Ligand compounds, organochromium compounds, and catalyst compositions containing the same

Abstract

The present invention relates to a ligand compound having a novel structure that exhibits high catalytic activity and high selectivity for 1-hexene and 1-octene, and is capable of carrying out ethylene oligomerization with excellent efficiency; an organochromium compound; a catalyst composition containing the organochromium compound; and a method for ethylene oligomerization using the same.

Description

[Technical Field]

[0001] The present invention claims the benefit of priority based on Korean Patent Application No. 10-2022-0123358, filed on September 28, 2022, and all contents disclosed in the documents of this Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a ligand compound, an organochromium compound, a catalyst composition containing the organochromium compound, and a process for oligomerizing ethylene using the same. [Background technology]

[0003] Linear alpha-olefins such as 1-hexene and 1-octene are used in detergents, lubricants, plasticizers, etc., and are primarily used as comonomers to adjust the density of polymers in the production of linear low-density polyethylene (LLDPE).

[0004] In the conventional manufacturing process of LLDPE (Linear Low-Density Polyethylene), ethylene is copolymerized with a comonomer such as α-olefin, e.g., 1-hexene or 1-octene, to form branches in the polymer backbone and adjust the density.

[0005] Therefore, in order to produce LLDPE with a high comonomer content, the cost of the comonomer accounts for a large portion of the production cost, and various attempts have been made to solve this problem.

[0006] Such linear α-olefins have typically been produced by the Shell Higher Olefin Process, but this process requires a separate separation step to obtain a specific α-olefin, since α-olefins of various lengths are simultaneously synthesized due to the Schultz-Flory distribution.

[0007] To solve this problem, methods have been proposed for selectively synthesizing 1-hexene through the trimerization of ethylene and for selectively synthesizing 1-octene through the tetramerization of ethylene. Much research has been conducted on catalyst systems that enable such selective ethylene oligomerization. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 5,064,802 Summary of the Invention [Problem to be solved by the invention]

[0009] The problem to be solved by the present invention is to provide a ligand compound and an organochromium compound having a novel structure, which exhibit high catalytic activity, high selectivity to 1-hexene and 1-octene, and are capable of carrying out ethylene oligomerization with excellent efficiency, and a catalyst composition containing the same. [Means for solving the problem]

[0010] To solve the above problems, the present invention provides a ligand compound, an organochromium compound, a catalyst composition, and a method for oligomerizing ethylene.

[0011] (1) The present invention provides a ligand compound represented by the following chemical formula 1:

[0012] [Chemical formula 1] [ka]

[0013] In the above chemical formula 1, R 1 ~R 4 are each independently an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 6 to 20 carbon atoms, an arylalkoxyalkyl group having 10 to 30 carbon atoms, or a trialkylsilyl group, and the alkyl groups of the trialkylsilyl groups are each independently an alkyl group having 1 to 10 carbon atoms; R 5 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0014] (2) The present invention is 1 ~R 4 are each independently an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group, or a tributylsilyl group.

[0015] (3) The present invention is 1 ~R 4 and each independently represent an n-decyl group, a tripropylsilyl group, or a tributylsilyl group.

[0016] (4) The present invention is 5 is an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with 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.

[0017] (5) The present invention provides the ligand compound according to any one of (1) to (4) above, wherein the ligand compound represented by Chemical Formula 1 is represented by Chemical Formula 2 below:

[0018] [Chemical formula 2] [ka]

[0019] In the above chemical formula 2, R 5 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0020] (6) The present invention provides the ligand compound according to (5) above, wherein the ligand compound represented by Chemical Formula 2 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 2-1 to 2-10:

[0021] [ka] [ka]

[0022] (7) The present invention provides the ligand compound according to any one of (1) to (4) above, wherein the ligand compound represented by Chemical Formula 1 is represented by Chemical Formula 3 below:

[0023] [Chemical formula 3] [ka]

[0024] In the above chemical formula 3, R 5is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0025] (8) The present invention provides the ligand compound according to (7) above, wherein the ligand compound represented by Chemical Formula 3 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 3-1 to 3-10:

[0026] [ka] [ka]

[0027] (9) The present invention provides the ligand compound according to any one of (1) to (4) above, wherein the ligand compound represented by Chemical Formula 1 is represented by Chemical Formula 4 below:

[0028] [Chemical formula 4] [ka]

[0029] In the above chemical formula 4, R 5 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0030] (10) The present invention provides the ligand compound according to (9) above, wherein the ligand compound represented by Chemical Formula 4 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 4-1 to 4-10:

[0031] [ka] [ka]

[0032] (11) The present invention provides the ligand compound according to any one of (1) to (4) above, wherein the ligand compound represented by Chemical Formula 1 is represented by Chemical Formula 5 below:

[0033] [Chemical formula 5] [ka]

[0034] In the above chemical formula 5, R 5 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0035] (12) The present invention provides the ligand compound according to (11) above, wherein the ligand compound represented by Chemical Formula 5 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 5-1 to 5-10:

[0036] [ka] [ka]

[0037] (13) The present invention provides the ligand compound according to any one of (1) to (4) above, wherein the ligand compound represented by Chemical Formula 1 is represented by Chemical Formula 6 below:

[0038] [Chemical formula 6] [ka]

[0039] In the above chemical formula 6, R 5 represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms, and n is an integer selected from 4 to 14.

[0040] (14) The present invention provides the ligand compound according to (13) above, wherein the ligand compound represented by Chemical Formula 6 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 6-1 to 6-10:

[0041] [ka] [ka]

[0042] (15) The present invention provides an organochromium compound comprising the ligand compound according to any one of (1) to (14) above and chromium coordinated to the ligand compound.

[0043] (16) The present invention provides the organochromium compound according to (15) above, wherein in the ligand compound represented by Chemical Formula 1, at least one lone electron pair of either N or two P is coordinated to chromium.

[0044] (17) The present invention provides a catalyst composition comprising the ligand compound according to any one of (1) to (14) above, chromium, and a cocatalyst.

[0045] (18) The present invention provides the catalyst composition according to (17) above, wherein the chromium is derived from a chromium source, and the chromium source comprises one or more selected from the group consisting of chromium(III) acetylacetonate, chromium(III) chloride tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetate, chromium(III) butyrate, chromium(III) pentanoate, chromium(III) laurate, chromium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), and chromium(III) stearate.

[0046] (19) The present invention provides the catalyst composition according to (17) or (18) above, wherein the co-catalyst is one or more compounds selected from the group consisting of compounds represented by the following chemical formulas 7 to 10:

[0047] [Chemical formula 7] -[Al(R 13 )-O] a -

[0048] In the above chemical formula 7, R 13 are each independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and a is an integer of 2 or greater; [Chemical formula 8] E(R 14 )3 In the above formula 8, E is aluminum or boron, and R 14 are each independently a hydrogen atom, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, [Chemical formula 9] [LH] + [G(Y)4] - [Chemical formula 10] [L] + [G(Y)4] - In the formulas 9 and 10, L is a neutral or cationic Lewis acid, [LH] +is a Bronsted acid, G is a Group 13 element, and each Y is 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, where, when the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbyl 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.

[0049] (20) The present invention provides a method for producing linear α-olefins, comprising a step (S10) of oligomerizing ethylene in the presence of the catalyst composition according to any one of (17) to (19).

[0050] (21) The present invention provides the method for producing linear α-olefins according to (20) above, wherein the linear α-olefin is 1-hexene, 1-octene, or a mixture thereof. [Effects of the Invention]

[0051] When ethylene oligomerization is carried out using the organochromium compound and catalyst composition containing the ligand compound of the present invention, the high catalytic activity allows for excellent productivity and the production of linear α-olefins with high selectivity to 1-hexene and 1-octene. DETAILED DESCRIPTION OF THE INVENTION

[0052] The present invention will now be described in more detail so that the present invention may be more easily understood.

[0053] The terms and words used in the description of the present invention and the claims should not be interpreted in a limited way to their ordinary or dictionary meanings, but should be interpreted in a way that is consistent with the technical idea of ​​the present invention, based on the principle that the inventors can appropriately define the concepts of terms in order to best describe their invention.

[0054] Ligand Compound The present invention provides a ligand compound applicable to a catalyst used in an ethylene oligomerization reaction. When the ligand compound is applied to an ethylene oligomerization reaction, specifically, to a catalyst composition for producing linear α-olefins, the ligand compound exhibits excellent catalytic activity and high selectivity for linear α-olefins. In particular, compared to conventional PNP-based catalysts as well as catalysts containing symmetric ligand compounds, the amount of solid polyethylene produced is lower under the same reaction conditions, enabling more efficient production of linear α-olefins.

[0055] According to one embodiment of the present invention, the organochromium compound coordinated with the ligand compound can be used to produce linear α-olefins using ethylene, and can undergo an oligomerization reaction under ethylene conditions to produce liquid α-olefins, specifically, liquid 1-hexene or 1-octene, with high selectivity. This is because the oligomerization of ethylene passes through a transition state in which a metallacycle is formed, resulting in high selectivity for α-olefins of a specific length.

[0056] According to one embodiment of the present invention, the ligand compound includes a diphosphinoaminyl moiety, and an aryl having a specific substituent is attached to the end of the diphosphinoaminyl moiety, which itself may have a configuration in which it functions as a strong electron-donating group. Due to this structural feature, the ligand compound can be applied to an ethylene oligomerization catalyst system and exhibit high activity, particularly high selectivity for 1-hexene, 1-octene, and the like. This is thought to be due to the interaction between adjacent chromium active sites. In particular, when an aryl having a specific substituent is attached to the phosphorus (P) atom of the diphosphinoaminyl, the electron density at the phosphorus (P) atom and nitrogen (N) atom contained in the diphosphinoaminyl increases, resulting in changes in the electronic and steric properties of the entire ligand compound. This results in a change in the bond between the ligand and the chromium atom, making the catalyst structure more stable and changing the transition state energy (activation energy) compared to conventional metallacycloheptane or metallacyclononane forms, enabling the formation of α-olefins with higher activity and selectivity, further reducing the amount of by-products such as solid α-olefins with high molecular weights, such as polyethylene wax (PE wax).

[0057] According to one embodiment of the present invention, the ligand compound is characterized in that the phenyl group at the terminal of the diphosphinoaminyl residue is asymmetrically substituted at the meta and para positions with alkyl groups of a specific carbon number or silyl groups substituted with alkyl groups of a specific carbon number. Considering the three-dimensional structure of the ligand compound itself and the catalyst structure bound to chromium, the substituent at the meta position of the phenyl induces relatively greater steric hindrance than the substituent at the para position. Therefore, the substituent at the meta position of the phenyl improves catalyst stability and can control the structure due to steric hindrance, thereby further improving selectivity to 1-hexene and 1-octene. However, if the steric hindrance is too great, the access of ethylene to the catalyst may be hindered, resulting in a decrease in catalytic activity. Therefore, it is important to adjust the steric hindrance of the ligand compound by adjusting the substituent at the meta position of the phenyl. On the other hand, a substituent substituted at the para-position of the phenyl group has less steric hindrance than a substituent substituted at the meta-position of the phenyl group, allowing ethylene to easily approach the catalyst and improving catalytic activity. However, there is a risk of reduced catalyst stability due to rotation of the nitrogen-phosphorus bond and the nitrogen-carbon bond, and the overreaction of ethylene can result in the production of high-molecular-weight by-products. Therefore, it is important to adjust the steric hindrance caused by the ligand compound by adjusting the substituent substituted at the para-position of the phenyl group. The ligand compound according to the present invention simultaneously adjusts the substituents substituted at the meta- and para-positions of the phenyl group to adjust the steric hindrance caused by the ligand compound and reduce the possibility of rotation of the nitrogen-phosphorus bond, thereby preventing dissociation of the ligand compound in the catalyst. This allows the production of a chromium catalyst with high stability, activity, and selectivity.

[0058] According to one embodiment of the present invention, the ligand compound has a bulky substituent, such as a cycloalkyl group or a phenyl group, bound to the nitrogen atom to which two phosphorus atoms are bonded. The bulky substituent bound to the nitrogen prevents the nitrogen-phosphorus bond from rotating, thereby further improving catalyst stability and activity. The activity, stability, and selectivity of the catalyst vary depending on the steric properties of the substituent bound to the nitrogen atom. If the steric strain of the substituent bound to the nitrogen atom is too high, the synthesis of the ligand and the formation of the metal complex compound become difficult, and the resulting complex compound becomes unstable. Furthermore, if the steric strain of the substituent bound to the nitrogen atom is too high, the access of raw materials such as ethylene becomes difficult, resulting in reduced catalyst activity. Furthermore, if 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 central atom cannot be protected, resulting in reduced catalyst activity and stability. In other words, if the steric strain of the substituent bound to the nitrogen atom is too high or too low, the catalyst activity and stability decrease, resulting in increased production of by-products such as polyethylene wax. Therefore, it is very important to select a substituent bonded to the nitrogen atom that has an appropriate level of steric strain relative to the substituent bonded to the phosphorus atom. In the ligand compound according to the present invention, the introduction of a substituent at the meta position of the phenyl group bonded to the phosphorus atom increases the steric strain around the PNP functional group. Therefore, the R of Chemical Formula 1 is selected so as not to excessively increase the steric strain of the substituent bonded to the nitrogen atom. 5 By introducing a substituent represented by the formula: 5 When a secondary alkyl group is introduced as the substituent represented by the formula (I), the efficiency is further improved. When an aryl group such as a phenyl group is introduced at the first or second carbon position of the primary alkyl group to compensate for the low steric strain, the appropriate steric strain can be formed, and the yield and selectivity can be improved.

[0059] According to one embodiment of the present invention, the ligand compound may be represented by the following Chemical Formula 1:

[0060] [Chemical formula 1] [ka]

[0061] In the above chemical formula 1, R 1 ~R 4 are each independently an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 6 to 20 carbon atoms, an arylalkoxyalkyl group having 10 to 30 carbon atoms, or a trialkylsilyl group, and the alkyl groups of the trialkylsilyl groups are each independently an alkyl group having 1 to 10 carbon atoms; R 5 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0062] In the present invention, the term "alkyl group" refers to a linear or branched hydrocarbon residue, and specific examples thereof may include, depending on the number of carbon atoms defined, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, and a hexyl group.

[0063] In the present invention, the term "cycloalkyl group" means a cyclic hydrocarbon residue, and specific examples thereof may include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, depending on the defined number of carbon atoms.

[0064] In the present invention, the term "alkoxyalkyl group" means an alkyl group substituted with an alkoxy group, and when referring to the number of carbon atoms in an alkoxyalkyl group, it may mean the total number of carbon atoms in the alkoxy group and the alkyl group.

[0065] In the present invention, the term "arylalkoxyalkyl group" means an alkyl group substituted with an alkoxy group containing an aryl group as a substituent, and when referring to the number of carbon atoms in an arylalkoxyalkyl group, it may mean the total number of carbon atoms in the alkoxy group and the alkyl group.

[0066] In the present invention, the term "trialkylsilyl group" refers to a substituent represented by -SiRd3, in which each R is independently an alkyl group, and when referring to the number of carbon atoms in a trialkylsilyl group, it may refer to the total number of carbon atoms in all Rs.

[0067] In the present invention, unless otherwise specified, "aryl" refers to an optionally substituted benzene ring or a ring system that can be formed by condensing one or more optional substituents. Exemplary optional substituents include a substituted C-C alkyl group, a substituted C-C alkenyl group, a substituted C-C alkynyl group, a heteroaryl group, a heterocyclic group, an aryl group, an alkoxy group, aryloxy group, aralkoxy group, acyl group, aroyl group, heteroaroyl group, acyloxy group, aroyloxy group, heteroaroyloxy group, sulfanyl group, sulfinyl group, sulfonyl group, aminosulfonyl group, sulfonylamino group, carboxamido group, aminocarbonyl group, carboxy group, oxo group, hydroxy group, mercapto group, amino group, nitro group, cyano group, halogen group, or ureido group, each of which optionally has one to three fluorine substituents. Such a ring or ring system may be optionally condensed to an aryl ring (e.g., a benzene ring), a carbocyclic ring, or a heterocyclic ring, each of which optionally has one or more substituents. It may include, but is not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl, or phenanthryl, and substituted derivatives thereof.

[0068] According to one embodiment of the present invention, R 1 ~R 4 may each independently represent an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group, or a tributylsilyl group, and specific examples thereof include R 1 ~R 4may each independently be a tripropylsilyl group, a tributylsilyl group, or an n-decyl group. That is, the ligand compound may be one in which the phenyl located at the terminal of the diphosphinoaminyl residue has, at the meta position, a silyl group substituted with an alkyl group having 10 carbon atoms or an alkyl group having 3 or 4 carbon atoms, as a substituent.

[0069] According to one embodiment of the present invention, the ligand compound comprises: i) R 1 and R 2 are identical to each other, and R 3 and R 4 may be identical to each other, and ii) R 1 and R 3 are identical to each other, and R 2 and R 4 may be identical to each other, and iii) R 1 ~R 4 may be identical to each other.

[0070] According to one embodiment of the present invention, R 5 may be an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with 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.

[0071] Hereinafter, specific examples of the ligand compound represented by Chemical Formula 1 according to the present invention will be described by dividing them into ligand compounds represented by Chemical Formulas 2 to 6, but this is merely for the sake of convenience, and each of the ligand compounds represented by Chemical Formulas 2 to 6 is a specific example of the ligand compound represented by Chemical Formula 1, and all of them exhibit the same effects.

[0072] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 1 may be represented by Chemical Formula 2 below.

[0073] [Chemical formula 2] [ka]

[0074] In the above chemical formula 2, R 5 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0075] According to one embodiment of the present invention, in Formula 2, "C3H7" may be an n-propyl group.

[0076] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 2 may be one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 2-1 to 2-10.

[0077] [ka] [ka]

[0078] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 1 may be represented by Chemical Formula 3 below.

[0079] [Chemical formula 3] [ka]

[0080] In the above chemical formula 3, R 5 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0081] According to one embodiment of the present invention, in Formula 3, "C4H9" may be an n-butyl group.

[0082] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 3 may be one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 3-1 to 3-10.

[0083] [ka] [ka]

[0084] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 1 may be represented by Chemical Formula 4 below.

[0085] [Chemical formula 4] [ka]

[0086] In the above chemical formula 4, R 5 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0087] According to one embodiment of the present invention, in the above Chemical Formula 4, "C3H7" may be an n-propyl group, and "C4H9" may be an n-butyl group.

[0088] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 4 may be one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 4-1 to 4-10.

[0089] [ka] [ka]

[0090] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 1 may be represented by Chemical Formula 5 below.

[0091] [Chemical formula 5] [ka]

[0092] In the above chemical formula 5, R 5 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

[0093] According to one embodiment of the present invention, in the above Chemical Formula 5, "C3H7" may be an n-propyl group, and "C4H9" may be an n-butyl group.

[0094] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 5 may be one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 5-1 to 5-10.

[0095] [ka] [ka]

[0096] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 1 may be represented by Chemical Formula 6 below.

[0097] [Chemical formula 6] [ka]

[0098] In the above chemical formula 6, R 5 represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms, and n is an integer selected from 4 to 14.

[0099] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 6 may be one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 6-1 to 6-10.

[0100] [ka] [ka]

[0101] According to one embodiment of the present invention, in the above Chemical Formulas 6-1 to 6-10, "C 10 H 21 " may be an n-decyl group.

[0102] According to one embodiment of the present invention, the ligand compound may be realized in various combinations other than the above specific examples as long as the above conditions are satisfied, and any compound represented by Chemical Formula 1 can be applied as the ligand compound of the present invention.

[0103] Organochromium compounds and catalyst compositions The present invention provides a ligand compound represented by Chemical Formula 1, and an organochromium compound containing chromium (Cr) coordinated to the ligand compound.

[0104] According to one embodiment of the present invention, the organochromium compound is a chromium complex compound of the ligand compound, and the chromium source may have a coordinate bond formed by one or more lone electron pairs of N and two P atoms in the ligand compound represented by Chemical Formula 1. That is, the phosphorus or nitrogen atom of the diphosphinoaminyl residue provides a lone electron pair to the chromium atom, and a bidentated state in which two lone electron pairs are coordinated is particularly preferred. The organochromium compound can be used in a catalyst system for the ethylene oligomerization reaction and exhibits excellent catalytic activity and high selectivity for 1-hexene or 1-octene.

[0105] In the present invention, the term "catalyst composition" refers to a catalyst obtained by adding three components, including a chromium source, a ligand compound, and a cocatalyst, or two components, a transition metal compound and a cocatalyst, simultaneously or in any order, to form an active catalyst composition. Here, 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 three or two components of the catalyst composition may be added in the presence or absence of a solvent and a monomer, and may be used in a supported or unsupported state.

[0106] The present invention provides a catalyst composition comprising the ligand compound, chromium, and a cocatalyst. The ligand compound represented by Chemical Formula 1 and chromium can be coordinated to form an organochromium compound, as described above. That is, the catalyst system may be a three-component catalyst system comprising chromium, the ligand compound represented by Chemical Formula 1, and a cocatalyst, or a two-component catalyst system comprising the organochromium compound and a cocatalyst. As a specific example, the catalyst composition may comprise the ligand compound, an organochromium compound containing chromium coordinated to the ligand compound, and a cocatalyst. Alternatively, the catalyst composition may comprise a chromium compound in which a portion of the cocatalyst is bound to the organochromium compound.

[0107] According to one embodiment of the present invention, the chromium is derived from a chromium source, which may be an organic or inorganic chromium compound having an oxidation state of chromium ranging from 0 to 6. Specific examples of the chromium source include chromium metal or a compound in which any organic or inorganic radical is bonded to chromium. The organic radical may be an alkyl, alkoxy, ester, ketone, amide, or carboxylate radical having 1 to 20 carbon atoms per radical, and the inorganic radical may be a halide, sulfate, or oxide.

[0108] According to one embodiment of the present invention, the chromium source is a compound that exhibits high activity in olefin oligomerization and is easy to use and obtain, and may be one or more compounds selected from the group consisting of chromium(III) acetylacetonate, chromium(III) chloride tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetate, chromium(III) butyrate, chromium(III) pentanoate, chromium(III) laurate, chromium(III) tris(2,2,6,6-tetramethyl-3.5-heptanedionate), and chromium(III) stearate.

[0109] According to one embodiment of the present invention, the co-catalyst may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 7 to 10.

[0110] [Chemical formula 7] -[Al(R 13 )-O] a -

[0111] In the above chemical formula 7, R 13 are each independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and a is an integer of 2 or greater.

[0112] [Chemical formula 8] E(R 14 )3

[0113] In the above formula 8, E is aluminum or boron, and R 14 are each independently hydrogen, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group.

[0114] [Chemical formula 9] [LH] + [G(Y)4] -

[0115] [Chemical formula 10] [L] + [G(Y)4] -

[0116] In the formulas 9 and 10, L is a neutral or cationic Lewis acid, [LH] + is a Bronsted acid, G is a Group 13 element, and each Y is 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, where, when the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbyl 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.

[0117] According to one embodiment of the present invention, the catalyst composition can be prepared by several methods. Specifically, first, the catalyst composition can be prepared by contacting the organochromium compound with the compound represented by Chemical Formula 7 or 8. Second, the catalyst composition can be prepared by contacting the organochromium compound with the compound represented by Chemical Formula 7 or 8 to obtain a mixture, and adding the compound represented by Chemical Formula 9 or 10 to the mixture. Third, the catalyst composition can be prepared by contacting the organochromium compound with the compound represented by Chemical Formula 9 or 10. Fourth, the catalyst composition can be prepared by contacting the organochromium compound with the compound represented by Chemical Formula 9 or 10 to obtain a mixture, and adding the compound represented by Chemical Formula 7 or 8 to the mixture. Fifth, the catalyst composition may be prepared by contacting the chromium source with the compound represented by Formula 9 or 10 to obtain a reactant, and contacting the reactant with the ligand compound.

[0118] According to one embodiment of the present invention, in the first or third method of preparing the catalyst composition, the molar ratio of the compound represented by Chemical Formula 7 or Chemical Formula 8 to the organochromium compound may be 1:2 to 5,000, specifically 1:100 to 3,000, and more specifically 1:300 to 1,500, respectively. When the molar ratio is within this range, the alkylation of the organochromium compound can be completed, improving the activity of the catalyst composition, preventing a decrease in the activity of the alkylated organochromium compound due to a side reaction between the remaining alkylating agent, and improving the economy and the purity of the produced linear α-olefin.

[0119] 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 Formula 9 or 10 to the organochromium compound may be 1:1 to 500, specifically 1:1 to 50, and more specifically 1:1 to 1:25. Within this range, the amount of activator is sufficient to completely activate the metal compound, improving the activity of the catalyst composition and minimizing residual activator, thereby improving economy and the purity of the produced linear α-olefins.

[0120] According to one embodiment of the present invention, the compound represented by Chemical Formula 7 may be an alkylaluminoxane, specific examples of which include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and a more specific example of which is methylaluminoxane.

[0121] According to one embodiment of the present invention, the compound represented by Chemical Formula 8 may be trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, dialkylaluminum hydride, alkylaluminum dihydride, trialkylboron, etc. Specific examples of the compound represented by Chemical Formula 8 include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, and tri-p-tolylaluminum; dialkylaluminum halides such as diethylaluminum chloride;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, phenylisopropylaluminum 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-butyl The aluminum hydride may be a dialkylaluminum hydride such as 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.

[0122] According to one embodiment of the present invention, the compound represented by Formula 9 or 10 is trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, triethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, tributylammonium tetra(p-tolyl)borate, N,N-dimethylanilinium tetra(p-tolyl)borate, N,N-diethylanilinium 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, N,N-dimethylanilinium tetra(o,p-dimethylphenyl)borate, p-dimethylphenyl)borate, N,N-diethylanilinium tetra(o,p-dimethylphenyl)borate, trimethylammonium tetrakis(p-trifluoromethylphenyl)borate, triethylammonium tetrakis(p-trifluoromethylphenyl)borate, tripropylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-diethylanilinium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, 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, tripropylammonium tetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetra(p-tolyl)aluminate, triethylammonium tetra(p-tolyl)aluminate, tripropylammonium tetra(p-tolyl)aluminate, tributylammonium tetra(p-tolyl)aluminate, etc. may be used.

[0123] According to one embodiment of the present invention, the content ratio of the components forming the catalyst composition may be determined in consideration of catalytic activity, selectivity for linear α-olefins, etc. Specifically, when the catalyst composition is a three-component catalyst composition, the molar ratio of the diphosphinoaminyl residue of the ligand compound:chromium source:cocatalyst may be adjusted to about 1:1:1 to about 10:1:10,000, or about 1:1:100 to 5:1:3,000. When the catalyst composition is a two-component catalyst composition, the molar ratio of the diphosphinoaminyl residue of the organochromium compound:cocatalyst may be adjusted to 1:1 to 1:10,000, or 1:1 to 1:5,000, or 1:1 to 1:3,000.

[0124] According to one embodiment of the present invention, a hydrocarbon solvent such as pentane, hexane, heptane, etc.; an aromatic solvent such as benzene, toluene, etc. may be used as a reaction solvent when preparing the catalyst composition.

[0125] According to one embodiment of the present invention, the components forming the catalyst composition can be added simultaneously or in any order in the presence or absence of a suitable solvent and monomer to form an active catalyst composition, where suitable solvents include heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, etc.

[0126] According to one embodiment of the present invention, the organochromium compound and the cocatalyst may be used in a form supported on a carrier, and the carrier may be silica or alumina.

[0127] According to one embodiment of the present invention, the catalyst composition may further include a support. For example, the ligand compound represented by Formula 1 may be supported on a support and applied to the ethylene oligomerization reaction. The support may be a metal, metal salt, or metal oxide used in a supported catalyst. For example, the support may be silica, silica-alumina, silica-magnesia, or the like, and may include a metal oxide, carbonate, sulfate, or nitrate component such as Na2O, K2CO3, BaSO4, or Mg(NO3)2.

[0128] According to one embodiment of the present invention, the catalyst composition can be used for the trimerization or tetramerization reaction of ethylene, and as described above, can produce 1-hexene or 1-octene with high selectivity.

[0129] Process for oligomerizing ethylene The present invention provides a method for producing linear α-olefins, which is a method for oligomerizing ethylene, comprising the step (S10) of oligomerizing ethylene in the presence of the catalyst composition.

[0130] In the present invention, "oligomerization" refers to the polymerization of olefins. Depending on the number of olefins to be polymerized, this is called trimerization or tetramerization, collectively referred to as multimerization. In particular, in this specification, it can refer to the selective production of 1-hexene and 1-octene, which are the main comonomers of LLDPE, from ethylene.

[0131] According to one embodiment of the present invention, the ethylene oligomerization reaction may be a trimerization or tetramerization reaction of ethylene, whereby 1-hexene or 1-octene is formed as a reaction result, and the linear α-olefin may be 1-hexene, 1-octene, or a mixture thereof.

[0132] According to one embodiment of the present invention, the ethylene oligomerization method may be carried out using ethylene as a raw material, the above-mentioned catalyst composition, and conventional equipment and contacting techniques. Specific examples of the ethylene oligomerization reaction include a homogeneous liquid phase reaction in the presence or absence of an inert solvent, a slurry reaction in which the catalyst composition is partially or completely undissolved, a bulk reaction in which the product α-olefins serve as the main medium, and a gas phase reaction.

[0133] According to one embodiment of the present invention, the ethylene oligomerization reaction may be carried out in an inert solvent, and specific examples of the inert solvent include benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, and 2,2,4-trimethylpentane.

[0134] According to one embodiment of the present invention, the ethylene oligomerization reaction may be carried out at a temperature of 0°C to 200°C, or 0°C to 150°C, or 30°C to 100°C, or 50°C to 100°C. The reaction may be carried out under a pressure of 15 psig to 3000 psig, or 15 psig to 1500 psig, or 15 psig to 1000 psig.

[0135] Although the present invention may be embodied in various different forms, it is not intended to be limited to the embodiments set forth herein, and the present invention is not limited to the embodiments set forth herein.

[0136] Synthesis examples and comparative synthesis examples In the following synthesis examples and comparative synthesis examples, -C3H7 is an n-propyl group, -C4H9 is an n-butyl group, and -C 10 H 21 is an n-decyl group.

[0137] Synthesis Example 1: Synthesis of ligand compound represented by chemical formula 2-1 A dried flask was charged with 0.94 g (11 mmol, 2.2 eq) of cyclopentylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.0 g (5 mmol) of N-cyclopentyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which was the intermediate compound 1, was obtained by column chromatography.

[0138] <Intermediate compound 1> [ka] 1 H NMR (500 MHz, DMSO): δ 7.62(m, 2H), 7.49(m, 2H), 7.37(m, 2H), 7.20(m, 2H), 2.65(m, 1H), 1.85(m, 4H), 1.77(m, 4H), 1.57(m, 1H), 1.52(m, 12H), 1.36(m, 12H), 0.98(m, 18H)

[0139] Next, 2.9 g (5 mmol, 1 eq) of N-cyclopentyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine (intermediate compound 1) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.3 g (4 mmol, 80% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-cyclopentyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-1.

[0140] <Ligand compound represented by chemical formula 2-1> [Chemical formula 2-1] [ka] 1H NMR (500 MHz, DMSO): δ 7.56-7.16(m, 16H), 2.64(m, 1H), 1.94-1.31(m, 56H), 0.96(m, 36H)

[0141] Synthesis Example 2: Synthesis of the ligand compound represented by chemical formula 2-2 A dried flask was charged with 1.09 g (11 mmol, 2.2 eq) of cyclohexylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.0 g (4.75 mmol) of N-cyclohexyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which was intermediate compound 2, was obtained by column chromatography.

[0142] <Intermediate compound 2> [ka] 1 H NMR (500 MHz, DMSO): δ 7.50(m, 2H), 7.40(m, 2H), 7.30(m, 2H), 7.10(m, 2H), 2.50(m, 1H), 1.70(m, 4H), 1.50(m, 1H), 1.40(m, 14H), 1.20(m, 16H), 0.90(m, 18H)

[0143] Next, 3.0 g (5 mmol, 1 eq) of N-cyclohexyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine (intermediate compound 2) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.80 g (4.4 mmol, 88% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-cyclohexyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-2.

[0144] <Ligand compound represented by chemical formula 2-2> [Chemical formula 2-2] [ka] 1H NMR (500 MHz, DMSO): δ 7.55-7.13(m, 16H), 2.57(m, 1H), 1.74(m, 4H), 1.46-1.43(m, 26H), 1.29-1.21(m, 28H), 0.94(m, 21H)

[0145] Synthesis Example 3: Synthesis of ligand compound represented by chemical formula 2-3 A dried flask was charged with 1.24 g (11 mmol, 2.2 eq) of cycloheptylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.0 g (5 mmol) of N-cycloheptyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which was intermediate compound 3, was obtained by column chromatography.

[0146] <Intermediate compound 3> [ka] 1 H NMR (500 MHz, C6D6): δ 7.89(m, 2H), 7.54(m, 2H), 7.26(m, 2H), 3.25(m, 1H), 1.94-1.24(m, 24H), 0.99-0.88(m, 18H), 0.81-0.78(m, 12H)

[0147] Next, 3.0 g (5 mmol, 1 eq) of N-cycloheptyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine (intermediate compound 3) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.4 g (4 mmol, 80% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-cycloheptyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-3.

[0148] <Ligand compound represented by chemical formula 2-3> [Chemical formula 2-3] [ka] 1H NMR (500 MHz, C6D6): δ 7.90-7.10(m, 16H), 3.75(m, 1H), 1.64-1.24(m, 36H), 0.99-0.88(m, 36H), 0.81-0.78(m, 24H)

[0149] Synthesis Example 4: Synthesis of ligand compound represented by chemical formula 2-4 A dried flask was charged with 1.40 g (11 mmol, 2.2 eq) of cyclooctylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged into the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.12 g (5 mmol) of N-cyclooctyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which was intermediate compound 4, was obtained by column chromatography.

[0150] <Intermediate compound 4> [ka] 1 H NMR (500 MHz, DMSO): δ 7.55(m, 2H), 7.40(m, 2H), 7.33(m, 2H), 7.13(m, 2H), 2.43(m, 1H), 1.59(m, 4H), 1.50(m, 1H), 1.43(m, 12H), 1.32(m, 2H), 1.30(m, 4H), 1.29(m, 12H), 1.26(m, 4H), 0.94(m, 18H)

[0151] Next, 3.12 g (5 mmol, 1 eq) of N-cyclooctyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which is the intermediate compound 4 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.37 g (3.9 mmol, 78% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-cyclooctyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-4.

[0152] <Ligand compound represented by chemical formula 2-4> [Chemical formula 2-4] [ka] 1H NMR (500 MHz, DMSO): δ 7.55-7.13(m, 16H), 2.43(m, 1H), 1.60-1.43(m, 28H), 1.32-1.26(m, 34H), 0.94(m, 36H)

[0153] Synthesis Example 5: Synthesis of ligand compound represented by chemical formula 2-5 A dried flask was charged with 1.46 g (11 mmol, 2.2 eq) of (2,3-dihydro-1H-inden-2-yl)amine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.15 g (5 mmol) of intermediate compound 5, N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, was obtained by column chromatography.

[0154] <Intermediate compound 5> [ka] 1H NMR (500 MHz, DMSO): δ 7.55(m, 2H), 7.40(m, 2H), 7.33(m, 2H), 7.26(m, 2H), 7.13(m, 2H), 7.06(m, 2H), 3.17(m, 1H), 3.13(m, 4H), 1.50(m, 1H), 1.43(m, 12H), 1.29(m, 12H), 0.94(m, 18H)

[0155] Next, 2.9 g (5 mmol, 1 eq) of N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine), which is the intermediate compound 5 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.01 g (4.45 mmol, 89%) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-5.

[0156] <Ligand compound represented by chemical formula 2-5> [Chemical formula 2-5] [ka] 1 H NMR (500 MHz, DMSO): δ 7.65-7.06(m, 20H), 3.17-3.13(m, 5H), 1.43-1.29(m, 48H), 0.90(m, 36H)

[0157] Synthesis Example 6: Synthesis of ligand compound represented by chemical formula 2-6 A dried flask was charged with 1.62 g (11 mmol, 2.2 eq) of (1,2,3,4-tetrahydronaphthalen-2-yl)amine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.2 g (5 mmol) of intermediate compound 6, N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, was obtained by column chromatography.

[0158] <Intermediate compound 6> [ka] 1 H NMR (500 MHz, DMSO): δ 7.55(m, 2H), 7.40(m, 2H), 7.33(m, 2H), 7.13(m, 2H), 6.92(m, 4H), 3.19(m, 2H), 2.90(m, 2H), 2.73(m, 1H), 1.95(m, 2H), 1.50(m, 1H), 1.43(m, 12H), 1.29(m, 12H), 0.94(m, 18H)

[0159] Next, 3.2 g (5 mmol, 1 eq) of N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine), which is the intermediate compound 6 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.3 g (3.75 mmol, 75% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-6.

[0160] <Ligand compound represented by chemical formula 2-6> [Chemical formula 2-6] [ka] 1 H NMR (500 MHz, DMSO): δ 7.70-6.92(m, 20H), 3.19(m, 2H), 2.90(m, 2H), 2.73(m, 1H), 1.95(m, 2H), 1.43(m, 24H), 1.29(m, 24H), 0.89(m, 36H)

[0161] Synthesis Example 7: Synthesis of ligand compound represented by chemical formula 2-7 A dried flask was charged with 0.65 g (11 mmol, 2.2 eq) of isopropylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.78 g (5 mmol) of N-isopropyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, intermediate compound 7, was obtained by column chromatography.

[0162] <Intermediate compound 7> [ka] 1H NMR (500 MHz, DMSO): δ 7.55(m, 2H), 7.40(m, 2H), 7.33(m, 2H), 7.13(m, 2H), 2.83(m, 1H), 1.50(m, 1H), 1.43(m, 12H), 1.29(m, 12H), 1.06(m, 6H), 0.94(m, 18H)

[0163] Next, 2.78 g (5 mmol, 1 eq) of N-isopropyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine (intermediate compound 7) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.26 g (3.1 mmol, 62% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-isopropyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-7.

[0164] <Ligand compound represented by chemical formula 2-7> [Chemical formula 2-7] [ka] 1 H NMR (500 MHz, DMSO): δ 7.70-7.13(m, 16H), 2.83(m, 1H), 1.43-1.29(m, 48H), 1.06(m, 6H), 0.94(m, 36H)

[0165] Synthesis Example 8: Synthesis of ligand compound represented by chemical formula 2-8 A dried flask was charged with 0.96 g (11 mmol, 2.2 eq) of (3-methylbutan-2-yl)amine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.9 g (5 mmol) of N-(3-methylbutan-2-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which was intermediate compound 8, was obtained by column chromatography.

[0166] <Intermediate compound 8> [ka] 1H NMR (500 MHz, DMSO): δ 7.55(m, 2H), 7.40(m, 2H), 7.33(m, 2H), 7.13(m, 2H), 2.53(m, 1H), 1.55(m, 1H), 1.50(m, 1H), 1.43(m, 12H), 1.29(m, 12H), 1.06(m, 3H), 0.94(m, 18H), 0.88(m, 6H)

[0167] Next, 2.9 g (5 mmol, 1 eq) of N-(3-methylbutan-2-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which is the intermediate compound 8 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.84 g (3.55 mmol, 71% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-(3-methylbutan-2-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-8.

[0168] <Ligand compound represented by chemical formula 2-8> [Chemical formula 2-8] [ka] 1 H NMR (500 MHz, DMSO): δ 7.51-7.02(m, 16H), 2.53(m, 1H), 1.55(m, 1H), 1.65-1.23(m, 48H), 1.06(m, 3H), 0.94(m, 36H), 0.88(m, 6H)

[0169] Synthesis Example 9: Synthesis of ligand compound represented by chemical formula 2-9 A dried flask was charged with 1.18 g (11 mmol, 2.2 eq) of benzylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.02 g (5 mmol) of N-benzyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which was intermediate compound 9, was obtained by column chromatography.

[0170] <Intermediate compound 9> [ka] 1 H NMR (500 MHz, DMSO): δ 7.55(m, 2H), 7.40(m, 2H), 7.33(m, 2H), 7.31(m, 4H), 7.29(m, 1H), 7.13(m, 2H), 3.91(m, 2H), 2.30(m, 1H), 1.43(m, 12H), 1.29(m, 12H), 0.94(m, 18H)

[0171] Next, 3.02 g (5 mmol, 1 eq) of N-benzyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine (intermediate compound 9) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the resulting mixture was purified by column chromatography to obtain 4.62 g (4.2 mmol, 84% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-benzyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-9.

[0172] <Ligand compound represented by chemical formula 2-9> [Chemical formula 2-9] [ka] 1H NMR (500 MHz, DMSO): δ 7.72-7.00(m, 21H), 3.91(m, 2H), 1.49-1.29(m, 48H), 0.94(m, 36H)

[0173] Synthesis Example 10: Synthesis of ligand compound represented by chemical formula 2-10 A dried flask was charged with 1.33 g (11 mmol, 2.2 eq) of phenethylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.66 g (5 mmol, 1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.09 g (5 mmol) of N-phenethyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, intermediate compound 10, was obtained by column chromatography.

[0174] <Intermediate compound 10> [ka] 1 H NMR (500 MHz, DMSO): δ 7.55(m, 2H), 7.40(m, 2H), 7.33(m, 2H), 7.25(m, 2H), 7.24(m, 2H), 7.19(m, 1H), 7.13(m, 2H), 2.98(m, 2H), 2.83(m, 2H), 1.50(m, 1H), 1.43(m, 12H), 1.29(m, 12H), 0.94(m, 18H)

[0175] Next, 3.09 g (5 mmol, 1 eq) of N-phenethyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine (intermediate compound 10) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.63 g (4.15 mmol, 83% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-phenethyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 2-10.

[0176] <Ligand compound represented by chemical formula 2-10> [Chemical formula 2-10] [ka] 1H NMR (500 MHz, DMSO): δ 7.75-7.13(m, 21H), 2.98(m, 2H), 2.83(m, 2H), 1.44-1.29(m, 48H), 0.94(m, 36H)

[0177] Synthesis Example 11: Synthesis of ligand compound represented by chemical formula 3-1 A dried flask was charged with 0.94 g (11 mmol, 2.2 eq) of cyclopentylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.33 g (5 mmol) of N-cyclopentyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, intermediate compound 11, was obtained by column chromatography.

[0178] <Intermediate compound 11> [ka] 1 H NMR (500 MHz, DMSO): δ 7.55(m, 2H), 7.40(m, 2H), 7.33(m, 2H), 7.13(m, 2H), 2.64(m, 1H), 1.85(m, 4H), 1.73(m, 4H), 1.50(m, 1H), 1.43(m, 12H), 1.30(m, 12H), 1.23(m, 12H), 0.89(m, 18H)

[0179] Next, 3.33 g (5 mmol, 1 eq) of N-cyclopentyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine (intermediate compound 11) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.49 g (4 mmol, 88% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-cyclopentyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-1.

[0180] <Ligand compound represented by chemical formula 3-1> [Chemical formula 3-1] [ka] 1H NMR (500 MHz, DMSO): δ 7.60-7.13(m, 16H), 2.68(m, 1H), 1.86(m, 4H), 1.77(m, 4H), 1.43-1.23(m, 72H), 0.91(m, 36H)

[0181] Synthesis Example 12: Synthesis of ligand compound represented by chemical formula 3-2 A dried flask was charged with 1.09 g (11 mmol, 2.2 eq) of cyclohexylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.4 g (5 mmol) of N-cyclohexyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, intermediate compound 12, was obtained by column chromatography.

[0182] <Intermediate compound 12> [ka] 1H NMR (500 MHz, DMSO): δ 7.57(m, 2H), 7.47(m, 2H), 7.38(m, 2H), 7.15(m, 2H), 2.58(m, 1H), 1.75(m, 4H), 1.55(m, 1H), 1.51(m, 2H), 1.45(m, 12H), 1.33(m, 12H), 1.28(m, 12H), 1.21(m, 4H), 0.94(m, 18H)

[0183] Next, 3.4 g (5 mmol, 1 eq) of N-cyclohexyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine (intermediate compound 12) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.05 g (4 mmol, 80% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-cyclohexyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-2.

[0184] <Ligand compound represented by chemical formula 3-2> [Chemical formula 3-2] [ka] 1 H NMR (500 MHz, DMSO): δ 7.60-7.19(m, 16H), 2.62(m, 1H), 1.78(m, 4H), 1.50(m, 26H), 1.30-1.22(m, 52H), 0.98(m, 36H)

[0185] Synthesis Example 13: Synthesis of ligand compound represented by chemical formula 3-3 A dried flask was charged with 1.24 g (11 mmol, 2.2 eq) of cycloheptylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.47 g (5 mmol) of N-cycloheptyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, intermediate compound 13, was obtained by column chromatography.

[0186] <Intermediate compound 13> [ka] 1 H NMR (500 MHz, DMSO): δ 7.64(m, 2H), 7.47(m, 2H), 7.38(m, 2H), 7.15(m, 2H), 2.45(m, 1H), 1.67(m, 4H), 1.58(m, 9H), 1.45(m, 12H), 1.35(m, 12H), 1.31(m, 12H), 0.92(m, 18H)

[0187] Next, 3.47 g (5 mmol, 1 eq) of N-cycloheptyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, which is the intermediate compound 13 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.2 g (4.09 mmol, 82% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-cycloheptyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-3.

[0188] <Ligand compound represented by chemical formula 3-3> [Chemical formula 3-3] [ka] 1H NMR (500 MHz, DMSO): δ 7.56-7.17(m, 16H), 2.47(m, 1H), 1.64-1.59(m, 12H), 1.45(m, 24H), 1.33-1.31(m, 48H), 0.96(m, 36H)

[0189] Synthesis Example 14: Synthesis of ligand compound represented by chemical formula 3-4 A dried flask was charged with 1.40 g (11 mmol, 2.2 eq) of cyclooctylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.54 g (5 mmol) of N-cyclooctyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, intermediate compound 14, was obtained by column chromatography.

[0190] <Intermediate compound 14> [ka] 1 H NMR (500 MHz, DMSO): δ 7.55 (m, 2H), 7.43(m, 2H), 7.37(m, 2H), 7.20(m, 2H), 2.48(m, 1H), 1.66(m, 4H), 1.55(m, 1H), 1.50(m, 12H), 1.39(m, 18H), 1.26(m, 16H), 0.91(m, 18H)

[0191] Next, 3.54 g (5 mmol, 1 eq) of N-cyclooctyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, which is the intermediate compound 14 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.44 g (3.45 mmol, 69% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-cyclooctyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-4.

[0192] <Ligand compound represented by chemical formula 3-4> [Chemical formula 3-4] [ka] 1H NMR (500 MHz, DMSO): δ 7.56-7.17(m, 16H), 2.50(m, 1H), 1.64(m, 4H), 1.47(m, 24H), 1.39-1.31(m, 58H), 0.90(m, 36H)

[0193] Synthesis Example 15: Synthesis of ligand compound represented by chemical formula 3-5 A dried flask was charged with 1.47 g (11 mmol, 2.2 eq) of (2,3-dihydro-1H-inden-2-yl)amine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.57 g (5 mmol) of intermediate compound 15, N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, was obtained by column chromatography.

[0194] <Intermediate compound 15> [ka] 1H NMR (500 MHz, DMSO): δ 7.57(m, 2H), 7.47(m, 2H), 7.37(m, 2H), 7.34(m, 2H), 7.18(m, 2H), 7.11(m, 2H), 3.18(m, 5H), 1.59(m, 1H), 1.52(m, 12H), 1.39(m, 12H), 1.26(m, 12H), 0.90(m, 18H)

[0195] Next, 3.57 g (5 mmol, 1 eq) of N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine), which is the intermediate compound 15 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 6.40 g (4.94 mmol, 99%) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-5.

[0196] <Ligand compound represented by chemical formula 3-5> [Chemical formula 3-5] [ka] 1 H NMR (500 MHz, DMSO): δ 7.58-7.15(m, 20H), 3.19(m, 1H), 3.13(m, 4H), 1.43(m, 24H), 1.30-1.26(m, 48H), 0.91(m, 36H)

[0197] Synthesis Example 16: Synthesis of ligand compound represented by chemical formula 3-6 A dried flask was charged with 1.62 g (11 mmol, 2.2 eq) of (1,2,3,4-tetrahydronaphthalen-2-yl)amine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction was stirred for 4 hours.1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the resulting product was purified by column chromatography to obtain 3.64 g (5 mmol) of intermediate compound 16, N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine.

[0198] <Intermediate compound 16> [ka] 1 H NMR (500 MHz, DMSO): δ 7.59(m, 2H), 7.49(m, 2H), 7.41(m, 2H), 7.21(m, 2H), 6.94(m, 4H), 3.20(m, 2H), 2.93(m, 2H), 2.78(m, 1H), 1.96(m, 2H), 1.54(m, 1H), 1.48(m, 12H), 1.35(m, 12H), 1.24(m, 12H), 0.93(m, 18H)

[0199] Next, 3.64 g (5 mmol, 1 eq) of N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine), which is the intermediate compound 16 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.02 g (3.83 mmol, 77% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-6.

[0200] <Ligand compound represented by chemical formula 3-6> [Chemical formula 3-6] [ka] 1 H NMR (500 MHz, DMSO): δ 7.61-6.93(m, 20H), 3.28(m, 2H), 2.93(m, 2H), 2.80(m, 1H), 1.99(m, 2H), 1.43(m, 24H), 1.39-1.24(m, 48H), 0.90(m, 36H)

[0201] Synthesis Example 17: Synthesis of ligand compound represented by chemical formula 3-7 A dried flask was charged with 0.65 g (11 mmol, 2.2 eq) of isopropylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.2 g (5 mmol) of intermediate compound 17, N-isopropyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, was obtained by column chromatography.

[0202] <Intermediate compound 17> [ka] 1H NMR (500 MHz, DMSO): δ 7.62(m, 2H), 7.40(m, 4H), 7.19(m, 2H), 2.89(m, 1H), 1.53(m, 1H), 1.51(m, 12H), 1.37(m, 12H), 1.32(m, 12H), 1.13(m, 6H), 0.94(m, 18H)

[0203] Next, 3.2 g (5 mmol, 1 eq) of N-isopropyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine (intermediate compound 17) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.76 g (3.08 mmol, 62% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-7.

[0204] <Ligand compound represented by chemical formula 3-7> [Chemical formula 3-7] [ka] 1 H NMR (500 MHz, DMSO): δ 7.61-7.17(m, 16H), 2.90(m, 1H), 1.52(m, 24H), 1.35-1.27(m, 48H), 1.09(m, 6H), 0.91(m, 36H)

[0205] Synthesis Example 18: Synthesis of ligand compound represented by chemical formula 3-8 A dried flask was charged with 0.96 g (11 mmol, 2.2 eq) of (3-methylbutan-2-yl)amine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.3 g (5 mmol) of intermediate compound 18, N-(3-methylbutan-2-yl)-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, was obtained by column chromatography.

[0206] <Intermediate compound 18> [ka] 1H NMR (500 MHz, DMSO): δ 7.62(m, 2H), 7.47(m, 2H), 7.38(m, 2H), 7.19(m, 2H), 2.56(m, 1H), 1.59(m, 1H), 1.56(m, 1H), 1.47(m, 12H), 1.33(m, 12H), 1.29(m, 12H), 1.08(m, 3H), 0.97(m, 18H), 0.94(m, 6H)

[0207] Next, 3.3 g (5 mmol, 1 eq) of N-(3-methylbutan-2-yl)-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine), which is the intermediate compound 18 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.0 g (3.2 mmol, 64% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-(3-methylbutan-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-8.

[0208] <Ligand compound represented by chemical formula 3-8> [Chemical formula 3-8] [ka] 1 H NMR (500 MHz, DMSO): δ 7.64-7.20(m, 16H), 2.55(m, 1H), 1.58(m, 1H), 1.48(m, 24H), 1.36-1.26(m, 48H), 1.11(m, 3H), 0.98(m, 36H), 0.94(m, 6H)

[0209] Synthesis Example 19: Synthesis of ligand compound represented by chemical formula 3-9 A dried flask was charged with 1.18 g (11 mmol, 2.2 eq) of benzylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.4 g (5 mmol) of intermediate compound 19, N-benzyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, was obtained by column chromatography.

[0210] <Intermediate compound 19> [ka] 1 H NMR (500 MHz, DMSO): δ 7.60(m, 2H), 7.48(m, 2H), 7.37(m, 2H), 7.35(m, 4H), 7.28(m, 1H), 7.13(m, 2H), 3.95(m, 2H), 2.32(m, 1H), 1.48(m, 12H), 1.35(m, 12H), 1.28(m, 12H), 0.91(m, 18H)

[0211] Next, 3.4 g (5 mmol, 1 eq) of N-benzyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine (intermediate compound 19) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.36 g (4.22 mmol, 84% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-benzyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-9.

[0212] <Ligand compound represented by chemical formula 3-9> [Chemical formula 3-9] [ka] 1H NMR (500 MHz, DMSO): δ 7.64(m, 21H), 3.96(m, 2H), 1.51(m, 24H), 1.35-1.31(m, 48H), 0.93(m, 36H)

[0213] Synthesis Example 20: Synthesis of ligand compound represented by chemical formula 3-10 A dried flask was charged with 1.33 g (11 mmol, 2.2 eq) of phenethylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 3.09 g (5 mmol, 1 eq) of chlorobis(3-(tributylsilyl)phenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 3.5 g (5 mmol) of N-phenethyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, intermediate compound 20, was obtained by column chromatography.

[0214] <Intermediate compound 20> [ka] 1 H NMR (500 MHz, DMSO): δ 7.62(m, 2H), 7.44(m, 2H), 7.37(m, 2H), 7.31(m, 2H), 7.27(m, 2H), 7.24(m, 1H), 7.14(m, 2H), 2.99(m, 2H), 2.85(m, 2H), 1.52(m, 1H), 1.45(m, 12H), 1.35(m, 12H), 1.30(m, 12H), 0.94(m, 18H)

[0215] Next, 3.4 g (5 mmol, 1 eq) of N-phenethyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine (intermediate compound 20) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to −78°C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.54 g (4.32 mmol, 86% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-phenethyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 3-10.

[0216] <Ligand compound represented by chemical formula 3-10> [Chemical formula 3-10] [ka] 1H NMR (500 MHz, DMSO): δ 7.62-7.20(m, 21H), 3.06(m, 2H), 2.92(m, 2H), 1.50(m, 24H), 1.37-1.30(m, 48H), 0.91(m, 36H)

[0217] Synthesis Example 21: Synthesis of ligand compound represented by chemical formula 4-1 2.9 g (5 mmol, 1 eq) of N-cyclopentyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine (intermediate compound 1 obtained in Synthesis Example 1) and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78°C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.85 g (3.44 mmol, 69% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-cyclopentyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-1.

[0218] <Ligand compound represented by chemical formula 4-1> [Chemical formula 4-1] [ka] 1 H NMR (500 MHz, DMSO): δ 7.61-7.13(m, 16H), 2.67(m, 1H), 1.85(m, 4H), 1.75(m, 4H), 1.46(m, 24H), 1.35-1.31(m, 36H), 0.99-0.96(m, 36H)

[0219] Synthesis Example 22: Synthesis of ligand compound represented by chemical formula 4-2 2.98 g (5 mmol, 1 eq) of N-cyclohexyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which is the intermediate compound 2 obtained in Synthesis Example 2, and 13 ml of methyl tert-butyl ether were placed in a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.12 g (4.6 mmol, 92% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-cyclohexyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-2.

[0220] <Ligand compound represented by chemical formula 4-2> [Chemical formula 4-2] [ka] 1 H NMR (500 MHz, DMSO): δ 7.59-7.19(m, 16H), 2.64-1.30(m, 71H), 0.96-0.94(m, 36H)

[0221] Synthesis Example 23: Synthesis of ligand compound represented by chemical formula 4-3 Into a dried flask, 3.5 g (5 mmol, 1 eq) of N-cycloheptyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which is the intermediate compound 3 obtained in Synthesis Example 3, and 13 ml of methyl tert-butyl ether were placed under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.04 g (4.39 mmol, 88% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-cycloheptyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-3.

[0222] <Ligand compound represented by chemical formula 4-3> [Chemical formula 4-3] [ka] 1H NMR (500 MHz, DMSO): δ 7.59-7.16(m, 16H), 2.49(m, 1H), 1.65-1.25(m, 72H), 0.95-0.91(m, 36H)

[0223] Synthesis Example 24: Synthesis of ligand compound represented by chemical formula 4-4 Into a dried flask, 3.1 g (5 mmol, 1 eq) of N-cyclooctyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which is intermediate compound 4 obtained in Synthesis Example 4, and 13 ml of methyl tert-butyl ether were placed under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.26 g (3.67 mmol, 73% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-cyclooctyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-4.

[0224] <Ligand compound represented by chemical formula 4-4> [Chemical formula 4-4] [ka] 1 H NMR (500 MHz, DMSO): δ 7.55-7.20(m, 16H), 2.44(m, 1H), 1.65-1.26(m, 74H), 1.02-0.96(m, 36H)

[0225] Synthesis Example 25: Synthesis of ligand compound represented by chemical formula 4-5 Into a dried flask were placed 3.2 g (5 mmol, 1 eq) of N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine), which was the intermediate compound 5 obtained in Synthesis Example 5, and 13 ml of methyl tert-butyl ether under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.70 g (4.88 mmol, 98% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-5.

[0226] <Ligand compound represented by chemical formula 4-5> [Chemical formula 4-5] [ka] 1 H NMR (500 MHz, DMSO): δ 7.64-7.12(m, 20H), 3.20(m, 5H), 1.48-1.26(m, 60H), 1.01-0.96(m, 36H)

[0227] Synthesis Example 26: Synthesis of ligand compound represented by chemical formula 4-6 Into a dried flask were placed 3.2 g (5 mmol, 1 eq) of N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which was intermediate compound 6 obtained in Synthesis Example 6, and 13 ml of methyl tert-butyl ether under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.92 g (4 mmol, 66% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-6.

[0228] <Ligand compounds represented by chemical formula 4-6> [Chemical formula 4-6] [ka] 1 H NMR (500 MHz, DMSO): δ 7.56-6.92(m, 20H), 3.22(m, 2H), 2.97(m, 2H), 2.76(m, 1H), 1.99(m, 2H), 1.45-1.23(m, 60H), 1.00-0.90(m, 36H)

[0229] Synthesis Example 27: Synthesis of ligand compound represented by chemical formula 4-7 2.7 g (5 mmol, 1 eq) of N-isopropyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine (compound 7 obtained in Synthesis Example 7) and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78°C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.5 g (3.2 mmol, 64% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-7.

[0230] <Ligand compound represented by chemical formula 4-7> [Chemical formula 4-7] [ka] 1 H NMR (500 MHz, DMSO): δ 7.59-7.13(m, 16H), 2.84(m, 1H), 1.45-1.15(m, 66H), 0.94-0.92(m, 36H)

[0231] Synthesis Example 28: Synthesis of ligand compound represented by chemical formula 4-8 Into a dried flask were placed 2.9 g (5 mmol, 1 eq) of N-(3-methylbutan-2-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which was the intermediate compound 8 obtained in Synthesis Example 8, and 13 ml of methyl tert-butyl ether under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.05 g (3.61 mmol, 72% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-(3-methylbutan-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-8.

[0232] <Ligand compound represented by chemical formula 4-8> [Chemical formula 4-8] [ka] 1H NMR (500 MHz, DMSO): δ 7.61-7.15(m, 16H), 2.55(m, 1H), 1.55-1.31(m, 61H), 1.09-0.91(m, 45H)

[0233] Synthesis Example 29: Synthesis of ligand compound represented by chemical formula 4-9 3.0 g (5 mmol, 1 eq) of N-benzyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine (intermediate compound 9 obtained in Synthesis Example 9) and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78°C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.05 g (4.42 mmol, 88% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-benzyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-9.

[0234] <Ligand compound represented by chemical formula 4-9> [Chemical formula 4-9] [ka] 1 H NMR (500 MHz, DMSO): δ 7.58-7.16(m, 21H), 3.95(m, 2H), 1.50-1.32(m, 60H), 1.03-0.98(m, 36H)

[0235] Synthesis Example 30: Synthesis of ligand compound represented by chemical formula 4-10 Into a dried flask were placed 3.09 g (5 mmol, 1 eq) of N-phenethyl-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which was the intermediate compound 10 obtained in Synthesis Example 10, and 13 ml of methyl tert-butyl ether under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 3.09 g (5 mmol, 1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.41 g (3.82 mmol, 76% yield) of N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-phenethyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 4-10.

[0236] <Ligand compound represented by chemical formula 4-10> [Chemical formula 4-10] [ka] 1 H NMR (500 MHz, DMSO): δ 7.61-7.16(m, 21H), 3.03(m, 2H), 2.92(m, 2H), 1.49-1.28(m, 60H), 0.95-0.93(m, 36H)

[0237] Synthesis Example 31: Synthesis of ligand compound represented by chemical formula 5-1 Into a dried flask, 3.3 g (5 mmol, 1 eq) of N-cyclopentyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, which is the intermediate compound 11 obtained in Synthesis Example 11, and 13 ml of methyl tert-butyl ether were placed under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.27 g (4 mmol, 76% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-cyclopentyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 5-1.

[0238] <Ligand compound represented by chemical formula 5-1> [Chemical formula 5-1] [ka] 1H NMR (500 MHz, DMSO): δ 7.61-7.10(m, 16H), 2.66(m, 1H), 1.90(m, 4H), 1.71(m, 4H), 1.51(m, 24H), 1.39-1.31(m, 36H), 0.98-0.93(m, 36H)

[0239] Synthesis Example 32: Synthesis of ligand compound represented by chemical formula 5-2 3.40 g (5 mmol, 1 eq) of N-cyclohexyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, which is the intermediate compound 12 obtained in Synthesis Example 12, and 13 ml of methyl tert-butyl ether were placed in a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.38 g (4 mmol, 95% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-cyclohexyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 5-2.

[0240] <Ligand compound represented by chemical formula 5-2> [Chemical formula 5-2] [ka] 1 H NMR (500 MHz, DMSO): δ 7.59-7.11(m, 16H), 2.64-1.35(m, 71H), 0.94-0.91(m, 36H)

[0241] Synthesis Example 33: Synthesis of ligand compound represented by chemical formula 5-3 In a dried flask, 3.47 g (5 mmol, 1 eq) of N-cycloheptyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, which is the intermediate compound 13 obtained in Synthesis Example 13, and 13 ml of methyl tert-butyl ether were placed under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.69 g (4.08 mmol, 82% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-cycloheptyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 5-3.

[0242] <Ligand compound represented by chemical formula 5-3> [Chemical formula 5-3] [ka] 1H NMR (500 MHz, DMSO): δ 7.69-7.12(m, 16H), 2.56(m, 1H), 1.68-1.25(m, 72H), 0.95-0.89(m, 36H)

[0243] Synthesis Example 34: Synthesis of ligand compound represented by chemical formula 5-4 3.54 g (5 mmol, 1 eq) of N-cyclooctyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, which is the intermediate compound 14 obtained in Synthesis Example 14, and 13 ml of methyl tert-butyl ether were placed in a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.91 g (4.22 mmol, 84% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-cyclooctyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 5-4.

[0244] <Ligand compound represented by chemical formula 5-4> [Chemical formula 5-4] [ka] 1 H NMR (500 MHz, DMSO): δ 7.55-7.02(m, 16H), 2.49(m, 1H), 1.65-1.30(m, 74H), 1.02-0.92(m, 36H)

[0245] Synthesis Example 35: Synthesis of ligand compound represented by chemical formula 5-5 3.54 g (5 mmol, 1 eq) of N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine), which is the intermediate compound 15 obtained in Synthesis Example 15, and 13 ml of methyl tert-butyl ether were placed in a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.55 g (4.75 mmol, 95% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 5-5.

[0246] <Ligand compound represented by chemical formula 5-5> [Chemical formula 5-5] [ka] 1 H NMR (500 MHz, DMSO): δ 7.45-7.21(m, 20H), 3.22(m, 5H), 1.48-1.31(m, 60H), 1.01-0.90(m, 36H)

[0247] Synthesis Example 36: Synthesis of ligand compound represented by chemical formula 5-6 3.64 g (5 mmol, 1 eq) of N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine), which is the intermediate compound 16 obtained in Synthesis Example 16, and 13 ml of methyl tert-butyl ether were placed in a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.91 g (4.15 mmol, 83% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 5-6.

[0248] <Ligand compound represented by chemical formula 5-6> [Chemical formula 5-6] [ka] 1 H NMR (500 MHz, DMSO): δ 7.65-6.90(m, 20H), 3.37(m, 2H), 2.97(m, 2H), 2.81(m, 1H), 2.04(m, 2H), 1.44-1.25(m, 60H), 1.04-0.94(m, 36H)

[0249] Synthesis Example 37: Synthesis of ligand compound represented by chemical formula 5-7 A dried flask was charged with 3.2 g (5 mmol, 1 eq) of N-isopropyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine (intermediate compound 17 obtained in Synthesis Example 17) and 13 mL of methyl tert-butyl ether under a nitrogen atmosphere, cooled to -78°C, and then stirred. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.26 g (2.98 mmol, 60% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-isopropyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 5-7.

[0250] <Ligand compounds represented by chemical formulas 5-7> [Chemical formula 5-7] [ka] 1 H NMR (500 MHz, DMSO): δ 7.72-7.11(m, 16H), 2.48(m, 1H), 1.54-1.21(m, 66H), 0.94-0.90(m, 36H)

[0251] Synthesis Example 38: Synthesis of ligand compound represented by chemical formula 5-8 3.34 g (5 mmol, 1 eq) of N-(3-methylbutan-2-yl)-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, which is intermediate compound 18 obtained in Synthesis Example 18, and 13 ml of methyl tert-butyl ether were placed in a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the resulting mixture was purified by column chromatography to obtain 3.71 g (3.31 mmol, 66% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-(3-methylbutan-2-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine, a compound represented by chemical formula 5-8.

[0252] <Ligand compounds represented by chemical formula 5-8> [Chemical formula 5-8] [ka] 1H NMR (500 MHz, DMSO): δ 7.67-7.21(m, 16H), 2.87(m, 1H), 1.54-1.28(m, 61H), 1.09-0.88(m, 45H)

[0253] Synthesis Example 39: Synthesis of ligand compound represented by chemical formula 5-9 3.44 g (5 mmol, 1 eq) of N-benzyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, which is the intermediate compound 19 obtained in Synthesis Example 19, and 13 ml of methyl tert-butyl ether were placed in a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.79 g (4.2 mmol, 84% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-benzyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 5-9.

[0254] <Ligand compound represented by chemical formula 5-9> [Chemical formula 5-9] [ka] 1 H NMR (500 MHz, DMSO): δ 7.63-7.19(m, 21H), 3.92(m, 2H), 1.51-1.23(m, 60H), 1.03-0.91(m, 36H)

[0255] Synthesis Example 40: Synthesis of ligand compound represented by chemical formula 5-10 3.51 g (5 mmol, 1 eq) of N-phenethyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine, which is intermediate compound 20 obtained in Synthesis Example 20, and 13 ml of methyl tert-butyl ether were placed in a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.66 g (5 mmol, 1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 5.16 g (4.46 mmol, 89% yield) of N-(bis(3-(tributylsilyl)phenyl)phosphaneyl)-N-phenethyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine), a compound represented by chemical formula 5-10.

[0256] <Ligand compound represented by chemical formula 5-10> [Chemical formula 5-10] [ka] 1 H NMR (500 MHz, DMSO): δ 7.65-7.15(m, 21H), 3.08(m, 2H), 2.90(m, 2H), 1.56-1.22(m, 60H), 0.95-0.87(m, 36H)

[0257] Synthesis Example 41: Synthesis of ligand compound represented by chemical formula 6-1 A dried flask was charged with 0.94 g (11 mmol, 2.2 eq) of cyclopentylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged into the flask. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.75 g (5 mmol) of intermediate compound 21, N-cyclopentyl-1,1-bis(3-decylphenyl)phosphanamine, was obtained by column chromatography.

[0258] <Intermediate compound 21> [ka] 1 H NMR (500 MHz, DMSO): δ 7.37(m, 2H), 7.27(m, 2H), 7.25(m, 2H), 7.13(m, 2H), 2.72(m, 1H), 1.92(m, 4H), 1.76(m, 6H), 1.62(m, 6H), 1.52(m, 1H), 1.29(m, 28H), 0.93(m, 6H)

[0259] Next, 2.75 g (5 mmol, 1 eq) of N-cyclopentyl-1,1-bis(3-decylphenyl)phosphanamine (intermediate compound 21) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.98 g (3.92 mmol, 78% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-cyclopentyl-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by chemical formula 6-1.

[0260] <Ligand compound represented by chemical formula 6-1> [Chemical formula 6-1] [ka] 1 H NMR (500 MHz, DMSO): δ 7.35-7.12(m, 16H), 2.65(m, 1H), 1.89-1.27(m, 78H), 0.97(m, 12H)

[0261] Synthesis Example 42: Synthesis of ligand compound represented by chemical formula 6-2 A dried flask was charged with 1.09 g (11 mmol, 2.2 eq) of cyclohexylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged into the flask. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.82 g (5 mmol) of N-cyclohexyl-1,1-bis(3-decylphenyl)phosphanamine, intermediate compound 22, was obtained by column chromatography.

[0262] <Intermediate compound 22> [ka] 1 H NMR (500 MHz, DMSO): δ 7.42(m, 2H), 7.26(m, 2H), 7.21(m, 2H), 7.06(m, 2H), 2.73(m, 4H), 2.65(m, 1H), 1.80(m, 4H), 1.69(m, 4H), 1.52(m, 3H), 1.27(m, 28H), 1.30(m, 4H), 0.93(m, 6H)

[0263] Next, 2.82 g (5 mmol, 1 eq) of N-cyclohexyl-1,1-bis(3-decylphenyl)phosphanamine (intermediate compound 22) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.43 g (4.31 mmol, 86% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-cyclohexyl-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by chemical formula 6-2.

[0264] <Ligand compound represented by chemical formula 6-2> [Chemical formula 6-2] [ka] 1 H NMR (500 MHz, DMSO): δ 7.44(m, 16H), 7.14(m, 2H), 2.64(m, 9H), 1.81-1.28(m, 74H), 0.91(m, 12H)

[0265] Synthesis Example 43: Synthesis of ligand compound represented by chemical formula 6-3 A dried flask was charged with 1.24 g (11 mmol, 2.2 eq) of cycloheptylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged into the flask. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.89 g (5 mmol) of N-cycloheptyl-1,1-bis(3-decylphenyl)phosphanamine, intermediate compound 23, was obtained by column chromatography.

[0266] <Intermediate compound 23> [ka] 1 H NMR (500 MHz, DMSO): δ 7.38(m, 2H), 7.29(m, 2H), 7.20(m, 2H), 7.08(m, 2H), 2.65(m, 4H), 2.46(m, 1H), 1.66(m, 4H), 1.60(m, 9H), 1.57(m, 4H), 1.34(m, 28H), 0.93(m, 6H)

[0267] Next, 2.89 g (5 mmol, 1 eq) of N-cycloheptyl-1,1-bis(3-decylphenyl)phosphanamine (intermediate compound 23) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.30 g (4.13 mmol, 83% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-cycloheptyl-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by formula 6-3.

[0268] <Ligand compound represented by chemical formula 6-3> [Chemical formula 6-3] [ka] 1 H NMR (500 MHz, DMSO): δ 7.38-7.05(m, 16H), 2.67-2.46(m, 9H), 1.70-1.28(m, 76H), 0.89(m, 12H)

[0269] Synthesis Example 44: Synthesis of ligand compound represented by chemical formula 6-4 A dried flask was charged with 1.40 g (11 mmol, 2.2 eq) of cyclooctylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged into the flask. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.96 g (5 mmol) of N-cyclooctyl-1,1-bis(3-decylphenyl)phosphanamine, intermediate compound 24, was obtained by column chromatography.

[0270] <Intermediate compound 24> [ka] 1 H NMR (500 MHz, DMSO): δ 7.40(m, 2H), 7.32(m, 2H), 7.24(m, 2H), 7.07(m, 2H), 2.73(m, 4H), 2.50(m, 1H), 1.67(m, 4H), 1.61(m, 4H), 1.58(m, 1H), 1.39(m, 2H), 1.34(m, 32H), 1.30(m, 4H), 0.93(m, 6H)

[0271] Next, 2.96 g (5 mmol, 1 eq) of N-cyclooctyl-1,1-bis(3-decylphenyl)phosphanamine (intermediate compound 24) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours.1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.05 g (3.84 mmol, 77% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-cyclooctyl-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by chemical formula 6-4.

[0272] <Ligand compound represented by chemical formula 6-4> [Chemical formula 6-4] [ka] 1 H NMR (500 MHz, DMSO): δ 7.35(m, 2H), 7.32(m, 2H), 7.28(m, 2H), 7.24(m, 4H), 7.17(m, 4H), 7.13(m, 2H), 2.65(m, 8H), 2.46(m, 1H), 1.69-1.35(m, 78H), 0.97(m, 12H)

[0273] Synthesis Example 45: Synthesis of ligand compound represented by chemical formula 6-5 A dried flask was charged with 1.47 g (11 mmol, 2.2 eq) of (2,3-dihydro-1H-inden-2-yl)amine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.99 g (5 mmol) of intermediate compound 25, N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(3-decylphenyl)phosphanamine, was obtained by column chromatography.

[0274] <Intermediate compound 25> [ka] 1 H NMR (500 MHz, DMSO): δ 7.43(m, 2H), 7.29(m, 2H), 7.26(m, 4H), 7.09(m, 4H), 3.21(m, 1H), 3.17(m, 4H), 2.64(m, 4H), 1.61(m, 4H), 1.53(m, 1H), 1.35(m, 28H), 0.91(m, 6H)

[0275] Next, 2.99 g (5 mmol, 1 eq) of N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(3-decylphenyl)phosphanamine, which is the intermediate compound 25 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.32 g (4.07 mmol, 81% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-(2,3-dihydro-1H-inden-2-yl)-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by formula 6-5.

[0276] <Ligand compound represented by chemical formula 6-5> [Chemical formula 6-5] [ka] 1H NMR (500 MHz, DMSO): δ 7.35-7.09(m, 20H), 3.21(m, 1H), 3.14(m, 4H), 2.64(m, 8H), 1.72-1.28(m, 64H), 0.93(m, 12H)

[0277] Synthesis Example 46: Synthesis of ligand compound represented by chemical formula 6-6 A dried flask was charged with 1.62 g (11 mmol, 2.2 eq) of (1,2,3,4-tetrahydronaphthalen-2-yl)amine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the product was purified by column chromatography to obtain 3.06 g (5 mmol) of intermediate compound 26, N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(3-decylphenyl)phosphanamine.

[0278] <Intermediate compound 26> [ka] 1H NMR (500 MHz, DMSO): δ 7.35(m, 2H), 7.32(m, 2H), 7.27(m, 2H), 7.09(m, 2H), 6.92(m, 4H), 3.28(m, 2H), 2.90(m, 2H), 2.74(m, 1H), 2.72(m, 4H), 2.02(m, 2H), 1.68(m, 4H), 1.56(m, 1H), 1.33(m, 28H), 0.93(m, 6H)

[0279] Next, 3.06 g (5 mmol, 1 eq) of N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(3-decylphenyl)phosphanamine, which is the intermediate compound 26 obtained above, and 13 ml of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, and the mixture was cooled to −78° C., and stirring was then initiated. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. Then, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 ml of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.95 g (3.67 mmol, 73% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-(1,2,3,4-tetrahydronaphthalen-2-yl)-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by chemical formula 6-6.

[0280] <Ligand compound represented by chemical formula 6-6> [Chemical formula 6-6] [ka] 1 H NMR (500 MHz, DMSO): δ 7.39-6.96(m, 20H), 3.26(m, 2H), 2.96(m, 2H), 2.80(m, 1H), 2.69(m, 8H), 2.03(m, 2H), 1.70-1.29(m, 64H), 0.95(m, 12H)

[0281] Synthesis Example 47: Synthesis of ligand compounds represented by chemical formulas 6-7 A dried flask was charged with 0.65 g (11 mmol, 2.2 eq) of isopropylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged into the flask. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.62 g (5 mmol) of N-isopropyl-1,1-bis(3-decylphenyl)phosphanamine, intermediate compound 27, was obtained by column chromatography.

[0282] <Intermediate compound 27> [ka] 1 H NMR (500 MHz, DMSO): δ 7.41(m, 2H), 7.28(m, 2H), 7.26(m, 2H), 7.08(m, 2H), 2.87(m, 1H), 2.72(m, 4H), 1.63(m, 4H), 1.57(m, 1H), 1.29(m, 28H), 1.11(m, 6H), 0.91(m, 6H)

[0283] Next, 2.62 g (5 mmol, 1 eq) of N-isopropyl-1,1-bis(3-decylphenyl)phosphanamine (intermediate compound 27) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 2.67 g (2.70 mmol, 54% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-isopropyl-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by chemical formula 6-7.

[0284] <Ligand compounds represented by chemical formulas 6-7> [Chemical formula 6-7] [ka] 1 H NMR (500 MHz, DMSO): δ 7.43-7.11(m, 16H), 2.91(m, 1H), 2.65(m, 8H), 1.67-1.08(m, 70H), 0.92(m, 12H)

[0285] Synthesis Example 48: Synthesis of ligand compound represented by chemical formula 6-8 A dried flask was charged with 0.96 g (11 mmol, 2.2 eq) of (3-methylbutan-2-yl)amine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged to the flask. The reaction was stirred for 4 hours. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.76 g (5 mmol) of intermediate compound 28, N-(3-methylbutan-2-yl)-1,1-bis(3-decylphenyl)phosphanamine, was obtained by column chromatography.

[0286] <Intermediate compound 28> [ka] 1 H NMR (500 MHz, DMSO): δ 7.39(m, 2H), 7.31(m, 2H), 7.29(m, 2H), 7.08(m, 2H), 2.66(m, 4H), 2.61(m, 1H), 1.61(m, 4H), 1.60(m, 1H), 1.57(m, 1H), 1.27(m, 28H), 1.14(m, 3H), 0.92(m, 12H)

[0287] Next, 2.76 g (5 mmol, 1 eq) of N-(3-methylbutan-2-yl)-1,1-bis(3-decylphenyl)phosphanamine (intermediate compound 28) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 3.62 g (3.56 mmol, 71% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-(3-methylbutan-2-yl)-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by chemical formula 6-8.

[0288] <Ligand compounds represented by chemical formulas 6-8> [Chemical formula 6-8] [ka] 1H NMR (500 MHz, DMSO): δ 7.42-7.12(m, 16H), 2.73(m, 8H), 2.56(m, 1H), 1.66-1.09(m, 68H), 0.89(m, 18H)

[0289] Synthesis Example 49: Synthesis of ligand compound represented by chemical formula 6-9 A dried flask was charged with 1.18 g (11 mmol, 2.2 eq) of benzylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged into the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.86 g (5 mmol) of intermediate compound 29, N-benzyl-1,1-bis(3-decylphenyl)phosphanamine, was obtained by column chromatography.

[0290] <Intermediate compound 29> [ka] 1 H NMR (500 MHz, DMSO): δ 7.42(m, 2H), 7.38(m, 5H), 7.26(m, 4H), 7.14(m, 2H), 3.94(m, 2H), 2.67(m, 4H), 2.39(m, 1H), 1.67(m, 4H), 1.35(m, 28H), 0.95(m, 6H)

[0291] Next, 2.86 g (5 mmol, 1 eq) of N-benzyl-1,1-bis(3-decylphenyl)phosphanamine (intermediate compound 29) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78 °C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.19 g (4.05 mmol, 81% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-benzyl-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by chemical formula 6-9.

[0292] <Ligand compound represented by chemical formula 6-9> [Chemical formula 6-9] [ka] 1 H NMR (500 MHz, DMSO): δ 7.37-7.06(m, 21H), 3.95(m, 2H), 2.67(m, 8H), 1.69-1.34(m, 64H), 0.93(m, 12H)

[0293] Synthesis Example 50: Synthesis of ligand compound represented by chemical formula 6-10 A dried flask was charged with 1.33 g (11 mmol, 2.2 eq) of phenethylamine and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. 2.51 g (5 mmol, 1 eq) of chlorobis(3-decylphenyl)phosphane diluted with 10 ml of dichloromethane was slowly charged into the flask. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and 2.92 g (5 mmol) of N-phenethyl-1,1-bis(3-decylphenyl)phosphanamine, intermediate compound 30, was obtained by column chromatography.

[0294] <Intermediate compound 30> [ka] 1 H NMR (500 MHz, DMSO): δ 7.36(m, 2H), 7.33(m, 4H), 7.28(m, 2H), 7.23(m, 2H), 7.18(m, 1H), 7.08(m, 2H), 3.04(m, 2H), 2.83(m, 2H), 2.72(m, 4H), 1.66(m, 4H), 1.50(m, 1H), 1.29(m, 28H), 0.96(m, 6H)

[0295] Next, 2.92 g (5 mmol, 1 eq) of N-phenethyl-1,1-bis(3-decylphenyl)phosphanamine (intermediate compound 30) obtained above and 13 mL of methyl tert-butyl ether were added to a dried flask under a nitrogen atmosphere, cooled to -78°C, and stirring was initiated. 2.1 mL (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was slowly added to the flask and stirred for 1 hour. After stirring, 2.51 g (5 mmol, 1 eq) of chlorobis(4-decylphenyl)phosphane diluted with 10 mL of methyl tert-butyl ether was slowly added. The reaction mixture was stirred for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and column chromatography was carried out to obtain 4.40 g (4.19 mmol, 84% yield) of N-(bis(3-decylphenyl)phosphaneyl)-N-phenethyl-1,1-bis(4-decylphenyl)phosphanamine, a compound represented by Chemical Formula 6-10.

[0296] <Ligand compound represented by chemical formula 6-10> [Chemical formula 6-10] [ka] 1 H NMR (500 MHz, DMSO): δ 7.35-7.09(m, 21H), 3.06(m, 2H), 2.87(m, 2H), 2.65(m, 8H), 1.66-1.31(m, 64H), 0.8(m, 12H)

[0297] Comparative Synthesis Example 1: Synthesis of Ligand Compound Represented by Chemical Formula 11 A dried flask was charged with 0.55 g (5.5 mmol, 0.5 eq) of cyclohexylamine, 2.23 g (22 mmol, 2 eq) of triethylamine, and 10 ml of dichloromethane under a nitrogen atmosphere, and stirring was initiated. After cooling to 0°C, 4.29 g (11 mmol, 1 eq) of chlorobis(4-cyclohexylphenyl)phosphane was slowly added. After the reaction was completed, the precipitated solid was removed using a filter, the solvent was removed under reduced pressure, and 2.50 g (3.25 mmol, yield 65%) of N-(bis(4-cyclohexylphenyl)phosphaneyl)-N-cyclohexyl-1,1-bis(4-cyclohexylphenyl)phosphanamine, a compound represented by chemical formula 11, was obtained by column chromatography.

[0298] <Ligand compound represented by chemical formula 11> [Chemical formula 11] [ka] 1 H NMR (500 MHz, C6D6): δ 7.58(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)

[0299] Comparative Synthesis Example 2: Synthesis of Ligand Compound Represented by Chemical Formula 12 A dried flask was charged with 0.55 g (5.5 mmol, 0.5 eq) of cyclohexylamine, 2.23 g (22 mmol, 2 eq) of triethylamine, and 10 ml of dichloromethane under a nitrogen atmosphere, and the mixture was cooled to 0°C. Then, 4.56 g (11 mmol, 1 eq) of di([1,1'-biphenyl]-4-yl)chlorophosphane was slowly added. After the reaction was completed, the precipitated solid was removed using a filter, the solvent was removed under reduced pressure, and 2.78 g (3.60 mmol, 72% yield) of 1,1-di([1,1'-biphenyl]-4-yl)-N-cyclohexyl-N-(di([1,1'-biphenyl]-4-yl)phosphaneyl)phosphanamine, a compound represented by chemical formula 12, was obtained by column chromatography.

[0300] <Ligand compound represented by chemical formula 12> [Chemical formula 12] [ka] 1 H NMR (500 MHz, C6D6): δ 7.92-7.42(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)

[0301] Comparative Synthesis Example 3: Synthesis of Ligand Compound Represented by Chemical Formula 13 A dried flask was charged with 0.55 g (5.5 mmol, 0.5 eq) of cyclohexylamine, 2.23 g (22 mmol, 2 eq) of triethylamine, and 10 ml of dichloromethane under a nitrogen atmosphere, and the mixture was cooled to 0°C. Then, 3.38 g (11 mmol, 1 eq) of chlorobis(3,5-dimethylphenyl)phosphane was slowly added. After the reaction was completed, the precipitated solid was removed using a filter, the solvent was removed under reduced pressure, and 2.32 g (4 mmol, 80% yield) of N-(bis(3,5-dimethylphenyl)phosphaneyl)-N-cyclohexyl-1,1-bis(3,5-dimethylphenyl)phosphanamine, a compound represented by chemical formula 12, was obtained by column chromatography.

[0302] <Ligand compound represented by chemical formula 13> [Chemical formula 13] [ka] 1 H NMR (500 MHz, C6D6): δ 7.38(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)

[0303] Examples and Comparative Examples Example 1 Under an argon gas atmosphere, 17.5 mg (0.05 mmol) of chromium (III) acetylacetonate (Cr(acac)3) and 0.5 mmol of the ligand compound represented by Chemical Formula 2-1 in Synthesis Example 1 were placed in a flask, and then 100 ml of methylcyclohexane was added and stirred to prepare a 5 mM (Cr basis) catalyst solution.

[0304] A 600 ml Parr reactor was prepared and evacuated at 120 °C for 2 hours. The interior was then flushed with argon and the temperature was reduced to 80 °C. Then, 180 ml of methylcyclohexane and 2 ml of MMAO (isoheptane solution, Al / Cr = 600) were added, followed by 2 ml of the catalyst solution (1.0 μmol Cr). After stirring at 1,000 rpm for 2 minutes, the ethylene line valve, adjusted to 30 bar, was opened to fill the reactor with ethylene, and the reactor was then stirred at 1,000 rpm for 60 minutes. The ethylene line valve was closed, and the reactor was cooled to 0 °C using a dry ice / acetone bath. Unreacted ethylene was slowly vented, and 0.5 ml of nonane (GC internal standard) was added. After stirring for 10 seconds, 2 ml of the liquid portion of the reactor was quenched with water. The resulting organic portion was filtered through a PTFE syringe filter to prepare a GC-FID sample. The distribution of the liquid product was analyzed by GC (Agilent 6890N, Alltech AT-5 (30m x 0.32mm ID x 0.25µm; series no. 12446)). 400ml of ethanol / HCl (10vol% of aqueous 12M HCl solution) was added to the remaining reaction mixture, stirred, filtered, and the amount of solid product was analyzed. The resulting polymer was dried overnight in a vacuum oven at 80°C.

[0305] Examples 2 to 50 and Comparative Examples 1 to 3 The same procedure as in Example 1 was repeated, except that the type of catalyst was changed as shown in Table 1 below.

[0306] [Table 1-1] [Table 1-2]

[0307] Experimental Example The results of the ethylene oligomerization reaction in the above examples and comparative examples are shown in Table 2 below.

[0308] *Catalytic activity (ton / mol·Cr / hr): The catalytic activity was calculated from the total weight (ton) of the product, which is the sum of the weight (ton) of the obtained liquid product and the weight (ton) of the solid product.

[0309] *1-C6 and 1-C8 selectivity (wt%): The contents of 1-hexene (1-C6) and 1-octene (1-C8) were calculated from the distribution of the liquid products analyzed by GC, and the wt% of 1-hexene or 1-octene was calculated based on the total weight of the products.

[0310] *Solid (wt%): The weight % of the solid product was calculated based on the total weight of the product. This is an insoluble solid that is not dissolved in the solvent, and indicates the degree to which polyethylene with a carbon number of about 40 or more is produced.

[0311] [Table 2-1] [Table 2-2]

[0312] As shown in Table 2, when an ethylene oligomerization reaction is carried out using a catalyst composition containing the ligand compound according to the present invention, the phenyl at the end of the diphosphinoaminyl residue is asymmetric, and has alkyl groups with a specific number of carbon atoms or silyl groups substituted with alkyls with a specific number of carbon atoms at the meta and para positions as substituents. In addition, the steric distortion around the PNP functional group is adjusted by the substituents substituted on the nitrogen atom, which has been confirmed to improve all of the catalytic activity, selectivity, and stability.

[0313] In contrast, in Comparative Examples 2 and 3, the catalyst did not exhibit any activity at all, and it was impossible to carry out ethylene oligomerization.

[0314] These results confirm that when ethylene oligomerization is carried out using an organochromium compound and catalyst composition containing a ligand compound of the present invention, the high catalytic activity results in excellent productivity and enables the production of linear α-olefins with high selectivity to 1-hexene and 1-octene.

Claims

1. A ligand compound represented by the following chemical formula 1. [Chemical formula 1] 【Chemical 1】 (In the above Chemical Formula 1, R １ ~R ４ are each independently an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 6 to 20 carbon atoms, an arylalkoxyalkyl group having 10 to 30 carbon atoms, or a trialkylsilyl group, and the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms, R ５ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

2. R １ ~R ４ and each independently represent an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group, or a tributylsilyl group.

3. R １ ~R ４ The ligand compound according to claim 1, wherein each of is independently an n-decyl group, a tripropylsilyl group, or a tributylsilyl group.

4. R ５ is an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with 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.

5. The ligand compound according to claim 1, wherein the ligand compound represented by Chemical Formula 1 is represented by the following Chemical Formula 2: [Chemical formula 2] 【Chemistry 2】 (In the above chemical formula 2, R ５ is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

6. The ligand compound according to claim 5, wherein the ligand compound represented by Chemical Formula 2 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 2-1 to 2-10: 【Chemistry 3】 【Chemistry 4】

7. The ligand compound according to claim 1, wherein the ligand compound represented by Chemical Formula 1 is represented by the following Chemical Formula 3: [Chemical formula 3] 【Chemistry 5】 (In the above chemical formula 3, R ５ is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

8. The ligand compound according to claim 7, wherein the ligand compound represented by Chemical Formula 3 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 3-1 to 3-10: 【Chemistry 6】 【Chemistry 7】

9. The ligand compound according to claim 1, wherein the ligand compound represented by Chemical Formula 1 is represented by the following Chemical Formula 4: [Chemical formula 4] 【Chemistry 8】 (In the above chemical formula 4, R ５ is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

10. The ligand compound according to claim 9, wherein the ligand compound represented by Chemical Formula 4 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 4-1 to 4-10: 【Chemistry 9】 【Chemistry 10】

11. The ligand compound according to claim 1, wherein the ligand compound represented by Chemical Formula 1 is represented by the following Chemical Formula 5: [Chemical formula 5] 【Chemistry 11】 (In the above chemical formula 5, R ５ is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

12. The ligand compound according to claim 11, wherein the ligand compound represented by Chemical Formula 5 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 5-1 to 5-10: 【Chemistry 12】 【Chemistry 13】

13. The ligand compound according to claim 1 , wherein the ligand compound represented by Chemical Formula 1 is represented by the following Chemical Formula 6: [Chemical formula 6] 【Chemistry 14】 (In the above chemical formula 6, R ５ represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms, n is an integer selected from 4 to 14.

14. The ligand compound according to claim 13, wherein the ligand compound represented by Chemical Formula 6 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 6-1 to 6-10: 【Chemistry 15】 【Chemistry 16】

15. An organochromium compound comprising the ligand compound of claim 1 and chromium coordinated to said ligand compound.

16. 16. The organochromium compound according to claim 15, wherein in the ligand compound represented by Chemical Formula 1, at least one lone pair of N and two P atoms is coordinated to chromium.

17. A catalyst composition comprising the ligand compound of claim 1, chromium, and a cocatalyst.

18. the chromium is derived from a chromium source; 18. The catalyst composition of claim 17, wherein the chromium source comprises one or more selected from the group consisting of chromium(III) acetylacetonate, chromium(III) chloride tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetate, chromium(III) butyrate, chromium(III) pentanoate, chromium(III) laurate, chromium(III) tris(2,2,6,6-tetramethyl-3.5-heptanedionate), and chromium(III) stearate.

19. The catalyst composition according to claim 17, wherein the co-catalyst is at least one selected from the group consisting of compounds represented by the following Chemical Formulas 7 to 10: [Chemical formula 7] <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 the above chemical formula 7, R １３ are each independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, a is an integer of 2 or more, [Chemical formula 8] E(R １４ ) ３ In the above Chemical Formula 8, E is aluminum or boron; R １４ are each independently a hydrogen atom, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, [Chemical formula 9] [L-H] ＋ [G(Y) ４ ] － [Chemical formula 10] [L] ＋ [G(Y) ４ ] － In the above chemical formulas 9 and 10, L is a neutral or cationic Lewis acid; [L-H] ＋ is a Brønsted acid, G is a group 13 element, Each Y is 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, and when the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbyl 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.

20. A method for producing linear α-olefins, comprising the step (S10) of oligomerizing ethylene in the presence of the catalyst composition according to claim 17.

21. The method for producing linear α-olefins according to claim 20, wherein the linear α-olefin is 1-hexene, 1-octene, or a mixture thereof.

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