Metal nanoclusters, preparation method and application thereof

Abstract

The application discloses a metal nanocluster and a preparation method and application thereof, and provides a mixture comprising a reaction substrate, a metal salt, an alkali and a reducing agent, the metal salt and the reducing agent are reacted on site under the action of the alkali to prepare the metal nanocluster, and the metal nanocluster catalyzes a hydrogen functionalization reaction of the reaction substrate on site as a catalyst of an organic reaction. The metal nanocluster has the advantages of simple catalyst, low cost and high catalytic activity in catalyzing the hydrogen functionalization reaction of an unsaturated bond.

Description

Technical Field

[0001] This invention relates to a metal nanocluster, its preparation method, and its application, specifically a metal nanocluster that can be used to catalyze hydrogen functionalization reactions and its preparation method. Background Technology

[0002] Enzymes, centered around abundant and inexpensive metals such as iron and cobalt, are widely found in nature and play a crucial catalytic role in various biosynthetic reactions within living organisms. Their active centers often contain reactive metal clusters, such as the iron-sulfur cluster in carbon monoxide dehydrogenase (CODH), which plays a vital role in electron transfer. However, our understanding of these metal clusters has been extremely limited to date, representing a challenging problem in modern organic chemistry.

[0003] Hydrogen functionalization reactions of unsaturated bonds, including hydridation, hydroboration, hydrosilylation, and hemihydrogenation of unsaturated triple bonds, are widely used in organic synthesis. These reactions mostly require the participation of noble metals and ligands to ensure conversion efficiency and chemoselectivity. In recent years, scientists have designed and synthesized a series of complexes of metals such as iron, cobalt, nickel, and manganese, and applied them to various organic chemical transformations. However, the ligands in these complexes mostly require multi-step synthesis, which is time-consuming, labor-intensive, and expensive, limiting their application in production. Furthermore, many ligands and complexes have poor stability and are difficult to exist stably in air, further limiting their application value.

[0004] Therefore, the development of ligand-free metal cluster catalysts has significant scientific and practical value. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a metal nanocluster that can be used as a catalyst to catalyze hydrogen functionalization reactions of unsaturated bonds, such as hydrogenation, hydroboration, hydrosilylation, and semi-hydrogenation of unsaturated triple bonds.

[0006] In a first aspect, the present invention provides a method for preparing metal nanoclusters, the method comprising the following steps:

[0007] The metal nanoclusters are obtained by reacting metal salts and reducing agents under alkaline conditions.

[0008] In another preferred embodiment, the metal salt is selected from the group consisting of manganese salts, iron salts, cobalt salts, nickel salts, and copper salts, wherein,

[0009] The manganese salt is one or more of the following: MnF2, MnCl2, MnCl2·4H2O, MnBr2, MnBr2·4H2O, MnI2, MnI2·4H2O, MnSO4, MnSO4·H2O, MnSO4·4H2O, Mn(CO)5Br, Mn(OAc)2, Mn(OAc)2·4H2O, Mn(OAc)3·2H2O, Mn(acac)2, Mn(acac)3, cyclopentadiene tricarbonyl manganese, and methylcyclopentadiene tricarbonyl manganese.

[0010] The iron salts are FeF2, FeCl2, FeBr2, FeI2, FeF3, FeCl3, FeCl3·6H2O, FeBr3, FeBr3·2THF, FeSO4, FeSO4·H2O, FeSO4·6H2O, Fe(OAc)2, Fe(OH)(OAc)2, Fe2(CO)9, and Fe3(CO). 12 One or more of the following: Fe(acac)2, Fe(acac)3, Fe(OTf)3, Fe(BF4)2·6H2O, Fe(NH3)2(SO4)2, Fe(NH3)2(SO4)2·6H2O, Fe2(SO4)3·H2O, K3Fe(CN)6, Fe(ClO4)3, Fe(ClO4)3·H2O;

[0011] The cobalt salt is one or more of the following: CoF2, CoF3, CoCl2, CoCl2·H2O, CoBr2, CoBr2·H2O, CoI2, Co(OAc)2, Co(acac)2, Co(acac)3, Co(NH3)6Cl3, Co(PPh3)3Cl, Co(dppe)Cl2, Co2CO3, and Co2(CO)8.

[0012] The nickel salt is one or more of the following: NiCl2, NiCl2·6H2O, NiBr2, NiBr2·H2O, NiI2, Ni(acac)2, Ni(OAc)2, Ni(OAc)2·4H2O, Ni(OTf)2, Ni(ClO4)2·6H2O, Ni(BF4)2·6H2O, Ni(NO3)2·6H2O, NiSO4·6H2O, Ni(cod)2, Ni(DME)Cl2, Ni(DME)Br2, Ni(dppe)Cl2, Ni(dppp)Cl2, Ni(PCy3)2Cl2, Ni(PPh3)2Cl2, Ni(PPh3)2Br2, and Ni(NH3)6Br2.

[0013] The copper salt is one or more of the following: CuCl, CuBr, CuI, CuF2, CuCl2, CuCl2·2H2O, CuBr2, CuCN, CuOAc, Cu(OAc)2, Cu(OAc)2·H2O, Cu(OTf)2, Cu(CN)4(PF6), Cu2(OTf)2Ph, CuSO4, Cu(NH4)2(SO4)2·6H2O, CuSO4·6H2O, Cu(BF4)2, and Cu(BF4)2·6H2O.

[0014] In another preferred embodiment, the reducing agent is borane or silane, wherein,

[0015] The borane is one or more of pinacol borane, 9-boronbicyclo[3.3.1]nonane, catechol borane, and borane-amine complex;

[0016] The silane is one or more of the following: benzylsilane, diphenylsilane, triphenylsilane, phenyldimethylsilane, dimethyl(ethyl)silane, dipropyl(ethyl)silane, dibutyl(ethyl)silane, diethylsilane, triethylsilane, dimethylbenzylsilane, dimethylphenylethylsilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, phenyldiethoxysilane, diisopropylethoxysilane, and 1,1,3,3-tetramethyldisiloxane.

[0017] In another preferred embodiment, the base is one or more of the following: potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium isopropoxide, sodium isopropoxide, lithium isopropoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium methoxide, sodium methoxide, lithium methoxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, cesium acetate, potassium acetate, sodium acetate, lithium acetate, potassium bis(trimethylsilylamine), sodium bis(trimethylsilylamine), lithium bis(trimethylsilylamine), potassium triethylborohydride, sodium triethylborohydride, lithium triethylborohydride, triethylamine, diisopropylethylamine, n-butyllithium, methyllithium, phenyllithium, and Grignard reagents.

[0018] In another preferred embodiment, the reaction is carried out in an organic solvent or without a solvent, wherein the organic solvent is one or a mixture of two or more of the following: benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, methanol, ethanol, isopropanol, tert-butanol, n-pentane, n-hexane, cyclohexane, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

[0019] In another preferred embodiment, the particle size of the metal nanoclusters is 0.1 to 200 nm, and the molar ratio of the reaction substrate to the metal salt can be 1:0.00001 to 0.1, or other ratios.

[0020] In another preferred embodiment, the molar ratio of the alkali to the reducing agent is 0.001 to 3:1.

[0021] In a second aspect, the present invention provides a metal nanocluster prepared by the preparation method described in the first aspect.

[0022] A third aspect of the invention provides the use of the metal nanoclusters described in the second aspect as catalysts.

[0023] In another preferred embodiment, the catalyst is used to catalyze the hydrogen functionalization reaction of unsaturated bonds.

[0024] In another preferred embodiment, the hydrogen functionalization reaction is selected from hydrogenation, borohydride, hydrosilylation, and half-hydrogenation of unsaturated triple bonds.

[0025] In a fourth aspect, the present invention provides a catalyst comprising the metal nanoclusters described in the third aspect.

[0026] In another preferred embodiment, the catalyst is used to catalyze the hydrogen functionalization reaction of unsaturated bonds.

[0027] In another preferred embodiment, the hydrogen functionalization reaction is selected from hydrogenation, borohydride, hydrosilylation, and half-hydrogenation of unsaturated triple bonds.

[0028] A fifth aspect of the present invention provides a method for hydrogen functionalization reaction, the method comprising the following steps:

[0029] A mixture is provided, the mixture comprising a reaction substrate, a metal salt, a base, and a reducing agent;

[0030] In this process, metal salts and reducing agents react under alkaline conditions to obtain metal nanoclusters, which then act as catalysts to catalyze the hydrogen functionalization reaction of the reaction substrate.

[0031] The reaction substrates are selected from alkenes, alkynes, nitriles, imines, aldehydes, ketones, acids, esters, and amides.

[0032] In another preferred embodiment, the metal salt is selected from the group consisting of manganese salts, iron salts, cobalt salts, nickel salts, and copper salts, wherein,

[0033] The manganese salt is one or more of the following: MnF2, MnCl2, MnCl2·4H2O, MnBr2, MnBr2·4H2O, MnI2, MnI2·4H2O, MnSO4, MnSO4·H2O, MnSO4·4H2O, Mn(CO)5Br, Mn(OAc)2, Mn(OAc)2·4H2O, Mn(OAc)3·2H2O, Mn(acac)2, Mn(acac)3, cyclopentadiene tricarbonyl manganese, and methylcyclopentadiene tricarbonyl manganese.

[0034] The iron salts are FeF2, FeCl2, FeBr2, FeI2, FeF3, FeCl3, FeCl3·6H2O, FeBr3, FeBr3·2THF, FeSO4, FeSO4·H2O, FeSO4·6H2O, Fe(OAc)2, Fe(OH)(OAc)2, Fe2(CO)9, and Fe3(CO). 12 One or more of the following: Fe(acac)2, Fe(acac)3, Fe(OTf)3, Fe(BF4)2·6H2O, Fe(NH3)2(SO4)2, Fe(NH3)2(SO4)2·6H2O, Fe2(SO4)3·H2O, K3Fe(CN)6, Fe(ClO4)3, Fe(ClO4)3·H2O;

[0035] The cobalt salt is one or more of the following: CoF2, CoF3, CoCl2, CoCl2·H2O, CoBr2, CoBr2·H2O, CoI2, Co(OAc)2, Co(acac)2, Co(acac)3, Co(NH3)6Cl3, Co(PPh3)3Cl, Co(dppe)Cl2, Co2CO3, and Co2(CO)8.

[0036] The nickel salt is one or more of the following: NiCl2, NiCl2·6H2O, NiBr2, NiBr2·H2O, NiI2, Ni(acac)2, Ni(OAc)2, Ni(OAc)2·4H2O, Ni(OTf)2, Ni(ClO4)2·6H2O, Ni(BF4)2·6H2O, Ni(NO3)2·6H2O, NiSO4·6H2O, Ni(cod)2, Ni(DME)Cl2, Ni(DME)Br2, Ni(dppe)Cl2, Ni(dppp)Cl2, Ni(PCy3)2Cl2, Ni(PPh3)2Cl2, Ni(PPh3)2Br2, and Ni(NH3)6Br2.

[0037] The copper salt is one or more of the following: CuCl, CuBr, CuI, CuF2, CuCl2, CuCl2·2H2O, CuBr2, CuCN, CuOAc, Cu(OAc)2, Cu(OAc)2·H2O, Cu(OTf)2, Cu(CN)4(PF6), Cu2(OTf)2Ph, CuSO4, Cu(NH4)2(SO4)2·6H2O, CuSO4·6H2O, Cu(BF4)2, and Cu(BF4)2·6H2O.

[0038] In another preferred embodiment, the reducing agent is borane or silane, wherein,

[0039] The borane is one or more of pinacol borane, 9-boronbicyclo[3.3.1]nonane, catechol borane, and borane-amine complex;

[0040] The silane is one or more of the following: benzylsilane, diphenylsilane, triphenylsilane, phenyldimethylsilane, dimethyl(ethyl)silane, dipropyl(ethyl)silane, dibutyl(ethyl)silane, diethylsilane, triethylsilane, dimethylbenzylsilane, dimethylphenylethylsilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, phenyldiethoxysilane, diisopropylethoxysilane, and 1,1,3,3-tetramethyldisiloxane.

[0041] In another preferred embodiment, the base is one or more of the following: potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium isopropoxide, sodium isopropoxide, lithium isopropoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium methoxide, sodium methoxide, lithium methoxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, cesium acetate, potassium acetate, sodium acetate, lithium acetate, potassium bis(trimethylsilylamine), sodium bis(trimethylsilylamine), lithium bis(trimethylsilylamine), potassium triethylborohydride, sodium triethylborohydride, lithium triethylborohydride, triethylamine, diisopropylethylamine, n-butyllithium, methyllithium, phenyllithium, and Grignard reagents.

[0042] In another preferred embodiment, the mixture either does not contain an organic solvent, or it does contain an organic solvent.

[0043] In another preferred embodiment, the reaction is carried out in an organic solvent or without a solvent, wherein the organic solvent is one or a mixture of two or more of the following: benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, methanol, ethanol, isopropanol, tert-butanol, n-pentane, n-hexane, cyclohexane, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

[0044] In another preferred embodiment, the molar ratio of the alkali to the reducing agent is 0.001 to 3:1.

[0045] In another preferred embodiment, the molar ratio of the base, reducing agent, and reaction substrate is 0.01–1:1–10:1.

[0046] In another preferred embodiment, the route of the hydrogen functionalization reaction is as follows:

[0047]

[0048] Under alkaline conditions, the metal salt and reducing agent react to form a metal nanocluster catalyst, which catalyzes the hydrogen functionalization reaction of compound 1 to yield compounds 2 and 3.

[0049] In each formula, R is selected from: H, C1-C6 alkyl, C1-C6 alkoxy, halogen, C1-C6 alkylsilyl (trimethylsilyl), (C1-C6 alkyl)3siloxy (tert-butyldimethylsiloxy).

[0050] In another preferred embodiment, the route of the hydrogen functionalization reaction is as follows:

[0051]

[0052] Under alkaline conditions, the metal salt and reducing agent react to generate a metal nanocluster catalyst, which catalyzes the hydrogen functionalization reaction of compound 4 to yield compound 5. Further acidification yields compound 6.

[0053] In each formula, R is selected from: C1-C10 alkyl, C3-C8 cycloalkyl, C6-C10 aryl; optionally substituted by a group selected from the group consisting of: C1-C6 alkyl, C1-C6 haloalkyl, halogen, C1-C6 alkoxy, C6-C10 aryl, C6-C10 aryl-O-.

[0054] In another preferred embodiment, the reducing agent is pinacolborane.

[0055] In another preferred embodiment, the hydrogen functionalization reaction is a borohydride reaction.

[0056] The present invention provides a mixture comprising a metal salt, a base, a reducing agent (silane or borane), and a reaction substrate; wherein the metal salt generates metal nanoclusters in the mixture system, and the metal nanoclusters catalyze the reaction of the reaction substrate in the in-situ; wherein the reaction substrate is selected from substituted or unsubstituted alkenes, alkynes, nitriles, imines, aldehydes, ketones, acids, esters, and amides, and is solvent-free or soluble in an organic solvent.

[0057] The metal nanoclusters provided in this invention are generated in situ in the reaction system and can efficiently catalyze the hydrogen functionalization reaction of unsaturated bonds. The metal nanoclusters of this invention have many advantages for catalyzing the hydrogen functionalization reaction of unsaturated bonds: (1) They use inexpensive metal salts that are abundant, cheap, and commercially available as catalyst precursors, avoiding the use of precious metals such as iridium, rhodium, and palladium; (2) They do not require various air-sensitive, unstable ligands that need to be prepared through multiple chemical reactions to participate in the reaction, making them economical; (3) They require less catalyst, have high activity, and have a fast reaction rate.

[0058] It should be understood that, within the scope of this invention, the above-described technical features of this invention and the technical features specifically described below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Each feature disclosed in the specification can be replaced by any alternative feature that provides the same, equivalent, or similar purpose. Due to space limitations, they will not be described in detail here. Attached Figure Description

[0059] Figure 1 This is a transmission electron microscope (TEM) image of the metal nanoclusters obtained in Example 1 of this invention using tetrahydrofuran as the solvent.

[0060] Figure 2 The image shows the SAESI-TOF mass spectrum of the intermediate formed by the metal nanoclusters obtained in Example 1 of this invention with tetrahydrofuran as the solvent and borane and styrene. Specific implementation methods

[0061] Typical embodiments embodying the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various variations in different embodiments without departing from the scope of the present invention, and the descriptions and illustrations herein are for illustrative purposes only and not intended to limit the present invention.

[0062] This invention provides a method for preparing metal nanoclusters, comprising: providing a mixture comprising a metal salt, an alkali, and a reducing agent; subjecting the mixture to a redox reaction to reduce the metal ions contained in the metal salt to metal atoms, wherein the metal atoms form the metal nanoclusters, and the metal nanoclusters act as catalysts for catalyzing organic reactions; wherein the reaction substrate is selected from substituted or unsubstituted alkenes, alkynes, nitriles, imines, aldehydes, ketones, acids, esters, and amides, and is solvent-free or soluble in an organic solvent.

[0063] Specifically, the molar ratio of the reaction substrate to the metal salt is preferably 1:0.00001 to 0.02.

[0064] Specifically, the metal salt is selected from the group consisting of manganese salts, iron salts, cobalt salts, nickel salts, and copper salts, wherein...

[0065] The manganese salt is one or more of the following: MnF2, MnCl2, MnCl2·4H2O, MnBr2, MnBr2·4H2O, MnI2, MnI2·4H2O, MnSO4, MnSO4·H2O, MnSO4·4H2O, Mn(CO)5Br, Mn(OAc)2, Mn(OAc)2·4H2O, Mn(OAc)3·2H2O, Mn(acac)2, Mn(acac)3, cyclopentadiene tricarbonyl manganese, and methylcyclopentadiene tricarbonyl manganese.

[0066] The iron salts are FeF2, FeCl2, FeBr2, FeI2, FeF3, FeCl3, FeCl3·6H2O, FeBr3, FeBr3·2THF, FeSO4, FeSO4·H2O, FeSO4·6H2O, Fe(OAc)2, Fe(OH)(OAc)2, Fe2(CO)9, and Fe3(CO). 12 One or more of the following: Fe(acac)2, Fe(acac)3, Fe(OTf)3, Fe(BF4)2·6H2O, Fe(NH3)2(SO4)2, Fe(NH3)2(SO4)2·6H2O, Fe2(SO4)3·H2O, K3Fe(CN)6, Fe(ClO4)3, Fe(ClO4)3·H2O;

[0067] The cobalt salt is one or more of the following: CoF2, CoF3, CoCl2, CoCl2·H2O, CoBr2, CoBr2·H2O, CoI2, Co(OAc)2, Co(acac)2, Co(acac)3, Co(NH3)6Cl3, Co(PPh3)3Cl, Co(dppe)Cl2, Co2CO3, and Co2(CO)8.

[0068] The nickel salt is one or more of the following: NiCl2, NiCl2·6H2O, NiBr2, NiBr2·H2O, NiI2, Ni(acac)2, Ni(OAc)2, Ni(OAc)2·4H2O, Ni(OTf)2, Ni(ClO4)2·6H2O, Ni(BF4)2·6H2O, Ni(NO3)2·6H2O, NiSO4·6H2O, Ni(cod)2, Ni(DME)Cl2, Ni(DME)Br2, Ni(dppe)Cl2, Ni(dppp)Cl2, Ni(PCy3)2Cl2, Ni(PPh3)2Cl2, Ni(PPh3)2Br2, and Ni(NH3)6Br2.

[0069] The copper salt is one or more of the following: CuCl, CuBr, CuI, CuF2, CuCl2, CuCl2·2H2O, CuBr2, CuCN, CuOAc, Cu(OAc)2, Cu(OAc)2·H2O, Cu(OTf)2, Cu(CN)4(PF6), Cu2(OTf)2Ph, CuSO4, Cu(NH4)2(SO4)2·6H2O, CuSO4·6H2O, Cu(BF4)2, and Cu(BF4)2·6H2O. Preferably, the metal salt is one of CoCl2, CoBr2, and CoI2; the metal salt can be added to an organic solution to prepare a solution of fixed concentration before adding it to the reaction system.

[0070] Specifically, the base is one or more of the following: potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium methoxide, sodium methoxide, lithium methoxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, cesium acetate, potassium acetate, sodium acetate, lithium acetate, bis(trimethylsilylamine)potassium, bis(trimethylsilylamine)sodium, bis(trimethylsilylamine)lithium, potassium triethylborohydride, sodium triethylborohydride, lithium triethylborohydride, triethylamine, diisopropylethylamine, n-butyllithium, methyllithium, phenyllithium, and Grignard reagents. Preferably, the base selected in the reaction is at least one of potassium tert-butoxide and sodium tert-butoxide.

[0071] Specifically, the mixture is solvent-free or contains an organic solvent. The selected organic solvent is at least one of benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, methanol, ethanol, isopropanol, tert-butanol, n-pentane, n-hexane, cyclohexane, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide. Preferably, the organic solvent selected in the reaction is one of diethyl ether and tetrahydrofuran. Preferably, the concentration of the reaction substrate in the solution is 0.2–5.0 mol / L.

[0072] Specifically, the reducing agent is borane or silane. The borane is at least one of pinacolborane, 9-boronbicyclo[3.3.1]nonane, catecholborane, and borane-amine complex; the silane is one or more of benzylsilane, diphenylsilane, triphenylsilane, phenyldimethylsilane, dimethyl(ethyl)silane, dipropyl(ethyl)silane, dibutyl(ethyl)silane, diethylsilane, triethylsilane, dimethylbenzylsilane, dimethylphenylethylsilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, phenyldiethoxysilane, diisopropylethoxysilane, and 1,1,3,3-tetramethyldisiloxane. Preferably, the reducing agent selected in the reaction is one of pinacolborane or benzylsilane.

[0073] Specifically, the molar ratio of the base, reducing agent, and reaction substrate is 0.01–1:1–10:1. Preferably, the molar ratio of the base, reducing agent, and reaction substrate is 0.05–0.1:1–5:1.

[0074] The metal nanoclusters prepared by the method of the present invention have a particle size of 0.1 to 200 nm, and each metal cluster contains several to several hundred metal atoms.

[0075] The metal nanoclusters provided in this invention are generated in situ in the reaction system and can efficiently catalyze the hydrogen functionalization reaction of unsaturated bonds. The catalytic reaction occurs in an inert gas atmosphere and the target product is obtained by reacting at -78℃ to 100℃ for 0.1 to 72 hours; preferably at 0 to 25℃.

[0076] The metal nanoclusters of the present invention have many advantages for catalyzing the hydrogen functionalization reaction of unsaturated bonds: (1) They use inexpensive metal salts that are abundant, cheap and commercially available as catalyst precursors, avoiding the use of precious metals such as iridium, rhodium and palladium; (2) They do not require various air-sensitive, unstable ligands that need to be prepared by multiple chemical reactions to participate in the reaction, which is economical; (3) They require less catalyst, have high activity and fast reaction rate.

[0077] The present invention will be specifically described below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention shall fall within the scope of protection of the present invention.

[0078] Example 1

[0079] In this embodiment, styrene is used as the reaction substrate, potassium tert-butoxide as the base, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with the metal salt CoCl2 to catalyze the hydroboration reaction of styrene under different solvents. The reaction formula is as follows:

[0080]

[0081] The reaction was as follows: In a glove box, CoCl2 (1.04 mg, 0.008 mmol), potassium tert-butoxide (4.5 mg, 0.04 mmol), and styrene (41.6 mg, 0.4 mmol) were added to separate 10 mL sample vials, along with 2 mL of the solvent listed in Table 1, and then pinacolborane (61.4 mg, 0.48 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product.

[0082] Figure 1 The image shows a transmission electron microscope (TEM) image of metal nanoclusters obtained with tetrahydrofuran as the solvent, indicating that cobalt salts formed nanoclusters under the action of a reducing agent and an alkali.

[0083] Figure 2 The image shows the SAESI-TOF mass spectrum of the intermediate formed by the metal nanoclusters obtained in tetrahydrofuran solvent with borane and styrene. Based on the molecular weight, it is determined to be the combination of Co3 with styrene and HBPin, which proves the presence of cobalt nanoclusters in the catalytic system.

[0084] Table 1: Effect of solvent on hydroboration reaction

[0085]

[0086] Yield and selectivity were determined by gas chromatography: 1 H NMR (400MHz, CDCl3) δ7.32–7.21(m,4H),7.19–7.12(m,1H),2.47(q,J=7.4Hz,1H),1.37(d,J=7.5Hz,3H),1.23(d,J=5.4Hz,12H)ppm. 13 CNMR (101MHz, CDCl3) δ145.0,128.4,127.9,125.2,83.3,24.7,24.7,17.1ppm.

[0087] Example 2

[0088] In this embodiment, styrene is used as the reaction substrate, different bases are used, tetrahydrofuran is used as the solvent, and pinacolborane is used as the reducing agent to prepare a metal nanocluster catalyst in-situ with the metal salt CoI2 to catalyze the Martensitic hydroboration reaction of the substrate styrene. The reaction formula is as follows:

[0089]

[0090] The reaction was as follows: In a glove box, CoI₂ (2.5 mg, 0.008 mmol), alkali (0.04 mmol), and styrene (41.6 mg, 0.4 mmol) were added to separate 10 mL sample vials, followed by THF (2 mL) and pinacol borane (61.4 mg, 0.48 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the hydroborated product.

[0091] Table 2: Effect of base on hydroboration reaction

[0092]

[0093] Example 3

[0094] In this embodiment, styrene is used as the reaction substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. Metal nanocluster catalysts are prepared in-situ with different cobalt salts to catalyze the hydroboration reaction of styrene. The reaction formula is as follows:

[0095]

[0096] The reaction was as follows: In a glove box, cobalt salt (0.008 mmol), base (4.5 mg, 0.04 mmol), and styrene (41.6 mg, 0.4 mmol) were added to separate 10 mL sample vials, followed by 2 mL of THF and pinacol borane (61.4 mg, 0.48 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product.

[0097] Table 3: Effect of cobalt metal salt precursors on the hydroboration reaction

[0098]

[0099] Example 4

[0100] In this embodiment, 4-methylstyrene is used as the reaction substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration reaction of olefins. The reaction formula is as follows:

[0101]

[0102] The reaction was as follows: In a glove box, CoI₂ (1.56 mg, 0.005 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-methylstyrene (118.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by THF (5 mL) and pinacolborane (153.6 mg, 1.2 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product. Product 2b was the main product, a colorless oil, with a 93% yield and a B / L ratio of 42 / 1. 1 H NMR (400MHz, Chloroform-d) δ7.20–7.03 (m, 4H), 2.43 (q, J = 7.5Hz, 1H), 2.34 (s, 3H), 1.35 (d, J = 7.5Hz, 3H), 1.24 (d, J = 5.1Hz, 12H) ppm. 13 C NMR (101 MHz, Chloroform-d) δ 142.0, 134.4, 129.1, 127.7, 83.3, 24.7, 24.7, 21.1, 17.4 ppm. Note: B / L in Examples 4-12 refers to the ratio of branched-chain hydroboride products to linear hydroboride products, determined by NMR. 1 Determined by H-NMR coarse spectrum.

[0103] Example 5

[0104] In this embodiment, 3-methylstyrene is used as the reaction substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration reaction of olefins. The reaction formula is as follows:

[0105]

[0106] The reaction was as follows: In a glove box, CoI₂ (1.56 mg, 0.005 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 3-methylstyrene (118.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by THF (5 mL) and pinacolborane (153.6 mg, 1.2 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product. 2C was the main product, a colorless oil, with a 91% yield and a B / L ratio of 43 / 1. 1H NMR(400MHz,Chloroform-d)δ7.25–7.17(m,1H),7.13–7.06(m,2H),7.04–6.97(m,1H) ,2.47(q,J=7.5Hz,1H),2.38(s,3H),1.40(d,J=7.4Hz,3H),1.27(d,J=5.5Hz,12H)ppm. 13 C NMR (101MHz, Chloroform-d) δ145.0,137.8,128.7,128.3,126.0,124.9,83.3,24.7,24.7,21.6,17.3ppm.

[0107] Example 6

[0108] In this embodiment, 4-tert-butylstyrene is used as the reaction substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration reaction of olefins. The reaction formula is as follows:

[0109]

[0110] The reaction was as follows: In a glove box, CoI₂ (1.56 mg, 0.005 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-tert-butylstyrene (160.3 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by THF (5 mL) and pinacol borane (153.6 mg, 1.2 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product. 2d was the main product, a colorless oil, with an 88% yield and a B / L ratio of 18 / 1. 1 H NMR (400MHz, Chloroform-d) δ7.36–7.29(m,2H),7.23–7.16(m,2H),2.46(q,J=7.5Hz,1H),1.41–1.31(m,12H),1.26(d,J=5.0Hz,12H)ppm. 13 C NMR (101MHz, Chloroform-d) δ147.6,141.7,127.4,125.2,83.2,34.3,31.5,24.7,24.7,17.3ppm.

[0111] Example 7

[0112] In this embodiment, 4-fluorostyrene is used as the reaction substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration reaction of olefins. The reaction formula is as follows:

[0113]

[0114] The reaction was as follows: In a glove box, CoI₂ (1.56 mg, 0.005 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-fluorostyrene (122.1 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by THF (5 mL) and pinacolborane (153.6 mg, 1.2 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product. 2e⁻ was the main product, a colorless oil, with a 96% yield and a B / L ratio of 31 / 1. 1 H NMR (400MHz, Chloroform-d) δ7.22–7.14(m,2H),7.00–6.91(m,2H),2.43(q,J=7.5Hz,1H),1.33(d,J=7.6Hz,3H),1.22(d,J=4.8Hz,12H)ppm. 13 C NMR (101MHz, Chloroform-d) δ162.0,159.6,140.5,140.5,129.0,128.9,115.0,114.8,83.3,24.6,24.5,17.2ppm. 19 F NMR(376MHz,Chloroform-d)δ-118.96ppm.

[0115] Example 8

[0116] In this embodiment, 3-fluorostyrene is used as the reaction substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration reaction of olefins. The reaction formula is as follows:

[0117]

[0118] The reaction was as follows: In a glove box, CoI₂ (1.56 mg, 0.005 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 3-fluorostyrene (122.1 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by THF (5 mL) and pinacolborane (153.6 mg, 1.2 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product. Product 2f was the main product, a colorless oil, in 84% yield, with a B / L ratio of 46 / 1. 1 H NMR(400MHz,Chloroform-d)δ7.28–7.16(m,1H),7.06–6.91(m,2H),6.88–6.79( m, 1H), 2.47 (q, J = 7.1Hz, 1H), 1.35 (d, J = 7.5Hz, 3H), 1.23 (d, J = 4.5Hz, 12H) ppm. 13 C NMR (101MHz, Chloroform-d) δ164.2,161.7,147.7,147.6,129.5,129.5,123.4,123.4,114.6,114.4,112.0,111.8,83.4,24.8,24.6,24.5,16.7ppm. 19 F NMR(376MHz,Chloroform-d)δ-113.97ppm.

[0119] Example 9

[0120] In this embodiment, 4-trimethylsilylstyrene was used as the reaction substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst was prepared in-situ with CoI2 to catalyze the hydroboration reaction of olefins. The reaction formula is as follows:

[0121]

[0122] The reaction was as follows: In a glove box, CoI₂ (1.56 mg, 0.005 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-trimethylsilylstyrene (176.3 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by THF (5 mL) and pinacolborane (153.6 mg, 1.2 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product. 2 g of the main product was a colorless oil, 70% yield, with a B / L ratio of 9 / 1. 1H NMR (400MHz, Chloroform-d) δ7.50–7.44(m,2H),7.29–7.23(m,2H),2.47(q,J=7.5Hz,1H),1.38(d,J=7.5Hz,3H),1.26(d,J=4.6Hz,12H),0.29(s,9H)ppm. 13 C NMR (101MHz, Chloroform-d) δ145.6,136.2,133.4,127.3,83.3,24.7,24.6,17.1,-1.0ppm.

[0123] Example 10

[0124] In this embodiment, 4-methoxystyrene is used as the reaction substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration of olefins. The reaction formula is as follows:

[0125]

[0126] The reaction was as follows: In a glove box, CoI₂ (1.56 mg, 0.005 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-methoxystyrene (134.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by THF (5 mL) and pinacolborane (153.6 mg, 1.2 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product. The main product was a colorless oil with a 94% yield and a B / L ratio of 26 / 1. 1 H NMR(400MHz,Chloroform-d)δ7.22–7.14(m,1H),6.86–6.77(m,2H),6.73–6.65(m,1H) ,3.79(s,3H),2.43(q,J=7.5Hz,1H),1.33(d,J=7.5Hz,3H),1.22(d,J=5.1Hz,12H)ppm. 13 C NMR (101MHz, Chloroform-d) δ159.6,146.6,129.2,120.3,113.5,110.5,83.3,55.0,24.6,24.6,17.0ppm.

[0127] Example 11

[0128] In this embodiment, 4-dimethyl-tert-butylsiloxystyrene was used as the substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst was prepared in-situ with CoI2 to catalyze the hydroboration of olefins. The reaction formula is as follows:

[0129]

[0130] The reaction was as follows: In a glove box, CoI₂ (1.56 mg, 0.005 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-dimethyl-tert-butylsiloxystyrene (234.4 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by THF (5 mL) and pinacolborane (153.6 mg, 1.2 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product. 2i was the main product, a colorless oil, in 89% yield, with a B / L ratio of 16 / 1. 1 HNMR(400MHz,Chloroform-d)δ7.11–7.03(m,2H),6.79–6.69(m,2H),2.37(q,J=7.5 Hz,1H),1.30(d,J=7.6Hz,3H),1.20(d,J=5.8Hz,12H),0.98(s,9H),0.19(s,6H)ppm. 13 CNMR(101MHz,Chloroform-d)δ153.0,137.4,128.5,119.8,83.1,25.7,24.6,24.5,18.2,17.1,-4.4ppm.

[0131] Example 12

[0132] In this embodiment, naphthalene-2-ethylene is used as the reaction substrate, potassium tert-butoxide as the base, tetrahydrofuran as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration reaction of olefins. The reaction formula is as follows:

[0133]

[0134] The reaction was as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and naphthalene-2-ethylene (154.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by THF (5 mL) and pinacolborane (153.6 mg, 1.2 mmol). After stirring at room temperature for one hour, the mixture was quenched in air and purified by column chromatography to obtain the borohydride product. 2j was the main product, a white solid, 97% yield, B / L = 12 / 1. 1H NMR(400MHz,Chloroform-d)δ7.85–7.75(m,3H),7.71–7.66(m,1H),7.51–7.37( m, 3H), 2.66 (q, J = 7.5Hz, 1H), 1.48 (d, J = 7.4Hz, 3H), 1.24 (d, J = 6.2Hz, 12H) ppm. 13 C NMR (101MHz, Chloroform-d) δ142.7,134.0,131.8,127.8,127.60,127.55,127.3,125.7,125.4,124.9,83.5,24.7,24.7,16.9ppm.

[0135] Example 13

[0136] In this embodiment, benzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, and pinacolborane as the reducing agent. Metal nanoclusters are prepared in-situ with CoI2 in different solvents to catalyze the hydroboration reaction of benzonitrile. The reaction formula is as follows:

[0137]

[0138] The reaction was carried out as follows: In a glove box, CoI₂ (1.56 mg, 0.005 mmol), potassium tert-butoxide (5.6 mg, 0.05 mmol), and benzonitrile (51.6 mg, 0.5 mmol) were added to separate 10 mL sample vials, along with 2 mL of different solvents, and pinacol borane (140.8 mg, 1.1 mmol). After stirring at room temperature for 4 hours, the reaction was quenched in air. Hydrochloric acid was then added to acidify the corresponding hydrochloride salts.

[0139]

[0140] The conversion rate of the reaction substrate was determined by gas chromatography; 1 H NMR (400MHz, DMSO-d6) δ8.38(s,3H),7.63–7.17(m,5H),4.02(s,2H)ppm. 13 C NMR (101MHz, DMSO-d6) δ134.6, 129.4, 128.9, 128.8, 42.5ppm.

[0141] Example 14

[0142] In this embodiment, 4-methylbenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst, prepared in-situ with CoI₂, is used to catalyze the hydroboration reaction of nitrile. The reaction formula is as follows:

[0143]

[0144] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-methylbenzonitrile (117.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. 6b, white solid, >99% yield. 1 H NMR (400MHz, DMSO-d6) δ8.25(s,3H),7.38–7.29(m,2H),7.25–7.15(m,2H),3.95(s,2H),2.29(s,3H)ppm. 13 CNMR(101MHz,DMSO-d6)δ138.1,131.5,129.4,129.4,42.3,21.2ppm.

[0145] Example 15

[0146] In this embodiment, 3-methylbenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst, prepared in-situ with CoI₂, is used to catalyze the hydroboration reaction of nitrile. The reaction formula is as follows:

[0147]

[0148] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 3-methylbenzonitrile (117.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid at 6°C, in 89% yield. 1 H NMR (400MHz, DMSO-d6) δ8.48(s,3H),7.35–7.24(m,3H),7.23–7.15(m,1H),3.96(s,2H),2.31(s,3H)ppm. 13 C NMR (101MHz, DMSO-d6) δ138.1,134.5,130.0,129.3,128.9,126.4,42.5,21.4ppm.

[0149] Example 16

[0150] In this embodiment, 2-methylbenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst, prepared in-situ with CoI₂, is used to catalyze the hydroboration reaction of nitrile. The reaction formula is as follows:

[0151]

[0152] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 2-methylbenzonitrile (117.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. After 6 days, a white solid was obtained, in 88% yield. 1 H NMR (400MHz, DMSO-d6) δ8.29(s,3H),7.42–7.33(m,1H),7.30–7.18(m,3H),3.99(s,2H),2.33(s,3H)ppm. 13 C NMR (101MHz, DMSO-d6) δ137.1,132.8,130.7,129.7,128.8,126.4,39.8,19.3ppm.

[0153] Example 17

[0154] In this embodiment, 4-tert-butylbenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst, prepared in-situ with CoI2, catalyzes the hydroboration reaction of the nitrile. The reaction formula is as follows:

[0155]

[0156] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-tert-butylbenzonitrile (159.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid, 92% yield, at 6°C. 1 H NMR (400MHz, DMSO-d6) δ8.30(s,3H),7.50–7.33(m,4H),3.98(s,2H),1.28(s,9H)ppm. 13C NMR (101MHz, DMSO-d6) δ151.3,131.6,129.2,125.7,42.2,34.8,31.5ppm.

[0157] Example 18

[0158] In this embodiment, 4-phenylbenzonitrile was used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst was prepared in-situ with CoI₂ to catalyze the hydroboration reaction of the nitrile. The reaction formula is as follows:

[0159]

[0160] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-phenylbenzonitrile (179.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid at 6°C, yield >99%. 1 H NMR (400MHz, DMSO-d6) δ8.41(s,3H),7.74–7.63(m,4H),7.59–7.53(m,2H),7.50–7.42(m,2H),7.41–7.33(m,1H),4.04(s,2H)ppm. 13 C NMR (101MHz, DMSO-d6) δ140.6,140.0,133.8,130.1,129.4,128.1,127.2,127.1,42.2ppm.

[0161] Example 19

[0162] In this embodiment, naphthalene-2-carboxynitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration reaction of nitrile. The reaction formula is as follows:

[0163]

[0164] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and naphthalene-2-carboxynitrile (153.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacol borane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was then acidified to the corresponding hydrochloride salts by adding diethyl ether hydrochloride solution.

[0165] 6g, white solid, 97% yield. 1 H NMR (400MHz, DMSO-d6) δ8.38(s,3H),8.03–7.82(m,4H),7.67–7.45(m,3H),4.18(s,2H)ppm. 13 C NMR (101MHz, DMSO-d6) δ133.0,132.2,128.6,128.4,128.2,128.1,127.1(2C),127.0,126.9,42.7ppm.

[0166] Example 20

[0167] In this embodiment, 4-methoxybenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration reaction of nitrile. The reaction formula is as follows:

[0168]

[0169] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-methoxybenzonitrile (133.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacol borane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. After 6 hours, a white solid was obtained, in 98% yield. 1 H NMR (400MHz, DMSO-d6) δ8.41(s,3H),7.46–7.32(m,2H),7.00–6.87(m,2H),3.90(s,2H),3.74(s,3H)ppm. 13 C NMR (101MHz, DMSO-d6) δ159.7,131.0,126.4,114.3,55.6,42.0ppm.

[0170] Example 21

[0171] In this embodiment, 4-fluorobenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst prepared in-situ with CoI2 is used to catalyze the hydroboration reaction of the nitrile. The reaction formula is as follows:

[0172]

[0173] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-fluorobenzonitrile (121.1 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid, 96% yield. 1 H NMR (400MHz, DMSO-d6) δ8.27(s,3H),7.61–7.45(m,2H),7.33–7.19(m,2H),4.02(s,2H)ppm. 13 C{ 19 F}NMR(101MHz,DMSO-d6)δ162.6,131.9,131.0,115.8,41.9ppm. 19 F NMR(376MHz,DMSO-d6)δ-112.96ppm.

[0174] Example 22

[0175] In this embodiment, 3-fluorobenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI₂ to catalyze the hydroboration reaction of the nitrile. The reaction formula is as follows:

[0176]

[0177] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 3-fluorobenzonitrile (121.1 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid, 99% yield. 1 H NMR(400MHz,D2O)δ7.56–7.34(m,1H),7.34–6.99(m,3H),4.16(s,2H)ppm. 13C NMR (151MHz, D2O) δ162.4,160.8,133.82,133.77,130.1,130.0,123.67,123.65,115.1,115.0,114.7,114.6,41.6ppm. 19 F NMR(376MHz,D2O)δ-110.33(q,J=8.4Hz)ppm

[0178] Example 23

[0179] In this embodiment, 2-fluorobenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst, prepared in-situ with CoI₂, is used to catalyze the hydroboration reaction of nitrile. The reaction formula is as follows:

[0180]

[0181] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 2-fluorobenzonitrile (121.1 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. At 6 K, a white solid was obtained in 99% yield. 1 H NMR(400MHz,D2O)δ7.54–7.37(m,2H),7.32–7.14(m,2H),4.23(s,2H)ppm. 13 C NMR (151MHz, D2O) δ160.7,159.1,130.8,130.7,130.3,130.2,124.0,123.9,118.6,118.5,114.8,114.7,36.21,36.19ppm. 19 F NMR (376MHz, D2O) δ-115.74 (q, J = 7.5, 7.1Hz) ppm.

[0182] Example 24

[0183] In this embodiment, 4-chlorobenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst, prepared in-situ with CoI₂, is used to catalyze the hydroboration reaction of nitrile. The reaction formula is as follows:

[0184]

[0185] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-chlorobenzonitrile (137.6 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. 6 μL, white solid, 99% yield. 1 H NMR(400MHz,DMSO-d6)δ8.28(s,3H),7.60–7.41(m,4H),4.03(s,2H)ppm. 13 C NMR (101MHz, DMSO-d6) δ133.6,133.5,131.5,128.9,41.8ppm.

[0186] Example 25

[0187] In this embodiment, 4-trifluoromethylbenzonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI2 to catalyze the hydroboration reaction of nitrile. The reaction formula is as follows:

[0188]

[0189] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-trifluoromethylbenzonitrile (171.1 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid, 95% yield. 1 H NMR (400MHz, DMSO-d6) δ8.62(s,3H),7.86–7.60(m,4H),4.11(s,2H)ppm. 13 C{ 19 F}NMR(101MHz,DMSO-d6)δ139.4,130.4,129.4,125.8,124.7,42.1ppm. 19 F NMR(376MHz,DMSO-d6)δ-60.32ppm.

[0190] Example 26

[0191] In this embodiment, 1-octanilide is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst is prepared in-situ with CoI₂ to catalyze the hydroboration reaction of nitriles. The reaction formula is as follows:

[0192]

[0193] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 1-octanoic acid (125.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid, 74% yield. 1 H NMR (400MHz, DMSO-d6) δ8.02 (s, 3H), 2.71 (t, J = 7.7Hz, 2H), 1.53 (p, J = 7.3Hz, 2H), 1.36–1.11 (m, 10H), 0.84 (t, J = 6.5Hz, 3H) ppm. 13 C NMR (101MHz, DMSO-d6) δ39.1, 31.6, 29.0, 28.9, 27.3, 26.3, 22.5, 14.4ppm.

[0194] Example 27

[0195] In this embodiment, tert-butyronitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst, prepared in-situ with CoI2, catalyzes the hydroboration reaction of the nitrile. The reaction formula is as follows:

[0196]

[0197] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and tert-butyronitrile (69.1 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid at 6°C, with a yield >99%. 1 H NMR (400MHz, DMSO-d6) δ8.05 (s, 3H), 2.61 (d, J = 7.0Hz, 2H), 1.88 (hept, J = 13.5, 6.8Hz, 1H), 0.92 (d, J = 6.7Hz, 6H) ppm.13 CNMR(101MHz,DMSO-d6)δ46.0,26.7,20.3ppm.

[0198] Example 28

[0199] In this embodiment, cyclohexanonitrile is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst, prepared in-situ with CoI2, catalyzes the hydroboration reaction of the nitrile. The reaction formula is as follows:

[0200]

[0201] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and cyclohexanonitrile (109.2 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacol borane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. 6p, white solid, 90% yield. 1 H NMR (400MHz, DMSO-d6) δ7.99 (s, 3H), 2.59 (d, J = 6.9Hz, 2H), 1.78–1.44 (m, 6H), 1.25–1.01 (m, 3H), 0.96–0.80 (m, 2H)ppm. 13 C NMR (101MHz, DMSO-d6) δ44.8, 35.8, 30.3, 26.1, 25.5ppm.

[0202] Example 29

[0203] In this embodiment, phenylbutyronitrile (PBT) is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst, prepared in-situ with CoI₂, is used to catalyze the hydroboration reaction of nitrile. The reaction formula is as follows:

[0204]

[0205] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and phenylbutyronitrile (140.6 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacol borane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid, 75% yield. 1H NMR (400MHz, DMSO-d6) δ8.13(s,3H),7.39–7.09(m,5H),2.76(t,J=7.0Hz,2H),2.59(t,J=7.1Hz,2H),1.70–1.48(m,4H)ppm. 13 C NMR (101MHz, DMSO-d6) δ142.2,128.8,128.7,126.2,38.9,35.0,28.2,27.0ppm.

[0206] Example 30

[0207] In this embodiment, 4-cyanopyridine is used as the reaction substrate, potassium tert-butoxide as the base, diethyl ether as the solvent, and pinacolborane as the reducing agent. A metal nanocluster catalyst prepared in-situ with CoI₂ is used to catalyze the hydroboration reaction of nitriles. The reaction formula is as follows:

[0208]

[0209] The reaction was carried out as follows: In a glove box, CoI₂ (6.26 mg, 0.02 mmol), potassium tert-butoxide (11.2 mg, 0.1 mmol), and 4-cyanopyridine (104.1 mg, 1.0 mmol) were added to separate 10 mL sample vials, followed by 2 mL of diethyl ether and pinacolborane (281.6 mg, 2.2 mmol). The mixture was stirred at room temperature for 4 hours and then quenched in air. The solution was acidified with diethyl ether hydrochloride to the corresponding hydrochloride salt. The product was a white solid, 74% yield. 1 H NMR (400MHz, D2O) δ8.86 (d, J = 6.0 Hz, 2H), 8.12 (d, J = 6.0 Hz, 2H), 4.57 (s, 2H) ppm. 13 C NMR (101MHz, D2O) δ153.2, 141.7, 126.2, 41.6ppm.

[0210] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A method for preparing metal nanoclusters, characterized in that, The preparation method includes the following steps: The metal nanoclusters are obtained by reacting metal salts and reducing agents under alkaline conditions. The metal salt is selected from the group consisting of manganese salts, iron salts, cobalt salts, nickel salts, and copper salts. The reducing agent is borane or silane; The base is one or more of the following: potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium isopropoxide, sodium isopropoxide, lithium isopropoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium methoxide, sodium methoxide, lithium methoxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, cesium acetate, potassium acetate, sodium acetate, lithium acetate, bis(trimethylsilylamine)potassium, bis(trimethylsilylamine)sodium, bis(trimethylsilylamine)lithium, potassium triethylborohydride, sodium triethylborohydride, lithium triethylborohydride, triethylamine, diisopropylethylamine, n-butyllithium, methyllithium, phenyllithium, and Grignard reagents.

2. The preparation method according to claim 1, characterized in that, The manganese salt is one or more of the following: MnF2, MnCl2, MnCl2·4H2O, MnBr2, MnBr2·4H2O, MnI2, MnI2·4H2O, MnSO4, MnSO4·H2O, MnSO4·4H2O, Mn(CO)5Br, Mn(OAc)2, Mn(OAc)2·4H2O, Mn(OAc)3·2H2O, Mn(acac)2, Mn(acac)3, cyclopentadiene tricarbonyl manganese, and methylcyclopentadiene tricarbonyl manganese. The iron salts are FeF2, FeCl2, FeBr2, FeI2, FeF3, FeCl3, FeCl3·6H2O, FeBr3, FeBr3·2THF, FeSO4, FeSO4·H2O, FeSO4·6H2O, Fe(OAc)2, Fe(OH)(OAc)2, Fe2(CO)9, and Fe3(CO). 12 One or more of the following: Fe(acac)2, Fe(acac)3, Fe(OTf)3, Fe(BF4)2·6H2O, Fe(NH3)2(SO4)2, Fe(NH3)2(SO4)2·6H2O, Fe2(SO4)3·H2O, K3Fe(CN)6, Fe(ClO4)3, Fe(ClO4)3·H2O; The cobalt salt is one or more of the following: CoF2, CoF3, CoCl2, CoCl2·H2O, CoBr2, CoBr2·H2O, CoI2, Co(OAc)2, Co(acac)2, Co(acac)3, Co(NH3)6Cl3, Co(PPh3)3Cl, Co(dppe)Cl2, Co2CO3, and Co2(CO)8. The nickel salt is one or more of the following: NiCl2, NiCl2·6H2O, NiBr2, NiBr2·H2O, NiI2, Ni(acac)2, Ni(OAc)2, Ni(OAc)2·4H2O, Ni(OTf)2, Ni(ClO4)2·6H2O, Ni(BF4)2·6H2O, Ni(NO3)2·6H2O, NiSO4·6H2O, Ni(cod)2, Ni(DME)Cl2, Ni(DME)Br2, Ni(dppe)Cl2, Ni(dppp)Cl2, Ni(PCy3)2Cl2, Ni(PPh3)2Cl2, Ni(PPh3)2Br2, and Ni(NH3)6Br2. The copper salt is one or more of the following: CuCl, CuBr, CuI, CuF2, CuCl2, CuCl2·2H2O, CuBr2, CuCN, CuOAc, Cu(OAc)2, Cu(OAc)2·H2O, Cu(OTf)2, Cu(CN)4(PF6), Cu2(OTf)2Ph, CuSO4, Cu(NH4)2(SO4)2·6H2O, CuSO4·6H2O, Cu(BF4)2, and Cu(BF4)2·6H2O.

3. The preparation method according to claim 1, characterized in that, The borane is one or more of pinacol borane, 9-boronbicyclo[3.3.1]nonane, catechol borane, and borane-amine complex; The silane is one or more of the following: benzylsilane, diphenylsilane, triphenylsilane, phenyldimethylsilane, dimethyl(ethyl)silane, dipropyl(ethyl)silane, dibutyl(ethyl)silane, diethylsilane, triethylsilane, dimethylbenzylsilane, dimethylphenylethylsilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, phenyldiethoxysilane, diisopropylethoxysilane, and 1,1,3,3-tetramethyldisiloxane.

4. The preparation method according to claim 1, characterized in that, The reaction is carried out in an organic solvent or without a solvent, wherein the organic solvent is benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, methanol, ethanol, isopropanol, tert-butanol, n-pentane, n-hexane, cyclohexane, etc. N,N -Dimethylformamide, N,N - One or more of dimethylacetamide or dimethyl sulfoxide as a solvent.

5. The preparation method according to claim 1, characterized in that, The particle size of the metal nanoclusters is 0.1–200 nm.

6. The preparation method according to claim 1, characterized in that, The molar ratio of the alkali to the reducing agent is 0.001 to 3:

1.

7. A metal nanocluster, characterized in that, It is prepared by the preparation method according to any one of claims 1-6.

8. The use of the metal nanoclusters as described in claim 7, characterized in that, Used as a catalyst.

9. The use as described in claim 8, characterized in that, The catalyst is used to catalyze the hydrogen functionalization reaction of unsaturated bonds.

10. The use as described in claim 9, characterized in that, The hydrogen functionalization reaction is selected from hydrogenation, borohydride, silylation, and semi-hydrogenation of unsaturated triple bonds.

11. A catalyst, characterized in that, The catalyst comprises the metal nanoclusters of claim 7.

12. The use of the catalyst as claimed in claim 11, characterized in that, The catalyst is used to catalyze the hydrogen functionalization reaction of unsaturated bonds.

13. The use as described in claim 12, characterized in that, The hydrogen functionalization reaction is selected from hydrogenation, borohydride, silylation, and semi-hydrogenation of unsaturated triple bonds.

14. A method for hydrogen functionalization reaction, characterized in that, The hydrogen functionalization reaction method includes the following steps: A mixture is provided, the mixture comprising a reaction substrate, a metal salt, a base, and a reducing agent; According to the preparation method of claim 1, the metal salt and the reducing agent react under the action of alkali to obtain metal nanoclusters, and the metal nanoclusters act as catalysts to catalyze the hydrogen functionalization reaction of the reaction substrate. The reaction substrates are selected from: alkenes, alkynes, nitriles, imines, aldehydes, ketones, acids, esters, and amides; The metal salt is selected from the group consisting of: manganese salts, iron salts, cobalt salts, nickel salts, and copper salts. The reducing agent is borane or silane; The base is one or more of the following: potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium isopropoxide, sodium isopropoxide, lithium isopropoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium methoxide, sodium methoxide, lithium methoxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, cesium acetate, potassium acetate, sodium acetate, lithium acetate, bis(trimethylsilylamine)potassium, bis(trimethylsilylamine)sodium, bis(trimethylsilylamine)lithium, potassium triethylborohydride, sodium triethylborohydride, lithium triethylborohydride, triethylamine, diisopropylethylamine, n-butyllithium, methyllithium, phenyllithium, and Grignard reagents.

15. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The manganese salt is one or more of the following: MnF2, MnCl2, MnCl2·4H2O, MnBr2, MnBr2·4H2O, MnI2, MnI2·4H2O, MnSO4, MnSO4·H2O, MnSO4·4H2O, Mn(CO)5Br, Mn(OAc)2, Mn(OAc)2·4H2O, Mn(OAc)3·2H2O, Mn(acac)2, Mn(acac)3, cyclopentadiene tricarbonyl manganese, and methylcyclopentadiene tricarbonyl manganese. The iron salts are FeF2, FeCl2, FeBr2, FeI2, FeF3, FeCl3, FeCl3·6H2O, FeBr3, FeBr3·2THF, FeSO4, FeSO4·H2O, FeSO4·6H2O, Fe(OAc)2, Fe(OH)(OAc)2, Fe2(CO)9, and Fe3(CO). 12 One or more of the following: Fe(acac)2, Fe(acac)3, Fe(OTf)3, Fe(BF4)2·6H2O, Fe(NH3)2(SO4)2, Fe(NH3)2(SO4)2·6H2O, Fe2(SO4)3·H2O, K3Fe(CN)6, Fe(ClO4)3, Fe(ClO4)3·H2O; The cobalt salt is one or more of the following: CoF2, CoF3, CoCl2, CoCl2·H2O, CoBr2, CoBr2·H2O, CoI2, Co(OAc)2, Co(acac)2, Co(acac)3, Co(NH3)6Cl3, Co(PPh3)3Cl, Co(dppe)Cl2, Co2CO3, and Co2(CO)8. The nickel salt is one or more of the following: NiCl2, NiCl2·6H2O, NiBr2, NiBr2·H2O, NiI2, Ni(acac)2, Ni(OAc)2, Ni(OAc)2·4H2O, Ni(OTf)2, Ni(ClO4)2·6H2O, Ni(BF4)2·6H2O, Ni(NO3)2·6H2O, NiSO4·6H2O, Ni(cod)2, Ni(DME)Cl2, Ni(DME)Br2, Ni(dppe)Cl2, Ni(dppp)Cl2, Ni(PCy3)2Cl2, Ni(PPh3)2Cl2, Ni(PPh3)2Br2, and Ni(NH3)6Br2. The copper salt is one or more of the following: CuCl, CuBr, CuI, CuF2, CuCl2, CuCl2·2H2O, CuBr2, CuCN, CuOAc, Cu(OAc)2, Cu(OAc)2·H2O, Cu(OTf)2, Cu(CN)4(PF6), Cu2(OTf)2Ph, CuSO4, Cu(NH4)2(SO4)2·6H2O, CuSO4·6H2O, Cu(BF4)2, and Cu(BF4)2·6H2O.

16. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The borane is one or more of pinacol borane, 9-boronbicyclo[3.3.1]nonane, catechol borane, and borane-amine complex; The silane is one or more of the following: benzylsilane, diphenylsilane, triphenylsilane, phenyldimethylsilane, dimethyl(ethyl)silane, dipropyl(ethyl)silane, dibutyl(ethyl)silane, diethylsilane, triethylsilane, dimethylbenzylsilane, dimethylphenylethylsilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, phenyldiethoxysilane, diisopropylethoxysilane, and 1,1,3,3-tetramethyldisiloxane.

17. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The mixture may contain no organic solvent or may contain organic solvent; The reaction is carried out in an organic solvent or without a solvent, wherein the organic solvent is benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, methanol, ethanol, isopropanol, tert-butanol, n-pentane, n-hexane, cyclohexane, etc. N,N -Dimethylformamide, N,N - One or more of dimethylacetamide or dimethyl sulfoxide as a solvent.

18. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The molar ratio of the alkali to the reducing agent is 0.001 to 3:

1.

19. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The molar ratio of the alkali, reducing agent and reaction substrate is 0.01-1:1-10:

1.

20. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The metal nanoclusters have a particle size of 0.1–200 nm, and the molar ratio of the reaction substrate to the metal salt is 1:0.00001–0.

1.

21. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The route of the hydrogen functionalization reaction is as follows: Under alkaline conditions, the metal salt and reducing agent react to form a metal nanocluster catalyst, which catalyzes the hydrogen functionalization reaction of compound 1 to yield compounds 2 and 3. In each formula, R is selected from: H, C1-C6 alkyl, C1-C6 alkoxy, halogen, C1-C6 alkylsilyl, (C1-C6 alkyl)3siloxy.

22. The hydrogen functionalization reaction method as described in claim 21, characterized in that, R is selected from: H, C1-C6 alkyl, C1-C6 alkoxy, halogen, trimethylsilyl, tert-butyldimethylsiloxy.

23. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The route of the hydrogen functionalization reaction is as follows: Under alkaline conditions, the metal salt and reducing agent react to generate a metal nanocluster catalyst, which catalyzes the hydrogen functionalization reaction of compound 4 to yield compound 5. Further acidification yields compound 6. In each formula, R is selected from: C1-C10 alkyl, C3-C8 cycloalkyl, C6-C10 aryl; optionally substituted by a group selected from the group consisting of: C1-C6 alkyl, C1-C6 haloalkyl, halogen, C1-C6 alkoxy, C6-C10 aryl, C6-C10 aryl-O-.

24. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The reducing agent is pinacolborane.

25. The hydrogen functionalization reaction method as described in claim 14, characterized in that, The hydrogen functionalization reaction is a borohydride reaction.

26. A mixture comprising a metal salt, an alkali, a reducing agent, and a reaction substrate; wherein, according to the preparation method of claim 1, the metal salt generates the metal nanoclusters in-situ within the mixture system, and the metal nanoclusters catalyze the reaction of the reaction substrate in-situ; wherein, The reaction substrates are selected from substituted or unsubstituted alkenes, alkynes, nitriles, imines, aldehydes, ketones, acids, esters and amides, and are solvent-free or soluble in organic solvents; The metal salt is selected from the group consisting of: manganese salts, iron salts, cobalt salts, nickel salts, and copper salts. The reducing agent is borane or silane; The base is one or more of the following: potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium isopropoxide, sodium isopropoxide, lithium isopropoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium methoxide, sodium methoxide, lithium methoxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, cesium acetate, potassium acetate, sodium acetate, lithium acetate, bis(trimethylsilylamine)potassium, bis(trimethylsilylamine)sodium, bis(trimethylsilylamine)lithium, potassium triethylborohydride, sodium triethylborohydride, lithium triethylborohydride, triethylamine, diisopropylethylamine, n-butyllithium, methyllithium, phenyllithium, and Grignard reagents.

27. The mixture as claimed in claim 26, characterized in that, The manganese salt is one or more of the following: MnF2, MnCl2, MnCl2·4H2O, MnBr2, MnBr2·4H2O, MnI2, MnI2·4H2O, MnSO4, MnSO4·H2O, MnSO4·4H2O, Mn(CO)5Br, Mn(OAc)2, Mn(OAc)2·4H2O, Mn(OAc)3·2H2O, Mn(acac)2, Mn(acac)3, cyclopentadiene tricarbonyl manganese, and methylcyclopentadiene tricarbonyl manganese. The iron salts are FeF2, FeCl2, FeBr2, FeI2, FeF3, FeCl3, FeCl3·6H2O, FeBr3, FeBr3·2THF, FeSO4, FeSO4·H2O, FeSO4·6H2O, Fe(OAc)2, Fe(OH)(OAc)2, Fe2(CO)9, and Fe3(CO). 12 One or more of the following: Fe(acac)2, Fe(acac)3, Fe(OTf)3, Fe(BF4)2·6H2O, Fe(NH3)2(SO4)2, Fe(NH3)2(SO4)2·6H2O, Fe2(SO4)3·H2O, K3Fe(CN)6, Fe(ClO4)3, Fe(ClO4)3·H2O; The cobalt salt is one or more of the following: CoF2, CoF3, CoCl2, CoCl2·H2O, CoBr2, CoBr2·H2O, CoI2, Co(OAc)2, Co(acac)2, Co(acac)3, Co(NH3)6Cl3, Co(PPh3)3Cl, Co(dppe)Cl2, Co2CO3, and Co2(CO)8. The nickel salt is one or more of the following: NiCl2, NiCl2·6H2O, NiBr2, NiBr2·H2O, NiI2, Ni(acac)2, Ni(OAc)2, Ni(OAc)2·4H2O, Ni(OTf)2, Ni(ClO4)2·6H2O, Ni(BF4)2·6H2O, Ni(NO3)2·6H2O, NiSO4·6H2O, Ni(cod)2, Ni(DME)Cl2, Ni(DME)Br2, Ni(dppe)Cl2, Ni(dppp)Cl2, Ni(PCy3)2Cl2, Ni(PPh3)2Cl2, Ni(PPh3)2Br2, and Ni(NH3)6Br2. The copper salt is one or more of the following: CuCl, CuBr, CuI, CuF2, CuCl2, CuCl2·2H2O, CuBr2, CuCN, CuOAc, Cu(OAc)2, Cu(OAc)2·H2O, Cu(OTf)2, Cu(CN)4(PF6), Cu2(OTf)2Ph, CuSO4, Cu(NH4)2(SO4)2·6H2O, CuSO4·6H2O, Cu(BF4)2, and Cu(BF4)2·6H2O.

28. The mixture as claimed in claim 26, characterized in that, The borane is one or more of pinacol borane, 9-boronbicyclo[3.3.1]nonane, catechol borane, and borane-amine complex; The silane is one or more of the following: benzylsilane, diphenylsilane, triphenylsilane, phenyldimethylsilane, dimethyl(ethyl)silane, dipropyl(ethyl)silane, dibutyl(ethyl)silane, diethylsilane, triethylsilane, dimethylbenzylsilane, dimethylphenylethylsilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, phenyldiethoxysilane, diisopropylethoxysilane, and 1,1,3,3-tetramethyldisiloxane.

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