CN110938086B - Half-sandwich ruthenium-thione complex and preparation method thereof, ammonia borane hydrolysis method and nitrobenzene compound reduction method - Google Patents
Half-sandwich ruthenium-thione complex and preparation method thereof, ammonia borane hydrolysis method and nitrobenzene compound reduction method Download PDFInfo
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Abstract
The invention discloses a half-sandwich ruthenium-thione complex and a preparation method thereof, an ammonia borane hydrolysis method and a nitrobenzene compound reduction method, wherein the structure of the half-sandwich ruthenium-thione complex is shown as a formula I, wherein R is C1-C6 alkyl. The half-sandwich ruthenium-thione complex has excellent catalytic performance, stability and water solubility, so that the half-sandwich ruthenium-thione complex can be applied to catalyzing the hydrolysis of ammonia borane and the reduction of nitrobenzene compounds, and meanwhile, the preparation method of the half-sandwich ruthenium-thione complex is simple and convenient to operate and can be used for mass production.
Description
Technical Field
The invention relates to a half-sandwich ruthenium complex, in particular to a half-sandwich ruthenium thione complex and a preparation method thereof, a hydrolysis method of ammonia borane and a reduction method of nitrobenzene compounds.
Background
Aromatic amine compounds are important starting materials and intermediates of amine compounds, and are mainly used for synthesizing pesticides, insecticides, pharmaceutical products and the like. With the increasing demand for aromatic amine compounds in production, the synthesis of aromatic amine compounds becomes of particular importance. The synthesis of aromatic amine compounds by catalytic reduction of aromatic nitro compounds is an important synthesis method commonly used in chemical production and experimental research.
In the above method for producing an aromatic amine compound, a reducing agent mainly containing hydrogen is often used. Hydrogen is a combustible gas, and has the defects of high requirements on equipment, difficulty in control and the like in actual production.
Disclosure of Invention
The invention aims to provide a half-sandwich ruthenium-thione complex and a preparation method thereof, an ammonia borane hydrolysis method and a nitrobenzene compound reduction method, the half-sandwich ruthenium-thione complex has excellent catalytic performance, stability and water solubility, so that the half-sandwich ruthenium-thione complex can be applied to catalysis of ammonia borane hydrolysis and nitrobenzene compound reduction, and meanwhile, the preparation method of the half-sandwich ruthenium-thione complex is simple and convenient to operate and can be used for mass production.
In order to achieve the purpose, the invention provides a half-sandwich ruthenium-thione complex, the structure of the half-sandwich ruthenium-thione complex is shown as a formula I,
wherein R is C1-C6 alkyl.
The invention also provides a preparation method of the half-sandwich ruthenium thione complex, which comprises the following steps: the thioketone substituted pyridine ligand with the structure shown as formula II and the precursor [ (cymene RuX) of ruthenium with the structure shown as formula III are added 2 ) 2 ]Carrying out coordination reaction in the presence of protective gas to prepare an intermediate, then carrying out contact reaction on the intermediate and hexafluorophosphate to prepare a half-sandwich ruthenium-thione complex shown as a formula I,
wherein R is C1-C6 alkyl, and X is halogen.
The invention also provides a hydrolysis method of ammonia borane, which comprises the following steps: in the presence of a protective gas, ammonia borane, water and a catalyst are subjected to a contact reaction to obtain hydrogen, wherein the catalyst is the half-sandwich ruthenium-thione complex.
The invention further provides a reduction method of the nitrobenzene compounds, which comprises the following steps: the method comprises the following steps of carrying out contact reaction on a nitrobenzene compound, acetonitrile (used for promoting the dissolution of a complex), water, ammonia borane, a surfactant and a catalyst to obtain an aniline compound, wherein the catalyst is the half-sandwich ruthenium thione complex.
In the technical scheme, the solubility of the coordination compound in water is improved by regulating and controlling the coordination anion of the coordination compound of the half-sandwich structure ruthenium and the coordination compound containing the pincerlike thione ligand, and when the coordination anion is PF 6 - When the water-soluble polymer is used, the water-soluble polymer has better water solubility. Meanwhile, the complex prepared by the invention has unique chemical stability and redox performance.
Under the condition of ammonia borane, hydrogen prepared by catalyzing ammonia borane hydrolysis under mild conditions by using half-sandwich ruthenium (II) and pyridine compound substituted by thioketone as catalysts is used as a reducing agent to efficiently catalyze the reduction of aromatic nitro compounds in water, so that series aromatic amine compounds are obtained with high yield.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound 2a in example 1;
FIG. 2 is a NMR carbon spectrum of Compound 2a of example 1;
FIG. 3 is a mass spectrum (265-272 m/Z) of Compound 2a of example 1;
FIG. 4 is a crystal structure diagram of the cationic moiety of Compound 2a in example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a half-sandwich ruthenium thione complex, the structure of which is shown as a formula I,
wherein R is C1-C6 alkyl.
In the above-mentioned half-sandwich ruthenium thione complex, the specific kind of the substituent may be selected within a wide range, but it is preferable that R is a methyl group, an ethyl group, an isopropyl group or an n-butyl group, from the viewpoints of structural stability and easiness of preparation.
The invention also provides a preparation method of the half-sandwich ruthenium-thione complex, which comprises the following steps: the thioketone substituted pyridine ligand with the structure shown as formula II and the precursor [ (cymene RuX) of ruthenium with the structure shown as formula III are added 2 ) 2 ]Carrying out coordination reaction in the presence of protective gas to prepare an intermediate, then carrying out contact reaction on the intermediate and hexafluorophosphate to prepare a half-sandwich ruthenium-thione complex shown as a formula I,
wherein R is C1-C6 alkyl, and X is halogen.
In the above preparation method, the specific kind of the substituent may be selected within a wide range, but from the viewpoint of structural stability of the complex and ease of preparation, it is preferable that R is methyl, ethyl, isopropyl or n-butyl, and X is bromine or iodine.
In the above production method, the specific kind of the hexafluorophosphate salt may be selected from a wide range, but from the viewpoint of structural stability and yield of the complex, preferably, the hexafluorophosphate salt is selected from potassium hexafluorophosphate, sodium hexafluorophosphate or ammonium hexafluorophosphate.
In the above-mentioned production method, the reaction conditions may be selected within a wide range, but from the viewpoint of the structural stability and yield of the complex, it is preferable that the coordination reaction satisfies the following conditions: the reaction temperature is 15-35 ℃, and the reaction time is 10-18h; and/or the contact reaction satisfies the following conditions: the reaction temperature is 15-35 ℃.
In the above-mentioned production method, the amount of each material to be used can be selected within a wide range, but from the viewpoint of the yield, it is preferable that the pyridine ligand, [ (cymene rux) 2 ) 2 ]The dosage ratio of the hexafluorophosphate is 0.1mmol:0.05-0.06mmol:0.2-0.26mmol.
In the above production method, in order to allow sufficient contact between the reactants to further improve the yield of the product, it is preferable that both the coordination reaction and the contact reaction are carried out in a solvent. Among them, the kind of the solvent can be also selected from a wide range, but in order to further improve the yield, more preferably, the solvent in the coordination reaction is selected from at least one of dichloromethane, 1,2-dichloroethane and chloroform, and the solvent in the contact reaction is selected from at least one of methanol, acetonitrile and ethanol. Similarly, the amount of the solvent may be selected from a wide range, but in order to further improve the yield, it is further preferable that the ratio of the amount of the pyridine ligand, the solvent in the coordination reaction, and the solvent in the contact reaction is 0.1mmol:4-10mL:5-15mL.
In the present invention, the source of the pyridine ligand may be selected within a wide range, but in order to further secure the purity of the pyridine ligand, preferably, the pyridine ligand is prepared by the following method: 2,6-disubstituted pyridine imidazole salt with a structure shown as formula IV is put in a solvent to be in contact reaction with sulfur and carbonate to prepare a pyridine ligand,
wherein R is C1-C6 alkyl, and X is halogen.
In the above-mentioned preparation method of pyridine ligand, the kind of substituent can also be selected within a wide range, but in order to further ensure the structural stability of the prepared complex, preferably, R is methyl, ethyl, isopropyl or n-butyl, X is bromine or iodine, and carbonate is selected from potassium carbonate, sodium carbonate or ammonium carbonate;
in the above preparation method of pyridine ligand, the amount of each material may be selected within a wide range, but in order to further ensure the structural stability of the prepared complex, it is preferable that the ratio of the amounts of 2,6-disubstituted pyridine imidazolium salt, sulfur, carbonate, solvent is 10mmol:20-25mmol:2.8-3g:40-60mL.
In the above-mentioned preparation method of pyridine ligand, the conditions of the contact reaction may also be selected within a wide range, but in order to further secure the structural stability of the complex obtained, it is preferable that the contact reaction satisfies the following conditions: the reaction temperature is 60-80 ℃, and the reaction time is 6-10h.
The invention also provides a hydrolysis method of ammonia borane, which comprises the following steps: in the presence of a protective gas, ammonia borane, water and a catalyst are subjected to a contact reaction to obtain hydrogen, wherein the catalyst is the half-sandwich ruthenium-thione complex.
In the above hydrolysis method, the amount of each material may be selected within a wide range, but in order to improve the hydrolysis yield of ammonia borane, it is preferable that the ratio of the amounts of ammonia borane, water, and catalyst is 10mg:1-3mL:0.015-0.018mmol.
In the above hydrolysis method, the conditions of the contact reaction may be selected within a wide range, but in order to improve the hydrolysis yield of ammonia borane, it is preferable that the temperature of the contact reaction is 15 to 35 ℃.
The invention further provides a reduction method of the nitrobenzene compounds, which comprises the following steps: the method comprises the step of carrying out contact reaction on a nitrobenzene compound, acetonitrile, water, ammonia borane, a surfactant and a catalyst to obtain an aniline compound, wherein the catalyst is the half-sandwich ruthenium-thione complex.
In the above-mentioned reduction method, the amount of each material may be selected within a wide range, but in order to improve the reduction efficiency of the nitrobenzene compound, it is preferable that the nitrobenzene compound, acetonitrile, water, ammonia borane, a surfactant and a catalyst are used in a ratio of: 0.3mmol:0.1-0.5mL:1.5-3mL:1.3-1.5mmol:0.020-0.025mmol:0.0007-0.0010mmol.
In the above-mentioned reduction method, the conditions of the contact reaction can be selected within a wide range, but in order to improve the reduction efficiency of the nitrobenzene-based compound, it is preferable that the contact reaction satisfies the following conditions: the reaction temperature is 60-100 ℃, and the reaction time is 1-2h.
In the above-mentioned reduction method, the kind of the nitrobenzene-based compound and the surfactant may be selected from a wide range, but in order to improve the reduction efficiency of the nitrobenzene-based compound, it is preferable that the nitrobenzene-based compound is selected from p-chloronitrobenzene, p-bromonitrobenzene, 4-cyanonitrobenzene, 4-aldehydinitrobenzene or 3-chloronitrobenzene, and the surfactant is selected from at least one of cetyltrimethylammonium bromide, n-butylammonium bromide and sodium dodecylbenzenesulfonate.
The present invention will be described in detail below by way of examples. In the following examples, NMR spectra and NMR spectra were obtained on Bruker AV400 and Bruker AV 500MHz NMR spectrometers, switzerland, mass spectra were obtained on MicroOTOF-Q10280 from Bruker, germany, and IR spectra were obtained on Shimadzu Infrared Spectroscopy FTIR-8400S spectrometer (KBr pellet); the single crystal structure of the complex is measured by a Brucker Smart-100 CCD X-ray single crystal diffractometer; the catalytic products were determined by analysis with a seemer-femtochromatograph-mass spectrometer (GC-MS).
Ruthenium raw materials, methanol and acetonitrile are products of Saen chemical technology (Shanghai) Co., ltd, and raw materials of aromatic nitro compounds and synthetic ligands are products of Shanghai Crystal pure technology Ltd. [ (cymene RuCl) 2 ) 2 ]Has a structure shown in formula V
Preparation example 1
2,6-dibromo/diiodopyridine imidazolium salt (10 mmol), sulfur powder (20 mmol) and K 2 CO 3 (2.80 g) was placed in a 100mL round-bottom flask, 50mL of methanol solvent was added, and the mixture was refluxed at 70 ℃ for 8 hours. Cooling to 25 deg.C, draining the solvent, adding 30mL CH twice 2 Cl 2 Filtered and spin-dried to give 2,6-dithione substituted pyridines (1 a-1 d),
example 1
Synthesis of half-sandwich ruthenium and 2,6-dithione substituted pyridine coordination Compound 2 a:
at 25 deg.C, [ (cymene RuCl) 2 ) 2 ](0.05 mmol), 2,6-dimethylimidazolethione substituted pyridine of the structure shown in formula 1a (0.1 mmol) was placed in a Schlenk reaction tube, and then added5ml DCM was stirred for 16 h under nitrogen. After the reaction was complete, the solution was filtered, the solvent was removed by rotary evaporator, and 2mL of CH was added 3 OH dissolves the solids and saturated KPF is added 6 Aqueous solution (containing 0.25mmol of KPF) 6 ) A solid was immediately produced, which was washed with a small amount of water and ether to give 58mg of a yellow-brown solid in 71% yield.
Product characterization figures see fig. 1-4, product characterization data: 1 H NMR(400MHz,CD 3 CN)：δ8.38(t,J＝16.4Hz,1H),7.68(d,J＝8Hz,2H),7.63(d,J＝2.4Hz,2H),7.45(d,J＝2.4Hz,2H),5.71(d,J＝6.4Hz,2H),5.39(d,J＝6.0Hz,2H),3.97(s,6H),2.81(m,1H),1.75(s,3H),1.22(d,J＝7.2Hz,6H).
13 C NMR(100MHz,CD 3 CN)δ158.08,148.23,145.07,124.29,122.19,119.62,105.44,104.98,88.03,86.99,35.93,30.77,21.54,17.72.
IR(KBr cm -1 ):3413(s),2852(s),1605(s),1477(s),1408(s),1238(w),838(Vs),729(w),559(s).
MS(micrOTOF-Q):calcd.for C 23 H 27 F 12 N 5 P 2 RuS 3 2+ [M-2PF 6 ] 2+ 269.537,Found 269.545.
example 2
Synthesis of half-sandwich ruthenium and 2,6-dithione substituted pyridine coordination Compound 2 c:
at 25 deg.C, [ (cymene RuCl) 2 ) 2 ](0.05 mmol), 2,6-diisopropylimidazolethione substituted pyridine of the structure shown in formula 1c (0.1 mmol) was placed in a Schlenk reaction tube, then 5ml DCM was added and stirred under nitrogen for 16 hours. After the reaction was complete, the solution was filtered, the solvent was removed using a rotary evaporator, 2mL CH 3 OH dissolving the solid, and adding saturated KPF 6 Aqueous solution (containing 0.25mmol of KPF) 6 ) A solid was immediately produced, which was washed with a small amount of water and ether to give 61mg of a brown solid in 69% yield.
Product characterization data: 1 H NMR(400MHz,CD 3 CN):δ8.37(t,J＝16.4Hz,1H),7.69(d,J＝3.2Hz,2H),7.68(d,J＝2Hz,2H),7.57(d,J＝2.8Hz,2H),5.64(d,J＝6.0Hz,2H),5.33(d,J＝6.4Hz,2H),5.25(m,2H),2.80(m,1H),1.76(d,J＝7.6Hz,9H),1.53(d,J＝6.8Hz,6H),1.20(d,J＝6.8Hz,6H).
13 C NMR(100MHz,CD 3 CN)：δ162.20,153.44,150.19,127.80,125.94,124.92,110.48,110.37,93.71,92.43,57.37,306.05,26.99,26.84,26.15,23.07.
IR(KBr cm -1 ):3424(s),3181(s),2979(w),1608(s),1463(s),1222(s),842(Vs),557(s).
MS(micrOTOF-Q):calcd.for C 27 H 35 F 12 N 5 P 2 RuS 3 2+ [M-2PF 6 ] 2+ 297.569,Found 297.578.
application example 1
Catalytic ammonia borane hydrogen production experiment:
the temperature of the water is set at 25 ℃, and ammonia borane NH is filled into the substrate by a needle tube under the protection of nitrogen 3 BH 3 (10 mg) A two necked round bottom flask was charged with 2mL of deionized water (strictly degassed) solution and allowed to stand for 15 minutes, 5mol% catalyst 2a (0.0165 mmol) was added and the evolved hydrogen collected by draining, yielding 17mL of hydrogen after 35 minutes.
Application example 2
The half-sandwich ruthenium complex 2a is used for catalyzing p-chloronitrobenzene to reduce to obtain p-chloroaniline:
placing polytetrafluoroethylene magnetic particles in a reaction tube in air atmosphere to obtain half-sandwich ruthenium coordination compound 2a 7.5 × 10 -4 mmol, adding 0.3mmol p-chloronitrobenzene, 0.0375ml CH 3 CN and 1.5ml of water, 1.3mmol of NH 3 BH 3 0.021mmol CTAB, and stirring at 80 ℃ for 1 hour under vacuum. After the reaction, the reaction solution was transferred to a separatory funnel, extracted 3 times (1 ml each) with ethyl acetate, and analyzed by gas chromatography-mass spectrometer (GC-MS) to give p-chloroaniline (yield 99.9%).
Application example 3
M-chloronitrobenzene is reduced to obtain m-chloroaniline by using half-sandwich ruthenium complex 2a as catalyst
In the air atmosphere, put polytetrafluoroethylene magneton one grain in the reaction tube, half sandwich ruthenium coordination compound 2a 7.5X 10 -4 mmol, adding 0.3mmol m-chloronitrobenzene, 0.0375ml CH 3 CN and 1.5ml of water, 1.3mmol of NH 3 BH 3 0.021mmol CTAB, and stirring at 80 ℃ for 1 hour under vacuum. After the reaction, the reaction solution was transferred to a separatory funnel, extracted 3 times (1 ml each) with ethyl acetate, and analyzed by gas chromatography-mass spectrometer (GC-MS) to obtain m-chloroaniline (yield 99.5%).
Application example 4
Para-bromonitrobenzene is catalyzed by half-sandwich ruthenium complex 2a to be reduced to obtain para-bromoaniline
In the air atmosphere, put polytetrafluoroethylene magneton one grain in the reaction tube, half sandwich ruthenium coordination compound 2a 7.5X 10 -4 mmol, adding 0.3mmol of p-bromonitrobenzene and 0.0375ml of CH 3 CN and 1.5ml of water, 1.3mmol of NH 3 BH 3 0.021mmol CTAB, and stirring at 80 deg.C for 1 hr under vacuum. After the reaction, the reaction solution was transferred to a separatory funnel, extracted 3 times (1 ml each) with ethyl acetate, and analyzed by gas chromatography-mass spectrometer (GC-MS) to obtain p-bromoaniline (yield 99.6%).
Application example 5
4-cyanoaniline is obtained by reducing 4-cyanonitrobenzene under catalysis of half-sandwich ruthenium complex 2a
In the air atmosphere, put polytetrafluoroethylene magneton one grain in the reaction tube, half sandwich ruthenium coordination compound 2a 7.5X 10 -4 mmol, 0.3mmol of 4-cyanonitrobenzene and 0.0375ml of CH are added 3 CN and 1.5ml of water, 1.3mmol of NH 3 BH 3 0.021mmol CTAB, and stirring at 80 ℃ for 10 hours under vacuum. After the reaction, the reaction solution was transferred to a separatory funnel, extracted 3 times (1 ml each) with ethyl acetate, and analyzed by gas chromatography-mass spectrometer (GC-MS) to give p-bromoaniline (yield 99.0%).
Application example 6
Semi-sandwich ruthenium complex 2a is used for catalyzing 4-aldehyde nitrobenzene to reduce to obtain p-aminobenzyl alcohol
In the air atmosphere, put polytetrafluoroethylene magneton one grain in the reaction tube, half sandwich ruthenium coordination compound 2a 7.5X 10 -4 mmol, 0.3mmol of 4-aldehyde nitrobenzene and 0.0375ml of CH are added 3 CN and 1.5ml of water, 1.3mmol of NH 3 BH 3 0.021mmol CTAB, and stirring at 80 ℃ for 10 hours under vacuum. After the reaction, the reaction solution was transferred to a separatory funnel, extracted 3 times (1 ml each) with ethyl acetate, and analyzed by gas chromatography-mass spectrometer (GC-MS) to obtain p-aminobenzyl alcohol (yield 99.2%).
The procedure was carried out as in application example 2, except that the catalyst 2a was changed to the catalyst 2c, and the reduction yield was also 99% or more.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (21)
1. A half-sandwich ruthenium-thione complex is characterized in that the structure of the half-sandwich ruthenium-thione complex is shown as a formula I,
wherein R is C1-C6 alkyl.
2. The half-sandwich ruthenium thione complex of claim 1 wherein R is methyl, ethyl, isopropyl or n-butyl.
3. A method of preparing the half-sandwich ruthenium thione complex of claim 1, comprising: the thioketone substituted pyridine ligand with the structure shown as formula II and the precursor [ (cymene RuX) of ruthenium with the structure shown as formula III are added 2 ) 2 ]Carrying out coordination reaction in the presence of protective gas to prepare an intermediate, then carrying out contact reaction on the intermediate and hexafluorophosphate to prepare a half-sandwich ruthenium-thione complex shown as a formula I,
wherein R is C1-C6 alkyl, and X is halogen.
4. The process according to claim 3, wherein R is methyl, ethyl, isopropyl or n-butyl, and X is bromine or iodine.
5. The production method according to claim 3, wherein the hexafluorophosphate salt is selected from potassium hexafluorophosphate, sodium hexafluorophosphate, or ammonium hexafluorophosphate.
6. The production method according to claim 3, wherein the coordination reaction satisfies the following condition: the reaction temperature is 15-35 ℃, and the reaction time is 10-18h; and/or the contact reaction satisfies the following conditions: the reaction temperature is 15-35 ℃.
7. The process for preparation according to claim 3, wherein the pyridine ligand, [ (cymene rux) 2 ) 2 ]The dosage ratio of the hexafluorophosphate is 0.1mmol:0.05-0.06mmol:0.2-0.26mmol.
8. The production method according to claim 3, wherein the coordination reaction and the contact reaction are carried out in a solvent.
9. The method according to claim 8, wherein the solvent in the coordination reaction is at least one selected from dichloromethane, 1,2-dichloroethane and chloroform, and the solvent in the contact reaction is at least one selected from methanol, acetonitrile and ethanol.
10. The production method according to claim 8, wherein the ratio of the amount of the pyridine ligand to the amount of the solvent in the coordination reaction to the amount of the solvent in the contact reaction is 0.1mmol:4-10mL:2-15mL.
11. The preparation method of claim 3, wherein the pyridine ligand is prepared by the following method: 2,6-disubstituted pyridine imidazole salt with the structure shown in formula IV is put in a solvent to be in contact reaction with sulfur and carbonate to prepare the pyridine ligand,
wherein R is C1-C6 alkyl, and X is halogen.
12. The method of claim 11, wherein R is methyl, ethyl, isopropyl or n-butyl, X is bromine or iodine, and the carbonate is selected from potassium carbonate, sodium carbonate or ammonium carbonate.
13. The preparation method according to claim 11, wherein the 2,6-disubstituted pyridine imidazolium salt, the sulfur, the carbonate and the solvent are used in a ratio of 10mmol:20-25mmol:2.8-3g:40-60mL.
14. The production method according to claim 11, wherein the contact reaction satisfies the following condition: the reaction temperature is 60-80 ℃, and the reaction time is 6-10h.
15. A method for hydrolyzing ammonia borane is characterized by comprising the following steps: in the presence of a protective gas, carrying out a contact reaction on ammonia borane, water and a catalyst to obtain hydrogen, wherein the catalyst is the half-sandwich ruthenium thione complex as claimed in claim 1.
16. The method for hydrolyzing ammonia borane according to claim 15, wherein the dosage ratio of the ammonia borane, the water and the catalyst is 10mg:1-3mL:0.015-0.018mmol.
17. The method of hydrolyzing ammonia borane according to claim 15, wherein the temperature of the contact reaction is 15-35 ℃.
18. A reduction method of nitrobenzene compounds is characterized by comprising the following steps: the method comprises the step of carrying out contact reaction on a nitrobenzene compound, acetonitrile, water, ammonia borane, a surfactant and a catalyst to obtain an aniline compound, wherein the catalyst is the half-sandwich ruthenium thione complex as claimed in claim 1.
19. The method for reducing nitrobenzene compounds according to claim 18 wherein the nitrobenzene compounds, acetonitrile, water, ammonia borane, surfactant and catalyst are used in the following ratio: 0.3mmol:0.1-0.5mL:1.5-3mL:1.3-1.5mmol:0.020-0.025mmol:0.0007-0.0010mmol.
20. The method for reducing a nitrobenzene compound according to claim 18, wherein the contacting reaction satisfies the following conditions: the reaction temperature is 60-100 ℃, and the reaction time is 1-2h.
21. The method for reducing a nitrobenzene-based compound according to claim 18, the nitrobenzene-based compound being selected from p-chloronitrobenzene, p-bromonitrobenzene, 4-cyanonitrobenzene, 4-aldehydic nitrobenzene or 3-chloronitrobenzene, the surfactant being selected from at least one of cetyltrimethylammonium bromide, n-butylammonium bromide and sodium dodecylbenzenesulfonate.
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