Supported diamine-imine catalysts bearing benzimidazole-amine ligands for the production of polyolefins

Abstract

Supported catalyst systems comprising a support, an activator, and a metal–ligand complex having a structure according to Formula (I): (I) where: M is a metal selected from the group consisting of titanium, zirconium, and hafnium; each X is a monodentate or bidentate ligand; n is 0, 1, or 2; R1 and R5 are independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–‍C30)aryl, and (C3–‍C30)heteroaryl; R2, R3, R4, and R6 are independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–‍C30)aryl, (C3–‍C30)heteroaryl, −ORC, −Si(RC)3, −Ge(RC)3, halogen, and –H, wherein each RC is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–‍C30)aryl, (C3–‍C30)heteroaryl, and –H; and R7, R8, R9, and R10 are independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–‍C30)aryl, (C3–‍C30)heteroaryl, -Si(RC)3, -Ge(RC)3, -N(RN)2, -ORC, and –H.

Description

86408-WO-PCT / DOW 86408 WO1SUPPORTED DIAMINE-IMINE CATALYSTS BEARING BENZIMIDAZOLE- AMINE LIGANDS FOR THE PRODUCTION OF POLYOLEFINSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 765,199 filed February 28, 2025, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

[0002] The present disclosure relates generally to catalyst systems and processes that may be utilized for olefin polymerization, and, more specifically, to supported catalyst systems involving diamine-imine metal-ligand complexs bearing benzimidazole-amine ligands and to olefin polymerization processes incorporating such supported catalyst systems.BACKGROUND

[0003] Olefin-based polymers such as polyethylene and ethylene-based polymers are produced via various catalyst systems. Selection of such catalyst systems used in the polymerization process of the olefin-based polymers is an important factor contributing to the characteristics and properties of such olefin-based polymers.

[0004] Ethylene-based polymers are manufactured for a wide variety of articles. The polyethylene polymerization process can be varied in a number of respects to produce a wide variety of resultant polyethylene resins having different physical properties that render the various resins suitable for use in different applications. The ethylene monomers and, optionally, one or more co-monomers are present in liquid diluents (such as solvents), such as an alkane or isoalkane, such as isoparaffin liquids (i.e., Isopar-E). Hydrogen may also be added to the reactor.

[0005] The catalyst systems for producing ethylene-based polymers may typically comprise a chromium-based catalyst system, a Ziegler-Natta catalyst system, and / or a molecular (either metallocene or non-metallocene (molecular)) catalyst system. The reactants in the diluent and the catalyst system are circulated at an elevated polymerization temperature around the reactor, thereby producing ethylene-based homopolymer or copolymer. Either periodically or continuously, part of the reaction mixture, including the polyethylene product dissolved in the diluent, together with unreacted ethylene and one or more optional co-monomers, is removed from86408-WO-PCT / DOW 86408 WO2the reactor. The reaction mixture, when removed from the reactor, may be processed to remove the polyethylene product from the diluent and the unreacted reactants, with the diluent and unreacted reactants typically being recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor, serially connected to the first reactor, where a second polyethylene fraction may be produced. Despite the research efforts in developing catalyst systems suitable for olefin polymerization, such as polyethylene polymerization, there is still a need to increase the efficiencies of catalyst systems that are capable of producing polymer with high ethylene selectivity and a range of molecular weight capabilities.SUMMARY

[0006] Supported catalyst systems disclosed herein include a support, an activator, and a metal-ligand complex having a structure according to Formula (I):

[0007] In Formula (I), M is a metal selected from the group consisting of titanium, zirconium, and hafnium, wherein the metal has a formal oxidation state of +2, +3, or +4. Each X is a monodentate or bidentate ligand independently selected from the group consisting of unsaturated (C2_C3o)hydrocarbon, unsaturated (C2_C3o)heterohydrocarbon, (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, halogen, -N(RX)2, and -(CH2)wSi(Rx)3, where w is 1 to 10 and each Rxis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl.86408-WO-PCT / DOW 86408 WO3

[0008] In Formula (I), n is 0, 1, or 2. R1and R5are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl. R2, R3, R4, and R6are independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, –ORC, –Si(RC)3, –Ge(RC)3, halogen, and –H, wherein each RCis independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H.

[0009] In Formula (I), R7, R8, R9, and R10are independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, –Si(RC)3, -Ge(Rc)3, -N(RN)2, — ORC, and -H, wherein each RNis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6-C3o)aryl, (C3-C3o)heteroaryl, and -H, and wherein optionally R7and R9, R7and R10, R8and R9, R8and R10, or combinations thereof are covalently connected as a (C2-C2o)hydrocarbylene comprising an aromatic ring structure, a non-aromatic ring structure, an aromatic multi-ring structure, or a non-aromatic multi-ring structure.

[0010] Polymerization processes, particularly methods of making ethylene-based polymers, include polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of the catalyst system including a metal-ligand complex having a structure according to Formula (I).DETAILED DESCRIPTION

[0011] Common abbreviations are listed below:

[0012] X, M and n: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; GC: gas chromatography; LC: liquid chromatography; RIBS-2 or RIBS-II: bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine; iPr: isopropyl; tBu: tert-butyl; nBu: n-butyl;IMLC: inventive metal-ligand complex; TEA: triethylaluminum; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimoles; mL: milliliters; M: molar; min or mins: minutes; h or hrs: hours; d: days.

[0013] The term “independently selected” followed by multiple options is used herein to indicate that the individual R groups appearing before the term, such as R1, R2, R3, R4, R5, and Rccan be86408-WO-PCT / DOW 86408 WO4identical or different, without dependency on the identity of any other Group also appearing before the term.

[0014] The term “catalyst” refers to a compound that has catalytic activity. The term “procatalyst” refers to a compound that has catalytic activity when combined with an activator. As used herein, the terms “procatalyst” and “precatalyst” are interchangeable terms. The term “activator” refers to a compound that chemically reacts with a procatalyst in a manner that converts the procatalyst to a catalytically active catalyst. As used herein, the terms “co-catalyst” and “activator” are interchangeable terms.

[0015] When used to describe certain carbon atom- containing chemical groups, a parenthetical expression having the form “(Cx-Cy)” means that the unsubstituted form of the chemical Group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (Ci-C3o)alkyl is an alkyl Group having from 1 to 30 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted by one or more substituents such as Rs. An Rssubstituted version of a chemical Group defined using the “(Cx-Cy)” parenthetical may contain more than y carbon atoms depending on the identity of any groups Rs. For example, a “(Ci-C5o)alkyl substituted with exactly one Group Rs, where Rsis phenyl (-CeHs)” may contain from 7 to 56 carbon atoms. Thus, in general when a chemical Group defined using the “(Cx-Cy)” parenthetical is substituted by one or more carbon atomcontaining substituents Rs, the minimum and maximum total number of carbon atoms of the chemical Group is determined by adding to both x and y the combined sum of the number of carbon atoms from all of the carbon atom- containing substituents Rs.

[0016] The term “substitution” means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional Group is replaced by a substituent (e.g., Rs). The term “persubstitution” means that every hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional Group is replaced by a substituent (e.g., Rs). The term “polysubstitution” means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional Group are replaced by a substituent. The term “-H” means a hydrogen or hydrogen radical that is covalently bonded to another atom. When describing chemical structures of various compounds, “Hydrogen” and “-H” are interchangeable, and unless clearly specified have identical meanings.86408-WO-PCT / DOW 86408 WO5

[0017] The term “(Ci-C3o)hydrocarbyl” means a hydrocarbon radical of from 1 to 30 carbon atoms and the term “(C2-C2o)hydrocarbylene” means a hydrocarbon diradical of from 2 to 20 carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (having three carbons or more, and including mono- and poly-cyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and substituted by one or more Rsor unsubstituted.

[0018] In this disclosure, a (Ci-C3o)hydrocarbyl may be an unsubstituted or substituted (Ci-C3o)alkyl, (C3-C3o)cycloalkyl, (C3-Ci5)cycloalkyl-(Ci-Ci5)alkylene, (Ce-C3o)aryl, or (C6-Ci5)aryl-(Ci-Ci5)alkylene (such as benzyl (-CH2-C6H5)).

[0019] The term “(Ci-C3o)alkyl” means a saturated straight or branched hydrocarbon radical of from 1 to 30 carbon atoms that is unsubstituted or substituted by one or more Rs. Other alkyl groups (e.g., (Cx-Cy)alkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. Examples of unsubstituted (Ci-C3o)alkyl are unsubstituted (Ci-C2o)alkyl; unsubstituted (Ci-Cio)alkyl; unsubstituted (Ci-C5)alkyl; methyl; ethyl; 1 -propyl; 2-propyl; 1 -butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1 -pentyl; 1 -hexyl; 1 -heptyl; 1 -nonyl; and 1 -decyl. Examples of substituted (C1-C15) alkyl are substituted (Ci-Ci5)alkyl (such as benzyl (-CH2-C6H5)), substituted (Ci-Cio)alkyl, trifluoromethyl, and [C2o]alkyl. The term “[C2o]alkyl” means there is a maximum of 20 carbon atoms in the radical, including substituents, and is, for example, a (C5-Ci5)alkyl substituted by one Rs, which is a (Ci-C5)alkyl, respectively. Each (Ci-C5)alkyl may be methyl, ethyl, 1 -propyl, 1 -methylethyl, 1,1 -dimethylethyl, or tert-butyl.

[0020] The term “(C6-C3o)aryl” means an unsubstituted or substituted (by one or more Rs) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 30 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms. Other aryl groups (e.g., (Cx-Cy)aryl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. A monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or non-fused and aromatic or non-86408-WO-PCT / DOW 86408 WO6aromatic. Examples of unsubstituted (Ce-C3o)aryl include: unsubstituted (C6-Ci5)aryl, unsubstituted (Ce-Cio)aryl; 2-(Ci-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (Ce-C3o)aryl include: substituted (Ci-C3o)aryl; substituted (C6-C3o)aryl; 2,4-bis([C8]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0021] The term “(C3-C3o)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 30 carbon atoms that is unsubstituted or substituted by one or more Rs. Other cycloalkyl groups (e.g., (Cx-Cy)cycloalkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. Examples of unsubstituted (C3-C3o)cycloalkyl are unsubstituted (C3-C3o)cycloalkyl, unsubstituted (C3-Ci5)cycloalkyl, unsubstituted (C3-Cio)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-Ci5)cycloalkyl are substituted (C3-Ci5)cycloalkyl, substituted (C3-Cio)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0022] Examples of (C2-C2o)hydrocarbylene include unsubstituted or substituted (C6-C2o)arylene, (C3-C2o)cycloalkylene, and (C2-C2o)alkylene (e.g., (C2-Ci5)alkylene). The diradicals may be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are spaced apart by one, two, or more than two intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or an a,a>-diradical, and others a 1,2-diradical. The a,a>-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2-C2o)alkylene a,a>-diradicals include ethan-1,2-diyl (i.e., -CH2CH2-), propan- 1,3 -diyl (i.e., -CH2CH2CH2-), 2-methylpropan- 1,3 -diyl (i.e., -CH2CH(CH3)CH2-). Some examples of (Ce-Csojarylene a,a>-diradicals include phenyl- 1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl.

[0023] The term “(Ci-C2o)alkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 20 carbon atoms that is unsubstituted or substituted by one or more Rs. Other alkylene groups (e.g., (Cx-Cy)alkylene) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. Examples of unsubstituted (Ci-C3o)alkylene are unsubstituted86408-WO-PCT / DOW 86408 WO7(Ci-C2o)alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CEE)?-, -(CH2)e-, -(CH2)?-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), in which “C*” denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (Ci-C2o)alkylene are substituted (Ci-Ci5)alkylene, -CF2-, -C(O)-, and - (CH2)i4C(CH3)2(CH2)s- (i.e., a 6,6-dimethyl substituted normal- 1,20-eicosylene). Since as mentioned previously two Rsmay be taken together to form a (Ci-Ci8)alkylene, examples of substituted (Ci-C2o)alkylene also include l,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3- bis (methylene)bicyclo [2.2.2] octane.

[0024] The term “(C3-C2o)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 20 carbon atoms that is unsubstituted or substituted by one or more Rs. Other cycloalkylene groups (e.g., (Cx-Cy)cycloalkylene) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs.

[0025] The term “heteroatom,” refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S(O), S(O)2, Si(Rc)2, P(Rp), N(RN), - N=C(RC)2, -Ge(Rc)2“, or -Si(Rc)-, where each Rcand each Rpis unsubstituted (Ci-Ci8)hydrocarbyl or -H, and where each RNis unsubstituted (Ci-Ci8)hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. The term “(Ci-C2o)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 20 carbon atoms, and the term “(Ci-C2o)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 20 carbon atoms. The heterohydrocarbon of the (Ci-C2o)heterohydrocarbyl or the (Ci-C2o)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be on a single carbon atom or on a single heteroatom. Additionally, one of the two radicals of the diradical may be on a carbon atom and the other radical may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the other radical on a different heteroatom. Each (Ci-C2o)heterohydrocarbyl and (Ci-C2o)heterohydrocarbylene may be unsubstituted or substituted (by one or more Rs), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic), or86408-WO-PCT / DOW 86408 WOacyclic. Other heterohydrocarbyl groups (e.g., (Cx-Cy) heterohydrocarbyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs.

[0026] The (Ci-C2o)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (Ci-C2o)heterohydrocarbyl include (Ci-C2o)heteroalkyl, (Ci-C2o)hydrocarbyl-0-, (Ci-C2o)hydrocarbyl-S-, (Ci-C2o)hydrocarbyl-S(0)-, (Ci-C2o)hydrocarbyl-S(0)2-, (Ci-C2o)hydrocarbyl-Si(Rc)2-, (Ci-C2o)hydrocarbyl-N(RN)-, (Ci-C2o)hydrocarbyl-P(Rp)-, (C2-C2o)heterocycloalkyl, (C2-Ci9)heterocycloalkyl- (Ci-C2o)alkylene, (C3-C2o)cycloalkyl-(Ci-Ci9)heteroalkylene, (C2-Ci9)heterocycloalkyl-(Ci-C2o)heteroalkylene, (Ci-C3o)heteroaryl, (Ci-Ci9)heteroaryl-(Ci-C2o)alkylene, (Ce-C2o)aryl-(Ci-Ci9)heteroalkylene, or (Ci-Ci9)heteroaryl-(Ci-C2o)heteroalkylene.

[0027] The (Ci-C2o)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (Ci-C2o)heterohydrocarbyl include (Ci-C2o)heteroalkyl, (Ci-C2o)hydrocarbyl-0-, (Ci-C2o)hydrocarbyl-S-, (Ci-C2o)hydrocarbyl-S(0)-, (Ci-C2o)hydrocarbyl-S(0)2-, (Ci-C2o)hydrocarbyl-Si(Rc)2-, (Ci-C2o)hydrocarbyl-N(RN)-, (Ci-C2o)hydrocarbyl-P(Rp)-, (C2-C2o)heterocycloalkyl, (C2-Cio)heterocycloalkyl-(Ci-Cio)alkylene, (C3-Cio)cycloalkyl-(Ci-Cio)heteroalkylene, (C2-Cio)heterocycloalkyl-(Ci-Cio)heteroalkylene, (Ci-C2o)heteroaryl, (Ci-Cio)heteroaryl-(Ci-Cio)alkylene, (Ce-Cio)aryl-(C i-C i o)heteroalkylene, or (C i-C i o)heteroaryl-(C i-C i o)heteroalkylene.

[0028] The term “(C3-C2o)heteroaryl” means an unsubstituted or substituted (by one or more Rs) mono-, bi-, or tricyclic heteroaromatic hydrocarbon radical of from 3 to 20 total carbon atoms and from 1 to 10 heteroatoms. A monocyclic heteroaromatic hydrocarbon radical includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may be independently fused or non- fused and aromatic or non-aromatic.

[0029] Other heteroaryl groups (e.g., (Cx-Cy)heteroaryl generally, such as (C4-Ci2)heteroaryl) are defined in an analogous manner as having from x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one Rs. The monocyclic heteroaromatic86408-WO-PCT / DOW 86408 WO9hydrocarbon radical is a 5-membered ring or a 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1, 2, or 3; and each heteroatom may be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol- 1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-l-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-l-yl; l,3,4-oxadiazol-2-yl; l,3,4-thiadiazol-2-yl; tetrazol-l-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1 or 2 and the heteroatoms may be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol-l-yl; and benzimidazole- 1-yl. Examples of the fused 6.6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin- 1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6, 6,6-ring system. An Example of the fused 5,6,5-ring system is l,7-dihydropyrrolo[3,2-f]indol-l-yl. An Example of the fused 5, 6,6-ring system is lH-benzo[f] indol-l-yl. An Example of the fused 6.5.6-ring system is 9H-carbazol-9-yl. An Example of the fused 6, 5,6-ring system is 9H-carbazol-9-yl. An Example of the fused 6, 6,6-ring system is acrydin-9-yl.

[0030] The term “(Ci-C2o)heteroalkyl” means a saturated straight or branched chain radicals containing one to twenty carbon atoms, or fewer carbon atoms and one or more of the heteroatoms. The term “(Ci-C2o)heteroalkylene” means a saturated straight or branched chain diradicals containing from 1 to 20 carbon atoms and one or more than one heteroatoms. The heteroatoms of the heteroalkyls or the heteroalkylenes may include Si(Rc)s, Ge(Rc)3, Si(Rc)2, Ge(Rc)2, P(Rp)2, P(Rp), N(RN)2, N(RN), N, O, ORC, S, SRC, S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups are unsubstituted or are substituted by one or more Rs.

[0031] Examples of unsubstituted (C2-C3o)heterocycloalkyl include unsubstituted (C2-C2o)heterocycloalkyl, unsubstituted (C2-Cio)heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophen-S, S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0032] The term “halogen atom” or “halogen” means the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term “halide” means the anionic form of the halogen atom: fluoride (F"), chloride (Cl"), bromide (Br ), or iodide (I").86408-WO-PCT / DOW 86408 WO10

[0033] The term “saturated” means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorous, and carbon-silicon double bonds. Where a saturated chemical Group is substituted by one or more substituents Rs, one or more double and / or triple bonds optionally may or may not be present in substituents Rs. The term “unsaturated” means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbonnitrogen, carbon-phosphorous, or carbon-silicon double bonds, not including double bonds that may be present in substituents Rs, if any, or in (hetero) aromatic rings, if any.

[0034] Supported catalyst systems and methods of making ethylene-based polymers using said systems will now be described. As described herein, the catalyst systems may have increased efficiencies that are capable of producing polymer with high ethylene selectivity and a range of molecular weight capabilities. Further, a combination of these features and similar-to-higher activity at lower reactor temperatures may allow for the production of polymers with improved product performance in linear low-to-high density polyethylene applications as well as additional process flexibility in the production of poly(ethylene-co-l -alkene) copolymers. It should be understood that the supported catalyst systems of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0035] Metal-Ligand Complex

[0036] Supported catalyst systems herein include a support, an activator, and a metal-ligand complex, according to Formula (I):86408-WO-PCT / DOW 86408 WO11R8R9Nill- W n

[0037] In Formula (I), M is a metal selected from the group consisting of titanium, zirconium, and hafnium, wherein the metal has a formal oxidation state of +2, +3, or +4. In particular examples of the metal-ligand complex according to Formula (I), M is a metal chosen from zirconium or hafnium. In other particular examples of the metal-ligand complex according to Formula (I), M is zirconium.

[0038] Each X is a monodentate or bidentate ligand independently selected from the group consisting of unsaturated (C2–C30)hydrocarbon, unsaturated (C2–C30)heterohydrocarbon, (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, halogen, –N(RX)2, and –(CH2)wSi(RX)3, where w is 1 to 10 and each Rxis independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl. In particular examples of the metal–ligand complex according to Formula (I), each X is a monodentate or bidentate ligand independently selected from the group consisting of unsubstituted (C1–C10)alkyl, substituted (C1–C10)alkyl, (C6–C20)aryl, and halogen.

[0039] In Formula (I), n is 0, 1, or 2.

[0040] In Formula (I), R1is independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl. In examples of the metal–ligand complex according to Formula (I), R1can be selected from the group consisting of unsubstituted (C1–C30)alkyl, substituted (C1–C30)alkyl, unsubstituted (C6–C30)aryl, and substituted (C6–C30)aryl. In particular examples, R1can be selected from the group consisting of unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl,86408-WO-PCT / DOW 86408 WO12unsubstituted naphthyl, and substituted naphthyl. In further particular examples, R1can be unsubstituted phenyl or substituted phenyl. In some examples, R1is substituted phenyl containing at least two (Ci-Cio)alkyl substituents, wherein the at least two (Ci-Cio)alkyl substituents may comprise two (Ci-Cio)alkyl / / z -substituents. In other particular examples of the metal-ligand complex according to Formula (I), R1is selected from the group consisting of 2-methylphenyl, 2-(isopropyl)phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-di(isopropyl)phenyl, 2.4.6-tri(isopropyl)phenyl, 3,5-di-tert-butylphenyl, 3,5-diphenylphenyl, 1 -naphthyl, 2-naphthyl, and 2,3,5,6-tetrafluorophenyl. In some specific examples, R1is selected from the group consisting of 2-methylphenyl, 2-(isopropyl)phenyl, 3,5-di-tert-butylphenyl, 1 -naphthyl, and 2-naphthyl.

[0041] In Formula (I), R5is selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl. In particular examples, R5can be selected from the group consisting of unsubstituted (C1–C20)alkyl, substituted (C1–C20)alkyl, unsubstituted (C6–C20)aryl, and substituted (C6–C20)aryl. In specific particular examples, R5is 4-butylphenyl.

[0042] In Formula (I), R2, R3, R4, and R6are independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, –ORC, –Si(RC)3, –Ge(RC)3, halogen, and –H, wherein each RCis independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H. In examples of the metal-ligand complex according to Formula (I), R2, R3, and R4are -H. In particular examples of the metal-ligand complex according to Formula (I), R6is selected from the group consisting of substituted carbazolyl, unsubstituted carbazolyl, unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted naphthyl, and substituted naphthyl. In specific examples of the metal-ligand complex according to Formula (I), R6is selected from the group consisting of 1 -naphthyl, 2-naphthyl, 2-propyl, cyclohexyl, 2-methylphenyl, 2-(isopropyl)phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2.6-di(isopropyl)phenyl, 2,4,6-tri(isopropyl)phenyl, 3,5-di-tert-butylphenyl, 3,5-diphenylphenyl, and 2,7-di-tert-butylcarbazolyl. In some specific examples, R6is 1-naphthyl or 2-methylphenyl.

[0043] In Formula (I), R7, R8, R9, and R10are independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, –Si(RC)3,86408-WO-PCT / DOW 86408 WO13–Ge(RC)3, –N(RN)2, –ORC, and –H, wherein each RNis independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H. In specific examples of the metal-ligand complex according to Formula (I), R7and R9, R7and R10, R8and R9, R8and R10, or combinations thereof may be covalently connected as a (C2-C2o)hydrocarbylene comprising an aromatic ring structure, a non-aromatic ring structure, an aromatic multi-ring structure, or a non-aromatic multi-ring structure.

[0044] In illustrative examples, one of R7and R8and one of R9and R10are covalently connected to form a hydrocarbylene comprising the structure according to any one of Formulas (Ila)-(IIf):wherein the dotted lines represent points of connection to the nitrogen atoms of the diamine-imine ligand of Formula (I), and each R11–38are independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, –Si(RC)3, –Ge(RC)3, –N(RN)2, –ORC, and –H.86408-WO-PCT / DOW 86408 WO14

[0045] In illustrative examples, one of R7and R8and one of R9and R10are covalently connected to form a cycloguanidine comprising the structure according to any one of Formulas (Illa)-(IIIb):iPr iPrIlla, and Illb;wherein the dotted lines represent a point of connection to M of Formula (I).

[0046] In illustrative embodiments, the metal-ligand complex can be selected from the group consisting of:IMLC-3, IMLC-4,86408-WO-PCT / DOW 86408 WO15nBuIMLC-5, IMLC-6IMLC-7, IMLC-8 nBuIMLC-9, IMLC-10,86408-WO-PCT / DOW 86408 WOIMLC-ll, and IMLC-12.

[0047] In other illustrative examples, the metal-ligand complex can be selected from the group consisting of the structure according to any one of Formulas (IVa)-(IVe):R'IVa, IVb,R'IVc,86408-WO-PCT / DOW 86408 WO17R~NMrlxN"-'A"’IVe;wherein R, R’, R”, and each R’” are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, -Si(Rc)3, -Ge(Rc)3, -N(RN)2, -ORC, and -H.

[0048] Example suitable monomers and / or comonomers for use in making the ethylene-based polymers of the present disclosure include ethylene and one or more 1 -alkene comonomer. Examples of suitable comonomers include straight-chain or branched a-olefins of 3 to 30, preferably 3 to 20, carbon atoms, such as propylene, 1 -butene, 1 -pentene, 3 -methyl- 1 -butene, 1-hexene, 4-methyl-l- pentene, 3 -methyl- 1 -pentene, 1-octene, 1-decene, 1-dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene and 1-eicosene.

[0049] Activator Component

[0050] As described above, the supported catalyst systems of the present disclosure include a support, an activator, and a metal-ligand complex having a structure according to Formula (I). The activator of the supported catalyst systems described herein may include any combination of reagents that increases the rate at which a metal-ligand complex oligomerizes or polymerizes unsaturated monomers, such as olefins. The activator may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer.

[0051] For example, the metal-ligand complex according to Formula (I) may be rendered catalytically active by contacting the metal-ligand complex to, or combining the metal-ligand complex with, one or more activators. Additionally, the metal-ligand complex according to Formula (I) may include both a procatalyst form, which is neutral, and a catalytic form, which may be positively charged due to the loss of a ligand, such as a benzyl ligand or a phenyl ligand. Suitable activators for use herein include, without limitation: alkyl aluminums; boron-based Bronsted or Lewis acids; polymeric or oligomeric alumoxanes (also known as aluminoxanes);86408-WO-PCT / DOW 86408 WO18neutral Lewis acids; non-polymeric, non-coordinating, ion- forming compounds (including the use of such compounds under oxidizing conditions); and combinations thereof. A suitable activating technique is bulk electrolysis. Combinations of one or more of the foregoing activators and techniques are also contemplated. The term “alkyl aluminum” means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Aluminum alkyl or organoaluminum compounds that may be utilized as activators (or scavengers) including trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.

[0052] Aluminoxane activators may be utilized as an activator for one or more of the metal-ligand complexes described herein. Alumoxane(s) or aluminoxane(s) are generally oligomeric compounds containing -A1(R)-O- subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further descriptions, see U. S. Patent Nos.4,665,208; 4,952,540; 5,041,584; 5,091,352; 5,206,199; 5,204,419; 4,874,734; 4,924,018; 4,908,463; 4,968,827; 5,329,032; 5,248,801; 5,235,081; 5,157,137; 5,103,031; and EP 0561 476; EP 0279 586; EP 0 516476; EP 0594218; and WO 94 / 10180. In some examples, the activator comprises methylalumoxane (MAO), such as solid methylalumoxane (SMAO).

[0053] In examples, the molar ratio of metal in the activator to metal in the metal-ligand complex is from 0.5:1 to 3500:1, such as from 0.5:1 to 1:1, from 1:1 to 5:1, from 5:1 to 10:1, from 10:1 to 20:1, from 20:1 to 50:1, from 50:1 to 100:1, from 100:1 to 250:1, from 250:1 to 500:1, from 500:1 to 1000:1, from 1000:1 to 1500:1, from 1500:1 to 2000:1, from 2000:1 to 2500:1, from 2500:1 to 3000:1, from 3000:1 to 3500:1, or any combination of two or more of these ranges.

[0054] Lewis acid activators include Group 13 metal compounds containing (C1–C20)hydrocarbyl substituents as described herein. In some examples, Group 13 metal compounds are tri((C1–C20)hydrocarbyl)-substituted-aluminum or tri((C1–C20)hydrocarbyl)-boron compounds. In other examples, Group 13 metal compounds are tri(hydrocarbyl)-substituted-aluminum, tri((Ci— C2o)hydrocarbyl)-boron compounds, tri((Ci-Cio)alkyl)aluminum, tri((C6-Ci8)aryl)boron compounds, and halogenated (including perhalogenated) derivatives thereof. In further embodiments, Group 13 metal compounds are tris(fluoro-substituted phenyl)boranes,86408-WO-PCT / DOW 86408 WO19tris(pentafluorophenyl)borane. In some examples, the activator is a tris((Ci-C2o)hydrocarbyl borate (e.g. trityl tetrafluoroborate) or a tri((Ci-C2o)hydrocarbyl)ammonium tetra((Ci-C2o)hydrocarbyl)borane (e.g. bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term “ammonium” means a nitrogen cation that is a ((Ci-C2o)hydrocarbyl)4N+a ((Ci-C2o)hydrocarbyl)3N(H)+, a ((Ci— C2o)hydrocarbyl)2N(H)2+, (Ci-C2o)hydrocarbylN(H)3+, or N(H)4+, wherein each (Ci-C2o)hydrocarbyl, when two or more are present, may be the same or different.

[0055] Combinations of neutral Lewis acid activators include mixtures comprising a combination of a tri((C1–C4)alkyl)aluminum and a halogenated tri((C6-Ci8)aryl)boron compound, especially a tris(pentafluorophenyl)borane. Other examples include combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Ratios of numbers of moles of (metal-ligand complex): (tris(pentafluoro-phenylborane): (alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluoro-phenylborane): (alumoxane)] are from 1:1:1 to 1:10:30, in other examples, from 1:1:1.5 to 1:5:10.

[0056] Exemplary suitable activators include, but are not limited to, methylaluminoxane (MAO), modified methyl aluminoxane (MMAO), triethylaluminum (TEA), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine (RIBS-2), and combinations thereof.

[0057] In particular examples, the activator comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0058] In particular examples, the activator comprises unsubstituted ammonium borate, a monosubstituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate.

[0059] In particular examples, the activator comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine (RIBS-2).

[0060] In some examples, more than one of the foregoing activators may be used in combination with each other. A specific example of an activator combination is a mixture of a tri((C1–C4)hydrocarbyl)aluminum, tri((C1–C4)hydrocarbyl)borane, or an ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of total number of moles of one or more metal-ligand complexes of Formula (I) to total number of moles of one or more of the activators may be from 1: 10,000 to 100: 1. In some embodiments, the ratio is at least 1:5,000, in some other86408-WO-PCT / DOW 86408 WO20embodiments, at least 1: 1,000; and 10:1 or less, and in some other embodiments, 1:1 or less. When an alumoxane alone is used as the activator, preferably the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane alone is used as the activator, in some other embodiments, the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more metal-ligand complexes of Formula (I) from 0.5: 1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activators are generally employed in approximately mole quantities equal to the total mole quantities of one or more metal-ligand complexes of Formula (I).

[0061] In some examples, the supported catalyst systems of the present disclosure may include a scavenger that reacts with any water or other impurities present in the system that might otherwise react with the catalyst leading to reduced efficiency. In embodiments, the supported catalyst systems described herein may include an activator or both an activator and a scavenger.

[0062] In some examples, the activator comprises unsubstituted ammonium borate, a monosubstituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate, and a scavenger comprising methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0063] In some examples, the activator comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine (RIBS-2), and a scavenger comprising methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0064] Support Component

[0065] As described above, the supported catalyst systems of the present disclosure include a support, an activator, and a metal-ligand complex having a structure according to Formula (I). The metal-ligand complexes described herein, the activator, or both, may be disposed on the support, which may include one or more support materials. For example, the metal-ligand complexes may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more support materials. The metal-ligand complexes, the activator, or both, may be combined with one or more support materials using one of the support methods well known in the art or as described below. As used in the present86408-WO-PCT / DOW 86408 WO21disclosure, the metal-ligand complexes, the activator, or both, may be in a supported form, for example, when deposited on, contacted with, or incorporated within, adsorbed or absorbed in, or on, one or more support materials.

[0066] In some embodiments the activator and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported activator in the inert hydrocarbon liquid, then the suspension is contacted with the metal-ligand complex to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.

[0067] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may include a step of decanting some of the inert hydrocarbon liquid from the suspension. In some embodiments the decanting method comprises pouring off excess inert hydrocarbon liquid from the suspension to give a concentrated suspension of the supported catalyst system.

[0068] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may comprise a step of drying the supported catalyst system. The drying step may comprise a spray-drying method.

[0069] A “support,” which may also be referred to as a “carrier,” refers to any support material, including a porous support material, such as talc, inorganic oxides, and inorganic chlorides. Other support materials include resinous support materials, e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

[0070] Suitable support materials, such as inorganic oxides, include oxides of metals of Group 2, 3, 4, 5, 13 or 14 of the IUPAC periodic table. In embodiments, support materials include silica, which may or may not be dehydrated, fumed silica, alumina (e.g., as described in International Patent Application No. 1999 / 060033), silica-alumina, and mixtures of these. The fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated). In embodiments, the support material is hydrophobic fumed silica, which may be prepared by treating an untreated fumed silica with a treating agent, such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, support materials include magnesia, titania, zirconia, magnesium chloride (e.g, as described in U. S. Patent No. 5,965,477), montmorillonite (e.g, as described in European Patent No. 0511 665), phyllosilicate, zeolites, talc, clays (e.g, as86408-WO-PCT / DOW 86408 WO22described in U. S. Patent No. 6,034,187), and mixtures of these. In other embodiments, combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these.

[0071] Additional support materials may also include those porous acrylic polymers described in European Patent No. 0 767 184. Other support materials may also include nanocomposites described in International Patent Application No. 1999 / 047598; aerogels described in International Patent Application No. 1999 / 048605; spherulites described in U. S. Patent No.5,972,510; and polymeric beads described in International Patent Application No. 1999 / 050311. An example of a support material is fumed silica available under the trade name CABOSIL TS-610, or other TS- or TG-series supports, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.

[0072] In embodiments, the support material has a surface area of from 10 square meters per gram (m2 / g) to 700 m2 / g, a pore volume of from 0.1 cubic meters per gram (cm3 / g) to 4.0 cm3 / g, and an average particle size of from 5 microns (pm) to 500 pm. In some embodiments, the support material has a surface area of from 50 m2 / g to 500 m2 / g, a pore volume of from 0.5 cm3 / g to 3.5 cm3 / g, and an average particle size of from 10 pm to 200 pm. In other embodiments, the support material may have a surface area of from 100 m2 / g to 400 m2 / g, a pore volume from 0.8 cm3 / g to 3.0 cm3 / g, and an average particle size of from 5 pm to 100 pm. The average pore size of the support material is typically from 10 Angstroms (A) to 1,000 A, such as from 50 A to 500 A or from 75 A to 350 A.

[0073] The support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica, e.g., from 500 to 1000 mAg. Such silicas are commercially available from several sources including the Davison Chemical Division of W. R. Grace and Company, e.g., Davison 952 and Davison 955 products, and PQ Corporation, e.g., ES70 product. The silica may be in the form of spherical particles, which may be obtained by a spray-drying process. Alternatively, MS3050 product is a silica from PQ Corporation that is not spray-dried. As procured, these silicas are not calcined (i.e., not dehydrated). Silica that is calcined prior to purchase may also be used as the support material.

[0074] In some embodiments the solid support is a hydrophobic fumed silica. The hydrophobic fumed silica is made by contacting an untreated fumed silica, having surfaces containing silicon-86408-WO-PCT / DOW 86408 WO23bonded hydroxyl groups (Si-OH groups), with a hydrophobing agent, described later. In some embodiments the hydrophobing agent is a silicon-based hydrophobing agent, containing on average per molecule one or more functional groups reactive with a Si-OH group, to give the hydrophobic fumed silica. The silicon-based hydrophobing agent may be selected from (CHs^SiCh, a polydimethylsiloxane, hexamethyldisilazane (HMDZ), and a (Ci-Cio)alkyl-Si((Ci-Cio)alkoxy)3 (e.g., an octyltrialkoxysilane such as octyltriethoxysilane, i.e., CH3(CH2)? Si(OCH2CH3)3). In some embodiments the silicon-based hydrophobing agent is dimethyldichlorosilane, i.e., (CHs^SiCh. In some embodiments the support material is a dimethyldichlorosilane-treated fumed silica, such as that sold as product TS-610 from Cabot Corporation.

[0075] The support material may be uncalcined or calcined. The calcined support material is made prior to being contacted with a metal-ligand complex, co-catalyst component, and / or hydrophobing agent, by heating the support material in air to give a calcined support material. The calcining comprises heating the support material at a peak temperature from 350 °C to 850 °C, alternatively from 400 °C to 800 °C, alternatively from 400 °C to 700 °C, alternatively from 500 °C to 650 °C and for a time period from 2 to 24 hours, alternatively from 4 to 16 hours, alternatively from 8 to 12 hours, alternatively from 1 to 4 hours, thereby making the calcined support material. If the support material has not been heated in this way it is an uncalcined support material.

[0076] In some examples, the ratio of total number of moles of one or more metal-ligand complexes of Formula (I) to the total weight of the support material, e.g., SMAO, may be from 1 pmol / g to 100 pmol / g, from 5 pmol / g to 100 pmol / g, from 10 pmol / g to 100 pmol / g, from 10 pmol / g to 80 pmol / g, from 20 pmol / g to 80 pmol / g, from 20 pmol / g to 60 pmol / g, from 30 pmol / g to 60 pmol / g, from 30 pmol / g to 55 pmol / g, from 35 pmol / g to 55 pmol / g, from 35 pmol / g to 50 pmol / g, or from 40 pmol / g to 50 pmol / g.

[0077] Polymerization Processes

[0078] As noted above, embodiments of this disclosure are also directed to methods of making an ethylene-based polymer. The methods may include polymerizing, via gas-phase polymerization or slurry-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of a supported catalyst system described herein comprising a metal-ligand complex according to Formula (I). Exemplary polymerization86408-WO-PCT / DOW 86408 WO24processes may be performed using one or more conventional reactors such as loop reactors, isothermal reactors, fluidized bed reactors, stirred tank reactors, batch reactors in parallel or series, or any combinations thereof.

[0079] In some examples, the method of making an ethylene-based polymer comprises polymerizing, via slurry-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of a supported catalyst system described herein comprising a metal-ligand complex according to Formula (I).

[0080] In some examples, the method of making an ethylene-based polymer comprises polymerizing, via gas-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of a supported catalyst system described herein comprising a metal-ligand complex according to Formula (I).

[0081] In some examples, the method comprises polymerizing the combination of ethylene monomer and at least one 1 -alkene comonomer. In some exemplary methods, the at least one 1 -alkene comonomer comprises 1 -hexene.

[0082] In some exemplary methods of the present disclosure, ethylene monomer, one or more solvents, a supported catalyst system of the present disclosure, and optionally one or more comonomers are fed continuously to the one or more reactors. Exemplary solvents for use as the inert hydrocarbon liquid include, but are not limited to, isobutane, isopentane, pentane, hexane, hexanes, heptane, octane, petroleum ether, methylcyclohexane and isoparaffins. For example, such isoparaffin solvents are commercially available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas. When slurry-polymerization is used, the residence time in slurry phase polymerization process can be in the range of from 2 to 180 minutes; for example, from 10 to 60 minutes. The resultant mixture of the ethylene based polymer and solvent is then removed from the reactor and the ethylene based polymer is isolated. Solvent is typically recovered via a solvent recovery unit, i.e. heat exchangers and vapor liquid separator drum, and is then recycled back into the polymerization system.

[0083] In some exemplary methods, the polymerizing is performed at a polymerization temperature less than or equal to the melting or “sintering” temperature of the polymer product. For example, the polymerizing may be performed at a polymerization temperature less than or equal to 130 °C, less than or equal to 125 °C, less than or equal to 120 °C, less than or equal to 115 °C, less than or equal to 110 °C, less than or equal to 105 °C, or less than or equal to 100 °C.86408-WO-PCT / DOW 86408 WO25

[0084] As discussed above, the supported catalysts systems described herein are able to achieve a combination of lower comonomer incorporation, a range of weight-average molecular weight Mwcapabilities, and similar-to-higher activity at lower reactor temperatures, which will allow for the production of polymers with improved product performance in linear low-to-high density polyethylene applications as well as additional process flexibility in the production of poly(ethylene-co-l -alkene) copolymers. Moreover, the high activity at lower reactor temperatures exhibited by the supported catalyst systems described herein is expected to be particularly advantageous in some gas-phase polymerization processes.

[0085] In some examples, the polymerizing may be performed at a polymerization temperature greater than or equal to 30 °C and less than or equal to 130 °C, greater than or equal to 40 °C and less than or equal to 130 °C, greater than or equal to 50 °C and less than or equal to 130 °C, greater than or equal to 60 °C and less than or equal to 130 °C, greater than or equal to 60 °C and less than or equal to 120 °C, greater than or equal to 65 °C and less than or equal to 120 °C, greater than or equal to 65 °C and less than or equal to 115 °C, greater than or equal to 70 °C and less than or equal to 115 °C, greater than or equal to 70 °C and less than or equal to 110 °C, greater than or equal to 75 °C and less than or equal to 110 °C, greater than or equal to 75 °C and less than or equal to 105 °C, greater than or equal to 80 °C and less than or equal to 105 °C, or greater than or equal to 80 °C and less than or equal to 100 °C.

[0086] In examples, the concentration of supported catalyst system suspended in an inert hydrocarbon liquid in the slurry-phase polymerization reactor may be up to 50 wt% (weight percent), based on the total weight of the reactor contents,. In some examples, the concentration of supported catalyst system in the slurry-phase polymerization reactor, based on the total weight of the reactor contents, may be up to 40 wt%, up to 30 wt%, up to 20 wt%, up to 10 wt%, up to 5 %, up to 1 %, from 0 to 0.001 wt%, from 0.001 to 0.01 wt%, from 0.01 to 0.1 wt%, from 0.1 to 50 wt%, from 0.1 to 1 wt%, from 1 wt% to 5 wt%, from 5 wt% to 10 wt%, from 10 wt% to 20 wt%, from 20 wt% to 30 wt%, from 30 wt% to 40 wt%, from 40 wt% to 50 wt%, or any combination of two or more of these ranges of solid supported catalyst suspended in the inert hydrocarbon liquid.

[0087] In examples, gases may be used to pressurize the polymerization reactor to a pressure of from 690 kPa (100 psig) to 6,896 kPa (1,000 psig). For example, the reactor pressure of the slurry -phase polymerization reactor may be from 690 kPa (100 psig) to 1,379 kPa (200 psig), from 1,37986408-WO-PCT / DOW 86408 WO26kPa (200 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig) to 2,759 kPa (400 psig), from 2,759 kPa (400 psig) to 3,448 kPa (500 psig), or any combination of two or more of these ranges.

[0088] In examples, ethylene monomer may be one of the gases used to pressurize the polymerization reactor. In embodiments, the ethylene partial pressure may be up to 2413 kPa (350 psig), such as from 35 kpa (5 psig) to 137 kPa (20 psig), from 137 kPa (20 psig) to 345 kPa (50 psig), from 345 kPa (50 psig) to 689 kPa (100 psig), from 689 kPa (100 psig) to 1034 kPa (150 psig), from 1034 kPa (150 psig) to 1378 kPa (200 psig), from 1378 kPa (200 psig) to 1723 kPa (250 psig), from 1723 kPa (250 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig) to 2413 kPa (350 psig), or any combination of two or more of these ranges.

[0089] In some examples, molecular hydrogen gas (H?) may be used in during polymerization to control the final properties of the ethylene-based polymer. The amount of hydrogen used during polymerization may be expressed as a mole ratio relative to the total polymerizable monomer, such as, for example, ethylene or a blend of ethylene and 1 -hexene. The amount of hydrogen used in the polymerization process may be controlled to achieve desired attributes of the ethylene-based polymer, such as, for example, the weight-average molecular weight of the ethylene-based polymer. In embodiments, the mole ratio of hydrogen to total polymerizable monomer (H2:monomer) is greater than or equal to 0.0001. For example, the mole ratio of hydrogen to total polymerizable monomer (H2:monomer) may be from 0.0001 to 1.8, from 0.0001 to 1.0, from 0.0001 to 0.10, from 0.0001 to 0.01, from 0.0001 to 0.005, from 0.0001 to 0.002, from 0.0005 to 1.8, from 0.0005 to 1.0, from 0.0005 to 0.10, from 0.0005 to 0.01, from 0.0005 to 0.005, or from 0.0005 to 0.002.

[0090] The amount of hydrogen in the polymerization may also be expressed as a mole ratio relative to the molar amount of ethylene monomer. For example, the mole ratio of hydrogen to total ethylene monomer (H2: C2, or H2 / C2) may be from 0.0001 to 1.8, from 0.0001 to 1.0, from 0.0001 to 0.10, from 0.0001 to 0.001, from 0.0001 to 0.0005, from 0.0005 to 1.8, from 0.0005 to 1.0, from 0.0005 to 0.10, from 0.0005 to 0.001, from 0.001 to 1.8, from 0.001 to 1.0, from 0.001 to 0.10, from 0.001 to 0.05, from 0.001 to 0.005, or from 0.001 to 0.003.

[0091] In some examples wherein at least one 1 -alkene comonomer is used during polymerization, the ratio between the at least one 1 -alkene comonomer to the ethylene monomer in the polymerization reactor may be from 0.001 to 3, from 0.001 to 2.5, from 0.001 to 2.0, from 0.01 to86408-WO-PCT / DOW 86408 WO272.0, from 0.1 to 2.0, from 0.1 to 1.5, from 0.2 to 1.2, from 0.2 to 1.0, from 0.2 to 0.8, or from 0.4 to 0.8.

[0092] Polyolefins

[0093] The supported catalyst systems described in the preceding paragraphs are utilized in the polymerization of olefin-based polymers. While the supported catalyst systems of this disclosure are utilized in the polymerization of ethylene, it should be understood that such supported catalyst systems may be utilized in the polymerization of other olefins, such as propylene. In some embodiments, there is only a single type of olefin or 1 -alkene (a-olefin) in the polymerization scheme, creating a homopolymer. However, additional a-olefins may be incorporated into the polymerization procedure. The additional a-olefin comonomers typically have no more than 20 carbon atoms. For example, the additional a-olefin comonomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary additional a-olefin comonomers include, but are not limited to, propylene, 1 -butene, 1 -pentene, 1 -hexene, 1 -heptene, 1 -octene, 1 -nonene, 1 -decene, and 4-methyl-l-pentene. For example, additional a-olefin comonomers may be selected from the group consisting of propylene, 1 -butene, 1 -hexene, and 1 -octene; or in the alternative, from the group consisting of 1 -hexene and 1 -octene. In some examples, the additional a-alkene comonomer is 1 -hexene.

[0094] The ethylene-based polymers, for example homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as a-olefins, may comprise from at least 50 percent by weight monomer units derived from ethylene, based on a total weight of the ethylene-based polymer. All individual values and subranges encompassed by “from at least 50 weight percent” are disclosed herein as separate embodiments; for example, the ethylene-based polymers, homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as a-olefins may comprise at least 60 weight percent monomer units derived from ethylene; at least 70 weight percent monomer units derived from ethylene; at least 80 weight percent monomer units derived from ethylene; or from 50 to 100 weight percent monomer units derived from ethylene; or from 80 to 100 weight percent units derived from ethylene. Common forms of ethylene-based polymer known in the art include: Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear86408-WO-PCT / DOW 86408 WO28Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

[0095] In some examples, a poly(ethylene-co-l -alkene) copolymer polymerized in the presence of a supported catalyst system described herein comprises units derived from the ethylene monomer making up at least 50 wt% of the poly(ethylene-co-l -alkene) copolymer, based on a total weight of the poly(ethylene-co-l -alkene) copolymer. For example, the poly(ethylene-co-l-alkene) copolymer may comprise units derived from the ethylene monomer making up at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt% at least 90 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt%, at least 99.5 wt%, at least 99.8 wt%, or at least 99.9 wt% of the poly(ethylene-co-l -alkene) copolymer, based on a total weight of the poly(ethylene-co-l -alkene) copolymer. In some examples, the poly(ethylene-co-l -alkene) copolymer may comprise units derived from the ethylene monomer making up from 50 to 99.99 wt%, from 60 to 99.99 wt%, from 70 to 99.99 wt%, from 80 to 99.99 wt%, from 90 to 99.99 wt%, from 95 to 99.99 wt%, from 96 to 99.99 wt%, from 97 to 99.99 wt%, from 98 to 99.99 wt%, from 99 to 99.99 wt%, from 99 to 99.99 wt%, or from 99.8 to 99.99 wt% of the poly(ethylene-co-l-alkene) copolymer, based on a total weight of the poly(ethylene-co-l -alkene) copolymer.

[0096] In some examples, the poly(ethylene-co-l -alkene) copolymer comprises units derived from the at least one 1 -alkene comonomer making up less than or equal to 10 wt%, less than or equal to 5 wt%, less than or equal to 4 wt%, less than or equal to 3 wt%, less than or equal to 2 wt%, less than or equal to 1 wt%, less than or equal to 0.5 wt% of the poly(ethylene-co-l -alkene) copolymer, based on a total weight of the poly(ethylene-co-l -alkene) copolymer. For example, the poly(ethylene-co-l -alkene) copolymer comprises units derived from the at least one 1 -alkene comonomer making up from 0.01 wt% to 10 wt%, from 0.01 wt% to 5 wt%, from 0.01 wt% to 4 wt%, from 0.01 wt% to 3 wt%, from 0.01 wt% to 2 wt%, from 0.01 wt% to 1 wt%, from 0.01 wt% to 0.5 wt% of the poly(ethylene-co-l -alkene) copolymer, based on a total weight of the poly(ethylene-co- 1 -alkene) copolymer.

[0097] In some embodiments, the ethylene-based polymers polymerized in the presence of a supported catalyst system described herein may have a weight-average molecular weight of greater than or equal to 50,000 g / mol, greater than or equal to 75,000 g / mol, greater than or equal to 100,000 g / mol, greater than or equal to 200,000 g / mol, greater than or equal to 300,000 g / mol, greater than or equal to 400,000 g / mol, greater than or equal to 500,000 g / mol, greater than or86408-WO-PCT / DOW 86408 WO29equal to 600,000 g / mol, or even greater than or equal to 700,000 g / mol. In some examples, the ethylene-based polymers polymerized in the presence of a supported catalyst system described herein may have a weight-average molecular weight of greater than or equal to 75,000 g / mol and less than or equal to 1,000,000 g / mol. In some examples, the ethylene-based polymers polymerized in the presence of a supported catalyst system described herein may have a weight-average molecular weight of greater than or equal to 200,000 g / mol and less than or equal to 1,000,000 g / mol, greater than or equal to 300,000 g / mol and less than or equal to 1,000,000 g / mol, greater than or equal to 400,000 g / mol and less than or equal to 1,000,000 g / mol, greater than or equal to 500,000 g / mol and less than or equal to 1,000,000 g / mol, or even greater than or equal to 600,000 g / mol and less than or equal to 1,000,000 g / mol.

[0098] In some embodiments, the ethylene-based polymers polymerized in the presence of a supported system described herein may have a polydispersity index (PDI) from 1 to 200, where PDI is defined as Mw / Mnwith Mwbeing a weight-average molecular weight and Mnbeing a number-average molecular weight. In some examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 120, from 1 to 50, from 5 to 50, 5 to 30, from 7 to 50, from 7 to 40, from 7 to 30, from 10 to 50, from 10 to 40, or from 10 to 30.

[0099] The ethylene-based polymers may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymers may contain any amounts of additives. The ethylene-based polymers may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene-based polymers and the one or more additives. The ethylene-based polymers may further comprise fdlers, which may include, but are not limited to, organic or inorganic fdlers. The ethylene-based polymers may contain from about 0 to about 20 weight percent fdlers such as, for example, calcium carbonate, talc, or Mg(OH)?, based on the combined weight of the ethylene-based polymers and all additives or fdlers. The ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0100] Embodiments of the supported catalyst systems described in this disclosure have the ability to achieve advantageous catalyst activity in combination with tunable polymer properties as will be shown by the examples that follow.86408-WO-PCT / DOW 86408 WO30

[0101] Emodiments of the supported catalyst systems described in this disclosure yield unique polymer properties as a result of the range of molecular weights of the polymers formed and the amount of the co-monomers incorporated into the polymers.

[0102] All commercial chemicals were used without further purification. Hexanes, Isopar E, and toluene that were used in the glove box were purified through a solvent purification system, then dried over molecular sieves.

[0103] General Procedure for Slurry PPR Experiments

[0104] The reactors were heated to 190 °C, purged with nitrogen for 10 hours, and cooled to 50 °C. On the day of the experiment, the reactors were purged twice with ethylene and vented completely to purge the lines. The reactors were then pre-heated to 50 °C and the stirrers turned on at 800 rpm.

[0105] The reactors were filled to the appropriate solvent level with Isopar-E and the comonomer (1 -hexene) using the robotic needle to give a final total volume of 5 mL (once all of the reagent solutions are added later). The solvent and comonomer injections loading modules 1-3 were performed using the left robotic arm and the solvent injections loading modules 4-6 used the right robotic arm with both arms operating simultaneously. Following solvent injection, the reactors were heated to final desired temperature (100 °C) and stirring increased to programmed set points. When the reactors reached the temperature set point, which required about 10-30 minutes depending on the desired temperature, the cells were pressurized to the desired set point with either pure ethylene, or a mixture of ethylene and hydrogen from the gas accumulator, and the solvent saturated (as observed by the gas uptake). If the ethylene-hydrogen mixture was used, once the solvent was saturated in all cells, the gas feed line was switched from the accumulator to pure ethylene for the remainder of the run.

[0106] The robotic synthesis protocol was then initiated whereby the activator slurry (SMAO) was injected first, followed by the supported catalyst slurries. The reagent and chase injections loading modules 1-3 were performed using the left robotic arm and the solvent injections loading modules 4-6 used the right robotic arm with both arms operating simultaneously. Both injections for a given cell were completed before the robot started the injection of the next cell in the sequence. Each reagent addition was chased with 500 uL of Isopar-E solvent to ensure the complete injection of the reagent. After each reagent addition the needles were washed with Isopar-E inside and outside the needle.86408-WO-PCT / DOW 86408 WO31

[0107] At the moment of the catalyst injection in each individual cell, a reaction timer was started and the PPR software began monitoring the pressure of each cell. The desired pressure (within approximately 2-6 psig) was maintained by the supplemental addition of ethylene gas by opening the valve at the set point minus 2 psi and closing it when the pressure reached 2 psi above set point. All drops in pressure were cumulatively recorded as uptake of the ethylene for the duration of the run. The polymerization reactions proceeded for 90 minutes or to an ethylene uptake of 90 psi, whichever occurred first, and then were quenched by adding a 60 psi overpressure of 10% (v / v) CO2 in argon. Data collection continued for 5 minutes after the quench of each cell. After the last cell finished quenching, any potential leaks identified from the pressure and uptake curves were noted, the reactors were cooled down to 50 °C, vented, and the PPR tubes removed from the module blocks. The PPR library tubes were removed from the drybox and the volatiles then removed using the Genevac rotary evaporator. Once the library vials were re-weighed to obtain the yields, the library was submitted for high throughput polymer analytical.

[0108] SymRAD HT-Compositional GPC Analysis

[0109] High temperature GPC analysis was performed using a Dow Robot Assisted Delivery (RAD) system equipped with a PolymerChar infrared detector (IR5) and Agilent PLgel Mixed A columns. Decane (10µL) was added to each sample for use as an internal flow marker. Samples were first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300ppm butylated hydroxyl toluene (BHT) at a concentration of 10mg / mL and dissolved by stirring at 160°C for 120 minutes. Prior to injection samples were further diluted with TCB stabilized with BHT to a concentration of 2 mg / mL. Samples (250 pL) were eluted through one PL-gel 20 pm (50 x 7.5mm) guard column followed by two PL-gel 20 pm (300 x 7.5mm) Mixed-A columns maintained at 160 °C with TCB stabilized with BHT at a flowrate of 1.0 mL / min. The total run time was 24 minutes. To calibrate for molecular weight (MW) Agilent EasiCal polystyrene standards (PS-1 and PS-2) were analyzed to create a 3rdorder MW calibration curve. Molecular weight units were converted from polystyrene (PS) to polyethylene (PE) using a daily Q-factor calculated around 0.4 using the average of 5 Dow 38-4 reference samples of known MW. Octene incorporation was determined by use of a linear calibration developed by analyzing ethyleneoctene samples with known compositions.86408-WO-PCT / DOW 86408 WO32EXAMPLES

[0110] It should be understood that the Examples are provided to illustrate embodiments described in this disclosure and are not intended to limit the scope of this disclosure or its appended claims.

[0111] Examples 1 to 39 are synthetic procedures for ligand intermediates, ligands, inventive metal-ligand complexes (IMLC), and comparative metal-ligand complexes (CMLC). Examples 7 to 16 correspond to Ligands 1 to 10. Examples 20 to 25 correspond to Metal Precursors 1 to 6. Examples 26 to 39 correspond to IMLC 1 to 12 and CMLC 2 to 3 synthesized from the Ligands and Metal Precursors. In Example 41, the results of the polymerization reactions of S-IMLC 1 -12 and S-CMLC 2 - 3 are tabulated and discussed. One or more features of the present disclosure are illustrated in view of the examples as follows:Example 13-Bromo-N-butyl-2-nitroanilineK2CO3ACN RT / 15h

[0112] A 250-mL round-bottom was charged with l-bromo-3-fluoro-2-nitrobenzene (10.00 g, 45.45 mmol), K2CO3 (7.54 g, 54.55 mmol), and acetonitrile (100 mL). n-BuNH2 (4.5 mL, 45.45 mmol) was added and the reaction was stirred for 2 d at room temperature. All volatiles were removed and the crude product was taken up in EtOAc and water. The organic layer was collected and dried over Na2SO4. Solids were fdtered off and all volatiles were removed to yield the product as an orange solid / oil. The NMR indicates a 75:25 ratio of product to starting material. The material was used on the next step without further purification. Yield: 12.20 g, 98%.

[0113] 'H NMR (400 MHz, CDCI3) 5 7.15 (dd, J = 8.5, 7.8 Hz, 1H), 6.94 (dd, J = 7.8, 1.1 Hz, 1H), 6.76 (dd, J = 8.6, 1.1 Hz, 1H), 5.73 (s, 1H), 3.20 (td, J = 7.1, 5.1 Hz, 2H), 1.66 (tt, J = 8.6, 6.8 Hz, 2H), 1.52 - 1.39 (m, 2H), 0.98 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 5 143.83, 132.99, 121.39, 116.29, 112.38, 43.23, 31.00, 20.14, 13.76.Example 23-bromo-N-(4-butylphenyl)-2-nitroaniline86408-WO-PCT / DOW 86408 WO33DMSO130C / 15 h

[0114] A 100 mL round bottom flask was charged with l-bromo-3-fluoro-2-nitrobenzene (12.15 g, 55.23 mmol, 1 equiv), 4-butylaniline (8.722 mL, 55.23 mmol, 1 equiv), and DMSO (50 mL). The mixture was heated to 130 C for 15 h. After the reaction, DMSO was distilled off and the crude product was purified by column chromatography (Hex: EtOAc 80:20). Yield: 15.2 g, 78.8 %.

[0115] 'H NMR (400 MHz, CDC13) 57.20 (tq, J = 10.6, 3.9 Hz, 4H), 7.13 - 7.06 (m, 3H), 2.64 (q, J = 7.8 Hz, 2H), 1.71 - 1.57 (m, 2H), 1.48 - 1.33 (m, 2H), 0.97 (td, J = 7.3, 2.8 Hz, 3H).13C NMR (101 MHz, CDCI3) 5 141.1, 139.8, 137.0, 132.4, 129.7, 124.7, 124.1, 122.6, 116.1, 103.1, 35.1, 33.7, 22.4, 14.0.Example 33 -bromo-N1-butylbenzene- 1,2-diamineZn (powder)1:1 EtOH:sataq. NH4CI

[0116] A 100 mL round bottom was charged with the 3-bromo-N-butyl-2-nitroaniline (2.64 g, 9.67 mmol), ethanol (30 mL), and sat. aq. NH4CI (10 mL). The mixture was stirred at room temperature under nitrogen, then Zn powder (5.06 g, 77.33 mmol)) was added in portions. The reaction was monitored by LC-MS. After stirring for 2 h EtOAc was added and the mixture was filtered through Celite. The organic layer was collected and purified by column chromatography (80:20 Hex: EtOAc). Yield: 1.72 g, 73%.

[0117] 'H NMR (400 MHz, CDCI3) 5 6.95 (dd, J = 8.1, 1.3 Hz, 1H), 6.70 (t, J = 8.0 Hz, 1H), 6.65 - 6.58 (m, 1H), 3.76 (s, 2H), 3.35 (s, 1H), 3.12 (td, J = 7.0, 3.6 Hz, 2H), 1.68 (dtd, J = 8.6, 7.3, 5.9 Hz, 2H), 1.56 - 1.42 (m, 2H), 1.00 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 5 138.89, 132.35, 121.60, 120.82, 111.23, 110.41, 44.14, 31.71, 20.41, 13.95.Example 486408-WO-PCT / DOW 86408 WO343-bromo-N-(4-butylphenyl)benzene-l,2-diamineZn (Powder) 1:1 EtOH:sat NH4CI OC to RT

[0118] A 100 mL round bottom was charged with the 3-bromo-N-(4-butylphenyl)-2-nitroaniline (1.30 g, 3.72 mmol), ethanol (30 mL), and sat. aq. NH4CI (10 mL). The mixture was stirred at room temperature under nitrogen then Zn powder (1.22 g, 18.6 mmol) was added in portions. The reaction was monitored by LC-MS. After stirring for 2 h EtOAc was added and the mixture filtered through Celite, then the organic layer was collected and purified by column chromatography (90:10 Hex: EtOAc). Yield = 1.10 g, 93%.

[0119] NMR (400 MHz, CDCI3) 57.27 (dd, J = 8.3, 1.5 Hz, 1H), 7.12 - 7.05 (m, 3H), 6.80 -6.71 (m, 2H), 6.64 (t, J = 7.9 Hz, 1H), 5.15 (s, 1H), 4.22 (s, 2H), 2.58 (t, J = 7.7 Hz, 2H), 1.68 -1.54 (m, 2H), 1.50 - 1.31 (m, 2H), 0.97 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 5 142.21, 139.62, 134.85, 130.53, 129.29, 128.14, 122.49, 119.10, 116.24, 110.05, 34.86, 33.92, 22.38, 14.02.Example 54-bromo-l-(4-butylphenyl)-2-(o-tolyl)-lH-benzo[d]imidazole1. EtOH 2. I2 / K2CO3CH2CI2

[0120] A 100 mL round bottom flask was charged with the 3-bromo-A1-(4-butylphenyl)benzene-1,2-diamine (2.50 g, 7.83 mmol), o-tolualdehyde (0.90 mL, 7.83 mmol), and EtOH (50 mL, absolute). The mixture was heated to 70 °C for 15 h. All volatiles were removed, then CH2Q2 (50 mL), K2CO3 (2.38 g, 17.2 mmol), and I2 (1.99 g, 7.83 mmol) were added and the mixture was allowed to stir for 3 h. Water was added to the mixture and the organic layer was collected. The86408-WO-PCT / DOW 86408 WOcrude product was purified by column chromatography (50:50 Hex: CH2Ch (2nd product). Yield = 2.39 g, 73%.

[0121] 'H NMR (400 MHz, CDC13) 57.56 (d, J = 7.7 Hz, 1H), 7.37 - 7.26 (m, 3H), 7.23 - 7.07 (m, 7H), 2.67 - 2.59 (m, 2H), 2.18 (s, 3H), 1.62 (tt, J = 7.8, 6.4 Hz, 2H), 1.37 (h, J = 7.3 Hz, 2H), 0.95 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 5 153.71, 143.32, 141.60, 137.93, 136.33, 133.45, 131.03, 130.22, 129.74, 129.67, 129.43, 126.28, 125.89, 125.41, 124.03, 113.31, 110.00, 35.21, 33.29, 22.34, 20.11, 13.94.Example 64-bromo-l -(4-butylphenyl)-2-(naphthalen-l -yl)-l H-benzo[d] imidazole1. EtOH H 2. I2 / K2CO:N CH2CI2I N

[0122] A 100 mL round bottom flask was charged with the 3-bromo-Nl-(4-butylphenyl)benzene-l,2-diamine (2.50 g, 7.83 mmol), 1 -napthylaldehyde (1.06 mL, 7.83 mmol), and EtOH (50 mL, absolute). The mixture was heated to 70 °C for 15 h. All volatiles were removed, then CH2Q2 (50 mL), K2CO3 (2.38 g, 17.2 mmol), and I2 (1.99 g, 7.83 mmol) were added and the mixture was allowed to stir for 3 h. Water was added to the mixture and the organic layer was collected. The crude product was purified by column chromatography (80:20 Hex: EtOAc). Yield = 2.22 g, 62%.

[0123] 'H NMR (400 MHz, CDCI3) 58.09 - 8.03 (m, 1H), 7.91 - 7.82 (m, 2H), 7.60 (d, J = 7.6 Hz, 1H), 7.48 (pd, J = 5.9, 5.0, 3.0 Hz, 3H), 7.38 (dd, J = 15.6, 8.0 Hz, 2H), 7.21 (t, J = 7.9 Hz, 1H), 7.09 (s, 4H), 2.61 - 2.51 (m, 2H), 1.55 (tt, J = 7.7, 6.4 Hz, 2H), 1.35 - 1.23 (m, 2H), 0.91 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 5 152.67, 143.31, 141.93, 136.77, 133.62, 133.44, 132.27, 130.14, 129.59, 129.39, 128.13, 127.41, 126.99, 126.35, 126.19, 125.95, 125.90, 124.53, 124.15, 113.56, 110.06, 35.13, 33.19, 22.22, 13.89.

[0124] In Examples 7-16, Ligands 1-10 were prepared using the following general procedure. The brominated compounds and amines were provided for a Buchwald-Hartwig cross-coupling reaction in a high throughput sequence beginning with CM3 manipulation. Brominated starting86408-WO-PCT / DOW 86408 WOmaterial were provided and reacted with excess amine (2:1). All reactants / reagents were delivered in solution (Toluene) with the exception of sodium t-butoxide and the catalyst (weighed as solids). Reactions were diluted with additional reaction solvent to ~10 mL before overnight reaction. The following day reaction conversion was checked via UPLC. After 16 h at 95 °C, conversion was high enough to proceed with purification. Purification consisted of three phases: liquid / liquid extraction, filtration through a plug, and Supercritical Fluid Chromatography (SFC). After removal from the glove box, 5 mL of chloroform and 5 mL of saturated aqueous sodium chloride were added to the reaction vial. The vial was capped, shaken, quickly vented, and then poured off into a 25 mL Biotage ISOLUTE® Phase separator column. An additional 5 mL of chloroform was added and the organic phase was collected after gravity filtration. The collected material was poured into a GL Sciences 20 mL InertSep PS-SL filter and gravity filtered again. One wash of 5 mL chloroform was similarly used to rinse the phase separation column, then InertSep filter. A final rinse of the silica pad was performed with 5 mL ethyl acetate and the collected samples were concentrated over 10 h at 80 °C under vacuum on a Savant SpeedVac, which ramped at 5 Torr / min. The solids were then subjected to purification using SFC. Preparative SFC was carried out using a 1-AA 130 A 5 pm OBD 30 x 150 mm column using CO2 as mobile phase A and 75% acetonitrile:25% isopropanol as mobile phase B. The gradient used was 5% B to 50% B over 10 min with a total flow rate of 100 mL / min. The collection make-up solvent used was ethyl acetate, the BPR pressure was 100 bar, oven temp was 40 °C, the sample concentration was 50 mg / mL and injection volume was 960 pL. The desired compounds were collected by mass spectrometry.Example 7Ligand 1NN86408-WO-PCT / DOW 86408 WO37

[0125] 'H NMR (400 MHz, CDCI3) 5 7.59 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 7.5 Hz, 1H), 7.34 -7.12 (m, 10H), 7.05 (t, J = 7.4 Hz, 1H), 6.92 (d, J = 7.9 Hz, 1H), 6.86 (d,. / = 8.1 Hz, 1H), 6.75 (s, 1H), 2.64 (t, J = 7.8 Hz, 2H), 2.41 (s, 3H), 2.23 (s, 3H), 1.63 (qd, J = 8.6, 6.2 Hz, 2H), 1.39 (h, J = 7.3 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 5 150.96, 142.69, 140.25, 137.98, 136.64, 136.39, 134.11, 132.74, 131.05, 131.01, 130.46, 130.44, 130.37, 129.45, 129.24, 126.61, 126.25, 125.54, 124.00, 122.92, 121.15, 104.73, 101.09, 35.22, 33.33, 22.36, 20.16, 18.09, 13.96.Example 8Ligand 2

[0126] 'H NMR (400 MHz, CDC13) 57.37 (dd, J = 7.8, 1.8 Hz, 1H), 7.34 - 7.08 (m, 14H), 6.87 (dt, J = 7.5, 1.0 Hz, 1H), 2.64 (t, J= 7.8 Hz, 2H), 2.21 (s, 3H), 1.70 - 1.57 (m, 2H), 1.38 (m, 18H+2H), 0.96 (t, J= 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 5151.79, 150.90, 142.71, 141.22, 137.92, 136.29, 136.07, 134.03, 132.61, 130.95, 130.45, 130.32, 129.47, 129.23, 126.22, 125.57, 124.14, 115.96, 113.97, 104.21, 101.01, 35.22, 34.96, 33.33, 31.50, 22.36, 20.07, 13.95.86408-WO-PCT / DOW 86408 WO38Example 9Ligand 3

[0127] 'H NMR (400 MHz, CDC13) 8 8.31 - 8.23 (m, 1H), 7.91 (dd, J = 7.0, 2.2 Hz, 1H), 7.73 (d, J = 7.4 Hz, 1H), 7.67 (d, J = 8.2 Hz, 1H), 7.58 - 7.47 (m, 3H), 7.44 - 7.39 (m, 1H), 7.38 - 7.30 (m, 2H), 7.25 - 7.09 (m, 7H), 6.94 (d,. / = 7.8 Hz, 1H), 6.89 (d,. / = 8.0 Hz, 1H), 2.70 - 2.60 (m, 2H), 2.25 (s, 3H), 1.69 - 1.58 (m, 2H), 1.38 (tt, J= 12.7, 6.4 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 8 151.13, 142.74, 137.97, 137.81, 137.22, 136.40, 134.77, 134.09, 132.81, 131.03, 130.44, 130.38, 129.50, 129.26, 128.67, 128.37, 126.25, 126.14, 125.95, 125.68, 125.58, 124.03, 123.61, 122.62, 117.72, 105.16, 101.25, 35.22, 33.33, 22.36, 20.16, 13.96.Example 10Ligand 486408-WO-PCT / DOW 86408 WO

[0128] 'H NMR (400 MHz, CDCI3) 5 7.86 - 7.73 (m, 4H), 7.54 - 7.11 (m, 14H), 6.95 (d, J = 8.1 Hz, 1H), 2.65 (t, J = 7.8 Hz, 2H), 2.22 (s, 3H), 1.64 (qd, J = 8.6, 6.4 Hz, 2H), 1.39 (h, J = 7.3 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 5 151.24, 142.83, 139.92, 137.91, 136.41, 135.19, 134.62, 133.95, 133.14, 130.96, 130.37, 130.34, 129.55, 129.45, 129.29, 129.09, 127.67, 126.75, 126.38, 126.23, 125.60, 124.04, 123.66, 121.01, 112.88, 105.49, 102.12, 35.22, 33.33, 22.36, 20.10, 13.96.Example 11Ligand 5NN

[0129] 'H NMR (400 MHz, CDCI3) 5 7.55 (dd, J= 7.8, 1.4 Hz, 1H), 7.43 - 7.35 (m, 2H), 7.34 - 7.08 (m, 11H), 6.86 - 6.80 (m, 1H), 6.79 - 6.71 (m, 2H), 3.42 (hept, J = 6.9 Hz, 1H), 2.71 -2.58 (m, 2H), 2.24 (s, 3H), 1.63 (tt, J = 8.0, 6.4 Hz, 2H), 1.39 (h, J = 7.3 Hz, 2H), 1.30 (d, J = 6.9 Hz, 6H), 0.97 (t, J= 7.3 Hz, 3H).13C NMR (101 MHz, CDCI3) 5 150.82, 142.78, 142.64, 138.66, 138.03, 138.00, 136.30, 134.17, 132.42, 131.07, 130.48, 130.37, 129.40, 129.22, 126.37, 126.26, 126.23, 125.52, 124.39, 124.07, 124.03, 103.96, 100.53, 35.22, 33.33, 27.73, 23.40, 22.36, 20.18, 13.95.86408-WO-PCT / DOW 86408 WO40Example 12Ligand 6

[0130] 'H NMR (400 MHz, CDC13) 5 8.20 (dt, J = 7.9, 2.8 Hz, 1H), 7.94 - 7.85 (m, 2H), 7.63 (dd, J = 8.1, 1.3 Hz, 1H), 7.58 - 7.45 (m, 3H), 7.41 (dd, J = 8.2, 7.1 Hz, 1H), 7.35 - 7.23 (m, 2H), 7.21 (t, J = 8.0 Hz, 1H), 7.17 - 7.04 (m, 5H), 6.96 (d, J = 7.9 Hz, 1H), 6.89 (d, J = 8.1 Hz, 1H), 6.83 (s, 1H), 2.58 (t,. / = 7.7 Hz, 2H), 2.43 (s, 3H), 1.58 (tt,. / = 9.1, 6.8 Hz, 2H), 1.33 (h, J = 7.3 Hz, 2H), 0.94 (t, J = 7.3 Hz, 3H).Example 13Ligand 7

[0131] 'H NMR (400 MHz, CDCI3) 58.23 (dt, J = 6.9, 3.5 Hz, 1H), 7.97 - 7.76 (m, 6H), 7.59 -7.30 (m, 11H), 7.21 - 7.10 (m, 4H), 7.02 (d,.7= 8.1 Hz, 1H), 2.61 (t, J = 7.7 Hz, 2H), 1.60 (dq, J = 9.1, 7.5 Hz, 2H), 1.36 (h, J= 7.3 Hz, 2H), 0.97 (t, J= 7.3 Hz, 3H).86408-WO-PCT / DOW 86408 WO41Example 14Ligand 8

[0132] ¹H NMR (400 MHz, CDCl3) δ 8.26 – 8.19 (m, 1H), 7.90 (dd, J = 8.9, 6.2 Hz, 2H), 7.59 (dd, J = 7.9, 1.5 Hz, 1H), 7.56 - 7.47 (m, 3H), 7.43 (dd, J = 7.7, 1.9 Hz, 2H), 7.32 - 7.07 (m, 7H), 6.86 (d, J = 7.9 Hz, 2H), 6.79 (d, J = 7.9 Hz, 1H), 3.46 (hept, J = 6.9 Hz, 1H), 2.58 (t, J = 7.7 Hz, 2H), 1.63 - 1.51 (m, 2H), 1.32 (m, 6H + 2H), 0.94 (t, J = 7.3 Hz, 3H).Example 15Ligand 9nBu

[0133] ¹H NMR (400 MHz, CDCl3) δ 7.44 – 7.38 (m, 1H), 7.34 - 7.26 (m, 2H), 7.18 (tt, J = 8.4, 4.3 Hz, 10H), 7.04 (t, J = 8.0 Hz, 1H), 6.77 (d,. / = 8.1 Hz, 1H), 6.49 (s, 1H), 6.05 (d, J = 7.8 Hz, 1H), 2.69 - 2.58 (m, 2H), 2.35 (s, 6H), 2.22 (s, 3H), 1.68 - 1.56 (m, 2H), 1.38 (dq, J = 14.0, 7.0 Hz, 2H), 0.96 (t, J = 7.3 Hz, 3H).86408-WO-PCT / DOW 86408 WO42Example 16Ligand 10nBu

[0134] ¹H NMR (400 MHz, CDCl3) δ 7.46 – 7.40 (m, 1H), 7.40 - 7.26 (m, 4H), 7.21 (s, 2H), 7.01 (t, J= 8.0 Hz, 1H), 6.74 (d, J= 8.1 Hz, 1H), 6.45 (s, 1H), 6.02 (d, J= 7.8 Hz, 1H), 3.40 (hept, J = 6.8 Hz, 2H), 2.70 - 2.56 (m, 2H), 2.25 (s, 3H), 1.63 (tt, J = 8.0, 6.4 Hz, 2H), 1.45 - 1.33 (m, 2H), 1.21 (d, J = 6.9 Hz, 12H), 0.96 (t, J = 7.3 Hz, 3H).Example 171,3 -bis(2,6-diisopropylphenyl)- 1,3 -dihy dro-2H-imidazol-2-imine (IPrNH) 1) N3SiMe3Toluene120 C, 14 h2) MeOHr.t., 2 h

[0135] In a glovebox, l,3-bis(2,6-diisopropylphenyl)-l,3-dihydro-lH-imidazole (1.00 g, 2.57 mmol, 1.0 equiv) was added to a 100 mL round bottom flask along with a magnetic stir bar and toluene (10 mL) at ambient temperature. Trimethylsilyl azide (1.03 mL, 7.72 mmol, 3.0 equiv) was added dropwise at room temperature while maintaining gentle stirring. After the addition was complete, the reaction was heated to 120 °C with a reflux condenser in place for 14 h. The volatiles were removed by vacuum and the resulting colorless, waxy solid was dissolved in toluene (5 mL) and methanol (2 mL) was added. The mixture was stirred for 2 h at room temperature. The volatiles were removed under vacuum and the resulting residue was suspended in hexanes and stored in the refrigerator overnight. The insoluble material was collected on a fdter and washed with additional portions of cold hexanes. Yield: 0.814 g, 78.4%.86408-WO-PCT / DOW 86408 WO43

[0136] 'H NMR (400 MHz, C6D6): 8 7.26 (m, 4 H6), 7.14 (s, 2 H), 5.84 (s, 2 H), 4.21 (s, 1H), 3.12 (sept, J = 6.9 Hz, 4 H), 1.34 (d, J = 6.9 Hz, 12 H), 1.19 (d, J = 6.9 Hz, 12 H).13C NMR (101 MHz, C6D6): 8 154.2, 148.3, 133.1, 130.0, 124.5, 114.0, 29.1, 24.0, 24.0.Example 18l,3-di-tert-butyl-l,3-dihydro-2H-imidazol-2-imine (tBuNH)1) N3SiMe3Toluene" KINI Ki 115, 3 d tBup N N—2) MeOH40 C, 1 h

[0137] In a glovebox, l,3-di-tbutyl-imidazoline-2-ylidene (L14g, 6.30 mmol, 1 equiv) was added to a 100 mL round bottom flask along with a magnetic stir bar and toluene (15 mL) at ambient temperature. Trimethylsilyl azide (1.17 mL, 8.82 mmol, 1.4 equiv) was added dropwise over the course of two minutes at room temperature while maintaining gentle stirring. After the addition was complete, the reaction was heated to 115 °C with a reflux condenser in place. After 52 h, additional TMS-N3 (0.4 mL, 3.0 mmol, 0.47 equiv) was added to compensate for any reagent loss due to evaporation and entrapment in the condenser. After 87 h, the reaction mixture was cooled to ambient temperature, filtered, and concentrated to dryness. The resulting residue was triturated with 4 mL of hexane and the volatiles were removed, affording a solid. An excess of anhydrous methanol (4.5 mL) was added to the solid and the resulting mixture was stirred for 45 min at 40 °C. The mixture was concentrated to a solid. The solid was triturated with hexanes (2 x 4 mL), extracted into hexanes (8 mL), and filtered. The resulting filtrate was concentrated to dryness, affording a nearly colorless solid. Yield: 1.15 g, 93.5%.

[0138] 'H NMR (400 MHz, C6D6) 8 5.96 (s, 2H), 4.65 (s, 1H), 1.40 (s, 18H).13C NMR (101 MHz, C6D6) 8 153.4, 107.3, 28.0.Example 19Tricyclohexyl-phosphinimine (CysPNH)Cy N3SiMe NH I3xSi'NNleOH II- p - Cy Cy Toluene CvxixCv Toluene Cy i CyC85 °C, 18 hyCyy40 °C, 12 h y

[0139] In a glovebox, tricyclohexylphosphine (0.750, 2.67 mmol, 1 equiv) was added to a 40 mL glass vial along with a magnetic stir bar and toluene (6 mL) at ambient temperature. Trimethylsilyl86408-WO-PCT / DOW 86408 WO44azide (0.531 mL, 4.01 mmol, 1.5 equiv) was added dropwise at ambient temperature while maintaining gentle stirring. After the addition was complete, the reaction was heated to 85 °C for 18 h. The reaction mixture was cooled to ambient temperature, fdtered, and concentrated to dryness. The resulting residue was triturated with hexanes (2 x 2 mL) and the volatiles were removed in vacuo, affording a solid. The material was redissolved in toluene (2 mL), and an excess of anhydrous methanol (2 mL) was added. The resulting mixture was stirred for 12 h at 40 °C. The mixture was concentrated to a solid. The solid was triturated with hexanes (3 x2 mL), washed with hexanes (2 x 2 mL), and dried in vacuo, affording a nearly colorless solid. Yield: 0.61 g, 77.2%. 'H NMR (400 MHz, C6D6) 82.01 - 1.80 (m, 6H), 1.80 - 1.48 (m, 12H), 1.48 - 1.23 (m, 6H), 1.21 - 0.99 (m, 9H), 0.23 (s, 1H).13C NMR (101 MHz, C6D6) 8 128.30, 128.29, 128.06, 128.05, 127.82, 127.81, 36.40, 35.85, 27.51, 27.40, 27.34, 27.23, 27.20, 26.87, 26.72, 26.70.31P NMR (162 MHz, C6D6) 836.57.Example 20Metal Precursor 1 - I PrN HfBm,Bn i Hf Bn I BnBn

[0140] In a glovebox, a 20 mL vial was charged with tetrab enzylhafnium(IV) (0.475 g, 0.875 mmol, 1 equiv), l,3-bis(2,6-diisopropylphenyl)-l,3-dihydro-2H-imidazol-2-imine (IPrNH) (0.353 g, 0.875 mmol, 1 equiv), and toluene (5 mL). The mixture was stirred for 18 h at room temperature. The mixture was fdtered and then concentrated under vacuum. The resulting material was triturated with hexanes (5 mL), affording a pale cream-colored precipitate that was collected by fdtration, washed with hexanes, and dried under vacuum. Yield: 0.58 g, 77%.

[0141] 'H NMR (500 MHz, C6D6) 87.25 (dd, J = 8.4, 7.1 Hz, 2H), 7.16 (d, J = 7.7 Hz, 4H), 7.06 (t, J = 7.6 Hz, 6H), 6.93 - 6.84 (m, 3H), 6.45 - 6.31 (m, 6H), 5.95 (s, 2H), 3.12 (hept, J = 6.9 Hz, 4H), 1.40 (d, J = 6.9 Hz, 12H), 1.20 (s, 6H), 1.15 (d, J = 6.9 Hz, 12H).13C NMR (126 MHz, C6D6) 8 147.42, 145.93, 143.13, 134.00, 130.25, 129.59, 127.95, 124.45, 122.41, 114.31, 70.78, 29.18, 24.43, 23.7.86408-WO-PCT / DOW 86408 WO45Example 21Metal Precursor 2- IPrNZrBm,Bn i Toluene Zr,, Bn i BnBn r.t., 18 hiPr iPr

[0142] In a glovebox, a 20 mL vial was charged with tetrabenzylzirconium(IV) (0.500 g, 0.875 mmol, 1 equiv), l,3-bis(2,6-diisopropylphenyl)-l,3-dihydro-2H-imidazol-2-imine (IPrNH) (0.442 g, 0.875 mmol, 1 equiv), and toluene (5mL). The mixture was stirred for 18 h at room temperature, followed by fdtration concentration under vacuum. The resulting material was triturated with hexanes (5 mL), collected by fdtration, washed with hexanes, and dried under vacuum, affording a yellow solid. Yield: 0.488 g, 58%.

[0143] 'H NMR (500 MHz, C6D6) 87.25 (dd, J = 8.4, 7.1 Hz, 2H), 7.16 (d, J = 7.5 Hz, 4H), 7.03 (t, J = 7.7 Hz, 6H), 6.92 - 6.84 (m, 3H), 6.36 - 6.19 (m, 6H), 5.92 (s, 2H), 3.14 (hept, J = 6.9 Hz, 4H), 1.41 (d, J = 6.9 Hz, 12H), 1.36 (s, 6H), 1.15 (d, J = 6.9 Hz, 12H).13C NMR (126 MHz, C6D6) 8 147.42, 143.01, 142.58, 134.10, 130.23, 130.10, 127.32, 124.46, 121.99, 114.39, 60.27, 29.20, 24.50, 23.65.Example 22Metal Precursor 3- tBuNHfBm,BnI TolueneHfBn l BnBn r.t, 4 h

[0144] In a glovebox, l,3-di-tert-butyl-l,3-dihydro-2H-imidazol-2-imine (tBuNH) (0.213 g, 1.09 mmol, 1 equiv) was added to a 20 mL vial and dissolved in toluene (15 mL). In a separate 50 mL glass jar, tetrabenzylhafnium(IV) (0.564 g, 1.04 mmol, 0.95 equiv) was dissolved in toluene (15 mL). At room temperature, the colorless solution of 2H-imidazol-2-imine was added dropwise to the stirring yellow solution of Hf precursor. The faint yellow reaction mixture was then allowed to stir at room temperature for 4 h. The volatiles were removed in vacuo, and the86408-WO-PCT / DOW 86408 WO46yellow-brown residue was triturated with hexanes (2 x 10 mL) to afford a sticky yellow solid. The solid was taken up in toluene, fdtered through celite, and the fdtrate was concentrated. The resulting yellow residue was triturated with hexanes (2 x 5 mL) and then extracted into hexanes (4 x 10 mL). The extracts were combined, fdtered, concentrated, and then stored at -25 °C. Colorless crystals formed and were collected and dried under vacuum. Additional crops of colorless crystals were collected from storage of the mother liquor at -25 °C. Yield: 0.465 g, 66.0%.

[0145] 'H NMR (500 MHz, C6D6) 8 7.22 - 7.17 (m, 6H), 7.00 - 6.94 (m, 3H), 6.91 - 6.88 (m, 6H), 5.92 (s, 2H), 1.95 (s, 6H), 1.39 (s, 18H).13C NMR (126 MHz, C6D6) 8 145.9, 144.2, 129.5, 128.4, 122.6, 107.6, 75.5, 56.3, 28.2.Example 23Metal Precursor 4- tBuNZrBm,Bn i TolueneZrBn i BnBn r.t., 4 h

[0146] In a glovebox, l,3-di-tert-butyl-l,3-dihydro-2H-imidazol-2-imine (tBuNH) (0.214 g, 1.10 mmol, 1 equiv) was added to a 20 mL vial and dissolved in toluene (15 mL). In a separate 50 mL glass jar, tetrabenzylzirconium(IV) (0.474 g, 1.04 mmol, 0.95 equiv) was dissolved in toluene (15 mL). At room temperature, the colorless solution of 2H-imidazol-2-imine was added dropwise to the stirring yellow-orange solution of Zr precursor. The yellow-orange reaction mixture was then allowed to stir at room temperature for 4 h. The volatiles were removed in vacuo, and the dark orange residue was triturated with hexanes (2 x 10 mL) to afford a pale peach-colored solid. The material was taken up in toluene, fdtered through celite. The fdtrate was concentrated, triturated with hexanes (2 x 5 mL), and then stirred in hexanes (20 mL). The hexanes insoluble was isolated by fdtration and dried under vacuum. Yield: 0.282 g, 46.0%.

[0147] 'll NMR (500 MHz, C6D6) 8 7.24 - 7.13 (m, 4H), 6.99 - 6.93 (m, 3H), 6.85 - 6.79 (m, 6H), 5.90 (s, 2H), 2.05 (s, 6H), 1.42 (s, 18H).13C NMR (126 MHz, C6D6) 8 144.1, 142.7, 130.0, 127.7, 122.4, 107.7, 63.7, 56.5, 28.3.86408-WO-PCT / DOW 86408 WO47Example 24Metal Precursor 5- CpZrBns! 3.15 equiv BnMgCICI' i 'CI - ► BnXlXBnCl TolueneBn-25 °C to r.t., 1 h

[0148] In a glovebox, CpZrCh (1.15 g, 4.37 mmol, 1 equiv), a magnetic stir bar, and toluene (10 mL) were combined in a 50 mL glass jar and stored at -25 °C for 60 min. Separately, a 1.0 M solution of BnMgCI in diethyl ether (13.78 mL, 13.78 mmol, 3.15 equiv) was added to a 20 mL vial and also stored at -25 °C for 60 min. After this cooling time, the Grignard solution was added dropwise to the gray / brown suspension of Zr precursor in toluene while stirring vigorously. The suspension gradually turned vibrant yellow / orange as the addition was carried out. The reaction mixture was then allowed to warm to room temperature and left to continue stirring vigorously at ambient temperature for 60 min. The resulting bright yellow suspension was then fdtered through a disposable fdter and the fdter cake was washed with toluene (10 mL). The golden yellow fdtrate was concentrated under vacuum, affording a bright yellow solid that was triturated with hexanes (2 x 10 mL) and washed with hexanes (2 x 20 mL). The bright yellow solid was then extracted into in toluene (2 x 20 mL) and concentrated to 10 mL prior to storage at -25 °C for 48 h. Yellow crystals were collected by separating the mother liquor and washing the crystals with hexanes (1.5 mL). The crystals were dried under vacuum and stored at -25 °C as a solid. Yield: 1.20 g, 63.9 %. 'H NMR (400 MHz, C6D6) 8 7.11 - 7.04 (m, 6H), 6.99 - 6.92 (m, 3H), 6.50 - 6.44 (m, 6H), 5.60 (s, 5H), 1.49 (s, 6H).13C NMR (101 MHz, C6D6) 8 143.5, 130.1, 127.6, 123.6, 111.9, 65.7.Example 25Metal Precursor 6 - Cy3PNZrBn3CyCy Cy^-CyCy^ Cy?nToluene IIP + Zr - ►NNHBn'BnBnr.t., 18 hBnZI BnBn

[0149] In a glovebox, a vial was charged with ZrB (0.500 g, 1.097 mmol) and CysPNH (0.324 g, 1.097 mmol) and toluene (5 mL). The mixture was stirred overnight, concentrated and triturated with hexanes to afford a pale yellow solid. 'H NMR (400 MHz, CeDe) 87.21 - 7.12 (m, 6H), 6.9586408-WO-PCT / DOW 86408 WO48(t, J = 7.4 Hz, 3H), 6.83 (d,. / = 6.8 Hz, 6H), 1.96 (s, 6H), 1.79 (d, J = 13.6 Hz, 6H), 1.75 - 1.66 (m, 6H), 1.64 - 1.52 (m, 6H), 1.29 (q, J = 12.5 Hz, 6H), 1.09 (d, J = 7.9 Hz, 9H).13C NMR (126 MHz, C6D6) 8 144.16, 129.76, 126.66, 121.50, 59.31, 36.04, 35.58, 26.88, 26.78, 26.71, 26.69, 26.14.31P NMR (202 MHz, C6D6) 8 16.62.

[0150] Inventive Metal Ligand Complexes (IMLC)

[0151] In Examples 26 to 39, IMLC 1 to 12 and CMLC 2 to 3 were prepared using the following general procedure: Inside a glovebox, a 0.5 - 2 mL aliquot from a 5 mM toluene solution of benzimidazole-amine ligand was transferred to a 7 mL glass vial and the volatiles were removed in vacuo. The resulting residue was massed and 1 equiv of a 5 mM CeDe solution of metal precursor was added to the vial at room temperature. After combining the ligand material and solution of metal precursor, the mixture was transferred to an NMR tube and checked by1H NMR spectroscopy to ensure conversion to the target complex, which was confirmed by the appearance of one equivalent of toluene. After confirmation, the NMR sample was returned to the glovebox and all volatiles were removed. Ligand and metal precursor were in contact at room temperature with each other for 2 - 24 h at ambient temperature to ensure product formation. All volatiles were removed and the crude product was used without further purification for supporting on SDMAO, and then PPRtesting.

[0152] The ligand and metal precursor used to make the IMLC and CMLC are summarized in Table 1:TABLE 1: IMLC 1-12 and CMLC 2-3Example IMLC Ligand Metal PrecursorEx. 26 IMLC-1 L3 IPrNZrBn?Ex. 27 IMLC-2 LI IPrNZrBn?Ex. 28 IMLC-3 L5 IPrNZrBn?Ex. 29 IMLC-4 L8 IPrNZrBn?Ex. 30 IMLC-5 L6 IPrNZrBn?Ex. 31 IMLC-6 L7 IPrNZrBn?Ex. 32 IMLC-7 L7 tBuNHfBn3Ex. 33 IMLC-8 L7 iBuNZrBniEx. 34 IMLC-9 L2 IPrNZrBn?Ex. 35 IMLC- 10 L2 iBuNZrBniEx. 36 IMLC- 11 L4 IPrNZrBn?Ex. 37 IMLC- 12 L4 iBuNZrBni86408-WO-PCT / DOW 86408 WO49Ex. 38 CMLC-2 L9 CpZrBnsEx. 39 CMLC-3 L10 Cy3PNZrBn3

[0153] The IMLC 1 to 12 were characterized using!H NMR and are summarized below:

[0154] Example 26- IMLC-1: NMR (500 MHz, C6D6) 8 8.02 (d,. / = 7.7 Hz, 1H), 7.83 (d, J = 8.2 Hz, 1H), 7.69 (d, J = 8.2 Hz, 1H), 7.58 - 7.49 (overlapping multiplets, 2H), 7.42 - 7.22 (overlapping multiplets, 2H), 7.13 - 6.98 (overlapping resonances, 8H), 6.90 (m, 2H), 6.80 - 6.68 (overlapping resonances, 8H), 6.63 (t, J= 8.0 Hz, 1H), 6.59 - 6.48 (m, 2H), 6.43 (s, 1H), 6.37 (d, J = 8.0 Hz, 1H), 6.18 (s, 2H), 5.91 (s, 2H), 5.46 (d,. / = 8.0 Hz, 1H), 3.39 (m, 2H), 3.15 (m, 2H), 2.74 (d,. / = 10.4 Hz, 1H), 2.28 (d, J= 11.1 Hz, 1H), 2.23 (t, J = 7.8 Hz, 2H), 1.84 (s, 3H), 1.80 (d, J = 11.3 Hz, 1H), 1.55 (br m, 1H), 1.37 (d, J = 6.8 Hz, 6H), 1.32- 1.21 (overlapping multiplets, 4H), 1.18 - 1.03 (overlapping multiplets, 18H), 0.78 (t, J = 7.3 Hz, 3H).

[0155] Example 27- IMLC-2:1HNMR(500MHz, C6D6) 87.87 (s, 1H), 7.22 - 7.19 (overlapping multiplets, 2H), 7.15 - 7.11 (overlapping multiplets, 4H), 7.10 - 6.99 (overlapping multiplets, 8H), 6.94 - 6.84 (overlapping multiplets, 4H), 6.79 (br m, 4H), 6.71 (d, J = 7.9 Hz, 4H), 6.48 (d, J = 8.0 Hz, 2H), 5.95 (s, 2H), 5.78 (d, J = 7.9 Hz, 1H), 3.32 (br m, 4H), 2.29 - 2.19 (m, 2H), 1.91 (s, 3H), 1.77 (s, 3H), 1.73 (br m, 2H), 1.34 (s, 4H), 1.31 - 1.23 (overlapping multiplets, 14H), 1.16 (overlapping multiplets, 12H), 1.14 - 1.05 (m, 2H), 0.78 (t, J = 7.3 Hz, 3H).

[0156] Example 28- IMLC-3:1H NMR (500 MHz, C6D6) 87.87 (d, J = 7.6 Hz, 1H), 7.70 (dd, J = 7.9, 1.4 Hz, 1H), 7.39 (dd, J= 7.7, 1.7 Hz, 1H), 7.35 (dd, J= 7.6, 1.4 Hz, 1H), 7.30 - 7.18 (overlapping multiplets, 3H), 7.09 - 6.99 (m, 4H), 6.99 - 6.82 (m, 4H), 6.81 - 6.66 (m, 4H), 6.51 - 6.43 (m, 2H), 6.34 (d, J = 7.5 Hz, 2H), 5.93 (s, 2H), 5.75 (d, J = 7.9 Hz, 1H), 3.36 (hept, J = 6.9 Hz, 2H), 3.27 (hept, J = 6.9 Hz, 2H), 2.51 (d, J = 9.7 Hz, 1H), 2.33 - 2.19 (overlapping multiplets, 7H), 1.93 (d, J = 11.5 Hz, 1H), 1.66 (s, 3H), 1.30 (d, J = 6.9 Hz, 6H), 1.26 (d, J = 6.9 Hz, 6H), 1.19 - 1.14 (overlapping multiplets, 12H), 1.13 - 1.05 (overlapping multiplets, 4H), 0.80 (t, J = 7.4 Hz, 1H).

[0157] Example 29- IMLC-4: *HNMR (500 MHz, C6D6) 87.60 (d, J = 8.2 Hz, 1H), 7.57 - 7.30 (overlapping multiplets, 5H), 7.30 - 7.18 (overlapping multiplets, 8H), 7.10 - 6.82 (overlapping multiplets, 10H), 6.79 - 6.61 (overlapping multiplets, 6H), 6.53 (d, J = 8.0 Hz, 2H), 6.50 - 6.40 (overlapping multiplets, 4H), 6.29 (d, J = 7.4 Hz, 1H), 6.13 (br s, 2H), 5.94 (s, 2H), 5.81 (d, J = 7.9 Hz, 1H), 3.50 - 3.33 (m, 2H), 3.28 (hept, J = 6.9 Hz, 2H), 2.56 (d, J = 9.4 Hz, 1H), 2.27 (d, J = 11.6 Hz, 1H), 2.07 - 1.96 (overlapping multiplets, 3H), 1.54 - 1.46 (m, 1H), 1.32 (d, J = 6.8 Hz,86408-WO-PCT / DOW 86408 WO506H), 1.26 (d, J = 6.6 Hz, 6H), 1.19- 1.04 (overlapping multiplets, 18H), 1.00 - 0.83 (m, 2H), 0.81 - 0.72 (m, 2H), 0.69 (t, J = 7.3 Hz, 3H).

[0158] Example 30- IMLC-5:1H NMR (500 MHz, C6D6) 87.58 (d, J = 8.3 Hz, 1H), 7.44 (t, J = 7.7 Hz, 1H), 7.34 (d, J = 8.2 Hz, 1H) 7.27 - 7.10 (overlapping with NMR solvent), 7.09 - 6.99 (overlapping multiplets, 6H), 6.99 - 6.83 (overlapping multiplets, 6H), 6.81 - 6.69 (overlapping multiplets, 4H), 6.62 - 6.43 (overlapping multiplets, 6H), 5.96 (s, 2H), 5.81 (d, J = 7.8 Hz, 1H), 3.40 (br m, 2H), 3.26 (br m, 2H), 2.28 - 2.22 (br m, 1H) 2.03 (t, J = 7.8 Hz, 2H), 1.98 - 1.83 (broad and overlapping, 3H), 1.34- 1.31 (broad and overlapping, 9H), 1.18 - 1.12 (m, 18H), 1.12 - 1.05 (m, 2H), 1.01 - 0.89 (m, 2H), 0.69 (t, J = 7.3 Hz, 3H).

[0159] Example 31- IMLC-6:nHNMR (500 MHz, C6D6) 88.20 (dd, J = 7.1, 1.3 Hz, 1H), 7.84 - 7.73 (overlapping multiplets, 3H), 7.63 (d, J = 8.6 Hz, 1H), 7.61 - 7.52 (overlapping doublets, J = 8.2, 8.2 Hz, 2H), 7.47 - 7.38 (overlapping multiplets, 2H), 7.38 - 7.26 (m, 4H), 7.16 - 6.99 (m, 10H), 6.99 - 6.82 (m, 6H), 6.78 - 6.68 (m, 3H), 6.57 (d, J = 8.2 Hz, 2H), 6.52 (dd, J = 8.0, 0.7 Hz, 1H), 6.37 (d, J = 8.0 Hz, 1H), 6.18 (t, J= 7.7 Hz, 1H), 6.12 (s, 1H), 6.11 - 6.07 (m, 1H), 6.00 (s, 2H), 3.57 (hept, J = 6.9 Hz, 1H), 3.49 (hept, J = 6.9 Hz, 1H), 3.29 (br m, 3H), 3.09 (hept, J = 6.8 Hz, 1H), 2.45 (d, J = 10.0 Hz, 2H), 2.04 (t, J = 7.7 Hz, 2H), 1.15 (s, 3H), 1.13 (d, J = 6.8 Hz, 13H), 1.12 (d, J = 6.9 Hz, 2H), 1.08 (d, J = 6.7 Hz, 2H), 1.06 (d, J = 6.8 Hz, 1H), 1.00 - 0.93 (m, 2H), 0.92 - 0.87 (m, 2H), 0.70 (t, J = 7.3 Hz, 3H).

[0160] Example 32- IMLC-7:1H NMR (500 MHz, CeDe) 87.84 - 7.79 (overlapping multiplets, 2H), 7.75 (t, J = 8.5 Hz, 1H), 7.69 - 7.59 (overlapping multiplets, 2H), 7.54 (dd,.7= 7.1, 1.2 Hz, 1H), 7.44 (dt, J = 8.4, 1.0 Hz, 1H), 7.40 (dd, J = 7.9, 1.7 Hz, 1H), 7.38 - 7.31 (m, 1H), 7.27 (ddd, J = 8.1, 6.8, 1.3 Hz, 1H), 7.15 - 7.06 (overlapping multiplets, 6H), 7.05 - 6.98 (overlapping multiplets, 8H), 6.94 (d, J = 8.4 Hz, 2H), 6.84 - 6.73 (overlapping multiplets, 2H), 6.58 (d, J = 8.4 Hz, 2H), 6.51 (ddd, J = 10.4, 8.0, 0.8 Hz, 2H), 5.80 (s, 2H), 2.23 - 2.19 (m, 2H), 2.09 - 2.04 (overlapping multiplets, 2H), 2.02 (d, J = 11.4 Hz, 1H), 1.97 (d, J = 10.9 Hz, 1H), 1.19 (s, 18H), 1.18 - 1.10 (m, 2H), 1.05 - 0.95 (m, 2H), 0.72 (t, J = 7.3 Hz, 3H)

[0161] Example 33- IMLC-8: *HNMR (500 MHz, C6D6) 87.94 (d, J = 2.0 Hz, 1H), 7.77 - 7.68 (overlapping multiplets, 3H), 7.66 (d, J = 8.1 Hz, 1H), 7.59 (dd, J = 8.4, 1.1 Hz, 1H), 7.45 - 7.41 (m, 2H), 7.41 - 7.36 (m, 1H), 7.34 - 7.22 (overlapping multiplets, 3H), 7.19 - 7.09 (NMR solvent and multiplets overlapping), 7.07 - 6.96 (overlapping multiplets, 9H), 6.87 (d, J = 7.6 Hz, 2H), 6.84 - 6.81 (m, 1H), 6.76 (t,. / = 7.2 Hz, 1H), 6.71 (dd,. / = 7.9, 0.7 Hz, 1H), 6.60 (d,. / = 8.1 Hz,86408-WO-PCT / DOW 86408 WO512H), 6.58 (dd, J = 8.0, 0.7 Hz, 1H), 5.75 (s, 2H), 2.57 (d, J = 10.6 Hz, 1H), 2.52 (d, J = 10.5 Hz, 1H), 2.12 - 2.05 (m, 2H), 2.06 (d, J = 9.9 Hz, 1H), 2.00 (d, J = 10.5 Hz, 1H), 1.23 (s, 18H), 1.18 - 1.08 (m, 2H), 1.02 (dt, J = 14.8, 7.3 Hz, 2H), 0.73 (t, J = 7.3 Hz, 3H)

[0162] Example 34- IMLC-9: 'H NMR (500 MHz, C6D6) 8 8.09 (dd,. / = 7.6, 1.4 Hz, 1H), 7.42 (t, J = 1.8 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.29 - 7.18 (overlapping multiplets, 10H), 7.08 - 6.71 (m, 16H), 6.41 (dd, J = 8.0, 0.7 Hz, 2H), 6.37 (s, 2H), 5.99 (s, 2H), 5.72 (d, J = 8.0 Hz, 1H), 3.36 (broad and overlapping multiplets, 4H), 2.29 - 2.20 (m, 2H), 1.84 (s, 3H), 1.62 (d, J = 9.6 Hz, 2H), 1.51 (s, 18H), 1.35 - 1.25 (broad and overlapping multiplets, 14H), 1.19 (d, J = 6.9 Hz, 12H), 1.16 - 1.03 (overlapping multiplets, 4H), 0.79 (t, J = 7.3 Hz, 3H).

[0163] Example 35- IMLC-10: ¹H NMR (500 MHz, C₆D₆) δ7.40 - 7.38 (overlapping multiplets, 3H), 7.36 (dd, J= 7.5, 1.5 Hz, 1H), 7.20 - 7.09 (NMR solvent and overlapping multiplets, 10H), 7.04 - 6.91 (overlapping multiplets, 8H), 6.88 - 6.80 (overlapping resonances, 4H), 6.78 - 6.69 (m, 2H), 6.48 (overlapping doublets, J = 7.9, 5.0 Hz, 2H), 5.86 (s, 2H), 2.43 (d, J = 10.5 Hz, 1H), 2.31 (d, J = 10.5 Hz, 1H), 2.24-2.18 (overlapping doublets, 2H), 1.94 (s, 3H), 1.41 (s, 18H), 1.33 (s, 18H), 1.31 - 1.22 (m, 2H), 1.15 - 1.06 (m, 2H), 0.78 (t, J = 7.3 Hz, 3H).

[0164] Example 36- IMLC-11: ¹H NMR (500 MHz, C₆D₆) δ8.05 (dd, J= 7.7, 1.4 Hz, 1H), 7.81 (d,.7= 8.1 Hz, 1H), 7.80 - 7.76 (overlapping multiplets, 2H), 7.62 (d, J = 8.6 Hz, 1H), 7.40 (ddd, J = 8.2, 6.8, 1.3 Hz, 1H), 7.37 - 7.28 (overlapping multiplets, 2H), 7.15 - 6.94 (m, 14H), 6.88 (t, J = 8.0 Hz, 1H), 6.78 - 6.70 (overlapping multiplets, 7H), 6.55 - 6.48 (overlapping multiplets, 2H), 6.50 (d, J = 8.0 Hz, 1H), 6.37 (overlapping multiplets, 2H), 6.34 (d, J = 7.9 Hz, 1H), 6.00 (s, 2H), 3.50 - 3.32 (broadened resonances, 4H), 2.50 (d, J = 9.7 Hz, 2H), 2.30 - 2.19 (m, 2H), 1.79 (s, 3H), 1.33 - 1.20 (overlapping multiplets), 1.15 (d, J = 6.7 Hz, 12H), 1.13 - 1.06 (m, 2H), 0.78 (t, J = 7.3 Hz, 3H).

[0165] Example 37- IMLC-12: 'H NMR (500 MHz, C6D6) 8 7.91 (d, J= 1.8 Hz, 1H), 7.75 -7.62 (overlapping multiplets, 4H), 7.37 - 7.18 (overlapping multiplets, 4H), 7.16 - 6.91 (NMR solvent and overlapping multiplets), 6.87 - 6.79 (overlapping multiplets, 3H), 6.76 (d, J= 8.2 Hz, 2H), 6.72 (d, J= 7.7 Hz, 1H), 6.67 (d, J= 7.8 Hz, 1H), 6.56 (dd, J= 8.0, 0.8 Hz, 1H), 5.81 (s, 2H), 2.53 (d, J= 10.7 Hz, 1H), 2.48 (d, J= 10.7 Hz, 1H), 2.36 (d, J= 10.6 Hz, 1H), 2.27 (d, J = 10.5 Hz, 1H), 1.97 (s, 3H), 1.29 (s, 18H), 1.29 - 1.22 (m, 2H), 1.19 - 1.04 (m, 2H), 0.79 (t, J = 7.3 Hz, 3H).

[0166] Comparative Metal-Ligand Complexes (CMLCs)86408-WO-PCT / DOW 86408 WO52

[0167] The structures of comparative metal-ligand complexes CMLC-2 and CMLC-3 are shown below:CMLC-2Example 38CMLC-2

[0168] 'H NMR (500 MHz, C6D6) 8 7.89 - 7.84 (m, 1H), 7.20 (t, J = 7.6 Hz, 2H), 7.14 - 7.08 (overlapping multiplets, 4H), 7.07 - 7.00 (overlapping multiplets, 4H), 6.99 - 6.95 (overlapping multiplets, 2H), 6.92 - 6.87 (m, 2H), 6.83 (t, J= 7.4 Hz, 2H), 6.69 (d, J = 8.1 Hz, 2H), 6.66 - 6.61 (m, 2H), 6.58 (dd, J = 8.1, 0.7 Hz, 1H), 5.89 (dd, J = 7.9, 0.7 Hz, 1H), 5.68 (s, 5H), 3.08 (d, J = 10.7 Hz, 1H), 2.51 (d, J = 10.6 Hz, 1H), 2.31 (d, J = 10.7 Hz, 1H), 2.22 - 2.15 (m, 3H), 2.14 (s, 3H), 2.09 (s, 3H), 1.85 (s, 3H), 1.28 - 1.18 (m, 2H), 1.14 - 1.04 (m, 2H), 0.76 (t, J = 7.3 Hz, 3H).Example 39CMLC-3

[0169] 1H NMR (500 MHz, C6D6) 87.81 (d, J= 7.5 Hz, 1H), 7.34 - 7.20 (overlapping multiplets, 6H), 7.13 - 6.98 (overlapping multiplets, 10H), 6.84 (d, J = 7.6 Hz, 2H), 6.76 - 6.67 (m, 2H), 6.67 - 6.58 (m, 2H), 5.99 (d, J= 7.9 Hz, 1H), 3.65 - 3.48 (m, 2H), 3.10 (br s, 1H), 3.00 (br s, 1H), 2.76 (br s, 1H), 2.64 (br s, 1H), 2.19 (t, J= 7.8 Hz, 2H), 1.92 (s, 3H), 1.70- 1.52 (broad and overlapping, 18H), 1.40 - 1.17 (broad and overlapping, 16H), 1.15 - 1.03 (broad and overlapping, 16H), 0.76 (t, J = 7.2 Hz, 3H).Example 40Synthesis of Supported Catalysts86408-WO-PCT / DOW 86408 WO53

[0170] In Example 40, IMLC 1 to 12 and CMLC 2 to 3 were used to prepare supported catalysts. In a nitrogen filled continuous purge glovebox, unsupported metal-ligand complexes (z.e., unsupported IMLC 1 to 12 or CMLC 2 to 3) are diluted to 4.21 mM in anhydrous deoxygenated toluene, and pipetted into oven-dried 4 mL or 8 mL scintillation vials containing a pre-weighed amount of SMAO such that the resultant slurry is 45 umol Zr or Hf per 1 g SMAO, unless otherwise noted. The metal-ligand complex slurries are stirred at 300 rpm and heated to 50 °C for 30 minutes, then returned to ambient temperature. Colorization of the previously white SMAO indicates the catalyst has been supported, but is not quantified or recorded at this stage.1H-NMR experiments of the remaining liquid reveals no remaining precatalyst or active catalyst present in the liquid layer. Therefore, supporting reactions are assumed to reach full conversion. The room temperature slurries are moved to a vortexing unit and agitated at 700 rpm for uniform dispersion. Slurries are agitated for at least one minute before an aliquot may be daughtered by positive displacement tip (PDT) into an 8 mL vial, and vortexing continues during the daughtering process. Daughters (or supported catalysts) will be diluted with Isopar E to 50 - 500 nmol per mL depending on the expected PPR performance. Catalyst materials and supported catalysts are kept in a glovebox freezer at -30 °C for storage.

[0171] Supported inventive metal-ligand complexes S-IMLC-1 to 12 were prepared using the above procedure for synthesizing supported catalysts with IMLC-1 to 12, respectively, as the metal-ligand complex to be supported. Supported comparative metal-ligand complexes S-CMLC-2 and S-CMLC-3 were prepared using the above procedure for synthesizing supported catalysts with CMLC-2 and CMLC-3, respectively, as the metal-ligand complex to be supported.Example 41Polymerization Reactions

[0172] Catalyst activity (in terms of quench time and polymer yield) and resulting polymer characteristics were assessed for supported IMLC 1 - 12 and CMLC 2 - 3, referred herein as S-IMLC 1 to 12 and S-CMLC 2 to 3, respectively. The polymerization reactions were carried out in a slurry parallel pressure reactor (PPR) under high density conditions.

[0173] The reaction conditions for the results tabulated in Tables 2 and 3 followed the General Procedure for Slurry PPR Experiments disclosed herein.86408-WO-PCT / DOW 86408 WO54TABLE 2: Catalyst activity (quench time), Mw, PDI, hexene incorporation and yield of polymers produced in slurry parallel pressure reactor under high density conditions at 100 °C.Supported Loading Uptake Quench Mw PDI C6 Yield MzCatalyst (nmol) (psi) Time (s) (g / mol) (Mw / Mn) (wt%) (mg) S-CMLC-2 25 90 1,344 206,597 14.4 1,637,742 0.0 113S-CMLC-3 25 90 1,239 89,656 3.4 585,277 3.7 168 S-IMLC-1 25 90 578 502,148 4.4 1,515,950 0.5 145 S-IMLC-2 25 90 1,170 737,266 5.0 1,747,280 0.7 137 S-IMLC-3 25 90 1,002 615,036 9.1 1,431,509 2.6 124 S-IMLC-4 25 90 1,580 78,835 3.0 198,004 3.4 138 S-IMLC-5 25 90 1,688 85,157 2.6 177,179 2.3 128 S-IMLC-6 25 90 1,082 346,790 7.3 937,247 0.2 141 S-IMLC-7 25 80 5,400 742,528 7.8 2,174,031 0.0 102 S-IMLC-8 25 47 5,401 517,321 13.1 1,898,051 0.3 62 S-IMLC-9 25 41 5,400 416,936 37.2 1,941,334 0.7 50 S-IMLC-10 25 56 5,400 440,343 14.3 1,722,589 1.1 37 S-IMLC-11 25 90 3,849 565,092 9.1 1,747,795 0.1 123 S-IMLC-12 25 79 5,402 607,704 8.9 1,832,261 0.4 100 *Slurry PPR conditions: Temp. = 100 °C, IsoparE = 5 mL, C6 / C2 (molar ratio) = 0.6 in liquid, H2 / C2 (molar ratio) = 0.0016 in liquid, run time = 90 mins max (5400 s), Quench time = time needed to uptake 90 psi of ethylene; the faster the quench time, the more active the catalyst is. All catalysts are 45 µmol Zr or Hf / g HEIGHT="469" WIDTH="523" SRC="imgf000054_0001_table.tif" / > SMAO; n.d. = not determined.TABLE 3: Catalyst activity (quench time), Mw, PDI, hexene incorporation and yield of polymers produced in slurry parallel pressure reactor under high density conditions at 80 °C. Supported Loading Uptake Quench Mw PDI C6 Yield MzCatalyst (nmol) (psi) Time (s) (g / mol) (Mw / Mn) (wt%) (mg) S-CMLC-2 25 90 1,826 146,911 8.7 612,321 0.0 102S-CMLC-3 25 90 1,504 753,663 6.2 2,029,355 0.6 130 S-IMLC-3 25 90 867 1,215,719 31.8 2,634,420 0.0 140 S-IMLC-4 25 90 1,158 828,540 4.5 1,844,052 0.7 136 S-IMLC-5 25 90 1,244 746,305 8.0 1,724,711 0.7 12686408-WO-PCT / DOW 86408 WO55S-IMLC-6 25 90 1,449 560,287 6.1 1,492,084 0.0 110 S-IMLC-7 25 90 3,865 1,071,568 5.7 2,447,988 0.0 112 S-IMLC-8 25 63 5,402 688,332 12.9 2,191,716 1.2 77 ♦Slurry PPR conditions: Temp. = 80 °C, IsoparE = 5 mL, C6 / C2 (molar ratio) = 0.6 in liquid, H2 / C2 (molar ratio) = 0.0016 in liquid, run time = 90 mins max (5400 s), Quench time = time needed to uptake 90 psi of ethylene; the faster the quench time, the more active the catalyst is. All catalysts are 45 µmol Zr or Hf / g SMAO; n.d. = notdetermined.

[0174] As shown in Tables 2 to 3, the slurry reactor results for the effective SMAO supported catalysts, S-IMLC 1 to 12, made from IMLC 1 to 12, which contain group IV diamine-imine complexes bearing benzimidazole-amine ligands with differentiated substituents on the organometallic complex framework are demonstrated. High activity is deemed as quench times of 1,500 seconds or faster at catalyst charges of 25 nmol or lower at 45 pmol Zr or Hf / g SMAO or lower. The quench time is the time it takes to consume 90 psi of ethylene during the experiment, where the faster the time, the more active the catalyst. Under process relevant high density conditions at 100 °C (Table 2), the activity for several of the SMAO-supported catalysts, S-IMLC-1-3, and -6 (each bearing a diamine-imine ligand) is greater to that of alternative heteroleptic comparative examples S-CMLC-2 (bearing a cyclopentadienyl ligand) and CMLC-3 (bearing a phosphinimide ligand). Specifically, S-IMLC-1-3 and -6 have quench times of 578 - 1,170 s, compared to the quench times of 1,239 - 1,344 s of S-CMLC-2 and -3. Of the SMAO-supported catalysts evaluated at 80 °C (Table 3), S-IMLC-3-6 displayed activities better than the comparative examples, S-CMLC-2 and -3, with quench times of 867 - 1,449 s, compared to the quench times of 1,504 - 1,826 s for S-CMLC-2 and -3. Moreover, S-IMLC-3-5 and -7 displayed higher activity at this lower 80 °C temperature condition than at the 100 °C condition, which may be additionally advantageous for the production of polymers with improved product performance in linear low-to-high density polyethylene applications as well as additional process flexibility in the production of poly(ethylene-co-l -alkene) copolymers. In contrast, the comparative examples S-CMLC-2 and -3 did not show increased activity at the lower reactor temperature condition (80 °C) versus the higher reactor temperature (100 °C). Optimal activity was observed for those inventive metal-ligand complexes possessing a combination of an ortAo-substituted aryl group on the 2-benzimidazole position such as, but not limited to, methyl, isopropyl, and 1 -naphthyl, in addition to an ortAo-substituted A-aryl amine group, such as, but not limited to, ortho-to y, 1-86408-WO-PCT / DOW 86408 WO56naphthyl, and 2-isopropyl-phenyl. Also, high activity was observed for the SMAO-supported catalysts that bear 2,6-diisopropylphenyl units on the N atoms comprising the cycloguanidine ring.

[0175] Moreover, based on the GPC analysis of the polyethylene-hexene copolymers produced, under these slurry process conditions at 100 °C (Table 2), the inventive supported catalysts produce polyethylene with a range of Mw. The good activity combined with a range of Mw capability in addition to, at times, ultra-low hexene incorporation offers a catalyst solution and resin with potential advantageous properties for both single and multi-catalyst applications. Furthermore, the improved activity at lower reactor temperatures (80 vs 100 °C) demonstrated by several of the S-IMLCs disclosed is an advantage in many gas phase polyolefin production processes where lower operating temperatures are required to enhance operability and achieve targeted resin designs.

[0176] It is noted that the terms “substantially” and “about” may be utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. The term “substantially” is used herein also to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. Thus, it is used to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation, referring to an arrangement of elements or features that, while in theory would be expected to exhibit exact correspondence or behavior, may in practice embody something less than exact.

[0177] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting. As used in the specification and appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0178] It is noted that one or more of the following claims utilize the term “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a86408-WO-PCT / DOW 86408 WO57recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0179] It should be understood that any two quantitative values assigned to a property or measurement may constitute a range of that property or measurement, and all combinations of ranges formed from all stated quantitative values of a given property or measurement are contemplated in this disclosure.

[0180] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover the modifications and variations of the various embodiments described herein provided such modification and variations come within the scope of the appended claims and their equivalents.

Claims

86408-WO-PCT / DOW 86408 WO58CLAIMS1. A supported catalyst system comprising a support, an activator, and a metal-ligand complex according to Formula (I):where:M is a metal selected from the group consisting of titanium, zirconium, and hafnium, wherein the metal has a formal oxidation state of +2, +3, or +4;each X is a monodentate or bidentate ligand independently selected from the group consisting of unsaturated (C2-C30)hydrocarbon, unsaturated (C2-C30)heterohydrocarbon, (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, halogen, -N(Rx)2, and -(CH2)wSi(Rx)3, where w is 1 to 10 and each Rxis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl;n is 0, 1, or 2;R1and R5are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl;R2, R3, R4, and R6are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H, wherein each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and-H;86408-WO-PCT / DOW 86408 WO59R7, R8, R9, and R10are independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, –Si(RC)3, -Ge(Rc)3, -N(RN)2, -ORC, and -H, wherein each RNis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and -H, and wherein optionally R7and R9, R7and R10, R8and R9, R8and R10, or combinations thereof are covalently connected as a (C2-C2o)hydrocarbylene comprising an aromatic ring structure, a non-aromatic ring structure, an aromatic multi-ring structure, or a non-aromatic multi-ring structure.

2. The supported catalyst system of claim 1, wherein:M is a metal chosen from zirconium or hafnium;each X is a monodentate or bidentate ligand independently selected from the group consisting of unsubstituted (Ci-Cio)alkyl, substituted (Ci-Cio)alkyl, (Ce-C2o)aryl, and halogen; andR1is selected from the group consisting of unsubstituted (Ci-C3o)alkyl, substituted (Ci-C3o)alkyl, unsubstituted (Ce-C3o)aryl, and substituted (Ce-C3o)aryl.

3. The supported catalyst system of any one of claims 1 and 2, wherein R2, R3, and R4are -H.

4. The supported catalyst system of any one of claims 1 to 3, wherein R1is selected from the group consisting of unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted naphthyl, and substituted naphthyl.

5. The supported catalyst system of any one of claims 1 to 4, wherein R1is unsubstituted phenyl or substituted phenyl.

6. The supported catalyst system of any one of claims 1 to 4, wherein R1is selected from the group consisting of 2-methylphenyl, 2-(isopropyl)phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-di(isopropyl)phenyl, 2,4,6-tri(isopropyl)phenyl,86408-WO-PCT / DOW 86408 WO603,5-di-tert-butylphenyl, 3,5-diphenylphenyl, 1 -naphthyl, 2-naphthyl, and 2.3.5.6-tetrafluorophenyl.

7. The supported catalyst system of any one of claims 1 to 6, wherein R5is selected from the group consisting of unsubstituted (Ci-C2o)alkyl, substituted (Ci-C2o)alkyl, unsubstituted (C6-C2o)aryl, and substituted (Ce-C2o)aryl.

8. The supported catalyst system of any one of claims 1 to 7, wherein R5is 4-butylphenyl.

9. The supported catalyst system of any one of claims 1 to 8, wherein R6is selected from the group consisting of substituted carbazolyl, unsubstituted carbazolyl, unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted naphthyl, and substituted naphthyl.

10. The supported catalyst system of any one of claims 1 to 9, wherein R6is selected from the group consisting of 1 -naphthyl, 2-naphthyl, 2-propyl, cyclohexyl, 2-methylphenyl, 2-(isopropyl)phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-di(isopropyl)phenyl, 2.4.6-tri(isopropyl)phenyl, 3,5-di-tert-butylphenyl, 3,5-diphenylphenyl, and 2,7-di-tert-butylcarbazolyl.

11. The supported catalyst system of any one of claims 1 to 10, wherein one of R7and R8and one of R9and R10are covalently connected to form a hydrocarbylene comprising the structure according to any one of Formulas (Ila)-(IIf):Ila, lib,86408-WO-PCT / DOW 86408 WO61wherein the dotted lines represent points of connection to the nitrogen atoms of the diamine-imine ligand of Formula (I), and each R11–38are independently selected from the group consisting of (C1–C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, –Si(RC)3, –Ge(RC)3, –N(RN)2, –ORC, and –H.

12. The supported catalyst system of any one of claims 1 to 11, wherein one of R7and R8and one of R9and R10are covalently connected to form a cycloguanidine comprising the structure according to any one of Formulas (Illa)-(IIIb):wherein the dotted lines represent a point of connection to M of Formula (I).86408-WO-PCT / DOW 86408 WO6213. The supported catalyst system of any one of claims 1 to 12, wherein the metal-ligand complex is selected from the group consisting of:IMLC-4,IMLC-5,86408-WO-PCT / DOW 86408 WO63IMLC-9, IMLC-10,IMLC-ll, and IMLC-12.86408-WO-PCT / DOW 86408 WO6414. The supported catalyst system of any one of claims 1 to 12, wherein the metal-ligand complex is selected from the group consisting of the structure according to any one of Formulas (IVa)-(IVe):IVa,R'IVc, IVd, and86408-WO-PCT / DOW 86408 WO65IVe;wherein R, R’, R”, and each R’” are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, -Si(Rc)3, -Ge(Rc)3, -N(RN)2, -ORC, and -H.

15. A method of making an ethylene-based polymer comprising polymerizing, via gas-phase polymerization or slurry-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of the supported catalyst system of any one of claims 1 to 14.

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