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

Abstract

Processes of polymerizing olefin monomers, including polar comonomers, using catalyst systems and catalysts systems that include a procatalyst having a structure according to formula (I).

Description

85652-WO-PCT / DOW 85652 WO ELECTRON-DEFICIENT PHOSPHINE-PHOSPHONIUM-PHENOL SUPPORTED NICKEL(II) AND PALLADIUM(II) CATALYSTS FOR THE COPOLYMERIZATION OF ETHYLENE AND ACRYLATE COMONOMERS CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 604,617 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 phosphine- phosphonium-phenol supported nickel(II) and 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 a highly branched microstructure similar to that of low-density polyethylene (LDPE). Coordination catalysis provides routes to highly linear ethylene / acrylate copolymers with structures similar to that of linear low-density polyethylene (LLDPE). 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,85652-WO-PCT / DOW 85652 WO the Group IV metal catalysts (Ti, Zr, Hf) used in the industrial manufacture of LLDPE (ethylene / α- 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, electron- rich metal catalysts containing Group 10 metals (Pd, Ni) have been explored in the copolymerization reactions of ethylene with acrylate monomers. However, many reported Ni- and Pd-containing metal catalysts suffer from (a) slow rates of polymerization and / or (b) low incorporation 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 phosphonium groups demonstrate high rates of activity and high levels of polar comonomer incorporation, while maintaining high 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):85652-WO-PCT / DOW 85652 WO

[0010] 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(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 positively charged and a heteroatom selected from nitrogen or phosphorous.

[0013] In formula (I), RP1, RP2, and RP3are independently selected from substituted (C1−C20)hydrocarbyl, unsubstituted (C1−C20) hydrocarbyl, (C1−C20)heterohydrocarbyl, unsubstituted (C1−C20)heterohydrocarbyl. In some embodiments, RP1, RP2, and RP3are independently chosen from substituted (C6−C40)aryl or unsubstituted (C6−C40)aryl.

[0014] 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.

[0015] In formula (I), R3, R4, and R5are 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(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 RC85652-WO-PCT / DOW 85652 WO is 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.

[0016] 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; and optionally, R4and R5are linked to form a ring structure; or optionally any two of RP1, RP2or RP3are linked to form a ring structure. DETAILED DESCRIPTION

[0017] 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.

[0018] Common abbreviations are listed below:

[0019] Me : methyl; Et : ethyl; Ph : phenyl; Bn: benzyl; i-Pr : iso-propyl; t-Bu : tert-butyl; t- Oct : tert-octyl (2,4,4-trimethylpentan-2-yl); THF : tetrahydrofuran; Et2O : diethyl ether; CH2Cl2 : dichloromethane; EtOAc : ethyl acetate; C6D6 : deuterated benzene or benzene-d6 : CDCl3 : deuterated chloroform; Na2SO4 : sodium sulfate; MgSO4 : magnesium sulfate; HCl : hydrogen chloride; n-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.

[0020] 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.

[0021] 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.

[0022] When used to describe certain carbon atom-containing chemical groups, a parenthetical expression having the form “(Cx^Cy)” means that the unsubstituted form of the85652-WO-PCT / DOW 85652 WO 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 or more 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.

[0023] The terms “substitution”, “(C1^C50)hydrocarbyl”, “(C1^C50)alkyl”, “(C6^C50)aryl”, “(C3^C50)cycloalkyl”, “(C1^C50)hydrocarbylene”, “(C1^C50)alkylene”, “(C3^C50)cycloalkylene”, “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.

[0024] In this disclosure, a (C1^C50)hydrocarbyl includes, without limitation, unsubstituted or substituted forms of the following groups: (C1^C50)alkyl, (C3^C50)cycloalkyl, (C3^C20)cycloalkyl-(C1^C20)alkylene, (C6^C40)aryl, or (C6^C20)aryl-(C1-C20)alkylene (such as benzyl (−CH2−C6H5)).

[0025] In this disclosure, (C1^C50)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (C1^C50)heterohydrocarbyl include (C1^C50)heteroalkyl, (C1^C50)hydrocarbyl-O^, (C1^C50)hydrocarbyl-S^, (C1^C50)hydrocarbyl-S(O)^, (C1^C50)hydrocarbyl-S(O)2^, (C1^C50)hydrocarbyl-Si(RC)2^, (Cl^C50)hydrocarbyl-N(RN)^, (Cl^C50)hydrocarbyl-P(RP)^, (C2^C50)heterocycloalkyl, (C2^C19)heterocycloalkyl- (C1^C20)alkylene, (C3^C20)cycloalkyl-(C1^C19)heteroalkylene, (C2^C19)heterocycloalkyl- (C1^C20)heteroalkylene, (C1^C50)heteroaryl, (C1^C19)heteroaryl-(C1^C20)alkylene, (C6^C20)aryl- (C1^C19)heteroalkylene, or (C1^C19)heteroaryl-(C1^C20)heteroalkylene. Additional examples include, but are not limited to −Si(RC)3-Q(ORC)Q, −OSi(RC)3-Q(ORC)Q, −Ge(RC)3-Q(ORC)Q, −P(RC)2-W(ORC)W, −P(O)(RC)2-W(ORC)W, −N(RC)2, −NH(RC)2, −ORC, −SRC, −NO2, −CN, −CF3,85652-WO-PCT / DOW 85652 WO −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.

[0026] Embodiments of this disclosure include catalyst systems. The catalyst systems include a procatalyst having a structure according to formula (I):

[0027] 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,−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.

[0028] In formula (I), each Y is a Lewis base. In some embodiments, X and Y are optionally linked.

[0029] In formula (I), A is an anion; E is positively charged and a heteroatom selected from nitrogen or phosphorous.

[0030] In formula (I), P is phosphorus.

[0031] In formula (I), RP1, RP2, and RP3are independently selected from substituted (C1−C20)hydrocarbyl, unsubstituted (C1−C20) hydrocarbyl, (C1−C20)heterohydrocarbyl, unsubstituted (C1−C20)heterohydrocarbyl. In some embodiments, RP1, RP2, and RP3are independently chosen from substituted (C6−C40)aryl or unsubstituted (C6−C40)aryl.

[0032] 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.85652-WO-PCT / DOW 85652 WO

[0033] In formula (I), R3, R4, and R5are 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(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.

[0034] 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; and optionally, R4and R5are linked to form a ring structure; or optionally any two of RP1, RP2or RP3are linked to form a ring structure.

[0035] In some embodiments, RP1, RP2, and RP3are independently selected from unsubstituted (C1−C20)hydrocarbyl and (C1−C20)hydrocarbyl substituted with one or more RS, wherein RSis selected from (C1−C10)alkyl, −ORC, −CN, −CF3, −SRC, −C(O)ORC, and −SiRC3, wherein each RCis independently (C1−C10)alkyl. In some embodiments, RP1, RP2, and RP3may include (C2−C10)alkenyl. An alkenyl is a hydrocarbon radical derived from an alkene (an unsaturated hydrocarbon containing a double bond).

[0036] In various embodiments, RP1, RP2, and RP3are independently selected from substituted (C1-C20)aryl, unsubstituted (C1−C10)alkyl and benzyl substituted with one or more RS, wherein RSis selected from (C1−C10)alkyl , −O(C1−C10)alkyl, and −CF3.

[0037] In some 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.

[0038] In various embodiments, R3, R4, and R5are independently selected from a substituted or unsubstituted (C1−C20)alkyl and substituted or unsubstituted (C6−C20)aryl. In one or more embodiments, R3, R4, and R5are (C1−C18)alkyl or –H.

[0039] 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 a85652-WO-PCT / DOW 85652 WO 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.

[0040] 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.

[0041] 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)aO−,(RR)5-b(ORW)bSi−,RWS(O)2O−, RW4B−, RW4Al−, 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 RWor RRis chosen from halogen, substituted or unsubstituted (C1^C20)alkyl, substituted or unsubstituted (C6^C20)aryl, or substituted or unsubstituted (C1^C20)heteroalkyl or substituted or unsubstituted (C4^C20)heteroaryl. In various embodiments, each RWis different. In other embodiments, each RWis the same. In various embodiments, each RRis different. In other embodiments, each RRis the same.

[0042] In various embodiments, A- is BF4-, B(3,5-(CF3)2C6H3)4-, B(C6F5)4-, B(4- (OCH2OCH3)C6H4)4-, or B(C6H5)4-.

[0043] In various embodiments, A- is F3CS(O)2O−.

[0044] 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.

[0045] In some embodiments, Y is (C1−C40)heterohydrocarbon, (C1−C40)heterohydrocarbyl, or (C1−C40)hydrocarbyl.

[0046] 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 the85652-WO-PCT / DOW 85652 WO (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.

[0047] 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^C10)hydrocarbyl, (C1^C40)hydrocarbyl, [(C1^C10)hydrocarbyl]3Si, or (C1^C40)heterohydrocarbyl and each RKand RLindependently is hydrogen, (C1^C40)hydrocarbyl, or (C1^C40)heterohydrocarbyl.

[0048] In some embodiments, the Lewis base is (C1−C20)hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene or 1,3-butadiene.

[0049] 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).

[0050] 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.85652-WO-PCT / DOW 85652 WO

[0051] 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-1-yl, 2-dimethylaminobenzyl, and 2-dimethylaminomethylphenyl.

[0052] 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.

[0053] 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(O)O−, (C1^C40)hydrocarbylC(O)N((C1^C20)hydrocarbyl)−, (C1^C40)hydrocarbylC(O)N(H)−, RKRLB−, RKRLN−, RKO−, RKS−, RKRLP−, or RMRKRLSi−, where each RK, RL, and RMindependently is hydrogen, (C1^C40)hydrocarbyl, or (C1^C40)heterohydrocarbyl, or RKand RLare taken together to form a (C2^C40)hydrocarbylene or (C1^C20)heterohydrocarbylene and RMis as defined above.

[0054] In embodiments, X is a substituted or unsubstituted (C1−C30)hydrocarbyl, a substituted or unsubstituted (C1−C30)heterohydrocarbyl. In some embodiments, X is a substituted or unsubstituted (C1−C20)hydrocarbyl, a substituted or unsubstituted (C1−C20)heterohydrocarbyl

[0055] In one or more embodiments, X is methyl, 2,2-dimethylpropyl, trimethylsilylmethyl, (n-butyl)dimethylsilylmethyl, (n-hexyl)dimethylsilylmethyl, (n-octyl)dimethylsilylmethyl, or benzyl.

[0056] In some embodiments, X is a halogen, (C1^C20)hydrocarbyl, (C1−C20)heterohydrocarbyl, (C1^C20)hydrocarbylC(O)O–, [(C1^C20)hydrocarbyl]3SiCH2– or RKRLN−, wherein each of RKand RLindependently is an (C1^C20)hydrocarbyl. In some85652-WO-PCT / DOW 85652 WO embodiments, each monodentate ligand X is a chlorine atom, (C1^C10)hydrocarbyl (e.g., (C1^C6)alkyl or benzyl), unsubstituted (C1^C10)hydrocarbylC(O)O–, [(C1^C20)hydrocarbyl]3SiCH2–, or RKRLN−, wherein each of RKand RLindependently is an unsubstituted (C1^C10)hydrocarbyl.

[0057] In further embodiments, X is selected from methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chloro.

[0058] 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.

[0059] In one or more embodiments X is –(CH2)Si(CH3)3, –(CH2)Si(CH3)2(CH2CH3); −(CH2)Si(CH3)(CH2CH3)2, –(CH2)Si(CH2CH3)3, –(CH2)Si(CH3)2(n-butyl), −(CH2)Si(CH3)2(n-hexyl), −(CH2)Si(CH3)(n-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.

[0060] In some embodiments, X is −CH2Si(RC)3-Q(ORC)Q, −Si(RC)3-Q(ORC)Q, −OSi(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.

[0061] 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, and R1−R2, R3−5, or RP1−P3of 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, R3−5, or RP1−P3may 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.85652-WO-PCT / DOW 85652 WO

[0062] Embodiments of this disclosure include polymerization processes. In some embodiments, the polymerization process includes polymerizing ethylene with one or more olefinic monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based copolymer. The catalyst system includes a metal–ligand complex according to formula (I) as described in this disclosure.

[0063] In some embodiments, the polymerization processes include polymerizing ethylene, one or more polar monomers, and optionally, one or more α-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 α-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.

[0064] In some embodiments of the polymerization process, the polymerization process comprises polymerizing ethylene and optionally one or more (C3−C10)α-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.

[0065] In some embodiments of the polymerization process, the polymerization process comprises polymerizing ethylene, a polar comonomer, and optionally one or more (C3−C10)α- 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.

[0066] 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 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 one85652-WO-PCT / DOW 85652 WO 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 to 3600 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.

[0067] 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 80°C to 200 °C. In various embodiments, the reactor temperature is from 90°C to 170°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 1000 psi. In various embodiments, the reactor pressure is 300 psi to 600 psi.

[0068] Olefinic monomers may include, but are not limited to, propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, styrene, cyclobutene, cyclopentene, norbornene, alkyl 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=CHCl, 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.

[0069] 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)T, CH2=CH- OSi(R)3−T(OR)T, CH2=CH(CH2)n-OSi(R)3−T(OR)Tor CH2=CHCl. 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.85652-WO-PCT / DOW 85652 WO

[0070] In some embodiments of the polymerization process, the alkyl acrylate monomer may be, 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 has an alkyl group with from 1 to 8 carbons. This is designated a C1−C8-alkyl acrylate. In particular embodiments, the alkyl acrylate is t-butyl acrylate or n-butyl acrylate.

[0071] 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 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.

[0072] In illustrative embodiments, the catalyst systems may include a procatalyst according to formula (I) having the structure of the Procatalysts 1−8 listed below:85652-WO-PCT / DOW 85652 WO85652-WO-PCT / DOW 85652 WO

[0073] 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.

[0074] In one or more embodiments, the polymerization process of this disclosure may include ethylene monomers, alkyl acrylate monomers, and optionally one or more α-olefins. In some embodiments of the polymerization process which includes α-olefins, the α-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.

[0075] 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.

[0076] General Procedure for PPR Screening Experiments85652-WO-PCT / DOW 85652 WO

[0077] 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.

[0078] 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.

[0079] HT-GPC Analysis

[0080] High temperature GPC analysis was performed using a Robot Assisted Delivery (RAD) system equipped with a Polymer Char infrared detector (IR5) and Agilent PLgel Mixed A columns. Decane (10 µL) was added to each sample for use as an internal flow marker. Samples were first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm of butylated85652-WO-PCT / DOW 85652 WO hydroxytoluene (BHT) at a concentration of 10 mg / mL and dissolved by stirring at 160 °C for 120 minutes. Prior to injection, samples were further diluted with TCB stabilized with BHT to a concentration of 3 mg / mL. Samples (250 µL) were eluted through one PL-gel 20 µm (50 x 7.5 mm) guard column followed by two PL-gel 20 µm (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 was 24 minutes. To calibrate for molecular weight (MW) Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 mL TCB stabilized with BHT and dissolved by stirring at 160 °C for 15 minutes. These standards were analyzed to create a 3rdorder MW calibration curve. Molecular weight units were 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.

[0081] Tert-Butyl Acrylate Incorporation IR Analysis

[0082] The 10 mg / mL samples prepared by GPC analysis were further utilized to quantify tBA incorporation by FTIR. A Dow robotic preparation station heated and stirred the samples at 160°C for 60 minutes then deposited 130-µL portions into stainless wells promoted on a silicon wafer. The TCB was evaporated off at 160 °C under nitrogen purge. IR spectra were 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 (CH2: 736-709 cm-1) peak areas were calculated and fit to a linear calibration curve to determine total tBA.

[0083] DSC Procedure

[0084] 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 °C Isothermal for 3 minutes Ramp 30.00 °C / min to 0.00 °C Ramp 10.00 °C / min to 175.00 °C85652-WO-PCT / DOW 85652 WO EXAMPLES

[0085] Examples 1 to 8 are synthetic procedures for ligands. Examples 9 to 16 are synthetic procedures for isolated procatalysts. In Example 17, the results of the polymerization reactions of Procatalysts 1 to 8 are tabulated and discussed. One or more features of the present disclosure are illustrated in view of the examples as follows:

[0086] General Considerations

[0087] 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 via passage 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 4Å 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 C181.8 μm 2.1x50 mm column coupled with an Agilent 6230 TOF Mass Spectrometer with electrospray ionization. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers.NMR data are reported as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet and m = multiplet), integration, and assignment). Chemical shifts for data are reported in ppm downfield from tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as references.13C NMR data were determined with1H 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 4Å molecular sieves in a nitrogen-purged glove box. Chlorobis(2,6-dimethoxyphenyl)phosphine, 2,6-bis(bis(2,6- dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol,and bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) were prepared according to literature procedures.85652-WO-PCT / DOW 85652 WO

[0088] Preparation of Ligands

[0089] Example 1: Ligand 1: [2-(bis(2,6-dimethoxyphenyl)(4-methylbenzyl)phosphonium)- 6-(bis(2,6-dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol][tetrakis(3,5- bis(trifluoromethyl)phenyl)borate]

[0090] In a N2-filled glovebox, a solution of 4-methylbenzyl bromide (15.8 mg, 0.085 mmol, 1 equiv.) in benzene (1 mL) was added to a solution of 2,6-bis(bis(2,6- dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol (65 mg, 0.085 mmol) in benzene (8 mL) in a 20 mL scintillation vial at room temperature. The resulting colorless solution was stirred for 18 hours at room temperature, yielding a colorless suspension. After completion of the reaction, all the volatiles were removed under reduced pressure. The resulting residue was treated with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (75.9 mg, 0.085 mmol, 1 equiv.) and fluorobenzene (6 mL) at room temperature and stirred for 3 hours. The colorless suspension was filtered through Celite and the filtrate was evaporated under reduced pressure. The oily, colorless residue was triturated with n-pentane (2 × 3 mL) and dried under vacuum for 3 hours to obtain a white powder. Overall Yield: 142 mg (0.082 mmol, 97%).1H NMR (400.1 MHz, C6D6): δ 8.42 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.86 (br s, 1H, OH), 7.80 (ddd, J = 7.9, 2.4, 0.8 Hz, 1H, ArH), 7.66 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.04 (td, J = 8.3, 0.7 Hz, 2H, ArH), 6.95 (t, J = 8.4 Hz, 2H, ArH), 6.88 (dd, J = 16.4, 2.4 Hz, 1H, ArH), 6.66 (dd, J = 8.2, 2.1 Hz, 2H, ArH), 6.51 (d, J = 7.9 Hz, 2H, ArH), 6.20 (dd, J = 8.4, 3.1 Hz, 4H. ArH), 5.97 (dd, J = 8.4, 5.2 Hz, 4H. ArH), 4.47 (d, J = 17.1 Hz, 2H, CH2Ar), 3.04 (s, 12H, OCH3), 2.90 (s, 12H, OCH3), 1.91 (d, J = 1.9 Hz, 3H, PhCH3), 0.99 (s, 9H, C(CH3)3);31P NMR (161.97 MHz, C6D6): 14.6 (d, J = 6.8 Hz), -64.2 (br s).

[0091] Example 2: Ligand 2: [2-(bis(2,6-dimethoxyphenyl)(4- (trifluoromethyl)benzyl)phosphonium)-6-(bis(2,6-dimethoxyphenyl)phosphino)-4-(tert- butyl)phenol][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate]85652-WO-PCT / DOW 85652 WO

[0092] In a N2-filled glovebox, a solid mixture of 2,6-bis(bis(2,6- dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol (50 mg, 0.066 mmol) and 1-(bromomethyl)-4- (trifluoromethyl)benzene (15.7 mg, 0.066 mmol, 1 equiv.) in a 20 mL scintillation vial was treated with toluene (5 mL) at room temperature under nitrogen atmosphere. The resulting colorless solution was stirred for 18 hours at room temperature, yielding a colorless suspension. After completion of the reaction, all the volatiles were removed under reduced pressure. The resulting residue was treated with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (58.4 mg, 0.066 mmol, 1 equiv.) and fluorobenzene (5mL) at room temperature and stirred for 4 hours. The colorless suspension was filtered through Celite and the filtrate was evaporated under reduced pressure. The oily, colorless residue was triturated with n-pentane (2 × 5 mL) and then dried under vacuum for 2 hours to obtain a white powder. Overall Yield: 108 mg (0.061 mmol, 92%).1H NMR (400.1 MHz, C6D6): δ 8.41 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.86 (br s, 1H, OH), 7.65 (br s, (4+1)H, B(C6H3-3,5-(CF3)2)4 + ArH; two signals overlap with each other), 7.06 (t, J = 8.4 Hz, 2H, ArH), 6.98 (t, J = 8.4 Hz, 2H, ArH), 6.76 (d, J = 8.0 Hz, 2H, ArH), 6.69 (d, J = 8.0 Hz, 2H, ArH), 6.64 (d, J = 16.9 Hz, 1H, ArH), 6.22 (dd, J = 8.2, 3.2 Hz, 4H. ArH), 6.00 (dd, J = 8.4, 5.2 Hz, 4H. ArH), 4.44 (d, J = 17.8 Hz, 2H, CH2Ar), 3.06 (s, 12H, OCH3), 2.96 (s, 12H, OCH3), 0.90 (s, 9H, C(CH3)3);31P NMR (161.97 MHz, C6D6): 14.6 (d, J = 8.6 Hz), -65.3 (br s);19F NMR (376.16 MHz, C6D6): -62.24 (s, 24F), -62.47 (s, 3F).

[0093] Example 3: Ligand 3: [2-(bis(2,6-dimethoxyphenyl)phosphino)-4-(tert-butyl)-6- ((3,5-di-tert-butylbenzyl)bis(2,6-dimethoxyphenyl)phosphonium)phenol][tetrakis(3,5- bis(trifluoromethyl)phenyl)borate]85652-WO-PCT / DOW 85652 WO

[0094] In a N2-filled glovebox, a solution of 1-(bromomethyl)-3,5-di-tert-butylbenzene (18.7 mg, 0.066 mmol, 1 equiv.) in benzene (1 mL) was added to a solution of 2,6-bis(bis(2,6- dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol (50 mg, 0.066 mmol) in benzene (4 mL) in a 20 mL scintillation vial at room temperature. The resulting colorless solution was stirred for 16 hours at room temperature, yielding a colorless suspension. After completion of the reaction, all the volatiles were removed under reduced pressure. The resulting residue was treated with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (58.4 mg, 0.066 mmol, 1 equiv.) and fluorobenzene (5mL) at room temperature and stirred for 3 hours. The colorless suspension was filtered through Celite and the filtrate was evaporated under reduced pressure. The oily, colorless residue was triturated with n-pentane (2 × 5 mL) and dried under vacuum for 2 hours to obtain a white powder. Overall Yield: 107 mg (0.059 mmol, 89%).1H NMR (400.1 MHz, C6D6): δ 8.42 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 8.00 (br s, 1H, OH), 7.97 (d, J = 9.2 Hz, 1H, ArH), 7.69 (br s, 4H, B(C6H3- 3,5-(CF3)2)4), 7.21 (s, 1H, ArH), 7.16 (d, 1H, ArH; this signal overlaps with the C6D5H signal), 7.02 (t, J = 8.6 Hz, 2H, ArH), 6.96 (t, J = 8.6 Hz, 2H, ArH), 6.83 (s, 2H, ArH), 6.19 (dd, 4H. ArH), 6.00 (dd, 4H. ArH), 4.51 (d, J = 16.8 Hz, 2H, CH2Ar), 3.04 (s, 12H, OCH3), 2.87 (s, 12H, OCH3), 1.12 (s, 18H, C(CH3)3) 1.11 (s, 9H, C(CH3)3; this signal overlaps with the signal at 1.12 ppm);31P NMR (161.97 MHz, C6D6): 13.3 (br s), -60.1 (br s).

[0095] Example 4 - Ligand 4: [2-(bis(2,6-dimethoxyphenyl)(methyl)phosphonium)-6- (bis(2,6-dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol][tetrakis(3,5- bis(trifluoromethyl)phenyl)borate]85652-WO-PCT / DOW 85652 WO

[0096] To a solution of 2,6-bis(bis(2,6-dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol (50 mg, 0.066 mmol) in toluene (5 mL) in aTeflon™-fitted Schlenk tube, a solution of MeI (9.35 mg, 0.066 mmol) in toluene (1 mL) was added at -78 °C under nitrogen atmosphere. After addition, the reaction mixture was allowed to warm to room temperature over 1 hour and stirred additionally for 18 hours. The resulting colorless suspension was evaporated to dryness under vacuum and the residue was treated with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (58.4 mg, 0.066 mmol, 1 equiv.) and fluorobenzene (4 mL) at room temperature and stirred for 2 hours. The suspension was filtered through Celite and the volatiles materials of the filtrate were removed under vacuum. The resulting oily residue was triturated with n-pentane (2×3 mL) and then dried under reduced pressure to obtain a colorless powder. Overall Yield: 105 mg (0.064 mmol, 97%).1H NMR (400.1 MHz, C6D6): δ 8.41 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 8.05 (d, J = 9.5 Hz, 1H, ArH), 7.68 (br s, 1H, OH; this signal overlaps with the signal at 7.66 ppm), 7.66 (br s, 4H, B(C6H3- 3,5-(CF3)2)4), 7.05 (t, J = 8.3 Hz, 2H, ArH), 7.00 (t, J = 8.3 Hz, 2H, ArH), 6.84 (d, J = 17.6 Hz, 1H, ArH), 6.21 (dd, J = 8.3, 3.1 Hz, 4H. ArH), 6.00 (dd, J = 8.5, 5.2 Hz, 4H. ArH), 3.09 (s, 12H, OCH3), 2.81 (s, 12H, OCH3), 2.29 (d, J = 15.2 Hz, 3H, PCH3), 1.02 (s, 9H, C(CH3)3);31P NMR (161.97 MHz, C6D6): 8.4 (d, J = 4.5 Hz), -62.3 (br s).

[0097] Example 5 - Ligand 5: [tert-butyl-3-((3-(bis(2,6-dimethoxyphenyl)phosphino)-5- (tert-butyl)-2-hydroxyphenyl)bis(2,6-dimethoxyphenyl)phosphonium)propanoate][tetrakis(3,5- bis(trifluoromethyl)phenyl)borate]85652-WO-PCT / DOW 85652 WO

[0098] In a N2-filled glovebox, a solution of tert-butyl 3-bromopropanoate (15.4 mg, 0.074 mmol) in benzene (1 mL) was added to a solution of 2,6-bis(bis(2,6- dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol (56 mg, 0.074 mmol) in benzene (3 mL) in a 20 mL scintillation vial at room temperature. The resulting solution was stirred at room temperature for 16 hours, leading to a colorless suspension. After completion of the reaction, all the volatiles were removed under reduced pressure. The resulting residue was washed with n- pentane (2 × 3 mL) and then dried under vacuum for 2 hours. The obtained white solid was dissolved in fluorobenzene (5 mL) and to this solution, a fluorobenzene solution (2 mL) of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (65.4 mg, 0.074 mmol, 1 equiv.) was added and stirred for 16 hours at room temperature. The resulting colorless suspension was filtered through Celite and the filtrate was evaporated to dryness under reduced pressure. The oily residue was triturated with n-pentane (2 × 5 mL) and dried under vacuum for 30 minutes to obtain the desired phosphonium salt as a white powder. Overall Yield: 71 mg (0.073 mmol, 99%).1H NMR (400.1 MHz, C6D6): δ 8.41 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 8.04 – 7.97 (ddd + br s, 2H, J = 8.8, 2.4, 0.9 Hz, ArH + OH; two signals overlap with each other), 7.67 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.06 (t, J = 8.3 Hz, 2H, ArH), 6.98 (t, J = 8.3 Hz, 2H, ArH), 6.85 (dd, J = 17.1, 2.4 Hz, 1H, ArH), 6.24 (dd, J = 8.3, 3.2 Hz, 4H. ArH), 5.98 (dd, J = 8.5, 5.2 Hz, 4H. ArH), 3.43 (m, 2H, CH2), 3.13 (s, 12H, OCH3), 2.86 (s, 12H, OCH3), 2.35 (m, 2H, CH2), 1.31 (s, 9H, C(CH3)3), 1.01 (s, 9H, C(CH3)3);31P NMR (161.97 MHz, C6D6): 15.2 (d, J = 5.9 Hz), -64.1 (br s).

[0099] Example 6 - Ligand 6: [2-(bis(2,6-dimethoxyphenyl)(pentyl)phosphonium)-6- (bis(2,6-dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol][tetrakis(3,5- bis(trifluoromethyl)phenyl)borate]85652-WO-PCT / DOW 85652 WO

[0100] In a N2-filled glovebox, a solution of 1-bromopentane (30 mg, 0.20 mmol, 3 equiv.) in toluene (3 mL) was added to a solution of 2,6-bis(bis(2,6-dimethoxyphenyl)phosphino)-4-(tert- butyl)phenol (50 mg, 0.066 mmol) in toluene-fluorobenzene mixture (5+5 mL) in a 20 mL scintillation vial at room temperature. After addition, the reaction mixture was stirred for 7 days for completion of the reaction. The resulting colorless suspension was evaporated to dryness under vacuum and the residue was triturated with hexane (3 mL) followed by toluene (3 mL) and then dried under reduced pressure to obtain a colorless solid (54 mg, 0.059 mmol). The resulting solid was treated with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (52.6 mg, 0.059 mmol, 1 equiv.) and fluorobenzene (5 mL) at room temperature and stirred for 2 hours. The suspension was filtered through Celite and the volatile materials of the filtrate were removed under vacuum. The resulting oily residue was triturated with n-pentane (2×3 mL) and then dried under reduced pressure for 3 hours to obtain a colorless powder. Overall Yield: 92 mg (0.054 mmol, 82%).

[0101] 1H NMR (400.1 MHz, C6D6): δ 8.41 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.91 (ddd, J = 7.3, 2.3, 0.8 Hz, 1H, ArH), 7.87 (br s, 1H, OH), 7.67 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.05 (t, J = 8.2 Hz, 2H, ArH), 7.00 (t, J = 8.4 Hz, 2H, ArH), 6.84 (dd, J = 16.9, 2.4 Hz, 1H, ArH), 6.21 (dd, J = 8.3, 3.2 Hz, 4H. ArH), 6.01 (dd, J = 8.4, 5.0 Hz, 4H. ArH), 3.10 (s, 12H, OCH3), 2.89 (s, 12H, OCH3), 2.86 (br m, 2H, PCH2), 1.11 (m, 4H, CH2; two CH2 signals overlap with each other), 1.00 (s, 9H, C(CH3)3), 0.77 (t, J = 7.0 Hz, 3H, CH3).31P NMR (161.97 MHz, C6D6): 15.7 (d, J = 7.8 Hz), −65.3 (br s).

[0102] Example 7 - Ligand 7: [2-(bis(2,6-dimethoxyphenyl)(pent-4-en-1-yl)phosphonium)- 6-(bis(2,6-dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol][tetrakis(3,5- bis(trifluoromethyl)phenyl)borate]85652-WO-PCT / DOW 85652 WO

[0103] In a N2-filled glovebox, a solution of 5-bromo-1-pentene (11.8 mg, 0.0.079 mmol, 1 equiv.) in toluene (1 mL) was added to a solution of 2,6-bis(bis(2,6-dimethoxyphenyl)phosphino)- 4-(tert-butyl)phenol (60 mg, 0.079 mmol) in toluene (8 mL) in a 20 mL scintillation vial at room temperature. After addition, the reaction mixture was stirred for 2 weeks for completion of the reaction. The resulting colorless suspension was evaporated to dryness under vacuum and the residue was triturated with n-pentane (2×5 mL) and then dried under reduced pressure to obtain a colorless solid. The resulting solid was treated with sodium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate (70 mg, 0.079 mmol, 1 equiv.) and fluorobenzene (5 mL) at room temperature and stirred for 3 hours. The suspension was filtered through Celite and the volatile materials of the filtrate were removed under vacuum. The resulting foamy residue was triturated with n-pentane (2×3 mL) and then dried under reduced pressure for 4 hours to obtain a colorless powder. Overall Yield: 110 mg (0.065 mmol, 82%).

[0104] 1H NMR (400.1 MHz, C6D6): δ 8.41 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.93 (ddd, J = 7.8, 2.4, 0.9 Hz, 1H, ArH), 7.88 (br s, 1H, OH), 7.66 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.05 (t, J = 8.2 Hz, 2H, ArH), 6.98 (t, J = 8.4 Hz, 2H, ArH), 6.83 (dd, J = 16.8, 2.4 Hz, 1H, ArH), 6.21 (dd, J = 8.3, 3.1 Hz, 4H. ArH), 5.99 (dd, J = 8.5, 5.1 Hz, 4H. ArH), 5.51 (m, 1H, CH2=CH), 4.90 (m, 2H, CH2=CH), 3.09 (s, 12H, OCH3), 2.94 (br m, 2H, PCH2), 2.86 (s, 12H, OCH3), 1.86 (br q, J = 7.1 Hz, 2H, CH2), 1.27 (m, 2H, CH2), 1.00 (s, 9H, C(CH3)3).31P NMR (161.97 MHz, C6D6): 15.7 (d, J = 6.9 Hz), −64.7 (br s).

[0105] Example 8 - Ligand 8: [2-(bis(2,6-dimethoxyphenyl)(methyl)phosphonium)-6- (bis(2,6-dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol][trifluoromethanesulfonate]85652-WO-PCT / DOW 85652 WO

[0106] In a N2-filled glovebox, a solution of methyl iodide (37 mg, 0.26 mmol, 1 equiv.) in toluene (0.5 mL) was added to a solution of 2,6-bis(bis(2,6-dimethoxyphenyl)phosphino)-4-(tert- butyl)phenol (200 mg, 0.26 mmol, 1 equiv.) in toluene (20 mL) in a 60 mL glass jar at -78 °C. The reaction was stirred at -78 °C for 15 minutes and allowed to come to room temperature slowly. The reaction mixture was stirred at room temperature for 18 hours, forming a white precipitate. The mixture was filtered over a glass fritted funnel and the solid residue was washed with toluene (3×10 mL), followed by n-pentane (3×2 mL). The resulting solid was dried in vacuo for 30 minutes and collected as a white powder (192 mg, 0.21 mmol). In a 20 mL scintillation vial, a portion of the isolated solid (50 mg, 0.06 mmol, 1 equiv.) and sodium triflate (9.5 mg, 0.06 mmol, 1 equiv.) were suspended in fluorobenzene (4 mL), forming a turbid off-white mixture. The reaction mixture was stirred for 72 hours at room temperature, then filtered through Celite to yield a colorless solution. The volatiles were removed in vacuo to yield a white powder. The powder was washed with n-pentane (3×2 mL) and dried under reduced pressure, affording Ligand 8 as a white powder. Overall Yield: 44 mg (0.051 mmol, 85%).1H NMR (400 MHz, FC6H5 / C6D6): 6.39 (dd, JHH = 8.3, 5.2 Hz, 4H, ArH), 6.33 (dd, JHH = 8.3, 3.1 Hz, 4H, ArH), 3.20 (s, 12H, OCH3), 3.16 (s, 12H, OCH3), 2.64 (d, JHP= 15.5 Hz, 3H, PCH3), 1.05 (s, 9H, C(CH3)3).31P NMR (162 MHz, FC6H5 / C6D6): -8.71 (s, 1P, PAr2Me+), -60.69 (s, 1P, PAr2).19F NMR (376 MHz, FC6H5 / C6D6): -77.74 (s, 3F, CF3).31P{1H} NMR (162 MHz, FC6H5 / C6D6): δ 8.71 (br s), ^60.69 (br s).

[0107] Example 9: Catalyst 185652-WO-PCT / DOW 85652 WOCatalyst 1In a N2-filled glovebox, a dark orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (31.5 mg, 0.080 mmol, 1 equiv.) in benzene (3 mL) was added to a colorless suspension of Ligand 1 (139 mg, 0.080 mmol) in benzene (5 mL) in a 20 mL scintillation vial at room temperature. The resulting solution was stirred for 30 minutes, leading to a light orange solution. All the volatiles were removed under reduced pressure and the residue was washed with n-pentane (2 × 5 mL). The resulting orange residue was extracted with benzene (15 mL) at room temperature. The orange extract was evaporated under vacuum to obtain the product as an orange powder. Overall Yield: 131 mg (0.067 mmol, 83%).1H NMR (400.1 MHz, THF-d8): δ 8.90 (m, 2H, py), 7.80 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.77 (m, 1H, py, this signal partially overlaps with the signal at 7.80 ppm), 7.74 (dq, J = 11.2, 1.3 Hz, 1H, ArH), 7.58 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.52 (t, J = 8.4 Hz, 2H, ArH), 7.35 (t, J = 8.4 Hz, 2H, ArH), 7.20 (t, J = 6.8 Hz, 2H, py), 6.78 (dd, 3H, ArH+benzyl-H, two signals overlap with each other), 6.71 (dd, J = 10.4, 2.4 Hz, 2H, benzyl-H), 6.65 (m, 8H, ArH, two signals overlap with each other), 4.47 (d, J = 18.2 Hz, 2H, CH2Ar), 3.56 (s, 12H, OCH3), 3.47 (s, 12H, OCH3), 2.12 (d, J = 1.9 Hz, Ar- Me), 1.01 (s, 9H, C(CH3)3), -0.58 (s, 9H, SiMe3), -0.83 (d, J = 9.3 Hz, 2H, NiCH2);13C NMR (101 MHz, THF-d8): δ 173.76 (dd, JCP= 25.0, 6.3 Hz, Ar-C)), 163.65 (s, Ar-C), 162.80 (q, JCF= 50.0 Hz, ArF-C), 162.20 (d, JCP = 1.6 Hz, Ar-C), 151.93 (s, py), 138.06 (s, py), 136.57 (d, JCP = 3.6 Hz, Ar-C), 136.05 (s, Ar-C), 135.58 (s, ArF-C), 134.79 (dd, JCP= 12.8, 6.8 Hz, Ar-C), 133.87 (t, JCP= 2.6 Hz, Ar-C), 132.75 (dd, JCP= 9.2, 1.3 Hz, Ar-C), 131.92 (s, Ar-C), 131.37 (d, JCP= 8.0 Hz, Ar-C), 130.47 (d, JCP = 7.6 Hz, Ar-C), 130.0 (qq, JCF = 31.5, 3.0 Hz, ArF-C), 129.18 (d, JCP = 2.6 Hz, Ar-C), 129.13 (dd, JCP = 51.4, 8.8 Hz, Ar-C), 125.49 (q, JCF = 272.5 Hz, CF3), 125.04 (d, JCP = 1.5 Hz, Ar-C), 118.16 (sept, JCF= 4.0 Hz, ArF-C), 110.05 (d, JCP= 50.5 Hz, Ar-C), 105.47 (d, JCP = 4.3 Hz, Ar-C), 105.29 (d, JCP = 6.3 Hz, Ar-C), 104.25 (d, JCP = 11.0 Hz, Ar-C), 101.12 (d, JCP = 90.5 Hz, Ar-C), 55.97 (s, OCH3), 55.93 (s, OCH3), 34.31 (s, C(CH3)3), 33.03 (d, JCP = 53.085652-WO-PCT / DOW 85652 WO Hz, P-CH2), 31.89 (s, C(CH3)3), 20.87 (d, JCP= 1.1 Hz, Ar-CH3), 1.95 (s, Si(CH3)3), -16.54 (d, JCP = 30.3 Hz, SiCH2);31P NMR (161.97 MHz, THF-d8): 14.3 (d, J = 12.8 Hz), -6.4 (d, J = 12.8 Hz).

[0108] Example 10: Catalyst 2In a N2-filled glovebox, a dark orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (22 mg, 0.056 mmol, 1 equiv.) in benzene (3 mL) was added to a colorless suspension of Ligand 2 (100 mg, 0.056 mmol) in benzene (5 mL) in a 20 mL scintillation vial at room temperature. The resulting solution was stirred for 30 minutes, leading to a light orange solution. All the volatiles were removed under reduced pressure and the residue was washed with n-pentane (2 × 5 mL). The resulting oily residue was extracted with benzene (10 mL) at room temperature. The orange extract was evaporated under vacuum to obtain the product as an orange powder. Overall Yield: 107 mg (0.053 mmol, 95%).1H NMR (400.1 MHz, C6D6): δ 8.55 (m, 2H, py), 8.43 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.70 (dq, J = 11.2, 1.2 Hz, 1H, ArH; this signal partially overlaps with the signal at 7.67ppm), 7.67 (br s, 4H, B(C6H3-3,5- (CF3)2)4), 7.12 (t, J = 8.4 Hz, 2H, ArH), 7.00 (t, J = 8.4 Hz, 2H, ArH), 6.94 (m, 3H, ArH + py), 6.74 (d, J = 7.8 Hz, 2H, ArH), 6.58 (dd, J = 17.7, 2.4 Hz, 1H, ArH), 6.40 (t, J = 6.9 Hz, 2H, py), 6.25 (dd, J = 8.4, 3.7 Hz, 4H, ArH), 6.02 (dd, J = 8.5, 5.0 Hz, 4H, ArH), 4.33 (d, J = 18.7 Hz, 2H, CH2Ar), 3.16 (s, 12H, OCH3), 2.99 (s, 12H, OCH3), 0.94 (s, 9H, C(CH3)3), -0.22 (s, 9H, SiMe3), -0.62 (d, J = 9.1 Hz, 2H, NiCH2);13C NMR (101 MHz, THF-d8): δ 173.67 (dd, JCP = 25.0, 5.9 Hz, Ar-C)), 163.74 (s, Ar-C), 162.80 (q, JCF= 50.0 Hz, ArF-C), 162.13 (d, JCP= 1.5 Hz, Ar-C), 151.84 (s, py), 139.26 (dd, JCP= 7.7, 1.5 Hz, Ar-C), 138.14 (s, py), 136.53 (s, Ar-C), 135.57 (s, ArF-C), 135.22 (dd, JCP = 12.8, 6.2 Hz, Ar-C), 134.27 (t, JCP = 2.6 Hz, Ar-C), 132.19 (dd, Ar-C; this signal overlaps with the signal at 132.12 ppm), 132.12 (s, Ar-C), 131.03 (d, JCP= 7.5 Hz, Ar-C),130.0 (qq, JCF= 31.5, 3.0 Hz, ArF-C), 129.38 (d, JCP= 8.8 Hz, Ar-C), 128.87 (d, JCP= 8.8 Hz, Ar-C),85652-WO-PCT / DOW 85652 WO 125.49 (q, JCF= 272.5 Hz, CF3), 125.22 (m, Ar-C), 125.18 (q, JCF= 272.0 Hz, CF3), 125.06 (d, JCP = 1.5 Hz, Ar-C), 118.17 (sept, JCF = 4.0 Hz, ArF-C), 109.64 (d, JCP = 50.7 Hz, Ar-C), 105.46 (d, JCP = 6.2 Hz, Ar-C), 104.85 (d, JCP = 10.8 Hz, Ar-C), 103.88 (d, JCP = 11.0 Hz, Ar-C), 100.50 (d, JCP= 92.1 Hz, Ar-C), 56.10 (s, OCH3), 55.89 (s, OCH3), 34.31 (s, C(CH3)3), 32.71 (d, JCP= 54.5 Hz, P-CH2), 31.82 (s, C(CH3)3), 1.96 (s, Si(CH3)3), -16.27 (d, JCP= 30.1 Hz, SiCH2);31P NMR (161.97 MHz, C6D6): 13.4 (dq, J = 12.8, 2.0 Hz), -6.5 (d, J = 12.8 Hz);19F NMR (376.16 MHz, C6D6): -62.21 (s, 24F), -62.44 (s, 3F).

[0109] Example 11: Catalyst 3In a N2-filled glovebox, a dark orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (22.9 mg, 0.059 mmol, 1 equiv.) in benzene (3 mL) was added to a colorless suspension of Ligand 3 (107 mg, 0.059 mmol) in benzene (5 mL) in a 20 mL scintillation vial at room temperature. The resulting solution was stirred for 20 minutes, leading to a light orange solution. All the volatiles were removed under reduced pressure and the residue was washed with n-pentane (2 × 3 mL). The resulting oily residue was extracted with benzene (15 mL) at room temperature. The filtrate was dried under vaccum to obtain the product as an orange powder. Overall Yield: 97 mg (0.047 mmol, 80%).1H NMR (400.1 MHz, C6D6): δ 8.67 (m, 2H, py), 8.44 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.77 (dq, J = 11.2, 1.2 Hz, 1H, ArH), 7.69 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.06 (t, J = 8.3 Hz, 2H, ArH), 6.98 (t, J = 8.3 Hz, 2H, ArH), 6.96 – 6.80 (m, 3H, ArH + py), 6.61 (s, 2H, ArH), 6.47 (t, J = 6.8 Hz, 2H, py), 6.23(dd, J = 8.3, 3.7 Hz, 4H, ArH), 6.01 (dd, J = 8.5, 4.8 Hz,4H, ArH), 4.47 (d, J = 17.7 Hz, 2H, CH2Ar), 3.16 (s, 12H, OCH3), 2.91 (s, 12H, OCH3), 1.08 (s, 9H, C(CH3)3), 1.05 (s, 18H, C(CH3)3), -0.26 (s, 9H, SiMe3), -0.63 (d, J = 9.2 Hz, 2H, NiCH2);13C NMR (101 MHz, THF-d8): δ 173.85 (dd, JCP= 25.0, 6.2 Hz, Ar-C)), 163.70 (s, Ar-C), 162.80 (q, JCF = 50.0 Hz, ArF-C), 162.17 (d, JCP = 1.5 Hz, Ar-C), 151.9385652-WO-PCT / DOW 85652 WO (s, py), 150.93 (s, Ar-C), 138.10 (s, py), 136.09 (s, Ar-C), 135.58 (s, ArF-C), 135.10 (s, Ar-C), 134.93 (dd, JCP = 12.8, 6.2 Hz, Ar-C), 134.42 (d, JCP = 7.4 Hz, Ar-C),134.02 (t, JCP = 2.6 Hz, Ar- C), 132.19 (dd, JCP = 9.8, 1.5 Hz, Ar-C), 131.91 (s, Ar-C), 130.01 (qq, JCF = 31.5, 3.0 Hz, ArF-C), 129.74 (d, JCP= 8.8 Hz, Ar-C), 129.24 (d, JCP= 8.8 Hz, Ar-C), 129.01 (s, Ar-C), 125.49 (q, JCF= 272.0 Hz, CF3), 124.88 (d, JCP= 1.3 Hz, Ar-C), 124.15 (d, JCP= 8.8 Hz, Ar-C), 120.76 (d, JCP= 2.0 Hz, Ar-C), 118.16 (sept, JCF = 4.0 Hz, ArF-C), 110.11 (d, JCP = 50.6 Hz, Ar-C), 106.09 (d, JCP = 10.8 Hz, Ar-C), 105.42 (m,Ar-C), 105.14 (d, JCP = 11.0 Hz, Ar-C), 100.86 (d, JCP = 92.2 Hz, Ar-C), 56.05 (s, OCH3), 55.89 (s, OCH3), 35.20 (s, C(CH3)3), 34.45 (s, C(CH3)3), 33.94 (d, JCP= 56.2 Hz, P-CH2), 32.01 (s, C(CH3)3), 31.66 (s, C(CH3)3), 1.84 (s, Si(CH3)3), -16.59 (d, JCP = 30.1 Hz, SiCH2);31P NMR (161.97 MHz, C6D6): 11.6 (d, J = 12.2 Hz), -6.7 (d, J = 12.2 Hz).

[0110] Example 12 - Catalyst 4In a N2-filled glovebox, a dark orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (25.1 mg, 0.064 mmol, 1 equiv.) in THF (2 mL) was added to a colorless solution of Ligand 4 (105 mg, 0.064 mmol) in THF (3 mL) in a 20 mL scintillation vial at room temperature. The resulting mixture was stirred for 20 minutes, leading to a light orange solution. All the volatiles were removed under reduced pressure and the residue was washed with n-pentane (2 × 2 mL). The resulting oily residue was extracted with benzene (15 mL) at room temperature and dried under vacuum to obtain the product as an orange powder. Overall Yield: 112 mg (0.060 mmol, 94%).1H NMR (400.1 MHz, C6D6): δ 8.50 (m, 2H, py), 8.43 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.81 (dq, J = 11.1, 1.2 Hz, 1H, ArH), 7.67 (br s, 4H, B(C6H3-3,5- (CF3)2)4), 7.09 (t, J = 8.3 Hz, 2H, ArH), 7.01 (t, J = 8.3 Hz, 2H, ArH), 6.95 (tt, J = 7.6, 1.5 Hz, 1H, py), 6.66 (ddd, J = 18.2, 2.4, 0.7 Hz, 1H, ArH), 6.38 (t, J = 6.82 Hz, 2H, py), 6.26 (dd, J = 8.4, 3.7 Hz, 4H, ArH), 6.07 (dd, J = 8.5, 4.9 Hz, 4H, ArH), 3.24 (s, 12H, OCH3), 3.07 (s, 12H, OCH3), 2.16 (d, J = 15.7 Hz, 3H, PCH3), 0.98 (s, 9H, C(CH3)3), -0.19 (s, 9H, SiMe3), -0.60 (d, J85652-WO-PCT / DOW 85652 WO = 9.3 Hz, 2H, NiCH2);13C NMR (101 MHz, THF-d8): δ 173.95 (dd, JCP= 25.0, 5.6 Hz, Ar-C)), 163.94 (s, Ar-C), 162.80 (q, JCF = 50.0 Hz, ArF-C), 162.07 (d, JCP = 1.3 Hz, Ar-C), 151.67 (s, py), 137.97 (s, py), 136.29 (s, Ar-C), 135.59 (s, ArF-C), 135.16 (dd,JCP = 13.2, 6.2 Hz, Ar-C), 134.3 (t, JCP= 2.5 Hz, Ar-C), 131.93 (s, Ar-C), 130.83 (dd, JCP= 11.3, 1.2 Hz, Ar-C), 130.02 (qq, JCF= 31.5, 2.8 Hz, ArF-C), 128.46 (dd, JCP= 50.5, 8.4 Hz, Ar-C), 125.51 (q, JCF= 272.0 Hz, CF3), 124.62 (d, JCP = 1.2 Hz, Ar-C), 118.18 (sept, JCF = 3.8 Hz, ArF-C), 109.96 (d, JCP = 50.1 Hz, Ar- C), 107.06 (dd, JCP = 99.8, 10.6 Hz, Ar-C), 105.66 (d, JCP = 6.2 Hz, Ar-C), 105.36 (d, JCP = 4.3 Hz, Ar-C), 101.47 (d, JCP= 95.4 Hz, Ar-C), 56.40 (s, OCH3), 55.88 (s, OCH3), 34.38 (s, C(CH3)3), 31.91 (s, C(CH3)3), 13.81 (d, JCP = 64.1 Hz, P-CH3), 1.92 (s, Si(CH3)3), -16.43 (d, JCP = 29.4 Hz, SiCH2);31P NMR (161.97 MHz, C6D6): 7.7 (d), -7.1 (d).

[0111] Example 13 - Catalyst 5In a N2-filled glovebox, a dark orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (28.8 mg, 0.074 mmol, 1 equiv.) in benzene (2 mL) was added to a colorless solution of Ligand 5 (129 mg, 0.074 mmol) ) in benzene (3 mL) in a 20 mL scintillation vial at room temperature. The resulting solution was stirred for 30 minutes, leading to a light orange solution. After completion of the reaction, the solution was treated with n-pentane (1 mL) and then filtered through Celite. All the volatiles of the orange filtrate were removed under reduced pressure and the residue was washed with n-pentane (3 × 3 mL). The resulting residue was dried under vacuum for 1 hour to obtain the product as an orange powder. Overall Yield: 112 mg (0.065 mmol, 88%).1H NMR (400.1 MHz, C6D6): δ 8.60 (m, 2H, py), 8.44 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.85 (dq, J = 11.2, 1.2 Hz, 1H, ArH), 7.68 (br s, 4H, B(C6H3-3,5- (CF3)2)4), 7.11 (t, J = 8.3 Hz, 2H, ArH), 6.95 (t, J = 8.3 Hz, 2H, ArH), 6.90 (tt, J = 7.6, 1.5 Hz, 1H, py), 6.63 (ddd, J = 17.6, 2.4, 0.8 Hz,1H, ArH), 6.54 (t, J = 6.8 Hz, 2H, py), 6.28 (dd, J = 8.4, 3.7 Hz, 4H, ArH), 6.02 (dd, J = 8.4, 4.9 Hz, 4H, ArH), 3.28 (s, 12H, OCH3), 3.02 (s, 14H, OCH385652-WO-PCT / DOW 85652 WO + CH2; two signals overlap with each other), 2.53 (m, 2H, CH2), 1.38 (s, 9H, C(CH3)3), 0.98 (s, 9H, C(CH3)3), -0.16 (s, 9H, SiMe3), -0.59 (d, J = 9.3 Hz, 2H, NiCH2);13C NMR (101 MHz, THF- d8): δ 174.37 (dd, JCP = 25.0, 5.4 Hz, Ar-C)), 172.52 (d, JCP = 1.5 Hz, C=O), 163.82 (s, Ar-C), 162.80 (q, JCF= 50.0 Hz, ArF-C), 162.05 (d, JCP= 1.5 Hz, Ar-C), 151.51 (s, py), 137.96 (s, py), 136.23 (s, Ar-C), 135.73 (d, JCP= 6.2 Hz, Ar-C), 135.58 (s, ArF-C), 134.84 (t, JCP= 2.5 Hz, Ar- C), 132.09 (s, Ar-C), 131.69 (dd, JCP = 10.4, 1.8 Hz, Ar-C), 130.01 (qq, JCF = 31.5, 2.9 Hz, ArF- C), 129.01 (s, Ar-C), 128.19 (d, JCP = 8.2 Hz, Ar-C), 127.69 (d, JCP = 8.2 Hz, Ar-C), 125.50 (q, JCF= 272.5 Hz, CF3), 124.83 (s, Ar-C), 118.17 (sept, JCF= 4.0 Hz, ArF-C), 109.43 (d, JCP= 49.7 Hz, Ar-C), 105.61 (d, JCP = 4.3 Hz, Ar-C), 105.15 (d, JCP = 4.3 Hz, Ar-C), 102.79 (dd, JCP = 96.9, 10.7 Hz, Ar-C), 99.68 (d, JCP = 94.4 Hz, Ar-C), 79.90 (s, CH2), 55.03 (s, OCH3), 54.57 (s, OCH3), 33.15 (s, C(CH3)3), 30.60 (s, C(CH3)3), 29.14 (s, C(CH3)3), 27.03 (s, C(CH3)3), 22.18 (d, JCP= 63.2 Hz, P-CH2), 0.90 (s, Si(CH3)3), -18.24 (d, JCP = 28.9 Hz, SiCH2);31P NMR (161.97 MHz, C6D6): 13.5 (d, J = 11.8 Hz), -7.7 (d, J = 11.8 Hz).

[0112] Example 14 - Catalyst 6bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (20.1 mg, 0.051 mmol, 1 equiv.) in benzene (5 mL) was added to a colorless solution of Ligand 6 (87 mg, 0.051 mmol) in benzene (10 mL) in a 20 mL scintillation vial at room temperature. The resulting mixture was stirred for 30 minutes, leading to a light orange solution. All the volatiles were removed under reduced pressure and the residue was washed with n-pentane (2 × 5 mL). The resulting orange residue was extracted with benzene (15 mL) at room temperature and dried under vacuum to obtain the product as an orange powder. Overall Yield: 90 mg (0.047 mmol, 92%).

[0114] 1H NMR (400.1 MHz, THF-d8): δ 8.71 (m, 2H, py), 7.83 (dd, ArH; a part of this signal overlaps with the signal at 7.81 ppm), 7.81 (br m, 8H, B(C6H3-3,5-(CF3)2)4), 7.71 (tt, J = 7.6, 1.685652-WO-PCT / DOW 85652 WO Hz, 1H, py), 7.58 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.55 (t, J = 8.4 Hz, 2H, ArH; this signal partially overlaps with the signal at 7.58 ppm), 7.36 (t, J = 8.3 Hz, 2H, ArH), 7.04 (br t, J = 6.8 Hz, 2H, py), 6.73 (dd, J = 8.4, 4.7 Hz, 4H, ArH), 6.66 (dd, J = 8.4, 3.7 Hz, 4H, ArH), 6.62 (ddd, J = 17.5, 2.4, 0.8 Hz, 1H, ArH; this signal partially overlaps with the signal at 6.66), 3.62 (s, 12H, OCH3), 3.61 (s, 12H, OCH3), 2.73 (m, 2H, PCH2), 1.35 (m, 2H, CH2), 1.23 (m, 4H, CH2), 1.04 (s, 9H, C(CH3)3), 0.87 (m, 2H, CH3), −0.48 (s, 9H, SiMe3), −0.83 (d, J = 9.2 Hz, 2H, NiCH2).13C NMR (101 MHz, THF-d8): δ 174.42 (dd, JCP = 25.0, 5.5 Hz, Ar-C)), 163.91 (s, Ar-C), 162.81 (q, JCF = 50.0 Hz, ArF-C), 162.11 (d, JCP= 1.6 Hz, Ar-C), 151.66 (s, py), 137.95 (s, py), 136.03 (s, Ar-C), 135.59 (s, ArF-C), 135.14 (dd, JCP = 12.9, 6.2 Hz, Ar-C), 134.46 (t, JCP = 2.5 Hz, Ar-C), 132.07 (s, Ar-C), 131.88 (dd, JCP = 9.8, 1.8 Hz, Ar-C), 130.02 (qq, JCF = 31.5, 2.8 Hz, ArF-C), 127.65 (dd, JCP= 51.5, 8.3 Hz, Ar-C), 125.50 (q, JCF= 272.0 Hz, CF3), 124.63 (d, JCP= 1.7 Hz, Ar-C), 118.18 (sept, JCF = 3.8 Hz, ArF-C), 109.67 (d, JCP = 49.5 Hz, Ar-C), 105.51 (d, JCP = 6.3 Hz, Ar- C), 105.25 (d, JCP = 4.2 Hz, Ar-C), 104.59 (dd, JCP = 96.6, 10.7 Hz, Ar-C), 101.55 (d, JCP = 92.1 Hz, Ar-C), 56.24 (s, OCH3), 55.88 (s, OCH3), 34.77 (d, JCP= 20.2 Hz, CH2), 34.42 (s, C(CH3)3), 31.96 (s, C(CH3)3), 27.51 (d, JCP= 56.8 Hz, P-CH2), 24.51 (d, JCP= 3.5 Hz, CH2), 23.29 (d, JCP= 1.5 Hz, CH2), 14.56 (s, CH3), 2.30 (s, Si(CH3)3), −17.14 (d, JCP = 29.4 Hz, SiCH2).31P NMR (161.97 MHz, THF-d8): 14.55 (d, J = 12.3 Hz), −7.64 (d, J = 12.3 Hz).

[0115] Example 15 - Catalyst 7

[0116] In a N2-filled glovebox, a dark orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (25.5 mg, 0.065 mmol, 1 equiv.) in benzene (4 mL) was added to a colorless suspension of Ligand 7 (110 mg, 0.065 mmol) in benzene (8 mL) in a 20 mL scintillaton vial, at room temperature. The resulting mixture was stirred for 30 minutes, leading to a light orange solution. All the volatiles were removed under reduced pressure and the residue was washed with n-pentane (2 × 3 mL) and dried under reduced pressure for 3 hours to obtain an orange solid. Overall Yield: 113 mg (0.059 mmol, 91%).85652-WO-PCT / DOW 85652 WO

[0117] 1H NMR (400.1 MHz, THF-d8): δ 8.73 (m, 2H, py), 7.85 (br d, J = 11.3 Hz, 1H, ArH), 7.81 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.71 (t, J = 7.6 Hz, 1H, py), 7.59 (br s, 4H, B(C6H3-3,5- (CF3)2)4), 7.55 (t, J = 8.3 Hz, 2H, ArH), 7.36 (t, J = 8.3 Hz, 2H, ArH), 7.04 (t, J = 6.7 Hz, 2H, py), 6.73 (dd, J = 8.4, 4.8 Hz, 4H, ArH), 6.67 (dd, J = 8.3, 3.7 Hz, 4H, ArH), 6.62 (dd, J = 15.8, 1.8 Hz, 1H, ArH; this signal partially overlaps with the signal at 6.67) 5.71 (m, 1H, CH2=CH), 4.90 (m, 2H, CH2=CH), 3.63 (s, 24H, OCH3; two signals overlap with each other), 2.73 (m, 2H, PCH2), 2.03 (q, J = 6.9 Hz, CH2), 1.44 (m, 2H, CH2), 1.04 (s, 9H, C(CH3)3), −0.48 (s, 9H, SiMe3), −0.81 (d, J = 9.2 Hz, 2H, NiCH2).13C NMR (101 MHz, THF-d8): δ 174.41 (dd, JCP= 25.1, 5.6 Hz, Ar- C), 163.89 (s, Ar-C), 162.81 (q, JCF = 50.0 Hz, ArF-C), 162.09 (d, JCP = 1.3 Hz, Ar-C), 151.67 (s, py), 138.75 (s, CH2=CH), 137.98 (s, py), 136.07 (s, Ar-C), 135.58 (s, ArF-C), 135.23 (dd, JCP = 12.8, 6.1 Hz, Ar-C), 134.64 (br s, Ar-C), 132.06 (s, Ar-C), 130.83 (d, JCP= 11.4 Hz, Ar-C), 130.02 (qq, JCF = 31.5, 2.8 Hz, ArF-C), 127.65 (dd, JCP = 51.4, 8.6 Hz, Ar-C), 125.50 (q, JCF = 272.0 Hz, CF3), 124.65 (s, py), 124.15 (s, Ar-C), 118.18 (sept, JCF = 3.8 Hz, ArF-C), 115.71(s, CH2=CH), 109.67 (d, JCP= 49.4 Hz, Ar-C), 105.55 (d, JCP= 6.2 Hz, Ar-C), 105.27 (d, JCP= 4.1 Hz, Ar-C), 104.52 (dd, JCP= 96.4, 9.8Hz, Ar-C), 101.55 (d, JCP= 94.4 Hz, Ar-C), 56.29 (s, OCH3), 55.90 (s, OCH3), 36.36 (d, JCP = 20.9 Hz, CH2), 34.42 (s, C(CH3)3), 31.94 (s, C(CH3)3), 27.30 (d, JCP = 57.7 Hz, P-CH2), 24.03 (s, CH2), 2.28 (s, Si(CH3)3), −17.06 (d, JCP = 29.4 Hz, SiCH2).31P NMR (161.97 MHz, THF-d8): 14.58 (d, J = 11.8 Hz), −7.66 (d, J = 11.8 Hz).

[0118] Example 16 - Catalyst 8

[0119] In a N2-filled glove box, bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (28 mg, 0.07 mmol, 1 equiv.) and Ligand 8 (66 mg, 0.07 mmol, 1 equiv.) were dissolved in benzene (5 mL) in a 20 mL scintillation vial, forming a dark red solution. The mixture was stirred for 20 minutes at room temperature and the solvent removed in vacuo to yield a dark brown, sticky gel. Trituration with n-pentane afforded a brown solid, which was washed with cold diethyl ether (3 x 3 mL). Volatiles were removed in vacuo, providing Catalyst 8 as a brown powder. The ethereal85652-WO-PCT / DOW 85652 WO washings yielded X-ray quality dark red crystals at room temperature over the course of 1 week. Overall Yield: 66 mg (0.06 mmol, 80%).1H NMR (400 MHz, THF-d8): δ 8.72 – 8.65 (m, 2H, ArH), 7.86 (tt,3JHH = 7.6, 1.7 Hz, 1H, ArH), 7.76 (ddd,4JHP= 11.1 Hz,4JHH= 2.5 Hz,5JHP= 1.2 Hz, 1H, ArH), 7.57 (t,3JHH= 8.4 Hz, 2H, PArH), 7.33 (t,3JHH= 8.4 Hz, 2H, PArH), 7.17 (t, J = 6.7 Hz, 2H, Py), 6.79 (dd,3JHH= 8.4,4JHH= 4.9 Hz, 4H, PArH), 6.67 (d, J = 3.7 Hz, 2H), 6.65 (d, J = 3.7 Hz, 2H), 6.60 (dd,4JHH = 2.5 Hz,5JHP= 0.9 Hz, 1H, ArH), 3.67 (s, 12H, OCH3), 3.63 (s, 12H, OCH3), 2.39 (d,2JHP= 15.6 Hz, 3H, PCH3), 1.01 (s, 9H, C(CH3)3), -0.59 (s, 9H, Si(CH3)3), -0.87 (d,3JHP= 9.4 Hz, 2H, NiCH2Si).13C{1H} NMR (101 MHz, THF-d8): δ 174.03 (dd, JCP = 24.7, 5.7 Hz, Ar-C)), 163.89 (s, Ar-C), 162.12 (d, JCP = 1.5 Hz, Ar-C), 151.38 (s, Ar-C), 138.87 (s, Ar-C), 136.55 (s, Ar-C), 134.89 (dd, JCP= 13.0, 5.9 Hz, Ar-C), 133.84 (t, JCP= 2.8 Hz, Ar-C), 131.79 (s, Ar-C), 130.67 (d, JCP= 11.3 Hz, Ar-C), 128.40 (dd, JCP= 50.6, 8.2 Hz, Ar-C)), 125.16 (s, Ar-C), 110.13 (d, JCP= 49.5 Hz, Ar- C), 107.56 (dd, JCP = 99.7, 10.6 Hz, Ar-C), 105.99 (d, J = 6.4 Hz, Ar-C), 105.25 (d, J = 4.3 Hz, Ar-C), 100.93 (d, J = 95.7 Hz, Ar-C), 56.80 (s, OCH3), 55.98 (s, OCH3) , 34.38 (s, C(CH3)3), 31.99 (s, C(CH3)3), 14.30 (d,2JCP= 64.3 Hz, PCH3), 1.96 (s, Si(CH3)3), −16.95 (d,2JCP= 29.3 Hz, SiCH2);19F{1H} NMR (362 MHz, THF-d8): δ -78.33 (s, 3F, CF3);31P{1H} NMR (162 MHz, THF- d8): δ 7.62 (d,4JPP= 12.3 Hz, PAr2Me+), −7.19 (d,4JPP= 11.9 Hz, PAr2).

[0120] Example 17 – Polymerization Process

[0121] For the polymerization reactions recorded in Table 1, a stock solution of catalyst was prepared (1-2 mM) in toluene, and immediately delivered to the parallel pressure reactor (PPR) reactor. Ethylene homopolymerization experiments were run at 200 psi ethylene pressure with 0.25 μmol catalyst loading at 90 °C. Ethylene copolymerization experiment were run at 400 psi ethylene pressure with 0.25 μmol catalyst loading at 90 °C. For copolymerizations, tert-butyl acrylate (tBA) was purified by filtering them through a column of activated alumina, and for delivery to the PPR a solution of tBA in toluene was prepared. Table 1. Ethylene homopolymerization and copolymerization (tBA) experiments in PPR*.85652-WO-PCT / DOW 85652 WO* Reactor details provided in the General Procedure for PPR Screening Experiments.aCatalyst 8 was injected into the reactor as a solution in THF due to limited solubility in toluene; reactor contained 4.75 mL of toluene and 0.25 mL of THF.

[0122] The data recorded in Table 1 demonstrates that Catalysts 1 to 8 are active in the homopolymerization of ethylene and copolymerization of ethylene and tert-butyl acrylate. 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 some of the first examples of tuning the performance of phosphinophenolnickel(II) catalysts through cation-anion interactions.

[0123] Catalysts 1-7 all contain the same anion, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, and differ only in the identity of the alkyl or benzyl group bound to the phosphonium center. Catalysts 1-7 were all highly active in the homopolymerization of ethylene (entries 1, 5, 8, 11, 14, 17, and 20), even at the lower pressure (200 psi) used in our85652-WO-PCT / DOW 85652 WO ethylene homopolymerization experiments. Catalysts 1-7 also demonstrated good activities (200 to 1100 kg / mol·h) in the copolymerization of ethylene (400 psi, 90 °C) and tert-butyl acrylate (125 to 500 µmol) and produced copolymers with relatively high molecular weights (38,000 g / mol to 96,000 g / mol).

[0124] Additionally, the catalysts were able to incorporate tBA monomer up to nearly 5 wt% in the copolymer. Catalyst 4, which demonstrated an activity of 1102 kg / mol·h in the copolymerization of ethylene and tBA (250 µmol) to produce a copolymer with a molecular weight greater than 85,000 g / mol and a t-BA incorporation of 2.6 wt% (entry 12) includes a methyl-substitution. Upon doubling the tBA loading in the experiment to 500 µmol (entry 13) from 250 µmol Catalyst 4 produced a copolymer with a molecular weight of greater than 70,000 g / mol with a tBA incorporation of 4.9%.

[0125] The structure of the anion also affected catalyst performance. Catalysts 4 and 8 contain the same cationic fragment, but differ in the identity of their anions. Catalyst 8, which contains a trifluoromethanesulfonate anion, gave a slower rate (116 kg / mol·h) in the copolymerization of ethylene and tBA (250 µ mol, entry 25) than Catalyst 4 (1102 kg / mol·h, entry 12), which contains a tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion.

Claims

85652-WO-PCT / DOW 85652 WO CLAIMS 1. 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, -CH2Si(RC)3-Q(ORC)Q, −Si(RC)3-Q(ORC)Q, -OSi(RC)3-Q(ORC)Q, −Ge(RC)3-Q(ORC)Q, −P(RC)2-W(ORC)W, −P(O)(RC)2-W(ORC)W, −N(RC)2, −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; each Y is a Lewis base, wherein X and Y are optionally linked; A is a anion chosen from halide, nitrate, perhalogenate, phosphate, sulfate, RWC(O)O−, RWOC(O)O−, RWRRNC(O)O−, RWO−, Si(RW)3-a(ORW)aO−,(RR)5-b(ORW)bSi−, RWS(O)2O−, RW4B−, RW4Al−, 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 wherein a is 0, 1, 2, or 3 and b is 0, 1, 2, 3, or 4;85652-WO-PCT / DOW 85652 WO E is positively charged and a heteroatom selected from nitrogen and phosphorous; RP1, RP2, and RP3are independently selected from (C1−C20)hydrocarbyl substituted with one or more RSor unsubstituted (C1−C20) hydrocarbyl, substituted (C6−C40)aryl or unsubstituted (C6−C40)aryl, wherein RSis selected from (C1−C10)alkyl, −ORC, −CN, −CF3, −SRC, −C(O)ORC, and −SiRC3, wherein each RCis independently (C1−C10)alkyl; R1and R2are independently selected from a substituted (C1−C30)hydrocarbyl, unsubstituted (C1−C30)hydrocarbyl, substituted (C1−C30)heterohydrocarbyl, or unsubstituted (C1−C30)heterohydrocarbyl; R3, R4, and R5are 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(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; 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, RP1and RP2are linked to form a ring structure; or optionally, RP1and RP3are linked to form a ring structure; or optionally, RP2and RP3are linked to form a ring structure.

2. The catalyst system of claim 1, wherein RP1, RP2, and RP3are independently selected from unsubstituted (C1−C20)hydrocarbyl and (C1−C20)hydrocarbyl substituted with one or more RS, wherein RSis selected from (C1−C10)alkyl, −ORC, −CN, −CF3, −SRC, −C(O)ORC, and −SiRC3, wherein each RCis independently (C1−C10)alkyl.85652-WO-PCT / DOW 85652 WO 3. The catalyst system of claim 1 or claim 2, wherein at least one of RP1, RP2, and RP3is independently selected from unsubstituted (C1−C10)hydrocarbyl or benzyl substituted with one or more RS, wherein RSis selected from (C1−C10)alkyl, −CF3, and −O(C1−C10)alkyl.

4. The catalyst system of any one of claim 1 to 3, 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.

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

7. The catalyst system of any one of the preceding claims, wherein R3, R4, and R5are (C1−C18)alkyl or –H.

8. 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.

9. The catalyst system of any one of the preceding claims, wherein X is methyl, 2,2- dimethylpropyl, trimethylsilylmethyl, (n-butyl)dimethylsilylmethyl, (n- hexyl)dimethylsilylmethyl, (n-octyl)dimethylsilylmethyl, or benzyl.

10. 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.

11. The catalyst system of any one of the preceding claims, wherein A- is BF4-, B(3,5- (CF3)2C6H3)4-, B(C6F5)4-, B(4-(OCH2OCH3)C6H4)4-, B(C6H5)4-, or trifluoromethanesulfonate.

12. A polymerization process comprising polymerizing ethylene and optionally polar comonomers and / or optionally a (C3−C20)alpha-olefin in the presence of the catalyst system of any preceding claims to form ethylene-based polymer.

13. The polymerization process, wherein the polar monomers comprise alkyl acrylates.85652-WO-PCT / DOW 85652 WO 14. The polymerization process of claim 13, wherein the alkyl acrylate is methyl acrylate or tert-butyl acrylate.

15. The polymerization process of any one of claims 12 to 14, wherein the polymerization occurs in a reactor at a reactor temperature of from 50 ºC to 250 ºC.

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