl in the carbonyl(C 1 -C 6 alkyl)amino group includes the same ones as described above, a carbonylmethylamino group, a carbonyltrifluoromethylamino group, A carbonylethylamino group, a carbonyl n-propylamino group, a carbonylisopropylamino group, a carbonyl n-butylamino group, a carbonylisobutylamino group, a carbonyl s-butylamino group and a carbonyl t-butylamino group are preferred.
  • the C 1 -C 6 alkyl in the carbonyldi(C 1 -C 6 alkyl)amino group includes the same ones as described above, carbonyldimethylamino group, carbonylbis(trifluoromethyl ) amino group, carbonyldiethylamino group, carbonyldi-n-propylamino group, carbonyldiisopropylamino group, carbonyldi-n-butylamino group, carbonyldiisobutylamino group, carbonyldi-s-butylamino group, carbonyldi-t-butylamino group preferable.
  • the C 1 -C 6 alkyl in the sulfonyl(C 1 -C 6 alkyl)amino group includes the same ones as described above, a sulfonylmethylamino group, a sulfonyltrifluoromethylamino group, A sulfonylethylamino group, a sulfonyl n-propylamino group, a sulfonylisopropylamino group, a sulfonyl n-butylamino group, a sulfonylisobutylamino group, a sulfonyl s-butylamino group and a sulfonyl t-butylamino group are preferred.
  • the C 1 -C 6 alkyl in the sulfonyldi(C 1 -C 6 alkyl)amino group includes the same ones as described above, a sulfonyldimethylamino group, a sulfonylbis(trifluoromethyl ) amino group, sulfonyldiethylamino group, sulfonyldi-n-propylamino group, sulfonyldiisopropylamino group, sulfonyldi-n-butylamino group, sulfonyldiisobutylamino group, sulfonyldi-s-butylamino group, sulfonyldi-t-butylamino group preferable.
  • the Ar 2 aryl group includes the same Ar 2 aryl groups as the above Ar 2 aryl groups, such as a phenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoro Methylphenyl, 3,5-bistrifluoromethylphenyl, 3,4,5-trifluorophenyl, 1-naphthyl and 2-naphthyl groups are preferred.
  • Ar 2 aryl groups such as a phenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoro Methylphenyl, 3,5-bistrifluoromethylphenyl, 3,4,5-trifluorophenyl, 1-naphthyl and 2-naphthyl groups are preferred.
  • More preferred electron-withdrawing groups in the method for producing ammonia of the present embodiment are —NH 3 cation, —N trimethyl cation, —N triethyl cation, —N dimethylphenyl cation, —CF 2 CF 3 , —(CF 2 ). 2CF3 , -(CF2) 3CF3 , - ( CF2) 4CF3 , - ( CF2 ) 5CF3 , -( CF2 ) 9CF3 , - ( CF2 ) 11CF3 , fluorine atoms, chlorine atoms and trifluoromethyl groups, and even more preferred electron withdrawing groups are fluorine atoms, chlorine atoms and trifluoromethyl groups.
  • R 2 and R 3 in the CNC ligands represented by formulas (1) and (2) will be explained.
  • R 2 and R 3 each independently include a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group and an Ar 1 aryl group, preferably R 2 and R 3 are a hydrogen atom, fluorine Atom, a phenyl group and a 3,4,5-trifluorophenyl group, more preferred R 2 and R 3 are a hydrogen atom and a phenyl group.
  • R 4 in the CNC ligands represented by formulas (1) and (2) will be described.
  • R 4 includes C 1 to C 10 alkyl groups and Ar 1 aryl groups, and preferred R 4 is isopropyl group, cyclopropyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, isopentyl group , 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, 2- methylhexyl group, 3-ethylpentyl group, 2,2,4-trimethylpentyl group, 2,5-dimethylhexyl group, 2,7-dimethyloctyl group, adamantyl group, phenyl group
  • R 5 and R 6 in the CNC ligands represented by formulas (1) and (2) will be explained.
  • R 5 and R 6 each independently include a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group, and preferred R 5 and R 6 are a hydrogen atom, They are a methyl group, a phenyl group and a 3,4,5-trifluorophenyl group.
  • R 7 , R 8 , R 9 and R 10 in the CNC ligands represented by formulas (1) and (2) will be explained.
  • R 7 , R 8 , R 9 and R 10 each independently include a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group, and preferred R 7 , R 8 , R 9 and R 10 are a hydrogen atom, a methyl group, a phenyl group and a 3,4,5-trifluorophenyl group.
  • Z in the CNC ligands represented by formulas (1) and (2) will be described.
  • Z represents an anion, and since the CNC ligand of the present invention is a divalent cation compound, Z is represented as 2Za when a monovalent anion is defined as Za.
  • Za which is a monovalent anion, includes fluoride ion (also referred to as F-), chloride ion (also referred to as Cl- ) , bromide ion (also referred to as Br- ) , iodide ion (also referred to as I-).
  • tetrafluoroborate also referred to as BF 4 -
  • trifluoro(trifluoromethyl)borate also referred to as [BF 3 (CF 3 )] -
  • dimethyl phosphate ion diethyl phosphate ion, hexafluorophosphate ion
  • phate also referred to as PF 6 -
  • tris(pentafluoroethyl)trifluorophosphate trifluoroacetate, methylsulfate, trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide and the like.
  • Preferred Za are chloride ion, bromide ion, iodide ion, tetrafluoroborate, hexafluorophosphate, and preferred Z are 2Cl ⁇ , 2Br ⁇ , 2I ⁇ , 2BF 4 ⁇ , 2PF 6 ⁇ .
  • Equation (3) and Equation (4) The molybdenum complex represented by will be described.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 in formulas (3) and (4) are the same as above.
  • X in the molybdenum complexes represented by formulas (3) and (4) will be described.
  • 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.
  • the reducing agent includes lanthanide metal halides
  • the lanthanide metals include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.
  • holmium, erbium, thulium, ytterbium, and lutetium among which samarium, europium, and ytterbium, which can be in a divalent state, are preferred.
  • Halogens include chlorine, bromine, and iodine, of which iodine is 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.
  • proton sources include alcohol and water.
  • alcohol to be used glycol may be used, or R a OH (R a is a linear, cyclic or branched alkyl having 1 to 6 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom). or a phenyl group optionally having an alkyl group) may be used.
  • Glycols include, for example, ethylene glycol, propylene glycol and diethylene glycol.
  • R a OH is, for example, linear or branched alkyl alcohols such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, s-butyl alcohol, isobutyl alcohol and t-butyl alcohol.
  • alkyl alcohols include cyclopropanol, cyclopentanol and cyclohexanol
  • examples of alcohols containing fluorine atoms include trifluoroethyl alcohol and tetrafluoroethyl alcohol
  • examples of phenol and its derivatives include phenol , cresol and xylenol.
  • preferred proton sources are water and ethylene glycol, with water being more preferred.
  • the production of ammonia from nitrogen molecules may be carried out in a solvent.
  • the solvent include, but are not particularly limited to, ether-based compounds, nitrile-based compounds and hydrocarbon-based compounds.
  • ether compounds include cyclic ether compounds such as tetrahydrofuran (thf), 4-methyltetrahydropyran, tetrahydropyran-4-methanol and 1,4-dioxane, as well as diethyl ether, diisopropyl ether, 1,2-dimethoxy
  • chain ether compounds such as ethane and cyclopentyl methyl ether.
  • nitrile compounds include acetonitrile and propionitrile.
  • hydrocarbon compounds examples include aromatic hydrocarbon compounds such as toluene and o-xylene, and saturated hydrocarbon compounds such as hexane, heptane and petroleum ether.
  • a preferable solvent in the method for producing ammonia of the present embodiment is tetrahydrofuran.
  • 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°C to 60°C, more preferably 0°C to 40°C.
  • the amount of catalyst used is preferably 0.0001 to 0.1 equivalents relative to the reducing agent, more preferably 0.001 to 0.01 equivalents. preferable.
  • the amount of the proton source used is preferably 0.5 to 5 equivalents, more preferably 1 to 2 equivalents, relative to the reducing agent.
  • Molybdenum complex represented by formula (9) was used to produce ammonia from molecular nitrogen.
  • Molybdenum complex (9) (1.3 mg, 20 ⁇ mol) and diiodobis(tetrahydrofuran)samarium (II) (197 mg, 0.36 mmol) and tetrahydrofuran (5.5 mL) were added to a Schlenk reaction vessel under nitrogen atmosphere at normal pressure.
  • Example 2 Ammonia production using the molybdenum complex represented by the formula (9)
  • the amount of the molybdenum complex represented by the formula (9), which is a catalyst was 0.05 ⁇ mol, and the reaction time was Experimental operations other than changing to 18 hours were performed in the same manner as in Example 1 to produce ammonia. As a result, 1530 equivalents of ammonia were produced per catalyst.
  • the present invention can be used for a method for producing ammonia.

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Abstract

[Problem] To provide a method for producing ammonia, a molybdenum complex used in said production method, and a ligand that is a raw material of said molybdenum complex. [Solution] Provided are: a method for producing ammonia from nitrogen molecules in the presence of a reducing agent and a proton source using, as a catalyst, a molybdenum complex obtained by reacting a molybdenum compound and a ligand represented by either formula (1) or formula (2) (in the formulas, R1 represents a hydrogen atom or an electron-withdrawing group, R2 and R3 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or an Ar1 aryl group, R4 represents a C1-C10 alkyl group or an Ar1 aryl group, R5 and R6 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or an Ar1 aryl group, R7, R8, R9, and R10 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or an Ar1 aryl group, and Z represents an anion); a molybdenum complex used in said production method; and a ligand that is a raw material of said molybdenum complex.

Description

アンモニアの製造方法、並びに該製造方法に用いるモリブデン錯体及び該モリブデン錯体の原料である配位子Ammonia production method, molybdenum complex used in said production method, and ligand as raw material for said molybdenum complex
　本発明は、アンモニアの製造方法、並びに該製造方法に用いるモリブデン錯体及び該モリブデン錯体の原料である配位子に関する。 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.
　窒素分子をアンモニアに変換する工業的な手法であるハーバー・ボッシュ法は、高温高圧の厳しい条件を必要とし、更には水素ガスの製造にエネルギーを消費するため、世界中での年間のエネルギー消費量の数パーセントがハーバー・ボッシュ法に使用されている、エネルギー多消費型のプロセスである。これに対して近年、常温常圧で水素ガスを使用しない、窒素分子からアンモニアを製造する方法において、触媒にモリブデン錯体を使用して、プロトン源に水を用いたアンモニアの製造に関する報告例がある（非特許文献１）。さらには、触媒にモリブデン錯体を使用して、還元剤としてヨウ化サマリウム（ＩＩ）を、プロトン源としてアルコール類又は水を用いたアンモニアの製造に関する報告例がある（非特許文献２）。非特許文献２には、例えば、式（Ａ）及び式（Ｂ）で表されるモリブデン錯体
Figure JPOXMLDOC01-appb-C000005
 の記載があり、これらのモリブデン錯体は、モリブデン金属を含む同一平面上の３方向から３つの配位原子が結合する、リン－炭素－リン型ピンサー配位子（以下、ＰＣＰ配位子と記載することがある）、リン－窒素－リン型ピンサー配位子（以下、ＰＮＰ配位子と記載することがある）を有していることが特徴であった。 The Haber-Bosch process, an industrial method for converting nitrogen molecules into ammonia, requires severe conditions of high temperature and high pressure, and consumes energy to produce hydrogen gas. is used in the Haber-Bosch process, which is an energy-intensive process. On the other hand, in recent years, in 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). Furthermore, there is a report on the production of ammonia using a molybdenum complex as a catalyst, samarium(II) iodide as a reducing agent, and alcohols or water as a proton source (Non-Patent Document 2). Non-Patent Document 2 describes, for example, molybdenum complexes represented by formulas (A) and (B)
Figure JPOXMLDOC01-appb-C000005
 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).
　モリブデン金属周りの配位子として、これまでのＰＮＰ配位子及びＰＣＰ配位子とは異なる配位子を有するモリブデン錯体にて、アンモニアの製造を可能し、工業化を目指す事ができる汎用性の高いモリブデン錯体反応の開発が期待されていた。 As a ligand around molybdenum metal, a molybdenum complex that has a different ligand from the conventional PNP ligand and PCP ligand makes it possible to produce ammonia and is versatile enough to aim for industrialization. The development of high molybdenum complex reaction was expected.
　上述した目的を達成するために、本発明者らは、炭素－窒素－炭素配位子（以下、ＣＮＣ配位子と記載することがある）を有するモリブデン錯体を分子設計し、新たに合成したＣＮＣ配位子を有するモリブデン錯体を創出して、アンモニアの製造の触媒として機能する事を見出し、本発明を完成するに至った。ＣＮＣ配位子を有するモリブデン錯体でアンモニアの製造を可能にした事例はない。 In order to achieve the above objects, the present inventors molecularly designed and newly synthesized a molybdenum complex having a carbon-nitrogen-carbon ligand (hereinafter sometimes referred to as a CNC ligand). The inventors created a molybdenum complex having a CNC ligand and discovered that it functions as a catalyst for the production of ammonia, thereby completing the present invention. There are no examples of molybdenum complexes with CNC ligands that enable the production of ammonia.
　即ち、本発明は下記〔１〕～〔８〕に関するものである。
　　〔１〕
　式（１）及び式（２）
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ１は、水素原子又は電子求引基を表し、
　Ｒ２及びＲ３は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｒ４は、Ｃ１～Ｃ１０アルキル基、又はＡｒ１アリール基を表し、
　Ｒ５及びＲ６は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｒ７、Ｒ８、Ｒ９及びＲ１０は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｚは、アニオンを表す。）の何れかで表される配位子とモリブデン化合物とを反応させて得られるモリブデン錯体を触媒として使用して、還元剤及びプロトン源の存在下、窒素分子からアンモニアを製造する方法。
　　〔２〕
　上記還元剤がランタノイド系金属のハロゲン化物（ＩＩ）である、上記〔１〕に記載の方法。
　　〔３〕
　上記プロトン源がアルコール又は水である、上記〔１〕又は〔２〕に記載の方法。
　　〔４〕
　式（３）及び式（４）
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ１は、水素原子又は電子求引基を表し、
　Ｒ２及びＲ３は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｒ４は、Ｃ１～Ｃ１０アルキル基、又はＡｒ１アリール基を表し、
　Ｒ５及びＲ６は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｒ７、Ｒ８、Ｒ９及びＲ１０は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｘは、ハロゲン原子を表す。）の何れかで表されるモリブデン錯体を触媒として使用して、還元剤及びプロトン源の存在下、窒素分子からアンモニアを製造する方法。
　　〔５〕
　上記還元剤がランタノイド系金属のハロゲン化物（ＩＩ）である、上記〔４〕に記載の方法。
　　〔６〕
　上記プロトン源がアルコール又は水である、上記〔４〕又は〔５〕に記載の方法。
　　〔７〕
　式（１）及び式（２）
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ１は、水素原子又は電子求引基を表し、
　Ｒ２及びＲ３は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｒ４は、Ｃ１～Ｃ１０アルキル基、又はＡｒ１アリール基を表し、
　Ｒ５及びＲ６は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｒ７、Ｒ８、Ｒ９及びＲ１０は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｚは、アニオンを表す。）の何れかで表される配位子。
　　〔８〕
　式（３）及び式（４）
Figure JPOXMLDOC01-appb-C000009
 （式中、Ｒ１は、水素原子又は電子求引基を表し、
　Ｒ２及びＲ３は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｒ４は、Ｃ１～Ｃ１０アルキル基、又はＡｒ１アリール基を表し、
　Ｒ５及びＲ６は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｒ７、Ｒ８、Ｒ９及びＲ１０は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
　Ｘは、ハロゲン原子を表す。）の何れかで表されるモリブデン錯体。 That is, the present invention relates to the following [1] to [8].
[1]
Formula (1) and Formula (2)
Figure JPOXMLDOC01-appb-C000006
 (Wherein, R 1 represents a hydrogen atom or an electron-withdrawing group,
R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group;
R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
Z represents an anion. ) in the presence of a reducing agent and a proton source, using a molybdenum complex obtained by reacting a molybdenum compound with a ligand represented by any of ) as a catalyst to produce ammonia from nitrogen molecules.
[2]
The method according to [1] above, wherein the reducing agent is a lanthanide metal halide (II).
[3]
The method according to [1] or [2] above, wherein the proton source is alcohol or water.
[4]
Equation (3) and Equation (4)
Figure JPOXMLDOC01-appb-C000007
 (Wherein, R 1 represents a hydrogen atom or an electron-withdrawing group,
R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group;
R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
X represents a halogen atom. ) as a catalyst to produce ammonia from nitrogen molecules in the presence of a reducing agent and a proton source.
[5]
The method according to [4] above, wherein the reducing agent is a lanthanide metal halide (II).
[6]
The method according to [4] or [5] above, wherein the proton source is alcohol or water.
[7]
Formula (1) and Formula (2)
Figure JPOXMLDOC01-appb-C000008
 (Wherein, R 1 represents a hydrogen atom or an electron-withdrawing group,
R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group;
R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
Z represents an anion. ) is a ligand represented by any one of
[8]
Equation (3) and Equation (4)
Figure JPOXMLDOC01-appb-C000009
 (Wherein, R 1 represents a hydrogen atom or an electron-withdrawing group,
R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group;
R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
X represents a halogen atom. ) a molybdenum complex represented by any one of
　本発明のＣＮＣ配位子を有するモリブデン錯体を用いたアンモニアの製造を実施できる新方法を提供する。 We provide a new method for producing ammonia using the molybdenum complex having the CNC ligand of the present invention.
　本明細書における「ｎ」はノルマルを、「ｉ」はイソを、「ｃ」はシクロを、「ｓ」はセカンダリーを、「ｔ」はターシャリーを表し、「ｏ」はオルトを、「ｍ」はメタを、「ｐ」はパラを表す。「Ｍｅ」はメチル基を、「Ｅｔ」はエチル基を、「ｔＢｕ」はターシャリーブチル基を、「ｔｈｆ」はテトラヒドロフランを表す。 As used herein, "n" represents normal, "i" iso, "c" cyclo, "s" secondary, "t" tertiary, "o" ortho, "m ' stands for meta and 'p' for para. “Me” represents a methyl group, “Et” represents an ethyl group, “ t Bu” represents a tertiary butyl group, and “thf” represents tetrahydrofuran.
　本明細書におけるＣａ～Ｃｂアルキル基の表記は、炭素原子数がａ乃至ｂ個よりなる直鎖状、分岐鎖状又は環状の脂肪族炭化水素から一つの水素原子を取り去った１価の基を表し、例えばメチル基、エチル基、ｎ－プロピル基、イソプロピル基、シクロプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、シクロブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔ－ペンチル基、１，１－ジメチルプロピル基、シクロペンチル基、ｎ－ヘキシル基、イソヘキシル基、３－メチルペンチル基、２，２－ジメチルブチル基、２，３－ジメチルブチル基、シクロヘキシル基、ｎ－ヘプチル基、２－メチルヘキシル基、３－エチルペンチル基、ｎ－オクチル基、２，２，４－トリメチルペンチル基、２，５－ジメチルヘキシル基、ｎ－ノニル基、２，７－ジメチルオクチル基、ｎ－デシル基、アダマンチル基、ｎ－ウンデシル基、１－メチルウンデシル基、ｎ－ドデシル基等が挙げられ、さらに加えて、トリフルオロメチル基が挙げられ、各々の指定の炭素原子数の範囲で設定される。炭素原子数を表す「Ｃａ～Ｃｂ」において、ａは１以上の整数であり、ｂはａ以上の整数である。 In the present specification, the notation of C a -C b alkyl group means monovalent 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-dimethylhexyl group, n-nonyl group, 2 , 7-dimethyloctyl group, n-decyl group, adamantyl group, n-undecyl group, 1-methylundecyl group, n-dodecyl group and the like. It is set within the specified range of the number of carbon atoms. In “C a to C b ” representing the number of carbon atoms, a is an integer of 1 or more and b is an integer of a or more.
　本明細書におけるＣａ～Ｃｂアルコキシ基の表記は、炭素原子数がａ乃至ｂ個よりなる前記の意味であるアルキル基が、酸素と結合した形の１価の基を表し、例えばメトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、シクロプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、シクロブトキシ基、ｎ－ペントキシ基、イソペントキシ基、ネオペントキシ基、ｔ－ペントキシ基、１，１－ジメチルプロポキシ基、シクロペントキシ基、ｎ－ヘキトキシ基、イソヘキトキシ基、３－メチルペントキシ基、２，２－ジメチルブトキシ基、２，３－ジメチルブトキシ基、シクロヘキトキシ基、ｎ－ヘプトキシ基、２－メチルヘキトキシ基、３－エチルペントキシ基、ｎ－オクトキシ基、２，２，４－トリメチルペントキシ基、２，５－ジメチルヘキトキシ基等が挙げられ、さらに加えてトリフルオロメトキシ基が挙げられ、各々の指定の炭素原子数の範囲で設定される。 In the present specification, the notation of a C a -C b alkoxy group represents a monovalent group in which the above-described alkyl group having a to b carbon atoms is bonded to oxygen, for example, a methoxy group , ethoxy group, n-propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, cyclobutoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, t-pentoxy group, 1,1-dimethylpropoxy group, cyclopentoxy group, n-hexythoxy group, isohexyxy group, 3-methylpentoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, cyclohexy Toxy group, n-heptoxy group, 2-methylhexyoxy group, 3-ethylpentoxy group, n-octoxy group, 2,2,4-trimethylpentoxy group, 2,5-dimethylhexyxy group and the like, and further Additionally, trifluoromethoxy groups are included, each with a specified number of carbon atoms.
　本明細書におけるハロゲン原子は、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 A halogen atom in the present specification includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
　本明細書におけるＡｒ１アリール基の表記は、炭素原子数が６個よりなる芳香族炭化水素の芳香環から一つの水素原子を取り去った１価の基を表し、例えばフェニル基、２位から６位の少なくとも１つに置換基を有するフェニル基等が挙げられる。Ａｒ１アリールの芳香環上の置換基としては、ハロゲン原子であるフルオロ基、クロロ基、ブロモ基及びヨード基並びにメチル基、トリフルオロメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基及びｔ－ブチル基等が挙げられる。Ａｒ１アリール基の具体例としては、フェニル基、ｏ－フルオロフェニル基、ｍ－フルオロフェニル基、ｐ－フルオロフェニル基、ｏ－トリフルオロメチルフェニル基、ｍ－トリフルオロメチルフェニル基、ｐ－トリフルオロメチルフェニル基、ｏ－クロロフェニル基、ｍ－クロロフェニル基、ｐ－クロロフェニル基、ｏ－ブロモフェニル基、ｍ－ブロモフェニル基、ｐ－ブロモフェニル基、ｏ－トリル基、ｍ－トリル基、ｐ－トリル基、ｏ－エチルフェニル基、ｍ－エチルフェニル基、ｐ－エチルフェニル基、ｏ－（ｔ－ブチル）フェニル基、ｍ－（ｔ－ブチル）フェニル基、ｐ－（ｔ－ブチル）フェニル基、２，６－ジメチルフェニル基、２，６－ビストリフルオロメチルフェニル基、３，５－ジメチルフェニル基、３，５－ビストリフルオロメチルフェニル基、２，６－ジエチルフェニル基、２，６－ジイソプロピルフェニル基、２，４，６－トリメチルフェニル基、２，４，６－トリエチルフェニル基、２，４，６－トリイソプロピルフェニル基、３，４，５－トリフルオロフェニル基、２，３，４，５、６－ペンタフルオロフェニル基、ｏ－メトキシフェニル基、ｍ－メトキシフェニル基、ｐ－メトキシフェニル基、２，６－ジメトキシフェニル基、２，６－ジエトキシフェニル基、２，６－ジイソプロポキシフェニル基、２，４，６－トリメトキシフェニル基、２，４，６－トリエトキシフェニル基、２，４，６－トリイソプロポキシフェニル基等が挙げられる。 The notation of Ar 1 aryl group in this specification represents a monovalent group obtained by removing one hydrogen atom from an aromatic ring of an aromatic hydrocarbon having 6 carbon atoms, such as a phenyl group, 2 to 6 Examples include a phenyl group having a substituent at at least one of the positions. The substituents on the aromatic ring of Ar 1 aryl include halogen atoms such as fluoro, chloro, bromo and iodo groups, as well as methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n- Examples include butyl, isobutyl, s-butyl and t-butyl groups. Specific examples of Ar 1 aryl groups include a phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluorophenyl group, fluoromethylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl group, p- tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-(t-butyl)phenyl group, m-(t-butyl)phenyl group, p-(t-butyl)phenyl group , 2,6-dimethylphenyl group, 2,6-bistrifluoromethylphenyl group, 3,5-dimethylphenyl group, 3,5-bistrifluoromethylphenyl group, 2,6-diethylphenyl group, 2,6-diisopropyl phenyl group, 2,4,6-trimethylphenyl group, 2,4,6-triethylphenyl group, 2,4,6-triisopropylphenyl group, 3,4,5-trifluorophenyl group, 2,3,4 , 5,6-pentafluorophenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, 2,6-dimethoxyphenyl group, 2,6-diethoxyphenyl group, 2,6-di isopropoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2,4,6-triethoxyphenyl group, 2,4,6-triisopropoxyphenyl group and the like.
　本発明の好適な実施形態を以下に示す。 A preferred embodiment of the present invention is shown below.
　式（１）及び式（２）
Figure JPOXMLDOC01-appb-C000010
 で表されるＣＮＣ配位子におけるＲ１の電子求引基について説明する。電子求引基において、メソメリー効果は電子供与性であるが誘起効果の電子求引性の寄与が大きい置換基としては、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子、－ＣＨ２Ｃｌ又は－ＣＨ＝ＣＨＮＯ２が挙げられる。メソメリー効果及び誘起効果が電子求引性である置換基としては、アニオンを対イオンとする第四級アンモニウム基、トリフルオロメチル基、パーフルオロアルキル基、トリクロロメチル基、シアノ基、ニトロ基、ホルミル基、カルボン酸基、カルボニル（Ｃ１～Ｃ６アルキル）基、カルボニル（Ｃ１～Ｃ６アルコキシ）基、カルボニル（Ａｒ２アリール）基、カルボニルアミノ基、カルボニル（Ｃ１～Ｃ６アルキル）アミノ基、カルボニルジ（Ｃ１～Ｃ６アルキル）アミノ基、スルホン酸基、スルホニルアミノ基、スルホニル（Ｃ１～Ｃ６アルキル）アミノ基、スルホニルジ（Ｃ１～Ｃ６アルキル）アミノ基、Ａｒ２アリール基が挙げられる。 Formula (1) and Formula (2)
Figure JPOXMLDOC01-appb-C000010
 The electron-withdrawing group of R 1 in the CNC ligand represented by will be explained. In the electron-withdrawing group, the mesomeric effect is electron-donating, but substituents that greatly contribute to the electron-withdrawing inductive effect include, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, —CH 2 Cl or — CH= CHNO2 can be mentioned. Substituents having electron-withdrawing mesomeric and inductive effects include quaternary ammonium groups, trifluoromethyl groups, perfluoroalkyl groups, trichloromethyl groups, cyano groups, nitro groups, and formyl groups, each having an anion as a counter ion. group, carboxylic acid group, carbonyl (C 1 -C 6 alkyl) group, carbonyl (C 1 -C 6 alkoxy) group, carbonyl (Ar 2 aryl) group, carbonylamino group, carbonyl (C 1 -C 6 alkyl)amino carbonyldi(C 1 -C 6 alkyl)amino group, sulfonic acid group, sulfonylamino group, sulfonyl(C 1 -C 6 alkyl)amino group, sulfonyldi(C 1 -C 6 alkyl)amino group, Ar 2 An aryl group is mentioned.
　本実施形態の電子求引基において、Ｃ１～Ｃ６アルキルは、各々独立して、炭素原子数１乃至６のアルキル基を表す。ここで、炭素原子数１乃至６のアルキル基としては、例えば、メチル基、トリフルオロメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔ－ペンチル基、１，１－ジメチルプロピル基、ｎ－ヘキシル基、イソヘキシル基、シクロヘキシル基等が挙げられる。 In the electron withdrawing group of this embodiment, each C 1 -C 6 alkyl independently represents an alkyl group having 1 to 6 carbon atoms. Here, the alkyl group having 1 to 6 carbon atoms includes, for example, methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t -butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, cyclohexyl group and the like.
　本実施形態の電子求引基において、Ｃ１～Ｃ６アルコキシは、前記のＣ１～Ｃ６アルキルが、酸素と結合した形の一価の基を表す。ここで、炭素原子数１乃至６のアルコキシ基としては、例えば、メトキシ基、トリフルオロメトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、ｎ－ペントキシ基、イソペントキシ基、ネオペントキシ基、ｔ－ペントキシ基、１，１－ジメチルプロポキシ基、ｎ－ヘキトキシ基、イソヘキトキシ基、シクロヘキトキシ基等が挙げられる。 In the electron-withdrawing group of this embodiment, C 1 -C 6 alkoxy represents a monovalent group in which the above C 1 -C 6 alkyl is bonded to oxygen. Here, the alkoxy group having 1 to 6 carbon atoms includes, for example, methoxy group, trifluoromethoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, t-pentoxy group, 1,1-dimethylpropoxy group, n-hexytoxy group, isohetoxy group, cyclohexytoxy group and the like.
　本実施形態の電子求引基において、Ａｒ２アリールは、各々独立して、炭素原子数６乃至１０のアリール基を表す。ここで、炭素原子数６乃至１０のアルキル基としては、例えば、フェニル基、ｏ－フルオロフェニル基、ｍ－フルオロフェニル基、ｐ－フルオロフェニル基、ｏ－トリフルオロメチルフェニル基、ｍ－トリフルオロメチルフェニル基、ｐ－トリフルオロメチルフェニル基、ｏ－クロロフェニル基、ｍ－クロロフェニル基、ｐ－クロロフェニル基、ｏ－ブロモフェニル基、ｍ－ブロモフェニル基、ｐ－ブロモフェニル基、ｏ－トリル基、ｍ－トリル基、ｐ－トリル基、ｏ－エチルフェニル基、ｍ－エチルフェニル基、ｐ－エチルフェニル基、ｏ－（ｔ－ブチル）フェニル基、ｍ－（ｔ－ブチル）フェニル基、ｐ－（ｔ－ブチル）フェニル基、３，５－ジメチルフェニル基、３，５－ビストリフルオロメチルフェニル基、３，４，５－トリフルオロフェニル基、ｏ－メトキシフェニル基、ｍ－メトキシフェニル基、ｐ－メトキシフェニル基、１－ナフチル基、２－ナフチル基、２－フルオロナフタレン－１－イル基、３－フルオロナフタレン－１－イル基、４－フルオロナフタレン－１－イル基、５－フルオロナフタレン－１－イル基、６－フルオロナフタレン－１－イル基、７－フルオロナフタレン－１－イル基、８－フルオロナフタレン－１－イル基、２－クロロナフタレン－１－イル基、３－クロロナフタレン－１－イル基、４－クロロナフタレン－１－イル基、５－クロロナフタレン－１－イル基、６－クロロナフタレン－１－イル基、７－クロロナフタレン－１－イル基、８－クロロナフタレン－１－イル基、２－ブロモナフタレン－１－イル基、３－ブロモナフタレン－１－イル基、４－ブロモナフタレン－１－イル基、５－ブロモナフタレン－１－イル基、６－ブロモナフタレン－１－イル基、７－ブロモナフタレン－１－イル基、８－ブロモナフタレン－１－イル基、２－ヨードナフタレン－１－イル基、３－ヨードナフタレン－１－イル基、４－ヨードナフタレン－１－イル基、５－ヨードナフタレン－１－イル基、６－ヨードナフタレン－１－イル基、７－ヨードナフタレン－１－イル基、８－ヨードナフタレン－１－イル基、２－メチルナフタレン－１－イル基、３－メチルナフタレン－１－イル基、４－メチルナフタレン－１－イル基、５－メチルナフタレン－１－イル基、６－メチルナフタレン－１－イル基、７－メチルナフタレン－１－イル基、８－メチルナフタレン－１－イル基、２－エチルナフタレン－１－イル基、３－エチルナフタレン－１－イル基、４－エチルナフタレン－１－イル基、５－エチルナフタレン－１－イル基、６－エチルナフタレン－１－イル基、７－エチルナフタレン－１－イル基、８－エチルナフタレン－１－イル基、２－ｎ－プロピルナフタレン－１－イル基、３－ｎ－プロピルナフタレン－１－イル基、４－ｎ－プロピルナフタレン－１－イル基、５－ｎ－プロピルナフタレン－１－イル基、６－ｎ－プロピルナフタレン－１－イル基、７－ｎ－プロピルナフタレン－１－イル基、８－ｎ－プロピルナフタレン－１－イル基、２－ｉ－プロピルナフタレン－１－イル基、３－ｉ－プロピルナフタレン－１－イル基、４－ｉ－プロピルナフタレン－１－イル基、５－ｉ－プロピルナフタレン－１－イル基、６－ｉ－プロピルナフタレン－１－イル基、７－ｉ－プロピルナフタレン－１－イル基、８－ｉ－プロピルナフタレン－１－イル基、２－ｃ－プロピルナフタレン－１－イル基、３－ｃ－プロピルナフタレン－１－イル基、４－ｃ－プロピルナフタレン－１－イル基、５－ｃ－プロピルナフタレン－１－イル基、６－ｃ－プロピルナフタレン－１－イル基、７－ｃ－プロピルナフタレン－１－イル基、８－ｃ－プロピルナフタレン－１－イル基、２－ｎ－ブチルナフタレン－１－イル基、３－ｎ－ブチルナフタレン－１－イル基、４－ｎ－ブチルナフタレン－１－イル基、５－ｎ－ブチルナフタレン－１－イル基、６－ｎ－ブチルナフタレン－１－イル基、７－ｎ－ブチルナフタレン－１－イル基、８－ｎ－ブチルナフタレン－１－イル基、１－フルオロナフタレン－２－イル基、３－フルオロナフタレン－２－イル基、４－フルオロナフタレン－２－イル基、５－フルオロナフタレン－２－イル基、６－フルオロナフタレン－２－イル基、７－フルオロナフタレン－２－イル基、８－フルオロナフタレン－２－イル基、１－クロロナフタレン－２－イル基、３－クロロナフタレン－２－イル基、４－クロロナフタレン－２－イル基、５－クロロナフタレン－２－イル基、６－クロロナフタレン－２－イル基、７－クロロナフタレン－２－イル基、８－クロロナフタレン－２－イル基、１－ブロモナフタレン－２－イル基、３－ブロモナフタレン－２－イル基、４－ブロモナフタレン－２－イル基、５－ブロモナフタレン－２－イル基、６－ブロモナフタレン－２－イル基、７－ブロモナフタレン－２－イル基、８－ブロモナフタレン－２－イル基、１－ヨードナフタレン－２－イル基、３－ヨードナフタレン－２－イル基、４－ヨードナフタレン－２－イル基、５－ヨードナフタレン－２－イル基、６－ヨードナフタレン－２－イル基、７－ヨードナフタレン－２－イル基、８－ヨードナフタレン－２－イル基、１－メチルナフタレン－２－イル基、３－メチルナフタレン－２－イル基、４－メチルナフタレン－２－イル基、５－メチルナフタレン－２－イル基、６－メチルナフタレン－２－イル基、７－メチルナフタレン－２－イル基、８－メチルナフタレン－２－イル基、１－エチルナフタレン－２－イル基、３－エチルナフタレン－２－イル基、４－エチルナフタレン－２－イル基、５－エチルナフタレン－２－イル基、６－エチルナフタレン－２－イル基、７－エチルナフタレン－２－イル基、８－エチルナフタレン－２－イル基、１－ｎ－プロピルナフタレン－２－イル基、３－ｎ－プロピルナフタレン－２－イル基、４－ｎ－プロピルナフタレン－２－イル基、５－ｎ－プロピルナフタレン－２－イル基、６－ｎ－プロピルナフタレン－２－イル基、７－ｎ－プロピルナフタレン－２－イル基、８－ｎ－プロピルナフタレン－２－イル基、１－ｉ－プロピルナフタレン－２－イル基、３－ｉ－プロピルナフタレン－２－イル基、４－ｉ－プロピルナフタレン－２－イル基、５－ｉ－プロピルナフタレン－２－イル基、６－ｉ－プロピルナフタレン－２－イル基、７－ｉ－プロピルナフタレン－２－イル基、８－ｉ－プロピルナフタレン－２－イル基、１－ｃ－プロピルナフタレン－２－イル基、３－ｃ－プロピルナフタレン－２－イル基、４－ｃ－プロピルナフタレン－２－イル基、５－ｃ－プロピルナフタレン－２－イル基、６－ｃ－プロピルナフタレン－２－イル基、７－ｃ－プロピルナフタレン－２－イル基、８－ｃ－プロピルナフタレン－２－イル基、１－ｎ－ブチルナフタレン－２－イル基、３－ｎ－ブチルナフタレン－２－イル基、４－ｎ－ブチルナフタレン－２－イル基、５－ｎ－ブチルナフタレン－２－イル基、６－ｎ－ブチルナフタレン－２－イル基、７－ｎ－ブチルナフタレン－２－イル基及び８－ｎ－ブチルナフタレン－２－イル基等が挙げられる。 In the electron withdrawing group of this embodiment, each Ar 2 aryl independently represents an aryl group having 6 to 10 carbon atoms. Here, the alkyl group having 6 to 10 carbon atoms includes, for example, phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-trifluoromethylphenyl group, m-trifluoro methylphenyl group, p-trifluoromethylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-(t-butyl)phenyl group, m-(t-butyl)phenyl group, p- (t-butyl)phenyl group, 3,5-dimethylphenyl group, 3,5-bistrifluoromethylphenyl group, 3,4,5-trifluorophenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p -Methoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 2-fluoronaphthalen-1-yl group, 3-fluoronaphthalen-1-yl group, 4-fluoronaphthalen-1-yl group, 5-fluoronaphthalene- 1-yl group, 6-fluoronaphthalene-1-yl group, 7-fluoronaphthalene-1-yl group, 8-fluoronaphthalene-1-yl group, 2-chloronaphthalene-1-yl group, 3-chloronaphthalene- 1-yl group, 4-chloronaphthalene-1-yl group, 5-chloronaphthalene-1-yl group, 6-chloronaphthalene-1-yl group, 7-chloronaphthalene-1-yl group, 8-chloronaphthalene- 1-yl group, 2-bromonaphthalen-1-yl group, 3-bromonaphthalen-1-yl group, 4-bromonaphthalen-1-yl group, 5-bromonaphthalen-1-yl group, 6-bromonaphthalene- 1-yl group, 7-bromonaphthalen-1-yl group, 8-bromonaphthalen-1-yl group, 2-iodonaphthalen-1-yl group, 3-iodonaphthalen-1-yl group, 4-iodonaphthalene- 1-yl group, 5-iodonaphthalen-1-yl group, 6-iodonaphthalen-1-yl group, 7-iodonaphthalen-1-yl group, 8-iodonaphthalen-1-yl group, 2-methylnaphthalene- 1-yl group, 3-methylnaphthalene-1-yl group, 4-methylnaphthalene-1-yl group, 5-methylnaphthalene-1-yl group, 6-methylnaphthalene-1-yl group, 7-methylnaphthalene- 1-yl group, 8-methylnaphthalen-1-yl group, 2-ethylna phthalen-1-yl group, 3-ethylnaphthalen-1-yl group, 4-ethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 6-ethylnaphthalen-1-yl group, 7-ethyl naphthalene-1-yl group, 8-ethylnaphthalene-1-yl group, 2-n-propylnaphthalene-1-yl group, 3-n-propylnaphthalene-1-yl group, 4-n-propylnaphthalene-1- yl group, 5-n-propylnaphthalen-1-yl group, 6-n-propylnaphthalen-1-yl group, 7-n-propylnaphthalen-1-yl group, 8-n-propylnaphthalen-1-yl group , 2-i-propylnaphthalen-1-yl group, 3-i-propylnaphthalen-1-yl group, 4-i-propylnaphthalen-1-yl group, 5-i-propylnaphthalen-1-yl group, 6 -i-propylnaphthalen-1-yl group, 7-i-propylnaphthalen-1-yl group, 8-i-propylnaphthalen-1-yl group, 2-c-propylnaphthalen-1-yl group, 3-c -Propylnaphthalen-1-yl group, 4-c-propylnaphthalen-1-yl group, 5-c-propylnaphthalen-1-yl group, 6-c-propylnaphthalen-1-yl group, 7-c-propyl naphthalene-1-yl group, 8-c-propylnaphthalene-1-yl group, 2-n-butylnaphthalene-1-yl group, 3-n-butylnaphthalene-1-yl group, 4-n-butylnaphthalene- 1-yl group, 5-n-butylnaphthalene-1-yl group, 6-n-butylnaphthalene-1-yl group, 7-n-butylnaphthalene-1-yl group, 8-n-butylnaphthalene-1- yl group, 1-fluoronaphthalene-2-yl group, 3-fluoronaphthalene-2-yl group, 4-fluoronaphthalene-2-yl group, 5-fluoronaphthalene-2-yl group, 6-fluoronaphthalene-2- yl group, 7-fluoronaphthalene-2-yl group, 8-fluoronaphthalene-2-yl group, 1-chloronaphthalene-2-yl group, 3-chloronaphthalene-2-yl group, 4-chloronaphthalene-2- yl group, 5-chloronaphthalene-2-yl group, 6-chloronaphthalene-2-yl group, 7-chloronaphthalene-2-yl group, 8-chloronaphthalene-2-yl group, 1-bromonaphthalene-2- yl group, 3-bromonaphthalen-2-yl group, 4-bromonaphthalen-2-yl group, 5-bromonaphthalen-2-yl group, 6-bromonaphthalen-2-yl group, 7-bromo Monaphthalen-2-yl group, 8-bromonaphthalen-2-yl group, 1-iodonaphthalen-2-yl group, 3-iodonaphthalen-2-yl group, 4-iodonaphthalen-2-yl group, 5-iodine naphthalene-2-yl group, 6-iodonaphthalen-2-yl group, 7-iodonaphthalen-2-yl group, 8-iodonaphthalen-2-yl group, 1-methylnaphthalene-2-yl group, 3-methyl naphthalene-2-yl group, 4-methylnaphthalene-2-yl group, 5-methylnaphthalene-2-yl group, 6-methylnaphthalene-2-yl group, 7-methylnaphthalene-2-yl group, 8-methyl naphthalene-2-yl group, 1-ethylnaphthalene-2-yl group, 3-ethylnaphthalene-2-yl group, 4-ethylnaphthalene-2-yl group, 5-ethylnaphthalene-2-yl group, 6-ethyl naphthalene-2-yl group, 7-ethylnaphthalene-2-yl group, 8-ethylnaphthalene-2-yl group, 1-n-propylnaphthalene-2-yl group, 3-n-propylnaphthalene-2-yl group , 4-n-propylnaphthalene-2-yl group, 5-n-propylnaphthalene-2-yl group, 6-n-propylnaphthalene-2-yl group, 7-n-propylnaphthalene-2-yl group, 8 -n-propylnaphthalen-2-yl group, 1-i-propylnaphthalen-2-yl group, 3-i-propylnaphthalen-2-yl group, 4-i-propylnaphthalen-2-yl group, 5-i -Propylnaphthalen-2-yl group, 6-i-propylnaphthalen-2-yl group, 7-i-propylnaphthalen-2-yl group, 8-i-propylnaphthalen-2-yl group, 1-c-propyl naphthalene-2-yl group, 3-c-propylnaphthalene-2-yl group, 4-c-propylnaphthalene-2-yl group, 5-c-propylnaphthalene-2-yl group, 6-c-propylnaphthalene- 2-yl group, 7-c-propylnaphthalene-2-yl group, 8-c-propylnaphthalene-2-yl group, 1-n-butylnaphthalene-2-yl group, 3-n-butylnaphthalene-2- yl group, 4-n-butylnaphthalene-2-yl group, 5-n-butylnaphthalene-2-yl group, 6-n-butylnaphthalene-2-yl group, 7-n-butylnaphthalene-2-yl group and 8-n-butylnaphthalen-2-yl group.
　本実施形態の電子求引基において、第四級アンモニウム基の対イオンであるアニオンとしては、例えば、ヘキサフルオロホスファートイオン、ヘキサクロロアンチモナートイオン、トリフルオロメタンスルホナートイオン、テトラフルオロボラートイオン、ホスフェートイオン、スルホナートイオン、クロリド、ブロミド、ヨージド、ヒドロキシド等が挙げられる。 In the electron-withdrawing group of the present embodiment, examples of the anion that is the counterion of the quaternary ammonium group include hexafluorophosphate ion, hexachloroantimonate ion, trifluoromethanesulfonate ion, tetrafluoroborate ion, phosphate ion, sulfonate ion, chloride, bromide, iodide, hydroxide and the like.
　本実施形態の電子求引基において、第四級アンモニウム基のアンモニウムカチオンとしては、例えば、－ＮＨ３カチオン、－Ｎモノ（Ｃ１～Ｃ１２アルキル）Ｈ２カチオン、－Ｎジ（Ｃ１～Ｃ１２アルキル）Ｈカチオン、－Ｎトリ（Ｃ１～Ｃ１２アルキル）カチオン、－Ｎモノ（Ａｒ２アリール）Ｈ２カチオン、－Ｎジ（Ａｒ２アリール）Ｈカチオン、－Ｎトリ（Ａｒ２アリール）カチオン、－Ｎ（Ｃ１～Ｃ１２アルキル）（Ａｒ２アリール）Ｈカチオン、－Ｎジ（Ｃ１～Ｃ１２アルキル）モノ（Ａｒ２アリール）カチオン、又は－Ｎモノ（Ｃ１～Ｃ１２アルキル）ジ（Ａｒ２アリール）カチオンが挙げられ、上記の「－」は結合を表す。 In the electron withdrawing group of the present embodiment, examples of the ammonium cation of the quaternary ammonium group include —NH 3 cation, —N mono(C 1 -C 12 alkyl)H 2 cation, —N di(C 1 - C 12 alkyl)H cation, —N tri(C 1 -C 12 alkyl) cation, —N mono(Ar 2 aryl)H 2 cation, —N di(Ar 2 aryl)H cation, —N tri(Ar 2 aryl ) cation, —N(C 1 -C 12 alkyl)(Ar 2 aryl)H cation, —N di(C 1 -C 12 alkyl)mono(Ar 2 aryl) cation, or —N mono(C 1 -C 12 Alkyl)di(Ar 2 aryl) cations are included, where the "-" above represents a bond.
　本実施形態の電子求引基において、第四級アンモニウム基のアンモニウムカチオンにおける、上記のＣ１～Ｃ１２アルキルは、各々独立して、炭素原子数１乃至１２のアルキル基を表す。ここで、炭素原子数１乃至１２のアルキル基としては、例えば、メチル基、トリフルオロメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔ－ペンチル基、１，１－ジメチルプロピル基、ｎ－ヘキシル基、イソヘキシル基、シクロヘキシル基、１－メチルヘキシル基、ｎ－ヘプチル基、イソヘプチル基、１，１，３，３－テトラメチルブチル基、１－メチルヘプチル基、３－メチルヘプチル基、ｎ－オクチル基、２－エチルヘキシル基、１，１，３－トリメチルヘキシル基、１，１，３，３－テトラメチルペンチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、１－メチルウンデシル基、ｎ－ドデシル基等が挙げられ、メチル基、トリフルオロメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基が好ましい。 In the electron-withdrawing group of this embodiment, each C 1 -C 12 alkyl in the ammonium cation of the quaternary ammonium group independently represents an alkyl group having 1 to 12 carbon atoms. Here, the alkyl group having 1 to 12 carbon atoms includes, for example, methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t -butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, cyclohexyl group, 1-methylhexyl group, n-heptyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, n-octyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, 1, 1,3,3-tetramethylpentyl group, n-nonyl group, n-decyl group, n-undecyl group, 1-methylundecyl group, n-dodecyl group and the like, methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group , n-undecyl group and n-dodecyl group are preferred.
　本実施形態の電子求引基において、第四級アンモニウム基のアンモニウムカチオンにおける、上記のＡｒ２アリールは、上記と同じものが挙げられ、フェニル基、ｏ－トリフルオロメチルフェニル基、ｍ－トリフルオロメチルフェニル基、ｐ－トリフルオロメチルフェニル基、３，５－ビストリフルオロメチルフェニル基、３，４，５－トリフルオロフェニル基、１－ナフチル基、２－ナフチル基が好ましい。 In the electron withdrawing group of this embodiment, the above Ar 2 aryl in the ammonium cation of the quaternary ammonium group includes the same ones as described above, phenyl group, o-trifluoromethylphenyl group, m-trifluoro A methylphenyl group, p-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 3,4,5-trifluorophenyl group, 1-naphthyl group and 2-naphthyl group are preferred.
　本実施形態の電子求引基において、第四級アンモニウム基のアンモニウムカチオンとしては、例えば、－ＮＨ３カチオン、－Ｎトリメチルカチオン、－Ｎトリエチルカチオン、－Ｎジメチルフェニルカチオンが好ましい。 In the electron-withdrawing group of this embodiment, the ammonium cation of the quaternary ammonium group is preferably -NH3 cation, -N trimethyl cation, -N triethyl cation, or -N dimethylphenyl cation, for example.
　本実施形態の電子求引基において、パーフルオロアルキル基としては、例えば、－ＣＦ２ＣＦ３、－（ＣＦ２）２ＣＦ３、－（ＣＦ２）３ＣＦ３、－（ＣＦ２）４ＣＦ３、－（ＣＦ２）５ＣＦ３、－（ＣＦ２）６ＣＦ３、－（ＣＦ２）７ＣＦ３、－（ＣＦ２）８ＣＦ３、－（ＣＦ２）９ＣＦ３、－（ＣＦ２）１０ＣＦ３、－（ＣＦ２）１１ＣＦ３等が挙げられ、－ＣＦ２ＣＦ３、－（ＣＦ２）２ＣＦ３、－（ＣＦ２）３ＣＦ３、－（ＣＦ２）４ＣＦ３、－（ＣＦ２）５ＣＦ３、－（ＣＦ２）９ＣＦ３及び－（ＣＦ２）１１ＣＦ３が好ましい。 Examples of the perfluoroalkyl group in the electron withdrawing group of the present embodiment include -CF 2 CF 3 , -(CF 2 ) 2 CF 3 , -(CF 2 ) 3 CF 3 , -(CF 2 ) 4 CF 3 , - ( CF2) 5CF3 , -(CF2) 6CF3 , -( CF2 ) 7CF3 , - ( CF2 ) 8CF3 , - ( CF2 ) 9CF3 , - ( CF 2 ) 10 CF 3 , -(CF 2 ) 11 CF 3 and the like, -CF 2 CF 3 , -(CF 2 ) 2 CF 3 , -(CF 2 ) 3 CF 3 , -(CF 2 ) 4 CF 3 , -(CF 2 ) 5 CF 3 , -(CF 2 ) 9 CF 3 and -(CF 2 ) 11 CF 3 are preferred.
　本実施形態の電子求引基において、カルボニル（Ｃ１～Ｃ６アルキル）基におけるＣ１～Ｃ６アルキルは、上記と同じものが挙げられ、カルボニルメチル基、カルボニルトリフルオロメチル基、カルボニルエチル基、カルボニルｎ－プロピル基、カルボニルイソプロピル基、カルボニルｎ－ブチル基、カルボニルイソブチル基、カルボニルｓ－ブチル基、カルボニルｔ－ブチル基が好ましい。 In the electron withdrawing group of the present embodiment, the C 1 -C 6 alkyl in the carbonyl (C 1 -C 6 alkyl) group includes the same ones as described above, a carbonylmethyl group, a carbonyltrifluoromethyl group, a carbonylethyl group , carbonyl n-propyl group, carbonyl isopropyl group, carbonyl n-butyl group, carbonyl isobutyl group, carbonyl s-butyl group and carbonyl t-butyl group are preferred.
　本実施形態の電子求引基において、カルボニル（Ｃ１～Ｃ６アルコキシ）基におけるＣ１～Ｃ６アルコキシは、上記と同じものが挙げられ、カルボニルメトキシ基、カルボニルトリフルオロメトキシ基、カルボニルエトキシ基、カルボニルｎ－プロポキシ基、カルボニルイソプロポキシ基、カルボニルｎ－ブトキシ基、カルボニルイソブトキシ基、カルボニルｓ－ブトキシ基、カルボニルｔ－ブトキシ基地が好ましい。 In the electron withdrawing group of the present embodiment, the C 1 -C 6 alkoxy in the carbonyl (C 1 -C 6 alkoxy) group includes the same ones as described above, a carbonylmethoxy group, a carbonyltrifluoromethoxy group, a carbonylethoxy group , carbonyl n-propoxy group, carbonyl isopropoxy group, carbonyl n-butoxy group, carbonyl isobutoxy group, carbonyl s-butoxy group and carbonyl t-butoxy group are preferred.
　本実施形態の電子求引基において、カルボニル（Ａｒ２アリール）基におけるＡｒ２アリールは、上記と同じものが挙げられ、カルボニルフェニル基、カルボニルｏ－トリフルオロメチルフェニル基、カルボニルｍ－トリフルオロメチルフェニル基、カルボニルｐ－トリフルオロメチルフェニル基、カルボニル３，５－ビストリフルオロメチルフェニル基、カルボニル３，４，５－トリフルオロフェニル基、カルボニル１－ナフチル基及びカルボニル２－ナフチル基が好ましい。 In the electron-withdrawing group of this embodiment, Ar 2aryl in the carbonyl (Ar 2aryl ) group is the same as those described above, and includes a carbonylphenyl group, a carbonyl o-trifluoromethylphenyl group, a carbonyl m-trifluoromethyl A phenyl group, a carbonyl p-trifluoromethylphenyl group, a carbonyl 3,5-bistrifluoromethylphenyl group, a carbonyl 3,4,5-trifluorophenyl group, a carbonyl 1-naphthyl group and a carbonyl 2-naphthyl group are preferred.
　本実施形態の電子求引基において、カルボニル（Ｃ１～Ｃ６アルキル）アミノ基におけるＣ１～Ｃ６アルキルは、上記と同じものが挙げられ、カルボニルメチルアミノ基、カルボニルトリフルオロメチルアミノ基、カルボニルエチルアミノ基、カルボニルｎ－プロピルアミノ基、カルボニルイソプロピルアミノ基、カルボニルｎ－ブチルアミノ基、カルボニルイソブチルアミノ基、カルボニルｓ－ブチルアミノ基、カルボニルｔ－ブチルアミノ基が好ましい。 In the electron-withdrawing group of the present embodiment, the C 1 -C 6 alkyl in the carbonyl(C 1 -C 6 alkyl)amino group includes the same ones as described above, a carbonylmethylamino group, a carbonyltrifluoromethylamino group, A carbonylethylamino group, a carbonyl n-propylamino group, a carbonylisopropylamino group, a carbonyl n-butylamino group, a carbonylisobutylamino group, a carbonyl s-butylamino group and a carbonyl t-butylamino group are preferred.
　本実施形態の電子求引基において、カルボニルジ（Ｃ１～Ｃ６アルキル）アミノ基におけるＣ１～Ｃ６アルキルは、上記と同じものが挙げられ、カルボニルジメチルアミノ基、カルボニルビス（トリフルオロメチル）アミノ基、カルボニルジエチルアミノ基、カルボニルジｎ－プロピルアミノ基、カルボニルジイソプロピルアミノ基、カルボニルジｎ－ブチルアミノ基、カルボニルジイソブチルアミノ基、カルボニルジｓ－ブチルアミノ基、カルボニルジｔ－ブチルアミノ基が好ましい。 In the electron-withdrawing group of the present embodiment, the C 1 -C 6 alkyl in the carbonyldi(C 1 -C 6 alkyl)amino group includes the same ones as described above, carbonyldimethylamino group, carbonylbis(trifluoromethyl ) amino group, carbonyldiethylamino group, carbonyldi-n-propylamino group, carbonyldiisopropylamino group, carbonyldi-n-butylamino group, carbonyldiisobutylamino group, carbonyldi-s-butylamino group, carbonyldi-t-butylamino group preferable.
　本実施形態の電子求引基において、スルホニル（Ｃ１～Ｃ６アルキル）アミノ基におけるＣ１～Ｃ６アルキルは、上記と同じものが挙げられ、スルホニルメチルアミノ基、スルホニルトリフルオロメチルアミノ基、スルホニルエチルアミノ基、スルホニルｎ－プロピルアミノ基、スルホニルイソプロピルアミノ基、スルホニルｎ－ブチルアミノ基、スルホニルイソブチルアミノ基、スルホニルｓ－ブチルアミノ基、スルホニルｔ－ブチルアミノ基が好ましい。 In the electron-withdrawing group of the present embodiment, the C 1 -C 6 alkyl in the sulfonyl(C 1 -C 6 alkyl)amino group includes the same ones as described above, a sulfonylmethylamino group, a sulfonyltrifluoromethylamino group, A sulfonylethylamino group, a sulfonyl n-propylamino group, a sulfonylisopropylamino group, a sulfonyl n-butylamino group, a sulfonylisobutylamino group, a sulfonyl s-butylamino group and a sulfonyl t-butylamino group are preferred.
　本実施形態の電子求引基において、スルホニルジ（Ｃ１～Ｃ６アルキル）アミノ基におけるＣ１～Ｃ６アルキルは、上記と同じものが挙げられ、スルホニルジメチルアミノ基、スルホニルビス（トリフルオロメチル）アミノ基、スルホニルジエチルアミノ基、スルホニルジｎ－プロピルアミノ基、スルホニルジイソプロピルアミノ基、スルホニルジｎ－ブチルアミノ基、スルホニルジイソブチルアミノ基、スルホニルジｓ－ブチルアミノ基、スルホニルジｔ－ブチルアミノ基が好ましい。 In the electron-withdrawing group of the present embodiment, the C 1 -C 6 alkyl in the sulfonyldi(C 1 -C 6 alkyl)amino group includes the same ones as described above, a sulfonyldimethylamino group, a sulfonylbis(trifluoromethyl ) amino group, sulfonyldiethylamino group, sulfonyldi-n-propylamino group, sulfonyldiisopropylamino group, sulfonyldi-n-butylamino group, sulfonyldiisobutylamino group, sulfonyldi-s-butylamino group, sulfonyldi-t-butylamino group preferable.
　本実施形態の電子求引基において、Ａｒ２アリール基は、上記Ａｒ２アリールと同じものが挙げられ、フェニル基、ｏ－トリフルオロメチルフェニル基、ｍ－トリフルオロメチルフェニル基、ｐ－トリフルオロメチルフェニル基、３，５－ビストリフルオロメチルフェニル基、３，４，５－トリフルオロフェニル基、１－ナフチル基及び２－ナフチル基が好ましい。 In the electron-withdrawing group of this embodiment, the Ar 2 aryl group includes the same Ar 2 aryl groups as the above Ar 2 aryl groups, such as a phenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoro Methylphenyl, 3,5-bistrifluoromethylphenyl, 3,4,5-trifluorophenyl, 1-naphthyl and 2-naphthyl groups are preferred.
　本実施形態のアンモニアの製造方法において、より好ましい電子求引基は、－ＮＨ３カチオン、－Ｎトリメチルカチオン、－Ｎトリエチルカチオン、－Ｎジメチルフェニルカチオン、－ＣＦ２ＣＦ３、－（ＣＦ２）２ＣＦ３、－（ＣＦ２）３ＣＦ３、－（ＣＦ２）４ＣＦ３、－（ＣＦ２）５ＣＦ３、－（ＣＦ２）９ＣＦ３、－（ＣＦ２）１１ＣＦ３、フッ素原子、塩素原子及びトリフルオロメチル基であり、更により好ましい電子求引基は、フッ素原子、塩素原子及びトリフルオロメチル基である。 More preferred electron-withdrawing groups in the method for producing ammonia of the present embodiment are —NH 3 cation, —N trimethyl cation, —N triethyl cation, —N dimethylphenyl cation, —CF 2 CF 3 , —(CF 2 ). 2CF3 , -(CF2) 3CF3 , - ( CF2) 4CF3 , - ( CF2 ) 5CF3 , -( CF2 ) 9CF3 , - ( CF2 ) 11CF3 , fluorine atoms, chlorine atoms and trifluoromethyl groups, and even more preferred electron withdrawing groups are fluorine atoms, chlorine atoms and trifluoromethyl groups.
　式（１）及び式（２）で表されるＣＮＣ配位子におけるＲ２及びＲ３について説明する。Ｒ２及びＲ３は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基及びＡｒ１アリール基が挙げられ、好ましいＲ２及びＲ３は、水素原子、フッ素原子、フェニル基及び３，４，５－トリフルオロフェニル基であり、より好ましいＲ２及びＲ３は、水素原子及びフェニル基である。 R 2 and R 3 in the CNC ligands represented by formulas (1) and (2) will be explained. R 2 and R 3 each independently include a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group and an Ar 1 aryl group, preferably R 2 and R 3 are a hydrogen atom, fluorine Atom, a phenyl group and a 3,4,5-trifluorophenyl group, more preferred R 2 and R 3 are a hydrogen atom and a phenyl group.
　式（１）及び式（２）で表されるＣＮＣ配位子におけるＲ４について説明する。Ｒ４は、Ｃ１～Ｃ１０アルキル基及びＡｒ１アリール基が挙げられ、好ましいＲ４は、イソプロピル基、シクロプロピル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、シクロブチル基、イソペンチル基、ネオペンチル基、ｔ－ペンチル基、１，１－ジメチルプロピル基、シクロペンチル基、イソヘキシル基、３－メチルペンチル基、２，２－ジメチルブチル基、２，３－ジメチルブチル基、シクロヘキシル基、２－メチルヘキシル基、３－エチルペンチル基、２，２，４－トリメチルペンチル基、２，５－ジメチルヘキシル基、２，７－ジメチルオクチル基、アダマンチル基、フェニル基、ｏ－フルオロフェニル基、ｍ－フルオロフェニル基、ｏ－トリフルオロメチルフェニル基、ｍ－トリフルオロメチルフェニル基、ｏ－クロロフェニル基、ｍ－クロロフェニル基、ｏ－ブロモフェニル基、ｍ－ブロモフェニル基、ｐ－ブロモフェニル基、ｏ－トリル基、ｍ－トリル基、ｏ－エチルフェニル基、ｍ－エチルフェニル基、ｏ－（ｔ－ブチル）フェニル基、ｍ－（ｔ－ブチル）フェニル基、２，６－ジメチルフェニル基、２，６－ビストリフルオロメチルフェニル基、２，６－ジエチルフェニル基、２，６－ジイソプロピルフェニル基、２，４，６－トリメチルフェニル基、２，４，６－トリエチルフェニル基、２，４，６－トリイソプロピルフェニル基、３，４，５－トリフルオロフェニル基、２，３，４，５、６－ペンタフルオロフェニル基、ｏ－メトキシフェニル基、ｍ－メトキシフェニル基、２，６－ジメトキシフェニル基、２，６－ジエトキシフェニル基、２，６－ジイソプロポキシフェニル基、２，４，６－トリメトキシフェニル基、２，４，６－トリエトキシフェニル基、２，４，６－トリイソプロポキシフェニル基であり、より好ましいＲ４は、イソプロピル基、イソブチル基、ｔ－ブチル基、１，１－ジメチルプロピル基、シクロヘキシル基、アダマンチル基、ｏ－トリフルオロメチルフェニル基、ｏ－トリル基、ｏ－エチルフェニル基、ｏ－（ｔ－ブチル）フェニル基、２，６－ジメチルフェニル基、２，６－ビストリフルオロメチルフェニル基、２，６－ジエチルフェニル基、２，６－ジイソプロピルフェニル基、２，４，６－トリメチルフェニル基、２，４，６－トリエチルフェニル基、２，４，６－トリイソプロピルフェニル基、２，３，４，５、６－ペンタフルオロフェニル基、ｏ－メトキシフェニル基、２，６－ジメトキシフェニル基、２，６－ジエトキシフェニル基、２，６－ジイソプロポキシフェニル基、２，４，６－トリメトキシフェニル基、２，４，６－トリエトキシフェニル基、２，４，６－トリイソプロポキシフェニル基であり、更により好ましいＲ４は、イソプロピル基、ｔ－ブチル基、アダマンチル基、２，４，６－トリメチルフェニル基である。 R4 in the CNC ligands represented by formulas (1) and (2) will be described. R 4 includes C 1 to C 10 alkyl groups and Ar 1 aryl groups, and preferred R 4 is isopropyl group, cyclopropyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, isopentyl group , 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, 2- methylhexyl group, 3-ethylpentyl group, 2,2,4-trimethylpentyl group, 2,5-dimethylhexyl group, 2,7-dimethyloctyl group, adamantyl group, phenyl group, o-fluorophenyl group, m- fluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, o-chlorophenyl group, m-chlorophenyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, o- tolyl group, m-tolyl group, o-ethylphenyl group, m-ethylphenyl group, o-(t-butyl)phenyl group, m-(t-butyl)phenyl group, 2,6-dimethylphenyl group, 2, 6-bistrifluoromethylphenyl group, 2,6-diethylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group, 2,4,6-triethylphenyl group, 2,4,6- triisopropylphenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, o-methoxyphenyl group, m-methoxyphenyl group, 2,6-dimethoxyphenyl group , 2,6-diethoxyphenyl group, 2,6-diisopropoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2,4,6-triethoxyphenyl group, 2,4,6-triiso a propoxyphenyl group, and more preferred R 4 is an isopropyl group, an isobutyl group, a t-butyl group, a 1,1-dimethylpropyl group, a cyclohexyl group, an adamantyl group, an o-trifluoromethylphenyl group, an o-tolyl group, o-ethylphenyl group, o-(t-butyl)phenyl group, 2,6-dimethylphenyl group, 2,6-bistrifluoromethylphenyl group, 2,6-diethylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group, 2,4,6-triethylphenyl group, 2,4,6-triisopropylphenyl group, 2,3,4,5,6-pentafluorophenyl group, o-methoxyphenyl group, 2,6-dimethoxyphenyl group, 2,6-diethoxyphenyl group, 2,6-diisopropoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2,4, 6-triethoxyphenyl group, 2,4,6-triisopropoxyphenyl group, and even more preferred R 4 is isopropyl group, t-butyl group, adamantyl group, 2,4,6-trimethylphenyl group .
　式（１）及び式（２）で表されるＣＮＣ配位子におけるＲ５及びＲ６について説明する。Ｒ５及びＲ６は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基が挙げられ、好ましいＲ５及びＲ６は、水素原子、メチル基、フェニル基及び３，４，５－トリフルオロフェニル基である。 R 5 and R 6 in the CNC ligands represented by formulas (1) and (2) will be explained. R 5 and R 6 each independently include a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group, and preferred R 5 and R 6 are a hydrogen atom, They are a methyl group, a phenyl group and a 3,4,5-trifluorophenyl group.
　式（１）及び式（２）で表されるＣＮＣ配位子におけるＲ７、Ｒ８、Ｒ９及びＲ１０について説明する。Ｒ７、Ｒ８、Ｒ９及びＲ１０は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基が挙げられ、好ましいＲ７、Ｒ８、Ｒ９及びＲ１０は、水素原子、メチル基、フェニル基及び３，４，５－トリフルオロフェニル基である。 R 7 , R 8 , R 9 and R 10 in the CNC ligands represented by formulas (1) and (2) will be explained. R 7 , R 8 , R 9 and R 10 each independently include a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group, and preferred R 7 , R 8 , R 9 and R 10 are a hydrogen atom, a methyl group, a phenyl group and a 3,4,5-trifluorophenyl group.
　式（１）及び式（２）で表されるＣＮＣ配位子におけるＺについて説明する。Ｚは、アニオンを表しており、本発明のＣＮＣ配位子は２価のカチオンの化合物であることより、１価のアニオンをＺａと定義するとＺは２Ｚａと表される。１価のアニオンであるＺａは、フッ化物イオン（Ｆ－とも記載する）、塩化物イオン（Ｃｌ－とも記載する）、臭化物イオン（Ｂｒ－とも記載する）、ヨウ化物イオン（Ｉ－とも記載する）、テトラフルオロボレート（ＢＦ４ －とも記載する）、トリフルオロ（トリフルオロメチル）ボレート（［ＢＦ３（ＣＦ３）］－とも記載する）、ジメチルホスファートイオン、ジエチルホスファートイオン、ヘキサフルオロホスファート（ＰＦ６ －とも記載する）、トリス（ペンタフルオロエチル）トリフルオロホスファート、トリフルオロアセテート、メチルスルファート、トリフルオロメタンスルホナート、ビス（トリフルオロメタンスルホニル）イミド等が挙げられる。好ましいＺａは、塩化物イオン、臭化物イオン、ヨウ化物イオン、テトラフルオロボレート、ヘキサフルオロホスファートであり、好ましいＺは、２Ｃｌ－、２Ｂｒ－、２Ｉ－、２ＢＦ４ －、２ＰＦ６ －である。 Z in the CNC ligands represented by formulas (1) and (2) will be described. Z represents an anion, and since the CNC ligand of the present invention is a divalent cation compound, Z is represented as 2Za when a monovalent anion is defined as Za. Za, which is a monovalent anion, includes fluoride ion (also referred to as F-), chloride ion (also referred to as Cl- ) , bromide ion (also referred to as Br- ) , iodide ion (also referred to as I-). ), tetrafluoroborate (also referred to as BF 4 - ), trifluoro(trifluoromethyl)borate (also referred to as [BF 3 (CF 3 )] - ), dimethyl phosphate ion, diethyl phosphate ion, hexafluorophosphate ion, phate (also referred to as PF 6 - ), tris(pentafluoroethyl)trifluorophosphate, trifluoroacetate, methylsulfate, trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide and the like. Preferred Za are chloride ion, bromide ion, iodide ion, tetrafluoroborate, hexafluorophosphate, and preferred Z are 2Cl − , 2Br − , 2I − , 2BF 4 − , 2PF 6 − .
　式（３）及び式（４）
Figure JPOXMLDOC01-appb-C000011
 で表されるモリブデン錯体について説明する。式（３）及び式（４）中のＲ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０は、前記と同じである。 Equation (3) and Equation (4)
Figure JPOXMLDOC01-appb-C000011
 The molybdenum complex represented by will be described. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 in formulas (3) and (4) are the same as above.
　式（３）及び式（４）で表されるモリブデン錯体におけるＸについて説明する。Ｘはハロゲン原子が挙げられ、好ましいＸはヨウ素原子、臭素原子、塩素原子であり、より好ましいＸはヨウ素原子、塩素原子である。 X in the molybdenum complexes represented by formulas (3) and (4) will be described. 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.
　本実施形態のアンモニアの製造方法において、還元剤としては、ランタノイド系金属のハロゲン化物が挙げられ、ランタノイド系金属としては、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム及びルテチウム等が挙げられ、このうち、２価の状態もとれるサマリウム、ユウロピウム及びイッテルビウムが好ましく、ハロゲンとしては塩素、臭素、ヨウ素が挙げられ、このうちヨウ素が好ましい。 In the ammonia production method of the present embodiment, the reducing agent includes lanthanide metal halides, and the lanthanide metals include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium. , holmium, erbium, thulium, ytterbium, and lutetium, among which samarium, europium, and ytterbium, which can be in a divalent state, are preferred. Halogens include chlorine, bromine, and iodine, of which iodine is preferred.
　ランタノイド系金属のハロゲン化物は、エーテル系化合物であるテトラヒドロフラン、４－メチルテトラヒドロピラン、ジエチルエーテル等が配位した錯体であってもよく、アンモニアの製造を溶媒中で実施する場合、例えば、ランタノイド系金属のハロゲン化物にテトラヒドロフランが配位した錯体を用いることも可能である。市販のランタノイド系金属のハロゲン化物は、例えば、ＥｕＣｌ２、ＥｕＩ２、ＳｍＩ２及びＹｂＩ２が、シグマアルドリッチジャパン社より入手できる。 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. Commercially available lanthanide metal halides, such as EuCl 2 , EuI 2 , SmI 2 and YbI 2 are available from Sigma-Aldrich Japan.
　好ましいランタノイド系金属のハロゲン化物としては、ハロゲン化サマリウム（ＩＩ）、ハロゲン化ユウロピウム（ＩＩ）、ハロゲン化イッテルビウム（ＩＩ）、及び前記の化合物にテトラヒドロフラン配位した錯体等が挙げられ、ヨウ化サマリウム（ＩＩ）、ヨウ化サマリウム（ＩＩ）のテトラヒドロフランが配位した錯体（例えば、ＳｍＩ２（ｔｈｆ）２が挙げられ、ＳｍＩ２をテトラヒドロフランに溶解させて、再結晶化することで得ることができる。）がより好ましい。 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.
　本実施形態のアンモニアの製造方法において、プロトン源は、アルコール及び水が挙げられる。用いるアルコールとしては、グリコールを用いてもよいし、ＲａＯＨ（Ｒａは水素原子がフッ素原子で置換されていてもよい炭素原子数１乃至６の直鎖状、環状又は分岐鎖状のアルキル基、又は、アルキル基を有していてもよいフェニル基）を用いてもよい。 In the method for producing ammonia of the present embodiment, proton sources include alcohol and water. As the alcohol to be used, glycol may be used, or R a OH (R a is a linear, cyclic or branched alkyl having 1 to 6 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom). or a phenyl group optionally having an alkyl group) may be used.
　グリコールは、例えば、エチレングリコール、プロピレングリコール及びジエチレングリコール等が挙げられる。 Glycols include, for example, ethylene glycol, propylene glycol and diethylene glycol.
　ＲａＯＨは、例えば、直鎖状又は分岐鎖状のアルキルアルコールとして、メタノール、エタノール、プロパノール、イソプロパノール、ｎ－ブチルアルコール、ｓ－ブチルアルコール、イソブチルアルコール及びｔ－ブチルアルコール等が挙げられ、環状のアルキルアルコールとしては、シクロプロパノール、シクロペンタノール及びシクロヘキサノール等が挙げられ、フッ素原子を含むアルコールとしては、トリフルオロエチルアルコール及びテトラフルオロエチルアルコール等が挙げられ、フェノール及びその誘導体としては、フェノール、クレゾール及びキシレノール等が挙げられる。本実施形態のアンモニアの製造方法において、好ましいプロトン源は水及びエチレングリコールであり、水がより好ましい。 R a OH is, for example, linear or branched alkyl alcohols such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, s-butyl alcohol, isobutyl alcohol and t-butyl alcohol. Examples of alkyl alcohols include cyclopropanol, cyclopentanol and cyclohexanol, examples of alcohols containing fluorine atoms include trifluoroethyl alcohol and tetrafluoroethyl alcohol, and examples of phenol and its derivatives include phenol , cresol and xylenol. In the method for producing ammonia of the present embodiment, preferred proton sources are water and ethylene glycol, with water being more preferred.
　本実施形態のアンモニアの製造方法において、窒素分子からアンモニアの製造は溶媒中で行ってもよい。溶媒としては、特に限定するものではないが、エーテル系化合物、ニトリル系化合物及び炭化水素系化合物等が挙げられる。エーテル系化合物としては、例えば、テトラヒドロフラン（ｔｈｆ）、４－メチルテトラヒドロピラン、テトラヒドロピラン－４－メタノール及び１，４－ジオキサン等の環状エーテル系化合物、並びにジエチルエーテル、ジイソプロピルエーテル、１，２－ジメトキシエタン、及びシクロペンチルメチルエーテル等の鎖状エーテル系化合物が挙げられる。ニトリル系化合物としては、例えばアセトニトリル及びプロピオニトリル等が挙げられる。炭化水素系化合物としては、例えばトルエン及びｏ－キシレン等の芳香族炭化水素化合物、並びにヘキサン、ヘプタン、石油エーテル等などの飽和炭化水素化合物が挙げられる。本実施形態のアンモニアの製造方法において、好ましい溶媒は、テトラヒドロフランである。 In the method for producing ammonia of this embodiment, the production of ammonia from nitrogen molecules may be carried out in a solvent. Examples of the solvent include, but are not particularly limited to, ether-based compounds, nitrile-based compounds and hydrocarbon-based compounds. Examples of ether compounds include cyclic ether compounds such as tetrahydrofuran (thf), 4-methyltetrahydropyran, tetrahydropyran-4-methanol and 1,4-dioxane, as well as diethyl ether, diisopropyl ether, 1,2-dimethoxy Examples include chain ether compounds such as ethane and cyclopentyl methyl ether. Examples of nitrile compounds include acetonitrile and propionitrile. Examples of hydrocarbon compounds include aromatic hydrocarbon compounds such as toluene and o-xylene, and saturated hydrocarbon compounds such as hexane, heptane and petroleum ether. A preferable solvent in the method for producing ammonia of the present embodiment is tetrahydrofuran.
　生成したアンモニアの収量は公知の方法により測定できる。硫酸水溶液中のアンモニアの定量は、例えば、公知のインドフェノール法（Analytical Chemistry,1967年,39巻，971-974ページ）を用いて行うことができる。 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).
　本実施形態のアンモニアの製造方法において、窒素分子として、常圧又は加圧の窒素ガスを用いることができ、常圧の窒素ガスを用いることが好ましい。窒素ガスは安価なため他の試薬に対して大過剰に用いてもよい。 In the method for producing ammonia of the present embodiment, 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.
　本実施形態のアンモニアの製造方法において、反応温度は、反応が進行する温度であれば特に限定されないが、－１０℃～６０℃が好ましく、０℃～４０℃がより好ましい。 In the method for producing ammonia of the present embodiment, the reaction temperature is not particularly limited as long as the reaction proceeds, but is preferably -10°C to 60°C, more preferably 0°C to 40°C.
　本実施形態のアンモニアの製造方法において、触媒の使用量は、還元剤に対して０．０００１当量～０．１当量使用するのが好ましく、０．００１当量～０．０１当量使用するのがより好ましい。プロトン源の使用量は、還元剤に対して０．５当量～５当量使用するのが好ましいが、１当量～２当量使用するのがより好ましい。 In the method for producing ammonia of the present embodiment, the amount of catalyst used is preferably 0.0001 to 0.1 equivalents relative to the reducing agent, more preferably 0.001 to 0.01 equivalents. preferable. The amount of the proton source used is preferably 0.5 to 5 equivalents, more preferably 1 to 2 equivalents, relative to the reducing agent.
　なお、本発明は上述した実施形態に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It goes without saying that the present invention is by no means limited to the above-described embodiments, and can be implemented in various forms as long as they fall within the technical scope of the present invention.
　以下に、本発明の実施例について説明する。なお、以下の実施例は本発明を何ら限定するものではない。 Examples of the present invention will be described below. In addition, the following examples do not limit the present invention.
［合成例１］式（７）で表される化合物の合成
Figure JPOXMLDOC01-appb-C000012
 　反応容器に２，６－ジクロロ－４－（トリフルオロメチル）ピリジン（６５３ｍｇ、３．０ｍｍｏｌ、東京化成工業社製）及び１－ｔ－ブチルイミダゾール（１．２ｍＬ、９．３ｍｍｏｌ、東京化成工業社製）を加え、窒素雰囲気下１２０℃で攪拌を行わず反応させて、得られた淡黄褐色の固体を室温の２０℃～２５℃まで冷却した後、テトラヒドロフラン（３ｍＬ、６回）及びジエチルエーテル（３ｍＬ、３回）で洗浄することで淡黄褐色の固体として、表題化合物（１２８８ｍｇ、２．８ｍｍｏｌ、収率９２％）を得た。 [Synthesis Example 1] Synthesis of compound represented by formula (7)
Figure JPOXMLDOC01-appb-C000012
 2,6-Dichloro-4-(trifluoromethyl)pyridine (653 mg, 3.0 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-t-butylimidazole (1.2 mL, 9.3 mmol, Tokyo Chemical Industry Co., Ltd.) were placed in a reaction vessel. product) was added and allowed to react without stirring at 120°C under a nitrogen atmosphere. (3 mL, 3 times) to give the title compound (1288 mg, 2.8 mmol, 92% yield) as a pale tan solid.
１Ｈ　ＮＭＲ（ＤＭＳＯ－ｄ６）：δ１０．６１（ｓ，２Ｈ）、９．１５（ｓ，２Ｈ）、９．００（ｓ，２Ｈ）、８．４４（ｓ，２Ｈ）、１．７３（ｓ，１８Ｈ）．
Anal Calcd for C20H26Cl2F3N5:
Ｃ，５１．７３；　Ｈ，５．６４；　Ｎ，１５．０８．
Found:
Ｃ，５１．７８；　Ｈ，５．６２；　Ｎ，１５．１２． 1 H NMR (DMSO-d 6 ): δ 10.61 (s, 2H), 9.15 (s, 2H), 9.00 (s, 2H), 8.44 (s, 2H), 1.73 ( s, 18H).
Anal Calcd for C20H26Cl2F3N5 :
C, 51.73; H, 5.64; N, 15.08.
Found:
C, 51.78; H, 5.62; N, 15.12.
［合成例２］式（８）で表される化合物の合成
Figure JPOXMLDOC01-appb-C000013
 　反応容器に式（７）で表される化合物（２３．６ｍｇ、０．０５１ｍｍｏｌ）及びテトラヒドロフラン（０．５ｍＬ、東京化成工業社製）を加え、反応容器を－７８℃に冷却した後、カリウムビス(トリメチルシリル)アミド（２２．０ｍｇ、０．１１ｍｍｏｌ、シグマアルドリッチジャパン社製）のテトラヒドロフラン（０．５ｍＬ）溶液を反応容器に加え、室温である２０℃～２５℃にて１時間攪拌した。その後、反応混合物を、セライトを用いたろ過を行い、ケークをテトラヒドロフラン（０．５ｍＬ、２回）で洗浄した液、及びろ液を合わせた溶液の溶媒を減圧留去することで、黄色の固体として、表題化合物（１８．８ｍｇ、０．０４８ｍｍｏｌ、収率９５％）を得た。 [Synthesis Example 2] Synthesis of compound represented by formula (8)
Figure JPOXMLDOC01-appb-C000013
 The compound represented by formula (7) (23.6 mg, 0.051 mmol) and tetrahydrofuran (0.5 mL, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to the reaction vessel, and the reaction vessel was cooled to -78°C. A solution of (trimethylsilyl)amide (22.0 mg, 0.11 mmol, manufactured by Sigma-Aldrich Japan Co., Ltd.) in tetrahydrofuran (0.5 mL) was added to the reaction vessel and stirred at room temperature, 20° C. to 25° C., for 1 hour. After that, the reaction mixture was filtered using celite, and the cake was washed with tetrahydrofuran (0.5 mL, twice), and the combined filtrate was evaporated under reduced pressure to obtain a yellow solid. to give the title compound (18.8 mg, 0.048 mmol, 95% yield).
１Ｈ　ＮＭＲ　（Ｃ６Ｄ６）：δ８．８７（ｓ，２Ｈ）、７．９１（ｓ，２Ｈ）、６．７３（ｓ，２Ｈ）、１．４５（ｓ，１８Ｈ）． 1 H NMR (C 6 D 6 ): δ 8.87 (s, 2H), 7.91 (s, 2H), 6.73 (s, 2H), 1.45 (s, 18H).
［合成例３］式（９）で表されるモリブデン錯体の合成
Figure JPOXMLDOC01-appb-C000014
 　反応容器に式（７）で表される化合物（５７．０ｍｇ、０．１２０ｍｍｏｌ）及びテトラヒドロフラン（１ｍＬ、東京化成工業社製）を加え、反応容器を－７８℃に冷却した後、カリウムビス(トリメチルシリル)アミド（５３．０ｍｇ、０．２６０ｍｍｏｌ、シグマアルドリッチジャパン社製）のテトラヒドロフラン（０．５ｍＬ）溶液を反応容器に加え、室温である２０℃～２５℃にて１時間攪拌した。その後、反応混合物の溶媒を減圧留去し、トルエン（２ｍＬ）を加え、セライトろ過を行い、ケークをトルエン（１ｍＬ、５回）で洗浄した液、及びろ液を合わせた溶液の溶媒を減圧留去することで、式（８）で表される化合物を合成した。連続して、前記の減圧留去した反応容器に、トリクロロトリス(テトラヒドロフラン)モリブデン（４２．０ｍｇ、０．１００ｍｍｏｌ）及びテトラヒドロフラン（５ｍＬ）を加えて、反応温度５０℃にて１８時間攪拌した後、溶媒を減圧留去して、ジクロロメタン（３ｍＬ）を加えて、セライトろ過を行い、ケークをジクロロメタン（１ｍＬ、４回）で洗浄した液、及びろ液を合わせた溶液に、ｎ－ヘキサン（１０ｍＬ）を滴下することで生成してきた沈殿物をろ過することで、暗青色の結晶性固体として表題化合物（５１ｍｇ、０．０８５ｍｍｏｌ、８５％収率）を得た。 [Synthesis Example 3] Synthesis of molybdenum complex represented by formula (9)
Figure JPOXMLDOC01-appb-C000014
 The compound represented by formula (7) (57.0 mg, 0.120 mmol) and tetrahydrofuran (1 mL, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the reaction vessel, and the reaction vessel was cooled to -78 ° C., then potassium bis(trimethylsilyl). ) A solution of amide (53.0 mg, 0.260 mmol, manufactured by Sigma-Aldrich Japan Co., Ltd.) in tetrahydrofuran (0.5 mL) was added to the reaction vessel and stirred at room temperature of 20° C. to 25° C. for 1 hour. After that, the solvent of the reaction mixture was distilled off under reduced pressure, toluene (2 mL) was added, filtration was performed with celite, and the cake was washed with toluene (1 mL, 5 times), and the filtrate was combined and the solvent of the solution was distilled off under reduced pressure. By removing, a compound represented by formula (8) was synthesized. Continuously, trichlorotris(tetrahydrofuran)molybdenum (42.0 mg, 0.100 mmol) and tetrahydrofuran (5 mL) were added to the reaction vessel which had been distilled off under reduced pressure, and the mixture was stirred at a reaction temperature of 50°C for 18 hours. The solvent was distilled off under reduced pressure, dichloromethane (3 mL) was added, celite filtration was performed, the cake was washed with dichloromethane (1 mL, 4 times), and the combined solution of the filtrate and n-hexane (10 mL). was filtered to give the title compound (51 mg, 0.085 mmol, 85% yield) as a dark blue crystalline solid.
磁化率(エバンズ法）：
μｅｆｆ＝３．５３　μＢ　ｉｎ　ＴＨＦ－ｄ８　ａｔ　２９４Ｋ．
Anal Calcd for C20H24Cl3F3MoN5:
Ｃ，４０．４６；　Ｈ，４．０７；　Ｎ，１１．８０．
Found:
Ｃ，４０．８６；　Ｈ，４．３５；　Ｎ，１１．５８． Magnetic susceptibility (Evans method):
μ eff =3.53 μ B in THF-d 8 at 294K.
Anal Calcd for C20H24Cl3F3MoN5 :
C, 40.46; H, 4.07; N, 11.80.
Found:
C, 40.86; H, 4.35; N, 11.58.
［実施例１］式（９）で表されるモリブデン錯体を用いたアンモニア製造
　式（９）で表されるモリブデン錯体
Figure JPOXMLDOC01-appb-C000015
 を用いて、窒素分子からアンモニアを製造した。常圧の窒素雰囲気下、シュレンク反応容器に、モリブデン錯体（９）（１．３ｍｇ、２０μｍｏｌ）及びジヨードビス（テトラヒドロフラン）サマリウム（ＩＩ）（１９７ｍｇ、０．３６ｍｍｏｌ）及びテトラヒドロフラン（５．５ｍＬ）を加えた後、水の濃度を０．７２ｍｏｌ／Ｌに調製したテトラヒドロフラン溶液（０．５ｍＬ、水としては、６．５ｍｇ，０．３６ｍｍｏｌ）を加え、室温である２０℃～２５℃にて１時間攪拌した。 [Example 1] Ammonia production using molybdenum complex represented by formula (9) Molybdenum complex represented by formula (9)
Figure JPOXMLDOC01-appb-C000015
 was used to produce ammonia from molecular nitrogen. Molybdenum complex (9) (1.3 mg, 20 μmol) and diiodobis(tetrahydrofuran)samarium (II) (197 mg, 0.36 mmol) and tetrahydrofuran (5.5 mL) were added to a Schlenk reaction vessel under nitrogen atmosphere at normal pressure. After that, a tetrahydrofuran solution (0.5 mL, 6.5 mg as water, 0.36 mmol) adjusted to a water concentration of 0.72 mol/L was added, and the mixture was stirred at room temperature, 20°C to 25°C, for 1 hour. .
　次に、水酸化カリウム水溶液（３０質量％、５ｍＬ）を反応容器に加え、本反応で発生したアンモニア量を定量するため、反応容器を減圧蒸留して蒸留液を硫酸水溶液（０．５Ｍ、１０ｍＬ）にて回収した。該硫酸水溶液中のアンモニア量はインドフェノール法にて決定した。その結果、触媒（モリブデン錯体）当たり５０当量のアンモニアを製造した。 Next, an aqueous solution of potassium hydroxide (30% by mass, 5 mL) was added to the reaction vessel, and the reaction vessel was distilled under reduced pressure to quantify the amount of ammonia generated in this reaction. ) was collected. The amount of ammonia in the aqueous sulfuric acid solution was determined by the indophenol method. As a result, 50 equivalents of ammonia were produced per catalyst (molybdenum complex).
［実施例２］式（９）で表されるモリブデン錯体を用いたアンモニア製造
　実施例２では、触媒である式（９）で表されるモリブデン錯体の使用量を０．０５μｍｏｌに、反応時間を１８時間に変更した以外の実験操作は、実施例１と同様の操作を行い、アンモニア製造を実施した。その結果、触媒当たり１５３０当量のアンモニアを製造した。 [Example 2] Ammonia production using the molybdenum complex represented by the formula (9) In Example 2, the amount of the molybdenum complex represented by the formula (9), which is a catalyst, was 0.05 µmol, and the reaction time was Experimental operations other than changing to 18 hours were performed in the same manner as in Example 1 to produce ammonia. As a result, 1530 equivalents of ammonia were produced per catalyst.
　本発明は、アンモニアの製造方法に利用可能である。 The present invention can be used for a method for producing ammonia.

Claims (8)

  1. 　式（１）及び式（２）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は、水素原子又は電子求引基を表し、
    　Ｒ２及びＲ３は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｒ４は、Ｃ１～Ｃ１０アルキル基、又はＡｒ１アリール基を表し、
    　Ｒ５及びＲ６は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｒ７、Ｒ８、Ｒ９及びＲ１０は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｚは、アニオンを表す。）の何れかで表される配位子とモリブデン化合物とを反応させて得られるモリブデン錯体を触媒として使用して、還元剤及びプロトン源の存在下、窒素分子からアンモニアを製造する方法。     Formula (1) and Formula (2)
    Figure JPOXMLDOC01-appb-C000001
     (Wherein, R 1 represents a hydrogen atom or an electron-withdrawing group,
    R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group;
    R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    Z represents an anion. ) in the presence of a reducing agent and a proton source, using a molybdenum complex obtained by reacting a molybdenum compound with a ligand represented by any of ) as a catalyst to produce ammonia from nitrogen molecules.
  2. 　前記還元剤がランタノイド系金属のハロゲン化物（ＩＩ）である、請求項１に記載の方法。 The method according to claim 1, wherein the reducing agent is a lanthanide metal halide (II).
  3. 　前記プロトン源がアルコール又は水である、請求項１又は請求項２に記載の方法。 The method according to claim 1 or 2, wherein the proton source is alcohol or water.
  4. 　式（３）及び式（４）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ１は、水素原子又は電子求引基を表し、
    　Ｒ２及びＲ３は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｒ４は、Ｃ１～Ｃ１０アルキル基、又はＡｒ１アリール基を表し、
    　Ｒ５及びＲ６は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｒ７、Ｒ８、Ｒ９及びＲ１０は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｘは、ハロゲン原子を表す。）の何れかで表されるモリブデン錯体を触媒として使用して、還元剤及びプロトン源の存在下、窒素分子からアンモニアを製造する方法。     Equation (3) and Equation (4)
    Figure JPOXMLDOC01-appb-C000002
     (Wherein, R 1 represents a hydrogen atom or an electron-withdrawing group,
    R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group;
    R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    X represents a halogen atom. ) as a catalyst to produce ammonia from nitrogen molecules in the presence of a reducing agent and a proton source.
  5. 　前記還元剤がランタノイド系金属のハロゲン化物（ＩＩ）である、請求項４に記載の方法。 The method according to claim 4, wherein the reducing agent is a lanthanide metal halide (II).
  6. 　前記プロトン源がアルコール又は水である、請求項４又は請求項５に記載の方法。 The method according to claim 4 or 5, wherein the proton source is alcohol or water.
  7. 　式（１）及び式（２）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ１は、水素原子又は電子求引基を表し、
    　Ｒ２及びＲ３は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｒ４は、Ｃ１～Ｃ１０アルキル基、又はＡｒ１アリール基を表し、
    　Ｒ５及びＲ６は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｒ７、Ｒ８、Ｒ９及びＲ１０は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｚは、アニオンを表す。）の何れかで表される配位子。     Formula (1) and Formula (2)
    Figure JPOXMLDOC01-appb-C000003
     (Wherein, R 1 represents a hydrogen atom or an electron-withdrawing group,
    R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group;
    R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    Z represents an anion. ) is a ligand represented by any one of
  8. 　式（３）及び式（４）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ１は、水素原子又は電子求引基を表し、
    　Ｒ２及びＲ３は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｒ４は、Ｃ１～Ｃ１０アルキル基、又はＡｒ１アリール基を表し、
    　Ｒ５及びＲ６は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｒ７、Ｒ８、Ｒ９及びＲ１０は、各々独立して水素原子、Ｃ１～Ｃ４アルキル基、Ｃ１～Ｃ４アルコキシ基、又はＡｒ１アリール基を表し、
    　Ｘは、ハロゲン原子を表す。）の何れかで表されるモリブデン錯体。
          Equation (3) and Equation (4)
    Figure JPOXMLDOC01-appb-C000004
     (Wherein, R 1 represents a hydrogen atom or an electron-withdrawing group,
    R 2 and R 3 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    R 4 represents a C 1 -C 10 alkyl group or an Ar 1 aryl group;
    R 5 and R 6 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an Ar 1 aryl group;
    X represents a halogen atom. ) a molybdenum complex represented by any one of
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