Sterically hindered phosphino-urea supported nickel(II) or palladium(II) catalysts for copolymerization of ethylene with polar comonomers

Abstract

A process for polymerizing olefin monomers using a catalyst system and a method of producing a polymer comprising the process of formula (I) [Formula 1] A catalytic system comprising a procatalyst having a structure according to JPEG2023520144000041.jpg23128.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 002,767, filed March 31, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure relate generally to catalyst systems and processes for the polymerization of ethylene and polar comonomers, and more specifically to catalyst systems for the copolymerization of ethylene and acrylates that include a sterically hindered phosphino-urea supported nickel(II) catalyst, and olefin polymerization processes incorporating the catalyst systems. [Background technology]

[0003] Commercially, ethylene / acrylate copolymers are formed through 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 a route to highly linear ethylene / acrylate copolymers with a structure similar to that of linear low-density polyethylene (LLDPE). Linear ethylene / acrylate copolymers formed by coordination catalysis exhibit superior crystallinity and higher heat resistance than copolymers formed through radical processes.

[0004] Common organometallic coordination catalysts suitable for ethylene polymerization are incompatible with systems containing acrylates as comonomers. For example, the Group IV metal catalysts (Ti, Zr, Hf) used in the industrial production of LLDPE (ethylene / α-olefin copolymers) are incompatible with polar olefin monomers, including acrylates. Because the oxygen atoms of acrylates strongly coordinate with Lewis acidic Group IV metals, during ethylene / acrylate polymerization, the active sites of the metal are blocked by the acrylate, preventing further olefin polymerization.

[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 reaction of ethylene with acrylate monomers. However, many reported Ni- and Pd-containing metal catalysts suffer from (a) slow polymerization rates and / or (b) low incorporation of symmetric polar monomers. Summary of the Invention

[0006] There is a continuing need to create ligand frameworks for Ni and Pd catalysts that promote both high rates of ethylene copolymerization activity and high incorporation of acrylate comonomers. Nickel or palladium ligand frameworks can be used to copolymerize ethylene with polar monomers via coordination catalysis to form highly linear LLDPE-like copolymers. Highly linear copolymers can exhibit improved creep resistance and dimensional stability at higher application temperatures, specifically between 80°C and 150°C, as opposed to temperatures below 80°C.

[0007] Embodiments of the present disclosure include a catalyst system, which includes a procatalyst having a structure according to formula (I).

[0008] [ka]

[0009] In formula (I), M is nickel(II) or palladium(II), and X is (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -Ge(RC ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -N(Si(R C )3)2, -NR C Si(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C )3, -OC(O)R C , -C(O)OR C , -C(O)R C , -C(O)HN(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -NHC(O)H, -C(O)N(R C )2, -C(O)NHR C , —C(O)NH2, halogen, or hydrogen. C independently and optionally one or more R S (C1~C 30 ) hydrocarbyl or optionally one or more R S (C1~C 30 ) heterohydrocarbyl. The subscript Q in the various ligands X is 0, 1, 2, or 3. The subscript W in the various ligands X is 0, 1, or 2. Y is a Lewis base. Optionally, Y and X are covalently bonded.

[0010] In formula (I), R1 and R 2 (C6~C 40 ) aryl or (C1-C 40 ) heteroaryl, any of which optionally contains one or more R S can be replaced by R 3 and R 4 is independently selected from the group having formula (II):

[0011] [ka]

[0012] In formula (II), R 11 , R 12 , R 13 , R 14 , and R 15 are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, -OR N , -NR N 2, -SR N , halogen, or -H, where R 11 and R 15 At least one of is not -H.

[0013] In formula (I), each R S are independently (C1~C 20 ) hydrocarbyl or halogen.

[0014] Embodiments of the present disclosure include a polymerization process comprising polymerizing ethylene and one or more polar monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based copolymer, wherein the catalyst system comprises a metal-ligand complex according to formula (I) of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0015] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0016] Common abbreviations are listed below.

[0017] Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: isopropyl, t-Bu: tert-butyl, t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl), THF: tetrahydrofuran, Et2O: diethyl ether, CH2Cl2: dichloromethane, EtOAc: ethyl acetate, C6D6: deuterated benzene or benzene-d6, CDCl3: deuterated chloroform, Na2SO4: sodium sulfate, MgSO4: magnesium sulfate hm, HCl: hydrogen chloride, n-BuLi: butyl lithium, t-BuLi: tert-butyl lithium, K2CO3: potassium carbonate, N2: nitrogen gas, PhMe: toluene, PPR: parallel pressure reactor, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: mole, min or mins: minute, h or hrs: hour, d: day, R f : retention factor, TLC: thin layer chromatography, rpm: revolutions per minute.

[0018] The term "independently selected" followed by multiple options is 1 , R 2 , R 3 , R 4 , and R C etc. are used herein to indicate that the individual groups that appear before the term may be the same or different and that there is no dependency on the identity of any other groups that appear before the term.

[0019] The term "procatalyst" refers to a compound that has catalytic activity after activation, for example, upon removal of a Lewis base coordinated to a Ni or Pd metal center.

[0020] When used to describe certain carbon atom-containing chemical groups, "(C x ~C y A bracketed expression having the form "(C1-C)" means that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive, including x and y. For example, (C1-C 50 ) Alkyl, in its unsubstituted form, is an alkyl group having 1 to 50 carbon atoms. In some embodiments and general structures, specific chemical groups are S and R S generally represents any substituent defined herein. x ~C y )" for the chemical group R S The substituted version can be any group R S Depending on the identity of "R", the group may contain more than y carbon atoms. For example, "R S exactly one group R is phenyl (-C6H5) S (C1~C 50 A "(C ) alkyl" can contain from 7 to 56 carbon atoms. Therefore, the parenthesized "(C ) alkyl" is generally used. x ~C y )" is a group defined using one or more carbon atom-containing substituents R S The minimum and maximum total number of carbon atoms in the chemical group are x and y, respectively, when the group is substituted by the carbon atom-containing substituent R S It is determined by adding up the total number of carbon atoms in

[0021] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R SThe term "persubstituted" or "persubstituted" means that all hydrogen atoms (H) bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are substituted with a substituent (e.g., R S ) means substituted by a fluorine atom. Thus, a "perfluorinated alkyl" is an alkyl group in which all hydrogen atoms have been replaced by fluorine atoms. The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group have been replaced by substituents. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0022] "(C1~C 50 The term "(C1-C)hydrocarbyl" means a hydrocarbon group of 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 50 carbon atoms, each hydrocarbon group and each hydrocarbon diradical being aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and containing one or more R S is or is not replaced by

[0023] In this disclosure, (C1 to C 50 ) Hydrocarbyl is selected from the following groups: (C1-C 50 ) Alkyl, (C3-C 50 ) cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 ) alkylene (such as benzyl (—CH 2 —C 6 H 5 )).

[0024] "(C1~C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an unsubstituted or alkyl group containing one or more R S and saturated straight-chain or branched hydrocarbon groups of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively, substituted by a group which may be present on any one carbon atom of the alkyl. 50 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 2,2-dimethylpropyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C n ] alkyl. n The term "alkyl" means that the group, including the substituents, contains up to n carbon atoms, where n is an integer from 1 to 45. For example, [C 45 ] alkyl is, for example, one R that is (C1-C5) alkyl. S replaced by (C 27 ~C 40 ) alkyl, or, for example, each (C1-C 10 ) two R's that are alkyl S substituted by a group (C 15 ~C 25 ) alkyl. Examples of (C1-C5) alkyl include methyl, ethyl, 1-propyl, 1-methylethyl, 2,2-dimethylpropyl, or 1,1-dimethylethyl. 1,1-Dimethylethyl is a four-carbon alkyl with its group on a tertiary carbon. The term "tertiary carbon atom" refers to a carbon atom covalently bonded to three other carbon atoms.

[0025] "(C6~C 50 The term "aryl" refers to an unsubstituted or (one or more R S "Aromatic hydrocarbon groups" refers to monocyclic, bicyclic, or tricyclic aromatic hydrocarbon groups substituted (by C6-C), where at least 6 to 14 of the carbon atoms are aromatic ring carbon atoms. Monocyclic aromatic hydrocarbon groups include one aromatic ring, bicyclic aromatic hydrocarbon groups have two rings, and tricyclic aromatic hydrocarbon groups have three rings. When bicyclic or tricyclic aromatic hydrocarbon groups are present, at least one of the rings of the group is aromatic. The other ring or rings of the aromatic group may independently be fused or non-fused, and aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl include unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18 )aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, anthracenyl, and phenanthrenyl. 40 Examples of aryl include substituted (C1-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, 3,5-bis([C 20 ]alkyl)-phenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0026] "(C3~C 50 The term "cycloalkyl" refers to an unsubstituted or substituted group having one or more R S means a saturated cyclic hydrocarbon group of 3 to 50 carbon atoms substituted with other cycloalkyl groups (e.g., (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R SUnsubstituted (C3 to C 40 Examples of cycloalkyl are unsubstituted (C-C 20 ) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0027] (C1~C 50 Examples of hydrocarbylenes include (C6-C 50 ) arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20 Divalent groups include, but are not limited to, unsubstituted or substituted forms of groups such as alkylene, alkoxy, methyl ... 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH-), and 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (C6-C 50Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0028] "(C1~C 50 The term "alkylene" refers to an unsubstituted or substituted group having one or more R S means a saturated straight or branched chain divalent group of 1 to 50 carbon atoms (i.e., the group is not on a ring atom) substituted by 50 Examples of alkylene are unsubstituted (C1-C) alkylenes, including unsubstituted —CH2CH2—, —(CH2)3—, —(CH2)4—, —(CH2)5—, —(CH2)6—, —(CH2)7—, —(CH2)8—, —CH2C*HCH3, and —(CH2)4C*(H)(CH3). 20 ) alkylene, where "C*" indicates a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl group. 50 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted 1,20-eicosylene). 50 Examples of alkylene also include 1,2-cyclopentanediylbis(methylene), 1,2-cyclohexanediylbis(methylene), 7,7-dimethyl-bicyclo[2.2.1]heptane-2,3-diylbis(methylene), and bicyclo[2.2.2]octane-2,3-diylbis(methylene).

[0029] "(C3~C 50 The term "cycloalkylene" refers to an unsubstituted or substituted group having one or more R S means a cyclic divalent group of 3 to 50 carbon atoms (i.e., the group is on a ring atom) substituted by

[0030] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include -O-, -S-, -S(O)-, -S(O)2-, -Si(R C )2-, -P(R P )-, -P(R P )2, -P(O)(R P )2, -N(R N )-, -N(R N )2, -N=C(R C )2, -N=C(NR N 2)(R C ), -Ge(R C )2-, or -Si(R C ) 3, wherein each R C and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or —H, wherein each R N is unsubstituted (C1 to C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 50 The term "(C-C) heterohydrocarbyl" means a heterohydrocarbon group having 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" means a heterohydrocarbon divalent radical having 1 to 50 carbon atoms. (C-C 50 ) heterohydrocarbyl or (C-C 50 The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The heterohydrocarbyl group can be on a carbon atom or a heteroatom. The two groups of the heterohydrocarbylene can be on a single carbon atom or a single heteroatom. In addition, one of the two groups of the divalent group can be on a carbon atom and the other group can be on a different carbon atom, one of the two groups can be on a carbon atom and the other group can be on a heteroatom, or one of the two groups can be on a heteroatom and the other group can be on a different heteroatom. Each (C1-C 50 ) heterohydrocarbyl and (C1-C 50) heterohydrocarbylene is unsubstituted or (one or more R S and may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0031] (C1~C 50 ) Heterohydrocarbyl can be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heterohydrocarbyls include (C1-C 50 ) heteroalkyl, (C1-C 50 ) hydrocarbyl-O-, (C1-C 50 ) hydrocarbyl-S-, (C1-C 50 ) hydrocarbyl-S(O)-, (C1-C 50 ) hydrocarbyl-S(O)2-, (C1-C 50 ) Hydrocarbyl-Si(R C )2, (C l ~C 50 )hydrocarbyl-N(R N )-, (C l ~C 50 ) hydrocarbyl-P(R P )-, (C2~C 50 ) heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 50 ) heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene. Additional examples include -Si(R C ) 3-Q(OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C )2, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=P(R C )3, -OC(O)R C , -C(O)R C , -C(O)OR C , -N(R C )C(O)R C , and -C(O)N(R C ) 2, but are not limited to these.

[0032] "(C4~C 50 The term "heteroaryl" refers to an unsubstituted or substituted heteroaryl group of 1 to 50 total carbon atoms and 1 to 10 heteroatoms. SThe heteroaryl group may be present on a carbon atom or a heteroatom. Monocyclic heteroaromatic hydrocarbon groups include one heteroaromatic ring, bicyclic heteroaromatic hydrocarbon groups have two rings, and tricyclic heteroaromatic hydrocarbon groups have three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon group is present, at least one of the rings in the group is heteroaromatic. The other ring(s) of the heteroaromatic group may independently be fused or non-fused, and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C4-C 12 ) heteroaryl, etc. x ~C y ) heteroaryl (general) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or contains one or more R SThe monocyclic heteroaromatic hydrocarbon group is defined in the same manner as being substituted with . The monocyclic heteroaromatic hydrocarbon group is a 5-membered or 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 heteroaromatic hydrocarbon groups include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. A 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and the heteroatoms can be N or P. Examples of 6-membered heteroaromatic hydrocarbon groups include pyridin-2-yl, pyrimidin-2-yl, pyrazin-2-yl, and 1,3,5-triazin-2-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon groups are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon groups can be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0033] "(C1~C 50 The term "(C1-C2) heteroalkyl" means a saturated straight or branched chain group containing 1 to 50 carbon atoms and one or more heteroatoms. 50The term "heteroalkylene" refers to a saturated, straight-chain or branched-chain divalent group containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatom of a heteroalkyl or heteroalkylene is selected from the group consisting of Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), P(O)(R P )2, N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O)2, each of which may be unsubstituted or may contain one or more R S has been replaced by

[0034] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0035] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom (fluoride (F) - ), chloride (Cl - ), bromide (Br - ), or iodide (I - )) means.

[0036] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be substituted by a substituent R S The term "unsaturated" means containing one or more carbon-carbon double or triple bonds, or one or more carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, or carbon-silicon double bonds (in heteroatom-containing groups), and if present, the substituent R S It does not include any double bonds which may be present in the (hetero)aromatic ring or, if any, in the (hetero)aromatic ring.

[0037] Embodiments of the present disclosure include catalyst systems, including procatalysts having a structure according to formula (I):

[0038] [ka]

[0039] In formula (I), M is nickel(II) or Pd(II), and X is (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C )2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -N(Si(R C )3)2, -NR C Si(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C ) 3、 -OC(O)R C , -C(O)OR C , -C(O)R C , -C(O)H, -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -NHC(O)H, -C(O)N(R C )2, -C(O)NHR C , —C(O)NH, halogen, or hydrogen, wherein each R C independently and optionally one or more R S (C1~C 30 ) hydrocarbyl, or optionally one or more R S (C1~C 30 ) heterohydrocarbyl, wherein the subscript Q is 0, 1, 2, or 3, and wherein the subscript W is 0, 1, or 2. Y is a Lewis base, and optionally Y and X are covalently bonded.

[0040] In one or more embodiments, R 1 and R 2 (C6~C 40 ) aryl, (C1-C 40) heteroaryl, optionally with one or more R S is replaced by .

[0041] In embodiments, R 3 and R 4 is independently selected from the group having formula (II):

[0042] [ka]

[0043] In formula (II), R 11 , R 12 , R 13 , R 14 , and R 15 are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, -OR N , -NR N 2, or -SR N where R N is (C1~C 30 ) hydrocarbyl, provided that R 11 and R 15 At least one of is not -H.

[0044] In one or more embodiments, in formula (I), R 1 and R 2 In one or more embodiments, in formula (I), R 3 and R 4 are identical.

[0045] In various embodiments, in formula (I), R 11 and R 15 are independently -O[(C1~C 10 ) alkyl]. In some embodiments, R 11 and R 15 is methoxy or ethoxy. In other embodiments, R 11 and R15 are independently -N[(C1~C 10 ) alkyl]2.

[0046] In one or more embodiments, R 1 and R 2 is at least one R S (C6~C 40 ) aryl, and each R S are independently (C1~C 30 ) hydrocarbyl, —CF, or a halogen atom. In some embodiments, R 1 and R 2 is independently phenyl, 3,5-bis(trifluoromethyl)phenyl, or 3,5-di-tert-butylphenyl.

[0047] In various embodiments, R 1 and R 2 is bonded, and the procatalyst has a structure according to formula (III).

[0048] [ka]

[0049] In formula (III), R 21~28 Each of the groups independently represents -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R R )3, -Ge(R R )3, -P(R R )2, -P(O)(R R )2, -N(R R )2, -OR R , -SR R , —NO2, —CN, —CF3, or halogen, wherein each R R is (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or -H, and M, Y, X, R 3, and R 4 is as defined in formula (I).

[0050] In various embodiments, in formula (III), R 22 and R 27 are independently optionally R S (C6~C 40 ) aryl, and R S is (C1~C 30 ) hydrocarbyl, —CF, or a halogen atom. In some embodiments, R 22 and R 27 is independently 3,5-bis(trifluoromethyl)phenyl or 3,5-di-tert-butylphenyl. 22 and R 27 are independently (C1~C 20 ) alkyl.

[0051] In one or more embodiments, R 23 and R 26 are independently optionally R S (C6~C 40 ) aryl, and R S is (C1~C 30 ) hydrocarbyl, —CF, or a halogen atom. In some embodiments, R 23 and R 26 are independently (C1~C 20 ) alkyl. In other embodiments, R 23 and R 26 is -CF3. In various embodiments, R 21~28 All of (i.e., R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 ) is -H.

[0052] Each R in formula (I) Care independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H, and each R in formula (I) S are independently (C1~C 20 ) hydrocarbyl or halogen.

[0053] In the metal-ligand complex according to Formula (I), each Y is bonded to M through a dative or 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 can donate an electron pair to an acceptor moiety. For 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 hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cycloethers, phosphines, or sulfides. Examples of neutral hydrocarbon Lewis bases include, but are not limited to, alkenes, alkynes, or arenes.

[0054] In one or more embodiments, Y is a neutral Lewis basic aprotic (C-C 40 ) Heterohydrocarbons. 40 ) Heterohydrocarbons are those (C-C) as defined above. 40 All hydrogen atoms of heterohydrocarbons have a pKa greater than 30, where pKa is the negative base 10 logarithm of the acid dissociation constant (Ka), (C2-C 40) heterohydrocarbon. In some embodiments, Y is an organic Lewis base. Examples of organic Lewis bases include pyridine or substituted pyridines, sulfoxides, trialkyl or triaryl phosphines, trialkyl or triaryl phosphine oxides, olefins or cyclic olefins, substituted or unsubstituted heterocycles, alkyl esters of aliphatic or aromatic carboxylic acids, aliphatic ketones, aliphatic amines, alkyl or cycloalkyl ethers, or mixtures thereof, wherein each electron donor has 2 to 20 carbon atoms. In various embodiments, the organic Lewis base is selected from alkyl and cycloalkyl ethers having 2 to 20 carbon atoms, and dialkyl, diaryl, and alkylaryl ketones having 3 to 20 carbon atoms, and alkyl esters having 2 to 20 carbon atoms. Specific examples of organic Lewis bases 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, picoline, pyridine, dimethyl sulfoxide, trimethylphosphine, triethylphosphine, triphenylphosphine, cyclooctadiene, cyclopentene, ethylene, propylene, tert-butylethylene, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, 1-methylimidazole, or 1-methylpyrazole.

[0055] In one or more embodiments, the Lewis base group Y of formula (I) can be a monodentate ligand, which can be a neutral ligand. In some embodiments, the neutral ligand can contain a heteroatom. In certain embodiments, Y is R T NR K R L , R K OR L , R K SR L , or R T PR KR L wherein each R T , R K , and R L are independently [(C1~C 10 )hydrocarbyl]3Si(C1-C 10 ) hydrocarbyl, (C1-C 40 ) hydrocarbyl, [(C1-C 10 )hydrocarbyl]3Si, (C1-C 40 ) heterohydrocarbyl, or hydrogen.

[0056] In some embodiments, the Lewis base group Y of formula (I) is (C1-C 20 ) hydrocarbon. In some embodiments, the Lewis base group Y is cyclopentadiene, 1,3-butadiene, or cyclooctene.

[0057] In various embodiments, the Lewis base group Y of formula (I) is (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, Y is tetrahydrofuran, pyrene, dioxane, diethyl ether, or methyl tert-butyl ether (MTBE).

[0058] In various embodiments, the Lewis base is (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is nitrogen. In some embodiments, Y is pyridine, picoline, lutidine, trimethylamine, or triethylamine.

[0059] In various embodiments, the Lewis base is (C1-C 20) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is phosphorus. In some embodiments, Y is trimethylphosphine, triethylphosphine, triphenylphosphine, triethylphosphite, trimethylphosphite, triphenylphosphine oxide.

[0060] In some embodiments, X and Y are covalently linked. Specific examples of organic Lewis bases Y covalently linked together with the X groups include, but are not limited to, 4-cycloocten-1-yl, 2-dimethylaminobenzyl, and 2-dimethylaminomethylphenyl.

[0061] In some embodiments, X and Y are linked and selected from the group consisting of:

[0062] [ka] In the formula, R C is -H or (C1 to C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, (C1-C 20 ) alkyl, or (C1-C 12 ) alkyl.

[0063] In the metal-ligand complex according to formula (I), X is bonded to M through a covalent or ionic bond. In some embodiments, X can be a monoanionic ligand having a net formal oxidation number of -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) hydrocarbyl carbanions, (C1-C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, hydrogen carbonates, dihydrogen phosphates, hydrosulfates, HC(O)O - , HC(O)N(H) - , (C1~C40 ) Hydrocarbyl C(O)O - , (C1~C 40 ) Hydrocarbyl C(O)N((C1-C 20 )hydrocarbyl) - , (C1~C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L Si - wherein each R K , R L , and R M are independently hydrogen, (C1 to C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, and R K and R L together, (C2~C 40 ) hydrocarbylene or (C1-C 20 ) form a heterohydrocarbylene, and R M is as defined above.

[0064] In some embodiments, X is halogen, (C1-C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O—, or R K R L N-, wherein R K and R L Each of is independently unsubstituted (C1 to C 20 In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10) hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) hydrocarbyl C(O)O—, or R K R L N-, wherein R K and R L Each of is independently unsubstituted (C1 to C 10 ) hydrocarbyl.

[0065] In further embodiments, X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2,-dimethylpropyl, trimethylsilylmethyl, dimethylphenylsilylmethyl, methyldiphenylsilylmethyl, triphenylsilylmethyl, benzyldimethylsilylmethyl, trimethylsilylmethyldimethylsilylmethyl, phenyl, benzyl, or chloro.

[0066] In one or more embodiments, each X is independently —(CH)SiR X 3, wherein each R X are independently (C1~C 30 ) alkyl or (C1-C 30 ) heteroalkyl, and at least one R X is (C1~C 30 ) alkyl. In some embodiments, R X One of them is (C1~C 30 ) heteroalkyl, wherein at least one heteroatom is a silicon atom or an oxygen atom. In some embodiments, R X is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0067] In one or more embodiments, X is selected from the group consisting of -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(C6H5), -(CH2)Si(CH3)(C6H5), -(CH2)Si(CH3)2(CH2C6H5), -(CH2)Si(CH3)2(CH2CH3), -(CH2)Si(CH3)(CH2CH3), -(CH2)Si(CH2CH3), -(CH2)Si(CH2CH3), -(CH2)Si(CH3)2(n-butyl), -(CH2)Si(CH3)2(n-hexyl), -(CH2)Si(CH3)(n-octo)R X , -(CH2)Si(CH3)2R X , -(CH2)Si(n-oct)R X 2, —(CH2)Si(CH3)2(2-ethylhexyl), —(CH2)Si(CH3)2(dodecyl), or —CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as —CH2Si(CH3)2(CH2TMS)). Optionally, in some embodiments, in a metal-ligand complex according to Formula (I), exactly two R X are covalently bonded or exactly three R X are covalently bonded.

[0068] In some embodiments, X is —CHSi(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q where the subscript Q is 0, 1, 2, or 3, and each R C are independently substituted or unsubstituted (C1 to C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl. In some embodiments, X is —CH 2 Si(CH 3 ) 3 , and in other embodiments, X is —CH 2 Si(CH 3 ) 2 OSi(CH 3 ) 3 .

[0069] In some embodiments, any or all of the chemical groups of the procatalyst of formula (I) are R 11 or R 15 R may be unsubstituted, except for any of 11 and R 15 In another embodiment, at least one of the chemical groups X and R of the metal-ligand complex of formula (I) is substituted. 1 ~R 4 , R 11~15 , or R 21~28 Any of the above may contain one or more R S or any or all of them may be substituted with one or more R S Two or more R S are attached to the same chemical group of the procatalyst of formula (I), the individual R S may be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, the chemical groups X and R 1 ~R 4 , R 11~15 , or R 21~28 Both of these are R S or any or all of them may be oversubstituted with R S It can be oversubstituted with R S In chemical groups that are over-substituted with S may all be the same or may be independently selected.

[0070] Embodiments of the present disclosure include polymerization processes. In some embodiments, the polymerization process includes polymerizing ethylene and one or more olefin monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based copolymer, wherein the catalyst system includes a metal-ligand complex according to Formula (I), as described herein. Olefin monomers include 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 acrylates, glycidyl acrylate, vinyl acetate, CH═CHC(O)(OR). X ), CH2=CHC(O)R X , CH2=CH(OR X ), CH2=CH(CH2)(OR X ), CH2=CHSi(R X ) 3-Y (OR X ) Y , CH2=CH-OSi(R X ) 3-Y (OR X ) Y or CH═CHCl, where R X is -H, substituted or unsubstituted (C1-C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl, and the subscript Y is 0, 1, 2, or 3.

[0071] In one or more embodiments, a polymerization process comprises polymerizing ethylene, one or more polar monomers, and optionally one or more α-olefin monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene / polar monomer copolymer, wherein the catalyst system comprises a procatalyst according to formula (I) of the present disclosure. In one or more embodiments, a polymerization process comprises polymerizing ethylene, one or more alkyl acrylate monomers, and optionally one or more α-olefin monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene / alkyl acrylate copolymer, wherein the catalyst system comprises a procatalyst according to formula (I) of the present disclosure.

[0072] In one or more embodiments, the polymerization process comprises polymerizing ethylene, one or more polar monomers, and optionally one or more cyclic olefin monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene / polar monomer copolymer, wherein the catalyst system comprises a procatalyst according to formula (I) of the present disclosure. Cyclic olefin monomers are cyclic compounds containing ethylenic unsaturation in the cyclic portion of the molecule. Examples of these include (C1-C6) olefins at the 5- and 6-positions. 20 In one or more embodiments, the polymerization process comprises polymerizing ethylene, one or more alkyl acrylate monomers, and optionally one or more cyclic olefin monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene / alkyl acrylate copolymer, wherein the catalyst system comprises a procatalyst according to formula (I) of the present disclosure.

[0073] In various embodiments of the polymerization process, polar comonomers include alkyl acrylate (CH=CHC(O)(OR)), glycidyl acrylate, CH=CH(CH) n C(O)(OR), CH2=CHC(O)R, CH2=CH(CH2) n C(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) n Si(R) 3-T (OR) T , CH2=CH-OSi(R) 3-T (OR) T , CH2=CH(CH2) n -OSi® 3-T (OR) T or CH2=CHCl. ​​Each R is -H, a substituted (C1-C 30 ) Hydrocarbyl, unsubstituted (C1-C 30 ) Hydrocarbyl, substituted (C1-C 30 ) heterohydrocarbyl, or unsubstituted (C1-C 30 ) heterohydrocarbyl. The subscript T is 0, 1, 2, or 3. The subscript n is 1 to 10. The polar monomer is selected from alkyl acrylate, substituted (C1-C 30 ) Hydrocarbyl acrylate, unsubstituted (C1-C 30 ) Hydrocarbyl acrylate, substituted (C1-C 30 ) heterohydrocarbyl acrylate, or unsubstituted (C1-C 30 In embodiments where the acrylate is a heterohydrocarbyl acrylate, the polar ethylene-based copolymer may be deesterified to form an acrylic acid ethylene-based copolymer.

[0074] In some embodiments of the polymerization process, the polar comonomer can be an alkyl acrylate, such as, by way of example and not limitation, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, or combinations thereof. In various embodiments, the alkyl acrylate is a C1-C8 alkyl acrylate, i.e., an alkyl ester of acrylic acid, where the alkyl has 1 to 8 carbon atoms. In certain embodiments, the polar comonomer is an alkyl acrylate selected from t-butyl acrylate or n-butyl acrylate.

[0075] In some embodiments of the polymerization process, the optional α-olefin 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 comprises the steps of: (C1-C6) 20 ) hydrocarbyl-substituted cyclic olefins such as cyclobutene, cyclopentene, norbornene, and norbornene derivatives.

[0076] In an exemplary embodiment, the catalyst system can include a procatalyst according to Formula (I) having the structures of Procatalysts 1-6 listed below:

[0077] [ka] In the formula, TMS is trimethylsilyl, Me is methyl, Et is ethyl, and tBu is t-butyl.

[0078] Ethylene / Acrylate Copolymer In various embodiments, the polymerization process of the present disclosure may produce a polar ethylene-based copolymer, wherein the polar ethylene-based copolymer contains at least 50 weight percent (wt%) ethylene, based on the weight of the polar ethylene-based copolymer. In some embodiments, the polar ethylene-based copolymer is the reaction product of 70 wt% to 99.9 wt% ethylene units and 0.1 wt% to 30 wt% polar comonomer units, based on the total of the ethylene units and the polar comonomer units.

[0079] In one or more embodiments, the polymerization process of the present disclosure can include ethylene monomer, alkyl acrylate monomer, and optionally one or more α-olefins. In some embodiments of the polymerization process including α-olefins, the α-olefins can be incorporated into the produced polymer in an amount of 0.01 to 49.9 wt.%, based on the weight of the ethylene-based copolymer.

[0080] In various embodiments, the polymerization process of the present disclosure may produce ethylene-based copolymers having a molecular weight of from 2,000 g / mol to 1,000,000 g / mol. In some embodiments, the produced polymers have a molecular weight of from 25,000 g / mol to 900,000 g / mol, from 30,000 g / mol to 800,000 g / mol, or from 10,000 g / mol to 300,000 g / mol.

[0081] General procedure for PPR screening experiments 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 (6 × 8 matrix) reactors within an inert atmosphere glovebox. Each cell was equipped with a glass insert (reactor tube) with an internal working liquid volume of approximately 5 mL. Each cell had independent pressure control and was continuously stirred at 500 Hz. Catalyst, ligand, and metal precursor solutions, as well as optional activator solutions (if used), were prepared in toluene unless otherwise noted. Unless otherwise indicated, ligands were metallated at a 1:1 ligand:metal (L:M) ratio by premixing the metal precursor solution with the ligand solution. In many cases, the procatalyst complexes resulting from the metallation reaction were isolated and purified before being introduced into the PPR reactor. All liquids (i.e., solvent, t-butyl acrylate, and catalyst solutions, as well as optional activator solutions (if used)) were added via robotic syringes. The gas reagent (i.e., ethylene) was added via a gas inlet. Before each run, the reactor was heated to 50°C, purged with ethylene, and evacuated. Tert-butyl acrylate was filtered through a short column of activated alumina before use to remove any polymerization inhibitors (e.g., 4-methoxyphenol).

[0082] All desired cells were injected with t-butyl acrylate, followed by a portion of toluene. The reactor was heated to the run temperature and then pressurized with ethylene to the appropriate pressure. The isolated procatalyst complex or in situ metallated ligand, and optional activator solution (if used), were then added to the cells. Each catalyst addition was chased with a small amount of toluene to bring the total reaction volume to 5 mL after the final addition. Once the catalyst was added, the PPR software began monitoring the pressure in each cell. The desired pressure (within approximately 2-6 psig) was maintained by opening the valve at 1 psi below the set point, closing the valve when the pressure reached 2 psi above, and adding supplemental ethylene gas. All pressure drops were recorded as ethylene "uptake" or "conversion" over the run period, or until the desired uptake or conversion value was reached, whichever occurred first. Each reaction was then quenched by adding 1% oxygen in nitrogen at 40 psi above the reactor pressure for 30 seconds (the elapsed time from the start of the run to the time the quench was initiated was designated the "quench time"). The shorter the "quench time," the more active the catalyst. To prevent excessive polymer formation in any given cell, the reaction was quenched when a predetermined uptake level of 80 psig was reached. After quenching, all reactors were allowed to cool to approximately 60°C. They were then vented, and the reactor tubes were removed and placed in a centrifugal evaporator. Polymer samples were then dried in the centrifugal evaporator at 60°C for 12 hours and weighed to determine polymer yield and were subjected to IR (t-butyl acrylate incorporation), GPC (molecular weight, polydispersity (PDI)), and DSC (melting point) analyses.

[0083] General procedure for batch reactor experiments NOTE: Contact with tert-butyl acrylate should be minimized, for example, by using a dump pot with a lid and a well-ventilated fume hood, as the acrylate is a sensitizer. Care must be taken when transferring the reactor contents to the dump pot and when emptying the dump pot in the fume hood.

[0084] The polymerization reaction was carried out in a 2 L Parr batch reactor. The reactor was heated by an electric heating mantle and cooled by an internal spiral cooling coil containing cooling water. Water was pretreated by passing it through an Evoqua water purification system. Both the reactor and the heating / cooling system were controlled and monitored by a Camile TG process computer. The bottom of the reactor was equipped with a dump valve that discharged the reactor contents into a covered dump pot. The dump pot was pre-filled with a catalyst deactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The covered dump pot was vented to a 15-gallon blowdown tank, and both the pot and the tank were purged with N2. All chemicals used for the polymerization or catalyst composition were passed through purification columns to remove any impurities that could affect the polymerization. Toluene was passed through two columns: the first column containing A2 alumina and the second column containing the Q5 reactant. tert-Butyl acrylate was filtered through activated alumina. Ethylene was passed through two columns, the first containing A204 alumina and 4 Å molecular sieves, and the second containing the Q5 reactant. The N2 used for transfer was passed through a single column containing A204 alumina, 4 Å molecular sieves, and the Q5 reactant.

[0085] The reactor was initially filled from a shot tank containing toluene and tert-butyl acrylate. The shot tank was filled to the fill setpoint using a differential pressure transducer. After the solvent / acrylate addition, the shot tank was rinsed twice with toluene, and the rinse was transferred to the reactor. The reactor was then heated to the desired polymerization temperature setpoint. Once the temperature setpoint was reached, ethylene was added to the reactor to reach the desired pressure setpoint. The rate of ethylene addition to the reactor was monitored by a Micro Motion flow meter.

[0086] The procatalyst was handled in an inert atmosphere glovebox and introduced to the reactor as a solution in toluene. The procatalyst solution was drawn into a syringe and pumped into the catalyst shot tank. The syringe was then rinsed three times with 5 mL of toluene. The procatalyst was added only after the reactor pressure set point was achieved.

[0087] Immediately after the procatalyst addition, a run timer was started. Ethylene was then fed to the reactor (via a Camile controller) to maintain the pressure set point. The ethylene / tert-butyl acrylate copolymerization reaction was run for 75 minutes or until 40 g of ethylene uptake occurred, whichever was shorter. The agitator was then stopped, and the bottom dump valve was opened to transfer the reactor contents to a lidded dump pot. The valve on the lidded dump pot was closed, and the sealed dump pot was disconnected from the reactor and removed to a fume hood. Once inside the fume hood, the lid was removed from the dump pot and the contents were poured onto a tray. The tray was left in the hood for a minimum of 36 hours to allow the solvent and tert-butyl acrylate to evaporate. The tray containing the remaining copolymer was then transferred to a vacuum oven, where it was heated to 140 °C under vacuum to remove any remaining volatiles. After the tray cooled to ambient temperature, the copolymer was weighed for yield / efficiency and, if desired, subjected to polymer testing.

[0088] GPC procedure High-temperature GPC analysis was performed using a Dow Robot Assisted Delivery (RAD) system equipped with a Polymer Char infrared detector (IR5) and an Agilent PL-gel Mixed A column. Decane (10 μL) was added to each sample for use as an internal flow marker. The polymer was first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxyltoluene (BHT) to a concentration of 10 mg polymer / mL TCB and dissolved by stirring at 160 °C for 120 min. Prior to injection into the instrument, the sample was further diluted with BHT-stabilized TCB to a concentration of 3 mg polymer / mL TCB. Samples (250 μL) were eluted at a flow rate of 1.0 mL / min through one PL-gel 20 μm (50 mm × 7.5 mm) guard column, followed by two PL-gel 20 μm (300 mm × 7.5 mm) Mixed-A columns, both maintained at 160 °C in BHT-stabilized TCB. The total run time was 24 min. To calibrate the molecular weight (MW), Agilent's EasiCal polystyrene standards (PS-1 and PS-2) were dissolved by diluting with 1.5 mL of BHT-stabilized TCB and stirring at 160 °C for 15 min. These standards were analyzed to generate a third-order MW calibration curve. The molecular weight units were converted from polystyrene (PS) units to polyethylene (PE) units using a 1-day Q factor calculated to be approximately 0.4 using the average of five Dowlex 2045 reference samples.

[0089] FT-IR procedure A 10 mg / mL sample prepared for GPC analysis was also utilized to quantify tert-butyl acrylate (tBA) incorporation by Fourier transform infrared spectroscopy (FTIR). A Dow robotic preparation station heated and stirred the sample at 160 °C for 60 minutes, then deposited 130 μL portions into stainless steel wells formed on a silicon wafer. The TCB was evaporated at 160 °C under a nitrogen purge. Resolution: 4 cm. -1 4000~400cm using 128 scans -1IR spectra were collected using a Nexus 6700 FT-IR equipped with a DTGS KBr detector. tBA (C=O): 1762–1704 cm -1 ) and ethylene (CH2: 736-709 cm -1 ) and fitted to a linear calibration curve to determine total tBA.

[0090] DSC procedure The melting temperature (Tm), glass transition temperature (Tg), crystallization temperature (Tc), and heat of fusion of solid polymer samples are measured by differential scanning calorimetry (DSC Q2000, TA Instruments, Inc.) using a heat-cool-heat temperature profile. Open-pan DSC samples of 3-6 mg of polymer were subjected to the following temperature profile, and the traces were analyzed individually using TA Universal Analysis software or TA Instruments TRIOS software. Equilibrate at 175.00°C Isothermal for 3 minutes 30.00℃ / min to 0.00℃ Rise to 175.00°C at 10.00°C / min [Example]

[0091] Examples 1-17 are synthetic procedures for the ligand intermediates and ligands. Examples 18-24 are synthetic procedures for the isolated procatalysts. Examples 25 and 26 summarize and discuss the results of polymerization reactions of procatalysts 1-6. One or more features of the present disclosure are illustrated in view of the following examples.

[0092] General Procedure All reactions were carried out in a nitrogen-purged glovebox unless otherwise noted. All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified via passage through activated alumina and, in some cases, the Q-5 reactant. The alumina for solvent purification was activated by passing a stream of nitrogen through the alumina at 300 °C for 8 hours. The Q-5 reactant was activated by heating at 200 °C under a stream of nitrogen for 4 hours, followed by heating at 200 °C under a stream of 5% hydrogen in nitrogen for 3 hours, and finally flushing with nitrogen gas. Solvents used in experiments conducted in a nitrogen-filled glovebox were further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware was dried overnight in an oven before use. HRMS analysis was performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. 1 H NMR data are reported as follows: chemical shifts (multiplicities (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integrals, and assignments). Residual protons in deuterated solvents are used as standards. 1 Chemical shifts for H NMR data are reported in ppm downfield from tetramethylsilane (TMS, δ scale). 13 C NMR data, 1 The phosphine groups were determined using H decoupling and chemical shifts are reported in ppm relative to tetramethylsilane. 13 The C NMR spectrum was complex due to C-P coupling. 31Chemical shifts for P NMR data are reported in ppm relative to external neat H3PO4. Deuterated solvents for NMR analysis were purchased from Cambridge Isotope Laboratories and stored over activated 4 Å molecular sieves in a nitrogen-purged glovebox. Chlorobis(2,6-dimethoxyphenyl)phosphine, chlorobis(2,6-diethoxyphenyl)phosphine, and bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) were prepared according to literature procedures.

[0093] Ligand preparation Example 1 - 2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazole

[0094] [ka]

[0095] 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 equipped with a reflux condenser and subsequently heated to 100 °C for 72 h. The reaction was cooled, filtered through a silica pad, and rinsed with dichloromethane. The filtrate was concentrated onto Celite, and the product was purified by column chromatography using 20% ​​dichloromethane / hexane. The product was isolated as a white powder. The reaction yielded 1.652 g (2.78 mmol, 85% yield) of product.

[0096] 1H NMR (400Mhz, chloroform-d) δ 8.34(s, 1H, NH), 8.25(d, J=8.1Hz, 2H), 8.16(s, 4H), 7.91(s, 2H), 7.75(d, J=1.6Hz, 2H), 7.56(dd, J=8.1, 1.6Hz, 2H)ppm. 13 C 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, 121.23-120.62 (m), 119.50, 109.56 ppm.

[0097] Example 2 - 2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazole

[0098] [ka]

[0099] In a fume hood, a mixture of 2,7-dibromocarbazole (1.06 g, 3.27 mmol), 3,5-di-t-butylphenylboronic acid (2.30 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 equipped with a reflux condenser and subsequently heated to 100 °C for 24 h. The reaction was cooled and filtered through a silica pad, rinsing with dichloromethane. The filtrate was concentrated onto Celite, and the product was purified by column chromatography using hexane / ethyl acetate. The product precipitated from 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.

[0100] 1H NMR (400MHz, chloroform-d)δ 8.17(s, 1H), 8.15(d, J=8.1Hz, 2H), 7.67(d, J=1.6Hz, 2H), 7.57(d, J=1.8Hz , 4H), 7.53(dd, J=8.1, 1.5Hz, 2H), 7.49(t, J=1.8Hz, 2H), 1.45(s, 36H)ppm. 13 C 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.

[0101] Example 3 - 9H-Carbazole-9-carboxamide

[0102] [ka]

[0103] In a glovebox, a 250 mL round-bottom Schlenk flask was charged with 9H-carbazole-9-carbonyl chloride (500 mg, 2.18 mmol), a stir bar, and 30 mL of diethyl ether. The flask was removed from the box and placed under a nitrogen stream on a Schlenk line. With vigorous stirring, a solution of ammonia in isopropanol (2.0 M) was added to the contents of the flask (16.3 mL, 32.66 mmol). A white precipitate immediately formed, and the solution was stirred at room temperature for 18 hours. All volatiles were then removed under vacuum, leaving a white solid 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 product.

[0104] 1H NMR (400MHz, chloroform-d) δ 8.15(d, J=8.4Hz, 2H), 8.07(d, J=7.7Hz, 2H), 7.53(t, J=7.7Hz, 2H), 7.40(t, J=7.5Hz, 2H), 5.61(s, 2H)ppm. 13 C NMR (126 MHz, chloroform-d) δ 178.67, 127.16, 122.73, 120.16, 114.14, 95.81, 95.77 ppm.

[0105] Example 4 - 2,7-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazole-9-carboxamide

[0106] [ka]

[0107] In a glove box, 2,7-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazole (515 mg, 1.31 mmol), a stir bar, and 10 mL of THF were added to a 20 mL vial. The solution was cooled to −35° C. in a glove box freezer. The vial was removed from the freezer, and solid NaN(SiMe3)2 (265 mg, 1.45 mmol, 1.1 equiv.) was slowly added. The reaction mixture was allowed to warm slowly to room temperature with stirring for 1.5 hours. To a separate vial was added 4-nitrophenyl chloroformate (268 mg, 1.45 mmol, 1.1 equiv.), a stir bar, and 3 mL of THF. With stirring, the carbazole-containing solution was added dropwise to the 4-nitrophenyl chloroformate-containing solution. Upon complete addition, the solution turned bright orange with the concomitant formation of a precipitate. The reaction mixture was stirred for 18 hours, then removed from the glovebox and quenched with water. The aqueous mixture was extracted with dichloromethane (3 x 15 mL), and the organic fraction was separated, dried over MgSO, and filtered. All volatiles were removed on a rotary evaporator, leaving a pale yellow solid. The solid was washed with hexane and collected by filtration. A total of 501 mg (67%) of precipitate was collected during filtration, confirming that the major component was the desired product. 1 The purity was confirmed by H NMR spectroscopy. The crude solid (501 mg, 0.90 mmol, based on 100% purity) was dissolved in DMF (2 mL) and transferred to a 20 mL vial. Ammonium carbonate (32 mg, 30% NH3, 1.85 mmol, 2.0 equiv.) was added, the vial was sealed, and the mixture was stirred at ambient temperature for 18 hours. The cap was carefully removed, and the reaction was quenched by the addition of water (15 mL). A white precipitate formed and was collected via 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 1 H and 13 The reaction was confirmed by C NMR spectroscopy. The reaction gave 213 mg (0.49 mmol, 37% yield over two steps) of product.

[0108] 1H NMR (500MHz, chloroform-d)δ 8.13(d, J=1.6Hz, 2H), 7.87(d, J=8.2Hz, 2H), 7.40(dd, J=8.2, 1.6Hz, 2H), 5.67(s, 2H), 1.85(s, 4H), 1.47(s, 12H), 0.73(s, 18H)ppm. 13 C 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.

[0109] Example 5 - 3,6-Di-tert-butyl-9H-carbazole-9-carboxamide

[0110] [ka]

[0111] In a glovebox, 3,6-di-t-butylcarbazole (735 mg, 2.63 mmol), a stir bar, and 10 mL of THF were added to a 20 mL vial and cooled overnight at -35 °C in a freezer. The vial was removed from the freezer, and n-butyllithium (2.0 M, 1.45 mL, 2.89 mmol, 1.1 equiv.) was slowly added, and the vial was returned to the freezer for 30 minutes. The vial was then removed from the freezer, and the reaction mixture was allowed to stir at room temperature for 1.5 hours. 4-Nitrophenyl chloroformate (537 mg, 2.89 mmol, 1.1 equiv.) was added to a 120 mL jar along with a stir bar and 15 mL of THF. With stirring, the lithium carbazole solution was added dropwise to the 4-nitrophenyl chloroformate 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 a sticky yellow solid. 1The H NMR spectrum was consistent with the carbamate intermediate. DMF (8 mL) was added to the crude reaction mixture, and the material was removed outside the glovebox. In a fume hood, ammonium carbonate (179 mg, 30% NH3, 3.16 mmol) was added to the mixture, the jar was sealed, and the contents were stirred at room temperature for 18 hours. The solution was diluted with 100 mL of deionized water, and the precipitate that formed was collected by filtration, washed several times with water, and dried under vacuum. The reaction yielded 768 mg (2.39 mmol, 91% yield).

[0112] 1 H NMR (400MHz, CDCl3)δ 8.18-7.98(m, 4H), 7.55(dd, J=8.6, 2.1Hz, 2H), 5.55(s, 2H), 1.48(s, 18H)ppm. 13 C NMR (126MHz, CDCl3) δ 153.78, 145.82, 136.70, 125.58, 124.70, 116.20, 113.72, 34.74, 31.77ppm.

[0113] Example 6 - 2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazole-9-carboxamide

[0114] [ka]

[0115] In a glove box, 2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazole (545 mg, 1.00 mmol), a stir bar, and 15 mL of THF were added to a 20 mL vial and cooled to -35 °C in a freezer for 2 hours. The vial was removed from the freezer, and n-butyllithium (2.0 M, 0.55 mL, 1.10 mmol, 1.1 equiv.) was slowly added, and the vial was returned to the freezer for 30 minutes. The vial was then removed from the freezer, and the reaction mixture was allowed to stir at room temperature for 1.5 hours. 4-Nitrophenyl chloroformate (205 mg, 1.10 mmol, 1.1 equiv.) was added to a 120 mL jar along with a stir bar and 15 mL of THF. While stirring, the lithium carbazole solution was added dropwise to the 4-nitrophenyl chloroformate 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 a sticky yellow solid. 1 The H NMR spectrum was consistent with the carbamate intermediate. The crude material from the reaction was dissolved in 8 mL of DMF, and the jar containing the material was sealed and removed outside the glovebox. In a fume hood, ammonium carbonate (67 mg, 30% NH3, 1.20 mmol) was added to the mixture, the jar was sealed, and the contents were stirred at room temperature for 18 hours. The solution was diluted with 100 mL of deionized water, and the precipitate that formed was collected by filtration, washed several times with water, and dried under vacuum. 1 The H NMR spectrum was consistent with the desired product. The reaction yielded 511 mg (0.87 mmol, 87% yield).

[0116] 1 H NMR (400MHz, chloroform-d)δ 8.36(d, J=1.4Hz, 2H), 8.11(d, J=8.0Hz, 2H), 7.64(dd, J=8.0, 1.5Hz, 2H), 7 .55(d, J=1.8Hz, 4H), 7.51(d, J=1.8Hz, 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.

[0117] Example 7 - 2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazole-9-carboxamide

[0118] [ka]

[0119] In a glovebox, 2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazole (770 mg, 1.30 mmol), a stir bar, and 15 mL of THF were added to a 20 mL vial and cooled to −35° C. in a freezer for 2 hours. The vial was removed from the freezer, and n-butyllithium (2.0 M, 0.72 mL, 1.43 mmol, 1.1 equiv.) was slowly added, and the reaction mixture was returned to the freezer for 30 minutes. The reaction mixture was then removed from the freezer and allowed to stir at room temperature for 1.5 hours. 4-Nitrophenyl chloroformate (289 mg, 1.43 mmol, 1.1 equiv.) was added to a 120 mL jar along with a stir bar and 15 mL of THF. With stirring, the lithium carbazole solution was added dropwise to the 4-nitrophenyl chloroformate 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 a sticky yellow solid. 1The H NMR spectrum was consistent with the carbamate intermediate. DMF (8 mL) was added to the crude reaction mixture, and the material was removed outside the glovebox. In a fume hood, ammonium carbonate (88 mg, 30% NH3, 1.56 mmol) was added to the mixture, the jar was sealed, and the contents were stirred at room temperature for 18 hours. The solution was diluted with 100 mL of deionized water, and the precipitate that formed was collected by filtration, washed several times with water, and dried under vacuum. The product was recrystallized from hot ethyl acetate and cooled at 2 °C overnight. The product was isolated by filtration as a white powder. The product was isolated to give 768 mg (1.21 mmol, 93% yield).

[0120] 1 H NMR (500MHz, chloroform-d) δ 8.37(d, J=1.5Hz, 2H), 8.20(d, J=8.1Hz, 2H), 8.12(s, 4H), 7.91(s, 2H), 7.65(dd, J=8.1, 1.5Hz, 2H), 5.70(s, 2H)ppm. 19 F NMR (376 MHz, chloroform-d) δ −62.75 ppm.

[0121] Example 8 - N-(bis(2,6-dimethoxyphenyl)phosphanyl)-9H-carbazole-9-carboxamide

[0122] [ka]

[0123] In a glovebox, a 20 mL vial was charged with 9H-carbazole-9-carboxamide (300 mg, 1.43 mmol), 8 mL of THF, and a stir bar. The solution was placed in a freezer at −35° C. for 1.5 hours. After removal from the freezer, 2.0 M n-butyllithium (0.79 mL, 1.57 mmol, 1.1 equiv.) was added dropwise with stirring, and the solution was immediately returned to the freezer. After 10 minutes, the reaction mixture was removed from the freezer, and a slurry of bis(2,6-dimethoxyphenyl)chlorophosphine (487 mg, 1.43 mmol) in 4 mL of THF was added. The reaction mixture was then warmed to room temperature and stirred for 1 hour. After 1 hour, the reaction mixture was dried under vacuum, and 15 mL of dichloromethane was added. The reaction mixture was filtered through a plug of 50 / 50 Celite and silica to remove LiCl. All volatiles were removed from the filtrate, and the product was triturated with diethyl ether and collected by filtration. NMR spectroscopy confirmed that the by-product was present only in the diethyl ether-soluble fraction, and the collected precipitate was pure product. The reaction yielded 378 mg (0.73 mmol, 51% yield).

[0124] 1 H NMR (400MHz, benzene-d6)δ 8.70(d, J=5.5Hz, 2H), 8.35(dt, J=8.2, 0.9Hz, 4H), 7.83-7.72(m, 4H), 7.19-7.13(m, 4H) , 7.12-7.06(m, 8H), 6.93(t, J=8.3Hz, 5H), 6.14(dd, J=8.3, 2.6Hz, 8H), 3.12(s, 20H)ppm. 13 C NMR (126MHz, benzene-d6)δ 162.04(d, J=10.0Hz), 153.73(d, J=22.4Hz), 139.11, 130.25, 126.55, 12 5.11, 121.74, 119.65, 116.21 (d, J=30.8Hz), 114.62, 104.53, 55.24ppm. 31 P NMR (162MHz, benzene-d6) δ-1.44ppm. HRMS(ESI+)(m / z):[M+H]C 29 H 28Calculated value of N2O5P: 515.1730, measured value: 515.1752.

[0125] Example 9-N-(bis(2,6-diethoxyphenyl)phosphanyl)-9H-carbazole-9-carboxamide

[0126] [ka]

[0127] In a glovebox, a glass jar was equipped with a stir bar, 9H-carbazole-9-carboxamide (1.0 g, 4.76 mmol), and dry THF (25 mL). The white slurry was placed in a glovebox freezer at −35° C. for 30 minutes. After 30 minutes, the jar was removed from the freezer, and 2.5 M n-butyllithium in hexanes (2.1 mL, 5.25 mmol) was added dropwise while stirring the contents. The resulting cloudy yellow solution was placed back in the freezer, and after 10 minutes, the reaction mixture was removed from the freezer and a cooled slurry 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 hours while slowly warming to room temperature. After 30 minutes, an aliquot of the reaction mixture (white slurry) was removed and 31 Analysis by 1 P NMR spectroscopy confirmed the conversion of the chlorophosphine. 31 The reaction was complete according to the P NMR spectrum. The reaction mixture was concentrated in vacuo to give a white solid, and dichloromethane (55 mL) was added. The cloudy solution was filtered through a plug of Celite and concentrated in vacuo to give a white solid. The solid was triturated with diethyl ether. The slurry was stirred at room temperature for 5 minutes, and the solid was collected by filtration, washed with diethyl ether, and dried under vacuum. The solid was 1 H NMR and 31Analysis by P NMR spectroscopy revealed the presence of several impurities. The product was purified by column chromatography using a gradient of 0-20% ethyl acetate in hexanes. Fractions from the column were analyzed by HRMS. The product-containing fractions were combined and concentrated by rotary evaporation to give a white solid. The solid was dried under high vacuum to give 0.844 g (1.48 mmol, 31% yield) of a white solid.

[0128] 1 H NMR (400MHz, chloroform-d)δ 8.43(d, J=5.6Hz, 1H), 8.11(d, J=8.3Hz, 2H), 8.00(d, J=7.7Hz, 2H), 7.39(t, J=7.7Hz, 3H), 7.30(t, J=7.4 Hz, 2H), 7.18(t, J=8.3Hz, 2H), 6.46(dd, J=8.3, 2.7Hz, 4H), 4.05-3.54(m, 8H), 1.01(t, J=7.0Hz, 12H)ppm. 13 C NMR (101 MHz, chloroform-d) δ 161.16 (d, J = 9.8 Hz), 153.92 (d, J = 24.2 Hz), 138.87, 130.46, 126.66, 125.11, 122.02, 119.85, 115.81 (d, J = 25.2 Hz), 114.52, 104.99, 64.38, 14.28 ppm. 31 P NMR (162 MHz, chloroform-d) δ −2.85 ppm.

[0129] Example 10-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazole-9-carboxamide

[0130] [ka]

[0131] In a glovebox, 2,7-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazole-9-carboxamide (213 mg, 0.49 mmol), a stir bar, and 5 mL of THF were added to a 20 mL vial and cooled to −35° C. in a freezer overnight. The solution was removed from the freezer, and n-butyllithium (2.0 M, 0.27 mL, 0.54 mmol, 1.1 equiv.) was slowly added, and the reaction mixture was returned to the freezer for 20 minutes. The reaction mixture was removed from the freezer, and a slurry of chlorobis(2,6-dimethoxyphenyl)phosphine (149 mg, 0.49 mmol) in 3 mL of THF was added. The reaction mixture was allowed to warm to room temperature and stirred for an additional hour. All volatiles were then removed under vacuum, and 10 mL of dichloromethane was added to the resulting residue. The dichloromethane solution was filtered through a plug of Celite to remove LiCl. All volatiles were then removed from the filtrate under vacuum, leaving a white solid. 1 H and 31 P NMR spectroscopy confirmed that the major component was the desired product. The crude reaction mixture was purified by column chromatography using hexane and ethyl acetate. The reaction yielded 193 mg (0.26 mmol, 53% yield) of product, which was isolated as a white powder.

[0132] 1 H NMR (400MHz, benzene-d6)δ 8.47(d, J=1.6Hz, 2H), 8.29(d, J=6.7Hz, 1H), 7.85(d, J=8.2Hz, 2H), 7.33(dd, J=8.2, 1.6Hz, 2H), 7.00(td, J=8.2, 0.8Hz, 2H), 6.23(dd, J=8.3, 2.6Hz, 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. 31 P NMR (162MHz, benzene-d6) δ-2.71ppm. HRMS(ESI+)(m / z):[M+H]C 45 H 60 Calculated value of N2O5P: 739.4239, measured value: 739.424.

[0133] Example 11-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,6-di-tert-butyl-9H-carbazole-9-carboxamide

[0134] [ka]

[0135] In a glovebox, a 20 mL vial was charged with 3,6-di-tert-butyl-9H-carbazole-9-carboxamide (50 mg, 0.16 mmol), bis(2,6-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 stir bar. The solution was heated with stirring at 60° C. for 18 hours. The solution was cooled and filtered to remove undesired salts. The filtrate was then concentrated under vacuum to a volume of approximately 1 mL, and hexanes (10 mL) were added. A large amount of white precipitate formed, which was subsequently collected by filtration, washed with hexanes, and dried under vacuum. 1H NMR spectroscopy revealed that the white solid was mostly the desired product, although some phosphorylated by-product appeared to be present. The product was purified by column chromatography in 20% ethyl acetate / hexane. The reaction yielded 81 mg (0.13 mmol, 83% yield) of product, which was isolated as a white powder.

[0136] 1 H NMR (500MHz, benzene-d6)δ 8.27(s, 2H), 8.16(s, 2H), 7.42(d, J=8.7Hz, 2H), 6.96(tt, J=8.2, 1.5Hz, 2H) , 6.14(ddd, J=8.3, 3.2, 1.1Hz, 4H), 2.93(d, J=1.2Hz, 12H), 1.36(s, 18H)ppm. 13 C NMR (101 MHz, benzene-d6) δ 151.51, 151.36, 138.00, 129.31, 128.51, 125.61, 122.94, 122.33, 111.21 (d, J = 13.9 Hz), 109.36 (d, J = 3.1 Hz), 46.45, 35.20, 31.80 (d, J = 1.6 Hz), 21.63 ppm. 31 P NMR (202MHz, benzene-d6) δ-1.75ppm. HRMS(ESI+)(m / z):[M+H]C 37 H 44 Calculated value of N2O5P: 627.2987, measured value: 627.291.

[0137] Example 12-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazole-9-carboxamide

[0138] [ka]

[0139] In a glovebox, 2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazole-9-carboxamide (287 mg, 0.49 mmol), a stir bar, and 5 mL of THF were added to a 20 mL vial and cooled overnight at −35° C. in a freezer. The vial was removed from the freezer, and n-butyllithium (2.0 M, 0.27 mL, 0.54 mmol, 1.1 equiv.) was slowly added, and the reaction mixture was returned to the freezer for 15 min. The reaction mixture was removed from the freezer, and a slurry of chlorobis(2,6-dimethoxyphenyl)phosphine (170 mg, 0.50 mmol) in 3 mL of THF was added. The reaction mixture was allowed to warm to room temperature and stirred for an additional hour. All volatiles were then removed under vacuum, and 10 mL of dichloromethane was added to the resulting residue. The dichloromethane solution was filtered through a plug of Celite 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 under vacuum to a volume of approximately 2 mL, and the product was triturated with hexane to give an off-white solid. The product was collected by filtration and dried under vacuum. A total of 87 mg of material was isolated during filtration. 1 H and 31 The desired product was confirmed by P NMR spectroscopy. All volatiles were removed from the filtrate, and the resulting crude solid was dissolved in a minimum amount of hexane. The hexane solution was placed in a freezer at −35° C. overnight. The next day, a white powder precipitated and was quickly collected by filtration and dried. A second crop of powder was also confirmed to be the desired product (98 mg) by NMR spectroscopy. Yield: 185 mg (2 crops, 0.21 mmol, 42% yield) of product was isolated.

[0140] 1H NMR (400MHz, benzene-d6)δ 8.93(d, J=5.5Hz, 1H), 8.90(d, J=1.4Hz, 2H), 8.01(d, J=8.0Hz, 2H), 7.71(dd, J=8.0, 1.5Hz, 2H), 7.66(d, J=1.8Hz, 4 H), 7.55(t, J=1.8Hz, 2H), 6.89(td, J=8.2, 0.8Hz, 2H), 6.08(dd, J=8.3, 2.6Hz, 4H), 3.07(s, 12H), 1.32(s, 36H)ppm. 13 C NMR (101 MHz, benzene-d6) δ 162.03 (d, J = 10.1 Hz), 151.09, 142.10 (d, J = 23.6 Hz), 140.28, 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, 31.36, 25.27, 20.51 ppm. 31 P NMR (162MHz, benzene-d6) δ-1.35ppm. HRMS(ESI+)(m / z):[M+H]C 57 H 68 Calculated value of N2O5P: 891.486, measured value: 891.481.

[0141] Example 13-N-(bis(2,6-diethoxyphenyl)phosphanyl)-2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazole-9-carboxamide

[0142] [ka]

[0143] In a glovebox, 2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazole-9-carboxamide (187 mg, 0.30 mmol), a stir bar, and 5 mL of THF were added to a 20 mL vial and cooled to −35° C. in a freezer overnight. The reaction mixture was removed from the freezer, and n-butyllithium (2.0 M, 0.16 mL, 0.32 mmol, 1.1 equiv.) was slowly added, and the reaction mixture was returned to the freezer for 15 min. The reaction mixture was removed from the freezer, and a slurry of chlorobis(2,6-diethoxyphenyl)phosphine (123 mg, 0.31 mmol, 1.05 equiv.) in 3 mL of THF was added. The reaction was allowed to warm to room temperature and stirred for an additional hour. All volatiles were then removed under vacuum, and 10 mL of dichloromethane was added to the resulting residue. The dichloromethane solution was filtered through a plug of Celite to remove LiCl. The filtrate was concentrated under vacuum to a volume of 2 mL, and the resulting residue was triturated with hexane to give a white solid. The product was collected by filtration and dried under vacuum. The product was further purified by column chromatography (20% ethyl acetate / hexane). The reaction yielded 44 mg (0.05 mmol, 18% yield) of product, which was isolated as a white powder.

[0144] 1 H NMR (500MHz, benzene-d6)δ 8.59(d, J=5.2Hz, 2H), 8.43(s, 2H), 7.83(d, J=8.0Hz, 2H), 7.79(s, 4H), 7.73(s, 2H), 7.07(dd, J=8.0, 1.6 Hz, 2H), 6.97(t, J=8.2Hz, 2H), 6.08(dd, J=8.4, 2.7Hz, 4H), 3.54-3.01(m, 8H), 0.70(t, J=7.0Hz, 11H)ppm. 31 P NMR (202 MHz, benzene-d6) δ -1.57 ppm.

[0145] Example 14-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,5-dimethyl-1H-pyrazole-1-carboxamide

[0146] [ka]

[0147] In a glovebox, 3,5-dimethyl-1H-pyrazole-1-carboxamide (460 mg, 3.13 mmol), a stir bar, and 12 mL of THF were added to a 60 mL jar 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 equiv.) was slowly added. The reaction mixture was returned to the freezer for 15 minutes. A suspension of chlorobis(2,6-dimethoxyphenyl)phosphine (1.183 g, 3.47 mmol) in 8 mL of THF was then added to the cooled reaction mixture. The mixture was allowed to slowly warm to room temperature with stirring for 2 hours. During this time, a large amount of precipitate formed 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 mostly the desired product (95% pure), with a small amount of phosphine oxide present (approximately 5%). All volatiles were removed from the filtrate under vacuum and diethyl ether was added, resulting in the precipitation of additional product. The precipitate was collected by filtration, washed with excess diethyl ether, and dried. A second batch of powder was obtained. 31 It was greater than 98% pure by P NMR spectroscopy and was combined with the first batch of powder to give a combined mass of 983 mg (2.10 mmol, 67% yield).

[0148] 1 H NMR (400MHz, chloroform-d)δ 10.02(d, J=5.9Hz, 1H), 7.21(t, J=8.3Hz, 2H), 6.50(dd, J=8.4, 2.7Hz, 4H), 5.89(s, 1H), 3.80(s, 12H), 2.58(s, 3H), 2.26(s, 3H)ppm. 13C NMR (101 MHz, chloroform-d) δ 161.97 (d, J = 9.8 Hz), 149.18, 143.54, 130.50, 115.19 (d, J = 25.6 Hz), 109.24, 104.32, 55.92, 25.62, 14.19, 13.78 ppm. 31 P NMR (162 MHz, chloroform-d) δ −4.46 ppm.

[0149] Example 15-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-5H-dibenzo[b,f]azepine-5-carboxamide

[0150] [ka]

[0151] In a glovebox, a 20 mL vial was charged with 9H-carbazole-9-carboxamide (104 mg, 0.44 mmol), THF (5 mL), and a stir bar. The resulting solution was cooled to −35° C. in a freezer for 2 hours. The solution was removed from the freezer, and n-butyllithium (272 μL, 0.54 mmol) was added dropwise with stirring. The reaction mixture was returned to the freezer for 2 hours. 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 cooled solution. The solution was allowed to slowly warm to room temperature with stirring for 18 hours. During this time, a large amount of white precipitate formed, which was collected by filtration, washed with hexane, and dried under vacuum. 1 H NMR spectrum indicated that the THF-insoluble material was the desired product. LiCl was presumably rinsed into the filtrate. Yield: 152 mg (0.25 mmol, 57% yield) of product was isolated.

[0152] 1H NMR (500MHz, chloroform-d)δ 7.43(dd, J=8.0, 1.3Hz, 2H), 7.36(ddd, J=7.9, 7.0, 1.7Hz, 2H), 7.31(dd, J=7.7, 1.8Hz, 2H), 7.27(ddd, J=7.7, 4.8, 2.2Hz, 3H), 7.12(t, J=8.2Hz, 2H), 6.39(dd, J=8.3, 2.6Hz, 4H), 3.71(d, J=12.8Hz, 1H), 3.55(s, 12H)ppm. 13 C NMR (126 MHz, benzene-d6) 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. 31 P NMR (202 MHz, chloroform-d) δ -3.89 ppm. HRMS (ESI+) (m / z): [M+H]C 31 H 30 Calculated value of N2O5P: 541.189, measured value: 541.179.

[0153] Example 16-N-(bis(4-(trifluoromethyl)phenyl)phosphanyl)-9H-carbazole-9-carboxamide

[0154] [ka]

[0155] In a glovebox, a 20 mL vial was charged with 9H-carbazole-9-carboxamide (173 mg, 0.825 mmol), a stir bar, and THF (8 mL). The solution was placed in a freezer (-35 °C) for 2 hours 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 for 15 minutes. Upon 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 to room temperature and stirred for 2 hours. All volatiles were then removed in vacuo, and the resulting crude solid was dissolved in dichloromethane and filtered through a Celite plug to remove LiCl. The filtrate was concentrated in vacuo to a volume of approximately 2 mL, and the product was triturated with hexanes. The resulting white precipitate was collected by filtration and dried under vacuum. 1 H NMR spectroscopy revealed the white solid to be the desired product. Yield: 355 mg (0.67 mmol, 81% yield) of product was isolated.

[0156] 1 H NMR (400MHz, chloroform-d)δ 8.14-8.00(m, 4H), 7.93(d, J=8.2Hz, 2H), 7.77-7.67(m, 8H), 7.55-7.35(m, 8H), 7.26-7.21(m, 1H), 6.33(d, J=3.0Hz, 1H)ppm. 13 C 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. 19 F NMR (376 MHz, chloroform-d) δ −63.01 ppm. 31P NMR (162MHz, chloroform-d) δ 26.70ppm. HRMS(ESI+)(m / z):[M+H]C 27 H 18 Calculated value of F6N2OP: 531.1055, measured value: 531.109.

[0157] Example 17 - 3-(bis(2,6-dimethoxyphenyl)phosphanyl)-1,1-dimethylurea

[0158] [ka]

[0159] In a glovebox, a glass jar equipped with a stir bar was charged with 1,1-dimethylurea (0.500 g, 5.67 mmol) and chilled, dry THF (30 mL). Not all of the starting material dissolved in solution. The reaction mixture was placed in the glovebox freezer at −35° C. for 30 minutes. After 30 minutes, it was removed from the freezer, and n-BuLi (2.5 M, 2.50 mL, 6.25 mmol) in hexanes was added dropwise with stirring. The resulting cloudy solution was placed back into the freezer (−35° C.). The reaction mixture was maintained at −35° C. for 3 hours, periodically removed and stirred. After 3 hours, the reaction mixture was removed from the freezer, and a chilled 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 1 hour while slowly warming to room temperature. After 1 hour, an aliquot of the reaction mixture (resulting pale yellow slurry) 31Analysis by P NMR spectroscopy indicated that the reaction was complete. The reaction mixture was concentrated in vacuo to give a pale yellow sticky solid, and dichloromethane (45 mL) was added. The cloudy solution was filtered through a plug of Celite and concentrated in vacuo to give an off-white crystalline solid. The solid was triturated with diethyl ether. The slurry was stirred at room temperature for 5 minutes, and the solid was collected by filtration and washed with diethyl ether. The solid was dried in vacuo to give 1.059 g (2.72 mmol, 48% yield) of the desired product as a white solid. 31 There was evidence of small amounts of oxidation by-products in the P NMR spectrum.

[0160] 1 H NMR (400MHz, CDCl3) δ 7.52(d, J=6.0Hz, 1H), 7.15(t, J=8.3Hz, 2H), 6.47(dt, J=8.4, 4.4Hz, 5H), 3.71(s, 12H), 2.92(s, 6H)ppm. 13 C NMR (101MHz, CDCl3) δ 161.83, 131.09, 130.33(d, J=3.7Hz), 116.59(d, J=26.5Hz), 104.88-104.66(m), 104.19, 56.12, 36.42ppm. 31 P NMR (162MHz, CDCl3) δ-2.82ppm.

[0161] Preparation of Ni complexes Example 18 - Synthesis of Procatalyst 1 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-9H-carbazole-9-carbimidate)(pyridine)(trimethylsilylmethyl)nickel(II)

[0162] [ka]

[0163] In a glovebox, a 20 mL vial was charged with bis(trimethylsilylmethyl)bis(pyridine)nickel (86 mg, 0.22 mmol, 1.0 equiv.), a stir bar, and 2 mL of toluene. Then, a solution of N-(bis(2,6-dimethoxyphenyl)phosphanyl)-9H-carbazole-9-carboxamide (113 mg, 0.22 mmol) in 8 mL of toluene was slowly added with stirring. The solution was orange and clear. The solution was slowly heated to 45° C. and stirred for 1 hour. All volatiles were then removed under vacuum. Hexane (3 mL) was added and subsequently removed under vacuum, leaving an orange sticky solid. The product was suspended in hexane and stirred for 15 minutes. The product was then collected by filtration and dried under vacuum. Yield: 147 mg (0.20 mmol, 89% yield) of product was isolated.

[0164] 1 H NMR (400MHz, benzene-d6)δ 9.11-8.89(m, 4H), 7.92(dd, J=7.8, 1.4Hz, 2H), 7.30(ddd, J=8.5, 7.2, 1.4Hz, 2H), 7.25-7.05(m, 4H+CDCl3), 6.97-6 .83(m, 1H), 6.67-6.53(m, 2H), 6.37(dd, J=8.3, 3.7Hz, 4H), 3.40(s, 12H), -0.12(s, 9H), -0.38(d, J=8.9Hz, 2H)ppm. 13 C NMR (126MHz, benzene-d6)δ 167.07(d, J=14.5Hz), 161.47(d, J=2.1Hz), 151.02, 140.77, 136.30, 130.31, 125.61, 125.11, 123.38(d, J=1.8H z), 120.75, 118.91, 117.78, 114.39(d, J=58.8Hz), 104.79(d, J=4.4Hz), 55.47, 1.93, -16.02(d, J=28.9Hz)ppm. 31 P NMR (202 MHz, benzene-d6) δ 46.84 ppm.

[0165] Example 19 - Synthesis of Procatalyst 2 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazole-9-carbimidate)(trimethylsilylmethyl)(pyridine)nickel(II)

[0166] [ka]

[0167] In a glovebox, a 20 mL vial was charged with bis(trimethylsilylmethyl)bis(pyridine)nickel (56 mg, 0.14 mmol, 1.05 equiv.), a stir bar, and 1 mL of toluene. Then, a solution of N-(bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazole-9-carboxamide (100 mg, 0.14 mmol) in 3 mL of toluene was added slowly with stirring. The solution was orange and clear. The reaction mixture was stirred at 60° C. for 1 hour. An aliquot of the reaction mixture was added. 31 P NMR spectroscopic analysis indicated complete conversion to the desired complex. The reaction mixture was then cooled, and all volatiles were removed under vacuum. The resulting crude material was dissolved in a minimum amount of hexane and placed in a freezer at −35° C. overnight. During this time, the desired product precipitated from solution. The orange precipitate was collected by filtration and dried under vacuum. The isolated orange solid was confirmed to be the desired product by NMR spectroscopy. The reaction yielded 71 mg (0.08 mmol, 54% yield) of product.

[0168] 1H NMR (400 MHz, benzene-d6) δ 9.12(dd, J=4.7, 1.7Hz, 2H), 9.01(s, 2H), 7.88(d, J=8.1Hz, 2H), 7.28(dd, J=8.2, 1.7Hz, 2H), 7.15-7.10(m, 2H+CDCl3), 6.98(tt, J=7.6, 1.7Hz, 2H) , 6.79-6.63(m, 2H), 6.38(dd, J=8.3, 3.7Hz, 4H), 3.41(s, 12H), 1.72(s, 4 H), 1.33(s, 12H), 0.72(s, 18H), -0.16(s, 9H), -0.40(d, J=8.8Hz, 2H)ppm. 13 C NMR (126MHz, benzene-d6)δ 167.59(d, J=14.2Hz), 161.39(d, J=1.8Hz), 150.93, 146.80, 141.29, 136.04, 130.18, 124.00(d, J=1.8Hz), 122.70, 119.33, 117.8 1, 115.50, 114.40(d, J=59.3Hz), 104.54(d, J=4.3Hz), 57.13, 55.41, 38.90, 32.14, 32.12, 31.69, 1.82, -16.46(d, J=29.5Hz)ppm. 31 P NMR (162 MHz, benzene-d6) δ 47.27 ppm.

[0169] Example 20 - Synthesis of Procatalyst 6 ((Z)-N-(bis(2,6-diethoxyphenyl)phosphanyl)-2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazole-9-carbimidate)(pyridine)(trimethylsilylmethyl)nickel(II)

[0170] [ka]

[0171] In a glovebox, a 20 mL vial was charged with bis(trimethylsilylmethyl)bis(pyridine)nickel (39 mg, 0.10 mmol, 1.0 equiv.), a stir bar, and 1 mL of toluene. Pyridine (8 μL, 0.10 mmol, 1.0 equiv.) was then added, followed by a solution of N-(bis(2,6-diethoxyphenyl)phosphanyl)-2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9H-carbazole-9-carboxamide (100 mg, 0.10 mmol) in 3 mL of toluene. The resulting solution was orange and clear and was stirred at 45 °C for 1 h. An aliquot of the reaction mixture was added. 31 P NMR spectroscopic analysis indicated complete conversion of the free ligand to the desired nickel complex. The mixture was filtered through a pad of Celite, 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 a light yellow sticky solid. The product was triturated with hexane and allowed to stir for 15 minutes. The product was collected by filtration, rinsed with pentane, and dried under vacuum. The reaction yielded 60 mg (0.07 mmol, 71% yield) of product.

[0172] 1 H NMR(500MHz, C6D6)δ 10.49-8.19(m, 4H), 7.90(d, J=8.0Hz, 2H), 7.78(d, J=16.4Hz, 5H), 7.17-7.10(m, 6H), 7.08(d, J=7.8Hz, 3H), 6.84 (t, J=7.7Hz, 1H), 6.45(t, J=6.6Hz, 2H), 6.38-6.32(m, 4H), 3.70(s, 8H), 0.92(s, 12H), -0.15--0.38(m, 11H)ppm. 13C NMR (126MHz, C6D6)δ 163.48(d, J=14.5Hz), 158.14, 148.21, 142.95, 139.15, 134.09, 133.88, 129.08(q, J=32.9Hz), 127.94, 122.29, 121.95, 12 0.87, 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=28.9Hz)ppm. 31 P NMR (202MHz, C6D6) δ 43.96ppm. 19 F NMR (376MHz, C6D6) δ-62.23ppm.

[0173] Example 21 - Synthesis of Procatalyst 4 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,6-di-tert-butyl-9H-carbazole-9-carbimidate)(trimethylsilylmethyl)(pyridine)nickel(II)

[0174] [ka]

[0175] In a glovebox, a 20 mL vial was charged with bis(trimethylsilylmethyl)bis(pyridine)nickel (66 mg, 0.17 mmol, 1.05 equiv.), a stir bar, and 1 mL of toluene. A solution of N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,6-di-tert-butyl-9H-carbazole-9-carboxamide (100 mg, 0.16 mmol) in 5 mL of toluene was added slowly with stirring. The solution was a clear red color. The reaction mixture was stirred at room temperature for 2 hours, and an aliquot was added. 31P NMR spectroscopic analysis indicated complete conversion of the free ligand to the desired nickel complex. The reaction mixture was filtered through a pad of Celite, and all volatiles were removed from the filtrate under vacuum. Hexane (5 mL) was added and then removed under vacuum, leaving an orange sticky solid. The product was triturated with pentane and allowed to stir for 15 minutes. The product was collected by filtration, rinsed with pentane, and dried under vacuum. The reaction yielded 52 mg (0.10 mmol, 61% yield) of product.

[0176] 1 H NMR (400 MHz, benzene-d6) δ 9.26-9.06(m, 2H), 8.95(d, J=8.9Hz, 2H), 8.20(d, J=2.1Hz, 2H), 7.41(d d, J=8.9, 2.1Hz, 2H), 7.19-7.08(m, 14H), 7.02(t, J=8.4Hz, 1H), 6.94-6. 89(m, 1H), 6.61(t, J=6.7Hz, 2H), 6.38(dd, J=8.3, 3.7Hz, 4H), 3.42(s, 12 H), 2.10(s, 2H), 1.38(s, 19H), -0.11(s, 8H), -0.39(d, J=8.8Hz, 2H)ppm. 13 C NMR (101MHz, benzene-d6)δ 167.30, 161.55 (d, J=2.0Hz), 151.10, 143.11, 139.32, 136.34, 130.27, 128.96, 125.27 (d, J=10.9Hz), 123.45, 117.52, 114.89(d, J=4.4Hz), 114.33, 104.85(d, J=4.5Hz), 55.54, 34.31, 31.72, 1.98, -16.17(d, J=28.9Hz)ppm 31 P NMR (162 MHz, benzene-d6) δ 47.05 ppm.

[0177] Example 22 - Synthesis of Procatalyst 5 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazole-9-carbimidate)(pyridine)(trimethylsilylmethyl)nickel(II)

[0178] [ka]

[0179] In a glovebox, a 20 mL vial was charged with bis(trimethylsilylmethyl)bis(pyridine)nickel (46 mg, 0.12 mmol, 1.05 equiv.), a stir bar, and 1 mL of toluene. A solution of N-(bis(2,6-dimethoxyphenyl)phosphanyl)-2,7-bis(3,5-di-tert-butylphenyl)-9H-carbazole-9-carboxamide (100 mg, 0.11 mmol) in 5 mL of toluene was added slowly with stirring. The resulting solution was a clear red color. The reaction mixture was stirred at room temperature for 90 minutes, and an aliquot was added. 31 P NMR spectroscopic analysis showed only partial conversion to the desired nickel complex. The solution was heated to 45 °C for 20 min, and an aliquot was 31 P NMR spectroscopic analysis indicated that the reaction achieved complete conversion to the desired nickel complex. The reaction mixture was filtered through a pad of Celite, 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 an orange sticky solid. The product was triturated with pentane and allowed to stir for 15 minutes. The product was collected by filtration, rinsed with pentane, and dried under vacuum. 1 The H NMR spectrum revealed the presence of some residual hexane. The reaction gave 42 mg (0.04 mmol, 34% yield) of product.

[0180] 1H NMR (400MHz, benzene-d6)δ 9.18(s, 2H), 8.89(d, J=5.3Hz, 2H), 7.97(d, J=8.0Hz, 2H), 7.60(dd, J=7.9, 1.6Hz, 2H), 7.54(d, J=1.8Hz, 4H), 7.48(t, J=1.8Hz, 2H), 7.07( ppm. 13 C NMR (126MHz, C6D6)δ 166.91(d, J=14.5Hz), 161.41(d, J=2.2Hz), 150.82, 150.41, 143.27, 141.65, 140.76, 136.24, 130.33, 123.93, 123.22, 122.46, 121.10, 120.16, 119.14, 116.78, 114.09(d, J=58.3Hz), 104.79(d, J=4.6Hz), 55.40, 34.67, 31.48, 1.94, -15.82(d, J=28.8Hz). 31 P NMR (202MHz, C6D6) δ 46.53.

[0181] Example 23 - Synthesis of Procatalyst 3 N-(bis(2,6-diethoxyphenyl)phosphanyl)-carbazole-9-carboxamido(trimethylsilylmethyl)(pyridine)nickel

[0182] [ka]

[0183] In a nitrogen-filled glovebox, crystals of bis(trimethylsilylmethyl)bis(pyridine)nickel (0.7100 g, 1.81 mmol) were added to a solution of N-(bis(2,6-diethoxyphenyl)phosphanyl)-carbazole-9-carboxamide (1.00 g, 2.18 mmol) in toluene (8 mL), instantly giving a reddish-brown solution. Within a few minutes, the color turned lighter brown, and then a yellow precipitate began to form. The mixture was stirred at room temperature for 1 hour. Volatiles were then removed from the reaction mixture under reduced pressure. The resulting solid was triturated with hexane, filtered, washed with hexane, and dried under reduced pressure to give the product as a yellow powder. The reaction yielded 1.20 g (1.56 mmol, 86% yield) of product.

[0184] 1 H NMR (400 MHz, benzene-d6) δ 9.12(dd, J=4.8, 1.8Hz, 2H), 9.03(s, 2H), 7.91(d, J=7.6Hz, 2H), 7.33(t, J= 7.8Hz, 2H), 7.19(t, J=7.4Hz, 2H), 7.12(d, J=8.3Hz, 2H), 6.90(tt, J=7.6, 1. 7Hz, 1H), 6.61(t, J=6.6Hz, 2H), 6.36(dd, J=8.3, 3.7Hz, 4H), 3.76(dp, J=22. 9, 7.8Hz, 8H), 1.04(t, J=7.0Hz, 12H), -0.16(s, 9H), -0.27(d, J=8.1Hz, 2H). 13 C NMR (101MHz, benzene-d6)δ 167.27(d, J=14.1Hz), 161.12(d, J=1.9Hz), 151.41(d, J=1.4Hz), 141.15, 136.78, 130.37, 125.90, 125.42, 123.74(d, J= 1.9Hz), 121.07, 119.27, 118.16, 115.05(d, J=59.2Hz), 105.12(d, J=4.6Hz), 64.04, 14.59, 2.31, -15.97(d, J=29.2Hz). 31 P NMR (162 MHz, benzene-d6) δ 46.29.

[0185] Example 24 Comparative Example - 3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-1,1-dimethylurea bis(trimethylsilylmethyl)nickel (Compound (2))

[0186] [ka]

[0187] N-Alkylphosphino-urea ligands, such as compound (3), did not proceed to the carbamimidonic acid complex (1), which is necessary for polymerization activity. As illustrated in the reaction above, in the case of compound (3), the corresponding amide complex, 3-(bis(2,6-dimethoxyphenyl)phosphanyl)-1,1-dimethylurea, compound (2), rapidly formed. However, deprotonation of the ligand to form compound (1), the carbamimidate complex, did not occur. While not wishing to be bound by theory, it is believed that N-arylphosphino-urea ligands are more likely than N-alkylphosphino-urea ligands to form Ni complexes similar to (1). The Ni carbamimidate complex (1) is significantly more active in olefin polymerization catalysis.

[0188] Example 25 - Ethylene / tert-butyl acrylate copolymerization - parallel pressure reactor study The catalytic activity (in terms of quench time and polymer yield) and the resulting polymer properties were evaluated for procatalysts 1 to 6. Polymerization reactions were carried out in a parallel pressure reactor (PPR) as previously described.

[0189] For these experiments, catalyst stock solutions were prepared in toluene (1–2 mM) and immediately fed to the PPR reactor. Polymerization experiments were carried out at 400 psi ethylene pressure with catalyst loadings of 0.25–0.75 μmol. For copolymerization, tert-butyl acrylate (t-BA) was purified by filtration through a column of activated alumina, and a solution of purified t-BA was prepared in toluene for feeding to the PPR reactor. The reactor temperature and tert-butyl acrylate loading were varied as shown in Table 1. Each entry in Table 1 represents the average of at least two replicate runs.

[0190] [Table 1]

[0191] Each of procatalysts 1-6 was capable of copolymerizing ethylene and t-BA with high activity (such as activities exceeding 20 kg / mol·hr). In addition, each of the catalysts produced polymers incorporating significant amounts of acrylate, specifically greater than 1.0 weight percent. In each of the polymerization reactions, the procatalysts of the present disclosure produced polymers with narrow polydispersity indices (PDIs) (2.04-2.86) and molecular weights (MWs) ranging from 7,180 g / mol to 158,000 g / mol.

[0192] In another series of experiments, the procatalyst complex was prepared in situ by combining the phosphino-urea ligand with bis(trimethylsilylmethyl)bis(pyridine)nickel(II) in a 1:1 ratio in toluene and heating the mixture at 50 °C for 1 h before feeding into the PPR. The results of the PPR copolymerization are summarized in Table 2. The values ​​in Table 2 are the average of at least two replicate experiments, except for entry 5.

[0193] The phosphino-urea ligand is as follows:

[0194] [ka]

[0195] [Table 2]

[0196] The results summarized in Table 2 show that R on P atoms 3 and R 4 Metal-ligand complexes in which the ring is substituted at the 2- and 6-positions are represented by R 3 and R 4 We show that these catalysts have significantly higher activity (i.e., L2 and L3) and produce polymers with higher MW than metal-ligand catalysts in which the R position remains unsubstituted (i.e., L1). For example, a catalyst produced by complexing ligand L1 with a nickel precursor had an activity of 55 kg / mol h and produced a polymer with a molecular weight (MW) of 483 g / mol. Ligand L1 is a ligand with a R 3 and R 4 The 4-trifluoromethylphenyl group does not have bulky substituents at the 2- and 6-positions of the phenyl ring. In comparison, the catalyst formed from the complexation of ligand L3 with nickel had an activity of 600 kg / mol·hr and produced a polymer with a molecular weight of 18,300 g / mol. Ligand L3 is a R 3 and R 4 Entries 3 (L3) and 4 (L2) in Table 2 contain 2,6-dimethoxyphenyl groups at R 3 and R 4 Metal-ligand complexes bearing sterically bulky groups at the 2- and 6-positions of the aryl ring show high activity for ethylene homopolymerization.

[0197] Example 26 - Ethylene / n-Butyl Acrylate Copolymerization - Parallel Pressure Reactor Study For these experiments, catalyst stock solutions were prepared in toluene (1–2 mM) and immediately fed to the PPR reactor. Polymerization experiments were carried out at 400 psi ethylene pressure with a catalyst loading of 0.25 μmol. For copolymerization, n-butyl acrylate was purified by filtration through a column of activated alumina, and a solution of purified n-butyl acrylate was prepared in toluene for feeding to the PPR reactor. The reactor temperature and n-butyl acrylate loading were varied as shown in Table 3. Each entry in Table 3 represents the average of at least two replicate runs.

[0198] [Table 3]

[0199] The entries in Table 3 are organized primarily by acrylate loading, although the temperature of a particular run may vary.

[0200] The relative trends in reactivity for tert-butyl acrylate copolymerization (Table 1) are also observed for n-butyl acrylate (Table 3). Catalyst activity and resulting copolymer molecular weight are inversely proportional to acrylate loading, while incorporation is directly related to acrylate loading.

[0201] It should be noted that at identical acrylate loadings, n-butyl acrylate is observed to result in higher acrylate incorporation into the copolymer than tert-butyl acrylate. For example, procatalyst 1 using 250 μmol of n-butyl acrylate produces a polymer with 1.9 mol% acrylate incorporation (entry 2, Table 3), whereas under similar conditions, 250 μmol of tert-butyl acrylate yields 1.0 mol% incorporation (entry 1, Table 1). These results indicate that these Ni catalysts readily catalyze the formation of ethylene / acrylate copolymers using both low steric bulk (n-BA) and high steric bulk (t-BA) acrylates.

[0202] Example 27 - Ethylene / Acrylate Copolymerization - Batch Reactor Data Ethylene / tert-butyl acrylate copolymerization reactions were catalyzed on a larger scale in a 2 L batch reactor using Ni(II) phosphino-urea complex (procatalyst 3) following the general batch reactor procedure described previously. Copolymerization experiments were carried out at 400 psi ethylene pressure. The reactor temperature and tert-butyl acrylate charge were varied as shown in Table 4. tert-Butyl acrylate (t-BA) was purified by filtration through a column of activated alumina before adding it to the reactor. The initial charge of toluene to the reactor was 640 g (740 mL). The ethylene / tert-butyl acrylate copolymerization reaction was carried out for 75 minutes or until 40 g of ethylene uptake had occurred, whichever was shorter.

[0203] Performance data is summarized in Table 4.

[0204] [Table 4]

[0205] As shown in Table 4, procatalyst 3 was run in a batch reactor at two different temperatures (90 °C and 110 °C) and two different t-BA loadings (74 mmol or 222 mmol tert-butyl acrylate). In entry 1, at 90 °C and with 74 mmol t-BA present in the reactor, procatalyst 3 had an activity of 1,300 kg / mol·h and produced 39.2 g of copolymer with a molecular weight of 60,700 g / mol and 0.9 mol% acrylate incorporation. In entry 2, when 222 mmol t-BA was added to the reactor, the acrylate incorporation more than doubled compared to entry 1. However, increasing the amount of acrylate incorporated into the polymer affects the molecular weight of the polymer. As reflected in entry 2, the molecular weight decreased to 35,100 g / mol and the activity was 490 kg / mol·h when compared to the results in entry 1. The inventions described in the original claims of this application are set forth below. [1] A procatalyst according to formula (I), [ka] During the ceremony, M is nickel(II) or palladium(II); X is (C 1 ~C 40 ) hydrocarbyl, (C 1 ~C 40 ) heterohydrocarbyl, -CH 2 Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C )Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C ) 2 , -N(Si(R C ) 3 ) 2 , -NR C Si(R C ) 3 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , -OCF 3 , -S(O)R C , -S(O) 2 R C , -OS(O) 2 R C , -N=C(R C ) 2 , -N=CH(R C ), -N=CH 2 , -N=P(R C ) 3 , -OC(O)R C , -C(O)OR C , -C(O)R C , -C(O)HN(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -NHC(O)H, -C(O)N(RC ) 2 , -C(O)NHR C , -C(O)NH 2 , halogen, or hydrogen; In the formula, each R C However, independently, (C 1 ~C 30 ) hydrocarbyl or (C 1 ~C 30 ) heterohydrocarbyl, optionally containing one or more R S is replaced by the subscript Q is 0, 1, 2, or 3; the subscript W is 0, 1, or 2; Y is a Lewis base optionally covalently bonded to X; R 1 and R 2 However, (C 6 ~C 40 ) aryl or (C 1 ~C 40 ) Heteroaryl and optionally one or more R S is replaced by R 3 and R 4 are independently selected from the group having formula (II):

change

change

[10] R 22 and R 27 is independently 3,5-bis(trifluoromethyl)phenyl or 3,5-di-tert-butylphenyl.

[11] R22 and R 27 However, independently, (C 1 ~C 20 ) alkyl.

[12] R 23 and R 26 independently and optionally R S (C 6 ~C 40 ) aryl, and R S However, (C 1 ~C 30 ) hydrocarbyl, -CF 3 or a halogen atom.

[13] R 23 and R 26 However, independently, (C 1 ~C 20 ) alkyl.

[14] R 23 and R 26 But -CF 3 The procatalyst according to any one of [8] to

[11] , wherein

[15] R 21-28 The procatalyst according to any one of [8] to

[14] , wherein all of are —H.

[16] R 1 and R 2 But there is at least one R S (C 6 ~C 40 ) aryl, and each R S However, independently, (C 1 ~C 30 ) hydrocarbyl, -CF 3 or a halogen atom.

[17] R 1 and R 2 are independently phenyl, 3,5-bis(trifluoromethyl)phenyl, or 3,5-di-tert-butylphenyl.

[18] X is -CH 2 Si(CH 3 ) 3 [1] to

[17] , Catalyst.

[19] Ethylene, and optionally one or more (C 3~C 10 ) A polymerization process comprising polymerizing an α-olefin monomer, or optionally one or more cyclic olefin monomers, in the presence of a procatalyst according to any one of [1] to

[18] .

[20] Ethylene, a polar comonomer, and optionally one or more (C 3 ~C 10 ) A polymerization process comprising polymerizing an α-olefin monomer, or optionally one or more cyclic olefin monomers, in the presence of a procatalyst according to any one of [1] to

[18] .

[21] The polar comonomer is an acrylate (CH 2 =CHC(O)(OR)), glycidyl acrylate, CH 2 =CH(CH 2 ) n C(O)(OR), CH 2 =CHC(O)R, CH 2 =CH(CH 2 ) n C(O)R, CH 2 =CH-OC(O)R, CH 2 =CH(CH 2 ) n -OC(O)R, CH 2 =CH(OR), CH 2 =CH(CH 2 ) n (OR), CH 2 =CHSi(R) 3-T (OR) T , C.H. 2 =CH(CH 2 ) n Si(R) 3-T (OR) T , C.H. 2 =CH-OSi(R) 3-T (OR) T , C.H. 2 =CH(CH 2 ) n -OSi® 3-T (OR) T , or CH 2 ═CHCl, wherein each R is selected from —H, substituted (C 1 ~C 30 ) hydrocarbyl, unsubstituted (C 1 ~C 30 ) hydrocarbyl, substituted (C 1 ~C 30 ) heterohydrocarbyl, or unsubstituted (C 1 ~C 30 ) heterohydrocarbyl, each T is 0, 1, 2, or 3, and each n is 1 to 10.

[22] The polymerization process of

[21] , wherein the polar comonomer is tert-butyl acrylate.

[23] The polymerization process of

[21] , wherein the polar comonomer is n-butyl acrylate.

Claims

1. A procatalyst according to formula (I): 【Chemical 1】 During the ceremony, M is nickel(II) or palladium(II); X is (C １ to C20) hydrocarbyl, (C １ to C20) heterohydrocarbyl, and —CH ２ Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Q is a ligand selected from In the formula, each R Ｃ But independently, (C １ ~C ３０ ) hydrocarbyl or (C １ ~C ３０ ) heterohydrocarbyl, optionally containing one or more R Ｓ is replaced by the subscript Q is 0, 1, 2, or 3; Y is a Lewis base optionally covalently bonded to X; R １ and R ２ However, (C ６ ~C ４０ ) aryl or (C １ ~C ４０ ) heteroaryl, optionally with one or more R Ｓ is replaced by R 1 and R 2 may be bonded to each other; R ３ and R ４ is independently selected from the group having formula (II): 【Chemistry 2】 During the ceremony, R 11 and R 15 are independently —O[(C 1 -C 10 )alkyl]; R １２ , R １３ , and R14 are independently selected from the group consisting of (C １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ ) heterohydrocarbyl, —OR Ｎ , -NR Ｎ ２ , -SR Ｎ , halogen, or —H, wherein each R Ｎ However, (C １ ~C ３０ ) hydrocarbyl, Each R in formula (I) Ｃ But independently, (C １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ ) heterohydrocarbyl, or —H; Each R in formula (I) Ｓ But independently, (C １ ~C ２０ ) a procatalyst which is a hydrocarbyl or halogen.

2. Y is a neutral Lewis basic aprotic (C ２ ~C ４０ 10. The procatalyst of claim 1, wherein the procatalyst is a heterohydrocarbon.

3. R ３ and R ４ The procatalyst of claim 1 or 2, wherein are the same.

4. R １１ and R １５ The procatalyst of claim 3 wherein is methoxy.

5. R １１ and R １５ The procatalyst of claim 3 wherein is ethoxy.

6. R １ and R ２ and wherein the procatalyst has a structure according to formula (III): 【Chemistry 3】 In the formula, R ２１－２８ each independently represents —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｒ ) ３ , -Ge(R Ｒ ) ３ , -P(R Ｒ ) ２ , -P(O)(R Ｒ ) ２ , -N(R Ｒ ) ２ , -OR Ｒ , -SR Ｒ , -NO ２ , -CN, -CF ３ or halogen, wherein each R Ｒ However, (C １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ ) heterohydrocarbyl, or —H; M, Y, X, R ３ , and R ４ The procatalyst of any one of claims 1 to 5, wherein is as defined in formula (I).

7. R ２２ and R ２７ independently and optionally R Ｓ (C ６ ~C ４０ ) aryl, and R Ｓ However, (C １ ~C ３０ ) hydrocarbyl, —CF ３ 7. The procatalyst of claim 6, wherein the procatalyst is a halogen atom.

8. R ２２ and R ２７ 8. The procatalyst of claim 7, wherein is independently 3,5-bis(trifluoromethyl)phenyl or 3,5-di-tert-butylphenyl.

9. R ２２ and R ２７ But independently, (C １ ~C ２０ 7. The procatalyst of claim 6, wherein:

10. R ２３ and R ２６ independently and optionally R Ｓ (C ６ ~C ４０ ) aryl, and R Ｓ However, (C １ ~C ３０ ) hydrocarbyl, —CF ３ or a halogen atom.

11. R １ and R ２ However, at least one R Ｓ (C ６ ~C ４０ ) aryl, and each R Ｓ But independently, (C １ ~C ３０ ) hydrocarbyl, —CF ３ or a halogen atom.

12. R １ and R ２ The procatalyst of any one of claims 1 to 5, wherein is independently phenyl, 3,5-bis(trifluoromethyl)phenyl, or 3,5-di-tert-butylphenyl.

13. X is -CH ２ Si(CH ３ ) ３ 13. The procatalyst of any one of claims 1 to 12, wherein

14. Ethylene, and optionally one or more (C ３ ~C １０ 14.) A polymerization process comprising polymerizing an α-olefin monomer, or optionally one or more cyclic olefin monomers, in the presence of the procatalyst of any one of claims 1 to 13.

15. Ethylene, a polar comonomer, and optionally one or more (C ３ ~C １０ 14.) A polymerization process comprising polymerizing an α-olefin monomer, or optionally one or more cyclic olefin monomers, in the presence of the procatalyst of any one of claims 1 to 13.

16. The polar comonomer is an acrylate (CH ２ = CHC(O)(OR)), glycidyl acrylate, CH ２ =CH(CH ２ ) ｎ C(O)(OR), CH ２ =CHC(O)R,CH ２ =CH(CH ２ ) ｎ C(O)R, CH ２ =CH-OC(O)R, CH ２ =CH(CH ２ ) ｎ -OC(O)R,CH ２ =CH (OR), CH ２ =CH(CH ２ ) ｎ (OR), CH ２ =CHSi(R) ３－Ｔ (OR) Ｔ , C.H. ２ =CH(CH ２ ) ｎ Si(R) ３－Ｔ (OR) Ｔ , C.H. ２ =CH-OSi(R) ３－Ｔ (OR) Ｔ , C.H. ２ =CH(CH ２ ) ｎ -OSi(R) ３－Ｔ (OR) Ｔ , or CH ２ =CHCl, wherein each R is —H, substituted (C １ ~C ３０ ) hydrocarbyl, unsubstituted (C １ ~C ３０ ) hydrocarbyl, substituted (C １ ~C ３０ ) heterohydrocarbyl, or unsubstituted (C １ ~C ３０ 16. The polymerization process of claim 15, wherein each T is 0, 1, 2, or 3 and each n is 1 to 10.

17. 17. The polymerization process of claim 16, wherein the polar comonomer is tert-butyl acrylate.

18. 17. The polymerization process of claim 16, wherein the polar comonomer is n-butyl acrylate.

19. The procatalyst of claim 13, wherein R 11 and R 15 are independently methoxy or ethoxy.

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