Phosphine-imino-quinoline and related ligands for use in ethylene oligomerization processes

Abstract

Catalyst compositions containing phosphine-imino-quinoline ligands and transition metal complexes having phosphine-imino-quinoline ligands are disclosed. These catalyst compositions can be used in ethylene oligomerization processes to produce 1-hexene and 1-octene.

Description

[Technical Field]

[0001] Reference to related applications This application was filed on April 23, 2024, as a PCT international patent application, claiming the benefits and priority of U.S. Provisional Patent Application No. 63 / 498,538, filed on April 27, 2023, the disclosures of which are incorporated herein by reference in their entirety.

[0002] This disclosure generally relates to heteroatom ligands and heteroatom ligand transition metal compound complexes, as well as catalytic compositions and their use in ethylene oligomerization processes. [Background technology]

[0003] Alpha-olefins such as 1-hexene and 1-octene can be produced using various combinations of ethylene reagents, catalyst systems, and oligomerization processes. It may be beneficial if the catalyst system used has high catalytic activity and thermal stability, and is more selective for desirable C6-C8 linear α-olefins. Therefore, the present invention generally addresses these objectives. [Overview of the project]

[0004] This summary is provided to introduce, in a simplified form, a selection of concepts further described herein. This summary is not intended to identify any necessary or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0005] This specification discloses catalyst compositions and methods for oligomerizing olefins using these catalyst compositions. In particular, the present invention relates to catalyst compositions and ethylene oligomerization processes utilizing heteroatom ligands and heteroatom ligand transition metal compound complexes. In one aspect of the present invention, the ligands and complexes may have formulas (IA) and (IB): [ka]

[0006] In formulas (IA) and (IB), X can be P or S; when X is S, y can be equal to 1; when X is P, y can be equal to 2; R 1 ~R 11 are, independently, H, halogen, a nitro group, a C1-C 18 hydrocarbyl group, or a C1-C 18 halogenated hydrocarbyl group; R 5 and R 6 can combine to form a ring or a ring system; each R 12 is, independently, a C1-C 18 hydrocarbyl group or a C1-C 18 halogenated hydrocarbyl group. Referring to formula (IB), M can be Fe, Co, or Cr; m can be the oxidation state of M; each Z is, independently, H, halogen, a C1-C 18 hydrocarbyl group, or a C1-C 18 halogenated hydrocarbyl group.

[0007] In another aspect of the present invention, the heteroatom ligand and the heteroatom ligand transition metal compound complex can have formulas (IIA) and (IIB):

Chemical formula

[0008] In formulas (IIA) and (IIB), X can be P or S; when X is S, y can be equal to 1; when X is P, y can be equal to 2; Y can be O, NH, or CH2; R B ~R J are, independently, H, halogen, a nitro group, a C1-C 18 hydrocarbyl group, or a C1-C 18 halogenated hydrocarbyl group; R D ~R E can combine to form a ring or a ring system; each R A is, independently, a C1-C 18Hydrocarbyl group or C1-C 18 It may be a halogenated hydrocarbyl group. Referring to formula (IIB), M can be Fe, Co, or Cr, m can be the oxidation state of M, and each Z is independently H, halogen, C1-C 18 Hydrocarbyl group, or C1-C 18 It may be a halogenated hydrocarbyl group.

[0009] Both the above summary and the following detailed description are illustrative and provide examples only. Therefore, the above summary and the following detailed description should not be considered limiting. Furthermore, additional features or variations may be provided beyond those described herein. For example, certain embodiments may involve combinations and partial combinations of the various features described in the embodiments for carrying out the invention.

[0010] The following drawings form part of this specification and are included to further support specific aspects of the invention. The invention can be better understood by referring to one or more of these drawings in conjunction with the detailed description. [Brief explanation of the drawing]

[0011] [Figure 1] The 1H NMR plot for ligand 9 is presented. [Figure 2] The 1H NMR plot of ligand 10 is presented. [Figure 3] The 1H NMR plot of ligand 11 is presented. [Figure 4] The 1H NMR plot of ligand 12 is presented. [Figure 5] The 1H NMR plot of ligand 13 is presented. [Figure 6] The 1H NMR plot of ligand 14 is presented. [Figure 7] The 1H NMR plot of ligand 15 is presented. [Figure 8] The 1H NMR plot of ligand 16 is presented. [Figure 9]The 1H NMR plot of ligand 16 is presented. [Figure 10] The 1H NMR plot of ligand 18 is presented. [Figure 11] The 1H NMR plot of ligand 19 is presented. [Figure 12] The 1H NMR plot of ligand 20 is presented. [Figure 13] The 1H NMR plot of ligand 21 is presented. [Figure 14] The 1H NMR plot of ligand 22 is presented. [Figure 15] The 1H NMR plot of ligand 23 is presented. [Figure 16] A magnified view of the high chemical shift region in Figure 15 is shown. [Figure 17] The 1H NMR plot of ligand 24 is presented. [Figure 18] A magnified view of the high chemical shift region in Figure 17 is shown. [Figure 19] The 1H NMR plot of ligand 25 is presented. [Figure 20] A magnified view of the high chemical shift region in Figure 19 is shown.

[0012] The invention disclosed herein is susceptible to various modifications and alternative forms, but only a few specific embodiments are shown in detail below and in the drawings, for example. The drawings and detailed description of these specific embodiments are not intended in any way to limit the scope or range of the concept of the invention or the appended claims. Rather, the drawings and detailed description illustrate the concept of the invention to those skilled in the art and provide them with the means to create and use the concept of the invention.

[0013] definition To more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used herein but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) may apply, provided that the definition does not conflict with any other disclosure or definition applicable herein, or make any patent claim to which the definition applies obscured or impossible. To the extent that any definition or use provided by any document incorporated herein by reference conflicts with any definition or use provided herein, the definition or use provided herein shall prevail.

[0014] In this specification, the features of the subject matter are described in such a way that different combinations of features may be envisioned within a particular embodiment. For all embodiments and features disclosed herein, all combinations that do not adversely affect the compounds, compositions, processes, or methods described herein, whether or not a particular combination is explicitly stated, are intended. In addition, unless expressly stated otherwise, any embodiment or feature disclosed herein may be combined to illustrate inventive compounds, compositions, processes, or methods consistent with this disclosure.

[0015] In this disclosure, compositions and processes / methods are described in terms of "including" various materials, components, and steps, but unless otherwise specified, such compositions and processes / methods may "essentially consist of" or "consist of" such various materials, components, and steps. For example, catalyst compositions consistent with aspects of the present invention may include, or can essentially consist of, heteroatom ligands, transition metal compounds, and organoaluminum compounds. Unless otherwise specified, the terms "a," "an," and "the" are intended to include multiple options, e.g., at least one. For example, the disclosure of "organoaluminum compounds" means, unless otherwise specified, to include one organoaluminum compound or a mixture or combination of two or more organoaluminum compounds.

[0016] Generally, groups of elements are indicated using the numbering system shown in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, groups of elements may be indicated using the common names assigned to the groups, for example, alkali metals for group 1 elements, alkaline earth metals for group 2 elements, transition metals for group 3-12 elements, and halogens or halides for group 17 elements.

[0017] For any comprehensive or specific compound or group disclosed herein, any name or structure presented is intended to encompass all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that may arise from a particular set of substituents, unless otherwise specified. The name or structure also encompasses all enantiomers, diastereomers, and other optical isomers (if any), as well as mixtures of stereoisomers, whether enantiomers or racemic forms, as recognized by those skilled in the art, unless otherwise specified. For example, a general reference to hexene (or hexenes) includes all linear or branched, acyclic or cyclic hydrocarbon compounds having six carbon atoms and one carbon-carbon double bond; a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and a general reference to butyl group includes n-butyl, sec-butyl, isobutyl, and t-butyl.

[0018] In this specification, the terms “contact” and “combine” are used, unless otherwise specified, to describe compositions and processes / methods in which materials are contacted or combined together in any order, in any way, and for any length of time. For example, materials may be blended, mixed, slurried, dissolved, reacted, treated, impregnated, formulated, or contacted or combined in several other ways or by any preferred method or technique.

[0019] As used herein and in the claims, the term “hydrocarbon” always means a saturated or unsaturated compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of a particular group in a hydrocarbon (for example, halogenated hydrocarbons indicate the presence of one or more halogen atoms substituting an equivalent number of hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is used herein according to the IUPAC definition and is a monovalent group formed by removing a hydrogen atom from a hydrocarbon (i.e., a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include, among other groups, alkyl, alkenyl, aryl, and aralkyl groups.

[0020] The term "oligomer" refers to a compound containing 2 to 20 monomer units. The terms "oligomerized product" and "oligomer product" include all products produced by the "oligomerization" process, including "oligomers" and non-oligomer products (e.g., products containing more than 20 monomer units or solid polymers), but exclude other non-oligomer components in the oligomerization reactor effluent, such as unreacted ethylene, organic reaction media, and hydrogen, among other components.

[0021] The terms “catalytic composition,” “catalytic mixture,” and “catalytic system” are independent of the actual products or compositions obtained from the contact or reaction of the initial components of the disclosed or claimed catalytic composition (or catalytic mixture or catalytic system), the properties of the active catalytic sites, or the fate of the organoaluminum compounds and heteroatom ligand transition metal compound complexes (or organoaluminum compounds, and heteroatom ligands, and transition metal compounds) after these components are combined. Therefore, the terms “catalytic composition,” “catalytic mixture,” and “catalytic system” encompass the initial starting components of the composition, as well as any product(s) that may result from the contact of these initial starting components, including both heterogeneous and homogeneous catalytic systems or compositions. The terms “catalytic composition,” “catalytic mixture,” and “catalytic system” may be used interchangeably throughout this disclosure.

[0022] In this invention, several types of ranges are disclosed. When disclosing or claiming any type of range, the intent is to individually disclose or claim each number that can be reasonably considered to be included in such range, including the endpoint values ​​of that range, as well as any partial ranges and combinations of partial ranges that fall within that range. For example, when disclosing or claiming a chemical part having a specific number of carbon atoms, the intent is to individually disclose or claim all numbers that can be considered to be included in such range and to be consistent with the disclosures herein. For example, herein a part is C1-C 18 The disclosure of a hydrocarbyl group, or in other words, a hydrocarbyl group having 1 to 18 carbon atoms, refers to a portion that may have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as any range between these two numbers (e.g., a C1-C8 hydrocarbyl group), and furthermore, any combination of these ranges (e.g., C2-C4 and C2). 12 ~C 16 It also contains a hydrocarbyl group.

[0023] Similarly, another representative example of the Al:transition metal molar ratio in the catalyst composition follows. The disclosure that the molar ratio may be in the range of 10:1 to 5,000:1 is intended to indicate that the molar ratio may be any ratio within that range, such as 10:1 to 5,000:1, for example, 50:1 to 3,000:1, 75:1 to 2,000:1, 100:1 to 2,000:1, or 100:1 to 1,000:1, or any combination thereof. Similarly, all other ranges disclosed herein should be interpreted in the same manner as these examples.

[0024] Generally, quantities, sizes, formulations, parameters, ranges, or other quantities or features are "about" or "approximately," whether or not they are explicitly stated as such. Whether or not they are modified by the terms "about" or "approximately," the claims include the equivalent of such quantity or feature.

[0025] Any methods and materials similar or equivalent to those described herein may be used in carrying out or testing the present invention, but representative methods and materials are described herein.

[0026] All publications and patents referenced herein, for example, constructs and methodologies described in those publications and patents, are incorporated herein by reference in their entirety for the purpose of describing and disclosing constructs and methodologies that may be used in connection with the present invention as described herein. [Modes for carrying out the invention]

[0027] This specification discloses heteroatomic ligand-transition metal compound complexes, catalyst compositions containing heteroatomic ligands and transition metal compounds, each complex (or each ligand and compound), and ethylene oligomerization processes that utilize these catalyst compositions to produce 1-hexene and / or 1-octene.

[0028] An object of the present invention is to develop a catalytic system using a heteroatomic ligand-transition metal compound complex (or a heteroatomic ligand and a transition metal compound) that provides excellent catalytic activity in the ethylene oligomerization process and yields high-yield oligomer products. Another object of the present invention is to develop a catalytic system using a heteroatomic ligand-transition metal compound complex (or a heteroatomic ligand and a transition metal compound) that is selective in the formation of desirable C6-C8 linear α-olefins in the ethylene oligomerization process.

[0029] Ligands and complexes In one aspect of the present invention, the heteroatomic ligands and heteroatomic ligand transition metal compound complexes incorporated herein may have formulas (IA) and (IB): [ka]

[0030] In another aspect of the present invention, the heteroatomic ligands and heteroatomic ligand transition metal compound complexes incorporated herein may have formulas (IIA) and (IIB): [ka]

[0031] In equation (IA), X, y, R 1 ~R 11 , and each R 12 X, y, and R are independent elements of the heteroatom ligand compound. Therefore, the heteroatom ligand compound having formula (IA) is disclosed herein. 1 ~R 11 , and R 12 This can be explained using any combination of the following: Similarly, in equation (IB), X, y, M, m, each Z, R 1 ~R 11 , and each R 12 is an independent element of the heteroatom ligand transition metal compound complex. Therefore, the heteroatom ligand transition metal compound complex having formula (IB) is disclosed herein by X, y, M, m, Z, R 1 ~R 11 , and R 12 This can be explained using any combination of the following.

[0032] Similarly, in equation (IIA), X, y, Y, R B ~R J , and each R A is an independent element of the heteroatom ligand compound. Therefore, the heteroatom ligand compound having formula (IIA) is X, y, Y, R disclosed herein. B ~R J , and R AThis can be explained using any combination of the following. Similarly, in equation (IIB), X, y, Y, M, m, each Z, R B ~R J , and each R A is an independent element of the heteroatom ligand transition metal compound complex. Therefore, the heteroatom ligand transition metal compound complex having formula (IIB) is X, y, Y, M, m, Z, R disclosed herein. B ~R J , and R A This can be explained using any combination of the following.

[0033] Unless otherwise specified, the above formulas (IA), (IB), (IIA), and (IIB), any other structural formulas disclosed herein, and any ligands, complexes, compounds, or species disclosed herein are not designed to indicate the stereochemistry or isomeric positions of different parts (for example, these formulas are not intended to indicate rac or meso isomers, or R or S diastereoisomers), but unless otherwise stated, such compounds are intended and encompassed by these formulas and / or structures.

[0034] First, regarding equations (IA) and (IB), X can be P or S, if X is S, then y can be equal to 1, if X is P, then y can be equal to 2, R 1 ~R 11 These are independently H, halogen, C1~C 18 Hydrocarbyl group, or C1-C 18 It can be a halogenated hydrocarbyl group, R 5 and R 6 They can bond to form a ring or ring system, and each R 12 These are, independently, C1~C 18 Hydrocarbyl group or C1-C 18 It may be a halogenated hydrocarbyl group. Referring to formula (IB), M can be Fe, Co, or Cr, m can be the oxidation state of M, and each Z is independently H, halogen, C1-C 18 Hydrocarbyl group, or C1-C 18It may be a halogenated hydrocarbyl group.

[0035] In one embodiment, in equations (IA) and (IB), X can be P and y can be equal to 2, but in another embodiment, in equations (IA) and (IB), X can be S and y can be equal to 1. In equations (IA) and (IB), R 1 ~R 11 These are independently H, halogen, C1~C 18 Hydrocarbyl group, or C1-C 18 It can be a halogenated hydrocarbyl group, R 5 and R 6 They can combine to form a ring or ring system. 1 ~R 11 It is intended that either of these may be the same or different.

[0036] For example, R 1 ~R 11 These are independently H, halogens (e.g., F, Cl, Br), and C1-C 18 Hydrocarbyl group, or C1-C 18 It can be a halogenated hydrocarbyl group, and the hydrocarbyl group and the halogenated hydrocarbyl group are independently C1-C 12 Base, or C1~C 10 The group may be a C1-C8 group, a C1-C6 group, or a C1-C4 group. Any hydrocarbyl group may independently be an alkyl group, a cycloalkyl group, an aryl group (e.g., a phenyl group or a naphthyl group, optionally substituted), or an aralkyl group (e.g., a benzyl group, optionally substituted), and the same applies to halogenated hydrocarbyl groups.

[0037] In some embodiments, R 1 ~R 11is independently H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3). For example, R 1 ~R 6 is independently H or a methyl group. Additionally or alternatively, R 7 ~R 11 is independently, in some embodiments, H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a cyclohexyl group, an adamantyl group, a phenyl group, a nitro group (-NO2), a pentafluorophenyl group, or a trifluoromethyl group (CF3). Additionally or alternatively, R 5 and R 6 can combine to form a ring or a ring system. Similarly, in some embodiments, R 7 and R 8 can combine to form a ring or a ring system.

[0038] Each R 12 in formulas (IA) and (IB) is independently a C1-C 18 hydrocarbyl group or a C1-C 18 halogenated hydrocarbyl group, and any of the hydrocarbyl and halogenated hydrocarbyl options referred to herein for R 1 ~R 11 also apply to R 12 . Thus, in one embodiment, each R 12is independently a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group (one or more methyl substituents), a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3). In another embodiment, each R 12 is independently a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a cyclohexyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3).

[0039] Referring to the complex of formula (IB), M can be Fe, Co, or Cr, m can be the oxidation state of M, and each Z is independently H, halogen, C1-C 18 hydrocarbyl group, or C1-C 18 halogenated hydrocarbyl group. The metal M in formula (IB) can be Fe, Co, or Cr. Thus, in one embodiment, for example, M can be Fe or Cr, but in another embodiment, M can be Fe, alternatively M can be Co, or alternatively M can be Cr.

[0040] In formula (IB), each Z is independently any suitable monoanionic ligand such as H, halogen, C1-C 18 hydrocarbyl group, or C1-C 18 halogenated hydrocarbyl group, and R 1 ~R 11Any halogen, hydrocarbyl, and halogenated hydrocarbyl options referred herein may also be applied to Z. Thus, in one embodiment, each Z may independently be H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl or isopropyl), a butyl group (n-butyl, isobutyl, sec-butyl, or tert-butyl), a pentyl group (n-pentyl, isopentyl, sec-pentyl, or neopentyl), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3). In another embodiment, each Z may independently be H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl or isopropyl), a butyl group (n-butyl, isobutyl, sec-butyl, or tert-butyl), a cyclohexyl group, an adamantyl group, a phenyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3). In yet another embodiment, each Z may be Cl. In yet another embodiment, two or more Zs may bond to form a dianionic, trianionic, or polyanionic ligand (e.g., a catechol or chelating group) to balance the oxidation state of M.

[0041] Referring to equations (IIA) and (IIB), X can be P or S, if X is S, y can be equal to 1, if X is P, y can be equal to 2, Y can be O, NH, or CH2, R B ~R J These are independently H, halogen, C1~C 18 Hydrocarbyl group, or C1-C 18 It can be a halogenated hydrocarbyl group, R D ~R E They can bond to form a ring or ring system, and each R A These are, independently, C1~C 18 Hydrocarbyl group or C1-C 18It may be a halogenated hydrocarbyl group. Referring to formula (IIB), M can be Fe, Co, or Cr, m can be the oxidation state of M, and each Z is independently H, halogen, C1-C 18 Hydrocarbyl group, or C1-C 18 It may be a halogenated hydrocarbyl group.

[0042] In one embodiment, in equations (IIA) and (IIB), X can be P and y can be equal to 2, but in another embodiment, in equations (IIA) and (IIB), X can be S and y can be equal to 1. In equations (IIA) and (IIB), R B ~R J These are independently H, halogen, C1~C 18 Hydrocarbyl group, or C1-C 18 It can be a halogenated hydrocarbyl group, R D and R E They can combine to form a ring or ring system. B ~R J It is intended that either of these may be the same or different.

[0043] For example, R B ~R J These are independently H, halogens (e.g., F, Cl, Br), and C1-C 18 Hydrocarbyl group, or C1-C 18 It can be a halogenated hydrocarbyl group, and the hydrocarbyl group and the halogenated hydrocarbyl group are independently C1-C 12 Base, or C1~C 10 The group may be a C1-C8 group, a C1-C6 group, or a C1-C4 group. Any hydrocarbyl group may independently be an alkyl group, a cycloalkyl group, an aryl group (e.g., a phenyl group or a naphthyl group, optionally substituted), or an aralkyl group (e.g., a benzyl group, optionally substituted), and the same applies to halogenated hydrocarbyl groups.

[0044] In some embodiments, R B ~R JR can independently be H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl or isopropyl), a butyl group (n-butyl, isobutyl, sec-butyl, or tert-butyl), a pentyl group (n-pentyl, isopentyl, sec-pentyl, or neopentyl), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3). For example, R B ~R E This can independently be an H or a methyl group. Additionally or alternatively, R F ~R J Independently, in some embodiments, may be H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl or isopropyl), a butyl group (n-butyl, isobutyl, sec-butyl, or tert-butyl), a cyclohexyl group, an adamantyl group, a phenyl group, a nitro group (-NO2), a pentafluorophenyl group, or a trifluoromethyl group (CF3). Additionally or alternatively, R D and R E They can combine to form a ring or ring system. Similarly, in some embodiments, R F and R G These can combine to form a ring or ring system.

[0045] Each R in equations (IIA) and (IIB) A These are, independently, C1~C 18 Hydrocarbyl group or C1-C 18 It can be a halogenated hydrocarbyl group, R B ~R J Any hydrocarbyl and halogenated hydrocarbyl options referred to herein with respect to R A This can be applied to each R. Therefore, in one embodiment, AR can independently be a methyl group, an ethyl group, a propyl group (n-propyl or isopropyl), a butyl group (n-butyl, isobutyl, sec-butyl, or tert-butyl), a pentyl group (n-pentyl, isopentyl, sec-pentyl, or neopentyl), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group (with one or more methyl substituents), a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3). In another embodiment, each R A These can independently be a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a cyclohexyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3).

[0046] In equations (IIA) and (IIB), Y can be O, NH, or CH2. Thus, in one embodiment, Y is O, in another embodiment, Y is NH, and in yet another embodiment, Y is CH2.

[0047] Here, referring to the complex of formula (IIB), M can be Fe, Co, or Cr, m can be the oxidation state of M, and each Z can independently be H, a halogen, or C1-C 18 Hydrocarbyl group, or C1-C 18 It may be a hydrocarbyl halide. The metal M in formula (IIB) may be Fe, Co, or Cr, and therefore in one embodiment, for example, M may be Fe or Cr, but in another embodiment, M may be Fe, alternatively M may be Co, or alternatively M may be Cr.

[0048] In equation (IIB), each Z is independently H, halogen, C1-C 18 Hydrocarbyl group, or C1-C 18It can be any suitable monoanionic ligand, such as a halogenated hydrocarbyl group, R B ~R J Any halogen, hydrocarbyl, and halogenated hydrocarbyl options referred herein may also be applied to Z. Thus, in one embodiment, each Z may independently be H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl or isopropyl), a butyl group (n-butyl, iso-butyl, sec-butyl, or tert-butyl), a pentyl group (n-pentyl, iso-pentyl, sec-pentyl, or neopentyl), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3). In another embodiment, each Z may independently be H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl or isopropyl), a butyl group (n-butyl, isobutyl, sec-butyl, or tert-butyl), a cyclohexyl group, an adamantyl group, a phenyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3). In yet another embodiment, each Z may be Cl. In yet another embodiment, two or more Zs may bond to form a dianionic, trianionic, or polyanionic ligand (e.g., a catechol or chelating group) to balance the oxidation state of M.

[0049] Catalyst composition and oligomerization process Catalyst compositions are also incorporated herein. An exemplary catalyst composition may contain (a) any of the heteroatom ligand transition metal compounds disclosed herein, and (b) an organoaluminum compound. Another exemplary catalyst composition may contain (A) any of the heteroatom ligands disclosed herein, (B) any of the transition metal compounds disclosed herein, and (C) an organoaluminum compound. Catalyst compositions can be prepared by contacting any of the aforementioned components in any order or sequence, at any suitable temperature and pressure, in or out of the presence of an olefin (e.g., an oligomerizable olefin such as ethylene). If the catalyst composition is formed in a reactor at the time of contact with the olefin, the suitable pressure and temperature are typical of the oligomerization process, which will be further discussed below.

[0050] In one embodiment, the heteroatom ligand (compound) used in the catalyst composition and oligomerization process may be ligand 5, ligand 7, ligand 9, or ligand 11, or mixtures or combinations thereof, as shown in Table 1 below. Therefore, for example, the heteroatom ligand (compound) used in the catalyst composition and oligomerization process may be ligand 5, alternatively ligand 7, alternatively ligand 9, or alternatively ligand 11.

[0051] In another embodiment, the heteroatom ligands (compounds) used in the catalyst composition and oligomerization process may be ligands 6, 8, 10, 12, 13, or 15, or mixtures or combinations thereof, as shown in Table 1 below. Therefore, for example, the heteroatom ligands (compounds) used in the catalyst composition and oligomerization process may be ligand 6, alternatively ligand 8, alternatively ligand 10, alternatively ligand 12, alternatively ligand 13, or alternatively ligand 15.

[0052] In many cases, the catalyst composition may further contain a hydrocarbon diluent (or solvent). For example, the hydrocarbon diluent (or solvent) may include any suitable saturated aliphatic hydrocarbon, any suitable aromatic hydrocarbon, or any combination thereof. Saturated aliphatic hydrocarbons may be linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, or cyclic aliphatic hydrocarbons, and combinations thereof. Thus, the hydrocarbon diluent (or solvent) may include linear alkanes, branched alkanes, cyclic alkanes, or combinations thereof. Specific examples of saturated aliphatic hydrocarbons that can be used as diluents (or solvents) either alone or in combination include propane, butane (e.g., n-butane or isobutane), pentane (e.g., n-pentane, neopentane, cyclopentane, or isopentane), hexane, heptane, octane, cyclohexane, methylcyclohexane, and combinations thereof. In certain embodiments of this disclosure, the hydrocarbon diluent (or solvent) may include (or consist essentially of, or consist of) cyclohexane.

[0053] Additionally or alternatively, the hydrocarbon diluent (or solvent) may include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, styrene, and mesitylene. A combination of two or more aromatic hydrocarbons may be used if desired.

[0054] The relative amount of organoaluminum compounds to the relative amount of heteroatom ligand-transition metal compound complexes (or the relative amounts of heteroatom ligands and transition metal compounds) is not particularly limited. Nevertheless, the molar ratio of Al:transition metal (e.g., Al:Cr or Al:Fe) or Al:ligand in the catalyst composition may be in the range of 10:1 to 5,000:1, for example, 50:1 to 3,000:1, 75:1 to 2,000:1, 100:1 to 2,000:1, or 100:1 to 1,000:1. For example, when multiple transition metals (or ligands) and / or multiple organoaluminum compounds are used, these ratios are based on the total moles of each transition metal, ligand, and organoaluminum compound.

[0055] When both heteroatomic ligands and transition metal compounds are present, the ligand-to-transition metal molar ratio is often in the range of 10:1 to 1:10, more often 8:1 to 1:8, 5:1 to 1:5, 4:1 to 1:4, or 2:1 to 1:2. In some embodiments, the transition metal compound is present in molar excess relative to the heteroatomic ligand, but this is not essential.

[0056] Generally speaking, the transition metal compounds in the transition metal compounds or heteroatom ligand transition metal compound complexes described herein are of the formula M(X 1 ) p It may have the following: In this formula, M can be Fe, Co, or Cr, and p is the oxidation state of M. Each X 1 This can independently be any suitable monoanionic ligand. Typically, the transition metal atom in a transition metal compound can have any positive oxidation state that the transition metal atom can take. For example, a cobalt atom can have oxidation states from +2, and an iron atom or a chromium atom can have various oxidation states including +2 and +3.

[0057] Monoanionic ligand (X 1) can be a halogen (e.g., fluorine or chlorine), carboxylate, β-diketonate, hydrocarboxylate, nitrate, or chlorate. Hydrocarboxylate can be an alkoxide, aryl oxide, or aralkoxide. In general, any carboxylate of a transition metal compound can be independently C1-C 20 Carboxylate, or alternatively, C1-C 10 It may be a carboxylate. In some embodiments, each carboxylate may independently be an acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate, or alternatively, a pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate. In some embodiments, each carboxylate is independently acetate, propionate, n-butyrate, valerate (n-pentanoate), neo-pentanoate, caproate (n-hexanoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate), or alternatively, valerate (n-pentanoate). Neo-pentanoate, capronate (n-hexanoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate), alternatively capronate (n-hexanoate), alternatively n-heptanoate, alternatively caprylate (n-octanoate), or alternatively 2-ethylhexanoate. In some embodiments, the carboxylate may be triflate (trifluoroacetate). In other embodiments, two or more X 1 These can bind to form dianionic, trianionic, or polyanionic ligands (e.g., catechol or chelating groups) to balance the oxidation state of M.

[0058] Generally speaking, each β-diketonate of a transition metal compound can independently form any C1-C 20 β-diketonate, or alternatively, any C1-C 10 It may be a β-diketonate. In some embodiments, each β-diketonate may independently be an acetylacetonate (i.e., 2,4-pentanedione), a hexafluoroacetylacetonate (i.e., 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), or a benzoylacetonate, alternatively an acetylacetonate, alternatively a hexafluoroacetylacetonate, or alternatively a benzoylacetonate.

[0059] Generally speaking, each hydrocarboxyde in a transition metal compound is independently any C1-C 20 Hydrocarboxylate, or alternatively, any C1-C 10 It can be a hydrocarboxyl. In one embodiment, each hydrocarboxyl is independently C1-C 20 Alkoxides, alternatively C1-C 10 Alkoxides, alternatively C6-C 20 Aryl oxides, or alternatively, C6-C 10 It may be an aryl oxide. In some embodiments, each alkoxide may independently be a methoxide, ethoxide, propoxide, or butoxide, alternatively a methoxide, ethoxide, isopropoxide, or tert-butoxide, alternatively a methoxide, alternatively an ethoxide, alternatively an isopropoxide, or alternatively a tert-butoxide. In some embodiments, the aryl oxide may be a phenoxide.

[0060] In some non-limiting embodiments, the transition metal compound in the transition metal compound and / or heteroatom ligand transition metal compound complex is cobalt(II) halide, chromium(II) halide, iron(II) halide, cobalt(II) carboxylate, chromium(II) carboxylate, iron(II) carboxylate, cobalt(II) β-diketonate, chromium(II) β-diketonate, or iron(II) β-diketonate, or alternatively, chromium(III) halide, iron(III) halide, chromium(III) carboxylate, iron(III) carboxylate The nitrate may include, or essentially consist of, or may consist of, a chromium(III) β-diketonate, or iron(III) β-diketonate, alternatively cobalt(II) nitrate, chromium(II) nitrate, iron(II) nitrate, chromium(III) nitrate, or iron(III) nitrate, or alternatively cobalt(II) acetylacetonate, chromium(II) acetylacetonate, iron(II) acetylacetonate, chromium(III) acetylacetonate, or iron(III) acetylacetonate.

[0061] Although not shown in the names and formulas of the transition metal compounds and / or the formulas and structures of the heteroatom ligand transition metal compound complexes described herein, those skilled in the art will recognize that the neutral ligand Q may associate with the transition metal compounds and / or heteroatom ligand transition metal compound complexes described herein that do not explicitly disclose / describe the neutral ligand. As a result, transition metal compounds and / or heteroatom ligand transition metal compound complexes having the neutral ligand Q can be considered equivalent to the transition metal compounds and / or heteroatom ligand transition metal compound complexes described herein that do not have the neutral ligand Q. In addition, while some of the transition metal compounds and / or heteroatomic ligand transition metal compound complexes described / represented / provided herein do not formally indicate the presence of neutral ligands, transition metal compounds and / or heteroatomic ligand transition metal compound complexes having neutral ligands (e.g., nitriles and ethers) are fully intended and encompassed herein as potential transition metal compounds and / or heteroatomic ligand transition metal compound complexes that can be utilized in catalytic systems used in aspects of this disclosure.

[0062] In general, any neutral ligand of any transition metal compound and / or heteroatomic ligand transition metal compound complex may, if present, independently form a separable compound with the transition metal compound and / or heteroatomic ligand transition metal compound complex. In some embodiments, each neutral ligand may independently be a nitrile or an ether, alternatively a nitrile, or alternatively an ether. The number q of neutral ligands may be any number that forms a separable compound with the transition metal compound and / or heteroatomic ligand transition metal compound complex. In some embodiments, the number of neutral ligands may be 0 to 6, alternatively 0 to 3, alternatively 0, alternatively 1, alternatively 2, alternatively 3, or alternatively 4.

[0063] Generally, each nitrile ligand is independent of C2-C 20 Nitriles, or alternatively C2-C 10It may be a nitrile. In some embodiments, each nitrile may independently be acetonitrile, propionitrile, butyronitrile, benzonitrile, or any combination thereof, alternatively acetonitrile, alternatively propionitrile, alternatively butyronitrile, or alternatively benzonitrile.

[0064] Generally, each ether ligand is independent of C2~C 40 Ether, alternatively C2~C 30 Ether, or alternatively, C2-C 20It may be an ether. In some embodiments, each ether ligand may independently be dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, tetrahydrofuran, dihydrofuran, 1,3-dioxolane, tetrahydropyran, dihydropyran, pyran, dioxane, furan, benzofuran, isobenzofuran, dibenzofuran, diphenyl ether, ditril ether, or any combination thereof. Alternatively, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, or any combination thereof, tetrahydrofuran, dihydrofuran, 1,3-dioxolane, tetrahydropyran, dihydropyran, pyran, dioxane, or the same. Any combination of the following may be furan, benzofuran, isobenzofuran, dibenzofuran, or any combination thereof, diphenyl ether, dityl ether, or any combination thereof, alternatively dimethyl ether, alternatively diethyl ether, alternatively dipropyl ether, alternatively dibutyl ether, alternatively methyl ethyl ether, alternatively methyl propyl ether, alternatively methyl butyl ether, alternatively tetrahydrofuran, alternatively dihydrofuran, alternatively 1,3-dioxolane, alternatively tetrahydropyran, alternatively dihydropyran, alternatively pyran, alternatively dioxane, alternatively furan, alternatively benzofuran, alternatively isobenzofuran, alternatively dibenzofuran, alternatively diphenyl ether, or alternatively dityl ether.

[0065] The formulas and structures of the heteroatomic ligand transition metal compound complexes shown herein are shown as neutral complexes; however, those skilled in the art will recognize that the heteroatomic ligand transition metal compound complex may include, or may exist as, an "ate" complex containing a negatively charged heteroatomic ligand transition metal compound complex and associated positively charged metal or metal complex cations. Additionally, although the heteroatomic ligand transition metal compound complexes described / depicted / provided herein are shown as neutral complexes, "ate" complexes containing a negatively charged heteroatomic ligand transition metal compound complex and associated positively charged metal or metal complex cations are expressly and entirely construed herein as potential heteroatomic ligand transition metal compound complexes that can be utilized in catalytic systems used in aspects of this disclosure.

[0066] In general, the organoaluminum compounds used in the catalytic systems disclosed herein may be any organoaluminum compounds that, in combination with a heteroatom ligand transition metal compound complex (or a transition metal compound and a heteroatom ligand), can catalyze the formation of oligomer products. In some embodiments, the organoaluminum compound may include, essentially consist of, or consist of aluminoxanes, alkylaluminum compounds, or any combination thereof, alternatively aluminoxanes, or alternatively alkylaluminum compounds. In some embodiments, the alkylaluminum compound may include, essentially consist of, or consist of trialkylaluminum, alkylaluminum halides, alkylaluminum alkoxides, or any combination thereof. In some embodiments, the alkylaluminum compound may include, essentially consist of, or consist of trialkylaluminum, alkylaluminum halides, or any combination thereof, alternatively trialkylaluminum, alkylaluminum alkoxides, or any combination thereof, or alternatively trialkylaluminum. In other embodiments, the alkylaluminum compound may be trialkylaluminum, alternatively alkylaluminum halides, or alternatively alkylaluminum alkoxides. In some embodiments, the aluminoxane used in the catalytic system may include, essentially consist of, or be composed of any aluminoxane that, in combination with a heteroatomic ligand transition metal compound complex (or a transition metal compound and a heteroatomic ligand), can catalyze the formation of oligomeric products. In non-limiting embodiments, the aluminoxane may have repeating units characterized by formula (III): [ka]

[0067] In formula (III), R' is a linear or branched alkyl group. Alkyl groups of aluminoxanes and alkylaluminum compounds are described separately herein and may be used non-limitingly to further describe aluminoxanes and / or alkylaluminum compounds having formula (III). Generally, n in formula (III) can be greater than 1, or alternatively greater than 2. In some embodiments, n may be in the range of 2 to 15, or alternatively in the range of 3 to 10.

[0068] In some embodiments, each halide of any alkylaluminum halide disclosed herein may independently be a fluoride, chloride, bromide, or iodide, or alternatively a chloride, bromide, or iodide. In some embodiments, each halide of any alkylaluminum halide disclosed herein may be a fluoride, alternatively a chloride, alternatively a bromide, or alternatively an iodide.

[0069] In one embodiment, each alkyl group of the aluminoxane and / or alkylaluminum compound is independently C1-C 20 Alkyl alkyl groups, or alternatively C1-C 10 The alkyl group may be an alkyl group, or alternatively a C1-C6 alkyl group. In some embodiments, each alkyl group of the aluminoxane and / or alkylaluminum compound may independently be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group, or alternatively a methyl group, an ethyl group, a butyl group, a hexyl group, or an octyl group. In some embodiments, each alkyl group of the aluminoxane and / or alkylaluminum compound may be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an n-hexyl group, or an n-octyl group, or alternatively a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an n-hexyl group, or an n-octyl group.

[0070] In one embodiment, each alkoxide group of any alkylaluminum alkoxide disclosed herein is independently C1-C 20 Alkoxy group, C1~C 10 The group may be an alkoxy group or a C1-C6 alkoxy group. In some embodiments, each alkoxy group of any alkylaluminum alkoxide disclosed herein may independently be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, or an octoxy group, or alternatively a methoxy group, an ethoxy group, a butoxy group, a hexoxy group, or an octoxy group. In some embodiments, each alkoxide group of any alkylaluminum alkoxide disclosed herein may independently be a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an iso-butoxy group, an n-hexoxy group, or an n-octoxy group, alternatively a methoxy group, an ethoxy group, an n-butoxy group, or an isobutoxy group, alternatively a methoxy group, alternatively an ethoxy group, alternatively an n-propoxy group, alternatively an n-butoxy group, alternatively an isobutoxy group, alternatively an n-hexoxy group, or alternatively an n-octoxy group.

[0071] In some non-limiting embodiments, useful trialkylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or mixtures thereof. In some non-limiting embodiments, useful trialkylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-hexylaluminum, tri-n-octylaluminum, or mixtures thereof, alternatively, triethylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof, alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof. In other non-limiting embodiments, useful trialkylaluminum compounds may include trimethylaluminum, alternatively triethylaluminum, alternatively tripropylaluminum, alternatively tri-n-butylaluminum, alternatively tri-isobutylaluminum, alternatively trihexylaluminum, or alternatively tri-n-octylaluminum.

[0072] In non-limiting embodiments, useful alkylaluminum halides may include diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. In some non-limiting embodiments, useful alkylaluminum halides may include diethylaluminum chloride, alternatively diethylaluminum bromide, alternatively ethylaluminum dichloride, or alternatively ethylaluminum sesquichloride.

[0073] In some non-limiting embodiments, aluminoxane may include, essentially consist of, or be composed of, methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, t-butylaluminoxane, 1-pentylaluminoxane, 2-entylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or mixtures thereof. In some non-limiting embodiments, aluminoxane may include, essentially consist of, or be composed of, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, t-butylaluminoxane, or mixtures thereof. In other non-limiting embodiments, aluminoxane may include, or may essentially consist of, methylaluminoxane (MAO), alternatively ethylaluminoxane, alternatively modified methylaluminoxane (MMAO), alternatively n-propylaluminoxane, alternatively isopropylaluminoxane, alternatively n-butylaluminoxane, alternatively sec-butylaluminoxane, alternatively isobutylaluminoxane, alternatively t-butylaluminoxane, alternatively 1-pentylaluminoxane, alternatively 2-pentylaluminoxane, alternatively 3-pentylaluminoxane, alternatively isopentylaluminoxane, or alternatively neopentylaluminoxane.

[0074] Oligomerization processes are also included herein. For example, an oligomerization process consistent with an aspect of the present invention may include (i) contacting ethylene, one of the catalyst compositions disclosed herein, an organic reaction medium, and optionally hydrogen in an oligomerization reactor; (ii) forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene; and (iii) discharging an effluent from the oligomerization reactor, wherein the effluent comprises unreacted ethylene and the oligomer product.

[0075] Along with other components, the effluent contains oligomeric products, including hexene, octene, and other C4 + Linear α-olefins may be included. The amount of octene in the oligomer product can typically be in the range of 5 to 99% by weight, based on the total amount of oligomers in the oligomer product. In some embodiments, the minimum amount of octene in the oligomer product may be 5, 10, 20, 30, or 40% by weight. In other embodiments, the maximum amount of octene in the oligomer product may be 99, 95, 92.5, 90, 87.5, or 85% by weight. Generally, the amount of octene in the oligomer product can range from any minimum to any maximum amount of octene in the oligomer product described herein. For example, the amount of octene in the oligomeric product, based on the total weight of the oligomers, can be 5-85% by weight, 10-90% by weight, 20-99% by weight, 30-95% by weight, 40-95% by weight, 40-90% by weight, 20-90% by weight, 30-87.5% by weight, 30-85% by weight, 40-87.5% by weight, 40-85% by weight, 20-60% by weight, 30-55% by weight, or 40-55% by weight of octene.

[0076] Additionally or alternatively, the oligomer product may contain any suitable amount of hexene. In one embodiment, the minimum amount of hexene in the oligomer product may be 15, 20, 25, 30, or 35% by weight. In another embodiment, the maximum amount of hexene in the oligomer product may be 75, 65, 60, 55, or 50% by weight. Generally, the amount of hexene in the oligomer product may range from any minimum to any maximum amount of hexene in the oligomer product described herein. For example, the amount of hexene in the oligomer product based on the total weight of the oligomer may be 20-60% by weight, 25-55% by weight, or 30-50% by weight of hexene.

[0077] The amount of ethylene converted in the oligomerization reactor is not particularly limited, and generally, the minimum conversion rate of ethylene can be at least 20, 30, 35, 40, 45, or 50% by weight, and the maximum conversion rate of ethylene can be 99, 95, 90, 80, 75, 70, or 65% by weight. Generally, the ethylene conversion rate in the reactor can range from any minimum to any maximum conversion rate described herein. For example, the ethylene conversion rate can be in the range of 20–95% by weight, 30–90% by weight, 40–80% by weight, 50–70% by weight, or 55–65% by weight. The ethylene conversion rate is based on the amount of ethylene flowing into the reactor and the amount of (unreacted) ethylene in the effluent.

[0078] Here, we refer to the step of contacting ethylene, a catalyst composition, an organic reaction medium, and optionally hydrogen in an oligomerization reactor. Since the use of hydrogen is optional in this step, in one embodiment, hydrogen is not present in this step of the process, while in another embodiment, hydrogen is present in this step of the process.

[0079] Ethylene, the catalyst composition, the organic reaction medium, and hydrogen can be combined in any order or sequence and can be introduced into the oligomerization reactor separately or in any combination. For example, hydrogen and ethylene can be combined and supplied to the reactor separately from the catalyst composition. The present invention is not limited by the manner in which each feed stream is introduced into the reactor. In one embodiment, for example, the catalyst composition can be formed first and then introduced into the oligomerization reactor. In this embodiment, the organoaluminum compound is contacted with the heteroatom ligand transition metal compound complex, or the heteroatom ligand and the transition metal compound, before being introduced into the reactor. However, in another embodiment, the catalyst composition can be formed within the oligomerization reactor. In this embodiment, the organoaluminum compound and the heteroatom ligand transition metal compound complex (or the heteroatom ligand and the transition metal compound) are introduced into the reactor separately, and the catalyst composition is formed within the reactor.

[0080] Any suitable organic reaction medium (e.g., hydrocarbons) may be used in the disclosed oligomerization process. Exemplary hydrocarbons include, for example, saturated aliphatic hydrocarbons, aromatic hydrocarbons, and combinations thereof. The organic reaction medium may be selected from the same materials as the hydrocarbon diluent (or solvent) in the catalyst composition. Thus, the organic reaction medium may include any alkanes or aromatic hydrocarbons disclosed herein, and any combination thereof. While not essential, the organic reaction medium may include the same materials as the hydrocarbon diluent or solvent. Furthermore, in certain embodiments of this disclosure, the organic reaction medium may include (or consist of, or essentially consist of) cyclohexane.

[0081] The formation of oligomeric products in an oligomerization reactor can be achieved at any suitable oligomerization temperature and pressure. Often, oligomeric products can be formed at the lowest temperatures of 0°C, 20°C, 30°C, 40°C, 45°C, or 50°C, and additionally or alternatively, at the highest temperatures of 165°C, 160°C, 150°C, 140°C, 130°C, 115°C, 100°C, or 90°C. Generally, the oligomerization temperature at which oligomeric products are formed can range from any lowest temperature disclosed herein to any highest temperature disclosed herein. Therefore, suitable non-limiting ranges may include: 0-165, 20-160, 20-115, 40-160, 40-140, 50-150, 50-140, 50-130, 50-100, 60-115, 70-100, or 75-95°C. Other suitable oligomerization temperatures and temperature ranges are readily apparent from this disclosure.

[0082] Oligomer products may be formed at minimum pressures (or ethylene partial pressures) of 50 psig (344 kPa), 100 psig (689 kPa), 200 psig (1.4 MPa), or 250 psig (1.5 MPa), and additionally or alternatively at maximum pressures (or ethylene partial pressures) of 4,000 psig (27.6 MPa), 3,000 psig (20.9 MPa), 2,000 psig (13.8 MPa), or 1,500 psig (10.3 MPa). Generally, the oligomerization pressure (or ethylene partial pressure) at which oligomer products are formed may range from any minimum pressure to any maximum pressure disclosed herein. Therefore, suitable non-limiting ranges may include: 50 psig (344 kPa) to 4,000 psig (27.6 MPa), 100 psig (689 kPa) to 3,000 psig (20.9 MPa), 100 psig (689 kPa) to 2,000 psig (13.8 MPa), 200 psig (1.4 MPa) to 2,000 psig (13.8 MPa), 200 psig (1.4 MPa) to 1,500 psig (10.3 MPa), or 250 psig (1.5 MPa) to 1,500 psig (10.3 MPa). Other suitable oligomerization pressures (or ethylene partial pressures) are readily apparent from this disclosure.

[0083] When used, hydrogen can be supplied directly to the reactor or combined with the ethylene feed before the reactor. In the reactor, the hydrogen partial pressure can be at least 1 psig (6.9 kPa), 5 psig (34 kPa), 10 psig (69 kPa), 25 psig (172 kPa), or 50 psig (345 kPa), and additionally or alternatively, 2000 psig (13.8 MPa), 1750 psig (12.1 MPa), 1500 psig (10.3 MPa), 1250 psig (8.6 MPa), 1000 psig (6.9 MPa), 750 psig (5.2 MPa), 500 psig (3.4 MPa), or 400 psig (2.8 MPa). Generally, the hydrogen partial pressure can range from any minimum hydrogen partial pressure disclosed herein to any maximum hydrogen partial pressure disclosed herein. Therefore, suitable non-limiting ranges for hydrogen partial pressure include the following: 1 psig (6.9 kPa) to 2000 psig (13.8 MPa), 1 psig (6.9 kPa) to 1750 psig (12.1 MPa), 5 psig (34 kPa) to 1500 psig (10.3 MPa), 5 psig (34 kPa) to 1250 psig (8.6 MPa), and 10 psig (69 kPa) to 1000 psig (6.9 MPa). MPa), 10 psig (69 kPa) to 750 psig (5.2 MPa), 10 psig (69 kPa) to 500 psig (3.5 MPa), 25 psig (172 kPa) to 750 psig (5.2 MPa), 25 psig (172 kPa) to 500 psig (3.4 MPa), 25 psig (172 kPa) to 400 psig (2.8 MPa), or 50 psig (345 kPa) to 500 psig (3.4 MPa). Other suitable hydrogen partial pressures in the reactor for the formation of oligomeric products are readily apparent from this disclosure.

[0084] The oligomerization reactor in which the oligomer product is formed may include any suitable reactor. Non-limiting examples of reactor types include stirred-tank reactors, plug-flow reactors, or any combination thereof; alternatively, fixed-bed reactors, continuous stirred-tank reactors, loop reactors, solution reactors, tubular reactors, recirculation reactors, or any combination thereof. In some embodiments, multiple reactors may be present in series or in parallel, including any combination of reactor type and arrangement. Furthermore, the oligomerization process used to form the oligomer product may be a continuous or batch process, or any reactor or tank used in the process may be operated continuously or in batches. [Examples]

[0085] The present invention will be further illustrated by the following embodiments, which should not be construed as limiting the scope of the invention. After reading this description, various other embodiments, modifications, and equivalents thereof can be suggested to those skilled in the art without departing from the spirit of the invention or the appended claims.

[0086] Disclosed below are methods for preparing heteroatomic ligands used in the preparation of heteroatomic ligand transition metal compound complexes and catalyst compositions of Examples 1 to 21. Heteroatomic ligand transition metal compound complexes are prepared by combining heteroatomic ligands with transition metal compounds (e.g., soluble iron sources). Advantageously, by including the disclosed heteroatomic ligand transition metal compound complexes in the catalyst composition, high catalyst productivity and C4-C 26 A catalytic system exhibiting selectivity for oligomer products is provided. Additionally, a method for preparing intermediate compounds necessary for the synthesis of heteroatom ligands is disclosed below.

[0087] 1 1H NMR data and 31For 1P NMR data, the general procedure involved using a Bruker Instrument (e.g., Av400x) and approximately 3–10 mg of each compound dissolved in a suitable NMR solvent (e.g., C6D6 and / or CDCl3).

[0088] Synthesis of intermediate compounds Intermediate C (1-(6-aminopyridine-2-yl)ethane-1-one) was prepared as follows: A solution of 6-aminopicolinonitrile (1 g, 8.4 mmol) in THF (20 mL) was prepared and stirred at 0°C for 15 minutes, and MeMgBr (14 mL, 42.0 mmol) was added dropwise. The reaction mixture was stirred at 25°C for 4 hours, then quenched with NH4Cl and extracted with SiO2. The solution was rinsed with brine and dried over Na2SO4. Volatile substances were removed under vacuum. The compound of intermediate C was obtained as a brown solid, which turned yellow when scraped with a spatula (1.12 g, 96% yield). 1 H NMR (500MHz, CDCl3), δ=7.56(t,J=7.8,1H),7.4(d,J=7.4,1H),6.67(d,J=8.2,1H),4.53(brs,2H),2.63(s,3H). The chemical structure of intermediate C is shown below: [ka]

[0089] Intermediate D (6-(1-mesitylimino)ethyl)pyridine-2-amine) was prepared as follows: In a round-bottom flask, a solution of 1-(6-aminopyridine-2-yl)ethane-1-one (1 g, 7.35 mmol) was added to 2,4,6-trimethylaniline (1.55 mL, 11.017 mmol), p-TsOH (14 mg, 0.073 mmol), and n-butanol (25 mL). The resulting solution was purged with N2 and refluxed for 24 hours using azeotropic removal of water with a Dean-Stark trap. Volatile substances were removed under vacuum. The residue was purified by flash chromatography (hexane to 1% NET3-containing ELISA in a 1:1 ratio) to obtain the compound of intermediate D (0.5505 g, yield 31.8%). 1H NMR(500MHz,CDCl3)δ=7.66(d,J=7.5,1H),7.54(t,J=7.8,1H),6.86(s,2H) ,6.58(d,J=7.7,1H),4.46(brs,2H),2.28(s,3H),2.08(s,3H),1.99(s,6H). The chemical structure of intermediate D is shown below: [ka]

[0090] Intermediate E (6-(1-((2,4-dimethylphenyl)imino)ethyl)pyridine-2-amine) was prepared as follows: In a round-bottom flask, a solution of 1-(6-aminopyridine-2-yl)ethane-1-one (1 g, 7.35 mmol) was added to 2,4-dimethylaniline (1.35 mL, 11.017 mmol), p-TsOH (14 mg, 0.073 mmol), and n-butanol (25 mL). The resulting solution was purged with N2 and refluxed for 24 hours using azeotropic removal of water with a Dean-Stark trap. Volatile substances were removed under vacuum. The residue was purified by flash chromatography (hexane to 1% NEt3-containing SiO5:1) to obtain the compound of intermediate E (117 mg, yield 6.6%). 1 H NMR(500MHz,CDCl3)δ=7.62-7.60(d,J=7.53,1H),7.55-7.52(t,J=7.92,1H),7.02(s,1H),6.59-6. 57(d,J=8.15,1H),6.56-6.54(d,J=7.91,1H),4.45(s,2H),2.31(s,3H),2.18(s,3H),2.06(s,3H). The chemical structure of intermediate E is shown below: [ka]

[0091] Intermediate F (6-(1-((2,4-dimethylphenyl)imino)ethyl)pyridine-2-amine) was prepared as follows: In a round-bottom flask, a solution of 1-(6-aminopyridine-2-yl)ethane-1-one (1 g, 7.35 mmol) was added to 2,6-methylaniline (1.35 mL, 11.017 mmol), p-TsOH (14 mg, 0.073 mmol), and n-butanol (25 mL). The resulting solution was purged with N2 and refluxed for 24 hours using azeotropic removal of water with a Dean-Stark trap. Volatile substances were removed under vacuum, and the residue was purified by flash chromatography (hexane to 1% NET3-containing SiO1) to obtain the compound of intermediate F (0.430 g, 56% yield). 1 H NMR(500MHz,CDCl3),δ=7.68-7.66(d,J=7.88,1H),7.57-7.54(t,J=7.88,1H),7.05-7.03(d,J=6.76 ,1H),6.93-6.90(t,J=7.32,1H),6.61-6.59(d,J=8.45,1H),4.51(s,2H),2.09(s,3H),2.02(s,6H). The chemical structure of intermediate F is shown below: [ka]

[0092] Intermediate G (3-(1-(o-tolylumino)ethyl)aniline) was prepared as follows: In a round-bottom flask, a solution of 1-(6-aminopyridine-2-yl)ethane-1-one (1 g, 7.35 mmol) was added to 2-methylaniline (1.18 g, 11.017 mmol), p-TsOH (14 mg, 0.073 mmol), and n-butanol (25 mL). The resulting solution was purged with N2 and refluxed for 24 hours using azeotropic removal of water with a Dean-Stark trap. Volatile substances were removed under vacuum. The residue was purified by flash chromatography (hexane:1% NET3 with SiO3 ratio) to obtain the compound of intermediate G (0.148 g, yield 9.0%). 1H NMR(500MHz,CDCl3)δ=7.65-7.63(m,1H),7.57-7.53(m,1H),7.39(s,1H),7.36-7.29(m,2H),6.75-6.73(d, J=8.08,1H),6.69-6.67(d,J=8.08,1H),6.60-6.58(d,J=8.08,1H),4.47(s,2H),2.24(s,3H),2.14(s,3H). The chemical structure of intermediate G is shown below: [ka]

[0093] Intermediate H (6-(1-(p-tolylimino)ethyl)pyridine-2-amine) was prepared as follows: In a round-bottom flask, a solution of 1-(6-aminopyridine-2-yl)ethane-1-one (1 g, 7.35 mmol) was added to 4-methylaniline (1.18 g, 11.017 mmol), p-TsOH (14 mg, 0.073 mmol), and n-butanol (25 mL). The resulting solution was purged with N2 and refluxed for 24 hours using azeotropic removal of water with a Dean-Stark trap. Volatile substances were removed under vacuum, and the residue was purified by flash chromatography (hexane:1% NET3 with SiO5:1) to obtain the compound of intermediate H (0.3961 g, yield 23.9%). 1 H NMR(500MHz,CDCl3),δ=7.55-7.51(m,2H),7.16-7.14(d,J=8.65,2H),6.72-6.70( d,J=8.07,2H),6.58-6.56(dt,J=7.00,1H),4.48(s,2H),2.35(s,3H),2.26(s,3H). The chemical structure of intermediate H is shown below: [ka]

[0094] The intermediate compounds I, J, K, L, and M were synthesized via the following reaction pathway: [ka]

[0095] Intermediate I (2-amino-3-bromophenyl)methanol) was prepared as follows: A solution of 2-amino-3-bromobenzoic acid (3 g, 13.9 mmol, 1 equivalent) in THF (12.5 mL) was prepared and stirred at 0°C. BH3THF (1.0 M in THF) (20.8 mL, 1.5 equivalents) was added dropwise to the solution and refluxed for 16 hours. The mixture was filtered and volatile substances were removed under vacuum. The product was purified by flash column chromatography (petroleum ether:ethyl acetate 1:1) to obtain the compound of intermediate I as a white solid (1.9 g, yield 69%). 1 H NMR (500MHz, CDCl3), δ=7.41-7.39(dd,J=1.5,8.1,1H),7.05-7.00(d,J=7.5,1H),6.59-6.55(t,J=7.8,1H),4.73(brs,2H),4.69(s,2H).

[0096] Intermediate J (2-amino-3-bromobenzaldehyde) was prepared as follows: MnO2 (1.05 g, 12 mmol, 4 equivalents) was added to a solution of intermediate I (2-amino-3-bromophenyl)methanol (610 mg, 3 mmol, 1 equivalent) in CH2Cl2 (15.3 mL), and the mixture was stirred at room temperature for 24 hours. The reaction mixture was filtered, and volatile substances were removed under vacuum to obtain the compound of intermediate J (0.572 g, 95% yield). 1 H NMR (500MHz, CDCl3), δ=9.83(s,1H),7.63-7.61(dd,J=1.4,7.9,1H),7.49-7.47(dd,J=1.2,7.7,1H),6.69-6.22(t,J=7.8,1H),6.67(brs,2H).

[0097] Intermediate K (5-bromo-3,3-dimethyl-1,2,3,4-tetrahydroacridin) was prepared as follows: A solution of intermediate J (2-amino-3-bromobenzaldehyde) (1.35 g, 6.8 mmol, 1 equivalent) was added to 3,3-dimethylcyclohexane-1-one (1 g, 8.1 mmol, 1.2 equivalents), KOtBu (1.8 g, 16 mmol, 2.4 equivalents), and 1,4-dioxane (34 mL), and refluxed for 1 hour. The reaction mixture was concentrated, rinsed with Et2O, and filtered. Purification by column chromatography (hexane:SiO10:1) yielded the compound of intermediate K as a yellow solid (1.8 g, 91% yield). 1 H NMR(500MHz,CDCl3),δ=7.95-7.93(dd,J=1.1,7.5,1H),7.84(s,1H),7.69-7.67(d,J=8.2,1H),7.29 -7.26(t,J=7.9,1H),3.06-3.03(t,J=6.9,2H),3.00(s,2H),1.71-1.69(t,J=6.9,2H),1.08(s,6H).

[0098] Intermediate L (5-bromo-3,3-dimethyl-2,3-dihydroacridine-4(1H)-one) was prepared as follows: Under an inert atmosphere, diisopropylamine (0.58 mL, 4.3 mmol, 2.5 equivalents) was cooled to -15°C, and n-butyllithium (1.38 mL, 3.4 mmol, 2 equivalents) was added dropwise. The reaction mixture was stirred for 15 minutes, and then THF (10 mL) was added. The reaction mixture was warmed to room temperature and stirred for 1 hour. The reaction mixture was then cooled to -15°C, and a solution of intermediate K (5-bromo-3,3-dimethyl-1,2,3,4-tetrahydroacridine) (0.500 g, 1.7 mmol, 1 equivalent) in THF (15 mL) was slowly added. The reaction mixture was stirred at room temperature for 3 hours. Next, the reaction mixture was cooled to -15°C, and isoamyl nitrate (2.3 mL, 11.7 mmol, 10 equivalents) was added. The mixture was stirred at room temperature for 4 hours. The reaction mixture was quenched with H2O, extracted by DCM, then concentrated, and HCl (18 mL) was added. The mixture was refluxed overnight. The mixture was neutralized with NaOH solution. The reaction mixture was extracted by DCM. Volatile substances were removed under vacuum, and the mixture was purified by column chromatography (3:1 PE:siRNA) to obtain compound intermediate L (0.315 g, 60% yield). 1 H NMR(500MHz,CDCl3),δ=8.11(s,1H),8.07-8.05(dd,J=1.0,7.5,1H),7.77-7.76(d,J=8.5,1H ),7.46-7.42(t,J=8.0,1H),3.25-3.22(t,J=6.6,2H),2.12-2.10(t,J=6.5,2H),1.34(s,6H).

[0099] Intermediate M((E)-5-bromo-N-mesityl-3,3-dimethyl-2,3-dihydroacridine-4(1H)-imine) was prepared as follows: A solution of intermediate L(5-bromo-3,3-dimethyl-2,3-dihydroacridine-4(1H)-one) (300 mg, 0.98 mmol, 1 equivalent) in CH2Cl2 (10 mL) was prepared and distilled. TiCl4 (0.11 mL, 0.98 mmol, 1 equivalent) was added to the solution at 0°C and stirred for 10 minutes. At 0°C, 2,4,6-trimethylaniline (0.300 g, 0.98 mmol, 1 equivalent) was added to the solution (0.98 mmol, 1 equivalent) and stirred for 10 minutes, followed by the addition of triethylamine (0.1 mL). The reaction mixture was warmed to room temperature and stirred overnight. The reaction mixture was quenched with NH4Cl, extracted with DCM, and washed with brine. Volatile substances were then removed under vacuum. The product was then purified by flash chromatography (petroleum ether:ethyl acetate, 50:1) to obtain the intermediate M compound (0.294 g, 71% yield). 1 H NMR(500MHz,CDCl3),δ7.93(s,1H),7.81-7.79(d,J=7.5,1H),7.62-7.60(dd,J=1.0,8.3,1H),7.26-7.24(t,J=7 .7,1H),6.71(s,2H),3.14-3.11(t,J=6.6,2H),2.20(s,3H),2.08-2.06(t,J=6.6,2H),1.87(s,6H),1.45(s,6H).

[0100] The intermediate N(1-(8-bromo-2-quinolinyl)ethenone) was prepared as follows: Under an inert atmosphere, 15 mL of dry, deoxygenated THF was placed in a 250 mL Schlenk flask, followed by 4.6 mL, 47 mmol, 4.0 equivalents of ethyl vinyl ether. The solution was cooled to -40°C, and n-BuLi (2.5 M in hexane, 9.5 mL, 23.7 mmol, 2 equivalents) was added dropwise. After the addition was complete, the reaction mixture was warmed to room temperature over 15 minutes and stirred at room temperature for 1 hour. The Schlenk flask was then cooled to -40°C, and dry ZnBr2 (0.5 M in THF, 47 mL, 23.7 mmol, 2.0 equivalents) was added. The reaction mixture was warmed to room temperature over 15 minutes and stirred at room temperature for a further 15 minutes. Pd2dba3 (123 mg, 0.107 mmol, 0.9 mol%) and triphenylphosphine (118 mg, 0.450 mmol, 3.8 mol%) were dissolved in dried and deoxygenated THF (15 mL) and added to the reaction mixture at room temperature for 15 minutes. Then, a solution of 2,8-dibromoquinoline (3.40 g, 11.9 mmol, 1.0 equivalent) in dried and deoxygenated THF (15 mL) was added at room temperature and the mixture was stirred for 16 hours. The reaction mixture was heated to 65°C for 4 hours. Then, aqueous HCl (1 M, 25 mL) was added and the reaction mixture was stirred at 65°C for a further 4 hours. The reaction mixture was cooled to room temperature and quenched by adding saturated aqueous NaHCO3 (5 mL), water (15 mL), and tert-butyl methyl ether (TBME) (2 × 25 mL). The organic layer was collected and the aqueous layer was extracted with TBME (2 × 25 mL). The combined organic layers were dried over MgSO4 and concentrated under reduced pressure. The brown residue was purified by column chromatography (SiO2, eluent: toluene; the third spot on the TLC plate corresponds to the product) to obtain the intermediate N compound as a yellowish-brown solid (1.34 g, yield 45%). 1 ¹H NMR (400 mHz, CDCl3): 8.24(d,1H), 8.14(d,1H), 8.09(d,1H), 7.81(d,1H), 7.47(t,1H), 2.94(s,3H). The chemical structure of intermediate N is shown below: [ka]

[0101] Alternatively, the compound of intermediate N can be synthesized using the compounds of intermediates O and P, as described below.

[0102] Intermediate O (8-bromo-2-quinoline carboxaldehyde) was prepared as follows: A solution of 8-bromo-2-methylquinoline (0.16 mol) was added to a hot solution of selenium dioxide (0.9 mol) in dioxane. The reaction mixture was heated under reflux for 5 hours and then hot-filtered. The solvent was removed under vacuum, and the mixture was purified by column chromatography (dichloromethane) to obtain the compound of intermediate O as a pale yellow solid (yield 93%). The chemical structure of intermediate O is shown below: [ka]

[0103] Intermediate P (8-bromo-α-methyl-2-quinoline methanol) was prepared as follows. A solution of intermediate O (8-bromo-2-quinoline carboxaldehyde) (10.0 mmol, 1.0 equivalent) in THF (100 mL, 0.1 M) was added to an oven-dried 250 mL round-bottom flask under N2 conditions. The mixture was cooled to 0°C in an ice bath, and methylmagnesium bromide (10 mL, 2 M solution in THF, 20.0 mmol, 2.0 equivalents) was added dropwise. The reaction mixture was stirred at 0°C for 1 hour, then warmed to room temperature and stirred for 3 hours. The reaction mixture was then cooled to 0°C and quenched by adding saturated ammonium chloride solution (40 mL) and brine (100 mL). The aqueous phase was extracted with ethyl acetate (100 mL x 2), the organic phase was combined, and the mixture was dried over anhydrous sodium sulfate. The organic fraction was filtered, and volatile substances were removed under vacuum. The product was purified by flash column chromatography (silica gel, PE / siRNA = 8:1 to 5:1) to obtain the intermediate P compound as a pale yellow solid (yield 87% to 98%). The chemical structure of intermediate P is shown below: [ka]

[0104] Alternatively, intermediate N (1-(8-bromo-2-quinolinyl)ethenone) was prepared as follows: A solution of intermediate P (8-bromo-α-methyl-2-quinoline methanol) (4.0 mmol, 1.0 equivalent) and MnO2 (2.09 g, 24.0 mmol, 6.0 equivalents) in toluene (40 mL) was added to an oven-dried 100 mL round-bottom flask. The reaction mixture was stirred at room temperature for 20 hours. The reaction mixture was then filtered and rinsed with ethyl acetate (30 mL x 2). The organic phases were combined, and volatile substances were removed under vacuum. The product was purified by flash column chromatography (silica gel, PE / siRNA = 8:1) to obtain the compound of intermediate N as a pale yellow solid (yield 90%~95%). The chemical structure of intermediate N is shown below: [ka]

[0105] Characterization data for intermediate compounds N, O, and P can be found, for example, in Yang, X., Shan, G., Rao, Y., Synthesis of 2-Aminophenols and Heterocycles by Ru-Catalyzed CH Mono- and Dihydroxylation, Organic Letters. 2013,15(10),2334-2337;Sun, H.-R., Zhao, Q., Yang, H., Yang, S., Gou, B.-B., Chen, J., Zhou, L., Chiral Phosphoric-Acid-Catalyzed Cascade Prins Cyclization,Organic Letters 2019, 21(17), 7143-7148; and Nagy, S., Nifantev, LE, Neal-Hawkins, KL, Mihan, S., Catalyst system based on quinoline. The term "donors" can be found in U.S. Patent Publication 2013 / 0023634.

[0106] The compounds of intermediates Q, R, and S can be synthesized using the compound of intermediate N, as described below.

[0107] Intermediate Q ((E)-N-(1-8-bromoquinoline-2-yl)ethylidene)-2,4,6-trimethylaniline) was prepared as follows: A solution of 2,4,6-trimethylaniline (1.04 mL, 7.39 mmol) and intermediate N 1-(8-bromoquinoline-2-yl)ethenone (1.54 g, 6.16 mmol) was added to a 25 mL flask in toluene (10 mL). 4-methylbenzenesulfonic acid (53 mg, 0.308 mmol) was added, and the mixture was refluxed under Dean-Stark conditions for 16 hours. Complete conversion of the starting materials was confirmed by TLC analysis (SiO2, eluent: toluene). The reaction solution was cooled to room temperature and filtered through silica packing while eluting with toluene (until no more yellow elution occurred). The solvent was removed under reduced pressure, and the compound of intermediate Q was obtained as a yellow-orange solid (2.35 g, 99% yield). The chemical structure of intermediate Q is shown below: [ka]

[0108] Intermediate R (1-(8-(dicyclohexylphosphino)-2-quinolinyl)ethenone) was prepared as follows: Under an inert atmosphere, diacetoxypalladium (0.056 g, 0.249 mmol, 7.5 mol%), 1,1'-bis(diisopropylphosphino)ferrocene (DiPPF, 0.126 g, 0.227 mmol, 9 mol%), sodium tert-butoxide (0.385 g, 4.00 mmol, 1.2 equivalents), and intermediate N (1.07 g, 4.27 mmol, 1 equivalent) were added to a 100 mL flask, followed by the addition of toluene (4 mL, 0.1 M). Dicyclohexylphosphine (0.583 mL, 2.285 mmol, 1.05 equivalents) was added by syringe, and the mixture was stirred at 110 °C for 24 hours. The reaction was monitored by TCL (SiO2, toluene). After cooling to room temperature, 10 mL of degassed saturated NaHCO3 aqueous solution was added and extracted. The organic layer was concentrated under reduced pressure to obtain a black residue. Purification was performed with CC (neutral alumina, toluene / heptane 2:1) and 20 g of alumina. Fractions 4-11 were recovered to obtain the compound of intermediate R as a red oil (0.814 g, yield 55%). The chemical structure of intermediate R is shown below: [ka]

[0109] Intermediate S (1-(8-(diphenylphosphino)-2-quinolinyl)ethenone) was prepared as follows: Under an inert atmosphere, diacetoxypalladium (0.056 g, 0.249 mmol, 7.5 mol%), 1,1'-bis(diisopropylphosphino)ferrocene (DiPPF, 0.126 g, 0.277 mmol, 9 mol%), sodium tert-butoxide (0.385 g, 4.00 mmol, 1.2 equivalents), and intermediate N (1.07 g, 4.27 mmol, 1 equivalent) were added to a 100 mL flask, followed by the addition of toluene (4 mL, 0.1 M). Diphenylphosphine (0.583 mL, 3.07 mmol, 1.05 equivalents) was added by syringe, and the mixture was stirred at 110 °C for 24 hours. The reaction was monitored by TCL (SiO2, toluene). After cooling to room temperature, 10 mL of degassed saturated NaHCO3 aqueous solution was added and extracted. The organic layer was concentrated under reduced pressure to obtain a black residue. Purification with CC (neutral alumina, toluene / heptane 2:1) and 20 g of alumina yielded the compound of intermediate S as a brown solid (0.318 g, yield 45%). The chemical structure of intermediate S is shown below: [ka]

[0110] Synthesis of heteroatom ligand compounds The following heteroatom ligand compounds were synthesized according to the following procedure.

[0111] Ligand 1((E)-N-(1-8-(diphenylphosphino)-2-yl)ethylidene)-2,4,6-trimethylaniline) was prepared as follows: Under an inert atmosphere, diacetoxypalladium (0.056 g, 0.251 mmol, 7.5 mol%), 1,1'-1,1'-bis(diisopropylphosphino)ferrocene (DiPPF, 0.126 g, 0.301 mmol), sodium tert-butoxide (0.385 g, 4.02 mmol), and intermediate Q (1.23 g, 3.35 mmol) were placed in a 100 mL flask, followed by the addition of toluene (34 mL). Diphenylphosphine (0.583 mL, 3.35 mmol) was added by syringe, and the mixture was stirred at 110 °C for 24 hours. The reaction mixture was filtered through Celite packing, eluted with toluene (2 × 20 mL), and the filtrate was concentrated under reduced pressure. The residue was further purified by column chromatography (neutral alox, heptane to 3:1 heptane / toluene) to obtain the desired ligand 1 product as a yellow solid (1.13 g, yield 71%). The chemical structure of ligand 1 is shown in Table 1 below.

[0112] Ligand 2((E)-N-(1-8-(diisobutylphosphino)-2-yl)ethylidene)-2,4,6-trimethylaniline) was prepared as follows: Under an inert atmosphere, diacetoxypalladium (7.5 mol%), 1,1'-bis(diisopropylphosphino)ferrocene (DiPPF, 9 mol%), sodium tert-butoxide (1.2 equivalents), and intermediate Q (1 g, 3.35 mmol, 1.0 equivalent) were placed in a 100 mL flask, followed by the addition of toluene (18 mL, 0.15 M). Diisobutylphosphine (1.1 equivalents) was added by syringe, and the mixture was stirred at 110 °C for 16 hours. The reaction mixture was filtered through Celite and concentrated under reduced pressure. The crude product was purified by column chromatography (neutral alumina, 20 g; 2:1 hept / tol) to remove DiPPF impurities, and then quinoline impurities were removed by a second column chromatography (silica, 20 g; 20:1 hept / siRNA) to obtain the desired ligand 2 product (0.447 g, yield 38%, purity 97%). The chemical structure of ligand 2 is shown in Table 1 below.

[0113] Ligand 3((E)-N-(1-8-(diisopropylphosphino)-2-yl)ethylidene)-2,4,6-trimethylaniline) was prepared as follows: Under an inert atmosphere, diacetoxypalladium (7.5 mol%), 1,1'-bis(diisopropylphosphino)ferrocene (DiPPF, 9 mol%), sodium tert-butoxide (1.2 equivalents), and intermediate Q (0.863 g, 1.0 equivalent) were placed in a 100 mL flask, followed by the addition of toluene (16 mL, 0.15 M). Diisopropylphosphine (1.1 equivalents) was added by syringe, and the mixture was stirred at 110 °C for 16 hours. The reaction mixture was filtered through Celite and concentrated under reduced pressure. The crude product was purified by column chromatography (silica, 20 g; 20:1 hept / ethyl). The product and impurities were analyzed. f Due to the similarity of the values, separation was difficult. Under these conditions, a fraction free of quinoline-derived impurities was obtained, but DiPPF co-eluted with the desired product (350 mg). To remove the DiPPF impurity, the obtained material was subjected to column chromatography (20 g neutral alumina, 2:1 hept / tol). This yielded the desired ligand 3 product (0.249 g, 26% yield, and 91% purity). The chemical structure of ligand 3 is shown in Table 1 below.

[0114] Ligand 4((E)-N-(1-8-(dicyclohexylphosphino)-2-yl)ethylidene)-2,4,6-trimethylaniline) was prepared as follows: Under an inert atmosphere, diacetoxypalladium (5 mol%), 1,1'-bis(diisopropylphosphino)ferrocene (DiPPF, 6 mol%), sodium tert-butoxide (1.2 equivalents), and intermediate Q (0.549 g, 1 equivalent) were placed in a 100 mL flask, followed by the addition of toluene (10 mL, 0.13 M). Dicyclohexylphosphine (1.05 equivalents) was added by syringe, and the mixture was stirred at 110 °C for 16 hours. By filtration through Celite and subsequent removal of the solvent, a crude product containing 10% unidentified by-products was obtained (no starting materials were present in the mixture). The crude product was purified by column chromatography (neutral alumina, 2:1 hept / tol). While this chromatography method successfully removed DiPPF impurities, quinoline-derived impurities remained. It was found that using completely dried silica gel as the steady-state phase and heptane / siRNA (20:1) as the mobile phase allowed for the removal of the remaining 10% of impurities. This yielded the desired ligand 4 product (0.324 g, 49% yield, and 99% purity). The chemical structure of ligand 4 is shown in Table 1 below.

[0115] Ligand 5 ((E)-N-(1-8-(diphenylphosphino)-2-yl)ethylidene)-2,4-trimethylaniline) was prepared as follows: Under an inert atmosphere, intermediate S (0.1000 g, 0.281 mmol, 1.0 equivalent) was added to a solution of 2,4-dimethylaniline (0.04 mL, 0.338 mmol, 1.2 equivalents) in anhydrous toluene, and molecular sieves (4 Å, 400 mg) and silica-alumina catalyst support (100 mg) were added to the reaction mixture. The reaction mixture was stirred at 50°C for 20 hours. After cooling to room temperature, the mixture was filtered and washed with degassed toluene (2 × 2 mL). The solvent was removed under reduced pressure to obtain the desired ligand 5 product as a red solid (220 mg, yield 82%). The orange solid was dissolved in anhydrous methanol, the product was crushed overnight in a freezer, and the precipitate was collected by filtration to obtain a more purified final product. The chemical structure of ligand 5 is shown in Table 1 below.

[0116] Ligand 6 ((E)-N-(1-8-(diphenylphosphino)-2-yl)ethylidene)-4-trimethylaniline) was prepared as follows. Under an inert atmosphere, intermediate S (0.2860 g, 0.805 mmol, 1.0 equivalent) was added to a solution of 4-methylaniline (0.11 mL, 0.965 mmol, 1.2 equivalents) in anhydrous toluene, and molecular sieves (4 Å, 200 mg) and silica-alumina catalyst support (50 mg) were added to the reaction mixture. The reaction mixture was stirred at 50°C for 20 hours. After cooling to room temperature, the mixture was filtered and washed with degassed toluene (2 × 2 mL). The solvent was removed under reduced pressure to obtain the desired ligand 6 product as a yellow solid (0.108 g, yield 86%). The chemical structure of ligand 6 is shown in Table 1 below.

[0117] Ligand 6-Fe was prepared as follows: Experiments to investigate the feasibility of template imine condensation to 6-Fe to avoid purification by column chromatography of the unstable PIQ ligand. A 15 mL vial containing p-toluidine (30.2 mg, 0.281 mmol, 1.05 equivalents), ligand 6 (100 mg, 0.281 mmol, 1.05 equivalents), and iron(II) chloride (34.0 mg, 0.268 mmol, 1.0 equivalent) was inactivated. Degassed isopropyl alcohol (3.4 mL) was added, and the reaction was stirred at 50 °C for 24 hours. The deep blue mixture was cooled to room temperature, filtered, and washed with iPrOAc (3 × 1 mL). The wet solid was dried under reduced pressure to obtain the desired ligand 6-Fe product (Fe4C-1) as a deep blue solid (128 mg, yield 84%). Elemental analysis: C, 63.08; H, 4.41; Cl, ​​12.41; Fe, 9.78; N, 4.90; P, 5.42. The chemical structure of ligand 6-Fe is shown in Table 1 below.

[0118] Ligand 7 ((E)-N-(1-8-(dicyclohexylphosphino)-2-yl)ethylidene)-2,4-trimethylaniline) was prepared as follows. Under an inert atmosphere, intermediate R (0.2000 g, 0.544 mmol, 1.0 equivalent) was added to a solution of 2,4-dimethylaniline (0.08 mL, 0.653 mmol, 1.2 equivalents) in anhydrous toluene, and molecular sieves (4 Å, 400 mg) and silica-alumina catalyst support (100 mg) were added to the reaction mixture. The reaction mixture was stirred at 50°C for 20 hours. After cooling to room temperature, the mixture was filtered and washed with degassed toluene (2 × 2 mL). The solvent was removed under reduced pressure to obtain the desired ligand 7 product as a red solid (0.327 g, yield 89%). The chemical structure of ligand 7 is shown in Table 1 below.

[0119] Ligand 8 ((E)-N-(1-8-(dicyclohexylphosphino)-2-yl)ethylidene)-4-trimethylaniline) was prepared as follows. Under an inert atmosphere, intermediate R (0.2000 g, 0.544 mmol, 1.0 equivalent) was added to a solution of 4-methylaniline (0.07 mL, 0.652 mmol, 1.2 equivalents) in anhydrous toluene, and molecular sieves (4 Å, 400 mg) and silica-alumina catalyst support (100 mg) were added to the reaction mixture. The reaction mixture was stirred at 50°C for 20 hours. After cooling to room temperature, the mixture was filtered and washed with degassed toluene (2 × 2 mL). The solvent was removed under reduced pressure to obtain the desired ligand 8 product as a yellow solid (0.208 g, yield 78%). The chemical structure of ligand 8 is shown in Table 1 below.

[0120] Ligands 9-22 were synthesized using the same techniques as those described above for ligands 1-8. The chemical structures of ligands 9-22 are shown in Table 1 below to confirm their structures. 1 The 1H NMR plots are shown in Figures 1-14. Similarly, ligands 23-25 ​​were synthesized using the same techniques as those described above for ligands 1-8. The chemical structures of ligands 23-25 ​​are shown in Table 1 below to confirm their structures. 1 The 1H NMR plots are shown in Figures 15-16, 17-18, and 19-20, respectively. Ligand 26 in Table 1 was prepared in the same manner as ligands 27-31 described below.

[0121] Ligand 27 (1,1-diphenyl-N-(3-(1-(o-trilyimino)ethyl)phenyl)phosphanamine) was prepared as follows: In a glove box, intermediate G (148 mg, 0.66 mmol) was dissolved in 3 mL of THF (0.2 M), degassed NEt3 (0.11 mL, 0.79 mmol, 1.2 equivalents) was added, followed by chlorodiphenylphosphine (0.13 mL, 0.73 mmol, 1.1 equivalents). The reaction mixture was stirred at room temperature for 16 hours. Following filtration, the solvent was removed under vacuum to obtain the desired ligand 27 product as a yellow oil (214.0 mg, 80% yield). 1H NMR(500MHz,CDCl3),δ=7.81-7.78(m,2H),7.73-7.70(m,1H),7.60-7.58(m,2H),7.50-7.49(m,5H),7.38(m,6H),7.03- 7.01(d,J=7.99,1H),6.84-6.82(d,J=8.52,1H),6.61-6.57(m,2H),5.28-5.26(d,J=9.031H),1.85(s,3H),1.55(s,3H); 31 1P NMR (202 MHz, CDCl3), δ 59.9, 27.2. The chemical structure of ligand 27 is shown in Table 1 below.

[0122] Ligand 28 (N-(3-(1-((2,4-dimethylphenyl)imino)ethyl)phenyl)-1,1-diphenylphosphanamine) was prepared as follows: In a glove box, intermediate E (148 mg, 0.66 mmol) was dissolved in 3 mL of THF (0.2 M), degassed NEt3 (0.11 mL, 0.79 mmol, 1.2 equivalents) was added, followed by chlorodiphenylphosphine (0.13 mL, 0.73 mmol, 1.1 equivalents). The reaction mixture was stirred at room temperature for 16 hours. Following filtration, the solvent was removed under vacuum to obtain the desired ligand 28 product as a yellow oil (0.214 g, 80% yield). 1 H NMR(500MHz,CDCl3),δ=7.70-7.68(d,J=6.91,1H),7.60-7.57(t,J=8.24,2H),7.51-7.48(m,5H),7.39-7.37(m,6H),7.09-7.07(d,J=8.46, 1H),7.01(s,1H),6.97-6.95(d,J=7.62,1H),6.54-6.52(d,J=8.04,1 H),5.26-5.24(d,J=8.73,1H),2.30(s,3H),2.13(s,3H),2.05(s,3H); 31 1P NMR (202 MHz, CDCl3), δ 59.9, 27.1. The chemical structure of ligand 28 is shown in Table 1 below.

[0123] Ligand 29 (N-(3-(1-(mesitylimino)ethyl)phenyl)-1,1-diphenylphosphanamine) was prepared as follows: In a glove box, intermediate D (250 mg, 0.987 mmol) was dissolved in 5 mL of THF (0.2 M), degassed NEt3 (0.16 mL, 1.18 mmol, 1.2 equivalents) was added, followed by chlorodiphenylphosphine (0.19 mL, 1.09 mmol, 1.1 equivalents). The reaction mixture was stirred at room temperature for 16 hours. Following filtration, the solvent was removed under vacuum to obtain the desired ligand 29 product as an orange-yellow oil (0.368 g, 85% yield). 1 H NMR(500MHz,CDCl3),δ=7.75-7.73(d,J=7.6,1H),7.61-7.58(t,J=8.14,1H),7.50(m,5H),7.38-7.37(m,6H) ,7.11-7.09(d,J=8.14,1H),6.85(s,2H),5.28-5.26(d,J=7.25,1H),2.27(s,3H),2.02(s,3H),1.97(s,6H); 31 1P NMR (202 MHz, CDCl3), δ 60.6, 27.1. The chemical structure of ligand 29 is shown in Table 1 below.

[0124] Ligand 30 (N-(3-(1-((2,6-dimethylphenyl)imino)ethyl)phenyl)-1,1-diphenylphosphanamine) was prepared as follows: In a glove box, intermediate F (250 mg, 1.05 mmol) was dissolved in 5.3 mL of THF, degassed NEt3 (0.17 mL, 1.25 mmol, 1.2 equivalents) was added, followed by chlorodiphenylphosphine (0.21 mL, 1.15 mmol, 1.1 equivalents). The reaction mixture was stirred at room temperature for 16 hours. After filtration, the solvent was removed under vacuum to obtain the desired ligand 30 product as a yellow oil (0.400 g, yield 44.4%). 1H NMR(500MHz,CDCl3),δ7.78-7.76(d,J=5.5,1H),7.62-7.59(t,J=7.9,1H),7.50-7.48(m,6H),7.39-7.36(m,4H),7.04-7.02(d,J =7.5,2H),7.00-6.98(d,J=7.5,1H),6.92-6.89(t,J=7.4,1H),5.28-5.26(d,J=7.5,1H),2.03(s,3H),2.01(s,3H),1.93(s,1H); 31 3P NMR (202 MHz, CDCl3), δ 60.63, 27.14. The chemical structure of ligand 30 is shown in Table 1 below.

[0125] Ligand 31 (1,1-diphenyl-N-(3-(1-(p-trilyimino)ethyl)phenyl)phosphanamine) was prepared as follows: In a glove box, intermediate H (250 mg, 1.11 mmol) was dissolved in 5.6 mL of THF, degassed NEt3 (0.19 mL, 1.33 mmol, 1.2 equivalents) was added, followed by chlorodiphenylphosphine (0.22 mL, 1.22 mmol, 1.1 equivalents). The reaction mixture was stirred at room temperature for 16 hours. After filtration, the solvent was removed under vacuum to obtain the desired ligand 31 product as a yellow oil (0.349 g, yield 64%). 1 H NMR(500MHz,CDCl3),δ=7.63-7.61(d,J=8.55,1H),7.59-7.56(t,J=7.48,1H),7.49-7.48(m,5H),7.38-7.37(m,6H),7. 15-7.13(d,J=8.0,2H),6.70-6.68(d,J=8.2,2H),6.63-6.61(d,J=8.2,1H),5.29(brs,1H),2.34(s,3H),2.19(s,3H),; 31 1P NMR (202 MHz, CDCl3), δ 59.82, 27.24. The chemical structure of ligand 31 is shown in Table 1 below.

[0126] Ligand 34((E)-5-((3,5-dimethylphenyl)thio-N-mesityl-3,3-dimethyl-2,3-dihydroacridine-4(1H)-imine) was prepared as follows: In a glove box, intermediate M((E)-5-bromo-N-mesityl-3,3-dimethyl-2,3-dihydroacridine-4(1H)-imine) (100 mg, 0.25 mmol, 1 equivalent), Pd(OAc)2 (2.9 mg, 5 mol%), DiPPF (8.5 mg, 6 mol%) ), NaOtBu (29.4 mg, 0.3 mmol, 1.2 equivalents), and toluene (2.5 mL) were combined and stirred at room temperature for 1 hour. Then, 3,5-dimethylthiophenyl (35.2 mg, 0.25 mmol, 1 equivalent) was added to the reaction solution and stirred at 120°C for 24 hours. The solvent was removed under vacuum and the mixture was purified by flash chromatography (hexane:siRNA5:1) to obtain the desired ligand 34 product as a deep red solid (0.096 g, yield 81%). 1 H NMR(500MHz,CDCl3),δ=7.88(s,1H),7.32-7.30(d,J=8.1,1H),7.16-7.13(t,J=7.6,1H),7.12(s,2H),7.05(s,1H),6.75(s,2H),6.7 0-6.69(dd,J=7.5,1.2,1H),3.12-3.09(t,J=6.7,2H),2.36(s,6H),2.23(s,3H),2.08-2.05(t,J=6.7,2H),1.90(s,6H),1.46(s,6H). The chemical structure of ligand 34 is shown below: [ka]

[0127] [Table 1] JPEG2026515813000023.jpg181162JPEG2026515813000024.jpg178162JPEG2026515813000025.jpg142162

[0128] Examples 1-21 The oligomerization experiments for Examples 1-21 were carried out as follows. The heteroatom ligands prepared above and shown in Table 1, along with an excess amount of a typical soluble iron source (transition metal compound), were combined in a small amount of aromatic or aliphatic hydrocarbon solvent, such as toluene, xylene, or cyclohexane, and added to a sealed NMR tube. This was then mounted on the impeller shaft of a high-pressure autoclave according to the procedure described in Organometallics 2003, 22, 3178 (Small). Cyclohexane solvent (200 mL) and MMAO-3A (modified MAO) were placed in a sealed, evacuated autoclave, the reactor was pressurized with ethylene (in the range of 400-800 psig), stirring was started, and the glass was broken to initiate the reaction. Initial reaction temperature (T initial ) and maximum temperature (T max The results are shown in Table 2. The reaction was terminated by supplying ethylene as needed and degassing after 15 minutes. The products were analyzed by gas chromatography using an internal standard.

[0129] Table 2 summarizes the ethylene oligomerization experiments in Examples 1-21. The yield of the volatile product (i.e., C4) was extrapolated using the Schultz-Flory constant K, and the total yield and productivity were calculated as C4-C 26 Based on the product. In some cases, the Schultz-Flory constant is known to typically drift upward with increasing carbon number. Therefore, extrapolation to calculate the K value for C6 / C4 was based on the rate of change of three prior fraction measurements. For example, C 12 / C 10 , C 10 If the K values ​​for / C8 and C8 / C6 are 0.52, 0.50, and 0.48, respectively, the extrapolated K value for calculating the amount of 1-butene formed would be 0.46.

[0130] As shown in Table 2, some examples unexpectedly show K(nC) below 0.5. 12 / nC 10 ) and K(nC 10 It had a molar value of / nC8). Furthermore, it had more than 20g of C4~C 26Product yields were also achieved, with catalytic productivity in the range of 10,000–60,000 g / mmol ligands. The K value of Example 16 (using ligand 14) was very high (above 0.8–0.9), which typically indicates the formation of oligomers or polymers with a very high degree of polymerization. In contrast, the K value of Example 14 (using ligand 12) was very low (less than 0.2), which typically indicates the selectivity of dimerization for the formation of 1-butene. For the formation of 1-hexene and 1-octene, K values ​​in the range of 0.4–0.6 are usually most suitable. Fortunately, some and several different ligands in Examples 1–21, such as Examples 6, 9, 11–13, and 17–21, had K values ​​within this general range. [Table 2] JPEG2026515813000027.jpg224162JPEG2026515813000028.jpg216162JPEG2026515813000029.jpg91162

[0131] The present invention is described herein with reference to numerous embodiments and specific examples. In view of the detailed description, many variations are suggested to those skilled in the art. All such obvious variations are within the fully intended scope of the appended claims. Other embodiments of the present invention may include, but are not limited to, the following (an embodiment is described as "including," but can instead be described as "essentially consisting of" or "consisting of").

[0132] Appearance 1. Heteroatom ligand transition metal compound complex having the following formula: [ka] [In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. M is Fe, Co, or Cr. m is the oxidation state of M, Each Z independently corresponds to H, halogen, C1~C 18Hydrocarbyl group or C1-C 18 It is a halogenated hydrocarbyl group, R 1 ~R 11 These are independently H, halogen, nitro group, C1-C 18 Hydrocarbyl group, or C1-C 18 It is a halogenated hydrocarbyl group, R 5 and R 6 They can combine to form a ring or ring system. Each R 12 These are, independently, C1~C 18 Hydrocarbyl group or C1-C 18 It is a halogenated hydrocarbyl group.

[0133] Embodiment 2. A complex as defined in Embodiment 1, wherein M is Fe.

[0134] Embodiment 3. A complex as defined in Embodiment 1 or 2, wherein each Z is Cl.

[0135] Applicable aspect 4. Heteroatom ligands (compounds) having the following formula: [ka] [In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. R 1 ~R 11 These are independently H, halogen, nitro group, C1-C 18 Hydrocarbyl group, or C1-C 18 It is a halogenated hydrocarbyl group, R 5 and R 6 They can combine to form a ring or ring system. Each R 12 These are, independently, C1~C 18 Hydrocarbyl group or C1-C 18 It is a halogenated hydrocarbyl group.

[0136] Embodiment 5. A complex or ligand defined in any one of Embodiments 1 to 4, wherein X is P and y is equal to 2.

[0137] Embodiment 6. A complex or ligand defined in any one of Embodiments 1 to 4, wherein X is S and y is equal to 1.

[0138] Appearance 7.R 1 ~R 6 A complex or ligand defined in any one of embodiments 1 to 6, wherein the compound is independently an H or a methyl group.

[0139] Appearance 8.R 5 and R 6 A complex or ligand defined in any one of embodiments 1 to 7, which is bonded to form a ring or ring system.

[0140] Appearance 9.R 7 ~R 11 A complex or ligand defined in any one of embodiments 1 to 8, wherein the group is independently H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a naphthyl group, a benzyl group, a nitro group, a pentafluorophenyl group, or a trifluoromethyl group (CF3).

[0141] Appearance 10.R 7 ~R 11 A complex or ligand defined in any one of embodiments 1 to 8, wherein the group is independently H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a cyclohexyl group, an adamantyl group, a phenyl group, a nitro group, a pentafluorophenyl group, or a trifluoromethyl group (CF3).

[0142] Appearance 11. Each R 12is, independently, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3), a complex or ligand defined in any one of Aspects 1 to 10.

[0143] Aspect 12. Each R 12 is, independently, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a cyclohexyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3), a complex or ligand defined in any one of Aspects 1 to 10.

[0144] Aspect 13. A heteroatom ligand transition metal compound complex having the following formula: [Chemical formula] [In the formula, X is P or S, when X is S, y is equal to 1, and when X is P, y is equal to 2, Y is O, NH, or CH2, M is Fe, Co, or Cr, m is the oxidation state of M, each Z is, independently, H, a halogen, a C1-C 18 hydrocarbyl group or a C1-C 18 halogenated hydrocarbyl group, B B ~R J are, independently, H, a halogen, a nitro group, a C1-C 18 hydrocarbyl group, or a C1-C18 a hydrocarbyl halide group, R D and R E may combine to form a ring or ring system, each R A is independently a C1-C 18 hydrocarbyl group or a C1-C 18 hydrocarbyl halide group].

[0145] Embodiment 14. A complex as defined in Embodiment 13, wherein M is Fe.

[0146] Embodiment 15. A complex as defined in Embodiment 13 or 14, wherein each Z is Cl.

[0147] Embodiment 16. A heteroatom ligand (compound) having the following formula:

Chemical formula

[0148] Embodiment 17. A complex or ligand as defined in any one of Embodiments 13 to 16, wherein X is P and y is equal to 2.

[0149] Embodiment 18. A complex or ligand as defined in any one of Embodiments 13 to 16, wherein X is S and y is equal to 1.

[0150] Embodiment 19. A complex or ligand defined in any one of Embodiments 13 to 18, wherein Y is O.

[0151] Embodiment 20. A complex or ligand defined in any one of Embodiments 13 to 18, wherein Y is NH.

[0152] Embodiment 21. A complex or ligand defined in any one of Embodiments 13 to 18, wherein Y is CH2.

[0153] Appearance 22.R B ~R E A complex or ligand defined in any one of embodiments 13 to 21, wherein the compound is independently an H or a methyl group.

[0154] Appearance 23.R D and R E A complex or ligand defined in any one of embodiments 13 to 22, which is bonded to form a ring or ring system.

[0155] Appearance 24.R F ~R J A complex or ligand defined in any one of embodiments 13 to 23, wherein the group is independently H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a naphthyl group, a benzyl group, a nitro group, a pentafluorophenyl group, or a trifluoromethyl group (CF3).

[0156] Appearance 25.R F ~R JA complex or ligand as defined in any one of embodiments 13 to 23, wherein the group is independently H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a cyclohexyl group, an adamantyl group, a phenyl group, a nitro group, a pentafluorophenyl group, or a trifluoromethyl group (CF3).

[0157] Appearance 26. Each R A A complex or ligand defined in any one of embodiments 13 to 25, wherein the group is independently a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3).

[0158] Appearance 27. Each R A A complex or ligand as defined in any one of embodiments 13 to 25, wherein the group is independently a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a cyclohexyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a pentafluorophenyl group, or a trifluoromethyl group (CF3).

[0159] Embodiment 28. A catalyst composition comprising (a) a heteroatom ligand transition metal compound complex as defined in any one of Embodiments 1-3, 5-15, and 17-27, and (b) an organoaluminum compound.

[0160] Aspect 29. A catalyst composition comprising (A) a heteroatom ligand defined in any one of Aspects 4 to 12 and 16 to 27, (B) a transition metal compound, and (C) an organoaluminum compound.

[0161] Aspect 30. The composition defined in Aspect 28 or 29, wherein the catalyst composition further comprises a hydrocarbon diluent (or solvent).

[0162] Aspect 31. The composition defined in Aspect 30, wherein the hydrocarbon diluent (or solvent) comprises a saturated aliphatic hydrocarbon, an aromatic hydrocarbon, or any combination thereof.

[0163] Aspect 32. The composition defined in Aspect 30, wherein the hydrocarbon diluent (or solvent) comprises a saturated aliphatic hydrocarbon, such as propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, or any combination thereof.

[0164] Aspect 33. The composition defined in Aspect 30, wherein the hydrocarbon diluent (or solvent) comprises cyclohexane.

[0165] Aspect 34. The composition defined in Aspect 30, wherein the hydrocarbon diluent (or solvent) comprises an aromatic hydrocarbon, such as benzene, toluene, xylene, cumene, ethylbenzene, or any combination thereof.

[0166] <着 Aspect 35. The transition metal compound has the formula M(X 1 ) p wherein M is Fe, Co, or Cr, p is the oxidation state of M, and each X 1 [[]]END]]is independently a monoanionic ligand, and the composition is defined in any one of Aspects 29 to 34.

[0167] Aspect 36. The composition defined in Aspect 35, wherein each X 1 is independently a halogen, carboxylate, β-diketonate, hydrocarboxide, nitrate, or chlorate.

[0168] Appearance 37. Each X 1 A composition as defined in embodiment 35, wherein the composition is independently an acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, dodecanoate, or acetylacetonate.

[0169] Embodiment 38. A composition as defined in any one of Embodiments 28 to 37, wherein the organoaluminum compound comprises an aluminoxane, an alkylaluminum compound, or any combination thereof.

[0170] Embodiment 39. A composition defined in any one of Embodiments 28 to 38, wherein the molar ratio of Al:transition metal (or Al:ligand) in the catalyst composition is within any range disclosed herein, for example, 10:1 to 5,000:1, 50:1 to 3,000:1, 50:1 to 3,000:1, 75:1 to 2,000:1, 100:1 to 2,000:1, or 100:1 to 1,000:1.

[0171] Embodiment 40. An oligomerization process comprising: (i) contacting ethylene, a catalyst composition defined in any one of Embodiments 28 to 39, an organic reaction medium, and optionally hydrogen in an oligomerization reactor; (ii) forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene; and (iii) discharging an effluent from the oligomerization reactor, wherein the effluent comprises unreacted ethylene and the oligomer product.

[0172] Embodiment 41. The process defined in Embodiment 40, wherein hydrogen is brought into contact within the oligomerization reactor.

[0173] Embodiment 42. The process as defined in Embodiment 41, wherein hydrogen and ethylene are combined and introduced into the reactor separately from the catalyst composition (or catalyst system components).

[0174] Embodiment 43. A process as defined in any one of Embodiments 40 to 42, wherein the organic reaction medium comprises saturated aliphatic hydrocarbons, aromatic hydrocarbons, or any combination thereof.

[0175] Embodiment 44. A process as defined in any one of Embodiments 40 to 43, wherein the organic reaction medium comprises saturated aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, or a combination thereof.

[0176] Embodiment 45. A process as defined in any one of Embodiments 40 to 44, wherein the organic reaction medium comprises cyclohexane.

[0177] Embodiment 46. A process as defined in any one of Embodiments 40 to 45, wherein the organic reaction medium comprises an aromatic hydrocarbon, such as benzene, toluene, xylene, cumene, ethylbenzene, or a combination thereof.

[0178] Embodiment 47. A process defined in any one of Embodiments 40 to 46, comprising forming the catalyst composition and then introducing it into the oligomerization reactor.

[0179] Embodiment 48. A process defined in any one of Embodiments 3 to 25 for forming the catalyst composition in the oligomerization reactor.

[0180] Embodiment 49. A process as defined in any one of Embodiments 40 to 48, wherein the oligomer product contains any amount of octene disclosed herein, for example, at least 5, 10, 20, 30 or 40% by weight; up to 99, 95, 92.5, 90, 87.5 or 85% by weight; or 5-85% by weight, 10-90% by weight, 20-99% by weight, 30-95% by weight, 40-95% by weight, 40-90% by weight, 20-90% by weight, 30-87.5% by weight, 30-85% by weight, 40-87.5% by weight, 40-85% by weight, 20-60% by weight, 30-55% by weight, or 40-55% by weight of octene.

[0181] Embodiment 50. A process as defined in any one of Embodiments 40 to 49, wherein the oligomer product comprises any amount of hexene disclosed herein, for example, at least 10, 15, 20, 25, 30, or 35% by weight; up to 75, 65, 60, 55, or 50% by weight; or 10 to 75% by weight, 15 to 65% by weight, 20 to 60% by weight, 25 to 55% by weight, or 30 to 50% by weight of hexene.

[0182] Embodiment 51. A process defined in any one of Embodiments 40 to 50, wherein the oligomerization reactor has any ethylene conversion rate disclosed herein, for example, at least 20, 30, 35, 40, 45, or 50% by weight, and at most 99, 95, 90, 80, 75, 70, or 65% by weight, or 20-95% by weight, 30-90% by weight, 40-80% by weight, 50-70% by weight, or 55-65% by weight, based on the amount of ethylene flowing into the reactor and the amount of ethylene in the effluent.

Claims

1. Heteroatom ligands having the following formula: 【Chemistry 1】 [In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. R １ ~R １１ These are independently H, halogen, nitro group, and C １ ~C １８ Hydrocarbyl group, or C １ ~C １８ It is a halogenated hydrocarbyl group, R ５ and R ６ They can combine to form a ring or ring system. Each R １２ is independently a C １ -C １８ hydrocarbyl group or a C １ -C １８ halogenated hydrocarbyl group].

2. R １ ~R ６ The compound according to claim 1, wherein the group is independently H or a methyl group.

3. R ５ and R ６ The compound according to claim 1, wherein the compounds bond to form a ring or ring system.

4. R ７ ~R １１ The compound according to any one of claims 1 to 3, wherein the group is independently H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a naphthyl group, a benzyl group, a nitro group, a pentafluorophenyl group, or a trifluoromethyl group.

5. Each R １２ The compound according to any one of claims 1 to 4, wherein the group is independently a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group.

6. The compound according to any one of claims 1 to 5, wherein X is P and y is equal to 2.

7. The compound according to any one of claims 1 to 5, wherein X is S and y is equal to 1.

8. Heteroatom ligands having the following formula: 【Chemistry 2】 [In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. Y is O, NH, or CH ２ And, B Ｂ ~R Ｊ These are independently H, halogen, nitro group, and C １ ~C １８ Hydrocarbyl group, or C １ ~C １８ It is a halogenated hydrocarbyl group, R Ｄ and R Ｅ They can combine to form a ring or ring system. Each R Ａ Independently, C １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group.

9. R Ｂ ~R Ｅ The compound according to claim 8, wherein the group is independently H or a methyl group.

10. R Ｄ and R Ｅ The compound according to claim 8, wherein the compounds bond to form a ring or ring system.

11. R Ｆ ~R Ｊ The compound according to any one of claims 8 to 10, wherein the group is independently H, Cl, F, a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a naphthyl group, a benzyl group, a nitro group, a pentafluorophenyl group, or a trifluoromethyl group.

12. Each R Ａ The compound according to any one of claims 8 to 11, wherein the group is independently a methyl group, an ethyl group, a propyl group (n-propyl group or isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, or neopentyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group.

13. The compound according to any one of claims 8 to 12, wherein X is P and y is equal to 2.

14. The compound according to any one of claims 8 to 12, wherein X is S and y is equal to 1.

15. The compound according to any one of claims 8 to 14, wherein Y is O.

16. The compound according to any one of claims 8 to 14, wherein Y is NH.

17. Y is CH ２ The compound according to any one of claims 8 to 14.

18. A catalyst composition, (A) A heteroatom ligand compound according to any one of claims 1 to 17, (B) Transition metal compounds, and (C) The catalyst composition comprising an organoaluminum compound.

19. The composition according to claim 18, wherein the catalyst composition further comprises a hydrocarbon diluent or a solvent.

20. The transition metal compound has the formula M(X １ ) ｐ It has, in the formula, M is Fe, Co, or Cr, p is the oxidation state of M, each X １ The composition according to claim 18 or 19, wherein the ligand is independently a monoanionic ligand.

21. The composition according to claim 20, wherein M is Fe.

22. each X １ The composition according to claim 20 or 21, wherein the constituent is independently an acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, dodecanoate, or acetylacetonate.

23. The composition according to any one of claims 18 to 22, wherein the organoaluminum compound comprises an aluminoxane, an alkylaluminum compound, or any combination thereof.

24. The composition according to any one of claims 18 to 23, wherein the molar ratio of Al to ligand compound in the catalyst composition is 10:1 to 5,000:1, 50:1 to 3,000:1, 75:1 to 3,000:1, 75:1 to 2,000:1, 100:1 to 2,000:1, or 100:1 to 1,000:

1.

25. It is an oligomerization process, (i) Contacting ethylene, the catalyst composition according to any one of claims 18 to 24, an organic reaction medium, and optionally hydrogen in an oligomerization reactor, (ii) Forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene, (iii) The oligomerization process comprising discharging an effluent from the oligomerization reactor, wherein the effluent contains unreacted ethylene and the oligomer product.

26. The process according to claim 25, wherein hydrogen is brought into contact with the oligomerization reactor.

27. The process according to claim 25 or 26, comprising forming the catalyst composition and then introducing it into the oligomerization reactor.

28. The process according to claim 25 or 26, wherein the catalyst composition is formed in the oligomerization reactor.

29. The process according to any one of claims 25 to 28, wherein hydrogen and ethylene are combined and introduced into the reactor separately from the catalyst composition or catalyst system components.

30. The process according to any one of claims 25 to 29, wherein the organic reaction medium comprises saturated aliphatic hydrocarbons, aromatic hydrocarbons, or any combination thereof.

31. The process according to any one of claims 25 to 30, wherein the organic reaction medium comprises cyclohexane.

32. Heteroatomic ligand transition metal compound complex having the following formula: 【Transformation 3】 [In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. M is Fe, Co, or Cr. m is the oxidation state of M, Each Z independently corresponds to H, halogen, and C. １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group, R １ ~R １１ These are independently H, halogen, nitro group, and C １ ~C １８ Hydrocarbyl group, or C １ ~C １８ It is a halogenated hydrocarbyl group, R ５ and R ６ They can combine to form a ring or ring system. Each R １２ Independently, C １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group.

33. Heteroatomic ligand transition metal compound complex having the following formula: 【Chemistry 4】 [In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. Y is O, NH, or CH ２ And, M is Fe, Co, or Cr. m is the oxidation state of M, Each Z independently corresponds to H, halogen, and C. １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group, B Ｂ ~R Ｊ These are independently H, halogen, nitro group, and C １ ~C １８ Hydrocarbyl group, or C １ ~C １８ It is a halogenated hydrocarbyl group, R Ｄ and R Ｅ They can combine to form a ring or ring system. Each R Ａ Independently, C １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group.

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