Pro-catalyst and polymerization process

Abstract

PRO-CATALYST, AND POLYMERIZATION PROCESS. The present invention relates to polymerization processes of olefinic monomers using catalyst systems, and catalyst systems that include a pro-catalyst having a structure according to formula (I):

Description

Pro-catalyst and polymerization process REFERENCE TO RELATED DEPOSIT REQUESTS

[0001] This application claims priority from US Provisional Patent Application No. 63 / 002,767, filed March 31, 2020, the entire disclosure of which is incorporated herein by reference. TECHNICAL FIELD

[0002] The embodiments of the present disclosure generally relate to processes and catalyst systems for the polymerization of ethylene and polar comonomer, and, more specifically, to catalyst systems for the copolymerization of ethylene and acrylate that include sterically hindered nickel(II) catalysts supported on phosphino-urea and to olefin polymerization processes that incorporate such catalyst systems. BACKGROUND

[0003] Commercially, ethylene / acrylate copolymers are formed by high-pressure and / or high-temperature radical processes and have a highly branched microstructure similar to that of low-density polyethylene (LDPE). Coordination catalysis provides routes to highly linear ethylene / acrylate copolymers with structures similar to that of linear low-density polyethylene (LLDPE). Linear ethylene / acrylate copolymers formed by coordination catalysis exhibit higher crystallinity and higher thermal resistance than those of copolymers formed through radical processes.

[0004] Common organometallic coordination catalysts suitable for ethylene polymerization are not compatible with systems that include acrylates as comonomers. For example, Group IV metal catalysts (Ti, Zr, Hf) used in the industrial manufacture of LLDPE (ethylene / α-olefin copolymers) are not compatible with polar olefinic monomers, which include acrylates. Because the oxygen atoms of acrylates coordinate strongly with Group IV Lewis acid metals, during ethylene / acrylate polymerization, the active site of the metal Petition 870240103366, dated 04 / 12 / 2024, page 12 / 143 2 / 60 becomes blocked by the acrylate, and further olefin polymerization is prevented.

[0005] Due to the incompatibility of Group IV metal catalysts with acrylates, electron-rich metal catalysts containing Group 10 metals (Pd, Ni) have been explored in the copolymerization reactions of ethylene with acrylate monomers. However, many reported Ni- and Pd-containing metal catalysts have a) low polymerization rates and / or b) low incorporation of the polar monomers of interest. SUMMARY

[0006] There is an ongoing need to create a novel linker structure for Ni and Pd catalysts that promotes both high ethylene copolymerization activity rates and high incorporation of the acrylate comonomer. With a novel linker structure for nickel or palladium, ethylene and polar monomers can be copolymerized via coordination catalysis to form a highly linear copolymer, similar to LLDPE. Highly linear copolymers can exhibit improved creep resistance and dimensional stability at higher application temperatures, specifically from 80 °C to 150 °C, as opposed to temperatures lower than 80 °C.

[0007] The embodiments of this disclosure include catalytic systems. Catalytic systems include a pro-catalyst having a structure according to formula (I): Y \ zxMR1 X / ^-R4 (I)'N^N R3 R2

[0008] In the formula, M is nickel(II) or palladium(II); X is a ligand chosen from hydrocarbyl(C1-C40), heterohydrocarbyl(C1-C40), -CH2Si(RC)3-Q(ORC)Q, -Si(Rc)3-q(ORc)q, -OSi(Rc)3-q(ORc)q, -Ge(RC)3-Q(ORC)Q, -P(Rc)2-w(ORc)w, -P(O)(RC)2-W(ORC)W, -N(RC)2, -N(Si(RC)3)2, -NRCSi(RC)3, -ORC, -SRC, -NO2, Petition 870240103366, dated 04 / 12 / 2024, page 13 / 143 3 / 60 -CN, -CF3, -OCF3, -S(O)Rc, -S(O)2Rc, -OS(O)2Rc, -N=C(Rc)2, -N=CH(Rc), -N=CH2, -N=P(Rc)3, -OC(O)Rc, -C(O)ORc, -C(O)Rc, -C(O)H, -N(Rc)C(O)Rc, -N(Rc)C(O)H, -NHC(O)Rc, -NHC(O)H, -C(O)N(Rc)2, C(O)NHRc, -C(O)NH2, a halogen or a hydrogen. Each Rc, in formula (I), is independently a hydrocarbyl (C1-C30) optionally substituted with one or more Rs or a heterohydrocarbyl (C1-C30) optionally substituted with one or more Rs. The subscript Q in various ligands X is 0, 1, 2, or 3. The subscript W in various ligands X is 0, 1, or 2. Y is a Lewis base. Optionally, Y and X are covalently connected.

[0009] In formula (I), R1 and R2 are chosen from aryl (C6-C40) or heteroaryl (C1-C40), either of which may optionally be replaced with one or more Rs. R3 and R4 are selected independently from radicals having formula (II): R13r^J^r12 IX (II) r15^

[0010] In formula (II), R11, R12, R13, R14, and R15 are independently hydrocarbyl(C1-C30), heterohydrocarbyl(C1-C30), -ORn, -NRn2, -SRn, halogen, or -H, provided that at least one of R11 and R15 is not -H.

[0011] In formula (I), each Rs in formula (I) is independently a hydrocarbyl (C1-C20) or a halogen.

[0012] The embodiments of this disclosure include a polymerization process. The polymerization process of this disclosure includes polymerizing ethylene and one or more polar monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based copolymer. The catalyst system includes a metal-ligand complex according to formula (I) of this disclosure. detailed description

[0013] Specific system modalities will now be described. Petition 870240103366, dated 04 / 12 / 2024, page 14 / 143 4 / 60 catalysts. It should be understood that the catalyst systems in this disclosure may be represented as embodiments in different forms and should not be interpreted as limited to the specific embodiments presented in this disclosure. Instead, the embodiments are provided so that this disclosure is detailed and complete and fully conveys the scope of the subject to those skilled in the art.

[0014] Common abbreviations are listed below: Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; i-Pr: isopropyl; t-Bu: tert-butyl; tOct: tert-octyl(2,4,4-trimethylpentan-2-yl); THF: tetrahydrofuran; Et2O: diethyl ether; CH2Cl2: dichloromethane; EtOAc: ethyl acetate; C6D6: deuterated benzene or benzene-06; CDCl3: deuterated chloroform; Na2SO4: sodium sulfate; 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: millimoles; mL: milliliters; M: molar; min or mins: minutes; h or hrs: hours; d: days; Rf: retention factor; TLC: thin-layer chromatography; rpm: revolutions per minute.

[0015] The term independently selected followed by multiple options is used in this document to indicate that individual groups appearing before the term, such as R1, R2, R3, R4, and RC, may be identical or different, without dependence on the identity of any other group that also appears before the term.

[0016] The term pro-catalyst refers to a compound that has catalytic activity after activation, for example, after removal of the Lewis base coordinated with the Ni or Pd metal center.

[0017] When used to describe certain chemical groups containing carbon atoms, a parenthetical expression of the form (Cx-Cy) means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, including x and y. For example, Petition 870240103366, dated 04 / 12 / 2024, page 15 / 143 5 / 60 An alkyl (C1-C50) is an alkyl group having from 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted with one or more substituents, such as RS, where RS generically represents any substituent defined in this application. An RS-substituted version of a chemical group defined by the use of the parenthetical expression (Cx-Cy) may contain more than y carbon atoms depending on the identity of any RS groups. For example, an alkyl (C1-C50) substituted with exactly one RS group, where RS is phenyl (-C6H5), may contain from 7 to 56 carbon atoms.Thus, in general, when a chemical group defined using the parenthetical expression (Cx-Cy) is substituted with one or more RS substituents containing carbon atoms, the minimum and maximum total number of carbon atoms in the chemical group will be determined by adding to both x and y, respectively, the combined sum of the number of carbon atoms of all RS substituents containing carbon atoms.

[0018] The term substitution means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding functional group or unsubstituted compound is replaced with a substituent (e.g., RS). The term persubstitution or persubstituted means that each hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding functional group or unsubstituted compound is replaced with a substituent (e.g., RS). Thus, a perfluorinated alkyl is an alkyl group in which each hydrogen atom is replaced with a fluorine atom. The term polysubstitution means that at least two, but less than all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding functional group or unsubstituted compound are replaced by a substituent. The term -H means a hydrogen or hydrogen radical that is covalently bonded to another atom.Hydrogen and -H are interchangeable and, unless clearly specified, have identical meanings. Petition 870240103366, dated 04 / 12 / 2024, page 16 / 143 6 / 60

[0019] The term hydrocarbyl(C1-C50) means a hydrocarbon radical of 1 to 50 carbon atoms, and the term hydrocarbylene(C1-C50) means a hydrocarbon diradical of 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, linear or branched chain, cyclic (having three or more carbons, and including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and substituted with one or more RS or unsubstituted.

[0020] In this disclosure, a hydrocarbyl (C1--C50), without limitation, includes unsubstituted or substituted forms of the following groups: alkyl (C1-C50), cycloalkyl (C3-C50), cycloalkyl (C3-C20)-alkylene (C1-C20), aryl (C6-C40), or aryl (C6-C20)-alkylene (C1-C20) (such as benzyl (-CH2-C6H5)).

[0021] The terms (C1-C50) alkyl and (C1-C18) alkyl mean a linear or branched saturated hydrocarbon radical of 1 to 50 carbon atoms and a linear or branched saturated hydrocarbon radical of 1 to 18 carbon atoms, respectively, that is unsubstituted or substituted with one or more RS. The radical may be on any carbon atom of the alkyl. Examples of unsubstituted (C1-C50) alkyl are unsubstituted (C1-C20) alkyl; unsubstituted (C1-C10) 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. Examples of substituted (C1-C40) alkyl are substituted (C1-C20) alkyl, substituted (C1-C10) alkyl, trifluoromethyl, and [C45] alkyl. The term [Cn] alkyl means that the radical, including substituents, contains up to a maximum of n carbon atoms, where n is an integer from 1 to 45.For example, a [C45] alkyl is, for instance, a (C27-C40) alkyl substituted with an RS group, which is a (C1-C5) alkyl, or it is, for example, a (C15-C25) alkyl substituted with two RS groups, each of which is a (C1-C10) alkyl. Each (C1-C5) alkyl may include methyl, ethyl, 1-propyl, 1-methylethyl, 2,2-dimethylpropyl; or 1,1-dimethylethyl. 1,1-Dimethylethyl is a four-carbon alkyl that has its radical on the tertiary carbon. The term tertiary carbon atom refers to... Petition 870240103366, dated 04 / 12 / 2024, p. 17 / 143 7 / 60 a carbon atom that is covalently bonded to three other carbon atoms.

[0022] The term aryl(C6-C50) means an unsubstituted or substituted monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical (with one or more RS) of 6 to 40 carbon atoms, of which at least 6 to 14 of the carbon atoms are carbon atoms of the aromatic ring. A monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or unfused, and aromatic or non-aromatic.Examples of unsubstituted (C6-C50) aryl compounds include: unsubstituted (C6-C20) aryl compounds; unsubstituted (C6-C18) aryl compounds; 2-alkyl(C1-C5)-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexaindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; anthracenyl; and phenanthrenyl. Examples of substituted (C6-C40) aryl compounds include: substituted (C1-C20) aryl compounds; substituted (C6-C18) aryl compounds; 2,4-bis[alkyl(C20)]-phenyl; 3,5-bis[(alkylC20)]-phenyl. pentafluorophenyl; and fluoren-9-one-1-yl.

[0023] The term cycloalkyl(C3-C50) means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms that is unsubstituted or substituted with one or more RS. Other cycloalkyl groups (e.g., (cycloalkylCx-Cy)) are defined in an analogous manner as having x and y carbon atoms and being either unsubstituted or substituted with one or more RS. Examples of unsubstituted cycloalkyl(C3-C40) are unsubstituted cycloalkyl(C3-C20), unsubstituted cycloalkyl(C3-C10), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted cycloalkyl(C3-C40) groups are substituted cycloalkyl(C3-C20), substituted cycloalkyl(C3-C10), cyclopentanonyl-2-yl, and 1-fluorocyclohexyl.

[0024] Examples of (C1-C50) hydrocarbylenes include, without limitation, Petition 870240103366, dated 04 / 12 / 2024, p. 18 / 143 8 / 60 unsubstituted or substituted forms of groups such as arylene(C6-C50), cycloalkylene(C3-C50), and alkylene(C1-C50) (e.g., alkylene(C1-C20)). Diradicals may be on the same carbon atom (e.g., ±CH2±) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are spaced separately by one, two, or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-diradicals, 1,3-diradicals, 1,4-diradicals, or an α,ω diradical, and others, a 1,2-diradical. The α,ω-diradical is a diradical that has maximum backbone carbon spacing between the carbons of the radical. Some examples of α,ω-alkylene diradicals (C2-C20) include etan-1,2di-yl (i.e. -CH2CH2-), propan-1,3-di-yl (i.e. -CH2CH2CH2-), 2methylpropan-1,3-di-yl (i.e. -CH2CH(CH3)CH2-). Some examples of α,ωarylene diradicals (C6-C50) include phenyl-1,4-diyl, naphthalen-2,6-diyl, or naphthalen-3,7-diyl.

[0025] The term (C1-C50) alkylene means a saturated linear or branched chain diradical (i.e., the radicals are not on the ring atoms) of 1 to 50 carbon atoms that is unsubstituted or substituted with one or more RS. Examples of unsubstituted (C1-C50) alkylenes are unsubstituted (C1-C20) alkylenes, including ±CH2CH2±, ±(CH2)3±, ±(CH2)4±, ±(CH2)5±, ±(CH2)6±, ±(CH2)7±, ±(CH2)8±, ±CH2C*HCH3, and ±(CH2)4C*(H)(CH3), where C* denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1-C50) alkylenes are substituted (C1-C20) alkylenes, ±CF2±, ±C(O)±, and ±(CH2)i4C(CH3)2(CH2)5± (i.e., a 6,6-dimethyl-substituted 1,20-eicosylene). Examples of substituted (C1-C50) alkylenes also include 1,2-cyclopentanediylbis(methylene), 1,2-cyclohexanediylbis(methylene), 7,7-dimethylbicyclo[2.2.1]heptane-2,3-diylbis(methylene), and bicyclo[2.2.2]octane-2,3-diylbis(methylene).

[0026] The term cycloalkylene(C3-C50) means a cyclic radical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms that is unsubstituted or substituted with one or more RS. Petition 870240103366, dated 04 / 12 / 2024, p. 19 / 143 9 / 60

[0027] 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(RC)2-, -P(RP)-, -P(Rp)2, -P(O)(Rp)2, -N(Rn)-, -N(Rn)2, -N=C(Rc)2, -N=C(NRN2)(Rc), -Ge(RC)2-, or -Si(RC)3, where each Rc and each Rp is an unsubstituted hydrocarbyl (C1-C18) or -H, and where each RN is an unsubstituted hydrocarbyl (C1-C18). The term heterohydrocarbon refers to a molecule or molecular structure in which one or more carbon atoms of a hydrocarbon are substituted by a heteroatom. The term heterohydrocarbyl (C1-C50) means a heterohydrocarbon radical of 1 to 50 carbon atoms, and the term heterohydrocarbylene (C1-C50) means a heterohydrocarbon diradical of 1 to 50 carbon atoms. The heterohydrocarbon of heterohydrocarbyl (C1-C50) or heterohydrocarbylene (C1-C50) has one or more heteroatoms.The heterohydrocarbyl radical can be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene can be on a single carbon atom or a single heteroatom. Additionally, one of the two radicals of the diradical can be on a carbon atom, and the other radical can be on a different carbon atom; one of the two radicals can be on a carbon atom, and the other on a heteroatom; or one of the two radicals can be on a heteroatom, and the other radical on a different heteroatom. Each heterohydrocarbyl (C1-C50) and heterohydrocarbylene (C1-C50) can be unsubstituted or substituted (with one or more Rs), aromatic or non-aromatic, saturated or unsaturated, linear or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic), or acyclic.

[0028] The C1-C50 heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of C1-C50 heterohydrocarbyl include C1-C50 heteroalkyl, C1-C50 hydrocarbyl-O-, C1-C50 hydrocarbyl-S-, C1-C50 hydrocarbyl-S(O)±, C1-C50 hydrocarbyl-S(O)²±, C1-C50 hydrocarbyl-Si(RC)²±, C1-C50 hydrocarbyl-N(RN)±, C-C50 hydrocarbyl-P(RP)±, C2-C50 heterocycloalkyl, C2-C19 heterocycloalkyl-C1-C20 alkylene, Petition 870240103366, dated 04 / 12 / 2024, page 20 / 143 10 / 60 cycloalkyl(C3-C2o)-heteroalkylene(C1-C19), heterocycloalkyl(C2-C19)heteroalkylene(C1-C20), heteroaryl(C1-C50), heteroaryl(C1-C19)alkylene(C1-C20), aryl(C6-C20)-heteroalkylene(C1-C19) or heteroaryl(C1-C19)-heteroalkylene(C1-C20). Additional examples include, but are not limited to, -Si(Rc)3-q(ORc)q, -OSi(Rc)3-q(ORc)q, -Ge(RC)3-Q(ORC)Q, -P(Rc)2-w(ORc)w, -P(O)(Rc)2-w(ORc)w, -N(Rc)2, -NH(Rc)2, -orc, -src, -NO2, -CN, -CF3, -OCF3, -S(O)Rc, -S(O)2RC, -OS(O)2RC, -N=C(Rc)2, -N=P(Rc)3, -OC(O)Rc, -C(O)Rc, -C(O)ORc, -N(Rc)C(O)Rc, and -C(O)N(Rc)2.

[0029] The term heteroaryl (C4-C50) means an unsubstituted or substituted monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical (with one or more RS) having a total of 1 to 50 carbon atoms and 1 to 10 heteroatoms. The heterohydrocarbyl radical may be on a single carbon atom or a heteroatom. A monocyclic heteroaromatic hydrocarbon radical includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may be independently fused or unfused, and aromatic or non-aromatic.Other heteroaryl groups (e.g., heteroaryl(Cx-Cy), generally, as heteroaryl(C4-C12)) are defined in an analogous manner as having x and a carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted with one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is either a 5-membered ring or a 6-membered ring. The 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 independently be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals are pyrrole-1-yl; pyrrole-2-yl; furan-3-yl; thiophen-2-yl; pyrazole-1-yl; isoxazole-2-yl; isothiazole-5-yl; imidazole-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazole-2. Petition 870240103366, dated 04 / 12 / 2024, p. 21 / 143 11 / 60 yl; and tetrazol-5-yl. The 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 are pyridine-2-yl; pyrimidin-2-yl; pyrazin-2-yl; 1,3,5-thiadiazole-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a 5,6- or 6,6-fused ring system. Examples of bicyclic heteroaromatic hydrocarbon radicals with a 5,6-fused ring system are indole-1-yl; and benzimidazole-1-yl. Examples of bicyclic heteroaromatic hydrocarbon radicals with a 6,6-fused ring system are quinolin-2-yl; and isoquinolin-1-yl. The bicyclic heteroaromatic hydrocarbon radical can be a 5,6,5; -5,6,6; -6,5,6; or -6,6,6 fused ring system. An example of the 5,6,5 fused ring system is 1,7-dihydropyrrole[3,2-f]indol-1-yl. An example of the 5,6,6 fused 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 acridin-9-yl.

[0030] The term heteroalkylene(C1-C50) means a saturated linear or branched chain diradical containing from 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of heteroalkyls or heteroalkylenes may include, but are not limited to, Si(RC)3, Ge(RC)3, Si(RC)2, Ge(RC)2, P(Rp)2, P(Rp), P(O)(Rp)2, N(Rn)2, N(Rn), N, O, ORC, S, SRC, S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or substituted with one or more RS.

[0031] Examples of unsubstituted (C2-C40) heterocycloalkyl include unsubstituted (C2-C20) heterocycloalkyl, unsubstituted (C2-C10) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0032] The term halogen atom or halogen means the radical of a fluorine (F) atom, chlorine (Cl) atom, bromine (Br) atom, or atom of Petition 870240103366, dated 04 / 12 / 2024, p. 22 / 143 12 / 60 Iodine (I). The term halide means the anionic form of the halogen atom: fluoride (F-), chloride (Cl-), bromide (Br-), or iodide (I-).

[0033] The term saturated means that it does not contain carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, and carbon-silicon double bonds. When a saturated chemical group is substituted with one or more RS substituents, one or more double bonds and / or triple bonds may or may not be present in the RS substituents. The term unsaturated means that it contains one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in groups containing heteroatoms) one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds, not including double bonds that may be present in the RS substituents, if any, or in (hetero)aromatic rings, if any.

[0034] The embodiments of this disclosure include catalytic systems. The catalytic system includes a pro-catalyst that has a structure according to formula (I): Y \ / xm Ri A / V(I)'NN R3 R2

[0035] In formula (I), M is nickel(II); or Pd (II); X is a ligand chosen from hydrocarbyl(C1-C40), heterohydrocarbyl(C1-C40), -CH2Si(RC)3-Q(ORC)Q, -Si(Rc)3-q(ORc)q, -OSi(Rc)3-q(ORc)q, -Ge(RC)3-Q(ORC)Q, -P(Rc)2-w(ORc)w, -P(O)(Rc)2-w(ORc)w, -N(Rc)2, -N(Si(Rc)3)2, -NRcSi(Rc)3, -ORc, -SRc, -NO2, -CN, -CF3, -OCF3, -S(O)Rc, -S(O)2Rc, -OS(O)2Rc, -N=C(Rc)2, -N=CH(Rc), -N=CH2, -N=P(Rc)3, -OC(O)Rc, -C(O)ORc, -C(O)Rc, -C(O)H, -N(Rc)C(O)Rc, -N(RC)C(O)H, -NHC(O)RC, -NHC(O)H, -C(O)N(RC)2, -C(O)NHRC, -C(O)NH2, a halogen or a hydrogen, wherein each RC is independently a hydrocarbyl (C1-C30) optionally substituted with one or more RS or a heterohydrocarbyl (C1-C30) optionally substituted with one or more RS, wherein the Petition 870240103366, dated 04 / 12 / 2024, p. 23 / 143 13 / 60 subscript Q is 0, 1, 2, or 3; where subscript W is 0, 1, or 2. Y is a Lewis basis; and optionally, Y and X are covalently connected.

[0036] In one or more embodiments, R1 and R2 are chosen from aryl(C6-C40), heteroaryl(C1-C40), and are optionally replaced with one or more RS.

[0037] In the modalities, R3 and R4 are independently selected from radicals that have the formula (II): R13 R'; _ R'2 IT (II) r15 ^

[0038] In formula (II), R11, R12, R13, R14, and R15 are independently hydrocarbyl(C1-C30), heterohydrocarbyl(C1-C30), -ORN, -NRn2, or -SRN, where Rn is hydrocarbyl(C1-C30), provided that at least one of R11 and R15 is not -H.

[0039] In one or more embodiments, in formula (I), R1 and R2 are identical. In one or more embodiments, in formula (I), R3 and R4 are identical.

[0040] In several embodiments, in formula (I), R11 and R15 are independently -O[C1-C10 alkyl]. In some embodiments, R11 and R15 are methoxyl or ethoxyl. In other embodiments, R11 and R15 are independently -N[C1-C10 alkyl]2.

[0041] In one or more embodiments, R1 and R2 are aryl (C6-C40) substituted with at least one RS, where each RS is independently hydrocarbyl (C1-C30), -CF3, or halogen atom. In some embodiments, R1 and R2 are independently phenyl, 3,5-bis(trifluoromethyl)phenyl, or 3,5-di-tert-butylphenyl.

[0042] In several embodiments, R1 and R2 are connected and the procatalyst has the structure according to formula (III): Petition 870240103366, dated 04 / 12 / 2024, p. 24 / 143 14 / 60 is independently chosen from -H, hydrocarbyl(C1-C40), heterohydrocarbyl(C1-C40), -Si(RR)3, -Ge(RR)3, -P(Rr)2, -P(O)(RR)2, -N(Rr)2, -ORr, -SRr, -NO2j-CN, -CF3, or halogen, where each RR is hydrocarbyl(C1-C30), heterohydrocarbyl(C1-C30), or -H; and M, Y, X, R3, and R4 are as defined in formula (I).

[0044] In several embodiments, in formula (III), R22 and R27 are independently aryl (C6-C40) optionally substituted with Rs, where Rs is hydrocarbyl (C1-C30), -CF3, or halogen atom. In some embodiments, R22 and R27 are independently 3,5-bis(trifluoromethyl)phenyl or 3,5-di-tert-butylphenyl. In other embodiments, R22 and R27 are independently alkyl (C1-C20).

[0045] In one or more embodiments, R23 and R26 are independently aryl (C6-C40) optionally substituted with Rs, where Rs is hydrocarbyl (C1-C30), -CF3, or a halogen atom. In some embodiments, R23 and R26 are independently alkyl (C1-C20). In other embodiments, R23 and R26 are -CF3. In several embodiments, all of R21-28 (i.e., R21, R22, R23, R24, R25, R26, R27, and R28) are -H.

[0046] Each Rc in formula (I) is independently a hydrocarbyl (C1-C30), heterohydrocarbyl (C1-C30), or -H; and each Rs in formula (I) is independently a hydrocarbyl (C1-C20) or halogen.

[0047] In the metal-ligand complex according to formula (I), each Y is linked to M through a dative bond or an ionic bond. In one or more embodiments, Y is a Lewis base. The Lewis base can be a compound or an ionic species, provided that the compound or ionic species Petition 870240103366, dated 04 / 12 / 2024, p. 25 / 143 15 / 60 can donate an electron pair to an acceptor moiety. For the purposes of this description, the acceptor moiety is M, the metal of the metal-ligand complex of formula (I). In some embodiments, Y is a Lewis base that is a neutral heterohydrocarbon or a neutral hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. Examples of neutral hydrocarbon Lewis bases include, but are not limited to, alkenes, alkynes, or arenes.

[0048] In one or more embodiments, Y is a neutral Lewis basic aprotic heterohydrocarbon (C2-C40). Aprotic (C2-C40) heterohydrocarbons are (C2-C40) heterohydrocarbons as previously defined, for which each hydrogen atom of the (C2-C40) heterohydrocarbon has a pKa greater than 30, where pKa is the negative logarithm to base 10 of the acid dissociation constant (Ka). In some embodiments, Y is an organic Lewis base. Examples of organic Lewis bases include pyridine, or a substituted pyridine, a sulfoxide, a trialkylphosphine or triarylphosphine, an oxide of trialkylphosphine or triarylphosphine, an olefin or cyclic olefin, a substituted or unsubstituted heterocycle, an alkyl ester of an aliphatic or aromatic carboxylic acid, an aliphatic ketone, an aliphatic amine, an alkyl or cycloalkyl ether, or mixtures thereof, each electron donor having from 2 to 20 carbon atoms.In various embodiments, the organic Lewis base is selected from alkyl and cycloalkyl ethers having from 2 to 20 carbon atoms; and dialkyl, diaryl, and alkylaryl ketones having from 3 to 20 carbon atoms; and alkyl esters having from 2 to 20 carbon atoms. Specific examples of an organic Lewis base include, but are not limited to: methyl formate, ethyl acetate, butyl acetate, ethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethyl formate, dimethylformamide, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, tetrahydrofuran, ethyl propionate, lutidine, picolin, dimethyl sulfoxide, trimethylphosphine, triethylphosphine, triphenylphosphine, cyclooctadiene, cyclopentene, ethylene. Petition 870240103366, dated 04 / 12 / 2024, page 26 / 143 16 / 60 propylene, tert-butylethylene, trimethylamine, tributylamine, N,N-dimethylaniline, 1methylimidazole, or 1-methylpyrazole.

[0049] In one or more embodiments, the Lewis base group Y of formula (I) may be a monodentate ligand that may be a neutral ligand. In some embodiments, the neutral ligand may contain a heteroatom. In specific embodiments, Y is a neutral ligand that is a neutral group, such as RTNRKRL, RKORL, RKSRL, or RTPRKRL, where each RT, RK, and RL are independently [hydrocarbyl(C1-C10)]3Si-hydrocarbyl(C1-C10), hydrocarbyl(C1-C40), [hydrocarbyl(C1-C10)]3Si, heterohydrocarbyl(C1-C40), or hydrogen.

[0050] In some embodiments, the Lewis base group Y of formula (I) is a hydrocarbon (C1-C20). In some embodiments, the Lewis base group Y is cyclopentadiene, 1,3-butadiene, or cyclooctene.

[0051] In several embodiments, the Lewis base group Y of formula (I) is a heterohydrocarbon (C1-C20), wherein the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, Y is tetrahydrofuran, pyrene, dioxane, diethyl ether, or methyl tert-butyl ether (MTBE).

[0052] In several embodiments, the Lewis base is a heterohydrocarbon (C1-C20), in which the heteroatom of the heterohydrocarbon is nitrogen. In some embodiments, Y is pyridine, picoline, lutidine, trimethylamine, or triethylamine.

[0053] In several embodiments, the Lewis base is a heterohydrocarbon (C1-C20), in which the heteroatom of the heterohydrocarbon is phosphorus. In some embodiments, Y is trimethylphosphine, triethylphosphine, triphenylphosphine, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, or triphenylphosphine oxide.

[0054] In some embodiments, X and Y are covalently linked. Specific examples of an organic Lewis base Y covalently linked together with a group X include, but are not limited to: 4-cycloocten-1-yl, 2-dimethylaminobenzyl, and 2-dimethylaminomethylphenyl.

[0055] In some modes, X and Y are connected and selected Petition 870240103366, dated 04 / 12 / 2024, p. 27 / 143 17 / 60 of the group consisting of: where RC is -H or hydrocarbyl (C1-C30), heterohydrocarbyl (C1-C30, alkyl (C1-C20), or alkyl (C1-C12).

[0056] In the metal-ligand complex according to formula (I), each X is linked to M through a covalent bond, or an ionic bond. In some embodiments, X may be a monoanionic ligand having a net formal oxidation state equal to -1. Each monoanionic ligand can independently be a hydride, hydrocarbyl(C1-C40) carbanion, heterohydrocarbyl(C1-C40) carbanion, halide, nitrate, hydrogen carbonate, dihydrogen phosphate, hydrogen sulfate, HC(O)O-, HC(O)N(H)-, hydrocarbyl(C1-C40)C(O)O-, hydrocarbyl(C1-C40)C(O)N(hydrocarbyl(C1-C20))-, hydrocarbyl(C1-C40)C(O)N(H)-, RKRLB-, RKRLN-, RKO-, RKS-, RKRLP-, or RMRKRLSi-, where each RK, RL, and RM is independently hydrogen, hydrocarbyl(C1-C40), or heterohydrocarbyl(C1-C40), or RKe RL are considered together to form a hydrocarbylene (C2-C40) or heterohydrocarbylene (C1-C20), and RM is as defined above.

[0057] In some embodiments, X is a halogen, hydrocarbyl (C1-C20), heterohydrocarbyl (C1-C20), unsubstituted hydrocarbyl (C1-C20)C(O)O-, or RKRLN-, wherein each of RK and RL is independently an unsubstituted hydrocarbyl (C1-C20). In some embodiments, each monodentate ligand X is a chlorine atom, hydrocarbyl (C1-C10) (e.g., alkyl (C1-C6) or benzyl), unsubstituted hydrocarbyl (C1-C10)C(O)O-, or RKRLN-, wherein each of RK and RL is independently an unsubstituted hydrocarbyl (C1-C10).

[0058] In additional embodiments, X is selected from methyl; ethyl; 1 Petition 870240103366, dated 04 / 12 / 2024, page 28 / 143 18 / 60 propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; dimethylphenylsilylmethyl; methyldiphenylsilylmethyl; triphenylsilylmethyl; benzyldimethylsilylmethyl; trimethylsilylmethyldimethylsilylmethyl; phenyl; benzyl; or chlorine.

[0059] In one or more embodiments, each X is independently (CH2)SiRX3, wherein each RX is independently an alkyl(C1-C30) or a heteroalkyl(C1-C30), and at least one RX is alkyl(C1-C30). In some embodiments, when one of the RX is a heteroalkyl(C1-C30), the heteroatom is a silicon atom or an oxygen atom. In some embodiments, RX is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0060] In one or more embodiments -(CH2)Si(CH3)(CH2CH3)2, — (CH2)Si(CH2CH3)3, -(CH2)Si(CH3)2(n-butyl), -(CH2)Si(CH3)2(n-hexyl), _(CH2)Si(CH3)(n-oct)RX, -(CH2)Si(CH3)2RX, -(CH2)Si(n-oct)RX2, _(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), or -CH2Si(CH3)2CH2Si(CH3)3 (in this document referred to as -CH2Si(CH3)2(CH2TMS). Optionally, in some embodiments, in the metal-ligand complex according to formula (I), exactly two RX are covalently bonded, or exactly three RX are covalently bonded.

[0061] In some embodiments, X is -CH2Si(Rc)3-q(ORc)q, -Si(RC)3q(ORc)q, -OSi(Rc)3-q(ORc)q, where the subscript Q is 0, 1, 2 or 3, and each RC is independently a substituted or unsubstituted hydrocarbyl (C1-C30), or a substituted or unsubstituted heterohydrocarbyl (C1-C30). In some embodiments, X is -CH2Si(CH3)3; In other embodiments, X is -CH2Si(CH3)2OSi(CH3)3

[0062] In some embodiments, any or all of the chemical groups of the pro-catalysts of formula (I) may be unsubstituted, except for either R11 or R15. At least one of R11 and R15 is substituted. In other embodiments, none, any, or all of the chemical groups X and Petition 870240103366, dated 04 / 12 / 2024, p. 29 / 143 19 / 60 R1-R4, R11-15, or R21-28 of the metal-ligand complex of formula (I) can be substituted with one or more RS. When two or more than two RS are attached to the same chemical group of the pro-catalysts of formula (I), the individual RS of the chemical group can be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, none, any, or all of the chemical groups X and R1-R4, R11-15, or R21-28 can be persubstituted with RS. In the chemical groups that are persubstituted with RS, the individual RS can all be the same, or they can be chosen independently.

[0063] The embodiments of this disclosure include polymerization processes. In some embodiments, the polymerization process includes polymerizing ethylene with one or more olefinic monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based copolymer, wherein the catalyst system comprises a metal-ligand complex according to formula (I) as described in this disclosure.Olefinic monomers may include, but are not limited to, propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, styrene, cyclobutene, cyclopentene, norbornene, ethylidene-norbornene, alkyl acrylate, glycidyl acrylate, vinyl acetate, CH2=CHC(O)(ORx), CH2=CHC(O)Rx, CH2=CH(ORx), CH2=CH(CH2)(ORx), CH2=CHSi(Rx)3-y(ORx)y, CH2=CH-OSi(Rx)3-y(ORx)y, or CH2=CHCl, where RX is chosen from -H, a substituted or unsubstituted hydrocarbyl (C1-C30), or a substituted or unsubstituted heterohydrocarbyl (C1-C30), and the subscript Y is 0, 1, 2, or 3.

[0064] In some embodiments, the polymerization process includes polymerizing ethylene, one or more polar monomers, and optionally, one or more α-olefinic monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene / polar monomer copolymer, the catalyst system comprising a procatalyst according to formula (I) of this disclosure. In one or more embodiments, the polymerization processes include polymerizing ethylene, one or Petition 870240103366, dated 04 / 12 / 2024, page 30 / 143 20 / 60 plus alkyl acrylate monomers and, optionally, one or more α-olefinic monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene / alkyl acrylate copolymer, the catalyst system comprising a pro-catalyst according to formula (I) of this disclosure.

[0065] In one or more embodiments, the polymerization processes include polymerizing ethylene, one or more polar monomers, and optionally, one or more cyclic olefinic monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene / polar monomer copolymer, the catalyst system comprising a pro-catalyst according to formula (I) of this disclosure. Cyclic olefinic monomers are cyclic compounds containing ethylenic unsaturation in the cyclic part of the molecule. Examples of these include cyclobutene, cyclopentene, norbornene, and norbornene derivatives that are substituted at the 5-position and 6-position with hydrocarbyl (C1-C20).In one or more embodiments, the polymerization processes include polymerizing ethylene, one or more alkyl acrylate monomers, and optionally, one or more cyclic olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene / alkyl acrylate copolymer, the catalyst system comprising a pro-catalyst according to formula (I) of this disclosure.

[0066] In several embodiments of the polymerization processes, the polar comonomer includes alkyl acrylates (CH2=CHC(O)(OR)), glycidyl acrylate, CH2=CH(CH2)nC(O)(OR), CH2=CHC(O)R, CH2=CH(CH2)nC(O)R, CH2=CH-OC(O)R, CH2=CH(CH2)n-OC(O)R, CH2=CH(OR), CH2=CH(CH2)n(OR), CH2=CHSi(R)3-t(OR)t, CH2=CH(CH2)nSi(R)3-T(OR)T, CH2=CH-OSi(R)3-t(OR)t, CH2=CH(CH2)n-OSi(R)3-T(OR)T or CH2=CHCl. ​​Each R is chosen from -H, substituted hydrocarbyl (C1-C30), unsubstituted hydrocarbyl (C1-C30), substituted heterohydrocarbyl (C1-C30), or unsubstituted heterohydrocarbyl (C1-C30). The subscript T is 0, 1, 2, or 3. The subscript n is from 1 to 10. In embodiments where the polar monomer is an acrylate of Petition 870240103366, dated 04 / 12 / 2024, p. 31 / 143 21 / 60 alkyl, substituted hydrocarbyl (C1-C30) acrylate, unsubstituted hydrocarbyl (C1-C30) acrylate, substituted heterohydrocarbyl (C1-C30) acrylate, or unsubstituted heterohydrocarbyl (C1-C30) acrylate, the ethylene-based polar copolymer can be de-esterified to form an acrylic acid-ethylene-based copolymer.

[0067] In some embodiments of the polymerization process, the polar monomer may be an alkyl acrylate such as, by way of example and not limitation, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, or combinations thereof. In several embodiments, the alkyl acrylate is a C1-C8 alkyl acrylate, which is an alkyl ester of acrylic acid, in which the alkyl group has from 1 to 8 carbon atoms. In particular embodiments, the polar comonomer is an alkyl acrylate chosen from t-butyl acrylate or n-butyl acrylate.

[0068] In some embodiments of the polymerization process, the optional α-olefinic monomer may be, by way of example and not limitation, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, styrene, or combinations thereof. In one or more embodiments of the polymerization process, the process may include a cyclic olefin, such as cyclobutene, cyclopentene, norbornene, and norbornene derivatives that are substituted at the 5-position and 6-position with hydrocarbyl (C1-C20).

[0069] In illustrative embodiments, the catalyst systems may include a pro-catalyst according to formula (I) having the structure of Pro-catalysts 1 to 6, as listed below: Petition 870240103366, dated 04 / 12 / 2024, p. 32 / 143 22 / 60 Pro-catalyst 2 Pro-Catalyst 1 tBu Pro-catalyst 3 Pro-catalyst 4 Pro-catalyst 6 f3c where TMS is trimethylsilyl, Me is methyl, Et is ethyl, and tBu is t-butyl. Ethylene / acrylate copolymer

[0070] In several embodiments, the polymerization process of this disclosure can produce an ethylene-based polar copolymer, wherein the ethylene-based polar copolymer contains at least 50 percent by weight. Petition 870240103366, dated 04 / 12 / 2024, page 33 / 143 23 / 60 (weight percent) of ethylene based on the weight of the ethylene-based polar copolymer. In some embodiments, the ethylene-based polar copolymer is the reaction product of 70% by weight to 99.9% by weight of ethylene units and 0.1% by weight to 30% by weight of polar comonomer units based on the sum of ethylene units and polar comonomer units.

[0071] In one or more embodiments, the polymerization process of this disclosure may include ethylene monomers, alkyl acrylate monomers, and optionally one or more α-olefins. In some embodiments of the polymerization process that includes α-olefins, the α-olefins may be incorporated into the polymers produced in amounts of 0.01 to 49.9% by weight based on the weight of the ethylene-based copolymer.

[0072] In several embodiments, the polymerization process of this disclosure can produce ethylene-based copolymer with a molecular weight of 2,000 g / mol to 1,000,000 g / mol. In some embodiments, the polymer produced has a molecular weight of 25,000 g / mol to 900,000 g / mol, 30,000 g / mol to 800,000 g / mol, or 10,000 g / mol to 300,000 g / mol. General procedure for screening experiments in PPR

[0073] Polyolefin catalysis screening was performed in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consisted of an array of 48 single-cell reactors (6 x 8 array) in an inert atmosphere glove box. Each cell was fitted with a glass insert (reactor tube) with an internal working liquid volume of approximately 5 mL. Each cell had independent pressure controls and was continuously stirred at 500 Hz. Catalyst, ligand, and metal precursor solutions, and optional activator solutions (if used), unless otherwise specified, were prepared in toluene. Unless otherwise specified, ligands were metallated at a 1:1 ligand:metal (L:M) ratio by premixing a metal precursor solution with a ligand solution. In many cases, the pro-catalyst complex resulting from the metallation reactions was isolated and purified before introduction into the PPR reactor.All liquids (i.e., solvent, acrylate of t. Petition 870240103366, dated 04 / 12 / 2024, page 34 / 143 24 / 60 butyl acrylate, and optional catalyst and activator solutions (if used) were added via robotic syringes. Gaseous reagents (i.e., ethylene) were added via a gas injection port. Before each run, the reactors were heated to 50 °C, purged with ethylene, and vented. The tert-butyl acrylate was filtered through a short activated alumina column before use to remove any polymerization inhibitors (e.g., 4-methoxyphenol).

[0074] All desired cells were injected with t-butyl acrylate followed by a portion of toluene. The reactors were heated to the operating temperature and then pressurized to the appropriate pressure with ethylene. Isolated pro-catalyst complexes or in situ metallized ligands and optional activator solutions (if used) were then added to the cells. Each catalyst addition was followed by a small amount of toluene so that after the final addition, a total reaction volume of 5 mL was achieved. After catalyst addition, the PPR software began monitoring the pressure of each cell. The desired pressure (within approximately 2 to 6 psig) was maintained by the supplemental addition of ethylene gas by opening the valve at the setpoint of minus 1 psi and closing it when the pressure reached 2 psi higher.All pressure drops were cumulatively recorded as ethylene absorption or conversion during the run or until the desired absorption or conversion value was reached, whichever occurred first. Each reaction was then deactivated by adding 1% oxygen to nitrogen for 30 seconds at 40 psi higher than the reactor pressure (the time elapsed from the start of the run until the point at which deactivation is initiated is the Deactivation Time). The shorter the Deactivation Time, the more active the catalyst. In order to avoid the formation of excess polymer in any given cell, the reaction was deactivated after reaching a predetermined absorption level of 80 psig. After all reactors were deactivated, they were allowed to cool to approximately 60 °C. They were then vented, and the reactor tubes were removed and placed in a centrifugal evaporator. Petition 870240103366, dated 04 / 12 / 2024, page 35 / 143 25 / 60 The polymer samples were then dried in a centrifugal evaporator at 60 °C for 12 hours, weighed to determine the polymer yield, and subjected to analysis by IR (t-butyl acrylate incorporation), GPC (molecular weight, polydispersity (PDI)), and DSC analysis (melting point). General procedure for experiments in a batch reactor

[0075] Note: Contact with tert-butyl acrylate should be minimized because acrylates are sensitizers, for example, by using a sealed discharge pot and a well-ventilated fume hood. Care should be taken when transferring the contents of the reactor to the discharge pot and while emptying the discharge pot in a fume hood.

[0076] The polymerization reactions are conducted in a 2 L Parr batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal coil cooling coil containing cooling water. The water has been pre-treated by passing it through an Evoqua water purification system. Both the reactor and the heating / cooling system are controlled and monitored by a Camille TG process computer. The bottom of the reactor is fitted with a discharge valve, which empties the reactor contents into a stainless steel discharge pot. The discharge pot is pre-loaded with a catalyst inactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The discharge pot is opened to a 15-gallon purge tank, with both the pot and the tank being purged with N2.All chemicals used for polymerization or catalyst composition were passed through purification columns to remove any impurities that could affect polymerization. Toluene was passed through two columns, the first containing alumina A2 and the second containing reagent Q5. tert-Butyl acrylate was filtered through activated alumina. Ethylene was passed through two columns, the first containing alumina A2O4 and 4 Å molecular sieves, the second containing reagent Q5. N2, used for transfers, was passed through one. Petition 870240103366, dated 04 / 12 / 2024, page 36 / 143 26 / 60 single column containing alumina A2O4, 4 Å molecular sieves, and reagent Q5.

[0077] The reactor was first charged from an injection tank containing toluene and tert-butyl acrylate. The injection tank was filled to the charge setpoints using a differential pressure transducer. After the addition of solvent / acrylate, the injection tank was washed twice with toluene, and the washes were also transferred to the reactor. The reactor was then heated to the desired polymerization temperature setpoint. After reaching the temperature setpoint, ethylene was added to the reactor to achieve the desired pressure setpoint. The amount of ethylene added to the reactor is monitored by a micro-motion flowmeter.

[0078] The pro-catalysts were handled in an inert atmosphere glove box and introduced into the reactor as solutions in toluene. The pro-catalyst solution is drawn into a syringe and transferred by pressure into the catalyst injection tank. The syringe is flushed three times with 5 mL of toluene. The pro-catalyst was added only after the reactor pressure setpoint had been reached.

[0079] Immediately after the addition of the pro-catalyst, the run timer started. Ethylene was then fed (via Camille control) into the reactor for the purpose of maintaining the pressure setpoint. The ethylene / tert-butyl acrylate copolymerization reactions were run for 75 minutes or until 40 g of ethylene was absorbed, whichever was sooner. The stirrer was then stopped and the bottom discharge valve was opened to empty the reactor contents into the capped discharge pot. The valves on the capped discharge pot were closed and the capped discharge pot was disconnected from the reactor and taken to a fume hood. Once in the fume hood, the lid was removed from the discharge pot and the contents were poured into trays. The trays were left in the hood for a minimum of 36 hours to allow the solvent and acrylate to... Petition 870240103366, dated 04 / 12 / 2024, page 37 / 143 27 / 60 tert-butyl and tert-butyl evaporated. The trays containing the remaining copolymer were then transferred to a vacuum oven, where they were heated to 140 °C under vacuum to remove any residual volatile materials. After the trays cooled to room temperature, the copolymers were weighed for yield / efficiencies and subjected to polymer testing if desired. GPC Procedure

[0080] High-temperature GPC analysis was performed using a Dow Robot Assisted Delivery (RAD) system equipped with a PolymerChar (IR5) infrared detector and Agilent PL-gel Mixed A columns. Decane (10 μL) was added to each sample for use as an internal flow marker. Samples were first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxytoluene (BHT) to a concentration of 10 mg / mL TCB and dissolved by stirring at 160 °C for 120 minutes. Before injection into the instrument, samples were further diluted with BHT-stabilized TCB to a concentration of 3 mg polymer / mL TCB. The samples (250 μL) are eluted through a PL-gel 20 pm (50 mm x 7.5 mm) guard column followed by two Mixed-A PL-gel 20 pm (300 mm x 7.5 mm) columns maintained at 160 °C with BHT-stabilized TCB at a flow rate of 1.0 mL / min. The total run time is 24 minutes.To calibrate the molecular weight (MW), Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 mL of BHT-stabilized TCB and dissolved by stirring at 160 °C for 15 minutes. These standards were analyzed to create a 3rd-order MW calibration curve. Molecular weight units were converted from polystyrene (PS) units to polyethylene (PE) units using a daily Q factor calculated to be approximately 0.4 using the average of 5 Dowlex 2045 reference samples. FT-IR procedure

[0081] The 10 mg / mL samples prepared for GPC analysis were also used to quantify the incorporation of tert-acrylate. Petition 870240103366, dated 04 / 12 / 2024, page 38 / 143 28 / 60 tert-butyl acrylate (tBA) was analyzed by Fourier transform infrared spectroscopy (FTIR). A Dow robotic preparation station heated and agitated the samples at 160 °C for 60 minutes, then deposited 130 pL portions into clean wells promoted on a silicon wafer. TCB was evaporated at 160 °C under nitrogen purge. IR spectra were collected using a Nexus 6700 FT-IR equipped with a 4000-400 cm⁻¹ KBr DTGS detector using 128 scans with a resolution of 4 cm⁻¹. The ratio between the peak area of ​​tBA (C=O: 1762-1704 cm-1) and the peak area of ​​ethylene (CH2: 736-709 cm-1) was calculated and fitted to a linear calibration curve to determine the total tBA. DSC Procedure

[0082] The melting temperature (Tm), glass transition temperature (Tg), crystallization temperature (Tc), and heat of fusion are measured in solid polymer samples by differential scanning calorimetry (DSC Q2000, TA Instruments, Inc.) using a heating-cooling-heating temperature profile. Open crucible DSC samples of 3 to 6 mg of polymer are subjected to the temperature profile below, and the traces were individually analyzed using TA Universal Analysis software or TA Instruments TRIOS software. Equilibrate at 175.00 °C Isothermal for 3 minutes Ramp from 30.00 °C / min to 0.00 °C Ramp of 10.00 °C / min to 175.00 °C Examples

[0083] Examples 1 to 17 are synthetic procedures for ligand intermediates and ligands. Examples 18 to 24 are synthetic procedures for isolated procatalysts. In Examples 25 and 26, the results of the polymerization reactions of procatalysts 1 to 6 are tabulated and discussed. One or more features of the present disclosure are Petition 870240103366, dated 04 / 12 / 2024, p. 39 / 143 29 / 60 illustrated in view of the examples as follows: General procedures

[0084] All reactions were carried out in a nitrogen-purged glove box unless otherwise indicated. All solvents and reagents were obtained from commercial sources and used as received unless otherwise indicated. Anhydrous toluene, anhydrous hexanes, anhydrous tetrahydrofuran, and anhydrous diethyl ether were purified by passing through activated alumina and, in some cases, reagent Q-5. The alumina for solvent purification was activated by passing a stream of nitrogen through the alumina for 8 hours at 300 °C. Reagent Q-5 was activated by heating at 200 °C under a stream of nitrogen for 4 hours, followed by a stream of 5% hydrogen in nitrogen at 200 °C for 3 hours, and finally washing with nitrogen gas. The solvents used for the experiments carried out in a nitrogen-filled glove box were additionally dried by storage on activated 4 Å molecular sieves.Glassware for moisture-sensitive reactions was dried in an oven overnight before use. High-resolution mass spectrometry (HRMS) analyses were performed using an Agilent 1290 Infinity LC instrument with a Zorbax Eclipse Plus C18 1.8 pm 2.1x50 mm column coupled to an Agilent 6230 TOF mass spectrometer with electrospray ionization. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. 1H NMR data are presented as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet, em = multiplet), integration, and assignment). Chemical shifts for 1H NMR data are reported in ppm in low field from tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as references.13C NMR data were determined with 1H decoupling, and chemical shifts are reported in ppm as a function of tetramethylsilane. The 13C NMR spectra of phosphines were complex. Petition 870240103366, dated 04 / 12 / 2024, page 40 / 143 30 / 60 due to CP coupling. Chemical shifts for the 31P NMR data are reported in ppm relative to external pure H3PO4. Deuterated solvents for NMR analysis were purchased from Cambridge Isotope Laboratories and stored on activated 4 Å molecular sieves in a nitrogen-purged glove box. Chlorobis(2,6-dimethoxyphenyl)phosphine, chlorobis(2,6-diethoxyphenyl)phosphine, and bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) were prepared according to literature procedures. Binder Preparation Exθmp]ol^J2i7ΞBis(3J52bis(trl·fluoromethyl)phenyl)Ξ9HΞçarbazol

[0085] In a fume hood, a mixture of 2,7-dibromocarbazole (1.06 g, 3.27 mmol), 3,5-bis(trifluoromethyl)phenylboronic acid (2.53 g, 9.80 mmol), Pd(PPh3)4 (755 mg, 0.65 mmol), and K3PO4 (6.24 g, 29.4 mmol) was added to a 100 mL Schlenk flask. The flask was evacuated under reduced pressure and purged with nitrogen three times. Under a positive nitrogen atmosphere, 30 mL of dioxane and 5 mL of degassed water were added. The flask was fitted with a reflux condenser and subsequently heated to 100 °C for 72 h. The reaction was cooled and filtered through a silica layer and washed with dichloromethane. The filtrate was concentrated in Celite and the product was purified by column chromatography with 20% dichloromethane / hexane. The product was isolated as a white solid. The reaction yielded 1.652 g (2.78 mmol, 85% yield) of the product.

[0086] 1H NMR (400 MHz, Chloroform-d) δ 8.34 (s, 1H, NH), 8.25 (d, J = 8.1 Hz, 2H), 8.16 (s, 4H), 7.91 (s, 2H), 7.75 (d, J = 1.6 Hz, 2H), 7.56 (dd, J = 8.1, 1.6 Hz, 2H) ppm. 13C NMR (101 MHz, Chloroform-d) δ 143.81, 140.67, 136.70, 132.18 (q, J = 33.3 Hz), 127.51, 124.80, 123.30, 121.49, 121.23 Petition 870240103366, dated 04 / 12 / 2024, p. 41 / 143 31 / 60 120.62 (m), 119.50, 109.56 ppm. Example 2 - 2,7-Bis(3,5-di-tert-butylphenyl)-9H-carbazole

[0087] In a fume hood, a mixture of 2,7-dibromocarbazole (1.06 g, 3.27 mmol), 3,5-dit-butylphenylboronic acid (2.30 g, 9.80 mmol), Pd(PPh3)4 (755 mg, 0.65 mmol), and K3PO4 (6.24 g, 29.4 mmol) were added to a 100 mL Schlenk flask. The flask was evacuated under reduced pressure and purged with nitrogen three times. Under a positive nitrogen atmosphere, 30 mL of dioxane and 5 mL of degassed water were added. The flask was fitted with a reflux condenser and subsequently heated to 100 °C for 24 h. The reaction was cooled and filtered through a silica layer and washed with dichloromethane. The filtrate was concentrated on Celite and the product was purified by hexane / ethyl acetate column chromatography. The product precipitated from the solution during column purification, and a significant amount of product was lost in the process. The reaction yielded 1.017 g (1.86 mmol, 57% yield) of product.

[0088] 1H NMR (400 MHz, Chloroform-d) δ 8.17 (s, 1H), 8.15 (d, J = 8.1 Hz, 2H), 7.67 (d, J = 1.6 Hz, 2H), 7.57 (d, J = 1.8 Hz, 4H), 7.53 (dd, J = 8.1, 1.5 Hz, 2H), 7.49 (t, J = 1.8 Hz, 2H), 1.45 (s, 36H) ppm. 13C NMR (101 MHz, Chloroform-d) δ 151.12, 141.35, 140.55 (d, J = 5.6 Hz), 122.34, 122.07, 121.29, 120.40, 119.71, 109.34, 35.04, 31.60 ppm. Example 3 - 9H-carbazol-9-carboxamide nh2

[0089] In a glove box, a round-bottomed Schlenk bottle of Petition 870240103366, dated 04 / 12 / 2024, p. 42 / 143 32 / 60 A 250 mL flask was loaded with 9H-carbazol-9-carbonyl chloride (500 mg, 2.18 mmol), a stirring bar, and 30 mL of diethyl ether. The flask was removed from the box and placed under a nitrogen stream in a Schlenk line. Under vigorous stirring, a solution of ammonia (2.0 M) in isopropanol (16.3 mL, 32.66 mmol) was added to the contents of the flask. A white precipitate formed immediately, and the solution was stirred for 18 h at room temperature. All volatiles were then removed under vacuum, leaving white solids on the walls of the flask. Water (100 mL) was added, and the resulting precipitate was collected by filtration and washed with excess water to remove NH4Cl. A final wash was performed with hexane, and the resulting white solid was dried under vacuum. The reaction yielded 445 mg (2.11 mmol, 97% yield) of the product.

[0090] 1H NMR (400 MHz, Chloroform-ο) δ 8.15 (d, J = 8.4 Hz, 2H), 8.07 (d, J = 7.7 Hz, 2H), 7.53 (t, J = 7.7 Hz, 2H), 7.40 (t, J = 7.5 Hz, 2H), 5.61 (s, 2H) ppm. 13C NMR (126 MHz, Chloroform-d) δ 178.67, 127.16, 122.73, 120.16, 114.14, 95.81,95.77 ppm. Example 4 - 2,7-Bis(2,4,4-trimethylpentan-2-yl)-9H-carbazol-9-carboxamide

[0091] In a glove box, 2,7-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazole (515 mg, 1.31 mmol), a stirring bar, and 10 mL of THF were added to a 20 mL flask. The solution was cooled to -35 °C in the freezer of the glove box. The flask was removed from the freezer and solid NaN(SiMe3)2 (265 mg, 1.45 mmol, 1.1 eq) was added slowly. The reaction mixture was allowed to warm naturally slowly to room temperature while stirring for 1.5 h. To a separate flask, 4-nitrophenyl chloroformate (268 mg, 1.45 mmol, 1.1 eq), a stirring bar Petition 870240103366, dated 04 / 12 / 2024, pp. 43 / 143 33 / 60 of stirring, and 3 mL of THF. While stirring, the carbazole-containing solution was added dropwise to the 4-nitrophenyl chloroformate-containing solution. As soon as the addition was complete, the solution turned bright orange with the concomitant formation of a precipitate. The reaction mixture was stirred for 18 h, then removed from the glove box and deactivated with water. The aqueous mixture was extracted with dichloromethane (3 x 15 mL), and the organic fraction was separated, dried with Mg2SO4, and filtered. All volatiles were removed in the rotary evaporator, leaving behind a light yellow solid. The solid was washed with hexane and collected by filtration. A total of 501 mg (67%) of precipitate was collected during filtration and was confirmed by 1H NMR spectroscopy that the major component was the desired product. The crude solids (501 mg, 0.90 mmol, based on 100% purity) were dissolved in DMF (2 mL) and transferred to a 20 mL vial.Ammonium carbonate (32 mg, NH3 30%, 1.85 mmol, 2.0 eq) was added, the flask was sealed, and the mixture was stirred at room temperature for 18 h. The cap was carefully removed, and the reaction was stopped by adding water (15 mL). A white precipitate formed, and it was collected by filtration. The precipitate was washed with water and dried under vacuum. The crude reaction mixture was purified by column chromatography. The structure and purity of the compound were confirmed by 1H and 13C NMR spectroscopy. The reaction yielded 213 mg (0.49 mmol, 37% yield in two steps) of the product.

[0092] 1H NMR (500 MHz, Chloroform-ο) δ 8.13 (d, J = 1.6 Hz, 2H), 7.87 (d, J = 8.2 Hz, 2H), 7.40 (dd, J = 8.2, 1.6 Hz, 2H), 5.67 (s, 2H), 1.85 (s, 4H), 1.47 (s, 12H), 0.73 (s, 18H) ppm. 13C NMR (126 MHz, Chloroform-d) δ 154.05, 149.43, 138.91, 122.97, 121.38, 118.96, 111.69, 57.20, 39.24, 32.43, 32.00, 31.83 ppm. Example 5 - 3,6-Di-tert-butyl-9H-carbazol-9-carboxamide Petition 870240103366, dated 04 / 12 / 2024, p. 44 / 143 34 / 60

[0093] In a glove box, 3,6-1-butylcarbazole (735 mg, 2.63 mmol), a stirring bar, and 10 mL of THF were added to a 20 mL flask and cooled to -35 °C in a freezer overnight. The flask was removed from the freezer, n-butyllithium (2.0 M, 1.45 mL, 2.89 mmol, 1.1 eq) was added slowly, and the flask was returned to the freezer and left there for 30 min. The flask was then removed from the freezer and the reaction mixture was allowed to stir at room temperature for 1.5 h. 4-Nitrophenyl chloroformate (537 mg, 2.89 mmol, 1.1 eq) was added to a 120 mL vessel along with a stirring bar and 15 mL of THF. While stirring, the lithium-carbazole-containing solution was added dropwise to the 4-nitrophenyl chloroformate-containing solution. Once the addition was complete, the reaction mixture was stirred for 1 hour at room temperature.All volatiles were then removed from the solution under vacuum, leaving a sticky yellow solid. The 1H NMR spectrum was consistent with the carbamate intermediate. DMF (8 mL) was added to the crude reaction mixture and the material was removed from the glove box. In a fume hood, ammonium carbonate (179 mg, NH3 30%, 3.16 mmol) was added to the mixture, the vessel was sealed, and the contents were stirred at room temperature for 18 h. The solution was diluted with 100 mL of deionized water and the precipitate that formed was collected by filtration, washed with water several times, and dried under vacuum. The reaction yielded 768 mg (2.38 mmol, 91% yield).

[0094] 1H NMR (400 MHz, CDCh) δ 8.18 - 7.98 (m, 4H), 7.55 (dd, J = 8.6, 2.1 Hz, 2H), 5.55 (s, 2H), 1.48 (s, 18H) ppm. 13C NMR (126 MHz, CDCh) δ 153.78, 145.82, 136.70, 125.58, 124.70, 116.20, 113.72, 34.74, 31.77 ppm. Petition 870240103366, dated 04 / 12 / 2024, page 45 / 143 35 / 60 Example 6 - 2,7-Bis(3,5-di-tert-butylphenyl)-9H-carbazol-9-carboxamide

[0095] In a glove box, 2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazole (545 mg, 1.00 mmol), a stirring bar, and 15 mL of THF were added to a 20 mL flask and cooled in a freezer at -35 °C for 2 h. The flask was removed from the freezer, n-butyllithium (2.0 M, 0.55 mL, 1.10 mmol, 1.1 eq) was added slowly, and the flask was returned to the freezer and left there for 30 min. The flask was then removed from the freezer and the reaction mixture was allowed to stir at room temperature for 1.5 h. 4-Nitrophenyl chloroformate (205 mg, 1.10 mmol, 1.1 eq) was added to a 120 mL vessel along with a stirring bar and 15 mL of THF. While stirring, the lithium-carbazole-containing solution was added dropwise to the 4-nitrophenyl chloroformate-containing solution. Once the addition was complete, the reaction mixture was stirred at room temperature for 1 hour.All volatiles were then removed from the solution under vacuum, leaving behind a sticky yellow solid. The 1H NMR spectrum was consistent with the carbamate intermediate. The crude reaction material was dissolved in 8 mL of DMF, and the vessel containing the material was sealed and removed from the glove box. In a fume hood, ammonium carbonate (67 mg, NH3 30%, 1.20 mmol) was added to the mixture, the vessel was sealed, and the contents were stirred at room temperature for 18 h. The solution was diluted with 100 mL of deionized water, and the precipitate that formed was collected by filtration, washed with water several times, and dried under vacuum. The 1H NMR spectrum of the precipitate was consistent with the desired product. The reaction yielded 511 mg (0.87 mmol, 87% yield).

[0096] 1H NMR (400 MHz, Chloroform-ο) δ 8.36 (d, J = 1.4 Hz, 2H), 8.11 (d, J = 8.0 Hz, 2H), 7.64 (dd, J = 8.0, 1.5 Hz, 2H), 7.55 (d, J = 1.8 Hz, 4H), Petition 870240103366, dated 04 / 12 / 2024, pp. 46 / 143 36 / 60 7.51 (d, J = 1.8 Hz, 2H), 5.69 (s, 2H), 1.45 (s, 36H) ppm. 13C NMR (101 MHz, Chloroform-d) δ 153.59, 151.29, 141.94, 141.04, 139.34, 124.25, 122.81, 122.11, 121.65, 120.19, 113.12, 35.05, 31.59 ppm. Example 7 - 2,7-Bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazol-9-carboxamide

[0097] In a glove box, 2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazole (770 mg, 1.30 mmol), a stirring bar, and 15 mL of THF were added to a 20 mL flask and cooled in a freezer at -35 °C for 2 h. The flask was removed from the freezer, n-butyllithium (2.0 M, 0.72 mL, 1.43 mmol, 1.1 eq) was added slowly, and the reaction mixture was returned to the freezer and left there for 30 min. The reaction mixture was then removed from the freezer and allowed to stir at room temperature for 1.5 h. 4-Nitrophenyl chloroformate (289 mg, 1.43 mmol, 1.1 eq) was added to a 120 mL vessel along with a stirring bar and 15 mL of THF. While stirring, the solution containing lithium carbazole was added dropwise to the solution containing 4-nitrophenyl chloroformate. Once the addition was complete, the reaction mixture was stirred at room temperature for 1 hour.All volatiles were then removed from the solution under vacuum, leaving behind a sticky yellow solid. The 1H NMR spectrum was consistent with the carbamate intermediate. DMF (8 mL) was added to the crude reaction mixture and the material was removed from the glove box. In a fume hood, ammonium carbonate (88 mg, NH3 30%, 1.56 mmol) was added to the mixture, the vessel was sealed, and the contents were stirred at room temperature for 18 h. The solution was diluted with 100 mL of deionized water and the precipitate that formed was collected by filtration, washed with water several times, and dried under vacuum. The product was recrystallized from hot ethyl acetate and cooled overnight at 2 °C. The product was isolated by filtration as a white powder. Petition 870240103366, dated 04 / 12 / 2024, page 47 / 143 37 / 60 The product was isolated and yielded 768 mg (1.21 g, 93% yield).

[0098] NMR de1H (500 MHz, Chloroformio-d) δ 8.37 (d, J = 1.5 Hz, 2H), 8.20 (d, J = 8.1 Hz, 2H), 8.12 (s, 4H), 7.91 (s, 2H, 7, 1.5, J Hz, 2H), 5.70 (s, 2H) ppm. NMR of19F (376 MHz, Chloroformio-d) δ -62.75 ppm. Example 8 - N-(Bis(2,6-dimethoxyphenyl)phosphanyl)-9H-carbazole-9-carboxamide OMe OMe MeO’ O

[0099] In a glove box, a 20 mL vial was loaded with 9Hcarbazol-9-carboxamide (300 mg, 1.43 mmol), 8 mL of THF, and a stirring bar. The solution was left in a freezer at -35°C for 1.5 h. After removal from the freezer, and while stirring, 2.0 M n-butyllithium (0.79 mL, 1.57 mmol, 1.1 eq) was added dropwise, and the solution was immediately returned to the freezer. After 10 minutes, the reaction mixture was removed from the freezer and a fluid paste of bis(2,6-dimethoxyphenyl)chlorophosphine (487 mg, 1.43 mmol) in 4 mL of THF was added. The reaction mixture was then allowed to warm naturally to room temperature and stirred for one hour. After one hour, the reaction was brought to dryness under vacuum and 15 mL of dichloromethane were added. The reaction mixture was filtered through a Celite and silica 50 / 50 plug to remove LiCl.All volatiles were removed from the filtrate, and the product was triturated with diethyl ether and collected by filtration. It was confirmed by NMR spectroscopy that the byproducts were only present in the diethyl ether-soluble fraction and that the collected precipitate was the pure product. The reaction yielded 378 mg (0.73 mmol, 51% yield).

[0100] 1H NMR (400 MHz, Benzene-d6) δ 8.70 (d, J = 5.5 Hz, 2H), 8.35 (dt, J = 8.2, 0.9 Hz, 4H), 7.83 - 7.72 (m, 4H), 7.19 - 7.13 (m, 4H), 7.12 - 7.06 (m, 8H), 6.93 (t, J = 8.3 Hz, 5H), 6.14 (dd, J = 8.3, 2.6 Hz, 8H), 3.12 (s, 20H) Petition 870240103366, dated 04 / 12 / 2024, pp. 48 / 143 38 / 60 ppm. 13C NMR (126 MHz, Benzene-d6) δ 162.04 (d, J = 10.0 Hz), 153.73 (d, J = 22.4 Hz), 139.11, 130.25, 126.55, 125.11, 121.74, 119.65, 116.21 (d, J = 30.8 Hz), 114.62, 104.53, 55.24 ppm. 31P NMR (162 MHz, Benzene-ds) δ 1.44 ppm. HRMS (ESI+) (m / z): [M+H] calculated for C29H28N2O5P: 515.1730; Found: 515.1752. Exemplo 9 - N-(Bis(2,6-dietoxifenil)fosfanil)-9H-carbazol-9-carboxamida

[0101] In a glove box, a glass vessel was fitted with a stirring bar, 9H-carbazol-9-carboxamide (1.0 g, 4.76 mmol), and dry THF (25 mL). The white, fluid paste was placed in the glove box freezer at -35 °C for 30 minutes. After 30 minutes, the vessel was removed from the freezer, and while the contents were being stirred, 2.5 M n-butyllithium in hexanes (2.1 mL, 5.25 mmol) was added dropwise. The resulting cloudy yellow solution was returned to the freezer, and after 10 minutes, the reaction mixture was removed from the freezer and a chilled, fluid paste of bis(2,6-diethoxyphenyl)chlorophosphine (1.982 g, 5.00 mmol) in THF (10 mL) was added. The resulting mixture was stirred for 30 minutes while slowly warming to room temperature. After 30 minutes, an aliquot of the reaction mixture (white fluid paste) was analyzed by 31P NMR spectroscopy to verify the conversion of chlorophosphine.According to the 31P NMR spectrum, the reaction was complete. The reaction mixture was concentrated under vacuum to give a white solid, and dichloromethane (55 mL) was added. The cloudy solution was filtered through a Celite plug and concentrated under vacuum to give a white solid. The solid was ground with diethyl ether. The fluid paste was stirred for 5 minutes at room temperature, and the solid was collected by filtration, washed with diethyl ether, and dried. Petition 870240103366, dated 04 / 12 / 2024, pp. 49 / 143 39 / 60 under vacuum. The solid was analyzed by 1H NMR and 31P NMR spectroscopy, which revealed the presence of some impurities. The product was purified by column chromatography using a gradient of 0 to 20% ethyl acetate in hexanes. The column fractions were analyzed by HRMS. The fractions containing the product were combined and concentrated by rotary evaporation to provide a white solid. The solid was dried under high vacuum to provide 0.844 g (1.48 mmol, 31% yield) of a white solid.

[0102] NMR of1H (400 MHz, Chloroformio-d) δ 8.43 (d, J = 5.6 Hz, 1H), 8.11 (d, J = 8.3 Hz, 2H), 8.00 (d, J = 7.7 Hz, 2H), 7.9, t, J = 7.7 Hz, 7, t 7.30 (t, J = 7.4 Hz, 2H), 7.18 (t, J = 8.3 Hz, 2H), 6.46 (dd, J = 8.3, 2.7 Hz, 4H), 4.05 3.54 (m, 8H), 1.01 (t, J = 7.0 Hz, p pm). NMR of13C (101 MHz, Chloroformio-d) δ 161.16 (d, J = 9.8 Hz), 153.92 (d, J = 24.2 Hz), 138.87, 130.46, 126.66, 125.11, 130.46, 126.66, 115.81 (d, J = 25.2 Hz), 114.52, 104.99, 64.38, 14.28 ppm. NMR of31P (162 MHz, Chloroformio-d) δ -2.85 ppm. Example 10 - N-(Bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(2,4,4-trimethylpentan-2-yl)9H-carbazole-9-carboxamide OMe OMe MeO’ O

[0103] In a glove box, 2,7-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazol-9-carboxamide (213 mg, 0.49 mmol), a stirring bar, and 5 mL of THF were added to a 20 mL flask and cooled to -35 °C in a freezer overnight. The solution was removed from the freezer, n-butyllithium (2.0 M, 0.27 mL, 0.54 mmol, 1.1 eq) was added slowly, and the reaction mixture was returned to the freezer and left there for 20 min. The reaction mixture was removed from the freezer and a paste Petition 870240103366, dated 04 / 12 / 2024, p. 50 / 143 40 / 60 fluid of chlorobis(2,6-dimethoxyphenyl)phosphine (149 mg, 0.49 mmol) in 3 mL of THF was added. The reaction was then allowed to heat naturally to room temperature and stirred for an additional hour. All volatiles were then removed under vacuum, and 10 mL of dichloromethane were added to the resulting residue. The dichloromethane solution was filtered through a Celite plug to remove LiCl. All volatiles were then removed from the filtrate under vacuum, leaving a white solid. 1H and 31P NMR spectroscopy confirmed that the major component was the desired product. The crude reaction mixture was purified by column chromatography with hexane and ethyl acetate. The reaction yielded 193 mg (0.26 mmol, 53% yield) of the product, isolated as a white powder.

[0104] 1H NMR (400 MHz, Benzene-d6) δ 8.47 (d, J = 1.6 Hz, 2H), 8.29 (d, J = 6.7 Hz, 1H), 7.85 (d, J = 8.2 Hz, 2H), 7.33 (dd, J = 8.2, 1.6 Hz, 2H), 7.00 (td, J = 8.2, 0.8 Hz, 2H), 6.23 (dd, J = 8.3, 2.6 Hz, 4H), 3.17 (s, 12H), 1.76 (s, 4H), 1.33 (s, 12H), 0.75 (s, 18H) ppm. 13C NMR (126 MHz, Benzene-d6) δ 162.25 (d, J = 10.0 Hz), 154.35 (d, J = 21.3 Hz), 148.74, 139.72, 130.19, 122.68, 120.68, 118.76, 116.75 (d, J = 29.6 Hz), 112.02, 104.90, 56.77, 55.48, 38.95, 32.11, 31.78, 31.68 ppm. 31P NMR (162 MHz, Benzene-d6) δ -2.71 ppm. HRMS (ESI+) (m / z): [M+H] calculated for C45H60N2O5P: 739.4239; found: 739.424. Example 11 - N-(Bis(2,6-dimethoxyphenyl)phosphanyl)-3,6-di-tert-butyl-9H-carbazol-9carboxamide tBu

[0105] In a glove box, a 20 mL vial was loaded with 3,6-di-tert-butyl-9H-carbazol-9-carboxamide (50 mg, 0.16 mmol), bis(2,6Petition 870240103366, dated 04 / 12 / 2024, page 51 / 143 41 / 60 dimethoxyphenyl)chlorophosphine (68 mg, 0.20 mmol, 1.28 equiv), 4-pyrrolidinopyridine (37 mg, 0.25 mmol, 1.6 equiv), THF (3 mL), and a stirring bar. The solution was heated with stirring at 60 °C for 18 h. The solution was cooled and filtered to remove unwanted salts. The filtrate was then concentrated to a volume of about 1 mL under vacuum and hexane (10 mL) was added. A large amount of white precipitate formed and was subsequently collected by filtration, washed with hexane, and dried under vacuum. 1H NMR spectroscopy revealed that the white solid was predominantly the desired product, but some phosphorus oxidation byproducts appeared. The product was purified by column chromatography on 20% ethyl acetate / hexane. The reaction produced 81 mg (0.13 mmol, 83% yield) of the product, which was isolated as a white powder.

[0106] 1H NMR (500 MHz, Benzeno-ds) δ 8.27 (s, 2H), 8.16 (s, 2H), 7.42 (d, J = 8.7 Hz, 2H), 6.96 (tt, J = 8.2, 1.5 Hz, 2Hz, 214), dd, J = 8.3, 3.2, 1.1 Hz, 4H), 2.93 (d, J = 1.2 Hz, 12H), 1.36 (s, 18H) ppm. NMR of de13C (101 MHz, Benzeno-d6) δ 151.51, 151.36, 138.00, 129.31, 128.51, 125.61, 122.94, 122.33, 111.21 (d, 3.9 = 1.9 Hz), (d, J = 3.1 Hz), 46.45, 35.20, 31.80 (d, J = 1.6 Hz), 21.63 ppm. NMR of31P (202 MHz, Benzeno-d6) δ -1.75 ppm. HRMS (ESI+) (m / z): [M+H] calculated for C37H44N2O5P: 627.2987; found: 627,291. Example 12 - N-(Bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(3,5-di-terc-butylphenyl)-9Hcarbazole-9-carboxamide Petition 870240103366, of 04 / 12 / 2024, p. 52 / 143 42 / 60

[0107] In a glove box, 2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazol-9carboxamide (287 mg, 0.49 mmol), a stirring bar, and 5 mL of THF were added to a 20 mL flask and cooled to -35 °C in a freezer overnight. The flask was removed from the freezer, n-butyllithium (2.0 M, 0.27 mL, 0.54 mmol, 1.1 eq) was added slowly, and the reaction mixture was returned to the freezer and left there for 15 min. The reaction mixture was removed from the freezer and a fluid paste of chlorobis(2,6-dimethoxyphenyl)phosphine (170 mg, 0.50 mmol) in 3 mL of THF was added. The reaction was then allowed to warm naturally to room temperature and stirred for an additional hour. All volatiles were then removed under vacuum and 10 mL of dichloromethane were added to the resulting residue. The dichloromethane solution was filtered through a Celite plug to remove LiCl, but in this case the filtrate was still cloudy.The filtrate solution was pushed through a 4 µm syringe filter, and the resulting solution was clear. The reaction was concentrated to a volume of ~2 mL under vacuum, and the product was ground with hexane to obtain a dirty-white solid. The solid material was collected by filtration and dried under vacuum. A total of 87 mg of material was isolated during filtration and was confirmed as the desired product by 1H and 31P NMR spectroscopy. All volatiles were removed from the filtrate, and the resulting crude solids were dissolved in a minimal amount of hexane. The hexane solution was left in the freezer at -35 °C overnight. The following day, a white powder had precipitated, and it was quickly collected by filtration and dried. The second powder collection was also confirmed to be the desired product (98 mg) by NMR spectroscopy. Yield: 185 mg (two collections, 0.21 mmol, 42% yield) of the product were isolated.

[0108] 1H NMR (400 MHz, Benzeno-d6) δ 8.93 (d, J = 5.5 Hz, 1H), 8.90 (d, J = 1.4 Hz, 2H), 8.01 (d, J = 8.0 Hz, 2H), 7.71 (dd, J = 8.0, 1.5 Hz, 2H), 7.66 (d, J = 1.8 Hz, 4H), 7.55 (t, J = 1.8 Hz, 2H), 8.2, 0.8 Hz, 2H), 6.08 (dd, J = 8.3, 2.6 Hz, 4H), 3.07 (s, 12H), 1.32 (s, 36H) ppm. NMR of de13C (101 MHz, Benzeno-ds) δ 162.03 (d, J = 10.1 Hz), 151.09, 142.10 (d, J = 23.6 Hz), 140.28, Petition 870240103366, of 04 / 12 / 2024, p. 53 / 143 43 / 60 130.22, 124.12, 122.40, 122.25, 120.95, 119.96, 116.19 (d, J = 30.2 Hz), 114.01, 104.57, 55.19, 34.71, 104.57, 20.27, ppm. NMR of31P (162 MHz, Benzeno-ds) δ -1.35 ppm. HRMS (ESI+) (m / z): [M+H] calculated for C57H68N2O5P: 891.486; found: 891,481. Example 13 - N-(Bis(2,6-diethoxyphenyl)phosphanyl)-2,7-bis(3,5-bis(trifluoromethyl)phenyl)9HΞcharbazole·9Ξcharboxamide

[0109] In a glove box, 2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazol-9-carboxamide (187 mg, 0.30 mmol), a stirring bar, and 5 mL of THF were added to a 20 mL flask and cooled to -35 °C in a freezer overnight. The reaction mixture was removed from the freezer, n-butyllithium (2.0 M, 0.16 mL, 0.32 mmol, 1.1 eq) was added slowly, and the reaction mixture was returned to the freezer and left there for 15 min. The reaction mixture was removed from the freezer and a fluid paste of chlorobis(2,6-diethoxyphenyl)phosphine (123 mg, 0.31 mmol, 1.05 eq) in 3 mL of THF was added. The solution was allowed to warm naturally to room temperature and stirred for an additional hour. All volatiles were then removed under vacuum and 10 mL of dichloromethane were added to the resulting residue. The dichloromethane solution was filtered through a Celite plug to remove LiCl.The filtrate was concentrated under vacuum to a volume of 2 mL, and the resulting residue was ground with hexane to obtain a white solid. The solid material was collected by filtration and dried under vacuum. The product was further purified by chromatography. Petition 870240103366, dated 04 / 12 / 2024, p. 54 / 143 44 / 60 in a column (20% ethyl acetate / hexane). The reaction produced 44 mg (0.05 mmol, 18% yield) of the product, which was isolated as a white powder.

[0110] 1H NMR (500 MHz, Benzene-d6) δ 8.59 (d, J = 5.2 Hz, 2H), 8.43 (s, 2H), 7.83 (d, J = 8.0 Hz, 2H), 7.79 (s, 4H), 7.73 (s, 2H), 7.07 (dd, J = 8.0, 1.6 Hz, 2H), 6.97 (t, J = 8.2 Hz, 2H), 6.08 (dd, J = 8.4, 2.7 Hz, 4H), 3.54 - 3.01 (m, 8H), 0.70 (t, J = 7.0 Hz, 11H) ppm. 31P NMR (202 MHz, Benzene-ds) δ -1.57 ppm. Example 14 - N-(Bis(2,6-dimethoxyphenyl)phosphanyl)-3,5-dimethyl-1H-pyrazol-1carboxamide

[0111] In a glove box, 3,5-dimethyl-1H-pyrazole-1-carboxamide (460 mg, 3.13 mmol), a stirring bar, and 12 mL of THF were added to a 60 mL beaker and cooled to -35 °C in a freezer overnight. The solution was removed from the freezer and n-butyllithium (2.0 M, 1.82 mL, 3.64 mmol, 1.1 eq) was added slowly. The reaction mixture was returned to the freezer and left there for 15 min. A suspension of chlorobis(2,6-dimethoxyphenyl)phosphine (1.183 g, 3.47 mmol) in 8 mL of THF was then added to the cold reaction mixture. The mixture was allowed to warm naturally slowly to room temperature while stirring for 2 h. A large amount of precipitate formed during this time and was collected by filtration. The solid was washed with a small amount of THF to remove LiCl, further washed with hexane, and then dried under vacuum.The isolated white powder was found to be predominantly the desired product (95% pure) with a small amount of oxidized phosphine present (~5%). All volatiles were removed from the filtrate under vacuum and ether. Petition 870240103366, dated 04 / 12 / 2024, page 55 / 143 45 / 60 diethyl ether was added, resulting in precipitation of additional product. The precipitate was collected by filtration, washed with excess diethyl ether, and dried. The second batch of powder was >98% pure by 31P NMR spectroscopy and was combined with the first batch of powder to produce a combined mass of 983 mg (2.10 mmol, 67% yield).

[0112] 1H NMR (400 MHz, Chloroform-d) δ 10.02 (d, J = 5.9 Hz, 1H), 7.21 (t, J = 8.3 Hz, 2H), 6.50 (dd, J = 8.4, 2.7 Hz, 4.8Hz), (s 3.80 (s, 12H), 2.58 (s, 3H), 2.26 (s, 3H) ppm. NMR of13C (101 MHz, Chloroformio-d) δ 161.97 (d, J = 9.8 Hz), 149.18, 143.54, 130.50, 115.19 (d, J = 25.6 Hz), 25.62, 14.19, 13.78 ppm. NMR of31P (162 MHz, Chloroformio-d) δ -4.46 ppm. Example 15 - N-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5H-dibenzo[b,f]azepine-5carboxamide MeO ,0 OMe OMe

[0113] In a glove box, a 20 mL vial was loaded with 9Hcarbazol-9-carboxamide (104 mg, 0.44 mmol), THF (5 mL), and a stirring bar. The resulting solution was cooled to -35 °C in the freezer for 2 h. The solution was removed from the freezer, and while stirring, n-butyllithium (272 pL, 0.54 mmol) was added dropwise. The reaction mixture was returned to the freezer and left there for 2 h. After removing the reaction mixture from the freezer, bis(2,6-(dimethoxyphenyl)chlorophosphine) (185 mg, 0.54 mmol) was added as a solid to the cold solution. The solution was slowly heated naturally to room temperature while stirring for 18 h. A large amount of white precipitate formed during this time and was collected by filtration, washed with hexane, and dried under vacuum. The 1H NMR spectrum indicated that the THF-insoluble material was the Petition 870240103366, dated 04 / 12 / 2024, p. 56 / 143 46 / 60 desired product. The LiCl was presumably removed by washing into the filtrate. Yield: 152 mg (0.25 mmol, 57% yield) of the product were isolated.

[0114] 1H NMR (500 MHz, Chloroform-d) δ 7.43 (dd, J = 8.0, 1.3 Hz, 2H), 7.36 (ddd, J = 7.9, 7.0, 1.7 Hz, 2H), 7.31 (dd, J = 7.7, 1.8 Hz, 2H), 7.27 (ddd, J = 7.7, 4.8, 2.2 Hz, 3H), 7.12 (t, J = 8.2 Hz, 2H), 6.39 (dd, J = 8.3, 2.6 Hz, 4H), 3.71 (d, J = 12.8 Hz, 1H), 3.55 (s, 12H) ppm. 13C NMR (126 MHz, Benzenods) δ 161.61 (d, J = 9.6 Hz), 156.28 (d, J = 21.6 Hz), 141.01, 135.02, 132.01, 130.96, 130.45 (d, J = 17.6 Hz), 129.91, 129.03, 128.89, 126.82, 104.14, 55.74 ppm. 31P NMR (202 MHz, Chloroform-d) δ -3.89 ppm. HRMS (ESI+) (m / z): [M+H] calculated for C31H30N2O5P: 541.189; Found: 541,179. Example 16 - N-(Bis(4-(trifluoromethyl)phenyl)phosphanyl)-9H-carbazol-9-carboxamide

[0115] In a glove box, a 20 mL vial was loaded with 9H carbazol-9-carboxamide (173 mg, 0.825 mmol), a stirring bar, and THF (8 mL). The solution was left in the freezer (-35 °C) for 2 h to cool. The solution was removed from the freezer and n-butyllithium (2.0 M, 0.45 mL, 0.91 mmol, 1.1 equiv) was added slowly with stirring. The reaction mixture was returned to the freezer and left there for 15 min. After removal from the freezer, a solution of bis(4-trifluoromethylphenyl)chlorophosphine (281 mg, 0.82 mmol, 1 equiv) in 3 mL of THF was added slowly. The solution was allowed to warm naturally to room temperature and stirred for 2 h. All volatiles were then removed under vacuum, and the resulting crude solids were dissolved in dichloromethane and filtered through a Celite plug to remove LiCl. The filtrate was concentrated under vacuum to a volume of approximately 2 mL and the product was triturated with hexane. Petition 870240103366, dated 04 / 12 / 2024, p. 57 / 143 47 / 60 The resulting white precipitate was collected by filtration and dried under vacuum. 1H NMR spectroscopy revealed that the white solid was the desired product. Yield: 355 mg (0.67 mmol, 81% yield) of the product were isolated.

[0116] 1H NMR (400 MHz, Chloroform-ο) δ 8.14 - 8.00 (m, 4H), 7.93 (d, J = 8.2 Hz, 2H), 7.77 - 7.67 (m, 8H), 7.55 - 7.35 (m, 8H), 7.26 - 7.21 (m, 1H), 6.33 (d, J = 3.0 Hz, 1H) ppm. 13C NMR (101 MHz, Chloroform-d) δ 153.50 - 152.84 (m), 141.43 (d, J = 17.1 Hz), 139.49, 138.23, 132.13 (d, J = 22.2 Hz), 127.37, 126.55 - 125.38 (m), 123.30 (d, J = 14.4 Hz), 120.40 (d, J = 12.2 Hz), 119.45, 113.78, 110.57 ppm. 19F NMR (376 MHz, Chloroform-d) δ -63.01 ppm. 31P NMR (162 MHz, Chloroform-d) δ 26.70 ppm. HRMS (ESI+) (m / z): [M+H] calculated for C27H18F6N2OP: 531.1055; found: 531.109. Example 17 - 3-(Bis(2,6-dimethoxyphenyl)phosfanyl)-1,1-dimethylurea

[0117] In a glove box, a glass vessel fitted with a stirring bar was loaded with 1,1-dimethylurea (0.500 g, 5.67 mmol) and cooled dry THF (30 mL). Not all of the starting material dissolved in the solution. The mixture was cooled in a freezer at -35 °C for 30 minutes. After 30 minutes, it was removed from the freezer and while stirring, n-BuLi in hexanes (2.5 M, 2.50 mL, 6.25 mmol) was added dropwise, and the resulting cloudy white solution was placed back in the freezer (-35 °C). The reaction mixture remained at -35 °C for three hours, but was periodically removed for stirring. After three hours, the reaction mixture was removed from the freezer, and a cooled suspension of bis(2,6-dimethoxyphenyl)chlorophosphine (2.03 g, 5.96 mmol) in dry THF (10 mL) was added. The resulting pale yellow solution was stirred for one hour while being slowly heated. Petition 870240103366, dated 04 / 12 / 2024, p. 58 / 143 48 / 60 at room temperature. After one hour, analysis of an aliquot of the reaction mixture (resulting light yellow fluid paste) by 31P NMR spectroscopy showed that the reaction was complete. The reaction mixture was concentrated under vacuum to give a light yellow sticky solid, and dichloromethane (45 mL) was added. The dark solution was filtered through a Celite plug and concentrated under vacuum to give a dirty white crystalline solid. The solid was ground with diethyl ether. The fluid paste was stirred for five minutes at room temperature, and the solid was collected by filtration and washed with diethyl ether. The solid was dried under vacuum to give 1.059 g (2.72 mmol, 48% yield) of the desired product as a white solid. There was evidence of insignificant oxidation byproducts in the 31P NMR spectra.

[0118] 1H NMR (400 MHz, CDCh) δ 7.52 (d, J = 6.0 Hz, 1H), 7.15 (t, J = 8.3 Hz, 2H), 6.47 (dt, J = 8.4, 4.4 Hz, 5H), 3.71 (s, 12H), 2.92 (s, 6H) ppm. 13C NMR (101 MHz, CDCh) δ 161.83, 131.09, 130.33 (d, J = 3.7 Hz), 116.59 (d, J = 26.5 Hz), 104.88 - 104.66 (m), 104.19, 56.12, 36.42 ppm. 31P NMR (162 MHz, CDCl3) δ -2.82 ppm. Preparation of Ni complexes Example 18 - Synthesis of Pro-catalyst 1 ((Z)-N-(Bis(2,6-dimethoxyphenyl)phosfanyl)-9H-carbazol-9-carbimidate)(pyridine)(trimethylsilylmethyl)nickel(II) MeO OMe

[0119] In a glove box, a 20 mL vial was loaded with bis(trimethylsilylmethyl)bis(pyridine)nickel (86 mg, 0.22 mmol, 1.0 eq), a stirring rod, and 2 mL of toluene. A solution of N-(bis(2,6-dimethoxyphenyl)phosfanyl) Petition 870240103366, dated 04 / 12 / 2024, p. 59 / 143 49 / 60 9H-carbazol-9-carboxamide (113 mg, 0.22 mmol) in 8 mL of toluene was then added slowly with stirring. The solution was orange and clear. The solution was heated slowly to 45°C and stirred for 1 h. All volatiles were then removed under vacuum. Hexane (3 mL) was added and subsequently removed under vacuum, leaving behind a sticky, orange solid. The product was suspended in hexane and stirred for 15 min. The product was then collected by filtration and dried under vacuum. Yield: 147 mg (0.20 mmol, 89% yield) of the product were isolated.

[0120] de1H NMR (400 MHz, Benzeno-d6) δ 9.11 - 8.89 (m, 4H), 7.92 (dd, J = 7.8, 1.4 Hz, 2H), 7.30 (ddd, J = 8.5, 7.2, 1.4 Hz, 7.25 - 7.2H), (m, 4H + CDCl3), 6.97 to 6.83 (m, 1H), 6.67 to 6.53 (m, 2H), 6.37 (dd, J = 8.3, 3.7 Hz, 4H), 3.40 (s, 12H), -0.12 (s, 9.0 H), - J, 38, Hz = 9.8 2H) ppm. NMR of de13C (126 MHz, Benzeno-ds) δ 167.07 (d, J = 14.5 Hz), 161.47 (d, J = 2.1 Hz), 151.02, 140.77, 136.30, 130.31, 123.38 (d, J = 1.8 Hz), 120.75, 118.91, 117.78, 114.39 (d, J = 58.8 Hz), 104.79 (d, J = 4.4 Hz), 55.47, 1.93, -1.06 (d, J = 2.9 ppm, Hz). NMR of31P (202 MHz, Benzeno-d6) δ 46.84 ppm. Example 19 - Synthesis of Pro-Catalyst 2 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(2,4,4-trimethylpentan-2-yl)-9Hcarbazole-9-carbimidate)(trimethylsilylmethyl)(pyridine(II)) MeO OMe

[0121] In a glove box, a 20 mL vial was loaded with bis(trimethylsilylmethyl)bis(pyridine)nickel (56 mg, 0.14 mmol, 1.05 eq), a stirring rod, and 1 mL of toluene. A solution of N-(bis(2,6 Petition 870240103366, dated 04 / 12 / 2024, pp. 60 / 143 50 / 60 dimethoxyphenyl)phosphanyl)-2,7-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazol-9carboxamide (100 mg, 0.14 mmol) in 3 mL of toluene was then added slowly with stirring. The solution was orange and clear. The reaction mixture was stirred for 1 hour at 60 °C. 31P NMR spectroscopic analysis of an aliquot of the reaction mixture showed complete conversion to the desired product. The reaction mixture was then cooled and all volatiles were removed under vacuum. The resulting crude material was dissolved in a minimal amount of hexane and left in the freezer at -35 °C overnight. The desired product precipitated from the solution during this time. The orange precipitate was collected by filtration and dried under vacuum. The isolated orange solid was confirmed as the desired product by NMR spectroscopy. The reaction produced 71 mg (0.08 mmol, 54% yield) of the product.

[0122] RMN de1H (400 MHz, Benzeno-d6) δ 9.12 (dd, J = 4.7, 1.7 Hz, 2H), 9.01 (s, 2H), 7.88 (d, J = 8.1 Hz, 2H), 7.28 (dd, J = 8.2, 1.7 Hz, 2H), 7.15 - 7.10 (m, 2H + CDCb), 6.98 (tt, J = 7.6, 1.7 Hz, 2H), 6.79 - 6.63 (m, 2H), 6.38 (dd, J = 8.3, 3.7 Hz, 4H), 3.41 (s, 12H), 1.72 (s, 4H), 1.33 (s, 12H); 0.72 (s, 18H), -0.16 (s, 9H), -0.40 (d, J = 8.8 Hz, 2H) ppm. RMN de13C (126 MHz, Benzeno-d6) δ 167.59 (d, J = 14.2 Hz), 161.39 (d, J = 1.8 Hz), 150.93, 146.80, 141.29, 136.04, 130.18, 124.00 (d, J = 1.8 Hz), 122.70, 119.33, 117.81, 115.50, 114.40 (d, J = 59.3 Hz), 104.54 (d, J = 4.3 Hz), 57.13, 55.41,38.90, 32.14, 32.12, 31.69, 1.82, -16.46 (d, J = 29.5 Hz) ppm. RMN de31P (162 MHz, Benzeno-d6) δ 47,27 ppm. Exemplo 20 - Síntese de pró-catalisador 6 ((Z)-N-(bis(2,6-dietoxifenil)fosfanil)-2,7-bis(3,5-bis(trifluorometil)fenil)-9Hcarbazol-9-carbimidato)(piridina)(trimetilsililmetil)níquel(II). K yCF3f3c

[0123] I have a lot of water, I have a 20 ml spray bottle on my car Petition 870240103366, dated 04 / 12 / 2024, p. 61 / 143 51 / 60 bis(trimethylsilylmethyl)bis(pyridine)nickel (39 mg, 0.10 mmol, 1.0 eq), a stirring bar, and 1 mL of toluene were added. Pyridine (8 μL, 0.10 mmol, 1.0 eq) was then added, followed by a solution of N-(bis(2,6-diethoxyphenyl)phosfanyl)-2,7bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazol-9-carboxamide (100 mg, 0.10 mmol) in 3 mL of toluene. The resulting solution was orange and clear and was stirred for 1 h at 45 °C. 31P NMR spectroscopic analysis of an aliquot of the reaction mixture showed complete conversion of the free ligand to the desired nickel complex. The mixture was filtered through a layer of Celite and the volatiles were removed from the filtrate under vacuum. Hexane (5 mL) was added to the resulting residue and then removed under vacuum, leaving behind a sticky, bright yellow solid. The product was ground with hexane and stirred for 15 min. The product was collected by filtration, washed with pentane, and dried under vacuum.The product reaction is 60 mg (0.07 mmol, 71% yield) of the product.

[0124] NMR de1H (500 MHz, C6Ü6) δ 10.49 - 8.19 (m, 4H), 7.90 (d, J = 8.0 Hz, 2H), 7.78 (d, J = 16.4 Hz, 5H), 7.17 - 7.10 (m, 6H), 7.08 (d, J = 7.8 Hz, 3H), 6.84 (t, J = 7.7 Hz, 1H), 6.45 (t, J = 6.6 Hz, 2H), 6.38 - 6.32 (m, 4H), 3.70 (s, 8H), 0.92 (s, 12H), -0.15 - -0.38 (m, 11H) ppm. NMR de13C (126 MHz, C6Ü6) δ 163.48 (d, J = 14.5 Hz), 158.14, 148.21, 142.95, 139.15, 134.09, 133.88, 129.08 (q, J = 32.9 Hz), 127.94, 122.29, 121.95, 120.87, 120.12, 118.21, 117.81 - 117.30 (m), 114.30, 111.27, 110.80, 102.18, 61.09, 11.65, 0.66, -18.76 (d, J = 28.9 Hz) ppm. NMR de31P (202 MHz, C6Ü6) δ 43.96 ppm. NMR de19F (376 MHz, C6Ü6) δ -62.23 ppm. Example 21 - Synthesis of catalyst 4 ((Z)-N-(Bis(2,6-dimethoxyphenyl)fosfanyl)-3,6-di-terc-butyl-9H-carbazol-9carbimidate)(trimethylsilylmethyl)(pyridine)níquel(II) Petition 870240103366, 04 / 12 / 2024, pág. 62 / 143 52 / 60

[0125] In a glove box, a 20 mL vial was loaded with bis(trimethylsilylmethyl)bis(pyridine)nickel (66 mg, 0.17 mmol, 1.05 eq), a stirring bar, and 1 mL of toluene. A solution of N-(bis(2,6-dimethoxyphenyl)phosfanyl)-3,6-di-tert-butyl-9H-carbazol-9-carboxamide (100 mg, 0.16 mmol) in 5 mL of toluene was added slowly with stirring. The solution was red and clear. The reaction mixture was stirred for 2 h at room temperature, and 31P NMR spectroscopic analysis of an aliquot showed complete conversion of the free ligand to the desired nickel complex. The reaction mixture was filtered through a Celite layer, and all volatiles were removed from the filtrate under vacuum. Hexane (5 mL) was added and then removed under vacuum, leaving behind a sticky, orange solid. The product was triturated with pentane and stirred for 15 min. The product was collected by filtration, washed with pentane, and dried under vacuum.The reaction produced 52 mg (0.10 mmol, 61% yield) of the product.

[0126] 1H NMR (400 MHz, Benzene-d6) δ 9.26 - 9.06 (m, 2H), 8.95 (d, J = 8.9 Hz, 2H), 8.20 (d, J = 2.1 Hz, 2H), 7.41 (dd, J = 8.9, 2.1 Hz, 2H), 7.19 7.08 (m, 14H), 7.02 (t, J = 8.4 Hz, 1H), 6.94 - 6.89 (m, 1H), 6.61 (t, J = 6.7 Hz, 2H), 6.38 (dd, J = 8.3, 3.7 Hz, 4H), 3.42 (s, 12H), 2.10 (s, 2H), 1.38 (s, 19H), 0.11 (s, 8H), -0.39 (d, J = 8.8 Hz, 2H) ppm. 13C NMR (101 MHz, Benzene-d6) δ 167.30, 161.55 (d, J = 2.0 Hz), 151.10, 143.11, 139.32, 136.34, 130.27, 128.96, 125.27 (d, J = 10.9 Hz) (162 MHz, Benzene-d6) δ 47.05 ppm. Example 22 - Synthesis of pro-catalyst 5 Petition 870240103366, dated 04 / 12 / 2024, p. 63 / 143 53 / 60 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazol9-carbimidate)(pyridine)(trimethylsilylmethyl)nickel(II) N tms MeO OMe

[0127] In a glove chamber, a 20 mL vial was loaded with bis(trimethylsilylmethyl)bis(pyridine)nickel (46 mg, 0.12 mmol, 1.05 eq), a stirring bar, and 1 mL of toluene. A solution of N-(bis(2,6-dimethoxyphenyl)phosfanyl)-2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazol-9-carboxamide (100 mg, 0.11 mmol) in 5 mL of toluene was added slowly with stirring. The resulting solution was red and clear. The reaction mixture was stirred for 90 min at room temperature, and 31P NMR spectroscopic analysis of an aliquot showed only partial conversion to the desired nickel complex. The solution was heated to 45 °C for 20 minutes, and 31P NMR spectroscopic analysis of an aliquot showed that the reaction achieved complete conversion to the desired nickel complex. The reaction mixture was filtered through a Celite layer, and all volatiles were removed from the filtrate under vacuum.Hexane (5 mL) was added to the resulting residue and then removed under vacuum, leaving behind a sticky, orange solid. The product was ground with pentane and stirred for 15 min. The product was collected by filtration, washed with pentane, and dried under vacuum. The 1H NMR spectrum of the product revealed the presence of some residual hexane. The reaction yielded 42 mg (0.04 mmol, 34% yield) of the product. Petition 870240103366, dated 04 / 12 / 2024, page 64 / 143 54 / 60

[0128] NMR of1H (400 MHz, Benzeno-d6) δ 9.18 (s, 2H), 8.89 (d, J = 5.3 Hz, 2H), 7.97 (d, J = 8.0 Hz, 2H), 7.60 (d, 5, J = 2.6, 9 J = 1.8 Hz, 4H), 7.48 (t, J = 1.8 Hz, 2H), 7.07 (t, J = 8.4 Hz, 2H), 6.67 (t, J = 7.6 Hz, 1H), 6.35 - 6.22 (m, 136H (3), 0.9 Hz, 36H), −0.18 (s, 9H), −0.48 (d, J = 8.8 Hz, 2H) ppm. NMR of13C (126 MHz, 0606) δ 166.91 (d, J = 14.5 Hz), 161.41 (d, J = 2.2 Hz), 150.82, 150.41, 143.27, 141.4 14.65, 1 130.33, 123.93, 123.22, 122.46, 121.10, 120.16, 119.14, 116.78, 114.09 (d, J = 58.3 Hz), 104.79, 35.4 (d, J = 6 = 31.48, 1.94, 15.82 (d, J = 28.8 Hz). NMR of31P (202 MHz, C606) δ 46.53. Example 23 - Synthesis of pro-catalyst 3 N-(Bis(2,6-diethoxyphenyl)phosphanyl)-carbazole-9carboxamide(trimethylsilylmethyl)(pyridine)nickel Try OEt

[0129] In a glove box filled with nitrogen, bis(trimethylsilylmethyl)bis(pyridine)nickel crystals (0.7100 g, 1.81 mmol) were added to a solution of N-(bis(2,6-diethoxyphenyl)phosfanyl)-carbazol-9-carboxamide (1.00 g, 2.18 mmol) in toluene (8 mL) to instantly obtain a reddish-brown solution. Within a few minutes, the color became a lighter brown and then a yellow precipitate began to form. The mixture was stirred for 1 hour at room temperature. The volatiles were then removed from the reaction mixture under reduced pressure. The resulting solid was ground with hexane, filtered, washed with hexane, and dried under reduced pressure to obtain the product as a yellow powder. The reaction yielded 1.20 g (1.56 mmol, 86% yield) of the product.

[0130] 1H NMR (400 MHz, Benzene-d6) δ 9.12 (dd, J = 4.8, 1.8 Hz, 2H), Petition 870240103366, dated 04 / 12 / 2024, page 65 / 143 55 / 60 9.03 (s, 2H), 7.91 (d, J = 7.6 Hz, 2H), 7.33 (t, J = 7.8 Hz, 2H), 7.19 (t, J = 7.4 Hz, 2H), 7.12 (d, J = 8.3 Hz, 2H, 6.90), J = 7.6, J Hz, 1H), 6.61 (t, J = 6.6 Hz, 2H), 6.36 (dd, J = 8.3, 3.7 Hz, 4H), 3.76 (dp, J = 22.9, 7.8 Hz, 8H), 1.04 (t, J = 7.0 Hz, 1H), (s -0.27 (d, J = 8.1 Hz, 2H). NMR of de13C (101 MHz, Benzeno-d6) δ 167.27 (d, J = 14.1 Hz), 161.12 (d, J= 1.9 Hz), 151.41 (d, J= 1.4 Hz), 125.42, 123.74 (d, J= 1.9 Hz), 121.07, 119.27, 118.16, 115.05 (d, J= 59.2 Hz), 105.12 (d, J = 4.6 Hz), 64.04, 14.59, (d, J = 29.2 Hz). NMR of de31P (162 MHz, Benzeno-d6) δ 46.29. Example 24 - Comparative Example - 3-(bis(2,6-dimethoxyphenyl)phosphanyl)-1,1dimethylurea-bis(trimethylsilylmethyl)nickel (compound (2)) (3) Ni(CH2TMS)2(pyridine)2 toluene, room temperature at 60 °C catalytically inactive form observed by NMR

[0131] N-alkylphosphino-urea based ligands, such as compound (3), did not proceed to the nickel carbamimide complex (1) that is required for polymerization activity. As illustrated in the reaction above, in the case of compound (3), 3-(bis(2,6-dimethoxyphenyl)phosphanyl)-1,1-dimethylurea, compound (2), the corresponding amide complex, formed rapidly. However, deprotonation of the ligand to form compound (1), the carbamimide complex, did not occur. Without adhering to theory, it is believed that N-arylphosphino-urea based ligands more readily form Ni complexes analogous to (1) than N-alkylphosphino-urea based ligands. Ni carbamimide complexes (1) are significantly more active in catalyzing olefin polymerization. Example 25 - Ethylene / tert-Butyl Acrylate Copolymerization - Studies in a Parallel Pressure Reactor Petition 870240103366, dated 04 / 12 / 2024, p. 66 / 143 56 / 60

[0132] Catalyst activity (in terms of deactivation time and polymer yield) and the resulting polymer characteristics were evaluated for Pro-catalysts 1 to 6. Polymerization reactions were carried out in a parallel pressure reactor (PPR), as previously described.

[0133] For these experiments, a catalyst stock solution was prepared (1 to 2 mM) in toluene and immediately fed to the PPR reactor. Copolymerization experiments were run at 400 psi ethylene pressure with a catalyst loading of 0.25 to 0.75 pmol. For copolymerizations, tert-butyl acrylate (t-BA) was purified by filtration through an activated alumina column, and for feeding to the PPR, a purified t-BA solution was prepared in toluene. The reactor temperature and tert-butyl acrylate loadings were varied as shown in Table 1. Each entry in Table 1 represents the average of at least 2 replicate runs. TABLE 1: Results in PPR for Nickel Catalysts Supported with Phosphine-Urea for Ethylene / tert-butyl Acrylate Copolymerization Catalyst Input (μmol) Acrylate Charge (μmol) Reactor Temp. (°C) Activity (kg / mol-h) Mw PDI Tm (°C) % mol of t-BA % wt of t-BA Yield (mg) 1 Pro-cat. 1 (0.75) 250 70 250 14,500 2.38 123 1.0 4.5 89 2 Pro-cat. 3 (0.75) 250 70 1,500 146,000 2.58 128 0.3 1.5 150 3 Pro-cat. 4 (0.75) 250 70 84 15,100 2.20 119 1.1 4.7 55 4 Pro-cat. 2 (0.75) 250 70 540 24,100 2.21 124 0.7 3.0 110 5 Pro-cat. 5 (0.75) 250 70 130 8,320 2.42 118 0.9 4.0 90 6 Pro-cat. 6 (0.50) 250 70 700 158,000 2.54 130 0.2 1.0 115 7 Pro-cat. 1 (0.75) 500 70 210 10,800 2.53 108 1.9 8.2 115 8 Pro-cat. 2 (0.75) 500 90 450 11,700 2.04 116 0.7 3.1 110 9 Pro-cat. 1 (0.75) 750 90 55 7,300 2.86 109 3.1 13 40 10 Pro-cat. 2 (0.75) 750 100 110 7,180 2.24 114 1.8 7.8 90 11 Pro-cat. 3 (0.50) 782 100 530 45,500 2.12 118 1.3 5.6 110 Petition 870240103366, dated 04 / 12 / 2024, page 67 / 143 57 / 60 12 Pro-cat. 6 (0.50) 750 90 160 47,000 2.26 121 0.9 3.8 80 13 Pro-cat. 3 (0.75) 1000 90 240 40,400 2.15 115 1.7 7.2 110 14 Pro-cat. 3 (0.75) 1250 90 130 33,600 2.13 113 1.9 8.3 100

[0134] Each of the pro-catalysts 1 to 6 is capable of copolymerization of ethylene and t-BA with high activities (such that the activity is greater than 20 kg / mol-h). In addition, each of the catalysts produced a polymer with significant amounts of acrylate incorporation, specifically, greater than 1.0 percent by weight. In each of the polymerization reactions, the pro-catalyst in this discovery produced a polymer with a narrow polydispersity index (PDI) (2.04 to 2.86) and molecular weights (MWs) in the range of 7,180 g / mol to 158,000 g / mol.

[0135] In another set of experiments, procatalyst complexes were prepared in situ by combining phosphinourea-based ligand and bis(trimethylsilylmethyl)bis(pyridine)nickel(II) in a 1:1 ratio in toluene and heating the mixture at 50 °C for 1 hour before being fed into PPR. The copolymerization results in PPR are summarized in Table 2. The values ​​in Table 2 are an average of at least two replicates, except for entry 5.

[0136] The following are phosphinourea-based binders: Ligand 1 (L1) Ligand 2 (L2) Binder 3 (L3) TABLE 2: Phosphine-Urea based binders tested in PPR using In situ metallation Metallized in situ catalysts evaluated in the PPR Catalyst Input (μmol) Acrylate Charge (pmol) Reactor Temp. (°C) Activity (kg / mol-h) Mw PDI Tm (°C) % mol of t-BA % wt of t-BA Yield (mg) 1 L1 (1.25) 250 90 55 483 1.43 44 0.4 2.0 75 Petition 870240103366, dated 04 / 12 / 2024, page 68 / 143 58 / 60 2 L3 (1.25) 250 90 600 18,300 4.32 123 1.0 4.4 100 3 L3 (1.25) 0 90 41,000 10,700 3.70 117 N / AN / A 284 4 L2 (1.25) 0 90 2,000 73,400 2.68 135 N / AN / A 125

[0137] The results tabulated in Table 2 indicate that metal-ligand complexes in which the R3 and R4 rings on the P atom are substituted at positions -2 and -6 are significantly more active (i.e., L2 and L3) and produce polymers with higher MW than metal-ligand catalysts in which the R3 and R4 positions remain unsubstituted (i.e., L1). For example, the catalyst produced by complexing Ligand L1 with the nickel precursor had an activity of 55 kg / mol and produced a polymer with a molecular weight (MW) of 483 g / mol. Ligand L1 includes 4-trifluoromethylphenyl groups at positions R3 and R4. The 4-trifluoromethylphenyl groups do not contain bulky substituents at positions -2 and -6 of the phenyl ring. Comparatively, the catalyst formed from the complexation of Ligand L3 and nickel had an activity of 600 kg / mol and produced a polymer with a molecular weight of 18,300 g / mol. Ligand L3 includes 2,6-dimethoxyphenyl groups at positions R3 and R4.Entries 3 (L3) and 4 (L2) in Table 2 demonstrate high activity for homopolymerization of ethylene when using metal-ligand complexes that have bulky steric groups located at positions -2 and -6 of the aryl rings at positions R3 and R4. Example 26 - Copolymerization of ethylene / n-butyl acrylate - studies in a parallel pressure reactor

[0138] For these experiments, a catalyst stock solution was prepared (1 to 2 mM) in toluene and immediately fed to the PPR reactor. Polymerization experiments were performed at 400 psi ethylene pressure with a catalyst loading of 0.25 pmol. For copolymerizations, n-butyl acrylate was purified by filtration through an activated alumina column, and for feeding to the PPR, an n-butyl acrylate solution in toluene was prepared. The reactor temperature and n-butyl acrylate loadings were varied as shown in Table 3. Each entry in Petition 870240103366, dated 04 / 12 / 2024, page 69 / 143 59 / 60 Table 3 represents the average of at least 2 replicated runs. TABLE 3: Results in PPR for Nickel Catalysts Supported with Phosphine-Urea for Ethylene / n-Butyl Acrylate Copolymerization Catalyst Input (pmol) Acrylate Charge (pmol) Reactor Temp. (°C) Activity (kg / mol-h) Mw PDI Tm (°C) mol% n-BA mol% n-BA Yield (mg) 1 Pro-cat. 1 (0.25) 125 70 500 14,900 2.36 122 1.0 4.2 100 2 Pro-cat. 1 (0.25) 250 70 230 8,180 2.19 113 1.9 8.2 60

[0139] The entries in Table 3 are organized primarily by acrylate charge, although the temperature for certain runs may vary.

[0140] The relative trends in reactivity for the copolymerization of tert-butyl acrylate (Table 1) are observed for n-butyl acrylate (Table 3). The catalyst activity and the molecular weight of the resulting copolymer are inversely related to the acrylate charge, while the incorporation is directly related to the acrylate charge.

[0141] It should be noted that, under identical acrylate loadings, higher acrylate incorporation in the copolymer is observed for n-butyl acrylate versus tert-butyl acrylate. For example, Pro-cat. 1 with 250 pmol n-butyl acrylate produces a polymer with 1.9 mol% acrylate incorporation (entry 2, Table 3), while under similar conditions but with 250 pmol tert-butyl acrylate, 1.0 mol% incorporation is observed (entry 1, Table 1). These results demonstrate that these Ni catalysts readily catalyze the formation of ethylene / acrylate copolymers with low steric volume (n-BA) and high steric volume (t-BA) acrylates. Example 27 - Ethylene / Acrylate Copolymerization - Batch Reactor Data

[0142] Ethylene / tert-butyl acrylate copolymerization reactions were catalyzed with a Ni(II)-phosphine-urea complex (Pro-catalyst 3) on a larger scale in a 2 L batch reactor according to the general Batch Reactor procedure previously described. The copolymerization experiments were performed at an ethylene pressure Petition 870240103366, dated 04 / 12 / 2024, pp. 70 / 143 60 / 60 at 400 psi. The reactor temperature and tert-butyl acrylate charge were varied as shown in Table 4. The tert-butyl acrylate (t-BA) was purified by filtration through an activated alumina column before addition to the reactor. The initial toluene charge to the reactor was 640 g (740 mL). The ethylene / tert-butyl acrylate copolymerization reactions were carried out for 75 minutes or until 40 g of ethylene absorption occurred, whichever was shorter.

[0143] Performance data is summarized in Table 4. TABLE 4: Performance of Pro-Catalyst 3 in a 2-Batch Reactor L at 400 psi of Ethylene Catalyst Input (mol) Acrylate Charge (mmol) Temp. Reactor Temperature (°C) Activity (kg / mol-h) Mw PDI Tm (°C) % mol of t-BA Yield (g) 1 Procatalyst 3 (178) 74 90 1,300 60,700 2.13 121 0.9 39.2 2 Procatalyst 3 (178) 222 90 490 35,100 2.09 114 2.3 49.4 3 Procatalyst 3 (178) 74 110 2,400 40,100 2.12 122 1.1 40.1 4 Procatalyst 3 (178) 222 110 690 21,900 2.21 113 2.7 47.0

[0144] As shown in Table 4, Pro-catalyst 3 was run in the batch reactor at two different temperatures (90 °C and 110 °C) and two different t-BA loadings (74 mmol or 222 mmol of tert-butyl acrylate). At inlet 1, at 90 °C with 74 mmol of t-BA present in the reactor, Pro-catalyst 3 had an activity of 1,300 kg / mol and produced 39.2 g of copolymer with a molecular weight of 60,700 g / mol and an acrylate incorporation of 0.9 mol%. At inlet 2, the acrylate incorporation more than doubled when 222 mmol of t-BA were added to the reactor, compared to inlet 1. However, the increased amount of acrylate incorporated into the polymer affected the molecular weight of the polymer. As reflected in entry 2, the molecular weight decreased to 35,100 g / mol and had an activity of 490 kg / mol h, when compared to the results in entry 1.

Claims

1. Pro-catalyst, according to formula (I): (I) characterized in that: M is nickel(II) or palladium(II); X being a ligand chosen from hydrocarbyl(C1-C40), heterohydrocarbyl(C1-C40), -CH2Si(Rc)3-q(ORc)q, -Si(Rc)3-q(ORc)q, -OSi(Rc)3q(ORc)q, -Ge(RC)3-Q(ORC)Q, -P(Rc)2_w(ORc)w, -P(O)(RC)2—w(ORC)w, -N(Rc)2, -N(Si(RC)3)2, -NRCSi(RC)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2Rc, -OS(O)2Rc, -N=C(Rc)2, -N=CH(Rc), -N=CH2, -N=P(Rc)3, -OC(O)RC, -C(O)ORC, -C(O)RC, -C(O)H, -N(RC)C(O)RC, -N(RC)C(O)H, -NHC(O)Rc, -NHC(O)H, -C(O)N(Rc)2, -C(O)NHRc, -C(O)NH2, a halogen, or a hydrogen, wherein: each RC is independently hydrocarbyl(C1-C30), heterohydrocarbyl(C1-C30), or -H, wherein hydrocarbyl(C1-C30) is unsubstituted or substituted with one or more RS, the subscript Q is 0, 1, 2, or 3; and the subscript w is 0, 1, or 2; Y is a Lewis base or a Lewis base covalently connected to X;R1 and R2 are chosen from aryl(C6-C40), heteroaryl(C1-C40), wherein the aryl (C6-C40) or heteroaryl (C1-C40) are unsubstituted or substituted with one or more RS; R3 and R4 are independently selected from radicals having the formula (II): Petition 870240103366, dated 04 / 12 / 2024, page 72 / 143 2 / 4 (II) wherein: R11, R12, R13, R14, and R15 are independently hydrocarbyl(C1-C30), heterohydrocarbyl(C1-C30), -ORN, -NRN2, -SRN, halogen or -H, wherein each RN is hydrocarbyl(C1-C30), provided that at least one of R11 and R15 is not -H; and each RS in formula (I) is independently hydrocarbyl (C1-C20) or halogen.; 2. Pro-catalyst, according to claim 1, characterized in that Y is a neutral Lewis basic aprotic heterohydrocarbon (C2-C40).

3. Pro-catalyst, according to either claim 1 or 2, characterized in that R3 and R4 are identical.

4. Pro-catalyst, according to claim 3, characterized in that R11 and R15 are independently alkyl (C1-C10).

5. Pro-catalyst, according to claim 3, characterized in that R11 and R15 are methoxyl.

6. Pro-catalyst, according to claim 3, characterized in that R11 and R15 are ethoxyl.

7. Pro-catalyst, according to claim 3, characterized in that R11 and R15 are independently -N[(C1-C10)alkyl]2.

8. Pro-catalyst, according to any one of claims 1 to 7, characterized in that R1 and R2 are connected and the pro-catalyst has the structure according to formula (III): Petition 870240103366, 04 / 12 / 2024, p. 73 / 143 3 / 4 (III) wherein each of R21 28 is independently chosen from -H, hydrocarbyl(C1-C40), heterohydrocarbyl(C1-C40), -Si(RR)3, -Ge(RR)3, -P(Rr)2, -P(O)(Rr)2, -N(Rr)2, -ORr, -SRr, -NO2, -CN, -CF3, or halogen, wherein each Rr is hydrocarbyl(C1-C30), heterohydrocarbyl(C1-C30), or -H; and M, Y, X, R3, and R4 are as defined in formula (I).

9. Pro-catalyst, according to claim 8, characterized in that R22 and R27 are independently aryl(C6-C40), wherein the aryl(C6-C40) is unsubstituted or substituted with one or more RS, wherein RS is hydrocarbyl(C1-C30), -CF3, or halogen atom.

10. Pro-catalyst, according to claim 9, characterized in that R22 and R27 are independently 3,5-bis(trifluoromethyl)phenyl or 3,5-di-tert-butylphenyl.

11. Pro-catalyst, according to claim 8, characterized in that R22 and R27 are independently alkyl (C1-C20).

12. Pro-catalyst, according to any one of claims 8 to 11, characterized in that R23 and R26 are independently aryl(C6-C40), wherein aryl(C6-C40) is unsubstituted or substituted with RS, where RS is hydrocarbyl(C1-C30), -CF3, or halogen atom.

13. Pro-catalyst, according to any one of claims 1 to 7, characterized in that R1 and R2 are aryl(C6-C40) substituted with at least one RS, where each RS is independently hydrocarbyl(C1-C30), -CF3, or halogen atom.

14. Pro-catalyst, according to any one of claims 1 to 7, characterized in that R1 and R2 are independently phenyl, 3,5-bis(trifluoromethyl)phenyl, or 3,5-di-tert-butylphenyl. Petition 870240103366, dated 04 / 12 / 2024, page 74 / 143 4 / 4 15. Pro-catalyst, according to any one of claims 1 to 14, characterized in that X is -CH2Si(CH3)3.

16. Polymerization process, characterized in that it comprises polymerizing ethylene or ethylene and one or more α-olefinic (C3-C10) monomers or one or more cyclic olefinic monomers or combinations thereof in the presence of a pro-catalyst as defined in any one of claims 1 to 15.

17. Polymerization process, characterized in that it comprises polymerizing ethylene and a polar comonomer, or ethylene and a polar comonomer and one or more α-olefinic (C3-C10) monomers, or one or more cyclic olefinic monomers, or combinations thereof, in the presence of a pro-catalyst as defined in any one of claims 1 to 15.

18. Polymerization process according to claim 16, characterized in that the polar comonomer is chosen from acrylate (CH2=CHC(O)(OR)), glycidyl acrylate, CH2=CH(CH2)nC(O)(OR), CH2=CHC(O)R, CH2=CH(CH2)nC(O)R, CH2=CH-OC(O)R, CH2=CH(CH2)n-OC(O)R, CH2=CH(OR), CH2=CH(CH2)n(OR), CH2=CHSi(R)3-t(OR)t, CH2=CH(CH2)nSi(R)3-T(OR)T, CH2=CH-OSi(R)3-t(OR)t, CH2=CH(CH2)n-OSi(R)3-T(OR)T or CH2=CHCl, where each R is chosen from -H, substituted hydrocarbyl (C1-C30), unsubstituted hydrocarbyl (C1-C30), substituted heterohydrocarbyl (C1-C30), or unsubstituted heterohydrocarbyl (C1-C30); each T being 0, 1, 2, or 3; and each n being from 1 to 10.

19. Polymerization process according to claim 18, characterized in that the polar comonomer is tert-butyl acrylate.

20. Polymerization process according to claim 18, characterized in that the polar comonomer is n-butyl acrylate.