A method for producing ammonia, and a molybdenum complex used in the production method and a ligand that is a raw material for the molybdenum complex.

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

[Technical Field]

[0001] 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. [Background technology]

[0002] The Haber-Bosch process, an industrial method for converting nitrogen molecules into ammonia, requires harsh conditions of high temperature and pressure, and also consumes energy for hydrogen gas production. As a result, it is an energy-intensive process, with several percent of the world's annual energy consumption being used for the Haber-Bosch process. In contrast, recent reports have described methods for producing ammonia from nitrogen molecules at room temperature and pressure without using hydrogen gas, employing molybdenum complexes as catalysts and water as the proton source (Non-Patent Literature 1). Furthermore, there are reports of ammonia production using molybdenum complexes as catalysts, samarium(II) iodide as a reducing agent, and alcohols or water as the proton source (Non-Patent Literature 2). Non-Patent Literature 2 includes, for example, molybdenum complexes represented by formulas (A) and (B). [ka] The description states that these molybdenum complexes are characterized by having a phosphorus-carbon-phosphorus pincer ligand (hereinafter sometimes referred to as PCP ligand) and a phosphorus-nitrogen-phosphorus pincer ligand (hereinafter sometimes referred to as PNP ligand), in which three coordinating atoms containing molybdenum metal are bonded from three directions on the same plane. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Proceedings of the 99th Annual Meeting of the Chemical Society of Japan, 2019, Presentation Number 4D1-37 [Non-Patent Document 2] Nature, Volume 568, Issue 7753 (2019), pp. 536 - 540 Summary of the Invention Problems to be Solved by the Invention

[0004] A molybdenum complex having a ligand different from the conventional PNP ligand and PCP ligand around the molybdenum metal has been expected to develop a highly versatile molybdenum complex reaction that enables the production of ammonia and aims at industrialization. Means for Solving the Problems

[0005] In order to achieve the above object, the inventors of the present invention designed a molybdenum complex having a carbon - nitrogen - carbon ligand (hereinafter sometimes referred to as a CNC ligand), created a newly synthesized molybdenum complex having a CNC ligand, and found that it functions as a catalyst for the production of ammonia, thus completing the present invention. There is no case where the production of ammonia is enabled by a molybdenum complex having a CNC ligand.

[0006] That is, the present invention relates to the following [1] to [8].[[]]END]] [1] Formula (1) and Formula (2) [Chemical Formula] (In the formula, R 1 represents a hydrogen atom or an electron - withdrawing group, R 2 and R 3 each independently represent a hydrogen atom, a C1 - C4 alkyl group, a C1 - C, alkoxy group, or an Ar 1 aryl group, R 4 represents a C1 - C 10 alkyl group, or an Ar 1 aryl group, R 5 and R 6 each independently represent a hydrogen atom, a C1 - C4 alkyl group, a C1 - C4 alkoxy group, or an Ar 1Represents an aryl group, R 7 , R 8 , R 9 and R 10 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an 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 molybdenum compound with a ligand represented by any of the following as a catalyst. [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] Equations (3) and (4) [ka] (In the formula, R 1 This represents a hydrogen atom or an electron-withdrawing group. R 2 and R 3 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an aryl group, R 4 C1~C 10 Alkyl group, or Ar 1 Represents an aryl group, R 5 and R 6 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an aryl group, R 7 , R 8 , R 9 and R 10 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an 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 represented by any of the following as a catalyst: X represents a halogen atom. [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] Equations (1) and (2) [ka] (In the formula, R 1 This represents a hydrogen atom or an electron-withdrawing group. R 2 and R 3 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an aryl group, R 4 C1~C 10 Alkyl group, or Ar 1 Represents an aryl group, R 5 and R 6 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an aryl group, R 7 , R 8 , R 9 and R 10 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an aryl group, Z represents an anion. ) A ligand represented by one of the following. [8] Equations (3) and (4) [ka] (In the formula, R 1 This represents a hydrogen atom or an electron-withdrawing group. R 2 and R 3Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an aryl group, R 4 C1~C 10 Alkyl group, or Ar 1 Represents an aryl group, R 5 and R 6 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an aryl group, R 7 , R 8 , R 9 and R 10 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Represents an aryl group, A molybdenum complex represented by one of the following: X represents a halogen atom. [Effects of the Invention]

[0007] This invention provides a novel method for producing ammonia using a molybdenum complex having the CNC ligand. [Modes for carrying out the invention]

[0008] In this specification, "n" represents normal, "i" represents iso, "c" represents cyclo, "s" represents secondary, "t" represents tertiary, "o" represents ortho, "m" represents meta, and "p" represents para. "Me" represents a methyl group, "Et" represents an ethyl group, t "Bu" represents the tert-butyl group, and "thf" represents tetrahydrofuran.

[0009] C in this specification a ~C bThe notation "alkyl group" represents a monovalent group obtained by removing one hydrogen atom from a linear, branched, or cyclic aliphatic hydrocarbon having a to b carbon atoms. Examples include 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, and 3-methylpentyl group. Examples include the 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, etc. In addition, the trifluoromethyl group is also included, and each is set within the specified range of carbon atoms. The number of carbon atoms is represented by "C a ~C b In this example, a is an integer greater than or equal to 1, and b is an integer greater than or equal to a.

[0010] C in this specification a ~C b The notation for alkoxy group refers to a monovalent group in which an alkyl group, having a to b carbon atoms as described above, is bonded to oxygen. Examples include 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, and cyclopene group. Examples include toxic groups, n-hexoxy groups, isohexoxy groups, 3-methylpentoxy groups, 2,2-dimethylbutoxy groups, 2,3-dimethylbutoxy groups, cyclohexoxy groups, n-heptoxy groups, 2-methylhexoxy groups, 3-ethylpentoxy groups, n-octoxy groups, 2,2,4-trimethylpentoxy groups, and 2,5-dimethylhexoxy groups, and in addition, trifluoromethoxy groups are also included, each set within a specified range of carbon atoms.

[0011] Examples of halogen atoms in this specification include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like.

[0012] Ar in this specification 1 The notation "aryl group" refers to a monovalent group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon consisting of six carbon atoms. Examples include the phenyl group and phenyl groups having substituents at least one of the positions from 2 to 6. 1 Substituents on the aromatic ring of aryl include halogen atoms such as fluoro, chloro, bromo, and iodo groups, as well as methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1Specific examples of aryl groups include phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl 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, 2,6-dimethylphenyl group, 2,6-bistrifluoromethylphenyl group, 3 Examples include ,5-dimethylphenyl group, 3,5-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, p-methoxyphenyl group, 2,6-dimethoxyphenyl group, 2,6-diethoxyphenyl group, 2,6-diisopropoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2,4,6-triethoxyphenyl group, and 2,4,6-triisopropoxyphenyl group.

[0013] Preferred embodiments of the present invention are shown below.

[0014] Equations (1) and (2) [ka] R in the CNC ligand represented by 1This section describes electron-withdrawing groups. In electron-withdrawing groups, substituents where the mesomeric effect is electron-donating but the inductive effect is electron-withdrawing contributes significantly include, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, -CH2Cl, or -CH=CHNO2. Substituents where both the mesomeric and inductive effects are electron-withdrawing include quaternary ammonium groups with anions as counterions, trifluoromethyl groups, perfluoroalkyl groups, trichloromethyl groups, cyano groups, nitro groups, formyl groups, carboxylic acid groups, carbonyl (C1-C6 alkyl) groups, carbonyl (C1-C6 alkoxy) groups, and carbonyl (Ar) groups. 2 Aryl group, carbonylamino group, carbonyl(C1~C6 alkyl)amino group, carbonyldi(C1~C6 alkyl)amino group, sulfonic acid group, sulfonylamino group, sulfonyl(C1~C6 alkyl)amino group, sulfonyldi(C1~C6 alkyl)amino group, Ar 2 An example is the aryl group.

[0015] In the electron-withdrawing group of this embodiment, C1-C6 alkyl groups each independently represent an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include 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.

[0016] In the electron-withdrawing group of this embodiment, C1-C6 alkoxy represents a monovalent group in which the aforementioned C1-C6 alkyl is bonded to oxygen. Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, isopentoxy, neopentoxy, t-pentoxy, 1,1-dimethylpropoxy, n-hexoxy, isohexoxy, and cyclohexoxy groups.

[0017] In the electron-withdrawing group of this embodiment, Ar 2Each aryl group independently represents an aryl group having 6 to 10 carbon atoms. Here, examples of alkyl groups having 6 to 10 carbon atoms include phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl 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, and p-ethylphenyl group. 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-fluoronaphthalen-1-yl group, 6-fluoronaphthalen-1-yl Group, 7-fluoronaphthalen-1-yl group, 8-fluoronaphthalen-1-yl group, 2-chloronaphthalen-1-yl group, 3-chloronaphthalen-1-yl group, 4-chloronaphthalen-1-yl group, 5-chloronaphthalen-1-yl group, 6-chloronaphthalen-1-yl group, 7-chloronaphthalen-1-yl group, 8-chloronaphthalen-1-yl group, 2-bromonaphthalen-1-yl group, 3-bromonaphthalen-1-yl group, 4-bromonaphthalen-1-yl group, 5-bromonaphthalen-1-yl group, 6-bromonaphthalen-1-yl group, 7-bromonaphthalene-1-yl group, 8-bromonaphthalene-1-yl group, 2-iodonaphthalene-1-yl group, 3-iodonaphthalene-1-yl group, 4-iodonaphthalene-1-yl group, 5-iodonaphthalene-1-yl group, 6-iodonaphthalene-1-yl group, 7-iodonaphthalene-1-yl group, 8-iodonaphthalene-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-methylnaphthalene-1-yl group, 2-ethylnaphthalene-1-yl group, 3-ethylnaphthalene-1-yl group, 4-ethylnaphthalene-1-yl group, 5-ethylnaphthalene-1-yl group, 6-ethylnaphthalene-1-yl group, 7-ethylnaphthalene-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-propylnaphthalene-1-yl group, 6-n-propylnaphthalene -1-yl group, 7-n-propylnaphthalene-1-yl group, 8-n-propylnaphthalene-1-yl group, 2-i-propylnaphthalene-1-yl group, 3-i-propylnaphthalene-1-yl group, 4-i-propylnaphthalene-1-yl group, 5-i-propylnaphthalene-1-yl group, 6-i-propylnaphthalene-1-yl group, 7-i-propylnaphthalene-1-yl group, 8-i-propylnaphthalene-1-yl group, 2-c-propylnaphthalene-1-yl group, 3-c-propylnaphthalene-1-yl group, 4-c-propylnaphthalene-1-yl group , 5-c-propylnaphthalene-1-yl group, 6-c-propylnaphthalene-1-yl group, 7-c-propylnaphthalene-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- Iyl group, 4-fluoronaphthalen-2-yl group, 5-fluoronaphthalen-2-yl group, 6-fluoronaphthalen-2-yl group, 7-fluoronaphthalen-2-yl group, 8-fluoronaphthalen-2-yl group, 1-chloronaphthalen-2-yl group, 3-chloronaphthalen-2-yl group, 4-chloronaphthalen-2-yl group, 5-chloronaphthalen-2-yl group, 6-chloronaphthalen-2-yl group, 7-chloronaphthalen-2-yl group, 8-chloronaphthalen-2-yl group, 1-bromonaphthalen-2-yl group, 3-bromonaphthalen-2-yl group,4-bromonaphthalene-2-yl group, 5-bromonaphthalene-2-yl group, 6-bromonaphthalene-2-yl group, 7-bromonaphthalene-2-yl group, 8-bromonaphthalene-2-yl group, 1-iodonaphthalene-2-yl group, 3-iodonaphthalene-2-yl group, 4-iodonaphthalene-2-yl group, 5-iodonaphthalene-2-yl group, 6-iodonaphthalene-2-yl group, 7-iodonaphthalene-2-yl group, 8-iodonaphthalene-2-yl group, 1-methylnaphthalene-2-yl group, 3-methylnaphthalene-2-yl group, 4 -methylnaphthalene-2-yl group, 5-methylnaphthalene-2-yl group, 6-methylnaphthalene-2-yl group, 7-methylnaphthalene-2-yl group, 8-methylnaphthalene-2-yl group, 1-ethylnaphthalene-2-yl group, 3-ethylnaphthalene-2-yl group, 4-ethylnaphthalene-2-yl group, 5-ethylnaphthalene-2-yl group, 6-ethylnaphthalene-2-yl group, 7-ethylnaphthalene-2-yl group, 8-ethylnaphthalene-2-yl group, 1-n-propylnaphthalene-2-yl group, 3-n-propylnaphthalene-2- Iyl 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-propylnaphthalene-2-yl group, 1-i-propylnaphthalene-2-yl group, 3-i-propylnaphthalene-2-yl group, 4-i-propylnaphthalene-2-yl group, 5-i-propylnaphthalene-2-yl group, 6-i-propylnaphthalene-2-yl group, 7-i-propylnaphthalene-2-yl group, 8-i-propylnaphthalene-2 -yl group, 1-c-propylnaphthalene-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,Examples include the 7-n-butylnaphthalene-2-yl group and the 8-n-butylnaphthalene-2-yl group.

[0018] In the electron-withdrawing group of this embodiment, examples of anions that are counterions to the quaternary ammonium group include hexafluorophosphate ions, hexachloroantimonate ions, trifluoromethanesulfonate ions, tetrafluoroborate ions, phosphate ions, sulfonate ions, chlorides, bromides, iodides, and hydroxides.

[0019] In the electron-withdrawing group of this embodiment, the ammonium cation of the quaternary ammonium group is, for example, a -NH3 cation, a -N mono(C1~C) cation, and 12 Alkyl)H2 cation, -N di(C1~C 12 Alkyl)H cation, -N tri(C1~C 12 Alkyl) cation, -N mono(Ar 2 Aryl)H2 cation, -N di(Ar 2 Aryl)H cation, -N tri(Ar 2 Aryl cation, -N(C1~C 12 Alkyl)(Ar 2 Aryl)H cation, -N di(C1~C 12 Alkyl) Mono(Ar 2 Aryl) cation, or -N mono(C1~C) 12 Alkyl)di(Ar 2 Examples include aryl cations, and the "-" above indicates a bond.

[0020] In the electron-withdrawing group of this embodiment, the above C1-C in the ammonium cation of the quaternary ammonium group 12Each alkyl group independently represents an alkyl group having 1 to 12 carbon atoms. Here, examples of alkyl groups having 1 to 12 carbon atoms include 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 Examples of groups include n-octyl 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, and n-dodecyl group, with 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 being preferred.

[0021] In the electron-withdrawing group of this embodiment, the above Ar in the ammonium cation of the quaternary ammonium group 2 Examples of aryl groups include those listed above, with phenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 3,4,5-trifluorophenyl group, 1-naphthyl group, and 2-naphthyl group being preferred.

[0022] In the electron-withdrawing group of this embodiment, preferred ammonium cations of the quaternary ammonium group are, for example, -NH3 cation, -N-trimethyl cation, -N-triethyl cation, and -N-dimethylphenyl cation.

[0023] In the electron-withdrawing group of the present embodiment, examples of the perfluoroalkyl group include, for example, -CF2CF3, -(CF2)2CF3, -(CF2)3CF3, -(CF2)4CF3, -(CF2)5CF3, -(CF2)6CF3, -(CF2)7CF3, -(CF2)8CF3, -(CF2)9CF3, -(CF2) 10 CF3, -(CF2) 11 CF3, etc., and -CF2CF3, -(CF2)2CF3, -(CF2)3CF3, -(CF2)4CF3, -(CF2)5CF3, -(CF2)9CF3, and -(CF2) 11 CF3 are preferred.

[0024] In the electron-withdrawing group of the present embodiment, the C1-C6 alkyl in the carbonyl(C1-C6 alkyl) group is the same as those described above, and the carbonylmethyl group, carbonyltrifluoromethyl group, carbonyethyl 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.

[0025] In the electron-withdrawing group of the present embodiment, the C1-C6 alkoxy in the carbonyl(C1-C6 alkoxy) group is the same as those described above, and the carbonylmethoxy group, carbonyltrifluoromethoxy group, carbonyethoxy 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.

[0026] In the electron-withdrawing group of the present embodiment, Ar 2 in the carbonyl(Ar 2 aryl) group is the same as those described above, and the carbonylphenyl group, carbonyl o-trifluoromethylphenyl group, carbonyl m-trifluoromethylphenyl group, carbonyl p-trifluoromethylphenyl group, carbonyl 3,5-bistrifluoromethylphenyl group, carbonyl 3,4,5-trifluorophenyl group, carbonyl 1-naphthyl group, and carbonyl 2-naphthyl group are preferred.

[0027] In the electron-withdrawing group of this embodiment, the C1-C6 alkyl group in the carbonyl (C1-C6 alkyl)amino group is the same as above, and carbonylmethylamino group, carbonyltrifluoromethylamino group, carbonylethylamino group, carbonyln-propylamino group, carbonylisopropylamino group, carbonyln-butylamino group, carbonylisobutylamino group, carbonyls-butylamino group, and carbonylt-butylamino group are preferred.

[0028] In the electron-withdrawing group of this embodiment, the C1-C6 alkyl in the carbonyldi(C1-C6 alkyl)amino group is the same as above, and carbonyldimethylamino group, carbonylbis(trifluoromethyl)amino group, carbonyldiethylamino group, carbonyldi-n-propylamino group, carbonyldiisopropylamino group, carbonyldi-n-butylamino group, carbonyldiisobutylamino group, carbonyldi-s-butylamino group, and carbonyldi-t-butylamino group are preferred.

[0029] In the electron-withdrawing group of this embodiment, the C1-C6 alkyl group in the sulfonyl (C1-C6 alkyl)amino group is the same as above, and sulfonylmethylamino group, sulfonyltrifluoromethylamino group, sulfonylethylamino group, sulfonyln-propylamino group, sulfonylisopropylamino group, sulfonyln-butylamino group, sulfonylisobutylamino group, sulfonyls-butylamino group, and sulfonylt-butylamino group are preferred.

[0030] In the electron-withdrawing group of this embodiment, the C1-C6 alkyl in the sulfonyldi(C1-C6 alkyl)amino group is the same as described above, and examples thereof include a sulfonyldimethylamino group, a sulfonylbis(trifluoromethyl)amino group, a sulfonyldiethylamino group, a sulfonyldi-n-propylamino group, a sulfonyldiisopropylamino group, a sulfonyldi-n-butylamino group, a sulfonyldiisobutylamino group, a sulfonyldi-s-butylamino group, and a sulfonyldi-t-butylamino group.

[0031] In the electron-withdrawing group of this embodiment, Ar 2 The aryl group is the same as the above Ar 2 and examples thereof include a phenyl group, an o-trifluoromethylphenyl group, a m-trifluoromethylphenyl group, a p-trifluoromethylphenyl group, a 3,5-bistrifluoromethylphenyl group, a 3,4,5-trifluorophenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0032] In the method for producing ammonia of this embodiment, more preferable electron-withdrawing groups are -NH3 cation, -N trimethyl cation, -N triethyl cation, -N dimethylphenyl cation, -CF2CF3, -(CF2)2CF3, -(CF2)3CF3, -(CF2)4CF3, -(CF2)5CF3, -(CF2)9CF3, -(CF2) 11 CF 3、 fluorine atom, chlorine atom, and trifluoromethyl group, and even more preferable electron-withdrawing groups are fluorine atom, chlorine atom, and trifluoromethyl group.

[0033] Regarding R 2 and R 3 in the CNC ligand represented by formula (1) and formula (2). R 2 and R 3 are each independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, and an Ar 1 aryl group, and preferable R 2 and R 3R is a hydrogen atom, a fluorine atom, a phenyl group, and a 3,4,5-trifluorophenyl group, and is more preferably R 2 and R 3 These are a hydrogen atom and a phenyl group.

[0034] R in the CNC ligand represented by equations (1) and (2) 4 This explains R. 4 C1~C 10 Alkyl and Ar 1 Examples include aryl groups, and preferred R 4 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-tri R is a more preferred group, and is a 2,6-dimethylphenyl 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-triisopropoxyphenyl group. 4The group is isopropyl, isobutyl, t-butyl, 1,1-dimethylpropyl, cyclohexyl, adamantyl, o-trifluoromethylphenyl, o-tolyl, o-ethylphenyl, o-(t-butyl)phenyl, 2,6-dimethylphenyl, 2,6-bistrifluoromethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, 2,3,4,5,6-pentafluorophenyl, o-methoxyphenyl, 2,6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-diisopropoxyphenyl, 2,4,6-trimethoxyphenyl, 2,4,6-triethoxyphenyl, and 2,4,6-triisopropoxyphenyl, and is even more preferred R 4 These are isopropyl group, t-butyl group, adamantyl group, and 2,4,6-trimethylphenyl group.

[0035] R in the CNC ligand represented by equations (1) and (2) 5 and R 6 This explains R. 5 and R 6 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Examples include aryl groups, and preferred R 5 and R 6 These are a hydrogen atom, a methyl group, a phenyl group, and a 3,4,5-trifluorophenyl group.

[0036] R in the CNC ligand represented by equations (1) and (2) 7 , R 8 , R 9 and R 10 This explains R. 7 , R 8 , R 9 and R 10 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or Ar 1 Examples include aryl groups, and preferred R 7 , R 8 , R9 and R 10 These are a hydrogen atom, a methyl group, a phenyl group, and a 3,4,5-trifluorophenyl group.

[0037] The Z in the CNC ligand represented by formulas (1) and (2) will be explained. Z represents an anion, and since the CNC ligand of the present invention is a compound of a divalent cation, if a monovalent anion is defined as Za, then Z is expressed as 2Za. The monovalent anion Za is a fluoride ion (F - (Also written as ), chloride ion (Cl - (Also written as), bromide ion (Br - (Also written as ), iodide ion (I - Also written as tetrafluoroborate (BF4 - (Also written as), trifluoro(trifluoromethyl)borate ([BF3(CF3)] - (Also written as), dimethyl phosphate ion, diethyl phosphate ion, hexafluorophosphate (PF6) - Examples include tris(pentafluoroethyl)trifluorophosphate, trifluoroacetate, methylsulfate, trifluoromethanesulfonate, and bis(trifluoromethanesulfonyl)imide (also written as ). Preferred Za is chloride ion, bromide ion, iodide ion, tetrafluoroborate, and hexafluorophosphate, and preferred Z is 2Cl - , 2Br - , 2I - , 2BF4 - , 2PF6 - That is the case.

[0038] Equations (3) and (4) [ka] The molybdenum complex represented by the formula (3) and (4) is described below. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R7 , R 8 , R 9 and R 10 This is the same as described above.

[0039] Let us explain X in the molybdenum complexes represented by formulas (3) and (4). X can be a halogen atom, preferred X is an iodine atom, a bromine atom, or a chlorine atom, and more preferred X is an iodine atom or a chlorine atom.

[0040] In the ammonia production method of this embodiment, examples of reducing agents include lanthanide metal halides, and examples of lanthanide metals include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, among which samarium, europium, and ytterbium, which can also exist in a divalent state, are preferred, and examples of halogens include chlorine, bromine, and iodine, among which iodine is preferred.

[0041] The lanthanide metal halides may also be complexes to which ether compounds such as tetrahydrofuran, 4-methyltetrahydropyran, and diethyl ether are coordinated. When ammonia is produced in a solvent, for example, a complex to which tetrahydrofuran is coordinated to the lanthanide metal halide can be used. Commercially available lanthanide metal halides, such as EuCl2, EuI2, SmI2, and YbI2, can be obtained from Sigma-Aldrich Japan.

[0042] Preferred lanthanide metal halides include samarium(II) halide, europium(II) halide, ytterbium(II) halide, and complexes obtained by coordinating these compounds with tetrahydrofuran. More preferred are samarium(II) iodide and complexes to which samarium(II) iodide is coordinated with tetrahydrofuran (for example, SmI2(thf)2, which can be obtained by dissolving SmI2 in tetrahydrofuran and recrystallizing it).

[0043] In the ammonia production method of this embodiment, the proton source may be alcohol and water. Glycol may be used as the alcohol, or R a OH(R a This may include a linear, cyclic, or branched alkyl group having 1 to 6 carbon atoms, in which hydrogen atoms may be substituted with fluorine atoms, or a phenyl group which may have an alkyl group.

[0044] Examples of glycols include ethylene glycol, propylene glycol, and diethylene glycol.

[0045] R a Examples of OH groups include linear or branched alkyl alcohols such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, s-butyl alcohol, isobutyl alcohol, and t-butyl alcohol; cyclic alkyl alcohols such as cyclopropanol, cyclopentanol, and cyclohexanol; alcohols containing a fluorine atom such as trifluoroethyl alcohol and tetrafluoroethyl alcohol; and phenols and their derivatives such as phenol, cresol, and xylenol. In the ammonia production method of this embodiment, preferred proton sources are water and ethylene glycol, with water being more preferred.

[0046] In the ammonia production method of this embodiment, the production of ammonia from nitrogen molecules may be carried out in a solvent. The solvent is not particularly limited, but examples include ether compounds, nitrile compounds, and hydrocarbon 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 linear ether compounds such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, 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, as well as saturated hydrocarbon compounds such as hexane, heptane, and petroleum ether. In the ammonia production method of this embodiment, the preferred solvent is tetrahydrofuran.

[0047] The yield of ammonia produced can be measured by known methods. The quantitative determination of ammonia in an aqueous sulfuric acid solution can be performed, for example, using the known indophenol method (Analytical Chemistry, 1967, Vol. 39, pp. 971-974).

[0048] In the ammonia production method of this embodiment, nitrogen gas at atmospheric pressure or pressurized can be used as the nitrogen molecule, and it is preferable to use nitrogen gas at atmospheric pressure. Since nitrogen gas is inexpensive, it may be used in large excess relative to other reagents.

[0049] In the ammonia production method of this embodiment, the reaction temperature is not particularly limited as long as it is within the temperature at which the reaction proceeds, but -10°C to 60°C is preferred, and 0°C to 40°C is more preferred.

[0050] In the ammonia production method of this embodiment, the amount of catalyst used is preferably 0.0001 to 0.1 equivalents relative to the reducing agent, and more preferably 0.001 to 0.01 equivalents. The amount of proton source used is preferably 0.5 to 5 equivalents relative to the reducing agent, and more preferably 1 to 2 equivalents.

[0051] It goes without saying that the present invention is not limited in any way to the embodiments described above, and can be implemented in various forms as long as they fall within the technical scope of the present invention. [Examples]

[0052] Examples of the present invention will be described below. Note that the following examples do not limit the present invention in any way.

[0053] [Synthesis Example 1] Synthesis of the compound represented by formula (7) [ka] 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, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and reacted under a nitrogen atmosphere at 120°C without stirring. The resulting pale yellowish-brown solid was cooled to room temperature (20°C to 25°C), and then washed with tetrahydrofuran (3 mL, 6 times) and diethyl ether (3 mL, 3 times) to obtain the title compound (1288 mg, 2.8 mmol, yield 92%) as a pale yellowish-brown solid.

[0054] 1 H 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 C 20 H 26 Cl2F3N5: C, 51.73; H, 5.64; N, 15.08. Found: C, 51.78; H, 5.62; N, 15.12.

[0055] [Synthesis Example 2] Synthesis of the compound represented by formula (8) [ka] The compound represented by formula (7) (23.6 mg, 0.051 mmol) and tetrahydrofuran (0.5 mL, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the reaction vessel. After cooling the reaction vessel to -78°C, a solution of potassium bis(trimethylsilyl)amide (22.0 mg, 0.11 mmol, manufactured by Sigma-Aldrich Japan) in tetrahydrofuran (0.5 mL) was added to the reaction vessel, and the mixture was stirred at room temperature (20°C to 25°C) for 1 hour. Subsequently, the reaction mixture was filtered using Celite, and the solvent was removed from the solution obtained by washing the cake with tetrahydrofuran (0.5 mL, twice) and the filtrate under reduced pressure to obtain the title compound (18.8 mg, 0.048 mmol, yield 95%) as a yellow solid.

[0056] 1 H NMR (C6D6): δ8.87(s,2H), 7.91(s,2H), 6.73(s,2H), 1.45(s,18H).

[0057] [Synthesis Example 3] Synthesis of a molybdenum complex represented by formula (9) [ka] 57.0 mg (0.120 mmol) of the compound represented by formula (7) and tetrahydrofuran (1 mL, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the reaction vessel. After cooling the reaction vessel to -78°C, a solution of potassium bis(trimethylsilyl)amide (53.0 mg, 0.260 mmol, manufactured by Sigma-Aldrich Japan) in tetrahydrofuran (0.5 mL) was added to the reaction vessel, and the mixture was stirred at room temperature (20°C to 25°C) for 1 hour. Subsequently, the solvent of the reaction mixture was removed by vacuum distillation, toluene (2 mL) was added, and the mixture was filtered using Celite. The solvent of the solution obtained by washing the cake with toluene (1 mL, 5 times) and the combined filtrate was removed by vacuum distillation to synthesize the compound represented by formula (8). Subsequently, trichlorotris(tetrahydrofuran)molybdenum (42.0 mg, 0.100 mmol) and tetrahydrofuran (5 mL) were added to the reaction vessel from which the solvent had been removed under reduced pressure. The mixture was stirred at a reaction temperature of 50°C for 18 hours, and then the solvent was removed under reduced pressure. Dichloromethane (3 mL) was added, and the mixture was filtered using Celite filtration. The cake was washed with dichloromethane (1 mL, 4 times), and the resulting solution was combined with the filtrate. N-hexane (10 mL) was added dropwise to the resulting precipitate, which was then filtered to obtain the title compound (51 mg, 0.085 mmol, 85% yield) as a dark blue crystalline solid.

[0058] Magnetic susceptibility (Evans method): μ eff = 3.53 μ B in THF-d8at 294K. Anal Calcd for C 20 H 24 Cl3F3MoN5: C, 40.46; H, 4.07; N, 11.80. Found: C, 40.86; H, 4.35; N, 11.58.

[0059] [Example 1] Ammonia production using a molybdenum complex represented by formula (9) Molybdenum complex represented by formula (9) [ka] Ammonia was produced from nitrogen molecules using the following method. Under atmospheric pressure and a nitrogen atmosphere, molybdenum complex (9) (1.3 mg, 20 μmol), diiodobis(tetrahydrofuran)samarium(II) (197 mg, 0.36 mmol), and tetrahydrofuran (5.5 mL) were added to a Schlenk reaction vessel. Then, a tetrahydrofuran solution (0.5 mL, equivalent to 6.5 mg of water and 0.36 mmol) prepared to a water concentration of 0.72 mol / L was added, and the mixture was stirred for 1 hour at room temperature (20°C to 25°C).

[0060] Next, an aqueous potassium hydroxide solution (30% by mass, 5 mL) was added to the reaction vessel. To quantify the amount of ammonia generated in this reaction, the reaction vessel was subjected to vacuum distillation, and the distillate was recovered in 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, 50 equivalents of ammonia were produced per catalyst (molybdenum complex).

[0061] [Example 2] Ammonia production using a molybdenum complex represented by formula (9) In Example 2, the experimental procedure was the same as in Example 1, except that the amount of molybdenum complex represented by formula (9), which is the catalyst, was changed to 0.05 μmol and the reaction time to 18 hours, and ammonia was produced. As a result, 1530 equivalents of ammonia were produced per catalyst. [Industrial applicability]

[0062] This invention can be used in a method for producing ammonia.

Claims

1. Equations (1) and (2) 【Chemistry 1】 (In the formula, R １ This represents a hydrogen atom or an electron-withdrawing group. R ２ and R ３ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, R ４ is a C １ to C １０ alkyl group, or Ar １ represents an aryl group, R ５ and R ６ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, R ７ , R ８ , R ９ and R １０ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, The aforementioned Ar1 aryl group represents a monovalent group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon consisting of six carbon atoms. If the Ar1 aryl group has substituents on the aromatic ring, the substituents may be fluoro, chloro, bromo, iodo, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl groups. , a methoxy group, an ethoxy group, or an isopropoxy 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 any of the following with a molybdenum compound as a catalyst.

2. The method according to claim 1, wherein the reducing agent is a lanthanide metal halide (II).

3. The method according to claim 1 or claim 2, wherein the proton source is alcohol or water.

4. Equations (3) and (4) 【Chemistry 2】 (In the formula, R １ This represents a hydrogen atom or an electron-withdrawing group. R ２ and R ３ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, R ４ C １ ~C １０ Alkyl alkyl group, or Ar １ Represents an aryl group, R ５ and R ６ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, R ７ , R ８ , R ９ and R １０ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, The aforementioned Ar1 aryl group represents a monovalent group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon consisting of six carbon atoms. If the Ar1 aryl group has substituents on the aromatic ring, the substituents are fluoro, chloro, bromo, iodo, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, methoxy, ethoxy, or isopropoxy groups. A method for producing ammonia from nitrogen molecules in the presence of a reducing agent and a proton source, using a molybdenum complex represented by any of the following as a catalyst: X represents a halogen atom.

5. The method according to claim 4, wherein the reducing agent is a lanthanide metal halide (II).

6. The method according to claim 4 or 5, wherein the proton source is alcohol or water.

7. Equations (1) and (2) 【Transformation 3】 (In the formula, R １ This represents an electron-withdrawing group, R ２ and R ３ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, R ４ C １ ~C １０ Alkyl alkyl group, or Ar １ Represents an aryl group, R ５ and R ６ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, R ７ , R ８ , R ９ and R １０ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, The aforementioned Ar1 aryl group represents a monovalent group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon consisting of six carbon atoms. If the Ar1 aryl group has substituents on the aromatic ring, the substituents are fluoro, chloro, bromo, iodo, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, methoxy, ethoxy, or isopropoxy groups. Z represents an anion. ) A ligand represented by one of the following.

8. Equations (3) and (4) 【Chemistry 4】 (In the formula, R １ This represents a hydrogen atom or an electron-withdrawing group. R ２ and R ３ each independently represents a hydrogen atom, C １ -C ４ alkyl group, C １ -C ４ alkoxy group, or Ar １ aryl group, and R ４ C １ ~C １０ Alkyl alkyl group, or Ar １ Represents an aryl group, R ５ and R ６ each independently represents a hydrogen atom, C １ to C ４ alkyl group, C １ to C ４ alkoxy group, or Ar １ aryl group, and R ７ , R ８ , R ９ and R １０ Each is an independent hydrogen atom, C １ ~C ４ alkyl group, C １ ~C ４ Alkoxy group, or Ar １ Represents an aryl group, The aforementioned Ar1 aryl group represents a monovalent group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon consisting of six carbon atoms. If the Ar1 aryl group has substituents on the aromatic ring, the substituents are fluorogroups. , chloro group, bromo group, iodine group, methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, methoxy group, ethoxy group or isopropoxy group, A molybdenum complex represented by one of the following: (where X represents a halogen atom.)

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