Aryl-heterocyclic-pyrrole catalysts for olefin polymerization

Abstract

A metal-ligand complex according to formula (I).

Description

[0001] Cross Reference to Related Applications

[0002] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 493,440, filed March 31, 2023, the contents of which are incorporated in their entirety. TECHNICAL FIELD

[0003] Embodiments of the present disclosure generally relate to methods for polymerizing olefin monomers in the presence of aryl-heterocycle-pyrrole catalysts, as well as the synthesis and study of aryl-heterocycle-pyrrole catalysts. BACKGROUND

[0004] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, are produced by various catalyst systems. The choice of such catalyst systems used in the polymerization process of olefin-based polymers is an important factor in contributing to the characteristics and properties of such olefin-based polymers.

[0005] Ethylene-based polymers and propylene-based polymers are manufactured for use in various articles. Polyethylene and polypropylene polymerization processes can vary in many aspects to produce various resulting polyethylene resins having different physical properties that make the various resins suitable for use in different applications. Ethylene monomer, and optionally one or more comonomers, are present in a liquid diluent, such as a solvent, such as an alkane or isoalkane, for example isobutene. Hydrogen gas can also be added to the reactor. Catalyst systems used to produce ethylene-based polyolefin resins can generally include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (metallocene or non-metallocene (molecular)) catalyst systems. The reactants in the diluent and catalyst system are circulated around the reactor at elevated polymerization temperatures, thereby producing an ethylene-based homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture containing the polyethylene product dissolved in the diluent, as well as unreacted ethylene and one or more optional comonomers, is removed from the reactor. The reaction mixture, when removed from the reactor, can be processed to remove the polyethylene product from the diluent and unreacted reactants, with the diluent and unreacted reactants generally being recycled back to the reactor. Alternatively, the reaction mixture can be sent to a second reactor connected in series with the first reactor, in which a second polyethylene fraction can be produced. Despite research efforts to develop catalyst systems suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, there remains a need to improve the efficiency of catalyst systems capable of producing polymers having high molecular weight and narrow molecular weight distribution. SUMMARY

[0006] There is a continuing need for catalyst systems or metal-ligand complexes that produce high selectivity for ethylene during copolymerization reactions of ethylene and alpha-olefins. Additionally, the metal-ligand complexes should have high catalyst efficiency and the general ability to produce polymers with high molecular weight at high reactor temperatures, such as greater than 120 °C, greater than 150 °C, or about 190 °C.

[0007] Embodiments of the present disclosure include metal-ligand complexes according to Formula (I):

[0008]

[0009] In Formula (I), M is a metal selected from titanium, zirconium, or hafnium, having a formal oxidation state of +2, +3, or +4. Each X is a monodentate or bidentate ligand independently selected from (C1-C 50 )hydrocarbyl, halogen, -(CH2) w Si(R X )3, -N(R N )2, and -NCOR C , wherein w is 1 to 10 and R X is (C1-C 20 )alkyl. When X is monodentate, the subscript n of (X) n is 2, and when X is bidentate, the subscript n of (X) n is 1 or 2.

[0010] In Formula (I), z1 is independently selected from N or C(R 1 ), and R 1 is not covalently linked to R 11 to form an aromatic or non-aromatic ring; z2 is independently selected from N or C(R 2 ), and R 1 may be covalently linked to R 2 to form an aromatic or non-aromatic ring; z3 is independently selected from O, S, N, NR N , or C(R 3 ), and R 3 may be covalently linked to R 4 to form an aromatic or non-aromatic ring; and z4 is independently selected from O, S, N, NR N , or C(R 4 ), and R 4 may be covalently linked to R 3 to form an aromatic or non-aromatic ring.

[0011] In Formula (I), R 1 , R 2 , R 3 , R 4 , R 11 , R12 , R 13 , R 14 , and R 15 are independently selected from the group consisting of (Ci-C 50 )hydrocarbyl, (Ci-C 50 )heterohydrocarbyl, (C6-C 50 )aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, and -H, wherein R 12 and R 13 are optionally linked to form a ring, R 13 and R 14 are optionally linked to form a ring, and R 14 and R 15 are optionally linked to form a ring.

[0012] In formula (I), each R N , R C , and R P is independently selected from the group consisting of (Ci-C 20 )hydrocarbyl, (Ci-C 20 )heterohydrocarbyl, and -H.

[0013] In one or more embodiments, the metal-ligand complex of formula (I) includes: z3 is CR 3 , z4 is CR 4 , and R 3 and R 4 are linked to form an aromatic ring, and the metal-ligand structure has a structure according to formula (II):

[0014]

[0015] In formula (I), z1, z2, z5, R 11 , R 12 , R13 , R 14 , R 15 , X, n and M are as defined in formula (I), and R z1 , R z2 , R z3 , R z4 is selected from the group consisting of hydrogen, (Ci-C 20 )alkyl, (C6-C 50 )aryl, (Ci-C 10 )heteroalkyl, -NR N , -OR C , -SR C , halogen, CF3- NO2, or -CN, wherein R C is (Ci-C 20 )alkyl, (C6-C 20 )aryl. In some embodiments, in formula (II), z5 is N.

[0016] In some embodiments, the metal-ligand complex of formula (I) comprises: R 11 is a group of formula (III):

[0017]

[0018] In formula (III), R 21 , R 22 , R 23 , R 24 and R 25 are independently selected from (Ci-C 10 )alkyl, (C6-C 10 )aryl, or -H.

[0019] In one or more embodiments, R 13 is covalently linked to R 14 to form an aromatic ring, the metal-ligand has a structure according to formula (IV):

[0020]

[0021] In formula (IV), R 11 , R 12 , R 15 , z1, z2, z3, z4, z5, M, X and n are as defined in formula (I). In formula (IV), R 13a , R 13b , R 14a and R 14b are selected from the group consisting of hydrogen, chlorine, fluorine, benzyl, (Ci-C 10 )alkyl, cyclic (Ci-C 10)heteroalkyl, -OR C , -NR N 2, wherein R C and R N are (C1-C 12 )alkyl. DETAILED DESCRIPTION

[0022] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure can be embodied in different forms and should not be interpreted as being limited to the specific embodiments set forth in the present disclosure.

[0023] The following list of abbreviations is commonly used:

[0024] R, Z, M, X and n: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; i-Pr: iso-propyl; t-Bu: tert-butyl; t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl); Tf: triflate; CV: column volume (used in column chromatography); EtOAc: ethyl acetate; TEA: triethylaluminum; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; LiCH2TMS: (trimethylsilyl)methyllithium; TMS: trimethylsilyl; Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II) chloride; Pd(AmPhos): chloro(pent-2-enyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II); Pd(dppf)Cl2: [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) chloride; ScCl3: scandium(III) chloride; PhMe: toluene; THF: tetrahydrofuran; CH2Cl2: dichloromethane; DMF: N,N-dimethylformamide; EtOAc: ethyl acetate; Et2O: diethyl ether; MeOH: methanol; NH4Cl: ammonium chloride; MgSO4: magnesium sulfate; Na2SO4: sodium sulfate; NaOH: sodium hydroxide; brine: saturated aqueous sodium chloride solution; SiO2: silica; CDCl3: chloroform-D; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimoles; mL: milliliters; M: molar; min or mins: minutes; h or hrs: hours; d: days; TLC: thin layer chromatography; rpm: revolutions per minute; rt: room temperature.

[0025] The term "independently selected from" is used herein to indicate that R groups such as R 1 , R 2 , R 3 , R 4 and R 5 , etc. can be the same or different (e.g., R 1 , R2 , R 3 , R 4 , and R 5 may each be substituted alkyl, or R 1 and R 2 may be substituted alkyl, and R 3 may be aryl, etc.). The chemical names associated with R groups are intended to convey the chemical structure as recognized in the art corresponding to the chemical name. Thus, the chemical names are intended to supplement and illustrate, rather than exclude, structural definitions known to those skilled in the art.

[0026] When used to describe certain carbon atom-containing chemical groups, the intervening expression having the form “(C x -C y )” means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, inclusive of x and y. For example, (C1-C 50 )alkyl is an alkyl group having from 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups can be substituted with one or more substituents such as R x -C y ” intervening definition. A R S substituted chemical group can contain more than y carbon atoms depending on the identity of any groups R S . For example, “(C1-C S )alkyl substituted with exactly one group R 50 may contain from 7 to 56 carbon atoms, where R S is phenyl (-C6H5). Thus, generally, when a chemical group defined using the “(C x -C y ” intervening definition is substituted with one or more carbon atom-containing substituents R S , the minimum and maximum total number of carbon atoms of the chemical group is determined by adding both x and y to the combined total number of carbon atoms from all carbon atom-containing substituents R S .

[0027] The term “substituted” means that at least one hydrogen atom (-H) bound to a carbon atom or heteroatom in the corresponding unsubstituted compound or functional group is replaced with a substituent (e.g., R S ). The term “fully substituted” means that every hydrogen atom (H) bound to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced with a substituent (e.g., R S) substitution. The term "poly-substituted" means that at least two but fewer than all of the hydrogen atoms bonded to a carbon atom or a heteroatom of the corresponding unsubstituted compound or functional group are replaced with a substituent. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly specified.

[0028] The term "(C1-C 50 )alkyl" means a saturated straight chain or branched hydrocarbon radical having from 1 to 50 carbon atoms. The term "(C1-C 50 )alkylene" means a saturated straight chain or branched hydrocarbon diradical having from 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (having three carbons or more, and including single and multiple rings, fused multiple rings and non-fused multiple rings and bicyclic rings) or acyclic, and unsubstituted or substituted with one or more R S .

[0029] In the present disclosure, (C1-C 50 )alkyl can be unsubstituted or substituted (C1-C 50 )alkyl, (C3-C 50 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 )aryl, or (C6-C 20 )aryl-(C1-C 20 )alkylene (such as benzyl (CH2-C6H5)).

[0030] The term "(C1-C 50 )alkyl" and "(C1-C 18 )alkyl" means a saturated straight chain or branched hydrocarbon radical having from 1 to 50 carbon atoms and a saturated straight chain or branched hydrocarbon radical having from 1 to 18 carbon atoms, respectively, which is unsubstituted or substituted with one or more R S . 50 Examples of unsubstituted (C1-C 20 )alkyl are unsubstituted (C1-C 10 )alkyl; unsubstituted (C1-C 40 )alkyl; unsubstituted (C1-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-C 20 )alkyl are substituted (C1-C 10 )alkyl, substituted (C1-C 45Alkyl group. The term "[C]" 45 "Alkyl" means that a group (including substituents) contains a maximum of 45 carbon atoms and is, for example, represented by an R of a (C1-C5) alkyl group. S Replacement (C) 27 -C 40 Alkyl group. Each (C1-C5) alkyl group may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl or 1,1-dimethylethyl.

[0031] The term "(CC)" 50 "Aryl" refers to an unsubstituted or substituted compound having 6 to 40 carbon atoms (one or more R groups). S A substituted monocyclic, bicyclic, or tricyclic aromatic hydrocarbon group, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon group comprises one aromatic ring; a bicyclic aromatic hydrocarbon group has two rings; and a tricyclic aromatic hydrocarbon group has three rings. When a bicyclic or tricyclic aromatic hydrocarbon group is present, at least one ring of the group is aromatic. The other one or more rings of the aromatic group may be independently fused or unfused and aromatic or non-aromatic. Unsubstituted (C6-C) 50 Examples of aryl groups include: unsubstituted (C6-C) 20 )Aryl, unsubstituted (C6-C) 18 ) aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indene; dihydroindene; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C5) 40 Examples of aryl groups include: substituted (C1-C) 20 ) aryl; substituted (C6-C 18 )Aryl; 2,4-bis([C 20 [alkyl]-phenyl; polyfluorophenyl; pentafluorophenyl; and fluorene-9-one-1-yl.

[0032] The term "(C3-C)" 50 "Cycloalkyl" refers to a saturated cyclic hydrocarbon group with 3 to 50 carbon atoms that is not substituted or is surrounded by one or more R groups. S Substitution. Other cycloalkyl groups (e.g., (C x -C y Cycloalkyl groups are defined in a similar manner as having x to y carbon atoms and being unsubstituted or derived from one or more R groups. S Substituted. Unsubstituted (C3-C) 40 Examples of cycloalkyl groups are unsubstituted (C3-C4) 20 )cycloalkyl, unsubstituted (C3-C 10) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3-C 40 ) cycloalkyl. Examples of (C3-C 20 ) cycloalkyl include substituted (C3-C 10 ) cycloalkyl, cyclopentanone-2-yl, and 1-fluorocyclohexyl.

[0033] (C1-C 50 ) alkylene. Examples of (C1-C 50 ) alkylene include unsubstituted (C1-C 50 ) alkylene and substituted (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). The bi-radicals can be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-bi-radicals), or spaced apart by one, two, or more intervening carbon atoms (e.g., 1,3-bi-radicals, 1,4-bi-radicals, etc.). Some bi-radicals include 1,2-bi-radicals, 1,3-bi-radicals, 1,4-bi-radicals, or a, w-bi-radicals and other 1,2-bi-radicals. An a, w-di-radical is a di-radical having the maximum carbon backbone separation between the group carbons. Some examples of (C2-C 20 ) alkylene a, w-bi-radicals include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). Some examples of (C6-C 50 ) arylene a, w-bi-radicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0034] The term “(C1-C 50 ) alkylene” means an unsubstituted or substituted saturated straight-chain or branched-chain divalent radical (i.e., the divalent radical is not on a ring atom). Unsubstituted (C1-C S ) alkylene. Examples of (C1-C 50 ) alkylene include unsubstituted (C1-C 20 ) alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), where “C*” denotes a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl group. Examples of substituted (C1-C 50 ) alkylene include substituted (C1-C 20alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosene). As mentioned previously, two R S may be taken together to form a (C1-C 18 )alkylene, a substituted (C1-C 50 )alkylene. Examples of substituted (C1-C 50 )alkylene also include 1,2-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.

[0035] The term “(C3-C 50 )cycloalkylene” means an unsubstituted or substituted cyclic diradical (i.e., the radicals are on ring atoms) having from 3 to 50 carbon atoms. S The term “(C3-C

[0036] 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(R C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, -Si(R C )-, boron (B), aluminum (Al), gallium (Ga), or indium (In), wherein each R C and each R P is unsubstituted (C1-C 18 )hydrocarbyl or H, and wherein each R N is unsubstituted (C1-C 18 )hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. The term “(C1-C 50 )heterohydrocarbyl” means a heterohydrocarbon group having from 1 to 50 carbon atoms, and the term “(C1-C 50 )heterohydrocarbylene” means a heterohydrocarbon diradical having from 1 to 50 carbon atoms. (C1-C 50 )heterohydrocarbyl or (C1-C 50A heteroalkyl group can be on a carbon atom or a heteroatom. Two groups of a heteroalkyl group can be on a single carbon atom or on a single heteroatom. Additionally, one of the two groups of a bivalent group can be on a carbon atom and the other group can be on a different carbon atom; one of the two groups can be on a carbon atom and the other group on a heteroatom; or one of the two groups can be on a heteroatom and the other group on a different heteroatom. Each (C1-C 50 A heteroalkyl group can be unsubstituted or (substituted with one or more R 50 A heteroalkyl group can be unsubstituted or (substituted with one or more R S aromatic or nonaromatic, saturated or unsaturated, straight-chain or branched, cyclic (including single and multiple rings, fused and non-fused multiple rings) or acyclic.

[0037] A heteroalkyl group can be unsubstituted or (substituted with one or more R 50 A heteroalkyl group can be unsubstituted or (substituted with one or more R 50 Non-limiting examples of (C1-C 50 )heteroalkyl, (C1-C 50 )heteroalkyl-O-, (C1-C 50 )heteroalkyl-S-, (C1-C 50 )heteroalkyl-S(O)-, (C1-C 50 )heteroalkyl-S(O)2-, (C1-C 50 )heteroalkyl-Si(R C )2-, (C1-C 50 )heteroalkyl-N(R N )-, (C1-C 50 )heteroalkyl-P(R P )-, (C2-C 50 )heterocycloalkyl, (C2-C 19 )heterocycloalkyl-(C1-C 20 )alkylene, (C3-C 20 )cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 )heterocycloalkyl-(C1-C 20 )heteroalkylene, (C1-C 50 )heteroaryl, (C1-C 19 )heteroaryl-(C1-C 20 )alkylene, (C6-C 20 )aryl-(C1-C 19 )heteroalkylene, or (C1-C 19 )heteroaryl-(C1-C 20 )heteroalkylene.

[0038] The term "(C1-C 50 )heteroaryl" means an unsubstituted or (substituted with one or more R S ) substituted monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical having 1 to 50 total carbon atoms and 1 to 10 heteroatoms. Monocyclic heteroaromatic hydrocarbon radicals include one heteroaromatic ring; bicyclic heteroaromatic hydrocarbon radicals have two rings; and tricyclic heteroaromatic hydrocarbon radicals have three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other one or more rings of the heteroaromatic radical can independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., typically (C x -C y )heteroaryl, such as (C1-C 12 )heteroaryl) are defined in an analogous manner as having x to y carbon atoms (such as 1 to 12 carbon atoms) and being unsubstituted or substituted with one or more R S )heteroaryl. Monocyclic heteroaromatic hydrocarbon radicals are 5-membered rings or 6-membered rings. A 5-membered ring monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3, or 4, and each heteroatom can be O, S, N, or P. Examples of 5-membered ring monocyclic heteroaromatic hydrocarbon radicals include: pyrrol-1-yl; piperidin-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. A 6-membered ring monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatom can be N or P. Examples of 6-membered ring monocyclic heteroaromatic hydrocarbon radicals include: pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl; and isoquinolin-1-yl. Bicyclic heteroaromatic hydrocarbon radicals can be fused 5,6,5-ring systems; 5,6,6-ring systems; 6,5,6-ring systems; or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0039] The term "(C1-C)" 50 "(C1-C5)" refers to a saturated straight-chain or branched group containing one to fifty carbon atoms and one or more heteroatoms. 50 "Hybrid alkylene" refers to a saturated straight-chain or branched bigroup containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene group may include Si(R) C 3. Ge(R) C 3. Si(R) C )2、Ge(R C )2、P(R P )2、P(R P ), N(R N )2、N(R N ), N, O, OR C , S, SR C S(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is not substituted or is occupied by one or more R groups. S replace.

[0040] Unreplaced (C2-C) 40 Examples of heterocyclic alkyl groups include unsubstituted (C2-C4) alkyl groups. 20 Heterocyclic alkyl groups, unsubstituted (C2-C) 10 Heterocyclic alkyl groups, aziridin-1-yl, oxetane-2-yl, tetrahydrofuran-3-yl, pyrrolidine-1-yl, tetrahydrothiophene-S,S-dioxo-2-yl, morpholin-4-yl, 1,4-dioxane-2-yl, hexahydroazaphen-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0041] The term "halogen atom" or "halogen" refers to a group consisting of a fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) atom. The term "halide" refers to the anionic form of the halogen atom: the fluoride ion (F...). - ), chloride ions (Cl) - ), bromide ions (Br) - ) or iodide ions (I - ).

[0042] The term "saturation" refers to the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. In saturated chemical groups, the presence of one or more substituents R... S In the case of substitution, one or more double and / or triple bonds may optionally be present in the substituent R. SThe term "unsaturated" means containing one or more carbon-carbon double bonds or carbon-carbon triple bonds or, in groups containing heteroatoms, one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, excluding the double bonds that can exist in substituents R S if any, in the double bond, if any, in the aromatic ring, or in the heteroaromatic ring.

[0043] Embodiments of the present disclosure include one or more catalyst systems. The catalyst system comprises one or more metal-ligand complexes according to formula (I):

[0044]

[0045] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, which metal is in the formal oxidation state +2, +3, or +4. Each X is a monodentate or bidentate ligand independently selected from the group consisting of (C1-C 50 )hydrocarbyl, halogen, -(CH2) w Si(R X )3, -N(R N )2, and -NCOR C wherein w is 1 to 10 and R X is (C1-C 20 )alkyl. When X is monodentate, the subscript n of (X) n is 2, and when X is bidentate, the subscript n of (X) n is 1 or 2.

[0046] In formula (I), z1 is independently selected from N or C(R 1 ), and R 1 is not covalently linked to R 11 to form an aromatic or non-aromatic ring; z2 is independently selected from N or C(R 2 ), and R 1 may be covalently linked to R 2 to form an aromatic or non-aromatic ring; z3 is independently selected from O, S, N, NR N , or C(R 3 ), and R 3 may be covalently linked to R 4 to form an aromatic or non-aromatic ring; and z4 is independently selected from O, S, N, NR N , or C(R 4 ), and R 4 may be covalently linked to R 3 to form an aromatic or non-aromatic ring.

[0047] In formula (I), R 1 , R 2 , R 3 , R4 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from the group consisting of (C1-C 50 )hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, and -H, wherein R 12 and R 13 are optionally linked to form a ring, R 13 and R 14 are optionally linked to form a ring, and R 14 and R 15 are optionally linked to form a ring.

[0048] In formula (I), each R N , R C , and R P is independently selected from the group consisting of (C1-C 20 )hydrocarbyl, (C1-C 20 )heterohydrocarbyl, and -H.

[0049] In one or more embodiments, when z3is CR 3 , z4is CR 4 , and R 3 and R 4 are linked to form an aromatic ring, and the metal-ligand structure has a structure according to formula (II):

[0050]

[0051] In formula (II), z1, z2, z5, R 11 , R12 R 13 R 14 R 15 X, n, and M are as defined in equation (I), and R z1 R z2 R z3 R z4 Choose from the following groups: hydrogen, (C1-C) 20 )alkyl, (C6-C 50 )Aryl, (C1-C 10 heterohydrocarbon group, -NR N -OR C -SR C Halogens, CF3-NO2 or -CN, where R C It is (C1-C) 20 )alkyl, (C6-C 20 Aryl. In some embodiments, z5 is N in formula (II).

[0052] In one or more embodiments, z5 is N in formula (I). In some embodiments, z1 is N; in other embodiments, z2 is N. In some embodiments, only one of z1 and z2 is N in formula (I) or formula (II).

[0053] In each implementation scheme, in equation (I) or (II), when z2 is N and z1 is CR 1 At that time, R 1 With R 11 Non-covalently linked, they form aromatic or non-aromatic rings.

[0054] In one or more embodiments, in formula (I) or formula (II), X is benzyl, (C1-C2) 20 )alkyl, -CH2Si[(C1-C 30 )alkyl]3、-N[(C1-C 20 [3] alkyl or halogen.

[0055] In one or more embodiments, in formula (I) or formula (II), X is benzyl, methyl, -CH2Si[(C1-C 20 )alkyl]3、-N[(C1-C 10 [alkyl]3 or chlorine.

[0056] In some implementations, in formula (I) or formula (II), R 11 It is 2,4,6-triisopropylphenyl, mesitylene, substituted and unsubstituted anthracene, 3,5-di-tert-butylphenyl, and naphthyl.

[0057] In some embodiments of the metal-ligand catalyst according to formula (I), R 11 is selected from 3,5-di-tert-butylphenyl; 2,4,6-trimethylphenyl; 2,4,6- triisopropylphenyl; 3,5-diisopropylphenyl; carbazolyl; carbazol-9-yl, 1,2,3,4- tetrahydrocarbazolyl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl; 3,6-bis-(3,5-di-tert- butylphenyl)carbazol-9-yl; 3,6-bis-(2,4,6-trimethylphenyl)carbazol-9-yl); 3,6-bis-(2,4,6- triisopropylphenyl)carbazol-9-yl; 2,7-di(tert-butyl)-carbazol-9-yl; 2,7-di(tert-octyl)- carbazol-9-yl; 2,7-diphenylcarbazol-9-yl; 2,7-bis(2,4,6-trimethylphenyl)-carbazol-9- ylanthryl; 1,2,3,4-tetrahydroanthryl; 1,2,3,4,5,6,7,8-octahydroanthryl; phenanthrene; 1,2,3,4,5,6,7,8-octahydrophenanthryl; 1,2,3,4-tetrahydronaphthyl; 2,6-dimethylphenyl; 2,6-diisopropylphenyl; 3,5-diphenylphenyl; 1-naphthyl; 2-methyl-1- naphthyl; 2-naphthyl; 1,2,3,4-tetrahydronaphth-5-yl; 1,2,3,4-tetrahydronaphth-6-yl; anthracen-9-yl; 1,2,3,4-tetrahydroanthracen-9-yl; 1,2,3,4,5,6,7,8- octahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydrophenanthren-9-yl; indolyl; dihydroindolyl; quinolinyl; 1,2,3,4-tetrahydroquinolinyl; isoquinolinyl; or 1,2,3,4- tetrahydroisoquinolinyl.

[0058] In various embodiments, in formula (I) or formula (II), R 11 is a group of formula (III):

[0059]

[0060] In formula (III), R 21 , R 22 , R 23 , R 24 and R 25 are independently selected from (Ci-C 10 )alkyl, (C6-C 10 )aryl, or -H.

[0061] In various embodiments, in formula (III), R 21 , R 22 , R 23 , R 24 and R 25 are independently selected from tert-butyl, 3,5-di-tert-butylphenyl, or -H.

[0062] In embodiments of the disclosure, R 13 is covalently linked to form an aromatic ring, the metal-ligand has a structure according to Formula (IV): 14

[0063]

[0064] In one or more embodiments, in Formulas (I), (II), and (IV), R 12 , R 13 (including R 13a and R 13b ), R 14 (including R 14a and R 14b ), and R 15 are selected from the group consisting of hydrogen, chloro, fluoro, benzyl, (Ci-C 10 )alkyl, cyclic (Ci-C 10 )heteroalkyl, -OR C , -NR N 2, wherein R C and R N are (Ci-C 12 )alkyl.

[0065] In one or more embodiments, R 13 and R 15 are chloro or fluoro, or (Ci-C 10 )alkyl.

[0066] In some embodiments, R 13 and R 14 are -OR C , wherein R C is (Ci-C8)alkyl.

[0067] In various embodiments, R 14 is selected from the group consisting of (Ci-C 10 )alkyl, cyclic (Ci-C 10 )heteroalkyl, -OR C , -NR N 2, wherein R C and R N are (Ci-C8)alkyl.

[0068] In some embodiments, any one or all of the chemical groups (e.g., X and R 1-59 ) of the metal-ligand complex of Formula (I) can be unsubstituted. In other embodiments, the chemical groups X and R 1-59 of the metal-ligand complex of Formula (I) are both unsubstituted for one or more R S ​substituted, or any one or all of which can be substituted with one or more R S substituted. When two or more R S substituted. When two or more R S may be bonded to the same carbon or heteroatom or to different carbon or heteroatoms. In some embodiments, the chemical group X and R 1-59 are both unsubstituted. In some embodiments, the chemical group X and R S substituted, or any one or all of which can be substituted with one or more R S substituted. When two or more R S substituted. When two or more R S may be all the same or can be independently selected. In one or more embodiments, R S is selected from (C1-C 20 )hydrocarbyl, (C1-C 20 )alkyl, (C1-C 20 )heterohydrocarbyl, or (C1-C 20 )heteroalkyl.

[0069] In the metal ligand complex according to formula (I), X is bonded to M through a covalent or ionic bond. In some embodiments, X can be a monoanionic ligand with a net formal oxidation state of -1. Each monoanionic ligand can independently be hydride, (C1-C 40 )hydrocarbyl carbanion, (C1-C 40 )heterohydrocarbyl carbanion, halide, nitrate, bicarbonate, dihydrogen phosphate, hydrogen sulfate, HC(O)O - , HC(O)N(H) - , (C1-C 40 )hydrocarbyl C(O)O - , (C1-C 40 )hydrocarbyl C(O)N((C1-C 20 )hydrocarbyl) - , (C1-C 40 )hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L Si- wherein each R K , R L and R M is independently hydrogen, (C1-C 40 )hydrocarbyl or (C1-C 40 )heterohydrocarbyl, or R K and R L taken together form a (C2-C 40 )hydrocarbylene or (C1-C 20 )heterohydrocarbylene, and R M is as defined above.

[0070] In some embodiments, X is halogen, unsubstituted (C1-C 20 )hydrocarbyl, unsubstituted (C1-C 20 )hydrocarbyl C(O)O-, or R K R L N-, wherein each of R K and R L is independently unsubstituted (C1-C 20 )hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10 )hydrocarbyl (e.g., (C1-C6)alkyl or benzyl), unsubstituted (C1-C 10 )hydrocarbyl C(O)O-, or R K R L N-, wherein each of R K and R L is independently unsubstituted (C1-C 10 )hydrocarbyl.

[0071] In further embodiments, X is selected from the group consisting of: methyl; ethyl; 1 -propyl; 2-propyl; 1 -butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. X is methyl; ethyl; 1 -propyl; 2-propyl; 1 -butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine. In one embodiment, n is 2, and at least two X are independently monanionic monodentate ligands. In a specific embodiment, n is 2, and the two X groups are joined to form a bidentate ligand. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-dimethylsilane- 1,3-diyl or 1,3-butadiene.

[0072] In one or more embodiments, each X is independently -(CH2)SiR X 3, wherein each R X is independently (C1-C 30 )alkyl or (C1-C 30 )heteroalkyl.)alkyl, and at least one R X is (C1-C 30 )alkyl. In some embodiments, when one of R X is (C1-C 30 )heteroalkyl, the heteroatom is silicon dioxide or an oxygen atom. In some embodiments, R X is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, t-octyl, or nonyl.

[0073] In one or more embodiments, X is -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(CH2CH3); -(CH2)Si(CH3)(CH2CH3)2, -(CH2)Si(CH2CH3)3, -(CH2)Si(CH3)2(n-butyl), -(CH2)Si(CH3)2(n-hexyl), -(CH2)Si(CH3)(n-octyl)R X , -(CH2)Si(n-octyl)R X 2, -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), -CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as -CH2Si(CH3)2CH2TMS). Optionally, in some embodiments, exactly two R X are covalently attached or exactly three R X are covalently attached.

[0074] In some embodiments, X is -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , wherein subscript Q is 0, 1, 2, or 3, and each R C is independently a substituted or unsubstituted (C1-C 30 )hydrocarbyl, or a substituted or unsubstituted (C1-C 30 )heterohydrocarbyl.

[0075] In illustrative embodiments, the catalyst system can include a metal-ligand complex according to formula (I) having the structure of any one of metal-ligand complexes 1 to 10:

[0076]

[0077]

[0078] Additive component

[0079] In some embodiments, the catalyst system does not include an additive. An additive is a chemical agent present during the polymerization process that does not prevent olefin growth. In one or more embodiments, the catalyst system further includes an additive. In some embodiments, the additive functions as a cocatalyst. In other embodiments, the additive functions as a scavenger or purifier. A cocatalyst is an agent that cooperates with the catalyst to catalyze the reaction or to increase the catalytic activity of the catalyst.

[0080] A purifier scavenges impurities in the reactor prior to the addition of the precatalyst and thus does not constitute an activator. Lower loadings of aluminoxanes are not used as cocatalysts, rather, they are used as purifiers.

[0081] Suitable additives can include, but are not limited to, alkylaluminums; polymeric or oligomeric aluminoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds, including the use of such compounds under oxidizing conditions. Combinations of one or more of the foregoing additives with techniques are also contemplated. The term "alkylaluminum" means a dihydrogen monoalkylaluminum or a dihalogen monoalkylaluminum, a dihydrogen dialkylaluminum or a dihalogen dialkylaluminum, or a trialkylaluminum. Examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0082] In some embodiments, the additive is a Lewis acid Group 13 metal compound containing (C1-C 20 ) hydrocarbyl substituents as described herein. In some embodiments, the additive includes a tri((C1-C 20 ) hydrocarbyl) substituted aluminum or a tri((C1-C 20 ) hydrocarbyl)-boron compound. In other embodiments, the additive is selected from the group consisting of tri(hydrocarbyl) substituted aluminum, tri((C1-C 20 ) hydrocarbyl)-boron compounds, tri((C6-C 10 ) alkyl) aluminum, tri((C6-C 18 ) aryl) boron compounds, and halogenated (including perhalogenated) derivatives thereof.

[0083] In one or more embodiments, the polymerization process further includes a borate- based additive. In some embodiments, the borate-based additive is selected from the group consisting of tri(fluoro-substituted phenyl) borane, tri(pentafluorophenyl) borane. In some embodiments, the cocatalyst is tri((C1-C 20)alkyl)ammonium tetrakis((C1-C 20 )alkyl)borates (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" means a nitrogen cation which is ((C1-C 20 )alkyl)4N + , ((C1-C 20 )alkyl)3N(H) + , ((C1-C 20 )alkyl)2N(H)2 + , (C1-C 20 )alkylN(H)3 + , or N(H)4 + , wherein each (C1-C 20 )alkyl group can be the same or different (when two or more are present).

[0084] In one or more embodiments, the additive can be selected from polymeric or oligomeric aluminoxanes, especially methylaluminoxane, and inert, compatible, non-coordinating ion forming compounds. Exemplary suitable additives include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallowalkyl)methyl, tetra(pentafluorophenyl)borate (1-)ammonium, triethylaluminum, butylhydroxytoluene diethylaluminum, bis-(butylhydroxytoluene)ethylaluminum, tri-(butylhydroxytoluene)aluminum, and combinations thereof.

[0085] In some embodiments, one or more co-catalysts can be used in combination with each other. A specific example of a co-catalyst combination is a mixture of a tri((C1-C8)alkyl)aluminum, a tri((C1-C4)alkyl)borane, a tri((C6-C 18 )aryl)borane, or an ammonium borate with an oligomeric or polymeric aluminoxane compound. The ratio of the total number of moles of one or more metal-ligand complexes of formula (I) to the total number of moles of one or more of the co-catalysts is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When aluminoxane is used as a co-catalyst alone, preferably the ratio of Al of the aluminoxane to the metal of the metal-ligand complex of formula (I) (Al / M) is at least 20. In some other embodiments, when tri(pentafluorophenyl)borane is used as a co-catalyst alone, the ratio of the number of moles of tri(pentafluorophenyl)borane employed to the total number of moles of one or more metal-ligand complexes of formula (I) is from 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1.

[0086] Polymerization process

[0087] Embodiments of the present disclosure include polymerization processes. The polymerization processes include polymerizing ethylene and one or more olefins in the presence of a catalyst system comprising a metal-ligand complex according to Formula (I) or Formula (II) or Formula (IV) under olefin polymerization conditions to form an ethylene-based polymer.

[0088] One or more embodiments of the present disclosure include a method of polymerizing a polymer, the method comprising: contacting ethylene and optionally one or more (C3-C 12 ) alpha-olefins in the presence of a catalyst system in a reactor. The catalyst system can include a procatalyst of a metal-ligand complex according to Formula (I) and an activator. The polymerization process can include, but is not limited to, for example, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, continuous stirred tank reactors, batch reactors in parallel or in series, and / or any combination thereof.

[0089] The polymerization processes of the present disclosure can produce ethylene-based polymers, for example, homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as alpha-olefins can be produced, for example, using one or more loop reactors, isothermal reactors, and combinations thereof by solution phase polymerization processes.

[0090] In some embodiments, the solution phase polymerization process occurs in one or more well-agitated reactors, such as one or more loop reactors or one or more spherical isothermal reactors, at a temperature in the range of 120 °C to 300 °C, for example, in the range of 150 °C to 190 °C, and at a pressure in the range of 300 psi to 1500 psi, for example, in the range of 400 psi to 750 psi. The residence time in the solution phase polymerization process is typically in the range of 2 minutes to 30 minutes; for example, 10 minutes to 20 minutes. Ethylene, one or more solvents, one or more catalyst systems, such as a catalyst system including a procatalyst of a metal-ligand complex according to Formula (I), optionally one or more co-catalysts, and optionally one or more comonomers are continuously fed into the one or more reactors. Exemplary solvents include, but are not limited to, isoparaffin. For example, such a solvent is commercially available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas. The resulting mixture of the ethylene-based polymer and the solvent is then removed from the reactor, and the ethylene-based polymer is isolated. The solvent is typically recovered via a solvent recovery unit (i.e., heat exchangers and vapor-liquid separator drums), and subsequently recycled back into the polymerization system.

[0091] Co-catalyst component

[0092] Catalytic activity can be achieved by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions, including metal-ligand complexes of formula (I). For example, the main catalyst of a metal-ligand complex according to formula (I) can be made catalytically active by contacting the complex with an activated co-catalyst or by combining the complex with an activated co-catalyst. Furthermore, the metal-ligand complex according to formula (I) comprises a neutral main catalytic form and a positively charged catalytic form due to the loss of a monoanionic ligand (such as benzyl or phenyl). Activating co-catalysts suitable for this document include alkylaluminum; polymeric or oligomeric aluminum oxanes (also known as aluminum oxanes); neutral Lewis acids; and non-polymeric, non-coordinated, ion-forming compounds (including those used under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating co-catalysts and techniques are also contemplated. The term "alkylaluminum" means dihydrogenated monoalkylaluminum or dihalogenated monoalkylaluminum, hydrogenated dialkylaluminum or halodialkylaluminum, or trialkylaluminum. Examples of polymeric or oligomeric aluminum oxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0093] In some embodiments, suitable cocatalysts include polymeric or oligomeric aluminum oxanes (especially methylaluminoxanes) and inert, compatible, noncoordinate ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetra(pentafluorophenyl)borate (1-)amine (RIBS-2), triethylaluminum (TEA), and combinations thereof.

[0094] Lewis acid activation cocatalysts include those containing (C1-C) as described herein. 20 A Group 13 metal compound with a hydrocarbon substituent. In some embodiments, the Group 13 metal compound is a tri((C1-C) group. 20 ()hydrocarbon-substituted aluminum or tri((C1-C) 20 (Hydrocarbon)-boron compounds. In other embodiments, the Group 13 metal compound is a tri(hydrocarbon)-substituted aluminum, tri((C1-C)-boron compound. 20 )hydro-boron compounds, tri((C1-C 10 Alkyl aluminum, tri((C6-C) 18 (Aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In other embodiments, the Group 13 metal compound is tri(fluorosubstituted phenyl)borane or tri(pentafluorophenyl)borane. In some embodiments, the activation cocatalyst is tri((C1-C)borane. 20 )hydrocarbonyl)borates (e.g., triphenylmethyltetrafluoroborate) or tri((C1-C 20hydrocarbyl)ammonium tetrakis((C1-C 20 )hydrocarbyl)boranes (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term “ammonium” means a nitrogen cation which is ((C1-C 20 )hydrocarbyl)4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 )hydrocarbylN(H)3 + , or N(H)4 + , where each (C1-C 20 )hydrocarbyl group can be the same or different (when two or more are present).

[0095] Combinations of neutral Lewis acid activating cocatalysts include mixtures comprising a tri((C1-C4)alkyl)aluminum and a halogenated tri((C6-C 18 )aryl)borane compound (especially tri(pentafluorophenyl)borane). Other embodiments are combinations of such neutral Lewis acid mixtures with polymeric or oligomeric aluminoxanes and combinations of a single neutral Lewis acid (especially tri(pentafluorophenyl)borane) with polymeric or oligomeric aluminoxanes. The molar ratio of (metal-ligand complex) to (tri(pentafluorophenyl)borane) to (aluminoxane) [e.g., the molar ratio of (Group 4 metal-ligand complex) to (tri(pentafluorophenyl)borane) to (aluminoxane)] is from 1:1:1 to 1:10:30, in other embodiments from 1:1:1.5 to 1:5:10.

[0096] Catalyst systems comprising a metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combination with one or more cocatalysts (e.g., cation-forming cocatalysts, strong Lewis acids, or combinations thereof). Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes (especially methylaluminoxane) and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallowalkyl)methyl, tetrakis(pentafluorophenyl)borate (1-)amine, and combinations thereof.

[0097] In some embodiments, one or more of the foregoing activating co-catalysts can be used in combination with one another. A specific example of a co-catalyst combination is a mixture of a tri((Ci-C4)hydrocarbyl)aluminum, a tri((Ci-C4)hydrocarbyl)borane or ammonium borate with an oligomeric or polymeric aluminoxane compound. The ratio of the total moles of one or more metal-ligand complexes of formula (I) to the total moles of one or more activating co-catalysts is 1 : 10,000 to 100: 1. In some embodiments, the ratio is at least 1 :5000, in some other embodiments at least 1 : 1000; and 10: 1 or less, and in some other embodiments 1 : 1 or less. When aluminoxane is used alone as the activating co-catalyst, preferably the moles of aluminoxane employed are at least 100 times the moles of metal-ligand complex of formula (I). In some other embodiments, when tri(pentafluorophenyl)borane is used alone as the activating co-catalyst, the ratio of the moles of tri(pentafluorophenyl)borane employed to the total moles of one or more metal-ligand complexes of formula (I) is 0.5: 1 to 10: 1, 1 : 1 to 6: 1, or 1 : 1 to 5: 1. The remaining activating co-catalyst is typically employed in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of formula (I).

[0098] Polyolefin

[0099] The foregoing paragraphs describe catalytic systems that are utilized to polymerize olefins, primarily ethylene and propylene. In some embodiments, only a single type of olefin or alpha-olefin is present in the polymerization scheme, thereby forming a homopolymer. However, additional alpha-olefin comonomers can be incorporated into the polymerization process. The additional alpha-olefin comonomers typically have no more than 20 carbon atoms. For example, the alpha-olefin comonomers can have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary alpha-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- 1-pentene. For example, the one or more alpha-olefin comonomers can 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.

[0100] Ethylene-based polymers, e.g., homopolymers and / or interpolymers (including copolymers) of ethylene with optional one or more comonomers such as alpha-olefins, can include at least 50 weight percent of monomer units derived from ethylene. All individual values and subranges encompassed by “at least 50 weight percent” are disclosed herein as individual embodiments; for example, ethylene-based polymers, i.e., homopolymers and / or interpolymers (including copolymers) of ethylene with optional one or more comonomers such as alpha-olefins, can include at least 60 weight percent of monomer units derived from ethylene; at least 70 weight percent of monomer units derived from ethylene; at least 80 weight percent of monomer units derived from ethylene; or 50 weight percent to 100 weight percent of monomer units derived from ethylene; or 80 weight percent to 100 weight percent of units derived from ethylene.

[0101] In some embodiments, ethylene-based polymers can include at least 90 mole percent of units derived from ethylene. All individual values and subranges from at least 90 mole percent are included herein and are disclosed herein as individual embodiments. For example, ethylene-based polymers can include at least 93 mole percent of units derived from ethylene; at least 96 mole percent of units; at least 97 mole percent of units derived from ethylene; or alternatively, 90 mole percent to 100 mole percent of units derived from ethylene; 90 mole percent to 99.5 mole percent of units derived from ethylene; or 97 mole percent to 99.5 mole percent of units derived from ethylene.

[0102] In some embodiments of ethylene-based polymers, the amount of additional alpha-olefin is less than 50%; other embodiments include at least 0.5 mole percent (mol%) to 25 mol%; and in further embodiments, the amount of additional alpha-olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional alpha-olefin is 1-octene.

[0103] Any conventional polymerization process can 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, for example, loop reactors, isothermal reactors, fluid bed gas phase reactors, stirred tank reactors, batch reactors in parallel or series, or any combination thereof.

[0104] In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system) where ethylene and optionally one or more alpha olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more co-catalysts. In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system) where ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described within this disclosure and as described herein and optionally one or more other catalysts. The catalyst system as described herein can optionally be used in the first reactor or the second reactor in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system) where ethylene and optionally one or more alpha-olefins are polymerized in both reactors in the presence of a catalyst system as described herein.

[0105] In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a single reactor system (e.g., a single loop reactor system) where ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described within this disclosure and optionally one or more co-catalysts as described in the preceding paragraph.

[0106] The ethylene-based polymer can further include 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 polymer can contain any amount of the additive. The ethylene-based polymer can comprise a combined weight of such additives from about 0 to about 10% by weight of the ethylene-based polymer and one or more additives. The ethylene-based polymer can further include fillers, which can include, but are not limited to, organic or inorganic fillers. The ethylene-based polymer can contain from about 0 to about 20 weight percent of fillers, such as calcium carbonate, talc, or Mg(OH)2, by weight of the combined weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer can further be blended with one or more polymers to form a blend.

[0107] In some embodiments, the polymerization process for producing the ethylene-based polymer can include polymerizing ethylene and at least one additional alpha-olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one metal-ligand complex of Formula (I). The density of the polymer produced from such a catalyst system incorporating a metal-ligand complex of Formula (I) can be, for example, 0.850 g / cm3according to ASTM D792 (incorporated by reference herein in its entirety).3 Up to 0.950 g / cm 3 0.880 g / cm 3 Up to 0.920 g / cm 3 0.880 g / cm 3 Up to 0.910 g / cm 3 or 0.880 g / cm 3 Up to 0.900 g / cm 3 .

[0108] In another embodiment, the melt flow ratio (I) of the polymer produced by the catalyst system containing the metal-ligand complex of formula (I) is... 10 The melt index I2 is between 5 and 15, where the melt index I2 is measured according to ASTM D1238 (in its entirety incorporated herein by reference) at 190°C and a 2.16 kg load, and the melt index I... 10 Measured according to ASTM D1238 at 190°C and a 10kg load. In other embodiments, the melt flow ratio (I 10 The melt flow ratio is 5 to 10, and in another embodiment, the melt flow ratio is 5 to 9.

[0109] In some embodiments, the polymer produced by the catalyst system comprising the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 1 to 25, wherein MWD is defined as M w / M n M w Where M is the weight-average molecular weight, and M n The molecular weight is the number average. In other embodiments, the polymer produced by the catalyst system has a molecular weight distribution (MWD) of 1 to 6. Another embodiment includes a MWD of 1 to 3; and other embodiments include a MWD of 1.5 to 2.5.

[0110] Due to the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer, the embodiments of the catalyst system described in this disclosure produce unique polymer properties.

[0111] Unless otherwise stated, all solvents and reagents were obtained from commercial sources and used as is. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by activated alumina, and in some cases by Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glove box were purified by activated alumina. stored on molecular sieves and further dried. Glassware used for moisture sensitive reactions was dried in an oven overnight prior to use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis was performed using a Waters e2695 Separations Module coupled with a Waters 2424ELS detector, Waters 2998 PDA detector, and Waters 3100 ESI mass detector. LC-MS separation was performed on an XBridge C18 3.5 μm 2.1 x 50 mm column using a gradient of acetonitrile to water in a ratio of 5:95 to 100:0 using 0.1% formic acid as the ionizing agent. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 μm 2.1 x 50 mm column coupled with an Agilent 6230 TOF Mass Spectrometer with electrospray ionization. 1 H NMR data is reported as follows: chemical shift (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet and m = multiplet), integration, and assignment. Chemical shifts (in ppm) were reported from the low field of internal tetramethylsilane (TMS, scale δ) using the residual protons in deuterated solvents as references. 1 H NMR data is reported as follows: chemical shift (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet and m = multiplet), integration, and assignment. Chemical shifts (in ppm) were reported from the low field of internal tetramethylsilane (TMS, scale δ) using the residual protons in deuterated solvents as references. 1 H decoupling method 13 C NMR data, and chemical shifts (in ppm) were reported from the low field of tetramethylsilane (TMS, scale δ) compared to using the residual protons in deuterated solvents as references.

[0112] HT-GPC analysis for detection of octene incorporation using IR

[0113] High temperature GPC analysis was performed using a Dow Robot Assisted Delivery (RAD) system equipped with PolymerChar infrared detector (IR5) and Agilent PLgel Mixed A columns. Decane (10 μί) was added to each sample to serve as an internal flow marker. The samples were first diluted to a concentration of 10 mg / mL in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxytoluene (BHT) and then dissolved by stirring at 160 °C for 120 minutes. Prior to injection, the samples were further diluted to a concentration of 2 mg / mL with BHT stabilized TCB. The samples (250 μί) were eluted through one PL-gel 20 μιη (50 mm x 7.5 mm) guard column followed by two PL-gel 20 μιη (300 mm x 7.5 mm) Mixed-A columns maintained at 160 °C with BHT stabilized TCB at a flow rate of 1.0 mL / min. The total run time was 24 minutes. To calibrate the molecular weights, Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 mL of BHT stabilized TCB and dissolved by stirring at 160 °C for 15 minutes. The PS standards were injected into the system without further dilution to create a 3rdorder MW calibration curve where the apparent units were adjusted to homopolyethylene (PE) using known Mark-Houwink coefficients for PS and PE. Octene incorporation was determined by using a linear calibration developed by analyzing copolymers of known composition.

[0114] Batch reactor polymerization procedure

[0115] Batch reactor polymerization was performed in a 2 L Parr TM The reactor was heated by an electric mantle and cooled by an internal coiled cooling coil containing chilled water. The reactor was stirred by a Camile TM A TG process computer controlled and monitored the reactor and heating / cooling system. The bottom of the reactor was fitted with a drain valve that emptied the reactor contents into a stainless steel drain pot that was pre-filled with a catalyst kill solution (typically 5 mL of Irgafos / Irganox / toluene mixture). The drain pot was drained into a 30 gallon blowdown tank, where both the pot and the tank were purged with nitrogen. All solvents used for polymerization or catalyst composition were passed through solvent purification columns to remove any impurities that could affect polymerization. The 1-octene and Isopar E were passed through two columns, the first containing activated A2 alumina and the second containing activated Q5 reactant. The ethylene was passed through two columns, the first containing A204 alumina and the second containing 5A molecular sieves. The catalyst was passed through two columns, the first containing activated Q5 reactant and the second containing activated Q5 reactant. The reactor was purged with nitrogen before and after each run. The reactor was purged with nitrogen for 10 minutes before the addition of the catalyst and the reactor was purged with nitrogen for 10 minutes after the addition of the catalyst. The reactor was purged with nitrogen for 10 minutes before the addition of the monomer and the reactor was purged with nitrogen for 10 minutes after the addition of the monomer. The reactor was purged with nitrogen for 10 minutes before the addition of the hydrogen and the reactor was purged with nitrogen for 10 minutes after the addition of the hydrogen. The reactor was purged with nitrogen for 10 minutes before the addition of the initiator and the reactor was purged with nitrogen for 10 minutes after the addition of the initiator. molecular sieves, and the second column contains Q5 reactant. N2 is used to transfer through the single column containing A204 alumina, molecular sieves, and the second column contains Q5 reactant. N2 is used to transfer through the single column containing A204 alumina,

[0116] The reactor is first loaded from a sparge can containing Isopar E solvent and / or 1-octene, depending on the desired reactor loading. The sparge can is filled to the loading set point by using a lab scale installed with the sparge can. After the liquid feed is added, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor at the reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored by a micro-motion flow meter.

[0117] The catalyst and activator are mixed with the appropriate amount of purified toluene to obtain the desired molar concentration of the solution. The catalyst and activator are handled in an inert glovebox, drawn into a syringe, and the pressure is transferred to the catalyst sparge can. The catalyst sparge can is then flushed with toluene three times, 5 mL each. Immediately after the catalyst is added, the timer is started. If ethylene is used, it is added by Camile to maintain the reaction pressure set point in the reactor. These polymerization runs for 10 minutes, then the stirrer is stopped, and the bottom drain valve is opened to empty the reactor contents into a drain pot. The drain pot contents are poured into a tray placed in the lab fume hood, where the solvent is evaporated overnight. The tray containing the remaining polymer is then transferred to a vacuum oven, where it is heated up to 140 °C under vacuum to remove any remaining solvent. After the tray cools to ambient temperature, the polymer is weighed to obtain the yield / efficiency, and submitted for polymer testing.

[0118] Examples

[0119] Examples 1-20 are synthesis procedures for ligand intermediates, ligands, and isolated procatalysts. Inventive metal-ligand complexes 1-10 (MLC-1-10) are synthesized from the various ligands disclosed herein. One or more features of the present disclosure are illustrated according to the following examples:

[0120] Example 1 - for synthesis of MLC-2

[0121] 3-bromo-1-(3,5-dimethylphenyl)-1H-indazole - for synthesis of MLC-2

[0122] A mixture of 3-bromo-1-(3,5-dimethylphenyl)-1H-indazole (99 mg, 0.33 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H- pyrrole (234 mg, 0.41 mmol, 125 mol%, 85% purity), Pd(PPh3)4 (38 mg, 0.03 mmol, 10 mol%) and K3PO4 (210 mg, 0.99 mmol, 300 mol%) was weighted into a vial. Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex→ Hex / DCM 7:3) to give the product as a yellow solid (82.7 mg) in 44% yield.

[0123] 1 H NMR (400 MHz, CDC13) δ 7.74 - 7.67 (m, 2H), 7.47 (ddd, J = 8.4, 6.9, 1.2 Hz, 1H), 7.33 - 7.27 (m, 3H), 7.02 (s, 1H), 2.41 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 139.98, 139.55, 139.52, 128.94, 128.32, 125.00, 123.57, 122.27, 120.79, 120.62, 110.98, 21.51.

[0124] 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,5-dimethylphenyl)-1H-indazol- for synthesis of MLC-2

[0125] A mixture of 3-bromo-1-(3,5-dimethylphenyl)-1H-indazole (99 mg, 0.33 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H- pyrrole (234 mg, 0.41 mmol, 125 mol%, 85% purity), Pd(PPh3)4 (38 mg, 0.03 mmol, 10 mol%) and K3PO4 (210 mg, 0.99 mmol, 300 mol%) was weighted into a vial. Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex→ Hex / DCM 7:3) to give the product as a yellow solid (82.7 mg) in 44% yield.

[0126] 1 H NMR (400 MHz, CDC13) δ 9.50 (s, 1H), 8.40 (s, 1H), 8.24 (dt, J = 8.1, 1.0 Hz, 1H), 8.08 (dt, J = 1.8, 0.8 Hz, 2H), 7.98 (d, J = 8.9 Hz, 2H), 7.82 - 7.77 (m, 1H), 7.57 (dd, J = 8.9, 1.9 Hz, 2H), 7.50 (ddd, J = 8.4, 7.0, 1.1 Hz, 1H), 7.39 - 7.32 (m, 3H), 7.20 (dd, J = 3.5, 2.6 Hz, 1H), 6.98 - 6.95 (m, 1H), 6.68 (dd, J = 3.5, 2.7 Hz, 1H), 2.40 (s, 6H), 1.38 (s, 18H). 13 C NMR (101 MHz, CDC13) δ 148.11, 140.22, 140.13, 139.63, 139.33, 131.75, 129.92, 128.97, 128.20, 127.54, 127.35, 126.43, 125.44, 124.55, 122.28, 121.81, 121.73, 120.98, 120.47, 112.88, 110.93, 108.76, 35.31, 31.08, 21.54.

[0127] Example 2 - for synthesis of MLC-3

[0128] 3-bromo-1-(3,5-dimethoxyphenyl)-1H-indazole - for synthesis of MLC-3

[0129] A mixture of 3-bromo-1H-indazole (600 mg, 3.05 mmol, 100 mol%), 1-iodo-3,5- dimethoxybenzene (1206 mg, 4.57 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (139 mg, 1.22 mmol, 40 mol%), CuI (116 mg, 0.61 mmol, 20 mol%) and K2CO3 (631 mg, 4.57 mmol, 150 mol%) was weighed into a vial. Toluene (3 mL) was added and the mixture was stirred at 110 °C overnight. The reaction was diluted with hexane (3 mL), filtered and the solvent was removed in vacuo. The residue was subjected to silica column chromatography (Hex→ Hex / DCM 4:6) to give the product (462.1 mg) in 46% yield.

[0130] 1.22 mmol, 40 mol%), CuI (116 mg, 0.61 mmol, 20 mol%) and K2CO3 (631 mg, 4.57 mmol, 150 mol%) was weighed into a vial. Toluene (3 mL) was added and the mixture was stirred at 110 °C overnight. The reaction was diluted with hexane (3 mL), filtered and the solvent was removed in vacuo. The residue was subjected to silica column chromatography (Hex→ Hex / DCM 4:6) to give the product (462.1 mg) in 46% yield.

[0131] 1H NMR (400 MHz, CDC13) δ 7.77 (dt, J = 8.7, 1.0 Hz, 1H), 7.70 - 7.66 (m, 1H), 7.48 (ddd, J = 8.4, 7.0, 1.2 Hz, 1H), 7.29 (ddd, J = 8.0, 6.9, 0.8 Hz, 1H), 6.87 (d, J = 2.2 Hz, 2H), 6.47 (t, J = 2.3 Hz, 1H), 3.86 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 161.52, 141.25, 139.94, 128.55, 125.20, 124.03, 122.49, 120.86, 111.11, 101.16, 99.34, 55.80.

[0132] 3-(5-(2,6-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,5-dimethoxyphenyl)-1H-indazol- for synthesis of MLC-3

[0133] To a vial were weighed 3-bromo-1-(3,5-dimethoxyphenyl)-1H-indazole (100 mg, 0.30 mmol, 100 mol%), 2-(2,6-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H- pyrrole (181 mg, 0.38 mmol, 125 mol%), Pd(PPh3)4 (35 mg, 0.03 mmol, 10 mol%) and K3PO4 (191 mg, 0.90 mmol, 300 mol%). Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 6:4) to give the product as a yellow solid in 76% yield (139.3 mg).

[0134] 1H NMR (400 MHz, CDC13) δ 9.68 (s, 1H), 8.37 (s, 1H), 8.16 (dt, J = 8.1, 1.0 Hz, 1H), 8.02 - 7.93 (m, 3H), 7.87 (d, J = 2.0 Hz, 1H), 7.77 (d, J = 8.5 Hz, 1H), 7.56 (dd, J = 8.9, 1.9 Hz, 1H), 7.48 (ddd, J = 8.4, 5.3, 1.6 Hz, 2H), 7.34 (ddd, J = 7.9, 6.9, 0.9 Hz, 1H), 7.16 (dd, J = 3.5, 2.6 Hz, 1H), 6.86 (d, J = 2.3 Hz, 2H), 6.62 (dd, J = 3.5, 2.7 Hz, 1H), 6.35 (t, J = 2.3 Hz, 1H), 3.77 (s, 6H), 1.44 (s, 9H), 1.35 (s, 9H). 13 C NMR (101 MHz, CDC13) δ 161.38, 147.87, 147.28, 141.73, 140.09, 139.91, 131.41, 131.30, 130.47, 130.27, 129.24, 128.10, 127.58, 127.26, 126.90, 126.48, 125.39, 125.22, 124.71, 122.61, 122.48, 121.95, 121.85, 120.91, 112.88, 111.10, 109.04, 100.69, 98.68, 55.66, 35.24, 34.94, 31.10, 31.04. HRMS (ESI) [M+H] + = 608.326

[0135] Example 3 - for synthesis of MLC-7

[0136] 3-bromo-1-(4-(tert-butyl)phenyl)-1H-pyrazole

[0137] A mixture of 3-bromo-l-(4-(tert-butyl)phenyl)-lH-pyrazole (83 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%) and K3PO4 (189 mg, 0.89 mmol, 300 mol%) was weighted into a vial. 1,4-Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 9:1) to give the product as a yellow solid (85.8 mg) in 52% yield.

[0138] 1 H NMR (400 MHz, CDC13) δ 7.77 (d, J = 2.5 Hz, 1H), 7.58 - 7.54 (m, 2H), 7.48 - 7.43 (m, 2H), 6.46 (d, J = 2.4 Hz, 1H), 1.34 (s, 9H).

[0139] 13 C NMR (101 MHz, CDC13) δ 150.35, 137.38, 128.74, 127.93, 126.48, 118.94, 110.42, 34.75, 31.46.

[0140] 1-(4-(tert-butyl)phenyl)-3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1H-pyrazol- for synthesis of MLC-7

[0141] A mixture of 3-bromo-l-(4-(tert-butyl)phenyl)-lH-pyrazole (83 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%) and K3PO4 (189 mg, 0.89 mmol, 300 mol%) was weighted into a vial. 1,4-Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 9:1) to give the product as a yellow solid (85.8 mg) in 52% yield.

[0142] 1 H NMR (400 MHz, CDC13) δ 9.24 (s, 1H), 8.38 (s, 1H), 8.02 (dd, J = 1.9, 0.9 Hz, 2H), 7.96 (d, J = 8.9 Hz, 2H), 7.91 (d, J = 2.5 Hz, 1H), 7.61 - 7.58 (m, 2H), 7.56 (dd, J = 8.9, 1.9 Hz, 2H), 7.45 - 7.40 (m, 2H), 6.82 (dd, J = 3.5, 2.5 Hz, 1H), 6.71 (d, J = 2.5 Hz, 1H), 6.55 (dd, J = 3.5, 2.7 Hz, 1H), 1.36 (s, 18H), 1.33 (s, 9H).

[0143] 13 C NMR (101 MHz, CDC13) δ 149.34, 148.08, 146.81, 137.85, 131.83, 129.93, 128.55, 128.16, 127.95, 127.81, 126.38, 126.32, 126.12, 124.53, 121.04, 118.61, 112.61, 107.67, 103.91, 35.30, 34.66, 31.48, 31.09.

[0144] Example 4 - for synthesis of MLC-4

[0145] 3-bromo-1-(4-methoxyphenyl)-1H-pyrazole

[0146] A small vial was charged with 3-bromo-lH-pyrazole (500 mg, 3.40 mmol, 100 mol%), l-iodo-4-methoxybenzene (1194 mg, 5.10 mmol, 150 mol%), trans-cyclohexane-l,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%) and K2CO3(705 mg, 5.10 mmol, 150 mol%). Toluene (3.4 mL) was added and the mixture was stirred at 110 °C overnight. The reaction was diluted with hexane (3 mL), filtered and the solvent was removed in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 1 : 1 → DCM) to give the product (136.8 mg) in 16% yield.

[0147] 1H NMR (400 MHz, CDC13) δ 7.70 (d, J = 2.4 Hz, 1H), 7.57 - 7.51 (m, 2H), 6.99 - 6.93 (m, 2H), 6.44 (d, J = 2.4 Hz, 1H), 3.84 (s, 3H).

[0148] 13 C NMR (101 MHz, CDC13) δ 158.76, 133.52, 128.89, 127.61, 120.98, 114.69, 110.23, 55.73.

[0149] 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(4-methoxyphenyl)-1H-pyrazol- for synthesis of MLC-4

[0150] To a vial were weighed 3-bromo-1-(4-methoxyphenyl)-1H-pyrazole (75 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H- pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%) and K3PO4 (189 mg, 0.89 mmol, 300 mol%). 1,4-Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 8:2→ Hex / DCM 4:6) to give the product as a yellow solid (103.0 mg) in 65% yield.

[0151] 1 H NMR (400 MHz, CDC13) δ 9.21 (s, 1H), 8.38 (s, 1H), 8.03 - 8.00 (m, 2H), 7.96 (d, J = 8.7 Hz, 2H), 7.84 (d, J = 2.5 Hz, 1H), 7.61 - 7.52 (m, 4H), 6.97 - 6.89 (m, 2H), 6.81 (dd, J = 3.5, 2.6 Hz, 1H), 6.69 (d, J = 2.5 Hz, 1H), 6.54 (dd, J = 3.5, 2.7 Hz, 1H), 3.82 (s, 3H), 1.36 (s, 18H).

[0152] 13C NMR (101 MHz, CDC13) δ 158.11, 148.05, 146.72, 134.08, 131.84, 129.93, 128.43, 128.16, 127.99, 127.84, 126.30, 126.19, 124.52, 121.05, 120.49, 114.65, 112.56, 107.49, 103.70, 55.71, 35.29, 31.09.

[0153] Example 5 - for synthesis of MLC-5

[0154] 3-bromo-1-(3,4-dimethoxyphenyl)-1H-pyrazole (EXP-21-CL5446-R1, DCI 19068)

[0155] A mixture of 3-bromo-lH-pyrazole (500 mg, 3.40 mmol, 100 mol%), 4-iodo- 1,2-dimethoxybenzene (1347 mg, 5.10 mmol, 150 mol%), trans-cyclohexane- 1,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%) and K2CO3(705 mg, 5.10 mmol, 150 mol%) was weighed into a vial. Toluene (3.4 mL) was added and the mixture was stirred at 110 °C overnight. The reaction was diluted with hexane (3 mL), filtered and the solvent was removed in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 1 : 1 → DCM) to give the product (210.0 mg) in 22% yield.

[0156] 1 H NMR (400 MHz, CDC13) δ 7.72 (d, J = 2.4 Hz, 1H), 7.27 (d, J = 2.5 Hz, 1H), 7.06 (dd, J = 8.6, 2.5 Hz, 1H), 6.89 (d, J = 8.6 Hz, 1H), 6.45 (d, J = 2.4 Hz, 1H), 3.95 (s, 3H), 3.91 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 149.83, 148.33, 133.76, 129.03, 127.65, 111.31, 110.93, 110.33, 104.41, 56.35, 56.33.

[0157] 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,4-dimethoxyphenyl)-1H-pyrazol- for synthesis of MLC-5

[0158] A mixture of 3-bromo-1-(3,4-dimethoxyphenyl)-1H-pyrazole (84 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%) and K3PO4 (189 mg, 0.89 mmol, 300 mol%) was weighed into a vial. 1,4-Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex / EtOAc 8:2→ Hex / EtOAc 1:1→ DCM) to give the product as a green solid (92.3 mg) in 55% yield.

[0159] 1 H NMR (400 MHz, CDC13) δ 9.25 (s, 1H), 8.38 (s, 1H), 8.03 - 8.01 (m, 2H), 7.98 - 7.94 (m, 2H), 7.85 (d, J = 2.5 Hz, 1H), 7.55 (dd, J = 8.9, 1.9 Hz, 2H), 7.33 (d, J = 2.5 Hz, 1H), 7.09 (dd, J = 8.7, 2.5 Hz, 1H), 6.87 (d, J = 8.7 Hz, 1H), 6.82 (dd, J = 3.5, 2.6 Hz, 1H), 6.69 (d, J = 2.5 Hz, 1H), 6.55 (dd, J = 3.5, 2.7 Hz, 1H), 3.90 (s, 3H), 3.89 (s, 3H), 1.36 (s, 18H).

[0160] 13 C NMR (101 MHz, CDC13) δ 149.78, 148.06, 147.61, 146.76, 134.31, 131.83, 129.93, 128.46, 128.18, 128.12, 127.85, 126.33, 126.10, 124.53, 121.04, 112.59, 111.45, 110.32, 107.63, 103.97, 103.85, 56.34, 56.23, 35.29, 31.08.

[0161] Example 6 - for synthesis of MLC-6

[0162] 1-(benzo[d][1,3]dioxol-5-yl)-3-bromo-1H-pyrazole

[0163] trans-Cyclohexane-1,2-diamine (163 μΐ^, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%) and K2C03(705 mg, 5.10 mmol, 150 mol%) were weighed into a vial. Toluene (3.4 mL) was added and the mixture was stirred at 1 10 °C overnight. The reaction was diluted with hexane (3 mL), filtered and the solvent was removed in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 1 :1 -> DCM) to give the product (154.8 mg) in 17% yield.

[0164] 1 H NMR (400 MHz, CDC13) δ 7.67 (d, J = 2.4 Hz, 1H), 7.17 (d, J = 2.2 Hz, 1H), 7.05 (dd, J = 8.4, 2.2 Hz, 1H), 6.84 (d, J = 8.4 Hz, 1H), 6.44 (d, J = 2.4 Hz, 1H), 6.03 (s, 2H).

[0165] 13 C NMR (101 MHz, CDC13) δ 148.62, 146.84, 134.68, 129.05, 127.75, 112.71, 110.39, 108.43, 101.98, 101.98.

[0166] 1-(benzo[d][1,3]dioxol-5-yl)-3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1H-pyrazol- for synthesis of MLC-6

[0167] 1-(benzo[d][1,3]dioxacyclopenten-5-yl)-3-bromo-1H-pyrazole (79 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-1H-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%), and K3PO4 (189 mg, 0.89 mmol, 300 mol%) were weighed into vials. 1,4-Dioxane (5 mL) and H2O (2 mL) were added, and the mixture was stirred at 90 °C for 16 hours. The reaction mixture was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL), and washed with brine (5 mL). The combined organic layers were dried with Na2SO4, filtered, and concentrated under vacuum. The residue was subjected to silica column chromatography (Hex / DCM 8:2 → Hex / DCM 4:6) to give a product as a yellow solid (114.0 mg) in 70% yield.

[0168] 1 H NMR (400MHz, CDCl3) δ9.21 (s, 1H), 8.38 (s, 1H), 8.01 (dt, J = 1.8, 0.8Hz, 2H), 7.96(dt,J=8.9,0.6Hz,2H),7.81(d,J=2.5Hz,1H),7.55(dd,J=8.9,1.9Hz,2 H),7.20(d,J=2.2Hz,1H),7.09(dd,J=8.4,2.2Hz,1H),6.84–6.79(m,2H),6. 68(d,J=2.5Hz,1H), 6.54(dd,J=3.5,2.7Hz,1H), 5.99(s,2H), 1.36(s,16H).

[0169] 13 C NMR (101MHz, CDCl3) δ148.54,148.08,146.75,146.11,135.25,131.84,129.92,128.59,128.20,128.16,127. 76,126.33,126.00,124.52,121.02,112.59,112.12,108.43,107.67,103.86,101.78,101.56,35.29,31.08.

[0170] Example 7 - for synthesis of MLC-8

[0171] 3-bromo-1-(3,5-dimethylphenyl)-1H-pyrazole (EXP-21-CL5446-R1, DCI 19068)

[0172] A mixture of 3-bromo-l-(3,5-dimethylphenyl)-lH-pyrazole (76 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4(34 mg, 0.03 mmol, 10 mol%) and K3PO4(189 mg, 0.89 mmol, 300 mol%) was weighted into a vial. 1,4-Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex→ Hex / DCM 4:6) to give the product as a yellow solid (93.3 mg) in 59% yield.

[0173] 1 H NMR (400 MHz, CDC13) δ 7.77 (d, J = 2.5 Hz, 1H), 7.26 (s, 2H), 6.94 (s, 1H), 6.45 (d, J = 2.5 Hz, 1H), 2.36 (s, 6H).

[0174] 13 C NMR (101 MHz, CDC13) δ 139.62, 139.53, 128.82, 128.78, 127.94, 116.99, 110.38, 21.46.

[0175] 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,5-dimethylphenyl)-1H-pyrazol- for synthesis of MLC-8

[0176] A mixture of 3-bromo-l-(3,5-dimethylphenyl)-lH-pyrazole (76 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4(34 mg, 0.03 mmol, 10 mol%) and K3PO4(189 mg, 0.89 mmol, 300 mol%) was weighted into a vial. 1,4-Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex→ Hex / DCM 4:6) to give the product as a yellow solid (93.3 mg) in 59% yield.

[0177] 1 H NMR (500 MHz, CDC13 ) δ 9.26 (s, 1H), 8.38 (s, 1H), 8.05 - 8.03 (m, 2H), 7.96 (d, J = 8.9 Hz, 2H), 7.91 (d, J = 2.5 Hz, 1H), 7.56 (dd, J = 8.9, 1.9 Hz, 2H), 7.31 (dt, J = 1.5, 0.7 Hz, 2H), 6.88 (tt, J = 1.6, 0.8 Hz, 1H), 6.82 (dd, J = 3.4, 2.6 Hz, 1H), 6.70 (d, J = 2.5 Hz, 1H), 6.55 (dd, J = 3.5, 2.7 Hz, 1H), 2.34 (s, 6H), 1.37 (s, 18H).

[0178] 13 C NMR (126 MHz, CDC13 ) δ 148.05, 146.80, 140.13, 139.35, 131.79, 129.94, 128.55, 128.18, 128.00, 127.86, 127.80, 126.30, 126.13, 124.52, 121.07, 116.68, 112.58, 107.65, 103.91, 35.30, 31.09, 21.51.

[0179] Example 8 - for synthesis of MLC-9

[0180] 3-bromo-1-(3,5-dimethoxyphenyl)-1H-pyrazole

[0181] A mixture of 3-bromo-lH-pyrazole (500 mg, 3.40 mmol, 100 mol%), l-iodo-3,5- dimethoxybenzene (1347 mg, 5.10 mmol, 150 mol%), trans-cyclohexane-l,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%) and K2CO3(705 mg, 5.10 mmol, 150 mol%) was weighed into a vial. Toluene (3.4 mL) was added and the mixture was stirred at 110 °C overnight. The reaction was diluted with hexane (3 mL), filtered and the solvent was removed in vacuo. The residue was subjected to silica column chromatography (Hex→ Hex / DCM 4:6) to give the product (308 mg) in 32% yield.

[0182] 1H NMR (400 MHz, CDC13) δ 7.77 (d, J = 2.5 Hz, 1H), 6.81 (d, J = 2.2 Hz, 2H), 6.46 (d, J = 2.5 Hz, 1H), 6.39 (t, J = 2.2 Hz, 1H), 3.84 (s, 6H).

[0183] 13 C NMR (101 MHz, CDC13) δ 161.58, 141.32, 129.00, 128.22, 110.69, 99.15, 97.69, 55.80.

[0184] 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,5-dimethoxyphenyl)-1H-pyrazol- for synthesis of MLC-9

[0185] Pd(PPh3)4(34 mg, 0.03 mmol, 10 mol%) and K3PO4(189 mg, 0.89 mmol, 300 mol%) were weighed into a vial. 1,4-Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 8:2→ Hex / DCM 4:6) to give the product as a yellow solid in 66% yield (111.1 mg).

[0186] 1 H NMR (500 MHz, CDC13) δ 9.31 (s, 1H), 8.39 (s, 1H), 8.01 - 7.99 (m, 2H), 7.96 (d, J = 8.9 Hz, 2H), 7.88 (d, J = 2.6 Hz, 1H), 7.55 (dd, J = 8.9, 1.9 Hz, 2H), 6.84 (d, J = 2.2 Hz, 2H), 6.82 (dd, J = 3.5, 2.6 Hz, 1H), 6.69 (d, J = 2.6 Hz, 1H), 6.54 (dd, J = 3.5, 2.7 Hz, 1H), 6.32 (t, J = 2.2 Hz, 1H), 3.80 (s, 6H), 1.36 (s, 18H).

[0187] 13C NMR (126 MHz, CDC13) δ 161.52, 148.08, 146.95, 141.73, 131.83, 129.92, 128.76, 128.21, 128.17, 127.77, 126.36, 125.83, 124.54, 121.01, 112.64, 108.04, 104.27, 98.43, 97.20, 55.73, 35.29, 31.08.

[0188] Example 9 - for synthesis of MLC-10

[0189] 4-(3-bromo-1H-pyrazol-1-yl)-N,N-dimethylaniline

[0190] A mixture of 3-bromo-lH-pyrazole (500 mg, 3.40 mmol, 100 mol%), 4-iodo-N,N- dimethylaniline (1000 mg, 4.05 mmol, 120 mol%), trans-cyclohexane-l,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%) and K2CO3(705 mg, 5.10 mmol, 150 mol%) was weighed into a vial. Toluene (3.4 mL) was added and the mixture was stirred at 110 °C overnight. The reaction was diluted with hexane (3 mL), filtered and the solvent was removed in vacuo. The residue was subjected to silica column chromatography (Hex→ Hex / DCM 4:6) to give the product (182 mg) in 20% yield.

[0191] 1 H NMR (400 MHz, CDC13) δ 7.66 (d, J = 2.4 Hz, 1H), 7.49 - 7.44 (m, 2H), 6.75 (d, J = 8.6 Hz, 2H), 6.41 (d, J = 2.4 Hz, 1H), 2.99 (s, 6H).

[0192] 13 C NMR (101 MHz, CDC13) δ 149.77, 128.76, 126.93, 120.95, 112.74, 109.73, 40.82.

[0193] 4-(3-(5-(2,7-di-tert-butylanthracen-9-yl)-1 H-pyrrol-2-yl)-1 H-pyrazol-1 -yl)-N,N- dimethyl Aniline - for synthesis of MLC-10

[0194] A mixture of 4-(3-bromo-lH-pyrazol-l-yl)-N,N-dimethylaniline (81 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4(34 mg, 0.03 mmol, 10 mol%) and K3PO4(189 mg, 0.89 mmol, 300 mol%) was weighed into a vial. 1,4-Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C for 16 h. The reaction was diluted with H2O (6 mL), extracted with EtOAc (2 x 8 mL) and washed with brine (5 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 8:2→ Hex / DCM 4:6) to give the product as a yellow solid (90.6 mg) in 56% yield.

[0195] 1 H NMR (500 MHz, CDC13) δ 9.20 (s, 1H), 8.37 (s, 1H), 8.04 - 8.02 (m, 2H), 7.96 (d, J = 8.9 Hz, 2H), 7.81 (d, J = 2.5 Hz, 1H), 7.55 (dd, J = 8.9, 1.9 Hz, 2H), 7.51 (d, J = 9.0 Hz, 2H), 6.80 (dd, J = 3.4, 2.6 Hz, 1H), 6.78 - 6.72 (m, 2H), 6.67 (d, J = 2.5 Hz, 1H), 6.54 (dd, J = 3.4, 2.7 Hz, 1H), 2.96 (s, 6H), 1.36 (s, 18H).

[0196] 13 C NMR (126 MHz, CDC13) δ 148.01, 146.37, 131.84, 129.93, 128.16, 128.13, 127.96, 127.86, 126.51, 126.22, 124.51, 121.10, 120.51, 113.06, 112.51, 107.16, 103.26, 40.96, 35.28, 31.09.

[0197] Example 10 - Synthesis of MLC-1

[0198] Synthesis of 3-bromo-1 -(p-tolyl)-1 H-indazole

[0199] A mixture of 3-bromo-lH-indazole (500 mg, 2.54 mmol, 100 mol%), 4-iodotoluene (830 mg, 3.81 mmol, 150 mol%), trans-cyclohexane-l,2-diamine (70 μL, 0.58 mmol, 23 mol%), CuI (53 mg, 0.28 mmol, 11 mol%) and K2CO3(526 mg, 3.81 mmol, 150 mol%) was weighed into a vial. DMF (10 mL) was added and the mixture was stirred at 120 °C overnight. The reaction was diluted with water (50 mL). The organics were extracted with ethyl acetate (30 mL x 3). The combined organics were washed with water (30 mL x 3) and brine (30 mL). The organics were dried over magnesium sulfate, filtered and concentrated. The residue was subjected to silica column chromatography (Hex / DCM 9: 1→ Hex / DCM 6.5:3.5) to give the product (671 mg) in 92% yield.

[0200] 1 H NMR (400 MHz, Chloroform-d) δ 7.73 - 7.62 (m, 2H), 7.59 - 7.54 (m, 2H), 7.47 (ddt, J = 8.8, 6.9, 1.0 Hz, 1H), 7.35 - 7.31 (m, 2H), 7.29 (dq, J = 8.1, 1.0 Hz, 1H), 2.44 (s, 3H).

[0201] 13 C NMR (101 MHz, CDC13) δ 139.88, 137.12, 137.04, 130.03, 130.01, 128.18, 128.10, 124.82, 123.37, 122.80, 122.74, 122.09, 121.90, 120.65, 110.62, 110.49, 21.09, -0.01.

[0202] 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1 H-pyrrol-2-yl)-1 -(p-tolyl)-1 H-indazol - for synthesis of MLC-1 Example 11 - Synthesis of metal-ligand complex 1 (MLC-1 )

[0203] A mixture of 3-bromo-1-(p-tolyl)-1H-indazole (49 mg, 0.171 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H- pyrrole (120 mg, 0.209 mmol, 123 mol%, 85% purity), Pd(PPh3)4 (12 mg, 0.010 mmol, 6 mol%) and K3PO4 (109 mg, 0.512 mmol, 300 mol%) was weighed into a vial. Dioxane (5 mL) and H2O (2 mL) were added and the mixture was stirred at 90 °C overnight. The reaction was diluted with H2O (15 mL) and brine (15 mL) and extracted with EtOAc (2 x 30 mL). The combined organic layers were dried over MgSO4, filtered and concentrated in vacuo. The residue was subjected to silica column chromatography (Hex / DCM 9:1→ Hex / DCM 7:3) to give the product as a yellow solid (83 mg) in 87% yield.

[0204] 1 H NMR (400 MHz, Chloroform-d) δ 9.50 (s, 1H), 8.43 (s, 1H), 8.27 (d, J = 8.1 Hz, 1H), 8.12 (s, 2H), 8.01 (d, J = 8.9 Hz, 2H), 7.78 (d, J = 8.5 Hz, 1H), 7.68 - 7.55 (m, 4H), 7.54 - 7.46 (m, 1H), 7.42 - 7.28 (m, 3H), 7.26 (d, J = 3.5 Hz, 1H), 6.73 (t, J = 3.1 Hz, 1H), 2.43 (s, 3H), 1.41 (s, 18H).

[0205] 13 C NMR (101 MHz, CDC13) δ 148.04, 140.17, 139.57, 137.78, 136.19, 131.74, 129.95, 129.82, 128.85, 128.11, 127.48, 127.23, 126.35, 125.43, 124.45, 122.56, 122.17, 121.69, 121.59, 120.88, 112.78, 110.62, 108.63, 35.19, 30.98, 21.07.

[0206] HRMS (ESI) [M+H] calcd for C26H32N4O4 488.2530, found 488.2530. + ​

[0207] Example 12 - Synthesis of metal-ligand complex 2 (MLC-2)

[0208] In a glovebox, a solution of 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(p- tolyl)-1H-indazole (15.0 mg, 0.03 mmol, 100 mol%) in C6D6(500 μί) was added dropwise to solid HfBn4(14.0 mg, 0.03 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. Five minutes after addition, the solution was transferred to an NMR tube and checked by 1 H and 13 C NMR. Complete conversion to the desired complex was observed.

[0209] 1 H NMR (400 MHz, C6D6) δ 8.41 (s, 1H), 8.36 - 8.31 (m, 2H), 7.94 (d, J = 9.0 Hz, 2H), 7.76 (dt, J = 8.2, 1.1 Hz, 1H), 7.46 (dd, J = 8.9, 1.9 Hz, 2H), 7.31 (d, J = 3.2 Hz, 1H), 7.25 (d, J = 1.9 Hz, 1H), 7.20 - 6.98 (m, 13H), 6.98 - 6.82 (m, 4H), 6.63 (t, J = 7.7 Hz, 4H), 6.56 - 6.50 (m, 1H), 6.39 (tt, J = 7.3, 1.3 Hz, 2H), 6.19 - 6.10 (m, 4H), 2.13 (s, 3H), 1.78 (d, J = 11.7 Hz, 2H), 1.36 (d, J = 11.7 Hz, 2H), 1.25 (s, 18H).

[0210] 13 C NMR (101 MHz, C6D6) δ 191.22, 148.19, 146.19, 145.78, 142.69, 139.56, 138.56, 137.58, 137.52, 137.32, 136.16, 133.32, 131.83, 130.87, 130.46, 130.18, 129.92, 129.31, 128.96, 128.61, 128.49, 128.27, 128.20, 127.00, 125.33, 124.81, 124.39, 122.98, 122.86, 121.80, 121.76, 119.32, 114.70, 111.87, 111.52, 110.98, 84.19, 34.94, 30.58, 21.07.

[0211] Example 13 - Synthesis of metal-ligand complex 3 (MLC-3)

[0212] In a glovebox, a solution of 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,5- dimethylphenyl)-1H-indazole (11.7 mg, 0.020 mmol, 100 mol%) in C6D6(600 μί) was added dropwise to solid HfBn4(11.0 mg, 0.020 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. Five minutes after addition, the solution was transferred to an NMR tube and checked by 1 H and 13 C NMR. A mixture of [3,2] and mono-[2,1] complex was observed. The solution was then heated in the NMR tube at 80 °C for 2 h.

[0213] 1 H NMR (400 MHz, C6D6) δ 8.45 (s, 1H), 8.42 - 8.40 (m, 2H), 7.99 (d, J = 9.0 Hz, 2H), 7.84 (dt, J = 8.2, 1.1 Hz, 1H), 7.47 (dd, J = 9.0, 1.9 Hz, 2H), 7.41 (d, J = 3.1 Hz, 1H), 7.35 (d, J = 8.9 Hz, 1H), 7.07 (q, J = 1.4 Hz, 1H), 6.99 (d, J = 3.1 Hz, 1H), 6.94 - 6.89 (m, 1H), 6.81 (s, 1H), 6.62 - 6.56 (m, 4H), 6.51 - 6.42 (m, 5H), 6.24 - 6.16 (m, 2H), 2.29 (s, 3H), 2.17 (d, J = 11.9 Hz, 2H), 2.06 (s, 3H), 1.31 (d, J = 11.9 Hz, 2H), 1.24 (s, 18H). 13 C NMR (101 MHz, C6D6) δ 188.89, 148.51, 147.70, 145.76, 144.39, 142.82, 140.25, 137.44, 136.63, 136.04, 133.65, 131.28, 130.61, 130.09, 128.81, 128.45, 128.21, 127.27, 126.29, 125.24, 123.67, 122.84, 122.19, 122.01, 119.84, 114.74, 111.67, 111.51, 110.46, 86.44, 35.36, 30.83, 23.89, 21.69.

[0214] Example 14 - Synthesis of metal-ligand complex 4 (MLC-4)

[0215] In a glovebox, a solution of 3-(5-(2,6-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,5- dimethoxyphenyl)-1H-indazole (12.2 mg, 0.020 mmol, 100 mol%) in C6D6(600 μL) was added dropwise to solid HfBn4(11.0 mg, 0.020 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. Five minutes after addition, the solution was transferred to an NMR tube and analyzed by 1 H and 13 C NMR check.

[0216] 1 H NMR (400 MHz, C6D6) δ 8.55 - 8.52 (m, 1H), 8.43 (t, J = 4.5 Hz, 2H), 8.03 - 7.95 (m, 2H), 7.78 (dt, J = 8.2, 1.1 Hz, 1H), 7.50 (td, J = 9.1, 1.9 Hz, 2H), 7.36 (d, J = 3.2 Hz, 1H), 7.21 (d, J = 8.7 Hz, 1H), 6.96 (d, J = 3.2 Hz, 1H), 6.91 - 6.85 (m, 1H), 6.68 - 6.51 (m, 9H), 6.43 (d, J = 1.6 Hz, 1H), 6.32 (tt, J = 6.3, 2.1 Hz, 1H), 6.24 (tt, J = 6.8, 1.9 Hz, 1H), 5.99 (d, J = 1.6 Hz, 1H), 3.30 (s, 3H), 3.22 (s, 3H), 2.16 - 2.11 (m, 2H), 1.49 (d, J = 6.4 Hz, 1H), 1.42 (d, J = 11.2 Hz, 1H), 1.29 (s, 9H), 1.27 (s, 9H). 13 C NMR (101 MHz, C6D6) δ 171.47, 167.78, 162.50, 148.62, 148.21, 147.67, 146.53, 143.17, 140.45, 138.46, 137.26, 136.50, 132.98, 132.38, 132.00, 131.17, 131.08, 130.35, 130.30, 128.98, 128.78, 127.63, 125.71, 125.36, 123.18, 122.97, 122.96, 122.26, 122.13, 119.98, 114.89, 111.96, 111.19, 91.95, 91.93, 88.64, 86.92, 54.79, 53.94, 35.37, 34.87, 30.93, 30.92.

[0217] Example 15 - Synthesis of metal-ligand complex 5 (MLC-5)

[0218] In a glove box, a solution of 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(4- methoxyphenyl)-1H-pyrazole (10.6 mg, 0.020 mmol, 100 mol%) in C6D6(600 μί) was added dropwise to solid ZrBn4(9.1 mg, 0.020 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. After addition, the solution was transferred to an NMR tube and the sample was allowed to react overnight at room temperature. Two equivalents of toluene were evident in the NMR.

[0219] 1 H NMR (400 MHz, C6D6) δ 8.35 (s, 1H), 8.26 - 8.14 (m, 2H), 7.91 (d, J = 8.9 Hz, 2H), 7.45 (dd, J = 8.9, 1.9 Hz, 2H), 6.80 (d, J = 2.5 Hz, 1H), 6.75 - 6.65 (m, 7H), 6.56 - 6.45 (m, 4H), 6.05 (d, J = 2.5 Hz, 1H), 5.93 - 5.87 (m, 4H), 3.32 (s, 3H), 2.05 (d, J = 10.0 Hz, 2H), 1.24 (s, 18H), 1.17 (d, J = 10.0 Hz, 2H).

[0220] 13 C NMR (101 MHz, C6D6) δ 181.58, 156.55, 151.57, 148.45, 140.16, 139.34, 138.30, 136.19, 133.64, 132.25, 130.52, 130.41, 129.15, 128.39, 127.32, 127.03, 125.18, 123.73, 122.30, 120.79, 113.73, 113.24, 111.51, 109.32, 100.16, 74.81, 54.95, 35.26, 30.94.

[0221] Example 16 - Synthesis of metal-ligand complex 6 (MLC-6)

[0222] In a glovebox, a solution of 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,4- dimethoxyphenyl)-1H-pyrazole (11.2 mg, 0.020 mmol, 100 mol%) in C6D6(600 μί) was added dropwise to solid ZrBn4(9.1 mg, 0.020 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. After addition, the solution was transferred to an NMR tube and the sample was allowed to react overnight at room temperature. Two equivalents of toluene were evident in the NMR.

[0223] 1 H NMR (400 MHz, C6D6) δ 8.37 (s, 1H), 8.24 - 8.20 (m, 2H), 7.92 (d, J = 9.0 Hz, 2H), 7.47 (dd, J = 8.9, 1.9 Hz, 2H), 7.19 (d, J = 3.1 Hz, 1H), 6.76 (d, J = 3.1 Hz, 1H), 6.73 - 6.68 (m, 5H), 6.59 (d, J = 2.5 Hz, 1H), 6.58 - 6.52 (m, 2H), 6.17 (s, 1H), 6.05 (d, J = 2.5 Hz, 1H), 5.93 - 5.89 (m, 4H), 3.42 (s, 3H), 3.38 (s, 3H), 2.06 (d, J = 10.1 Hz, 2H), 1.25 (s, 18H), 1.19 (d, J = 10.1 Hz, 2H).

[0224] 13 C NMR (101 MHz, C6D6) δ 173.43, 151.86, 149.76, 148.44, 146.07, 140.29, 139.67, 138.76, 136.11, 133.67, 132.25, 130.53, 130.23, 129.09, 128.39, 127.44, 127.02, 125.19, 123.60, 122.37, 119.51, 113.73, 109.42, 100.18, 96.41, 74.43, 55.86, 55.82, 35.27, 30.94.

[0225] Example 17 - Synthesis of metal-ligand complex 7 (MLC-7)

[0226] In a glovebox, a solution of 1 -(benzo[d][1,3]dioxol-5-yl)-3-(5-(2,7-di-tert- butylanthracen-9-yl)-1 H-pyrrol-2-yl)-1 H-pyrazole (10.8 mg, 0.020 mmol, 100 mol%) in C6D6(600 μί) was added dropwise to solid ZrBn4(9.1 mg, 0.020 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. After addition, the solution was transferred to an NMR tube and the sample was allowed to react overnight at room temperature. Two equivalents of toluene were evident in the NMR.

[0227] 1 H NMR (500 MHz, C6D6) δ 8.39 (s, 1 H), 8.20 - 8.18 (m, 2H), 7.95 (d, J = 9.0 Hz, 2H), 7.45 (dd, J = 8.9, 2.0 Hz, 2H), 6.76 (d, J = 2.5 Hz, 1 H), 6.70 (d, J = 3.1 Hz, 1 H), 6.69 - 6.63 (m, 4H), 6.52 - 6.48 (m, 2H), 6.40 - 6.36 (m, 1 H), 6.34 (d, J = 8.1 Hz, 1 H), 6.22 - 6.17 (m, 4H), 6.06 (d, J = 2.5 Hz, 1 H), 5.99 (d, J = 8.1 Hz, 1 H), 5.13 (s, 2H), 1.86 (d, J = 9.6 Hz, 2H), 1.59 (d, J = 9.5 Hz, 2H), 1.23 (d, J = 1.7 Hz, 18H).

[0228] 13 C NMR (126 MHz, C6D6) δ 157.23, 151.32, 148.34, 143.49, 141.17, 140.78, 137.78, 135.88, 133.63, 132.63, 131.04, 130.60, 130.49, 128.95, 128.47, 128.35, 127.63, 126.74, 125.16, 124.16, 122.21, 114.05, 109.25, 106.50, 103.93, 100.27, 99.05, 74.79, 35.24, 30.93.

[0229] Example 18 - Synthesis of metal-ligand complex 8 (MLC-8)

[0230] In a glovebox, a solution of 1 -(4-(tert-butyl)phenyl)-3-(5-(2,7-di-tert- butylanthracen-9-yl)-1 H-pyrrol-2-yl)-1 H-pyrazole (11.1 mg, 0.020 mmol, 100 mol%) in C6D6(600 μί) was added dropwise to solid ZrBn4(9.1 mg, 0.020 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. After addition, the solution was transferred to an NMR tube and the sample was allowed to react overnight at room temperature. Two equivalents of toluene were evident in the NMR.

[0231] 1 H NMR (500 MHz, C6D6) δ 8.37 (s, 1H), 8.21 - 8.18 (m, 2H), 7.92 (d, J = 8.9 Hz, 2H), 7.46 (dd, J = 8.9, 1.9 Hz, 2H), 7.22 (d, J = 2.1 Hz, 1H), 7.18 (d, J = 3.1 Hz, 1H), 6.94 (dd, J = 8.3, 2.2 Hz, 1H), 6.75 - 6.70 (m, 6H), 6.55 (t, J = 7.4 Hz, 2H), 6.51 (d, J = 8.3 Hz, 1H), 6.07 (d, J = 2.5 Hz, 1H), 5.91 (d, J = 7.5 Hz, 4H), 2.01 (d, J = 10.0 Hz, 2H), 1.24 (s, 18H), 1.22 (d, J = 10.3 Hz, 2H), 1.18 (s, 9H).

[0232] 13 C NMR (126 MHz, C6D6) δ 180.30, 151.87, 148.45, 146.26, 143.08, 140.38, 138.55, 136.21, 133.65, 132.94, 132.28, 130.53, 130.32, 129.05, 128.35, 127.69, 126.99, 125.20, 124.34, 123.62, 122.31, 113.69, 110.13, 109.43, 100.46, 74.51, 35.25, 34.61, 31.68, 30.92.

[0233] Example 19 - Synthesis of metal-ligand complex 9 (MLC-9)

[0234] In a glovebox, a solution of 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,5- dimethylphenyl)-1H-pyrazole (10.5 mg, 0.020 mmol, 100 mol%) in C6D6(600 μί) was added dropwise to solid ZrBn4(9.1 mg, 0.020 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. After addition, the solution was transferred to an NMR tube and the sample was allowed to react overnight at room temperature. Two equivalents of toluene were evident in the NMR.

[0235] 1 H NMR (500 MHz, C6D6) δ 8.41 (s, 1H), 8.32 (s, 2H), 7.96 (dd, J = 8.9, 2.3 Hz, 2H), 7.45 (d, J = 9.0 Hz, 2H), 7.20 - 7.17 (m, 1H), 6.87 - 6.84 (m, 1H), 6.74 - 6.72 (m, 1H), 6.65 - 6.59 (m, 4H), 6.52 - 6.47 (m, 4H), 6.41 - 6.36 (m, 2H), 6.28 (s, 1H), 6.10 - 6.05 (m, 2H), 2.32 (d, J = 10.7 Hz, 2H), 1.98 (s, 3H), 1.94 (s, 3H), 1.57 (d, J = 10.8 Hz, 2H), 1.24 (s, 18H).

[0236] 13 C NMR (126 MHz, C6D6) δ 179.77, 150.86, 148.36, 144.20, 143.54, 140.55, 136.96, 136.84, 136.09, 133.68, 132.02, 130.61, 129.07, 128.68, 127.76, 127.63, 126.99, 126.65, 125.15, 123.58, 122.12, 113.34, 109.01, 108.65, 100.43, 76.71, 35.30, 30.84, 24.08, 21.20.

[0237] Example 20 - Synthesis of metal-ligand complex 10 (MLC-10)

[0238] In a glovebox, a solution of 3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1-(3,5- dimethoxyphenyl)-1H-pyrazole (11.2 mg, 0.020 mmol, 100 mol%) in C6D6(600 μί) was added dropwise to solid ZrBn4(9.1 mg, 0.020 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. After addition, the solution was transferred to an NMR tube and the sample was allowed to react overnight at room temperature. Two equivalents of toluene were evident in the NMR.

[0239] 1 H NMR (500 MHz, C6D6) δ 8.40 (s, 1H), 8.31 (s, 2H), 7.95 (d, J = 8.6 Hz, 2H), 7.45 (dd, J = 9.0, 2.1 Hz, 2H), 7.20 - 7.17 (m, 1H), 6.84 - 6.81 (m, 1H), 6.71 - 6.60 (m, 5H), 6.50 - 6.44 (m, 2H), 6.40 - 6.35 (m, 4H), 6.06 - 6.02 (m, 1H), 5.79 (dd, J = 15.1, 2.6 Hz, 2H), 3.27 (s, 3H), 3.02 (s, 3H), 2.03 (d, J = 10.1 Hz, 2H), 1.87 (d, J = 10.2 Hz, 2H), 1.25 (s, 18H).

[0240] 13 C NMR (126 MHz, C6D6) δ 167.20, 162.47, 161.78, 151.64, 148.25, 145.85, 141.05, 137.92, 135.99, 133.71, 132.43, 130.62, 129.01, 128.59, 128.40, 128.35, 126.97, 125.09, 123.29, 122.27, 113.60, 109.33, 100.53, 93.06, 89.13, 76.45, 54.85, 53.51, 35.29, 30.91.

[0241] Example 21 - Batch reactor screening of metal-ligand complexes 1 to 3 and 4 to 10

[0242] In a glovebox, a solution of 4-(3-(5-(2,7-di-tert-butylanthracen-9-yl)-1H-pyrrol-2-yl)-1H- pyrazol-1-yl)-N,N-dimethylaniline (10.8 mg, 0.020 mmol, 100 mol%) in C6D6(600 μί) was added dropwise to solid ZrBn4(9.1 mg, 0.020 mmol, 100 mol%) at room temperature. The vial was swirled after each drop to ensure mixing. After addition, the solution was transferred to an NMR tube and the sample was allowed to react overnight at room temperature. Two equivalents of toluene were evident in the NMR.

[0243] 1 H NMR (500 MHz, C6D6) δ 8.37 (s, 1H), 8.26 - 8.23 (m, 2H), 7.92 (d, J = 8.9 Hz, 2H), 7.46 (dd, J = 8.9, 1.9 Hz, 2H), 7.16 (s, 1H), 6.76 - 6.71 (m, 5H), 6.70 (d, J = 2.5 Hz, 1H), 6.62 (d, J = 2.7 Hz, 1H), 6.60 - 6.54 (m, 3H), 6.31 (dd, J = 8.7, 2.7 Hz, 1H), 6.05 (d, J = 2.5 Hz, 1H), 5.96 - 5.92 (m, 4H), 2.53 (s, 6H), 2.10 (d, J = 10.0 Hz, 2H), 1.25 (s, 18H), 1.19 (d, J = 10.0 Hz, 2H).

[0244] 13 C NMR (126 MHz, C6D6) δ 181.54, 151.11, 148.39, 147.79, 139.89, 138.59, 136.86, 136.47, 133.71, 132.45, 130.55, 130.15, 129.30, 128.37, 126.99, 126.71, 125.16, 123.49, 122.44, 119.96, 113.65, 111.86, 111.21, 108.99, 99.81, 74.55, 40.89, 35.26, 30.96.

[0245] Table 3. Batch reactor results

[0246] Table 4: Number of batch reactors used for MLC-4 to MLC-10

[0247]

[0248] 120 °C semi-batch reactor conditions: 46 g ethylene, 300 g 1-octene, 610 g IsoparE, 1.2 equivalents, RIBS-II activator / catalyst, 10 μmol MMAO-3A, 310 psi reactor pressure. 150 °C semi-batch reactor conditions: 43 g ethylene, 300 g 1-octene, 546 g IsoparE, 1.2 equivalents, RIBS-II activator / catalyst, 10 μmol MMAO-3A, 360 psi reactor pressure. 190 °C semi-batch reactor conditions: 43 g ethylene, 300 g 1-octene, 520 g IsoparE, 1.2 equivalents, RIBS-II activator / catalyst, 10 μmol MMAO-3A, 420 psi reactor pressure.

[0249]

[0250] The polymer produced from Comparative CI has a high level of comonomer incorporation. Thus, the expected melt temperature is very low, as indicated by the negative number in Table 1. When compared to Inventive Examples MLC-1 to MLC-3, the efficiency of Comparative CI is not great at higher temperatures, such as 150 °C. The Examples are more efficient at 150 °C. Inventive Examples MLC-1 to MLC-3 also have much higher reaction rates than Comparative CI.

[0251] ​ According to.

[0252]

[0253]

[0254] At 120 °C, semi-batch reactor conditions include: 46 g ethylene, 300 g 1-octene, 610 g IsoparE, 1.2 equivalents, RIBS-II activator / catalyst, 10 μmol MMAO-3A, 310 psi reactor pressure. 150 °C semi-batch reactor conditions: 43 g ethylene, 300 g 1-octene, 546 g IsoparE, 1.2 equivalents, RIBS-II activator / catalyst, 10 μmol MMAO-3A, 360 psi reactor pressure. At 190 °C, semi-batch reactor conditions include: 43 g ethylene, 300 g 1-octene, 520 g IsoparE, 1.2 equivalents, RIBS-II activator / catalyst, 10 μmol MMAO-3A, 420 psi reactor pressure.

Claims

1. A metal-ligand complex according to formula (I): wherein: M is a metal selected from titanium, zirconium or hafnium, said metal having a formal oxidation state of +2, +3 or +4; n is 2 when X is monodentate and 1 or 2 when X is bidentate; each X is a monodentate or bidentate ligand independently selected from the group consisting of (Ci-C 50 )hydrocarbyl, halogen, -(CH2) w Si(R X )3, -N(R N )2, and -NCOR C , wherein w is 1 to 10 and R X is (Ci-C 20 )alkyl; z5is independently selected from N or C; z1 is independently selected from N or C(R) 1 ), and R 1 With R 11 Uncovalently bonded rings can form aromatic or non-aromatic rings; z2is independently selected from N or C(R 2 ), and R 1 and R 2 may be covalently linked to form an aromatic or non-aromatic ring; z3is independently selected from O, S, N, R N or C(R 3 ), and R 3 and R 4 may be covalently linked to form an aromatic or non-aromatic ring; z4is independently selected from O, S, N, NR N or C(R 4 ), and R 4 and R 3 may be covalently linked to form an aromatic or non-aromatic ring; z5is N. R 1 , R 2 , R 3 , R 4 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from the group consisting of (C1-C 50 )hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, and -H, wherein R 12 and R 13 are optionally linked to form a ring, R 13 and R 14 are optionally linked to form a ring, and R 14 and R 15 are optionally linked to form a ring, wherein each R N , R C , and R P are independently selected from the group consisting of (Ci-C 20 )hydrocarbyl, (Ci-C 20 )heterohydrocarbyl, and -H.

2. The metal-ligand complex of claim 1, wherein z3 is CR 3 , z4 is CR 4 , and R 3 is connected to R 4 to form an aromatic ring, and the metal-ligand structure has a structure according to formula (II): wherein z1, z2, R 11 , R 12 , R 13 , R 14 , R 15 , X, n and M are as defined in formula (I), R z1 , R z2 , R z3 , R z4 is selected from the group consisting of hydrogen, (Ci-C 20 )alkyl, (C6-C 50 )aryl, (Ci-C 10 )heteroalkyl, -NR N , -OR C , -SR C , halogen, CF3- NO2or -CN, wherein R C is (Ci-C 20 )alkyl, (C6-C 20 )aryl; and 7. The metal-ligand complex according to any one of the preceding claims, wherein only one of z1and z2is N.

3. The metal-ligand complex according to any one of the preceding claims, wherein X is benzyl, methyl, or -CH2Si[(C1-C 20 )alkyl]3、-N[(C1-C 20 [alkyl]3 or chlorine.

4. The metal-ligand complex according to any one of the preceding claims, wherein R 11 is 2,4,6-triisopropylphenyl, mesityl, substituted and unsubstituted anthryl, 3,5-di-tert- butylphenyl, naphthyl.

5. The metal-ligand complex of any one of claims 1 to 3, wherein R 11 is a group of formula (III): wherein R 21 , R 22 , R 23 , R 24 and R 25 are independently selected from (Ci-C 10 )alkyl, (C6-C 10 )aryl or -H.

6. The metal-ligand complex of claim 5, wherein R 21 , R 22 , R 23 , R 24 , and R 25 are independently selected from t-butyl, 3,5-di-t-butylphenyl, or -H.

15. A polymerization process comprising contacting ethylene and optionally one or more alpha-olefin monomers in the presence of a catalyst system, wherein the catalyst system comprises one or more procatalysts and a co-catalyst, wherein the procatalyst is a metal-ligand complex according to any one of claims 1 to 14, and producing an ethylene-based polymer.

8. The metal-ligand complex of any one of the preceding claims, wherein when z2 is N and z1 is CR 1 1 11 is not covalently linked to form an aromatic or non-aromatic ring.​​ 9. The metal-ligand complex of any one of claims 1 to 8, wherein R 12 , R 13 , R 14 , and R 15 are selected from the group consisting of hydrogen, chloro, fluoro, benzyl, (Ci-C 10 )alkyl, cyclic (Ci-C 10 )heteroalkyl, -OR C , -NR N 2, wherein R C and R N are (Ci-C 12 )alkyl.

10. The metal-ligand complex of any one of claims 1 to 9, wherein R 12 with R 13 connected to form a heterocyclic ring.

11. The metal-ligand complex of any one of claims 1 to 9, wherein R 13 and R 15 is chloro or fluoro, or (Ci-C 10 )alkyl.

12. The metal-ligand complex of any one of claims 1 to 9, wherein R 13 and R 14 is -OR C wherein R C is (Ci-C8)alkyl.

13. The metal-ligand complex of any one of claims 1 to 9, wherein R 14 is selected from the group consisting of (Ci-C 10 )alkyl, cyclic (Ci-C 10 )heteroalkyl, -OR C , -NR N 2, wherein R C and R N are (Ci-C8)alkyl.

14. The metal-ligand complex of any one of the preceding claims, wherein R 13 is covalently linked to form an aromatic ring, the metal-ligand having a structure according to Formula (IV): 14 ​ ​

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