Germanium-bridged cyclopentadienyl-phenoxy complexes of titanium for olefin polymerization

Abstract

Catalyst systems comprising a metal-ligand complex having a structure according to Formula (I): Y and Z are independently a monodentate or bidentate ligand selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, halogen and –H. R1, R2, R3, and R4 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; R5, R6, R7, and R8 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; R9 and R10 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; and each RC is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, and –H.

Description

86263 -WO-PCT / DOW 86263 WO1GERMANIUM-BRIDGED CYCLOPENTADIENYL-PHENOXY COMPLEXES OF TITANIUM FOR OLEFIN POLYMERIZATIONCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U. S. Provisional Application Serial No. 63 / 736,068 filed December 19, 2024, the entire disclosure of which is hereby incorporated by reference.TECHNICAL FIELD

[0002] The present disclosure generally relates to catalyst systems and processes that may be utilized for olefin polymerization, and, more specifically, to catalyst systems involving germanium-bridged cyclopentadienyl-phenoxy complexes and to olefin polymerization processes incorporating such 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. 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 from the 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. Despite86263 -WO-PCT / DOW 86263 WO2the 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

[0005] Catalyst systems disclosed herein include a metal-ligand complex having a structure according to Formula (I):

[0006] In Formula (I), R1, R2, R3, and R4may be 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, where each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and -H.

[0007] In Formula (I), R5, R6, R7, and R8may be 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, where each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and -H.

[0008] In Formula (I), R9and R10are 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, where each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and-H.86263 -WO-PCT / DOW 86263 WO3

[0009] In Formula (I) Y may be selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3“C3o)heteroaryl, halogen, and -H. Z may be selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, halogen, and -H.

[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), wherein the polymerizing comprises solution polymerization.DETAILED DESCRIPTION

[0011] Catalyst systems will now be described. It should be understood that the 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.

[0012] Common abbreviations are listed below:

[0013] R, M, X, Y, and Z: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl;Mes: mesityl (2,4,6-trimethylphenyl); i-Pr: iso-propyl; n-Bu: n-butyl; n-BuLi: n-butyllithium; t-Bu: tert-butyl; t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl); Tf: trifluoromethane sulfonate; : Et₂O: diethyl ether; EtOH: ethanol; DCM or CH₂Cl₂: dichloromethane; DME: dimethoxyethane; DIW: deionized water; C₆D₆: deuterated benzene or benzene-d6: CDCl₃: deuterated chloroform; THF: tetrahydrofuran; NEt₃: trimethylamine; TiCl₄: titanium tetrachloride; GeMe₂Cl₂: dimethylgermanium dichloride; MeMgBr: methylmagnesium bromide; LiCH₂SiMe₃:(trimethylsilyl)methyllithium; CpMe₄: 6-tetramethylcyclopentadienyllithium Na₂SO₄: sodium sulfate; MgSO₄: magnesium sulfate; HCl: hydrogen chloride; NaHCO₃: sodium bicarbonate;NH₄Cl: ammonium chloride; N₂: nitrogen gas; PhMe: toluene; PPR: parallel pressure reactor;MAO: methylaluminoxane; MMAO: modified methylaluminoxane; GC: gas chromatography; LC: liquid chromatography; RIBS-2: bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimoles; mL: milliliters; M: molar; min or mins: minutes; h or hrs: hours; d: days; rpm: revolution per minute.86263 -WO-PCT / DOW 86263 WO4

[0014] 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 be identical or different, without dependency on the identity of any other Group also appearing before the term.

[0015] The term “procatalyst” refers to a compound that has catalytic activity when combined with an activator. 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.

[0016] 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 atom-containing 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.

[0017] 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.86263 -WO-PCT / DOW 86263 WO5

[0018] The term “(Ci-C3o)hydrocarbyl” means a hydrocarbon radical of from 1 to 30 carbon atoms and the term “(Ci-C3o)hydrocarbylene” means a hydrocarbon diradical of from 1 to 30 carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or nonaromatic, 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.

[0019] 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)).

[0020] 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 (Ci-C3o)alkyl are substituted (Ci-C2o)alkyl (such as benzyl (-CH2-C6H5)), substituted (Ci-Cio)alkyl, trifluoromethyl, and [C3s]alkyl. The term “[Cssjalkyl” means there is a maximum of 35 carbon atoms in the radical, including substituents, and is, for example, a (Ci5-C3o)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.

[0021] 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-aromatic. Examples of86263 -WO-PCT / DOW 86263 WO6unsubstituted (Ce-C3o)aryl include: unsubstituted (Ce-C2o)aryl, unsubstituted (Ce-Cisjaryl; 2-(Ci-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C6-C3o)aryl include: substituted (Ci-C2o)aryl; substituted (Ce-Cisjaryl; 2,4-bis([C2o]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0022] 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-C2o)cycloalkyl, unsubstituted (C3-Cio)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C3o)cycloalkyl are substituted (C3-C2o)cycloalkyl, substituted (C3-Cio)cycloalkyl, cyclopentanon-2-yl, and 1 -fluorocyclohexyl.

[0023] Examples of (Ci-C3o)hydrocarbylene include unsubstituted or substituted (C6-C3o)arylene, (C3-C3o)cycloalkylene, and (Ci-C3o)alkylene (e.g., (Ci-C2o)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.

[0024] The term “(Ci-C3o)alkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 30 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 unsubstituted (Ci-C2o)alkylene, including unsubstituted -CH2CH2-, -(CEbjs-, -(CH2)4-, -(CEEjs-, -(CEEje-,86263 -WO-PCT / DOW 86263 WO7-(CH?)?-, — (CH?)s—, -CH? C*HCH3, and -(CH?)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-C3o)alkylene are substituted (Ci-C2o)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-C3o)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.

[0025] The term “(C3-C3o)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 30 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.

[0026] 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)?, Si(Rc)?, P(RP), N(RN), - N=C(RC)2, -Ge(Rc)?-, or -Si(Rc)-, where each Rcand each Rpis unsubstituted (Ci-Cis)hydrocarbyl or -H, and where each RNis unsubstituted (Ci-Cis)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-C3o)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 30 carbon atoms, and the term “(Ci-C3o)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 30 carbon atoms. The heterohydrocarbon of the (Ci-C3o)heterohydrocarbyl or the (Ci-C3o)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-C3o)heterohydrocarbyl and (Ci-C3o)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), or acyclic. Other heterohydrocarbyl groups (e.g.,86263 -WO-PCT / DOW 86263 WO8(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.

[0027] The (Ci-C3o)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (Ci-C3o)heterohydrocarbyl include (Ci-C3o)heteroalkyl, (Ci-C3o)hydrocarbyl-0-, (Ci-C3o)hydrocarbyl-S-, (Ci-C3o)hydrocarbyl-S(0)-, (Ci-C3o)hydrocarbyl-S(0)2-, (Ci-C3o)hydrocarbyl-Si(Rc)2-, (Ci-C3o)hydrocarbyl-N(RN)-, (Ci-C3o)hydrocarbyl-P(Rp)-, (C2-C3o)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, (C6-C2o)aryl-(Ci-Ci9)heteroalkylene, or (Ci-Ci9)heteroaryl-(Ci-C2o)heteroalkylene.

[0028] The (Ci-C3o)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (Ci-C3o)heterohydrocarbyl include (Ci-C3o)heteroalkyl, (Ci-C3o)hydrocarbyl-0-, (Ci-C3o)hydrocarbyl-S-, (Ci-C3o)hydrocarbyl-S(0)-, (Ci-C3o)hydrocarbyl-S(0)2-, (Ci-C3o)hydrocarbyl-Si(Rc)2-, (Ci-C3o)hydrocarbyl-N(RN)-, (Ci-C3o)hydrocarbyl-P(Rp)-, (C2-C3o)heterocycloalkyl, (C2-C2o)heterocycloalkyl-(Ci-Cio)alkylene, (C3-C2o)cycloalkyl-(Ci-Cio)heteroalkylene, (C2-C2o)heterocycloalkyl-(Ci-Cio)heteroalkylene, (Ci-C3o)heteroaryl, (Ci-C2o)heteroaryl-(Ci-Cio)alkylene, (C6-C2o)aryl-(Ci-Cio)heteroalkylene, or (Ci-C2o)heteroaryl-(Ci-Cio)heteroalkylene.

[0029] The term “(C3-C3o)heteroaryl” means an unsubstituted or substituted (by one or more Rs) mono-, bi-, or tricyclic heteroaromatic hydrocarbon radical of from 3 to 30 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.

[0030] 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 monocyclic86263 -WO-PCT / DOW 86263 WO9heteroaromatic hydrocarbon 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.

[0031] The term “(Ci-C3o)heteroalkyl” means a saturated straight or branched chain radicals containing one to fifty carbon atoms, or fewer carbon atoms and one or more of the heteroatoms. The term “(Ci-C3o)heteroalkylene” means a saturated straight or branched chain diradicals containing from 1 to 30 carbon atoms and one or more than one heteroatoms. The heteroatoms of the heteroalkyls or the heteroalkylenes may include Si(Rc)3, 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.

[0032] 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.

[0033] 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").86263 -WO-PCT / DOW 86263 WO10

[0034] The term “saturated” means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorous, and carbonsilicon 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 carbon-nitrogen, carbonphosphorous, 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.

[0035] Catalyst systems herein include a metal-ligand complex having a structure according to Formula (I):

[0036] In Formula (I), Y is a monodentate or bidentate ligand selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, halogen and -H. Z is a monodentate or bidentate ligand selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, halogen and -H. R1, R2, R3, and R4may be 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. R5, R6, R7, and R8are 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. R9and R10are 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. In Formula (I), each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and -H.86263 -WO-PCT / DOW 86263 WO11

[0037] In Formula (I), Y may bond with M through a covalent bond, a dative bond, or an ionic bond and may be a monodentate monoanionic ligand or a monodentate neutral ligand. In examples in which Y is a monodentate ligand, the monodentate ligand may be a neutral ligand or a monoanionic ligand. In examples in which Y is a bidentate ligand, the bidentate ligand may be a neutral ligand, a monoanionic ligand, or a dianionic ligand. Monoanionic ligands have a net formal oxidation state of -1. Dianionic ligands have a net formal oxidation state of -2.

[0038] In example metal-ligand complexes in which Y is a monodentate monoanionic ligand, the monoanionic ligand may be hydride, (Ci-C3o)hydrocarbyl carbanion, (Ci-C3o)heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O, HC(O)N(H)−, (Ci-C2o)hydrocarbylC(0)0, (Ci-C2o)hydrocarbylC(0)N((Ci-C2o)hydrocarbyl), (Ci-C2o)hydrocarbylC(0)N(H)’, RKRLB)−, RKRLN, RKO, RKS, RKRLP, or RMRKRLSi, where RK, RL, and RMare independently hydrogen, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl, or RKand RLare taken together to form a (C2-C2o)hydrocarbylene or (C2-C2o)heterohydrocarbylene and RMis as defined above. In some particular metal ligand complexes where Y is a dianionic ligand, the dianionic ligand may be carbonate, oxalate (i.e., O2CC(O)O, (C2-C4o)hydrocarbylene dicarbanion, (Ci-C4o)heterohydrocarbylene dicarbanion, phosphate, or sulfate.

[0039] In example metal-ligand complexes in which Y is a monodentate neutral ligand, the neutral ligand may be a neutral Lewis base group such as RJNRKRL, RKORL, RKSRL, or RJPRKRL, where each RJindependently is hydrogen, [(Ci-Cio)hydrocarbyl]3Si(Ci-Cio)hydrocarbyl, (Ci-C2o)hydrocarbyl, [(Ci-Cio)hydrocarbyl]3Si, or (Ci-C2o)heterohydrocarbyl and each RKand RLindependently is as previously defined.

[0040] In example metal-ligand complexes, Y may be -R'Si(Rc)3, each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and -H, and R' is independently selected from the group consisting of (Ci-C3o)hydrocarbylene, and (Ci-C3o)heterohydrocarbylene. In specific example metal-ligand complexes, Y may be chosen from -R'Si(Rc)3, wherein each Rcis independently selected from the group consisting of (Ci-C5)hydrocarbyl and (Ci-C5)heterohydrocarbyl, and R' is independently selected from the group consisting of (Ci-C5)hydrocarbylene and (Ci-C5)heterohydrocarbylene. Y may be -CH2Si(CH3)3.86263 -WO-PCT / DOW 86263 WO12

[0041] In example metal-ligand complexes, Y may be −(CH2)wSi(RX)3, where w is from 1 to 10, each RXis independently selected from (C1-C30)hydrocarbyl and (C1-C30)heterohydrocarbyl, and optionally two or more Rxgroups are covalently linked.

[0042] In example metal-ligand complexes, Y is (Ci-Cio)alkyl, -CH2Si[(Ci-C2o)alkyl], (C6-C2o)aryl, or a halogen. In some example metal-ligand complexes, Y may be (Ci-Cio)alkyl or -CH2Si[(Ci-C2o)alkyl]. In some example metal-ligand complexes, Y may be methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro. In specific example metal-ligand complexes, Y may be methyl or trimethylsilyl methyl.

[0043] Any portion of the disclosure herein related to Y of Formula (I) may apply to Z of Formula (I). For example, in Formula (I), Z may bond with M through a covalent bond, a dative bond, or an ionic bond and may be a monodentate monoanionic ligand or a monodentate neutral ligand, and Z may be chosen from any of the specific ligands disclosed herein for Y. In Formula (I) Y and Z may be independently selected. In some example metal-ligand complexes, Y and Z may be the same. In some example metal-ligand complexes, Y and Z may be different.

[0044] In example metal-ligand complexes, R1, R2, R3, and R4may be independently a (Ci-Cs)alkyl. In particular example metal-ligand complexes, R1, R2, R3, and R4are methyl.

[0045] In example metal-ligand complexes, R5, R6, R7, and R8may be independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ce-C3o)aryl, halogen, and -H. In particular example metal-ligand complexes, R5, R6, R7, and R8may be independently selected from the group consisting of (Ci-Cio)hydrocarbyl, halogen, and -H. In various example metal-ligand complexes, at least one of R5, R6, R7, or R8may be tert-butyl. In various example metal-ligand complexes, R5and R7may be -H, R6and R8may be independently selected from (Ci-Cio)hydrocarbyl, or both. In particular example metal-ligand complexes, R5and R7are -H, R6is methyl, and R8is tert-butyl.

[0046] R9and R10may be independently selected from the group consisting of (Ci-Cio)hydrocarbyl, (Ci-Cio)heterohydrocarbyl, (Ce-Ci2)aryl, (C3-Ci2)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H. In example metal-ligand complexes, R9and R10may be independently selected from (Ci-Cio)hydrocarbyl. R9and R10may be independently selected from the group consisting of methyl, ethyl propyl, and butyl. R9and R10may be independently selected from the group consisting of methyl and ethyl. In specific example metal-ligand complexes, R9and R10are methyl.86263 -WO-PCT / DOW 86263 WO13

[0047] In some example metal-ligand complexes, R1and R2may be covalently linked to form an aromatic ring or a non-aromatic ring. In so some example metal-ligand complexes, R2and R3may be covalently linked to form an aromatic ring or a non-aromatic ring. In some example metal-ligand complexes, R3and R4may be covalently linked to form an aromatic ring or a non-aromatic ring. In some example metal-ligand complexes, R1and R2may be covalently linked to form an aromatic ring or a non-aromatic ring and R3and R4may be covalently linked to form an aromatic ring or a non-aromatic ring.

[0048] In various example metal-ligand complexes wherein R1and R2are covalently linked to form an aromatic ring, the metal-ligand complex may have a structure according to Formula (II):

[0049] In Formula (II), R3, R4, R5, R6, R7, R8, R9, R10, Y, and Z are defined as in Formula (I); and R11, R12, R13, and R14may be 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. In formula (II), R11and R12may be covalently linked to form an aromatic ring or a non-aromatic ring. In formula (II), R12and R13may be covalently linked to form an aromatic ring or a non-aromatic ring. In formula (II), R13and R14may be covalently linked to form an aromatic ring or a non-aromatic ring.

[0050] In various example metal-ligand complexes wherein R1and R2are covalently linked to form an aromatic ring and R3and R4are covalently linked to form an aromatic ring the metal-ligand complex may have a structure according to Formula (III):86263 -WO-PCT / DOW 86263 WO14(III)

[0051] In Formula (III), R3, R4, R5, R6, R7, R8, R9, R10, Y, and Z are defined as in Formula (I); and R15, R16, R17, and R18may be 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, R19is selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6–C30)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H, and R20, R21, R22, R23, and R24are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6–C30)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H.

[0052] In some example metal-ligand complexes of Formula (III), R15, R16, R17, and R18are independently selected from the group consisting of (Ci-C5)hydrocarbyl, and -H. In some example metal-ligand complexes of Formula (III), R20, R21, R22, R23, and R24are -H. In some example metalligand complexes of Formula (III), R15, R17, and R18are methyl and R16is -H.

[0053] In some example metal-ligand complexes, any or all of the chemical groups (e.g., Y, Z, and R'-R10) of the metal-ligand complex of Formula (I) may be unsubstituted. In other example metal-ligand complexes, none, any, or all of the chemical groups Y, Z, and R1–R10of the metal-ligand complex of Formula (I) may be substituted with one or more than one Rs. When two or more than two Rsare bonded to a same chemical group of the metal-ligand complex of Formula (I), the individual Rsof the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some example metal-ligand complexes, none, any, or all of the chemical groups Y, Z, and R1–R10may be persubstituted with Rs. In the chemical groups that are persubstituted with Rs, the individual Rsmay all be the same or may be independently chosen.86263 -WO-PCT / DOW 86263 WO15

[0054] In some example metal-ligand complexes, any or all of the chemical groups (e.g., Y, Z, and R4-R14) of the metal-ligand complex of Formula (II) may be unsubstituted. In other example metal-ligand complexes, none, any, or all of the chemical groups Y, Z, and R4-R14of the metal-ligand complex of Formula (II) may be substituted with one or more than one Rs. When two or more than two Rsare bonded to a same chemical group of the metal-ligand complex of Formula (II), the individual Rsof the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, none, any, or all of the chemical groups Y, Z, and R4-R14may be persubstituted with Rs. In the chemical groups that are persubstituted with Rs, the individual Rsmay all be the same or may be independently chosen.

[0055] In some example metal-ligand complexes, any or all of the chemical groups (e.g., Y, Z, and R4-R10, R15-R23) of the metal-ligand complex of Formula (III) may be unsubstituted. In other example metal-ligand complexes, none, any, or all of the chemical groups Y, Z, R4-R10, and R15-R23of the metal-ligand complex of Formula (III) may be substituted with one or more than one Rs. When two or more than two Rsare bonded to a same chemical group of the metal-ligand complex of Formula (III), the individual Rsof the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, none, any, or all of the chemical groups Y, Z, and R4-R14may be persubstituted with Rs. In the chemical groups that are persubstituted with Rs, the individual Rsmay all be the same or may be independently chosen.

[0056] In illustrative embodiments, the catalyst systems may include a metal-ligand complex according to Formula (I) having the structure of any of the metal-ligand complexes (MLC) 1-8 listed below:86263 -WO-PCT / DOW 86263 WO16MLC 1, MLC 2,MLC 3,MLC 6,86263 -WO-PCT / DOW 86263 WOMLC 7, MLC 8, or combinations thereof.

[0057] In particular embodiments, the metal-ligand complex may be any one of MLC 1, MLC 2, MLC 3, MLC 4, or MLC 5, or combinations thereof. In particular embodiments, the metal-ligand complex may be any one of MLC 1, MLC 2, MLC 3, or MCL 4, or combinations thereof.

[0058] Polymerization processes herein include polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of a catalyst system comprising a metal-ligand complex according to Formula (I).Co-catalyst Component

[0059] The catalyst systems described herein may include a co-catalyst component. The catalyst system comprising a metal-ligand complex of Formula (I) may be rendered catalytically active by any technique known in the art for activating metal -based catalysts of olefin polymerization reactions. 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 activating co-catalysts (also referred to herein as an “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 de-coordination of the Lewis base. Suitable activating co-catalysts for use herein include, without limitation: alkyl aluminums; boron-based Bronsted or Lewis acids; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral 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 activating co-catalysts and techniques are also contemplated. The term “alkyl aluminum” means a86263 -WO-PCT / DOW 86263 WO18monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0060] Lewis acid activating co-catalysts include Group 13 metal compounds containing (Ci-C2o)hydrocarbyl substituents as described herein. In some embodiments, Group 13 metal compounds are tri((Ci-C2o)hydrocarbyl)-substituted-aluminum or tri((Ci-C2o)hydrocarbyl)-boron compounds. In other embodiments, 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, tris(pentafluorophenyl)borane.

[0061] In some embodiments, the activating co-catalyst is a tris((C1-C20)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.

[0062] Combinations of neutral Lewis acid activating co-catalysts include mixtures comprising a combination of a tri((Ci-C4)alkyl)aluminum and a halogenated tri((C6-Ci8)aryl)boron compound, especially a tris(pentafluorophenyl)borane. Other embodiments are 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 embodiments, from 1:1:1.5 to 1:5:10.

[0063] Exemplary suitable activating co-catalysts include, but are not limited to, methylaluminoxane (MAO), modified methyl aluminoxane (MMAO), triethylaluminum (TEA),86263 -WO-PCT / DOW 86263 WO19bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine (RIBS-2), and combinations thereof.

[0064] In particular example catalyst systems, the activating co-catalyst comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0065] In particular example catalyst systems, the activating co-catalyst comprises unsubstituted ammonium borate, a mono-substituted ammonium borate, a bi-substituted ammonium borate, a trisubstituted ammonium borate, or a tetra-substituted ammonium borate.

[0066] In particular example catalyst systems, the activating co-catalyst comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine (RIBS-2).

[0067] In some example catalyst systems, more than one of the foregoing activating co-catalysts are included in the catalyst system in combination with each other. A specific example of an activating co-catalyst combination is a mixture of a tri((Ci-C4)hydrocarbyl)aluminum, tri((Ci— 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 activating co-catalysts is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5,000, in some other embodiments, at least 1: 1,000; and 10:1 or less, and in some other embodiments, 1:1 or less.

[0068] When an alumoxane alone is used as the activating co-catalyst, preferably the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the metalligand complex of Formula (I). When tris(pentafluorophenyl)borane alone is used as the activating co-catalyst, 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 activating co-catalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more metal-ligand complexes of Formula (I).

[0069] In some example catalyst systems, when more than one of the foregoing co-catalyst components is used in combination, one or more of the co-catalyst components may function as a scavenger. The purpose of the scavenger is to react with any water or other impurities present in the system that might otherwise react with the catalyst leading to reduced efficiency. In particular86263 -WO-PCT / DOW 86263 WO20example metal-ligand complexes, the catalyst systems described herein may include an activator or both an activator and a scavenger.

[0070] In some example catalyst systems, the co-catalyst component includes an activator comprising unsubstituted ammonium borate, a mono-substituted 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.

[0071] In some example catalyst systems, the co-catalyst component includes an activator comprising 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.Polymerization Methods

[0072] Polymerization methods disclosed herein include polymerizing, in a polymerization reactor, ethylene and at least one α-olefin in the presence of any of the catalyst systems described herein, including catalyst systems comprising a metal-ligand complex according to Formula (I). Any conventional polymerization processes may be employed to produce the ethylene-based polymers. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof using one or more conventional reactors such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors in parallel, series, or any combinations thereof, for example.

[0073] In particular embodiments the ethylene-based polymer may be produced via solution polymerization. In one polymerization method, the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and at least one α-olefin are polymerized in the presence of the catalyst system, as described herein, and optionally one or more co-catalyst components. The catalyst system, as described herein, can be used in the first reactor, or second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene86263 -WO-PCT / DOW 86263 WO21and at least one α-olefin are polymerized in the presence of the catalyst system, as described herein, in both reactors.

[0074] In another embodiment, the ethylene-based polymer may be produced via solution polymerization in a single reactor system, for example, single loop reactor system, in which ethylene and at least one α-olefin are polymerized in the presence of the catalyst system, as described within this disclosure, and optionally one or more co-catalyst components, as described in the preceding paragraphs. In embodiments, hydrogen may be added to the reactor.

[0075] In some polymerization methods described herein, the at least one α-olefin may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-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, the at least one α-olefin may be selected from the group consisting of propylene, 1 -butene, 1 -hexene, and 1 -octene. In some polymerization methods, the at least one a-olefrn may be selected from the group consisting of 1 -hexene and 1 -octene. In specific polymerization methods, the at least one α-olefin comprises 1 -octene.

[0076] As discussed above and demonstrated through the examples submitted herewith, it has been unexpectedly found that the catalyst systems described herein comprising metal-ligand complexes of Formula (I) are able to achieve high ethylene selectivity and high activity, even at high polymerization temperatures (e.g., > 140 °C). In embodiments, the polymerizing is performed at a polymerization temperature of at least 140 °C, at least 150 °C, at least 160 °C, at least 170 °C, at least 180 °C, or at least 190 °C.

[0077] In some polymerization methods described herein, the polymerization methods described herein produce at least 200,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, or at least 250,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex (g poly / g metal). In some embodiments, the polymerization methods described herein produce at least 300,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 400,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 500,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 1,000,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 2,000,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 3,000,000 grams of ethylene-based polymer per gram metal of the metal-ligand86263 -WO-PCT / DOW 86263 WO22complex, at least 4,000,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, or at least 5,000,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex.Polyolefins

[0078] The catalyst systems and polymerization methods described in the preceding paragraphs may be utilized to produce olefin-based polymers. Though the exemplary catalyst systems of this disclosure are utilized in the polymerization of ethylene-based polymers, it should be understood that such catalyst systems may be utilized in the polymerization of other olefins, such as propylene-based polymers including any of the additional ot-olefms described herein above. The ethylene-based polymers may also be interpolymers comprising ethylene and more than one additional a-olefin. 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 Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

[0079] As examples, the ethylene-based polymer produced by the methods described herein may comprise at least 50 weight percent (wt%) units derived from ethylene, at least 60 wt% units derived from ethylene, at least 70 wt% units derived from ethylene, at least 80 wt% units derived from ethylene, at least 90 wt% units derived from ethylene, at least 95 wt% units derived from ethylene, at least 99 wt% units derived from ethylene, at least 99.5 wt% units derived from ethylene, or at least 99.9 wt% units derived from ethylene.

[0080] As further examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a weight-average molecular weight from 1,000 g / mol to 500,000 g / mol, from 1,000 g / mol to 400,000 g / mol, from 1,000 g / mol to 300,000 g / mol, from 1,000 g / mol to 250,000 g / mol, from 1,000 g / mol to 200,000 g / mol, from 2,000 g / mol to 200,000 g / mol, from 4,000 g / mol to 200,000 g / mol, or from 4,000 g / mol to 175,000 g / mol.

[0081] As further examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has 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. As further examples, the ethylene-based polymer polymerized in the presence of a catalyst86263 -WO-PCT / DOW 86263 WO23system described herein has a PDI from 1 to 50. In other embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 20. As further examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 15. As further examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 10, from 1 to 5, from 1 to 3, from 1 to 2.5, or from 1.5 to 2.5. As further examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI less than 2.

[0082] As further examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a melt temperature of at least 100 °C, at least 110 °C, at least 115 °C, at least 120 °C, at least 122 °C, at least 124 °C, at least 126 °C, at least 128 °C, or at least 130 °C. In embodiments, the ethylene-based polymer has a melt temperature of from 124 °C to 132 °C.

[0083] 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 fillers. The ethylene-based polymers may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the combined weight of the ethylene-based polymers and all additives or fillers. The ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0084] The 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.

[0085] The catalyst systems described in this disclosure yield unique polymer properties as a result of the high molecular weights of the polymers formed and the amount of the co-monomers incorporated into the polymers.86263 -WO-PCT / DOW 86263 WO24EXAMPLES

[0086] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted.

[0087] 1H NMR data are reported as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, hept = heptet and m = multiplet), integration, and assignment). Chemical shifts for 1H NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, 8 scale) using residual protons in the deuterated solvent as references. 13C NMR data were determined with 1 H decoupling, and the chemical shifts are reported downfield from tetramethylsilane (TMS, 8 scale) in ppm versus the using residual carbons in the deuterated solvent as references.

[0088] Examples 1 to 5 are synthetic procedures for ligand intermediates, ligands, and catalysts. In Example 6, the results of the polymerization reactions of metal-ligand complexes (MLC) 1 -4 and comparative metal-ligand complexes (CMLC) A-D are tabulated and discussed. The structures of the MLC and CMLC of the Examples are depicted below.

[0089] One or more features of the present disclosure are illustrated in view of the examples as follows:86263 -WO-PCT / DOW 86263 WO25Example 1(2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodimethylgermane [2]Brn-BuLithen GeMe2CI2Et2O, -78 °C to rt

[0090] A 100 mL round bottom flask was charged with the bromoarene 1 (1.48 g, 5.23 mmol, 1.00 equiv) and 35 mL dry diethyl ether. The mixture was stirred at -78 °C and n-butyllithium (2.5 M in hexane, 2.13 mL, 5.33 mmol, 1.02 equiv) was added dropwise. The mixture stirred for 120 minutes. Dichlorodimethylgermane (0.998 g, 5.75 mmol, 1.10 equiv) was injected rapidly. The mixture stirred overnight and was allowed to warm to ambient temperature. The solvent was removed by rotary evaporation, leaving a white, heterogeneous residue. The residue was transferred to a glovebox, and was diluted with 20 mL dry hexane. The slurry was fdtered to remove solids. The fdtrate was concentrated to a waxy white solid (1.70 g, 95%).

[0091] 'H NMR (400 MHz, C6D6) 87.50 (d, J = 2.2 Hz, 1H), 7.22 (d, J = 2.2 Hz, 1H), 5.77 (ddt, J = 17.3, 10.8, 4.3 Hz, 1H), 5.51 - 5.40 (m, 1H), 5.09 (dq, J = 10.8, 1.9 Hz, 1H), 4.33 (dt, J = 4.1, 1.9 Hz, 2H), 2.13 (s, 3H), 1.39 (s, 9H), 0.86 (s, 6H).13C NMR (101 MHz, C6D6) 8 159.68, 142.20, 133.71, 133.58, 133.48, 132.77, 131.24, 115.80, 76.30, 35.03, 31.04, 20.65, 5.31.86263 -WO-PCT / DOW 86263 WO26Example 2(2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)dimethyl(2-methyl-3H-cyclopenta[a]naphthalen-3- yl)germane [4] and MLC 1

[0092] In a glovebox, a 50 mL jar was charged with the indene 3 (0.831 g, 4.61 mmol, 1.05 equiv) and 30 mL dry hexane. After solids dissolved, n-butyllithium (2.5 M in hexane, 1.85 mL, 4.61 mmol, 1.05 equiv) was injected. The mixture became cloudy white and heterogeneous. After 3 hours, the germanyl chloride 2 (1.50 g, 4.39 mmol, 1.00 equiv) was added in 30 mL dry THF. The mixture stirred for 1 hour. The mixture was removed from the glovebox and was quenched with aqueous ammonium chloride. Product was extracted with portions of diethyl ether. Combined organic fractions were dried with magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (0 to 40 % dichloromethane in hexane). 1.747 g of product was isolated as a clear, colorless oil (82%).

[0093] 'H NMR (400 MHz, CDC13) 58.08 (d, J = 8.2 Hz, 1H), 7.83 (d, J= 8.1 Hz, 1H), 7.45 (dd, J = 8.0, 5.9 Hz, 2H), 7.41 - 7.36 (m, 1H), 7.24 (s, 1H), 7.20 (d, J = 2.1 Hz, 1H), 7.09 (s, 1H), 6.92 (d,. / = 2.2 Hz, 1H), 6.14 - 5.97 (m, 1H), 5.54 (dd, J = 17.3, 2.0 Hz, 1H), 5.33 - 5.25 (m, 1H), 4.45 (ddt, J = 14.0, 4.2, 1.9 Hz, 1H), 4.37 (ddt, J = 13.9, 4.3, 2.0 Hz, 1H), 4.26 (s, 1H), 2.27 (s, 3H), 2.02 (s, 3H), 1.43 (s, 9H), 0.33 (s, 3H), 0.10 (s, 3H).13C NMR (101 MHz, CDCI3) 5 160.44, 148.15, 142.20, 142.02, 140.19, 134.09, 133.64, 133.55, 132.74, 131.79, 129.76, 128.17, 127.30, 124.81, 124.13, 123.83, 122.37, 122.19, 122.00, 116.16, 75.84, 50.16, 35.23, 31.10, 21.03, 16.98, -1.82, -3.79.86263 -WO-PCT / DOW 86263 WO27

[0094] In a glovebox, a 50 mL round bottom flask was charged with the allyl ligand 4 (0.360 g, 0.742 mmol, 1.00 equiv) and 8 mL toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Triethylamine (0.465 mL, 3.34 mmol, 4.50 equiv) was added, followed by n-butyllithium (0.623 mL, 1.56 mmol, 2.10 equiv). The cooling bath was removed and the mixture stirred at ambient temperature for 90 minutes. The solution was recooled to -78 °C and a solution of TiCh (0.122 mL, 1.11 mmol, 1.50 equiv) in 1 mL toluene was added. The solution was transferred to a glovebox and was stirred at 80 °C for 4 hours. The heterogeneous mixture was cooled and filtered to remove solids. The red filtrate was concentrated to dryness. The material was triturated with hexane and dried under vacuum to give 0.120 g of the red solid. The Ti-Cl complex 5 was taken onto the next step.

[0095] 1H NMR (400 MHz, C6D6) 8 8.12 (d, J = 8.0 Hz, 1H), 7.39 (t, J = 8.0 Hz, 2H), 7.28 -7.20 (m, 2H), 7.17 (s, 2H), 7.14 (d, J = 2.1 Hz, 2H), 2.25 (s, 3H), 2.22 (s, 3H), 1.42 (s, 9H), 0.67 (s, 3H), 0.61 (s, 3H). 13C NMR (101 MHz, C6D6) 8 166.26, 142.11, 137.20, 134.05, 133.68, 132.90, 132.49, 131.74, 131.69, 130.15, 129.23, 128.95, 128.68, 124.87, 121.85, 118.23, 113.46, 34.85, 29.78, 20.94, 17.25, -0.77, -1.04.

[0096] The Ti-Cl complex 5 (0.108 g, 0.192 mmol, 1.00 equiv) was dissolved in 10 mL dry diethyl ether. The solution was chilled in a -30 °C glovebox freezer for 1 hour. The solution was stirred vigorously and methylmagnesium bromide (3.0 M in diethyl ether, 0.135 mL, 0.404 mmol, 2.10 equiv) was injected. The color lightened (pale yellow) and the mixture stirred for 30 minutes. Solvent was removed by vacuum pump and the residue was suspended in 6 mL of 4:1 toluene:hexane. The slurry was filtered through a 0.45 um syringe filter. The filtrate was concentrated and suspended in pentane. The mixture was stirred for a few minutes and volatiles were removed by vacuum pump. The pentane wash / evaporation cycle was repeated two more times. 75.4 mg of a pale yellow solid was isolated (75%).

[0097] 'H NMR (400 MHz, C6D6) 8 8.18 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 7.9 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.33 - 7.24 (m, 5H), 7.12 (d, J = 2.1 Hz, 1H), 2.28 (s, 3H), 1.77 (s, 3H), 1.69 (s, 9H), 0.98 (s, 3H), 0.58 (s, 3H), 0.56 (s, 3H), 0.02 (s, 3H).13C NMR (101 MHz, C6D6) 8 163.07, 136.23, 135.36, 132.62, 131.85, 131.62, 131.30, 130.38, 128.84, 128.66, 128.63, 128.58, 127.15, 126.58, 126.44, 124.19, 123.41, 110.82, 103.99, 60.43, 51.90, 34.98, 29.83, 20.88, 14.80, 0.05, -1.19.86263 -WO-PCT / DOW 86263 WO28Example 3((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l- yl)germane [8] and MLC 2

[0098] In a glovebox, a 20 mL vial was charged with the chlorogermane 2 (1.06 g, 3.10 mmol, 1.00 equiv) and 30 mL dry THF. This solution was treated with the solid lithium CpMe4 complex (0.398 g, 3.10 mmol, 1.00 equiv). The mixture stirred overnight. The solution was removed from the glovebox and quenched with aqueous ammonium chloride. Product was extracted with several portions of diethyl ether. Combined organic fractions were concentrated and the residue purified by chromatography on silica gel (0 to 10% EtOAc in hexane). 0.475 g of product was isolated as a colorless oil (56%).

[0099] 'H NMR (400 MHz, CDC13) 5 7.13 (d, J= 2.2 Hz, 1H), 6.97 (d, J= 2.2 Hz, 1H), 6.05 (ddt,. / = 17.0, 10.6, 4.3 Hz, 1H), 5.53 (dq,. / = 17.2, 1.9 Hz, 1H), 5.30 - 5.25 (m, 1H), 4.38 (dt, J = 4.1, 2.0 Hz, 2H), 3.48 (s, 1H), 2.29 (s, 3H), 1.79 (s, 6H), 1.70 (s, 6H), 1.38 (s, 9H), 0.26 (s, 6H).13C NMR (101 MHz, CDCI3) 5 160.37, 141.95, 134.74, 134.01, 133.83, 133.12, 132.36, 129.22, 116.05, 75.43, 35.16, 31.02, 21.10, 13.67, 11.04, -2.40.

[0100] In a glovebox, a 100 mL round bottom flask was charged with the allyl ligand 8 (1.06 g, 2.48 mmol, 1.00 equiv) and 25 mL dry toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Triethylamine (1.56 mL, 11.2 mmol, 4.50 equiv) was added, followed by n-butyllithium (2.08 mL, 5.21 mmol, 2.10 equiv). The cooling bath was removed, and the mixture stirred for 90 minutes. The flask was re-cooled to -78 °C and TiC14 (0.299 mL, 2.73 mmol, 1.10 equiv) in approximately 5 mL toluene was added dropwise. The mixture was warmed to room temperature and transferred to a glovebox. The flask was stirred at 8086263 -WO-PCT / DOW 86263 WO29°C for 4 hours. The slurry was filtered to remove solids. The filtrate was concentrated to a brownorange solid. The solid was suspended in approximately 10 mL pentane and the mixture was stirred for a few minutes. The solvent was removed by vacuum pump. The pentane wash / evaporation cycle was repeated two more times. The orange residue was suspended in 10 mL hexane and stirred for 20 minutes. The slurry was chilled in a -30 °C freezer for 1 hour, and the mixture filtered to isolate 0.653 g of the orange solid TiCh complex (52%).

[0101] 'H NMR (500 MHz, C6D6) 87.16 (s, 1H), 7.05 (s, 1H), 2.23 (s, 3H), 2.03 (s, 6H), 1.93 (s, 6H), 1.58 (s, 9H), 0.50 (s, 6H).

[0102] The TiC12 complex 9 (0.653 g, 1.30 mmol, 1.00 equiv) was dissolved in 25 mL diethyl ether, and the orange solution was treated with methylmagnesium bromide (3.0 M in diethyl ether, 0.907 mL, 2.72 mmol, 2.10 equiv). The mixture stirred for 2 hours and solvent was removed by vacuum pump. The residue was suspended in 25 mL of 5:1 toluene:hexane and was filtered through a filter frit, then a 0.45 um syringe filter. The filtrate was concentrated to dryness. The solid was suspended in approximately 10 mL pentane and the mixture was stirred for a few minutes. The solvent was removed by vacuum pump. The pentane wash / evaporation cycle was repeated two more times. 0.418 g of a tan-white solid was isolated (70%).

[0103] 1H NMR (400 MHz, C6D6) 8 7.26 (d, J = 2.2 Hz, 1H), 7.07 (d, J = 2.3 Hz, 1H), 2.28 (s, 3H), 1.96 (s, 6H), 1.78 (s, 9H), 1.70 (s, 6H), 0.68 (s, 6H), 0.46 (s, 6H).13C NMR (101 MHz, C6D6) 8162.74, 135.92, 133.00, 131.73, 130.85, 129.09, 128.55, 128.36, 110.27, 53.27, 35.04, 29.87, 20.89, 13.02, 11.67, -0.15.86263 -WO-PCT / DOW 86263 WO30Example 410-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)dimethylgermyl)-5,8-dimethyl-5,10- dihydroindeno[l,2-b] indole

[0011] and MLC 3n 3

[0104] The organolithium reagent 10 was prepared by taking a sample of the parent fluorene in toluene and treating with 1.05 equiv n-butyllithium at ambient temperature overnight. The heterogeneous slurry was diluted with hexane (approximately 5x) and fdtered to isolate an off-white solid. The solid organolithium was dried under vacuum and used without further purification. Ajar was charged with the chlorogermane 2 (1.20 g, 3.51 mmol, 1.00 equiv) and 35 mL dry THF. The organolithium solid 10 (0.883 g, 3.69 mmol, 1.05 equiv) was added. The mixture stirred for 4 hours. The solution was removed from the glovebox and quenched with aqueous ammonium chloride. Product was extracted with several portions of diethyl ether. Combined organic fractions were concentrated and the residue purified by chromatography on silica gel (0 to 40% dichloromethane in hexane). 0.443 g of product was isolated as a colorless oil (23%).

[0105] 1H NMR (400 MHz, CDC13) 87.72 - 7.63 (m, 1H), 7.29 - 7.24 (m, 3H), 7.19 (d, J = 8.3 Hz, 1H), 7.08 (td, J = 7.5, 1.1 Hz, 1H), 6.99 - 6.92 (m, 2H), 6.58 (s, 1H), 6.04 (ddt, J = 17.3, 10.8, 4.2 Hz, 1H), 5.53 (dq, J = 17.3, 2.0 Hz, 1H), 5.29 - 5.24 (m, 1H), 4.35 (tt, J = 3.9, 2.0 Hz, 2H), 4.03 (s, 3H), 2.30 (s, 3H), 2.26 (s, 3H), 1.44 (s, 9H), 0.19 (s, 3H), 0.10 (s, 3H). 13C NMR (101 MHz, CDC13) 8 160.61, 150.11, 143.31, 142.21, 140.42, 134.68, 133.96, 133.83, 133.48, 132.67, 129.78, 127.76, 124.91, 124.65, 123.66, 123.43, 122.94, 122.37, 120.03, 117.28, 115.92, 108.82, 75.81, 36.12, 35.25, 31.23, 31.20, 21.29, 21.01, -2.76, -3.15.86263 -WO-PCT / DOW 86263 WO31

[0106] In a glovebox, a 100 mL round bottom flask was charged with the allyl ligand 11 (0.410 g, 0.762 mmol, 1.00 equiv) and 7 mL dry toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Triethylamine (0.342 mL, 2.45 mmol, 3.22 equiv) was added, followed by n-butyllithium (0.628 mL, 1.57 mmol, 2.06 equiv). The cooling bath was removed, and the mixture stirred for 120 minutes. The flask was re-cooled to -78 °C and a solution of Ti(NMe2)2Cl2(0.181 g, 0.876 mmol, 1.15 equiv) in 2 mL toluene was added. The flask was warmed to ambient temperature over 30 minutes and transferred to a glovebox. The flask was stirred at 90 °C for 2 hours. The heating mantle was adjusted to 80 °C and chlorotrimethylsilane (0.244 mL, 1.92 mmol, 2.52 equiv) was injected. The mixture stirred at 80 °C overnight. The mixture was cooled and concentrated under vacuum to remove approximately 20-30% of volatiles. The brown solution was filtered to remove solids, and the brown filtrate was concentrated to dryness.

[0107] The residue from the filtrate was suspended in approximately 20 mL of hot hexane and then chilled in a glovebox freezer overnight. The mixture was filtered to remove solids. The solids were dried under vacuum. Meanwhile, the cake of solid isolated from the first filtration was washed with hot toluene (approximately 60 mL) and then 10 mL dichloromethane. The filtrate was concentrated to dryness. The solid was suspended in approximately 15 mL of hot hexane and was chilled in a glovebox freezer. The chilled solutions were combined and filtered to remove a browngreen solid. The solid was dried under vacuum to give 0.121 g of TiC12 complex 12 (26%). The material was taken onto the next step without further purification.

[0108] The TiC12 complex 12 (0.121 g, 0.197 mmol, 1.00 equiv) was suspended in 3 mL dry toluene. Methylmagnesium bromide (3.0 M in diethyl ether, 0.144 mL, 0.433 mmol, 2.20 equiv) was added. The mixture stirred for 2 hours and solvent was removed by vacuum pump. The residue was suspended in 5 mL toluene and was filtered through a 0.45 um syringe filter. The filtrate was concentrated to dryness and was suspended in approximately 3 mL dry pentane. The slurry stirred for a few minutes and solvent was removed by vacuum pump. The pentane wash / evaporation cycle was repeated two more times to give 71 mg of a dry orange solid (63%).

[0109] 1H NMR (400 MHz, C6D6) 87.89 (dd, J= 8.4, 1.4 Hz, 1H), 7.64 (dd,. / = 8.6, 1.4 Hz, 1H), 7.33 (d, J= 2.2 Hz, 1H), 7.25 (d, J= 2.2 Hz, 1H), 7.18 (dd, J= 6.8, 1.1 Hz, 1H), 7.14 - 7.08 (m, 1H), 7.01 (dd,.7= 8.3, 1.8 Hz, 1H), 6.84 (d, J= 8.7 Hz, 2H), 3.52 (s, 3H), 2.36 (s, 3H), 2.11 (s, 3H), 1.35 (s, 9H), 0.81 (s, 3H), 0.74 (s, 3H), 0.27 (s, 3H), 0.12 (s, 3H).13C NMR (101 MHz, C6D6) 8 164.37,86263 -WO-PCT / DOW 86263 WO32144.49, 136.68, 136.08, 134.02, 131.96, 131.82, 131.09, 129.22, 128.55, 128.08, 124.30, 124.01, 121.62, 121.59, 121.35, 121.10, 116.13, 108.66, 87.80, 57.78, 51.63, 34.70, 30.90, 29.47, 20.92, 20.91, -0.16, -0.84.Example 50-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylgermyl)-5,8-dimethyl-5,10- dihydroindeno[1,2-b] indole

[0014] and MLC 4

[0110] A 100 mL round bottom flask was charged with 5,8-dimethyl-5,10-dihydroindeno[l,2-b]indole 13 (0.660 g, 2.83 mmol, 1.00 equiv) and 15 mL dry THF. The solution was stirred at -78 °C under a blanket of nitrogen. N-butyllithium (2.5 M in hexane, 1.19 mmol, 2.97 mmol, 1.05 equiv) was injected. The mixture was allowed to warm to ambient temperature over two hours. The solution turned dark red. The solution was returned to -78 °C and the chlorogermane 2 (1.15 g, 3.11 mmol, 1.10 equiv) was added as a solution in 15 mL THF. The mixture was allowed to stir overnight and gradually warm to ambient temperature. The solution was quenched with aqueous ammonium chloride. Product was extracted with several portions of diethyl ether. Combined organic fractions were dried with magnesium sulfate and concentrated to dryness. The residue was purified by chromatography on silica gel (0 to 20% EtOAc in hexane). 0.981 g of a colorless oil was isolated that solidified upon standing (61%).

[0111] 1H NMR (500 MHz, CDC13) 8 7.67 (dt, J = 7.6, 0.9 Hz, 1H), 7.35 (dd, J = 7.6, 0.9 Hz, 1H), 7.26 (dt, J = 7.5, 0.8 Hz, 1H), 7.23 (d, J = 2.2 Hz, 1H), 7.19 (d, J = 8.4 Hz, 1H), 7.08 (td, J = 7.5, 1.1 Hz, 1H), 6.95 (dd, J = 8.4, 1.7 Hz, 1H), 6.85 (dd, J = 2.2, 0.8 Hz, 1H), 6.57 (dt, J = 1.7, 0.8 Hz, 1H), 6.01 (ddt, J = 17.3, 10.8, 4.1 Hz, 1H), 5.52 (dq, J = 17.3, 2.0 Hz, 1H), 5.26 (dq, J = 10.8,86263 -WO-PCT / DOW 86263 WO331.8 Hz, 1H), 4.45 (s, 1H), 4.33 (qdt, J = 14.2, 4.1, 2.0 Hz, 2H), 4.02 (s, 3H), 2.30 (s, 3H), 2.24 (s, 3H), 1.42 (s, 9H), 0.99 - 0.95 (m, 2H), 0.90 - 0.87 (m, 3H), 0.79 (t, J= 7.8 Hz, 3H), 0.67 - 0.65 (m, 2H).13C NMR (126 MHz, CDCl3) 5 160.89, 150.55, 143.23, 142.13, 140.40, 135.47, 133.84, 133.53, 132.37, 131.82, 129.59, 127.71, 124.89, 124.86, 123.72, 123.31, 123.28, 122.34, 120.05, 117.31, 115.69, 108.80, 75.70, 35.49, 35.20, 34.66, 31.20, 31.16, 25.27, 21.31, 21.03, 8.96, 8.76, 5.44, 5.17.

[0112] In a glovebox, a 50 mL round bottom flask was charged with the allyl ligand 14 (0.505 g, 0.892 mmol, 1.00 equiv) and 5 mL dry toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Triethylamine (0.400 mL, 2.87 mmol, 3.22 equiv) was added, followed by n-butyllithium (0.735 mL, 1.84 mmol, 2.06 equiv). The cooling bath was removed, and the mixture stirred for 90 minutes. The flask was re-cooled to -78 °C and a solution of Ti(NMe2)2Cl2(0.212 g, 1.03 mmol, 1.15 equiv) in 3 mL toluene was added. The flask was warmed to ambient temperature over 30 minutes and transferred to a glovebox. The flask was stirred at 90 °C for 1 hour. The heating mantle was adjusted to 80 °C and chlorotrimethylsilane (0.285 mL, 2.25 mmol, 2.52 equiv) was injected. The mixture stirred at 80 °C overnight. The mixture was cooled and concentrated under vacuum to remove approximately 20-30% of volatiles. The brown solution was filtered to remove solids, and the brown filtrate was concentrated to dryness. Proton NMR of the crude brown residue from the filtrate showed signals consistent with the TiC12 complex. The residue from the filtrate was suspended in approximately 10 mL of pentane and then chilled in a glovebox freezer overnight. The brown mixture was filtered to isolate a brown solid. The solid was dried under vacuum. Proton / Carbon NMR were consistent with clean TiC12 complex 15 (0.327 g, 57%).

[0113] 1H NMR (500 MHz, C6D6) 87.83 (dd, J = 15.4, 8.5 Hz, 2H), 7.42 - 7.29 (m, 2H), 7.29 -7.19 (m, 2H), 7.03 (d, J = 8.4 Hz, 1H), 6.84 (d, J = 8.3 Hz, 1H), 6.65 (s, 1H), 3.59 (s, 3H), 2.35 (s, 3H), 2.09 (s, 3H), 1.87 - 1.76 (m, 1H), 1.54 (dq, J = 12.7, 7.8 Hz, 1H), 1.46 - 1.34 (m, 2H), 1.19 -1.02 (m, 15H). 13C NMR (126 MHz, C6D6) 8 167.87, 145.15, 143.82, 137.47, 135.95, 133.41, 132.82, 132.64, 131.01, 129.57, 128.76, 127.29, 122.99, 121.83, 121.63, 121.44, 119.68, 109.73, 102.75, 34.71, 31.20, 29.35, 21.00, 20.91, 8.99, 8.94, 7.64, 6.74.

[0114] The TiC12 complex 15 (0.327 g, 0.509 mmol, 1.00 equiv) was dissolved in 7 mL dry toluene. The brown solution was treated with methylmagnesium bromide (3.0 M in diethyl ether, 0.373 mL, 1.12 mmol, 2.20 equiv). The mixture stirred at ambient temperature for 1 hour. Solvent was removed by vacuum pump. The residue was suspended in approximately 7.5 mL of dry 5:186263 -WO-PCT / DOW 86263 WO34toluene: hexane, and was filtered through a 0.45 um syringe filter. The filtrate was concentrated to dryness. The residue was suspended in 3 mL dry pentane and volatiles were removed by vacuum pump. This pentane wash / evaporation cycle was repeated two more times to yield 0.259 g of an orange solid (85%).

[0115] 'H NMR (500 MHz, C6D6) 8 7.93 - 7.87 (m, 1H), 7.71 - 7.65 (m, 1H), 7.33 (d, J = 2.3 Hz, 1H), 7.28 (d, J= 2.2 Hz, 1H), 7.21 - 7.16 (m, 2H), 6.99 (d, J = 8.4 Hz, 1H), 6.81 (dd, J = 8.4, 1.8 Hz, 1H), 6.74 (s, 1H), 3.52 (s, 3H), 2.38 (s, 3H), 2.11 (s, 3H), 1.48 - 1.37 (m, 4H), 1.32 (s, 9H), 1.19 (t, J = 8.8 Hz, 3H), 1.13 (t, J = 8.8 Hz, 3H), 0.28 (s, 3H), 0.10 (s, 3H).13C NMR (126 MHz, C6D6) 8 165.02, 144.46, 136.84, 136.22, 132.76, 132.46, 131.42, 130.80, 129.54, 128.58, 126.70, 124.41, 124.10, 121.87, 121.50, 121.38, 121.09, 116.31, 108.58, 87.05, 57.82, 51.41, 34.68, 30.89, 29.45, 20.98, 20.93, 9.08, 9.01, 7.16, 6.57.

[0116] The complex of CMLC A was prepared using published methods disclosed in WO 2019 / 038605 Al.

[0117] The complex of CMLC B was prepared using published methods disclosed in Journal of Organometallic Chemistry 2007, 692(19), 4059-4066).

[0118] The complexes of CMLC C and CMLC D were prepared using published methods disclosed in WO 2023 / 042155 ALExample 6Polymerization Reactions

[0119] Catalyst activity (in terms of efficiency) and resulting polymer characteristics were assessed for MLCs 1 -4 and CMLCs A-D. The polymerization reactions were carried out in a batch reactor.

[0120] The reaction conditions for the results tabulated in Table 1 is as follows: The standard ethylene-octene copolymerization batch reactor conditions of the results in Table 1 and Table 2 for polymerization reaction at 150 °C include 43 g of ethylene, 300 g of 1 -octene, 500 g of Isopar E, 1.2 eq. of [HNMe(Ci8H3?)2][B(C6F5)4 activator with respect to the MLC / CMLC, 10 pmol of MMA0-3A, no hydrogen, and 310 psi reactor pressure for a reaction time of 10 minutes, d. The standard ethylene-octene copolymerization batch reactor conditions of the results in Table 2 for polymerization reaction at 190 °C include 43 g of ethylene, a varied amount of 1 -octene, 500 g of86263 -WO-PCT / DOW 86263 WO35Isopar E, 1.2 eq. of [HNMe(Ci8H3?)2][B(C6F5)4 activator with respect to the MLC / CMLC, 10 pmol of MMA0-3A, no hydrogen, and 390 psi reactor pressure for a reaction time of 10 minutes.Batch Reactor Polymerization Procedure

[0121] The batch reactor polymerizations are conducted in a 2 L Parr™ batch reactor. The reactor is heated by an electrical heating mantle and is cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is fitted with a dump valve, which empties the reactor contents into a stainless-steel dump pot, prefilled with a catalystkill solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The dump pot is vented to a 30 gallon blow-down tank, with both the pot and the tank purged with nitrogen.

[0122] All solvents used for polymerization or catalyst makeup are run through solvent purification columns to remove any impurities that may affect polymerization. The 1 -octene and Isopar E are passed through two columns, the first containing activated A2 alumina, the second containing activated Q5. The ethylene is passed through two columns, the first containing activated A204 alumina and activated 4A mol sieves, the second containing Q5 reactant. The N2, used for transfers, is passed through a single column containing A204 alumna, 4 A mol sieves, and Q5.

[0123] The reactor is loaded first from the shot tank that contains Isopar E solvent and / or 1 -octene, depending on desired reactor loading. The shot tank is filled to the load set points using a differential pressure method. After liquid feed addition, the reactor is heated up to the polymerization temperature set point. Ethylene is added to the reactor when at reaction temperature to maintain reaction pressure set point. Ethylene addition amounts are monitored by a micro-motion flow meter.

[0124] The metal-ligand complex and co-catalyst components are mixed with the appropriate amount of purified toluene to achieve a solution of desired molarity. The metal-ligand complex and co-catalyst components are handled in an inert glove box, drawn into a syringe and pressure transferred into the catalyst shot tank. This is followed by three rinses of toluene, 5 mL each. Immediately after catalyst addition the run timer begins. If ethylene is used, it is then added by the Camile to maintain reaction the pressure set point in the reactor. These polymerizations are run for 10 minutes, then the agitator is stopped, and the bottom dump valve is opened to empty the reactor contents into the dump pot. The dump pot contents are poured into trays placed in a lab hood where the solvent is evaporated off overnight. The trays containing the remaining polymer are then86263 -WO-PCT / DOW 86263 WO36transferred to a vacuum oven, where they are heated at 140 °C under vacuum to remove any remaining solvent. After the trays cool to ambient temperature, the polymers are weighed for yield / efficiencies, and submitted for polymer testing.

[0125] Tables 1-2 present results of ethylene / 1 -octene copolymerization reactions for MLC-A to MLC-D and CMLC-A to CMLC-D, following the Batch Reactor Polymerization Procedure disclosed herein. Polymerization experiments were performed at polymerization temperatures of 150 °C, and 190 °C, and for each run, the catalyst efficiency and resulting polymer properties in terms of the polydispersity index (PDI), weight-average molecular weight, and octene incorporation were determined and are reported in Tables 1-2.TABLE 1: Batch reactor results for ethylene-octene copolymerization data at 150 °C.Catalyst Eff. (gMetal-LigandExample # Loading poly / g Mw(g / mol) PDI C8 (wt%) Complex(mmol) metal)IE1 MLC 1 0.7 340,000 32,161 2.2 66 CE1 CMLC A 1.2 1,018,000 30,591 2.3 64 IE2 MLC 2 0.5 1,015,000 40,527 2.2 61CE2 CMLC B 0.5 1,074,000 35,687 2.2 64TABLE 2: Batch reactor results for ethylene-octene copolymerization data at 190 °C.Catalyst 1 -Octene Eff. (gMwC8 Example # Catalyst Loading Loading (g) poly / g MWD(g / mol) (wt%) (mmol) metal)CE5 CMLC A 1.0 28 178,000 77,348 2.4 18 IE5 MLC 1 1.2 28 472,000 82,966 2.5 14 CE6 CMLC A 1.0 300 501,000 21,800 2.2 60 IE6 MLC 1 1.2 300 1,489,000 18,389 2.4 59 CE7 CMLC B 0.75 28 315,000 66,113 2.7 18 IE7 MLC 2 0.65 28 254,000 68,795 2.5 17 CE8 CMLC B 1.5 300 1,442,000 13,129 2.6 58 IE8 MLC 2 0.75 300 919,000 15,470 2.6 59 CE9 CMLC C 0.1 28 6,015,000 217,995 2.5 12 IE9 MLC 3 0.1 28 6,161,000 283,138 2.9 10 CE10 CMLC C 0.1 300 4,010,000 51,941 2.2 54 IE10 MLC 13 0.1 300 3,676,000 58,543 2.3 52 CE11 CMLC D 0.1 28 3,175,000 249,149 2.3 11 IE11 MLC 4 0.1 28 3,467,000 261,839 2.3 11 CE12 CMLC D 0.1 300 3,739,000 49,306 2.2 53IE12 MLC 4 0.1 300 3,551,000 55,918 2.2 5286263 -WO-PCT / DOW 86263 WO37

[0126] As shown in Table 1 and Table 2 of the batch reactor experiments (IE1 - IE 12) demonstrate how the identity of the metal-ligand complex that includes a structure according to Formula (I) impacts the catalyst efficiency, and polymerization capabilities.MEASUREMENT STANDARDS HT-GPC Analysis with IR Detection of Octene Incorporation

[0127] Mw, Mn, and Polydispersity Index (Mw / Mn) are determined via high-temperature GPC analysis using a Dow Robot Assisted Delivery (RAD) system equipped with a PolymerChar infrared detector (IR5) and Agilent PLgel Mixed A columns. Decane (10 pL) was added to each sample for use as an internal flow marker. Samples were first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm of butylated hydroxytoluene (BHT) to a concentration of 10 mg / 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 7.5 mm) guard column followed by two PL-gel 20 pm (300 x 7.5 mm) Mixed-A columns maintained at 160 °C with TCB stabilized with BHT at a flow rate of 1.0 mL / min. The total run time was 24 minutes. To calibrate for molecular weight, Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 mL of TCB stabilized with BHT and dissolved by stirring at 160 °C for 15 minutes. The PS standards were injected into the system without further dilution to create a 3rd-order MW calibration curve with apparent units adjusted to homo-polyethylene (PE) using known Mark-Houwink coefficients for PS and PE. Octene incorporation was determined by use of a linear calibration developed by analyzing copolymers of known compositions.

[0128] 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, while86263 -WO-PCT / DOW 86263 WO38in theory would be expected to exhibit exact correspondence or behavior, may in practice embody something less than exact.

[0129] 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.

[0130] 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 a recitation 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.”

[0131] 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.

[0132] 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

86263 -WO-PCT / DOW 86263 WO39CLAIMS1. A catalyst system comprising a metal-ligand complex having a structure according to Formula (I):where:Y is a monodentate or bidentate ligand selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl,(C3-C3o)heteroaryl, halogen, and -H; andZ is a monodentate or bidentate ligand selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl,(C3-C3o)heteroaryl, halogen, and -H;R1, R2, R3, and R4are independently selected from the group consisting of(Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl,(C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H, wherein: R1and R2are optionally covalently linked to form an aromatic ring or a nonaromatic ring, R2and R3are optionally covalently linked to form an aromatic ring or a non-aromatic ring, and R3and R4are optionally covalently linked to form an aromatic ring or a non-aromatic ring;R5, R6, R7, and R8are 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;R9and R10are independently selected from the group consisting of(Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl,(C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H; and86263 -WO-PCT / DOW 86263 WO40each Rcis independently selected from the group consisting of(Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6-C30)aryl,(C3-C3o)heteroaryl, and -H.2 The catalyst system of claim 1, wherein R1, R2, R3, and R4are independently a(Ci-C5)alkyl.3 The catalyst system of any preceding claim, wherein R1, R2, R3, and R4are methyl.4 The catalyst system of claim 1 or claim 2, wherein:R1and R2are covalently linked to form an aromatic ring;R3and R4are covalently linked to form an aromatic ring;or both.5 The catalyst system of claim 1 or claim 2, wherein R1and R2are covalently linked to form an aromatic ring, and the metal-ligand complex has a structure according to Formula (II):where:R3, R4, R5, R6, R7, R8, R9, R10, Y, and Z are defined as in Formula (I); and R11, R12, R13, and R14are 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;R11and R12are optionally covalently linked to form an aromatic ring or a nonaromatic ring;86263 -WO-PCT / DOW 86263 WO41R12and R13are optionally covalently linked to form an aromatic ring or a nonaromatic ring; andR13and R14are optionally covalently linked to form an aromatic ring or a nonaromatic ring.6 The catalyst system of claim 1 or claim 2, wherein R1and R2are covalently linked to form an aromatic ring, R3and R4are covalently linked to form an aromatic ring, and the metal-ligand complex has a structure according to Formula (III):where:R3, R4, R5, R6, R7, R8, R9, R10, Y, and Z are defined as in Formula (I); and R15, R16, R17, and R18are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6–C30)aryl,(C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H;R19is selected from the group consisting of (Ci-C3o)hydrocarbyl,(Ci-C3o)heterohydrocarbyl, (C6–C30)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H; andR20, R21, R22, R23, and R24are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6–C30)aryl,(C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H.7 The catalyst system of claim 6, wherein R15, R16, R17, and R18are independently selected from the group consisting of (Ci-C5)hydrocarbyl, and -H.8 The catalyst system of claim 6, wherein R20, R21, R22, R23, and R24are -H.86263 -WO-PCT / DOW 86263 WO429. The catalyst system of claim 6, wherein R15, R17, and R18are methyl and wherein R16is -H.

10. The catalyst system of any preceding claim, wherein at least one of R5, R6, R7, or R8is tertbutyl.

11. The catalyst system of any preceding claim, wherein R5and R7are -H.

12. The catalyst system of any preceding claim, wherein R6and R8are independently selected from (Ci-Cio)hydrocarbyl.

13. The catalyst system of any preceding claim, wherein R5and R7are -H, wherein R6is methyl, and wherein R8is tert-butyl.

14. The catalyst system of any preceding claim, wherein R9and R10are independently selected from (Ci-Cio)hydrocarbyl.

15. The catalyst system of any preceding claim, wherein R9and R10are independently selected from the group consisting of methyl and ethyl.

16. The catalyst system of any preceding claim, wherein Y and Z are independently selected from (Ci-Cio)hydrocarbyl.

17. The catalyst system of any preceding claim, wherein Y and Z are methyl.

18. The catalyst system of any preceding claim, wherein the metal-ligand complex according to Formula (I) has the structure of any of the metal-ligand complexes (MLC) 1-8, listed below:86263 -WO-PCT / DOW 86263 WO43MLC 3,MLC 7, MLC 8, or combinations thereof.86263 -WO-PCT / DOW 86263 WO4419. The catalyst system of claim 18, wherein the metal-ligand complex is chosen from MLC 1, MLC 2, MLC 3, MLC 4, or combinations thereof.

20. The catalyst system of any preceding claim, wherein the catalyst system comprises a cocatalyst component.

21. The catalyst system of claim 20, wherein the co-catalyst component comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

22. A method of making an ethylene-based polymer, the method comprising polymerizing, in a solution polymerization reactor, ethylene, or a combination of ethylene and at least one 1 -alkene, in the presence of the catalyst system of any one of the preceding claims.

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