Ruthenium metal complex and preparation method and application thereof

Abstract

The invention discloses a ruthenium metal complex and a preparation method and application thereof, and belongs to the technical field of organic metal synthesis. The preparation method of the ruthenium metal complex specifically comprises the following steps: (1) under anhydrous and anaerobic conditions, adding ethylene glycol monoethyl ether and RuCl3.H2O into a reaction flask, introducing CO, heating, and reacting; (2) continuously heating, reacting and cooling; and (3) adding 3-chloro-2-methylpropan-1-ene, uniformly mixing, heating, stirring, cooling, adding a potassium tert-butoxide tetrahydrofuran solution, heating until boiling, stirring again, stopping heating, reacting, filtering, cleaning a filter cake with tetrahydrofuran, removing the solvent from the filtrate to obtain a reddish brown oily liquid, and condensing to obtain a Ru (tmm) (CO) 3 product, namely the ruthenium metal complex. The ruthenium metal complex prepared by the method has the advantages of high yield (62.8%), high purity (99.6%), low synthesis cost and simple synthesis steps.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organometallic synthesis, and more particularly to a ruthenium metal complex and a preparation method and application thereof. BACKGROUND

[0002] Ruthenium-containing metal precursors have wide applications in catalysis, thin film deposition technology, and precursor development.

[0003] Catalysis: Ruthenium complexes have remarkable effects in olefin metathesis and hydrogenation reactions, such as Grubbs catalysts, which are commonly used in organic synthesis. Ruthenium-based catalysts perform well in fuel cells, especially in oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR). Ruthenium-based catalysts have high activity in fuel cell electrode reactions, which can improve the performance and efficiency of fuel cells. Ruthenium-containing metal precursors are important raw materials for preparing high-performance catalysts. Ruthenium catalysts have wide applications in petrochemical industry, fine chemical industry, etc., which can improve the efficiency and selectivity of chemical reactions.

[0004] Thin film deposition technology is divided into chemical vapor deposition (CVD) and atomic layer deposition (ALD). Chemical vapor deposition (CVD): Ruthenium precursors such as Ru(CO)3(C6H8) and Ru(Cp)(CO)2 are widely used for the deposition of high-quality ruthenium thin films, which are used as diffusion barriers and electrode materials in semiconductor devices. Atomic layer deposition (ALD): Precursors such as Ru(Cp)2 and Ru(EtCp)2 are used to precisely control the thickness and composition of thin films, which are suitable for high-k gate dielectrics and metal gates.

[0005] In recent years, researchers have been developing new types of ruthenium precursors to improve the efficiency and quality of thin film deposition. For example, Ru(CO)3(C6H8) and Ru(Cp)(CO)2 have good volatility and stability at low temperatures. The development of high-purity ruthenium precursors is crucial for reducing impurities and defects in thin films, thereby improving the performance of semiconductor devices. In addition, by optimizing parameters such as deposition temperature, pressure, and reaction gas flow, the uniformity and adhesion of ruthenium thin films can be improved; the interface properties of ruthenium thin films and substrate materials are studied to improve the interface adhesion and electrical properties. Ruthenium-containing metal precursors have great potential in multiple fields, and their application prospects are broad as technology advances and environmental requirements improve.

[0006] As the market for ruthenium-containing metal precursors continues to expand, more and more companies are entering the field, and market competition is becoming increasingly fierce. Companies compete in product quality, price, service, and other aspects, prompting them to continuously improve their competitiveness. In order to gain an advantage in market competition, companies have increased their research and development efforts on ruthenium-containing metal precursors and continuously introduced new products and technologies. Technological innovation has become a key factor for companies in market competition.

[0007] In addition, with the increasing global emphasis on environmental protection, the production process of ruthenium-containing metal precursors needs to meet higher environmental protection requirements. Enterprises need to adopt green production technology to reduce pollutant emissions and reduce environmental impact. In the context of sustainable development, the development and application of ruthenium-containing metal precursors need to consider sustainable use of resources. Enterprises need to strengthen the recycling and reuse of raw materials, improve resource utilization efficiency, and achieve sustainable development.

[0008] In summary, ruthenium-containing metal precursors have made significant progress in research and development, application field expansion, market competition intensification, environmental protection and sustainable development, and their application in diffusion barrier layers, electrode materials and high dielectric constant materials will further enhance the performance and reliability of semiconductor devices. These characteristics collectively drive the continuous development and expansion of the market for ruthenium-containing metal precursors.

[0009] In the prior art (WO 2023 / 021064 A1), 45 g of triruthenium dodecacarbonyl and 3-chloro-2-methylprop-1-ene (315 g) were reacted in a solution of n-heptane (690 mL) at 60°C for 3 days, and then the intermediate product [Ru(MeC(CH2)2)Cl(CO)3] was precipitated by filtration and desolventization. Then it was dissolved with tetrahydrofuran (50 g, 1.0 eq), followed by the addition of 164 g of potassium tert-butoxide tetrahydrofuran solution (about 181 mL = 181 mmol), and the reaction was heated to boiling with stirring for 4 h, then the heating was stopped, and the reaction was carried out at room temperature overnight. After filtration and desolventization, the target product was obtained.

[0010] However, the existing technology has the following problems:

[0011] 1. Low yield: The highest yield of the existing synthesis method is only 34%.

[0012] The disadvantages of low yield mainly include the following aspects: ① Raw material waste: Low yield means that a large amount of raw materials are consumed in the process of synthesizing ruthenium-containing precursors without being converted into effective products. This leads to low utilization of raw materials and increases the cost of raw materials per unit of product. For some rare and expensive raw materials, this waste is more obvious, which greatly increases the cost of preparing ruthenium-containing precursors and reduces the market competitiveness of the product. ② Energy and resource consumption: Low-yield synthesis processes often require more energy and resource inputs. In order to obtain a certain amount of target product, longer reaction time, higher temperature or pressure conditions may be required, which will consume more energy. At the same time, the consumption of various auxiliary materials, reagents and other resources in the production process will also increase accordingly, not only increasing the production cost, but also causing greater environmental burden. ③ Performance limitations: Due to low yield, it may not be possible to obtain ruthenium-containing precursors with high enough purity or ideal structure, which will affect their subsequent application performance. For example, in some catalytic reactions, the purity and structure of the precursor have an important influence on the activity, selectivity and other properties of the catalyst. If the yield of the precursor is low and the quality is not good, the performance of the catalyst may not meet the expected requirements, affecting the efficiency and effectiveness of related chemical reactions.

[0013] 2. Low purity: The existing synthesis method has an ICP (Inductively Coupled Plasma) purity of 42%, which cannot be directly applied to the semiconductor industry. Because even trace amounts of impurities can have a significant impact on semiconductor devices.

[0014] The disadvantages of low purity mainly include the following aspects: ① Catalyst performance decline: If ruthenium is used to prepare catalysts such as ammonia synthesis catalysts, low-purity precursors will contain more impurities in the catalyst. These impurities may cover the active sites, preventing reactants from fully contacting the active sites, thereby reducing the activity and selectivity of the catalyst and affecting the catalytic effect and product yield. ② Material performance impairment: In the preparation of ruthenium-containing electronic materials, optical materials and other functional materials, low-purity precursors will introduce impurities that will destroy the crystal structure of the materials and affect their electrical, optical and other properties, resulting in performance indicators that do not meet the expected requirements. ③ Chemical stability deterioration: The presence of impurities may react with ruthenium or promote oxidation, reduction and other chemical reactions of ruthenium in specific use environments, causing the chemical stability of the product to decline. For example, in high-temperature, humid or corrosive environments, impurities may accelerate the corrosion or deterioration of ruthenium. ④ Physical stability affected: Impurities may change the physical properties of the product, such as hardness, toughness, melting point, etc. In ruthenium-containing alloy or coating materials, impurities may cause the mechanical properties of the material to decline, resulting in cracking, peeling and other phenomena, affecting the service life of the product.

[0015] 3. High synthesis cost: The existing synthesis method uses very expensive triruthenium dodecacarbonyl as raw material, increasing the cost of synthesis.

[0016] The disadvantages of high synthesis cost mainly include the following aspects: ① Raw material cost: Ruthenium is a rare metal with limited reserves in nature, which makes its raw material cost relatively high. For example, compared with some common transition metals such as iron and copper, the price of ruthenium is much higher, which directly leads to an increase in the synthesis cost of ruthenium-containing precursors. ② Complex preparation process: The synthesis process of ruthenium-containing precursors often involves complex chemical reactions and delicate operation steps. For example, the preparation of some ruthenium-containing precursors requires strict temperature, pressure, and atmosphere conditions, and the use of special reagents and equipment. This not only increases the difficulty of the preparation process, but also increases the maintenance cost and energy consumption of the equipment, further increasing the production cost. ③ Difficulty in purification: Due to the similar physical and chemical properties of ruthenium and other impurity elements, it is difficult to completely separate them from other impurities during extraction and purification, which requires more complex separation techniques and higher purification times, increasing production costs. At the same time, the yield loss in the purification process also increases the consumption of raw materials, further increasing the cost. ④ Limited scale production: Currently, the synthesis process of ruthenium-containing precursors is mostly in the laboratory research and small-batch production stage, and has not yet achieved large-scale industrial production. Small-scale production has low production efficiency, and the fixed cost is distributed to each product at a higher cost, which is also an important reason for the high synthesis cost of ruthenium-containing precursors. ⑤ Market supply and demand imbalance: Due to the relatively narrow application range of ruthenium, mainly in some specific high-end fields such as electronics, chemical industry, aerospace, etc., the market demand is relatively small. This makes it difficult to expand the production scale of ruthenium-containing precursors, and it is impossible to reduce costs through large-scale production, thus keeping the price high. In summary, the high synthesis cost of ruthenium-containing precursors is the result of the combined action of multiple factors. These factors limit the widespread application and large-scale production of ruthenium-containing precursors, and also prompt researchers to continuously explore new synthesis methods and processes to reduce the synthesis cost.

[0017] 4. Complex synthesis steps: After synthesizing the intermediate [Ru(MeC(CH2)2)Cl(CO)3], the existing synthesis method requires filtering and desolventizing to precipitate the intermediate [Ru(MeC(CH2)2)Cl(CO)3], and then dissolving it in the next reaction, which is extremely cumbersome.

[0018] The disadvantages of complicated synthesis steps mainly lie in: unstable product quality, complicated synthesis steps can produce multiple intermediate products, and the quality of each intermediate product will affect the quality of the final product. If the purity of the intermediate product is not enough, the structure is unstable or there are impurities, it will cause the quality and performance of the final product to decline. For example, when synthesizing a precursor containing ruthenium nanoparticles, if the ruthenium ions in the intermediate product are not completely reduced, it may cause the final nanoparticles to have uneven particle size and low crystallinity, affecting their catalytic performance. Complex synthesis process is easy to cause side reactions, generating some unnecessary by-products. These by-products may be difficult to separate from the target product, thereby affecting the purity and quality of the product. Moreover, the occurrence of side reactions will also reduce the utilization rate of raw materials and increase production costs. Therefore, in practical applications, new synthesis methods and process conditions need to be continuously explored to overcome these shortcomings and improve the synthesis efficiency and quality of the ruthenium-containing precursor.

[0019] Therefore, how to quickly and simply prepare a ruthenium metal complex is a problem that those skilled in the art need to solve. SUMMARY

[0020] Therefore, the purpose of the present application is to provide a ruthenium metal complex and its preparation method and application to solve the deficiencies in the prior art.

[0021] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0022] A preparation method of a ruthenium metal complex, specifically comprising the following steps:

[0023] (1) Under anhydrous and anaerobic conditions, add ethylene glycol monoethyl ether and RuCl3·H2O into a reaction bottle, pass CO, heat, react, and obtain a reaction liquid;

[0024] (2) Continue to heat the reaction liquid, react, stop heating, and cool;

[0025] (3) Add 3-chloro-2-methylprop-1-ene into the reaction liquid, mix uniformly, heat, stir, cool, add potassium tert-butoxide tetrahydrofuran solution, heat to boiling, stir again, stop heating, react, filter, wash the filter cake with tetrahydrofuran, remove the solvent from the filtrate, obtain a red-brown oily liquid, and condense to obtain Ru(tmm)(CO)3 product, which is the ruthenium metal complex.

[0026] The reaction equation of the present application is:

[0027]

[0028] The innovation of the present application lies in:

[0029] 1. Temperature control, temperature control during the synthesis of dodecacarbonyl triruthenium and the final product, temperature control determines whether the invention can successfully synthesize.

[0030] 2. Control of reaction time, through repeated comparison of experimental data, it is found that the reaction time data provided by the invention is the shortest and the best reaction time required for the reaction.

[0031] 3. Synthesis method, the invention changes the specific operation of the existing synthesis method, so that the reaction is simpler, easier to operate, and the yield is successfully improved.

[0032] 4. Selection of solvent, through repeated solvent replacement experiments, it is found that the solvent selected by the invention is the most suitable solvent for the invention.

[0033] Further, in the above step (1), the amount ratio of ethylene glycol monoethyl ether and RuCl3·H2O is 2.5L:(50-100)g.

[0034] Further, in the above step (1), the temperature is raised to 70-90℃; the reaction time is 1.5-3h.

[0035] Further, in the above step (2), the temperature is raised to 120-150℃; the reaction time is 30-60min; and the temperature is cooled to room temperature.

[0036] Further, in the above step (3), the amount ratio of 3-chloro-2-methylprop-1-ene and potassium tert-butoxide tetrahydrofuran solution is 315g:164g.

[0037] Further, in the above step (3), the temperature is raised to 90-100℃; the stirring time is 18-20h.

[0038] Further, in the above step (3), the temperature is cooled to room temperature; and the stirring time is 3-4h.

[0039] Further, in the above step (3), the reaction temperature is room temperature, and the time is 8-12h.

[0040] The invention also claims a ruthenium metal complex prepared by the above preparation method.

[0041] The invention also claims the application of a ruthenium metal complex prepared by the above preparation method in catalysis, thin film deposition and precursor development.

[0042] Through the above technical solution, compared with the prior art, the beneficial effects of the invention are as follows:

[0043] 1. High yield: the highest yield of the existing synthesis method is only 34%; while the synthesis yield of the invention is as high as 62.8%.

[0044] High synthesis yield has many advantages, which are analyzed as follows: ① Reduce production cost: high yield means that under the same raw material input and production conditions, more target products can be obtained. For ruthenium, a noble metal element, the cost of raw materials is usually high, and improving the synthesis yield can effectively reduce the amount of raw materials needed per unit product, thereby reducing production costs. ② Improve production efficiency: high-yield synthesis process can obtain more products in a shorter time, thereby improving the overall production efficiency. This is crucial for the production and operation of enterprises, as it can meet more market demand in the same time, increase product output and supply, and reduce production cycle, speed up product delivery, and improve capital turnover efficiency and economic benefits. ③ Promote process optimization and innovation: in the process of pursuing high yield, researchers need to continuously study the mechanism and influencing factors of synthesis reaction, explore more efficient and environmentally friendly synthesis methods and process conditions. This helps to promote the innovation and development of ruthenium precursor synthesis technology and provides new ideas and methods for related research. At the same time, high-yield synthesis process can also support the technical upgrading and transformation of enterprises and improve the core competitiveness of enterprises. In summary, high yield of ruthenium-containing precursors has multiple advantages such as reducing costs, improving production efficiency, and promoting innovation, which not only improves the economic benefits and market competitiveness of enterprises, but also promotes the continuous development and progress of ruthenium precursor synthesis technology.

[0045] 2. High purity: the existing synthesis method has an ICP (Inductively Coupled Plasma, Inductively Coupled Plasma technology) purity of 42%, which cannot be directly applied to the semiconductor industry, because even trace amounts of impurities can have a significant impact on semiconductor devices; while the ICP purity of the present application is as high as 99.6%, which can be directly used in atomic layer deposition (ALD) and the semiconductor industry.

[0046] High purity synthesis has many advantages, which are described in detail as follows: ① For ruthenium-containing electronic materials, high-purity precursors help to obtain purer and more complete-structure materials, improving the electrical, optical and other properties of the materials, such as increasing conductivity, reducing resistivity, enhancing photoelectric conversion efficiency, etc., thereby improving the performance and reliability of electronic equipment. In the preparation of ruthenium-based catalysts, such as ammonia synthesis catalysts, high-purity precursors can reduce the coverage and interference of impurities on active sites, making the catalyst have higher activity and selectivity, thereby improving the catalytic efficiency and product yield. For example, the ammonia synthesis catalyst prepared by using ruthenium acetate as a precursor has high ammonia synthesis activity and thermal stability, and is free of harmful impurities such as chloride ions and explosive components such as nitrate, has a higher cost performance, and has a better application prospect. In the preparation of ruthenium-containing ceramic materials, high-purity precursors can make the microstructure of the ceramic more uniform and dense, reduce defects such as pores and cracks, and improve the mechanical properties of the ceramic, such as hardness, toughness, wear resistance, and chemical stability such as high temperature resistance and corrosion resistance. ② Reduce the purification steps: high-purity ruthenium-containing precursors do not need complex purification operations and can be directly used for subsequent product preparation, saving time and cost and improving production efficiency. For example, if the purity of the precursor is low, multiple purification steps such as chemical precipitation, solvent extraction, and chromatographic separation may be required, while high-purity precursors can avoid these tedious processes. ③ Expand application fields: in some high-end scientific and technological fields that require extremely high purity of materials, such as aerospace, national defense and military industry, and electronic information, high-purity ruthenium-containing precursors can meet the demand for high-performance materials in these fields, providing strong support for the technological development and industrial upgrading of our country in these key fields. With the continuous development of science and technology, the demand for new materials is increasing. High-purity ruthenium-containing precursors provide a better foundation for the research and development of new ruthenium-containing materials, helping to develop new materials with unique properties and application value, and promoting the progress of materials science. In summary, high-purity synthesis of ruthenium-containing precursors has the advantages of improving product performance, simplifying subsequent processing technology, improving the stability and consistency of product quality, and expanding application fields, which is of great significance for promoting the development of ruthenium-related industries and technological progress.

[0047] 3. Low synthesis cost: the existing synthesis method uses very expensive triruthenium dodecacarbonyl as raw material, increasing the cost of synthesis; while the present application greatly reduces the synthesis cost by synthesizing the expensive triruthenium dodecacarbonyl first and then synthesizing the target product through one-pot synthesis. In addition, the existing synthesis method takes three days to synthesize the intermediate product [Ru(MeC(CH2)2)Cl(CO)3], while the present application only takes one day to synthesize the intermediate product [Ru(MeC(CH2)2)Cl(CO)3], and the total reaction time for synthesizing triruthenium dodecacarbonyl is longer, thereby reducing the labor cost and time cost.

[0048] The advantages of low synthesis cost mainly include the following aspects: ① raw material cost: the content of ruthenium in the earth's crust is relatively high, which makes the raw material cost relatively low. Compared with other rare metals, ruthenium is less difficult to obtain and has a relatively low price, thereby reducing the overall synthesis cost of the ruthenium-containing precursor. ② Simplified preparation process: with the continuous development of science and technology, the synthesis process of the ruthenium-containing precursor has been continuously optimized and improved. Some new synthesis methods can be carried out under relatively mild conditions, reducing the dependence on expensive equipment and complex operation steps, making the preparation process simpler and more efficient, and further reducing the production cost. ③ Improve production efficiency: the ruthenium-containing precursor with low synthesis cost usually has good reactivity and solubility, which can participate in chemical reaction faster, thereby improving the production efficiency. This not only helps to shorten the production cycle and increase the yield, but also reduces the energy consumption and equipment loss per unit product and other costs. ④ Stable product quality: low-cost synthesis process does not mean sacrificing product quality. On the contrary, by optimizing the synthesis method and strictly controlling the reaction conditions, the ruthenium-containing precursor with stable quality and excellent performance can be prepared. This helps to improve the consistency and reliability of the product, reduce the rate of defective products, and reduce the cost loss caused by quality problems. ⑤ Beneficial to large-scale production: due to the low synthesis cost of the ruthenium-containing precursor, enterprises can carry out large-scale production, thereby realizing the scale economy effect. With the increase of production, the cost per unit product will be further reduced, improving the market competitiveness of enterprises. At the same time, large-scale production can also meet the growing demand of the market for ruthenium-containing catalysts and other products. In summary, the low synthesis cost of the ruthenium-containing precursor has many advantages, which not only helps to reduce the production cost of ruthenium-containing catalysts and other related products, improves the economic benefit of enterprises, but also promotes the wide application of ruthenium in various fields and promotes the development of related industries.

[0049] 4. Simple synthesis steps: the existing synthesis method synthesizes the intermediate product [Ru(MeC(CH2)2)Cl(CO)3] and then precipitates the intermediate product [Ru(MeC(CH2)2)Cl(CO)3] by filtering and desolventizing, and then dissolves it in the next reaction, which is extremely cumbersome; the one-pot method of the present application is used to synthesize the intermediate product [Ru(MeC(CH2)2)Cl(CO)3], and then potassium tert-butoxide tetrahydrofuran solution is directly added to the reaction liquid, which is very simple to operate, and greatly reduces the labor cost and time cost of synthesis.

[0050] The advantages of simple synthesis steps mainly include the following aspects: ① improving production efficiency: simple synthesis steps mean shorter production cycles and higher production efficiency. In industrial applications, this can significantly reduce production costs, improve production capacity, and meet the needs of large-scale production. ② reducing technical difficulty: complex synthesis steps often require advanced technical support and professional equipment, while simple synthesis steps reduce the technical threshold, allowing more laboratories and enterprises to master and produce ruthenium-containing precursors. This helps to promote technological innovation and application expansion in this field. ③ enhancing market competitiveness: due to the cost advantage and technical advantage brought by simple synthesis steps, enterprises that adopt simple synthesis steps have more competitiveness in the market. This helps to promote the development and growth of the ruthenium-containing precursor-related industry. ④ improving product quality: simple synthesis steps help to achieve more precise process control, thereby reducing the introduction of impurities and improving product purity. This is particularly important for application fields that require high-purity ruthenium-containing precursors, such as electronics, pharmaceuticals, etc. In summary, the advantages of simple synthesis steps for ruthenium-containing precursors include improving production efficiency, reducing technical difficulty, improving product quality, and enhancing market competitiveness. These advantages collectively promote the rapid development and widespread application of the ruthenium-containing precursor-related field. DETAILED DESCRIPTION

[0051] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0052] Terminology explanation:

[0053] Synthesis: Synthesis (chemical synthesis) refers to the process of converting raw materials into target compounds with specific chemical structures and properties through chemical reactions. In chemical synthesis, multiple steps are usually involved, including the selection of reaction conditions, the order of reagent addition, reaction time, temperature, etc.

[0054] One-pot synthesis: One-pot synthesis is a method of synthesizing compounds, which requires mixing all raw materials and reagents in one container, and then converting them into the desired compounds through chemical reactions. This method is often used to prepare high-purity compounds, as it can reduce unnecessary reactions and the generation of impurities.

[0055] Filtration: Filtration is an operation in which liquid (or gas) in a suspension (or gas containing solid particles) is filtered through a medium under the action of a driving force or other external force, and solid particles and other substances are retained by the filter medium, thereby separating the solid and other substances from the liquid (or gas).

[0056] Solvent removal: Solvent removal (removal of solvent) is a chemical method used to remove or separate solvents contained in certain substances. In some scientific experiments, solvent removal is used to separate one or more organic compounds from a mixture, thus separating them from other substances. Solvent removal also has wide applications in laboratory and industrial production.

[0057] Example 1

[0058] The preparation method of ruthenium metal complexes specifically includes the following steps:

[0059] (1) Under anhydrous and oxygen-free conditions, 2.5L of ethylene glycol monoethyl ether and RuCl3·H2O (50g, 0.191mol) were added to a 5L reaction flask. Then CO was passed into the reaction solution to raise the temperature of the reaction solution to 90℃. The reaction solution was obtained after 3h.

[0060] (2) Continue heating the reaction solution to 150°C, react for 60 minutes, then stop heating and allow the reaction solution to cool naturally to room temperature;

[0061] (3) Add 315g of 3-chloro-2-methylprop-1-ene to the reaction solution and mix well. Stir the reaction solution at 100℃ for 20h, then cool to room temperature. Add 164g of potassium tert-butoxide tetrahydrofuran solution (about 181mL = 181mmol) to the reaction solution. Heat the reaction solution to boiling and stir for 4h, then stop heating. React at room temperature for 12h. Prepare a 1L sand core funnel for filtration, which contains 50g of dry diatomaceous earth. Wash the filter cake with 200mL of tetrahydrofuran. The filtrate is dark orange and the filter cake is orange-yellow. Remove the solvent from the filtrate to obtain a reddish-brown oily liquid.

[0062] (4) The reddish-brown oily liquid was condensed at 90°C into a clean bottle cooled with liquid nitrogen to obtain ICP (Inductively Coupled Plasma) purity of 99.6%, and NMR (nuclear magnetic resonance) 1 27.2 g of Ru(tmm)(CO)3 product with a purity of 99.7% (H NMR) was obtained, with a yield of 62.8%.

[0063] 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 ruthenium metal complex, characterized in that, Specifically, the following steps are included: (1) Under anhydrous and oxygen-free conditions, ethylene glycol monoethyl ether and RuCl3·H2O were added to the reaction flask, CO was passed through, the temperature was raised, and the reaction was carried out to obtain the reaction solution. (2) Continue heating the reaction solution to allow the reaction to proceed, then stop heating and allow it to cool. (3) Add 3-chloro-2-methylprop-1-ene to the reaction solution, mix well, heat, stir, cool, add potassium tert-butoxide tetrahydrofuran solution, heat to boiling, stir again, stop heating, react, filter, wash the filter cake with tetrahydrofuran, remove solvent from the filtrate, and obtain a reddish-brown oily liquid. Condense to obtain Ru(tmm)(CO)3 product, which is the ruthenium metal complex.

2. The method for preparing a ruthenium metal complex according to claim 1, characterized in that, In step (1), the ratio of ethylene glycol monoethyl ether to RuCl3·H2O is 2.5L:(50~100)g.

3. The method for preparing a ruthenium metal complex according to claim 1, characterized in that, In step (1), the temperature is raised to 70-90°C; the reaction time is 1.5-3 hours.

4. The method for preparing a ruthenium metal complex according to claim 1, characterized in that, In step (2), the temperature is raised to 120-150°C; the reaction time is 30-60 min; and the temperature is cooled to room temperature.

5. The method for preparing a ruthenium metal complex according to claim 1, characterized in that, In step (3), the ratio of the amount of 3-chloro-2-methylprop-1-ene to potassium tert-butoxide tetrahydrofuran solution is 315g:164g.

6. The method for preparing a ruthenium metal complex according to claim 1, characterized in that, In step (3), the temperature is raised to 90-100°C; the stirring time is 18-20 hours.

7. The method for preparing a ruthenium metal complex according to claim 1, characterized in that, In step (3), the cooling to room temperature is carried out; the stirring time is 3 to 4 hours.

8. The method for preparing a ruthenium metal complex according to claim 1, characterized in that, In step (3), the reaction is carried out at room temperature for 8 to 12 hours.

9. A ruthenium metal complex prepared by the preparation method according to any one of claims 1-8.

10. The application of a ruthenium metal complex prepared by any one of claims 1-8 in catalysis, thin film deposition and precursor development.

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