CN115785166A - Triplecene-bridged metallocene compound and application thereof - Google Patents

Abstract

The invention relates to the technical field of organic synthesis, and discloses a tricyclene bridged metallocene compound and application thereof, wherein in the figure 1, R can beAre the same or different and are each independently represented by R ₁ ‑(Z ₁ ‑A‑Z ₂ ) _x -, wherein said R ₁ Each independently selected from-H, -D, -T, -Cl, -CN, -CD ₃ 、‑CF ₃ 、‑OCF ₃ Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms, a fluorinated alkoxy group having 1 to 15 carbon atoms, or a fluorinated linear alkenyl group having 2 to 15 carbon atoms. The tricyclene bridged metallocene compound and the application thereof have the advantages of simple preparation and high yield, are suitable for various substrates when used as a catalyst, can greatly reduce the using amount of the catalyst, and have better catalytic effect on reactions catalyzed by various metals. Has important application value for researching the progress and the application of the catalytic reaction.

Description

Triplecene-bridged metallocene compound and application thereof

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a tricyclene bridged metallocene compound and application thereof.

Background

The metal catalyst has rich reactivity, plays an important role in organic synthesis, and becomes the most widely applied catalyst in various organic chemical reactions such as hydrogenation, coupling, cycloaddition and the like. In the last decades, the metal catalyst has the advantages of mild reaction conditions, wide substrate application range, no toxic and harmful by-products, easy product treatment and the like, so that the metal catalyst is widely applied to the fields of laboratory research and fine chemical engineering in the pharmaceutical industry and is used for synthesizing various types of organic compounds.

Taking the Suzuki reaction as an example, the Suzuki reaction is one of the most commonly used coupling reactions for constructing aromatic rings, wherein the most commonly used is a metal palladium catalyst, the catalytic system of the type is widely researched, and the palladium metal catalyst has relatively high stability to air and heat, is easy to recycle in the catalytic reaction, has high activity in the reaction, and some mature systems can catalyze, activate and non-activate the coupling of chlorobenzene and phenylboronic acid under relatively mild conditions, so the catalyst becomes one of the most important means for modern organic synthesis and is applied to the field of synthesis of many organic molecules.

Although the research on metal catalysts has been greatly advanced, there are still many problems and disadvantages in its industrial application. Because of its high price, for many ligands and catalyst systems, there are problems of complex structure, harsh preparation conditions, easy deactivation and difficult recycling after reaction, so the metal catalyst with high stability, high activity, wide substrate application range, recyclability, low cost, very high TON and TOF is still very important research content.

Disclosure of Invention

Technical problem to be solved

In view of the deficiencies of the prior art, the present invention provides a tricyclene bridged metallocene compound and its application to solve the problems mentioned in the background art.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: in the figure 1, R can be the same or different and are respectively and independently represented as R ₁ -(Z ₁ -A-Z ₂ ) _x -；

Wherein each R1 is independently selected from-H, -D, -T, -Cl, -CN, -CD ₃ 、-CF ₃ 、-OCF ₃ Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms, a fluorinated alkoxy group having 1 to 15 carbon atoms, or a fluorinated linear alkenyl group having 2 to 15 carbon atoms.

Preferably, Z1 and Z2 are independently selected from-O-, -S-, -OCO-, -COO-, -CO-, -CH ₂ O-、-OCH ₂ -、-OCF ₂ A linear alkyl group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms a linear alkynyl group having 2 to 15 carbon atoms, a fluorinated linear alkyl group having 1 to 15 carbon atoms, a fluorinated alkyl group,At least one of an alkylene group having 2 to 15 carbon atoms and a carbon-carbon single bond, or none thereof, is fluorinated.

Preferably, each of A is independently one or none selected from 1, 4-cyclohexylene, 1, 4-phenylene, diphenylphosphinophosphonyl, N-phenyl-carbazol-2-yl, N-phenyl-carbazol-3-yl, 9, 10-anthracenyl, 1-naphthyl, 2-naphthyl, 4-triphenylamino, 2, 5-pyrimidyl, 3, 9-carbazolyl, 2, 5-pyridyl, 2, 5-tetrahydro-2H-pyranyl, 1, 3-dioxan-2, 5-yl, 1,2, 4-oxadiazol-3, 5-yl, fluorinated 1, 4-cyclohexylene, fluorinated pyranocycldiyl, cycloalkanediyl, pentaoxaheterocyclediyl, pentathienyldiyl, pentaazacyclediyl, or a carbon-carbon single bond;

m represents Fe, ru, ti, zr or Hf;

when M represents Fe and Ru, n is 0;

when M represents Ti, zr or Hf, n is 2;

x represents Cl, br or I.

Preferably, the tricycloalkene-bridged metallocene compound is used in a catalyst.

Preferably, the catalyst is used in applications including, but not limited to, suzuki reactions, buchwald-Hartwig reactions, heck reactions, still reactions, or Negishi reactions.

(III) advantageous effects

Compared with the prior art, the invention provides a tricyclene bridged metallocene compound and application thereof, and the invention has the following beneficial effects:

the tricyclene bridged metallocene compound and the application thereof have the advantages of simple preparation and high yield, are suitable for various substrates when used as a catalyst, can greatly reduce the use amount of the catalyst, and have better catalytic effect on reactions catalyzed by various metals. Has important application value for researching the progress and the application of the catalytic reaction.

Drawings

FIG. 1 is a schematic diagram of the structure of a tricyclene-bridged metallocene compound of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Referring to the attached figure 1, the invention provides a technical scheme, a tricyclene bridged metallocene compound and application thereof, wherein in the figure 1, R can be the same or different and are respectively and independently represented as R ₁ -(Z ₁ -A-Z ₂ ) _x -, wherein R1 is independently selected from-H, -D, -T, -Cl, -CN, -CD ₃ 、-CF ₃ 、-OCF ₃ Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms, a fluorinated alkoxy group having 1 to 15 carbon atoms, or a fluorinated linear alkenyl group having 2 to 15 carbon atoms.

Z1 and Z2 are independently selected from-O-, -S-, -OCO-, -COO-, -CO-, -CH ₂ O-、-OCH ₂ -、-OCF ₂ -, at least one or none of a linear alkyl group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a linear alkynyl group having 2 to 15 carbon atoms, a fluorinated linear alkyl group having 1 to 15 carbon atoms, a fluorinated alkenyl group having 2 to 15 carbon atoms, or a carbon-carbon single bond.

A is independently selected from one or none of 1, 4-cyclohexylene, 1, 4-phenylene, diphenylphosphinyl, N-phenyl-carbazol-2-yl, N-phenyl-carbazol-3-yl, 9, 10-anthracenyl, 1-naphthyl, 2-naphthyl, 4-triphenylamino, 2, 5-pyrimidyl, 3, 9-carbazolyl, 2, 5-pyridyl, 2, 5-tetrahydro-2H-pyranyl, 1, 3-dioxan-2, 5-yl, 1,2, 4-oxadiazol-3, 5-yl, fluorinated 1, 4-cyclohexylene, fluorinated pyran ring diyl, cyclolactone diyl, five-membered oxaheterocyclic diyl, five-membered thiaheterocyclic diyl, five-membered azaheterocyclic diyl or carbon-carbon single bond;

m represents Fe, ru, ti, zr or Hf;

when M represents Fe and Ru, n is 0;

when M represents Ti, zr or Hf, n is 2;

x represents Cl, br or I.

The tricycloalkene-bridged metallocene compound is applied to a catalyst, and the catalyst is applied to Suzuki reaction, buchwald-Hartwig reaction, heck reaction, still reaction or Negishi reaction.

EXAMPLE 1 preparation of the Compound Cat-001

3.8g (10.0 mmol) of Cat-001a and 100mL of tetrahydrofuran are added into a 500mL two-neck flask, the mixture is cooled to 0 ℃ in an ice bath, 10mL (2.0 mol/L) of butyl lithium solution in hexane is slowly dripped, the reaction is kept for 2 hours after the dripping is finished, 2.4g (10.0 mmol) of iron dichloride tetrahydrofuran complex is added, the reaction is carried out for 2 hours at room temperature, the solvent is pumped out under reduced pressure, alumina column chromatography is carried out, and petroleum ether is leached to obtain 4.1g of black solid with the yield of 88%.

Elemental analysis C ₃₀ H ₁₈ Theoretical value of Fe: c,82.96; h,4.18. Measured value: c,82.77; h,4.10.

Mass spectrum (ESI): m/z 433.07 (M +).

The structure is confirmed to be correct.

EXAMPLE 2 preparation of the Compound Cat-002

Adding 4.8g (10.0 mmol) of Cat-002a and 100mL of tetrahydrofuran into a 500mL two-neck flask, cooling to 0 ℃ in an ice bath, slowly dropwise adding 10mL (2.0 mol/L) of butyl lithium hexane solution, keeping the reaction for 2 hours after the dropwise adding is finished, then adding 2.6g (10.0 mmol) of ruthenium trichloride trihydrate, reacting for 2 hours at room temperature, decompressing and draining the solvent, performing alumina column chromatography, and leaching with petroleum ether to obtain 5.2g of orange solid with the yield of 90%.

Elemental analysis C ₃₇ H ₃₀ Theoretical value of Ru: c,77.19; h,5.25. Measured value: c,77.32; h,5.06.

Mass spectrum (ESI): m/z 575.13 (M +).

The structure is confirmed to be correct.

EXAMPLE 3 Synthesis of Cat-003 Compound

5.8g (10.0 mmol) of Cat-003a and 100mL of tetrahydrofuran are added into a 500mL two-neck flask, the mixture is cooled to 0 ℃ in an ice bath, 10mL (2.0 mol/L) of butyl lithium solution in hexane is slowly dripped, the reaction is kept for 2 hours after the dripping is finished, then 3.3g (10.0 mmol) of titanium tetrachloride tetrahydrofuran complex is added, the reaction is carried out for 2 hours at room temperature, the solvent is pumped out under reduced pressure, alumina column chromatography is carried out, and petroleum ether is leached to obtain 5.2g of red solid, and the yield is 84%.

Elemental analysis C ₄₄ H ₂₉ Cl ₂ Theoretical NTi value: c,76.54; h,4.23; and N,2.03. Measured value: c,76.41; h,4.20; and N is 1.99.

Mass spectrum (ESI): m/z 688.11 (M +).

The structure is confirmed to be correct.

EXAMPLE 4 Synthesis of Cat-004 Compound

6.8g (10.0 mmol) of Cat-004a and 100mL of tetrahydrofuran are added into a 500mL two-neck flask, the mixture is cooled to 0 ℃ in an ice bath, 10mL (2.0 mol/L) of butyl lithium hexane solution is slowly dripped, the reaction is kept for 2 hours after the dripping is finished, then 3.8g (10.0 mmol) of zirconium tetrachloride tetrahydrofuran complex is added, the reaction is carried out for 2 hours at room temperature, the solvent is pumped out under reduced pressure, the alumina column chromatography is carried out, and the petroleum ether is leached to obtain 7.1g of yellow solid, and the yield is 85%.

Elemental analysis C ₅₁ H ₄₄ Cl ₂ Theoretical value of OZr: c,73.36; h,5.31. Measured value: c,73.15; h,5.28.

Mass spectrum (ESI): m/z 831.17 (M +).

The structure is confirmed to be correct.

Example 5 catalytic comparison of Suzuki coupling reactions

To a Schlenk tube containing magnetons were added 1.5mmol of phenylboronic acid, 1.1mmol of potassium tert-butoxide, and 0.01 mmol of a catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 1 and ferrocene) in this order, followed by 1.0mmol of p-methoxybromobenzene, 1mL of isopropanol, and stirring at 80 ℃ for 2 hours. Then dissolved in dichloromethane and stirred into alumina, column chromatographed (eluent dichloromethane/petroleum ether = 2.

Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are synthesized in the examples 1 to 4, the compound 1 is a commercial comparative catalyst, diindene iron is used as a reference substance, and the reaction general formula is as follows:

the reaction results are shown in table 1 below:

TABLE 1 comparative test results of Suzuki reaction

From the above, it can be seen that the tricyclene-bridged metallocene compounds (examples 1 to 4, test nos. 1 to 4) prepared by the patented method of the present invention have improved catalytic efficiency in application compared with the comparative example 1 (test No. 5) because the tricyclene-bridged metallocene compounds contain a large steric hindrance group to stabilize intermediates in catalytic circulation, and can realize Suzuki catalytic reaction with very high yield with one ten thousand of the catalyst, while in industrial production, the amount of the catalyst has a great influence on cost control of raw materials and difficulty of post-treatment, and has a great advantage in cost control, which cannot be achieved by the comparative example. Similarly, ferrocene without tricyclene bridging as a catalyst for catalyzing Suzuki reaction (experiment No. 6) has little reactivity due to η of cyclopentadiene in ferrocene ⁵ The cyclopentadienyl ring has certain reaction activity, and the stability is far lower than that of a benzene ring, so that the cyclopentadienyl ring has almost no catalytic activity, but has no catalytic activity in the siteThe stability of the compound can be obviously improved by the introduction of a large steric hindrance triptycene bridging structure, so that higher catalytic activity is realized.

Example 6Hartwig-Buchwald coupling catalytic comparison

To a Schlenk tube containing magnetons, 1.0mmol of p-methoxybromobenzene, 1.1mmol of potassium tert-butoxide and 0.01 mmol of a catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 2 and ruthenocene) were added in this order, followed by 1.2mmol of diphenylamine and 1mL of toluene and stirring at 100 ℃ for 2 hours. Then dissolved with dichloromethane and stirred into alumina, column chromatographed (eluent dichloromethane/petroleum ether = 2.

Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are synthesized in the embodiments 1 to 4, the compound 2 is a commercial comparative catalyst, ruthenocene is used as a reference substance, and the reaction general formula is as follows:

the reaction results are shown in table 2 below:

TABLE 2 results of comparative test of Hartwig-Buchwald reaction

As can be seen from the above, similar to example 5, the tricyclene bridged metallocene compounds (examples 1-4, test No. 7-10) prepared by the patented method of the present invention can stabilize the intermediates in the catalytic cycle, improve the catalytic efficiency, and can realize the Hartwig-Buchwald catalytic reaction with a very high yield by using only one in ten thousandth of the amount, compared with the comparative example 2 (test No. 11), the catalyst amount is controlled for the cost of raw materials in industrial production, and the post-treatment is difficultThe easiness degree has great influence, and the cost control has great advantage which cannot be achieved by a comparative example. Similarly, ruthenium bis without tridentate bridge as a catalyst for Hartwig-Buchwald reaction (experiment No. 12) has almost no reactivity because cyclopentadiene of ruthenium bis is eta ⁵ The structure of (1) has certain reaction activity, the stability is far lower than that of a benzene ring, so that the metallocene ring almost has no catalytic activity, and the stability of the compound can be obviously improved by the introduced large steric hindrance triptycene bridging structure in the invention, so that higher catalytic activity is realized.

Example 7Heck coupling reaction catalysis comparison

1.0mmol of p-bromobenzoic acid, 1.2mmol of potassium carbonate and 0.01 mmol of the catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 3 and titanocene dichloride) were added in this order to a Schlenk tube equipped with magnetons, followed by 1.2mmol of acrylic acid, 1mL of xylene and stirring at 120 ℃ for 2 hours. Then dissolved with dichloromethane and stirred into alumina, column chromatographed (eluent dichloromethane/petroleum ether = 4.

Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are synthesized in the examples 1 to 4, the compound 3 is a commercial comparative catalyst, titanocene dichloride is used as a reference substance, and the reaction general formula is as follows:

the reaction results are shown in table 3 below:

TABLE 3 results of comparative test of Heck reaction

As can be seen from the above, similarly to example 5, the tricyclene-bridged metallocene compounds obtained by the patented process of the present invention (examples 1 to 4, test Nos. 13 to 16) can stabilize catalytic cycle in use compared with comparative example 3 (test No. 17) due to the presence of the large sterically hindered group of tricycleneThe intermediate in the preparation method improves the catalytic efficiency, and can realize Heck catalytic reaction with very high yield by using one ten-thousandth of the dosage, and in industrial production, the dosage of the catalyst has very great influence on the cost control of raw materials and the difficulty degree of post-treatment, so that the preparation method has great advantages in cost control, which cannot be achieved by a comparative example. Similarly, dichlorotitanocene without tridecene bridge as a catalyst for Heck reaction (Experimental number 18) has almost no reactivity because cyclopentadiene of dichlorotitanocene is eta ⁵ The structure of (1) has certain reaction activity, the stability is far lower than that of a benzene ring, so that the metallocene ring almost has no catalytic activity, and the stability of the compound can be obviously improved by the introduced large steric hindrance triptycene bridging structure in the invention, so that higher catalytic activity is realized.

Example 8Still reaction catalysis comparison

To a Schlenk tube containing magnetons were added 1.0mmol of p-methoxybromobenzene, 1.2mmol of potassium fluoride and 0.01 mmol of a catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 4 and zirconocene dichloride) in that order, followed by 1.2mmol of tributylphenylane and 1mL of dioxane, and stirred at 100 ℃ for 6 hours. Then dissolved with dichloromethane and stirred into alumina, column chromatographed (eluent dichloromethane/petroleum ether = 4.

Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are the compounds synthesized in examples 1 to 4, the compound 4 is a commercial comparative catalyst, zirconocene dichloride is used as a reference substance, and the reaction formula is as follows:

the reaction results are shown in table 4 below:

TABLE 4 Still reaction comparative test results

From the above, withExample 5 similarly, the tridentate alkene bridged metallocene compound (examples 1-4, test No. 19-22) prepared by the patented method of the invention can stabilize the intermediate in the catalytic cycle, improve the catalytic efficiency, realize Still catalytic reaction with a ten-thousandth dosage and a very high yield compared with the comparative example 4 (test No. 23), and have great advantages in cost control because the dosage of the catalyst has great influence on the cost control of raw materials and the difficulty of post-treatment in industrial production, which cannot be achieved by the comparative example. Similarly, zirconocene dichloride without tricyclene bridging as catalyst for Still reaction (experiment No. 24) has little reactivity due to the η of cyclopentadiene of zirconocene dichloride ⁵ The structure of (A) has certain reaction activity, the stability is far less than that of a benzene ring, so that the metallocene ring has almost no catalytic activity, and the stability of the compound can be obviously improved by introducing a large steric hindrance tridentate alkene bridging structure into the catalyst, so that the high catalytic activity is realized.

Example 9Negishi reaction catalysis comparison

To a Schlenk tube containing magnetons were added 1.0mmol of p-methoxybromobenzene, 1.2mmol of potassium carbonate and 0.01 mmol of a catalyst (compounds Cat-001, cat-002, cat-003, cat-004, 5 and zirconocene dichloride) in that order, followed by 1.2mmol of phenylzinc chloride and 1mL of tetrahydrofuran, and stirred at 60 ℃ for 6 hours. Then dissolved with dichloromethane and stirred into alumina, column chromatographed (eluent dichloromethane/petroleum ether = 4.

Wherein the compounds Cat-001, cat-002, cat-003 and Cat-004 are the compounds synthesized in the examples 1 to 4, the compound 5 is a commercial comparative catalyst, zirconocene dichloride is used as a reference substance, and the reaction general formula is as follows:

the reaction results are shown in table 5 below:

TABLE 5 results of comparative experiments with Negishi reaction

From the above, similar to example 5, the tricyclene bridged metallocene compounds (examples 1 to 4, test nos. 25 to 28) prepared by the patented method of the present invention have improved catalytic efficiency in application compared to comparative example 5 (test No. 29) because they contain the tricyclene bulky steric hindrance group to stabilize the intermediates in the catalytic cycle, and Negishi catalytic reaction can be achieved with a very high yield with only one in ten thousand, while in industrial production, the amount of the catalyst has a great influence on the cost control of raw materials and the difficulty of post-treatment, and has a great advantage in cost control, which cannot be achieved by the comparative example. Similarly, zirconocene dichloride without tridentate bridge as a catalyst for Negishi reaction (Experimental number 30) has little reactivity due to the η of cyclopentadiene in zirconocene dichloride ⁵ The structure of (A) has certain reaction activity, the stability is far less than that of a benzene ring, so that the metallocene ring has almost no catalytic activity, and the stability of the compound can be obviously improved by introducing a large steric hindrance tridentate alkene bridging structure into the catalyst, so that the high catalytic activity is realized.

In conclusion, compared with the conventional catalyst, the tricyclene bridged metallocene compound prepared by the invention has better catalytic effect, has good universal applicability to reaction substrates with various substituents, has obvious advantages in catalyst dosage, can ensure the catalytic reaction only by one ten-thousandth of the dosage, and can be generally suitable for the reactions catalyzed by various metals. The synthesis method is simple and convenient, has high yield and high popularization and application value, which cannot be realized by the conventional metal catalyst, and the effect cannot be expected by the technical personnel in the field.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (5)

1. A tricyclene bridged metallocene compound and application thereof are characterized in that: in the above FIG. 1, R may be the same or different and each independently represents R ₁ -(Z ₁ -A-Z ₂ ) _x -；

Wherein said R ₁ Each independently selected from-H, -D, -T, -Cl, -CN, -CD ₃ 、-CF ₃ 、-OCF ₃ Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a linear alkenyl group having 2 to 15 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms, a fluorinated alkoxy group having 1 to 15 carbon atoms, or a fluorinated linear alkenyl group having 2 to 15 carbon atoms.

2. The tricyclene-bridged metallocene compound and its use according to claim 1, characterized in that: z1 and Z2 are independently selected from-O-, -S-, -OCO-, -COO-, -CO-, -CH ₂ O-、-OCH ₂ -、-OCF ₂ Linear alkyl group having 1 to 15 carbon atoms, linear alkenyl group having 2 to 15 carbon atomsAt least one or none of a linear alkynyl group having 2 to 15 carbon atoms, a fluorinated linear alkyl group having 1 to 15 carbon atoms, a fluorinated alkylene group having 2 to 15 carbon atoms, or a carbon-carbon single bond.

3. The tricyclene-bridged metallocene compound and its use according to claim 1, characterized in that: each A is independently one or none selected from 1, 4-cyclohexylene, 1, 4-phenylene, diphenylphosphino, N-phenyl-carbazol-2-yl, N-phenyl-carbazol-3-yl, 9, 10-anthracenyl, 1-naphthyl, 2-naphthyl, 4-triphenylamino, 2, 5-pyrimidinyl, 3, 9-carbazolyl, 2, 5-pyridinyl, 2, 5-tetrahydro-2H-pyranyl, 1, 3-dioxan-2, 5-yl, 1,2, 4-oxadiazol-3, 5-yl, fluorinated 1, 4-cyclohexylene, fluorinated pyran ring diyl, cyclic lactone diyl, five-membered oxaheterocyclic diyl, five-membered thiaheterocyclic diyl, five-membered azaheterocyclic diyl or carbon-carbon single bond;

m represents Fe, ru, ti, zr or Hf;

when M represents Fe and Ru, n is 0;

when M represents Ti, zr or Hf, n is 2;

x represents Cl, br or I.

4. The tricyclene-bridged metallocene compound and its use according to claim 1, characterized in that: the tricyclene-bridged metallocene compounds are used in catalysts.

5. The tricyclene-bridged metallocene compound and the use thereof according to claim 4, wherein: the catalyst is applied to Suzuki reaction, buchwald-Hartwig reaction, heck reaction, still reaction or Negishi reaction.

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