Ligand compound, organic chromium compound, and catalyst composition comprising same

Abstract

The present invention relates to a ligand compound having a novel structure, which exhibits high selectivity to 1-hexene and 1-octene while exhibiting high catalytic activity, enables the oligomerization of ethylene with excellent efficiency, and has excellent selectivity to 1-hexene and 1-octene. The invention also relates to an organic chromium compound, a catalyst composition containing the organic chromium compound and a method for performing ethylene oligomerization by using the catalyst composition.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0051231 filed on April 19, 2023, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.

[0003] The present invention relates to a ligand compound, an organic chromium compound, a catalyst composition containing the organic chromium compound, and an ethylene oligomerization method using the catalyst composition. Background Art

[0004] Linear alpha-olefins, such as hexene or 1-octene, are used as detergents, lubricants or plasticizers, and are used as comonomers to control polymer density, in particular in the production of linear low-density polyethylene (LLDPE).

[0005] In the traditional production process of linear low density polyethylene (LLDPE), copolymerization with α-olefins (for example, comonomers such as 1-hexene or 1-octene) is allowed to occur in order to control the density by forming branches in the polymer backbone together with ethylene.

[0006] Therefore, in order to produce LLDPE with a high comonomer content, there is a problem in that the price of the comonomer accounts for a large part of the production cost. Various attempts have been made to solve this problem.

[0007] Such linear α-olefins are mainly produced by the Shell Advanced Olefins process, but this process simultaneously synthesizes α-olefins with different lengths according to the Schultz-Flory distribution, so additional separation processes are required to obtain specific α-olefins, which is very inconvenient.

[0008] To address this problem, methods for selectively synthesizing 1-hexene through ethylene trimerization or 1-octene through ethylene tetramerization have been proposed. Furthermore, extensive research has been conducted on catalyst systems that can achieve this selective oligomerization of ethylene.

[0009] Related technical literature

[0010] Patent Literature

[0011] Patent Document 1: US5064802B2 Summary of the Invention

[0012] Technical issues

[0013] The present invention aims to provide a ligand compound having a novel structure, an organochromium compound, and a catalyst composition containing the ligand compound, wherein the ligand compound exhibits high catalytic activity, high selectivity for 1-hexene and 1-octene, and can carry out ethylene oligomerization with excellent efficiency.

[0014] Technical Solution

[0015] In order to achieve the above object, the present invention provides a ligand compound, an organic chromium compound, a catalyst composition and an ethylene oligomerization method.

[0016] (1) The present invention provides a ligand compound represented by Chemical Formula 1.

[0017] [Chemical Formula 1]

[0018]

[0019] In Chemical Formula 1, R 1 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 6 Combine to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; when R 6 Not with R 1 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 6 is hydrogen; R 2 and R 3 are each independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an arylalkoxyalkyl group having 7 to 30 carbon atoms, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), wherein R 2 and R 3 Not hydrogen at the same time; R 4is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 7 Combine to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; when R 7 Not with R 4 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 7 is hydrogen; R 5 It is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

[0020] (2) The present invention provides the ligand compound according to (1),

[0021] Among them, R 1 is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 6 are combined to form a monocyclic or polycyclic heterocycle, and

[0022] R 4 is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 7 Combine to form a monocyclic or polycyclic heterocycle.

[0023] (3) The present invention provides the ligand compound according to (1) or (2),

[0024] where R 1 is fluoro, trifluoromethyl, methoxy, methyl, trifluoromethoxy, trifluoromethylthio, methylthio, methylsulfonate or trimethylsilyl, or is 6Combine to form furans or dibenzofurans, and

[0025] R 4 is fluoro, trifluoromethyl, methoxy, methyl, trifluoromethoxy, trifluoromethylthio, methylthio, methylsulfonate or trimethylsilyl, or is 7 Combined to form furan or dibenzofuran.

[0026] (4) The present invention provides the ligand compound according to any one of (1) to (3),

[0027] Among them, R 2 and R 3 Each is independently an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group or a tributylsilyl group.

[0028] (5) The present invention provides the ligand compound according to any one of (1) to (4),

[0029] Among them, R 2 and R 3 Each is independently n-decyl, tripropylsilyl or tributylsilyl.

[0030] (6) The present invention provides the ligand compound according to any one of (1) to (5),

[0031] Among them, R 5 It is an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

[0032] (7) The present invention provides the ligand compound according to any one of (1) to (6),

[0033] The ligand compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 2 to 5.

[0034] [Chemical Formula 2]

[0035]

[0036] [Chemical Formula 3]

[0037]

[0038] [Chemical Formula 4]

[0039]

[0040] [Chemical Formula 5]

[0041]

[0042] In Chemical Formulas 2 to 5, R 1 to R 7 The same as defined in (1) to (6), respectively.

[0043] (8) The present invention provides a ligand compound according to any one of (1) to (7), wherein the ligand compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 2-1 to 2-76 or Chemical Formulas 5-1 to 5-20.

[0044]

[0045]

[0046]

[0047]

[0048] (9) The present invention provides an organic chromium compound comprising the ligand compound according to any one of (1) to (8), and

[0049] Chromium coordinated to the ligand compound.

[0050] (10) The present invention provides an organic chromium compound according to (9), wherein the organic chromium compound has a form in which any one or more unshared electron pairs of N and two P in the ligand compound represented by Chemical Formula 1 are coordinated with chromium.

[0051] (11) The present invention provides a catalyst composition comprising the ligand compound according to any one of (1) to (8), chromium, and a co-catalyst.

[0052] (12) The present invention provides a catalyst composition according to (11), wherein the chromium is derived from a chromium source, and the chromium source comprises one or more selected from chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) valerate, chromium (III) laurate, tris(2,2,6,6-tetramethyl-3,5-heptanedione)chromium (III), and chromium (III) stearate.

[0053] (13) The present invention provides a catalyst composition according to (11) or (12), wherein the co-catalyst is at least one or more selected from the compounds represented by Chemical Formula 6 to Chemical Formula 9.

[0054] [Chemical Formula 6]

[0055] -[Al(R 13 )-O] a -

[0056] In Chemical Formula 6, R 13 Each is independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen group, and a is an integer of 2 or greater.

[0057] [Chemical Formula 7]

[0058] E(R 14 )3

[0059] In Chemical Formula 7, E is aluminum or boron, and R 14 are each independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group,

[0060] [Chemical Formula 8]

[0061] [LH] + [G(Y)4] -

[0062] [Chemical Formula 9]

[0063] [L] + [G(Y)4] -

[0064] In Formulas 8 and 9, L is a neutral or cationic Lewis acid, [LH] + is a Bronsted acid, G is a Group 13 element, and Y is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or the aryl group is substituted, the substituent is a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0065] (14) The present invention provides a method for producing linear α-olefins, which includes the step (S10) of oligomerizing ethylene in the presence of the catalyst composition according to any one of (11) to (13).

[0066] (15) The present invention provides a method for producing a linear α-olefin according to (14), wherein the linear α-olefin is 1-hexene, 1-octene, or a mixture thereof.

[0067] Beneficial effects

[0068] When ethylene oligomerization is carried out using an organochromium compound and a catalyst composition containing the ligand compound of the present invention, excellent productivity can be maintained due to high catalytic activity, and linear α-olefins can be produced with high selectivity for 1-hexene and 1-octene. DETAILED DESCRIPTION

[0069] Below, the present invention is described in more detail to facilitate understanding of the present invention.

[0070] The terms and words used in the description of this specification and claims should not be restrictively interpreted as their ordinary meanings or dictionary meanings, but should be interpreted in accordance with meanings and concepts consistent with the technical ideas of the present invention based on the principle that the inventor can appropriately define the concepts of the terms to describe his invention in the best way.

[0071] Ligand compounds

[0072] The present invention provides a ligand compound suitable for use in an ethylene oligomerization catalyst. When used in an ethylene oligomerization reaction, specifically in a catalyst composition for forming linear α-olefins, this ligand compound exhibits excellent catalytic activity while achieving high selectivity for linear α-olefins. In particular, compared to existing PNP catalysts and catalysts containing symmetrical ligand compounds, even under the same reaction conditions, this ligand compound produces less solid polyethylene, thereby enabling more efficient production of linear α-olefins.

[0073] According to one embodiment of the present invention, when linear α-olefins are produced using ethylene, an organochromium compound coordinated with a ligand compound can be used. Since the oligomerization reaction is carried out under ethylene conditions, liquid α-olefins, specifically liquid 1-hexene or 1-octene, can be formed with high selectivity. This is because, in the oligomerization reaction of ethylene, the selectivity for α-olefins of a specific length is increased by forming a transition state of a metal-containing cyclic compound (metallocycle).

[0074] According to one embodiment of the present invention, described ligand compound comprises diphosphino moiety, and the aryl with specific substituent is connected to the end of diphosphino moiety, therefore itself can have the form as strong electron donating group.Due to such structural characteristic, described ligand compound can be applied in ethylene oligomerization catalytic system to show high activity, particularly 1-hexene, 1-octene etc. are shown high selectivity.This may be due to the interaction between adjacent chromium active sites, particularly when the aryl replaced with specific substituent is connected to the phosphorus (P) atom of diphosphino group, the electron density at phosphorus (P) atom and nitrogen (N) atom contained in diphosphino group increases, thereby the electrical property and the three-dimensional property of whole ligand compound change.As a result, the key between part and the chromium atom changes, and makes the structure of catalyst more stable.In addition, compared with existing metal cycloheptane or metal cyclononane form, the energy (activation energy) of transition state changes, and this makes it possible to form the alpha-olefin with more high activity and selectivity, and the amount of by product can be further reduced, for example, there is the solid alpha-olefin of high molecular weight, for example polyethylene wax (PE wax).

[0075] According to one embodiment of the present invention, the ligand compound is characterized in that, the phenyl group at the end of the diphosphino moiety has the following groups as substituents in the ortho position: halogen groups, alkyl groups with 1 to 10 carbon atoms substituted or unsubstituted by halogen groups, alkoxy groups with 1 to 10 carbon atoms substituted or unsubstituted by halogen groups, alkylthio groups with 1 to 10 carbon atoms substituted or unsubstituted by halogen groups, alkyl sulfonate groups with 1 to 10 carbon atoms substituted or unsubstituted by halogen groups, or trialkylsilyl groups (the alkyl group of the trialkylsilyl group is each independently an alkyl group with 1 to 10 carbon atoms), or fused with the phenyl group to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, and each has the following groups as substituents in the meta and para positions: an alkyl group with a specific number of carbon atoms or a silyl group substituted by an alkyl group with a specific number of carbon atoms. The substituents substituted in the ortho position of the phenyl group increase the steric strain around the metal atom, thereby improving the selectivity for 1-hexene. Furthermore, it protects the metal atom or directly forms a coordination bond, thereby improving the stability of the metal complex. Simultaneously, the substituents substituted at the meta and para positions of the phenyl group increase the solubility of the ligand compound and the metal complex in various polymerization solvents, thereby improving activity and selectivity. Therefore, when using this ligand compound, chromium catalysts with high stability, excellent activity, and excellent selectivity can be prepared.

[0076] According to one embodiment of the present invention, since a macromolecular substituent such as a cycloalkyl or phenyl group is bound to the nitrogen atom that is bound to two phosphorus atoms, and the macromolecular substituent bound to the nitrogen prevents the rotation of the bond between nitrogen and phosphorus, the ligand compound can further improve the stability and activity of the catalyst. In this case, the activity, stability and selectivity of the catalyst vary according to the three-dimensional properties of the substituent bound to the nitrogen atom. When the steric strain of the substituent bound to the nitrogen atom is too high, the problem is that the synthesis of the ligand and the formation of the metal complex are difficult, and the resulting complex is unstable. In addition, when the steric strain of the substituent bound to the nitrogen atom is too high, the problem is that the raw materials such as ethylene are difficult to access, so the activity of the catalyst is reduced. In addition, when the steric strain of the substituent bound to the nitrogen atom is too low, the rotation of the bond between the nitrogen atom and the phosphorus atom cannot be prevented, and the metal center atom cannot be protected, resulting in a decrease in the activity and stability of the catalyst. That is, when the steric strain of the substituent bound to the nitrogen atom is too high or too low, the activity of the catalyst decreases, and its stability decreases, which can lead to the problem of an increase in the amount of by-products such as polyethylene wax. Therefore, it is very important to select a substituent with an appropriate level of steric strain relative to the substituent bound to the phosphorus atom. In the ligand compound according to the present invention, as the substituent is introduced at the ortho position of the phenyl group bound to the phosphorus atom, the steric strain around the PNP functional group increases. Therefore, when R is introduced into the chemical formula 1, 5 In the case of a substituent represented by , the steric strain of the substituent bound to the nitrogen atom does not increase too much, and the yield and selectivity can be improved in the ethylene oligomerization reaction by using a catalyst composition containing the ligand compound according to the present invention. In particular, by introducing a substituent in the form of a secondary alkyl group as R in Chemical Formula 1 5 In the case of substituents represented by , the efficiency is further improved, and for substituents in the form of primary alkyl groups, appropriate steric strain can be formed by introducing an aromatic group (such as a phenyl group) at the 1st or 2nd carbon position to compensate for the low steric strain, thereby improving the yield and selectivity.

[0077] According to one embodiment of the present invention, the ligand compound may be represented by Chemical Formula 1.

[0078] [Chemical Formula 1]

[0079]

[0080] In Chemical Formula 1, R 1is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 6 Combine to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; when R 6 Not with R 1 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 6 is hydrogen; R 2 and R 3 are each independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an arylalkoxyalkyl group having 7 to 30 carbon atoms, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), wherein R 2 and R 3 Not hydrogen at the same time; R 4 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 7 Combine to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; when R 7 Not with R 4 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 7 is hydrogen; R 5 It is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

[0081] In the present invention, the "halogen group" refers to fluorine (-F), chlorine (-Cl), bromine (-Br), and iodine (-I).

[0082] In the present invention, the term "substituted by a halogen group" may mean that at least one hydrogen atom bonded to a carbon atom of each substituent is replaced by a halogen group atom, and when the number of carbon atoms of each substituent is mentioned, it may mean the number of carbon atoms of each substituent.

[0083] In the present invention, "alkyl" may refer to a straight-chain or branched hydrocarbon residue, and specific examples thereof may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and hexyl, depending on the number of carbon atoms defined.

[0084] In the present invention, the "alkylthio group" may refer to an alkylthio group in which any one substituent centered around a sulfur bond is an alkyl group, and when the number of carbon atoms is mentioned, it may refer to the number of carbon atoms of the alkyl group.

[0085] In the present invention, the "alkylsulfonate group" may refer to an alkylsulfonate group in which the sulfur atom of the sulfonate is substituted with an alkyl group, and in the case where the number of carbon atoms is mentioned, it may refer to the number of carbon atoms of the alkyl group.

[0086] In the present invention, "trialkylsilyl group" is represented by -SiR3, wherein each R independently represents an alkyl group as a substituent, and when the number of carbon atoms of the trialkylsilyl group is mentioned, it may refer to the total number of carbon atoms of each R.

[0087] In the present invention, a "monocyclic aromatic hydrocarbon ring" may refer to an aromatic hydrocarbon consisting of one ring, such as a benzene ring, and a "polycyclic aromatic hydrocarbon ring" may refer to an aromatic hydrocarbon consisting of two or more rings, such as a naphthalene ring.

[0088] In the present invention, a "monocyclic heterocycle" may refer to a heterocycle consisting of one ring containing heteroatoms, such as furan, thiophene, pyrrole, or pyridine; and a "polycyclic heterocycle" may refer to a heterocycle consisting of two or more rings containing heteroatoms, such as benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, benzopyrrole, or dibenzopyrrole. The heterocycles may form an aliphatic ring or an aromatic ring.

[0089] In the present invention, "cycloalkyl" may refer to a hydrocarbon residue having a ring form, and specific examples may include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, depending on the number of carbon atoms defined.

[0090] In the present invention, the "alkoxyalkyl group" may refer to an alkyl group substituted with an alkoxy group, and when the number of carbon atoms of the alkoxyalkyl group is mentioned, it may refer to the sum of the carbon atoms of the alkoxy group and the alkyl group.

[0091] In the present invention, the "arylalkoxyalkyl group" may refer to an alkyl group substituted with an alkoxy group containing an aryl group as a substituent, and when the number of carbon atoms of the arylalkoxyalkyl group is mentioned, it may refer to the sum of the carbon atoms of the alkoxy group and the alkyl group.

[0092] In the present invention, unless otherwise specified, "aryl" refers to an optionally substituted benzene ring or a ring system formed by fusing one or more optional substituents. Examples of optional substituents include substituted alkyl groups having 1 to 2 carbon atoms, substituted alkenyl groups having 2 to 3 carbon atoms, substituted alkynyl groups having 2 to 3 carbon atoms, heteroaryl groups, heterocyclyl groups, aryl groups, alkoxy groups optionally having 1 to 3 fluorine substituents, aryloxy groups, aralkyloxy groups, acyl groups, aroyl groups, heteroaroyl groups, acyloxy groups, aroyloxy groups, heteroaroyloxy groups, sulfanyl groups, sulfinyl groups, sulfonyl groups, aminosulfonyl groups, sulfonamido groups, carboxamide groups, aminocarbonyl groups, carboxyl groups, oxo groups, hydroxyl groups, thiol groups, amino groups, nitro groups, cyano groups, halogen groups, or ureido groups. The ring or ring system may be optionally fused to an aromatic ring (e.g., a benzene ring), a carbocyclic ring, or a heterocyclic ring, which may optionally have one or more substituents, which may include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracenyl, and phenanthrenyl, and substituted derivatives thereof.

[0093] In the present invention, the abbreviation "Me" represents a methyl group, the abbreviation "iPr" represents an isopropyl group, the abbreviation "Bu" represents an n-butyl group, the abbreviation "Cy" represents a cyclohexyl group, the abbreviation "Ph" represents a phenyl group, the abbreviation "Bz" represents a benzyl group, and the abbreviation "MsO-" or "-OMs" represents a methanesulfonate group (MeO2SO-).

[0094] According to one embodiment of the present invention, R 1 It may be a fluoro group, a chloro group, a bromo group, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or a group which is in the group consisting of R 6 Combine to form a monocyclic or polycyclic heterocycle. As a specific example, R 1 It can be a fluoro group, a trifluoromethyl group, a methoxy group, a methyl group, a trifluoromethoxy group, a trifluoromethylthio group, a methylthio group, a methylsulfonate group, or a trimethylsilyl group, or 6 Combine to form furans or dibenzofurans.

[0095] According to one embodiment of the present invention, R 4It may be a fluoro group, a chloro group, a bromo group, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or a group which is in the group consisting of R 7 Combine to form a monocyclic or polycyclic heterocycle. As a specific example, R 4 It can be a fluoro group, a trifluoromethyl group, a methoxy group, a methyl group, a trifluoromethoxy group, a trifluoromethylthio group, a methylthio group, a methylsulfonate group, or a trimethylsilyl group, or 7 Combine to form furans or dibenzofurans.

[0096] According to one embodiment of the present invention, R 1 and R 4 They may be the same as or different from each other.

[0097] According to one embodiment of the present invention, R 2 and R 3 Each of the R groups may be independently an alkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkoxyalkyl group having 6 to 12 carbon atoms, an arylalkoxyalkyl group having 10 to 20 carbon atoms, or a trialkylsilyl group, wherein the alkyl group of the trialkylsilyl group may be independently an alkyl group having 1 to 5 carbon atoms. As a specific example, R 2 and R 3 Each of the groups R and R is independently an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group, or a tributylsilyl group. As a more specific example, R 2 and R 3 can be independently tripropylsilyl, tributylsilyl or n-decyl. That is, the ligand compound can be: the phenyl group at the end of the diphosphino part has R 1 and R 4 The substituent also has an alkyl group having 10 carbon atoms or a silyl group substituted with an alkyl group having 3 or 4 carbon atoms as a substituent at the meta-position or para-position.

[0098] According to one embodiment of the present invention, R 5 It may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused to an aryl group having 6 to 10 carbon atoms. As a specific example, R 5It may be an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms fused to an aryl group having 6 to 10 carbon atoms.

[0099] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 1 may be a compound represented by any one of Chemical Formulas 2 to 5.

[0100] [Chemical Formula 2]

[0101]

[0102] [Chemical Formula 3]

[0103]

[0104] [Chemical Formula 4]

[0105]

[0106] [Chemical Formula 5]

[0107]

[0108] In Chemical Formulas 2 to 5, R 1 to R 7 are the same as defined in Chemical Formula 1, respectively.

[0109] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 1 may be represented by any one of Chemical Formulas 2-1 to 2-76 or Chemical Formulas 5-1 to 5-20.

[0110]

[0111]

[0112]

[0113]

[0114] According to one embodiment of the present invention, in addition to the above specific examples, the ligand compound may be implemented in various combinations within the scope of satisfying the above conditions, and any compound represented by Chemical Formula 1 may be used as the ligand compound according to the present invention.

[0115] Organochromium compounds and catalyst compositions

[0116] The present invention provides an organic chromium compound comprising a ligand compound represented by Chemical Formula 1 and chromium (Cr) coordinated to the ligand compound.

[0117] According to one embodiment of the present invention, the organochromium compound is a chromium complex of a ligand compound, wherein the chromium of the chromium source forms a coordination bond with any one or more of the unshared electron pairs of N and two P atoms in the ligand compound represented by Chemical Formula 1. Specifically, the phosphorus atom or nitrogen atom of the diphosphino moiety provides an unshared electron pair to the chromium atom. In particular, a bidentate state in which two pairs of unshared electron pairs are coordinated is ideal. This organochromium compound can be used in a catalytic system for ethylene oligomerization, exhibiting excellent catalytic activity and high selectivity for 1-hexene or 1-octene.

[0118] In the present invention, a "catalyst composition" refers to a catalyst composition that can be obtained as an active catalyst composition by adding three components: a chromium source, a ligand compound, and a co-catalyst, or two components: a transition metal compound and a co-catalyst, simultaneously or in any order. The catalyst composition may also be referred to as a catalyst system, and in the present invention, the terms catalyst composition and catalyst system have the same meaning. The catalyst composition may be added in the presence or absence of a solvent and monomer, and may be used in a supported or unsupported state, as a three-component or two-component catalyst composition.

[0119] The present invention provides a catalyst composition comprising a ligand compound, chromium, and a co-catalyst. As described above, the ligand compound represented by Chemical Formula 1 and chromium can coordinate to form an organochromium compound. That is, the catalyst system can be a three-component catalyst system comprising chromium, the ligand compound represented by Chemical Formula 1, and a co-catalyst, or can be a two-component catalyst system comprising an organochromium compound and a co-catalyst. As a specific example, the catalyst composition can be a composition comprising a ligand compound, an organochromium compound containing chromium coordinated with the ligand compound, and a co-catalyst. In addition, the catalyst composition can be a composition comprising a chromium compound, wherein some components of the co-catalyst are combined with the organochromium compound.

[0120] According to one embodiment of the present invention, the chromium may be derived from a chromium source, which may be an organic or inorganic chromium compound having an oxidation state of 0 to 6. Specifically, the chromium source may be chromium metal or any compound comprising chromium bonded to an organic or inorganic group. The organic group may be, for example, an alkyl, alkoxy, ester, ketone, amide, or carboxylate group, each having 1 to 20 carbon atoms, and the inorganic group may be a halide, sulfate, oxide, or the like.

[0121] According to one embodiment of the present invention, the chromium source is a compound that exhibits high activity in olefin oligomerization reactions, is easy to use, and is easily available, and can be one or more compounds selected from chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) valerate, chromium (III) laurate, tris(2,2,6,6-tetramethyl-3,5-heptanedione)chromium (III), and chromium (III) stearate.

[0122] According to one embodiment of the present invention, the co-catalyst may be at least one or more selected from the group consisting of compounds represented by Chemical Formula 6 to Chemical Formula 9.

[0123] [Chemical Formula 6]

[0124] -[Al(R 13 )-O] a -

[0125] In Chemical Formula 6, R 13 Each is independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen group, and a is an integer of 2 or greater.

[0126] [Chemical Formula 7]

[0127] E(R 14 )3

[0128] In Chemical Formula 7, E is aluminum or boron, and R 14 Each is independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group.

[0129] [Chemical Formula 8]

[0130] [LH] + [G(Y)4] -

[0131] [Chemical Formula 9]

[0132] [L] + [G(Y)4] -

[0133] In Formulas 8 and 9, L is a neutral or cationic Lewis acid, [LH] +is a Bronsted acid, G is a Group 13 element, and Y is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or the aryl group is substituted, the substituent is a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0134] According to one embodiment of the present invention, the catalyst composition can be prepared by any of a variety of methods. As a specific example, first, the catalyst composition can be prepared by a step including contacting an organic chromium compound with a compound represented by Chemical Formula 6 or Chemical Formula 7. Second, the catalyst composition can be prepared by a step including contacting an organic chromium compound with a compound represented by Chemical Formula 6 or Chemical Formula 7 to obtain a mixture; and adding a compound represented by Chemical Formula 8 or Chemical Formula 9 to the mixture. Third, the catalyst composition can be prepared by a step including contacting an organic chromium compound with a compound represented by Chemical Formula 8 or Chemical Formula 9. Fourth, the catalyst composition can be prepared by a step including contacting an organic chromium compound with a compound represented by Chemical Formula 8 or Chemical Formula 9 to obtain a mixture; and adding a compound represented by Chemical Formula 6 or Chemical Formula 7 to the mixture. Fifth, the catalyst composition can be prepared by a step including contacting a chromium source with a compound represented by Chemical Formula 8 or Chemical Formula 9 to obtain a mixture; and contacting a ligand compound with a reactant.

[0135] According to one embodiment of the present invention, in the case of the first or third method of preparing the catalyst composition, the molar ratio of the compound represented by Chemical Formula 6 or Chemical Formula 7 to the organochromium compound may be 1:2 to 1:5,000, and as a specific example, may be 1:100 to 1:3,000, and as a more specific example, may be 1:300 to 1:1,500. Within this range, the alkylation of the organochromium compound can be completely carried out, thereby improving the activity of the catalyst composition, and can prevent the activity of the alkylated organochromium compound from being reduced due to side reactions between the residual alkylating agent, while improving the economic efficiency and the purity of the linear α-olefin produced.

[0136] According to one embodiment of the present invention, in the second method of preparing the catalyst composition, the molar ratio of the compound represented by Chemical Formula 8 or Chemical Formula 9 to the organochromium compound can be 1:1 to 1:500, specifically 1:1 to 1:50, and more specifically 1:1 to 1:25. Within this range, the amount of activator is sufficient, so the metal compound is fully activated, thereby improving the activity of the catalyst composition. In addition, the amount of residual activator is minimized, which can improve economic efficiency and the purity of the linear α-olefin produced.

[0137] According to one embodiment of the present invention, the compound represented by Chemical Formula 6 may be an alkylaluminoxane, specifically methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and more specifically methylaluminoxane.

[0138] According to one embodiment of the present invention, the compound represented by Chemical Formula 7 may be trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, dialkylaluminum hydride, alkylaluminum dihydride, trialkylboron, or the like. As a specific example, the compound represented by Chemical Formula 6 may be a trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum or tri-p-tolylaluminum; a dialkylaluminum halide such as diethylaluminum chloride; a dialkylaluminum hydride such as diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenyl isopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, or benzyl-n-octylaluminum hydride; an alkylaluminum dihydride, such as n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, or n-octylaluminum dihydride; or a trialkylboron, such as trimethylboron, triethylboron, triisobutylboron, tripropylboron, or tributylboron.

[0139] According to one embodiment of the present invention, the compound represented by Chemical Formula 8 or Chemical Formula 9 may be trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dioctadecylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, triethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, tributylammonium tetra(p-tolyl)borate, methyldioctadecylammonium tetra(p-tolyl)borate, N,N-dimethylanilinium tetra(p-tolyl)borate , N,N-diethylanilinium tetra(p-tolyl)borate, N,N-dioctadecylanilinium tetra(p-tolyl)borate, trimethylammonium tetra(o, p-dimethylphenyl)borate, triethylammonium tetra(o, p-dimethylphenyl)borate, tripropylammonium tetra(o, p-dimethylphenyl)borate, tributylammonium tetra(o, p-dimethylphenyl)borate, methyldioctadecylammonium tetra(o, p-dimethylphenyl)borate, N,N-dimethylanilinium tetra(o, p-dimethylphenyl)borate, N,N-diethylanilinium tetra(o, p-dimethylphenyl)borate, N,N-dioctadecylanilinium tetra(o, p-dimethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, triethylammonium tetra(o, p-dimethylphenyl)borate (p-Trifluoromethylphenyl)borate, tripropylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, methyldioctadecylammonium tetrakis(p-trifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-diethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-dioctadecylammonium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate Salt, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dioctadecylanilinium tetrakis(pentafluorophenyl)borate, trimethylphosphonium tetraphenylborate, triethylphosphonium tetraphenylborate, tripropylphosphonium tetraphenylborate, tributylphosphonium tetraphenylborate, trimethylcarbonium tetraphenylborate, triethylcarbonium tetraphenylborate, tripropylcarbonium tetraphenylborate, tributylcarbonium tetraphenylborate, trimethylammonium tetraphenylaluminate, triethylammonium tetraphenylaluminate, tripropyltetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetrakis(p-tolyl)aluminate, triethylammonium tetrakis(p-tolyl)aluminate, tripropylammonium tetrakis(p-tolyl)aluminate, tributylammonium tetrakis(p-tolyl)aluminate, and the like.

[0140] According to one embodiment of the present invention, the content ratio of the components forming the catalyst composition can be determined based on factors such as catalytic activity and selectivity for linear α-olefins. As a specific example, in the case of a three-component catalyst composition, the molar ratio of the ligand compound (diphosphino moiety: chromium source: co-catalyst) can be adjusted to about 1:1:1 to about 10:1:10,000, or about 1:1:100 to 5:1:3,000. Furthermore, in the case of a two-component catalyst composition, the molar ratio of the organochromium compound (diphosphino moiety: co-catalyst) can be adjusted to about 1:1 to 1:10,000, 1:1 to 1:5,000, or 1:1 to 1:3,000.

[0141] According to one embodiment of the present invention, in the production of the catalyst composition, the reaction solvent used may be a hydrocarbon-based solvent, such as pentane, hexane, or heptane; and an aromatic solvent, such as benzene or toluene.

[0142] According to one embodiment of the present invention, the components forming the catalyst composition are added simultaneously or in any order, in the presence or absence of a suitable solvent and monomer, so that the catalyst composition can be used as an active catalyst composition. In this case, the suitable solvent can be heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, etc.

[0143] According to one embodiment of the present invention, the organochromium compound and the co-catalyst may be used in a form in which the organochromium compound and the co-catalyst are supported on a carrier, and in this case, the carrier may be silicon oxide or aluminum oxide.

[0144] According to one embodiment of the present invention, the catalyst composition may further include a carrier. As a specific example, the ligand compound represented by Chemical Formula 1 may be applied to ethylene oligomerization in the form of a ligand compound represented by Chemical Formula 1 being supported on a carrier. The carrier may be a metal, a metal salt or a metal oxide, applied to a supported catalyst. As a specific example, the carrier may be silicon oxide, silicon oxide-aluminum oxide or silicon oxide-magnesium oxide, and may include metal oxides, carbonates, sulfates or nitrate components, such as Na2O, K2CO3, BaSO4 or Mg(NO3)2.

[0145] According to one embodiment of the present invention, the catalyst composition can be used for the trimerization or tetramerization reaction of ethylene, and can produce 1-hexene or 1-octene with high selectivity as described above.

[0146] Ethylene oligomerization process

[0147] The present invention provides a method for producing linear α-olefins as an ethylene oligomerization method, comprising the step of oligomerizing ethylene in the presence of a catalyst composition (S10).

[0148] In this invention, "oligomerization" refers to the oligomerization of olefins. Depending on the number of olefins polymerized, this reaction is also referred to as trimerization or tetramerization, or collectively as a polymerization reaction. Specifically, in this specification, it refers to the selective production of 1-hexene and 1-octene, the primary comonomers of LLDPE, from ethylene.

[0149] According to one embodiment of the present invention, the oligomerization reaction of ethylene may be a trimerization or tetramerization reaction of ethylene to produce 1-hexene or 1-octene, and the linear α-olefin may be 1-hexene, 1-octene, or a mixture thereof.

[0150] According to one embodiment of the present invention, an ethylene oligomerization method can be carried out using ethylene as a feedstock and employing the aforementioned catalyst composition, conventional apparatus, and contacting techniques. Specifically, the ethylene oligomerization reaction can be carried out as a homogeneous liquid phase reaction in the presence or absence of an inert solvent, as a slurry reaction in which the catalyst composition is partially or completely undissolved, or as a bulk phase reaction or gas phase reaction using the product α-olefin as the primary medium.

[0151] According to one embodiment of the present invention, the oligomerization reaction of ethylene can be carried out in an inert solvent. As a specific example, the inert solvent can be benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, or 2,2,4-trimethylpentane.

[0152] According to one embodiment of the present invention, the oligomerization reaction of ethylene may be carried out at a temperature of 0° C. to 200° C., 0° C. to 150° C., 30° C. to 100° C., or 50° C. to 100° C. In addition, the above reaction may be carried out at a pressure of 15 psig to 3,000 psig, 15 psig to 1,500 psig, or 15 psig to 1,000 psig.

[0153] The embodiments of the present invention will be described in detail below so that those skilled in the art can easily implement the embodiments of the present invention. However, the present invention can be implemented in various different forms and is not limited to the embodiments described herein.

[0154] Synthesis Examples and Comparative Synthesis Examples

[0155] Synthesis Example 1: Synthesis of the ligand compound represented by Chemical Formula 2-1

[0156] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.37 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 22 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-fluorophenyl)-N-((2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 2.75 g (yield 66%).

[0157] [Chemical Formula 2-1]

[0158]

[0159] 1 H NMR (500MHz, CDCl3): δ7.71(m,2H),7.48(m,4H),7.28(m,2H),7.27(m,2H),7.2 0(m,6H),2.51(m,3H),1.50(m,12H),1.31(m,12H),1.27(m,12H),0.93(m,18H)

[0160] Synthesis Example 2: Synthesis of the ligand compound represented by Chemical Formula 2-2

[0161] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 21 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-methyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)-1-(2-(trifluoromethyl)phenyl)phosphinamine, 3.64 g (yield 78%).

[0162] [Chemical Formula 2-2]

[0163]

[0164] 1H NMR (500MHz, CDCl3): δ7.52(m,2H),7.46(m,2H),7.42(m,4H),7.29(m,2H),7.17(m,4 H),7.10(m,2H),2.47(m,3H),1.44(m,12H),1.40(m,12H),1.23(m,12H),0.91(m,18H)

[0165] Synthesis Example 3: Synthesis of the ligand compound represented by Chemical Formula 2-3

[0166] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 17 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-methoxyphenyl)-N-((2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 4.07 g (95% yield).

[0167] [Chemical formula 2-3]

[0168]

[0169] 1 H NMR (500MHz, CDCl3): δ7.43(m,2H),7.40(m,4H),7.19(m,2H),7.15(m,2H),7.14(m,4H),7.0 1(m,2H),3.86(m,6H),2.48(m,3H),1.51(m,12H),1.36(m,12H),1.31(m,12H),0.91(m,18H)

[0170] Synthesis Example 4: Synthesis of the ligand compound represented by Chemical Formula 2-4

[0171] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.33 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 20 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, N-methyl-1-(o-tolyl)-N-(o-tolyl(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 2.47 g (yield 60%).

[0172] [Chemical formula 2-4]

[0173]

[0174] 1 H NMR (500MHz, CDCl3): δ7.41(m,4H),7.35(m,2H),7.30(m,2H),7.22(m,2H),7.16(m,4H),7.1 5(m,2H),2.57(m,3H),2.42(m,6H),1.51(m,12H),1.35(m,12H),1.25(m,12H),0.96(m,18H)

[0175] Synthesis Example 5: Synthesis of the ligand compound represented by Chemical Formula 2-5

[0176] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 16 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-methyl-1-(4-tributylsilyl)phenyl)-N-((4-tributylsilyl)phenyl)(2-trifluoromethoxy)phenyl)phosphino)-1-(2-trifluoromethoxy)phenyl)phosphinamine, 4.39 g (91% yield).

[0177] [Chemical Formula 2-5]

[0178]

[0179] 1H NMR (500MHz, CDCl3): δ7.50(m,4H),7.49(m,2H),7.20(m,2H),7.16(m,4H),7.14(m,2 H),7.03(m,2H),2.53(m,3H),1.49(m,12H),1.32(m,12H),1.30(m,12H),0.94(m,18H)

[0180] Synthesis Example 6: Synthesis of the ligand compound represented by Chemical Formula 2-6

[0181] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.07 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 18 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-methyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphino)-1-(2-(trifluoro-14-sulfanyl)phenyl)phosphinamine, 3.74 g (yield 77%).

[0182] [Chemical Formula 2-6]

[0183]

[0184] 1 H NMR (500MHz, CDCl3): δ7.41(m,4H),7.40(m,2H),7.36(m,2H),7.23(m,2H),7.14(m,4 H),7.03(m,2H),2.56(m,3H),1.45(m,12H),1.38(m,12H),1.30(m,12H),0.93(m,18H)

[0185] Synthesis Example 7: Synthesis of the ligand compound represented by Chemical Formula 2-7

[0186] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.65 g of chloro(2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 13 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-methyl-1-(2-(methylthio)phenyl)-N-((2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.73 g (84% yield).

[0187] [Chemical Formula 2-7]

[0188]

[0189] 1 H NMR (500MHz, CDCl3): δ7.45(m,4H),7.40(m,2H),7.35(m,2H),7.21(m,2H),7.16(m,4H),7.0 8(m,2H),2.56(m,3H),2.52(m,6H),1.46(m,12H),1.34(m,12H),1.29(m,12H),0.97(m,18H)

[0190] Synthesis Example 8: Synthesis of the ligand compound represented by Chemical Formula 2-8

[0191] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 5.13 g of 2-(chloro(4-(tributylsilyl)phenyl)phosphino)phenyl methanesulfonate was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 15 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield 3.94 g (80% yield) of the desired product, ((methylazanediyl)bis((4-(tributylsilyl)phenyl)phosphinediyl))bis(2,1-phenylene) dimethanesulfonate.

[0192] [Chemical Formula 2-8]

[0193]

[0194] 1H NMR (500MHz, CDCl3): δ7.55(m,2H),7.50(m,2H),7.46(m,4H),7.32(m,2H),7.30(m,2H),7.1 7(m,4H),3.54(m,6H),2.47(m,3H),1.50(m,12H),1.37(m,12H),1.29(m,12H),0.89(m,18H)

[0195] Synthesis Example 9: Synthesis of the ligand compound represented by Chemical Formula 2-9

[0196] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.91 g of chloro(4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 11 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-methyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphino)-1-(2-(trimethylsilyl)phenyl)phosphinamine, 3.67 g (yield 78%).

[0197] [Chemical Formula 2-9]

[0198]

[0199] 1 H NMR (500MHz, CDCl3): δ7.42(m,8H),7.32(m,2H),7.13(m,6H),2.49(m,3H),1.44(m,12H),1.39(m,12H),1.26(m,12H),0.90(m,18H),0.27(m,18H)

[0200] Synthesis Example 10: Synthesis of the ligand compound represented by Chemical Formula 2-10

[0201] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.59 g of benzofuran-7-ylchloro(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 11 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(benzofuran-7-yl)-N-(benzofuran-7-yl(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.29 g (yield 75%).

[0202] [Chemical Formula 2-10]

[0203]

[0204] 1 H NMR (500MHz, CDCl3): δ7.69(m,2H),7.64(m,2H),7.48(m,6H),7.41(m,2H),7.17(m,4 H),6.78(m,2H),2.55(m,3H),1.51(m,12H),1.38(m,12H),1.29(m,12H),0.91(m,18H)

[0205] Synthesis Example 11: Synthesis of the ligand compound represented by Chemical Formula 2-11

[0206] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dry flask, followed by stirring and cooling to 0°C. 5.09 g of chloro(dibenzo[b,d]furan-4-yl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 18 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(dibenzo[b,d]furan-4-yl)-N-(dibenzo[b,d]furan-4-yl(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 4.25 g (yield 87%).

[0207] [Chemical Formula 2-11]

[0208]

[0209] 1H NMR (500MHz, CDCl3): δ8.02(m,4H),7.54(m,2H),7.50(m,2H),7.47(m,4H),7.43(m,2H),7.4 1(m,4H),7.16(m,4H),2.50(m,3H),1.47(m,12H),1.37(m,12H),1.31(m,12H),0.93(m,18H)

[0210] Synthesis Example 12: Synthesis of the ligand compound represented by Chemical Formula 2-12

[0211] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.37 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 21 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(2-fluorophenyl)-N-((2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.67 g (84% yield).

[0212] [Chemical Formula 2-12]

[0213]

[0214] 1 H NMR (500MHz, CDCl3): δ7.68(m,2H),7.44(m,4H),7.25(m,2H),7.21(m,2H),7.20(m,6 H),2.64(m,2H),1.54(m,2H),1.50(m,12H),1.32(m,14H),1.29(m,12H),0.98(m,21H)

[0215] Synthesis Example 13: Synthesis of the ligand compound represented by Chemical Formula 2-13

[0216] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 11 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)-1-(2-(trifluoromethyl)phenyl)phosphinamine, 3.26 g (yield 67%).

[0217] [Chemical Formula 2-13]

[0218]

[0219] 1 H NMR (500MHz, CDCl3): δ7.50(m,4H),7.49(m,2H),7.47(m,2H),7.28(m,2H),7.18(m,4H),7.1 5(m,2H),2.71(m,2H),1.61(m,2H),1.48(m,12H),1.36(m,14H),1.27(m,12H),0.98(m,21H)

[0220] Synthesis Example 14: Synthesis of the ligand compound represented by Chemical Formula 2-14

[0221] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 24 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(2-methoxyphenyl)-N-((2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.14 g (70% yield).

[0222] [Chemical Formula 2-14]

[0223]

[0224] 1H NMR (500MHz, CDCl3): δ7.45(m,2H),7.40(m,4H),7.18(m,6H),7.14(m,2H),7.03(m,2H),3.8 9(m,6H),2.73(m,2H),1.59(m,2H),1.47(m,12H),1.30(m,14H),1.28(m,12H),0.96(m,21H)

[0225] Synthesis Example 15: Synthesis of the ligand compound represented by Chemical Formula 2-15

[0226] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.33 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 13 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N-butyl-1-(o-tolyl)-N-(o-tolyl(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 2.82 g (yield: 65%).

[0227] [Chemical Formula 2-15]

[0228]

[0229] 1 H NMR (500MHz, CDCl3): δ7.42(m,4H),7.37(m,2H),7.34(m,2H),7.19(m,2H),7.17(m,4H),7.13(m,2 H),2.73(m,2H),2.37(m,6H),1.61(m,2H),1.44(m,12H),1.37(m,14H),1.31(m,12H),0.91(m,21H)

[0230] Synthesis Example 16: Synthesis of the ligand compound represented by Chemical Formula 2-16

[0231] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 24 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 3.37 g (67% yield) of N-butyl-1-(4-tributylsilyl)phenyl)-N-((4-tributylsilyl)phenyl)(2-trifluoromethoxy)phenyl)phosphino)-1-(2-trifluoromethoxy)phenyl)phosphinamine.

[0232] [Chemical Formula 2-16]

[0233]

[0234] 1 H NMR (500MHz, CDCl3): δ7.43(m,4H),7.42(m,2H),7.20(m,4H),7.19(m,4H),7.04(m,2 H),2.65(m,2H),1.59(m,2H),1.47(m,12H),1.34(m,14H),1.29(m,12H),0.94(m,21H)

[0235] Synthesis Example 17: Synthesis of the ligand compound represented by Chemical Formula 2-17

[0236] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.07 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 20 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield 3.4 g (67% yield) of the desired product, N-butyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphino)-1-(2-(trifluoro-14-sulfanyl)phenyl)phosphinamine.

[0237] [Chemical Formula 2-17]

[0238]

[0239] 1H NMR (500MHz, CDCl3): δ7.48(m,4H),7.43(m,2H),7.33(m,2H),7.27(m,2H),7.18(m,4H),7.0 0(m,2H),2.68(m,2H),1.54(m,2H),1.47(m,12H),1.35(m,14H),1.27(m,12H),0.95(m,21H)

[0240] Synthesis Example 18: Synthesis of the ligand compound represented by Chemical Formula 2-18

[0241] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.65 g of chloro(2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 12 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(2-(methylthio)phenyl)-N-((2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.77 g (81% yield).

[0242] [Chemical Formula 2-18]

[0243]

[0244] 1 H NMR (500MHz, CDCl3): δ7.43(m,2H),7.42(m,4H),7.41(m,2H),7.23(m,2H),7.13(m,4H),7.06(m,2 H),2.73(m,2H),2.51(m,6H),1.57(m,2H),1.51(m,12H),1.31(m,14H),1.28(m,12H),0.92(m,21H)

[0245] Synthesis Example 19: Synthesis of the ligand compound represented by Chemical Formula 2-19

[0246] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, then stirred and cooled to 0°C. 5.13 g of 2-(chloro(4-(tributylsilyl)phenyl)phosphino)phenyl methanesulfonate was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 12 hours, the conversion was determined by NMR. After completion of the reaction, the precipitate was filtered off, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, ((butylazanediyl)bis((4-(tributylsilyl)phenyl)phosphinediyl))bis(2,1-phenylene) dimethanesulfonate, 4.11 g (yield 80%).

[0247] [Chemical Formula 2-19]

[0248]

[0249] 1 H NMR (500MHz, CDCl3): δ7.52(m,2H),7.49(m,4H),7.45(m,2H),7.32(m,2H),7.28(m,2H),7.21(m,4 H),3.57(m,6H),2.65(m,2H),1.56(m,2H),1.50(m,12H),1.38(m,14H),1.26(m,12H),0.93(m,21H)

[0250] Synthesis Example 20: Synthesis of the ligand compound represented by Chemical Formula 2-20

[0251] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.91 g of chloro(4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 16 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphino)-1-(2-(trimethylsilyl)phenyl)phosphinamine, 3.98 g (yield 81%).

[0252] [Chemical Formula 2-20]

[0253]

[0254] 1H NMR (500MHz, CDCl3): δ7.49(m,8H),7.32(m,2H),7.20(m,6H),2.68(m,2H),1.5 5(m,2H),1.50(m,12H),1.38(m,14H),1.25(m,12H),0.93(m,21H),0.31(m,18H)

[0255] Synthesis Example 21: Synthesis of the ligand compound represented by Chemical Formula 2-21

[0256] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.59 g of benzofuran-7-ylchloro(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 18 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(benzofuran-7-yl)-N-(benzofuran-7-yl(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 4.41 g (96% yield).

[0257] [Chemical Formula 2-21]

[0258]

[0259] 1 H NMR (500MHz, CDCl3): δ7.69(m,2H),7.64(m,2H),7.50(m,2H),7.46(m,4H),7.34(m,2H),7.14(m,4 H),6.76(m,2H),2.72(m,2H),1.57(m,2H),1.44(m,12H),1.33(m,14H),1.32(m,12H),0.97(m,21H)

[0260] Synthesis Example 22: Synthesis of the ligand compound represented by Chemical Formula 2-22

[0261] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dry flask, followed by stirring and cooling to 0°C. 5.09 g of chloro(dibenzo[b,d]furan-4-yl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 15 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(dibenzo[b,d]furan-4-yl)-N-(dibenzo[b,d]furan-4-yl(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 4.43 g (87% yield).

[0262] [Chemical Formula 2-22]

[0263]

[0264] 1 H NMR (500MHz, CDCl3): δ8.00(m,4H),7.57(m,2H),7.42(m,6H),7.39(m,2H),7.38(m,2H),7.37(m,2 H),7.15(m,4H),2.69(m,2H),1.59(m,2H),1.47(m,12H),1.31(m,14H),1.27(m,12H),0.99(m,21H)

[0265] Synthesis Example 23: Synthesis of the ligand compound represented by Chemical Formula 2-23

[0266] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, then stirred and cooled to 0°C. 4.37 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and then slowly added to the flask. After stirring the reactants for 20 hours, the conversion rate was detected by NMR. After the reaction was complete, the precipitate was filtered off and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N,N-bis((2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphino)benzamide, 4.06 g (yield: 88%).

[0267] [Chemical Formula 2-23]

[0268]

[0269] 1H NMR (500MHz, CDCl3): δ8.02(m,2H),7.67(m,1H),7.61(m,2H),7.55(m,2H),7.45(m,4H),7.2 8(m,2H),7.23(m,2H),7.17(m,6H),1.51(m,12H),1.36(m,12H),1.29(m,12H),0.95(m,18H)

[0270] Synthesis Example 24: Synthesis of the ligand compound represented by Chemical Formula 2-24

[0271] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, then stirred and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 10 hours, the conversion rate was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N,N-bis((4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)benzamide, 3.99 g (yield: 78%).

[0272] [Chemical Formula 2-24]

[0273]

[0274] 1 H NMR (500MHz, CDCl3): δ8.00(m,2H),7.70(m,1H),7.59(m,2H),7.56(m,2H),7.50(m,2H),7.49(m,4 H),7.28(m,2H),7.21(m,4H),7.18(m,2H),1.43(m,12H),1.39(m,12H),1.32(m,12H),0.97(m,18H)

[0275] Synthesis Example 25: Synthesis of the ligand compound represented by Chemical Formula 2-25

[0276] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 13 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N,N-bis((2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphino)benzamide, 3.36 g (yield: 71%).

[0277] [Chemical Formula 2-25]

[0278]

[0279] 1 H NMR (500MHz, CDCl3): δ7.99(m,2H),7.68(m,1H),7.58(m,2H),7.49(m,4H),7.42(m,2H),7.21(m,6 H),7.12(m,2H),6.99(m,2H),3.87(m,6H),1.47(m,12H),1.33(m,12H),1.30(m,12H),0.95(m,18H)

[0280] Synthesis Example 26: Synthesis of the ligand compound represented by Chemical Formula 2-26

[0281] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.33 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and then slowly added to the flask. After stirring the reactants for 24 hours, the conversion was detected by NMR. After the reaction was complete, the precipitate was removed by filtration and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N,N-bis(o-tolyl(4-(tributylsilyl)phenyl)phosphino)benzamide, 3.2 g (yield: 70%).

[0282] [Chemical Formula 2-26]

[0283]

[0284] 1H NMR (500MHz, CDCl3): δ7.99(m,2H),7.62(m,1H),7.56(m,2H),7.46(m,4H),7.41(m,2H),7.34(m,2H),7.2 0(m,2H),7.19(m,2H),7.18(m,4H),2.36(m,6H),1.52(m,12H),1.32(m,12H),1.24(m,12H),0.98(m,18H)

[0285] Synthesis Example 27: Synthesis of the ligand compound represented by Chemical Formula 2-27

[0286] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 14 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N,N-bis((4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphino)benzamide, 3.95 g (yield: 75%).

[0287] [Chemical Formula 2-27]

[0288]

[0289] 1 H NMR (500MHz, CDCl3): δ8.00(m,2H),7.67(m,1H),7.59(m,2H),7.47(m,4H),7.41(m,2H),7.21(m,4 H),7.18(m,2H),7.17(m,2H),6.98(m,2H),1.47(m,12H),1.32(m,12H),1.30(m,12H),0.91(m,18H)

[0290] Synthesis Example 28: Synthesis of the ligand compound represented by Chemical Formula 2-28

[0291] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 5.07 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 11 hours, the conversion was determined by NMR. After completion of the reaction, the precipitate was filtered off, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, N,N-bis((4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphino)benzamide, 3.29 g (yield: 62%).

[0292] [Chemical Formula 2-28]

[0293]

[0294] 1 H NMR (500MHz, CDCl3): δ7.96(m,2H),7.72(m,1H),7.59(m,2H),7.48(m,4H),7.37(m,2H),7.3 2(m,2H),7.22(m,6H),7.03(m,2H),1.48(m,12H),1.33(m,12H),1.27(m,12H),0.97(m,18H)

[0295] Synthesis Example 29: Synthesis of the ligand compound represented by Chemical Formula 2-29

[0296] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, then stirred and cooled to 0°C. 4.65 g of chloro(2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 15 hours, the conversion rate was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N,N-bis((2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphino)benzamide, 4.31 g (yield 88%).

[0297] [Chemical Formula 2-29]

[0298]

[0299] 1H NMR (500MHz, CDCl3): δ8.01(m,2H),7.63(m,3H),7.47(m,4H),7.46(m,2H),7.38(m,2H),7.26(m,2 H),7.21(m,4H),7.14(m,2H),2.56(m,6H),1.45(m,12H),1.36(m,12H),1.23(m,12H),0.91(m,18H)

[0300] Synthesis Example 30: Synthesis of the ligand compound represented by Chemical Formula 2-30

[0301] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dry flask, stirred, and cooled to 0°C. 5.13 g of 2-(chloro(4-(tributylsilyl)phenyl)phosphino)phenyl methanesulfonate was diluted in 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 14 hours, the conversion was determined by NMR. After completion of the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, ((benzoylazanediyl)bis((4-(tributylsilyl)phenyl)phosphino))bis(2,1-phenylene) dimethanesulfonate, 3.49 g (yield: 65%).

[0302] [Chemical Formula 2-30]

[0303]

[0304] 1 H NMR (500MHz, CDCl3): δ8.01(m,2H),7.66(m,1H),7.60(m,2H),7.50(m,2H),7.44(m,2H),7.42(m,4H),7.3 1(m,2H),7.24(m,2H),7.20(m,4H),3.57(m,6H),1.53(m,12H),1.34(m,12H),1.23(m,12H),0.97(m,18H)

[0305] Synthesis Example 31: Synthesis of the ligand compound represented by Chemical Formula 2-31

[0306] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, then stirred and cooled to 0°C. 4.91 g of chloro(4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 15 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, N,N-bis((4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphino)benzamide, 3.66 g (yield 71%).

[0307] [Chemical Formula 2-31]

[0308]

[0309] 1 H NMR (500MHz, CDCl3): δ8.01(m,2H),7.71(m,1H),7.61(m,2H),7.50(m,8H),7.31(m,2H ),7.19(m,6H),1.52(m,12H),1.38(m,12H),1.29(m,12H),0.95(m,18H),0.34(m,18H)

[0310] Synthesis Example 32: Synthesis of the ligand compound represented by Chemical Formula 2-32

[0311] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.59 g of benzofuran-7-ylchloro(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. The reaction was stirred for 23 hours, and the conversion was determined by NMR. After completion of the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N,N-bis(benzofuran-7-yl(4-(tributylsilyl)phenyl)phosphino)benzamide, 3.53 g (yield: 73%).

[0312] [Chemical Formula 2-32]

[0313]

[0314] 1H NMR (500MHz, CDCl3): δ7.97(m,2H),7.70(m,1H),7.67(m,2H),7.60(m,2H),7.56(m,2H),7.48(m,6 H),7.36(m,2H),7.16(m,4H),6.80(m,2H),1.50(m,12H),1.33(m,12H),1.26(m,12H),0.91(m,18H)

[0315] Synthesis Example 33: Synthesis of the ligand compound represented by Chemical Formula 2-33

[0316] Under a nitrogen atmosphere, 0.54 g of benzylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, then stirred and cooled to 0°C. 5.09 g of chloro(dibenzo[b,d]furan-4-yl)(4-(tributylsilyl)phenyl)phosphine was diluted in 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 14 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N,N-bis(dibenzo[b,d]furan-4-yl(4-(tributylsilyl)phenyl)phosphino)benzamide, 3.79 g (71% yield).

[0317] [Chemical Formula 2-33]

[0318]

[0319] 1 H NMR (500MHz, CDCl3): δ8.04(m,4H),7.96(m,2H),7.62(m,1H),7.57(m,4H),7.47(m,2H),7.42(m,2 H),7.41(m,6H),7.35(m,2H),7.14(m,4H),1.49(m,12H),1.31(m,12H),1.27(m,12H),0.96(m,18H)

[0320] Synthesis Example 34: Synthesis of the ligand compound represented by Chemical Formula 2-34

[0321] Under nitrogen protection, 0.54g of isopropylamine, 1.26g of triethylamine, and 10ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.37g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10ml of dichloromethane and then slowly added to the flask. After stirring the reactants for 15 hours, the conversion rate was detected by NMR. After the reaction was completed, the precipitate was filtered to remove the solvent, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, 1-(2-fluorophenyl)-N-((2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 2.67g (yield 62%).

[0322] [Chemical Formula 2-34]

[0323]

[0324] 1 H NMR (500MHz, CDCl3): δ7.67(m,2H),7.48(m,4H),7.26(m,2H),7.20(m,2H),7.17(m,6 H),2.93(m,1H),1.51(m,12H),1.33(m,12H),1.30(m,12H),1.13(m,6H),0.97(m,18H)

[0325] Synthesis Example 35: Synthesis of the ligand compound represented by Chemical Formula 2-35

[0326] Under a nitrogen atmosphere, 0.54 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 16 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-isopropyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)-1-(2-(trifluoromethyl)phenyl)phosphinamine, 3.22 g (yield 67%).

[0327] [Chemical Formula 2-35]

[0328]

[0329] 1H NMR (500MHz, CDCl3): δ7.48(m,6H),7.44(m,2H),7.28(m,2H),7.23(m,4H),7. 11(m,2H),2.92(m,1H),1.45(m,12H),1.31(m,24H),1.07(m,6H),0.91(m,18H)

[0330] Synthesis Example 36: Synthesis of the ligand compound represented by Chemical Formula 2-36

[0331] Under a nitrogen atmosphere, 0.54 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 23 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-isopropyl-1-(2-methoxyphenyl)-N-((2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 4.38 g (99% yield).

[0332] [Chemical Formula 2-36]

[0333]

[0334] 1 H NMR (500MHz, CDCl3): δ7.46(m,2H),7.41(m,4H),7.25(m,2H),7.15(m,4H),7.12(m,2H),6.96(m,2 H),3.89(m,6H),2.93(m,1H),1.52(m,12H),1.37(m,12H),1.32(m,12H),1.08(m,6H),0.93(m,18H)

[0335] Synthesis Example 37: Synthesis of the ligand compound represented by Chemical Formula 2-37

[0336] Under nitrogen protection, 0.54g of isopropylamine, 1.26g of triethylamine, and 10ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.33g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10ml of dichloromethane and then slowly added to the flask. After stirring the reactants for 11 hours, the conversion rate was detected by NMR. After the reaction was completed, the precipitate was filtered off and the solvent was removed under reduced pressure. The resulting organic matter was purified by column chromatography to obtain the target product, N-isopropyl-1-(o-tolyl)-N-(o-tolyl(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.2g (yield 75%).

[0337] [Chemical Formula 2-37]

[0338]

[0339] 1 H NMR (500MHz, CDCl3): δ7.44(m,4H),7.37(m,2H),7.34(m,2H),7.24(m,2H),7.22(m,4H),7.12(m,2 H),2.93(m,1H),2.37(m,6H),1.48(m,12H),1.37(m,12H),1.29(m,12H),1.13(m,6H),0.99(m,18H)

[0340] Synthesis Example 38: Synthesis of the ligand compound represented by Chemical Formula 2-38

[0341] Under a nitrogen atmosphere, 0.54 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 21 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 3.77 g (76% yield) of N-isopropyl-1-(4-tributylsilyl)phenyl)-N-((4-tributylsilyl)phenyl)(2-trifluoromethoxy)phenyl)phosphino)-1-(2-trifluoromethoxy)phenyl)phosphinamine.

[0342] [Chemical Formula 2-38]

[0343]

[0344] 1H NMR (500MHz, CDCl3): δ7.47(m,4H),7.44(m,2H),7.21(m,4H),7.15(m,2H),7.12(m,2H),7.0 5(m,2H),2.91(m,1H),1.48(m,12H),1.34(m,12H),1.27(m,12H),1.07(m,6H),0.97(m,18H)

[0345] Synthesis Example 39: Synthesis of the ligand compound represented by Chemical Formula 2-39

[0346] Under a nitrogen atmosphere, 0.54 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.07 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 19 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield 3.3 g (66% yield) of the desired product, N-isopropyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphino)-1-(2-(trifluoro-14-sulfanyl)phenyl)phosphinamine.

[0347] [Chemical Formula 2-39]

[0348]

[0349] 1 H NMR (500MHz, CDCl3): δ7.43(m,6H),7.28(m,2H),7.27(m,2H),7.19(m,4H),6.99(m,2 H),2.88(m,1H),1.46(m,12H),1.39(m,12H),1.25(m,12H),1.12(m,6H),0.95(m,18H)

[0350] Synthesis Example 40: Synthesis of the ligand compound represented by Chemical Formula 2-40

[0351] Under a nitrogen atmosphere, 0.54 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.65 g of chloro(2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 21 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-isopropyl-1-(2-(methylthio)phenyl)-N-((2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.35 g (yield 73%).

[0352] [Chemical Formula 2-40]

[0353]

[0354] 1 H NMR (500MHz, CDCl3): δ7.50(m,4H),7.40(m,2H),7.37(m,2H),7.21(m,2H),7.14(m,4H),7.10(m,2 H),2.92(m,1H),2.51(m,6H),1.48(m,12H),1.37(m,12H),1.32(m,12H),1.15(m,6H),0.92(m,18H)

[0355] Synthesis Example 41: Synthesis of the ligand compound represented by Chemical Formula 2-41

[0356] Under a nitrogen atmosphere, 0.54 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 5.13 g of 2-(chloro(4-(tributylsilyl)phenyl)phosphino)phenyl methanesulfonate was diluted in 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 22 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was filtered off, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, ((isopropylazanediyl)bis((4-(tributylsilyl)phenyl)phosphinediyl))bis(2,1-phenylene) dimethanesulfonate, 3.64 g (yield: 72%).

[0357] [Chemical Formula 2-41]

[0358]

[0359] 1H NMR (500MHz, CDCl3): δ7.54(m,2H),7.42(m,2H),7.41(m,4H),7.32(m,2H),7.23(m,2H),7.17(m,4 H),3.61(m,6H),2.91(m,1H),1.49(m,12H),1.39(m,12H),1.30(m,12H),1.11(m,6H),0.90(m,18H)

[0360] Synthesis Example 42: Synthesis of the ligand compound represented by Chemical Formula 2-42

[0361] Under a nitrogen atmosphere, 0.54 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.91 g of chloro(4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 12 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-isopropyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphino)-1-(2-(trimethylsilyl)phenyl)phosphinamine, 3.39 g (70% yield).

[0362] [Chemical Formula 2-42]

[0363]

[0364] 1 H NMR (500MHz, CDCl3): δ7.43(m,8H),7.32(m,2H),7.20(m,6H),2.88(m,1H),1.4 4(m,12H),1.35(m,12H),1.24(m,12H),1.12(m,6H),0.93(m,18H),0.27(m,18H)

[0365] Synthesis Example 43: Synthesis of the ligand compound represented by Chemical Formula 2-43

[0366] Under a nitrogen atmosphere, 0.54 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.59 g of benzofuran-7-ylchloro(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 20 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(benzofuran-7-yl)-N-(benzofuran-7-yl(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.35 g (yield 74%).

[0367] [Chemical Formula 2-43]

[0368]

[0369] 1 H NMR (500MHz, CDCl3): δ7.61(m,2H),7.60(m,2H),7.50(m,2H),7.42(m,4H),7.40(m,2H),7. 20(m,4H),6.81(m,2H),2.88(m,1H),1.46(m,12H),1.30(m,24H),1.10(m,6H),0.97(m,18H)

[0370] Synthesis Example 44: Synthesis of the ligand compound represented by Chemical Formula 2-44

[0371] Under a nitrogen atmosphere, 0.54 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dry flask, stirred, and cooled to 0°C. 5.09 g of chloro(dibenzo[b,d]furan-4-yl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 21 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(dibenzo[b,d]furan-4-yl)-N-(dibenzo[b,d]furan-4-yl(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.16 g (yield 63%).

[0372] [Chemical Formula 2-44]

[0373]

[0374] 1H NMR (500MHz, CDCl3): δ8.02(m,4H),7.60(m,2H),7.52(m,2H),7.42(m,4H),7.41(m,2H),7.37(m,2H),7.3 2(m,2H),7.18(m,4H),2.89(m,1H),1.49(m,12H),1.34(m,12H),1.32(m,12H),1.11(m,6H),0.93(m,18H)

[0375] Synthesis Example 45: Synthesis of the ligand compound represented by Chemical Formula 2-45

[0376] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.37 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 18 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, N-cyclohexyl-1-(2-fluorophenyl)-N-((2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.42 g (yield 76%).

[0377] [Chemical Formula 2-45]

[0378]

[0379] 1 H NMR (500MHz, CDCl3): δ7.65(m,2H),7.47(m,4H),7.29(m,2H),7.22(m,2H),7.19(m,6H),2.61(m,1H),1.78(m,2 H),1.53(m,2H),1.52(m,1H),1.45(m,13H),1.38(m,12H),1.29(m,12H),1.28(m,2H),1.15(m,2H),0.96(m,18H)

[0380] Synthesis Example 46: Synthesis of the ligand compound represented by Chemical Formula 2-46

[0381] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 11 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 4.7 g (94% yield) of N-cyclohexyl-1-(4-tributylsilyl)phenyl)-N-((4-tributylsilyl)phenyl)(2-trifluoromethyl)phenyl)phosphino)-1-(2-trifluoromethyl)phenyl)phosphinamine.

[0382] [Chemical Formula 2-46]

[0383]

[0384] 1 H NMR (500MHz, CDCl3): δ7.51(m,2H),7.50(m,2H),7.44(m,4H),7.32(m,2H),7.14(m,4H),7.08(m,2H),2.62(m,1H),1.8 4(m,2H),1.53(m,1H),1.50(m,14H),1.46(m,1H),1.38(m,12H),1.26(m,2H),1.24(m,12H),1.14(m,2H),0.90(m,18H)

[0385] Synthesis Example 47: Synthesis of the ligand compound represented by Chemical Formula 2-47

[0386] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 15 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N-cyclohexyl-1-(2-methoxyphenyl)-N-((2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.7 g (80% yield).

[0387] [Chemical Formula 2-47]

[0388]

[0389] 1 H NMR (500MHz, CDCl3): δ7.50(m,4H),7.48(m,2H),7.23(m,4H),7.16(m,2H),7.11(m,2H),7.04(m,2H),3.90(m,6H),2.6 5(m,1H),1.79(m,2H),1.52(m,15H),1.51(m,1H),1.31(m,12H),1.27(m,12H),1.23(m,2H),1.19(m,2H),0.92(m,18H)

[0390] Synthesis Example 48: Synthesis of the ligand compound represented by Chemical Formula 2-48

[0391] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.33 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 13 hours, the conversion was determined by NMR. After the reaction was completed, the precipitate was removed by filtration and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N-cyclohexyl-1-(o-tolyl)-N-(o-tolyl(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.57 g (yield 80%).

[0392] [Chemical Formula 2-48]

[0393]

[0394] 1 H NMR (500MHz, CDCl3): δ7.45(m,4H),7.39(m,2H),7.33(m,2H),7.18(m,4H),7.16(m,2H),7.12(m,2H),2.58(m,1H),2.36(m,6H),1.7 9(m,2H),1.57(m,2H),1.54(m,1H),1.48(m,12H),1.44(m,1H),1.34(m,12H),1.29(m,12H),1.24(m,2H),1.17(m,2H),0.90(m,18H)

[0395] Synthesis Example 49: Synthesis of the ligand compound represented by Chemical Formula 2-49

[0396] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 15 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 3.92 g (76% yield) of N-cyclohexyl-1-(4-tributylsilyl)phenyl)-N-((4-tributylsilyl)phenyl)(2-trifluoromethoxy)phenyl)phosphino)-1-(2-trifluoromethoxy)phenyl)phosphinamine.

[0397] [Chemical Formula 2-49]

[0398]

[0399] 1 H NMR (500MHz, CDCl3): δ7.49(m,4H),7.48(m,2H),7.18(m,2H),7.16(m,2H),7.13(m,4H),6.97(m,2H),2.60(m,1H),1.8 2(m,2H),1.57(m,2H),1.47(m,1H),1.45(m,1H),1.44(m,12H),1.38(m,12H),1.30(m,14H),1.16(m,2H),0.94(m,18H)

[0400] Synthesis Example 50: Synthesis of the ligand compound represented by Chemical Formula 2-50

[0401] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.07 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 17 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-cyclohexyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphino)-1-(2-(trifluoro-14-sulfanyl)phenyl)phosphinamine, 4.94 g (95% yield).

[0402] [Chemical Formula 2-50]

[0403]

[0404] 1 H NMR (500MHz, CDCl3): δ7.45(m,4H),7.42(m,2H),7.31(m,2H),7.27(m,2H),7.17(m,4H),6.99(m,2H),2.65(m,1H),1.7 7(m,2H),1.56(m,2H),1.49(m,13H),1.48(m,1H),1.31(m,12H),1.30(m,2H),1.25(m,12H),1.12(m,2H),0.96(m,18H)

[0405] Synthesis Example 51: Synthesis of the ligand compound represented by Chemical Formula 2-51

[0406] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.65 g of chloro(2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 14 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 3.78 g (79% yield) of N-cyclohexyl-1-(2-methylthio)phenyl)-N-((2-methylthio)phenyl)(4-tributylsilyl)phenyl)phosphino)-1-(4-tributylsilyl)phenyl)phosphinamine.

[0407] [Chemical Formula 2-51]

[0408]

[0409] 1 H NMR (500MHz, CDCl3): δ7.42(m,2H),7.41(m,4H),7.39(m,2H),7.25(m,2H),7.14(m,2H),7.13(m,4H),2.64(m,1H),2.53(m,6H),1.7 4(m,2H),1.53(m,2H),1.50(m,1H),1.47(m,12H),1.46(m,1H),1.35(m,12H),1.28(m,12H),1.24(m,2H),1.11(m,2H),0.96(m,18H)

[0410] Synthesis Example 52: Synthesis of the ligand compound represented by Chemical Formula 2-52

[0411] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.13 g of 2-(chloro(4-(tributylsilyl)phenyl)phosphino)phenyl methanesulfonate was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 16 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield 3.95 g (75% yield) of the desired product, ((cyclohexylazanediyl)bis((4-(tributylsilyl)phenyl)phosphinediyl))bis(2,1-phenylene) dimethanesulfonate.

[0412] [Chemical Formula 2-52]

[0413]

[0414] 1 H NMR (500MHz, CDCl3): δ7.51(m,2H),7.43(m,6H),7.39(m,2H),7.28(m,2H),7.17(m,4H),3.58(m,6H),2.66(m,1H),1.83(m,2 H),1.56(m,1H),1.52(m,2H),1.47(m,12H),1.44(m,1H),1.35(m,12H),1.27(m,12H),1.23(m,2H),1.21(m,2H),0.89(m,18H)

[0415] Synthesis Example 53: Synthesis of the ligand compound represented by Chemical Formula 2-53

[0416] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.91 g of chloro(4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 23 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-cyclohexyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphino)-1-(2-(trimethylsilyl)phenyl)phosphinamine, 4.34 g (86% yield).

[0417] [Chemical Formula 2-53]

[0418]

[0419] 1 H NMR (500MHz, CDCl3): δ7.42(m,8H),7.33(m,2H),7.15(m,6H),2.66(m,1H),1.74(m,2H),1.53(m,14H),1. 52(m,1H),1.48(m,1H),1.31(m,12H),1.30(m,2H),1.25(m,12H),1.18(m,2H),0.97(m,18H),0.33(m,18H)

[0420] Synthesis Example 54: Synthesis of the ligand compound represented by Chemical Formula 2-54

[0421] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.59 g of benzofuran-7-ylchloro(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 17 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(benzofuran-7-yl)-N-(benzofuran-7-yl(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 4.3 g (91% yield).

[0422] [Chemical Formula 2-54]

[0423]

[0424] 1 H NMR (500MHz, CDCl3): δ7.68(m,2H),7.63(m,2H),7.50(m,2H),7.48(m,4H),7.38(m,2H),7.15(m,4H),6.85(m,2H),2.62(m,1H),1.8 0(m,2H),1.57(m,2H),1.55(m,1H),1.52(m,1H),1.46(m,12H),1.35(m,12H),1.32(m,12H),1.23(m,2H),1.12(m,2H),0.94(m,18H)

[0425] Synthesis Example 55: Synthesis of the ligand compound represented by Chemical Formula 2-55

[0426] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dry flask, stirred, and cooled to 0°C. 5.09 g of chloro(dibenzo[b,d]furan-4-yl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 19 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-cyclohexyl-1-(dibenzo[b,d]furan-4-yl)-N-(dibenzo[b,d]furan-4-yl(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 4.75 g (91% yield).

[0427] [Chemical Formula 2-55]

[0428]

[0429] 1 H NMR (500MHz, CDCl3): δ8.05(m,4H),7.55(m,2H),7.47(m,2H),7.46(m,2H),7.44(m,4H),7.35(m,2H),7.34(m,2H),7.20(m,4H),2.5 8(m,1H),1.79(m,2H),1.50(m,3H),1.49(m,1H),1.47(m,12H),1.36(m,12H),1.29(m,12H),1.24(m,2H),1.12(m,2H),0.93(m,18H)

[0430] Synthesis Example 56: Synthesis of the ligand compound represented by Chemical Formula 2-56

[0431] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.37 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 15 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-fluorophenyl)-N-((2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.53 g (79% yield).

[0432] [Chemical Formula 2-56]

[0433]

[0434] 1 H NMR (500MHz, CDCl3): δ7.69(m,2H),7.43(m,4H),7.23(m,10H),7.18(m,2H),6. 88(m,2H),6.83(m,1H),1.49(m,12H),1.33(m,12H),1.24(m,12H),0.98(m,18H)

[0435] Synthesis Example 57: Synthesis of the ligand compound represented by Chemical Formula 2-57

[0436] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 23 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-phenyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)-1-(2-(trifluoromethyl)phenyl)phosphinamine, 3.88 g (yield 78%).

[0437] [Chemical Formula 2-57]

[0438]

[0439] 1 H NMR (500MHz, CDCl3): δ7.48(m,2H),7.47(m,6H),7.28(m,2H),7.22(m,4H),7.18(m,2 H),7.08(m,2H),6.85(m,3H),1.48(m,12H),1.30(m,12H),1.24(m,12H),0.90(m,18H)

[0440] Synthesis Example 58: Synthesis of the ligand compound represented by Chemical Formula 2-58

[0441] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 15 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-methoxyphenyl)-N-((2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.54 g (yield 77%).

[0442] [Chemical Formula 2-58]

[0443]

[0444] 1 H NMR (500MHz, CDCl3): δ7.46(m,4H),7.43(m,2H),7.28(m,2H),7.19(m,2H),7.18(m,2H),7.13(m,4H),6.9 7(m,2H),6.86(m,1H),6.81(m,2H),3.86(m,6H),1.45(m,12H),1.32(m,12H),1.29(m,12H),0.91(m,18H)

[0445] Synthesis Example 59: Synthesis of the ligand compound represented by Chemical Formula 2-59

[0446] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.33 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 22 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, (N-phenyl-1-(o-tolyl)-N-(o-tolyl(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.24 g (yield 73%).

[0447] [Chemical Formula 2-59]

[0448]

[0449] 1H NMR (500MHz, CDCl3): δ7.48(m,4H),7.41(m,2H),7.29(m,2H),7.26(m,2H),7.23(m,4H),7.20(m,4 H),6.91(m,1H),6.85(m,2H),2.43(m,6H),1.52(m,12H),1.32(m,12H),1.27(m,12H),0.93(m,18H)

[0450] Synthesis Example 60: Synthesis of the ligand compound represented by Chemical Formula 2-60

[0451] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 18 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-phenyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphino)-1-(2-(trifluoromethoxy)phenyl)phosphinamine, 3.34 g (yield 65%).

[0452] [Chemical Formula 2-60]

[0453]

[0454] 1 H NMR (500MHz, CDCl3): δ7.44(m,2H),7.43(m,4H),7.25(m,2H),7.23(m,2H),7.17(m,4H),7.15(m,2 H),7.05(m,2H),6.83(m,1H),6.81(m,2H),1.49(m,12H),1.38(m,12H),1.30(m,12H),0.93(m,18H)

[0455] Synthesis Example 61: Synthesis of the ligand compound represented by Chemical Formula 2-61

[0456] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.07 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 11 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-phenyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphino)-1-(2-(trifluoro-14-sulfanyl)phenyl)phosphinamine, 3.83 g (yield 74%).

[0457] [Chemical Formula 2-61]

[0458]

[0459] 1 H NMR (500MHz, CDCl3): δ7.49(m,4H),7.42(m,2H),7.36(m,2H),7.28(m,2H),7.20(m,2H),7.1 4(m,4H),7.04(m,2H),6.87(m,3H),1.53(m,12H),1.32(m,12H),1.29(m,12H),0.93(m,18H)

[0460] Synthesis Example 62: Synthesis of the ligand compound represented by Chemical Formula 2-62

[0461] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.65 g of chloro(2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 10 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, (1-(2-methylthio)phenyl)-N-((2-methylthio)phenyl)(4-tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-tributylsilyl)phenyl)phosphinamine, 3.66 g (yield 77%).

[0462] [Chemical Formula 2-62]

[0463]

[0464] 1H NMR (500MHz, CDCl3): δ7.45(m,4H),7.42(m,2H),7.37(m,2H),7.25(m,4H),7.14(m,4H),7.08(m,2 H),6.91(m,1H),6.81(m,2H),2.54(m,6H),1.51(m,12H),1.32(m,12H),1.28(m,12H),0.90(m,18H)

[0465] Synthesis Example 63: Synthesis of the ligand compound represented by Chemical Formula 2-63

[0466] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, which was then stirred and cooled to 0°C. 5.13 g of 2-(chloro(4-(tributylsilyl)phenyl)phosphino)phenyl methanesulfonate was diluted in 10 ml of dichloromethane and slowly added to the flask. The reaction was stirred for 18 hours, and the conversion was determined by NMR. After the reaction was complete, the precipitate was filtered off, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, ((phenylazanediyl)bis((4-(tributylsilyl)phenyl)phosphinediyl))bis(2,1-phenylene) dimethanesulfonate, 3.77 g (yield: 72%).

[0467] [Chemical Formula 2-63]

[0468]

[0469] 1 H NMR (500MHz, CDCl3): δ7.49(m,2H),7.47(m,2H),7.45(m,4H),7.35(m,2H),7.31(m,2H),7.22(m,2H),7.2 1(m,4H),6.90(m,2H),6.83(m,1H),3.60(m,6H),1.53(m,12H),1.37(m,12H),1.31(m,12H),0.93(m,18H)

[0470] Synthesis Example 64: Synthesis of the ligand compound represented by Chemical Formula 2-64

[0471] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.91 g of chloro(4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 24 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-phenyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphino)-1-(2-(trimethylsilyl)phenyl)phosphinamine, 4.31 g (yield 86%).

[0472] [Chemical Formula 2-64]

[0473]

[0474] 1 H NMR (500MHz, CDCl3): δ7.45(m,8H),7.33(m,2H),7.27(m,2H),7.23(m,6H),6.85(m,1H ),6.82(m,2H),1.50(m,12H),1.37(m,12H),1.28(m,12H),0.98(m,18H),0.28(m,18H)

[0475] Synthesis Example 65: Synthesis of the ligand compound represented by Chemical Formula 2-65

[0476] Under nitrogen, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.59 g of benzofuran-7-ylchloro(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. The mixture was stirred for 23 hours, and the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(benzofuran-7-yl)-N-(benzofuran-7-yl(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 3.57 g (yield 76%).

[0477] [Chemical Formula 2-65]

[0478]

[0479] 1H NMR (500MHz, CDCl3): δ7.63(m,2H),7.61(m,2H),7.46(m,2H),7.45(m,4H),7.42(m,2H),7.27(m,2H),7.1 6(m,4H),6.87(m,1H),6.86(m,2H),6.79(m,2H),1.51(m,12H),1.34(m,12H),1.23(m,12H),0.97(m,18H)

[0480] Synthesis Example 66: Synthesis of the ligand compound represented by Chemical Formula 2-66

[0481] Under a nitrogen atmosphere, 0.47 g of aniline, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.09 g of chloro(dibenzo[b,d]furan-4-yl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 20 hours, the conversion was determined by NMR. After the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(dibenzo[b,d]furan-4-yl)-N-(dibenzo[b,d]furan-4-yl(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 4.26 g (yield 82%).

[0482] [Chemical Formula 2-66]

[0483]

[0484] 1 H NMR (500MHz, CDCl3): δ8.06(m,4H),7.56(m,2H),7.44(m,4H),7.41(m,4H),7.40(m,2H),7.36(m,2H),7.2 5(m,2H),7.18(m,4H),6.89(m,1H),6.84(m,2H),1.50(m,12H),1.33(m,12H),1.29(m,12H),0.90(m,18H)

[0485] Synthesis Example 67: Synthesis of the ligand compound represented by Chemical Formula 5-1

[0486] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.37 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 14 hours, the conversion was determined by NMR. After the reaction, the precipitate was filtered and the solvent removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-fluorophenyl)-N-((2-fluorophenyl)(3-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(3-(tributylsilyl)phenyl)phosphinamine, 2.83 g (yield 68%).

[0487] [Chemical Formula 5-1]

[0488]

[0489] 1 H NMR (500MHz, CDCl3): δ7.65(m,2H),7.64(m,2H),7.44(m,2H),7.34(m,2H),7.25(m,2H),7.2 4(m,2H),7.19(m,4H),2.57(m,3H),1.53(m,12H),1.33(m,12H),1.32(m,12H),0.98(m,18H)

[0490] Synthesis Example 68: Synthesis of the ligand compound represented by Chemical Formula 5-2

[0491] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 22 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was filtered off, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-methyl-1-(3-(tributylsilyl)phenyl)-N-((3-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)-1-(2-(trifluoromethyl)phenyl)phosphinamine, 3.17 g (yield 68%).

[0492] [Chemical Formula 5-2]

[0493]

[0494] 1H NMR (500MHz, CDCl3): δ7.65(m,2H),7.57(m,2H),7.49(m,2H),7.45(m,2H),7.37(m,2H),7.29(m,2 H),7.20(m,2H),7.13(m,2H),2.57(m,3H),1.47(m,12H),1.35(m,12H),1.33(m,12H),0.91(m,18H)

[0495] Synthesis Example 69: Synthesis of the ligand compound represented by Chemical Formula 5-3

[0496] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 16 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-methoxyphenyl)-N-((2-methoxyphenyl)(3-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(3-(tributylsilyl)phenyl)phosphinamine, 2.57 g (yield 60%).

[0497] [Chemical Formula 5-3]

[0498]

[0499] 1 H NMR (500MHz, CDCl3): δ7.63(m,2H),7.49(m,4H),7.41(m,2H),7.17(m,2H),7.14(m,2H),7.13(m,2 H),6.98(m,2H),3.85(m,6H),2.48(m,3H),1.51(m,12H),1.33(m,12H),1.29(m,12H),0.96(m,18H)

[0500] Synthesis Example 70: Synthesis of the ligand compound represented by Chemical Formula 5-4

[0501] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.33 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 23 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was filtered off, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-methyl-1-(o-tolyl)-N-(o-tolyl(3-(tributylsilyl)phenyl)phosphino)-1-(3-(tributylsilyl)phenyl)phosphinamine, 3.96 g (96% yield).

[0502] [Chemical Formula 5-4]

[0503]

[0504] 1 H NMR (500MHz, CDCl3): δ7.63(m,2H),7.50(m,2H),7.40(m,2H),7.32(m,2H),7.28(m,2H),7.19(m,2H),7.1 8(m,2H),7.14(m,2H),2.51(m,3H),2.36(m,6H),1.48(m,12H),1.35(m,12H),1.23(m,12H),0.99(m,18H)

[0505] Synthesis Example 71: Synthesis of the ligand compound represented by Chemical Formula 5-5

[0506] Under a nitrogen atmosphere, 0.34 g of methylamine hydrochloride, 1.77 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 17 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-methyl-1-(3-(tributylsilyl)phenyl)-N-((3-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphino)-1-(2-(trifluoromethoxy)phenyl)phosphinamine, 2.94 g (yield 61%).

[0507] [Chemical Formula 5-5]

[0508]

[0509] 1H NMR (500MHz, CDCl3): δ7.57(m,2H),7.43(m,2H),7.42(m,2H),7.35(m,2H),7.19(m,2H),7.17(m,2 H),7.14(m,2H),6.98(m,2H),2.57(m,3H),1.50(m,12H),1.37(m,12H),1.24(m,12H),0.90(m,18H)

[0510] Synthesis Example 72: Synthesis of the ligand compound represented by Chemical Formula 5-6

[0511] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.37 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 16 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(2-fluorophenyl)-N-((2-fluorophenyl)(3-(tributylsilyl)phenyl)phosphino)-1-(3-(tributylsilyl)phenyl)phosphinamine, 3.02 g (yield 69%).

[0512] [Chemical Formula 5-6]

[0513]

[0514] 1 H NMR (500MHz, CDCl3): δ7.71(m,2H),7.62(m,2H),7.44(m,2H),7.34(m,2H),7.29(m,2H),7.24(m,2 H),7.17(m,4H),2.65(m,2H),1.60(m,2H),1.44(m,12H),1.39(m,14H),1.32(m,12H),0.91(m,21H)

[0515] Synthesis Example 73: Synthesis of the ligand compound represented by Chemical Formula 5-7

[0516] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 17 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(3-(tributylsilyl)phenyl)-N-((3-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)-1-(2-(trifluoromethyl)phenyl)phosphinamine, 4.09 g (84% yield).

[0517] [Chemical Formula 5-7]

[0518]

[0519] 1 H NMR (500MHz, CDCl3): δ7.64(m,2H),7.49(m,2H),7.47(m,2H),7.43(m,2H),7.39(m,2H),7.32(m,2H),7.1 8(m,2H),7.11(m,2H),2.65(m,2H),1.53(m,2H),1.45(m,12H),1.33(m,14H),1.25(m,12H),0.91(m,21H)

[0520] Synthesis Example 74: Synthesis of the ligand compound represented by Chemical Formula 5-8

[0521] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 21 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(2-methoxyphenyl)-N-((2-methoxyphenyl)(3-(tributylsilyl)phenyl)phosphino)-1-(3-(tributylsilyl)phenyl)phosphinamine, 3.68 g (82% yield).

[0522] [Chemical Formula 5-8]

[0523]

[0524] 1H NMR (500MHz, CDCl3): δ7.62(m,2H),7.47(m,2H),7.43(m,4H),7.20(m,2H),7.16(m,2H),7.13(m,2H),6.9 8(m,2H),3.87(m,6H),2.66(m,2H),1.54(m,2H),1.49(m,12H),1.31(m,14H),1.26(m,12H),0.89(m,21H)

[0525] Synthesis Example 75: Synthesis of the ligand compound represented by Chemical Formula 5-9

[0526] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.33 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 24 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, N-butyl-1-(o-tolyl)-N-(o-tolyl(3-(tributylsilyl)phenyl)phosphino)-1-(3-(tributylsilyl)phenyl)phosphinamine, 2.69 g (yield 62%).

[0527] [Chemical Formula 5-9]

[0528]

[0529] 1 H NMR (500MHz, CDCl3): δ7.64(m,2H),7.49(m,2H),7.42(m,2H),7.37(m,2H),7.28(m,2H),7.23(m,2H),7.15(m,2 H),7.13(m,2H),2.67(m,2H),2.37(m,6H),1.62(m,2H),1.44(m,12H),1.34(m,14H),1.27(m,12H),0.94(m,21H)

[0530] Synthesis Example 76: Synthesis of the ligand compound represented by Chemical Formula 5-10

[0531] Under a nitrogen atmosphere, 0.37 g of butylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 23 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-butyl-1-(3-(tributylsilyl)phenyl)-N-((3-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphino)-1-(2-(trifluoromethoxy)phenyl)phosphinamine, 4.83 g (96% yield).

[0532] [Chemical Formula 5-10]

[0533]

[0534] 1 H NMR (500MHz, CDCl3): δ7.60(m,2H),7.43(m,2H),7.41(m,2H),7.39(m,2H),7.21(m,2H),7.18(m,2H),7.1 3(m,2H),6.98(m,2H),2.68(m,2H),1.58(m,2H),1.47(m,12H),1.31(m,12H),1.30(m,14H),0.97(m,21H)

[0535] Synthesis Example 77: Synthesis of the ligand compound represented by Chemical Formula 5-11

[0536] Under a nitrogen atmosphere, 0.3 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.37 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 20 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-fluorophenyl)-N-((2-fluorophenyl)(3-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(3-(tributylsilyl)phenyl)phosphinamine, 3.23 g (75% yield).

[0537] [Chemical Formula 5-11]

[0538]

[0539] 1H NMR (500MHz, CDCl3): δ7.67(m,2H),7.61(m,2H),7.45(m,2H),7.37(m,2H),7.25(m,2H),7.2 1(m,6H),2.84(m,1H),1.50(m,12H),1.38(m,12H),1.27(m,12H),1.13(m,6H),0.90(m,18H)

[0540] Synthesis Example 78: Synthesis of the ligand compound represented by Chemical Formula 5-12

[0541] Under a nitrogen atmosphere, 0.3 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, stirred, and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 12 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, N-isopropyl-1-(3-(tributylsilyl)phenyl)-N-((3-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)-1-(2-(trifluoromethyl)phenyl)phosphinamine, 4.51 g (94% yield).

[0542] [Chemical Formula 5-12]

[0543]

[0544] 1 H NMR (500MHz, CDCl3): δ7.57(m,2H),7.51(m,4H),7.46(m,2H),7.39(m,2H),7.32(m,2H),7.18(m,2 H),7.08(m,2H),2.92(m,1H),1.49(m,12H),1.32(m,12H),1.30(m,12H),1.08(m,6H),0.92(m,18H)

[0545] Synthesis Example 79: Synthesis of the ligand compound represented by Chemical Formula 5-13

[0546] Under a nitrogen atmosphere, 0.3 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, stirred, and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 19 hours, the conversion was determined by NMR. After the reaction was completed, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N-isopropyl-1-(2-methoxyphenyl)-N-((2-methoxyphenyl)(3-(tributylsilyl)phenyl)phosphino)-1-(3-(tributylsilyl)phenyl)phosphinamine, 3.45 g (yield 78%).

[0547] [Chemical Formula 5-13]

[0548]

[0549] 1 H NMR (500MHz, CDCl3): δ7.56(m,2H),7.48(m,2H),7.43(m,2H),7.38(m,2H),7.21(m,2H),7.19(m,2H),7.16(m,2 H),7.02(m,2H),3.83(m,6H),2.92(m,1H),1.52(m,12H),1.34(m,12H),1.29(m,12H),1.14(m,6H),0.94(m,18H)

[0550] Synthesis Example 80: Synthesis of the ligand compound represented by Chemical Formula 5-14

[0551] Under a nitrogen atmosphere, 0.3 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, then stirred and cooled to 0°C. 4.33 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 13 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N-isopropyl-1-(o-tolyl)-N-(o-tolyl(3-(tributylsilyl)phenyl)phosphino)-1-(3-(tributylsilyl)phenyl)phosphinamine, 4.13 g (yield 97%).

[0552] [Chemical Formula 5-14]

[0553]

[0554] 1H NMR (500MHz, CDCl3): δ7.57(m,2H),7.47(m,2H),7.41(m,2H),7.35(m,2H),7.34(m,2H),7.23(m,2H),7.20(m,2 H),7.14(m,2H),2.83(m,1H),2.40(m,6H),1.50(m,12H),1.39(m,12H),1.27(m,12H),1.14(m,6H),0.93(m,18H)

[0555] Synthesis Example 81: Synthesis of the ligand compound represented by Chemical Formula 5-15

[0556] Under a nitrogen atmosphere, 0.3 g of isopropylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 23 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-isopropyl-1-(3-(tributylsilyl)phenyl)-N-((3-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphino)-1-(2-(trifluoromethoxy)phenyl)phosphinamine, 3.72 g (yield 75%).

[0557] [Chemical Formula 5-15]

[0558]

[0559] 1 H NMR (500MHz, CDCl3): δ7.64(m,2H),7.43(m,2H),7.42(m,2H),7.40(m,2H),7.22(m,4H),7.14(m,2 H),7.01(m,2H),2.85(m,1H),1.44(m,12H),1.33(m,12H),1.31(m,12H),1.13(m,6H),0.98(m,18H)

[0560] Synthesis Example 82: Synthesis of the ligand compound represented by Chemical Formula 5-16

[0561] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.37 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 18 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, N-cyclohexyl-1-(2-fluorophenyl)-N-((2-fluorophenyl)(3-(tributylsilyl)phenyl)phosphino)-1-(3-(tributylsilyl)phenyl)phosphinamine, 3.91 g (91% yield).

[0562] [Chemical Formula 5-16]

[0563]

[0564] 1 H NMR (500MHz, CDCl3): δ7.63(m,2H),7.59(m,2H),7.42(m,2H),7.39(m,2H),7.25(m,2H),7.22(m,4H),7.21(m,2H),2.59(m,1 H),1.82(m,2H),1.57(m,2H),1.53(m,1H),1.47(m,13H),1.36(m,12H),1.30(m,2H),1.27(m,12H),1.18(m,2H),0.90(m,18H)

[0565] Synthesis Example 83: Synthesis of the ligand compound represented by Chemical Formula 5-17

[0566] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.87 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring for 13 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, N-cyclohexyl-1-(3-(tributylsilyl)phenyl)-N-((3-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)-1-(2-(trifluoromethyl)phenyl)phosphinamine, 4.75 g (99% yield).

[0567] [Chemical Formula 5-17]

[0568]

[0569] 1 H NMR (500MHz, CDCl3): δ7.57(m,2H),7.49(m,4H),7.47(m,2H),7.34(m,2H),7.33(m,2H),7.22(m,2H),7.16(m,2H),2.60(m,1H),1.8 0(m,2H),1.56(m,1H),1.54(m,2H),1.51(m,12H),1.47(m,1H),1.40(m,12H),1.27(m,12H),1.23(m,2H),1.17(m,2H),0.94(m,18H)

[0570] Synthesis Example 84: Synthesis of the ligand compound represented by Chemical Formula 5-18

[0571] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 4.49 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 11 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N-cyclohexyl-1-(2-methoxyphenyl)-N-((2-methoxyphenyl)(3-(tributylsilyl)phenyl)phosphino)-1-(3-(tributylsilyl)phenyl)phosphinamine, 3.05 g (yield 69%).

[0572] [Chemical Formula 5-18]

[0573]

[0574] 1 H NMR (500MHz, CDCl3): δ7.63(m,2H),7.43(m,2H),7.42(m,2H),7.37(m,2H),7.24(m,2H),7.18(m,2H),7.12(m,2H),6.98(m,2H),3.87(m,6H),2.6 1(m,1H),1.77(m,2H),1.55(m,2H),1.54(m,1H),1.51(m,12H),1.49(m, 1H),1.40(m,12H),1.24(m,2H),1.23(m,12H),1.17(m,2H),0.99(m,18H)

[0575] Synthesis Example 85: Synthesis of the ligand compound represented by Chemical Formula 5-19

[0576] In a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, then stirred and cooled to 0°C. 4.33 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and then slowly added to the flask. After stirring the reactants for 20 hours, the conversion rate was detected by NMR. After the reaction was completed, the precipitate was filtered off and the solvent was removed under reduced pressure. The resulting organic matter was purified by column chromatography to obtain the target product, N-cyclohexyl-1-(o-tolyl)-N-(o-tolyl(3-(tributylsilyl)phenyl)phosphino)-1-(3-(tributylsilyl)phenyl)phosphinamine, 3.03 g (yield 71%).

[0577] [Chemical Formula 5-19]

[0578]

[0579] 1 H NMR (500MHz, CDCl3): δ7.56(m,2H),7.43(m,2H),7.35(m,2H),7.33(m,2H),7.31(m,2H),7.19(m,2H),7.18(m,2H),7.15(m,2H),2.66(m,1 H),2.38(m,6H),1.79(m,2H),1.54(m,1H),1.52(m,1H),1.49(m,14H),1.32(m,12H),1.30(m,12H),1.29(m,2H),1.19(m,2H),0.98(m,18H)

[0580] Synthesis Example 86: Synthesis of the ligand compound represented by Chemical Formula 5-20

[0581] Under a nitrogen atmosphere, 0.5 g of cyclohexylamine, 1.26 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, stirred, and cooled to 0°C. 5.03 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 15 hours, the conversion was determined by NMR. After the reaction was completed, the precipitate was filtered off, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target product, N-cyclohexyl-1-(3-(tributylsilyl)phenyl)-N-((3-(tributylsilyl)phenyl)(2-(trifluoromethoxy)phenyl)phosphino)-1-(2-(trifluoromethoxy)phenyl)phosphinamine, 3.92 g (yield 79%).

[0582] [Chemical Formula 5-20]

[0583]

[0584] 1 H NMR (500MHz, CDCl3): δ7.61(m,2H),7.49(m,2H),7.43(m,2H),7.35(m,2H),7.18(m,2H),7.17(m,2H),7.16(m,2H),6.98(m,2H),2.6 4(m,1H),1.80(m,2H),1.52(m,2H),1.49(m,1H),1.47(m,12H),1.45(m,1H),1.39(m,12H),1.23(m,14H),1.14(m,2H),0.93(m,18H)

[0585] Synthesis Example 87: Synthesis of the intermediate compound represented by Chemical Formula 10 and the ligand compound represented by Chemical Formula 2-67

[0586] In a nitrogen atmosphere, 2.03 g of methylamine hydrochloride, 10.62 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, then stirred and cooled to 0°C. 13.11 g of chloro(2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and then slowly added to the flask. After stirring the reactants for 22 hours, the conversion rate was detected by NMR. After the reaction was complete, the precipitate was filtered off and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the target intermediate, 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 8.55 g (yield 66%).

[0587] [Chemical Formula 10]

[0588]

[0589] 1 H NMR (500MHz, CDCl3): δ7.66(m,1H),7.40(m,2H),7.29(m,1H),7.25(m,1H),7.20(m ,3H),2.47(m,3H),1.59(m,1H),1.47(m,6H),1.35(m,6H),1.26(m,6H),0.98(m,9H)

[0590] Subsequently, under a nitrogen atmosphere, 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 10.62 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, stirred, and cooled to 0°C. 2.44 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 20 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoromethyl)phenyl)phosphino)phosphineamine, 4.15 g (yield 94%).

[0591] [Chemical Formula 2-67]

[0592]

[0593] 1 H NMR (500MHz, CDCl3): δ7.66(m,1H),7.49(m,1H),7.48(m,5H),7.28(m,2H),7.25(m,1H),7.2 1(m,5H),7.10(m,1H),2.56(m,3H),1.50(m,12H),1.36(m,12H),1.28(m,12H),0.95(m,18H)

[0594] Synthesis Example 88: Synthesis of the ligand compound represented by Chemical Formula 2-68

[0595] Under a nitrogen atmosphere, 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 10.62 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 2.25 g of chloro(2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 15 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-fluorophenyl)-N-((2-methoxyphenyl)(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 3.46 g (yield 82%).

[0596] [Chemical Formula 2-68]

[0597]

[0598] 1 H NMR (500MHz, CDCl3): δ7.61(m,1H),7.47(m,1H),7.43(m,4H),7.25(m,1H),7.23(m,1H),7.21(m,1H),7.20(m,5 H),7.10(m,1H),7.01(m,1H),3.85(m,3H),2.48(m,3H),1.44(m,12H),1.37(m,12H),1.32(m,12H),0.95(m,18H)

[0599] Synthesis Example 89: Synthesis of the ligand compound represented by Chemical Formula 2-69

[0600] Under a nitrogen atmosphere, 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 10.62 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 2.17 g of chloro(o-tolyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 19 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to obtain the desired product, 1-(2-fluorophenyl)-N-methyl-N-(o-tolyl(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphineamine, 3.11 g (yield 75%).

[0601] [Chemical Formula 2-69]

[0602]

[0603] 1 H NMR (500MHz, CDCl3): δ7.68(m,1H),7.44(m,4H),7.37(m,1H),7.29(m,1H),7.23(m,1H),7.21(m,6H),7.1 6(m,1H),7.12(m,1H),2.51(m,3H),2.33(m,3H),1.52(m,12H),1.32(m,12H),1.29(m,12H),0.92(m,18H)

[0604] Synthesis Example 90: Synthesis of the ligand compound represented by Chemical Formula 2-70

[0605] Under a nitrogen atmosphere, 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphine, 10.62 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, stirred, and cooled to 0°C. 2.52 g of (chloro(4-tributylsilyl)phenyl)(2-trifluoromethoxy)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 19 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was filtered off, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 2.74 g (yield 61%) of 1-(2-fluorophenyl)-N-methyl-1-(4-tributylsilyl)phenyl)-N-((4-tributylsilyl)phenyl)(2-trifluoromethoxy)phenyl)phosphino)phosphineamine.

[0606] [Chemical Formula 2-70]

[0607]

[0608] 1 H NMR (500MHz, CDCl3): δ7.68(m,1H),7.48(m,1H),7.46(m,4H),7.29(m,1H),7.22(m,1H),7.21(m,1 H),7.18(m,6H),6.98(m,1H),2.54(m,3H),1.44(m,12H),1.35(m,12H),1.25(m,12H),0.91(m,18H)

[0609] Synthesis Example 91: Synthesis of the ligand compound represented by Chemical Formula 2-71

[0610] Under a nitrogen atmosphere, 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 10.62 g of triethylamine, and 10 ml of dichloromethane were placed in a dried flask, followed by stirring and cooling to 0°C. 2.54 g of chloro(4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reactants for 11 hours, the conversion was determined by NMR. After completion of the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified using column chromatography to afford the desired product, 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trifluoro-14-sulfanyl)phenyl)phosphino)phosphinamine, 3.74 g (83% yield).

[0611] [Chemical Formula 2-71]

[0612]

[0613] 1 H NMR (500MHz, CDCl3): δ7.70(m,1H),7.47(m,4H),7.41(m,1H),7.28(m,1H),7.22(m,3H),7.1 9(m,5H),7.01(m,1H),2.50(m,3H),1.47(m,12H),1.31(m,12H),1.25(m,12H),0.98(m,18H)

[0614] Synthesis Example 92: Synthesis of the ligand compound represented by Chemical Formula 2-72

[0615] 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 10.62 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask under a nitrogen atmosphere, followed by stirring and cooling to 0°C. 2.33 g of chloro(2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 17 hours, the conversion was determined by NMR. After completion of the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-fluorophenyl)-N-methyl-N-((2-(methylthio)phenyl)(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphineamine, 2.88 g (yield 67%).

[0616] [Chemical Formula 2-72]

[0617]

[0618] 1 H NMR (500MHz, CDCl3): δ7.64(m,1H),7.44(m,4H),7.37(m,2H),7.28(m,2H),7.24(m,1H),7.20(m,5 H),7.12(m,1H),2.56(m,3H),2.54(m,3H),1.47(m,12H),1.32(m,12H),1.25(m,12H),0.91(m,18H)

[0619] Synthesis Example 93: Synthesis of the ligand compound represented by Chemical Formula 2-73

[0620] Under a nitrogen atmosphere, 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 10.62 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 2.57 g of 2-(chloro(4-(tributylsilyl)phenyl)phosphino)phenyl methanesulfonate was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 21 hours, the conversion was determined by NMR. After completion of the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 2-((((2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphino)(methyl)amino)(4-(tributylsilyl)phenyl)phosphino)phenyl methanesulfonate, 3.68 g (yield 81%).

[0621] [Chemical Formula 2-73]

[0622]

[0623] 1 H NMR (500MHz, CDCl3): δ7.65(m,1H),7.53(m,1H),7.47(m,1H),7.40(m,4H),7.30(m,1H),7.25(m,2H),7.2 3(m,1H),7.15(m,5H),3.62(m,3H),2.54(m,3H),1.52(m,12H),1.36(m,12H),1.31(m,12H),0.89(m,18H)

[0624] Synthesis Example 94: Synthesis of the ligand compound represented by Chemical Formula 2-74

[0625] Under a nitrogen atmosphere, 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 10.62 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 2.46 g of chloro(4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 15 hours, the conversion was determined by NMR. After the reaction was complete, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)-N-((4-(tributylsilyl)phenyl)(2-(trimethylsilyl)phenyl)phosphino)phosphineamine, 4.3 g (97% yield).

[0626] [Chemical Formula 2-74]

[0627]

[0628] 1 H NMR (500MHz, CDCl3): δ7.67(m,1H),7.49(m,6H),7.33(m,1H),7.27(m,2H),7.17(m,6 H),2.56(m,3H),1.51(m,12H),1.32(m,12H),1.31(m,12H),0.89(m,18H),0.27(m,9H)

[0629] Synthesis Example 95: Synthesis of the ligand compound represented by Chemical Formula 2-75

[0630] Under a nitrogen atmosphere, 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 10.62 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 2.3 g of benzofuran-7-ylchloro(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. The reaction was stirred for 11 hours, and the conversion was determined by NMR. After the reaction, the precipitate was filtered and the solvent was removed under reduced pressure. The resulting organic material was purified by column chromatography to yield the desired product, 1-(benzofuran-7-yl)-N-((2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 4.23 g (yield 99%).

[0631] [Chemical Formula 2-75]

[0632]

[0633] 1 H NMR (500MHz, CDCl3): δ7.62(m,3H),7.50(m,4H),7.48(m,1H),7.33(m,1H),7.25(m,1H),7.2 1(m,6H),6.83(m,1H),2.54(m,3H),1.47(m,12H),1.31(m,12H),1.29(m,12H),0.96(m,18H)

[0634] Synthesis Example 96: Synthesis of the ligand compound represented by Chemical Formula 2-76

[0635] Under a nitrogen atmosphere, 2.16 g of 1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphineamine, 10.62 g of triethylamine, and 10 ml of dichloromethane were added to a dried flask, stirred, and cooled to 0°C. 2.55 g of chloro(dibenzo[b,d]furan-4-yl)(4-(tributylsilyl)phenyl)phosphine was diluted with 10 ml of dichloromethane and slowly added to the flask. After stirring the reaction for 20 hours, the conversion was determined by NMR. After completion of the reaction, the precipitate was removed by filtration, and the solvent was removed under reduced pressure. The resulting organic material was purified using column chromatography to give the desired product, 1-(dibenzo[b,d]furan-4-yl)-N-((2-fluorophenyl)(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine, 2.94 g (yield 65%).

[0636] [Chemical Formula 2-76]

[0637]

[0638] 1 H NMR (500MHz, CDCl3): δ8.02(m,2H),7.71(m,1H),7.59(m,1H),7.49(m,1H),7.46(m,1H),7.45(m,4H),7.40(m,2 H),7.23(m,1H),7.21(m,1H),7.18(m,5H),2.48(m,3H),1.43(m,12H),1.40(m,12H),1.26(m,12H),0.96(m,18H)

[0639] Comparative Synthesis Example 1: Synthesis of the Ligand Compound Represented by Chemical Formula 11

[0640] Under a nitrogen atmosphere, 5.5 mmol (0.5 equivalent) of 3-methyl-2-butylamine, 22 mmol (2 equivalents) of triethylamine, and 10 ml of dichloromethane were added to a dried flask and stirred. After cooling to 0°C, 11 mmol (1 equivalent) of chlorobis(4-(tributylsilyl)phenyl)phosphine was slowly added. After the reaction was completed, the precipitated solid was filtered out, the solvent was removed under reduced pressure, and the compound represented by Chemical Formula 11 was obtained by column chromatography.

[0641] [Chemical Formula 11]

[0642]

[0643] N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-(3-methylbutan-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0644] 1 H NMR (500MHz, C6D6): δ7.96-7.34(m,16H),3.64-3.53(m,1H),1.81-1.72(m,1H),1. 38-1.29(m,48H),1.05(d,3H),0.91-0.84(m,39H),0.82-0.76(m,24H),0.55(d,3H)

[0645] Comparative Synthesis Example 2: Synthesis of the Ligand Compound Represented by Chemical Formula 12

[0646] Under a nitrogen atmosphere, 5.5 mmol (0.5 equivalent) of cyclohexylamine, 22 mmol (2 equivalents) of triethylamine, and 10 ml of dichloromethane were added to a dry flask and stirred. After cooling to 0°C, 11 mmol (1 equivalent) of chlorobis(4-cyclohexylphenyl)phosphine was slowly added. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the compound represented by Chemical Formula 12 was obtained by column chromatography.

[0647] [Chemical Formula 12]

[0648]

[0649] N-(bis(4-cyclohexylphenyl)phosphino)-N-cyclohexyl-1,1-bis(4-cyclohexylphenyl)phosphinamine

[0650] 1 H NMR (500MHz, C6D6): δ7.58(br.s,8H),7.08(d,8H),3.47(pent,1H),2.35(t, 4H),2.21-2.11(m,2H),1.80(d,8H),1.71-1.56(m,16H),1.44-1.11(m,24H)

[0651] Comparative Synthesis Example 3: Synthesis of the Ligand Compound Represented by Chemical Formula 13

[0652] Under a nitrogen atmosphere, 5.5 mmol (0.5 equivalent) of cyclohexylamine, 22 mmol (2 equivalents) of triethylamine, and 10 ml of dichloromethane were added to a dried flask and stirred. Then, after cooling to 0°C, 11 mmol (1 equivalent) of chlorobis(4-phenylphenyl)phosphine was slowly added. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the compound represented by Chemical Formula 13 was obtained by column chromatography.

[0653] [Chemical Formula 13]

[0654]

[0655] 1,1-Bis([1,1'-biphenyl]-4-yl)-N-cyclohexyl-N-(bis([1,1'-biphenyl]-4-yl)phosphino)phosphinamine

[0656] 1 H NMR (500MHz, C6D6): δ7.92-7.42(m,24H),7.17(t,8H),7.10(t,4H),3.58(pent,1H),2.28 -2.17(m,2H),1.84-1.77(m,2H),1.67-1.60(m,2H),1.48-1.42(m,1H),1.18-1.07(m,3H)

[0657] Comparative Synthesis Example 4: Synthesis of the Ligand Compound Represented by Chemical Formula 14

[0658] Under a nitrogen atmosphere, 5.5 mmol (0.5 equivalent) of cyclohexylamine, 22 mmol (2 equivalents) of triethylamine, and 10 ml of dichloromethane were added to a dry flask and stirred. After cooling to 0°C, 11 mmol (1 equivalent) of chlorobis(3,5-dimethylphenyl)phosphine was slowly added. After the reaction was complete, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the compound represented by Chemical Formula 14 was obtained by column chromatography.

[0659] [Chemical Formula 14]

[0660]

[0661] N-(bis(3,5-dimethylphenyl)phosphino)-N-cyclohexyl-1,1-bis(3,5-dimethylphenyl)phosphinamine

[0662] 1 H NMR (500MHz, C6D6): δ7.38(br.s,8H),6.79(s,4H),3.63(pent,1H),2.24-2.13(m, 2H),2.10(s,24H),1.77(d,2H),1.60(d,2H),1.45-1.39(m,1H),1.19-1.00(m,3H)

[0663] Examples and Comparative Examples

[0664] Example 1

[0665] In an argon atmosphere, 0.5 mmol of tetrahydrofuran chromium (III) chloride (Cr (THF) 3 Cl 3), 0.5 mmol of the ligand compound represented by Chemical Formula 2-1 according to Synthesis Example 1, and 0.5 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) as a co-catalyst were placed in a flask. 30 ml of dichloromethane was then added, stirred for 1 hour, and then the solvent was removed by vacuum. The mixture was then dissolved in methylcyclohexane, filtered, and the solvent was removed by vacuum again. The mixture was dissolved in methylcyclohexane to prepare a 0.15 mM (Cr-based) catalyst solution.

[0666] Prepare a Parr reactor with a capacity of 600ml, vacuumize at 120 ℃ for 2 hours.Then, replace its inside with argon, and reduce the temperature to 70 ℃.Then, inject 180ml methylcyclohexane and 2ml of 725μmol diisobutylaluminum hydride as activator, and inject the catalyst solution of 5ml (0.75μmol Cr). After stirring at 1,000rpm for 2 minutes, open the ethylene pipeline valve that is set to 40bar, fill the reactor with ethylene, then stir at 1,000rpm for 60 minutes. Close the ethylene pipeline valve, use dry ice / acetone bath that reactor is cooled to 0 ℃.Then, slowly discharge unreacted ethylene, then add the nonane (GC internal standard) of 0.5ml wherein. After stirring for 10 seconds, take out the 2ml liquid portion in the reactor and quench with water, the gained organic part is filtered to make GC-FID sample by PTFE syringe filter. The distribution of the liquid product was then analyzed by GC (Agilent 6890N, manufactured by Agilent Technologies, Alltech AT-530m x 0.32mm ID x 0.25μm; Serial No. 12446). Furthermore, 400ml of ethanol / HCl (10vol% 12M HCl aqueous solution) was added to the remaining reaction solution, and the resulting mixture was stirred and filtered, and then analyzed for the amount of solid product. The resulting polymer was dried in a vacuum oven at 80°C overnight.

[0667] Examples 2 to 96 and Comparative Examples 1 to 4

[0668] The same method as in Example 1-1 was performed except that the kind of catalyst was changed as shown in Table 1 below.

[0669] [Table 1]

[0670]

[0671]

[0672]

[0673]

[0674] Experimental example

[0675] Table 2 below shows the results of ethylene oligomerization reactions according to the above examples and comparative examples.

[0676] Catalytic activity (tons / mol·Cr / hour): The catalytic activity was calculated from the total weight (tons) of the product, which was obtained by adding the weight (tons) of the obtained liquid product and the obtained solid product.

[0677] 1-C6 and 1-C8 selectivity (wt %): The contents of 1-hexene (1-C6) and 1-octene (1-C8) were calculated from the results of GC analysis of the liquid product distribution, and then the weight percentage of 1-hexene or 1-octene in the total weight of the product was calculated.

[0678] Solids (wt%): Calculate the weight percentage of solid product relative to the total weight of the product. This indicates the extent to which polyethylene having a carbon number of about 40 or more is produced, where the polyethylene is an insoluble solid that is insoluble in the solvent.

[0679] [Table 2]

[0680]

[0681]

[0682]

[0683]

[0684] As shown in Table 2 above, it was confirmed that, in the case of conducting ethylene oligomerization using a catalyst composition containing the ligand compound according to the present invention, the phenyl group located at the terminal of the diphosphino moiety had a specific substituent at the ortho position, and had an alkyl group having a specific number of carbon atoms or a silyl group substituted with an alkyl group having a specific number of carbon atoms as a substituent at each of the meta and para positions, and further, due to the substituent substituted on the nitrogen atom, steric strain around the PNP functional group was controlled, which improved the catalytic activity, selectivity, and stability.

[0685] From these results, it can be confirmed that in the case of ethylene oligomerization using an organochromium compound and a catalyst composition containing the ligand compound according to the present invention, linear α-olefins with high selectivity for 1-hexene and 1-octene can be produced while maintaining excellent productivity due to high catalytic activity.

Claims

1. A ligand compound represented by Chemical Formula 1: [Chemical formula 1] In Chemical Formula 1, R 1 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 6 combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; When R 6 Not with R 1 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 6 is hydrogen; R 2 and R 3 Each is independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an arylalkoxyalkyl group having 7 to 30 carbon atoms, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), wherein, R 2 and R 3 Not at the same time hydrogen; R 4 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 7 combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; When R 7 Not with R 4 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 7 is hydrogen; and R 5 It is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

2. The ligand compound according to claim 1, in, R 1 is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 6 Combined to form a monocyclic or polycyclic heterocycle, and R 4 is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 7 Combine to form a monocyclic or polycyclic heterocycle.

3. The ligand compound according to claim 1, in, R 1 is fluoro, trifluoromethyl, methoxy, methyl, trifluoromethoxy, trifluoromethylthio, methylthio, methylsulfonate or trimethylsilyl, or is 6 Combine to form furans or dibenzofurans, and R 4 is fluoro, trifluoromethyl, methoxy, methyl, trifluoromethoxy, trifluoromethylthio, methylthio, methylsulfonate or trimethylsilyl, or is 7 Combine to form furan or dibenzofuran.

4. The ligand compound according to claim 1, in, R 2 and R 3 Each is independently an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group or a tributylsilyl group.

5. The ligand compound according to claim 1, in, R 2 and R 3 Each is independently n-decyl, tripropylsilyl or tributylsilyl.

6. The ligand compound according to claim 1, in, R 5 It is an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms condensed with an aryl group having 6 to 10 carbon atoms.

7. The ligand compound according to claim 1, in, The ligand compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 2 to 5: [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] [Chemical formula 5] In Chemical Formulae 2 to 5, R 1 To R 7 The same as defined in claim 1 respectively.

8. The ligand compound according to claim 1, in, The ligand compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 2-1 to 2-76 or Chemical Formulas 5-1 to 5-20:

9. An organic chromium compound comprising: The ligand compound according to claim 1, and chromium coordinated with the ligand compound.

10. The organochromium compound according to claim 9, wherein The organic chromium compound has a form in which any one or more unshared electron pairs of N and two P in the ligand compound represented by Chemical Formula 1 are coordinated with chromium.

11. A catalyst composition comprising: The ligand compound according to claim 1; chromium; as well as Co-catalyst.

12. The catalyst composition according to claim 11, in, The chromium is derived from a chromium source, and The chromium source comprises one or more selected from chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) valerate, chromium (III) laurate, tris (2,2,6,6-tetramethyl-3,5-heptanedione) chromium (III), and chromium (III) stearate.

13. The catalyst composition according to claim 11, in, The co-catalyst is at least one or more selected from the compounds represented by Chemical Formula 6 to Chemical Formula 9: [Chemical formula 6] <h2 style=";text-align:left;direction:ltr">-[Al(R<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> )-O]<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> - In Chemical Formula 6, R 13 are each independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, and a is an integer greater than 2; [Chemical formula 7] E(R 14 )3 In Chemical Formula 7, E is aluminum or boron, and R 14 are each independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, [Chemical formula 8] [L-H] + [G(Y)4] - [Chemical formula 9] [L] + [G(Y)4] - In chemical formulas 8 and 9, L is a neutral or cationic Lewis acid, [LH] + is a Brønsted acid, G is a Group 13 element, and Y is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or the aryl group is substituted, the substituent is a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

14. A method for producing linear α-olefins, comprising: A step of oligomerizing ethylene in the presence of the catalyst composition according to claim 11 (S10).

15. The method for producing linear α-olefins according to claim 14, in, The linear α-olefin is 1-hexene, 1-octene, or a mixture thereof.

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