Magnesium cyclopentadienyl complex, preparation process therefor, and use thereof

Abstract

A magnesium cyclopentadienyl complex, a preparation process therefor, and a use thereof. The magnesium cyclopentadienyl complex Cp1MgCp2 has a structural formula of formula (A). Cp1 and Cp2 are cyclopentadiene ligands formula (B) and formula (C), and R1-R10 are independently H and alkyl groups of 1 to 5 carbon atoms. The magnesium cyclopentadienyl complex has advantages such as a simple preparation process, mild process conditions, and a high yield.

Description

A cyclopentadienyl magnesium complex and its preparation process and application Technical Field

[0001] The present invention relates to the technical field of cyclopentadienyl magnesium complexes, in particular to a cyclopentadienyl magnesium complex and a preparation process and application thereof. Background Art

[0002] Magnesium cyclopentadienyl complex is a very important metal organic complex. As shown in Figure 1, R1-R 10 An alkyl group with five or fewer carbon atoms or a hydrogen atom. In organic synthesis, cyclopentadienyl ligands can be introduced to transition metal elements. High-purity reagents can be used to prepare high-performance solar cells and laser diodes. Common cyclopentadienyl magnesium complexes currently on the market include those with homogeneous ligands, such as bis(ethylcyclopentadienyl)magnesium.

[0003] Other heterogeneous magnesium complexes with cyclopentadienyl ligands have not been reported. Theoretical inference suggests that the inherent asymmetry of heterogeneous magnesium complexes with cyclopentadienyl ligands significantly lowers their melting points, allowing them to achieve both room-temperature liquid states and high saturated vapor pressures. These complexes are highly suitable for atomic layer deposition and are used in advanced integrated circuit manufacturing processes. Therefore, there is an urgent need for a method to prepare heterogeneous magnesium complexes with cyclopentadienyl ligands.

[0004] Summary of the Invention

[0005] To solve the above technical problems, the present invention provides a cyclopentadienyl magnesium complex and its preparation process and application. The cyclopentadienyl magnesium complex obtained by the present invention has good asymmetry, so its melting point is also low, and it is liquid at room temperature and has a high saturated vapor pressure.

[0006] The present invention utilizes the unique molecular structure of the Grignard reagent to design a two-step substitution process: the alkyl group attached to magnesium can undergo a substitution reaction with a ligand containing an active hydrogen, and the halogen atom attached to magnesium can undergo a substitution reaction with the ligand's alkali metal salt. Both reactions are very mild and can be carried out at room temperature. Because the reactions are divided into two separate, non-simultaneous steps, this process can be used to prepare heterogeneous magnesium complexes with monocyclopentadienyl ligands.

[0007] In order to solve the above technical problems, the purpose of the present invention is achieved through the following solutions:

[0008] The first object of the present invention is to provide a cyclopentadienyl magnesium complex, wherein the cyclopentadienyl magnesium complex Cp1MgCp2 has the structural formula Among them, Cp1 is Cp2 is R1-R 10 are independently H, an alkyl group of 1 to 5 carbon atoms, and Cp1 and Cp2 are different.

[0009] The second object of the present invention is to provide a process for preparing an asymmetric cyclopentadienyl magnesium complex, comprising the following steps:

[0010] (1) mixing a solution of cyclopentadiene or its derivative Cp1H with a solution of a Grignard reagent RMgX to react and prepare a cyclopentadiene magnesium halide Cp1MgX, wherein R is an alkyl group with 1 to 5 carbon atoms;

[0011] (2) mixing the cyclopentadienyl magnesium halide Cp1MgX obtained in step (1) with the cyclopentadienyl salt Cp2M solution to react and obtain the cyclopentadienyl magnesium complex.

[0012] Wherein, M is a metal element; X is chlorine, bromine, or iodine;

[0013] The structural formula of the cyclopentadienyl magnesium halide Cp1MgX is

[0014] The structural formula of the cyclopentadienyl salt Cp2M is

[0015] R1-R 10 and independently H, an alkyl group of 1 to 5 carbon atoms.

[0016] In one embodiment of the present invention, in step (1), the molar ratio of cyclopentadiene or its derivative Cp1H in the cyclopentadiene or its derivative Cp1H solution to RMgX in the Grignard reagent RMgX solution is (1-2):1.

[0017] In one embodiment of the present invention, in step (1), the reaction is carried out under an inert atmosphere.

[0018] In one embodiment of the present invention, in step (1), the reaction time is 0.5-10 h, and the reaction temperature is -20°C to 120°C.

[0019] In one embodiment of the present invention, in steps (1) and (2), the molar ratio of cyclopentadiene or its derivative Cp1H, Grignard reagent RMgX and cyclopentadiene salt Cp2M is (1-2):1:(1-2).

[0020] In one embodiment of the present invention, in step (2), the reaction time is 0.5-10 h, and the reaction temperature is -20°C to 120°C.

[0021] In one embodiment of the present invention, in step (2), the metal element is selected from lithium, sodium, and potassium.

[0022] In one embodiment of the present invention, in step (1) and step (2), the solvent of the cyclopentadiene salt Cp2M solution and the solvent of the cyclopentadiene or its derivative Cp1H solution are independently one or more of tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-methyl ether, toluene, n-hexane, n-pentane, and n-heptane.

[0023] The third object of the present invention is to provide the use of the cyclopentadienyl magnesium complex in an atomic layer deposition process.

[0024] The above technical solution of the present invention has the following advantages over the prior art (traditional symmetrical cyclopentadienyl magnesium compounds):

[0025] 1. This invention overcomes the limitation of existing processes that only allow the preparation of mono-ligand cyclopentadienyl magnesium compounds and enables the synthesis of asymmetric cyclopentadienyl magnesium complexes. Asymmetric cyclopentadienyl magnesium compounds exhibit good asymmetry, resulting in low melting points, liquid states at room temperature, and high saturated vapor pressures.

[0026] 2. Compared with solids such as bismuth magnesium, the melting point brought about by the asymmetric structure is greatly reduced, making the product easier to flow without clogging, easier to vaporize, and conducive to the reaction.

[0027] 3. Compared with liquids such as diethylcyclopentadienyl magnesium, the molecular weight of asymmetriccyclopentadienyl magnesium is relatively low, which increases the saturated vapor pressure and is more conducive to special gas related applications.

[0028] In addition, the process conditions of the present invention are mild and can also be used for the synthesis of traditional uniform ligand cyclopentadienyl magnesium compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below based on specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:

[0030] FIG1 is a nuclear magnetic resonance spectrum of the (cyclopentadienyl)(methylcyclopentadienyl) magnesium complex obtained in Example 1 of the present invention.

[0031] FIG2 is an NMR spectrum of the bis(cyclopentadienyl)magnesium complex obtained in Example 5 of the present invention.

[0032] FIG3 is an NMR spectrum of the (cyclopentadienyl)(ethylcyclopentadienyl) magnesium complex obtained in Example 6 of the present invention.

[0033] FIG4 is a graph showing the ALD (atomic layer deposition) thickness and cycle number of the (cyclopentadienyl)(methylcyclopentadienyl) magnesium complex obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] In order to solve the technical problems pointed out in the background technology, the present invention provides a cyclopentadienyl magnesium complex and its preparation method and application.

[0035] The present invention provides a cyclopentadienyl magnesium complex, wherein the cyclopentadienyl magnesium complex Cp1MgCp2 has the structural formula Among them, Cp1 is Cp2 is R1-R 10 are independently H, an alkyl group of 1 to 5 carbon atoms. and It is an asymmetric structure, R1-R5 and R6-R 10 The corresponding positions are not completely identical, that is, Cp1 and Cp2 are different, which is asymmetry, meaning that the two structures are asymmetric on both sides of the magnesium atom.

[0036] Furthermore, the R1-R 10 are independently H, methyl, ethyl, propyl, butyl, or pentyl.

[0037] The present invention also provides a novel process for preparing a cyclopentadienyl magnesium complex, comprising the following steps:

[0038] (1) mixing a solution of cyclopentadiene or its derivative Cp1H with a solution of a Grignard reagent RMgX to react and prepare a cyclopentadiene magnesium halide Cp1MgX, wherein R is an alkyl group with 1 to 5 carbon atoms;

[0039] (2) mixing the cyclopentadienyl magnesium halide Cp1MgX obtained in step (1) with the cyclopentadienyl salt Cp2M solution to react and obtain the cyclopentadienyl magnesium complex.

[0040] Wherein, M is a metal element;

[0041] The structural formula of the cyclopentadienyl magnesium halide Cp1MgX is

[0042] The structural formula of the cyclopentadienyl salt Cp2M is

[0043] R1-R 10 and independently H, an alkyl group of 1 to 5 carbon atoms.

[0044] In a specific embodiment, in step (1), the molar ratio of cyclopentadiene or its derivative Cp1H in the cyclopentadiene or its derivative Cp1H solution to RMgX in the Grignard reagent RMgX solution is (1-2):1.

[0045] In a specific embodiment, in step (1), the reaction is carried out under an inert atmosphere.

[0046] Furthermore, the inert gas in the inert atmosphere is selected from nitrogen and / or argon.

[0047] In a specific embodiment, in step (1), the reaction time is 0.5-10 h, and the reaction temperature is -20°C to 120°C.

[0048] Furthermore, the reaction temperature is preferably 40-120°C, and the temperature is gradually increased until the temperature of the reaction solution is refluxed. By controlling the temperature, the reaction is more thorough, the conversion rate of the raw materials is improved, and the production of products is increased.

[0049] In a specific embodiment, in steps (1) and (2), the molar ratio of cyclopentadiene or its derivative Cp1H, Grignard reagent RMgX and cyclopentadiene salt Cp2M is (1-2):1:(1-2).

[0050] Furthermore, in the Grignard reagent RMgX, R is selected from methyl, ethyl, propyl, butyl, and pentyl. X is chlorine, bromine, or iodine.

[0051] Furthermore, the Grignard reagent RMgX is selected from one or more of methylmagnesium bromide, methylmagnesium iodide, and ethylmagnesium bromide.

[0052] In a specific embodiment, in step (2), the reaction time is 0.5-10 h, and the reaction temperature is -20°C to 120°C.

[0053] In a specific embodiment, in step (2), the metal element is selected from lithium, sodium, and potassium.

[0054] In a specific embodiment, in step (1) and step (2), the solvent of the cyclopentadiene salt Cp2M solution or the solvent of the cyclopentadiene or its derivative Cp1H solution is one or more of tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-methyl ether, toluene, n-hexane, n-pentane, and n-heptane.

[0055] The present invention also provides application of the cyclopentadienyl magnesium complex in an atomic layer deposition process.

[0056] The present invention will be further described below with reference to the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it. However, the embodiments are not intended to limit the present invention.

[0057] Example 1

[0058] This embodiment provides a method for preparing a (cyclopentadienyl)(methylcyclopentadienyl) magnesium complex, as follows:

[0059] In a fume hood, the gas in the reaction bottle was replaced with nitrogen, methylmagnesium iodide solution (0.1 mol) was added to the reaction bottle, and freshly distilled cyclopentadiene monomer (8.0 g, 0.1 mol) was added and stirred for 3 hours; a solution of methylcyclopentadienyl sodium (10.2 g, 0.1 mol) in tetrahydrofuran (150 mL) was added, stirred for 6 hours and dried, and then dissolved in n-hexane, filtered and the filtrate was taken. After the filtrate was dried, it was distilled to obtain a colorless transparent liquid (cyclopentadienyl) (methylcyclopentadienyl) magnesium complex (13.5 g, 0.08 mmol) with a yield of 80%. The product was in liquid form when first prepared, and became solid when placed at room temperature for a long time. It melted when heated between 35-45 ° C. The metal purity of the substance was 5N using ICP-MS. The obtained material was structurally characterized, and the nuclear magnetic spectrum is shown in Figure 1. The nuclear magnetic data are: 1 H NMR(400MHz,C6D6)d(ppm):6.14(s,5H,ring-CH),5.92-5.86(m,4H,ring-CH),2.22(s,3H,CH3).

[0060] Reaction equation: CH3MgI+CpH=CpMgI+CH4; CpMgI+MeCpNa=MeCpMgCp+NaI.

[0061] Example 2:

[0062] This example provides the preparation of (cyclopentadienyl)(methylcyclopentadienyl)magnesium complex:

[0063] In a fume hood, the gas in the reaction flask was replaced with nitrogen, methylmagnesium iodide solution (0.1 mol) was added to the reaction flask, and freshly distilled cyclopentadiene monomer (8.0 g, 0.1 mol) was added and stirred for 3 hours. A solution of methylcyclopentadienyl lithium (8.6 g, 0.1 mol) in tetrahydrofuran (150 mL) was added and stirred for 6 hours, and the mixture was pulled dry. After dissolving in n-hexane, the filtrate was filtered and distilled to obtain a colorless transparent liquid (10.1 g, 0.06 mmol) with a yield of 60%.

[0064] Reaction equation: CH3MgI+CpH=CpMgI+CH4; CpMgI+MeCpLi=MeCpMgCp+LiI.

[0065] Example 3:

[0066] This example provides the preparation of (cyclopentadienyl)(methylcyclopentadienyl)magnesium complex:

[0067] In a fume hood, the gas in the reaction flask was replaced with nitrogen, methylmagnesium bromide solution (0.1 mol) was added to the reaction flask, and freshly distilled cyclopentadiene monomer (8.0 g, 0.1 mol) was added and stirred for 3 hours. A solution of methylcyclopentadienyl sodium (10.2 g, 0.1 mol) in tetrahydrofuran (150 mL) was added and stirred for 6 hours, and the mixture was pulled dry. After dissolving in n-hexane, the filtrate was filtered and the filtrate was pulled dry and distilled to obtain a colorless transparent liquid (11.12 g, 0.066 mmol) with a yield of 66%.

[0068] Reaction equation: CH3MgBr+CpH=CpMgBr+CH4; CpMgBr+MeCpLi=MeCpMgCp+LiBr.

[0069] Example 4:

[0070] This example provides the preparation of (cyclopentadienyl)(methylcyclopentadienyl)magnesium complex:

[0071] In a fume hood, the gas in the reaction flask was replaced with nitrogen, methylmagnesium iodide solution (0.1 mol) was added to the reaction flask, and freshly distilled cyclopentadiene monomer (8.0 g, 0.1 mol) was added and stirred for 3 hours. A solution of methylcyclopentadienyl potassium (11.82 g, 0.1 mol) in tetrahydrofuran (150 mL) was added and stirred for 6 hours, and the mixture was pulled dry. After dissolving in n-hexane, the filtrate was filtered and the filtrate was pulled dry and distilled to obtain a colorless transparent liquid (13.14 g, 0.078 mmol) with a yield of 78%.

[0072] Reaction equation: CH3MgI+CpH=CpMgI+CH4; CpMgI+MeCpK=MeCpMgCp+KI.

[0073] Example 5:

[0074] This example provides the preparation of a bis(cyclopentadienyl)magnesium complex:

[0075] In a fume hood, the atmosphere in the reaction flask was replaced with nitrogen. Methylmagnesium iodide solution (0.1 mol) was added to the reaction flask, followed by freshly distilled cyclopentadiene monomer (13.2 g, 0.2 mol). The mixture was stirred for 3 hours. A solution of cyclopentadienyl sodium (8.8 g, 0.1 mol) in tetrahydrofuran (150 mL) was added. The mixture was stirred for 6 hours and then dried. The mixture was dissolved in n-hexane and filtered to obtain the filtrate. The filtrate was dried and sublimed to give a white solid (12.3 g, 0.08 mmol) with an 80% yield. The metal purity of the substance was 5N as determined by ICP-MS. The NMR spectrum is shown in Figure 2.

[0076] Reaction equation: CH3MgI+CpH=CpMgI+CH4; CpMgI+CpNa=Cp2Mg+NaI.

[0077] Example 6

[0078] This embodiment provides another method for preparing an asymmetric cyclopentadienyl magnesium (cyclopentadienyl) (ethylcyclopentadienyl) magnesium complex, as follows:

[0079] In a fume hood, the gas in the reaction flask was replaced with nitrogen, methylmagnesium iodide solution (0.1mol) was added to the reaction flask, and freshly distilled cyclopentadiene monomer (8.0g, 0.1mol) was added and stirred for 3 hours; a solution of ethylcyclopentadienyl sodium (11.6g, 0.1mol) in tetrahydrofuran (150mL) was added, and the mixture was dried after 6 hours of stirring. The mixture was then dissolved in n-hexane and filtered to obtain the filtrate. The filtrate was dried and then distilled to obtain a colorless transparent liquid (10.5g, 0.05mmol) in a yield of 50%. The resulting material was subjected to structural characterization. The NMR spectrum is shown in Figure 3. The product is unstable. During the detection process, the value is constantly changing, indicating that the structure is unstable.

[0080] Reaction equation: CH3MgI+CpH=CpMgI+CH4; CpMgI+EtCpNa=EtCpMgCp+NaI.

[0081] Application Example 1

[0082] The results of atomic layer deposition of MeCpMgCp samples are as follows:

[0083] The MeCpMgCp obtained in Example 1 can react with H2O, H2O2, O3, O2 plasma, alcohols, etc. at a deposition temperature of 150-300°C, with a refractive index of 1.65-1.72, a deposition rate of 0.09-0.12 nm / cycle, and a carbon content of less than 3 at%. The results are shown in FIG4 , which shows that the sample has good linear growth characteristics and very good stability.

[0084] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A cyclopentadienyl magnesium complex, characterized in that, The formula of the cyclopentadienyl magnesium complex is Cp 1 MgCp 2 , and the structural formula is Among them, Cp 1 is Cp 2 is R 1 -R 10 independently represents H or an alkyl group with 1 to 5 carbon atoms.

2. The cyclopentadienyl magnesium complex according to claim 1, characterized in that, The cyclopentadienyl magnesium complex has an asymmetric structure, and Cp 1 is different from Cp 2 .

3. A preparation process of the cyclopentadienyl magnesium complex according to claim 1 or 2, characterized in that, comprising the following steps: (1) Mix cyclopentadiene or its derivative Cp 1 H solution with Grignard reagent RMgX solution, and react to prepare cyclopentadienyl magnesium halide Cp 1 MgX, where R is an alkyl group with 1-5 carbon atoms; (2) Mix the cyclopentadienyl magnesium halide Cp 1 MgX obtained in step (1) with the cyclopentadiene salt Cp 2 M solution for reaction to obtain the cyclopentadienyl magnesium complex, wherein, M is a metal element; The cyclopentadienyl magnesium halide Cp 1 The structural formula of MgX is The cyclopentadienyl salt Cp 2 The structural formula of M is R 1 -R 10 Independently, R is H, an alkyl group having 1 to 5 carbon atoms, and X is chlorine, bromine, or iodine.

4. The preparation process according to claim 3, characterized in that, In step (1), the cyclopentadiene or its derivative Cp 1 Cyclopentadiene or its derivative Cp in an H solution 1 The molar ratio of RMgX in the RMgX solution to H is (1 - 2):

1.

5. The preparation process according to claim 3, characterized in that, In step (1), the reaction is carried out under an inert atmosphere.

6. The preparation process according to claim 3, characterized in that, In step (1), the reaction time is 0.5 - 10 h and the reaction temperature is -20°C to 120°C.

7. The preparation process according to claim 3, characterized in that, In steps (1) and (2), the molar ratio of cyclopentadiene or its derivative Cp 1 H, Grignard reagent RMgX and cyclopentadienyl salt Cp 2 M is (1 - 2):1:(1 - 2).

8. The preparation process according to claim 3, characterized in that, In step (2), the reaction time is 0.5 - 10 h and the reaction temperature is -20°C to 120°C; the metal element is selected from lithium, sodium, and potassium.

9. The preparation process according to claim 3, characterized in that, In step (1) and step (2), the cyclopentadienyl salt Cp 2 The solvent of the M solution or cyclopentadiene or its derivative Cp 1 The solvent of the H solution is independently one or more of tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, toluene, n-hexane, n-pentane, and n-heptane.

10. Application of the cyclopentadienyl magnesium complex according to claim 1 or 2 in an atomic layer deposition process.

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