A ferrocenyl aminobidentate phosphine ligand compound, and a preparation method and application thereof

Abstract

This invention provides a ferrocene-amine-based bidentate phosphine ligand compound, its preparation method, and its application. The structure of the ferrocene-amine-based bidentate phosphine ligand compound is shown below: wherein R 1 Selected from any one of isopropyl, tert-butyl, n-butyl, dimethyltert-butylsilyl, or triisopropylsilyl; R 2 R 3 R 4 R 5 The ligands are independently selected from any one of phenyl, tert-butyl, pyridyl, cyclohexyl, N-methylpyrroleyl, N-methylimidazolyl, quinolinyl, furanyl, thiofuranyl, or adamantyl. The novel ferroceneamine-based bidentate phosphine ligands provided by this invention have the advantages of high activity and high selectivity.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, specifically relating to a ferrocene-amine-based bidentate phosphine ligand compound, its preparation method, and its application, and particularly to a ferrocene-amine-based bidentate phosphine ligand compound with good activity, its preparation method, and its application. Background Technology

[0002] Ferrocene, a bicyclic sandwich structure, has been a research hotspot in both scientific and industrial fields since its discovery by Pauson and Kealy in 1951. Due to its unique molecular structure and bonding properties, it has exhibited excellent properties in molecular structure, chemical engineering, pharmaceuticals, and organic catalysis. Meanwhile, phosphine ligands are important catalyst ligands. Biphosphine ligands such as Xphos, Sphos, and Ruphos exhibit excellent performance in catalytic coupling reactions (suzuki) when combined with palladium and rhodium in catalytic systems. Furthermore, in alkoxycarbonylation reactions, palladium catalyst systems modified with electron-rich bidentate phosphine ligands exhibit better catalytic performance compared to traditional triphenylphosphine-modified palladium catalyst systems due to their greater steric hindrance effect (described in Chem. Commun. 2004, 1720–1721). For example, the most mature and advanced palladium / phosphine complex catalytic system currently in industrial use is the 1,2-bis((di-tert-butylphosphine)benzyl)benzene catalytic system developed by Whiston's research group (as described in the literature Chem. Commun. 1999, 1877-1878). Its greatest advantage is that it can efficiently catalyze the alkoxycarbonylation reaction of olefins under relatively mild reaction conditions.

[0003] In recent years, ferrocene-based phosphine ligands have attracted considerable attention from the scientific and industrial communities due to their structural stability, tunable ligands, and high catalytic activity in olefin alkoxycarbonylation reactions (e.g., CN114014895A). Their bidentate bisphosphine skeleton also plays a crucial role in catalyst activity and product selectivity (Angew. Chem. Int. Ed. 2017, 56, 1–6). Furthermore, their development has facilitated breakthroughs in many palladium-catalyzed reactions, leading to their wide application in the synthesis of functional materials, natural products, and bioactive materials.

[0004] Currently reported ferrocene-based phosphine ligands, while exhibiting some activity and selectivity, still suffer from low activity and poor selectivity. Furthermore, the limited number of substitution sites in the ferrocene framework leads to a lack of novel structures, affecting the regulatory and catalytic performance of the ligands and hindering their development. Therefore, providing a ferrocene-based phosphine ligand compound with high activity and good selectivity has become an urgent problem to be solved. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a ferrocene-amine-based bidentate phosphine ligand compound, its preparation method, and its applications, particularly a highly active ferrocene-amine-based bidentate phosphine ligand compound, its preparation method, and its applications. The novel ferrocene-amine-based bidentate phosphine ligand compound provided by the present invention possesses the advantages of high activity and high selectivity.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a ferrocene-amine-based bidentate phosphine ligand compound, the structure of which is shown below:

[0008]

[0009] Where R 1 It is selected from any one of isopropyl, tert-butyl, n-butyl, dimethyltert-butylsilyl or triisopropylsilyl.

[0010] R 2 R 3 R 4 R 5 It is independently selected from any one of phenyl, tert-butyl, pyridyl, cyclohexyl, N-methylpyrroleyl, N-methylimidazolyl, quinolinyl, furanyl, thiofuranyl or adamantyl.

[0011] The compounds with the above-mentioned specific structures can effectively catalyze coupling reactions in conjunction with palladium catalysts, exhibiting the advantages of high activity and high selectivity.

[0012] Preferably, the R 1 Selected from dimethyl tert-butylsilyl or triisopropylsilyl.

[0013] Preferably, the R 2 R 3 R 4 R 5 It is independently selected from phenyl, tert-butyl, pyridyl or cyclohexyl.

[0014] Preferably, the ferroceneamine-based bidentate phosphine ligand compound is selected from any one of the L1-L6 structures:

[0015]

[0016] Secondly, the present invention provides a method for preparing the ferroceneamine-based bidentate phosphine ligand compound as described above, the method comprising the following steps:

[0017] (1) Ferrocene, N,N,N,N-tetramethylethylenediamine and n-butyllithium were mixed and reacted to obtain ferrocene dilithium compound;

[0018] (2) The ferrocene dilithium compound obtained in step (1) is mixed and reacted with 1,1,2,2-tetrabromoethane to obtain ferrocene dibromo;

[0019] (3) The ferrocene dibromo obtained in step (2) is mixed with sodium azide and cuprous chloride and reacted to obtain ferrocene azide compound;

[0020] (4) The ferrocene azide compound obtained in step (3) is reacted with palladium on carbon in a hydrogen atmosphere to obtain ferrocene diamine;

[0021] (5) The ferrocene diamine obtained in step (4) is reacted with R 1 The reaction of Cl with the first organic amine yields a ferrocene disecondary amine compound;

[0022] (6) The ferrocene di-secondary amine compound obtained in step (5) is reacted with a second organic amine and a monochlorophosphine compound to obtain the ferrocene-amine didentate phosphine ligand compound.

[0023] The first organic amine and the second organic amine are independently selected from any one or a combination of at least two of triethylamine, pyridine, triisopropylamine, butylamine, benzyl potassium, or benzyl sodium.

[0024] The monochlorophosphine includes PClR 2 R 3 and PClR 4 R 5 .

[0025] Where R 1 R 2 R 3 R 4 R 5 It has the same scope of limitation as described above.

[0026] Preferably, the molar ratio of ferrocene, N,N,N,N-tetramethylethylenediamine and n-butyllithium in step (1) is 1:(1-2):(2-4).

[0027] Preferably, the reaction in step (1) is carried out in a solvent, including n-hexane.

[0028] Preferably, the molar ratio of the ferrocene dilithium compound in step (2) to 1,1,2,2-tetrabromoethane is 1:(2-3).

[0029] Preferably, the molar ratio of ferrocene dibromo, sodium azide and cuprous chloride in step (3) is 1:(4-5):(2-3).

[0030] Preferably, the mass ratio of the ferrocene azide compound to palladium on carbon in step (4) is 1:(0.018-0.022).

[0031] Preferably, the ferrocene diamine in step (5) and R 1 The molar ratio of Cl to the first organic amine is 1:(2-3):(2-3).

[0032] Preferably, the molar ratio of the ferrocene di-secondary amine compound to the second organic amine and the monochlorophosphine compound in step (6) is 1:(2-3):(2-3).

[0033] The molar ratio of ferrocene, N,N,N,N-tetramethylethylenediamine, and n-butyllithium can be 1:1:2, 1:1.3:2.5, 1:1.5:3, 1:1.8:3.5, or 1:2:4, etc. The molar ratio of the ferrocene dilithium compound to 1,1,2,2-tetrabromoethane can be 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, or 1:3, etc. Ferrocene dibromoethane... The molar ratio of sodium azide and cuprous chloride can be 1:4:2.15, 1:4.1:2.3, 1:4.2:2.5, 1:4.3:2.7, 1:4.4:2.9, or 1:4.5:3, etc. The mass ratio of ferrocene azide to palladium on carbon can be 1:0.018, 1:0.019, 1:0.02, 1:0.021, or 1:0.022, etc. The molar ratio of ferrocene diamine to R... 1 The molar ratio of Cl and the first organic amine can be 1:2:3, 1:2.2:2.2, 1:2.4:2.4, 1:2.6:2.6, 1:2.8:2.8, or 1:3:3, etc. The molar ratio of the ferrocene diamine compound to the second organic amine and the monochlorophosphine compound can be 1:2.2:2, 1:2.5:2.2, 1:2.5:2.5, 1:2.5:2.7, or 1:3:3, etc., but is not limited to the values ​​listed above. Other unlisted values ​​within the above range are also applicable.

[0034] Preferably, the first organic amine and the second organic amine are independently selected from triethylamine and / or pyridine.

[0035] Thirdly, the present invention also provides the application of the ferroceneamine-based bidentate phosphine ligand compound as described above in the preparation of catalyst ligands.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] This invention provides a ferrocene-amine-based bidentate phosphine ligand compound with a specific structure, which can effectively catalyze coupling reactions in conjunction with palladium catalysts, exhibiting the advantages of high activity and high selectivity. Detailed Implementation

[0038] To further illustrate the technical means and effects of the present invention, the following describes the technical solution of the present invention in conjunction with preferred embodiments of the present invention. However, the present invention is not limited to the scope of the embodiments.

[0039] Example 1: Synthesis of Compound L1

[0040] (1) Preparation of ferrocene dilithium compounds

[0041]

[0042] First, ferrocene (7.0 g, 37.6 mmol) and N,N,N,N-tetramethylethylenediamine (5.25 g, 45.1 mmol) were added to a reactor under a nitrogen or argon atmosphere, followed by the addition of 200 mL of hexane, and then dropwise addition of n-butyllithium hexane solution (31.4 mL, 2.4 M) to obtain mixture a. The reactor containing mixture a was placed at 20 °C and reacted for 20 h. After filtration, the filter cake was washed three times with cold hexane, and the filter cake was dried under vacuum to obtain 14.9 g of orange-red ferrocene dilithium compound, with a yield of 85%.

[0043] (2) Preparation of ferrocene dibromide compound

[0044]

[0045] The red solid lithium ferrocene compound (9.0 g, 28.6 mmol) from step (1) was added to a reactor using diethyl ether as a solvent. Then, a solution of 1,1,2,2-tetrabromoethane (21.7 g, 62.9 mmol) in diethyl ether was added dropwise at -30°C to obtain reaction solution c. Reaction solution c was reacted at 20°C for 20 h, followed by quenching with water. The organic phase was then extracted three times with diethyl ether. The organic phases were combined, dried over anhydrous magnesium sulfate for 15 min, filtered, and the solvent was removed under vacuum to obtain a red solution. Methanol was then added, and the solution was recrystallized in a refrigerator. The solution was filtered the next day to obtain 7.86 g of the red target product, with a yield of 80%. 1 HNMR; 1 H NMR (C6D6, 400MHz, 298K), δ, ppm: 4.16 (s, 4H, CH on Cp), 3.71 (s, 4H, CH on Cp).

[0046] (3) Preparation of ferrocene azide compounds

[0047]

[0048] First, the ferrocene dibromo compound (10.34 g, 30.1 mmol) described in step (2) was added to the reactor. Ethanol and water were used as solvents. Then, sodium azide (7.82 g, 120.3 mmol) and cuprous chloride (6.4 g, 20.6 mmol) were added to obtain mixture d. The volume ratio of ethanol to water was 3:1. The mixture was placed in the dark at 20 °C for 48 h. Then, water was added to quench the reaction. The mixture was filtered, and the filter cake was washed with a large amount of diethyl ether until it was colorless. The filtrate was washed twice with saturated brine. The mixture was separated, and the organic phase was dried with anhydrous magnesium sulfate for 20 min. The mixture was filtered, and the solvent was removed under vacuum to obtain a red viscous substance. The substance was dissolved in n-pentane at 20 °C and then recrystallized. The product was filtered the next day to obtain 4.1 g of red needle-like target product (note that it should be stored in the dark). The yield was 51%. 1 H NMR (C6D6, 400MHz, 298K), δ, ppm: 3.98 (s, 4H, CH on Cp), 3.66 (s, 4H, CH on Cp).

[0049] (4) Preparation of ferrocene diamine compounds

[0050]

[0051] Inside a glove box, the ferrocene azide compound (2.0 g, 7.52 mmol), Pd / C (200 mg, 0.1 mmol, palladium on carbon mass fraction 2%), and 150 mL of methanol described in step (3) were added sequentially to a Schlenk flask. The flask was then removed from the glove box, wrapped with aluminum foil, and connected to a double-row tube. Nitrogen gas was evacuated from the flask, and hydrogen gas was introduced at 20°C for 2 hours. This process was repeated 6 times, and after 24 hours of reaction, the Schlenk flask was moved back to the glove box, filtered (lined with diatomaceous earth), and the solvent was removed under vacuum. A small amount of diethyl ether was added, and the flask was placed in a refrigerator. The next day, the diethyl ether was removed, and the solid was dried to obtain 1.97 g of the yellow-red target product, yield: 90%. 1 H NMR (C6D6, 400MHz, 298K), δ, ppm: 3.74 (s, 4H, CH on Cp), 3.65 (s, 4H, CH on Cp), 1.86 (s, 4H, NH).

[0052] (5) Preparation of ferrocene secondary amine compounds

[0053]

[0054] The ferrocene diamine compound (5.85 g, 27.07 mmol) described in step (4) was added to a reactor using 150 mL of dichloromethane as a solvent. Then, dimethyl tert-butylchlorosilane (9.38 g, 62.26 mmol) and triethylamine (5.89 g, 58.2 mmol) were added to obtain reaction solution f. The reaction solution was reacted at 20 °C for 24 h, filtered, and the filter cake was washed with hexane. The filtrate was dried under vacuum to obtain 10.83 g of a red compound, yield: 90%. 1 H NMR (C6D6, 400MHz, 298K), δ, ppm: 3.85 (s, 4H, CHon Cp), 3.82 (s, 4H, CH on Cp), 2.07 (s, 2H, NH), 0.94 (s, 18H, C (CH3) 3), 0.17 (s, 12H, SiCH3).

[0055] (6) Preparation of ferrocene-amine-based didentate phosphine compounds

[0056]

[0057] The ferrocene di-secondary amine compound (5.0 g, 11.25 mmol) and triethylamine (2.85 g, 28.13 mmol) from step (5) were added to the reactor. Using THF as solvent, the mixture was placed at -30°C, followed by the addition of di-tert-butylphosphine chloride (4.45 g, 24.75 mmol) to obtain reaction solution i. The reaction was carried out at 20°C for 24 h. Degassed water was added, and the mixture was separated, washed, and dried. The organic phase was filtered, the solvent was removed under vacuum, and cold methanol was added to obtain 7.0 g of the target product, yield: 85%. 1 H NMR(C6D6,400MHz,298K),δ,ppm:3.83(s,4H,CH on Cp),3.80(s,4H,CH on Cp),1.15(s,18H,C(CH3)3),1.12(s,36H,C(CH3)3), 0.90(s,18H,C(CH3)3),0.15(s,12H,SiCH3).

[0058] Example 2 Synthesis of compound L2

[0059]

[0060] The ferrocene diamine compound (5.85 g, 27.07 mmol) described in Example 1 was added to a reactor using 120 ml of dichloromethane as a solvent. Triisopropylchlorosilane (11.4 g, 59.55 mmol) and triethylamine (5.89 g, 58.2 mmol) were then added to obtain reaction solution f, wherein the molar ratio of the ferrocene diamine compound, haloalkane, and triethylamine was 1:2.2:2.4. The reaction solution was reacted at 20°C for 24 h, filtered, and the filter cake was washed with hexane. The filtrate was dried under vacuum to obtain red compound g. Compound g was added to a reactor using diethyl ether as a solvent, and then benzyl potassium was added at -30°C. The molar ratio of g to benzyl potassium was 1:2.05, yielding reaction solution h. The reaction was carried out at 20°C for 12 h. The solvent was removed under vacuum, and the mixture was washed with cold hexane, filtered, and the solid was dried to obtain the intermediate ferrocene diamine salt compound h. The intermediate ferrocene diamine salt compound h (5.95 g, 11.25 mmol) was added to a reactor, using THF as solvent, and placed at -30°C. Then, di-tert-butylphosphine chloride (4.45 g, 24.75 mmol) was added to obtain reaction solution i. The reaction was carried out at 20°C for 24 h. Degassed water was added, and the mixture was separated, washed, and the organic phase dried. The mixture was filtered, the solvent was removed under vacuum, and cold methanol was added to obtain 6.35 g of the target product, yield: 80%. 1 HNMR(C6D6,400MHz,298K),δ,ppm:3.92(s,4H,CH on Cp),3.84(s,4H,CH on Cp),2.3(br,2H,NH),1.12(s,42H,CH(CH3)2),0.87(s,36H,C(CH3)3).

[0061] Example 3 Synthesis of compound L3

[0062]

[0063] The ferrocene di-secondary amine compound (5.0 g, 11.25 mmol) and triethylamine (2.85 g, 28.13 mmol) obtained in step (5) of Example 1 were added to a reactor. Using THF as solvent, the mixture was placed at -30°C, followed by the addition of diphenylphosphine chloride (5.46 g, 24.75 mmol) to obtain a reaction solution. The reaction was carried out at 20°C for 24 h. Degassed water was added, and the mixture was separated, washed, and dried. The organic phase was filtered, the solvent was removed under vacuum, and cold methanol was added to obtain 7.5 g of the target product, yield: 86%. 1H NMR (C6D6, 400MHz, 298K), δ, ppm: 7.2-7.6 (m, 20H, Ph), 3.84 (s, 4H, CH on Cp), 3.82 (s, 4H, CH on Cp), 1.15 (s, 18H, C (CH3) 3), 1.07 (s, 36H, C (CH3) 3).

[0064] Example 4 Synthesis of compound L4

[0065]

[0066] The ferrocene diamine compound (5.85 g, 27.07 mmol) described in Example 1 was added to a reactor using 120 ml of dichloromethane as a solvent. Triisopropylchlorosilane (11.4 g, 59.55 mmol) and triethylamine (5.89 g, 58.2 mmol) were then added to obtain a reaction solution in which the molar ratio of the ferrocene diamine compound, haloalkane, and triethylamine was 1:2.2:2.4. The reaction solution was reacted at 20°C for 24 h, filtered, and the filter cake was washed with hexane. The filtrate was dried under vacuum to obtain a red compound. The compound was added to a reactor using diethyl ether as a solvent, and then benzyl potassium was added at -30°C. The reaction mixture was prepared by mixing ferrocene diamine salt (5.95 g, 11.25 mmol) with benzyl potassium at a molar ratio of 1:2.05. The reaction was carried out at 20 °C for 12 h. The solvent was removed under vacuum, and the mixture was washed with cold hexane, filtered, and the solid was dried to obtain the intermediate ferrocene diamine salt. The intermediate ferrocene diamine salt (5.95 g, 11.25 mmol) was added to a reactor, and THF was used as the solvent. The reactor was placed at -30 °C, followed by the addition of diphenylphosphine chloride (5.46 g, 24.75 mmol). The reaction mixture was carried out at 20 °C for 24 h. Degassed water was added, and the mixture was washed separately, dried, filtered, and the solvent was removed under vacuum. Cold methanol was added to obtain 6.21 g of the target product, with a yield of 76%. 1 HNMR(C6D6,400MHz,298K), δ,ppm:7.3-7.7(m,20H,Ph)3.90(s,4H,CH on Cp),3.83(s,4H,CH on Cp),2.2(br,2H,NH),1.11(s,42H,CH(CH3)2).

[0067] The synthesis steps for L5-L6 are similar to those for the ligand synthesis in Examples 1-4, except that the monochlorophosphine compound is replaced with an equal amount of (pyridin-2-yl)-tert-butylphosphine chloride.

[0068] Example 5: Synthesis of Compound L5

[0069] Compound L5, 1H NMR(C6D6,400MHz,298K),δ,ppm:8.41-8.38(m,2H,Py),7.71-7.67(m,2H,Py),7.05-6.96(m,2H,Py),6.58-6.47(m,2H,Py),3.83(s,4H,CH on Cp), 3.80(s,4H,CH on Cp), 1.15(s,18H,C(CH3)3), 1.08(d,J=13.3Hz,18H,C(CH3)3), 0.90(s,18H,C(CH3)3), 0.15(s,12H,SiCH3).

[0070] Example 6 Synthesis of compound L6

[0071] Compound L6, 1 HNMR(C6D6,400MHz,298K),δ,ppm:8.39-8.35(m,2H,Py),769-7.65(m,2H,Py),7.03-6.93(m,2H,Py),6.55-6.45(m,2H,Py),3.92(s,4H,CH on Cp), 3.84 (s, 4H, CHon Cp), 2.3 (br, 2H, NH), 1.12 (s, 42H, CH (CH3) 2), 1.06 (d, J = 13.3Hz, 18H).

[0072] Effect test:

[0073] The catalytic system for olefin carbonyl esterification described in this invention is prepared by complexing a metal center with a ferrocene-amine-based bidentate phosphine ligand in a certain proportion and with an acidic promoter. The metal center can be a compound of iron, cobalt, nickel, ruthenium, rhodium, iridium, or palladium, preferably a compound of cobalt or rhodium, and most preferably a compound of palladium, which can be PdCl2, Pd(Oac)2, Pd(acac)2, Pd2(dba)3, or PdCl2(COD); wherein acac is acetylacetone, COD is 1,5-cyclooctadiene, and the ferrocene-amine-based diamine bidentate phosphine is as shown in formula (I).

[0074] The evaluation method for olefin carbonyl esterification is as follows: Ethylene is preferred as the olefin. Palladium acetate (0.1 mmol), a ligand (0.4 mmol), p-toluenesulfonic acid (5 mmol, 0.86 g), and 50 mL of methanol solvent are added to a 300 mL stainless steel autoclave equipped with a pressure gauge under air atmosphere. The mixture is slowly stirred to generate a palladium / ligand catalytic system. A gas line is connected, and the gas inside the autoclave is purged three times with nitrogen. A mixture of ethylene and carbon monoxide is then introduced to the specified pressure. The mixture is heated to the specified temperature (80 °C) under magnetic stirring. Gas is added several times during the reaction to maintain the specified pressure. After the specified reaction time (12 hours), the reactor is cooled, and the residual gas is vented in a fume hood. The mixture is weighed, the autoclave is opened, and a sample is taken for gas chromatography (GC) to determine the ratio of methyl propionate to methanol.

[0075] To investigate the effects of various monophosphine and diphosphine ligands on the carbonylation reaction of ethylene to prepare methyl propionate, which requires electron-donating and sterically hindered phosphine ligand structures, we have conducted a preliminary study.

[0076] Table 1. Exploration of the effects of different ligand structures on the ethylene carbonyl esterification reaction.

[0077]

[0078]

[0079] Reaction conditions: a Ethylene (0.22 mol), Pd2(DBA)3 (0.13 mol%), PTSA (0.38 mol%), methanol (70 g), CO (2.5 MPa); b Ethylene (0.22 mol), Pd(acac)2 (0.04 mol%), methanol (70 g), CO (2.5 MPa), ligand L6 (0.16 mol%), PTSA (172.2 mg, 61 mg, 0.6 mol%), ethylene conversion rate 98%.

[0080] The applicant declares that this invention illustrates the ferroceneamine-based bidentate phosphine ligand compound, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

[0081] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0082] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

Claims

1. A ferrocenyl amido bidentate phosphine ligand compound characterized by, The structure of the ferrocenyl amido bidentate phosphine ligand compound is as follows: wherein R 1 is selected from dimethyl-tert-butylsilyl or triisopropylsilyl; R 2 , R 3 , R 4 , R 5 is independently selected from phenyl, t-butyl, pyridyl or cyclohexyl.

2. The ferrocenyl amido bidentate phosphine ligand compound according to claim 1, characterized in that, The ferrocenyl amido bidentate phosphine ligand compound is selected from any one of L1-L6 structures: 。 3. A process for the preparation of a ferrocenyl amido bidentate phosphine ligand compound according to claim 1, characterized by, The preparation method comprises the following steps: (1) mixing ferrocene, N,N,N,N-tetramethylethylenediamine and n-butyllithium to obtain a ferrocene dilithium compound; (2) mixing the ferrocene dilithium compound obtained in step (1) with 1,1,2,2-tetrabromoethane to obtain a ferrocene dibromide; (3) mixing the ferrocene dibromide obtained in step (2) with sodium azide and cuprous chloride to obtain a ferrocene azide compound; (4) reacting the ferrocene azide compound obtained in step (3) with palladium-carbon in a hydrogen environment to obtain a ferrocene diamine; (5) reacting the ferrocene diamine obtained in step (4) with R 1 Cl, a first organic amine to obtain a ferrocene di- secondary amine compound; (6) reacting the ferrocene di-secondary amine compound obtained in step (5) with a second organic amine and a monochlorophosphine compound to obtain the ferrocenyl amido bidentate phosphine ligand compound; The first organic amine and the second organic amine are independently selected from any one or a combination of at least two of triethylamine, pyridine, triisopropylamine, butylamine, potassium benzyl or sodium benzyl; The monochlorophosphine includes PClR 2 R 3 and PClR 4 R 5 ; wherein R 1 , R 2 , R 3 , R 4 , R 5 have the same scope of limitation as claim 1.

4. The production method according to claim 3, characterized by, In step (1), the molar ratio of the ferrocene, N,N,N,N-tetramethylethylenediamine and n-butyllithium is 1:(1-2):(2-4).

5. The preparation method according to claim 3, characterized in that, In step (1), the reaction is carried out in a solvent, and the solvent comprises n-hexane.

6. The preparation method according to claim 3, characterized in that, In step (2), the molar ratio of the ferrocene dilithium compound to 1,1,2,2-tetrabromoethane is 1:(2-3).

7. The preparation method according to claim 3, characterized in that, In step (3), the molar ratio of the ferrocene dibromide, sodium azide and cuprous chloride is 1:(4-4.5):(2.15-3).

8. The preparation method according to claim 3, characterized in that, In step (4), the mass ratio of the ferrocene azide compound to palladium-carbon is 1:(0.018-0.022).

9. The preparation method according to claim 3, characterized in that, Step (5) said ferrocene diamine and R 1 Cl, the molar ratio of the first organic amine is 1: (2-3): (2-3).

10. The method of claim 3, wherein, In step (6), the molar ratio of the ferrocene di-secondary amine compound to the second organic amine and the monochlorophosphine compound is 1:(3-5):(2-3).

11. The preparation method according to claim 3, characterized in that, The first organic amine and the second organic amine are independently selected from triethylamine and / or pyridine.

12. Use of the ferrocenyl amido bidentate phosphine ligand compound according to claim 1 or 2 as a catalyst ligand.

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