Tridentate alkyl thiol group bridged ferromolybdenum heteronuclear complex as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of preparation of metal complexes, and discloses a tridentate alkyl thiol group bridged ferromolybdenum heteronuclear complex as well as a preparation method and application thereof. The tridentate alkyl thiol group bridged ferromolybdenum complex has a structure as shown in a general formula I, and comprises tridentate alkyl thiol groups, halogen, metal coordinated cyclopentadiene ligands and substituted cyclopentadiene ligands. A mononuclear molybdenum precursor reacts with tridentate alkyl thiol lithium salt to obtain a mononuclear molybdenum complex with tridentate alkyl thiol groups, and the mononuclear molybdenum complex and a mononuclear iron precursor are subjected to assembly reaction to obtain the tridentate alkyl thiol group bridged ferromolybdenum heteronuclear complex. The novel heteronuclear complex with excellent catalytic performance is synthesized by reasonably designing a ligand structure and reaction conditions, a new thought and method are provided for research and application of heteronuclear metal complexes, hydrazine can be catalyzed to be disproportionated into ammonia and nitrogen under certain reaction conditions, the reaction temperature is-20 DEG C to 50 DEG C, and the reaction time is 0.5-48 h.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal complex preparation, and relates to a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex, a preparation method and an application thereof, and particularly relates to a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex, a preparation method thereof and an application thereof in catalyzing the disproportionation of hydrazine to ammonia and nitrogen. Background Art

[0002] Ammonia, as an important inorganic compound, is widely used in agriculture, the chemical industry, and energy. Currently, there are two main methods for synthesizing ammonia: industrial synthesis and biological nitrogen fixation. Industrial synthesis is known as the Haber-Bosch process. This process requires high temperatures and pressures, consumes significant amounts of energy, and produces large amounts of the greenhouse gas carbon dioxide. Compared to the demanding conditions of industrial synthesis, the nitrogenase enzyme found in some naturally occurring microorganisms can catalyze the reduction of nitrogen to ammonia at room temperature and pressure, using water as a proton source.

[0003] Nitrogenase can not only catalyze the reduction of nitrogen to ammonia under mild conditions, but also mediate the catalytic conversion of other nitrogen-containing substrates such as hydrazine. Studies have shown that the active center of nitrogenase is an iron-molybdenum cofactor (FeMoco), which is a heteronuclear polymetallic sulfur cluster [Fe7S9MoC]. Although the geometric structure is clear, the specific activation site is still unclear. In this context, based on the types of metals contained in FeMoco (iron and molybdenum), scientists have synthesized a variety of biomimetic iron or molybdenum metal model complexes and explored their ability to reduce N2 and capture key N x H y In sharp contrast, there are no reports on the biomimetic simulation of the key {Fe(μ-S)2Mo(tS)} functional region.

[0004] The reported sulfur-bridged iron-molybdenum complexes mainly include: representative examples containing monodentate sulfur ligands (Nat. Commun. 2024, 15, 7729), representative examples containing bidentate sulfur ligands (Angew. Chem. Int. Ed. 2022, 30, e202203121; Dalton Trans. 2020, 49, 9048; Inorg. Chem. 2019, 58, 679; 2014, 53, 11345), and representative examples containing multidentate sulfur ligands (Nature 2022, 607, 86; Nat. Chem. 2021, 13, 666).

[0005] These studies not only reveal the unique properties of heteronuclear clusters in catalytic transformation reactions but also provide important insights into the design of novel catalysts. However, relatively few studies have reported on tridentate alkylthiol-bridged molybdenum-iron heteronuclear complexes. These complexes possess unique structural features and may exhibit excellent catalytic activity and selectivity, holding potential for applications in organic synthesis, energy conversion, and other fields. Summary of the Invention

[0006] The present invention aims to provide a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex, a preparation method thereof, and application thereof in catalyzing the disproportionation of hydrazine to ammonia and nitrogen.

[0007] The technical solution of the present invention:

[0008] The tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex (I) has the following structure:

[0009]

[0010] In the general structural formula I:

[0011] R 1 Selected from cyclopentadiene ligands, monomethylcyclopentadiene ligands, dimethylcyclopentadiene ligands, trimethylcyclopentadiene ligands, tetramethylcyclopentadiene ligands, pentamethylcyclopentadiene ligands, and 1,2,4-tri-tert-butylcyclopentadiene ligands;

[0012] X 2 Selected from S, O, NH, PH, NPh, PPh;

[0013] X 1 Selected from F, Cl, Br, I;

[0014] Y - As an anti-negative ion, selected from Cl - Br - , I - PF6 - 、SbF6 - 、BF4 - , BPh4 - CF3SO3 - and B(C6F5)4 - ;

[0015] n is 0, 1, or 2;

[0016] According to the above description, the specific complex structures are listed (Table 1), where: Cp, Cp 1 、Cp 2 、Cp 3 、Cp 4 , Cp* and Cp' represent the following structures:

[0017]

[0018] Table 1 Specific structures of tridentate alkylthiol-bridged molybdenum-iron heteronuclear complexes

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032] In the preferred embodiment of the present invention, X 2 =S or O;

[0033] In another preferred embodiment, R 1 =Cp* or Cp′;

[0034] In another preferred embodiment, X 1 =Cl or Br;

[0035] In another preferred embodiment, Y - =PF6 - or BPh4 - ;

[0036] More preferably, the complex of the present invention is selected from:

[0037] Complex 1: X 2 =S, R 1 =Cp*,X 1 =Cl, Y - =PF6- ;

[0038] Complex 2: X 2 =S, R 1 =Cp*,X 1 =Br,Y - =BPh4 - ;

[0039]

[0040] The preferred tridentate alkylthiol-bridged molybdenum-iron heteronuclear complexes 1 and 2 have the general structure of Formula I, with different substituents as shown in Table 2:

[0041] Table 2 Preferred tridentate alkylthiol-bridged molybdenum-iron heteronuclear complexes containing substituents

[0042]

[0043] The present invention aims to provide a method for preparing a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex, which is prepared according to the route shown in the following scheme.

[0044]

[0045] (1) Preparation of tridentate alkylthiol mononuclear molybdenum complex A

[0046] At -100 to 50° C., 2 to 10 equivalents of salt are added to the mononuclear molybdenum precursor [Cp*MoCl4] for reaction. After the temperature rises to room temperature, the reaction is continued for 1 to 48 hours to obtain a tridentate alkylthiol-based mononuclear molybdenum complex A.

[0047] (2) Preparation of tridentate alkylthiol mononuclear molybdenum complex B

[0048] At -100 to 50° C., 2 to 10 equivalents of salt are added to the mononuclear molybdenum precursor [Cp*MoBr4] for reaction. After the temperature rises to room temperature, the reaction is continued for 1 to 48 hours to obtain a tridentate alkylthiol-based mononuclear molybdenum complex B.

[0049] (3) Preparation of tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex 1

[0050] At -100 to 25°C, 2 to 10 equivalents of [Cp*Fe(MeCN)3][PF6] were added to the tridentate alkylthiol mononuclear molybdenum complex A for reaction. After the temperature rose to room temperature, the reaction was continued for 1 to 48 hours to obtain the tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex 1.

[0051] (4) Preparation of tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex 2

[0052] At -100 to 25°C, 2 to 10 equivalents of [Cp*Fe(MeCN)3][PF6] were added to the tridentate alkylthiol mononuclear molybdenum complex B for reaction. After the temperature rose to room temperature, 2 to 10 equivalents of sodium tetraphenylborate were added and the reaction was continued for 1 to 48 hours to obtain the tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex 2.

[0053] Furthermore, the reaction of step (1) and step (2) is carried out at a carbon number C 10 The following ethers, benzene, carbon number C 10 The following alkylbenzenes, carbon number C5~C 10 The reaction is carried out in any one of the solvents selected from alkanes, halogenated alkanes with a carbon number of less than C6, alcohols with a carbon number of less than C5, chlorobenzene, fluorobenzene, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide, preferably tetrahydrofuran or ethylene glycol dimethyl ether; the salt used is potassium salt, sodium salt, and lithium salt, preferably lithium salt of bismercaptoethyl sulfide.

[0054] Furthermore, the reaction of step (3) and step (4) is carried out at carbon number C 10 The following ethers, benzene, carbon number C 10 The following alkylbenzenes, carbon number C5~C 10 The solvent is selected from alkanes, dichloromethane, alcohols with carbon numbers below C5, chlorobenzene, fluorobenzene, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide, preferably dichloromethane, n-hexane and ethylene glycol dimethyl ether.

[0055] The method provided by the present invention also includes steps of product purification, such as distillation, extraction, filtration, etc. The purification steps are common knowledge in the art and are well known to those skilled in the art, and will not be described in detail here.

[0056] Another object of the present invention is to provide the use of a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex, wherein the complex is mainly used to catalyze the disproportionation of hydrazine into ammonia and nitrogen.

[0057] Specifically, a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex catalyzes the disproportionation of hydrazine into ammonia and nitrogen, comprising the following steps:

[0058] In an argon atmosphere, a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex can disproportionate three molecules of hydrazine to four molecules of ammonia and one molecule of nitrogen using dichloromethane as the reaction solvent. The reaction temperature is -20 to 40°C and the reaction time is 0.5 to 48 hours.

[0059]

[0060] Compared with the prior art, the advantages of the present invention are:

[0061] (1) The present invention provides for the first time a novel method for preparing tridentate alkylthiol-based mononuclear molybdenum complexes, which provides a mononuclear molybdenum precursor for subsequent heteronuclear bimetallic assembly.

[0062] (2) The present invention provides for the first time a method for preparing a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex; it simulates the {Fe(μ-S)2Mo(tS)} region of nitrogenase FeMoco, providing a powerful tool for studying the process of nitrogen reduction to ammonia catalyzed by nitrogenase FeMoco.

[0063] (3) The present invention provides for the first time a novel binuclear catalyst that can catalyze the disproportionation of hydrazine into ammonia and nitrogen without the action of external protons and electrons.

[0064] The present invention synthesizes a novel heteronuclear complex with excellent catalytic performance by rationally designing the ligand structure and reaction conditions, providing new ideas and methods for the research and application of heteronuclear metal complexes. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 is the crystal structure of complex A;

[0066] Figure 2 is the crystal structure of complex B;

[0067] Figure 3 is the crystal structure of complex 1;

[0068] Figure 4 The crystal structure of complex 2. DETAILED DESCRIPTION

[0069] The following examples are provided to enable those skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and the experimental equipment, materials, reagents, etc. used are all commercially available.

[0070] The specific preparation methods of complexes 1 and 2 of the present invention are given below. The other complexes listed in Table 1 are all prepared using the same method.

[0071] Example 1 Preparation of tridentate alkylthiol mononuclear molybdenum complex A

[0072] At -78 ° C, bis (2-mercaptoethyl) sulfide lithium salt (1.66g, 10.00mmol) was added to a tetrahydrofuran solution of [Cp * MoCl4] (1.87g, 5.00mmol), and the color of the solution immediately turned dark green. As the reaction temperature slowly increased from -78 ° C to room temperature, the solution changed from dark green to brownish red. The reaction solvent was removed under vacuum, and the crude product was extracted with dichloromethane (60mL) and concentrated under vacuum. The crude product was recrystallized using n-hexane (160mL) / dichloromethane (20mL), and the filter cake retained by filtration was the crude product. The crude product was washed with n-hexane (40mL×3) and dried under reduced pressure to obtain a brownish red solid powder [Cp * Mo (η 3 -tpdt)Cl](A, 1.84 g, 4.40 mmol), with a yield of 88%. Crystals suitable for X-ray single crystal diffraction were obtained by diffusion crystallization in a dichloromethane / n-hexane dual solvent. 1 H NMR (400MHz, CD2Cl2, ppm, 298K): δ4.08 (d, J=5.36Hz, 2H, SCH2CH2), 3.87 (d, J=7.56H z,2H,SCH2CH2),2.64(d,J=6.64Hz,4H,SCH2CH2),1.80(s,15H,Cp*-CH3).IR(Film; cm -1 ):2954,2903,2818,1490,1415,1372,1262,1142,1024,842,798,620.Anal.Calcd.for C 14 H 23 ClS3:C,40.14,H,5.53.Found:C,40.37;H,5.32.

[0073] Example 2 Preparation of tridentate alkylthiol mononuclear molybdenum complex B

[0074] At -78 ° C, bis (2-mercaptoethyl) sulfide lithium salt (1.66g, 10.00mmol) was added to a tetrahydrofuran solution of [Cp * MoBr4] (2.75g, 5.00mmol), and the color of the solution immediately turned dark green. As the reaction temperature slowly increased from -78 ° C to room temperature, the solution changed from dark green to brownish red. The reaction solvent was removed under vacuum, and the crude product was extracted with dichloromethane (60mL) and concentrated under vacuum. The crude product was recrystallized using n-hexane (160mL) / dichloromethane (20mL), and the filter cake, i.e., the crude product, was retained by filtration. The crude product was washed twice with n-hexane (40mL×3) and dried under reduced pressure to obtain a brownish red solid powder [Cp * Mo (η 3-tpdt)Br](B, 1.93 g, 4.15 mmol), with a yield of 83%. Crystals suitable for X-ray single crystal diffraction were obtained by diffusion crystallization in a dichloromethane / n-hexane dual solvent. 1 H NMR (400MHz, CD2Cl2, ppm, 298K): δ4.03 (d, J=4.84Hz, 2H, SCH2CH2), 3.87 (d, J=8.21H z,2H,SCH2CH2),2.57(d,J=4.72Hz,4H,SCH2CH2),1.85(s,15H,Cp*-CH3).IR(Film; cm -1 ):2960,2900,2852,1415,1373,1254,1007,932,834,791,614.Anal.Calcd.for C 14 H 23 BrMoS3:C,36.29;H,5.00.Found:C,35.88;H,5.44.

[0075] Example 3 Preparation of Tridentate Alkylthiol-Bridged Molybdenum-Iron Heteronuclear Complex 1

[0076] At -78 ° C, a dichloromethane solution of tridentate alkylthiol mononuclear molybdenum complex A (418.9 mg, 1.00 mmol) was added dropwise to a dichloromethane solution of [Cp*Fe(MeCN)3][PF6] (459 mg, 1.00 mmol). The reaction temperature was maintained at -78 ° C during the addition. After the addition was completed, the color of the solution immediately turned dark red. As the reaction temperature gradually increased from -78 ° C to room temperature, the solution gradually changed from dark red to yellow-green. Filter and retain the filtrate, and concentrate the filtrate to 10 mL under vacuum. Recrystallize using ether (80 mL) / dichloromethane (10 mL), filter and retain the filter cake (the crude product). Then wash with ether three times (20 mL × 3) and dry under reduced pressure to obtain a yellow-green solid powder [Cp*Mo(μ-1κ 3 SSS′:2κ 2 SS-tpdt)(μ-Cl)FeCp*][PF6] (1,491.4 mg, 0.65 mmol) with a yield of 65%. Crystals suitable for single-crystal X-ray diffraction were obtained by dichloromethane / n-hexane dual solvent diffusion crystallization. 1 H NMR (400MHz, CD2Cl2, ppm, 298K): δ2.94-2.77(m,7H,SCH2CH2),2.33(s,1H,SCH2CH2),1.72(s,15H,Cp*-CH3),1.48(s,15H,Cp*-CH3).IR(Film; cm -1):2962,2921,1426,1379,1263,1157,1020,841,739,558.Anal.Calcd.forC 24 H 38 ClF6FeMoPS3:C,38.18;H,5.07.Found:C,38.08;H,5.25.

[0077] Example 4 Preparation of Tridentate Alkylthiol-Bridged Molybdenum-Iron Heteronuclear Complex 2

[0078] At -78°C, a dichloromethane solution of tridentate alkylthiol mononuclear molybdenum complex B (463.4 mg, 1.00 mmol) was added dropwise to a dichloromethane solution of [Cp*Fe(MeCN)3][PF6] (459.0 mg, 1.00 mmol). The reaction temperature was maintained at -78°C during the addition. After the addition was completed, the color of the solution immediately turned deep red. The reaction temperature was slowly raised from -78°C to room temperature, and the solution gradually turned from deep red to yellow-green. The filtrate was filtered and retained, and the filtrate was concentrated under vacuum to 10 mL. Recrystallization was carried out using ether (80 mL) / dichloromethane (10 mL), and the filter cake was filtered and retained, which was the crude product. It was then washed three times with ether (20 mL×3) and dried under reduced pressure to obtain a yellow-green solid powder [Cp*Mo(μ-1κ 3 SSS′:2κ 2 SS-tpdt)(μ-Br)FeCp*][BPh4] (2,564.7 mg, 0.58 mmol), with a yield of 58%. Crystals suitable for single-crystal X-ray diffraction were obtained by diffusion crystallization in a dichloromethane / n-hexane dual solvent. 1 H NMR (400MHz, CD2Cl2, ppm, 298K): 7.30 (m, 8H, Ph-H), 7.03 (t, J1 = 14.28Hz, 8H, Ph-H), 6.88 (t, J1 = 7.00Hz, 8H, Ph-H), 2.70-2.77 (m, 4H,SCH2CH2),2.48-2.57(m,2H,SCH2CH2),1.04-1.10(m,2H,SCH2CH2),1.76(s,15H,Cp*-CH3),1.53(s,15H,Cp*-CH3).IR(Film; cm -1 ):3053,2981,2908,2850,1938,1883,1819,1577,1480,1421,1373,1265,1061,1023,744,711,609.Anal.Calcd.for C 48 H 58BBrFeMoS3:C,59.21;H,6.00.Found:C,59.24;H,6.30.

[0079] The structures of complexes A, B, 1 and 2 were characterized by X-ray single crystal diffraction (instrument used: Brüker Smart ApexCCD single crystal diffractometer). The important crystallographic data are shown in Tables 3 and 4. The crystal structures are shown in Figure 1-4 The main structural parameters are shown in Table 5-8.

[0080] Table 3 Crystallographic data of complexes A and B

[0081]

[0082] Table 4 Crystallographic data of complexes 1 and 2

[0083]

[0084] Table 5 Main bond lengths and bond angles of complex A

[0085]

[0086] Table 6 Main bond lengths and bond angles of complex B

[0087]

[0088] Table 7 Main bond lengths and bond angles of complex 1

[0089]

[0090] Table 8 Main bond lengths and bond angles of complex 2

[0091]

[0092] Example 5 Complex A catalyzes the disproportionation of hydrazine to ammonia

[0093] Under argon, complex A (10.5 mg, 25 μmol), hydrazine (32 μL, 0.5 mmol), and dichloromethane (5 mL) were added to a Schlenk flask equipped with a gas outlet. The reaction system was then left at room temperature for 12 hours to complete the catalytic reaction. The yields of NH3 and N2 products were determined as follows.

[0094] Ammonia: The supernatant gas and solution in the reaction system were pumped into a reaction flask containing HCl·Et2O solution to convert NH3 to NH4Cl. The solvent was removed under vacuum, and ferrocene (internal standard) was added. H NMR analysis using DMSO-d6 (deuterated reagent) determined the presence of NH4Cl (8.18 mg, 0.153 mmol), with a yield of 23%.

[0095] Nitrogen: The top gas of the reaction flask was quantitatively extracted through the gas outlet and analyzed using an Agilent gas chromatograph. The yield of N2 (0.042 mmol) was calculated using a standard curve, and the yield was 25%.

[0096] Example 6 Complex 1 catalyzes the disproportionation of hydrazine to ammonia

[0097] Under argon, complex 1 (18.9 mg, 25 μmol), hydrazine (32 μL, 0.5 mmol), and dichloromethane (5 mL) were added to a Schlenk flask equipped with a gas outlet. The reaction system was then left at room temperature for 12 hours to complete the catalytic reaction. The catalytic products, NH3 and N2, were quantified using the same method as above. H NMR spectroscopy revealed NH4Cl (20.7 mg, 0.387 mmol) in a 58% yield, while gas chromatography indicated a 49% yield of N2 (0.082 mmol).

[0098] The above-described embodiments are only preferred embodiments of the present invention, and are not intended to be all feasible embodiments of the present invention. Any obvious modifications made by a person skilled in the art without departing from the principles and spirit of the present invention should be considered to be included within the scope of protection of the claims of the present invention.

Claims

1. A tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex, characterized in that: The general structural formula I is as follows: In the general structural formula I: R 1 Selected from cyclopentadiene ligands, monomethylcyclopentadiene ligands, dimethylcyclopentadiene ligands, trimethylcyclopentadiene ligands, tetramethylcyclopentadiene ligands, pentamethylcyclopentadiene ligands, and 1,2,4-tri-tert-butylcyclopentadiene ligands; X 2 Selected from S, O, NH, PH, NPh, PPh; X 1 Selected from F, Cl, Br, I; Y- is an anti-anion, selected from Cl - Br - 、I-、PF6 - 、SbF6 - 、BF4 - , BPh4 - CF3SO3 - and B(C6F5)4 - ; n is 0, 1 or 2.

2. The tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex according to claim 1, characterized in that: R 1 The ligand is selected from cyclopentadiene ligands, pentamethylcyclopentadiene ligands and 1,2,4-tri-tert-butylcyclopentadiene ligands.

3. The tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex according to claim 1, characterized in that: X 1 Selected from Cl, Br.

4. The tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex according to claim 1, characterized in that: X 2 Selected from S, O, NH, NPh.

5. The tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex according to claim 1, characterized in that: Y - Selected from BPh4 - and PF6 - .

6. The tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex according to claim 1, characterized in that: Select complexes 1 and 2: Complex 1: R 1 =pentamethylcyclopentadiene ligand, X 2 =S,X 1 =Cl, Y-=PF6 - ; Complex 2: R 1 =pentamethylcyclopentadiene ligand, X 2 =S,X 1 =Br, Y-=BPh4 - .

7. A method for preparing a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex, characterized in that: The following steps are involved: (1) Prepared by reacting a mononuclear molybdenum complex having four halogen atoms with 2 to 10 equivalents of a tridentate alkylthiol lithium salt: (2) Preparation by assembly reaction of a tridentate alkylthiol-based mononuclear molybdenum complex and a mononuclear iron precursor:

8. The method for preparing the tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex according to claim 7, characterized in that: The reaction temperature is -80 to 40°C, and the reaction time is 1 to 24 hours; the reaction in step (1) is carried out at a carbon number C 10 The following ethers, benzene, carbon number C 10 The following alkylbenzenes, carbon number C5~C 10 Alkanes, alcohols with carbon numbers below C5, chlorobenzene, fluorobenzene, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide; the reaction in step (2) is carried out in a 10 The following ethers, benzene, carbon number C 10 The following alkylbenzenes, carbon number C5~C 10 The method is carried out in the following ways: alkanes, dichloromethane, alcohols with carbon numbers below C5, chlorobenzene, fluorobenzene, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide.

9. An application of a tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex, characterized in that: Used to catalyze the disproportionation of hydrazine to ammonia and nitrogen.

10. The use of the tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex according to claim 9, characterized in that: Under an argon atmosphere, the tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex catalyzes the disproportionation of hydrazine into ammonia and nitrogen at a reaction temperature of -20 to 50° C. for 0.5 to 48 hours. The amount of the tridentate alkylthiol-bridged molybdenum-iron heteronuclear complex is 0.1 to 30% of the amount of the substrate hydrazine substance.

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