CN110563769B - Ruthenium carbene olefin metathesis catalyst chelated by bidentate sulfur ligand and preparation method and application thereof - Google Patents

Abstract

The invention provides a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation, and its structural formula is:

And disclose the preparation method and application thereof, the preparation method is simple, the obtained olefin metathesis catalyst has excellent catalytic activity and stereoselectivity, and has high structural stability, and is applied to norbornene ROMP reaction, with high yield and relatively high stability. Good Z‑selectivity.

Description

A kind of ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation and preparation method and application thereof

technical field

The invention relates to the technical field of transition metal organic catalysts, in particular to a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligands chelated, and a preparation method and application thereof.

Background technique

At present, alkenes with Z-structure have a wide range of applications in the fields of chemistry, biology and medicine. They need to be prepared by fast, efficient and stereoselective catalytic reactions, and the key to catalytic reactions is catalysts. Highly active olefin metathesis catalyst with effectively controlled stereoselectivity.

Olefin metathesis is a reversible process, Z-olefin products are mainly kinetically controlled, while E-olefin products are mainly thermodynamically controlled, especially in the later stages of the reaction, often a very complex process, resulting in high yields and Z-selectivity It is very difficult to generate olefin metathesis products with specific properties, so the research of high activity olefin metathesis catalysts with effective control of stereoselectivity is of great significance.

At present, great progress has been made in the research of olefin metathesis catalysts, including stereoselective catalysts Mo- and W-monoaryloxypyrrolidine compounds for the preparation of biologically active natural products; bidentate P ligand chelation The ruthenium catalyst is Z-selective for ring-opening metathesis polymerization (ROMP); the nitrogen-heterocyclic carbene (NHC) bidentate chelated ruthenium catalyst is Z-selective for various metathesis reactions of olefins; Ruthenium carbene catalysts chelated by dentate sulfur ligands for ring-opening polymerization/ring-opening cross-metathesis (ROMP/ROCM), cross-metathesis (CM), and macrocycle-forming ring-closing metathesis (RCM) reactions of olefins, all with catalytic properties activity and Z-selectivity.

However, the catalytic activity and Z-selectivity of the existing olefin metathesis catalysts are not high, especially the catalytic activity and Z-selectivity during the cross-metathesis reaction need to be improved.

Therefore, it is an urgent problem for those skilled in the art to provide a novel and efficient catalyst to improve its catalytic activity and Z-selectivity during the cross-metathesis reaction.

SUMMARY OF THE INVENTION

In view of this, the present invention provides a ruthenium carbene olefin metathesis catalyst containing a bidentate sulfur ligand chelated, and a preparation method and application thereof, the preparation method is simple, and the obtained olefin metathesis catalyst has excellent catalytic activity and stereoselectivity, In addition, it has high structural stability and can be used in norbornene ROMP reaction with high yield and good Z-selectivity.

In order to achieve the above object, the present invention adopts the following technical solutions:

A ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation is characterized in that, the structural formula of the ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation is:

The beneficial effect of the above preferred technical scheme is: the catalyst disclosed in the present invention contains a bidentate sulfur ligand, which can increase the repulsive force between it and the nitrogen heterocyclic carbene ligand, thereby forcing the ligand as far as possible away from the nitrogen heterocyclic ring that also has a large steric hindrance. The carbene ligand makes the intermediate transition state between the catalyst and the alkene close to the triangular bipyramid coordination structure, which is beneficial to improve the catalytic activity of the catalyst; due to the steric hindrance of the bidentate sulfur ligand, the triangular bipyramid in the intermediate transition state is more It is compact and more crowded, which is beneficial to the ability of transition state intermediates to control the stereo control of substituent groups and improve stereoselectivity; in addition, the bidentate sulfur ligand contained in it has a large electronegativity, which can effectively reduce the para-sulfur of nitrogen-heterocyclic carbene. Electrophilic reaction of atoms to carbon-ruthenium double bonds, thereby improving catalyst stability.

The present invention also provides a preparation method of a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelated, which specifically comprises the following steps:

A preparation method of a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation is characterized in that, specifically comprises the following steps:

(1) Dissolve compound (I) in methanol, add sodium tert-butoxide methanol solution, complete the reaction under stirring conditions, filter and remove the solvent after the reaction, and dry the solid product under vacuum to obtain compound (II);

(2) Compound (II) and Hoveyda-Grubbs II catalyst were added to dry tetrahydrofuran solvent, and the reaction was complete under stirring conditions. After the reaction, vacuum filtration was performed to dry the solvent to obtain a brown-red solid product; Add n-hexane to the solid product, stir evenly to obtain a mixed solution, centrifuge the mixed solution to obtain a solid product, filter the remaining solid with suction and then dry to obtain compound (III), which is a ruthenium carbene chelated with bidentate sulfur ligands Olefin metathesis catalyst;

The chemical structural formula of the compound (I) is:

The chemical structure of the compound (II) is:

The chemical structural formula of the compound (III) is:

Preferably, in step (1), the molar ratio of the compound (I) to the sodium tert-butoxide is (1-3): (2-6).

Preferably, the compound (I) in step (1) is dissolved in methanol at a concentration of 0.1-0.4 mmol/mL, which can form a colorless solution.

Preferably, the concentration of sodium tert-butoxide in the methanol solution of sodium tert-butoxide in step (1) is 0.1-0.6 mmol/mL, which can form a colorless solution.

Preferably, the reaction temperature in step (1) is 15-30°C, the stirring speed is 600r/min-1000r/min, and the reaction time is 2-5h; the reaction solution gradually changes from colorless to dark red solution.

The beneficial effect of the above preferred technical solution is that the compound (II) with a yield greater than 75% can be obtained.

Preferably, the molar ratio of the Hoveyda-GrubbsII catalyst described in step (2) to compound (II) is (1-3): (2-3).

Preferably, in step (2), the concentration of the Hoveyda-Grubbs II catalyst dissolved in dry tetrahydrofuran is 0.01-0.2 mmol/ml, and the concentration of the compound (II) in dry tetrahydrofuran is 0.02-0.2 mmol /ml.

Preferably, in the step (2), the reaction temperature is 15-30°C, the stirring speed is 600r/min-1000r/min, and the reaction time is 0.5-1.5h; the liquid-solid ratio of the added n-hexane to the brown-red solid product 20-30mL/g.

The beneficial effects of the above preferred technical solution are: according to the preferred conditions of step (2), compound (III) with a yield greater than 60% can be obtained.

The invention also provides the application of a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelated in the norbornene ring-opening metathesis polymerization reaction.

As can be seen from the above technical solutions, compared with the prior art, the present invention discloses a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelated and its preparation method and application, which have the following beneficial effects:

(1) the catalyst prepared by the present invention has high catalytic activity, high stereoselectivity, and the catalyst itself has excellent stability;

(2) The method disclosed in the present invention has simple steps, mild reaction conditions, can be obtained by reaction at room temperature, and has excellent development prospects;

(3) the ruthenium olefin metathesis catalyst prepared by the present invention has obvious catalytic effect on norbornene ROMP reaction, can improve the yield of the reaction, and has better Z-selectivity, so that after the norbornene ROMP reaction, Z-formula is obtained Olefins.

Description of drawings

In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only It is an embodiment of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to the provided drawings without creative efforts.

The accompanying drawing of Fig. 1 is the ¹ H-NMR spectrum of compound (III);

The accompanying drawing of Fig. 2 is the ¹³ C-NMR spectrum of compound (III);

Fig. 3 accompanying drawing is the ¹ H-NMR spectrum of poly(1,3-divinylcyclopentane);

Figure 4 is a ¹³ C-NMR spectrum of poly(1,3-divinylcyclopentane).

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

The embodiment of the present invention provides a preparation method of a ruthenium carbene olefin metathesis catalyst containing a bidentate sulfur ligand chelated, which specifically includes the following steps:

(1) Dissolve compound (I) in methanol to form a solution with a concentration of 0.1-0.4 mmol/mL, and then according to the molar ratio of compound (I) to sodium tert-butoxide (1-3): (2-6) , add a methanol solution of sodium tert-butoxide with a concentration of 0.1-0.6 mmol/mL, react at a stirring speed of 600 r/min-1000 r/min and a temperature of 15-30 ° C for 2-5 h, after the reaction is completed, filter to remove the solvent to obtain The solid product is dried under vacuum to obtain compound (II);

(2) According to the molar ratio of (1-3): (2-3), the Hoveyda-GrubbsII catalyst and the compound (II) were added to a dry tetrahydrofuran solvent to form a Hoveyda-GrubbsII catalyst with a concentration of 0.01-0.2 mmol/ml, The reaction system with compound (II) concentration of 0.02-0.2 mmol/ml is then reacted under stirring conditions of 600r/min-1000r/min and temperature of 15-30℃ for 0.5-1.5h, after the reaction is completed, the solvent is drained with a vacuum pump to obtain a brown-red solid product; add n-hexane to the brown-red solid product, and the liquid-solid ratio of the added n-hexane to the brown-red solid product is 20-30 mL/g; stir evenly to obtain a mixed solution, and separate the mixed solution after centrifugation. liquid, the remaining solid is drained and then dried to obtain compound (III), which is a ruthenium carbene olefin metathesis catalyst containing chelated bidentate sulfur ligands;

The chemical structural formula of compound (I) is:

The chemical structure of compound (II) is:

The chemical structural formula of compound (III) is:

Example 1

Synthesis of 1,3-Dithiol-2-one-4,5-dithiodisodium Salt (Ⅱ)

1,3,4,6-Tetrathiacyclopentene-2,5-dione (208.3 mg, 1 mmol) was dissolved in 5 mL of methanol. To this solution was added 5 mL of methanolic sodium tert-butoxide (211.4 mg, 2.2 mmol). The solution was stirred at a speed of 800 r/min at room temperature for 2 hours, and the solution turned from colorless to dark red. After the reaction, the solvent was sucked dry and dried under vacuum to obtain a red solid powder (II) (201 mg, yield: 89.0%).

Example 2

Synthesis of 1,3-Dithiol-2-one-4,5-dithiodisodium Salt (Ⅱ)

1,3,4,6-tetrathiacyclopentene-2,5-dione (104.2 mg, 0.5 mmol) was dissolved in 5 mL of methanol. To this solution was added 5 mL of methanolic sodium tert-butoxide (144.1 mg, 1.5 mmol). The solution was stirred at a speed of 700 r/min at room temperature for 3 hours, and the solution turned from colorless to dark red. After the reaction, the solvent was sucked dry and dried under vacuum to obtain a red solid powder (II) (169 mg, yield: 75.0%).

Example 3

Synthesis of 1,3-Dithiol-2-one-4,5-dithiodisodium Salt (Ⅱ)

1,3,4,6-Tetrathiacyclopentene-2,5-dione (208.3 mg, 1 mmol) was dissolved in 5 mL of methanol. To this solution was added 5 mL of methanolic sodium tert-butoxide (240.2 mg, 2.5 mmol). The solution was stirred at a speed of 900 r/min at room temperature for 4 hours, and the solution turned from colorless to dark red. After the reaction, the solvent was sucked to dryness and dried under vacuum to obtain a red solid powder (II) (194 mg, yield: 86.0%).

Example 4

Synthesis of 1,3-Dithiol-2-one-4,5-dithiodisodium Salt (Ⅱ)

1,3,4,6-tetrathiacyclopentene-2,5-dione (104.2 mg, 0.5 mmol) was dissolved in 5 mL of methanol. To this solution was added 5 mL of methanolic sodium tert-butoxide (288.3 mg, 3.0 mmol). The solution was stirred at a speed of 800 r/min at room temperature for 5 hours, and the solution turned from colorless to dark red. After the reaction, the solvent was sucked dry and dried under vacuum to obtain a red solid powder (II) (151 mg, yield: 67.0%).

Example 5

Synthesis of 1,3-Dithiol-2-one-4,5-dithiodisodium Salt (Ⅱ)

1,3,4,6-Tetrathiacyclopentene-2,5-dione (208.3 mg, 1 mmol) was dissolved in 5 mL of methanol. To this solution was added 5 mL of methanolic sodium tert-butoxide (240.2 mg, 2.5 mmol). Stir at a speed of 1000 r/min at 30° C. for 4 hours, and the solution turned from colorless to dark red. After the reaction, the solvent was sucked dry and dried under vacuum to obtain a red solid powder (II) (192 mg, yield: 85.0%).

Example 6

Synthesis of 1,3-Dithiol-2-one-4,5-dithiol-chelated Ruthenium Carbene Compound (Ⅲ)

Take Grubbs-Hoveyda II catalyst (464.0 mg, 0.74 mmol) and compound II (201.0 mg, 0.9 mmol,) prepared in Example 1 into a 25 mL round-bottomed flask. Add 15 mL of dry THF, and stir at a speed of 800 r/min at room temperature for 30 min. After the reaction, the solvent was drained by a vacuum pump to obtain a brown-red solid. Add n-hexane to the solid, stir well, the color of n-hexane will change to red at this time, centrifuge the mixture, pour off the liquid, and drain the solid. Compound III (385 mg, yield: 70.6%) was obtained as a brown solid powder.

The synthesized compound III was detected by nuclear magnetic resonance spectrometer, and the results are shown in Figures 1-2.

It can be clearly seen from the results in Figures 1-2 that the ruthenium complex (III) ¹ HNMR (400MHz, CDCl ₃ )δ14.57(s, 1H), 7.26(s, 1H), 7.08(d, J=8.3Hz, 1H), 6.95(s, 2H), 6.79(t, J=7.3Hz, 2H), 6.62(d, J=7.3Hz, 1H), 6.10(s, 1H), 5.33(dd, J=14.1, 7.4 Hz,1H),4.01–3.84(m,4H),2.44(s,6H),2.29(s,6H),2.22(s,3H),1.74(d,J=6.7Hz,3H),1.61(s , 3H), 1.40 (d, J=6.5Hz, 3H); ¹³ CNMR (100MHz, CDCl ₃ ) δ 216.21, 201.16, 154.55, 141.69, 136.04, 130.54, 129.35, 127.45, 124.39, 122.42, 118.40, 111.769, 8 51.31, 31.61, 24.35, 22.68, 21.00, 14.16.

Example 7

Synthesis of 1,3-Dithiol-2-one-4,5-dithiol-chelated Ruthenium Carbene Compound (Ⅲ)

Grubbs-Hoveyda II catalyst (201 mg, 0.32 mmol) and compound II (169.0 mg, 0.75 mmol) prepared in Example 2 were put into a 25 mL round-bottomed flask. 15 mL of dry THF was added, and the mixture was stirred at a speed of 600 r/min at room temperature for 1 hour. After the reaction, the solvent was drained by a vacuum pump to obtain a brown-red solid. Add n-hexane to the solid, stir well, the color of n-hexane will change to red at this time, centrifuge the mixture, pour off the liquid, and drain the solid. Compound III (552 mg, yield: 70.1%) was obtained as a brown solid powder.

The synthesized compound III was detected by nuclear magnetic resonance spectrometer, and the results are shown in Figures 1-2.

Example 8

Synthesis of 1,3-Dithiol-2-one-4,5-dithiol-chelated Ruthenium Carbene Compound (Ⅲ)

Grubbs-Hoveyda II catalyst (418.6 mg, 0.67 mmol) and compound II (151 mg, 0.67 mmol, prepared in Example 4) were put into a 25 mL round-bottomed flask. 15 mL of dry THF was added, and the mixture was stirred at a speed of 1000 r/min at room temperature for 1.5 hours. After the reaction, the solvent was drained by a vacuum pump to obtain a brown-red solid. Add n-hexane to the solid, stir well, the color of n-hexane will change to red at this time, centrifuge the mixture, pour off the liquid, and drain the solid. Compound III (133 mg, yield: 67.5%) was obtained as a brown solid powder.

The synthesized compound III was detected by nuclear magnetic resonance spectrometer, and the results are shown in Figures 1-2.

Example 9

Synthesis of 1,3-Dithiol-2-one-4,5-dithiol-chelated Ruthenium Carbene Compound (Ⅲ)

Grubbs-Hoveyda II catalyst (106.4 mg, 0.17 mmol) and compound II (192 mg, 0.85 mmol, prepared in Example 5) were put into a 25 mL round-bottomed flask. 15 mL of dry THF was added, and the mixture was stirred at a speed of 800 r/min at 30° C. for 1 hour. After the reaction, the solvent was drained by a vacuum pump to obtain a brown-red solid. Add n-hexane to the solid, stir well, the color of n-hexane will change to red at this time, centrifuge the mixture, pour off the liquid, and drain the solid. Compound III (87 mg, yield: 69.3%) was obtained as a brown solid powder.

The synthesized compound III was detected by nuclear magnetic resonance spectrometer, and the results are shown in Figures 1-2.

Example 10

Synthesis of Catalytic Product Poly(1,3-Divinylcyclopentane)

Under nitrogen protection, 0.1 mL of CH ₂ Cl ₂ solution and compound III (0.7 mg, 0.001 mmol) prepared in Example 6 were added to a 5 mL vial containing a magnetron, and 1.5 mL of norbornene (94.1 mg, 1.00 mmol) was added. mmol ₎ in _CH2Cl2 . The solution was stirred at room temperature for 1 hour, and the solution became very viscous after the reaction was complete. Then 5 mL of MeOH was added and the white polynorbornene precipitated with vigorous stirring. Washing with MeOH (3 x 4 mL) and drying in vacuo for 24 h gave the product as a white solid with a Z/E ratio of 82:18 (82.8 mg, 88% yield).

The above-mentioned white solid product was detected by a nuclear magnetic resonance spectrometer, and the results are shown in Figures 3-4.

It can be clearly seen from the results in Figs. 3 to 4 that ¹ HNMR (400MHz, CDCl ₃ )δ5.22(d, J=5.9Hz, 2H), 2.79(s, 2H), 1.93-1.87(m, 1H), 1.82 (d, J=13.3Hz, 2H), 1.36 (s, 2H), 1.02 (dd, J=22.2, 10.7Hz, 1H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 133.8, 42.7, 38.6, 33.2 .

The Z/E ratio was determined to be 82:18 from the ratio of the peak areas in the H NMR spectrum.

Example 11

Synthesis of Catalytic Product Poly(1,3-Divinylcyclopentane)

Under nitrogen protection, 0.1 mL of CH ₂ Cl ₂ solution and compound III (0.35 mg, 0.0005 mmol) prepared in Example 7 were added to a 5 mL vial containing a magnetron, and 1.5 mL of norbornene (94.1 mg, 1.0 mmol) was added. mmol ₎ in _CH2Cl2 . The solution was stirred at room temperature for 1 hour, and the solution became very viscous after the reaction was complete. Then 5 mL of MeOH was added and the white polynorbornene precipitated with vigorous stirring. Washing with MeOH (3 x 4 mL) and drying in vacuo for 24 h gave the product as a white solid with a Z/E ratio of 82:18 (71.5 mg, 76% yield).

The above-mentioned white solid product was detected by a nuclear magnetic resonance spectrometer, and the results are shown in Figures 3-4.

It can be clearly seen from the results in Figs. 3 to 4 that ¹ HNMR (400MHz, CDCl ₃ )δ5.22(d, J=5.9Hz, 2H), 2.79(s, 2H), 1.93-1.87(m, 1H), 1.82 (d, J=13.3Hz, 2H), 1.36 (s, 2H), 1.02 (dd, J=22.2, 10.7Hz, 1H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 133.8, 42.7, 38.6, 33.2 .

The Z/E ratio was determined to be 82:18 from the ratio of the peak areas in the H NMR spectrum.

Example 12

Synthesis of Catalytic Product Poly(1,3-Divinylcyclopentane)

Under nitrogen protection, 0.1 mL of CH ₂ Cl ₂ solution and compound III prepared in Example 9 (1.05 mg, 0.0015 mmol) were added to a 5 mL vial containing a magnetron, and 1.5 mL of norbornene (94.1 mg, 1.0 mmol) was added. mmol ₎ in _CH2Cl2 . The solution was stirred at room temperature for 1 hour, and the solution became very viscous after the reaction was complete. Then 5 mL of MeOH was added and the white polynorbornene precipitated with vigorous stirring. Washing with MeOH (3 x 4 mL) and drying in vacuo for 24 h gave the product as a white solid with a Z/E ratio of 82:18 (82.8 mg, 88% yield).

The above-mentioned white solid product was detected by a nuclear magnetic resonance spectrometer, and the results are shown in Figures 3-4.

It can be clearly seen from the results in Figs. 3 to 4 that ¹ HNMR (400MHz, CDCl ₃ )δ5.22(d, J=5.9Hz, 2H), 2.79(s, 2H), 1.93-1.87(m, 1H), 1.82 (d, J=13.3Hz, 2H), 1.36 (s, 2H), 1.02 (dd, J=22.2, 10.7Hz, 1H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 133.8, 42.7, 38.6, 33.2 .

The Z/E ratio was determined to be 82:18 from the ratio of the peak areas in the H NMR spectrum.

The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments, and the same and similar parts between the various embodiments can be referred to each other. As for the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant part can be referred to the description of the method.

The above description of the disclosed embodiments enables any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended 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 (10)

1. a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation is characterized in that, the structural formula of the ruthenium carbene olefin metathesis catalyst is:

. 2. a preparation method of a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation, is characterized in that, specifically comprises the steps: (1) Dissolve compound (I) in methanol, add sodium tert-butoxide methanol solution, complete the reaction under stirring conditions, filter and remove the solvent after the reaction, and dry the solid product under vacuum to obtain compound (II); (2) Compound (II) and Hoveyda-Grubbs II catalyst were added to dry tetrahydrofuran solvent, and the reaction was complete under stirring conditions. After the reaction, vacuum filtration was performed to dry the solvent to obtain a brown-red solid product; Add n-hexane to the solid product, stir evenly to obtain a mixed solution, centrifuge the mixed solution to obtain a solid product, filter the remaining solid with suction and then dry to obtain compound (III), which is a ruthenium carbene chelated with bidentate sulfur ligands Olefin metathesis catalyst; The chemical structural formula of the compound (I) is:

The chemical structure of the compound (II) is:

The chemical structural formula of the compound (III) is:

3. the preparation method of a kind of ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation according to claim 2, is characterized in that, described in step (1), compound (I) and described tert-butanol The molar ratio of sodium is (1-3):(2-6). 4. the preparation method of a kind of ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation according to claim 3, is characterized in that, the described compound (I) of step (1) is dissolved in described methanol The concentration is 0.1 to 0.4 mmol/mL. 5. the preparation method of a kind of ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation according to claim 4, is characterized in that, in the described sodium tert-butoxide methanol solution of step (1), sodium tert-butoxide The concentration of 0.1-0.6mmol/mL. 6. the preparation method of a kind of ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation according to claim 5, is characterized in that, in step (1), reaction temperature is 15-30 ℃, and stirring speed is 600r /min-1000r/min, the reaction time is 2-5h. 7. the preparation method of a kind of ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation according to claim 2 or 6, is characterized in that, described in step (2), Hoveyda-GrubbsII catalyst and compound (II) ) in a molar ratio of (1-3):(2-3). 8. the preparation method of a kind of ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation according to claim 7, is characterized in that, described in step (2), the Hoveyda-GrubbsII catalyst dissolved in dry tetrahydrofuran The concentration is 0.01-0.2 mmol/ml, and the concentration of the compound (II) dissolved in dry tetrahydrofuran is 0.02-0.2 mmol/ml. 9. the preparation method of a kind of ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation according to claim 8, is characterized in that, in described step (2), reaction temperature is 15-30 ℃, and stirring speed is 600r/min-1000r/min, the reaction time is 0.5-1.5h; the liquid-solid ratio of the added n-hexane and the brown-red solid product is 20-30mL/g. 10 . The application of a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelation according to claim 1 in norbornene ring-opening metathesis polymerization. 11 .

Images