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

Abstract

The present invention provides methods of polymerizing olefin monomers, including polar comonomers, using catalyst systems and catalyst systems comprising procatalysts having a structure according to Formula (I).

Description

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 herein by reference in their entirety. Technical Field

[0002] The embodiments of this disclosure generally relate to catalyst systems and methods for the polymerization of ethylene and polar comonomers, and more specifically to catalyst systems for the polymerization of ethylene and acrylates comprising nickel(II) and palladium(II) catalysts supported on electron-deficient phosphine-phosphonium-phenol, and to olefin polymerization methods incorporating such catalyst systems. Background Technology

[0003] Ethylene / acrylate copolymers typically possess reinforcing properties conferred by polar functional groups, such as improved hot tack strength, oil resistance, abrasion resistance and static puncture resistance, low-temperature impact toughness, and adhesion to polar substrates such as aluminum and glass compared to nonpolar polymers.

[0004] Most methods for introducing ester functional groups into ethylene copolymers involve the free radical polymerization of ethylene and acrylate monomers under high pressure and high temperature, resulting in highly branched microstructures similar to low-density polyethylene (LDPE). Coordination catalysis provides a pathway for highly linear ethylene / acrylate copolymers with structures similar to linear low-density polyethylene (LLDPE). Linear ethylene / acrylate copolymers formed via coordination catalysis exhibit greater crystallinity and higher thermal resistance than those formed via free radical methods.

[0005] Common organometallic coordination catalysts suitable for ethylene polymerization are incompatible with systems containing acrylates as comonomers. For example, Group IV metal catalysts (Ti, Zr, Hf) used in the industrial production of LLDPE (ethylene / α-olefin copolymer) are incompatible with polar olefin monomers (including acrylates). Because the oxygen atoms of the acrylate monomers are strongly coordinated with Lewis acidic Group IV metals, the active sites of the metals are blocked by the acrylates during ethylene-acrylate polymerization, and further olefin polymerization is hindered.

[0006] Due to the incompatibility of Group IV metal catalysts with acrylates, electron-rich metal catalysts containing Group 10 metals (Pd, Ni) have been explored in the copolymerization of ethylene and acrylate monomers. However, many reported Ni-containing and Pd-containing metal catalysts suffer from the following problems: (a) slow polymerization rates and / or (b) low incorporation of the polar monomers of interest. Summary of the Invention

[0007] There remains a need to develop ligand frameworks for Ni and Pd catalysts to promote high rates of ethylene copolymerization activity and high incorporation of acrylate comonomers. Using nickel or palladium ligand frameworks, ethylene and polar monomers can be copolymerized via coordination catalysis to form highly linear LLDPE-like copolymers. These highly linear copolymers exhibit improved creep resistance and dimensional stability at higher temperatures, particularly in the range of 80°C to 150°C, compared to temperatures below 80°C.

[0008] Nickel and palladium catalysts with phosphono-phenol ligand structures bearing positively charged phosphonium groups exhibit high activity rates and high levels of polar comonomer incorporation while maintaining high molecular weights. Most importantly, copolymer properties can be tuned through cation-anion interactions. Linear LLDPE-like copolymers formed from these catalysts exhibit improved thermal properties compared to commercially available branched (LDPE-like) copolymers.

[0009] Embodiments of this disclosure include a catalyst system. The catalyst system comprises a pre-catalyst having a structure according to formula (I):

[0010]

[0011] In equation (I), M is nickel (II) or palladium (II); and X is selected from (C1-C2). 40 ) hydrocarbon group, (C1-C 40 heteroalkyl groups, -CH2Si(R) C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3-Q (OR C ) Q -P(R) C ) 2-W (OR C ) W -P(O)(R C ) 2-W (OR C ) W -N(R) C )2、-NH(R C ), -N(Si(R) C )3)2、-NR C Si(RC )3、-NHSi(R C 3. -OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C )2、-N=CH(R C -N=CH2, -N=P(R) C ) 3、 -OC(O)R C -C(O)OR C -N(R) C )C(O)R C -N(R) C )C(O)H、-NHC(O)R C -C(O)N(R) C )2、-C(O)NHR C -C(O)NH2, halogen or hydrogen ligands, wherein each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 30 ( ) heterohydrocarbon group, and Q is 0, 1, 2 or 3 and W is 0, 1 or 2.

[0012] In formula (I), each Y is a Lewis base. In some embodiments, X and Y are optionally connected.

[0013] In formula (I), A is an anion; E is a positively charged heteroatom selected from nitrogen or phosphorus.

[0014] In equation (I), R P1 R P2 and R P3 Independently selected from substituted (C1-C) 20 ) hydrocarbon group, unsubstituted (C1-C) 20 ) hydrocarbon group, (C1-C 20 Heterohydrocarbon group, unsubstituted (C1-C) 20 ) heterohydrocarbon group. In some embodiments, R P1 R P2 and R P3 Independently selected from substituted (C6-C) 40 ) aryl or unsubstituted (C6-C 40 Aryl.

[0015] In equation (I), R 1 and R 2Independently selected from substituted (C1-C) 30 ) hydrocarbon group, unsubstituted (C1-C) 30 ) hydrocarbon group, substituted (C1-C) 30 Heteroalkyl groups or unsubstituted (C1-C) 30 ) heterohydrocarbon group.

[0016] In equation (I), R 3 R 4 and R 5 Independently selected from substituted (C1-C) 30 ) hydrocarbon group, unsubstituted (C1-C) 30 ) hydrocarbon group, substituted (C1-C) 30 Heterohydrocarbon group, unsubstituted (C1-C) 30 ) heterohydrocarbon group, Si(R) C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3-Q (OR C ) Q -P(R) C ) 2-W (OR C ) W -P(O)(R C ) 2-W (OR C ) W -N(R) C )2、-NH(R C )2、-OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C 2. -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R)C(O)R C -C(O)N(R) C )2 or halogen, where each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 30() Heterohydrocarbon group; Q is 0, 1, 2 or 3 and W is 0, 1 or 2.

[0017] In one or more implementation schemes, the implementation scheme includes, optionally, R 1 and R 2 Connect to form a ring structure; and optionally, R 3 and R 4 Connect to form a ring structure; and optionally, R 4 and R 5 Connect to form a ring structure; or optionally, R P1 R P2 Or R P3 Any two connections in the loop can form a ring structure. Detailed Implementation

[0018] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system 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, the provision of embodiments makes this disclosure thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art.

[0019] The following is a list of common abbreviations:

[0020] Me: Methyl; Et: Ethyl; Ph: Phenyl; Bn: Benzyl; i-Pr: Isopropyl; t-Bu: Tert-Butyl; t-Oct: Tert-Octyl (2,4,4-Trimethylpentan-2-yl); THF: Tetrahydrofuran; Et2O: Diethyl ether; CH2Cl2: Dichloromethane; EtOAc: Ethyl acetate; C6D6: Deuterated benzene or benzene-d6; CDCl3: Deuterated chloroform; Na2SO4: Sodium sulfate; MgSO4: Magnesium sulfate; HCl: Chloride Hydrogen; n-BuLi: Butyllithium; t-BuLi: Tert-Butyllithium; K2CO3: Potassium Carbonate; N2: Nitrogen; PhMe: Toluene; PPR: Parallel Pressure Reactor; MAO: Methylaluminoxane; MMAO: Modified Methylaluminoxane; GC: Gas Chromatography; LC: Liquid Chromatography; NMR: Nuclear Magnetic Resonance; MS: Mass Spectrometry; mmol: Millimole; mL: Milliliter; M: Mole; min or mins: Minute; h or hrs: Hour; d: Day; R f Retention coefficient; TLC: Thin-layer chromatography; rpm: Revolutions per minute.

[0021] The term “independent selection” used in this article is followed by several options to indicate the individual groups (such as R) that appear before the term. 1 R 2 R 3 and R C() can be the same or different, without depending on the properties of any other groups that also appear before the term.

[0022] The term "pre-catalyst" refers to a compound that retains catalytic activity after activation, such as in the removal of Lewis bases coordinated to Ni or Pd metal centers.

[0023] When used to describe certain carbon-containing chemical groups, the form is "(C x -C y The parenthetical expression “)” indicates that the unsubstituted form of the chemical group has x to y carbon atoms (inclusive). For example, (C1-C 50 Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be replaced by one or more substituents (such as R...). S ) replace, where R S Generally refers to any substituent defined in this application. Use "(C x -C y The chemical groups defined in parentheses () are R S The form of substitution can be based on any group R S The property contains more than y carbon atoms. For example, "exactly bound by a group R". S Replacement (C1-C) 50 ) alkyl, wherein R S The phenyl group (-C6H5) can contain 7 to 56 carbon atoms. Therefore, generally speaking, when using the parenthetical phrase "(C6H5)", the phenyl group is considered to have 7 to 56 carbon atoms. x -C y The chemical group defined as ")" is substituent for one or more carbon atoms by one or more carbon-containing substituents R. S When substituted, the minimum and maximum total number of carbon atoms in the chemical group are determined by the substituents R from all carbon-containing atoms, respectively. S The sum of the number of carbon atoms is added to x and y to determine the value.

[0024] The terms "substitution", "(C1-C" 50 )hydrocarbon group", (C1-C 50 )alkyl", (C6-C 50 )Aryl", (C3-C 50 )cycloalkyl", (C1-C 50 )hydroalkyl group", (C1-C 50 )alkylene", (C3-C 50 "(C1-C)alkylene", "heteroatom", "heterohydrocarbon", "(C1-C)" 50 ) heterohydrocarbon group", (C4-C 50 ) mixed aryl", (C1-C 50(Hypohydrogen group), (C1-C) 50 "Heteroalkyl" and "saturated" are defined in US application number US2021 / 025152, which is published as WO 2021 / 202714.

[0025] In this disclosure, (C1-C 50 Hydrocarbon groups include, but are not limited to, the unsubstituted or substituted forms of the following groups: (C1-C2) 50 )alkyl, (C3-C 50 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 ) aryl or (C6-C 20 )aryl-(C1-C 20 Alkylene (such as benzyl (-CH2-C6H5)).

[0026] In this disclosure, (C1-C 50 The heteroalkyl group can be unsubstituted or substituted. (C1-C) 50 Non-limiting examples of heteroalkyl groups include (C1-C 50 (heteroalkyl, (C1-C) 50 )hydrocarbon group -O-, (C1-C 50 )hydrocarbon group -S-, (C1-C 50 )hydrocarbon group -S(O)-, (C1-C 50 )hydrocarbon group -S(O)2-, (C1-C 50 )hydrocarbon-Si(R C )2-、(C l -C 50 )hydrocarbon-N(R N )-、(C l -C 50 )hydrocarbon-P(R P )-、(C2-C 50 Heterocyclic alkyl groups, (C2-C 19 Heterocyclic alkyl-(C1-C) 20 )alkylene, (C3-C 20 )cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 Heterocyclic alkyl-(C1-C) 20 )heteroalkylene, (C1-C 50 () heteroaryl, (C1-C 19 ) heteroaryl-(C1-C 20 )alkylene, (C6-C 20 )aryl-(C1-C 19 )heteroalkylene, or (C1-C19 ) heteroaryl-(C1-C 20 ) Heteroalkylene groups. Other examples include, but are not limited to, -Si(R C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3-Q (OR C ) Q -P(R) C ) 2-W (OR C ) W -P(O)(R C ) 2-W (OR C ) W -N(R) C )2、-NH(R C )2、-OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C 2. -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R) C )C(O)R C and -C(O)N(R) C )2.

[0027] Embodiments of this disclosure include a catalyst system. The catalyst system comprises a pre-catalyst having a structure according to formula (I):

[0028]

[0029] In equation (I), M is nickel (II) or palladium (II); and X is selected from (C1-C2). 40 ) hydrocarbon group, (C1-C 40 heteroalkyl groups, -CH2Si(R) C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C )Q -OSi(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3-Q (OR C ) Q -P(R) C ) 2-W (OR C ) W -P(O)(R C ) 2-W (OR C ) W -N(R) C )2、-NH(R C ), -N(Si(R) C )3)2、-NR C Si(R C )3、-NHSi(R C 3. -OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C )2、-N=CH(R C -N=CH2, -N=P(R) C ) 3、 -OC(O)R C -C(O)OR C -N(R) C )C(O)R C -N(R) C )C(O)H、-NHC(O)R C -C(O)N(R) C )2、-C(O)NHR C -C(O)NH2, halogen or hydrogen ligands, wherein each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 30 ( ) heterohydrocarbon group, and Q is 0, 1, 2 or 3 and W is 0, 1 or 2.

[0030] In formula (I), each Y is a Lewis base. In some embodiments, X and Y are optionally connected.

[0031] In formula (I), A is an anion; E is a positively charged heteroatom selected from nitrogen or phosphorus.

[0032] In formula (I), P is phosphorus.

[0033] In equation (I), R P1 R P2 and R P3 Independently selected from substituted (C1-C) 20 ) hydrocarbon group, unsubstituted (C1-C) 20 ) hydrocarbon group, (C1-C 20 Heterohydrocarbon group, unsubstituted (C1-C) 20 ) heterohydrocarbon group. In some embodiments, R P1 R P2 and R P3 Independently selected from substituted (C6-C) 40 ) aryl or unsubstituted (C6-C 40 Aryl.

[0034] In equation (I), R 1 and R 2 Independently selected from substituted (C1-C) 30 ) hydrocarbon group, unsubstituted (C1-C) 30 ) hydrocarbon group, substituted (C1-C) 30 Heteroalkyl groups or unsubstituted (C1-C) 30 ) heterohydrocarbon group.

[0035] In equation (I), R 3 R 4 and R 5 Independently selected from substituted (C1-C) 30 ) hydrocarbon group, unsubstituted (C1-C) 30 ) hydrocarbon group, substituted (C1-C) 30 Heterohydrocarbon group, unsubstituted (C1-C) 30 ) heterohydrocarbon group, Si(R) C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3-Q (OR C ) Q -P(R) C ) 2-W (OR C ) W -P(O)(R C )2-W (OR C ) W -N(R) C )2、-NH(R C )2、-OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C 2. -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R)C(O)R C -C(O)N(R) C )2 or halogen, where each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 30 () Heterohydrocarbon group; Q is 0, 1, 2 or 3 and W is 0, 1 or 2.

[0036] In one or more implementation schemes, the implementation scheme includes, optionally, R 1 and R 2 Connect to form a ring structure; and optionally, R 3 and R 4 Connect to form a ring structure; and optionally, R 4 and R 5 Connect to form a ring structure; or optionally, R P1 R P2 Or R P3 Any two connections in the loop can form a ring structure.

[0037] In some implementation schemes, R P1 R P2 and R P3 Independently selected from unsubstituted (C1-C) 20 ) hydrocarbon group and one or more R S Replacement (C1-C) 20 ) hydrocarbon group, where R S Selected from (C1-C) 10 )alkyl, -OR C -CN, -CF3, -SR C -C(O)OR C and -SiR C 3, where each R C Independently for (C1-C) 10)alkyl. In some embodiments, R P1 R P2 and R P3 It may include (C2-C) 10 Alkenyl groups are hydrocarbon groups derived from alkenes (unsaturated hydrocarbons containing double bonds).

[0038] In various implementation schemes, R P1 R P2 and R P3 Independently selected from substituted (C1-C) 20 )Aryl, unsubstituted (C1-C 10 )alkyl and one or more R S Substituted benzyl, wherein R S Selected from (C1-C) 10 )alkyl, -O(C1-C 10 )alkyl and -CF3.

[0039] In some implementation schemes, R 1 and R 2 It is 2,6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-diphenoxyphenyl, 2,4,6-triethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-phenylphenyl or 2,6-diisopropoxyphenyl.

[0040] In various implementation schemes, R 3 R 4 and R 5 Independently selected from substituted or unsubstituted (C1-C) 20 )alkyl and substituted or unsubstituted (C6-C 20 )Aryl. In one or more embodiments, R 3 R 4 and R 5 For (C1-C 18 )alkyl or -H.

[0041] In the implementation plan, A - It is an anion. In one or more embodiments, A - It is a noncoordinate anion. A noncoordinate anion is a negatively charged counterion that can be a separate entity from the cation due to the diffusion properties of its charge or high steric hindrance that limits its interaction with the associated cation. In some embodiments, A - It is a weakly coordinating anion. A weakly coordinating anion is a negatively charged counterion; it does not need to be a standalone entity and can weakly interact with a cation. In some embodiments, A - It is a strongly coordinating anion. A strongly coordinating anion is a negatively charged counterion that is localized and interacts closely with the associated cation.

[0042] In some implementation schemes, A - It can be a weakly coordinating or noncoordinating anion substituted by a donor group (e.g., -OR). C -N(R) C )2), which can interact with cations or catalyst metal centers.

[0043] In some implementation schemes, A - It can be halides, nitrates, perhalates, phosphates, sulfates, R W C(O)O - R W OC(O)O - R W R R NC(O)O - R W O - Si(R) W ) 3-a (OR W ) a O - 、(R R ) 5-b (OR W ) b Si - R W S(O)2O - R W 4B - R W 4Al - R W 4Ga - R W 6P - R W 6As - Or R W 6Sb - , where each R W Or R R Independently halogenated, hydrogen-containing, substituted or unsubstituted (C1-C) 40 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 40 The subscript a is 0, 1, 2, or 3, and the subscript b is 0, 1, 2, 3, or 4. In some embodiments, each R... W Or R R Selected from halogens, substituted or unsubstituted (C1-C) 20 )alkyl, substituted or unsubstituted (C6-C 20 ) aryl, or substituted or unsubstituted (C1-C 20 Heteroalkyl or substituted or unsubstituted (C4-C)20 ) heteroaryl. In various embodiments, each R W For different purposes. In other implementations, each R W They are all the same. In various implementation schemes, each R R For different purposes. In other implementations, each R R They are all the same.

[0044] In various implementation schemes, A - BF4 - B(3,5-(CF3)2C6H3)4 - B(C6F5)4 - B(4-(OCH2OCH3)C6H4)4 - Or B(C6H5)4 - .

[0045] In various implementation schemes, A - F3CS(O)2O - .

[0046] In the metal-ligand complex according to formula (I), each Y is bonded to M via a coordinate or ionic bond. In one or more embodiments, Y is a Lewis base. A Lewis base can be a compound or an ionic substance that can donate an electron pair to the acceptor moiety. For the purposes of this embodiment, the acceptor moiety is M, which is the metal of the metal-ligand complex of formula (I). In some embodiments, the Lewis base can be a heterohydrocarbon or a hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cyclic ethers, or sulfides. Examples of neutral hydrocarbon Lewis bases include, but are not limited to, alkenes, alkynes, or aromatics.

[0047] In some implementations, Y is (C1-C 40 ( ) heterohydrocarbons, (C1-C 40 ) heterohydrocarbon group or (C1-C 40 ) hydrocarbon group.

[0048] In one or more embodiments, Y is a neutral Lewis basic aprotic (C2-C) 40 Heterohydrocarbons. Aprotic (C2-C) 40 Heterohydrogen compounds are those defined previously (C2-C...) 40 ) heterohydrocarbons, this (C2-C 40The pKa of each hydrogen atom in the heterohydrocarbon is greater than 30, where pKa is the negative logarithm of the acid dissociation constant (Ka) to the base 10. In some embodiments, Y is an organic Lewis base. Examples of organic Lewis bases include pyridine or substituted pyridine, sulfoxide, trialkyl or triarylphosphine, trialkyl or triarylphosphine oxide, olefin or cyclic olefin, substituted or unsubstituted heterocycle, alkyl ester of aliphatic or aromatic carboxylic acid, aliphatic ketone, aliphatic amine, 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 organic Lewis bases include, but are not limited to: methyl formate, ethyl acetate, butyl acetate, diethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethyl formate, dimethylformamide, methyl acetate, ethyl anisinate, ethylene carbonate, tetrahydropyran, tetrahydrofuran, ethyl propionate, dimethylpyridine, methylpyridine, pyridine, dimethyl sulfoxide, trimethylphosphine, triethylphosphine, triphenylphosphine, cyclooctadiene, cyclopentene, ethylene, propylene, tert-butylethylene, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, 1-methylimidazole, or 1-methylpyrazole.

[0049] In one or more embodiments, the Lewis base may be a monodentate ligand, which may be a neutral ligand. In some embodiments, the neutral ligand may contain a heteroatom. In a specific embodiment, the neutral ligand is a neutral group, such as R... T NR K R L R K OR L R K SR L Or R T PR K R L , where each R T Independently for [(C1-C 10 [Hydrocarbon group]3Si(C1-C 10 ) hydrocarbon group, (C1-C 40 ) hydrocarbon group, [(C1-C 10 [Hydrocarbon group]3Si or (C1-C 40 ) heterohydrocarbon group, and each R K and R L Independently hydrogen, (C1-C 40 ) hydrocarbon group or (C1-C 40 ) heterohydrocarbon group.

[0050] In some implementations, the Lewis base is (C1-C1) 20Hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene or 1,3-butadiene.

[0051] In various implementation schemes, the Lewis base is (C1-C1) 20 The heteroatom of the heterohydrocarbon is oxygen. In some embodiments, Y is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0052] In various implementation schemes, the Lewis base is (C1-C1) 20 The heteroatom of the heterohydrocarbon is nitrogen. In some embodiments, Y is pyridine, methylpyridine, dimethylpyridine, trimethylamine, or triethylamine.

[0053] In some embodiments, X and Y are covalently linked. Specific examples of organoLewis bases Y covalently linked to the X group include, but are not limited to: 4-cycloocten-1-yl, 2-dimethylaminobenzyl, and 2-dimethylaminomethylphenyl.

[0054] In some implementations, X and Y are connected and selected from a group consisting of the following:

[0055]

[0056] ,

[0057] Where R C -H or (C1-C) 30 ) hydrocarbon group, (C1-C 20 )alkyl or (C1-C 12 )alkyl.

[0058] In the metal-ligand complex according to formula (I), X is bonded to M via a covalent or ionic bond. In some embodiments, X may be a monoanionic ligand with a net oxidation state of -1. Each monoanionic ligand may independently be a hydride, (C1-C2) 40 ) hydrocarbon-based carbanion, (C1-C 40 Heteroalkyl carbanions, halide ions, nitrate ions, bicarbonate ions, dihydrogen phosphate ions, hydrogen sulfate ions, HC(O)O - HC(O)N(H) - (C1-C) 40 )hydrocarbon C(O)O - (C1-C) 40 )hydrocarbon group C(O)N((C1-C 20 (hydrocarbon group) - (C1-C) 40 Hydrocarbon group C(O)N(H) - R K R L B- R K R L N - R K O - R K S - R K R L P - Or R M R K R L Si - , where each R K R L and R M Independently hydrogen, (C1-C 40 ) hydrocarbon group or (C1-C 40 ) heterohydrocarbon group, or R K and R L Together they form (C2-C) 40 ) alkylene group or (C1-C 20 ) heterohydrocarbon group, and R M As defined above.

[0059] In the implementation scheme, X is substituted or unsubstituted (C1-C1) 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 ( ) heteroalkyl group. In some embodiments, X is a substituted or unsubstituted (C1-C ) group. 20 ) hydrocarbon group, substituted or unsubstituted (C1-C 20 ) heterohydrocarbon group.

[0060] In one or more embodiments, X is methyl, 2,2-dimethylpropyl, trimethylsilylmethyl, (n-butyl)dimethylsilylmethyl, (n-hexyl)dimethylsilylmethyl, (n-octyl)dimethylsilylmethyl, or benzyl.

[0061] In some implementations, X is a halogen, (C1-C) 20 ) hydrocarbon group, (C1-C 20 ) heterohydrocarbon group, (C1-C 20 )hydrocarbon group C(O)O-, [(C1-C 20 [Hydrocarbon group]3SiCH2– or R K R L N-, where R K and R L Each of them is independently (C1-C) 20 ) hydrocarbon group. In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10 ) hydrocarbon group (e.g., (C1-C6)alkyl or benzyl), unsubstituted (C1-C6)10 )hydrocarbon group C(O)O-, [(C1-C 20 [Hydrocarbon group]3SiCH2- or R K R L N-, where R K and R L Each of them is independently unsubstituted (C1-C) 10 ) hydrocarbon group.

[0062] In another embodiment, X is selected from: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine.

[0063] In one or more embodiments, X is -(CH2)SiR X 3, where each R X Independently for (C1-C) 30 )alkyl or (C1-C 30 ) heteroalkyl, and at least one R X For (C1-C 30 )alkyl. In some embodiments, when R X One of them is (C1-C) 30 When it is a heteroalkyl group, the heteroatom is a silicon or oxygen atom. In some embodiments, R X It can be methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0064] 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-octyl)R X -(CH2)Si(CH3)2R X -(CH2)Si(n-octyl)R X 2. -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), -CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as -CH2Si(CH3)2(CH2TMS)). Optionally, in some embodiments, in the metal-ligand complex according to formula (I), exactly two R X Covalent connection or exactly three R X Covalent connection.

[0065] In some implementations, X is -CH2Si(R) C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q Where the subscript Q is 0, 1, 2 or 3, and each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 30 ( ) Heteroalkyl group. In some embodiments, X is -CH2Si(CH3)3.

[0066] In some implementation schemes, in addition to R 1 Or R 2 In addition, any or all of the chemical groups in the precatalyst of formula (I) may be unsubstituted. R 1 and R 2 At least one of them is substituted. In other embodiments, the chemical groups X, A, and R of the metal-ligand complex of formula (I) are substituted. 1 -R 2 R 3-5 Or R P1-P3 None of them were controlled by one or more Rs. S Substitution, or any one or all of them may be substituted by it. When two or more R S When bonded to the same chemical group as the precatalyst of formula (I), each R of the chemical group S They can be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, the chemical groups X, A, and R... 1 -R 2 R 3-5 Or R P1-P3 None of them were R S Replacement, or any one or all of them may be replaced by it. In the case of R S In fully substituted chemical groups, each R S They can all be the same or they can be chosen independently.

[0067] Embodiments of this disclosure include polymerization methods. In some embodiments, the polymerization method includes polymerizing ethylene with one or more olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form a vinyl copolymer. The catalyst system comprises a metal-ligand complex according to formula (I) as described in this disclosure.

[0068] In some embodiments, the polymerization method includes 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 comprises a pre-catalyst according to formula (I) of this disclosure. In one or more embodiments, the polymerization method includes 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 pre-catalyst according to formula (I) of this disclosure.

[0069] In some embodiments of the polymerization method, the polymerization method includes reacting ethylene and optionally one or more (C3-C4) compounds in the presence of a catalyst system under olefin polymerization conditions. 10 The catalyst system comprises a metal-ligand complex precatalyst having a structure according to formula (I) as described in this disclosure. α-olefin monomers or cyclic olefin monomers are polymerized to form vinyl copolymers.

[0070] In some embodiments of the polymerization method, the polymerization method includes, under olefin polymerization conditions in the presence of a catalyst system, reacting ethylene, a polar comonomer, and optionally one or more (C3-C4) monomers. 10 The catalyst system comprises a metal-ligand complex precatalyst having a structure according to formula (I) as described in this disclosure. α-olefin monomers or cyclic olefin monomers are polymerized to form vinyl copolymers.

[0071] In various embodiments, the polymerization method includes polymerizing ethylene and optionally a polar comonomer 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 the use of one or more conventional reactors, such as loop reactors, isothermal reactors, adiabatic reactors, fluidized bed gas-phase reactors, stirred tank reactors, or batch reactors, in parallel, series, or any combination thereof. Such high-pressure reactors include stirred autoclave vessels with one or more reaction zones. Autoclave reactors typically have several injection points for catalyst and / or monomer feed. Another type of high-pressure reactor is a jacketed vessel with one or more reaction zones. Suitable, but not limiting, reactor lengths can be from 100 to 3600 meters (m) or from 1000 to 2800 meters (m). For any type of high-pressure reactor, the start of the reaction zone is typically defined by the injection of the catalyst, ethylene, comonomer, and any combination thereof at a designated site.

[0072] In one or more embodiments, the polymerization of ethylene and optionally a polar comonomer occurs at a reactor temperature of 50°C to 250°C. In some embodiments, the reactor temperature is 80°C to 200°C. In various embodiments, the reactor temperature is 90°C to 170°C. In one or more embodiments, the polymerization of ethylene and optionally a polar comonomer occurs at a reactor pressure of 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.

[0073] Olefin 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 acrylates, CH2=C(H)C(O)(OR X CH2=CHC(O)R X CH2=CH(OR) X CH2=CH(CH2)(OR) X CH2=CHSi(R) X ) 3-Y (OR X ) Y CH2=CH-OSi(R) X ) 3-Y (OR X ) Y Or CH2=CHCl, where R X Selected from -H, substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C 30 ( ) heterohydrocarbon group, and the subscript Y is 0, 1, 2 or 3.

[0074] In various embodiments of the polymerization method, the polar comonomers include alkyl acrylates, CH2=CHC(O)(OR), and CH2=CH(CH2). n C(O)(OR), CH2=CHC(O)R, CH2=CH(CH2) n C(O)R, CH2=CH-OC(O)R, CH2=CH(CH2) n -OC(O)R、CH2=CH(OR)、CH2=CH(CH2) n (OR), CH2=CHSi(R) 3-T (OR) T CH2=CH(CH2) n Si(R) 3-T (OR)T CH2=CH-OSi(R) 3-T (OR) T CH2=CH(CH2) n -OSi(R) 3-T (OR) T Or CH2=CHCl. ​​Each R is selected from substituted (C1-C) 30 ) hydrocarbon group, unsubstituted (C1-C) 30 ) hydrocarbon group, substituted (C1-C) 30 Heteroalkyl groups or unsubstituted (C1-C) 30 Heteroalkyl group. Subscript T is 0, 1, 2 or 3. Subscript n is 1 to 10. In this group, the polar monomer is an alkyl acrylate, a substituted (C1-C2) alkyl acrylate, or a substituted (C1-C2) alkyl acrylate. 30 ) hydrocarbon acrylates, unsubstituted (C1-C) 30 ) hydrocarbon acrylates, substituted (C1-C) 30 Heteroalkyl acrylates or unsubstituted (C1-C1) acrylates 30 Heteroalkyl acrylates or unsubstituted (C1-C1) acrylates 30 In embodiments of heteroalkyl acrylates, the polar vinyl copolymer may be deesterified to form an acrylic vinyl copolymer.

[0075] In some embodiments of the polymerization method, the alkyl acrylate monomer may be, for example, but not limited to, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, or combinations thereof. In various embodiments, the alkyl acrylate has an alkyl group containing one to eight carbon atoms. It is designated as C1-C8-alkyl acrylate. In a specific embodiment, the alkyl acrylate is tert-butyl acrylate or n-butyl acrylate.

[0076] In some embodiments of the polymerization method, the optional α-olefin monomer may be, for example, but not limited to, 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 method, the method may also include cyclic olefins, such as cyclobutene, cyclopentene, norbornene, and norbornene derivatives, which are determinated at the 5- and / or 6-positions by (C1-C6) determinatements. 20 Hydrocarbon groups are substituted.

[0077] In exemplary embodiments, the catalyst system may comprise a precatalyst according to formula (I), which has the structure of precatalysts 1 to 8 listed below:

[0078]

[0079]

[0080] In various embodiments, the polymerization method of this disclosure can produce vinyl copolymers, wherein the polar vinyl copolymers contain at least 50 wt.% (wt.%) of ethylene based on the weight of the polar vinyl copolymer. In some embodiments, the polar vinyl copolymer is a reaction product of 70 wt% to 99.9 wt% of ethylene units and 0.1 wt% to 30 wt% of polar comonomer units, based on the sum of ethylene units and polar comonomer units.

[0081] In one or more embodiments, the polymerization method of this disclosure may include ethylene monomers, alkyl acrylate monomers, and optionally one or more α-olefins. In some embodiments of the polymerization method including α-olefins, the α-olefin may be incorporated into the resulting polymer in an amount from 0.01% by weight to 45% by weight, based on the weight of the ethylene copolymer.

[0082] In various embodiments, the polymerization method of this disclosure can produce ethylene copolymers with molecular weights from 5,000 g / mol to 1,000,000 g / mol. In some embodiments, the resulting polymers have molecular weights from 25,000 g / mol to 900,000 g / mol, 30,000 g / mol to 800,000 g / mol, or 10,000 g / mol to 300,000 g / mol.

[0083] General procedure for PPR screening experiments

[0084] Polyolefin catalytic screening was performed in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consisted of an array of 48 individual units (6×8 matrix) within an inert atmosphere glove box. Each unit was equipped with a glass insert containing approximately 5 mL of internal working liquid. Each unit had independent pressure control and was continuously stirred at a frequency of 500–800 rpm. Unless otherwise specified, the catalyst, ligand, and metal precursor solutions were prepared in toluene. All liquids (i.e., solvent, tert-butyl acrylate (tBA), and catalyst solution) were added via a robotic injector. Gaseous reagents (i.e., ethylene) were added through a gas inlet. Before each run, the reactor was heated to 50°C, purged with ethylene, and vented.

[0085] All intended units were injected with a solution of tBA in toluene, followed by a portion of pure toluene. The reactor was heated to operating temperature and pressurized to the appropriate psig with ethylene. The catalyst or in-situ metallized ligand was then added to the unit. Each catalyst addition was made with a small amount of toluene so that the total reaction volume reached 5 mL after the last addition. After catalyst addition, the PPR software began monitoring the pressure of each unit. The requested pressure (approximately 2 psig to 6 psig) was maintained by supplementing with ethylene gas by opening the valve at a setpoint of -1 psi and closing the valve when the pressure reached 2 psi. During operation or until the absorption or conversion requirement value (whichever occurs first) was reached, all pressure drops were cumulatively recorded as “absorption” or “conversion” of ethylene. Each reaction was then quenched by adding 1% oxygen in nitrogen for 30 seconds at a pressure 40 psi higher than the reactor pressure. The shorter the “quenching time” (the cumulative reaction time during which the reaction is quenched), the higher the catalyst activity. To prevent excessive polymer formation in any given unit, the reaction was quenched after reaching the predetermined absorption level of 80 psig. After quenching all reactors, allow them to cool to approximately 60°C. Then, vent them and remove the tubes. Dry the polymer sample in a centrifugal evaporator at 60°C for 12 hours, weigh it to determine the polymer yield, and perform IR (tBA incorporation), DSC (melt temperature), and GPC (molecular weight) analyses.

[0086] HT-GPC Analysis

[0087] High-temperature GPC analysis was performed using a Robot-Assisted Delivery (RAD) system equipped with a Polymer Char infrared detector (IR5) and an Agilent PL-gel Mixed A column. Decane (10 µL) was added to each sample as an internal flow marker. The sample was first diluted to a concentration of 10 mg / mL in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxytoluene (BHT), and then dissolved by stirring at 160 °C for 120 min. Prior to injection, the sample was further diluted to a concentration of 3 mg / mL using BHT-stabilized TCB. The sample (250 µL) was eluted through a PL-gel 20 µm (50 mm × 7.5 mm) guard column, followed by elution through two PL-gel 20 µm (300 mm × 7.5 mm) Mixed-A columns maintained at 160 °C, with TCB stabilized with BHT at a flow rate of 1.0 mL / min. The total run time was 24 min. To calibrate the molecular weight (MW), Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 mL of BHT-stabilized TCB and stirred at 160 °C for 15 minutes to dissolve. These standards were analyzed to create a third-order MW calibration curve. The molecular weight units were converted from polystyrene (PS) to polyethylene (PE) using a daily Q factor (approximately 0.4, calculated from the average of five Dowlex 2045 reference samples).

[0088] IR analysis of tert-butyl acrylate doping

[0089] A 10 mg / mL sample prepared via GPC analysis was further used for FTIR quantification of tBA incorporation. The sample was heated and stirred at 160 °C for 60 min using a Dow robotic preparation station, and then a 130 µL fraction was placed into a stainless steel orifice on a silicon wafer. TCB was evaporated at 160 °C under nitrogen purging. FTIR was performed from 4000 to 400 cm⁻¹ using a Nexus 6700 FTIR system equipped with a DTGS KBr detector. -1 IR spectra were collected and scanned 128 times at resolution 4. tBA (C=O: 1762 to 1704 cm⁻¹) was calculated. -1 ) and ethylene (CH2: 736 to 709 cm -1 The ratio of the peak areas of ) was used to fit a linear calibration curve to determine the total tBA.

[0090] DSC program

[0091] Melting temperature (Tm), glass transition temperature (Tg), crystallization temperature (Tc), and heat of fusion were measured on solid polymer samples using differential scanning calorimetry (DSC Q2000, TA Instruments) with heat-cool-heat profiles. The following temperature profiles were analyzed for open-pan DSC samples of 3 mg to 6 mg polymer, and the traces were analyzed individually using TA UniversalAnalysis software or TA Instruments TRIOS software.

[0092] Maintain equilibrium at 175.00℃

[0093] Wait 3 minutes

[0094] Heat to 0.00℃ at a rate of 30.00℃ / minute.

[0095] Increase the temperature to 175.00℃ at a rate of 10.00℃ / minute.

[0096] Example

[0097] Examples 1 to 8 are procedures for the synthesis of ligands. Examples 9 to 16 are procedures for the synthesis of isolated pre-catalysts. In Example 17, the results of the polymerization reactions of pre-catalysts 1 to 8 are tabulated and discussed. One or more features of this disclosure are illustrated by the following examples:

[0098] General Precautions

[0099] Unless otherwise specified, all reactions were carried out in a nitrogen-purged glove box. Unless otherwise specified, all solvents and reagents were obtained from commercial sources and used directly. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing them through activated alumina and, in some cases, through Q-5 reactants. The alumina used for solvent purification was activated by passing a nitrogen stream through it for 8 hours at 300°C. The Q-5 reactants were activated by heating at 200°C for 4 hours under a nitrogen stream, followed by heating at 200°C for 3 hours under a nitrogen stream containing 5% hydrogen, and finally rinsing with nitrogen. Solvents used for experiments conducted in a nitrogen-purged glove box were further dried by storing them on activated 4Å molecular sieves. Glassware used for humidity-sensitive reactions was dried overnight in an oven before use. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 μm (2.1 mm × 50 mm) column connected to an Agilent 6230 TOF mass spectrometer with electrospray ionization. NMR spectra were recorded on a Varian 400-MR and VNMRS-500 spectrometer. 1HNMR data are reported as follows: chemical shifts (multiplicity (br=broad, s=singlet, d=doublet, t=triplet, q=quadruplet, p=quintruplet, sex=sextruple, sept=septruplet and m=multiplicity), integration, and assignment). Residual protons in the deuterated solvent are used as a reference, and data are reported in ppm. 1 1H NMR data for chemical shift relative to a low magnetic field of tetramethylsilane (TMS, δ-scale). 13 C NMR data used 1 H decoupling is used to determine and the chemical shift relative to tetramethylsilane is reported in ppm. Due to CP coupling, phosphine... 13 C10 NMR spectroscopy is complex. Reporting is done in ppm. 31 P NMR data relative to the chemical shift of externally pure H3PO4. The deuterated solvent used for NMR analysis was purchased from Cambridge Isotope Labs and stored on active 4Å molecular sieves in a nitrogen-purged glove box. Bis(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.

[0100] Preparation of ligands

[0101] Example 1: Ligand 1: [2-(bis(2,6-dimethoxyphenyl)(4-methylbenzyl)phosphonium)-6 ...)phosphonium)-6-(bis(2,6-dimethoxyphenyl)phosphonium)-6-(bis(2,6-dimethoxyphenyl)phosphonium)-6-(bis(2, [Oxyphenyl)phosphino)-4-(tert-butyl)phenol][tetra(3,5-bis(trifluoromethyl)phenyl)boronic acid ester]

[0102]

[0103] In a glove box filled with N2, a solution of 4-methylbenzyl bromide (15.8 mg, 0.085 mmol, 1 equivalent) 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 at room temperature for 18 hours to obtain a colorless suspension. After the reaction was complete, all 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 equivalent) and fluorobenzene (6 mL) at room temperature and stirred for 3 hours. The colorless suspension was filtered through diatomaceous earth, and the filtrate was evaporated under reduced pressure. The oily colorless residue was ground 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(400.1MHz, 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, 0.8Hz, 1H, ArH), 7.66 (br s, 4H, B(C6H3-3,5-(CF3)2)4),7.04 (td, J = 8.3, 0.7Hz, 2H, ArH), 6.95 (t, J = 8.4Hz, 2H, ArH), 6.88 (dd, J= 16.4, 2.4Hz, 1H, ArH), 6.66 (dd, J = 8.2, 2.1Hz, 2H, ArH), 6.51 (d, J =7.9Hz, 2H, ArH), 6.20 (dd, J = 8.4, 3.1Hz, 4H. ArH), 5.97 (dd, J = 8.4,5.2Hz, 4H. ArH), 4.47 (d, J = 17.1Hz, 2H, CH2Ar), 3.04 (s, 12H, OCH3), 2.90(s, 12H, OCH3), 1.91 (d, J = 1.9Hz, 3H, PhCH3), 0.99 (s, 9H, C(CH3)3); 31 P NMR(161.97MHz, C6D6): 14.6 (d, J = 6.8Hz), -64.2 (br s)。

[0104] Example 2: Ligand 2: [2-(bis(2,6-dimethoxyphenyl)(4-(trifluoromethyl)benzyl)phosphonium)-6-(bis(2, [6-Dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol][tetra(3,5-bis(trifluoromethyl)phenyl)boronic acid ester]

[0105]

[0106] In a nitrogen-filled glove box at room temperature under a nitrogen atmosphere, 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 equivalent) in a 20 mL scintillation vial was treated with toluene (5 mL). The resulting colorless solution was stirred at room temperature for 18 hours to obtain a colorless suspension. After the reaction was complete, all 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 equivalent) and fluorobenzene (5 mL) at room temperature and stirred for 4 hours. The colorless suspension was filtered through diatomaceous earth, and the filtrate was evaporated under reduced pressure. The oily, colorless residue was ground 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%). 1 ¹H NMR (400.1MHz, 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; the two signals overlap), 7.06 (t, J = 8.4Hz, 2H, ArH), 6.98 (t, J = 8.4Hz, 2H, ArH), 6.76 (d, J = 8.0Hz, 2H, ArH), 6.69 (d, J = 8.0Hz, 2H, ArH), 6.64 (d, J = 16.9Hz, 1H, ArH), 6.22 (dd, J = 8.2, 3.2Hz, 4H. ArH), 6.00 (dd, J = 8.4, 5.2Hz, 4H. ArH), 4.44 (d, J = 17.8Hz, 2H, CH2Ar), 3.06 (s, 12H, OCH3), 2.96 (s, 12H, OCH3), 0.90 (s, 9H, C(CH3)3); 31 P NMR (161.97MHz, C6D6): 14.6 (d, J = 8.6Hz), -65.3 (brs); 19 F NMR (376.16MHz, C6D6): -62.24 (s, 24F), -62.47 (s, 3F).

[0107] Example 3: Ligand 3: [2-(bis(2,6-dimethoxyphenyl)phosphino)-4-(tert-butyl)-6-((3,5-di-tert-butyl ... [Butylbenzyl)bis(2,6-dimethoxyphenyl)phosphonium)phenol][tetra(3,5-bis(trifluoromethyl)phenyl)boronic acid ester]

[0108]

[0109] In a nitrogen-filled glove box, a solution of 1-(bromomethyl)-3,5-di-tert-butylbenzene (18.7 mg, 0.066 mmol, 1 equivalent) 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 at room temperature for 16 hours to obtain a colorless suspension. After the reaction was complete, all 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 equivalent) and fluorobenzene (5 mL) at room temperature and stirred for 3 hours. The colorless suspension was filtered through diatomaceous earth, and the filtrate was evaporated under reduced pressure. The oily, colorless residue was ground 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%). 1 ¹H NMR (400.1MHz, C6D6): δ 8.42 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 8.00 (br s, 1H, OH), 7.97 (d, J = 9.2Hz, 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 = 8.6Hz, 2H, ArH), 6.96 (t, J = 8.6Hz, 2H, ArH), 6.83 (s, 2H, ArH), 6.19 (dd, 4H, ArH), 6.00 (dd, 4H. ArH), 4.51 (d, J = 16.8Hz, 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 1.12ppm); 31 P NMR (161.97MHz, C6D6): 13.3 (br s), -60.1 (brs).

[0110] Example 4 - Ligand 4: [2-(bis(2,6-dimethoxyphenyl)(methyl)phosphonium)-6-(bis(2,6-dimethoxyphenyl)... [phosphino-4-(tert-butyl)phenol][tetra(3,5-bis(trifluoromethyl)phenyl)boronic acid ester]

[0111]

[0112] At -78°C, under a nitrogen atmosphere, in aTeflon ™ A solution of 2,6-bis(bis(2,6-dimethoxyphenyl)phosphino)-4-(tert-butyl)phenol (50 mg, 0.066 mmol) in toluene (5 mL) was added to a Schlenk tube containing a solution of MeI (9.35 mg, 0.066 mmol) in toluene (1 mL). After addition, the reaction mixture was warmed to room temperature for 1 hour and then stirred 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 equivalent) and fluorobenzene (4 mL) at room temperature and stirred for 2 hours. The suspension was filtered through diatomaceous earth, and the volatiles of the filtrate were removed under vacuum. The resulting oily residue was ground with n-pentane (2 × 3 mL) and then dried under reduced pressure to give a colorless powder. Overall yield: 105 mg (0.064 mmol, 97%). 1 ¹H NMR (400.1MHz, C6D6): δ 8.41 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 8.05 (d, J = 9.5Hz, 1H, ArH), 7.68 (br s, 1H, OH; this signal overlaps with the signal at 7.66ppm), 7.66 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.05 (t, J = 8.3Hz, 2H, ArH), 7.00 (t, J = 8.3Hz, 2H, ArH), 6.84 (d, J = 17.6Hz, 1H, ArH), 6.21 (dd, J = 8.3, 3.1Hz, 4H, ArH), 6.00 (dd, J = 9.5Hz, 1H, ArH). 8.5, 5.2Hz, 4H. ArH), 3.09 (s, 12H, OCH3), 2.81 (s, 12H, OCH3), 2.29(d, J = 15.2Hz, 3H, PCH3), 1.02 (s, 9H, C(CH3)3); 31 P NMR (161.97MHz, C6D6): 8.4(d, J = 4.5Hz), -62.3 (br s).

[0113] Example 5 - Ligand 5: [tert-butyl-3-((3-(bis(2,6-dimethoxyphenyl)phosphino)-5-(tert-butyl)-2-] [Hydroxyphenyl)bis(2,6-dimethoxyphenyl)phosphonium)propionate][Tetra(3,5-bis(trifluoromethyl)phenyl)boronate]

[0114]

[0115] In a nitrogen-filled glove box, a solution of tert-butyl 3-bromopropionate (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 to obtain a colorless suspension. After the reaction was complete, all 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 a solution of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (65.4 mg, 0.074 mmol, 1 equivalent) in fluorobenzene (2 mL) was added to this solution, and the mixture was stirred at room temperature for 16 hours. The resulting colorless suspension was filtered through diatomaceous earth, and the filtrate was evaporated to dryness under reduced pressure. The oily residue was ground 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%). 1 ¹H NMR (400.1MHz, 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, 0.9Hz, ArH + OH; the two signals overlap), 7.67 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.06 (t, J = 8.3Hz, 2H, ArH), 6.98 (t, J = 8.3Hz, 2H, ArH), 6.85 (dd, J = 17.1, 2.4Hz, 1H, ArH), 6.24 (dd, J = 8.3, 3.2Hz, 4H, ArH), 5.98 (dd, J = 8.5, 5.2Hz, 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); 31 P NMR (161.97MHz, C6D6): 15.2 (d, J =5.9Hz), -64.1 (br s).

[0116] Example 6 - Ligand 6: [2-(bis(2,6-dimethoxyphenyl)(pentyl)phosphonium)-6-(bis(2,6-dimethoxyphenyl)phosphonium) [phosphino-4-(tert-butyl)phenol][tetra(3,5-bis(trifluoromethyl)phenyl)boronic acid ester]

[0117]

[0118] In a nitrogen-filled glove box at room temperature, a solution of 1-bromopentane (30 mg, 0.20 mmol, 3 equivalents) 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 a toluene-fluorobenzene mixture (5 + 5 mL). After addition, the reaction mixture was stirred for 7 days to allow the reaction to complete. The resulting colorless suspension was evaporated to dryness under vacuum, and the residue was ground with hexane (3 mL), followed by toluene (3 mL), and then dried under reduced pressure to give 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 equivalent) and fluorobenzene (5 mL) at room temperature and stirred for 2 hours. The suspension was filtered through diatomaceous earth, and volatile substances in the filtrate were removed under vacuum. The resulting oily residue was ground 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%).

[0119] 1H NMR (400.1MHz, C6D6): δ 8.41 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.91(ddd, J = 7.3, 2.3, 0.8Hz, 1H, ArH), 7.87 (br s, 1H, OH), 7.67 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.05 (t, J = 8.2Hz, 2H, ArH), 7.00 (t, J = 8.4Hz, 2H,ArH), 6.84 (dd, J = 16.9, 2.4Hz, 1H, ArH), 6.21 (dd, J = 8.3, 3.2Hz, 4H.ArH), 6.01 (dd, J = 8.4, 5.0Hz, 4H (ArH), 3.10 (s, 12H, OCH3), 2.89 (s, 12H, OCH3), 2.86 (br m, 2H, PCH2), 1.11 (m, 4H, CH2; the two CH2 signals overlap), 1.00 (s, 9H, C(CH3)3), 0.77 (t, J = 7.0Hz, 3H, CH3). 31 P NMR (161.97MHz, C6D6): 15.7 (d,J = 7.8Hz), -65.3 (br s).

[0120] Example 7 - Ligand 7: [2-(bis(2,6-dimethoxyphenyl)(pent-4-en-1-yl)phosphonium)-6-(bis(2,6-di-... [Methoxyphenyl)phosphino)-4-(tert-butyl)phenol][tetra(3,5-bis(trifluoromethyl)phenyl)boronic acid ester]

[0121]

[0122] In a glove box filled with N2, at room temperature, a solution of 5-bromo-1-pentene (11.8 mg, 0.079 mmol, 1 equivalent) 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. After addition, the reaction mixture was stirred for 2 weeks to complete the reaction. The resulting colorless suspension was evaporated to dryness under vacuum, and the residue was ground with n-pentane (2 × 5 mL) and then dried under reduced pressure to give a colorless solid. The resulting solid was treated with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (70 mg, 0.079 mmol, 1 equivalent) and fluorobenzene (5 mL) at room temperature and stirred for 3 hours. The suspension was filtered through diatomaceous earth, and volatile substances in the filtrate were removed under vacuum. The resulting foamy residue was ground 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%).

[0123] 1 H NMR (400.1MHz, C6D6): δ 8.41 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.93(ddd, J = 7.8, 2.4, 0.9Hz, 1H, ArH), 7.88 (br s, 1H, OH), 7.66 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.05 (t, J = 8.2Hz, 2H, ArH), 6.98 (t, J = 8.4Hz, 2H,ArH), 6.83 (dd, J = 16.8, 2.4Hz, 1H, ArH), 6.21 (dd, J = 8.3, 3.1Hz, 4H.ArH), 5.99 (dd, J = 8.5, 5.1Hz, 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 = 7.1Hz, 2H, CH2), 1.27 (m, 2H, CH2), 1.00 (s, 9H, C(CH3)3). 31 P NMR (161.97MHz, C6D6): 15.7 (d, J = 6.9Hz), -64.7 (br s).

[0124] Example 8 - Ligand 8: [2-(bis(2,6-dimethoxyphenyl)(methyl)phosphonium)-6-(bis(2,6-dimethoxyphenyl)... [phosphono)-4-(tert-butyl)phenol][trifluoromethanesulfonate]

[0125]

[0126] In a nitrogen-filled glove box at -78°C, a solution of methyl iodine (37 mg, 0.26 mmol, 1 equivalent) 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 equivalent) in toluene (20 mL). The reaction was stirred at -78°C for 15 minutes and allowed to slowly reach room temperature. The reaction mixture was stirred at room temperature for 18 hours, resulting in the formation of a white precipitate. The mixture was filtered through a sintered glass funnel, and the solid residue was washed with toluene (3 × 10 mL) followed by washing with n-pentane (3 × 2 mL). The resulting solid was dried under vacuum for 30 minutes and collected as a white powder (192 mg, 0.21 mmol). In a 20 mL scintillation vial, a portion of the separated solid (50 mg, 0.06 mmol, 1 equivalent) and sodium trifluoromethanesulfonate (9.5 mg, 0.06 mmol, 1 equivalent) were suspended in fluorobenzene (4 mL), forming a turbid, grayish-white mixture. The reaction mixture was stirred at room temperature for 72 hours and then filtered through diatomaceous earth to obtain a colorless solution. Volatile substances were removed under vacuum, yielding a white powder. The powder was washed with n-pentane (3 × 2 mL) and dried under reduced pressure to give ligand 8 as a white powder. Overall yield: 44 mg (0.051 mmol, 85%).

[0127] 1 H NMR (400MHz, FC6H5 / C6D6): 6.39 (dd, J HH = 8.3, 5.2Hz, 4H, ArH), 6.33(dd, J HH = 8.3, 3.1Hz, 4H, ArH), 3.20 (s, 12H, OCH3), 3.16 (s, 12H, OCH3), 2.64 (d, J HP = 15.5Hz, 3H, PCH3), 1.05 (s, 9H, C(CH3)3). 31 P NMR (162MHz, FC6H5 / C6D6): -8.71 (s, 1P, PAr2Me + ), -60.69 (s, 1P, PAr2). 19F NMR (376MHz, FC6H5 / C6D6): -77.74 (s, 3F, CF3). 31 P{ 1 H} NMR (162MHz, FC6H5 / C6D6): δ 8.71 (br s), -60.69 (brs).

[0128] Example 9: Catalyst 1

[0129]

[0130] In a nitrogen-filled glove box, a deep orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (31.5 mg, 0.080 mmol, 1 equivalent) 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 to give a light orange solution. All 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 give the product as an orange powder. Overall yield: 131 mg (0.067 mmol, 83%). 1¹H NMR (400.1MHz, 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 overlaps with the signal at 7.80ppm), 7.74 (dq, J = 11.2, 1.3Hz, 1H, ArH), 7.58 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.52 (t, J = 8.4Hz, 2H, ArH), 7.35 (t, J = 8.4Hz, 2H, ArH), 7.20 (t, J = 6.8Hz, 2H, py), 6.78 (dd, 3H, ArH+benzyl-H, two signals overlap), 6.71 (dd, J = 10.4, 2.4Hz, 2H, benzyl-H), 6.65 (m, 8H, ArH, two signals overlap), 4.47 (d, J = 18.2Hz, 2H, CH2Ar), 3.56 (s, 12H, OCH3), 3.47 (s, 12H, OCH3), 2.12 (d, J = 1.9Hz, Ar-Me), 1.01 (s, 9H, C(CH3)3), -0.58 (s, 9H, SiMe3), -0.83 (d, J = 9.3Hz, 2H, NiCH2); 13 C NMR (101MHz, THF-d8): δ 173.76 (dd, J CP = 25.0, 6.3Hz, Ar-C)), 163.65 (s, Ar-C), 162.80 (q, J CF = 50.0Hz, Ar F -C), 162.20 (d, J CP = 1.6Hz, Ar-C), 151.93 (s, py), 138.06 (s, py), 136.57 (d, J CP = 3.6Hz, Ar-C), 136.05 (s, Ar-C), 135.58 (s, Ar F -C), 134.79 (dd, J CP = 12.8, 6.8Hz, Ar-C), 133.87 (t, J CP = 2.6Hz, Ar-C), 132.75 (dd, J CP= 9.2, 1.3Hz, Ar-C), 131.92 (s, Ar-C), 131.37 (d, J CP = 8.0Hz,Ar-C), 130.47 (d, J CP = 7.6Hz, Ar-C), 130.0 (qq, J CF = 31.5, 3.0Hz, Ar F -C),129.18 (d, J CP = 2.6Hz, Ar-C), 129.13 (dd, J CP = 51.4, 8.8Hz, Ar-C), 125.49(q, J CF = 272.5Hz, CF3), 125.04 (d, J CP = 1.5Hz, Ar-C), 118.16 (septet, J CF =4.0Hz, Ar F -C), 110.05 (d, J CP = 50.5Hz, Ar-C), 105.47 (d, J CP = 4.3Hz, Ar-C),105.29 (d, J CP = 6.3Hz, Ar-C), 104.25 (d, J CP = 11.0Hz, Ar-C), 101.12 (d, J CP =90.5Hz, Ar-C), 55.97 (s, OCH3), 55.93 (s, OCH3), 34.31 (s, C(CH3)3), 33.03 (d,J CP = 53.0Hz, P-CH2), 31.89 (s, C(CH3)3), 20.87 (d, J CP = 1.1Hz, Ar-CH3), 1.95(s, Si(CH3)3), -16.54 (d, J CP = 30.3Hz, SiCH2); 31 P NMR (161.97MHz, THF-d8): 14.3(d, J = 12.8Hz), -6.4 (d, J = 12.8Hz).

[0131] Example 10: Catalyst 2

[0132]

[0133] In a nitrogen-filled glove box, a deep orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (22 mg, 0.056 mmol, 1 equivalent) 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 to give a light orange solution. All 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 give the product as an orange powder. Overall yield: 107 mg (0.053 mmol, 95%). 1 ¹H NMR (400.1MHz, 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, 1.2Hz, 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 = 8.4Hz, 2H, ArH), 7.00 (t, J = 8.4Hz, 2H, ArH), 6.94 (m, 3H, ArH + py), 6.74 (d, J = 7.8Hz, 2H, ArH), 6.58 (dd, J = 17.7, 2.4Hz, 1H, ArH), 6.40 (t, J = 6.9Hz, 2H, py), 6.25 (dd, J = 8.4, 3.7Hz, 4H, ArH), 6.02 (dd, J = 8.5, 5.0Hz, 4H, ArH), 4.33 (d, J= 18.7Hz, 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 = 9.1Hz, 2H, NiCH2); 13 C NMR (101MHz, THF-d8): δ 173.67 (dd, J CP = 25.0, 5.9Hz, Ar-C)), 163.74 (s, Ar-C), 162.80 (q,J CF= 50.0Hz, Ar F -C), 162.13 (d, J CP = 1.5Hz, Ar-C), 151.84 (s, py), 139.26(dd, J CP = 7.7, 1.5Hz, Ar-C), 138.14 (s, py), 136.53 (s, Ar-C), 135.57 (s,Ar F -C), 135.22 (dd, J CP = 12.8, 6.2Hz, Ar-C), 134.27 (t, J CP = 2.6Hz, Ar-C), 132.19 (dd, Ar-C; this signal overlaps with the signal at 132.12ppm), 132.12 (s, Ar-C), 131.03 (d, J) CP = 7.5Hz, Ar-C), 130.0 (qq, J CF = 31.5, 3.0Hz, Ar F -C), 129.38 (d, J CP =8.8Hz, Ar-C), 128.87 (d, J CP = 8.8Hz, Ar-C), 125.49 (q, J CF = 272.5Hz, CF3),125.22 (m, Ar-C), 125.18 (q, J CF = 272.0Hz, CF3), 125.06 (d, J CP = 1.5Hz, Ar-C), 118.17 (septet, J CF = 4.0Hz, Ar F -C), 109.64 (d, J CP = 50.7Hz, Ar-C), 105.46(d, J CP = 6.2Hz, Ar-C), 104.85 (d, J CP = 10.8Hz, Ar-C), 103.88 (d, J CP =11.0Hz, Ar-C), 100.50 (d, J CP= 92.1Hz, Ar-C), 56.10 (s, OCH3), 55.89 (s,OCH3), 34.31 (s, C(CH3)3), 32.71 (d, J CP = 54.5Hz, P-CH2), 31.82 (s, C(CH3)3),1.96 (s, Si(CH3)3), -16.27 (d, J CP = 30.1Hz, SiCH2); 31 P NMR (161.97MHz, C6D6):13.4 (dq, J = 12.8, 2.0Hz), -6.5 (d, J = 12.8Hz); 19 F NMR (376.16MHz, C6D6): -62.21 (s, 24F), -62.44 (s, 3F).

[0134] Example 11: Catalyst 3

[0135]

[0136] In a nitrogen-filled glove box, a deep orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (22.9 mg, 0.059 mmol, 1 equivalent) 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 to give a light orange solution. All 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 vacuum to give the product as an orange powder. Overall yield: 97 mg (0.047 mmol, 80%). 1H NMR (400.1MHz, 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, 1.2Hz, 1H, ArH), 7.69 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.06 (t, J = 8.3Hz, 2H, ArH), 6.98 (t, J = 8.3Hz, 2H,ArH), 6.96 – 6.80 (m, 3H, ArH + py), 6.61 (s, 2H, ArH), 6.47 (t, J = 6.8Hz,2H, py), 6.23(dd, J = 8.3, 3.7Hz, 4H, ArH), 6.01 (dd, J = 8.5, 4.8Hz,4H,ArH), 4.47 (d, J = 17.7Hz, 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 = 9.2Hz, 2H, NiCH2); 13 C NMR (101MHz, THF-d8): δ 173.85 (dd, J CP =25.0, 6.2Hz, Ar-C)), 163.70 (s, Ar-C), 162.80 (q, J CF = 50.0Hz, Ar F -C), 162.17(d, J CP = 1.5Hz, Ar-C), 151.93 (s, py), 150.93 (s, Ar-C), 138.10 (s, py),136.09 (s, Ar-C), 135.58 (s, Ar F -C), 135.10 (s, Ar-C), 134.93 (dd, J CP = 12.8,6.2Hz, Ar-C), 134.42 (d, J CP = 7.4Hz, Ar-C),134.02 (t, J CP = 2.6Hz, Ar-C),132.19 (dd, JCP = 9.8, 1.5Hz, Ar-C), 131.91 (s, Ar-C), 130.01 (qq, J CF = 31.5, 3.0Hz, Ar F -C), 129.74 (d, J CP = 8.8Hz, Ar-C), 129.24 (d, J CP = 8.8Hz, Ar-C), 129.01 (s, Ar-C), 125.49 (q, J CF = 272.0Hz, CF3), 124.88 (d, J CP = 1.3Hz, Ar-C), 124.15 (d, J CP = 8.8Hz, Ar-C), 120.76 (d, J CP = 2.0Hz, Ar-C), 118.16 (septet, J CF = 4.0Hz, Ar F -C), 110.11 (d, J CP = 50.6Hz, Ar-C), 106.09 (d, J CP = 10.8Hz, Ar-C), 105.42 (m, Ar-C), 105.14 (d, J CP = 11.0Hz, Ar-C), 100.86 (d, J CP = 92.2Hz, 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, J CP = 56.2Hz, P-CH2), 32.01 (s, C(CH3)3), 31.66 (s, C(CH3)3), 1.84 (s, Si(CH3)3), -16.59 (d, J CP = 30.1Hz, SiCH2); 31 P NMR (161.97MHz, C6D6): 11.6 (d, J = 12.2Hz), -6.7 (d, J = 12.2Hz).

[0137] Example 12: Catalyst 4

[0138]

[0139] In a nitrogen-filled glove box, a deep orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (25.1 mg, 0.064 mmol, 1 equivalent) 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 to give a light orange solution. All 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 give the product as an orange powder. Overall yield: 112 mg (0.060 mmol, 94%). 1 H NMR (400.1MHz, 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, 1.2Hz, 1H, ArH), 7.67 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.09 (t, J = 8.3Hz, 2H, ArH), 7.01 (t, J = 8.3Hz, 2H, ArH), 6.95(tt, J = 7.6, 1.5Hz, 1H, py), 6.66 (ddd, J = 18.2, 2.4, 0.7Hz, 1H, ArH), 6.38(t, J = 6.82Hz, 2H, py), 6.26 (dd, J = 8.4, 3.7Hz, 4H, ArH), 6.07 (dd, J =8.5, 4.9Hz, 4H, ArH), 3.24 (s, 12H, OCH3), 3.07 (s, 12H, OCH3), 2.16 (d, J =15.7Hz, 3H, PCH3), 0.98 (s, 9H, C(CH3)3), -0.19 (s, 9H, SiMe3), -0.60 (d, J =9.3Hz, 2H, NiCH2); 13 C NMR (101MHz, THF-d8): δ 173.95 (dd, J CP = 25.0, 5.6Hz,Ar-C)), 163.94 (s, Ar-C), 162.80 (q, J CF = 50.0Hz, Ar F-C), 162.07 (d, J CP = 1.3Hz, Ar-C), 151.67 (s, py), 137.97 (s, py), 136.29 (s, Ar-C), 135.59 (s,Ar F -C), 135.16 (dd,J CP = 13.2, 6.2Hz, Ar-C), 134.3 (t, J CP = 2.5Hz, Ar-C),131.93 (s, Ar-C), 130.83 (dd, J CP = 11.3, 1.2Hz, Ar-C), 130.02 (qq, J CF =31.5, 2.8Hz, Ar F -C), 128.46 (dd, J CP = 50.5, 8.4Hz, Ar-C), 125.51 (q, J CF =272.0Hz, CF3), 124.62 (d, J CP = 1.2Hz, Ar-C), 118.18 (septet, J CF = 3.8Hz, Ar F -C), 109.96 (d, J CP = 50.1Hz, Ar-C), 107.06 (dd, J CP = 99.8, 10.6Hz, Ar-C),105.66 (d, J CP = 6.2Hz, Ar-C), 105.36 (d, J CP = 4.3Hz, Ar-C), 101.47 (d, J CP =95.4Hz, 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, J CP = 64.1Hz, P-CH3), 1.92 (s, Si(CH3)3), -16.43 (d, J CP =29.4Hz, SiCH2); 31 P NMR (161.97MHz, C6D6): 7.7 (d), -7.1 (d).

[0140] Example 13 - Catalyst 5

[0141]

[0142] In a nitrogen-filled glove box, a deep orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (28.8 mg, 0.074 mmol, 1 equivalent) 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 to give a light orange solution. After the reaction was complete, the solution was treated with n-pentane (1 mL) and then filtered through diatomaceous earth. All volatiles in 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 give the product as an orange powder. Overall yield: 112 mg (0.065 mmol, 88%). 1 H NMR (400.1MHz, 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, 1.2Hz,1H, ArH), 7.68 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.11 (t, J = 8.3Hz, 2H, ArH), 6.95 (t, J = 8.3Hz, 2H, ArH), 6.90 (tt, J = 7.6, 1.5Hz, 1H, py), 6.63 (ddd, J= 17.6, 2.4, 0.8Hz,1H, ArH), 6.54 (t, J = 6.8Hz, 2H, py), 6.28 (dd, J = 8.4, 3.7Hz, 4H, ArH), 6.02 (dd, J = 8.4, 4.9Hz, 4H, ArH), 3.28 (s, 12H, OCH3), 3.02 (s, 14H, OCH3 + CH2; the two signals overlap), 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 = 9.3Hz, 2H, NiCH2); 13 C NMR (101MHz, THF-d8): δ 174.37 (dd, J CP= 25.0, 5.4Hz, Ar-C)),172.52 (d, J CP = 1.5Hz, C=O), 163.82 (s, Ar-C), 162.80 (q, J CF = 50.0Hz, Ar F -C), 162.05 (d, J CP = 1.5Hz, Ar-C), 151.51 (s, py), 137.96 (s, py), 136.23 (s,Ar-C), 135.73 (d, J CP = 6.2Hz, Ar-C), 135.58 (s, Ar F -C), 134.84 (t, J CP =2.5Hz, Ar-C), 132.09 (s, Ar-C), 131.69 (dd, J CP = 10.4, 1.8Hz, Ar-C), 130.01(qq, J CF = 31.5, 2.9Hz, Ar F -C), 129.01 (s, Ar-C), 128.19 (d, J CP = 8.2Hz, Ar-C), 127.69 (d, J CP = 8.2Hz, Ar-C), 125.50 (q, J CF = 272.5Hz, CF3), 124.83 (s,Ar-C), 118.17 (septet, J CF = 4.0Hz, Ar F -C), 109.43 (d, J CP = 49.7Hz, Ar-C),105.61 (d, J CP = 4.3Hz, Ar-C), 105.15 (d, J CP = 4.3Hz, Ar-C), 102.79 (dd, J CP =96.9, 10.7Hz, Ar-C), 99.68 (d, J CP= 94.4Hz, 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, J CP = 63.2Hz, P-CH2), 0.90 (s, Si(CH3)3),-18.24 (d, J CP = 28.9Hz, SiCH2); 31 P NMR (161.97MHz, C6D6): 13.5 (d, J =11.8Hz), -7.7 (d, J = 11.8Hz).

[0143] Example 14 - Catalyst 6

[0144]

[0145] In a nitrogen-filled glove box, a deep orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (20.1 mg, 0.051 mmol, 1 equivalent) 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 to give a light orange solution. All 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 give the product as an orange powder. Overall yield: 90 mg (0.047 mmol, 92%).

[0146] 1¹H NMR (400.1MHz, THF-d8): δ 8.71 (m, 2H, py), 7.83 (dd, ArH; part of this signal overlaps with the signal at 7.81ppm), 7.81 (br m, 8H, B(C₆H₃⁻³,₅₁₂(CF₃)₂)₄), 7.71 (tt, J = 7.6, 1.6Hz, 1H, py), 7.58 (br s, 4H, B(C₆H₃⁻³,₅₁₂(CF₃)₂)₄), 7.55 (t, J = 8.4Hz, 2H, ArH; this signal partially overlaps with the signal at 7.58ppm), 7.36 (t, J = 8.3Hz, 2H, ArH), 7.04 (br t, J = 6.8Hz, 2H, py), 6.73 (dd, J = 8.4, 4.7Hz, 4H, ArH), 6.66 (dd, J = 8.4, 3.7Hz, 4H, ArH), 6.62 (ddd, J = 17.5, 2.4, 0.8Hz, 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 = 9.2Hz, 2H, NiCH2). 13 CNMR (101MHz, THF-d8): δ 174.42 (dd, J CP = 25.0, 5.5Hz, Ar-C)), 163.91 (s, Ar-C), 162.81 (q, J CF = 50.0Hz, Ar F -C), 162.11 (d, J CP = 1.6Hz, Ar-C), 151.66 (s,py), 137.95 (s, py), 136.03 (s, Ar-C), 135.59 (s, Ar F -C), 135.14 (dd, J CP =12.9, 6.2Hz, Ar-C), 134.46 (t, J CP= 2.5Hz, Ar-C), 132.07 (s, Ar-C), 131.88(dd, J CP = 9.8, 1.8Hz, Ar-C), 130.02 (qq, J CF = 31.5, 2.8Hz, Ar F -C), 127.65(dd, J CP = 51.5, 8.3Hz, Ar-C), 125.50 (q, J CF = 272.0Hz, CF3), 124.63 (d, J CP =1.7Hz, Ar-C), 118.18 (septet, J CF = 3.8Hz, Ar F -C), 109.67 (d, J CP = 49.5Hz, Ar-C), 105.51 (d, J CP = 6.3Hz, Ar-C), 105.25 (d, J CP = 4.2Hz, Ar-C), 104.59 (dd,J CP = 96.6, 10.7Hz, Ar-C), 101.55 (d, J CP = 92.1Hz, Ar-C), 56.24 (s, OCH3),55.88 (s, OCH3), 34.77 (d, J CP = 20.2Hz, CH2), 34.42 (s, C(CH3)3), 31.96 (s, C(CH3)3), 27.51 (d, J CP = 56.8Hz, P-CH2), 24.51 (d, J CP = 3.5Hz, CH2), 23.29 (d,J CP = 1.5Hz, CH2), 14.56 (s, CH3), 2.30 (s, Si(CH3)3), -17.14 (d, J CP = 29.4Hz,SiCH2). 31 P NMR (161.97MHz, THF-d8): 14.55 (d, J = 12.3Hz), -7.64 (d, J =12.3Hz).

[0147] Example 15 - Catalyst 7

[0148]

[0149] In a nitrogen-filled glove box, a deep orange solution of bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (25.5 mg, 0.065 mmol, 1 equivalent) 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 scintillation vial at room temperature. The resulting mixture was stirred for 30 min to give a light orange solution. All volatiles were removed under reduced pressure, and the residue was washed with n-pentane (2 × 3 mL) and dried under reduced pressure for 3 h to give an orange solid. Overall yield: 113 mg (0.059 mmol, 91%).

[0150] 1 H NMR (400.1MHz, THF-d8): δ 8.73 (m, 2H, py), 7.85 (br d, J = 11.3Hz,1H, ArH), 7.81 (br s, 8H, B(C6H3-3,5-(CF3)2)4), 7.71 (t, J = 7.6Hz, 1H, py), 7.59 (br s, 4H, B(C6H3-3,5-(CF3)2)4), 7.55 (t, J = 8.3Hz, 2H, ArH), 7.36 (t, J= 8.3Hz, 2H, ArH), 7.04 (t, J = 6.7Hz, 2H, py), 6.73 (dd, J = 8.4, 4.8Hz, 4H,ArH), 6.67 (dd, J = 8.3, 3.7Hz, 4H, ArH), 6.62 (dd, J = 15.8, 1.8Hz, 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; the two signals overlap), 2.73 (m, 2H, PCH2), 2.03 (q, J = 6.9Hz, CH2), 1.44 (m, 2H, CH2), 1.04 (s, 9H, C(CH3)3), -0.48 (s, 9H, SiMe3), -0.81 (d, J =9.2Hz, 2H, NiCH2). 13 C NMR (101MHz, THF-d8): δ 174.41 (dd, J CP= 25.1, 5.6Hz, Ar-C), 163.89 (s, Ar-C), 162.81 (q, J CF = 50.0Hz, Ar F -C), 162.09 (d, J CP = 1.3Hz, Ar-C), 151.67 (s, py), 138.75 (s, CH2=CH), 137.98 (s, py), 136.07 (s, Ar-C), 135.58 (s, Ar F -C), 135.23 (dd, J CP = 12.8, 6.1Hz, Ar-C), 134.64 (br s, Ar-C), 132.06 (s, Ar-C), 130.83 (d, J CP = 11.4Hz, Ar-C), 130.02 (qq, J CF = 31.5, 2.8Hz, Ar F -C), 127.65 (dd, J CP = 51.4, 8.6Hz, Ar-C), 125.50 (q, J CF = 272.0Hz, CF3), 124.65 (s, py), 124.15 (s, Ar-C), 118.18 (septet, J CF = 3.8Hz, Ar F -C), 115.71 (s, CH2=CH), 109.67 (d, J CP = 49.4Hz, Ar-C), 105.55 (d, J CP = 6.2Hz, Ar-C), 105.27 (d, J CP = 4.1Hz, Ar-C), 104.52 (dd, J CP = 96.4, 9.8Hz, Ar-C), 101.55 (d, J CP = 94.4Hz, Ar-C), 56.29 (s, OCH3), 55.90 (s, OCH3), 36.36 (d, J CP = 20.9Hz, CH2), 34.42 (s, C(CH3)3), 31.94 (s, C(CH3)3), 27.30 (d, J CP=57.7Hz, P-CH2), 24.03 (s, CH2), 2.28 (s, Si(CH3)3), -17.06 (d, J CP = 29.4Hz, SiCH2). 31 P NMR (161.97MHz, THF-d8): 14.58 (d, J = 11.8Hz), -7.66 (d, J =11.8Hz).

[0151] Example 16 - Catalyst 8

[0152]

[0153] In a nitrogen-filled glove box, bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (28 mg, 0.07 mmol, 1 equivalent) and ligand 8 (66 mg, 0.07 mmol, 1 equivalent) were dissolved in 5 mL of benzene in a 20 mL scintillation vial to form a deep red solution. The mixture was stirred at room temperature for 20 minutes, and the solvent was removed under vacuum to produce a deep brown viscous gel. The gel was ground with n-pentane to obtain a brown solid, which was washed with cold diethyl ether (3 × 3 mL). The volatiles were removed under vacuum to give catalyst 8 as a brown powder. Ether washing over a period of 1 week at room temperature produced X-ray-quality deep red crystals. Overall yield: 66 mg (0.06 mmol, 80%).

[0154] 1 H NMR (400MHz, THF-d8): δ 8.72 – 8.65 (m, 2H, ArH), 7.86 (tt, 3 J HH =7.6, 1.7Hz, 1H, ArH), 7.76 (ddd, 4 J HP = 11.1Hz, 4 J HH = 2.5Hz, 5 J HP = 1.2Hz, 1H,ArH), 7.57 (t, 3 J HH = 8.4Hz, 2H, PArH), 7.33 (t, 3 J HH = 8.4Hz, 2H, PArH), 7.17(t, J = 6.7Hz, 2H, Py), 6.79 (dd, 3 J HH = 8.4,4 J HH = 4.9Hz, 4H, PArH), 6.67 (d,J = 3.7Hz, 2H), 6.65 (d, J = 3.7Hz, 2H), 6.60 (dd, 4 J HH = 2.5Hz, 5 J HP = 0.9Hz,1H, ArH), 3.67 (s, 12H, OCH3), 3.63 (s, 12H, OCH3), 2.39 (d, 2 J HP = 15.6Hz, 3H,PCH3), 1.01 (s, 9H, C(CH3)3), -0.59 (s, 9H, Si(CH3)3), -0.87 (d, 3 J HP = 9.4Hz,2H, NiCH2Si)。 13 C{ 1 H} NMR (101MHz, THF-d8): δ 174.03 (dd, J CP = 24.7, 5.7Hz, Ar-C)), 163.89 (s, Ar-C), 162.12 (d, J CP = 1.5Hz, Ar-C), 151.38 (s, Ar-C), 138.87(s, Ar-C), 136.55 (s, Ar-C), 134.89 (dd, J CP = 13.0, 5.9Hz, Ar-C), 133.84 (t,J CP = 2.8Hz, Ar-C), 131.79 (s, Ar-C), 130.67 (d, J CP = 11.3Hz, Ar-C), 128.40(dd, J CP = 50.6, 8.2Hz, Ar-C)), 125.16 (s, Ar-C), 110.13 (d, J CP = 49.5Hz, Ar-C), 107.56 (dd, J CP= 99.7, 10.6Hz, Ar-C), 105.99 (d, J = 6.4Hz, Ar-C), 105.25(d, J = 4.3Hz, Ar-C), 100.93 (d, J = 95.7Hz, 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, 2 J CP = 64.3Hz,PCH3), 1.96 (s, Si(CH3)3), -16.95 (d, 2 J CP = 29.3Hz, SiCH2); 19 F{ 1 H} NMR (362MHz,THF-d8): δ -78.33 (s, 3F, CF3); 31 P{ 1 H} NMR (162MHz, THF-d8): δ 7.62 (d, 4 J PP =12.3Hz, PAr2Me + ), -7.19 (d, 4 J PP = 11.9Hz, PAr2).

[0155] Example 17 - Polymerization Method

[0156] For the polymerization reactions recorded in Table 1, stock solutions of the catalyst (1 mM to 2 mM) were prepared in toluene and immediately delivered to a parallel pressure reactor (PPR). Ethylene homopolymerization experiments were run at 90 °C and 200 psi ethylene pressure with a 0.25 μmol catalyst loading. Ethylene copolymerization experiments were run at 90 °C and 400 psi ethylene pressure with a 0.25 μmol catalyst loading. For copolymerization, tert-butyl acrylate (tBA) was purified by the following steps: filtration through an activated alumina column and delivery to the PPR, with a tBA solution prepared in toluene.

[0157] Table 1. Ethylene homopolymerization and copolymerization (tBA) experiments in PPR * .

[0158]

[0159] * Reactor details are provided in the general procedure for PPR screening experiments. aDue to its limited solubility in toluene, catalyst 8 was injected into the reactor as a solution in THF; the reactor contained 4.75 mL of toluene and 0.25 mL of THF.

[0160] The data recorded in Table 1 indicate that catalysts 1 through 8 are active in the homopolymerization of ethylene and the copolymerization of ethylene with tert-butyl acrylate. The data recorded in Table 1 show that the structures of both the cationic and anionic groups influence the rate of (co)polymerization and the properties of the resulting (co)polymer. It is generally understood that these catalysts represent some of the first embodiments of phosphine nickel(II) catalysts whose performance is modulated through cation-anion interactions.

[0161] Catalysts 1 through 7 all contain the same anion, tetra(3,5-bis(trifluoromethyl)phenyl)boronic acid ester, and differ only in the nature of the alkyl or benzyl group bonded to the phosphonium center. Catalysts 1 through 7 are all highly active in ethylene homopolymerization (entries 1, 5, 8, 11, 14, 17, and 20), even at the relatively low pressures (200 psi) used in our ethylene homopolymerization experiments. Catalysts 1 through 7 also exhibit good activity (200 kg / mol·h to 1100 kg / mol·h) in the copolymerization of ethylene (400 psi, 90 °C) and tert-butyl acrylate (125 to 500 µmol), producing copolymers with relatively high molecular weights (38,000 g / mol to 96,000 g / mol).

[0162] Furthermore, the catalyst is capable of incorporating up to nearly 5% by weight of tBA monomer into the copolymer. Catalyst 4, comprising methyl substitution, exhibits an activity of 1102 kg / mol·h in copolymerizing ethylene and tBA (250 µmol) to produce a copolymer with a molecular weight greater than 85,000 g / mol and t-BA incorporation of 2.6% by weight (Entry 12). In experiments, when the tBA loading was doubled from 250 µmol to 500 µmol (Entry 13), catalyst 4 produced a copolymer with a molecular weight greater than 70,000 g / mol and tBA incorporation of 4.9%.

[0163] The structure of the anion also affects catalyst performance. Catalysts 4 and 8 contain the same cationic segment, but their anionic properties differ. Catalyst 8, containing the trifluoromethanesulfonate anion, produces a slower rate (116 kg / mol / h) in the copolymerization of ethylene and tBA (250 μmol, entry 25) than catalyst 4, containing the tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion (1102 kg / mol·h, entry 12).

Claims

1. A catalyst system comprising a precatalyst having a structure according to formula (I): in: M is either nickel(II) or palladium(II); X is selected from (C1-C) 40 ) hydrocarbon group, (C1-C 40 heteroalkyl groups, -CH2Si(R) C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3-Q (OR C ) Q -P(R) C ) 2-W (OR C ) W -P(O)(R C ) 2-W (OR C ) W -N(R) C )2、-NH(R C ), -N(Si(R) C )3)2、-NR C Si(R C )3、-NHSi(R C 3. -OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C )2、-N=CH(R C -N=CH2, -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R) C )C(O)R C -N(R) C )C(O)H、-NHC(O)R C -C(O)N(R) C )2、-C(O)NHR C -C(O)NH2, halogen or hydrogen ligands, wherein each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 30 ( ) heterohydrocarbon group, 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 connected; A is selected from halides, nitrates, perhalates, phosphates, sulfates, and R. W C(O)O - R W OC(O)O - R W R R NC(O)O - R W O - Si(R) W ) 3-a (OR W ) a O - 、 (R R ) 5-b (OR W ) b Si - R W S(O)2O - R W 4B - R W 4Al - R W 4Ga - R W 6P - R W 6As - or R W 6Sb - anions, where each R W or R R Independently halogenated, hydrogen-containing, substituted or unsubstituted (C1-C) 40 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 40 (a) heterohydrocarbon group, wherein a is 0, 1, 2 or 3, and b is 0, 1, 2, 3 or 4; E is a positively charged heteroatom selected from nitrogen and phosphorus; R P1 R P2 and R P3 Independently selected from one or more R S Replacement (C1-C) 20 ) hydrocarbon group or unsubstituted (C1-C) 20 Hydrocarbon group, substituted (C6-C) 40 ) aryl or unsubstituted (C6-C 40 ) aryl, wherein R S Selected from (C1-C) 10 )alkyl, -OR C -CN, -CF3, -SR C -C(O)OR C and -SiR C 3, where each R C Independently for (C1-C 10 )alkyl; R 1 and R 2 Independently selected from substituted (C1-C) 30 ) hydrocarbon group, unsubstituted (C1-C 30 ) hydrocarbon group, substituted (C1-C) 30 heteroalkyl groups or unsubstituted (C1-C) 30 Heterohydrocarbons; R 3 R 4 and R 5 Independently selected from substituted (C1-C) 30 ) hydrocarbon group, unsubstituted (C1-C 30 ) hydrocarbon group, substituted (C1-C) 30 Heterohydrocarbon groups, unsubstituted (C1-C) 30 heterohydrocarbon group, Si(R) C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3-Q (OR C ) Q -P(R) C ) 2-W (OR C ) W -P(O)(R C ) 2-W (OR C ) W -N(R) C )2、-NH(R C )2、-OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C 2. -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R)C(O)R C -C(O)N(R) C )2 or halogen, where each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 30 (Heterohydrocarbon group; Q is 0, 1, 2 or 3 and W is 0, 1 or 2;) Optional, R 1 and R 2 Connect to form a ring structure; and Optional, R 3 and R 4 Connect to form a ring structure; or Optional, R 4 and R 5 Connect to form a ring structure; or Optional, R P1 and R P2 Connect to form a ring structure; or Optional, R P1 and R P3 Connect to form a ring structure; or Optional, R P2 and R P3 Connect to form a ring structure.

2. The catalyst system according to claim 1, wherein R P1 R P2 and R P3 Independently selected from unsubstituted (C1-C) 20 ) hydrocarbon group and one or more R S Replacement (C1-C) 20 ) hydrocarbon group, where R S Selected from (C1-C) 10 )alkyl, -OR C -CN, -CF3, -SR C -C(O)OR C and -SiR C 3, where each R C Independently for (C1-C 10 )alkyl.

3. The catalyst system according to claim 1 or claim 2, wherein R P1 R P2 and R P3 At least one of them is independently selected from unsubstituted (C1-C) 10 ) hydrocarbon group or one or more R S Substituted benzyl, wherein R S Selected from (C1-C) 10 )alkyl, -CF3 and -O(C1-C 10 )alkyl.

4. The catalyst system according to any one of claims 1 to 3, wherein R 1 and R 2 It is 2,6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-diphenoxyphenyl, 2,4,6-triethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-phenylphenyl or 2,6-diisopropoxyphenyl.

5. The catalyst system according to any one of the preceding claims, wherein Y is pyridine, methylpyridine, dimethylpyridine, trimethylamine or triethylamine.

6. The catalyst system according to any one of the preceding claims, wherein R 3 R 4 and R 5 For (C1-C 18 )alkyl or -H.

7. The catalyst system according to any one of the preceding claims, wherein X is a substituted or unsubstituted (C1-C2) catalyst. 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 ) heterohydrocarbon group.

8. The catalyst system according to 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.

9. The catalyst system according to any one of the preceding claims, wherein A - It can be a coordinated anion, a weakly coordinated anion, or an uncoordinated anion.

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

11. A polymerization method comprising reacting ethylene and optionally a polar comonomer and / or optionally (C3-C4) in the presence of a catalyst system according to any of the preceding claims. 20 α-olefins are polymerized to form ethylene-based polymers.

12. The polymerization method, wherein the polar monomer comprises an alkyl acrylate.

13. The polymerization method according to claim 13, wherein the alkyl acrylate is methyl acrylate or tert-butyl acrylate.

14. The polymerization method according to any one of claims 12 to 14, wherein the polymerization occurs in a reactor at a reactor temperature of 50°C to 250°C.

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