Electron-deficient pyridinium-phosphine-phenol supported nickel(II) or palladium (II) catalysts for the copolymerization of ethylene and acrylate comonomers

Abstract

Processes of polymerizing olefin monomers using catalyst systems and catalysts systems that include a procatalyst having a structure according to formula (I):

Description

ELECTRON-DEFICIENT PYRIDINIUM-PHOSPHINE-PHENOL SUPPORTED NICKEL(II) OR PALLADIUM (II) CATALYSTS FOR THE COPOLYMERIZATION OF ETHYLENE AND ACRYLATE COMONOMERSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No.63 / 604,608 filed November 30, 2023, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

[0002] Embodiments of the present disclosure generally relate to ethylene and polar comonomer polymerization catalyst systems and processes, and, more specifically, to ethylene and acrylate polymerization catalyst systems including electron-deficient pyridinium substituted phosphine-phenol supported nickel(II) or palladium(II) catalysts, and to olefin polymerization processes incorporating the catalyst systems.BACKGROUND

[0003] Ethylene / acrylate copolymers generally have an enhanced performance imparted by polar functionality, such as improved hot tack strength, oil and grease resistance, abrasion and static puncture resistance, low-temperature impact toughness, and adhesion to polar substrates like aluminum and glass when compared to non-polar polymers.

[0004] Most methods for incorporating ester functionality into ethylene copolymers involve free-radical polymerization of ethylene and acrylate monomers under high pressure and temperatures, producing highly branched microstructure similar to that of low-density polyethylene (L.DPE). Coordination catalysis provides routes to highly linear ethylene / acrylate copolymers with structures similar to that of linear low-density polyethylene (LLDPE). The linear ethylene / acrylate copolymers formed by coordination catalysis exhibit greater crystallinity and higher thermal resistance than those of the copolymers formed through the radical processes.

[0005] Common organometallic coordination catalysts appropriate for ethylene polymerization are not compatible with systems including acrylates as comonomers. For example,the Group IV metal catalysts (Ti, Zr, Hf) used in the industrial manufacture of LLDPE (ethylene / a- olefin copolymers) are not compatible with polar olefin monomers, including acrylates. Because the oxygen atoms of acrylate monomers strongly coordinate to Lewis-acidic Group IV metals, the active site of the metal becomes blocked by the acrylate during ethylene / acrylate polymerization and further olefin polymerization is hindered.

[0006] Owing to the incompatibility of the Group IV metal catalysts with acrylates, electronrich metal catalysts containing Group 10 metals (Pd, Ni) have been explored in the copolymerization reactions of ethylene with acrylate monomers. However, many reported Ni- and Pd-containing metal catalysts suffer from (a) slow rates of polymerization and / or (b) low incorporati on of the polar monomers of interest.SUMMARY

[0007] Ongoing needs exist to create a ligand framework for Ni and Pd catalysts that promote both high rates of ethylene copolymerization activity and high incorporation of the acrylate comonomer. With a ligand framework for nickel or palladium, ethylene and polar monomers may be copolymerized via coordination catalysis to form a highly linear, LLDPE-like copolymer. The highly linear copolymers may exhibit improved creep resistance and dimensional stability at higher temperatures, specifically from 80°C to 150°C, as opposed to temperatures of less than 80 °C.

[0008] Nickel and palladium catalysts having phosphino-phenol ligand architectures bearing positively charged pyridinium groups demonstrate high rates of activity and high levels of polar comonomer incorporation, while maintaining high copolymer molecular weights. Most importantly, the copolymer properties can be tuned through cation-anion interactions. The linear, LLDPE-like copolymers formed by these catalysts demonstrate improved thermal properties over the commercial branched (LDPE-like) copolymers.

[0009] Embodiments of this disclosure include catalyst systems. The catalyst systems include a procatalyst having a structure according to formula (I):

[0010] In formula (I), M is nickel(II) or palladium(II); and X is a ligand chosen from (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, -CH2S1(RC)3-Q(ORC)Q,-Si(Rc)3-Q(ORc)Q, -OSi(Rc)3-Q(ORc)Q, -Ge(Rc)3-Q(ORc)Q, -P(Rc)2-w(ORc)w, -P(O)(RC)2-W(ORC)W, -N(RC)2, -NH(RC), -N(Si(Rc)3)2, -NRcSi(Rc)3, -NHSi(Rc)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(RC), -N=CH2, -N=P(RC)3, -OC(O)RC, -C(O)ORC, -N(RC)C(O)RC, -N(RC)C(O)H, -NHC(O)RC, -C(O)N(RC)2, -C(O)NHRC, -C(O)NH2, a halogen, or a hydrogen, wherein each Rcis independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl, and Q is 0, 1, 2 or 3 and W is 0, 1, or 2.

[0011] In formula (I), each Y is a Lewis base. In some embodiments, X and Y are optionally linked.

[0012] In formula (I), A is an anion; E is a heteroatom selected from nitrogen and phosphorous.

[0013] In formula (I), R1and R2are independently selected from a substituted (C1-C30)hydrocarbyl, unsubstituted (C1-C30)hydrocarbyl, substituted(C1-C30)heterohydrocarbyl, or unsubstituted (C1-C30)heterohydrocarbyl.

[0014] In formula (I), R3, R4, R5, R6, R7, R8, R9, and R10are independently selected from a substituted (C1-C30)hydrocarbyl, unsubstituted (C1-C30)hydrocarbyl, substituted (C1-C30)heterohydrocarbyl, unsubstituted (C1-C30)heterohydrocarbyl, -S1(RC)3-Q(ORC)Q, -OSi(Rc)3-Q(ORc)Q, -Ge(Rc)3-Q(ORc)Q, -P(Rc)2-w(ORc)w, -P(O)(Rc)2-w(ORc)w, -N(RC)2, -NH(RC)2, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=P(RC)3, -OC(O)RC, -C(O)ORC, -N(R)C(O)RC, -C(O)N(RC)2, or a halogen, wherein each Rcis independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl; Q is 0, 1, 2, or 3 and W is 0, 1, or 2.

[0015] In one or more embodiments, embodiments includes optionally, R1and R2are linked to form a ring structure; and optionally, R3and R4are linked to form a ring structure; or optionally,R4and R5are linked to form a ring structure; or optionally, R6and R7are linked to form a ring structure; or optionally, R7and R8are linked to form a ring structure; or optionally, R8and R9are linked to form a ring structure; or optionally, R9and R10are linked to form a ring structure.DETAILED DESCRIPTION

[0016] Specific embodiments of catalyst systems will now be described. It should be understood that the catalyst systems of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0017] Common abbreviations are listed below:

[0018] Me : methyl; Et : ethyl; Ph : phenyl; Bn: benzyl; z-Pr : zso-propyl; / -Bu : tert-butyl; t- Oct : tert-octyl (2,4,4-trimethylpentan-2-yl); THF : tetrahydrofuran; Et2O : diethyl ether; CH2CI2 : dichloromethane; EtOAc : ethyl acetate; CeDe : deuterated benzene or bcnzcnc-c / 6 : CDCh : deuterated chloroform; Na2SO4 : sodium sulfate; MgSCh : magnesium sulfate; HC1 : hydrogen chloride; zz-BuLi : butyllithium; 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 : millimoles; mL : milliliters; M : molar; min or mins: minutes; h or hrs : hours; d: days; Rf ; retention factor; TLC ; thin-layer chromatography; rpm: revolutions per minute.

[0019] The term “independently selected” followed by multiple options is used herein to indicate that individual groups appearing before the term, such as R1, R2, R3, and Rc, can be identical or different, without dependency on the identity of any other group also appearing before the term.

[0020] The term “procatalyst” refers to a compound that has catalytic activity after activation, for example upon removal of the Lewis base coordinated to the Ni or Pd metal center.

[0021] When used to describe certain carbon atom-containing chemical groups, a parenthetical expression having the form “(Cx-Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (C1-C50)alkyl is an alkyl group having from 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted by one ormore substituents such as Rswherein Rsgenerically represents any substituent defined in this application. An Rssubstituted version of a chemical group defined using the “(Cx-Cy)” parenthetical may contain more than y carbon atoms depending on the identity of any groups Rs. For example, a “(C1-C50)alkyl substituted with exactly one group Rs, where Rsis phenyl (-C6H5)” may contain from 7 to 56 carbon atoms. Thus, in general when a chemical group defined using the “(Cx-Cy)” parenthetical is substituted by one or more carbon atom-containing substituents Rs, the minimum and maximum total numbers of carbon atoms of the chemical group are determined by adding to both x and y, respectively, the combined sum of the number of carbon atoms from all of the carbon atom-containing substituents Rs.

[0022] The terms “substitution”, “(C1-C50)hydrocarbyl”, “(C1-C50lalkyl”, “(C6-C50)aryl”,“(C3-C50)cycloalkyl”, “(C1-C50)hydrocarbylene”, “(C1-C50)alkylene”, “(C3-C50)ycloalkylene”, “heteroatom,” “heterohydrocarbon”, “(C1-C50)heterohydrocarbyl”, “(C4-C50)heteroaryl”, “(C1-C50)heterohydrocarbylene”, “(C1~C50)heteroalkyl”, and “saturated” are defined in United States Application no. US2021 / 025152, which published as WO 2021 / 202714.

[0023] In this disclosure, a (C1-C50)hydrocarbyl includes, without limitation, unsubstituted or substituted forms of the following groups: (C i-C50)alky 1, (C2-C50 / cycloalkyl, (C3-C20)cycloalkyl-(C1-C20)alkylene, (C2-C40)aryl, or (C6-C20)aryl-(C1-C20)alkylene (such as benzyl (-CH2-C6H5)).

[0024] In this disclosure, (Cj~C50)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (C1~C50)heterohydrocarbyl include (C1~C50)heteroalkyl, (C’.-C50)hydrocarbyl-0-, (C1-C50)hydrocarbyl-S-, (C1-C50)hydrocarbyl-S(0)~, (C1“C50)hydrocarbyl-S(0)2~, (C1~C50)hydrocarbyl-Si(Rc)2“, (C1~C50)hydrocarbyl-N(RN)~, (C1-C50)hydrocarbyl-P(Rp)-, (C2-C50jheterocycloalkyl, (Cc-C19)heterocycloalkyl- (C1~C20)alkylene, (C3-C20)cycloalkyl-(C1“C19)heteroalkylene, (C-2“C19)heterocycloalkyl- (C’.-C20)heteroalkylene, (Cr-C50)heteroaryl, (C1-C19)heteroaryl-(Cj-C20)alkylene, (C6-C20)aryl- (C i-C19)heteroalkylene, or (C1~C19)heteroaryl-(C i -C20)heteroalkylene. Additional examples include, but are not limited to -S1(RC)3-Q(ORC)Q, -OS1(RC)3-Q(ORC)Q, -GC(RC)3-Q(ORC)Q, -P(RC)2-W(ORC)W, -P(O)(RC)2-W(ORC)W, -N(RC)2, -NH(RC)2, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=P(RC)3, -OC(O)RC, -C(O)ORC, -N(Rc)C(O)Rc, and -C(O)N(Rc)2.

[0025] Embodiments of this disclosure include catalyst systems. The catalyst systems include a procatalyst having a structure according to formula (I):

[0026] In formula (I), M is nickel(II) or palladium(II); and X is a ligand chosen from (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, -CH2Si(Rc)3-Q(ORc)Q,-Si(Rc)3-Q(ORc)Q, -OSi(Rc)3-Q(ORc)Q, -Ge(Rc)3-Q(ORc)Q, -P(Rc)2-w(ORc)w, -P(O)(RC)2. w(0Rc)w, -N(RC)2, -NH(RC), -N(Si(Rc)3)2, -NRcSi(Rc)3, -NHSi(Rc)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(RC), -N=CH2, -N=P(RC)3, -OC(O)Rc, -C(O)ORc, -N(Rc)C(O)Rc, -N(Rc)C(O)H, -NHC(O)Rc, -C(O)N(RC)2, -C(O)NHRC, -C(O)NH2, a halogen, or a hydrogen, wherein each Rcis independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl, and Q is 0, 1, 2 or 3 and W is 0, 1, or 2.

[0027] In formula (I), each Y is a Lewis base. In some embodiments, X and Y are optionally linked.

[0028] In formula (I), A is an anion; E is a cation and is a heteroatom selected from nitrogen and phosphorous.

[0029] In formula (I), R1and R2are independently selected from a substituted (C1-C30)hydrocarbyl, unsubstituted (C1-C30)hydrocarbyl, substituted(C1-C30)heterohydrocarbyl, or unsubstituted (C1-C30)heterohydrocarbyl.

[0030] In formula (I), R3, R4, R5, R6, R7, R8, R9, R10are independently selected from a substituted (C1-C30)hydrocarbyl, unsubstituted (C1-C30)hydrocarbyl, substituted (C1-C30)heterohydrocarbyl, unsubstituted (C1-C30)heterohydrocarbyl, -S1(RC)3-Q(ORC)Q, -OSi(Rc)3-Q(ORc)Q, -Ge(Rc)3-Q(ORc)Q, -P(Rc)2.w(ORc)w, -P(O)(Rc)2.w(ORc)w, -N(RC)2, -NH(RC)2, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=P(RC)3, -OC(O)RC, -C(O)ORC, -N(R)C(O)RC, -C(O)N(RC)2, or a halogen, wherein each Rcis independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl; Q is 0, 1, 2, or 3 and W is 0, 1, or 2.

[0031] In one or more embodiments, embodiments includes optionally, R1and R2are linked to form a ring structure; and optionally, R3and R4are linked to form a ring structure; or optionally, R4and R5are linked to form a ring structure; or optionally, R6and R7are linked to form a ring structure; or optionally, R7and R8are linked to form a ring structure; or optionally, R8and R9are linked to form a ring structure; or optionally, R9and R10are linked to form a ring structure.

[0032] In various embodiments, R1is different from R2. In other embodiments, R1is the same as R2. In some embodiments, R1and R2are phenyl substituted with one or more Rs, in which each Rsis selected from (C1-C10)alkyl, -ORC, or -SiRC3, where each Rcis selected from the group consisting of (C1-C10)alkyl or -H. In one or more embodiments, R1and R2are 2,6- dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-diphenoxyphenyl, 2,4,6-triethoxyphenyl, 2,4,6- trimethoxyphenyl, 2-phenylphenyl, or 2,6-diisopropoxyphenyl.

[0033] In one or more embodiments, R3, R4, and R5are (C1-C1s)alkyl or -H. In various embodiments, R3, R4, and R5are independently selected from a substituted or unsubstituted (C1-C20)alkyl and substituted or unsubstituted (Ce-C20)aryl.

[0034] In some embodiments, R6, R7, R8, R9, and R10are independently -H, substituted (C1-C20)alkyl, unsubstituted (C1-C20) alkyl, substituted (Ce-C20)aryl, or unsubstituted (C6-C20)aryl. The alkyl or aryl are substituted with one or more Rs, in which each Rsis selected from (C1-C10)alkyl, -ORC, -SiRC3 or a halogen atom, where each Rcis selected from the group consisting of (C1-C10)alkyl or -H.

[0035] In some embodiments, R6, R7, R8, R9, and R10are independently -H, methyl, ethyl, 1 -propyl, 2 -propyl, 1 -butyl, 2-butyl, 2-methylpropyl, 1,1 -dimethylethyl (also called tert -butyl), 1- pentyl, 1 -hexyl, 1 -heptyl, 1 -octyl, 1,1,3,3-tetra-methylbutyKalso called tert-octyl), 1 -nonyl, 1- decyl, -CF3, or -OCH3.

[0036] In embodiments, A" is an anion. In one or more embodiments, A" is a non-coordinating anion. A non-coordinating anion refers to a negatively charged counterion that may be a separate entity from the cation due to the diffuse nature of the charge or high steric hinderance limiting the degree of interaction with the associated cation. In some embodiments, A" is a weakly coordinating anion. A weakly coordinating anion is a negatively charge counterion that does not have to be a separate entity and may interact weakly with the cation. In some embodiments, A" is a strongly coordinating anion. A strongly coordinating anion is a negatively charged counterion that is localized and closely interacts with the associated cation.

[0037] In some embodiments, A" can be a weakly-coordinating or non-coordinating anion substituted with donor groups (e.g., -ORC, -N(RC)2), which can interact with the cation or catalyst metal center.

[0038] In some embodiments, A may be a halide, nitrate, perhalogenate, phosphate, sulfate, RWC(O)O“, RWOC(O)O”, RWRRNC(O)O", RWO", Si(Rw)3-a(ORw)aCF (RR)5-b(ORw)bSr RWS(O)2O~ RW4B~, RM-, RW4Ga~ RW6P~ Rw6As”, or Rw6Sb”, wherein each Rwor RRis independently a halogen, hydrogen, substituted or unsubstituted (C1-C40)hydrocarbyl, or substituted or unsubstituted (C1-C40)heterohydrocarbyl and subscript a is 0, 1, 2, or 3 and subscript b is 0, 1, 2, 3, or 4. In some embodiments, each R* or RRis chosen from halogen, substituted or unsubstituted (C1-C20)alkyl, substituted or unsubstituted (Ce-C50jaryl, or substituted or unsubstituted (C1-(3?.o)heteroalkyl or substituted or unsubstituted (C4-C20)heteroary[. In various embodiments, each Rwis different. In other embodiments, each Rwis the same.

[0039] In various embodiments, A' is BF4‘, B(3,5-(CF3)2C6H3)4; B(CeF5)4; B(4- (OCH2OCH3)C6H4)4-, or B(C6H5)4-.

[0040] In the metal-ligand complex according to formula (I), each Y bonds with M through a dative bond or an ionic bond. In one or more embodiments, Y is a Lewis base. The Lewis base may be a compound or an ionic species, which 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, the Lewis base may be a heterohydrocarbon or a hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. Examples of neutral hydrocarbon Lewis bases include, but are not limited to, alkenes, alkynes, or arenes.

[0041] In some embodiments, Y is (C1-C40)heterohydrocarbon, (C1-C40)heterohydrocarbyl, or (C1-C40)hydrocarbyl.

[0042] In one or more embodiments, Y is a neutral Lewis basic aprotic (C2-C40)heterohydrocarbon. Aprotic (C2-C40)heterohydrocarbons are(C2-C40)heterohydrocarbons as previously defined, for which every hydrogen atom of the (C2-C40)heterohydrocarbon has a pKa of greater than 30 wherein pKa is the negative base- 10 logarithm of the acid dissociation constant (Ka). In some embodiments, Y is an organic Lewis base. Examples of organic Lewis bases include pyridine, or a substituted pyridine, a sulfoxide, a trialkyl or triaryl phosphine, a trialkyl or triaryl phosphine oxide, an olefin or cyclic olefin, a substituted or unsubstituted heterocycle, an alkyl ester of an aliphatic or aromatic carboxylic acid,an aliphatic ketone, an aliphatic amine, an alkyl or cycloalkyl ether, or mixtures thereof, each electron donor having 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 an organic Lewis base include, but are not limited to: methyl formate, ethyl acetate, butyl acetate, ethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethyl formate, dimethylformamide, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, tetrahydrofuran, ethyl propionate, lutidine, picoline, pyridine, dimethyl sulfoxide, trimethylphosphine, triethylphosphine, triphenylphosphine, cyclooctadiene, cyclopentene, ethylene, propylene, tert-butyl ethylene, trimethylamine, triethylamine, tributylamine, N,N- dimethylaniline, 1 -methylimidazole, or 1-methylpyrazole.

[0043] In some embodiments, Y is pyridine, picoline, lutidine, trimethylamine, or trimethylamine.

[0044] In one or more embodiments, the Lewis base may be a monodentate ligand that may be a neutral ligand. In some embodiments, the neutral ligand may contain a heteroatom. In specific embodiments, the neutral ligand is a neutral group such as RTNRKRL, RKORL, RKSRL, or RTPRKRL, where each RTindependently is [(C1-C10)hydrocarbyl]3Si(C1-(?jo)hydrocarbyl, (C1-C40)hydrocarbyl, [(C1-C10)hydrocarby!]3Si, or (C1-C40)heterohydrocarbyl and each RKand RLindependently is hydrogen, (C1-C40)hydrocarbyl, or (C1-C40)heterohydrocarbyl.

[0045] In some embodiments, the Lewis base is (C1~C20)hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene or 1,3 -butadiene.

[0046] In various embodiments, the Lewis base is (C1-C20)heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, Y is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0047] In various embodiments, the Lewis base is (C1-C20)heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is nitrogen. In some embodiments, Y is pyridine, picoline, lutidine, trimethylamine, or triethylamine.

[0048] In some embodiments, X and Y are covalently linked. Specific examples of an organic Lewis base Y covalently linked together with an X group include, but are not limited to: 4- cycloocten-l-yl, 2-dimethylaminobenzyl, and 2-dimethylaminomethylphenyl.

[0049] In some embodiments, X and Y are linked and selected from the group consisting of:where Rcis -H or (C1-C30)hydrocarbyl, (C1-C20)alkyl, or (C1-C12)alkyl.

[0050] In the metal-ligand complex according to formula (I), X bonds with M through a covalent bond or an ionic bond. In some embodiments, X may be a monoanionic ligand having a net formal oxidation state of -1. Each monoanionic ligand may independently be hydride, (C1-C40)hydrocarbyl carbanion, (C1-C40)heterohydrocarbyl carbanion, halide, nitrate, hydrogencarbonate, dihydrogenphosphate, hydrogensulfate, HC(O)O-, HC(O)N(H)-, (C1-C40)hydrocarbylC(0)0~, (C1“C40)hydrocarbyiC(0)N((Cj-C20)hydrocarbyl)_,(C1-C40)hydrocarbylC(0)N(Il)”, RKR!B-, RKRLN-- RKO-- RKS-, RKRLP-, or RMRKRLSF, where each RE RL, and RMindependently is hydrogen, (Cj-C40)hydrocarbyi, or (C 1-C14o)heterohydrocarbyl, or RKand RLare taken together to form a (C2-C40)hydrocarbyiene or (C1.-C20)heterohydrocarbylene and RMis as defined above.

[0051] In embodiments, X is a substituted or unsubstituted (C1-C30)hydrocarbyl, a substituted or unsubstituted (C1-C30)heterohydrocarbyl.

[0052] In one or more embodiments, X is methyl, 2,2-dimethylpropyl, trimethylsilylmethyl, (n-butyl)dimethylsilylmethyl, (n-hexyl)dimethylsilylmethyl, (n-octyl)dimethylsilylmethyl, or benzyl

[0053] In some embodiments, X is a halogen, (C1-C20)hydrocarbyl, (C1~C20)heterohydrocarbyl, (C1-C20)hydrocarbylC(0)0-, or RKRLN~, wherein each of RKand RLindependently is an (C1-C20 )hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C10)hydrocarbyl (e.g., (C1-C6)alkyl or benzyl), unsubstituted (C1-C10)hydrocarbylC(0)0- or RKRLN-, wherein each of RKand RLindependently is an unsubstituted (C1-C10)hydrocarbyl.

[0054] In further embodiments, X is selected from methyl; ethyl; 1 -propyl; 2 -propyl; 1-butyl; 2, 2, -dimethyl propyl; trimethylsilylmethyl: phenyl; benzyl; or chloro.

[0055] In one or more embodiments, X is-(CH2)SiRX3, in which each Rxis independently a (C1-C30)alkyl or a (C1-C30)heteroalkyl and at least one Rxis (C1-C30)alkyl. In some embodiments, when one of Rxis a (C1-C30)heteroalkyl, the heteroatom is a silicon or oxygen atom. In some embodiments, Rxis methyl, ethyl, propyl, 2-propyl, butyl, 1,1 -dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0056] In one or more embodiments X is -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(CH2CH3); -(CH2)Si(CH3)(CH2CH3)2, -CCH2)Si(CH2CH3)3, -(CH2)Si(CH3)2(n-butyl),-(CH2)Si(CH3)2(n-hexyl), -(CH2)Si(CH3)(n-oct)Rx, -(CH2)Si(CH3)2Rx, -(CH2)Si(n-oct)RX2, -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), -CH2Si(CH3)2CH2Si(CH3)3 (herein referred to as -CH2Si(CH3)2(CH2TMS). Optionally, in some embodiments, in the metal-ligand complex according to formula (I), exactly two Rxare covalently linked or exactly three Rxare covalently linked.

[0057] In some embodiments, X is -CH2S1(RC)3-Q(ORC)Q, -S1(RC)3-Q(ORC)Q, -OS1(RC)3-Q(ORC)Q, in which subscript Q is 0, 1, 2 or 3 and each Rcis independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl. In some embodiments, X is -CH2Si(CH3)3.

[0058] In some embodiments, any or all of the chemical groups of the procatalysts of formula (I) may be unsubstituted, except for either R1or R2. At least one of R1and R2is substituted. In other embodiments, none, any, or all of the chemical groups X, A, R1R2, or R3-10of the metal-ligand complex of formula (I) may be substituted with one or more than one Rs. When two or more than two Rsare bonded to a same chemical group of the procatalysts of formula (I), the individual Rsof the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, none, any, or all of the chemical groups X, A and R1-R2, or R3-10may be persubstituted with Rs. In the chemical groups that are persubstituted with Rs, the individual Rsmay all be the same or may be independently chosen.

[0059] Embodiments of this disclosure include polymerization processes. In some embodiments, the polymerization process includes polymerizing ethylene with one or more olefinic monomers in the presence of a catalyst system under olefin polymerization conditions toform an ethylene-based copolymer. The catalyst system includes a metal-ligand complex according to formula (I) as described in this disclosure.

[0060] In some embodiments, the polymerization processes include polymerizing ethylene, one or more polar monomers, and optionally, one or more a-olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene / polar monomer copolymer. The catalyst system includes a procatalyst according to formula (I) of this disclosure. In one or more embodiments, the polymerization processes include polymerizing ethylene, one or more alkyl acrylate monomers, and optionally, one or more a-olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene / alkyl acrylate copolymer, the catalyst system comprising a procatalyst according to formula (I) of this disclosure.

[0061] In some embodiments of the polymerization process, the polymerization process comprises polymerizing ethylene and optionally one or more (C3-C10)a-olefin monomers or cyclic olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based copolymer, the catalyst system comprising a metal-ligand complex procatalyst having a structure according to formula (I) as described in this disclosure.

[0062] In some embodiments of the polymerization process, the polymerization process comprises polymerizing ethylene, a polar comonomer, and optionally one or more (C3-C10)a- olefin monomers or cyclic olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based copolymer, the catalyst system comprising a metal-ligand complex procatalyst having a structure according to formula (I) as described in this disclosure.

[0063] In various embodiments, the polymerization process includes polymerizing ethylene and optionally polar comonomers in a reactor at a reactor temperature. In one or more embodiments, the reactor may include a single reactor, a dual reactor, a solution reactor, a slurry reactor, gas reactor, or a high pressure reactor. Such solution polymerization processes include using one or more conventional reactors such as loop reactors, isothermal reactors, adiabatic reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors in parallel, series, or any combinations thereof, for example. Such high pressure reactors include agitated autoclave vessels having one or more reaction zones. The autoclave reactor normally has several injection points for catalyst and / or monomer feeds. Another type of high pressure reactor is a jacketed tube having one or more reaction zones. Suitable, but not limiting, reactor lengths may be from 100 to3600 meters (m) or from 1000 to 2800 m. The beginning of reaction zone, for either type of high pressure reactor, is typically defined by the site injection of the catalyst, ethylene, comonomer(s), and any combination thereof.

[0064] In one or more embodiments, the polymerization process polymerizing ethylene and optionally polar comonomers occurs at reactor temperature from 50 °C to 250°C. In some embodiments, the reactor temperature is from 70°C to 200 °C or 70°C to 150°C. In various embodiments, the reactor temperature is from 100°C to 190°C. In one or more embodiments, the polymerization process polymerizing ethylene and optionally polar comonomers occurs at a reactor pressure from 100 psi to 30,000 psi. In some embodiments, the reactor pressure is 200 psi to 600 psi.

[0065] Olefinic monomers may include, but are not limited to, propylene, 1 -butene, 1 -hexene, 1 -octene, 1 -nonene, 1 -decene, 1 -undecene, 1 -dodecene, 4-methyl-l -pentene, styrene, cyclobutene, cyclopentene, norbornene, alkyl acrylate, glycidyl acrylate, CH2=C(H)C(O)(ORX), CH2=CHC(O)RX, CH2=CH(ORX), CH2=CH(CH2)(ORX), CH2=CHSi(Rx)3-Y(ORx)Y, CH2=CH-OSi(Rx)3-Y(ORx)Y, or CH2=CHC1, where Rxis chosen from -H, a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl, and subscript Y is 0, 1, 2, or 3.

[0066] In various embodiments of the polymerization processes, the polar comonomer includes alkyl acrylates, CH2=CHC(O)(OR), CH2=CH(CH2)nC(O)(OR), CH2=CHC(O)R, CH2=CH(CH2)nC(O)R, CH2=CH-OC(O)R, CH2=CH(CH2)n-OC(O)R , CH2=CH(OR), CH2=CH(CH2)n(OR), CH2=CHSi(R)3-T(OR)T, CH2=CH(CH2)nSi(R)3-T(OR)TiCH2=CH- OSi(R)3-T(OR)T, CH2=CH(CH2)n-OSi(R)3-T(OR)Tor CH2=CHC1. Each R is chosen from substituted (C1-C30)hydrocarbyl, unsubstituted (C1-C30)hydrocarbyl, substituted (C1-C30)heterohydrocarbyl, or unsubstituted (C1-C30)heterohydrocarbyl. Subscript T is 0, 1, 2, or 3. Subscript n is 1 to 10. In embodiments in which the polar monomer is an alkyl acrylate, substituted (C1-C30)hydrocarbyl acrylate, unsubstituted (C1-C30)hydrocarbyl acrylate, substituted (C1-C30)heterohydrocarbyl acrylate, or unsubstituted (C1-C30)heterohydrocarbyl acrylate, or unsubstituted (C1-C30)heterohydrocarbyl acrylate, the polar ethylene-based copolymer may be de-esterified to form an acrylic acid ethylene-based copolymer.

[0067] In some embodiments of the polymerization process, the alkyl acrylate monomer may be, by way of example and not limitation, methyl acrylate, ethyl acrylate, «-butyl acrylate, isobutyl acrylate, / -butyl acrylate, or combinations thereof. In various embodiments, the alkylacrylate has an alkyl group with from 1 to 8 carbons. This is designated a C1-C2-alkyl acrylate. In particular embodiments, the alkyl acrylate is / -butyl acrylate or n-butyl acrylate.

[0068] In some embodiments of the polymerization process the optional a-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-l -pentene, styrene, or combinations thereof. In one or more embodiments of the polymerization process, the process may further comprise a cyclic olefin, such as cyclobutene, cyclopentene, norbornene, and norbornene derivatives that are substituted in the 5-position and / or 6-positions with (C1- C20)hydrocarbyl groups.

[0069] In illustrative embodiments, the catalyst systems may include a procatalyst according to formula (I) having the structure of the Procatalysts 1-4 listed below:

[0070]

[0071] In various embodiments, the polymerization process of this disclosure may produce ethylene-based copolymer, in which the polar ethylene-based copolymer contains at least 50 percent by weight (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 sum of the ethylene units and the polar comonomer units.

[0072] In one or more embodiments, the polymerization process of this disclosure may include ethylene monomers, alkyl acrylate monomers, and optionally one or more a-olefins. In some embodiments of the polymerization process which includes a-olefins, the a-olefins may be incorporated into the produced polymers in amounts of from 0.01 wt.% to 45 wt.% based on the weight of the ethylene-based copolymer.

[0073] In various embodiments, the polymerization process of this disclosure may produce ethylene-based copolymer with a molecular weight of from 5,000 g / mol to 1,000,000 g / mol. In some embodiments, the produced polymer has 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.

[0074] General Procedure for PPR Screening Experiments

[0075] Polyolefin catalysis screening is performed in a high-throughput parallel polymerization reactor (PPR) system. The PPR system comprises an array of 48 single-cell (6 x 8 matrix) reactors in an inert atmosphere glovebox. Each cell is equipped with a glass insert with an internal working liquid volume of approximately 5 mL. Each cell has independent controls for pressure and can be continuously stirred at 500-800 rpm. Catalyst, ligand, and metal precursor solutions, unless otherwise noted, may be prepared in toluene. All liquids (i.e., solvent, tert-butyl acrylate (tBA), and catalyst solutions) are added via robotic syringes. Gaseous reagents (i.e.,ethylene) are added via a gas injection port. Prior to each run, the reactors are heated to 50 °C, purged with ethylene, and vented.

[0076] All intended cells are injected with a solution of tBA in toluene followed by a portion of neat toluene. The reactors are heated to the run temperature and then pressured to the appropriate psig with ethylene. Catalysts or in situ metallated ligands are then added to the cells. Each catalyst addition is chased with a small amount of toluene so that after the final addition, a total reaction volume of 5 mL was reached. Upon addition of the catalyst, the PPR software begins monitoring the pressure of each cell. The requested pressure (within approximately 2-6 psig) is maintained by the supplemental addition of ethylene gas by opening the valve at the set point minus 1 psi and closing it when the pressure reached 2 psi higher. All drops in pressure are cumulatively recorded as “Uptake” or “Conversion” of the ethylene for the duration of the run or until the uptake or conversion requested value is reached, whichever occurs first. Each reaction is then quenched by addition of 1% oxygen in nitrogen for 30 seconds at 40 psi higher than the reactor pressure. The shorter the “Quench Time” (the cumulative reaction time until the reaction is quenched), the more active the catalyst. To prevent the formation of too much polymer in any given cell, the reactions are quenched upon reaching a predetermined uptake level of 80 psig. After all the reactors are quenched, they are allowed to cool to about 60 °C. They are then vented, and the tubes are removed. The polymer samples are dried in a centrifugal evaporator at 60 °C for 12 hours, weighed to determine polymer yield, and submitted for IR (tBA incorporation), DSC (melting temperature), and GPC (molecular weight) analysis.

[0077] HT-GPC Analysis

[0078] High temperature GPC analysis was performed using a Robot Assisted Delivery (RAD) system equipped with a Polymer Char infrared detector (IR5) and Agilent PEgel Mixed A columns. Decane (10 pL) is added to each sample for use as an internal flow marker. Samples are first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm of butylated hydroxytoluene (BHT) at a concentration of 10 mg / mL and dissolved by stirring at 160 °C for 120 minutes. Prior to injection, samples are further diluted with TCB stabilized with BHT to a concentration of 3 mg / mE. Samples (250 pL) are eluted through one PL-gel 20 pm (50 x 7.5 mm) guard column followed by two PL-gel 20 pm (300 x 7.5 mm) Mixed-A columns maintained at 160 °C with TCB stabilized with BHT at a flowrate of 1.0 mL / min. The total run time is 24 minutes. To calibrate for molecular weight (MW) Agilent EasiCal polystyrene standards (PS-1 and PS-2) are diluted with 1.5 mL TCB stabilized with BHT and dissolved by stirring at 160 °Cfor 15 minutes. These standards are analyzed to create a 3rdorder MW calibration curve. Molecular weight units are converted from polystyrene (PS) to polyethylene (PE) using a daily Q-factor calculated to be around 0.4 using the average of 5 Dowlex 2045 reference samples.

[0079] Tert-Butyl Acrylate Incorporation IR Analysis

[0080] The 10 mg / mE samples prepared by GPC analysis are further utilized to quantify tBA incorporation by FTIR. A robotic preparation station heated and stirred the samples at 160°C for 60 minutes then deposited 130-pL portions into stainless wells promoted on a silicon wafer. The TCB was evaporated off at 160 °C under nitrogen purge. IR spectra are collected using a Nexus 6700 FT-IR equipped with a DTGS KBr detector from 4000-400 cm'1utilizing 128 scans with a resolution of 4. Ratio of tBA (C=O: 1762-1704 cm'1) to ethylene (CEE: 736-709 cm'1) peak areas are calculated and fit to a linear calibration curve to determine total tBA.

[0081] DSC Procedure

[0082] Melt temperature (Tm), glass transition temperature (Tg), crystallization temperature (Tc), and Heat of Melt were measured on solid polymer samples 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 are subjected to the temperature profile below and traces were analyzed individually using TA Universal Analysis software or TA Instruments TRIOS software.Equilibrate at 175.00 °CIsothermal for 3 minutesRamp 30.00 °C / min to 0.00 °CRamp 10.00 °C / min to 175.00 °CEXAMPLES

[0083] Examples 1 to 8 are synthetic procedures for ligand intermediates and ligands. Examples 9 to 12 are synthetic procedures for isolated procatalysts. In Example 13, the results of the polymerization reactions of Procatalysts 1 to 4 are tabulated and discussed. One or more features of the present disclosure are illustrated in view of the examples as follows:

[0084] General Considerations

[0085] All reactions were performed in a nitrogen-purged glove box unless otherwise noted. All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexanes, tetrahydrofuran, and diethyl ether were purified viapassage through activated alumina and, in some cases, Q-5 reactant. Alumina for solvent purification was activated by passing a stream of nitrogen through the alumina for 8 hours at 300 °C. Q-5 reactant was activated by heating at 200 °C under a stream of nitrogen for 4 hours, followed by a stream of 5% hydrogen in nitrogen at 200 °C for 3 hours, and finally flushing with nitrogen gas. Solvents used for experiments performed in a nitrogen-filled glovebox were further dried by storage over activated 4 A molecular sieves. Glassware for moisture-sensitive reactions was dried in an oven overnight prior to use. HRMS analyses were performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 pm 2.1x50 mm column coupled with an Agilent 6230 EOF Mass Spectrometer with electrospray ionization. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers.XH NMR data are reported as follows: chemical shift (multiplicity (hr = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet and m = multiplet), integration, and assignment). Chemical shifts forXH NMR data are reported in ppm downfield from tetramethylsilane (TMS, 8 scale) using residual protons in the deuterated solvent as references.13C NMR data were determined withXH decoupling, and the chemical shifts are reported in ppm versus tetramethylsilane.13C NMR spectra of phosphines were complex due to C-P coupling. Chemical shifts for31P NMR data are reported in ppm relative to external neat H3PO4. Deuterated solvents for NMR analyses were purchased from Cambridge Isotope Labs and stored over activated 4A molecular sieves in a nitrogen-purged glove box. Chlorobis(2,6-dimethoxyphenyl)phosphine, 1 ,3-dibromo-5-(terL butyl)-2-(ethoxymethoxy)benzene and bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) were prepared according to literature procedures.

[0086] Preparation of Ligands

[0087] Example 1: (3-Bromo-5-(terCbutyl)-2-(ethoxymethoxy)phenyl)bis(2,6- dimethoxyphenyl)phosphane, ligand precursor

[0088] In a nitrogen-purged glovebox, a Schlenk flask equipped with a stir bar and a septum was charged with a solution of 1 ,3-dibromo-5-(terLbutyl)-2-(ethoxymethoxy)benzene (9.00 g,24.5 mmol) in THF (500 mL). The flask was sealed and was taken from the glovebox to the hood. The flask was connected to a nitrogen line and was placed under nitrogen atmosphere. The reaction mixture was cooled to -78 °C (dry ice / acetone bath) and a 2.5 M solution of n-BuTi in hexanes (7.9 mT, 19.8 mmol) was slowly added to the light-yellow solution. The resulting yellow- orange solution was stirred for 1 hour at -78 °C. A solution of chlorobis(2,6- dimethoxyphenyl)phosphine (6.70 g, 19.7 mmol) in THF (45 mF) was slowly added to the murky yellow-orange solution. The resulting yellow-orange solution was stirred for 30 minutes at -78 °C, then the cold bath was removed, and the reaction mixture was stirred for 3 hours while warming to ambient temperature, resulting in a yellow solution. The flask was sealed and taken from the hood to the nitrogen-purged glovebox. An aliquot was removed from the reaction mixture for31P NMR analysis. The31P NMR spectrum showed formation of the desired product with no chlorobis(2,6-dimethoxyphenyl)phosphine remaining, therefore the reaction was determined to be complete. The reaction mixture was concentrated under vacuum to afford a light-yellow solid. The solid was dissolved in a 1 : 1 mixture of dichloromethane (30 mL):toluene (30 mL). The solution was fdtered, washed with a 1 : 1 mixture of dichloromethane :toluene (2 x 10 mL portions), and concentrated under high vacuum to afford a yellow solid (13.53 g). The solid was triturated in hexanes at room temperature for ~1 hour. The mixture was fdtered to afford a pale yellow solid and the solid was washed with hexanes. The solid was analyzed by ' l l NMR and31P NMR. The solid was dried under high vacuum to afford 10.50 g (90.2 %) of the product as pale-yellow solid.

[0089] 1H NMR (400 MHz, C6D6) 5 7.50 (dd, J= 2.4, 1.4 Hz, 1H), 7.29 (t, J= 2.9 Hz, 1H), 7.02 (t, J= 8.2 Hz, 2H), 6.23 (dd, J= 8.2, 2.7 Hz, 4H), 5.47 (d, J = 1.1 Hz, 2H), 3.83 (q, J= 7.1 Hz, 2H), 3.14 (s, 12H), 1.09 (t, J= 7.0 Hz, 3H), 1.00 (s, 9H).

[0090] 13C NMR (101 MHz, C6D6) 5 162.90 (d, J= 9.4 Hz), 153.46 (d, J= 22.7 Hz), 146.47,136.52 (d, .7= 20.1 Hz), 130.00, 129.73, 128.72, 114.15 (d, J= 25.7 Hz), 104.23, 97.26 (d, J= 9.1 Hz), 65.23 (d, J= 4.4 Hz), 55.18 (d, J= 5.5 Hz), 34.04, 31.49, 31.01, 15.10.

[0091] 31P NMR (162 MHz, C6D6) 5 -49.27.

[0092] Example 2: N-(3-(bis(2,6-dimethoxyphenyl)phosphanyl)-5-(ter / -butyl)-2-(ethoxymethoxy)phenyl)-l,l-diphenylmethanimine, ligand precursor

[0093] In a nitrogen-purged glovebox, a 50-mL jar was charged with tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3, 62 mg, 0.07 mmol, 1 mol %), 2,2f- bis(diphenylphosphino)-l,T-bmaphthyl (BINAP, 105 mg, 0.169 mmol, 2.5 mol %), NaO-t-Bu (909 mg, 9.47 mmol), toluene (10 mL), and a stir bar. The jar was sealed and heated to 50 °C for 15 min. The resulting solution was dark red. (3-Bromo-5-(tert-butyl)-2- (ethoxymethoxy)phenyl)bis(2,6-dimethoxyphenyl)phosphane (4.00 g, 6.76 mmol), benzophenone imine (1.13 mL, 6.76 mmol), and toluene (10 mT) were added to a separate vial to form a substrate solution. The substrate solution was slowly added to the first jar containing the catalyst mixture, and the vial was rinsed with toluene (10 mT, 0.2 M total concentration). The jar containing the resulting solution was sealed, heated to 100 °C, and stirred for 18 h. A31P NMR spectrum of the reaction mixture indicated that the reaction was 80 % complete. Additional Pd2dba3 (31 mg, 0.034 mmol, 0.5 mol %) was added and the reaction was allowed to stir for an additional 18 h at 100 °C, after which the31P NMR spectrum indicated the reaction was complete.

[0094] The reaction mixture was cooled to room temperature, basic alumina (~3-5 g) was added to the jar, and the reaction mixture was allowed to stir for 2 h. It was then filtered through a pad of basic alumina and all volatiles were removed from the filtrate under reduced pressure to give the protected phosphino-phenol. The residue was carried on to the next step without further purification.

[0095] Example 3: 3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5-(tert-butyl)-2-(ethoxy methoxy) aniline, ligand precurosr

[0096] In a nitro gen-purged glovebox, a 50-mL jar was charged with N-(3-(bis(2,6- dimethoxyphenyl)phosphanyl)-5-(tert-butyl)-2-(ethoxymethoxy)phenyl)-l,l- diphenylmethanimine (6.76 mmol (theoretical amount from the previous step), hydroxylamine hydrogen chloride (316 mg, 4.55 mmol, 1.8 eq), NaOAc (496 mg, 6.08 mmol, 2.4 eq), methanol (25 mL, 0.1 M), and a stir bar. The jar was sealed, heated to 50 °C, and the reaction mixture was allowed to stir for 18 h. The reaction was cooled to room temperature and all volatiles were removed by vacuum. The resultant crude product was suspended in diethyl ether, NaOMe (1.00 g, 18.5 mmol, 2.7 eq) was added, and the reaction mixture was stirred for 30 min. It was then fdtered through a pad of basic alumina to remove hydroxylimine byproduct. All volatiles were removed from the fdtrate under reduced pressure and the product was purified on a column using ethyl acetate / hexanes where the product eluted at 60 % ethyl acetate. Yield of protected amino phenol: 1.57 g, 2.97 mmol, 44 %, 2 steps.

[0097] 'H NMR (500 MHz, C6D6) 5 7.08 (td, J= 8.2, 0.9 Hz, 2H), 6.86 (dd, J = 4.1, 2.4 Hz, 1H), 6.52 (dd, J= 2.4, 1.0 Hz, 1H), 6.31 (dd, J= 8.2, 2.7 Hz, 4H), 5.30 (d, J= 0.8 Hz, 2H), 3.69 (s, 2H), 3.61 (q, J= 7.1 Hz, 2H), 3.23 (s, 12H), 1.21 (s, 9H), 1.03 (t, J= 7.1 Hz, 3H).

[0098] 13C NMR (101 MHz, CeDe) 5 163.02 (d, J= 9.0 Hz), 145.51 (d, J= 23.8 Hz), 145.13,138.83 (d, .7= 4.3 Hz), 132.95 (d, J= 13.3 Hz), 129.28, 120.16, 115.39 (d, .7= 26.1 Hz), 112.30, 104.32, 97.71 (d, J= 8.0 Hz), 64.85, 55.20, 34.11, 31.46, 15.19.

[0099] 31P NMR (202 MHz, C6D6) 5 -51.98.

[0100] Example 4: 2-Amino-6-(bis(2,6-dimethoxyphenyl)phosphanyl)-4-(ter / - butyl)phenol, ligand precursor

[0101] In a nitrogen-purged glove box, a 60-mT jar was charged with 3-(Bis(2,6- dimethoxyphenyl)phosphanyl)-5-(tert-butyl)-2-(ethoxymethoxy)aniline (1.50 g, 2.84 mmol) and 15 mL of MeOH. THF (2 mT) was added to help homogenize the reaction mixture, although it was slightly cloudy even after the THF was added. This was followed by addition of an HC1 solution (2.31 mL, 8.52 mmol, 3 eq, 4.0 M in dioxane), which resulted in a homogeneous reactionmixture. The jar was sealed, heated to 60 °C, and the reaction mixture was stirred overnight. The reaction mixture was cooled to room temperature, and 5 mT of water was added. Then Nal ICO3 (954 mg, 4 eq, 11.36 mmol) was added slowly to avoid bubbling over. After stirring for 15 min, water was added to dissolve the sodium salts. The product oiled out on the side of the jar. It was redissolved with ethanol and then triturated with water to produce a free-flowing white solid. It was collected via fdtration and washed with hexane. Then the product was dried overnight to remove excess water. The NMR was consistent with the desired product. Final yield: 1.09 g, 2.32 mmol, 82 % yield.

[0102] 'H NMR (500 MHz, CDCh) 5 7.22 (t, J = 8.2 Hz, 2H), 7.16 (dd, J = 13.7, 2.4 Hz, 1H), 7.03 (d, J = 3.4 Hz, 1H), 6.73 (d, J = 2.3 Hz, 1H), 6.50 (dd, J = 8.3, 2.9 Hz, 4H), 3.56 (s, 12H), 1.25 (s, 9H).31P NMR (202 MHz, CDCh) 5 -60.80 (d, J= 13.8 Hz).

[0103] Example 5: Ligand 2 l-(3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5-(terCbutyl)-2-hydroxyphenyl)-2,4,6-triphenylpyridin-l-ium tetrafluoroborate

[0104] In a nitro gen-purged glove box, 2-Amino-6-(bis(2,6-dimethoxyphenyl)phosphanyl)-4- (tert-butyl)phenol (181 mg, 0.38 mmol), 2,4, 6-triphenylpyrylium tetrafluoroborate (143 mg, 0.36 mmol), 4 mF of ethanol, and a stir bar were added to a 20-mL vial. The reaction vial was sealed, heated to 70 °C, and the reaction mixture was allowed to stir for 72 h. The reaction mixture was cooled to room temperature and the product was triturated from the crude reaction mixture using hexane. The product was isolated by fdtration as an orange powder. Yield of Figand 2: 269 mg, 0.34 mmol, 89 %.

[0105] 1H NMR (500 MHz, CDCh) 5 8.00 (s, 2H), 7.87 (dd, J= 7.6, 1.8 Hz, 2H), 7.58 - 7.52(m, 3H), 7.40 (d, J= 7.7 Hz, 4H), 7.34 (d, J= 2.3 Hz, 1H), 7.31 - 7.27 (m, 2H), 7.23 - 7.15 (m, 3H), 7.06 (t, J= 7.6 Hz, 4H), 6.50 (dd, J= 8.3, 3.2 Hz, 4H), 3.42 (s, 12H), 0.98 (s, 9H).

[0106] 13C NMR (126 MHz, CDCh) 5 161.55 (d, J= 7.8 Hz), 157.38, 157.23, 148.42 (d, J=20.7 Hz), 141.71 (d, J= 4.4 Hz), 134.74, 132.89, 132.36 (d, J= 9.5 Hz), 131.87, 130.54, 129.68, 129.62, 128.97, 128.36, 127.81, 126.80, 125.73, 125.47 (d, J= 4.1 Hz), 123.51 (d, J= 4.9 Hz), 109.55 (d, J= 10.9 Hz), 104.15, 55.61, 34.03, 31.00.

[0107] 31P NMR (202 MHz, CDCh) 5 -64.60.19F NMR (471 MHz, CDCh) 5 -153.45.HRMS (ESI+) (m / z): [M(0x)]+calcd for C49H47NO6P: 776.314; found: 776.316.

[0108] Example 6: Ligand 1 - l-(3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5-(ter / - butyl)-2-hydroxyphenyl)-2,4,6-triphenylpyridin-l-ium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate

[0109] In a nitro gen-purged glove box, l-(3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5-(tert- butyl)-2-hydroxyphenyl)-2,4,6-triphenylpyridin-l-ium tetrafluoroborate (Ligand 2, 250 mg, 0.30 mmol), sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBArF, 279 mg, 0.31 mmol), dichloromethane (4 mL), and a stir bar were added to a 20-mL vial. The reaction mixture was stirred at room temperature for 1 h. The NaBF4 was removed by filtration and the volatiles were removed from the filtrate. The product (Ligand 1) was isolated as a yellow / orange solid: 482 mg, 0.29 mmol, 97 % yield.

[0110] 'H NMR (500 MHz, CDCh) 5 8.12 (s, 2H), 7.83 (d, J= 7.6 Hz, 2H), 7.78 - 7.71 (m, 9H - m-C-HBArF+ impurity), 7.66 (t, J= 7.5 Hz, 1H), 7.58 (t, J= 7.8 Hz, 2H), 7.52 (s, 4H), 7.33 (t, J= 8.5 Hz, 2H), 7.31 - 7.24 (m, 5H), 7.19 (d, J= 7.7 Hz, 4H), 7.11 (t, J= 7.7 Hz, 4H), 6.70 (s, 1H), 6.52 (dd, J= 8.4, 3.4 Hz, 4H), 3.45 (s, 12H), 0.94 (s, 9H).

[0111] 13C NMR (126 MHz, CDCh) 5 162.29, 161.90, 161.50, 161.10, 158.00, 157.58,134.78, 133.30, 133.14, 131.97, 130.65, 130.20, 129.59 - 128.42 (m), 128.33 (d, J = 7.5 Hz),127.84, 127.80, 125.63, 125.10, 123.47, 121.30, 119.30 - 116.49 (m), 104.39, 68.18, 55.72, 33.80, 30.81, 25.40.

[0112] 31P NMR (202 MHz, CDCh) 5 10.15 (Ox), -63.87.19F NMR (471 MHz, CDCh) 5-62.42. HRMS (ESI+) (m / z): [M(Ox)]+calcd for C49H47NO6P: 776.314; found: 776.316. HRMS (ESI-) (m / z): [M]’ calcd for C32H12BF24: 863.065; found: 863.076.

[0113] Example 7: Ligand 3 - l-(3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5-(ter / - butyl)-2-hydroxyphenyl)-2,4,6-triphenylpyridin-l-ium tetrakis(4-(methoxymethoxy)phenyl)borate

[0114] In a nitro gen-purged glove box, l-(3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5-(tert- butyl)-2-hydroxyphenyl)-2,4,6-triphenylpyridin-l-ium tetrafluoroborate (Ligand 2, 150 mg, 0.176 mmol), sodium tetrakis(4-(methoxymethoxy)phenyl)borate (103 mg, 0.176 mmol), dichloromethane (5 mL), and a stir bar were added to a 20-mL vial. The reaction mixture was stirred at room temperature for 1 h. The NaBF4 was removed by fdtration and the volatiles were removed from the fdtrate. The product, Ligand 3, was isolated as a beige powder: 176 mg, 0.134 mmol, 76 % yield.

[0115] 1H NMR (500 MHz, CDCh) 5 8.10 - 7.86 (m, 2H), 7.60 (t, J= 7.2 Hz, 2H), 7.57 - 7.45 (m, 4H), 7.32 (m, 2H), 7.25 (m, 11H), 6.66 (d, J= 6.6 Hz, 8H), 6.52 - 6.48 (m, 4H), 5.06 (s, 9H), 3.42 (m (overlapping singlets), 24H), 0.99 (s, 9H).

[0116] 13C NMR (126 MHz, CDCh) 5 161.44 (d, J= 7.9 Hz), 158.23, 157.83, 157.45, 157.37,157.04, 152.82, 136.69 (d, J= 3.0 Hz), 133.26, 133.16, 133.08 (d, J= 3.4 Hz), 132.89, 132.05, 130.77, 130.32, 130.06, 128.68, 128.31, 128.16, 126.81, 125.21, 114.02 - 113.84 (m), 104.19, 95.18, 55.74, 33.93, 31.01.

[0117] 31P NMR (202 MHz, CDCh) 5 -63.81.11B NMR (160 MHz, CDCh) 5 -7.55 - -7.64(m).

[0118] Example 8: Ligand 4 - l-(3-(bis(2,6-dimethoxyphenyl)phosphaneyl)-5-(tertbutyl)-2-hydroxyphenyl)-2,4,6-trimethylpyridin-l-ium tetrafluoroborate

[0119] In a nitrogen-filled glovebox, a 20-mL vial was charged with 2-amino-6-(bis(2,6- dimethoxyphenyl)phosphaneyl)-4-(tert-butyl)phenol (47 mg, 1.0 equiv. 0.10 mmol), 2,4,6- trimethylpyrylium tetrafluoroborate (21 mg, 1.0 equiv. 0.10 mmol), and degassed ethanol (2.0 mL). The resulting solution was then stirred at 70 °C for 16 h. Then the reaction was allowed to be cooled to room temperature and the solvent was reduced under vacuum to 0.5 mL. To this mixture, 2 mL of pentane was added, and a solid residue was obtained. The residue was fdtered off and washed with pentane (2 X 2 mL). It was then dried under reduced pressure to afford the desired product, Ligand 4: 49 mg, 0.078 mmol, 74% yield.

[0120] 'H NMR (500 MHz, Chloroform-* / ) 8 7.86 (d, J = 12.0 Hz, 1H), 7.62 (s, 2H), 7.29 (d, J= 8.3 Hz, 2H), 7.18 (s, 1H), 6.52 (dd, J= 8.5, 3.2 Hz, 4H), 3.56 (s, 12H), 2.60 (s, 3H), 2.27 (s, 6H), 1.28 (s, 9H).

[0121] 13C NMR (101 MHz, Chloroform-* / ) 8 161.45, 161.38, 159.60, 155.32, 135.60,135.26, 130.95, 127.70, 124.26, 123.30, 104.32, 55.88, 34.51, 31.35, 22.33, 21.92, 21.14, 14.05.

[0122] 31P NMR (202 MHz, Chloroform-* / ) 8 -60.01.19F NMR (471 MHz, Chloroform- d) 8 -153.72. HRMS-ESI: m / z = 574.2717 (calculated for pyridinium moiety), observed m / z = 574.2727.

[0123] Example 9: Catalyst 1 - (l-(3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5-(ter / - butyl)-2-hydroxyphenyl)-2,4,6-triphenylpyridm-l-ium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate)(pyridme)(trimethylsilylmethyl)nickel(II)

[0124] In a nitrogen purged glove, bis(pyridine)bis[(trimethylsilyl)methyl] nickel (47 mg, 0.12 mmol), pyridine (10 pL), toluene (1 mL), and a stir bar were added to a 20-mL vial. In a separate vial, was added Ligand 1 (200 mg, 0.12 mmol) and THF (4 mL). The ligand solution was then slowly added to the Ni-containing solution. The resulting solution was dark brown. The reaction mixture was stirred for 1 h and then the reaction mixture was fdtered through a 2.5 pm syringe fdter. All volatiles were removed from the fdtrate under reduced pressure. The resultant residue was washed several times with pentane and the orange solid was dried under vacuum to yield Catalyst 1 : 112 mg, 0.061 mmol, 51 % yield.

[0125] 'H NMR (500 MHz, Tol) 8 8.77 - 8.70 (m, 2H), 8.45 - 8.32 (m, 10H), 8.16 (d, J = 5.6 Hz, 1H), 7.66 (s, 6H), 7.41 (s, 2H), 7.34 (dd, J= 10.8, 2.3 Hz, 1H), 7.28 - 7.00 (m, 50H), 6.94 (t, J = 7.6 Hz, 4H), 6.88 (t, J = 7.1 Hz, 1H), 6.57 (t, J = 6.6 Hz, 2H), 6.29 (dd, J = 8.3, 3.9 Hz, 4H), 6.24 (d, J= 2.4 Hz, 2H), 3.20 (s, 12H), 0.88 (s, 9H), -0.23 (s, 9H), -0.73 (d, J= 9.5 Hz, 2H).

[0126] 13C NMR (126 MHz, Tol) 8 164.89 (d, J= 24.4 Hz), 162.91, 162.51, 162.12, 161.72,160.91, 157.97, 155.76, 150.34, 150.13, 135.10, 133.00, 132.82, 132.41, 131.23, 130.22, 129.56, 125.96, 124.13, 123.79, 123.44, 121.62, 117.60 (d, J= 5.4 Hz), 107.97 (d, J= 50.7 Hz), 104.03 (d, J= 4.2 Hz), 54.71, 33.11, 30.84, 1.65, -16.15 (d, J= 29.6 Hz).

[0127] 19F NMR (376 MHz, Tol) 8 -67.24.nB NMR (160 MHz, Tol) 8 -2.33 - -9.00 (m).31P NMR (202 MHz, Tol) 8 -6.18. Anal calcd for C9oH74BF24N2NiOsPSi: C (58.49 %), N (1.52 %), H (4.04 %); found: C (56.22 %), N (1.53 %), H (3.85 %).

[0128] Example 10: Catalyst 2 - (l-(3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5-(tert- butyl)-2-hydroxyphenyl)-2,4,6-triphenylpyridin-l-ium tetrafluoroborate)(pyridine)(trimethylsilylmethyl)nickel(II)

[0129] In a nitrogen-purged glove box, bis(pyridine)bis[(trimethylsilyl)methyl]nickel (46 mg, 0.12 mmol), pyridine (one drop), a stir bar and THF (2 mL) were added to a 20 mL vial. In a separate vial, Ligand 2 (100 mg, 0.118 mmol) was combined with THF (2 mL). The ligand solution was slowly added to the nickel containing solution with stirring and then the reaction mixture was stirred for 1 h. The solution was then filtered through a syringe fdter and the fdtrate was concentrated to dryness under vacuum. The resulting material was washed with diethyl ether, dried, and isolated as a light brown powder. Yield of Catalyst 2: 109 mg, 0.101 mmol, 82 % yield.

[0130] 'H NMR (500 MHz, C6D6) 5 8.81 (d, J= 5.5 Hz, 2H), 7.80 (s, 5H), 7.59 (s, 5H), 7.37 - 7.28 (m, 4H), 7.06 - 6.98 (m, 3H), 6.31 (dd, J= 8.4, 3.6 Hz, 5H), 3.21 (s, 13H), 1.09 (s, 9H), - 0.21 (s, 9H), -0.72 (d, J= 9.5 Hz, 2H).

[0131] 13C NMR (126 MHz, CeDe) 5 161.13, 157.27, 155.62, 150.40, 137.72, 135.71, 134.83,134.20, 129.94, 129.33, 125.49, 124.15, 108.95 (d, J= 49.2 Hz), 103.97 (d, J= 4.3 Hz), 65.53, 54.89, 31.34, 22.34, 21.05, 15.21, 13.88, 1.89, -17.32 (d, J= 30.0 Hz).

[0132] nB NMR (160 MHz, C6D6) 50.24.19F NMR (471 MHz, C6D6) 5 -150.69.31P NMR (202 MHz, C6D6) 5 -6.13.

[0133] Example 11: Catalyst 3 - (l-(3-(Bis(2,6-dimethoxyphenyl)phosphanyl)-5-(tert- butyl)-2-hydroxyphenyl)-2,4,6-triphenylpyridin-l-ium tetrakis(4-(methoxymethoxy)phenyl)borate)(pyridine)(trimethylsilylmethyl)nickel(H)

[0134] In a nitrogen-purged glove box, bis(pyridine)bis[(trimethylsilyl)methyl]nickel (44 mg, 0.11 mmol), THF (2 mL), and a drop of pyridine were added to a 20 mL vial. In a separate vial, a solution of Ligand 3 (150 mg, 0.113 mmol) was prepared in THF (5 mL). The ligand solution was added dropwise to the nickel-containing solution with stirring. The reaction mixture was allowed to stir for 30 min at room temperature before being filtered through a syringe filter. The filtrate was concentrated to dryness under vacuum. The resulting brown residue was suspended in diethyl ether and rinsed three times. The resulting brown powder was collected by filtration, rinsed a final time with pentane, and then dried under vacuum. Yield of Catalyst 3: 108 mg, 0.070 mmol, 62 % yield.

[0135] 'H NMR (500 MHz, z) 8 8.79 - 8.56 (2H), 7.76 - 7.66 (2H), 7.52 (13H), 7.32 - 7.20 (10H), 7.07 - 6.99 (2H), 6.96 (4H), 6.85 (3H), 6.75 (12H), 6.37 (4H), 4.91 (11H), 3.27 - 3.23 (m, 15H), 3.22 - 3.17 (17H), 0.86 - 0.78 (13H), -0.44 (9H), -0.88 (d, J= 10.1 Hz, 2H).

[0136] 31P NMR (202 MHz, C6D6) 8 -6.22.

[0137] Example 12: Catalyst 4 - l-(3-(bis(2,6-dimethoxyphenyl)phosphaneyl)-5-(tert- butyl)-2-hydroxyphenyl)-2,4,6-trimethylpyridin-l-ium tetrafluoroborate(pyridine)(trimethylsilylmethyl)nickel(H)

[0138] In a nitrogen-purged glove box, bis(pyridine)bis[(trimethylsilyl)methyl]nickel (24 mg, 0.060 mmol), toluene (1 mL), and a drop of pyridine were added to a 20 mL vial. In a separate vial a solution of Ligand 4 (40 mg, 0.06 mmol) was prepared in THF (1 mL). The ligand solution was added dropwise to the nickel-containing solution with stirring. The reaction mixture was allowed to stir for 30 minutes at room temperature before being fdtered through a syringe fdter. The fdtrate was evaporated to dryness under vacuum. The resulting dark yellow residue was suspended in diethyl ether and rinsed three times. The resulting yellow powder was collected by fdtration, rinsed a final time with pentane, and then dried under vacuum. Yield of catalyst 4: 35mg, 0.039 mmol, 65%.

[0139] 1H NMR (500 MHz, THF-rfs) 5 8.68 (d, J = 5.3 Hz, 2H), 7.79 - 7.67 (m, 4H), 7.35(dt, J= 21.4, 7.4 Hz, 4H), 7.08 (s, 1H), 6.64 (dd, J= 8.3, 3.7 Hz, 4H), 3.64 (s, 12H), 2.52 (s, 3H), 2.38 (s, 6H), 1.19 (s, 9H), -0.64 (s, 9H), -0.93 (d, J= 9.6 Hz, 2H).

[0140] 31P NMR (202 MHz, TIllAZs) 5 -7.83.

[0141] Example 13 - Polymerization Processes

[0142] The polymerization reactions were carried out in a parallel polymerization reactor (PPR). Catalyst efficiency (kg polymer yield / mol of polymer / hour) and resulting polymer characteristics were assessed for Catalysts 1 - 4 using a parallel pressure reactor (PPR) and / or a semi-batch reactor.

[0143] For these experiments, a stock solution of catalyst was prepared (1-2 mM) in toluene, and immediately delivered to the parallel pressure reactor (PPR) reactor. Polymerization experiments were run at 400 psi ethylene pressure with 0.25 pmol catalyst loading. For copolymerizations, tert-butyl acrylate (tBA) was purified by filtration through a column of activated alumina, and for delivery to the PPR, a solution of tBA was prepared in toluene. All of the experiments in Table 1 were performed at 400 psi ethylene and 90 °C while varying comonomer loading. The data in each row is an average of two replicate reactions.Table 1. Ethylene homo- and copolymerization results.

[0144] The data recorded in Table 1 demonstrates that the structure of both the cation and the anion affect the rate of (co)polymerization and the properties of the (co)polymers formed. It is generally understood that these catalysts represent the first examples of turning the performance of phosphinophenolnickel(II) catalysts through cation-anion interactions.

[0145] For Example, Catalysts 1 to 3 include the same cation with three different borate anions. In the homopolymerization of ethylene, all three catalysts yield polymers of significantly different molecular weights ranging from 25,000 to 65,000 g / mol (Entries 1-3). The same holds for the copolymerization of ethylene and tBA with Catalysts 1-3 (Entries 7-9 and 11-13). When 250 pmol of tBA was added to the copolymerization reactions (Entries 7-9), Catalysts 1 and 2 gave very high molecular weight copolymer (145,000 to 133,000 g / mol) compared to Catalyst 3 (75,700 g / mol).

[0146] The amount of tBA incorporated into the copolymer was also affected by the identity of the borate anion associated with the catalyst. Catalyst 2 demonstrated nearly double the tBA incorporation (1.12 mol %, entry 8), compared to Catalyst 1 (0.6 mol%, entry 7), despite the two catalysts containing the exact same cationic nickel(II) species. Catalyst 1 demonstrated lower activity in both the homopolymerization of ethylene and the copolymerization of ethylene andtBA than both catalysts 2 and 3. Catalyst 3 gave more than 3 times the activity of Catalyst 1 in ethylene / tBA copolymerization experiments.

[0147] In a similar manner, making small changes to the structure of the cationic fragment, while keeping the anion the same, leads to different (co)polymerization behavior. Catalysts 2 and 4 are identical except for the identity of the substituents on the pyridinium ring: Catalyst 2 has 2,4, 6-triphenyl substitution and Catalyst 4 has 2,4,6-trimethyl substitution. Both catalysts contain a tetrafluoroborate anion. At 250 pmol tBA loading (Entries 7 and 10), Catalyst 4 produced copolymer of less than half the molecular weight (62,200 g / mol) of that produced by Catalyst 2 (133,000 g / mol). At the same time, both catalysts gave similar tBA incorporation and demonstrated similar rates.

Claims

CLAIMS1. A catalyst system comprising a procatalyst having a structure according to formula (I):where:M is nickel(II) or palladium(II);X is a ligand chosen from (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, -CH2S1(RC)3-Q(ORC)Q, -Si(Rc)3-Q(ORc)Q, -OSi(Rc)3-Q(ORc)Q, -Ge(Rc)3-Q(ORc)Q, -P(RC)2-W(ORC)W, -P(O)(RC)2.W(ORC)W, -N(RC)2, -NH(RC), -N(Si(Rc)3)2, -NRcSi(Rc)3, -NHSi(Rc)3, -ORC, -SRC, -NO2, -CN, -CF3, -0CF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(Rc), -N=CH2, -N=P(RC)3I-OC(O)RC, -C(O)ORC, -N(Rc)C(O)Rc, -N(Rc)C(O)H, -NHC(O)Rc, -C(O)N(Rc)2, -C(O)NHRc, -C(0)NH2, a halogen, or a hydrogen, wherein each Rcis independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl, and Q is 0, 1, 2 or 3 and W is 0, 1, or 2; each Y is a Lewis base, wherein X and Y are optionally linked;A is an anion chosen from halide, nitrate, perhalogenate, phosphate, sulfate, RWC(O)O", RWOC(O)O”, RWRENC(O)O", RWO", Si(Rw)3-a(ORw)aCF (RK)5-b(ORw)bSL RWS(O)2O‘‘, RW4B , RW4A1“, Rw4Ga“, RW6P~, R '' .As . or RW6Sb”, wherein each Ru' or RKis independently a halogen, hydrogen, substituted or unsubstituted (C1-C40)hydrocarbyl, or substituted or unsubstituted (C1-C40)heterohydrocarbyl, and wherein a is 0, 1, 2, or 3 and b is 0, 1, 2, 3, or 4;E is positively charged and is a heteroatom selected from nitrogen or phosphorous;R1and R2are independently selected from a substituted (C1-C30)hydrocarbyl, unsubstituted (C1-C30)hydrocarbyl, substituted (C1-C30)heterohydrocarbyl, or unsubstituted (C1-C30)heterohydrocarbyl;R3-R10are independently selected from a substituted (C1-C30)hydrocarbyl, unsubstituted (C1-C30)hydrocarbyl, substituted (C1-C30)heterohydrocarbyl, unsubstituted (C1-C30)heterohydrocarbyl, Si(Rc)3-Q(ORc)Q, -OSi(Rc)3-Q(ORc)Q-Ge(Rc)3-Q(ORc)Q, -P(RC)2- w(ORc)w, -P(0)(RC)2-W(0RC)W, -N(RC)2, -NH(RC)2, -ORC, -SRC, -NO2, - CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, - N=P(RC)3, -OC(O)RC, -C(O)ORC, -N(R)C(O)RC, -C(0)N(RC)2, or a halogen, wherein each Rcis independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl; Q is 0, 1, 2, or 3 and W is 0, 1, or 2; optionally, R1and R2are linked to form a ring structure; or optionally R3and R4are linked to form a ring structure; or optionally R4and R5are linked to form a ring structure; or optionally R6and R7are linked to form a ring structure; or optionally R7and R8are linked to form a ring structure; or optionally R8and R9are linked to form a ring structure; or optionally R9and R10are linked to form a ring structure.

2. The catalyst system of claim 1, wherein R1and R2are 2,6-dimethoxyphenyl, 2,6- diethoxyphenyl, 2,6-diphenoxyphenyl, 2,4,6-triethoxyphenyl, 2,4,6-trimethoxyphenyl, 2- phenylphenyl, or 2,6-diisopropoxyphenyl.

3. The catalyst system of either one of claims 1 to 2, wherein R3, R4, and R5are independently selected from a substituted or unsubstituted (C1-C20)alkyl and substituted or unsubstituted (Ce-C20)aryl.

4. The catalyst system of any of claims 1 to 3, wherein R6, R7, R8, R9, and R10are independently -H , substituted or unsubstituted (C1-C20)alkyl, or substituted or unsubstituted (C6-C2o)aryl.

5. The catalyst system of any one of the preceding claims, wherein Y is pyridine, picoline, lutidine, trimethylamine, or triethylamine.

6. The catalyst system of any one of the preceding claims, wherein R3, R4, and R5are (C1-C1s)alkyl or -H.

7. The catalyst system of any one of the preceding claims, wherein X is a substituted or unsubstituted (C1-C30)hydrocarbyl, a substituted or unsubstituted (C1-C30)heterohydrocarbyl.

8. The catalyst system of any one of claims 1 to 5, wherein X is methyl, 2,2- dimethylpropyl, trimethylsilylmethyl, (n-butyl)dimethylsilylmethyl, (n- hexyljdimethylsiiylmethyl, (n-octyl)dimethylsilylmethyl, or benzyl.

9. The catalyst system of any one of the preceding claims, wherein A" is a coordinating anion, a weakly coordinating anion, or a non-coordinating anion.10 The catalyst system of any one of the preceding claims, wherein A' is BFT, B(3,5- (CF3)2C6H3)4; B(C6F5)4: B(4-(OCH2OCH3)C6H4)4-, or B(C6H5)4-.

11. A polymerization process comprising polymerizing ethylene and optionally polar comonomers and / or optionally (C3-C20)alpha-olefins in the presence of the catalyst system of any one of the preceding claims to form ethylene-based copolymer.

12. The polymerization process of claim 11, wherein the polar monomers comprise an alkyl acrylate.

13. The polymerization process of claim 12, wherein the alkyl acrylate is methyl acrylate or tert-butyl acrylate.

14. The polymerization process of any one of claims 11 to 13, wherein the polymerization occurs in a reactor at a reactor temperature of from 50 °C to 250 °C.

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