Ruthenium complex compound, catalyst comprising same, and method for synthesizing ruthenium complex compound

Abstract

Disclosed are a ruthenium complex compound, a catalyst comprising same, and a method for synthesizing the ruthenium complex compound. The ruthenium complex compound may be represented by chemical formula 1 described above.

Description

Ruthenium complex, catalyst comprising the same, and method for synthesizing the ruthenium complex

[0001] The present disclosure relates to a ruthenium complex, a catalyst comprising the same, and a method for synthesizing the ruthenium complex.

[0002] Cyclic polymers are structures in which the ends of polymer chains are interconnected. Unlike linear polymers, cyclic polymers possess physical properties such as small mechanical dimensions, low intrinsic viscosity, and high glass transition temperatures. These properties are attracting considerable attention in the field of biomaterials and next-generation polymer materials.

[0003] The synthesis of cyclic polymers utilizes metal complex catalysts for ring expansion polymerization. Examples of metal complex catalysts for ring expansion polymerization include cyclic alkylaminocarbene-based metal complexes and nitrogen-heterocyclic carbene (NHC)-based metal complexes.

[0004] Metal complexes based on cyclic alkylaminocarbenes exhibit stronger nucleophilicity and electrophilicity than N-heterocyclic carbene (NHC)-based metal complexes, demonstrating superior activity when used as catalysts compared to conventional catalysts. However, conventional cyclic alkylaminocarbene-based metal complexes have limitations in synthesizing cyclic polymers in large quantities in a single reaction.

[0005] Therefore, there is still a need for novel metal complexes, catalysts comprising the same, and the novel metal complexes.

[0006] One aspect is to provide a novel ruthenium complex compound.

[0007] Another aspect is to provide a catalyst comprising the above ruthenium complex compound.

[0008] Another aspect is to provide a method for synthesizing the above ruthenium complex compound.

[0009] According to one aspect,

[0010] A ruthenium complex represented by the following chemical formula 1 is provided:

[0011] [Chemical Formula 1]

[0012]

[0013] Among the foods,

[0014] n can be an integer from 1 to 20;

[0015] R1, R2, R3, R4 are C1-C independently substituted or unsubstituted 10 may be an alkyl group;

[0016] R5, R6, R7 is independently a hydrogen atom, substituted or unsubstituted C1-C 30 Alkyl group, substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 a heteroaryl group, or a combination thereof;

[0017] R1, R2, R3, R4, R5, R6, Among R7, the above substitution is such that one of the hydrogen atoms is independently a halogen group, a hydroxyl group, a nitro group, a cyano group, an amino group, a C1-C 30 Alkyl amino group of C6- 30 Aryl amino group of C6- 30 Aryl silyl group, C1-C 30 Alkyl C6- 30 Aryl silyl group, C1-C 30 Alkyl group of C1-C 30 Haloalkyl group of C6- 30 Aryl C1-C 30 Alkyl group of C1-C 30 Alkoxy group, C3-C30 Cycloalkyl group of C6- 30 Aryl group of C1-C 30 Alkyl C6- 30 Aryl group of C6- 30 Aryloxy group of C3- 30 Heteroaryl group of C1-C 30 Alkyl C3- 30 Heteroaryl group of C6- 30 Aryl C3- 30 may be substituted with a heteroaryl group, or a combination thereof; and

[0018] X1 and X2 can independently be a halogen atom, a substituted benzenethiol ligand, a substituted benzopyrazine ligand, or a combination thereof,

[0019] Among X1 and X2, the above substitution may be such that one of the hydrogen atoms may independently be a halogen group, a thiol group, a dithiol group, an amino group, or a combination thereof.

[0020] Depending on other aspects,

[0021] A catalyst comprising the above-described ruthenium complex is provided.

[0022] According to another aspect,

[0023] A method for synthesizing a ruthenium complex compound is provided, comprising the step of reacting a cyclic alkylaminocarbine linked to isopropoxystyrene represented by the following chemical formula 9 and a ruthenium precursor to synthesize a ruthenium complex compound according to claim 1:

[0024] [Chemical Formula 9]

[0025]

[0026] Among the foods,

[0027] n' can be an integer from 1 to 20;

[0028] R'1, R'2, R'3, R'4 are C1-C independently substituted or unsubstituted 10 may be an alkyl group;

[0029] R'5, R'6 are each independently a hydrogen atom, substituted or unsubstituted C1-C 30 Alkyl group, substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 a heteroaryl group, or a combination thereof;

[0030] Among R'1, R'2, R'3, R'4, R'5, R'6, the above substitution is such that one of the hydrogen atoms is independently a halogen group, a hydroxyl group, a nitro group, a cyano group, an amino group, a C1-C 30 Alkyl amino group of C6- 30 Aryl amino group of C6- 30 Aryl silyl group, C1-C 30 Alkyl C6- 30 Aryl silyl group, C1-C 30 Alkyl group of C1-C 30 Haloalkyl group of C6- 30 Aryl C1-C 30 Alkyl group of C1-C 30 Alkoxy group, C3-C 30 Cycloalkyl group of C6- 30 Aryl group of C1-C 30 Alkyl C6- 30 Aryl group of C6- 30 Aryloxy group of C3- 30 Heteroaryl group of C1-C 30 Alkyl C3- 30 Heteroaryl group of C6- 30 Aryl C3- 30 may be substituted with a heteroaryl group, or a combination thereof; and

[0031] X ' is Cl - , Br - , I - , NO3 - , BF4 - , CF3SO3 - , C 32 H12 BF 24 - , (C6F5)3B - Or it could be a combination of these.

[0032] The ruthenium complex according to one aspect is represented by the chemical formula 1 described above. The ruthenium complex can introduce various steric hindrances and provide a complex with excellent thermal stability. The ruthenium complex is used as a catalyst in ring-expansion metathesis polymerization, enabling the synthesis of cyclic polymers in large quantities using a simple single reaction.

[0033] Figure 1a is a diagram of compound Ru-1 prepared in Example 1. 1 H NMR spectrum; Figure 1b is the compound Ru-1 prepared in Example 1. 13 This is a C NMR spectrum.

[0034] Figure 2a is a graph of compound Ru-2 prepared in Example 2. 1 H NMR spectrum; Figure 2b is the compound Ru-2 prepared in Example 2. 13 This is a C NMR spectrum.

[0035] Figure 3a is a graph of compound Ru-3 prepared in Example 3. 1 H NMR spectrum; Figure 3b is the compound Ru-3 prepared in Example 3. 13 This is a C NMR spectrum.

[0036] Figure 4a is a graph of compound Ru-4 prepared in Example 4. 1 H NMR spectrum; Figure 4b is the compound Ru-4 prepared in Example 4. 13 This is a C NMR spectrum.

[0037] Figure 5a is a graph of compound Ru-5 prepared in Example 5. 1 H NMR spectrum; Figure 5b is the compound Ru-5 prepared in Example 5. 13 This is a C NMR spectrum.

[0038] Figure 6a is a graph of compound Ru-6 prepared in Example 6.1 H NMR spectrum; Figure 6b is the compound Ru-6 prepared in Example 6. 13 This is a C NMR spectrum.

[0039] Figure 7a is a graph of compound Ru-7 prepared in Example 7. 1 H NMR spectrum; Figure 7b is the compound Ru-7 prepared in Example 7. 13 This is a C NMR spectrum.

[0040] Figure 8 shows the results of a thermal stability test of compounds Ru-1, Ru-4, Ru-5, and Ru-6 manufactured in Examples 1, 4, 5, and 6, and compound UltraNitroCat-1 of Reference Example 1.

[0041] Hereinafter, with reference to the attached drawings, a ruthenium complex according to one embodiment of the present invention, a catalyst comprising the same, and a method for synthesizing the ruthenium complex will be described in detail. The following is provided as an example, and the present invention is not limited thereto, and the present invention is defined only by the scope of the claims set forth below.

[0042] Hereinafter, singular expressions include plural expressions unless the context clearly indicates otherwise. Furthermore, when a part is said to "include" a component, this does not exclude other components, but rather implies the inclusion of other components, unless otherwise specifically stated.

[0043] The term "combination" in this specification includes any combination or all combinations of the components listed above, unless otherwise specifically stated.

[0044] “Or” means “and / or” unless otherwise specified.

[0045] Throughout this specification, references to “one embodiment,” “an embodiment,” “an exemplary embodiment,” “an exemplary embodiment,” and the like mean that a particular element described in connection with the embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments.

[0046] It should also be understood that the described elements may be combined in any suitable manner in various embodiments. Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. All patents, patent applications, and other references cited herein are incorporated herein by reference in their entirety. However, if a term in this specification contradicts or conflicts with a term in an incorporated reference, the term from this specification shall supersede the conflicting term in the incorporated reference. While specific embodiments and implementations have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are presently unanticipated or unforeseen may occur to applicants or those skilled in the art. Accordingly, the appended claims and their subject matter are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0047] Synthetic methods for cyclic polymers can be categorized into ring closure and ring expansion polymerization. Ring closure requires the use of low-concentration solutions to avoid unwanted side reactions between polymer chains. Consequently, ring closure poses limitations in terms of large-scale synthesis for industrial applications.

[0048] On the other hand, ring expansion polymerization allows for the mass synthesis of cyclic polymers using a simpler synthetic method than ring closure reactions, but it must be possible to selectively obtain polymers with a desired molecular weight with low polydispersity (PDI).

[0049] Taking these points into consideration, the present inventors propose a novel ruthenium complex, a catalyst including the same, and a method for synthesizing the ruthenium complex.

[0050] According to one embodiment, a ruthenium complex represented by the following chemical formula 1 is provided:

[0051] [Chemical Formula 1]

[0052]

[0053] Among the foods,

[0054] n can be an integer from 1 to 20;

[0055] R1, R2, R3, R4 are C1-C independently substituted or unsubstituted 10 may be an alkyl group;

[0056] R5, R6, R7 is independently a hydrogen atom, substituted or unsubstituted C1-C 30 Alkyl group, substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 a heteroaryl group, or a combination thereof;

[0057] R1, R2, R3, R4, R5, R6, Among R7, the above substitution is such that one of the hydrogen atoms is independently a halogen group, a hydroxyl group, a nitro group, a cyano group, an amino group, a C1-C 30 Alkyl amino group of C6- 30 Aryl amino group of C6- 30 Aryl silyl group, C1-C30 Alkyl C6- 30 Aryl silyl group, C1-C 30 Alkyl group of C1-C 30 Haloalkyl group of C6- 30 Aryl C1-C 30 Alkyl group of C1-C 30 Alkoxy group, C3-C 30 Cycloalkyl group of C6- 30 Aryl group of C1-C 30 Alkyl C6- 30 Aryl group of C6- 30 Aryloxy group of C3- 30 Heteroaryl group of C1-C 30 Alkyl C3- 30 Heteroaryl group of C6- 30 Aryl C3- 30 may be substituted with a heteroaryl group, or a combination thereof; and

[0058] X1 and X2 can independently be a halogen atom, a substituted benzenethiol ligand, a substituted benzopyrazine ligand, or a combination thereof,

[0059] Among X1 and X2, the above substitution may be such that one of the hydrogen atoms may independently be a halogen group, a thiol group, a dithiol group, an amino group, or a combination thereof.

[0060] According to one embodiment, a ruthenium complex can provide a complex capable of introducing various steric hindrances and exhibiting excellent thermal stability. This ruthenium complex can be used as a catalyst in ring-expansion metathesis polymerization, enabling the synthesis of large-scale cyclic polymers using a simple, single reaction.

[0061] According to an exemplary embodiment, n in Chemical Formula 1 may be an integer from 1 to 20, an integer from 5 to 12, or an integer from 5 to 10. When n is within the above range, an appropriate strain may be maintained between the benzene ring and the heterocycle connected to the alkylene group, and excellent activity may be achieved as a catalyst for cyclic polymer synthesis.

[0062] According to an exemplary embodiment, in the formula 1, R1, R2, R3, R4 are It can be a substituted or unsubstituted C1-C5 alkyl group independently of each other. In chemical formula 1, a benzene ring having R1 and R2 substituents can have better catalytic activity than a linear substituent.

[0063] According to an exemplary embodiment, in the chemical formula 1, R1 and R2 can be the same group.

[0064] According to an exemplary embodiment, in the chemical formula 1, R5, R6, At least one of R7 is substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 heteroaryl group, or a combination thereof.

[0065] Cyclic alkylaminocarbines with R5 and R6 substituents possess both strong nucleophilicity and strong electrophilicity. Due to this, cyclic alkylaminocarbines possess a small energy band gap between singlet and triplet states, enabling them to exhibit excellent catalytic activity. Furthermore, cyclic alkylaminocarbines exhibit superior catalytic resistance to oxygen (O2) or water (H2O) compared to conventional catalysts, and side reactions are unlikely to occur. Furthermore, cyclic alkylaminocarbines with chiral centers can synthesize cyclic polymers of various structures through asymmetric reactions.

[0066] According to an exemplary embodiment, at least one of R6 and R7 in the formula 1 is substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 heteroaryl group, or a combination thereof.

[0067] According to an exemplary embodiment, X1 and X2 in Chemical Formula 1 may be halogen atoms. For example, they may be Cl, Br, and I atoms in Chemical Formula 1.

[0068] In an exemplary embodiment, examples of substituted benzenethiol ligands include 3,6-dichloro-1,2-benzenethiol.

[0069] In an exemplary embodiment, examples of substituted benzopyrazine (i.e., quinoxazine) ligands include 2,3-dithiol-benzopyrazine.

[0070] According to an exemplary embodiment, the ruthenium complex may include one or more of the complex compounds represented by the following chemical formulae 2 to 8:

[0071] [Chemical Formula 2]

[0072] ,

[0073] [Chemical Formula 3]

[0074] ,

[0075] [Chemical Formula 4]

[0076] ,

[0077] [Chemical Formula 5] ,

[0078] ,

[0079] [Chemical Formula 6]

[0080] ,

[0081] [Chemical Formula 7]

[0082] ,

[0083] [Chemical Formula 8]

[0084] .

[0085] According to an exemplary embodiment, the ruthenium complex may have a monoclinic crystal structure, a triclinic crystal structure, or a combination thereof, and may have a space group of P-1, P21 / c, P21 / n, or a combination thereof.

[0086] According to another embodiment, a catalyst comprising the above-described ruthenium complex is provided. The catalyst enables the mass synthesis of a cyclic polymer through a simple single reaction.

[0087] In one exemplary embodiment, the catalyst can be used in ring expansion metathesis polymerization. In ring expansion metathesis polymerization, a catalyst can be used to form a cyclic polymer through intermolecular chain transfer. Ring expansion metathesis polymerization is similar to backbiting in linear ring-opening metathesis polymerization (ROMP). Intermolecular chain transfer may occur before all monomers are consumed. Therefore, the introduction of various steric hindrances through ring expansion metathesis polymerization and the use of the above-described catalyst with excellent thermal stability can facilitate the formation of high-density cyclic polymers.

[0088] According to an exemplary embodiment, the catalyst may have a micelle shape, a nanoparticle shape, or a combination thereof. However, the catalyst is not limited to these shapes and can be manufactured in various shapes within the art.

[0089] In one exemplary embodiment, the catalyst may be used as a lubricant or coating agent.

[0090] According to another embodiment, a method for synthesizing a ruthenium complex compound is provided, comprising the step of reacting a cyclic alkylaminocarbine linked to isopropoxystyrene represented by the following chemical formula 9 and a ruthenium precursor to synthesize a ruthenium complex compound according to claim 1:

[0091] [Chemical Formula 9]

[0092]

[0093] Among the foods,

[0094] n' can be an integer from 1 to 20;

[0095] R'1, R'2, R'3, R'4 are C1-C independently substituted or unsubstituted 10 may be an alkyl group;

[0096] R'5, R'6 are each independently a hydrogen atom, substituted or unsubstituted C1-C 30 Alkyl group, substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 a heteroaryl group, or a combination thereof;

[0097] Among R'1, R'2, R'3, R'4, R'5, R'6, the above substitution is such that one of the hydrogen atoms is independently a halogen group, a hydroxyl group, a nitro group, a cyano group, an amino group, a C1-C 30 Alkyl amino group of C6- 30 Aryl amino group of C6- 30 Aryl silyl group, C1-C 30 Alkyl C6- 30 Aryl silyl group, C1-C 30 Alkyl group of C1-C 30 Haloalkyl group of C6- 30 Aryl C1-C 30 Alkyl group of C1-C 30 Alkoxy group, C3-C 30 Cycloalkyl group of C6-30 Aryl group of C1-C 30 Alkyl C6- 30 Aryl group of C6- 30 Aryloxy group of C3- 30 Heteroaryl group of C1-C 30 Alkyl C3- 30 Heteroaryl group of C6- 30 Aryl C3- 30 may be substituted with a heteroaryl group, or a combination thereof; and

[0098] X ' is Cl - , Br - , I - , NO3 - , BF4 - , CF3SO3 - , C 32 H 12 BF 24 - , (C6F5)3B - , Or it could be a combination of these.

[0099] According to one embodiment, the method for synthesizing a ruthenium complex can synthesize a cyclic polymer in large quantities through a simple single reaction.

[0100] According to an exemplary embodiment, n' in chemical formula 9 may be an integer from 1 to 20, an integer from 5 to 12, or an integer from 5 to 10. When n' is within the above range, an appropriate strain may be maintained between the benzene ring and the heterocycle connected to the alkylene group, and excellent activity may be exhibited as a catalyst for cyclic polymer synthesis.

[0101] According to an exemplary embodiment, the ruthenium precursor may include a precursor represented by the following chemical formula 10:

[0102] [Chemical Formula 10]

[0103]

[0104] Among the foods,

[0105] R7 is a hydrogen atom, substituted or unsubstituted C1-C 30 Alkyl group, substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 a heteroaryl group, or a combination thereof;

[0106] The above substitution is performed by substituting one of the hydrogen atoms independently with a halogen group, a hydroxyl group, a nitro group, a cyano group, an amino group, or a C1-C 30 Alkyl amino group of C6- 30 Aryl amino group of C6- 30 Aryl silyl group, C1-C 30 Alkyl C6- 30 Aryl silyl group, C1-C 30 Alkyl group of C1-C 30 Haloalkyl group of C6- 30 Aryl C1-C 30 Alkyl group of C1-C 30 Alkoxy group, C3-C 30 Cycloalkyl group of C6- 30 Aryl group of C1-C 30 Alkyl C6- 30 Aryl group of C6- 30 Aryloxy group of C3- 30 Heteroaryl group of C1-C 30 Alkyl C3- 30 Heteroaryl group of C6- 30 Aryl C3- 30 It may be substituted with a heteroaryl group, or a combination thereof.

[0107] According to an exemplary embodiment, the step of synthesizing a ruthenium complex may include a process of synthesizing a ruthenium complex by stirring at a temperature of 25° C. to 70° C. for 48 hours or more. For example, the step of synthesizing a ruthenium complex may include a first step of stirring at a temperature of 25° C. to 40° C. for 24 hours and a second step of stirring at a temperature of 70° C. for 24 hours.

[0108]

[0109] In this specification, the definitions of the substituents of Chemical Formula 1, Chemical Formula 9, and Chemical Formula 10 are as follows.

[0110] An alkyl group refers to a group of fully saturated branched or unbranched (or straight-chain or linear) hydrocarbons. Non-limiting examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, iso-amyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, etc. At least one hydrogen atom in the alkyl group may be substituted with the above-described substituents.

[0111] A cycloalkyl group refers to an aliphatic hydrocarbon containing one or more rings. The alkyl group is as described above.

[0112] An aryl group, used alone or in combination, refers to an aromatic hydrocarbon containing one or more rings. The aryl group also includes a group in which an aromatic ring is fused to one or more cycloalkyl rings. Non-limiting examples of the aryl group include a phenyl group, a naphthyl group, and a tetrahydronaphthyl group. In addition, one or more hydrogen atoms in the aryl group may be replaced with a substituent similar to the alkyl group described above.

[0113] A heteroaryl group refers to a monocyclic or bicyclic organic compound containing one or more heteroatoms selected from N, O, P, or S, and the remaining ring atoms being carbon. The heteroaryl group may contain, for example, 1 to 5 heteroatoms and 5 to 10 ring members. The S or N may be oxidized to have various oxidation states. Monocyclic heteroaryl groups include, for example, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, 1,2,3-oxadiazolyl group, 1,2,4-oxadiazolyl group, 1,2,5-oxadiazolyl group, 1,3,4-oxadiazolyl group, 1,2,3-thiadiazolyl group, 1,2,4-thiadiazolyl group, 1,2,5-thiadiazolyl group, 1,3,4-thiadiazolyl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5-yl group, oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, isoxazol-3-yl group, isoxazol-4-yl group, Examples thereof include isoxazol-5-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, tetrazolyl, pyrid-2-yl, pyrid-3-yl, 2-pyrazin-2-yl, pyrazin-4-yl, pyrazin-5-yl, 2-pyrimidin-2-yl, 4-pyrimidin-2-yl, or 5-pyrimidin-2-yl. Heteroaryl includes a case where a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocycle. Examples of bicyclic heteroaryls include indolyl, isoindolyl, indazolyl, indolizinyl, purinyl, quinolizinyl, quinolinyl, and isoquinolinyl.One or more hydrogen atoms in such heteroaryl may be substituted with a substituent similar to that in the case of the alkyl group described above.

[0114] The halogen group is -F, -Cl, -Br, or -I.

[0115] The hydroxyl group is -OH.

[0116] The nitro group is -NO2.

[0117] The cyano group is -CN.

[0118] The amino group is -NH2.

[0119] The thiol group is -SH.

[0120] An alkyl amino group refers to an amino group in which one or more hydrogen atoms are replaced by an alkyl group. The alkyl group is as described above.

[0121] An aryl amino group refers to an amino group in which one or more hydrogen atoms are replaced by an aryl group. The aryl group is as described above.

[0122] An aryl silyl group refers to a silyl group in which one or more hydrogen atoms are replaced by an aryl group. In this case, the silyl group is -SiH3 and the aryl group is as described above.

[0123] An alkyl aryl silyl group refers to a silyl group in which one or more hydrogen atoms are replaced by an alkyl group and an aryl group. In this case, the silyl group is -SiH3 and the alkyl group and aryl group are as described above.

[0124] A haloalkyl group refers to an alkyl group substituted with a halogen atom. In this case, the alkyl group is as described above.

[0125] An aryl alkyl group refers to an alkyl group in which one or more hydrogen atoms are replaced by an aryl group. In this case, the alkyl group is as described above.

[0126] An alkoxy group is an alkyl group bonded to oxygen. Examples of alkoxy groups include methoxy, ethoxy, and propoxy.

[0127] An alkyl aryl group refers to an aryl group in which one or more hydrogen atoms are replaced by an alkyl group. In this case, the alkyl group and aryl group are as described above.

[0128] An aryloxy group refers to an aryl group bonded to oxygen. Examples of aryloxy groups include a phenoxy group. In this case, the aryl group is as described above.

[0129] An alkyl heteroaryl group refers to a heteroaryl group in which one or more hydrogen atoms are replaced by an alkyl group. In this case, the alkyl group and the heteroaryl group are as described above.

[0130] An aryl heteroaryl group refers to a heteroaryl group in which one or more hydrogen atoms are replaced by an aryl group. In this case, the aryl group and heteroaryl group are as described above.

[0131]

[0132] Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are merely exemplary of the present invention, and the present invention is not limited to the following examples.

[0133]

[0134] [Example]

[0135] All air- and moisture-sensitive manipulations were performed under a N2 atmosphere. Toluene was distilled from sodium benzophenone ketyl. Acetonitrile was distilled from P2O5. Chloroform-d1 and acetonitrile-d3 were dried using activated molecular sieves (3Å). 4-Amino-3,5-diethylphenol was prepared according to Adv. Synth. Catal. 2014, 356, 460-474. 4-amino-3,5-bis(1-methylethyl)phenol was prepared according to Organic Letters 2007, 9, 3845-3848. 3-Ethenyl-4-(1-methylethoxy)phenol was prepared according to Organometallics 2014, 33, 338-346. Rac-2,4-dimethyl-2-phenylpent-4-enal was prepared according to The Journal of Organic Chemistry 2022, 87, 3511-3518. Ruthenium precursor (first generation Grubbs complex) was prepared according to Inorganica Chimica Acta 2008, 361, 1059-1065. All other chemicals were purchased from commercial sources and used as received. All deuterated solvents were purchased from the Cambridge Isotope Laboratory.

[0136] 1 H NMR spectrum, proton decoupled 13 C NMR spectrum ( 13 C{ 1 H}) and proton-decoupled 19F NMR spectra (19F{1H}) were recorded using a Bruker DRX 500 spectrometer, a Bruker Avance III HD 500, and a Varian / Oxford As-500. 1 H and 13 The chemical shift of C acquisition is the residual solvent peak ( 1 H: CDCl3, δ=7.26; CD3CN, δ=1.94; C6D6, δ=7.16 ppm, 13 C: CDCl3, δ= 77.16; CD3CN, δ= 118.26 ppm) were used. High-resolution mass spectrometry was performed using a JEOL JMS 700 high-resolution mass spectrometer at the Korea Basic Science Institute.

[0137]

[0138] Examples 1 to 7: Preparation of ruthenium complexes (Ru-1 to Ru-7 complexes)

[0139] Ru-1 complex to Ru-7 complex were prepared according to the steps of the following reaction scheme.

[0140] Reaction Scheme

[0141]

[0142] (Step 1) Preparation of compounds 1a to 1c

[0143] Under air atmosphere, rac-2,4-dimethyl-2-phenylpent-4-enal (1.05 eq.), aminophenol (1.00 eq.), and acetic acid (AcOH, 0.05 eq.) were placed in a round-bottomed flask, and ethanol was added to obtain a reaction mixture. The reaction mixture was then refluxed for 24 h. The reaction mixture was cooled to room temperature, and the solvent was concentrated in vacuo to obtain the product. The product was washed with cold methanol and pentane and dried in vacuo to obtain light brown solid compounds (1a, 1b, 1c).

[0144]

[0145] 화합물 1a (R 11 = Me, 2.49 g, 52%)

[0146] 1 H NMR (500 MHz, CD3CN): δ (ppm) 7.69 (s, 1H), 7.47 (d,J= 7.8 Hz, 2H), 7.36 (t,J= 7.6 Hz, 2H), 7.25 (t,J= 7.3 Hz, 1H), 6.45 (s, 2H), 6.42 (s, 1H), 4.78 (s, 1H), 4.62 (s, 1H), 2.85 (dd,J= 36.6, 13.9 Hz, 2H), 1.96 (s, 6H), 1.60 (s, 3H), 1.35 (s, 3H).

[0147] 13 C NMR (125 MHz, CD3CN): δ (ppm) 173.6, 153.5, 144.8, 144.4, 143.8, 129.2, 129.1, 128.3, 127.4, 115.4, 115.3, 48.4, 47.7, 24.6, 22.4, 18.6.

[0148] HRMS(EI) for C 21 H 25 NO (M + ): calc.: 307.1936, found: 307.1938.

[0149]

[0150] 화합물 1b (R 11 = Et, 4.66 g, 82%)

[0151] 1H NMR (500 MHz, CD3CN): δ (ppm) 7.66 (s, 1H), 7.47 (d,J= 8.3 Hz, 2H), 7.37 (t,J= 7.8 Hz, 2H), 7.26 (t,J= 7.3 Hz, 1H), 6.47 (s, 2H), 6.45 (s, 1H), 4.77 (s, 1H), 4.62 (s, 1H), 2.94 (d,J= 14.0 Hz, 1H), 2.78 (d,J= 14.0 Hz, 1H), 2.32 (q,J= 7.5 Hz, 4H), 1.60 (s, 3H), 1.33 (s, 3H), 1.00 (t,J= 7.5 Hz, 6H).

[0152] 13 C NMR (125 MHz, CD3CN): δ (ppm) 173.1, 153.9, 144.5, 143.8, 143.5, 135.4, 129.2, 128.3, 127.5, 115.3, 113.9, 48.4, 47.5, 25.3, 24.6, 22.0, 15.1.

[0153] HRMS(EI) for C 23 H 29 NO (M + ): calc.: 335.2249, found: 335.2246.

[0154]

[0155] 화합물 1c (R 11 = i Pr, 3.65 g, 92%)

[0156] 1H NMR (500 MHz, CD3CN): δ (ppm) 7.63 (s, 1H), 7.47 (d, J= 8.3 Hz, 2H), 7.37 (t, J= 7.8 Hz, 2H), 7.26 (t, J= 7.3 Hz, 1H), 6.53 (s, 2H), 6.43 (s, 1H), 4.78 (s, 1H), 4.62 (s, 1H), 2.96 (d, J= 14.0 Hz, 1H), 2.86-2.77 (m, 3H), 1.61 (s, 3H), 1.34 (s, 3H), 1.05 (d, J= 6.9 Hz, 6H), 1.02 (d, J= 6.9 Hz, 6H).

[0157] 13 C NMR (125 MHz, CD3CN): δ (ppm) 173.3, 154.3, 144.5, 143.8, 142.3, 140.0, 129.2, 128.4, 127.5, 115.4, 110.7, 48.5, 47.5, 28.3, 24.6, 23.6, 23.6, 22.1.

[0158] HRMS(EI) for C 25 H 33 NO (M + ): calc.: 363.2562, found: 363.2564.

[0159]

[0160] (Step 2) Preparation of compounds 2a to 2c

[0161] Under a nitrogen atmosphere, 3-ethenyl-4-(1-methylethoxy)phenol (1.00 eq.), dibromoalkane (2.00 eq.), cesium carbonate (Cs2CO3, 3.0 eq.), and potassium iodide (KI, 0.01 eq.) were placed in a round-bottomed flask, and dried acetonitrile was added to obtain a reaction mixture. Then, the reaction mixture was stirred in a dark room at 70°C for 24 h. The reaction mixture was cooled to room temperature, the acetonitrile solution was filtered, and the solvent was concentrated in vacuo to obtain the product. The product was extracted with dichloromethane (DCM). Dichloromethane was removed in vacuo and the product was purified by fresh column chromatography, eluted with DCM / hexane (2:8) to give pale yellow oily compounds (2a, 2b, 2c).

[0162]

[0163] Compound 2a (n = 6, 526 mg, 51%)

[0164] 1 H NMR (500 MHz, CDCl3): δ (ppm) 7.06-7.01 (m, 2H), 6.83 (d,J= 8.8 Hz, 1H), 6.75 (d,J= 8.6 Hz, 1H), 5.71 (d,J= 17.8 Hz, 1H), 5.24 (d,J= 11.1 Hz, 1H), 4.37 (quint,J= 6.0 Hz, 1H), 3.93 (t,J= 6.2 Hz, 2H), 3.43 (t,J= 6.7 Hz, 2H), 1.91-1.77 (m, 4H), 1.53-1.48 (m, 4H), 1.31 (d,J= 6.0 Hz, 6H).

[0165] 13 C NMR (125 MHz, CDCl3): δ (ppm) 153.5, 149.6, 132.0, 129.5, 117.2, 114.9, 114.2, 112.1, 72.5, 68.4, 33.9, 32.8, 29.4, 28.1, 25.5, 22.4.

[0166] HRMS(EI) for C 17 H 25 BrO2(M + ): calc.: 340.1038, found: 340.1036.

[0167]

[0168] 화합물 2b (n = 8, 1.07g, 74%)

[0169] 1 H NMR (500 MHz, CDCl3): δ (ppm) 7.06-7.00 (m, 2H), 6.82 (d,J= 8.8 Hz, 1H), 6.75 (dd,J= 8.8, 3.0 Hz, 1H), 5.70 (d,J= 17.6 Hz, 1H), 5.23 (d,J= 11.1 Hz, 1H), 4.37 (quint,J= 6.1 Hz, 1H), 3.92 (t,J= 6.4 Hz, 2H), 3.41 (t,J= 6.8 Hz, 2H), 1.89-1.73 (m, 4H), 1.47-1.36 (m, 8H), 1.31 (d,J= 6.0 Hz, 6H).

[0170] 13 C NMR (125 MHz, CDCl3): δ (ppm) 153.6, 149.5, 132.0, 129.5, 117.2, 114.9, 114.2, 112.1, 72.5, 68.6, 34.1, 32.9, 29.5, 29.3, 28.8, 28.3, 26.1, 22.4.

[0171] HRMS(EI) for C 19 H 29 BrO2(M + ): calc.: 368.1351, found: 368.1352.

[0172]

[0173] 화합물 2c (n = 10, 2.90g, 65%)

[0174] 1H NMR (500 MHz, CDCl3): δ (ppm) 7.06-7.01 (m, 2H), 6.82 (d,J= 8.8 Hz, 1H), 6.75 (dd,J= 8.9, 3.0 Hz, 1H), 5.70 (d,J= 17.7, 1.2 Hz, 1H), 5.23 (d,J= 11.1, 1.2 Hz, 1H), 4.37 (quint,J= 6.1 Hz, 1H), 3.92 (t,J= 6.5 Hz, 2H), 3.41 (t,J= 6.9 Hz, 2H), 1.88-1.73 (m, 4H), 1.48-1.40 (m, 4H), 1.34-1.30 (m, 14H).

[0175] 13 C NMR (125 MHz, CDCl3): δ (ppm) 153.7, 149.5, 132.1, 129.5, 117.2, 114.9, 114.2, 112.1, 72.5, 68.6, 34.2, 33.0, 29.6, 29.6, 29.5, 28.9, 28.3, 26.2, 22.4.

[0176] HRMS(FAB) for C 21 H 33 BrO2(M + ): calc.: 396.1664, found: 396.1661.

[0177]

[0178] (Step 3) Preparation of compounds 3a to 3g

[0179] Under a nitrogen atmosphere, compound 1a, compound 1b or compound 1c (1.10 eq.), compound 2a, compound 2b or compound 2c (1.00 eq.), cesium carbonate (Cs2CO3, 2.0 eq.) and potassium iodide (KI, 0.01 eq.) were placed in a round-bottomed flask, and dry acetonitrile was added to obtain a reaction mixture. Then, the reaction mixture was stirred in a dark room at 70°C for 24 h. The reaction mixture was cooled to room temperature, the acetonitrile solution was filtered, and the solvent was concentrated in vacuo to obtain the product. The product was extracted with dichloromethane (DCM). Dichloromethane was removed in vacuo, and the product was obtained by extraction with pentane. The pentane solution was filtered through Celite and the solvent was concentrated in vacuo to obtain brown oil compounds (3a, 3b, 3c, 3d, 3e, 3f, 3g) to be used in the next step without further purification.

[0180]

[0181] (Step 4) Preparation of compounds 4a to 4g

[0182] Under a nitrogen atmosphere, compounds 3a, 3b, 3c, 3d, 3e, 3f, or 3g (1.00 eq.) were placed in a round-bottomed flask, and dry hydrochloric acid (2 M in ethanol, 1.10 eq.) was added at 0°C to obtain a reaction mixture. The reaction mixture was stirred at room temperature for 30 minutes. The remaining hydrochloric acid was removed in vacuo until bubbling disappeared, and the reaction mixture was stirred at 70°C for 24 hours. The reaction mixture was cooled to room temperature, the acetonitrile solution was filtered, and the solvent was concentrated in vacuo to obtain the product. The product was redissolved in dichloromethane (DCM), and an aqueous sodium tetrafluoroborate (NaBF4) solution was added, followed by stirring for 2 hours to obtain the product. The product was extracted with dichloromethane, washed with distilled water and brine, and then dried over anhydrous sodium sulfate (Na2SO4). The dichloromethane solution was removed in vacuo and the product was washed with ethanol and pentane and dried in vacuo to give brown jelly solid compounds (4a, 4b, 4c, 4d, 4e, 4f, 4g).

[0183]

[0184] Compound 4a (n = 6, R 11 = Me, R 12 = H, 784mg, 78%)

[0185] 1H NMR (500 MHz, CD3CN): δ (ppm) 9.22 (s, 1H), 7.53-7.41 (m, 5H), 7.05-6.98 (m, 2H), 6.89 (d,J= 8.9 Hz, 1H), 6.84 (dd,J= 16.1, 2.4 Hz, 1H), 6.79 (dd,J= 8.9, 3.1 Hz, 1H), 5.76 (dd,J= 17.8, 1.3 Hz, 1H), 5.23 (dd,J= 11.2, 1.3 Hz, 1H), 4.43 (quint,J= 6.1 Hz, 1H), 4.02 (t,J= 6.5 Hz, 2H), 3.96 (t,J= 6.5 Hz, 2H), 3.00 (d,J= 14.0 Hz, 1H), 2.74 (d,J= 14.0 Hz, 1H), 2.29 (s, 3H), 2.14 (s, 3H), 1.92 (s, 3H), 1.81-1.75 (m, 4H), 1.59 (s, 3H), 1.54-1.51 (m, 4H), 1.42 (s, 3H), 1.26 (d,J= 6.0 Hz, 6H).

[0186] 13 C NMR (125 MHz, CD3CN): δ (ppm) 190.4, 161.0, 154.4, 150.2, 142.1, 136.7, 132.7, 130.7, 129.8, 129.5, 126.9, 126.6, 117.9, 116.2, 116.0, 114.8, 112.5, 85.6, 72.8, 69.2, 69.1, 55.9, 49.5, 29.9, 29.6, 28.4, 28.0, 27.7, 26.4, 26.3, 22.4, 20.1, 19.9.

[0187] 19 F NMR (470 MHz, CD3CN): δ (ppm) -151.8, -151.9.

[0188] HRMS(FAB) for C 38 H 50 NO3(M + ): calc.: 568.3791, found: 568.3788.

[0189]

[0190] 화합물 4b (n = 8, R 11 = Me, R 12 = H, 1.10g, 64%)

[0191] 1 H NMR (500 MHz, CD3CN): δ (ppm) 9.04 (s, 1H), 7.53-7.42 (m, 5H), 7.04-6.97 (m, 2H), 6.89 (d,J= 8.9 Hz, 1H), 6.84 (d,J= 13.7 Hz, 2H), 6.78 (dd,J= 8.9, 2.7 Hz, 1H), 5.76 (d,J= 17.8 Hz, 1H), 5.23 (d,J= 11.2 Hz, 1H), 4.42 (quint,J= 6.0 Hz, 1H), 4.01 (t,J= 6.5 Hz, 2H), 3.94 (t,J= 6.5 Hz, 2H), 3.00 (d,J= 14.1 Hz, 1H), 2.75 (d,J= 14.1 Hz, 1H), 2.29 (s, 3H), 2.14 (s, 3H), 1.92 (s, 3H), 1.80-1.71 (m, 4H), 1.59 (s, 3H), 1.46-1.40 (m, 11H), 1.26 (d,J= 6.1 Hz, 6H).

[0192] 13 C NMR (125 MHz, CD3CN): δ (ppm) 190.2, 161.1, 154.4, 150.2, 142.0, 136.7, 136.6, 132.7, 130.7, 129.8, 129.5, 126.9, 117.9, 116.2, 116.0, 114.8, 112.5, 85.7, 72.8, 69.3, 69.2, 55.9, 49.5, 30.0, 29.9, 29.9, 29.7, 28.3, 28.0, 27.7, 26.6, 26.5, 22.4, 20.1, 19.9.

[0193] 19 F NMR (470 MHz, CD3CN): δ (ppm) -151.8, -151.9.

[0194] HRMS(FAB) for C 40 H 54 NO3(M + ): calc.: 596.4104, found: 596.4107.

[0195]

[0196] 화합물 4c (n = 10, R 11 = Me, R 12 = H, 3.93g, 88%)

[0197] 1 H NMR (500 MHz, CD3CN): δ (ppm) 9.11 (s, 1H), 7.53-7.41 (m, 5H), 7.04-6.97 (m, 2H), 6.89 (d,J= 8.9 Hz, 1H), 6.84 (dd,J= 15.9, 2.4 Hz, 2H), 6.78 (dd,J= 8.9, 3.0 Hz, 1H), 5.75 (dd,J= 17.8, 1.3 Hz, 1H), 5.23 (dd,J= 11.2, 1.3 Hz, 1H), 4.42 (quint,J= 6.0 Hz, 1H), 4.00 (t,J= 6.5 Hz, 2H), 3.94 (t,J= 6.5 Hz, 2H), 3.00 (d,J= 14.1 Hz, 1H), 2.75 (d,J= 14.1 Hz, 1H), 2.29 (s, 3H), 2.14 (s, 3H), 1.92 (s, 3H), 1.79-1.69 (m, 4H), 1.59 (s, 3H), 1.46-1.43 (m, 7H), 1.40-1.32 (m, 8H), 1.26 (d,J= 6.1 Hz, 6H).

[0198] 13C NMR (125 MHz, CD3CN): δ (ppm) 190.3; 116.2, 116.0, 114.8, 112.6, 85.6, 72.9, 69.3, 69.2, 55.9, 49.5, 30.1, 30.1, 30.0, 30.0, 29.9, 29.7, 28.3, 28.0, 27.7,000. 26.7, 26.6, 22.4, 20.1,

[0199] 19 F NMR (470 MHz, CD3CN): δ (ppm) -151.8, -151.8.

[0200] HRMS(FAB) for C 42 H 58 NO3(M + ): calc.: 624.4417, found:

[0201]

[0202] 4d (n = 6, R). 11 = And, R 12 = H, 1.15g, 77%)

[0203] 1H NMR (500 MHz, CD3CN): δ (ppm) 9.25 (s, 1H), 7.54-7.51 (m, 2H), 7.46-7.42 (m, 3H), 7.05-6.98 (m, 1H), 6.93-6.89 (m, 2H), 6.79 (dd,J= 8.9, 3.1 Hz, 1H), 5.76 (d,J= 17.8 Hz, 1H), 5.23 (d,J= 11.2 Hz, 1H), 4.43 (quint,J= 6.1 Hz, 1H), 4.06 (t,J= 6.5 Hz, 2H), 3.96 (t,J= 6.5 Hz, 2H), 3.03 (d,J= 14.1 Hz, 1H), 2.75 (d,J= 14.1 Hz, 1H), 2.63 (dt,J= 7.5 Hz, 1H), 2.51-2.43 (m, 2H), 2.28 (dt,J= 7.4 Hz, 1H), 1.92 (s, 3H), 1.83-1.75 (m, 4H), 1.55-1.52 (m, 7H), 1.36 (s, 3H), 1.27-1.23 (m, 9H), 1.14 (t,J= 7.5 Hz, 3H).

[0204] 13 C NMR (125 MHz, CD3CN): δ (ppm) 190.7, 161.8, 154.5, 150.3, 142.7, 142.5, 142.3, 132.8, 130.7, 129.9, 129.5, 126.9, 124.5, 118.0, 116.1, 114.8, 114.5, 114.5, 112.7, 85.1, 72.9, 69.2, 56.0, 49.2, 30.0, 29.7, 28.5, 27.5, 27.4, 26.5, 26.4, 26.1, 25.9, 22.4, 15.8, 15.6.

[0205] 19 F NMR (470 MHz, CD3CN): δ (ppm) -151.6, -151.6.

[0206] HRMS(FAB) for C 40 H 54 NO3(M +): calc.: 596.4104, found: 596.4102.

[0207]

[0208] 화합물 4e (n = 6, R 11 = i Pr, R 12 = H, 1.63g, 84%)

[0209] 1 H NMR (500 MHz, CD3CN): δ (ppm) 9.18 (s, 1H), 7.53 (t,J= 7.5 Hz, 2H), 7.46-7.42 (m, 3H), 7.05-6.98 (m, 2H), 6.95-6.88 (m, 3H), 6.79 (dd,J= 8.9, 2.9 Hz, 1H), 5.76 (d,J= 17.8 Hz, 1H), 5.23 (d,J= 11.2 Hz, 1H), 4.43 (quint,J= 6.1 Hz, 1H), 4.08 (t,J= 6.5 Hz, 1H), 3.96 (t,J= 6.4 Hz, 2H), 3.06 (d,J= 14.1 Hz, 1H), 2.80-2.72 (m, 2H), 2.51 (quint,J= 6.7 Hz, 1H), 1.91 (s, 3H), 1.83-1.76 (m, 4H), 1.56-1.54 (m, 7H), 1.37-1.36 (m, 6H), 1.26 (d,J= 6.0 Hz, 6H), 1.23 (d,J= 6.7 Hz, 3H), 1.15 (d,J= 6.7 Hz, 3H), 1.08 (d,J= 6.6 Hz, 3H).

[0210] 13C NMR (125 MHz, CD3CN): δ (ppm) 190.0; 118.0, 116.1, 114.8, 112.7, 112.3, 112.2, 85.2, 72.9, 69.3, 69.2, 55.9, 49.1, 30.7, 30.5, 30.0, 29.8, 27.8, 27.5. 27.4, 26.5, 26.4, 26.1, 26.0, 22.4, 22.1, 22.0.

[0211] 19 F NMR (470 MHz, CD3CN): δ (ppm) -151.7, -151.7.

[0212] HRMS(FAB) for C 42 H 58 NO3(M + ): calc.: 624.4417, found:

[0213]

[0214] scaffold 4f (n = 6, R). 11 = And, R 12 = Ph, 1.56g, 75%)

[0215] 1H NMR (500 MHz, CD3CN): δ (ppm) 9.12 (s, 1H), 7.56-7.51 (m, 4H), 7.45-7.41 (m, 5H), 7.37-7.34 (m, 1H), 7.14-7.08 (m, 2H), 6.90 (dd,J= 16.9, 2.7 Hz, 2H), 6.83 (d,J= 3.1 Hz, 1H), 5.81 (d,J= 17.8 Hz, 1H), 5.30 (d,J= 11.1 Hz, 1H), 4.07-4.02 (m, 4H), 3.61 (quint,J= 6.2 Hz, 1H), 3.03 (d,J= 14.1 Hz, 1H), 2.75 (d,J= 14.1 Hz, 1H), 2.63 (dt,J= 7.5 Hz, 1H), 2.50-2.43 (m, 2H), 2.27 (dt,J= 7.5 Hz, 1H), 1.91 (s, 3H), 1.84-1.77 (m, 4H), 1.56-1.53 (m, 7H), 1.36 (s, 3H), 1.23 (t,J= 6.9 Hz, 3H), 1.13 (t,J= 6.9 Hz, 3H), 0.90 (d,J= 6.2 Hz, 6H).

[0216] 13 C NMR (125 MHz, CD3CN): δ (ppm) 190.0, 161.8, 156.1, 147.3, 142.7, 142.5, 142.1, 140.2, 137.8, 134.2, 133.5, 130.8, 130.1, 129.6, 129.1, 128.2, 126.8, 124.5, 117.8, 115.3, 114.5, 114.5, 110.9, 85.3, 76.5, 69.3, 69.2, 55.9, 49.3, 30.0, 29.7, 28.1, 27.5, 27.5, 26.5, 26.4, 26.0, 25.9, 22.1, 15.7, 15.6.

[0217] 19 F NMR (470 MHz, CD3CN): δ (ppm) -151.8, -151.9.

[0218] HRMS(FAB)for C46 H 58 NO3(M + ): calc.: 672.4417, found: 672.4414.

[0219]

[0220] 화합물 4g(n = 6, R 11 = i Pr, R 12 = Ph, 1.97g, 87%)

[0221] 1 H NMR (500 MHz, CD3CN): δ (ppm) 9.18 (s, 1H), 7.56-7.52 (m, 4H), 7.46-7.41 (m, 5H), 7.37-7.34 (m, 1H), 7.14-7.08 (m, 2H), 6.92 (dd,J= 19.4, 2.7 Hz, 2H), 6.83 (d,J= 3.1 Hz, 1H), 5.80 (d,J= 17.7 Hz, 1H), 5.30 (d,J= 11.1 Hz, 1H), 4.08 (t,J= 6.5 Hz, 2H), 4.04 (t,J= 6.5 Hz, 2H), 3.61 (quint,J= 6.2 Hz, 1H), 3.06 (d,J= 14.1 Hz, 1H), 2.79-2.71 (m, 2H), 2.51 (quint,J= 6.7 Hz, 1H), 1.91 (s, 3H), 1.83-1.79 (m, 4H), 1.56-1.54 (m, 7H), 1.37-1.35 (m, 6H), 1.22 (d,J= 6.7 Hz, 6H), 1.14 (d,J= 6.7 Hz, 6H), 1.07 (d,J= 6.7 Hz, 6H), 0.90 (d,J= 6.2 Hz, 6H).

[0222] 13C NMR (125 MHz, CD3CN): δ (ppm) 190.0, 162.5, 156.1, 147.6, 147.4, 147.3, 142.1, 140.2, 137.8, 134.2, 133.5, 130.8, 130.2, 129.6, 129.1, 128.2, 126.7, 122.7, 117.8, 115.3, 112.3, 112.2, 110.9, 85.2, 76.5, 69.3, 69.2, 55.9, 49.1, 30.7, 30.5, 30.0, 29.8, 27.8, 27.5, 27.4, 26.5, 26.4, 26.1, 26.0, 22.1, 22.0.

[0223] 19 F NMR (470 MHz, CD3CN): δ (ppm) -151.7, -151.7.

[0224] HRMS(FAB) for C 48 H 62 NO3(M + ): calc.: 700.4730, found: 700.4731.

[0225]

[0226] (Step 5) Preparation of compounds Ru-1 to Ru-7

[0227] Under a nitrogen atmosphere, compounds 4a, 4b, 4c, 4d, 4e, 4f, or 4g (2.00 eq.) were placed in a round-bottomed flask, dry toluene was added, and lithium bis(trimethylsilyl)amide (LiHMDS, 1 M in toluene, 2.10 eq.) was added at room temperature to obtain a reaction mixture. The reaction mixture was stirred at room temperature for 30 min. A dry toluene solution of a ruthenium precursor (a first-generation Grubbs complex) was slowly added to the stirred reaction mixture. The reaction mixture containing the ruthenium precursor was stirred at 40°C overnight and then at 70°C overnight. Then, the reaction product, after removing toluene in vacuo, was purified by fresh column chromatography eluting with ethyl acetate (EtOAc) / hexane (2:8) to obtain a solid. The solid was diluted in a small amount of dichloromethane (DCM) and precipitated in pentane to obtain dark green solid compounds (Ru-1 to Ru-7).

[0228] Compound Ru-1 1 H NMR spectrum and 13 The C NMR spectra of compound Ru-2 are shown in Fig. 1a and Fig. 1b. 1 H NMR spectrum and 13 The C NMR spectra of compound Ru-3 are shown in Fig. 2a and Fig. 2b. 1 H NMR spectrum and 13 The C NMR spectra of compound Ru-4 are shown in Fig. 3a and Fig. 3b. 1 H NMR spectrum and 13 The C NMR spectra of compound Ru-5 are shown in Fig. 4a and Fig. 4b. 1 H NMR spectrum and 13 The C NMR spectra of compound Ru-6 are shown in Fig. 5a and Fig. 5b. 1 H NMR spectrum and 13 The C NMR spectra of compound Ru-7 are shown in Fig. 6a and Fig. 6b. 1 H NMR spectrum and13 The C NMR spectra are shown in Figs. 7a and 7b.

[0229]

[0230] Compound Ru-1 (n-1 = 5, R 11 = Me, R 12 = H, 38mg, 18%)

[0231] 1 H NMR (500 MHz, CDCl3): δ (ppm) 16.27 (s, 1H), 8.20 (d,J= 7.5 Hz, 2H), 7.54 (t,J= 7.8 Hz, 2H), 7.37 (t,J= 7.4 Hz, 1H), 7.12 (dd,J= 8.9, 2.9 Hz, 1H), 6.83 (dd,J= 23.5, 2.5 Hz, 2H), 6.74 (d,J= 9.0 Hz, 1H), 6.39 (d,J= 2.9 Hz, 1H), 4.87 (quint,J= 6.2 Hz, 1H), 4.25 (t,J= 5.1 Hz, 2H), 3.99 (m, 2H), 3.12 (d,J= 12.8 Hz, 1H), 2.38 (d,J= 12.8 Hz, 1H), 2.35 (s, 3H), 2.32 (s, 3H), 2.22 (s, 3H), 1.82-1.70 (m, 4H), 1.65-1.55 (m, 7H), 1.49 (s, 3H), 1.45 (d,J= 6.1 Hz, 3H), 1.34 (d,J= 6.1 Hz, 3H).

[0232] 13 C NMR (125 MHz, CDCl3): δ (ppm) 302.4, 264.0, 158.1, 154.2, 146.8, 144.9, 142.6, 140.3, 140.2, 133.3, 129.4, 129.1, 127.7, 121.2, 115.4, 115.3, 114.1, 109.2, 78.4, 74.5, 70.0, 67.1, 63.3, 49.1, 31.6, 28.4, 28.0, 27.6, 27.5, 25.2, 24.5, 22.3, 22.3, 22.1, 20.8.

[0233] HRMS(EI) for C 37 H 47 Cl2NO3Ru (M +· ): calc.: 725.1976, found: 725.1978.

[0234]

[0235] 화합물 Ru-2 (n-1 = 7, R 11 = Me, R 12 = H, 49mg, 15%)

[0236] 1 H NMR (500 MHz, CDCl3): δ (ppm) 16.35 (s, 1H), 8.20 (d,J= 7.5 Hz, 2H), 7.53 (t,J= 7.8 Hz, 2H), 7.36 (t,J= 7.4 Hz, 1H), 7.08 (dd,J= 8.9, 2.9 Hz, 1H), 6.83 (dd,J= 28.7, 2.7 Hz, 2H), 6.73 (d,J= 9.0 Hz, 1H), 6.41 (d,J= 2.9 Hz, 1H), 4.87 (quint,J= 6.2 Hz, 1H), 4.09 (t,J= 5.9 Hz, 2H), 3.88 (m, 2H), 3.11 (d,J= 12.8 Hz, 1H), 2.38 (d,J= 12.8 Hz, 1H), 2.34 (s, 3H), 2.32 (s, 3H), 2.20 (s, 3H), 1.92-1.73 (m, 4H), 1.62-1.42 (m, 17H), 1.34 (d,J= 6.1 Hz, 3H).

[0237] 13C NMR (125 MHz, CDCl3): δ (ppm) 302.9, 263.9, 158.9, 154.4, 146.6, 145.2, 142.6, 140.0, 139.9, 133.1, 129.3, 129.2, 127.6, 117.5, 115.5, 115.1, 113.5, 110.4, 78.4, 74.4, 70.3, 67.3, 63.3, 49.2, 31.5, 28.8, 28.5, 28.3, 28.0, 28.0, 27.5, 25.7, 25.2, 22.3, 22.2, 22.1, 20.7.

[0238] HRMS(EI) for C 39 H 51 Cl2NO3Ru (M +· ): calc.: 753.2289, found: 753.2286.

[0239]

[0240] 화합물 Ru-3 (n-1 = 9, R 11 = Me, R 12 = H, 27mg, 8%)

[0241] 1 H NMR (500 MHz, CDCl3): δ (ppm) 16.51 (s, 1H), 8.19 (d,J= 7.4 Hz, 2H), 7.53 (t,J= 7.9 Hz, 2H), 7.36 (t,J= 7.4 Hz, 1H), 7.06 (dd,J= 9.0, 3.0 Hz, 1H), 6.83 (dd,J= 27.5, 2.8 Hz, 2H), 6.73 (d,J= 8.9 Hz, 1H), 6.41 (d,J= 3.0 Hz, 1H), 4.87 (quint,J= 6.1 Hz, 1H), 4.04 (t,J= 6.4 Hz, 2H), 3.84 (t,J= 6.1 Hz, 2H), 3.09 (d,J= 12.8 Hz, 1H), 2.37 (d,J= 12.8 Hz, 1H), 2.34 (s, 3H), 2.32 (s, 3H), 2.21 (s, 3H), 1.92-1.70 (m, 4H), 1.60-1.28 (m, 24H).

[0242] 13 C NMR (125 MHz, CDCl3): δ (ppm) 303.0, 263.7, 159.0, 154.3, 146.5, 145.3, 142.6, 139.8, 139.7, 132.9, 129.3, 129.3, 127.6, 116.0, 115.3, 115.0, 113.3, 110.0, 78.5, 74.5, 68.7, 67.6, 63.3, 49.3, 31.5, 28.9, 28.8, 27.8, 27.6, 27.5, 27.3, 25.4, 25.2, 22.3, 22.2, 22.0, 20.6.

[0243] HRMS(FAB) for C 41 H 55 Cl2NO3Ru (M +· ): calc.: 781.2602, found: 781.2606.

[0244]

[0245] compound Ru-4 (n-1 = 5, R 11 = And, R 12 = H, 19mg, 9%)

[0246] 1H NMR (500 MHz, CDCl3): δ (ppm) 16.35 (s, 1H), 8.23 (d,J= 7.5 Hz, 2H), 7.54 (t,J= 7.9 Hz, 2H), 7.36 (t,J= 7.4 Hz, 1H), 7.11 (dd,J= 8.9, 3.0 Hz, 1H), 6.97 (dd,J= 22.2, 2.9 Hz, 2H), 6.75 (d,J= 9.0 Hz, 1H), 6.32 (d,J= 3.0 Hz, 1H), 4.87 (quint,J= 6.2 Hz, 1H), 4.32 (t,J= 5.3 Hz, 2H), 4.01-3.93 (m, 2H), 3.13 (d,J= 12.6 Hz, 1H), 2.65 (heptet,J= 7.8 Hz, 2H), 2.52-2.43 (m, 2H), 2.36 (d,J= 12.6 Hz, 1H), 2.32 (s, 3H), 1.88-1.83 (m, 2H), 1.72-1.62 (m, 4H), 1.58-1.51 (m, 8H), 1.39-1.38 (m, 6H), 1.08 (t,J= 7.4 Hz, 3H), 0.86 (t,J= 7.4 Hz, 3H).

[0247] 13 C NMR (125 MHz, CDCl3): δ (ppm) 300.6, 264.3, 158.7, 154.2, 147.0, 145.4, 145.2, 144.4, 143.4, 132.1, 129.5, 128.7, 127.6, 120.9, 114.2, 112.8, 112.8, 108.6, 77.6, 74.5, 70.0, 67.1, 63.3, 48.4, 31.3, 28.6, 28.0, 27.7, 27.6, 26.0, 25.3, 24.6, 24.5, 22.6, 22.4, 14.8, 14.2.

[0248] HRMS(FAB) for C 39 H 51 Cl2NO3Ru (M +· ): calc.: 753.2289, found: 753.2294.

[0249]

[0250] 화합물 Ru-5 (n-1 = 5, R 11 = i Pr, R 12 = H, 94mg, 42%)

[0251] 1 H NMR (500 MHz, CDCl3): δ (ppm) 16.49 (s, 1H), 8.25 (d,J= 7.9 Hz, 2H), 7.53 (t,J= 7.8 Hz, 2H), 7.36 (t,J= 7.9 Hz, 7.J= 28 Hz, 1H), 6.99 (dd,J= 21.0, 2.9 Hz, 2H), 6.75 (d,J= 9.0 Hz, 1H), 6.26 (d,J= 2.9 Hz, 1H), 4.86 (quint,J= 6.1 (3 Hz, 3H), 2H), 3.99-3.91 (m, 2H), 3.13 (d,J= 12.8 Hz, 1H), 3.05 (quint,J= 6.5 Hz, 2H), 2.95 (quint,J= 6.5 Hz2, 2H), 2.1-H-34 (m, 2.42). 4H), 1.74-1.61 (m, 4H), 1.54 (d,J= 6.1 Hz, 3H), 1.51 (s, 3H), 1.40 (s, 3H), 1.38 (d,Jd= 6.1 Hz, 3H), 1,3.32.3.3 (d,J), 1,3. 6.6 Hz, 3H), 0.85 (d,J= 6.5 Hz, 3H), 0.54 (d,J= 6.3 Hz, 3H).

[0252] 13C NMR (125 MHz, CDCl3): δ (ppm) 296.9; 114.3, 112.0, 111.9, 107.9, 74.6, 69.7, 67.2, 63.2, 48.2, 32.8, 31.8, 31.2, 29.2, 28.8, 28.7, 28.6, 27.9, 27.5, 27.4. 27.4, 27.3, 26.5, 26.0, 25.5, 24.8, 24.6, 24.5, 22.7, 22.4.

[0253] HRMS(FAB) for C 41 H 55 Cl2NO3Ru (M +· ): calc.: 781.2602, found: 781.2604.

[0254]

[0255] dielectric Ru-6 (n-1 = 5, R 11 = And, R 12 = Ph, 31mg, 13%)

[0256] 1H NMR (500 MHz, CDCl3): δ (ppm) 16.59 (s, 1H), 8.38 (d,J= 8.1 Hz, 2H), 7.57-7.54 (m, 4H), 7.40-7.31 (m, 4H), 7.03 (d,J= 3.0 Hz, 1H), 6.98 (dd,J= 13.5, 2.7 Hz, 2H), 6.27 (d,J= 3.0 Hz, 1H), 4.35-4.31 (m, 3H), 4.01 (t,J= 7.4 Hz, 2H), 3.18 (d,J= 12.5 Hz, 1H), 2.65-2.59 (m, 2H), 2.49 (q,J= 7.5 Hz, 2H), 2.35 (d,J= 12.5 Hz, 1H), 2.29 (s, 3H), 1.90-1.85 (m, 2H), 1.80-1.76 (m, 2H), 1.71-1.65 (m, 2H), 1.62-1.57 (m, 2H), 1.52 (s, 3H), 1.40 (s, 3H), 1.10 (t,J= 7.4 Hz, 3H), 1.00-0.98 (m, 6H), 0.93 (t,J= 7.4 Hz, 3H).

[0257] 13 C NMR (125 MHz, CDCl3): δ (ppm) 305.0, 264.2, 158.7, 154.9, 149.0, 145.5, 145.1, 145.0, 144.5, 139.1, 133.6, 131.9, 130.2, 128.8, 127.9, 127.7, 127.4, 123.4, 112.9, 112.7, 106.1, 69.8, 67.3, 63.9, 47.3, 31.3, 29.1, 28.6, 27.6, 27.5, 26.0, 25.3, 24.6, 24.4, 21.5, 21.3, 14.6, 14.2.

[0258] HRMS(FAB) for C 45 H 55 Cl2NO3Ru (M +· ): calc.: 829.2602, found: 829.2602.

[0259]

[0260] 화합물 Ru-7 (n-1 = 5, R 11 = i Pr, R 12 = Ph, 38mg, 15%)

[0261] 1 H NMR (500 MHz, CDCl3): δ (ppm) 16.74 (s, 1H), 8.37 (d,J= 7.6 Hz, 2H), 7.55-7.52 (m, 4H), 7.39-7.31 (m, 4H), 7.01-6.98 (m, 3H), 6.21 (d,J= 3.0 Hz, 1H), 4.38-4.31 (m, 3H), 4.01-3.97 (m, 2H), 3.21 (d,J= 12.6 Hz, 1H), 3.08 (quint,J= 6.5 Hz, 1H), 2.95 (quint,J= 6.6 Hz, 1H), 2.32 (d,J= 12.6 Hz, 1H), 2.24 (s, 3H), 1.92-1.85 (m, 2H), 1.79-1.65 (m, 4H), 1.57-1.53 (m, 2H), 1.51 (s, 3H), 1.43 (s, 3H), 1.30 (d,J= 6.6 Hz, 3H), 1.25 (d,J= 6.6 Hz, 3H), 1.02 (d,J= 6.3 Hz, 3H), 0.87 (d,J= 6.3 Hz, 3H), 0.83 (d,J= 6.4 Hz, 3H), 0.62 (d,J= 6.3 Hz, 3H).

[0262] 13 C NMR (125 MHz, CDCl3): δ (ppm) 300.3, 265.2, 158.8, 154.7, 150.3, 150.2, 147.6, 145.1, 144.4, 139.2, 133.6, 130.2, 129.8, 128.7, 128.7, 128.2, 127.9, 127.5, 123.2, 112.2, 111.8, 105.8, 69.5, 67.2, 63.6, 47.2, 33.0, 29.2, 28.8, 28.5, 28.5, 27.5, 27.4, 26.9, 25.5, 24.8, 24.7, 24.5, 21.8, 20.8.

[0263] HRMS(FAB) for C 47 H 59 Cl2NO3Ru (M +· ): calc.: 857.2915, found: 857.291

[0264]

[0265] Reference Example 1: Compound UltraNitroCat-1

[0266] [1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-yl](2-isopropoxy-5-nitrobenzylidene)ruthenium(II) chloride (UltraNitroCat-1, Tokyo Chemical Industry Co., Ltd) represented by the following chemical formula A was purchased and used.

[0267] [Chemical Formula A]

[0268]

[0269]

[0270] Analysis Example 1: X-ray crystal analysis

[0271] X-ray crystallography was performed on compounds Ru-1 to Ru-7 prepared in Examples 1 to 7. The crystals used for X-ray crystallography were coated with paratone-Noil. Diffraction data were measured by synchrotron radiation at the 2D and 11C beamlines at the Pohang Accelerator Laboratory, Korea. The structures were solved by ShelXT according to Sheldrick, G. Acta Crystallographica Section A2015, 71, 3-8 using intrinsic phase using Olex2 according to Journal of Applied Crystallography2009, 42, 339-341 and refined by ShelXL according to Sheldrick, G. Acta Crystallographica SectionC2015, 71, 3-8 using least squares minimization. The results are shown in Table 1 below.

[0272]

[0273]

[0274] Referring to Table 1, compounds Ru-1 to Ru-7 prepared in Examples 1 to 7 have a monoclinic crystal structure or a triclinic crystal structure and have a P-1 space group, a P21 / c space group or a P21 / n space group. In addition, compounds Ru-6 and Ru-7 prepared in Examples 6 to 7 have a further Ru-C1 distance, Ru-O distance and Ru-Cl1 distance compared to compounds Ru-1 to Ru-5 prepared in Examples 1 to 5. This means that compounds Ru-6 and Ru-7 prepared in Examples 6 to 7 have a further Ru-C1 distance, Ru-O distance and Ru-Cl1 distance. 11 This ethyl group or isopropyl group ( i Pr) and R 12 It is thought that the steric interaction is maximized compared to compounds Ru-1 to Ru-5 prepared in Examples 1 to 5 because it has a benzene ring.

[0275] From this, it can be confirmed that compounds Ru-1 to Ru-7 manufactured in Examples 1 to 7 can introduce various steric hindrances.

[0276]

[0277] Analysis Example 2: Analysis of thermal stability and steric bulk effects

[0278] Thermal stability tests were performed on compounds Ru-1, Ru-4, Ru-5, and Ru-6 prepared in Examples 1, 4, 5, and 6, and on compound UltraNitroCat-1 of Reference Example 1. The thermal stability tests were performed on the compounds in 0.024 M degassed toluene-d8 (manufactured by Merck) at 80°C in an air atmosphere. Thermal decomposition analysis of the compounds was performed using 1,3,5-trimethoxybenzene as an internal standard. 1 This was performed by monitoring the benzylidene peak by H NMR spectroscopy. The results are shown in Fig. 8.

[0279] Referring to FIG. 8, compounds Ru-1, Ru-4, and Ru-6 prepared in Examples 1, 4, and 6 maintained 70% purity even after one month. In comparison, compound UltraNitroCat-1 of Reference Example 1 showed 5% purity after the same period. The compound prepared in Example 6 showed similar thermal stability to compound Ru-4 prepared in Example 4 despite the crowded Blechert-type ligand. This is believed to be due to the rigid three-coordinate cyclic alkylaminocarbine ligand (CAAC).

[0280] In addition, the steric bulkiness effect of the N-aryl substituent was analyzed from the thermal stabilities of compounds Ru-1, Ru-4, and Ru-5 prepared in Examples 1, 4, and 5. Compound Ru-1 prepared in Example 1, which has the smallest methyl group as a substituent, showed faster thermal decomposition, whereas compound Ru-5 prepared in Example 5, which has a bulky isopropyl group, showed 95% purity after one month.

[0281] From this, it can be confirmed that compounds Ru-1, Ru-4, Ru-5, and Ru-6 prepared in Examples 1, 4, 5, and 6 have excellent thermal stability as catalysts used in ring expansion metathesis polymerization (REMP).

[0282]

[0283] To facilitate understanding of the present invention, exemplary embodiments have been described and illustrated in the accompanying drawings. However, it should be understood that these embodiments are merely illustrative and not limiting. Furthermore, it should be understood that the present invention is not limited to the illustrated and described descriptions, as various other modifications will occur to those skilled in the art.

Claims

1. A ruthenium complex represented by the following chemical formula 1: [Chemical Formula 1] Among the foods, n is an integer from 1 to 20; R1, R2, R3, R4 are C1-C independently substituted or unsubstituted 10 is an alkyl group; R5, R6, R7 is independently a hydrogen atom, substituted or unsubstituted C1-C 30 Alkyl group, substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 a heteroaryl group, or a combination thereof; R1, R2, R3, R4, R5, R6, Among R7, the above substitution is such that one of the hydrogen atoms is independently a halogen group, a hydroxyl group, a nitro group, a cyano group, an amino group, a C1-C 30 Alkyl amino group of C6- 30 Aryl amino group of C6- 30 Aryl silyl group, C1-C 30 Alkyl C6- 30 Aryl silyl group, C1-C 30 Alkyl group of C1-C 30 Haloalkyl group, C6- 30 Aryl C1-C 30 Alkyl group of C1-C 30 Alkoxy group, C3-C 30 Cycloalkyl group of C6- 30 Aryl group of C1-C 30 Alkyl C6- 30 Aryl group of C6- 30 Aryloxy group of C3- 30 Heteroaryl group of C1-C 30 Alkyl C3- 30 Heteroaryl group of C6- 30 Aryl C3- 30 substituted with a heteroaryl group, or a combination thereof; and X1 and X2 are independently a halogen atom, a substituted benzenethiol ligand, a substituted benzopyrazine ligand, or a combination thereof, Among X1 and X2, the above substitution is such that one of the hydrogen atoms is independently a halogen group, a thiol group, a dithiol group, an amino group, or a combination thereof.

2. In paragraph 1, A ruthenium complex compound, wherein n is an integer from 5 to 12.

3. In paragraph 1, The above R1, R2, R3, R4 A ruthenium complex, which is an unsubstituted C1-C5 alkyl group independently of each other.

4. In paragraph 1, The above R1 and R2 are the same group, ruthenium complex.

5. In paragraph 1, The above R5, R6, C3-C, wherein at least one of R7 is substituted or unsubstituted 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 A ruthenium complex, which is a heteroaryl group of , or a combination thereof.

6. In paragraph 1, C3-C wherein at least one of the above R6 and R7 is substituted or unsubstituted 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 A ruthenium complex, which is a heteroaryl group of , or a combination thereof.

7. In paragraph 1, X1, X2 are halogen atoms, ruthenium complex.

8. In paragraph 1, A ruthenium complex compound comprising at least one of the complex compounds represented by the following chemical formulas 2 to 8: [Chemical Formula 2] , [Chemical Formula 3] , , [Chemical Formula 4] , [Chemical Formula 5] , [Chemical Formula 6] , [Chemical Formula 7] , [Chemical Formula 8] .

9. In paragraph 1, The above complex has a monoclinic crystal structure, a triclinic crystal structure, or a combination thereof, A ruthenium complex having a space group of P-1, P21 / c, P21 / n, or a combination thereof.

10. A catalyst comprising a ruthenium complex according to any one of claims 1 to 9.

11. In paragraph 10, A catalyst used in ring expansion metathesis polymerization.

12. In paragraph 10, A catalyst having a micelle shape, a nanoparticle shape, or a combination thereof.

13. In paragraph 10, A catalyst used as a lubricant or coating agent.

14. A method for synthesizing a ruthenium complex, comprising: a step of reacting a cyclic alkylaminocarbine linked to isopropoxystyrene represented by the following chemical formula 9 and a ruthenium precursor to synthesize a ruthenium complex according to claim 1; [Chemical Formula 9] Among the foods, n' is an integer from 1 to 20; R'1, R'2, R'3, R'4 are C1-C independently substituted or unsubstituted 10 is an alkyl group; R'5, R'6 are each independently a hydrogen atom, substituted or unsubstituted C1-C 30 Alkyl group, substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 a heteroaryl group, or a combination thereof; Among R'1, R'2, R'3, R'4, R'5, R'6, the above substitution is such that one of the hydrogen atoms is independently a halogen group, a hydroxyl group, a nitro group, a cyano group, an amino group, a C1-C 30 Alkyl amino group of C6- 30 Aryl amino group of C6- 30 Aryl silyl group, C1-C 30 Alkyl C6- 30 Aryl silyl group, C1-C 30 Alkyl group of C1-C 30 Haloalkyl group, C6- 30 Aryl C1-C 30 Alkyl group of C1-C 30 Alkoxy group, C3-C 30 Cycloalkyl group of C6- 30 Aryl group of C1-C 30 Alkyl C6- 30 Aryl group of C6- 30 Aryloxy group of C3- 30 Heteroaryl group of C1-C 30 Alkyl C3- 30 Heteroaryl group of C6- 30 Aryl C3- 30 substituted with a heteroaryl group, or a combination thereof; and X ' is Cl - , Br - , I - , NO3 - , BF4 - , CF3SO3 - , C 32 H 12 BF 24 - , (C6F5)3B - , Or a combination of these.

15. In paragraph 14, A synthesis method wherein the above n' is an integer from 5 to 12.

16. In paragraph 14, A synthetic method wherein the ruthenium precursor comprises a precursor represented by the following chemical formula 10: [Chemical Formula 10] Among the foods, R7 is a hydrogen atom, substituted or unsubstituted C1-C 30 Alkyl group, substituted or unsubstituted C3-C 30 Cycloalkyl group, substituted or unsubstituted C6- 30 Aryl group, substituted or unsubstituted C3-C 30 a heteroaryl group, or a combination thereof; The above substitution is performed by substituting one of the hydrogen atoms independently with a halogen group, a hydroxyl group, a nitro group, a cyano group, an amino group, or a C1-C 30 Alkyl amino group of C6- 30 Aryl amino group of C6- 30 Aryl silyl group, C1-C 30 Alkyl C6- 30 Aryl silyl group, C1-C 30 Alkyl group of C1-C 30 Haloalkyl group, C6- 30 Aryl C1-C 30 Alkyl group of C1-C 30 Alkoxy group, C3-C 30 Cycloalkyl group of C6- 30 Aryl group of C1-C 30 Alkyl C6- 30 Aryl group of C6- 30 Aryloxy group of C3- 30 Heteroaryl group of C1-C 30 Alkyl C3- 30 Heteroaryl group of C6- 30 Aryl C3- 30 is substituted with a heteroaryl group, or a combination thereof.

17. In paragraph 14, A synthesis method, wherein the step of synthesizing the above ruthenium complex compound includes a process of synthesizing the ruthenium complex compound by stirring at a temperature of 25°C to 70°C for 48 hours or more.

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