CN111468191A - Synthetic method of ruthenium carbene catalyst - Google Patents
Synthetic method of ruthenium carbene catalyst Download PDFInfo
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- CN111468191A CN111468191A CN202010456680.3A CN202010456680A CN111468191A CN 111468191 A CN111468191 A CN 111468191A CN 202010456680 A CN202010456680 A CN 202010456680A CN 111468191 A CN111468191 A CN 111468191A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
Abstract
The invention relates to a synthesis method of a ruthenium carbene catalyst, which comprises the following steps: (1) adding benzyl halide and triphenylphosphine into a reactor, reacting in a medium, and reacting the obtained reaction product under the action of strong alkali to obtain an intermediate product I; (2) reacting the intermediate product I with triphenylphosphine ruthenium chloride in a solvent, replacing triphenylphosphine with tricyclohexylphosphine, filtering and washing to obtain a ruthenium carbene complex precursor; (3) and carrying out complex addition reaction on the ruthenium carbene complex precursor and the functional ligand to obtain the target product ruthenium carbene catalyst. Compared with the prior art, the method has the characteristics of high-efficiency control of reaction speed, short preparation period, simplicity in operation, stable process, environmental friendliness, good atom economy and the like, and has a wide application prospect in the aspect of industrial amplification.
Description
Technical Field
The invention belongs to the technical field of preparation of ruthenium carbene catalysts, and relates to a ruthenium carbene catalyst.
Background
Transition metal carbene complexes have attracted considerable research interest due to their unique structures, reaction characteristics, and applications in organic synthesis and catalytic reactions. Metal carbenes can be viewed as free-based metal complexes formed by complexing a free-state carbene with a metal. Free carbene is an unstable intermediate with short service life and high activity, but after the free carbene is complexed with metal to form metal carbene, the stability is improved, and the corresponding reactivity is also improved. Since the advent of the first metal carbene complexes, numerous methods of synthesizing metal carbenes have been developed, which can be broadly divided into three categories: 1. conversion from a metal-carbon bond; 2. addition of a carbene source to a metal complex; 3. conversion from the existing carbene complex.
Through research on the prior documents, the synthesis of the ruthenium carbene catalyst is basically realized by changing a ligand and an atom coordinated with a central atom ruthenium so as to improve the properties of the catalyst, such as catalytic efficiency, universality of use, stability, recoverability and the like.
In 1996, the Grubbs group used phenyldiazomethane (PhCH (N)2) And first RuCl was generated at-78 deg.C2(＝CHPh)(PPh3)2Reuse of PCy3Replacement of PPh3The first compound was synthesized (Schwab, P.; Grubbs, R.H.; Ziller, J.W.J.am.chem.Soc.1996,118.100) via the reaction scheme:
however, the starting material in this process is very explosive phenyldiazomethane (PhCH (N)2) The reaction temperature must be well controlled at extremely low temperatures (-78 ℃), the operating procedure is demanding and can only be applied to small quantities.
1997, Grubbs group developed a more practical method by first synthesizing the ruthenium hydride, RuCl2(H2)(H2)2(PCy3)2Then with RuCl which is a hydride of ruthenium2(H2)(H2)2(PCy3)2And an excess of olefin and then reacted with PhCHCl2Reaction to obtain RuCl2(＝CHPh)(PPh3)2。
The method has safe and convenient operation steps compared with the above method, but has a serious problem that the product RuCl is generated2(＝CHPh)(PPh3)2Metathesis reactions with an excessive amount of olefins in the system occur, which not only lowers the reaction yield but also makes separation of products difficult.
Milstein et al 2001 used a sulfoylide as a carbene donor with RuCl at-30 deg.C2(PPh3)33Reacted and then used with PCy at room temperature3In situ substitution of PPh3The target product is obtained, and the separation yield reaches 96%. The reaction conditions are mild, few by-products are produced, high separation yield can be achieved, and the method can be used for synthesizing various alkylene compounds, such as: phenylalkylene (═ CH-Ph), vinylalkylene (═ CH-CH ═ CH)2) Methoxycarbonylalkylene (═ CH-CO)2CH3) And alkylene (═ CHCH)3,＝CH2). The synthesis of sulfur ylide can use methylene chloride solution of diphenyl sulfur and benzyl bromide, AgBF4Or Me3SiOTf reaction.
The method of the Milstein group has clear advantages over the methods of the Grubbs group mentioned previously: firstly, the reaction conditions are milder than those of the first method, and the safety performance is high; however, the sulfur ylide preparation is difficult, sensitive to water and oxygen, and very strict in operation requirements, so that the method is also difficult to be applied to industrial production.
In 2004, Nolan et al developed a new synthesis of ruthenium carbene complexes, which was derived from RuCl2(PPh3)3Starting from this, an indenyl ruthenium carbene complex is synthesized by cyclization with alkynol ligands and then subjected to an olefin exchange reaction with styrene to give Grubbs's catalyst. The method utilizes excessive styrene to carry out olefin exchange reaction (20 equivalents), and the post-treatment is complex and is not beneficial to industrial production.
The present invention has been developed in view of the above problems occurring in the preparation of ruthenium carbene catalysts.
Disclosure of Invention
The invention aims to provide a synthesis method of a ruthenium carbene catalyst, which comprises the steps of introducing a benzylidene coordination group in a phosphorus ylide mode to synthesize a series of ruthenium metal carbene catalyst precursors, carrying out ligand exchange reaction with tricyclohexylphosphine to obtain a corresponding ruthenium carbene catalyst containing tricyclohexylphosphine, and finally synthesizing a series of ruthenium carbene catalysts with a corresponding functional catalytic ligand. The new synthesis method has the characteristics of high-efficiency control of reaction speed, short preparation period, simple operation, stable process, environmental friendliness, good atom economy and the like, and has a wide application prospect in the aspect of industrial amplification.
The purpose of the invention can be realized by the following technical scheme:
a synthetic method of a ruthenium carbene catalyst comprises the following steps:
(1) adding benzyl halide and triphenylphosphine into a reactor, reacting in a medium, and reacting the obtained reaction product under the action of strong alkali to obtain an intermediate product I (phosphorus ylide reagent);
(2) reacting the intermediate product I with triphenylphosphine ruthenium chloride in a solvent, replacing triphenylphosphine with tricyclohexylphosphine, filtering and washing to obtain a ruthenium carbene complex precursor;
(3) and carrying out complex addition reaction on the ruthenium carbene complex precursor and the functional ligand to obtain the target product ruthenium carbene catalyst.
The specific preparation process refers to the following steps:
further, in the step (1), the benzyl halide is benzyl bromide or benzyl chloride, R1May also be-CH3、-CH(CH3)2、-CF3、-NO2、-NH2、-N(CH3)2And the like, which may affect the chemical environment surrounding the catalyst body metal.
Further, in the step (1), the molar ratio of the benzyl halide to the triphenylphosphine is 1:1-1: 10.
Further, in the step (1), the medium used in the reaction is one or a mixture of more of 1, 4-dioxane, tetrahydrofuran, anhydrous ether or methyl tert-butyl ether.
Further, in the step (1), the reaction time is 2-20 h.
Further, in the step (1), the strong base is one or a mixture of more of potassium tert-butoxide, n-butyllithium and sodium methoxide.
Further, in the step (2), the feeding molar ratio of the intermediate product I to the triphenylphosphine ruthenium chloride is 1:1-1: 10.
Further, in the step (2), the solvent is one or more of toluene, cyclohexane, anhydrous ether or tetrahydrofuran.
Further, in the step (2), the reaction temperature is 0-100 ℃.
Further, in the step (2), the ruthenium carbene complex precursor obtained after filtration and washing is subjected to recrystallization purification treatment to obtain a high-purity ruthenium carbene complex precursor. Preferably, the recrystallization purification reagent is one selected from toluene/methanol, toluene/n-hexane, anhydrous ether/n-pentane, anhydrous ether/petroleum ether, ethyl acetate/petroleum ether, dichloromethane/methanol and other mixed solvents, and the ratio of the good solvent to the poor solvent in the recrystallization purification reagent is 1:5-1: 100.
Further, in the step (3), the feeding molar ratio of the ruthenium carbene complex precursor to the functional ligand is 1:1-1: 10.
Further, in the step (3), the complex addition reaction is carried out in a reaction medium, and the reaction medium is selected from one or more of 1, 4-dioxane, tetrahydrofuran, anhydrous ether or methyl tert-butyl ether.
Further, in the step (3), the temperature of the complex addition reaction is 25-110 ℃.
Further, in the step (3), the functional ligand is one or more of pyridine and its substitute, alkyl and its substituted phosphine ligand, aromatic and its substituted phosphine ligand, benzylidene alkyl ether, chain imine, imidazole hydrochloride (NHCs), chloroform carbene adduct, nitrogen heterocyclic carbene adduct, phenol oxygen imine ligand, chelate indenyl ligand and other functional compounds which have temperature, light or chemical response and can be complexed with active metal ruthenium. .
Compared with the prior art, the invention has the following advantages:
1) the reaction condition is mild, and the reaction controllability is high;
2) the preparation method is simple to operate, and the raw materials are convenient and easy to obtain. .
3) The atom utilization rate is high, and the metal utilization rate is particularly remarkable.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, chloroform carbene adducts and imidazole hydrochloride salts can be prepared by referring to the following documents: chem., vol.66, No.23,2001. The remainder, unless otherwise indicated, are all conventional commercial materials or conventional processing techniques in the art.
Example 1: synthesis of Grubbs catalyst
Step 1) C6H5CH＝PPh3Preparation of
To a 100ml round bottom flask was added 20.7g of triphenylphosphine (PPh)3) And 50ml of toluene, stirring at 40 ℃ for 0.5 hour until the triphenylphosphine is completely dissolved, and slowly adding 6.8g of benzyl bromide (C) dropwise into the above system by using a constant pressure dropping funnel6H5CH2Br) and keeping the temperature of 40 ℃ for reacting for 4 hours, gradually suspending the reaction liquid, and observing that a large amount of white solid is generated in the reaction system. Filtering and washing to obtain white solid C6H5CH2-PPh3]Br was about 16.5g, yield 96%.1H NMR(C6D6,500M):7.63-7.70(m,6H),7.01-7.71(m,7H),6.92-6.96(m,6H),6.67-6.69(m,1H),2.85(d,1H),；31P NMR(C6D6,200M):7.9(s,PCy3)。
A100 ml Schlenk reaction flask was charged with 4.32g of [ C ]6H5CH2-PPh3]Br, replacing air for 3 times, injecting 40ml of anhydrous ether, injecting 7.5ml of n-butyllithium-n-hexane solution (1.6M) into the system under the condition of ice-water bath, stirring at room temperature for 2 hours, stopping reaction when the reaction liquid gradually becomes orange-red, and performing vacuum filtration to obtain orange-red liquid, namely C6H5CH＝PPh3The reaction solution can be directly put into the next reaction.31P NMR(C6D6,200M):9.7(s,PCy3)。
Step 2) preparation of ruthenium carbene complex precursor (Grubbs I catalyst)
Another 100ml Schlenk reaction flask was put into a glove box with 4.5g RuCl2(PPh3)3Adding 50ml of dry dichloromethane in nitrogen atmosphere, and slowly adding C prepared in the step (1) at-30 DEG C6H5CH＝PPh3(2 times equivalent by [ C ]6H5CH2-PPh3]Br meter), the color of the reaction liquid is gradually deepened,after stirring and reacting for 2 hours, 5.6g of PCy was added3The reaction was returned to room temperature and stirred for 1 hour to terminate the reaction. The reaction solvent was removed under vacuum, recrystallized, washed and filtered to give Grubbs I catalyst, 2.6g, 63% yield.1H NMR(C6D6,500M):20.62(s,1H),8.73(d,2H),7.30(br,3H),2.93-2.80,1.98-1.17(all m,66H)；31P NMR(C6D6,200M):36.3(s,PCy3)。
Step 3) preparation of functional ruthenium carbene catalyst (Grubbs II catalyst)
A100 ml Schlenk reaction flask was taken, and 1.6 g of Grubbs I catalyst and 1.7g of chloroform-carbene adduct were sequentially added, air was replaced 3 times, 60 ml of toluene was added, the reaction was allowed to proceed at 70 ℃ for 4 hours, T L C was observed to observe that the reaction was near the end, the reaction solvent was removed in vacuo, and filtration and washing were carried out to obtain 1.4g of Grubbs II catalyst, with a yield of 82%.1H NMR(C6D6,500M):19.03(s,1H),7.26(t,2H),7.04-6.80(m,7H),3.84-3.65(br,4H),2.66-0.66(m,51H)；31P NMR(C6D6,200M):28.9(s,PCy3)。
Example 2:
in comparison with example 1, which is largely identical, the benzyl bromide in step 2) is exchanged for benzyl chloride, and a white solid [ C ] is likewise obtained6H5CH2-PPh3]Cl was about 10.3g, yield 67%.1H NMR(C6D6,500M):7.69-7.75(m,9H),7.58-7.61(m,6H),7.18-7.20(m,1H),7.07-7.10(m,4H),5.45(d,2H),；31P NMR(C6D6,200M):23.6(s,PCy3)。
3.88g of [ C ] was added to a 100ml Schlenk reaction flask6H5CH2-PPh3]Replacing air with Cl for 3 times, adding 40ml of anhydrous ether, adding 7.5ml of n-butyllithium-n-hexane solution (1.6M) into the system under the condition of ice-water bath, stirring at room temperature for 2 hours, stopping reaction when the reaction solution gradually becomes orange-red, and vacuum filtering to obtain orange-redLiquid, i.e. as C6H5CH＝PPh3The reaction solution can be directly put into the next reaction.31P NMR(C6D6,200M):9.7(s,PCy3)。
Further complexation with ruthenium triphenylphosphine chloride gave similar yields of Grubbs generation 1 catalyst.
Example 3:
compared with example 1, largely identical, the reaction medium dichloromethane in step 2) is replaced by methyltetrahydrofuran.
Another 100ml Schlenk reaction flask was put into a glove box with 4.5g RuCl2(PPh3)3Adding 50ml of dry methyl tetrahydrofuran under nitrogen atmosphere, and slowly adding C prepared in the step (1) at-30 DEG C6H5CH＝PPh3(2 times equivalent by [ C ]6H5CH2-PPh3]X is Cl or Br), the color of the reaction solution gradually deepens, and 5.6g of PCy is added after the reaction is stirred for 2 hours3The reaction was returned to room temperature and stirred for 1 hour to terminate the reaction. The reaction solvent was removed under vacuum, recrystallized, washed and filtered to give Grubbs I catalyst, 1.7g, 41% yield.
Example 4:
comparing with example 1, most of which are the same, C in step 2)6H5CH＝PPh3The amount of (A) is 10 times equivalent.
Another 100ml Schlenk reaction flask was put into a glove box with 4.5g RuCl2(PPh3)3Adding 50ml of dry methyl tetrahydrofuran under nitrogen atmosphere, and slowly adding C prepared in the step (1) at-30 DEG C6H5CH＝PPh3(10 times equivalent by [ C ]6H5CH2-PPh3]Br meter), the color of the reaction liquid gradually deepens, 5.6g of PCy is added after stirring and reacting for 2 hours3The reaction was returned to room temperature and stirred for 1 hour to terminate the reaction. The reaction solvent was removed under vacuum, recrystallized, washed and filtered to give Grubbs I catalyst, 2.5g, 61% yield.
Example 5:
compared with example 1, the reaction temperature in step 3) was changed to 100 ℃ in most parts.
A100 ml Schlenk reaction flask was taken, and 1.6 g of Grubbs I catalyst and 1.7g of chloroform-carbene adduct were sequentially added thereto, air was replaced 3 times, 60 ml of toluene was added thereto, the reaction was carried out at 100 ℃ for 4 hours, T L C was observed to see that the reaction was near the end, the reaction solvent was removed in vacuo, and filtration and washing were carried out to obtain 0.9g of Grubbs II catalyst in a yield of 53%.
Example 6:
compared with example 1, most of the results are the same, except that in this example, the molar ratio of benzyl bromide to triphenylphosphine was 1: 1.
Example 7:
compared with example 1, most of the results are the same, except that in this example, the molar ratio of benzyl bromide to triphenylphosphine was 1: 10.
Example 8:
compared to example 1, most of the same except that in this example the molar ratio of the phosphorus ylide reagent to the triphenylphosphine ruthenium chloride feed was 1: 1.
Example 9:
compared to example 1, most of the results are the same, except that in this example, the molar ratio of the phosphorus ylide reagent to the triphenylphosphine ruthenium chloride feed is 1: 10.
Example 10:
compared to example 1, most of them are the same except that in this example, the molar ratio of the ruthenium carbene complex precursor to the functional ligand (i.e., the chloroform carbene adduct) is 1: 1.
Example 11:
compared to example 1, most of them are the same except that in this example, the molar ratio of the ruthenium carbene complex precursor to the functional ligand (i.e., the chloroform carbene adduct) is 1: 10.
In the above embodiments, in step (1), the medium used in the reaction may be replaced by any one or a mixture of any several of 1, 4-dioxane, tetrahydrofuran, anhydrous ether and methyl tert-butyl ether; the strong base can be replaced by any one or mixture of any more of potassium tert-butoxide, n-butyllithium or sodium methoxide;
in the step (2), the solvent can be replaced by any one or mixture of any more of toluene, cyclohexane, anhydrous ether or tetrahydrofuran; the purification reagent used for recrystallization can be selected from one group of mixed solvents such as toluene/methanol, toluene/n-hexane, anhydrous ether/n-pentane, anhydrous ether/petroleum ether, ethyl acetate/petroleum ether, dichloromethane/methanol and the like, and in the recrystallization purification reagent, the proportion of the good solvent to the poor solvent can be adjusted at will in the range of 1:5-1:100 according to the needs;
in the step (3), the reaction medium used in the complex addition reaction can be replaced by any one or mixture of any more of 1, 4-dioxane, tetrahydrofuran, anhydrous ether or methyl tert-butyl ether;
the chloroform carbene adduct can also be replaced by one or more of pyridine and substitutes thereof, alkyl and substituted phosphine ligands thereof, aromatic and substituted phosphine ligands thereof, benzylidene alkyl ether, chain imine, imidazole hydrochloride (NHCs), nitrogen heterocyclic carbene adduct, phenol-oxygen imine ligands, chelate indenyl ligands and other functional compounds which have temperature, light or chemical response and can be complexed with active metal ruthenium.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A synthetic method of a ruthenium carbene catalyst is characterized by comprising the following steps:
(1) adding benzyl halide and triphenylphosphine into a reactor, reacting in a medium, and reacting the obtained reaction product under the action of strong alkali to obtain an intermediate product I;
(2) reacting the intermediate product I with triphenylphosphine ruthenium chloride in a solvent, replacing triphenylphosphine with tricyclohexylphosphine, filtering and washing to obtain a ruthenium carbene complex precursor;
(3) and carrying out complex addition reaction on the ruthenium carbene complex precursor and the functional ligand to obtain the target product ruthenium carbene catalyst.
2. The method for synthesizing a ruthenium carbene catalyst according to claim 1, wherein in the step (1), the benzyl halide is benzyl bromide or benzyl chloride.
3. The method for synthesizing the ruthenium carbene catalyst according to claim 1, wherein in the step (1), the molar ratio of the benzyl halide to the triphenylphosphine is 1:1-1: 10.
4. The method for synthesizing the ruthenium carbene catalyst according to claim 1, wherein in the step (1), a medium used in the reaction is one or a mixture of 1, 4-dioxane, tetrahydrofuran, anhydrous ether or methyl tert-butyl ether;
in the step (1), the reaction time is 2-20 h;
in the step (1), the strong base is one or a mixture of more of potassium tert-butoxide, n-butyllithium and sodium methoxide.
5. The method for synthesizing the ruthenium carbene catalyst according to claim 1, wherein in the step (2), the feeding molar ratio of the intermediate product I to the triphenylphosphine ruthenium chloride is 1:1-1: 10.
6. The method for synthesizing the ruthenium carbene catalyst according to claim 1, wherein in the step (2), the solvent is one or more of toluene, cyclohexane, anhydrous ether or tetrahydrofuran;
in the step (2), the reaction temperature is 0-100 ℃.
7. The method for synthesizing a ruthenium carbene catalyst according to claim 1, wherein in the step (2), the ruthenium carbene complex precursor obtained after filtration and washing is subjected to recrystallization purification treatment, the recrystallization purification reagent is one selected from toluene/methanol, toluene/n-hexane, anhydrous diethyl ether/n-pentane, anhydrous diethyl ether/petroleum ether, ethyl acetate/petroleum ether and dichloromethane/methanol, and the ratio of the good solvent to the poor solvent in the recrystallization purification reagent is 1:5-1: 100.
8. The method for synthesizing the ruthenium carbene catalyst according to claim 1, wherein in the step (3), the feeding molar ratio of the ruthenium carbene complex precursor to the functional ligand is 1:1-1: 10.
9. The method for synthesizing the ruthenium carbene catalyst according to claim 1, wherein in the step (3), the complex addition reaction is carried out in a reaction medium, and the reaction medium is one or more selected from 1, 4-dioxane, tetrahydrofuran, anhydrous ether and methyl tert-butyl ether;
in the step (3), the temperature of the complex addition reaction is 25-110 ℃.
10. The method for synthesizing a ruthenium carbene catalyst according to claim 1, wherein in the step (3), the functional ligand is one or more of functional compounds which have temperature, light or chemical response and can be complexed with active metal ruthenium, and is specifically selected from one or more of pyridine and its substitutes, alkyl and its substituted phosphine ligands, aromatic and its substituted phosphine ligands, benzylidene alkyl ether, chain imine, imidazole hydrochloride, nitrogen heterocyclic carbene adduct, chloroform carbene adduct, phenol oxygen imine ligands or chelate indenyl ligands.
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| CN112547126A (en) * | 2020-12-21 | 2021-03-26 | 上海中化科技有限公司 | Ruthenium carbene compound, composition, preparation method and application thereof |
| CN112547126B (en) * | 2020-12-21 | 2023-03-21 | 上海中化科技有限公司 | Ruthenium carbene compound, composition, preparation method and application thereof |
| CN114957336A (en) * | 2021-05-13 | 2022-08-30 | 上海化工研究院有限公司 | Synthesis method of Hoveyda catalyst |
| CN115216102A (en) * | 2022-07-29 | 2022-10-21 | 上海化工研究院有限公司 | Cyclic olefin resin composition and preparation method and application thereof |
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