Transition metal catalysts for olefin polymerization

Abstract

A process for polymerizing olefin monomers using a catalyst system and the catalyst system comprises a procatalyst having a structure according to formula (I). [Formula 1] JPEG2023500591000059.jpg101170

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 928,098, filed October 30, 2019, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more specifically to the synthesis of heterocyclic ligands, such as five-membered nitrogen-containing heterocycles like pyrrole or indole, that can be complexed with Group IV transition metals to form catalysts for olefin polymerization. [Background technology]

[0003] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, are produced by various catalyst systems. The selection of such catalyst system used in the polymerization process of an olefin-based polymer is an important factor that contributes to the characteristics and properties of such an olefin-based polymer.

[0004] Ethylene- and propylene-based polymers are produced for a wide variety of products. Polyethylene and polypropylene polymerization processes can be varied in several ways to produce a wide variety of resulting polyethylene resins with 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 (e.g., solvent), such as an alkane or isoalkane, e.g., isobutane. Hydrogen may also be added to the reactor. Catalyst systems for producing ethylene-based polymers typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (metallocene or nonmetallocene) catalyst systems. The diluent and the reactants in the catalyst system are circulated in the reactor at elevated polymerization temperatures, thereby producing an ethylene-based homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture, including the polyethylene product dissolved in the diluent, is removed from the reactor along with unreacted ethylene and one or more optional comonomers. Upon removal from the reactor, the reaction mixture may be treated to remove the polyethylene product from the diluent and unreacted reactants, which are typically recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, where a second polyethylene fraction may be produced. Despite research efforts to develop catalyst systems suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, there remains a need for improved catalyst system efficiency capable of producing polymers with high molecular weights and narrow molecular weight distributions. Summary of the Invention

[0005] Embodiments of the present disclosure include catalyst systems comprising metal-ligand complexes according to formula (I). [ka]

[0006] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4. Each X is independently an unsaturated (C2-C 50 ) Hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C6-C 50 ) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C where the subscript n is 1, 2, or 3, and the subscript m is 1 or 2. The metal-ligand complex has six or fewer metal-ligand bonds.

[0007] In formula (I), each T is nitrogen or CR 4 and each R 4 are independently (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, halogen, or —H. 1 are independently aliphatic (C1-C 50 ) Hydrocarbyl, Aliphatic (C1-C 50 ) selected from the group consisting of heterohydrocarbyl, -halogen, and -H, and when m is 2, two R 1 are optionally covalently bonded to each R 2 are independently (C1-C 50 ) hydrocarbyl, (C1-C 50) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, Si(R C )3, and Ge(R C )3 is selected from R 1 and R 2 are optionally covalently linked to form a ring structure.

[0008] In formula (I), each R 3 and each R 5 are independently (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)-, 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, or -H. 6 are independently (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)-, R C S(O)2-, (R C )2C=N-, R CC(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, or halogen; R 5 and R 6 are optionally covalently linked to form a ring structure, and each R in formula (I) C and R N are independently (C1-C 50 ) hydrocarbyl. DETAILED DESCRIPTION OF THE INVENTION

[0009] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as being limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present subject matter to those skilled in the art.

[0010] Common abbreviations are listed below.

[0011] R C , R Z , R 1 , R 2 , R 3 , R 4, Z1, Z2, Z3, X, Y, Q, and W: 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), THF: tetrahydrofuran, Et2O: diethyl ether, CH2Cl2: dichloromethane, EtOAc: ethyl acetate, C6D6: deuterated benzene or benzene-d6, CDCl3: deuterated chloroform, Na2SO4: sodium sulfate hm, MgSO4: magnesium sulfate, HCl: hydrogen chloride, n-BuLi: butyllithium, t-BuLi: tert-butyllithium, K2CO3: potassium carbonate, N2: nitrogen gas, PhMe: toluene, PPR: parallel pressure reactor, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: mole, min or mins: minute, h or hrs: hour, d: day, R f : Retained fraction, TLC: Thin layer chromatography, rpm: Revolutions per minute.

[0012] The term "independently selected" followed by multiple options is 1 , R 2 , R 3 , R 4 , and R C etc. are used herein to indicate that the individual groups that appear before the term may be the same or different and that there is no dependency on the identity of any other groups that appear before the term.

[0013] The term "procatalyst" refers to a compound that has catalytic activity after being activated.

[0014] When used to describe a chemical group containing a specific carbon atom, "(C x -C yA parenthetical expression having the form "(C1-C2)" means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, (C1-C2) 50 ) Alkyl, in its unsubstituted form, is an alkyl group having 1 to 50 carbon atoms. In some embodiments and general structures, certain chemical groups are R S and R S generally represents any substituent defined herein. x -C y )" for the chemical group R S Substituted versions may be formed by adding any group R S may contain more than y carbon atoms depending on the identity of S Exactly one group R is phenyl (-C6H5) S (C1-C 50 A "(C ) alkyl" can contain from 7 to 56 carbon atoms. Thus, the parenthesized "(C ) alkyl" is generally used. x -C y )" is a group defined using one or more carbon atom-containing substituents R S If substituted by, the minimum and maximum total number of carbon atoms in the chemical group are both x and y, respectively, and all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0015] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom or functional group of the corresponding unsubstituted compound is replaced by a substituent (e.g., R S The prefix "per" has its ordinary meaning of "completely" or "totally," for example, the term "persubstituted" or "persubstituted" means that all hydrogen atoms (H) bonded to carbon or hetero atoms of the corresponding unsubstituted compound or functional group have been replaced by a substituent (e.g., R S), and similarly, in the case of "perfluorinated alkyl," all of the hydrogens in the alkyl group are replaced by fluorine atoms. The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to carbon or heteroatoms in the corresponding unsubstituted compound or functional group are replaced by substituents. 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 otherwise specified.

[0016] "(C1-C 50 The term "(C-C)hydrocarbyl" means a hydrocarbon radical having 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a 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 or branched chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and contains one or more R S is or is not replaced by

[0017] In the present disclosure, (C1-C 50 ) hydrocarbyl is unsubstituted or substituted (C-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).

[0018] "(C1-C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an unsubstituted or alkyl group containing one or more R Sand saturated straight-chain or branched hydrocarbon radicals of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively, which are substituted by unsubstituted (C1-C 50 Examples of alkyl are unsubstituted (C-C 20 ) alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 2,2-dimethylpropyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" means that there are up to 45 carbon atoms in the radical, including the substituents, e.g., one R that is (C-C) alkyl. S is replaced by (C 27 -C 40 Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, 2,2-dimethylpropyl, or 1,1-dimethylethyl.

[0019] "(C6-C 50 The term "aryl" refers to an unsubstituted or substituted (one or more R) aryl group in which at least 6 to 14 of the 6 to 40 carbon atoms are aromatic ring carbon atoms. S(according to the formula: monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical). A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may independently be fused or non-fused, aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl include unsubstituted (C-C 20 )Aryl, unsubstituted (C6-C 18 )aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrenyl. 40 Examples of aryl include substituted (C-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, 3,5-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-one-l-yl.

[0020] "(C3-C 50 The term "cycloalkyl" refers to a group that is unsubstituted or has one or more R S means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms, substituted by other cycloalkyl groups, such as (C x -C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S unsubstituted (C3-C 40 Examples of cycloalkyl are unsubstituted (C-C 20 ) cycloalkyl, unsubstituted (C3-C 10) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C-C 20 ) cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0021] (C1-C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C-C 50 ) arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). Diradicals can be on the same carbon atom (e.g., —CH—) or adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include 1,2-diradicals. α,ω-diradicals are diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH-), and 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (C-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0022] "(C1-C 50 The term "alkylene" refers to a group that is unsubstituted or has one or more R Smeans a saturated straight or branched chain diradical of 1 to 50 carbon atoms (i.e., the radical is not on a ring atom) substituted by 50 Examples of alkylene are unsubstituted (C-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*" represents a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 50 Examples of alkylenes are substituted (C-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted 1,20-eicosylene). As mentioned above, the two R S together (C1-C 18 ) alkylene, so that substituted (C1-C 50 Examples of )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.

[0023] "(C3-C 50 The term "cycloalkylene" refers to a group that is unsubstituted or has one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms substituted by

[0024] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include -O-, -S-, -S(O)-, -S(O)2-, -Si(R C )2-, -P(R P )-, -P(R P )2, -N(R N )-, -N(R N)2-N=C(R C )2, -N=C(NR2 N )(R C ) 、 -Ge(R C )2-, or -Si(R C )3 are listed, and each R C and each R P is unsubstituted (C1-C 18 ) hydrocarbyl or —H, and each R N is unsubstituted (C1-C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 50 The term "(C-C)heterohydrocarbyl" means a heterohydrocarbon radical of 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" means a heterohydrocarbon diradical of 1 to 50 carbon atoms. (C-C 50 ) heterohydrocarbyl or (C-C 50 The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The heterohydrocarbyl radical may be present on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be present on a single carbon atom or a single heteroatom. In addition, one of the two radicals of the diradical may be present on a carbon atom and the other radical on a different carbon atom, or one of the two radicals may be present on a carbon atom and the other radical on a heteroatom, or one of the two radicals may be present on a heteroatom and the other radical on a different heteroatom. Each (C-C 50 ) heterohydrocarbyl and (C-C 50 ) heterohydrocarbylene is unsubstituted or substituted (one or more R S The aromatic ring may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0025] (C1-C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. (C-C 50 Non-limiting examples of heterohydrocarbyls include (C-C 50 ) heteroalkyl, (C1-C 50 ) hydrocarbyl-O—, (C1-C 50 ) hydrocarbyl-S-, (C1-C 50 ) hydrocarbyl-S(O)-, (C-C 50 ) hydrocarbyl-S(O)2-, (C1-C 50 ) Hydrocarbyl-Si(R C )2-, (C l -C 50 )hydrocarbyl-N(R N )-, (C l -C 50 ) hydrocarbyl-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. Additional examples include -Si(R C ) 3-Q (OR C ) Q , -Osi(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C )2, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=P(R C )3, -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , and -C(O)N(R C ) 2, but are not limited to these.

[0026] "(C4-C 50 The term "heteroaryl" refers to unsubstituted or substituted (one or more R) heteroaryls of a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms. S (C) means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical. A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has 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 ring or rings of the heteroaromatic radical may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., generally (C) x -C y ) heteroaryl, (C4-C 12 ) heteroaryl, etc.) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or has one or more R SThe monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as when substituted by . The monocyclic heteroaromatic hydrocarbon radical is a 5- or 6-membered ring. A 5-membered ring 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 heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-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 has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and the heteroatoms can be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, pyrazin-2-yl, and 1,3,5-triazin-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be fused 5,6,5-, 5,6,6-, 6,5,6-, 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 6,6,6-ring system is acridine-9-yl.

[0027] "(C1-C 50The term "(C1-C2)heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms, or fewer, and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene 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, S.R. C , S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or contains one or more R S has been replaced by

[0028] Unsubstituted (C2-C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 )heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0029] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom: fluoride (F - ), chloride (Cl - ), bromide (Br -), or iodide (I - ).

[0030] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, and carbon-silicon double bonds. A saturated chemical group may be bound to one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be substituted by a substituent R S The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, or carbon-silicon double bonds, and the substituent R S , or may be absent, but does not include double bonds which may be present in (hetero)aromatic rings.

[0031] In one or more embodiments, the catalyst system comprises a metal-ligand complex according to formula (I). [ka]

[0032] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4. Each X is independently an unsaturated (C2-C 50 ) Hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C6-C 50 ) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR Cwhere the subscript n is 1, 2, or 3, and the subscript m is 1 or 2. The metal-ligand complex has six or fewer metal-ligand bonds.

[0033] In formula (I), each T is nitrogen or CR 4 and each R 4 are independently (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, halogen, or —H. 1 are independently aliphatic (C1-C 50 ) Hydrocarbyl, Aliphatic (C1-C 50 ) selected from the group consisting of heterohydrocarbyl, -halogen, and -H, and when m is 2, two R 1 are optionally covalently bonded to each R 2 are independently (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, Si(R C )3, and Ge(R C )3 is selected from R 1 and R 2 are optionally covalently linked to form a ring structure.

[0034] In formula (I), each R 3 and each R 5 are independently (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C50 ) 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)-, 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, or -H. 6 are independently (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)-, 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 )NC(O)-, or halogen; R 5 and R 6 are optionally covalently linked to form a ring structure, and each R in formula (I) C and R N are independently (C1-C 50 ) hydrocarbyl.

[0035] In some embodiments, M is zirconium or hafnium and each X is independently (C-C 20 ) aryl, (C4-C 20) heteroaryl, (C4-C 12 ) a diene, or a halogen, and each R 6 are independent, (C1-C 50 ) aryl, (C4-C 50 ) heteroaryl.

[0036] In one or more embodiments, each R 6 is phenyl or substituted phenyl. In various embodiments, each R 6 is a substituted phenyl selected from 2,4,6-trimethylphenyl, 2,6-di(isopropyl)phenyl, 3,5-di-tert-butylphenyl, or 3,5-diphenylphenyl. 6 is anthracenyl, disubstituted anthracenyl, or trisubstituted anthracenyl.

[0037] In some embodiments, R 5 and R 6 are covalently linked to form a six-membered aromatic ring. 5 and R 6 are covalently bonded to form a six-membered aromatic ring, and R 3 is -H and R 2 is methyl.

[0038] In one or more embodiments, the subscript m in formula (I) is 2 and the metal-ligand complex has a structure according to formula (II). [ka]

[0039] In formula (II), M, T, R 1 , R 2 , R 3 , R 4 , R 5 , R 6and X are as defined in formula (I), n is 1 or 2, and the dotted line indicates an optional covalent bond. All compounds according to formula (II) are also compounds according to formula (I). Thus, unless otherwise specified, general references herein to metal-ligand complexes having formula (I) should be understood to include, but not necessarily be limited to, all metal-ligand complexes having formula (II).

[0040] In some embodiments of the catalyst system that is a metal-ligand complex of formula (II), M is zirconium or hafnium and each X is independently (C-C 50 ) aryl, (C6-C 50 ) heteroaryl, (C4-C 12 ) a diene, or a halogen, and each R 1 and R 2 are independently (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, or halogen.

[0041] In some embodiments of the catalyst system that is a metal-ligand complex of formula (II), both R 1 are covalently bonded, and each R 2 are independently (C1-C 10 In one or more embodiments of the catalyst system that is a metal-ligand complex of formula (II), both R 1 -CH2CH2-, -CH2CH2CH 2- , or -CH2CH2CH2CH 2- is covalently attached as an alkylene selected from

[0042] In some embodiments of the catalyst system, m is 2 and the metal-ligand complex has a structure according to formula (III). [ka]

[0043] In formula (III), M, T, R 3 , R 4 , R 5 , R 6 and X are as defined in formula (I), the subscript n is 1 or 2, and each dotted line represents an optional covalent bond. All compounds according to formula (III) are also compounds according to formula (I). Thus, unless otherwise specified, a general reference herein to a metal-ligand complex having formula (I) should be understood to include, but not necessarily be limited to, all metal-ligand complexes having formula (III).

[0044] In one or more embodiments of the catalyst system, in formula (III), each R 6 is independently selected from di-[(C1-C4)alkyl]phenyl or tri-[(C1-C4)alkyl]phenyl.

[0045] In some embodiments of the catalyst system, in formula (III), each R 6 is independently carbazolyl, 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, or 3,5-di-iso-propylphenyl.

[0046] In some embodiments of the catalyst system, in formulas (I), (II), and (III), T is N. In other embodiments, T is CR 4 and R 4 are independently (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, halogen, or —H. In some embodiments, each R4 is hydrogen, and in other embodiments, R 4 (C1-C 20 ) alkyl.

[0047] One or more embodiments of the present disclosure include a polymerization process for producing an ethylene-based polymer, the polymerization process comprising polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system according to the present disclosure and at least one activator to form a polymer.

[0048] In exemplary embodiments, the catalyst system can include a metal-ligand complex according to any of formulas (I), (II), or (III) having the structure of any of procatalysts 1-7. [ka]

[0049] In exemplary embodiments, metal-ligand complexes according to any of formulas (I), (II), or (III) having the structure of any of procatalysts 1-7 can be formed from ligands 1-12. [ka]

[0050] promoter component Catalyst systems containing metal-ligand complexes of formula (I) can be catalytically activated by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, procatalysts based on metal-ligand complexes of formula (I) can be made catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Furthermore, metal-ligand complexes based on formula (I) include both neutral procatalyst forms and positively charged catalyst forms that can be positively charged by the loss of a monoanionic ligand such as benzyl or phenyl. Activating cocatalysts suitable for use in the present invention include alkylaluminums, polymeric or oligomeric alumoxanes (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 aforementioned activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0051] The Lewis acid activating cocatalyst may be any of the compounds described herein (C1-C 20 In some embodiments, the Group 13 metal compound includes a tri((C-C) hydrocarbyl substituent. 20 )hydrocarbyl)-substituted aluminum or tri((C-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C-C 20 )hydrocarbyl)-boron compounds, tri((C-C 10 ) alkyl) aluminum, tri((C6-C 18)aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C-C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borates (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to a ((C-C 20 ) Hydrocarbyl) 4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + means a nitrogen cation, each (C1-C 20 When two or more hydrocarbyls are present, they may be the same or different.

[0052] The combination of neutral Lewis acid activating cocatalysts is tri((C1-C4) alkyl)aluminum and tri((C6-C 18 )aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments include mixtures containing such neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The ratio of the number of moles of (metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane)] is 1:1:1 to 1:10:5000, and in other embodiments, 1:1:1.5 to 1:5:10.

[0053] A catalyst system comprising the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining it with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, ammonium tetrakis(pentafluorophenyl)borate(1-), and combinations thereof.

[0054] In some embodiments, two or more of the aforementioned activating cocatalysts may be used in combination with one another. A specific example of a cocatalyst combination is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of the one or more metal-ligand complexes of Formula (I) to the total number of moles of the one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000, in other embodiments at least 1:1000, and 10:1 or less, and in still other embodiments, 1:1 or less. When alumoxane is used alone as the activating cocatalyst, preferably the number of moles of alumoxane used is at least 100 times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of the one or more metal-ligand complexes of Formula (I) is from 0.5:1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of the one or more metal-ligand complexes of Formula (I).

[0055] Polyolefin Catalyst systems according to embodiments are utilized in the polymerization of olefins, primarily ethylene and propylene. In some embodiments, only a single type of olefin, or α-olefin, is present in the polymerization scheme, producing a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomer typically has 20 or fewer carbon atoms. For example, the α-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0056] An ethylene-based polymer, e.g., a homopolymer and / or interpolymer (including copolymer) of ethylene, and optional one or more comonomers, such as an α-olefin, can include at least 50 weight percent ethylene-derived monomer units. All individual values ​​and subranges encompassed by "from at least 50 weight percent" are disclosed herein as separate embodiments; for example, an ethylene-based polymer, a homopolymer and / or interpolymer (including copolymer) of ethylene, and optional one or more comonomers, such as an α-olefin, can include at least 60 weight percent ethylene-derived monomer units, at least 70 weight percent ethylene-derived monomer units, at least 80 weight percent ethylene-derived monomer units, from 50 to 100 weight percent ethylene-derived monomer units, or from 80 to 100 weight percent ethylene-derived monomer units.

[0057] In some embodiments, the ethylene-based polymer can comprise at least 90 mole percent monomeric units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer can comprise at least 93 mole percent units derived from ethylene, at least 96 mole percent units, at least 97 mole percent units derived from ethylene, or alternatively, 90 to 100 mole percent units derived from ethylene, 90 to 99.5 mole percent units derived from ethylene, or 97 to 99.5 mole percent units derived from ethylene.

[0058] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50%, other embodiments include at least 1 mole percent (mol %) to 25 mol %, and in further embodiments, the amount of additional α-olefin is at least 5 mol % to 100 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0059] Any conventional polymerization process may be used to produce the ethylene-based polymers, including, but not limited to, a solution polymerization process, a gas phase polymerization process, a slurry phase polymerization process, and any combination thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, and the like, in parallel, series, or any combination thereof.

[0060] In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and, optionally, one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be used in the first reactor or the second reactor. In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of a catalyst system described herein.

[0061] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system, for example a single loop reactor system, in which ethylene, and optionally one or more α-olefins, are polymerized as described in the previous paragraph in the presence of a catalyst system described within this disclosure and optionally one or more cocatalysts.

[0062] The ethylene-based polymer may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer may comprise any amount of additives. The ethylene-based polymer may comprise from about 0 to about 10 weight percent of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may comprise from about 0 to about 20 weight percent of a filler, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer may be further compounded with one or more polymers to form a blend.

[0063] In some embodiments, a polymerization process for producing an ethylene-based polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, where the catalyst system incorporates at least one metal-ligand complex of Formula (I), (II), or (III). Polymers obtained from such catalyst systems incorporating a metal-ligand complex of Formula (I), (II), or (III) can have a molecular weight of, for example, 0.850 g / cm or less according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.950g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm 3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density may be

[0064] In another embodiment, the polymers obtained from the catalyst system comprising a metal-ligand complex of any of formulas (I), (II), or (III) have a melt flow ratio (I) of 5 to 15.10 / I2), where the melt index I2 is measured at 190°C and a load of 2.16 kg in accordance with ASTM D1238 (which is incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 190°C and a load of 10 kg. In other embodiments, the melt flow ratio (I 10 / I2) is 5-10, and in another embodiment the melt flow ratio is 5-9.

[0065] In some embodiments, the polymer obtained from the catalyst system comprising a metal-ligand complex of any of Formulas (I), (II), and (III) has a molecular weight distribution (MWD) of 1 to 40, wherein the MWD is w / M n is defined as M w is the weight average molecular weight, and M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1 to 6. Another embodiment includes an MWD of 1 to 3, and another embodiment includes an MWD of 1.5 to 2.5.

[0066] Embodiments of the catalyst systems described in this disclosure result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0067] All solvents and reagents are obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether are purified by passage through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glovebox are further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware is dried overnight in an oven before use. NMR spectra are recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis is performed using a Waters e2695 separations module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a 5:95 to 100:0 gradient of acetonitrile and water (with 0.1% formic acid as the ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 H NMR data are reported as follows: chemical shifts (multiplicities (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integrals, and assignments). Using residual protons in deuterated solvents as reference standards, 1 Chemical shifts for 1 H NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, δ scale). 13 C NMR data is 1 Determined with 1 H decoupling, chemical shifts are reported as ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

[0068] General procedure for PPR screening experiments Polyolefin catalyst screening is performed in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consists of an array of 48 single-cell (6 × 8 matrix) reactors within an inert atmosphere glovebox. Each cell is equipped with a glass insert with an internal working liquid volume of approximately 5 mL. Each cell has independent pressure control, continuously stirring the liquid within the cell at 800 rpm. Catalyst solutions are prepared by dissolving the appropriate amount of procatalyst in toluene, unless otherwise noted. All liquids (e.g., solvent, 1-octene, scavenger solution appropriate for the experiment, and catalyst solution) are added to the single-cell reactor via robotic syringes. Gaseous reagents (i.e., ethylene, H2) are added to the single-cell reactor via a gas injection port. Before each run, the reactor is heated to 80 °C, purged with ethylene, and vented.

[0069] A portion of Isopar-E is added to the reactor. The reactor is heated to the run temperature and pressurized with ethylene to the appropriate psig. A toluene solution of the reagents is added in the following order: (1) 1-octene with 500 nmol of scavenger MMAO-3A, ​​(2) activator (Cocatalyst-1, Cocatalyst-2, etc.), and (3) catalyst.

[0070] A small amount of Isopar-E is added after each liquid addition, ensuring a total reaction volume of 5 mL after the final addition. Once the catalyst is added, the PPR software begins monitoring the pressure in each cell. The pressure (within approximately 2–6 psig) is maintained by adding additional ethylene gas by opening the valve at 1 psi below the setpoint and closing the valve when the pressure rises above 2 psi. All pressure drops are cumulatively recorded as ethylene "uptake" or "conversion" over the duration of the run or until the desired uptake or conversion value is reached, whichever occurs first. Each reaction is quenched by the addition of 10% carbon monoxide in argon for 4 minutes at a pressure 40–50 psi above the reactor pressure. A shorter "quench time" indicates a more active catalyst. To prevent excessive polymer formation in any given cell, the reaction is quenched when a predetermined uptake level (50 psig for the 120°C run, 75 psig for the 150°C run) is reached. After all reactions are quenched, the reactor is cooled to 70°C. The reactor is vented and purged with nitrogen for 5 minutes to remove carbon monoxide, and the tube is removed. The polymer sample is dried in a centrifugal evaporator at 70°C for 12 hours, weighed, and subjected to IR (1-octene incorporation) and GPC (molecular weight) analysis to determine the polymer yield.

[0071] SymRAD HT-GPC analysis Molecular weight data are determined by analysis on a hybrid Symyx / Dow-built robot-assisted dilution high-temperature gel permeation chromatography instrument (Sym-RAD-GPC). Polymer samples are dissolved at a concentration of 10 mg / mL in 1,2,4-trichlorobenzene (TCB) stabilized with 300 parts per million (ppm) butylated hydroxytoluene (BHT) by heating at 160 °C for 120 minutes. Each sample was diluted to 1 mg / mL immediately before injection of a 250 μL aliquot. The GPC is equipped with two Polymer Labs PLgel 10 μm mixed-B columns (300 × 10 mm) at a flow rate of 2.0 mL / min at 160 °C. Sample detection is performed using a PolyChar IR4 detector in concentration mode. Conventional calibration of narrow polystyrene (PS) standards is utilized in apparent units adjusted to homopolyethylene (PE) using the known Mark-Houwink coefficients for PS and PE in TCB at this temperature.

[0072] 1-Octene Incorporated IR Analysis Samples run for HT-GPC analysis precede IR analysis. For IR analysis, a 48-well HT silicon wafer is utilized for sample deposition and analysis of 1-octene incorporation. For analysis, the sample is heated to 160 °C for up to 210 minutes, then reheated to remove the magnetic GPC stir bar and shaken with a glass rod stir bar in a J-KEM Scientific heated robotic shaker. Samples are deposited with heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene is evaporated from the wafer deposition wells at 160 °C under a nitrogen purge. Analysis of 1-octene is performed on the HT silicon wafer using a NEXUS 670 ESP FT-IR.

[0073] Batch Reactor Polymerization Procedure Batch reactor polymerization reactions are carried out in a 2 L Parr™ batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is fitted with a dump valve that transfers the reactor contents to a stainless steel dump pot. The dump pot is pre-filled with a catalyst deactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). Both the pot and the tank are purged with nitrogen, and the dump pot is vented to a 30-gallon blowdown tank. All solvents used for polymerization or catalyst make-up are passed through a solvent purification column to remove any impurities that may affect the polymerization. 1-Octene and Isopar E are passed through two columns: the first containing A2 alumina and the second containing Q5. Ethylene is passed through two columns, the first containing A204 alumina and 4 Å molecular sieves, the second containing Q5 reactant, and N2, used for transport, is passed through a single column containing A204 alumina, 4 Å molecular sieves, and Q5.

[0074] The reactor is first charged from a shot tank, which may contain Isopar-E solvent and / or 1-octene, depending on the reactor load. The shot tank is filled to the load setpoint using a lab scale equipped with the shot tank. After the liquid feed is added, the reactor is heated to the polymerization temperature setpoint. If ethylene is used, it is added to the reactor at the reaction temperature to maintain the reaction pressure setpoint. The amount of ethylene added is monitored by a micromotion flowmeter. For some experiments, the standard conditions at 120°C are 46 g ethylene and 303 g 1-octene in 611 g Isopar-E, and the standard conditions at 150°C are 43 g ethylene and 303 g 1-octene in 547 g Isopar-E.

[0075] The procatalyst and activator were mixed with the appropriate amount of purified toluene to obtain a molar solution. The procatalyst and activator were processed in an inert glovebox, drawn into a syringe, and pressure-transferred into a catalyst shot tank. The syringe was rinsed three times with 5 mL of toluene. Immediately after the catalyst was added, a run timer was started. If ethylene was used, it was added by Camile to maintain the reaction pressure set point in the reactor. The polymerization reaction was run for 10 minutes, then the agitator was stopped, the bottom dump valve was opened, and the reactor contents were transferred to a dump pot. The dump pot contents were poured into a tray and placed in a lab hood, where the solvent was allowed to evaporate overnight. The tray containing the remaining polymer was transferred to a vacuum oven and heated to 140 °C under vacuum to remove any remaining solvent. After the tray cooled to ambient temperature, the polymer yield was measured to determine efficiency and the polymer was subjected to polymer testing. [Example]

[0076] Examples 1-40 are synthetic procedures for ligand intermediates, the ligands themselves, and isolated procatalysts. Procatalysts 1-7 were synthesized from Ligands 1-7. Examples 41-42 contain results from polymerization reactions in a batch reactor and a parallel pressure reactor. One or more features of the present disclosure are illustrated in light of the following examples.

[0077] Example 1: Synthesis of tert-butyl 2-phenyl-1H-pyrrole-1-carboxylate (3) [ka] A 250 mL round-bottom flask was charged with N-Boc-pyrrole 2-boronic acid (5.00 g, 23.7 mmol, 1.1 equiv) and XPhos palladacycle mesylate precatalyst (0.137 g, 0.162 mmol, 0.75 mol%). The vessel was sealed with a septum and subsequently evacuated and backfilled with nitrogen three times. Chlorobenzene (2.2 mL, 21.5 mmol, 1 equiv), THF (44 mL), and degassed 0.5 M KPO solution (86 mL, 43 mmol, 2 equiv) were added sequentially via syringe, and the reaction was stirred at room temperature for 3 h. The reaction was extracted with diethyl ether (2 × 50 mL). The combined organic layers were dried over MgSO, filtered, and concentrated in vacuo. The material was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 220 g silica gel, 1-3% EtOAc in hexanes) to give the product as a pale yellow oil (4.80 g, 92% yield).

[0078] 1 H NMR (400 MHz, chloroform-d) δ 7.40-7.27 (m, 6H), 6.25-6.22 (m, 1H), 6.21-6.18 (m, 1H), 1.35 (s, 9H). 13 C NMR (101 MHz, chloroform-d) δ 149.37, 135.00, 134.45, 129.18, 127.53, 127.12, 122.49, 114.34, 110.52, 83.49, 27.58.

[0079] Example 2: Synthesis of 2-phenyl-1H-pyrrole (4) [ka] In a nitrogen-filled glovebox, sodium methoxide (2.86 g, 53.0 mmol, 3 equiv.) was added to a solution of tert-butyl 2-phenyl-1H-pyrrole-1-carboxylate (3) (4.30 g, 17.7 mmol, 1 equiv.) in THF (50 mL). The solution immediately turned dark brown. The vessel was capped with a septum and removed from the glovebox. Anhydrous methanol (14 mL) was added via syringe, and the reaction was stirred at room temperature for 18 h. The solution was concentrated in vacuo to a volume of approximately 5 mL. Water (100 mL) was added, and the aqueous phase was extracted with diethyl ether (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo to give a brown solid. The solid was recrystallized from boiling hexane (approximately 130 mL) to give a light brown solid (1.93 g, 76% yield).

[0080] 1 H NMR (400 MHz, chloroform-d) δ 8.39 (br s, 1H), 7.48 (d, J = 8.2 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.22 (t, J = 7.8 Hz, 1H), 6.85 (s, 1H), 6.55 (s, 1H), 6.32 (d, J = 3.0 Hz, 1H). 13 C NMR (101 MHz, chloroform-d) δ 132.75, 132.10, 128.89, 126.20, 123.84, 118.87, 110.11, 105.95.

[0081] Example 3: Synthesis of N,N-dimethyl-1-(5-phenyl-1H-pyrrol-2-yl)methanamine - Ligand 1 [ka] To a reaction vial was added dimethylamine hydrochloride (1.07 g, 13.1 mmol, 1 equiv.), 37% formaldehyde solution (1.03 mL, 13.7 mmol, 1.05 equiv.), and isopropanol (8 mL). The vial was capped, and the reaction was stirred at room temperature for 30 minutes. The solution was then added via syringe to a vial containing 2-phenylpyrrole (4) (1.87 g, 3.50 mmol, 1 equiv.) under a nitrogen atmosphere. The reaction was stirred at 40° C. for 24 hours. 10% aqueous KOH solution (75 mL) was added, and the reaction was stirred for 2 hours. The aqueous phase was extracted with dichloromethane (3×50 mL). The combined organic phase was dried over MgSO4, filtered, and concentrated in vacuo to give the product as a pink solid (2.54 g, 97% yield).

[0082] 1 H NMR (500 MHz, chloroform-d) δ 9.04 (br s, 1H), 7.48-7.44 (m, 2H), 7.34 (t, J = 7.8 Hz, 2H), 7.19-7.15 (m, 1H), 6.43 (t, J = 3.1 Hz, 1H), 6.10 (t, J = 2.9 Hz, 1H), 3.47 (s, 2H), 2.27 (s, 6H). 13 C NMR (126 MHz, chloroform-d) δ 132.93, 132.00, 130.59, 128.74, 125.83, 123.65, 109.19, 105.46, 56.81, 45.23.

[0083] Example 4: Synthesis of tert-butyl 2-(3,5-di-tert-butylphenyl)-1H-pyrrole-1-carboxylate (7) [ka] A 250 round-bottom flask was charged with N-Boc-pyrrole-2-boronic acid (3.95 g, 18.7 mmol, 1.1 equiv.), 1-bromo-3,5-di-tert-butylbenzene (4.58 g, 17.0 mmol, 1 equiv.), and XPhos palladacycle mesylate precatalyst (288 mg, 0.340 mmol, 2 mol%). The vessel was sealed with a septum and subsequently evacuated and refilled with nitrogen three times. THF (34 mL) and degassed 0.5 M aqueous KPO solution (68 mL, 34.0 mmol, 2 equiv.) were added sequentially via syringe, and the reaction was stirred at room temperature for 8 h. The reaction was extracted with diethyl ether (2 × 60 mL). The combined organic layers were dried over MgSO, filtered, and concentrated in vacuo. Purification by ISCO (silica gel, 220 g, 0.5-1% EtOAc in hexanes) afforded the product as a white solid (4.95 g, 81% yield).

[0084] 1 H NMR (400 MHz, chloroform-d) δ 7.41-7.40 (m, 1H), 7.38-7.36 (m, 1H), 7.19-7.17 (m, 2H), 6.30-6.24 (m, 1H), 6.22-6.19 (m, 1H), 1.36 (s, 18H), 1.30 (s, 9H). 13 C NMR (101 MHz, chloroform-d) δ 149.70, 149.50, 135.95, 133.81, 123.52, 121.96, 121.34, 113.88, 110.38, 82.98, 34.82, 31.54, 27.48.

[0085] Example 5: Synthesis of 2-(3,5-di-tert-butylphenyl)-1H-pyrrole (8) [ka] In a nitrogen-filled glovebox, sodium methoxide (2.34 g, 43.3 mmol, 3 equiv.) was added to a solution of tert-butyl 2-(3,5-di-tert-butylphenyl)-1H-pyrrole-1-carboxylate (7) (5.13 g, 14.4 mmol, 1 equiv.) in THF (41 mL). The suspension was yellowish. The vessel was capped with a septum and removed from the glovebox. Anhydrous methanol (12 mL) was added via syringe, and the reaction was stirred at room temperature for 18 h. Upon addition of methanol, all solids dissolved, and the reaction turned pinkish in color. After approximately 5 min, the solution became cloudy due to the formation of a small amount of precipitate. The solution was concentrated in vacuo. Water (100 mL) was added, and the aqueous phase was extracted with diethyl ether (3 × 50 mL). The combined organic phase was dried over MgSO4, filtered, and concentrated in vacuo to give an off-white solid (3.65 g, 99% yield).

[0086] 1 H NMR (400 MHz, chloroform-d) δ 8.44 (br s, 1H), 7.33 (s, 3H), 6.89-6.84 (m, 1H), 6.54-6.48 (m, 1H), 6.32 (q, J = 2.9 Hz, 1H), 1.37 (s, 18H). 13 C NMR (101 MHz, chloroform-d) δ 151.23, 133.30, 132.20, 120.71, 118.74, 118.33, 109.88, 105.64, 34.90, 31.47.

[0087] Example 6: Synthesis of 1-(5-(3,5-di-tert-butylphenyl)-1H-pyrrol-2-yl)-N,N-dimethylmethanamine (9) [ka] To a reaction vial was added dimethylamine hydrochloride (1.28 g, 15.7 mmol, 1 equiv.), 37% formaldehyde solution (1.24 mL, 16.4 mmol, 1.05 equiv.), and isopropanol (7 mL). The vial was capped, and the reaction was stirred at room temperature for 30 minutes. The solution was then added via syringe to a vial containing 2-(3,5-di-tert-butylphenyl)-1H-pyrrole (8) (4.00 g, 13.3 mmol, 1 equiv.) under a nitrogen atmosphere. The formaldehyde vial was rinsed with additional isopropanol (1 mL), which was added to the pyrrole solution. The reaction was stirred at 40 °C for 72 hours. 10% aqueous KOH (100 mL) was added, and the reaction was stirred for 1 hour. The aqueous phase was extracted with dichloromethane (3 × 60 mL). The combined organic phase was dried over MgSO4, filtered, and concentrated in vacuo to give the product as a red oil (4.95 g, quantitative yield). The material resisted solidification and still contained some solvent, resulting in a slightly higher mass than the theoretical yield. Several cycles of drying in vacuo, dissolving in hexane, and drying in vacuo again were required to remove residual isopropanol.

[0088] 1 H NMR (400MHz, chloroform-d) δ9.08 (br s,1H),7.45(d,J=1.8Hz,2H),7.40(t,J=1.8Hz,1H),6.51(dd,J=3.4,2.6Hz ,1H),6.19(dd,J=3.4,2.4Hz,1H),3.56(s,2H),2.33(s,6H),1.47(s,18H). 13 C NMR (101 MHz, chloroform-d) δ 151.13, 133.48, 132.49, 129.95, 120.45, 118.62, 109.47, 105.39, 56.96, 45.20, 34.97, 31.62.

[0089] Example 7: Synthesis of 1-(5-(3,5-di-tert-butylphenyl)-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (10) [ka] In a nitrogen-filled glovebox, a 500 mL round-bottom flask was charged with 1-(5-(3,5-di-tert-butylphenyl)-1H-pyrrol-2-yl)-N,N-dimethylmethanamine (9) (4.89 g, 15.6 mmol, 1 equiv.) and dissolved in THF (85 mL). The flask was sealed with a septum and removed from the glovebox. A solution of methyl iodide (0.97 mL, 15.6 mmol, 1 equiv.) in THF (8 mL) was added dropwise to the stirring pyrrole solution. The mixture was stirred at room temperature for 2.5 h, at which time a fine white solid precipitated from the red solution. The suspension was filtered, but the precipitated solid was too fine to pass through the frit. Approximately 1 mL of the solution was concentrated in vacuo to give a purple solid. The solution was concentrated to one-third volume and stored in a −30° C. freezer for 3 days. Hexane (200 mL) was added, causing a purple solid to precipitate. The suspension was chilled in a -30 °C freezer for 1 day. The solid was filtered, washed with cold hexane (-30 °C), and dried in vacuo to give a purple solid (4.45 g, 63% yield). The initial APT spectrum looked promising, so the sample was added to the night queue. However, by the time the spectrum was acquired, the material appeared to have decomposed. The material is not stable in chloroform for long periods of time.

[0090] 1 H NMR (400 MHz, chloroform-d) δ 11.19 (s, 1H), 7.55 (s, 2H), 7.28 (s, 1H), 6.49-6.41 (m, 1H), 6.38-6.29 (m, 1H), 5.06 (s, 2H), 3.16 (s, 9H), 1.33 (s, 18H). 13 C NMR (101 MHz, chloroform-d) δ 151.42, 136.81, 130.71, 121.29, 119.25, 117.84, 115.54, 106.02, 62.09, 52.52, 35.05, 31.57.

[0091] Example 8: Synthesis of (2S,2'S)-1,1'-bis((5-(3,5-di-tert-butylphenyl)-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine(11)-ligand 8 [ka] A reaction vial was charged with 1-(5-(3,5-di-tert-butylphenyl)-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (10) (1.00 g, 2.20 mmol, 2 equiv.), (2S,2'S)-2,2'-bipyrrolidine (0.154 g, 1.10 mmol, 1 equiv.), and anhydrous K2CO3 (1.52 g, 11.0 mmol, 10 equiv.). The vial was capped and purged with nitrogen. Acetonitrile (9 mL) was added, and the reaction was stirred at 72 °C for 19 h. The suspension was poured into water (75 mL). The aqueous phase was extracted with dichloromethane (3 × 25 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto Celite and purified by reverse-phase flash column chromatography (ISCO, RediSepRf Gold C-18 reverse phase). The initial reverse-phase column eluent was water:MeCN (20:80 to 0:100 gradient), followed by THF:water (100:0 to 80:20 gradient), but this did not yield clean material. A second purification using MeCN:THF (100:0 to 0:100 gradient) allowed for more efficient separation. The product was obtained as a red oil (0.172 g, 23% yield).

[0092] 1 H NMR (400MHz, chloroform-d)δ 9.67(s,2H),7.26-7.20(m,6H),6.40-6.34(m,2H),6.08-6.03(m,2H),3.94(d,J=14.2Hz,2H),3.75(d,J=14.2Hz,2H),2.86(dt,J=11. 0,6.1Hz,2H),2.71-2.63(m,2H),2.51-2.38(m,2H),1.85(dt,J=14.8,7.1Hz,2H),1.76-1.58(m,4H),1.58-1.48(m,2H),1.26(s,36H). 13C NMR (101 MHz, chloroform-d) δ 151.00, 133.04, 132.65, 130.56, 120.21, 118.59, 108.40, 105.78, 66.43, 54.43, 52.43, 34.76, 31.37, 27.71, 23.29. 46 H 66 N4[M+H] + HRMS(ESI) calculated for: 675.5360, found: 675.5354.

[0093] Example 9: Synthesis of tert-butyl 2-mesityl-1H-pyrrole-1-carboxylate (12) [ka] A 250 mL round-bottom flask was charged with N-Boc-pyrrole 2-boronic acid (6.62 g, 31.4 mmol, 1.5 equiv.), anhydrous KPO (8.88 g, 41.8 mmol, 2 equiv.), Pd(OAc) (94 mg, 0.418 mmol, 2 mol%), and SPhos (0.343 g, 0.836 mmol, 4 mol%). The vessel was sealed with a septum and subsequently evacuated and refilled with nitrogen three times. 2-Bromomesitylene (3.2 mL, 20.9 mmol, 1 equiv.) and anhydrous 1-butanol (42 mL) were added via syringe, and the reaction was stirred at 100 °C for 5 h. The black slurry was cooled to room temperature and filtered through a short plug of silica gel, which was eluted with EtOAc (approximately 75 mL) to give a pale yellow solution. All volatiles were removed in vacuo. The remaining oil was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 330 g silica gel, 1-4% EtOAc in hexanes eluent) to give a mixture of a clear oil and a white solid material (4.96 g). 1 The H NMR spectrum showed the material to be 84% pure, possibly containing some N-Boc-pyrrole from protodeboronation. The actual yield of product is 4.42 g (74% yield).

[0094] 1H NMR (400MHz, chloroform-d)δ 7.38(dd,J=3.4,1.8Hz,1H),6.86(s,2H),6.26(t,J=3.3Hz,1H),5.98(dd,J=3.2,1.8Hz,1H),2.29(s,3H),2.01(s,6H),1.21(s,9H). 13 C NMR (101 MHz, chloroform-d) δ 149.38, 137.84, 137.14, 131.92, 131.83, 127.43, 120.81, 113.16, 110.65, 82.72, 27.37, 21.09, 20.18.

[0095] Example 10: Synthesis of 2-mesityl-1H-pyrrole (13) [ka] In a nitrogen-filled glovebox, sodium methoxide (2.51 g, 46.46 mmol, 3 equiv.) was added to a solution of tert-butyl 2-phenyl-1H-pyrrole-1-carboxylate (12) (4.42 g, 15.5 mmol, 1 equiv.) in THF (45 mL). The vessel was capped with a septum and removed from the glovebox. Anhydrous methanol (12 mL) was added via syringe, and the reaction was stirred at room temperature for 18 h. No significant color change was observed. The solution was concentrated in vacuo to give an off-white solid. Water (120 mL) was added, and the aqueous phase was extracted with diethyl ether (3 × 60 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo to give a white solid (2.55 g, 89% yield).

[0096] 1 H NMR (400 MHz, chloroform-d) δ 7.85 (br s, 1H), 6.94 (s, 2H), 6.87-6.82 (m, 1H), 6.31 (td, J = 3.1, 2.2 Hz, 1H), 6.06 (td, J = 2.6, 1.4 Hz, 1H), 2.33 (s, 3H), 2.13 (s, 6H). 13C NMR (101 MHz, chloroform-d) δ 138.55, 137.59, 130.68, 129.47, 128.06, 116.82, 108.44, 108.16, 21.06, 20.53.

[0097] Example 11: Synthesis of 1-(5-mesityl-1H-pyrrol-2-yl)-N,N-dimethylmethanamine - Ligand 2 [ka] To a reaction vial was added dimethylamine hydrochloride (1.0854 g, 13.3 mmol, 1 equiv.), 37% formaldehyde solution (1.05 mL, 14.0 mmol, 1.05 equiv.), and isopropanol (6 mL). The vial was capped, and the reaction was stirred at room temperature for 30 minutes. The solution was then added via syringe to a vial containing 2-mesityl-1H-pyrrole (13) (2.466 g, 13.3 mmol, 1 equiv.) under a nitrogen atmosphere. The formaldehyde vial was rinsed with additional isopropanol (1 mL), which was added to the pyrrole solution. The reaction was stirred at 40 °C for 96 hours. 10% aqueous KOH (75 mL) was added, and the reaction was stirred for 1 hour. The aqueous phase was extracted with dichloromethane (3 × 60 mL). The combined organic phase was dried over MgSO4, filtered and concentrated in vacuo to give the product as a red solid (3.36 g, 98% yield).

[0098] 1 H NMR (400MHz, chloroform-d) δ 9.15(br s,1H),6.88(d,J=0.9Hz,2H),6.06(t,J=2.9Hz,1H),5.89(t,J=2.9Hz,1H),3.41(s,2H),2.29(s,3H),2.10(s,6H),2.06(s,6H). 13 C NMR (101 MHz, chloroform-d) δ 138.29, 137.23, 131.22, 129.55, 128.11, 127.89, 107.94, 107.43, 56.77, 44.69, 21.06, 20.60.

[0099] Example 12: Synthesis of 1-(5-mesityl-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (14) [ka] In a nitrogen-filled glovebox, a 250 mL round-bottom flask was charged with 1-(5-mesityl-1H-pyrrol-2-yl)-N,N-dimethylmethanamine (2.91 g, 12.0 mmol, 1 equiv.) and dissolved in THF (140 mL). The flask was sealed with a septum and removed from the glovebox. A solution of methyl iodide (0.75 mL, 12.0 mmol, 1 equiv.) in THF (12 mL) was added dropwise to the stirring pyrrole solution. The mixture was stirred at room temperature for 2 h, at which time a large amount of white solid precipitated. The slurry was filtered, and the solid was washed with THF (3 × 20 mL) and dried in vacuo to give an off-white solid (3.586 g, 78% yield).

[0100] 1 H NMR(400MHz,DMSO-d6)δ 11.19(br s,1H),6.90(s,2H),6.43-6.38(m,1H),6.01-5.94(m,1H),4.42(s,2H),2.97(s,9H),2.23(s,3H),2.03(s,6H). 13 C NMR(101MHz,DMSO-d6)δ 137.73,137.41,132.46,130.49,128.29,118.16,114.56,109.15,62.48,51.91,51.87,51.83,21.12,20.78.

[0101] Example 13: Synthesis of (2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine-ligand 3 [ka] A reaction vial was charged with 1-(5-mesityl-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (14) (1.20 g, 3.12 mmol, 2 equiv.), (2S,2'S)-2,2'-bipyrrolidine (0.219 g, 1.56 mmol, 1 equiv.), and anhydrous K2CO3 (2.16 g, 15.6 mmol, 10 equiv.). The vial was capped and purged with nitrogen. Acetonitrile (12 mL) was added via syringe, and the reaction was stirred at 72 °C for 20 h. The suspension was poured into water (150 mL). The aqueous phase was extracted with dichloromethane (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto basic alumina and purified by flash column chromatography (ISCO, 160 g basic alumina, 15-35% EtOAc in hexanes) to give the product as a white powder (0.573 g, 69% yield).

[0102] 1 H NMR (400MHz, chloroform-d) δ9.58 (br s,2H),6.91(s,4H),6.01-5.98(m,2H),5.95-5.92(m,2H),3.93(d,J=14.2Hz,2H),3.50(d,J=14 .2Hz,2H),2.82-2.68(m,4H),2.32(s,6H),2.14(s,12H),2.13-2.07(m,2H),1.88-1.40(m,8H). 13 C NMR (101 MHz, chloroform-d) δ 138.18, 136.99, 131.27, 129.31, 128.34, 128.03, 108.15, 105.37, 65.73, 54.82, 52.46, 26.91, 23.71, 21.05, 20.84. 36 H 46 N4[M+H] + HRMS(ESI) calculated for: 535.3795, found: 535.3798.

[0103] Example 14: N 1 ,N 2 -bis((5-mesityl-1H-pyrrol-2-yl)methyl)-N 1 ,N 2Synthesis of -dimethylethane-1,2-diamine-ligand 9 [ka] A 50 mL round-bottom flask was charged with 1-(5-mesityl-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (14) (2.0 g, 5.20 mmol, 2 equiv.) and anhydrous K2CO3 (3.60 g, 26.0 mmol, 10 equiv.). The vial was capped and purged with nitrogen. DMEDA (0.28 mL, 2.60 mmol, 1 equiv.) and acetonitrile (20 mL) were added via syringe, and the reaction was stirred at 72 °C for 20 h. The suspension was poured into water (150 mL). The aqueous phase was extracted with dichloromethane (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto basic alumina and purified by flash column chromatography (ISCO, 160 g basic alumina, 30-70% EtOAc in hexanes) to give the product as a white solid (0.494 g, 39% yield).

[0104] 1 H NMR (400MHz, chloroform-d) δ9.01 (br s,2H),6.88(s,4H),6.01(t,J=2.9Hz,2H),5.92(t,J=2.9Hz,2H),3.54(s,4H),2.48(s,4H),2.29(s,6H),2.10(s,12H),2.07(s,6H). 13 C NMR (101 MHz, chloroform-d) δ 1138.08, 137.08, 131.02, 128.82, 128.28, 128.02, 108.11, 106.65, 55.07, 54.32, 42.65, 21.04, 20.71. 32 H 42 N4[M+H] + HRMS(ESI) calculated for: 483.3482, found: 483.3486.

[0105] Example 15: Synthesis of 2-(anthracen-9-yl)-1H-pyrrole (17) [ka] A 250 mL round-bottom flask was charged with 9-bromoanthracene (12.85 g, 50.0 mmol, 1 equiv.), N-Boc-pyrrole 2-boronic acid (15.2 g, 75.0 mmol, 1.5 equiv.), anhydrous KPO (21.2 g, 99.9 mmol, 2 equiv.), Pd(OAc) (224 mg, 0.999 mmol, 2 mol%), and SPhos (0.821 g, 1.99 mmol, 4 mol%). The vessel was sealed with a septum and subsequently evacuated and refilled with nitrogen three times. Anhydrous 1-butanol (100 mL) was added via cannula, and the reaction was stirred at 100 °C for 4.5 h. The suspension was allowed to cool to room temperature for 16 h. The green slurry was cooled and filtered through a short plug of silica gel, which was eluted with EtOAc (3 × 50 mL) to give a dark green solution. All volatiles were removed in vacuo. The remaining oil was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 330 g silica gel, 1-3.8% EtOAc in hexanes eluent) to yield two large initial peaks. The first peak contained a mixture of a clear oil and a yellow solid (11.53 g). This material was determined to be a mixture of 9-bromoanthracene, N-Boc-pyrrole (via protodeboronation), and tert-butyl 2-(anthracen-9-yl)-1H-pyrrole-1-carboxylate (13). The second peak was a bright yellow solid corresponding to 2-(anthracen-9-yl)-1H-pyrrole (14) (4.73 g).

[0106] In a nitrogen-filled glovebox, sodium methoxide (6.00 g, 111 mmol) was added to a solution of a mixture containing 9-bromoanthracene, N-Boc-pyrrole (via protodeboronation), and tert-butyl 2-(anthracen-9-yl)-1H-pyrrole-1-carboxylate (16) (11.53 g) in THF (105 mL). The solution immediately turned red. The vessel was capped with a septum and removed from the glovebox. Anhydrous methanol (30 mL) was added via syringe, and the reaction immediately turned amber. The solution was stirred at room temperature for 18 hours to give a green solution. The solution was concentrated in vacuo to give a bright yellow solid. Water (150 mL) was added, and the aqueous phase was extracted with diethyl ether (3 × 75 mL), giving a dark black organic phase and a brown organic phase. The combined organic phases were dried over MgSO4, changing the color to tan. The suspension was filtered and concentrated in vacuo to give a yellow solid (6.34 g). NMR indicated the material was a mixture of 9-bromoanthracene and the desired product. The material was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 330 g silica gel, 0.1-6% EtOAc in hexanes) to give the product as a bright yellow solid (2.89 g).

[0107] Total yield of 2-anthracen-9-yl-1H-pyrrole (17) over two steps: 7.62 g, 63% yield. 1 H NMR (400MHz, chloroform-d) δ 8.44(s,1H),8.17(br s,1H),8.01(d,J=8.4Hz,2H),7.93(d,J=8.7Hz,2H),7.47(ddd,J=8.3,6.5,1.3Hz,2H),7.4 1(ddd,J=8.1,6.5,1.4Hz,2H),7.05-6.96(m,1H),6.54(q,J=3.0Hz,1H),6.52-6.50(m,1H). 13 C NMR (101 MHz, chloroform-d) δ 131.75, 131.34, 128.58, 128.36, 127.36, 127.24, 126.70, 125.78, 125.24, 118.09, 111.36, 108.98.

[0108] Example 16: Synthesis of 1-(5-(anthracen-9-yl)-1H-pyrrol-2-yl)-N,N-dimethylmethanamine (18) [ka] Dimethylamine hydrochloride (2.46 g, 30.2 mmol, 1 equiv.) was added to the reaction vial. The vessel was sealed with a screw-top septum, and the vessel was evacuated and backfilled with nitrogen three times. 37% formaldehyde solution (2.38 mL, 31.7 mmol, 1.05 equiv.) and isopropanol (16 mL) were added via syringe, and the solution was stirred at room temperature for 30 minutes. The solution was then added via syringe to a 100 mL round-bottom flask containing 2-(anthracen-9-yl)-1H-pyrrole (17) (7.34 g, 30.2 mmol, 1 equiv.) under a nitrogen atmosphere. The formaldehyde vial was rinsed with additional isopropanol (3 mL), which was added to the pyrrole solution. The reaction was stirred at 40 °C for 10 minutes, but a large amount of solid material was still present. An additional amount of isopropanol (20 mL) was added and the yellow suspension was stirred at 45 °C for 5 days. A large amount of yellow solid still remained. 10% aqueous KOH (200 mL) was added and the reaction was stirred for 2 hours. The aqueous phase was extracted with dichloromethane (3 x 75 mL). The combined organic phases were dried over MgSO4 and filtered to give a bright yellow solution. The solution was concentrated in vacuo to give the product as a yellow solid (8.77 g, 97% yield). The material still contained a small amount of isopropanol, even though it was concentrated and washed multiple times with hexane and dried in vacuo overnight.

[0109] 1 H NMR (400MHz, chloroform-d)δ 9.46(s,1H),8.46(s,1H),8.04-7.94(m,4H),7.43(dddd,J=19.3,8.0,6.5,1.3 Hz,4H),6.34(t,J=2.9Hz,1H),6.24(t,J=3.0Hz,1H),3.46(s,2H),2.01(s,6H). 13C NMR (101MHz, Chloroform-d) δ 131.78,131.35,129.52,129.31,128.25,127.05,127.03,126.86,125.58,125.16,110.95,108.33,56.75,44.80.

[0110] Example 17: Synthesis of 1-(5-(anthracen-9-yl)-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (19) [ka] In a nitrogen-filled glovebox, a 500 mL round-bottom flask was charged with 1-(5-(anthracen-9-yl)-1H-pyrrol-2-yl)-N,N-dimethylmethanamine (18) (8.41 g, 28.0 mmol, 1 equiv.) and dissolved in THF (250 mL). The vessel was sealed with a septum and removed from the glovebox. A solution of methyl iodide (1.74, 28.0 mmol, 1 equiv.) in THF (15 mL) was added via cannula to the stirring pyrrole solution. The mixture was stirred at room temperature for 3 h, at which time a large amount of yellow solid precipitated. The slurry was filtered, and the solid was washed with THF (3 × 20 mL) and dried in vacuo to give the solid as a yellow powder (4777-A, 11.6 g, 94% yield).

[0111] 1 H NMR(400MHz,DMSO-d6)δ 11.79(s,1H),8.69(s,1H),8.15-8.09(m,2H),7.81-7.76(m,2H),7.54-7.43( m,4H),6.67(t,J=2.9Hz,1H),6.41(t,J=2.9Hz,1H),4.58(s,2H),3.09(s,9H). 13 C NMR(101MHz,DMSO-d6)δ 131.45,131.28,130.06,128.81,128.30,128.30,127.83,126.66,126.59,125.88,119.66,115.01,112.15,62.40,52.15,52.11,52.07.

[0112] Example 18: Synthesis of (2S,2'S)-1,1'-bis((5-(anthracen-9-yl)-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine-ligand 10 [ka] A 50 mL round-bottom flask was charged with (2S,2'S)-2,2'-bipyrrolidine (0.317 g, 2.26 mmol, 1 equiv.), 1-(5-(anthracen-9-yl)-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (19) (2.00 g, 4.52 mmol, 2 equiv.), and anhydrous K2CO3 (3.12 g, 21.1 mmol, 10 equiv.). The vial was capped and purged with nitrogen. Acetonitrile (20 mL) was added via syringe, and the reaction was stirred at 72 °C for 19 h. The suspension was poured into water (150 mL). The aqueous phase was extracted with dichloromethane (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto basic alumina and purified by flash column chromatography (ISCO, 160 g basic alumina, 20-50% EtOAc in hexanes) to give the product as a bright yellow solid (1.08 g, 74% yield).

[0113] 1 H NMR (400MHz, chloroform-d) δ11.30(s,2H),8.43(s,2H),8.24(dd,J=8.8,1.2Hz,4H), 8.03-7.97(m,4H),7.43(ddd,J=8.3,6.5,1.2Hz,4H),7.31(ddd,J=8.9,6.5,1.3Hz ,4H),6.43(dd,J=3.2,2.5Hz,2H),6.06(t,J=2.8Hz,2H),3.74(d,J=14.6Hz,2H), 3.00(d,J=14.6Hz,2H),2.80-2.72(m,2H),2.41-2.27(m,2H),1.78-1.14(m,10H). 13C NMR (101 MHz, chloroform-d) δ 131.42, 131.29, 130.91, 129.72, 128.19, 127.08, 126.45, 125.80, 125.36, 125.14, 111.65, 105.34, 66.32, 54.31, 52.76, 27.18, 23.66. C 46 H 42 N4[M+H] + HRMS(ESI) calculated for: 651.3482, found: 651.3481.

[0114] Example 19: Synthesis of sodium pyrrol-1-ide [ka] In a nitrogen-filled glovebox, pyrrole (1.9 mL, 27.4 mmol, 1 equiv.) and THF (50 mL) were added to a 200 mL reaction jar. Sodium hydride (1.31 g, 54.8 mmol, 2 equiv.) was added slowly, allowing hydrogen gas to evolve. The reaction was stirred at room temperature for 30 minutes, after which gas evolution had ceased. The suspension was filtered, the solid washed with THF (2 × 5 mL), and the solution concentrated in vacuo to give a white solid containing some thick oil. The material was triturated with hexane (30 mL) and dried under vacuum at 60 °C to give a white powder (2.35 g, 96% yield).

[0115] 1 H NMR (400MHz, THF-d8) δ 6.77 (s, 2H), 6.03 (s, 2H). 13 C NMR(101MHz,THF-d8)δ 128.48,106.81.

[0116] Example 20: Synthesis of 2-(2,6-diisopropylphenyl)-1H-pyrrole (21) [ka] In a nitrogen-filled glovebox, a 200 mL round-bottom flask was charged with sodium pyrrole-1-ide (13.0 g, 146 mmol, 4 equiv.) and THF (36 mL). The flask was attached to an aluminum heating block to act as a heat sink. Anhydrous ZnCl2 (19.9 g, 146 mmol, 4 equiv.) was slowly added. However, even with the slow addition, the THF suddenly began to reflux, so an air-cooled coil reflux condenser was attached. The slurry was stirred at room temperature for 15 min. Subsequently, the reflux condenser was removed, and CyJohnPhos (0.511 g, 1.46 mmol, 4 mol%), Pd2dba3 (0.667 mg, 0.7283 mmol, 2 mol%), and 1-bromo-2,6-diisopropylbenzene (7.5 mL, 36.4 mmol, 1 equiv.) were added sequentially. The reflux condenser was reattached and the black solution was stirred at 100°C for 42 hours. The reaction was then cooled to room temperature, capped, and transferred to a fume hood. Water (10 mL) was added to quench the remaining pyrrol-1-idenatrium, and all volatiles were removed in vacuo. The black material was dissolved in water (200 mL) and ether (150 mL). A thick emulsion formed that did not separate. A large amount of black, slimy solid, presumably zinc salts, was present. The water / ether emulsion was filtered through a short pad of Celite. During the filtration, it was necessary to continuously scrape the top of the Celite to allow the liquid to pass through. The remaining solid filter cake was washed with additional ether (4 x 50 mL). This resulted in sufficient separation of the clear yellow aqueous and black organic phases to allow extraction. The aqueous phase was washed with additional ether (3 x 50 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 330 g silica gel, 1-3.5% EtOAc in hexanes) to give the product as a yellow solid (6.18 g, 75% yield).

[0117] 1H NMR (400MHz, chloroform-d) δ7.91(s,1H),7.37(t,J=7.7Hz,1H),7.20(d,J=7.7Hz,2H),6.85(dt,J=2.8,1 .6Hz,1H),6.32(q,J=2.9Hz,1H),6.14-6.06(m,1H),2.73(hept,J=6.9Hz,2H),1.14(d,J=6.9Hz,12H). 13 C NMR (101MHz, CDCL3) δ 149.85,131.17,128.86,128.83,122.49,116.63,108.93,108.35,30.52,24.58.

[0118] Example 21: Synthesis of 1-(5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)-N,N-dimethylmethanamine (22) [ka] To the reaction vial was added dimethylamine hydrochloride (1.97 g, 24.2 mmol, 1 equiv.), 37% formaldehyde solution (1.91 mL, 25.40 mmol, 1.05 equiv.), and isopropanol (11 mL). The reaction was stirred at room temperature for 45 hours. The solution was then added via syringe to a 50 mL round-bottom flask containing 2-(2,6-diisopropylphenyl)-1H-pyrrole (21) (5.50 g, 24.2 mmol, 1 equiv.) under a nitrogen atmosphere. The formaldehyde vial was rinsed with additional isopropanol (2 mL), which was added to the pyrrole solution. The reaction was stirred at 40 °C, although initially, a significant amount of pyrrole did not dissolve in solution. Additional isopropanol (5 mL) was added, and the reaction was stirred at 45 °C, and all material dissolved after 30 minutes. The reaction was stirred at 45 °C for 72 hours. 10% aqueous KOH (125 mL) was added and the reaction was stirred for 1 h. The aqueous phase was extracted with dichloromethane (3 x 75 mL). The combined organic phases were dried over MgSO, filtered, and concentrated in vacuo to give the product as a light brown solid (6.80 g, 99% yield). Several cycles of dissolving in hexane, concentrating, and drying in vacuo were required to remove all residual solvent.

[0119] 1 H NMR (400MHz, chloroform-d) δ8.18 (br s,1H),7.34(t,J=7.7Hz,1H),7.17(d,J=7.7Hz,2H),6.07(t,J=3.0Hz,1H),5.96(t,J=2 .9Hz,1H),3.46(s,2H),2.79(hept,J=6.9Hz,2H),2.21(s,6H),1.13(d,J=7.0Hz,12H). 13 C NMR (Error! Reference source not found. 101 MHz, chloroform-d) δ 149.68, 131.53, 128.65, 128.37, 128.29, 122.34, 108.46, 107.05, 56.66, 44.97, 30.48, 24.50.

[0120] Example 22: Synthesis of 1-(5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (23) [ka] In a nitrogen-filled glovebox, a 250 mL round-bottom flask was charged with 1-(5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)-N,N-dimethylmethanamine (22) (6.2 g, 21.8 mmol, 1 equiv.) and dissolved in THF (150 mL). The flask was sealed with a septum and removed from the glovebox. A solution of methyl iodide (1.36 mL, 21.8 mmol, 1 equiv.) in THF (15 mL) was added dropwise to the stirring pyrrole solution. The mixture was stirred at room temperature for 2 h, at which time a large amount of white solid precipitated. The slurry was filtered, and the solid was washed with THF (2 × 10 mL) and dried in vacuo to give a white solid (5.94 g, 71% yield).

[0121] 1H NMR (400MHz, chloroform-d) δ10.22 (br s,1H),7.34(t,J=7.7Hz,1H),7.13(d,J=7.8Hz,2H),6.40(t,J=3.0Hz,1H),6.01(d,J=3 .0Hz,1H),4.95(s,2H),3.17(s,9H),2.58(hept,J=6.8Hz,2H),1.07(d,J=6.9Hz,12H). 13 C NMR (101 MHz, chloroform-d) δ 149.38, 132.83, 129.97, 129.20, 122.49, 116.81, 114.56, 109.99, 62.18, 52.28, 30.67, 24.88, 24.09.

[0122] Example 23: Synthesis of (2S,2'S)-1,1'-bis((5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine-ligand 7 [ka] A 50 mL round-bottom flask was charged with (2S,2'S)-2,2'-bipyrrolidine (0.296 g, 2.11 mmol, 1 equiv.), 1-(5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (23) (1.80 g, 4.22 mmol, 2 equiv.), and anhydrous K2CO3 (2.92 g, 21.1 mmol, 10 equiv.). The vial was capped and purged with nitrogen. Acetonitrile (16 mL) was added via syringe, and the reaction was stirred at 72 °C for 19 h. The suspension was poured into water (150 mL). The aqueous phase was extracted with dichloromethane (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto basic alumina and purified by flash column chromatography (ISCO, 160 g basic alumina, 10-50% EtOAc in hexanes) to give the product as a white solid (1.15 g, 88% yield).

[0123] 1H NMR (400MHz, chloroform-d) δ 8.50(br s,2H),7.34(t,J=7.7Hz,2H),7.17(d,J=7.7Hz,4H),6.00(t,J=2.9Hz,2H),5.94(t,J=2.9Hz,2H),3.95(d,J=14.0Hz,2H),3 .40(d,J=14.0Hz,2H),2.92-2.82(m,4H),2.73-2.64(m,4H),2.19-2.10(m,2H),1.76-1.48(m,8H),1.11(d,J=6.9Hz,24H). 13 C NMR (101 MHz, chloroform-d) δ 149.68, 131.75, 129.26, 128.61, 127.58, 122.45, 108.69, 105.71, 65.00, 55.38, 51.94, 30.52, 26.30, 25.16, 24.58, 24.14, 23.67. 42 H 58 N4[M+H] + HRMS(ESI) calculated for: 619.4734, found: 617.4753.

[0124] Example 24: N 1 ,N 2 -bis((5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)methyl)-N 1 ,N 2 Synthesis of -dimethylethane-1,2-diamine-ligand 6 [ka] A 50 mL round-bottom flask was charged with 1-(5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (23) (1.80 g, 4.22 mmol, 2 equiv.) and anhydrous K2CO3 (2.92 g, 21.1 mmol, 10 equiv.). The vial was capped and purged with nitrogen. DMEDA (0.23 mL, 2.11 mmol, 1 equiv.) and acetonitrile (16 mL) were added via syringe, and the reaction was stirred at 72 °C for 19 h. The suspension was poured into water (150 mL). The aqueous phase was extracted with dichloromethane (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto basic alumina and purified by flash column chromatography (ISCO, 160 g basic alumina, 30–70% EtOAc in hexanes) to give the product as a thick, foamy, sticky white semi-solid (0.833 g, 74% yield).

[0125] 1 H NMR (400MHz, chloroform-d) δ8.35 (br s,2H),7.32(t,J=7.7Hz,2H),7.15(d,J=7.7Hz,4H),6.04-5.99(m,2H),5.93(t,J=2.9Hz,2H ),3.52(s,4H),2.76(hept,J=6.8Hz,4H),2.50(s,4H),2.15(s,6H),1.09(d,J=6.9Hz,24H). 13 C NMR (101 MHz, chloroform-d) δ 149.63, 131.57, 128.68, 128.20, 127.97, 122.39, 108.69, 107.19, 55.17, 54.58, 42.43, 30.50, 24.78, 24.28. 38 H 54 N4[M+H] + HRMS(ESI) calculated for: 567.4421, found: 567.4429.

[0126] Example 25:N 1 ,N 3 -bis((5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)methyl)-N 1 ,N3 Synthesis of -dimethylpropane-1,3-diamine-ligand 11 [ka] A 50 mL round-bottom flask was charged with 1-(5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)-N,N,N-trimethylmethanaminium iodide (23) (1.80 g, 4.22 mmol, 2 equiv.) and anhydrous K2CO3 (2.92 g, 21.1 mmol, 10 equiv.). The vial was capped and purged with nitrogen. 1 ,N 3 -Dimethylpropane-1,3-diamine (0.26 mL, 2.11 mmol, 1 equiv) and acetonitrile (16 mL) were added, and the reaction was stirred at 72 °C for 19 h. The suspension was poured into water (150 mL). The aqueous phase was extracted with dichloromethane (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto basic alumina and purified by flash column chromatography (ISCO, 160 g basic alumina, 30–70% EtOAc in hexanes) to give the product as a white solid (0.607 g, 49% yield).

[0127] 1 H NMR (400MHz, chloroform-d) δ8.83 (br s,2H),7.33(t,J=7.7Hz,2H),7.17(d,J=7.7Hz,4H),5.99(t,J=2.9Hz,2H),5.95(t,J=2.9Hz,2H),3.46(s,4H) ,2.76(hept,J=6.9Hz,4H),2.39(t,J=7.2Hz,4H),2.05(s,6H),1.67(t,J=7.2Hz,2H),1.10(d,J=6.9Hz,24H). 13 C NMR (101 MHz, chloroform-d) δ 149.67, 131.88, 128.63, 128.06, 127.84, 122.30, 108.73, 106.42, 55.09, 54.12, 41.86, 30.47, 25.07, 24.84, 23.90. 39 H 56 N4[M+H] +HRMS(ESI) calculated for: 581.4578, found: 584.4598.

[0128] Example 26: Synthesis of N,N-dimethyl-1-(1H-pyrrol-2-yl)methanamine (27) [ka] Under nitrogen, a 100 mL round-bottom flask equipped with a condenser was charged with pyrrole (2.55 mL, 36.8 mmol, 1.0 equiv) and isopropanol (20 mL). Dimethylamine hydrochloride (3.00 g, 36.8 mmol, 1.0 equiv) was added. This was followed by the dropwise addition of 37% formaldehyde solution (3.10 mL, 40.4 mmol, 1.10 equiv). The reaction was stirred at 40 °C for 3 days. 5% aqueous sodium hydroxide solution (50 mL) was added and the reaction was stirred for 15 minutes. The aqueous phase was extracted with ether (3 × 60 mL). The combined organic phase was washed with water (30 mL) and brine (30 mL). The organic phase was dried over MgSO4, filtered, and concentrated in vacuo to give a brown oil. The material was purified by vacuum distillation. (External temperature ranged from 88-100°C. Internal temperature was 47°C.) A white crystalline product was isolated (3.290 g, 72% yield).

[0129] 1 H NMR (400 MHz, chloroform-d) δ 8.92 (br s, 1H), 6.70 (ddd, J = 2.7, 2.0, 1.1 Hz, 1H), 6.09 (q, J = 2.9 Hz, 1H), 6.03-5.98 (m, 1H), 3.41 (s, 2H), 2.21 (s, 6H). 13 C NMR (101 MHz, chloroform-d) δ 129.24, 117.52, 107.65, 107.31, 56.62, 45.10.

[0130] Example 27: Synthesis of tert-butyl 2-((dimethylamino)methyl)-1H-pyrrole-1-carboxylate (28) [ka] To a 250 mL round-bottom flask was added N,N-dimethyl-1-(1H-pyrrol-2-yl)methanamine (27) (2.675 g, 21.5 mmol, 1.00 equiv.) and anhydrous dichloromethane (90 mL). The reaction flask was cooled in an ice bath, and 4-(dimethylamino)pyridine (0.394 g, 3.23 mmol, 0.15 equiv.) was added, followed by di-tert-butyl dicarbonate (5.17 g, 23.7 mmol, 1.1 equiv.). The reaction was stirred for a total of 18 hours, allowing it to warm to room temperature. The reaction was quenched by the addition of water (100 mL), and the mixture was stirred for 20 minutes. The organic phase was extracted, and the aqueous phase was extracted with ether (2 × 50 mL). The combined organic phase was extracted with water (2 × 50 mL) and brine (50 mL). The organic phase was dried over MgSO, filtered, and concentrated in vacuo. The material was purified by vacuum distillation. (External temperature ranged from 88 to 108 °C. Internal temperature was 60 °C.) A clear oil was isolated (2.694 g, 56% yield).

[0131] 1 H NMR (400 MHz, chloroform-d) δ 7.20 (dd, J = 3.3, 1.8 Hz, 1H), 6.16-6.12 (m, 1H), 6.10 (t, J = 3.3 Hz, 1H), 3.67 (s, 2H), 2.28 (s, 6H), 1.59 (s, 9H). 13 C NMR (101 MHz, chloroform-d) δ 149.38, 132.75, 121.54, 113.32, 109.74, 83.35, 56.66, 45.56, 28.04.

[0132] Example 28: Synthesis of N-(t-butoxycarbonyl)-2-(trimethylaminomethyl)pyrrole iodide (29) [ka] Under nitrogen, a 250 mL round-bottom flask was charged with tert-butyl 2-((dimethylamino)methyl)-1H-pyrrole-1-carboxylate (28) (2.69 g, 120 mmol, 1 equiv.) and THF (50 mL). To the stirring solution of BOC-protected pyrrole, methyl iodide (0.82 mL, 13.2 mmol, 1.1 equiv.) was added dropwise. The mixture was stirred at room temperature for 18 h, at which time a white solid precipitated. The suspension was placed in a freezer to cool. The slurry was filtered, and the solid was washed with THF (30 mL) and dried in vacuo to give a white solid (4.184 g, 95% yield).

[0133] 1 H NMR (400 MHz, chloroform-d) δ 7.32 (dd, J = 3.4, 1.7 Hz, 1H), 6.85 (dd, J = 3.5, 1.7 Hz, 1H), 6.24 (t, J = 3.4 Hz, 1H), 5.21 (s, 2H), 3.36 (s, 9H), 1.55 (s, 9H). 13 C NMR (101MHz, CDCL3) δ 149.30,125.40,123.16,120.94,111.28,85.88,61.31,52.82,52.79,52.75,27.88.

[0134] Example 29:N 1 ,N 2 -bis((1H-pyrrol-2-yl)methyl)-N 1 ,N 2 -Dimethylethane-1,2-diamine (30) -Synthesis of comparative ligand C1 [ka] In a nitrogen-filled glovebox, a 250 mL round-bottom flask was charged with N-(t-butoxycarbonyl)-2-(trimethylaminomethyl)pyrrole iodide (29) (2.0 g, 5.46 mmol, 2.1 equiv.) and anhydrous K2CO3 (3.59 g, 26.0 mmol, 10 equiv.). DMEDA (0.28 mL, 2.69 mmol, 1 equiv.) and acetonitrile (60 mL) were added, and the reaction was stirred at reflux (105 °C) for 41 h. The suspension was diluted with ether (150 mL). The suspension was filtered, and the solid was washed with ether. The filtrate was concentrated in vacuo. The material was purified by flash column chromatography (ISCO, 160 g basic alumina, 60–100% EtOAc in hexanes, then 1–10% methanol in ethyl acetate) to give the product as a reddish-brown solid (0.214 g, 16% yield).

[0135] 1 H NMR (400MHz, chloroform-d) δ9.21(br s,2H), 6.71-6.65(m,2H), 6.12(q,J=2.9Hz,2H), 6.02-5.96(m,2H), 3.56(s,4H), 2.47(s,4H), 2.23(s,6H). 13 C NMR (101 MHz, chloroform-d) δ 129.23, 117.15, 107.99, 106.61, 54.76, 54.43, 42.93. C 14 H 22 HRMS(ESI) calculated for N4[M+H]+: 247.1917, found: 247.1941.

[0136] Example 30:N 1 ,N 2 -bis((1H-benzo[d]imidazol-2-yl)methyl)-N 1 ,N 2 Synthesis of -dimethylethane-1,2-diamine-ligand 5 [ka] A 100 mL round-bottom flask was charged with 2-(chloromethyl)benzimidazole (1.50 g, 9.03 mmol, 2 equiv.) and anhydrous K2CO3 (6.24 g, 45.2 mmol, 10 equiv.). The vessel was capped and purged with nitrogen. DMEDA (0.49 mL, 4.52 mmol, 1 equiv.) and acetonitrile (40 mL) were added via syringe, and the reaction was stirred at 72 °C for 19 h. Upon initial heating, the septum dislodged due to slight pressure from heating, exposing the reaction to oxygen. The septum was quickly reattached, and the reaction was stirred overnight without incident. The suspension was poured into water (150 mL). The aqueous phase was extracted with dichloromethane (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. This material was adsorbed onto basic alumina and purified by flash column chromatography (ISCO, 160 g basic alumina, 2–5% MeOH in CHCl) to give a pale yellow solid (1.21 g). HRMS was consistent with the expected product [M+1], but NMR contained a broad peak and other minor species. The broad peak may be due to tautomerism, but the minor peaks need to be removed prior to metallation. The solid was recrystallized from hot toluene (approximately 50 mL). Initial cooling at room temperature or in the freezer did not precipitate a significant amount of material. However, leaving the material at room temperature for 3 days resulted in the precipitation of a solid. The suspension was again cooled in the freezer. The solid was filtered, washed with cold toluene, and dried in vacuo to give a yellow solid (0.759 g, 48% yield).

[0137] 1 H NMR (400 MHz, chloroform-d, −40° C.) δ 13.11 (br s, 2H), 7.71 (d, J=7.5 Hz, 2H), 7.34-7.13 (m, 6H), 4.14 (s, 4H), 2.66 (s, 4H), 2.44 (s, 6H). 13 C NMR (101 MHz, chloroform-d) δ 152.79, 143.26, 133.79, 122.68, 122.21, 118.80, 111.26, 56.00, 54.72, 43.69. 20 H 24 N6[M+H] +HRMS(ESI) calculated for: 349.2135, found: 349.2140.

[0138] Example 31: Synthesis of (2S,2'S)-1,1'-bis((1H-benzo[d]imidazol-2-yl)methyl)-2,2'-bipyrrolidine-ligand 12 [ka] A 100 mL round-bottom flask was charged with (2S,2'S)-2,2'-bipyrrolidine (0.634 g, 4.52 mmol, 1 equiv.), 2-(chloromethyl)benzimidazole (1.50 g, 9.03 mmol, 2 equiv.), and anhydrous K2CO3 (6.24 g, 45.2 mmol, 10 equiv.). The vessel was capped and purged with nitrogen. Acetonitrile (40 mL) was added via syringe, and the reaction was stirred at 72 °C for 19 h. The suspension was poured into water (150 mL). The aqueous phase was extracted with dichloromethane (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto basic alumina and purified by flash column chromatography (ISCO, 160 g basic alumina, 1–3% MeOH in CHCl) to give an off-white powder (0.563 g, 31% yield). Upon cooling to −40 °C, several peaks appeared, but unlike 32, they were still very broad.

[0139] 1 H NMR (400MHz, chloroform-d) δ 13.91(br s,2H),7.52(br s,4H),7.19(dd,J=6.1,3.2Hz,4H),4.42(d,J=15.5Hz,2H),4.11(d,J=15.5Hz,2H),3.03(dt,J=11.0,6.6Hz,2H),2.98- 2.91(m,2H),2.82(dt,J=11.5,6.5Hz,2H),2.01-1.90(m,2H),1.88-1.77(m,2H),1.77-1.64(m,2H),1.47-1.36(m,2H). 13C NMR (101 MHz, chloroform-d) δ 152.74, 122.25, 67.25, 54.58, 54.23, 27.80, 24.01.

[0140] Example 32:N 1 ,N 3 -bis((1H-benzo[d]imidazol-2-yl)methyl)-N 1 ,N 3 Synthesis of -dimethylpropane-1,3-diamine-ligand 4 [ka] A 100 mL round-bottom flask was charged with 2-(chloromethyl)benzimidazole (1.50 g, 9.03 mmol, 2 equiv.) and anhydrous K2CO3 (6.24 g, 45.2 mmol, 10 equiv.). The vessel was capped and purged with nitrogen. N,N'-Dimethyl-1,3-propanediamine (0.57 mL, 4.52 mmol, 1 equiv.) and acetonitrile (40 mL) were added via syringe, and the reaction was stirred at 72 °C for 17 h. The suspension was poured into water (150 mL). The aqueous phase was extracted with dichloromethane (3 × 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The material was adsorbed onto basic alumina and purified by flash column chromatography (ISCO, 160 g basic alumina, 1-3% MeOH in CHCl) to give two major peaks. The first peak (0.492 g) was isolated as a pale yellow solid. Upon cooling, more material precipitated from solution. The material was dissolved in hot chloroform, which was then slowly cooled to -30 °C. Hexane was layered onto the chloroform solution, and the biphasic solution was allowed to stand at room temperature for 72 hours, at which point a yellow solid precipitated. The suspension was cooled in a -30 °C freezer for 4 hours. The material was filtered, washed with hexane, and dried in vacuo to give a yellow solid (254 mg, 16% yield).

[0141] 1H NMR (400MHz, chloroform-d) δ 12.4-11.4(br s,2H),7.45(s,4H),7.16(dd,J=6.1,3.1Hz,4H),4.07(s,4H),2.68(t,J=6.3Hz,4H),2.50(s,6H),1.85(p,J=6.4Hz,2H). 13 C NMR (101 MHz, chloroform-d) δ 152.17, 122.28, 56.40, 53.67, 42.68, 23.23. C 21 H 26 N6[M+H] + HRMS(ESI) calculated for: 363.2292, found: 363.2273.

[0142] Example 33: Synthesis of dimethyl[(2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine]hafnium-procatalyst 1 [ka] In a nitrogen-filled glovebox, a reaction vial was charged with (2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine (ligand 3) (400 mg, 0.7480 mmol, 1 equiv.). The solid was dissolved in toluene (10 mL) and added to a vial containing bis(dimethylamino)bis(tetrahydrofuran)hafnium(IV) chloride (360.3 mg, 0.748 mmol, 1 equiv.). The vial of (2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine was rinsed with toluene (2 × 5 mL), which was added to the vial of bis(dimethylamino)bis(tetrahydrofuran)hafnium(IV) chloride. The reaction was stirred at room temperature for 42 h. An off-white precipitate formed. The suspension was filtered and washed with toluene (5 × 1 mL). The solid was dried in vacuo to give 367 mg of an off-white solid. Toluene (20 mL) was added to the vial containing the off-white solid. A 3 M solution of MeMgBr in EtO (0.55 mL, 1.65 mmol, 2.2 equiv.) was added to the suspension, and the reaction was stirred at room temperature for 72 h. A clear solution and a white precipitate resulted. Over the weekend, a small plug of white solid material formed, which floated on top of the clear solution. A significant amount of solid was still present, so the material was filtered. The filter cake was washed with toluene (3 × 5 mL). All volatiles were removed in vacuo to give approximately 370 mg of a white solid. The solid was triturated with toluene (10 mL). The solution was passed through a 0.45 μm syringe filter. The vial and filter were washed with toluene (2 × 5 mL). The combined organic phases were dried in vacuo to give a white solid (155.4 mg, 28% yield). NMR indicated that the material was exclusively the desired LHfMe2 complex. However, not all of the material was soluble in benzene-d6. The solid was triturated with toluene (10 mL) and passed through a 0.45 μm syringe filter. The vial and filter were washed with toluene (2 × 2 mL). The combined organic phases were dried in vacuo to give a white solid (141.3 mg, 25% yield).

[0143] <h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H NMR (400MHz, d6)δ6.95(s,2H),6.84(s,2H),6.23-6.12(m,4H),3.53(d,J=13.2Hz,2H),3.05(d,J=13.3Hz,2H),2.97-2.90(m,2H),2.60-2.47(m,2H),2.42(s,6H),2.37(s,6H),2.19(s,6H),1.29-0.92(m,8H),0.54-0.40(m,2H),0.17(s,6H).<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> C NMR(101MHz、ベンゼン-d6)δ 140.81,140.05,137.19,136.24,135.76,135.71,128.34,127.56,110.52 ,107.07,68.51,59.57,55.83,54.24,23.82,21.70,21.53,20.98,20.87。<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0144] <h2 style=";text-align:left;direction:ltr"> Alternative Method (Metalation of HfMe): In a nitrogen-filled glovebox, a 3 M solution of MeMgBr in EtO (0.14 mL, 0.42 mmol, 4.5 equiv.) was added to a stirred suspension of HfCl (29.9 mg, 0.0935 mmol, 1 equiv.) in toluene (1 mL) at −30 °C. The reaction was stirred vigorously for 3 min, resulting in the formation of a gel. A solution of (2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine (50 mg, 0.0935 mmol, 1 equiv.) in toluene (1 mL) at −30 °C was added to the hafnium solution. The ligand vial was rinsed with additional toluene (0.5 mL), which was added to the hafnium solution. The reaction was stirred for 18 h while warming to room temperature, during which time the solution turned dark. The material was filtered, and the filter cake was washed with toluene (3 × 1 mL) to give a pale tan solution. The solution was further filtered through a 0.2 μm syringe filter to give a pale yellow solution. All volatiles were removed from the filtrate in vacuo to give an off-white solid. NMR indicated a mixture of the desired product and other pyrrole-containing species. The solid was partially dissolved in toluene (5 mL) and filtered through a 0.2 μm syringe filter to give a clear solution. All volatiles were removed in vacuo to give a white solid. NMR indicated some by-product was still present. The material was dissolved in toluene (2 mL), and hexane (10 mL) was added. The solution was filtered through a 0.2 μm syringe filter. The solution was stored in a -30 °C freezer for 16 h, at which point a solid precipitated. The solution was filtered, washed with cold hexane (-30 °C), and dried in vacuo to give the product as a pale tan solid (21.4 mg, 31% yield).

[0145] Example 34: Synthesis of dimethyl[(2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine]zirconium-procatalyst 2 [ka] In a nitrogen-filled glovebox, a reaction vial was charged with (2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine (193 mg, 0.361 mmol, 1 equiv.). The solid was dissolved in toluene (5 mL) and added to a vial containing bis(dimethylamino)bis(tetrahydrofuran-2-yl)zirconium(IV) chloride (160.7 mg, 0.374 mmol, 1 equiv.). The vial of (2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine was rinsed with toluene (5 mL), which was added to the vial of bis(dimethylamino)bis(tetrahydrofuran-2-yl)zirconium(IV) chloride. The reaction was stirred at room temperature for 22 hours. A yellow precipitate formed. The suspension was filtered and washed with toluene (3 × 2 mL). The solid was dried in vacuo to give 180.8 mg of a yellow solid. Toluene (10 mL) was added to the vial containing the pale yellow solid. A 3 M solution of MeMgBr in EtO (0.26 mL, 0.794 mmol, 2.2 equiv.) was added to the suspension, and the reaction was stirred at room temperature for 72 h. A clear solution with an off-white precipitate was obtained. All volatiles were removed in vacuo. The solid was triturated with toluene (5 mL). The solution was passed through a 0.45 μm syringe filter. The vial and filter were washed with toluene (2 × 5 mL). The combined organic phase was dried in vacuo. The solid was triturated with toluene (6 mL) and passed through a 0.45 μm syringe filter. The vial and filter were washed with toluene (2 × 1 mL). The combined organic phase was dried in vacuo to give an off-white solid (95.2 mg, 40% yield).

[0146] 1H NMR (400MHz, benzene-d6) δ6.94(s,2H),6.84(s,2H),6.19-6.11(m,4H),3.53(d,J=13.2Hz,2H),3.03(d,J=13.3Hz,2H),3.00- 2.96(m,2H),2.56-2.46(m,2H),2.45(s,6H),2.37(s,6H),2.18(s,6H),1.34-0.93(m,8H),0.59-0.47(m,2H),0.45(s,6H). 13 C NMR (101 MHz, benzene-d6) δ 140.36, 139.76, 137.31, 136.38, 135.89, 135.68, 128.34, 127.59, 109.70, 106.96, 68.12, 56.24, 54.27, 54.17, 23.65, 21.53, 21.52, 21.01, 20.87.

[0147] Example 35: Synthesis of bis(dimethylamido)[(2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine]hafnium-procatalyst 5 [ka] In a nitrogen-filled glovebox, a solution of tetrakis(dimethylamido)hafnium (199 mg, 0.5610 mmol, 1 equiv.) in toluene (5 mL) was added to a vial containing (2S,2'S)-1,1'-bis((5-mesityl-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine (300 mg, 0.5610 mmol, 1.0 equiv.). The tetrakis(dimethylamido)hafnium vial was washed with additional toluene (5 mL), which was added to the ligand vial. The clear solution was stirred at room temperature for 2.5 h. The solution was passed through a 0.45 μm syringe filter, the filter was washed with additional toluene (2 mL), and all volatiles were removed in vacuo to yield an off-white solid (0.447 g, quantitative yield).

[0148] 1H NMR (400MHz, toluene-d8)δ 6.88(s,4H),6.21(dd,J=2.8,0.9Hz,2H),6.13(d,J=2.9Hz,2H),3.62(d,J=12.4Hz,2H),3.24(d,J=13.0Hz,2H),3.16-3.10(m,2H) ,3.01-2.86(m,2H),2.74-2.68(m,2H),2.65(s,12H),2.33(s,6H),2.31(s,6H),2.25(s,6H),1.52-1.20(m,6H),0.87-0.74(m,2H). 13 C NMR (101 MHz, toluene-d8) δ 140.53, 140.05, 137.60, 137.15, 135.41, 135.14, 127.88, 127.59, 111.49, 106.49, 66.99, 55.21, 54.12, 42.74, 23.93, 21.70, 21.68, 21.30, 20.74.

[0149] Example 36: Synthesis of dimethyl[(2S,2'S)-1,1'-bis((5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine]hafnium-procatalyst 3 [ka] In a nitrogen-filled glovebox, a reaction vial was charged with (2S,2'S)-1,1'-bis((5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine (300 g, 0.4847 mmol, 1 equiv.). The solid was dissolved in toluene (6.5 mL) and added to a vial containing bis(dimethylamino)bis(tetrahydrofuran)hafnium(IV) chloride (233.5 mg, 0.4847 mmol, 1 equiv.). The (2S,2'S)-1,1'-bis((5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)methyl)-2,2'-bipyrrolidine vial was rinsed with toluene (2 × 3 mL), which was added to the vial of bis(dimethylamino)bis(tetrahydrofuran)hafnium(IV) chloride. The reaction was stirred at room temperature for 42 hours. Initially, a precipitate did not form immediately, as with EXP-15-BE7500. However, upon prolonged stirring, a white precipitate formed. The suspension was cooled in a -30 °C freezer for 6 hours. The suspension was filtered and washed with cold hexane (2 × 1 mL). The solid was dried in vacuo to yield 207.4 mg of an off-white solid. Toluene (9 mL) was added to the vial containing the off-white solid. A 3 M solution of MeMgBr in EtO (0.36 mL, 1.07 mmol, 2.2 equiv.) was added to the suspension, and the reaction was stirred at 90 °C for 16 hours. The reaction was allowed to cool to room temperature, and the volatiles were removed in vacuo. The solid was triturated with toluene (7 mL). The solution was passed through a 0.45 μm syringe filter. The vial and filter were washed with toluene (2 × 3 mL). The combined organic phases were concentrated in vacuo to give approximately 200 mg of a white solid. The solid was triturated with toluene (7 mL). The solution was passed through a 0.2 μm syringe filter. The filter clogged during the process. The vial and filter were washed with toluene (1×2 mL). The combined organic phases were concentrated in vacuo to give a white solid (195.5 mg, 49% yield).

[0150] 1H NMR (400MHz, toluene-d8)δ 7.30-7.25(m,2H),7.24-7.15(m,4H),6.25-6.22(m,2H),6.19-6.15(m,2H),3.54(dd,J =13.4,1.4Hz,2H),3.34(hept,J=6.8Hz,2H),3.27-3.13(m,4H),3.06-2.97(m,2H),2.75 -2.57(m,4H),1.48(d,J=7.0Hz,6H),1.38-1.35(m,2H),1.34(d,J=6.6Hz,6H),1.28(d,J =6.9Hz,6H),1.24-1.14(m,4H),1.07(d,J=6.9Hz,6H),0.66-0.57(m,2H),-0.00(s,6H). 13 C NMR (101 MHz, toluene-d8) δ 150.42, 147.17, 139.42, 137.10, 136.56, 127.99, 122.16, 121.68, 112.47, 106.59, 68.69, 60.28, 56.22, 53.91, 30.61, 30.13, 27.19, 26.09, 23.88, 23.35, 22.14, 21.49.

[0151] Example 37: Dimethyl [N 1 ,N 2 -bis((5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)methyl)-N 1 ,N 2 Synthesis of [(dimethylethane-1,2-diamine)hafnium-promoter catalyst 4 [ka] In a nitrogen-filled glovebox, a 3 M solution of MeMgBr in EtO (0.53 mL, 1.59 mmol, 4.5 equiv.) was added to a stirred suspension of HfCl (113 mg, 0.353 mmol, 1 equiv.) in toluene (4 mL) at -30 °C. The reaction was stirred vigorously for 3 min, resulting in the formation of a gel. 1 ,N 2 -bis((5-(2,6-diisopropylphenyl)-1H-pyrrol-2-yl)methyl)-N 1 ,N 2A solution of 200 mg of dimethylethane-1,2-diamine (0.353 mmol, 1 equiv.) was added to the hafnium solution. The ligand vial was rinsed with additional toluene (1 mL), which was added to the hafnium solution. The reaction was stirred for 18 hours while warming to room temperature, during which time the solution turned dark. The material was filtered, and the filter cake was washed with toluene (3 × 1 mL) to give a pale yellow solution. The solution was further filtered through a 0.45 μm syringe filter to give a pale yellow solution. All volatiles were removed from the filtrate in vacuo to give a yellow solid. The solid was dissolved in toluene (5 mL) and filtered through a 0.45 μm syringe filter, followed by a 0.2 μm syringe filter to give a pale yellow solution. All volatiles were removed in vacuo to give an off-white solid with a thick oil. The material was dissolved in toluene (3 mL), and hexane (15 mL) was added. The solution was filtered through a 0.45 μm syringe filter and stored in a -30 °C freezer for 18 hours, during which very little solid precipitated from the solution. All volatiles were removed in vacuo, and the solid was dissolved in toluene (2 mL). Hexane (10 mL) was added, causing a solid to precipitate. The solution was filtered through a 0.45 μm syringe filter. After filtration, the syringe and filter were washed with toluene (5 mL), and the precipitated solid was examined. All volatiles were removed in vacuo to yield an off-white solid (41 mg). NMR indicated the material was >95% pure product. The solid was dissolved in toluene (1 mL), diluted with hexane (5 mL), filtered through a 0.45 μm syringe filter, and stored in a -30 °C freezer for 18 hours, causing a crystalline solid to precipitate. The solid was filtered, washed with cold hexane (-30 °C), and dried under vacuum to give the desired product as a white solid (15.9 mg, 6% yield). The residue in the crystallization vial was reserved for possible crystal structure. The filtrate from the initial toluene:hexane solution was stored in a -30°C freezer for 18 hours, causing the powder to precipitate. The solid was washed with cold hexane (-30°C) and dried under vacuum to give a pale yellow solid (17.1 mg, 6% yield). Total yield: 33 mg, 12% yield.

[0152] 1H NMR (400MHz, toluene-d8)δ 7.24(t,J=7.6Hz,2H),7.16(ddd,J=13.2,7.6,1.5Hz,4H),6.20(d,J=2.8Hz,2H),6.18-6. 15(m,2H),3.69(d,J=13.4Hz,2H),3.26(Hept, J=6.9Hz,2H),3.09(Hept, J=6.7Hz,2H),2.92 (d,J=13.6Hz,2H),2.89(d,J=9.6Hz,2H),1.89(s,6H),1.44(d,J=6.9Hz,6H),1.34-1.31( m,2H),1.28(d,J=6.7Hz,6H),1.19(d,J=6.9Hz,6H),1.03(d,J=6.7Hz,6H),-0.05(s,6H). 13 C NMR (101 MHz, toluene-d8) δ 150.46, 147.13, 139.17, 136.85, 136.38, 128.03, 122.14, 121.71, 112.65, 106.70, 61.23, 58.94, 54.97, 44.22, 30.49, 30.12, 27.35, 26.09, 22.91, 21.93.

[0153] Example 38: Dimethyl [N 1 ,N 2 -bis((1H-pyrrol-2-yl)methyl)-N 1 ,N 2 Synthesis of [(dimethylethane-1,2-diamine)hafnium]-comparative procatalyst C1 [ka] In a nitrogen-filled glove box, add N 1 ,N 2 -bis((1H-pyrrol-2-yl)methyl)-N 1 ,N 2 N-dimethylethane-1,2-diamine (100 g, 0.4059 mmol, 1 equiv.) was placed in a vial containing bis(dimethylamino)bis(tetrahydrofuran)hafnium(IV) chloride (195.6 mg, 0.4059 mmol, 1 equiv.). 1 ,N 2-bis((1H-pyrrol-2-yl)methyl)-N 1 ,N 2 A vial of -dimethylethane-1,2-diamine was rinsed with toluene (2 × 2 mL) and added to the vial of bis(dimethylamino)bis(tetrahydrofuran)hafnium(IV) chloride. The reaction was stirred at room temperature for 18 hours. The solution remained tan throughout the course of the reaction (the starting ligand was also tan). No appreciable precipitate formed during the reaction, as was observed with the mesityl or DIPP-substituted analogs. All volatiles were removed in vacuo, yielding a red / brown solid. Toluene (11 mL) was added to the vial. A 3 M solution of MeMgBr in EtO (0.30 mL, 0.893 mmol, 2.2 equiv.) was added to the suspension, and the reaction was stirred at room temperature for 20 hours. Initially, the suspension was red / brown, but turned dark brown after stirring overnight. All volatiles were removed in vacuo. The residue was dissolved in toluene (10 mL). A significant amount of salt remained insoluble. The mixture was filtered, and the filter cake was washed with toluene (2 × 5 mL). The brown solution was concentrated in vacuo. NMR was more complex than expected, containing multiple species. However, APT indicated that the desired complex was formed as the major product. The residue was dissolved in toluene (10 mL), passed through a 0.45 μm syringe filter, and concentrated in vacuo. The NMR spectrum still showed multiple species. Toluene (3 mL) was added to the solid and stirred overnight, but not all of the material dissolved. Additional toluene (1 mL) was added, but some solid remained. Hexane (10 mL) was added, and the solution was passed through a 0.45 μm syringe filter to give a clear, light brown solution. The solution was stored in a -30 °C freezer for 3 days, during which time a solid precipitated. The solid was filtered, washed with cold hexane (-30 °C), and dried in vacuo to give the product as a brown solid (53.6 mg, 29% yield).

[0154] 1H NMR (400MHz, benzene-d6)δ 7.40-7.35(m,2H),6.48-6.41(m,2H),6.22-6.18(m,2H),3.68(d,J=13.4Hz,2H),2.83(d ,J=13.4Hz,2H),2.57(d,J=9.3Hz,2H),1.60(s,6H),1.07(d,J=9.1Hz,2H),0.70(s,6H). 13 C NMR (101 MHz, benzene-d6) δ 137.51, 129.05, 109.81, 106.35, 59.40, 57.71, 54.78, 43.86.

[0155] Example 39: Synthesis of dibenzyl[(2S,2'S)-1,1'-bis((1H-benzo[d]imidazol-2-yl)methyl)-2,2'-bipyrrolidine]hafnium-procatalyst 6 [ka] In a nitrogen-filled glovebox, a reaction vial was charged with (2S,2'S)-1,1'-bis((1H-benzo[d]imidazol-2-yl)methyl)-2,2'-bipyrrolidine (120 mg, 0.300 mmol, 1 equiv.). HfBn4 (163 mg, 0.300 mmol, 1 equiv.) was dissolved in toluene (10 mL) and added to the vial containing the ligand. The HfBn4 vial was rinsed with additional toluene (2 × 10 mL), which was added to the reaction. The ligand did not immediately dissolve into solution. The suspension was stirred at room temperature for 18 h, resulting in a hazy yellow solution. The solution was passed through a 0.4 μm syringe filter. The resulting clear yellow solution was concentrated to a volume of approximately 2 mL. Hexane (20 mL) was added, causing a large amount of solid to precipitate. The suspension was cooled in a -30 °C freezer for 3 h. The solid was filtered, washed with hexanes, and dried in vacuo to give the product as an off-white solid (0.1627 g, 72% yield).

[0156] 1H NMR (400MHz, benzene-d6)δ 8.11-7.99(m,4H),7.33-7.22(m,4H),6.89(t,J=7.7Hz,4H),6.72-6.63(m,6H),3.62(d,J=15.0Hz,2H),3.49(d,J=15.1Hz,2H),2.60 (d,J=12.2Hz,2H),2.55-2.38(m,6H),2.31-2.16(m,2H),1.09-0.95(m,2H),0.93-0.79(m,2H),0.62-0.43(m,2H),0.26-0.11(m,2H). 13 C NMR (101 MHz, benzene-d6) δ 161.38, 147.40 (br), 144.04 (br), 141.95, 128.78, 128.31, 123.38, 122.21, 121.95, 119.11, 115.15, 81.86, 70.89, 57.63, 54.53, 23.67, 21.41.

[0157] Example 40: Dibenzyl [N 1 ,N 2 -bis((1H-benzo[d]imidazol-2-yl)methyl)-N 1 ,N 2 Synthesis of [(dimethylethane-1,2-diamine)hafnium-promoter catalyst 7 [ka] In a nitrogen-filled glove box, add N 1 ,N 2 -bis((1H-benzo[d]imidazol-2-yl)methyl)-N 1 ,N 2-dimethylethane-1,2-diamine (100 mg, 0.287 mmol, 1 equiv.) was placed in the reaction mixture. HfBn4 (155.8 mg, 0.287 mmol, 1 equiv.) was dissolved in toluene (10 mL) and added to the vial containing the ligand. The HfBn4 vial was rinsed with additional toluene (2 × 10 mL), which was added to the reaction mixture. The ligand was resistant to dissolving in the solution. The suspension was stirred at room temperature for 17 h, during which time most of the ligand dissolved into solution, resulting in a hazy yellow solution. The solution was passed through a 0.4 μm syringe filter and concentrated to a volume of approximately 3 mL. Hexane (20 mL) was added, causing a large amount of solid to precipitate. The suspension was cooled in a -30 °C freezer for 1 h. The suspension was filtered, washed with hexane, and dried in vacuo to give the product as an off-white solid (0.1561 g, 77% yield).

[0158] 1 H NMR (400MHz, benzene-d6) δ8.09-8.03(m,2H),8.00-7.94(m,2H),7.30-7.21(m,4H),6.88(t,J=7.7Hz,4H),6.66(t,J=7.4Hz,2H),6.60(d,J=7.4Hz,4H) ,3.50(d,J=15.5Hz,2H),3.27(d,J=15.5Hz,2H),2.60(d,J=12.5Hz,2H),2 .53(d,J=12.6Hz,2H),1.95-1.84(m,2H),1.43(s,6H),1.28-1.16(m,2H). 13 C NMR (101 MHz, benzene-d6) δ 161.36, 147.14, 143.96, 141.69, 128.57, 127.67, 123.17, 122.24, 122.09, 119.28, 114.72, 86.05, 60.45, 57.67, 45.21.

[0159] Example 41: Polymers obtained from procatalysts in a batch reactor The catalytic activity (polymer yield) and the resulting polymer properties were evaluated for procatalysts 1 to 3. The polymerization reactions were carried out in a 2 L semi-batch reactor. [Table 1]

[0160] Example 42: Polymers obtained from procatalysts in PPR Olefin polymerization reactions were first carried out in a parallel polymerization reactor (PPR) using in situ generated complexes prepared by mixing solutions of ligands (ligands 1–12) and metal precursors (ZrBn or HfBn) at a metal:ligand ratio of 1:1 or 2:1 for 30 min prior to the polymerization experiment. Activator 1 was [HNMe(C 18 H 37 )2][B(CF)4] was added in an amount of 1.5 equivalents relative to the metal (Zr or Hf). Activator 2 was B(CF)3, added in an amount of 5 equivalents relative to the metal (Zr or Hf). The data in Tables 2–4 were obtained at 120°C and 150 psi ethylene pressure, or at 150°C and 213 psi ethylene pressure. The molar ratio of 1-octene to ethylene in the liquid phase was 2.24:1. The quench time was determined based on the time the reaction reached an ethylene uptake of 50 (for runs at 120°C) or 75 (for runs at 150°C) psi, or after 1800 seconds, whichever occurred first. The polymerization was then quenched with CO to quench the catalyst and terminate the experiment. Molar % octene is defined as (moles of 1-octene incorporated into the polymer / (total moles of 1-octene and ethylene)) × 100. M:L refers to the amount of added ligand relative to ZrBn4 or HfBn4. [Table 2] [Table 3]

[0161] Olefin polymerization reactions were carried out in a parallel polymerization reactor (PPR) using the isolated metal complexes. The results and data obtained from the polymerization reactions are shown in Tables 5-7. Activator 1 was [HNMe(C 18 H 37)2][B(CF)4] was added in an amount of 1.5 equivalents relative to the metal (Zr or Hf). Activator 2 was B(CF)3, added in an amount of 5 equivalents relative to the metal (Zr or Hf). The molar ratio of ethylene to 1-octene in the liquid phase was 2.24:1. The quench time was determined based on the time the reaction reached 50 (for runs at 120 °C) or 75 (for runs at 150 °C) psi ethylene uptake, or after 1800 seconds, whichever came first. The polymerization was then quenched with CO to quench the catalyst and terminate the experiment. Mol % octene or C8 / olefin is defined as (moles of 1-octene incorporated into the polymer / (total moles of 1-octene and ethylene)) × 100. [Table 4] [Table 5] [Table 6]

[0162] The data shown in Table 7 are the results for the comparative procatalysts. Polymerization reactions were carried out in a PPR reactor as previously described. [ka] [Table 7]

[0163] When used in the polymerization process, procatalyst C1 produced less than 10 mg of polymer. The results showed that there was ethylene uptake, but this was due to ethylene dissolution and does not represent ethylene consumed by the polymerization. The present invention includes the following aspects. Section 1. A catalyst system comprising a metal-ligand complex according to formula (I), [ka] During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, said metal having a formal oxidation state of +2, +3, or +4; Each X is independently an unsaturated (C2-C 50 ) Hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C6-C 50 ) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C is a monodentate or bidentate ligand selected from n is 1, 2, or 3; m is 1 or 2; the metal-ligand complex has six or fewer metal-ligand bonds; Each T is nitrogen or CR 4 and each R 4 However, independently, (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, halogen, or -H; Each R 1 are independently aliphatic (C1-C 50 ) Hydrocarbyl, Aliphatic (C1-C 50 ) selected from the group consisting of heterohydrocarbyl, -halogen, and -H, and when m is 2, two R 1 are optionally covalently bonded to each other; Each R 2However, independently, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, Si(R C )3, and Ge(R C )3 is selected from R 1 and R 2 are optionally covalently linked to form a ring structure; Each R 3 and each R 5 However, independently, (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)-, 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, or -H; Each R 6 However, independently, (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)-, R CS(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, or halogen; R 5 and R 6 are optionally covalently linked to form a ring structure; Each R in formula (I) C and R N However, independently, (C1-C 50 ) hydrocarbyl catalyst system. Section 2. M is zirconium or hafnium; Each X is independently (C6-C 20 ) aryl, (C4-C 20 ) heteroaryl, (C4-C 12 ) a diene, or a halogen; Each R 6 However, independently, (C1-C 50 ) aryl or (C4-C 50 Item 1. The catalytic system according to item 1, wherein the heteroaryl is selected from the group consisting of: Section 3. R 5 and R 6 are covalently bonded to form a six-membered aromatic ring. Section 4. R 5 and R 6 are covalently bonded to form a six-membered aromatic ring, and R 3 is -H and R 2 4. The catalyst system according to any one of items 1 to 3, wherein is methyl. Section 5. Each R 6 Item 3. The catalyst system according to item 1 or 2, wherein is anthracenyl, disubstituted anthracenyl, or trisubstituted anthracenyl. Section 6. Each R 6 Item 3. The catalyst system according to item 1 or 2, wherein is phenyl or substituted phenyl. Section 7. Each R 63. The catalyst system according to item 1 or 2, wherein is a substituted phenyl selected from 2,4,6-trimethylphenyl, 2,6-di(isopropyl)phenyl, 3,5-di-tert-butylphenyl, or 3,5-diphenylphenyl. Section 8. m is 2 and the metal-ligand complex has a structure according to formula (II); [ka] In the formula, M, T, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and X is as defined in formula (I), n is 1 or 2, and the dotted line represents an optional covalent bond. Section 9. M is zirconium or hafnium; Each X is independently (C6-C 50 ) aryl, (C6-C 50 ) heteroaryl, (C4-C 12 ) a diene, or a halogen; Each R 1 and R 2 However, independently, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 Item 9. The catalytic system according to item 8, wherein the heteroaryl is selected from the group consisting of heteroaryl, heteroaryl, and halogen. Section 10. The two R 1 are covalently bonded to each other, and each R 2 However, independently (C1-C 10 Item 10. The catalyst system according to item 8 or 9, wherein the alkyl is . Section 11. The two R 1 is covalently attached as an alkylene selected from -CH2CH2-, -CH2CH2CH2-, or -CH2CH2CH2CH2-. Section 12. m is 2 and the metal-ligand complex has a structure according to formula (III); [ka] In the formula, M, T, R 3 , R 4 , R 5 , R 6 and X is as defined in formula (I), n is 1 or 2, and the dotted line represents an optional covalent bond. Section 13. Each R 6 13. The catalyst system of claim 12, wherein is independently selected from carbazolyl, 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, or 3,5-di-iso-propylphenyl. Section 14. Each R 6 Item 13. The catalyst system according to item 12, wherein is 2,6-di-iso-propylphenyl. Section 15. Each R 6 Item 13. The catalyst system according to item 12, wherein is 2,4,6-trimethylphenyl. Section 16. 16. The catalyst system according to any one of items 1 to 15, wherein T is N. Section 17. T is CR 4 and R 4 16. The catalyst system according to any one of items 1 to 15, wherein is —H. Section 18. 1. A polymerization process for producing an ethylene-based polymer, comprising: Item 18. A polymerization process comprising polymerizing ethylene and at least one additional α-olefin and at least one activator in the presence of the catalyst system according to any one of items 1 to 17 to form a polymer. Section 19. Item 19. The polymerization process of item 18, wherein the activator comprises MMAO, bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate, or tris(pentafluorophenyl)borane.

Claims

1. A catalyst system for olefin polymerization comprising a metal-ligand complex according to formula (I), 【Chemical 1】 During the ceremony, M is a metal selected from zirconium or hafnium, said metal having a formal oxidation state of +2, +3, or +4; Each X is independently an unsaturated (C ２ -C ５０ ) hydrocarbons, unsaturated (C ２ -C ５０ ) heterohydrocarbons, (C １ -C ５０ ) hydrocarbyl, (C １ -C ５０ ) heterohydrocarbyl, (C ６ -C ５０ )aryl, (C 4 -C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C ４ -C １２ ) diene, halogen, -N(R Ｎ ) ２ , or -NCOR Ｃ is a monodentate or bidentate ligand selected from n is 1, 2, or 3; m is 1 or 2; the metal-ligand complex has six or fewer metal-ligand bonds; Each T is nitrogen or CR ４ and each R ４ But independently, (C １ -C ５０ ) hydrocarbyl, (C １ -C ５０ ) heterohydrocarbyl, (C ６ -C ５０ ) aryl, (C ４ -C ５０ ) heteroaryl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , halogen, or —H; Each R １ are independently aliphatic (C １ -C ５０ ) hydrocarbyl, aliphatic (C １ -C ５０ ) selected from the group consisting of heterohydrocarbyl, -halogen, and -H, and when m is 2, two R １ are optionally covalently bonded to each other; Each R ２ But independently, (C １ -C ５０ ) hydrocarbyl, (C １ -C ５０ ) heterohydrocarbyl, (C ６ -C ５０ ) aryl, (C ４ -C ５０ ) heteroaryl, Si(R Ｃ ) ３ , and Ge(R Ｃ ) ３ is selected from R １ and R ２ are optionally covalently linked to form a ring structure; Each R ３ and each R ５ But independently, (C １ -C ５０ ) hydrocarbyl, (C １ -C ５０ ) heterohydrocarbyl, (C ６ -C ５０ ) aryl, (C ４ -C ５０ ) heteroaryl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ selected from NC(O)—, halogen, or —H; Each R ６ is independently selected from (C 6 -C 50 )aryl, or (C 4 -C 50 )heteroaryl; R ５ and R ６ are optionally covalently linked to form a six-membered aromatic ring structure; Each R in formula (I) Ｃ , R P and R Ｎ But independently, (C １ -C ５０ ) hydrocarbyl catalyst system.

2. Each X is independently selected from the group consisting of (C ６ -C ２０ ) aryl, (C ４ -C ２０ ) heteroaryl, (C ４ -C １２ ) a diene, or a halogen; Each R ６ are independently (C 6 -C 50 )aryl or (C ４ -C ５０ 2. The catalyst system of claim 1, wherein the heteroaryl is selected from the group consisting of:

3. R ５ and R ６ 10. The catalyst system of claim 1, wherein:

4. R ５ and R ６ are covalently bonded to form a six-membered aromatic ring, and R ３ is -H, and R ２ 2. The catalyst system of claim 1, wherein is methyl.

5. Each R ６ 2. The catalyst system of claim 1, wherein is anthracenyl, disubstituted anthracenyl, or trisubstituted anthracenyl.

6. Each R ６ 10. The catalyst system of claim 1, wherein is phenyl or substituted phenyl.

7. Each R ６ 2. The catalyst system of claim 1, wherein is a substituted phenyl selected from 2,4,6-trimethylphenyl, 2,6-di(iso-propyl)phenyl, 3,5-di-tert-butylphenyl, or 3,5-diphenylphenyl.

8. m is 2 and the metal-ligand complex has a structure according to formula (II); 【Chemistry 2】 In the formula, M, T, R １ , R ２ , R ３ , R ４ , R ５ , R ６ 2. The catalyst system of claim 1, wherein X is as defined in formula (I), n is 1 or 2, and the dotted line indicates an optional covalent bond.

9. Each X is independently selected from the group consisting of (C ６ -C ５０ ) aryl, (C ６ -C ５０ ) heteroaryl, (C ４ -C １２ ) a diene, or a halogen; 9. The catalyst system of claim 8, wherein each R 1 is independently selected from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, or halogen, and each R 2 is independently selected from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, or (C 4 -C 50 )heteroaryl.

10. The two R １ are covalently bonded to each other, and each R ２ But independently (C １ -C １０ 9. The catalyst system of claim 8, wherein the alkyl is .

11. The two R １ But -CH ２ CH ２ -, -CH ２ CH ２ CH ２ - or -CH ２ CH ２ CH ２ CH ２ 3. The catalyst system of claim 1, wherein the alkylene is covalently attached as an alkylene selected from:

12. m is 2 and the metal-ligand complex has a structure according to formula (III); 【Chemistry 3】 In the formula, M, T, R ３ , R ４ , R ５ , R ６ 2. The catalyst system of claim 1, wherein X is as defined in formula (I), n is 1 or 2, and the dotted line indicates an optional covalent bond.

13. Each R ６ 13. The catalyst system of claim 12, wherein is independently selected from carbazolyl, 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, or 3,5-di-iso-propylphenyl.

14. Each R ６ 13. The catalyst system of claim 12, wherein is 2,6-di-iso-propylphenyl.

15. Each R ６ 13. The catalyst system of claim 12, wherein is 2,4,6-trimethylphenyl.

16. 2. The catalyst system of claim 1, wherein T is N.

17. T is CR ４ and R ４ The catalyst system of claim 1, wherein is —H.

18. 1. A polymerization process for producing an ethylene-based polymer, comprising:

10. A polymerization process comprising polymerizing ethylene and at least one additional α-olefin and at least one activator in the presence of the catalyst system of claim 1 to form a polymer.

19. 20. The polymerization process of claim 18, wherein the activator comprises MMAO, bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate, or tris(pentafluorophenyl)borane.

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