Dicarbonyl cyclopentadienyl cobalt complex as well as preparation method and application thereof

Abstract

The invention discloses a dicarbonyl cyclopentadienyl cobalt complex as well as a preparation method and application thereof, and belongs to the technical field of organic metal synthesis. The preparation method of the dicarbonyl cyclopentadienyl cobalt complex specifically comprises the following steps: (1) dissolving cobalt octacarbonyl in carbon monoxide pre-saturated dichloromethane, and continuously introducing carbon monoxide gas for protection to obtain a reaction system; (2) dissolving cyclopentadiene in dichloromethane, and continuously introducing carbon monoxide gas for protection to obtain a cyclopentadiene solution; (3) adding a cyclopentadiene solution into the reaction system, heating and stirring for reaction; and (4) carrying out pressurized distillation and rectification on the reaction system. According to the invention, the carbon monoxide protective gas is introduced and the cyclopentadiene solution is prepared in the whole process to reduce the decomposition of the raw materials and reduce the generation of byproducts, so that the subsequent purification difficulty is reduced, and the reaction yield and the economic benefit of the product are improved.

Description

Technical Field

[0001] This invention relates to the field of organometallic synthesis technology, and more specifically to a dicarbonylcyclopentadienyl cobalt complex, its preparation method, and its application. Background Technology

[0002] Dicarbonylcyclopentadienylcobalt is an organic compound with the chemical formula C7H5CoO2, primarily used in organic synthesis. Its applications in chip manufacturing are mainly concentrated in thin-film deposition processes and advanced interconnect technologies. Due to its unique volatility, low-temperature decomposition characteristics, and excellent electrochemical properties, it has become one of the key precursor materials in the semiconductor industry.

[0003] The traditional method for synthesizing dicarbonylcyclopentadienyl cobalt involves refluxing octacarbonyl dicobalt (Co2(CO)8) and cyclopentadiene (CP) with dichloromethane (DCM) for 48 hours. However, this method suffers from problems such as easy decomposition of the raw material octacarbonyl dicobalt and excessive byproducts, which leads to difficulty in purifying the product and reduced yield, seriously affecting the stability of the production process.

[0004] Therefore, how to provide an efficient method for preparing dicarbonylcyclopentadienyl cobalt is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a dicarbonylcyclopentadienyl cobalt complex, its preparation method and application, so as to overcome the shortcomings of the prior art.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A method for preparing a dicarbonylcyclopentadienyl cobalt complex specifically includes the following steps:

[0008] (1) Dissolve cobalt octacarbonyl in dichloromethane presaturated with carbon monoxide and continuously pass carbon monoxide gas for protection to obtain the reaction system;

[0009] (2) Dissolve cyclopentadiene in dichloromethane and continuously pass carbon monoxide gas through it for protection to obtain a cyclopentadiene solution;

[0010] (3) Add cyclopentadiene solution to the reaction system, heat and stir to react;

[0011] (4) The reaction system is subjected to pressure distillation and rectification to obtain the dicarbonylcyclopentadienyl cobalt complex.

[0012] Furthermore, in step (3) above, the mass ratio of octacarbonyldicobalt to cyclopentadiene is (2:1)-(1:20), preferably (2:1)-(1:3).

[0013] Furthermore, in step (3) above, the temperature is raised to 40°C.

[0014] Furthermore, in step (3) above, the temperature of the stirring reaction is 40°C and the time is 10-48h, preferably 48h.

[0015] The present invention also claims protection for a dicarbonylcyclopentadienyl cobalt complex prepared by the above-described preparation method.

[0016] The present invention also claims the application of a dicarbonylcyclopentadienyl cobalt complex prepared by the above preparation method in chemical vapor deposition and atomic layer deposition.

[0017] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:

[0018] 1. This invention uses CO-presaturated dichloromethane to dissolve cobalt octacarbonyl, and an excess of CO gas is introduced throughout the reaction to maintain a reducing atmosphere, reduce the decomposition of raw materials, and inhibit cobalt oxidation.

[0019] 2. In this invention, the addition of a cyclopentadiene solution to the reaction system can reduce the generation of byproducts.

[0020] 3. This invention uses octacarbonyldicobalt and cyclopentadiene as raw materials, dichloromethane as solvent, and carbon monoxide as protective gas to prepare a cyclopentadiene solution, obtaining the optimal solution. After the reaction, the proportion of by-products is monitored using a central control method, and subsequent purification is carried out through methods such as solvent removal and distillation to obtain qualified products.

[0021] 4. This invention reduces the decomposition of raw materials and the generation of byproducts by introducing carbon monoxide protective gas throughout the process and preparing cyclopentadiene solution, thereby reducing the difficulty of subsequent purification and improving the reaction yield and the economic benefits of the product.

[0022] 5. In the process of synthesizing dicarbonylcyclopentadienyl cobalt complex, this invention observes the reaction progress by taking samples at intervals, analyzes the content of by-products and product yield, and determines the reaction endpoint.

[0023] 6. The dicarbonylcyclopentadienyl cobalt complex synthesized in this invention is a volatile organic cobalt precursor that can be used in the metal deposition step of chip manufacturing to provide cobalt atoms or ions for forming cobalt-related thin films or wires and other structures. It has wide applications in chemical vapor deposition (CVD) and atomic layer deposition (ALD). Attached Figure Description

[0024] Figure 1 The image shows the nuclear magnetic resonance (NMR) spectrum of the dicarbonylcyclopentadienyl cobalt complex prepared in Example 1. Detailed Implementation

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] Example 1

[0027] The preparation method of the dicarbonylcyclopentadienyl cobalt complex specifically includes the following steps:

[0028] (1) Dissolve 1g of cobalt octacarbonyl in dichloromethane presaturated with carbon monoxide and continuously pass carbon monoxide gas through it for protection to obtain the reaction system.

[0029] (2) Dissolve 0.5g of cyclopentadiene in dichloromethane and continuously pass carbon monoxide gas through it for protection to obtain a cyclopentadiene solution;

[0030] (3) Heat the reaction system to 40°C, add cyclopentadiene solution, and stir the reaction at 40°C for 48 hours;

[0031] (3) The reaction system was subjected to pressure distillation and rectification to obtain a brownish-black liquid, which is the dicarbonylcyclopentadienyl cobalt complex.

[0032] Example 2

[0033] The preparation method of the dicarbonylcyclopentadienyl cobalt complex specifically includes the following steps:

[0034] (1) Dissolve 1g of cobalt octacarbonyl in dichloromethane presaturated with carbon monoxide and continuously pass carbon monoxide gas through it for protection to obtain the reaction system.

[0035] (2) Dissolve 3g of cyclopentadiene in dichloromethane and continuously pass carbon monoxide gas through it for protection to obtain a cyclopentadiene solution.

[0036] (3) Heat the reaction system to 40°C, add cyclopentadiene solution, and stir the reaction at 40°C for 48 hours;

[0037] (3) The reaction system was subjected to pressure distillation and rectification to obtain a brownish-black liquid, which is the dicarbonylcyclopentadienyl cobalt complex.

[0038] Example 3

[0039] The preparation method of the dicarbonylcyclopentadienyl cobalt complex specifically includes the following steps:

[0040] (1) Dissolve 1g of cobalt octacarbonyl in dichloromethane presaturated with carbon monoxide and continuously pass carbon monoxide gas through it for protection to obtain the reaction system.

[0041] (2) Dissolve 10g of cyclopentadiene in dichloromethane and continuously pass carbon monoxide gas through it for protection to obtain a cyclopentadiene solution.

[0042] (3) Heat the reaction system to 40°C, add cyclopentadiene solution, and stir the reaction at 40°C for 48 hours;

[0043] (3) The reaction system was subjected to pressure distillation and rectification to obtain a brownish-black liquid, which is the dicarbonylcyclopentadienyl cobalt complex.

[0044] Example 4

[0045] The preparation method of the dicarbonylcyclopentadienyl cobalt complex specifically includes the following steps:

[0046] (1) Dissolve 1g of cobalt octacarbonyl in dichloromethane presaturated with carbon monoxide and continuously pass carbon monoxide gas through it for protection to obtain the reaction system.

[0047] (2) Dissolve 20g of cyclopentadiene in dichloromethane and continuously pass carbon monoxide gas through it for protection to obtain a cyclopentadiene solution, which is protected by carbon monoxide gas.

[0048] (3) Heat the reaction system to 40°C, add cyclopentadiene solution, and stir the reaction at 40°C for 48 hours;

[0049] (3) The reaction system was subjected to pressure distillation and rectification to obtain a brownish-black liquid, which is the dicarbonylcyclopentadienyl cobalt complex.

[0050] Performance testing

[0051] 1. NMR characterization

[0052] The nuclear magnetic resonance (NMR) spectrum of the dicarbonylcyclopentadienyl cobalt complex prepared in Example 1 is as follows: Figure 1 As shown.

[0053] Depend on Figure 1 As can be seen, Example 1 of the present invention successfully synthesized a dicarbonylcyclopentadienyl cobalt complex.

[0054] 2. Byproduct content and product yield

[0055] Dicarbonylcyclopentadienyl cobalt complexes were prepared according to the methods in Examples 1-4, and the reaction process was observed by intermittent sampling and central control monitoring. The content of by-products and the yield of the product (dicarbonylcyclopentadienyl cobalt complex) were analyzed.

[0056] The results are shown in Table 1.

[0057] Table 1. Byproduct content and product yield of the preparation methods in Examples 1-4

[0058] Preparation method Octacarbonyldicobalt:cyclopentadiene Byproduct content / % Product yield / % Example 1 2:1 1.0 95 Example 2 1:3 1.4 94 Example 3 1:10 2.5 80 Example 4 1:20 3.1 75

[0059] As shown in Table 1, the ratio of octacarbonyldicobalt to cyclopentadiene has a significant impact on the yield. The ratio of 2:1 results in the lowest by-product content and the highest product yield.

[0060] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a dicarbonylcyclopentadienyl cobalt complex, characterized in that, Specifically, the following steps are included: (1) Dissolve cobalt octacarbonyl in dichloromethane pre-saturated with carbon monoxide and continuously pass carbon monoxide gas for protection to obtain the reaction system; (2) Dissolve cyclopentadiene in dichloromethane and continuously pass carbon monoxide gas through it for protection to obtain a cyclopentadiene solution; (3) Add cyclopentadiene solution to the reaction system, heat and stir to react; (4) The reaction system is subjected to pressure distillation and rectification to obtain the dicarbonylcyclopentadienyl cobalt complex.

2. The method for preparing a dicarbonylcyclopentadienyl cobalt complex according to claim 1, characterized in that, In step (3), the mass ratio of the octacarbonyl dicobalt to cyclopentadiene is (2:1)-(1:20).

3. The method for preparing a dicarbonylcyclopentadienyl cobalt complex according to claim 2, characterized in that, In step (3), the mass ratio of the octacarbonyl dicobalt to cyclopentadiene is (2:1)-(1:3).

4. The method for preparing a dicarbonylcyclopentadienyl cobalt complex according to claim 3, characterized in that, In step (3), the mass ratio of the octacarbonyl dicobalt to cyclopentadiene is 2:

1.

5. The method for preparing a dicarbonylcyclopentadienyl cobalt complex according to claim 1, characterized in that, In step (3), the temperature is raised to 40°C.

6. The method for preparing a dicarbonylcyclopentadienyl cobalt complex according to claim 1, characterized in that, In step (3), the temperature of the stirring reaction is 40°C and the time is 10-48h.

7. A dicarbonylcyclopentadienyl cobalt complex prepared by any one of claims 1-6.

8. The application of a dicarbonylcyclopentadienyl cobalt complex prepared by any one of claims 1-6 in chemical vapor deposition and atomic layer deposition.

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