Amino-benzimidazole catalyst for the preparation of polyolefins

Abstract

The present invention relates to catalyst systems comprising metal-ligand complexes according to formula (I).

Description

[0001] Cross-referencing

[0002] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 153,980, filed on February 26, 2021, which is incorporated herein by reference in its entirety. Technical Field

[0003] The embodiments disclosed herein relate generally to olefin polymerization catalyst systems and methods, and more specifically to amino-benzimidazole catalysts. Background Technology

[0004] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, have been produced using various catalyst systems. The choice of such catalyst system used in the polymerization of olefin-based polymers is an important factor contributing to the properties and characteristics of these polymers.

[0005] Ethylene-based polymers and propylene-based polymers are manufactured for a variety of articles. Polyethylene and polypropylene polymerization methods can vary in many ways to produce a variety of resulting polyethylene resins with different physical properties, making each resin suitable for different applications. Ethylene monomers, as well as optionally one or more comonomers, are present in a liquid diluent (such as a solvent), such as alkanes or isoalkanes, for example, isobutylene. Hydrogen may also be added to the reactor. Catalyst systems used to produce ethylene-based products typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (metallocene or non-metallocene) catalyst systems. The reactants in the diluent and catalyst systems circulate around the reactor at elevated polymerization temperatures, thereby producing ethylene-based homopolymers or copolymers. A portion of the reaction mixture, containing polyethylene product dissolved in the diluent, along with unreacted ethylene and one or more optional comonomers, is periodically or continuously removed from the reactor. The reaction mixture, when removed from the reactor, can be processed to remove polyethylene product from the diluent and unreacted reactants, wherein the diluent and unreacted reactants are typically recycled back to the reactor. Alternatively, the reaction mixture can be fed into a second reactor connected in series with the first reactor, where a second polyethylene fraction can be produced. Although research has focused on developing catalyst systems suitable for olefin polymerization such as polyethylene or polypropylene polymerization, there remains a need to improve the efficiency of catalyst systems capable of producing polymers with high molecular weights and narrow molecular weight distributions. Summary of the Invention

[0006] 1. A catalyst system comprising a metal-ligand complex according to formula (I):

[0007]

[0008] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, said metal having an oxidation state of +2, +3, or +4; each X is independently selected from unsaturated (C2-C4) metals. 50 Hydrocarbons, unsaturated (C2-C) 50 ( ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C6-C 50 )Aryl, (C6-C 50 Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C) 12 Dienes, halogens and -CH2SiR C 3 monodentate or bidentate ligands; wherein each R C Choose the group consisting of the following items: (C1-C) 30 (X) Hydrocarbon group or –H. n The subscript n is 2 or 3; and the subscript m is 1 or 2. The metal-ligand complex of formula (I) has 6 or fewer metal-ligand bonds.

[0009] In equation (I), each R 1 Independently select the group consisting of the following items: substituted (C1-C) 50 )alkyl, unsubstituted (C1-C 50 )alkyl, substituted (C6-C) 50 ) aryl and unsubstituted (C6-C 50 )Aryl. Each R 2 R 3 and R 4 Independently selected from –H, (C1-C 50 ) hydrocarbon group, (C1-C 50 (C6-C) heterohydrocarbon group, (C6-C) 50 )Aryl, (C4-C 50 Heteroaryl, halogen atom, -OR C 、-Si(R C )3 and -Ge(R C )3; and each R 5 Selected from S, -NR N or CR N 2, where each R N For (C1-C 20 ) hydrocarbon group or -H; and each R 6 Independently selected from –H, (C1-C 50 ) hydrocarbon group, (C1-C 50 (C6-C) heterohydrocarbon group, (C6-C) 50 )Aryl, (C4-C 50) heteroaryl, -Si(R C )3 and -Ge(R C 3. Detailed Implementation

[0010] 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.

[0011] The following is a list of common abbreviations:

[0012] R, Z, M, X and n: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; i-Pr: isopropyl; t-Bu: tert-butyl; t-Oct: tert-octyl(2,4,4-trimethylpentane-2-yl); Tf: trifluoromethanesulfonate; CV: column volume (used in column chromatography); EtOAc: ethyl acetate; TEA: triethylaluminum; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; LiCH2TMS: (trimethylsilyl)methyllithium; TMS: trimethylsilyl; Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II) dichloride; Pd(AmPhos): chloro(crotonyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II); Pd(dppf)Cl2: [1, 1'-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride; ScCl3: scandium(III) chloride; PhMe: toluene; THF: tetrahydrofuran; CH2Cl2: dichloromethane; DMF: N,N-dimethylformamide; EtOAc: ethyl acetate; Et2O: diethyl ether; MeOH: methanol; NH4Cl: ammonium chloride; MgSO4: magnesium sulfate; Na2SO4: sodium sulfate; NaOH: sodium hydroxide; brine: saturated sodium chloride aqueous solution; SiO2: silicon dioxide; CDCl3: chloroform-D; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimole; mL: milliliter; M: mole; min or mins: minutes; h or hrs: hours; d: days; TLC: thin-layer chromatography; rpm: revolutions per minute; rt: room temperature.

[0013] The term “independently selected” is used in this document to indicate, as R 1 R 2 R 3 R 4 and R 5 The R groups can be the same or different (e.g., R... 1 R 2 R 3 R 4 and R5 Both can be substituted alkyl groups, or R 1 and R 2 It can be a substituted alkyl group, and R 3 (This could be an aryl group, etc.). Chemical names associated with the R group are intended to convey the chemical structure recognized in the art as corresponding to the chemical structure of the chemical name. Therefore, chemical names are intended to supplement and describe, rather than exclude, structural definitions known to those skilled in the art.

[0014] 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 substituted with one or more substituents such as RS. The parenthetical phrase "(C x -C y The definition of R S The substituted chemical group can contain more than y carbon atoms, depending on any group R. S The characteristics. For example, "just being controlled 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, it is common practice to use the parenthetical phrase "(C6H5)" when referring to phenyl groups. 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 During substitution, both x and y are added with substituents R from all carbon atoms. S The minimum and maximum total number of carbon atoms in a chemical group are determined by the sum of the combinations of carbon atoms.

[0015] The term "substitution" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R). S Substitution. The term "total substitution" means that each hydrogen atom (H) bonded to the carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R). S Substitution. The term "multi-substitution" means that at least two, but fewer than all, hydrogen atoms bonded to the carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen group covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly stated otherwise.

[0016] The term "(C1-C)" 50 "(C1-C50) hydrocarbon group" refers to a hydrocarbon group having 1 to 50 carbon atoms, and the term "(C1-C50) hydrocarbon group" is used in this context. 50 "Hydroalkylene" refers to a hydrocarbon bigroup having 1 to 50 carbon atoms, wherein each hydrocarbon group and each hydrocarbon bigroup is aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched, cyclic (having three or more carbon atoms, including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and is surrounded by one or more R... S Replaced or not replaced.

[0017] In this disclosure, (C1-C 50 The hydrocarbon group can be unsubstituted or substituted (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)).

[0018] The term "(C1-C)" 50 alkyl and (C1-C) 18 "alkyl" refers to either an unsubstituted or alkyl compound with one or more R groups. S Substituted saturated straight-chain or branched hydrocarbon groups having 1 to 50 carbon atoms and saturated straight-chain or branched hydrocarbon groups having 1 to 18 carbon atoms. Unsubstituted (C1-C2) 50 Examples of alkyl groups are unsubstituted (C1-C1) alkyl groups. 20 )alkyl; unsubstituted (C 1- C 10 )alkyl; unsubstituted (C 1- C5) alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C1-C5) 40 Examples of alkyl groups are substituted (C1-C2) 20 )alkyl, substituted (C1-C 10 )alkyl, trifluoromethyl and [C 45 Alkyl group. The term "[C]" 45 "Alkyl" means that the group (including substituents) contains a maximum of 45 carbon atoms, and is, for example, (C 27 -C 40 ) alkyl groups, each being separated by an RS (It is a (C1-C5) alkyl) substitution. Each (C1-C5) alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl or 1,1-dimethylethyl.

[0019] The term "(C6-C)" 50 "Aryl" refers to an unsubstituted or substituted compound with 6 to 40 carbon atoms (one or more R groups). S A substituted monocyclic, bicyclic, or tricyclic aromatic hydrocarbon group, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon group comprises one aromatic ring; a bicyclic aromatic hydrocarbon group has two rings; and a tricyclic aromatic hydrocarbon group has three rings. When a bicyclic or tricyclic aromatic hydrocarbon group is present, at least one ring of the group is aromatic. The other one or more rings of the aromatic group may be independently fused or unfused and aromatic or non-aromatic. Unsubstituted (C 6- C 50 Examples of aryl groups include: unsubstituted (C6-C) 20 )Aryl, unsubstituted (C6-C) 18 ) aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indene; dihydroindene; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C5) 40 Examples of aryl groups include: substituted (C1-C) 20 ) aryl; substituted (C6-C 18 )Aryl; 2,4-bis([C 20 ]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluorene-9-one-1-yl.

[0020] The term "(C3-C)" 50 "Cycloalkyl" refers to a saturated cyclic hydrocarbon group having 3 to 50 carbon atoms, which is unsubstituted or surrounded by one or more R groups. S Substitution. Other cycloalkyl groups (e.g., (C10) x -C y Cycloalkyl groups are defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted by one or more R groups. S Replaced. Unreplaced (C3-C) 40 Examples of cycloalkyl groups are unsubstituted (C3-C4) 20 )cycloalkyl, unsubstituted (C3-C 10 Cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3-C) 40 Examples of cycloalkyl groups are substituted (C3-C4) 20)cycloalkyl, substituted (C3-C 10 )cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

[0021] (C 1- C 50 Examples of alkylene groups include unsubstituted or substituted (C6-C) groups. 50 () aryl, (C3-C 50 )cycloalkylene and (C1-C 50 )alkylene (e.g., (C 1- C 20 Alkylene). Dimers can be on the same carbon atom (e.g., -CH2-), on adjacent carbon atoms (i.e., 1,2-dimers), or separated by one, two, or more than two intermediate carbon atoms (e.g., 1,3-dimers, 1,4-dimers, etc.). Some dimers include 1,2-dimers, 1,3-dimers, 1,4-dimers, or α,ω-dimers and other 1,2-dimers. α,ω-dimers are dimers with the largest intercarbon backbone spacing between the group carbons. (C2-C) 20 Some examples of alkylene α,ω-bigroups include ethyl-1,2-diyl (i.e., -CH2CH2-), propan-1,3-diyl (i.e., -CH2CH2CH2-), and 2-methylpropan-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6-C) 50 Some examples of arylene α,ω-dimethyl groups include phenyl-1,4-dimethyl, naphth-2,6-dimethyl, or naphth-3,7-dimethyl.

[0022] The term "(C1-C)" 50 "alkylene" refers to an unsubstituted or compounded alkylene group having 1 to 50 carbon atoms. S Substituted saturated straight-chain or branched bigroups (i.e., the group is not on a ring atom). Unsubstituted (C1-C) 50 Examples of alkylene groups are unsubstituted (C 1- C 20 Alkylene groups, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3 and -(CH2)4C*(H)(CH3), where "C*" indicates the carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. Substituted (C1-C 50 Examples of alkylene groups are substituted (C1-C2) 20 Alkylene, -CF2-, -C(O)-, and -(CH2) 14C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosene). As previously stated, the two R... S They can form together (C1-C) 18 )alkylene, substituted (C1-C 50 Examples of alkylene groups also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane and 2,3-bis(methylene)bicyclo[2.2.2]octene.

[0023] The term "(C3-C)" 50 "Cycloalkylene" refers to an unsubstituted or compounded alkylene oxide having 3 to 50 carbon atoms. S Substituted cyclic diradicals (i.e., radicals on ring atoms).

[0024] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O)2, and Si(R). C )2、P(R P ), N(R N -N=C(R) C )2、-Ge(R C )2-、-Si(R C - Boron (B), aluminum (Al), gallium (Ga), or indium (In), where each R C and each R P It is unreplaced (C1-C) 18 ) hydrocarbon group or -H, and each R N It is unreplaced (C1-C) 18 (C1-C2) hydrocarbon group. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms. 50 "(C1-C50)" refers to a heterohydrocarbon group having 1 to 50 carbon atoms, and the term "(C1-C50)" is used in conjunction with the meaning of "(C1-C50)" in this context. 50 "Heterohydrocarbon group" refers to a heterohydrocarbon bigroup having 1 to 50 carbon atoms. (T(C1-C)) 50 ) heterohydrocarbon group or (C1-C 50The heterohydrocarbon group has one or more heteroatoms. The heterohydrocarbon group can be on a carbon atom or a heteroatom. The two groups of the heterohydrocarbon group can be on a single carbon atom or a single heteroatom. Additionally, in a bigroup, one group can be on a carbon atom and the other group can be on a different carbon atom; one group can be on a carbon atom and the other group on a heteroatom; or one group can be on a heteroatom and the other group on a different heteroatom. Each (C1-C 50 ) heterohydrocarbon groups and (C1-C 50 Heteroalkyl groups can be unsubstituted or substituted with (one or more R groups). S Substituted, aromatic or non-aromatic, saturated or unsaturated, straight or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0025] (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-, (C 1- 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-C 19 ) heteroaryl-(C1-C20 ) Heteroalkylene.

[0026] The term "(C1-C)" 50 "Heteroaryl" refers to an unsubstituted or substituted aryl group having a total of 1 to 50 carbon atoms and 1 to 10 heteroatoms. S A heteroaromatic hydrocarbon free radical consisting of a monocyclic, bicyclic, or tricyclic ring. A monocyclic heteroaromatic hydrocarbon group comprises one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon group has two rings; and a tricyclic heteroaromatic hydrocarbon group has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon free radical is present, at least one ring in the free radical is heteroaromatic. The other one or more rings of the heteroaromatic group may be independently fused or unfused and aromatic or non-aromatic. Other heteroaromatic groups (e.g., typically (C...) x -C y ) heteroaryl groups, such as (C1-C 12 (Heteroaryl) is defined in a similar manner as having x to y carbon atoms (such as 1 to 12 carbon atoms) and being unsubstituted or substituted by one or more R atoms. SSubstituted. Monocyclic heteroaromatic hydrocarbon groups are 5-membered or 6-membered rings. A 5-membered monocyclic heteroaromatic hydrocarbon group has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3, or 4, and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon groups include: pyrrolo-1-yl; piperidin-2-yl; furan-3-yl; thiophene-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. A 6-membered ring monocyclic heteroaromatic hydrocarbon group has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon groups include: pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6- or 6,6-cyclic systems. Examples of fused 5,6-cyclic bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-cyclic bicyclic heteroaromatic hydrocarbon groups are quinoline-2-yl; and isoquinoline-1-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6,5-cyclic systems; 5,6,6-cyclic systems; 6,5,6-cyclic systems; or 6,6,6-cyclic systems. Examples of fused 5,6,5-cyclic systems are 1,7-dihydropyrrolo[3,2-f]indol-1-yl. Examples of fused 5,6,6-cyclic systems are 1H-benzo[f]indol-1-yl. Examples of fused 6,5,6-cyclic systems are 9H-carbazole-9-yl. Examples of fused 6,5,6-cyclic systems are 9H-carbazole-9-yl. Examples of fused 6,6,6-cyclic systems are acridine-9-yl.

[0027] The term "(C1-C)" 50 "(C1-C5)" refers to a saturated straight-chain or branched group containing one to fifty carbon atoms and one or more heteroatoms. 50 "Hybrid alkylene" refers to a saturated straight-chain or branched bigroup containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene group may include Si(R) C 3. Ge(R) C 3. Si(R) C )2、Ge(R C )2、P(R P )2、P(R P ), N(R N )2、N(R N ), N, O, OR C , S, SR CS(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is not substituted or is occupied by one or more R groups. S replace.

[0028] Unreplaced (C2-C) 40 Examples of heterocyclic alkyl groups include unsubstituted (C2-C4) alkyl groups. 20 Heterocyclic alkyl groups, unsubstituted (C2-C) 10 Heterocyclic alkyl groups, aziridin-1-yl, oxetane-2-yl, tetrahydrofuran-3-yl, pyrrolidine-1-yl, tetrahydrothiophene-S,S-dioxo-2-yl, morpholino-4-yl, 1,4-dioxane-2-yl, hexahydroacetane-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0029] The term "halogen atom" or "halogen" refers to a free radical of a fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) atom. The term "halide" refers to the anionic form of a halogen atom: the fluoride ion (F...). - ), chloride ions (Cl) - ), bromide ions (Br) - ) or iodide ions (I - ).

[0030] The term "saturation" refers to the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. In saturated chemical groups, the presence of one or more substituents R... S In the case of substitution, one or more double and / or triple bonds may optionally be present in the substituent R. S In this context, the term "unsaturated" means containing one or more carbon-carbon double or triple bonds, or (in groups containing heteroatoms) one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds, excluding those that may exist in the substituent R. S (If any) double bonds in an aromatic ring or a heteroaromatic ring.

[0031] Embodiments of this disclosure include one or more catalyst systems. The catalyst system comprises one or more metal-ligand complexes according to formula (I):

[0032]

[0033] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, said metal having an oxidation state of +2, +3, or +4; each X is independently selected from unsaturated (C2-C4) metals. 50 Hydrocarbons, unsaturated (C2-C) 50 ( ) heterohydrocarbons, (C1-C 50) hydrocarbon group, (C6-C 50 )Aryl, (C6-C 50 Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C) 12 Dienes, halogens and -CH2SiR C 3 monodentate or bidentate ligands; wherein each R C Choose the group consisting of the following items: (C1-C) 30 (X) is a hydrocarbon group or –H. In formula (I), (X) n The subscript n is 2 or 3, and the subscript m is 1 or 2. The metal-ligand complex of formula (I) has 6 or fewer metal-ligand bonds.

[0034] In equation (I), each R 1 Independently select the group consisting of the following items: (C1-C) 50 )alkyl or (C6-C 50 )Aryl; each R 2 R 3 and R 4 Independently selected from –H, (C1-C 50 ) hydrocarbon group, (C1-C 50 (C6-C) heterohydrocarbon group, (C6-C) 50 )Aryl, (C4-C 50 ) heteroaryl, -OR C 、-Si(R C )3 and -Ge(R C )3; Each R 5 Selected from S, -NR N or CR N 2, where each R N For (C1-C 20 ) hydrocarbon group or -H; and each R 6 Independently selected from –H, (C1-C 50 ) hydrocarbon group, (C1-C 50 (C6-C) heterohydrocarbon group, (C6-C) 50 )Aryl, (C4-C 50 ) heteroaryl, -Si(R C )3 and -Ge(R C 3.

[0035] In one or more embodiments of the metal-ligand complex of formula (I), M is zirconium or hafnium; each X is independently selected from unsubstituted (C1-C2) metals. 10 )alkyl, substituted (C1-C 10 )alkyl, (C6-C 20 ) aryl or halogen; and each R 1 Independently selected from (C6-C) 50) aryl or (C1-C 50 )alkyl.

[0036] In some implementations, each R 3 R 4 and R 5 For –H.

[0037] In various implementation schemes, each R 1 It is an unsubstituted phenyl, a substituted phenyl, an unsubstituted anthraquinone, a substituted anthraquinone, an unsubstituted naphthyl, or a substituted naphthyl. In one or more embodiments, each R 1 It is a substituted phenyl group; the substituted phenyl group is selected from 2-methylphenyl, 2-(isopropyl)phenyl, 2,4,6-trimethylphenyl, 2,6-di(isopropyl)phenyl, 2,4,6-tri(isopropyl)phenyl, 3,5-di-tert-butylphenyl, 3,5-diphenylphenyl, and 2,3,5,6-tetrafluorophenyl.

[0038] In various implementation schemes, R 5 For NR N , where R N For (C1-C 20 )alkyl or (C6-C 20 )Aryl; in some implementations, R N For straight chain (C1-C) 12 )alkyl.

[0039] In an embodiment, the metal-ligand complex may include two bidentate ligands, where m is 2 and the metal-ligand complex has a structure according to formula (II):

[0040]

[0041] In equation (II), each R 1 R 2 R 3 R 4 R 5 R 6 X is as defined in equation (I); and n is 1 or 2.

[0042] In the metal-ligand complex according to formula (I) or (II), each X is bonded to M via a covalent, coordinate, or ionic bond. In some embodiments, each X is identical. The metal-ligand complex has six or fewer metal-ligand bonds and may be overall charge neutral or may have a positive charge associated with the metal center. In some embodiments, the catalyst system comprises a metal-ligand complex according to formula (I), wherein M is zirconium or hafnium; each X is independently selected from (C1-C2). 20 )alkyl, (C1-C20 (heteroalkyl, (C6-C) 20 )Aryl, (C4-C 20 () heteroaryl, (C4-C 12 Diene or halogen. In one or more embodiments, each X is independently benzyl, phenyl, or chlorine.

[0043] In some implementations, the monodentate ligand can be a monoanionic ligand. The net oxidation state of the monoanionic ligand is -1. Each monoanionic ligand can independently be a hydride, (C1-C2) 40 ) hydrocarbon-based carbanion, (C1-C 40 Heteroalkyl carbanions, halide ions, nitrate ions, carbonate ions, phosphate ions, 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.

[0044] In other embodiments, at least one monodentate ligand X, independent of any other ligand X, can be a neutral ligand. In specific embodiments, the neutral ligand is a neutral Lewis base group, such as R...Q NR K R L R K OR L R K SR L Or R Q PR K R L , where each R Q Independently hydrogen, [(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 as previously defined.

[0045] Additionally, each X can be a monodentate ligand, which, independently of any other ligand, is halogenated and unsubstituted (C1-C2). 20 ) hydrocarbon group, unsubstituted (C1-C) 20 ) hydrocarbon group C(O)O– or R K R L N-, where R K and R L Each of them is independently unsubstituted (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-C 10 ) hydrocarbon group C(O)O– or R K R L N-, where R K and R L Each of them is independently unsubstituted (C1-C) 10 ) hydrocarbon group. In one or more embodiments of formula (I), (II) and (III), X is benzyl, chlorine, -CH2SiMe3 or phenyl.

[0046] In another embodiment, each X is selected from: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. In some embodiments, each X is the same. In other embodiments, at least two Xs are different from each other. In embodiments where at least two Xs are different from at least one X, X is one of the following: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine. In another embodiment, the bidentate ligand is 2,2-dimethyl-2-dimethylsilane-1,3-diyl or 1,3-butadiene.

[0047] In some embodiments, the chemical groups (e.g., X and R) of the metal-ligand complex of formula (I) 1 -R 4 Any or all of them may be unsubstituted. In other embodiments, the chemical groups X and R of the metal-ligand complex of formula (I) are... 1 -R 4 None of them, any one or all of them can be one or more R S Replacement. When two or more R S When bonded to the same chemical group of a metal-ligand complex of formula (I), each R of the chemical group S It can be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, chemical groups X and R 1 -R 4 None, any, or all of them can be R S Complete replacement. 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.

[0048] In an illustrative embodiment, the catalyst system may comprise a metal-ligand complex according to formula (I) having the structure of any one of the metal-ligands 1 to 13 listed below:

[0049]

[0050]

[0051]

[0052] In illustrative embodiments, the catalyst system may comprise a metal-ligand complex having the structure of any one of metal-ligand complexes 1 to 13 according to formula (I), or an in-situ formed metal-ligand complex synthesized from the following corresponding ligands:

[0053]

[0054]

[0055]

[0056]

[0057]

[0058] Embodiments of this disclosure include polymerization methods. The polymerization methods include polymerizing ethylene and one or more olefins under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based polymer, the catalyst system comprising a metal-ligand complex according to formula (I) or formula (II).

[0059] One or more embodiments of this disclosure include a method for polymerizing a polymer, the method comprising: contacting ethylene in a reactor in the presence of a catalyst system and optionally one or more (C3-C4) polymers. 12 α-olefins. The catalyst system may include a main catalyst of a metal-ligand complex according to formula (I) and an activator. The polymerization method may include, but is not limited to, solution polymerization, gas-phase polymerization, slurry polymerization, and combinations thereof, using one or more reactors such as ring reactors, isothermal reactors, fluidized bed gas-phase reactors, continuous stirred tank reactors, parallel or series batch reactors, and / or any combination thereof.

[0060] The polymerization method disclosed herein can produce ethylene-based polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, which can be produced, for example, by solution-phase polymerization using one or more circulating reactors, isothermal reactors, and combinations thereof.

[0061] In some embodiments, the solution-phase polymerization method occurs in one or more well-stirred reactors, such as one or more loop reactors or one or more spherical isothermal reactors, at temperatures ranging from 120°C to 300°C, for example, from 150°C to 190°C, and at pressures ranging from 300 psi to 1500 psi, for example, from 400 psi to 750 psi. The residence time in the solution-phase polymerization method is typically in the range of 2 minutes to 30 minutes; for example, from 10 minutes to 20 minutes. Ethylene, one or more solvents, one or more catalyst systems (such as catalyst systems comprising a metal-ligand complex according to formula (I) as the main catalyst), optionally one or more cocatalysts, and optionally one or more comonomers are continuously fed into one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents may be available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas. The resulting mixture of the ethylene-based polymer and solvent is then removed from the reactor, and the ethylene-based polymer is separated. Solvents are typically recovered via solvent recovery units (i.e., heat exchangers and vapor-liquid separator drums) and then recycled back into the polymerization system.

[0062] Chain shuttle and / or chain transfer agent

[0063] In one or more embodiments, the polymerization method of this disclosure includes contacting ethylene and / or one or more (C3-C4) compounds in a reactor in the presence of a catalyst system and a chain transfer agent or chain shuttle agent. 12 α-olefins. In such embodiments, the polymerization method comprises three components: (A) a main catalyst comprising a metal-ligand complex having a structure of formula (I) and optionally a co-catalyst; (B) an olefin polymerization catalyst having a comonomer selectivity different from that of the main catalyst (A); and (C) a chain transfer agent or chain shuttle.

[0064] As additives to a catalyst system, chain transfer agents and chain shuttles are compounds capable of transferring polymer chains between two catalyst molecules in a single polymerization reactor. Catalyst molecules can have the same structure or different structures. When catalyst molecules have different structures, they may have different monomer selectivity. Whether these compounds act as chain transfer agents or chain shuttles depends on the type of polymerization reactor, even though the three components (A)-(C) described above may be chemically identical in any type of polymerization reactor. For example, in batch reactors with a single catalyst system or a dual catalyst system, the compounds act as chain transfer agents. In continuous reactors with a dual catalyst system, these compounds act as chain shuttles. Generally, compounds used as chain transfer agents in batch reactors can also be used as chain shuttles in continuous reactors; conversely, molecules used as chain shuttles can also be used as chain transfer agents. Therefore, in embodiments of the polymerization method disclosed herein, it should be understood that the disclosure of compounds as "chain transfer agents" further constitutes the disclosure of the same compounds as "chain shuttles." Therefore, the terms "chain transfer agent" and "chain shuttle" are interchangeable with respect to chemical compounds, but they are distinguishable when a process occurs within a specific type of polymerization reactor.

[0065] The chain transfer capability of catalysts was initially assessed by conducting activities to vary the level of chain transfer agent, or shuttler (CSA), to observe the decrease in molecular weight and the overall effect on the expected PDI of the shuttle catalyst. The molecular weight of polymers generated by catalysts with the potential to become good chain shuttlers will be more sensitive to the addition of CSA compared to polymers generated by catalysts exhibiting poor shuttle or slow chain transfer kinetics. The Mayo equation (Equation 1) describes how the chain transfer agent changes from the natural number-average chain length in the absence of a chain transfer agent. Reduce average chain length Equation 2 defines the chain transfer or chain shuttle constant Ca as the ratio of chain transfer to the growth rate constant. By assuming that the vast majority of chain growth occurs through ethylene insertion rather than comonomer incorporation, Equation 3 describes the expected Mn of the polymerization. Mn0 is the native molecular weight of the catalyst in the absence of a chain shuttle, and Mn is the molecular weight observed in the presence of a chain shuttle (Mn = Mn0, no chain shuttle).

[0066]

[0067]

[0068]

[0069] [Monomer] = (mol% C2) × [Ethylene] + (mol% C8) × [Octenene] Formula 4

[0070] Typically, chain transfer agents comprise Al, B, or Ga metals in the form of an oxidation state of +3; or Zn or Mg metals in the form of an oxidation state of +2. Chain transfer agents suitable for the methods of this disclosure are described in U.S. Patent Application Publication No. US2007 / 0167315, which is incorporated herein by reference in its entirety.

[0071] In one or more embodiments of the polymerization method, the chain transfer agent (when present) may be selected from diethylzinc, di(isobutyl)zinc, di(n-hexyl)zinc, di(n-octyl)zinc, triethylaluminum, trioctylaluminum, triethylgallium, bis(dimethyl(tert-butyl)siloxane)isobutylaluminum, bis(di(trimethylsilyl)amide)isobutylaluminum, bis(pyridin-2-methanol)n-octylaluminum, bis(n-octadecyl)isobutylaluminum, bis(di(n-pentyl)amide)isobutylaluminum, bis(2,6-di-tert-butylphenol)n-octyl Aluminum, di(ethyl(l-naphthyl)amide)n-octylaluminum, bis(tert-butyldimethylsiloxane)ethylaluminum, di(bis(trimethylsilyl)amide)ethylaluminum, bis(2,3,6,7-dibenzo-l-azacycloheptanamide)ethylaluminum, bis(2,3,6,7-dibenzo-l-azacycloheptanamide)n-octylaluminum, bis(dimethyl(tert-butyl)siloxide)n-octylaluminum, (2,6-diphenylphenol)ethylzinc, (tert-butanol)ethylzinc, dimethylmagnesium, dibutylmagnesium, and n-butyl-sec-butylmagnesium.

[0072] co-catalyst components

[0073] Catalytic activity can be achieved by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions, including metal-ligand complexes of formula (I). For example, the main catalyst of a metal-ligand complex according to formula (I) can be made catalytically active by contacting the complex with an activated co-catalyst or by combining the complex with an activated co-catalyst. Additionally, metal-ligand complexes according to formula (I) comprise both a neutral main catalyst form and a catalytic form that may be positively charged due to the loss of monomeric ionic ligands (such as benzyl or phenyl). Activating co-catalysts suitable for this document include alkylaluminum; polymeric or oligomeric aluminum oxanes (also known as aluminum oxanes); neutral Lewis acids; and non-polymeric, non-coordinated, ion-forming compounds (including those used under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating co-catalysts and techniques are also contemplated. The term "alkylaluminum" means dihydrogenated monoalkylaluminum or dihalogenated monoalkylaluminum, hydrogenated dialkylaluminum or halodialkylaluminum, or trialkylaluminum. Examples of polymeric or oligomeric aluminum oxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0074] In some embodiments, suitable cocatalysts include polymeric or oligomeric aluminum oxanes (especially methylaluminoxanes) and inert, compatible, noncoordinate ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetra(pentafluorophenyl)borate (1-)amine (RIBS-2), triethylaluminum (TEA), and combinations thereof.

[0075] Lewis acid activation cocatalysts contain (C1-C) as described herein. 20 A Group 13 metal compound with a hydrocarbon substituent. In some embodiments, the Group 13 metal compound is a tri((C1-C) group. 20 ()hydrocarbon-substituted aluminum or tri((C1-C) 20 (Hydrocarbon)-boron compounds. In other embodiments, the Group 13 metal compound is a tri(hydrocarbon)-substituted aluminum, tri((C1-C)-boron compound. 20 )hydro-boron compounds, tri((C1-C 10 Alkyl aluminum, tri((C6-C) 18 (Aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In other embodiments, the Group 13 metal compound is tris(fluorosubstituted phenyl)borane or tris(pentafluorophenyl)borane. In some embodiments, the activation cocatalyst is tris((C1-C)borane. 20 ) hydrocarbon borates (e.g., triphenylmethyltetrafluoroborate) or tri((C1-C 20 )hydro-based)ammonium tetra((C1-C 20 (e.g., bis(octadecyl)methylammonium tetra(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a nitrogen cation that is ((C1-C2) 20 )hydrocarbon group)4N + 、((C1-C 20 )hydrocarbon group)3N(H) + 、((C1-C 20 )hydrocarbon group)2N(H)2 + (C1-C) 20 )hydrocarbon group 3 + or N(H)4 + Where there are two or more (C1-C) 20 When there are hydrocarbon groups, they can be the same or different.

[0076] The combination of neutral Lewis acid activation cocatalysts includes tris((C1-C4)alkyl)aluminum and tris((C6-C4)halogenated tris((C6-C4)alkyl)aluminum. 18Mixtures of aryl boron compounds (especially tris(pentafluorophenyl)borane). Other embodiments are combinations of such neutral Lewis acid mixtures with polymeric or oligomeric aluminum oxanes, and combinations of single neutral Lewis acids (especially tris(pentafluorophenyl)borane) with polymeric or oligomeric aluminum oxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenyl)borane):(aluminoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenyl)borane):(aluminoxane)] is from 1:1:1 to 1:10:30, and in other embodiments from 1:1:1.5 to 1:5:10.

[0077] Catalytic systems comprising metal-ligand complexes of formula (I) can be activated to form active catalyst compositions by combination with one or more cocatalysts (e.g., cation-forming cocatalysts, strong Lewis acids, or combinations thereof). Suitable activation cocatalysts comprise polymeric or oligomeric aluminum oxanes (especially methylaluminoxanes) and inert, compatible, noncoordinate, ionic compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetra(pentafluorophenyl)boronic acid (1-)amine, and combinations thereof.

[0078] In some embodiments, one or more of the aforementioned activation cocatalysts may be used in combination with each other. Specific examples of cocatalyst combinations are mixtures of tris((C1-C4)alkyl)aluminum, tris((C1-C4)alkyl)borane, or ammonium borate with oligomeric or polymeric aluminum oxane compounds. The ratio of the total molar number of one or more metal-ligand complexes of formula (I) to the total molar number of one or more activation cocatalysts is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments at least 1:1000; and 10:1 or less, and in some other embodiments 1:1 or less. When an aluminum oxane is used alone as an activation cocatalyst, preferably, the molar number of the aluminum oxane used is at least 100 times the molar number of the metal-ligand complex of formula (I). In some other embodiments, when tris(pentafluorophenyl)borane is used alone as an activation cocatalyst, the molar ratio of tris(pentafluorophenyl)borane to the total molar ratio of one or more metal-ligand complexes of formula (I) is from 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activation cocatalyst is typically used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of formula (I).

[0079] Polyolefins

[0080] The catalytic system described in the preceding paragraphs is used to polymerize olefins, primarily ethylene and propylene. In some embodiments, the polymerization scheme contains only a single type of olefin or α-olefin, thereby forming a homopolymer. However, additional α-olefins may be incorporated into the polymerization process. These additional α-olefin comonomers typically have no more than 20 carbon atoms. For example, α-olefin comonomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or, alternatively, from the group consisting of 1-hexene and 1-octene.

[0081] For example, ethylene-based polymers, homopolymers and / or interpolymers (including copolymers) of ethylene, and optionally one or more comonomers such as α-olefins may comprise at least 50% by weight of ethylene-derived monomer units. All individual values ​​and subranges covered by “at least 50% by weight” are disclosed herein as separate embodiments; for example, ethylene-based polymers, i.e., homopolymers and / or interpolymers (including copolymers) of ethylene with optionally one or more comonomers such as α-olefins, may comprise at least 60% by weight of ethylene-derived monomer units; at least 70% by weight of ethylene-derived monomer units; at least 80% by weight of ethylene-derived monomer units; or 50% by weight to 100% by weight of ethylene-derived monomer units; or 80% by weight to 100% by weight of ethylene-derived units.

[0082] In some embodiments, the ethylene-based polymer may comprise at least 90 mol% of ethylene-derived units. All individual values ​​and subranges from at least 90 mol% are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may comprise at least 93 mol% of ethylene-derived units; at least 96 mol% of units; at least 97 mol% of ethylene-derived units; or alternatively, 90 mol% to 100 mol% of ethylene-derived units; 90 mol% to 99.5 mol% of ethylene-derived units; or 97 mol% to 99.5 mol% of ethylene-derived units.

[0083] In some embodiments of the ethylene-based polymer, the additional α-olefin is less than 50%; other embodiments include at least 0.5 mol% to 25 mol%; and in still other embodiments, the additional α-olefin comprises at least 5 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0084] Ethylene polymers can be produced using any conventional polymerization process. Such conventional polymerization methods include, but are not limited to, solution polymerization, gas-phase polymerization, slurry polymerization, and combinations thereof, using one or more conventional reactors such as ring reactors, isothermal reactors, fluidized bed gas-phase reactors, stirred tank reactors, parallel or series batch reactors, or any combination thereof.

[0085] In one embodiment, ethylene-based polymers can be produced by solution polymerization in a dual-reactor system (e.g., a dual-ring reactor system), wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more co-catalysts. In another embodiment, ethylene-based polymers can be produced by solution polymerization in a dual-reactor system, such as a dual-ring reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system disclosed herein and as described herein, and optionally one or more other catalysts. The catalyst system described herein can optionally be used in combination with one or more other catalysts in either the first or second reactor. In one embodiment, ethylene-based polymers can be produced via solution polymerization in a dual-reactor system (e.g., a dual-ring reactor system), wherein ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of a catalyst system as described herein.

[0086] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system (e.g., a single loop reactor system), wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described in this disclosure and optionally one or more co-catalysts as described in the preceding paragraphs.

[0087] Ethylene-based polymers may further include one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. Ethylene-based polymers may contain any amount of additives. Ethylene-based polymers may contain a combined weight of about 0 to about 10% of such additives based on the weight of the ethylene-based polymer and one or more additives. Ethylene-based polymers may further include fillers, which may include, but are not limited to, organic or inorganic fillers. Based on the combined weight of the ethylene-based polymer and all additives or fillers, the ethylene-based polymer may contain about 0 to about 20% by weight of fillers, such as calcium carbonate, talc, or Mg(OH)₂. Ethylene-based polymers may further be blended with one or more polymers to form blends.

[0088] In some embodiments, polymerization methods for producing ethylene-based polymers may involve polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, wherein the catalyst system is incorporated with at least one metal-ligand complex of formula (I). According to ASTM D792 (in its entirety incorporated herein by reference), polymers produced by such catalyst systems incorporating metal-ligand complexes of formula (I) may have, for example, a concentration of 0.850 g / cm³. 3 Up to 0.950 g / cm 3 0.880 g / cm 3 Up to 0.920 g / cm 3 0.880 g / cm 3 Up to 0.910 g / cm 3 Or 0.880 g / cm 3 Up to 0.900 g / cm 3 The density.

[0089] In another embodiment, the melt flow ratio (I) of the polymer produced by the catalyst system containing the metal-ligand complex of formula (I) is... 10 The melt index I2 is between 5 and 15, where the melt index I2 is measured according to ASTM D1238 (in its entirety incorporated herein by reference) at 190°C and a load of 2.16 kg, and the melt index I... 10 It was measured according to ASTM D1238 at 190°C and a 10kg load. In other embodiments, the melt flow ratio (I 10 The melt flow ratio is 5 to 10, and in another embodiment, the melt flow ratio is 5 to 9.

[0090] In some embodiments, the polymer produced by a catalyst system comprising a metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 1 to 25, wherein MWD is defined as M w / M n M w Where M is the weight-average molecular weight, and M n The molecular weight is the number average. In other embodiments, the polymer produced by the catalyst system has a molecular weight distribution (MWD) of 1 to 6. Another embodiment includes a MWD of 1 to 3; and other embodiments include a MWD of 1.5 to 2.5.

[0091] Due to the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer, the embodiments of the catalyst system described in this disclosure produce unique polymer properties.

[0092] Unless otherwise stated, all solvents and reagents were obtained from commercial sources and used as is. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by activated alumina, and in some cases by Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glove box were purified by activated alumina. The samples were stored on molecular sieves and then further dried. Glassware used for moisture-sensitive reactions was dried overnight in an oven before use. NMR spectra were recorded on a Varian 400-MR and VNMRS-500 spectrometer. LC-MS analysis was performed using a Waters e2695 SeparationsModule coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation was performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a gradient of acetonitrile to water from 5:95 to 100:0, with 0.1% formic acid as the ionizing agent. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax EclipsePlus C18 1.8μm 2.1×50mm column coupled to an Agilent 6230 TOF Mass Spectrometer with electrospray ionization. 1 The H NMR data are reported as follows: chemical shifts (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quadruplet, p = quintuplet, sex = hexatuplet, sept = heptet and m = multiplicity), integration, and assignment). Low-field data from the inner tetramethylsilane (TMS, scale δ) are reported using the protons remaining in the deuterated solvent as a reference. 1 Chemical shifts (in ppm) from H NMR data. 1 H-decoupling method was used to determine 13 C NMR data were used, and chemical shifts (in ppm) were reported from the low field of tetramethylsilane (TMS, scale δ) compared to using protons remaining in the deuterated solvent as a reference.

[0093] High-throughput parallel polymerization reactor polymerization program (PPR) screening

[0094] 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 controls and was continuously stirred at 800 rpm. Unless otherwise specified, the catalyst solution was prepared in toluene. All liquids (i.e., solvent, 1-octene, chain shuttle solution, and catalyst solution) were added via a robotic injector. Gaseous reagents (i.e., ethylene, CO) were added via gas inlets. Before each run, the reactor was heated to 80°C, purged with ethylene, and vented.

[0095] The reactor was heated to the operating temperature and pressurized to the appropriate psig with ethylene. Isopar E waiss was added, followed by toluene solutions of the reagents in the following order: (1) 1-octene with 500 nmol of scavenger MMAO-3A; (2) activator (RIBS-II, FAB, etc.); and (3) catalyst (100 nmol).

[0096] Each time liquid was added, a small amount of Isopar E was used for tracking to ensure a total reaction volume of 5 mL after the final addition. After catalyst addition, the PPR software began monitoring the pressure in each unit. The required pressure (approximately 2 psig to 6 psig) was maintained by supplementing with ethylene gas by opening the valve when the setpoint was -1 psi and closing the valve when the pressure was above 2 psi. All pressure drops were cumulatively recorded during operation as either “absorption” or “conversion” of ethylene, or until the required absorption or conversion value was reached, whichever occurred first. Each reaction was quenched for 4 minutes at 40 to 50 psi higher than the reactor pressure by adding 10% carbon monoxide to argon. The shorter the “quenching time,” the higher the catalyst activity. To prevent excessive polymer formation in any given unit, the reaction was quenched after reaching the predetermined absorption level (50 psig for 120°C operation, 75 psig for 150°C operation). After quenching the reactor, it was cooled to 70°C, vented, purged with nitrogen for 5 minutes to remove carbon monoxide, and the tubing was removed. The polymer sample was then dried in a centrifugal evaporator at 70°C for 12 hours, weighed to determine the polymer yield, and analyzed by IR (1-octene incorporation) and GPC (molecular weight).

[0097] Batch reactor polymerization process

[0098] Batch reactor polymerization in 2L Parr TM The process is carried out in a batch reactor. The reactor is heated by an electrically heated hood and cooled by internal, meandering cooling coils containing cooling water. (The text abruptly ends here, likely due to an incomplete sentence or missing information.) TMThe TG process is computer-controlled and monitored for the reactor and heating / cooling system. A tilt valve is fitted at the bottom of the reactor to empty the reactor contents into a stainless steel tilting pan pre-filled with a catalyst inactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The tilting pan is drained into a 30-gallon purging tank, which is purged with nitrogen. All solvents used in the polymerization or catalyst composition are passed through solvent purification columns to remove any impurities that might affect the polymerization. 1-Octene and Isopar E are passed through two columns, the first containing active A2 alumina and the second containing active Q5 reactants. Ethylene is passed through two columns, the first containing A2O4 alumina and... Molecular sieve, the second column contains reactant Q5. N2 for transfer passes through a column containing alumina (A2O4). Molecular sieves and Q5 single columns.

[0099] Depending on the required reactor load, the reactor is first loaded from a spray tank containing Isopar E solvent and / or 1-octene. The spray tank is then filled to the load setpoint using a laboratory-scale reactor equipped with the spray tank. After adding the liquid feed, the reactor is heated to the polymerization temperature setpoint. If ethylene is used, it is added to the reactor at the reaction temperature to maintain the reaction pressure setpoint. The amount of ethylene added is monitored using a micro-motion flow meter.

[0100] The catalyst and activator were mixed with an appropriate amount of purified toluene to obtain a solution of the desired molar concentration. The catalyst and activator were treated in an inert glove box, aspirated into a syringe, and pressure transferred to the catalyst injection vessel. The mixture was then flushed three times with 5 mL of toluene each time. Immediately after adding the catalyst, a timer was started. If ethylene was used, it was added via Camile to maintain the reaction pressure set point in the reactor. These polymerizations were run for 10 minutes, after which the stirrer was stopped and the bottom drain valve was opened to empty the reactor contents into a pouring pan. The pouring pan contents were poured into a tray placed in a laboratory fume hood, where the solvent was evaporated overnight. The tray containing the remaining polymer was then transferred to a vacuum oven, where it was heated under vacuum to up to 140°C to remove any remaining solvent. After the tray cooled to ambient temperature, the polymer was weighed to obtain the yield / efficiency and submitted for polymer testing.

[0101] Octene-doped HT-GPC analysis using IR detection

[0102] High-temperature GPC analysis was performed using a Dow Robot Assisted Delivery (RAD) system equipped with a PolymerChar 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 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 2 mg / mL with 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 minutes. To calibrate the molecular weight, Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 mL of BHT-stabilized TCB and dissolved by stirring at 160°C for 15 minutes. The PS standards were injected into the system without further dilution to create a third-order MW calibration curve, where the apparent units were adjusted to homopolymer polyethylene (PE) using known Mark-Houwink coefficients for PS and PE. Octene incorporation was determined using a linear calibration developed by analyzing copolymers with known compositions.

[0103] SymRAD HT-GPC Analysis

[0104] Molecular weight data were determined by analysis on a robot-assisted dilution high-temperature gel permeation chromatography (Sym-RAD-GPC) system constructed using a hybrid Symyx / Dow. Polymer samples were dissolved in 10 mg / mL 1,2,4-trichlorobenzene (TCB) at 160 °C for 120 min, a concentration stabilized by 300 ppm butylated hydroxytoluene (BHT). Each sample was diluted to 1 mg / mL immediately before injecting 250 μL aliquots. The GPC was equipped with two Polymer Labs PLgel 10 μm MIXED-B columns (300 × 10 mm) at a flow rate of 2.0 mL / min at 160 °C. Samples were detected in concentration mode using a PolyChar IR4 detector. Routine calibration with narrow-band polystyrene (PS) standards was performed, adjusting to the apparent units of homopolymer polyethylene (PE) using known Mark-Houwink coefficients for PS and PE in TCB at this temperature.

[0105] IR analysis of 1-octene doping

[0106] Samples used for HT-GPC analysis were run prior to IR analysis. For IR analysis, 1-octene doping in the samples was deposited and analyzed using a 48-well HT silicon wafer. For this analysis, the samples were heated to 160°C for ≤210 min; the samples were then reheated to remove the magnetic GPC stir bar and agitated with a glass rod stir bar on a J-KEM Scientific heated mechanical oscillator. Samples were deposited while heated using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene was evaporated from the deposited wafer wells at 160°C under nitrogen purging. 1-Octenene analysis was performed on the HT silicon wafer using a NEXUS 670E.SPFT-IR.

[0107] Example

[0108] Examples 1 to 90 are synthetic procedures for ligand intermediates, ligands, and isolated master catalysts of ligand structures 1 to 43. The metal-ligand complexes 1 to 13 (IMLC-1 to IMLC-13) of the present invention are synthesized from various ligands 1 to 43. In Examples 91 and 92, the results of polymerization reactions of IMLC-1 to IMLC-13 and in-situ generated metal-ligand complexes are listed and discussed. One or more features of this disclosure are illustrated by the following examples:

[0109] Synthesis of metal-ligand complexes

[0110] Example 1–N 1 Synthesis of 1,2-hexyl-3-nitrobenzene-1,2-diamine

[0111]

[0112] To a 250 mL round-bottom flask, charge 3-nitrobenzene-1,2-diamine (5.00 g, 32.65 mmol), K₂CO₃ (9.02 g, 65.30 mmol), and DMF (80 mL). Add 1-bromohexane (4.6 mL, 32.65 mmol) and stir at 75 °C for 15 hours under nitrogen. Add water and EtOAc, collect the organic layer, and wash several times with brine. Remove all volatiles and purify the crude product by column chromatography (100% hexane gradient to 100% EtOAc). Some impurities remain but are carried over to the next step. Yield: 7.75 g, 71%.

[0113] 1H NMR (400MHz, CDCl3) δ7.68(dd,J=8.7,1.3Hz,1H),6.86(dd,J=7.7,1.4Hz,1H),6.72(dd,J=8.7,7.6Hz,1H),5.97(s,2 H), 3.11 (t, J = 7.1Hz, 2H), 1.71 (dq, J = 15.7, 7.2, 6.6Hz, 2H), 1.54-1.42 (m, 2H), 1.42-1.30 (m, 6H), 0.96-0.91 (m, 3H).

[0114] 13 C NMR (101MHz, CDCl3) δ138.41,136.35,133.28,117.07,117.05,115.98,45.00,31.64,29.52,26.93,22.62,14.04.

[0115] Example 2 – Synthesis of 2-(3,5-di-tert-butylphenyl)-1-hexyl-4-nitro-1H-benzo[d]imidazole

[0116]

[0117] Add N to a 20mL vial 1 1,2-Hexyl-3-nitrobenzene-1,2-diamine (0.263 g, 1.11 mmol), 3,5-di-tert-butylbenzaldehyde (0.242 g, 1.11 mmol), and EtOH (7 mL) were added. The solution was heated overnight at 75 °C. All volatiles were removed, and then K₂CO₃ (0.337 g, 2.44 mmol) and CH₂Cl₂ (8 mL) were added, followed by iodine (0.281 g, 1.11 mmol). The reaction was stirred at room temperature for 2 hours. Water was added, and the organic layer (solvent) was extracted. All volatiles were removed, and the crude product was purified by column chromatography (hexane:EtOAc, 70:30). Yield: 0.483 g, 54%.

[0118] 1 H NMR (400MHz, CDCl3) δ8.18(dd,J=8.1,0.9Hz,1H),7.73(dd,J=8.1,1.0Hz,1H),7.62(t,J=1.9Hz,1H),7.53(d,J=1.8Hz,2 H),7.40(t,J=8.1Hz,1H),4.30-4.20(m,2H),1.86(p,J=7.5Hz,2H),1.39(s,18H),1.33-1.18(m,6H),0.89-0.80(m,3H).

[0119] 13C NMR (101MHz, CDCl3) δ158.74,151.38,139.19,138.33,136.94,128.77,124.56,123. 90,121.42,119.23,116.15,45.26,35.04,31.41,31.22,29.95,26.37,22.40,13.92.

[0120] Example 3 – Synthesis of 2-(3,5-di-tert-butylphenyl)-1-hexyl-1H-benzo[d]imidazol-4-amine

[0121]

[0122] A 100 mL round-bottom flask was filled with 2-(3,5-di-tert-butylphenyl)-1-hexyl-4-nitro-1H-benzo[d]imidazole (2.10 g, 4.82 mmol), ethanol (30 mL), and a saturated aqueous solution of NH4Cl (10 mL). The mixture was stirred at room temperature under nitrogen, and then Zn powder (1.58 g, 24.10 mmol) was added in portions. The reaction was monitored by LC-MS. After stirring for 2 hours, EtOAc was added, and the mixture was filtered through diatomaceous earth. The organic layer was collected and purified by column chromatography (70:30 hexane:EtOAc). Yield: 1.96 g, 92%.

[0123] 1 H NMR (400MHz, CDCl3) δ7.62(t,J=1.9Hz,1H),7.56(d,J=2.0Hz,2H),7.18(t,J=7.9Hz,1H),6.87(d,J=8.1Hz,1H),6.67(d,J= 7.7Hz,1H),5.00(s,2H),4.18(t,J=7.8Hz,2H),1.90(p,J=7.5Hz,2H),1.39(s,18H),1.36-1.19(m,6H),0.92-0.78(m,3H).

[0124] 13 C NMR (101MHz, CDCl3) δ151.57,135.42,124.60,123.85,108.1,100.47,45.28,35.08,31.43,31.27,29.80,26.43,22.45,13.95.

[0125] Example 4 – Synthesis of 1-hexyl-2-trimethylyl-1H-benzo[d]imidazol-4-amine

[0126]

[0127] A 100 mL round-bottom flask was filled with 1-hexyl-2-trimethyl-4-nitro-1H-benzo[d]imidazole (1.10 g, 3.01 mmol), ethanol (30 mL), and a saturated aqueous solution of NH4Cl (10 mL). The mixture was stirred at room temperature under nitrogen, and then Zn powder (1.58 g, 24.10 mmol) was added in portions. The reaction was monitored by LC-MS. After stirring for 2 hours, EtOAc was added, and the mixture was filtered through diatomaceous earth. The organic layer was collected and purified by column chromatography (100% EtOAc). Yield: 0.97 g, 96%.

[0128] 1 H NMR(400MHz, CDCl3)δ7.10(t,J=7.9Hz,1H),6.81(dd,J=8.1,0.9Hz,1H),6.97(s,2H),6.56(dd,J=7.7,0.9Hz,1H), 4.43(s,2H),3.87-3.74(m,2H),2.07(s,6H),2.05(s,3H),1.72-1.57(m,2H),1.26-1.13(m,6H),0.90-0.77(m,3H).

[0129] 13 C NMR (101MHz, CDCl3) δ150.57,139.19,138.82,138.07,135.33,132.50,128.32,127. 31,123.21,105.68,99.88,44.15,31.22,29.41,26.46,22.38,21.25,19.86,13.93.

[0130] Example 5 – 1-Hexyl-2-trimethylyl-N-(2,4,6-triisopropylphenyl)-1H-benzo[d]imidazol-4- Amine Synthesis

[0131]

[0132] Inside the glove box, add 2,4,6-triisopropylphenylbromide (0.093 g, 0.33 mmol), 1-hexyl-2-trimethylmethyl-1H-benzo[d]imidazol-4-amine (0.100 g, 0.33 mmol), Pd(BINAP)-G4 (0.030 g, 0.03 mmol), and NaO to a 20 mL vial. t Bu (0.072 g, 0.75 mmol) and toluene (8 mL). The vials were heated to 100 °C for 6 hours and examined by LC-MS. The product was confirmed by LC-MS. Water and EtOAc were added, the organic layer was collected, and all volatiles were removed. The crude product was purified by column chromatography (hexane:EtOAc 80:20).1 ¹H NMR revealed some residual impurities. The sample was purified by supercritical CO₂ column purification, yielding the pure product in a low yield (yield: 0.008 g, 5%).

[0133] 1 H NMR (400MHz, CDCl3) δ7.10 (s, 2H), 7.01 (m, 3H), 6.75 (d, J = 8.0Hz, 1H), 6.42 (s ,1H),5.99(d,J=7.8Hz,1H),3.91-3.78(m,2H),3.42-3.23(m,J=6.8Hz,2H),2. 95(h,J=6.9Hz,1H),2.38(s,3H),2.14(s,6H),1.72(p,J=7.7Hz,2H),1.33(d,J =6.9Hz, 6H), 1.32-1.20 (m, 6H), 1.17 (d, J = 6.9Hz, 12H), 0.85 (t, J = 6.6Hz, 3H).

[0134] 13 C NMR (101MHz, CDCl3) δ150.08,147.56,147.23,140.66,139.28,138.21,134.82,132.87,131.27,128.37,127.28 ,123.37,121.56,102.18,98.45,44.27,34.22,31.21,29.47,28.28,26.53,24.16,22.41,21.30,19.96,13.95.

[0135] Example 6 – Synthesis of 3-bromo-N-butyl-2-nitroaniline

[0136]

[0137] 1-Bromo-3-fluoro-2-nitrobenzene (10.00 g, 45.45 mmol), K₂CO₃ (7.54 g, 54.55 mmol), and acetonitrile (100 mL) were added to a 250 mL round-bottom flask. n-BuNH₂ (4.5 mL, 45.45 mmol) was added, and the reaction was stirred at room temperature for 2 days. All volatiles were removed, and the crude product was absorbed in EtOAc and water. The organic layer was collected and dried over Na₂SO₄. The solid was filtered off, and all volatiles were removed to give the product as an orange solid / oil. NMR showed a product-to-starting material ratio of 75:25. This material was ready for the next step without further purification. Yield: 12.20 g, 98%.

[0138] 1H NMR (400MHz, CDCl3) δ7.15(dd,J=8.5,7.8Hz,1H),6.94(dd,J=7.8,1.1Hz,1H),6.76(dd,J=8.6,1.1Hz,1H),5. 73(s,1H),3.20(td,J=7.1,5.1Hz,2H),1.66(tt,J=8.6,6.8Hz,2H),1.52-1.39(m,2H),0.98(t,J=7.3Hz,3H).

[0139] 13 C NMR (101MHz, CDCl3) δ143.83,132.99,121.39,116.29,112.38,43.23,31.00,20.14,13.76.

[0140] Example 7 – 3-Bromo-N 1 Synthesis of 1,2-butylphenyl-1,2-diamine

[0141]

[0142] 3-Bromo-N-butyl-2-nitroaniline (2.64 g, 9.67 mmol), ethanol (30 mL), and saturated NH4Cl aqueous solution (10 mL) were added to a 100 mL round-bottom flask. The mixture was stirred at room temperature under nitrogen, and then Zn powder (5.06 g, 77.33 mmol) was added in portions. The reaction was monitored by LC-MS. After stirring for 2 hours, EtOAc was added, and the mixture was filtered through diatomaceous earth. The organic layer was collected and purified by column chromatography (80:20 hexane:EtOAc). Yield: 1.72 g, 73%.

[0143] 1 H NMR (400MHz, CDCl3) δ6.95(dd,J=8.1,1.3Hz,1H),6.70(t,J=8.0Hz,1H),6.65-6.58(m,1H),3.76(s,2H),3.35( s,1H),3.12(td,J=7.0,3.6Hz,2H),1.68(dtd,J=8.6,7.3,5.9Hz,2H),1.56-1.42(m,2H),1.00(t,J=7.3Hz,3H).

[0144] 13 C NMR (101MHz, CDCl3) δ138.89,132.35,121.60,120.82,111.23,110.41,44.14,31.71,20.41,13.95.

[0145] Example 8 – Synthesis of 4-bromo-1-butyl-2-(3,5-di-tert-butylphenyl)-1H-benzo[d]imidazole

[0146]

[0147] 3-Bromo-N-methyl ... 1 1,2-Butylbenzene-1,2-diamine (1.70 g, 6.99 mmol), 3,5-di-tert-butylbenzaldehyde (1.53 g, 6.99 mmol), and EtOH (100 mL, anhydrous) were added. The mixture was heated to 70 °C for 15 hours. All volatiles were removed, and then CH₂Cl₂ (100 mL), K₂CO₃ (2.13 g, 15.38 mmol), and I₂ (1.78 g, 6.99 mmol) were added, and the mixture was stirred for 3 hours. Water was added to the mixture, and the organic layer was collected. The crude product was purified by column chromatography (80:20 hexane:EtOAc, second product). Yield: 2.56 g, 83%.

[0148] 1 H NMR (400MHz, CDCl3) δ7.58(t,J=1.9Hz,1H),7.49(m,3H),7.36(dd,J=8.1,0.9Hz,1H),7.16(t,J=7.9H z,1H),4.18-4.08(m,2H),1.90-1.72(m,2H),1.39(s,18H),1.36-1.22(m,2H),0.86(t,J=7.4Hz,3H).

[0149] 13 C NMR (101MHz, CDCl3) δ155.69,151.08,141.82,135.93,129.40,125.21,123.9 6,123.90,123.30,113.31,109.29,44.90,34.99,31.95,31.43,19.97,13.54.

[0150] Example 8 – N-(3,5-di-tert-butylphenyl)-1-hexyl-2-trimethylmethyl-1H-benzo[d]imidazol-4-amine Synthesis

[0151]

[0152] Inside the glove box, add 1-hexyl-2-trimethyl-1H-benzo[d]imidazol-4-amine (0.060 g, 0.18 mmol), 1-bromo-3,5-di-tert-butylbenzene (0.053 g, 0.20 mmol), Pd(BINAP-G3) (0.009 g, 0.01 mmol), and NaO to a 20 mL vial. tBu (0.043 g, 0.45 mmol) and toluene (8 mL). The vials were heated to 100 °C for 6 hours and examined by LC-MS. The product was confirmed by LC-MS. Water and EtOAc were added, the organic layer was collected, and all volatiles were removed. The crude product was purified by column chromatography (hexane:EtOAc 80:20). 1 ¹H NMR revealed some residual impurities. The sample was purified by supercritical CO₂ column chromatography to obtain a clean product. Yield: 0.036 g, 38%.

[0153] 1 H NMR (400MHz, CDCl3) δ7.26(d,J=1.5Hz,3H),7.22(t,J=4.5Hz,5H),7.10(q,J=1.6Hz,1H),7.02(s,2H),6.97-6.88(m,1H),3 .88(t,J=7.7Hz,2H),2.40(s,3H),2.12(s,6H),1.72(h,J=6.9Hz,2H),1.39(s,18H),1.34-1.17(m,6H),0.93-0.81(m,3H).

[0154] 13 C NMR (101MHz, CDCl3) δ151.72,150.62,141.35,139.42,138.13,135.99,135.11,132.86,128.43,127.05,123 .27,115.71,113.72,103.63,100.53,44.27,34.96,31.52,31.26,29.52,26.52,22.42,21.31,19.93,13.98.

[0155] Example 9 – 1-Butyl-2-(3,5-di-tert-butylphenyl)-N-(o-tolyl)-1H-benzo[d]imidazol-4-amine Synthesis

[0156]

[0157] Inside the glove box, add 4-bromo-1-butyl-2-(3,5-di-tert-butylphenyl)-1H-benzo[d]imidazole (0.060 g, 0.14 mmol), toluidine (0.016 g, 0.15 mmol), Pd(BINAP) (0.007 g, 0.01 mmol), and NaO to a 20 mL vial. tBu (0.033 g, 0.34 mmol) and toluene (8 mL). The vials were heated to 100 °C for 6 hours and examined by LC-MS. The product was confirmed by LC-MS. Water and EtOAc were added, the organic layer was collected, and all volatiles were removed. The crude product was purified by column chromatography (hexane:EtOAc 80:20). Yield: 0.064 g, 36%.

[0158] 1 H NMR (400MHz, CDCl3) δ7.60(t,J=1.8Hz,1H),7.55(t,J=1.9Hz,2H),7.31-7.26(m,1H ),7.23(td,J=7.7,1.7Hz,1H),7.17(t,J=8.0Hz,1H),7.11-6.99(m,1H),6.90(ddd, J=10.6,8.0,0.9Hz,2H),6.77-6.66(m,1H),4.23-4.10(m,2H),2.40(s,3H),1.90(d dt,J=9.3,7.7,3.7Hz,2H),1.42(s,18H),1.40-1.34(m,2H),0.91(t,J=7.4Hz,3H).

[0159] 13 C NMR (101MHz, CDCl3) δ153.01,151.18,140.47,136.52,136.13,132.95,130.93,130.23,129.97,126.55,1 23.77,123.71,123.35,122.65,120.75,104.63,100.65,44.76,35.03,32.11,31.47,20.09,18.16,13.63.

[0160] Example 10 – 1-Butyl-2-(3,5-di-tert-butylphenyl)-N-(2,6-diisopropylphenyl)-1H-benzo[d] Synthesis of imidazole-4-amine

[0161]

[0162] Inside the glove box, add 2,6-diisopropylaniline (0.052 g, 0.29 mmol), 4-bromo-1-butyl-2-(3,5-di-tert-butylphenyl)-1H-benzo[d]imidazole (0.100 g, 0.23 mmol), Pd(BINAP) (0.011 g, 0.01 mmol), and NaO to a 20 mL vial. tBu (0.054 g, 0.57 mmol) and toluene (8 mL). The vials were heated to 100 °C for 6 hours and examined by LC-MS. The product was confirmed by LC-MS. Water and EtOAc were added, the organic layer was collected, and all volatiles were removed. The crude product was purified by column chromatography (hexane:EtOAc 80:20). 1 ¹H NMR revealed some residual impurities. The sample was purified by supercritical CO₂ column chromatography to obtain the pure product. Yield: 0.056 g, 46%.

[0163] 1 H NMR (400MHz, CDCl3) δ7.60 (dd, J=12.2, 1.9Hz, 3H), 7.37 (dd, J=8.6, 6.5Hz, 1H), 7.30 (d ,J=8.3Hz,2H),7.04(t,J=7.9Hz,1H),6.78(d,J=8.0Hz,1H),6.48(s,1H),5.97(d,J=7.8 Hz, 1H), 4.16 (dt, J=10.5, 7.5Hz, 2H), 3.40 (hept, J=6.9Hz, 2H), 1.94 (dq, J=9.5, 7.4 Hz, 2H), 1.44 (s, 18H), 1.42-1.35 (m, 2H), 1.20 (d, J = 6.9Hz, 12H), 0.94 (t, J = 7.3Hz, 3H).

[0164] 13 C NMR (101MHz, CDCl3) δ152.43,151.11,148.19,140.36,135.81,135.02,131.06,130.08,127.27,123. 84,123.76,123.70,123.63,102.43,98.68,44.78,35.04,32.23,31.50,28.17,23.58,20.19,13.67.

[0165] Example 11 – N-(2,7-di-tert-butylanthracene-9-yl)-1-hexyl-2-trimethylyl-1H-benzo[d]imidazol- Synthesis of 4-amines

[0166]

[0167] Inside the glove box, add 9-bromo-2,7-di-tert-butylanthracene (0.121 g, 0.33 mmol), 1-hexyl-2-trimethyl-1H-benzo[d]imidazol-4-amine (0.100 g, 0.30 mmol), Pd(BINAP) (0.030 g, 0.03 mmol), and NaO to a 20 mL vial. tBu (0.072 g, 0.75 mmol) and toluene (8 mL). The vials were heated to 100 °C for 6 hours and examined by LC-MS. The product was confirmed by LC-MS. Water and EtOAc were added, the organic layer was collected, and all volatiles were removed. The crude product was purified by column chromatography (hexane:EtOAc 80:20). 1 ¹H NMR revealed some residual impurities. The sample was purified by supercritical CO₂ column chromatography to obtain the pure product. Yield: 0.027 g, 15%.

[0168] 1 H NMR (400MHz, CDCl3) δ8.36 (s, 1H), 8.32-8.26 (m, 2H), 8.03 (d, J = 8.9Hz, 2H), 7.61 (dd ,J=8.9,1.9Hz,2H),7.54(s,1H),7.10(s,2H),6.96(t,J=7.9Hz,1H),6.86(dd,J=8.1 ,0.9Hz,1H),6.08(dd,J=7.8,0.9Hz,1H),4.02-3.90(m,2H),2.46(s,3H),2.26(s,6H ), 1.79 (h, J = 9.6, 8.6 Hz, 2H), 1.39 (s, 18H), 1.36-1.24 (m, 2H), 0.91 (t, J = 6.7 Hz, 3H).

[0169] 13 C NMR (101MHz, CDCl3) δ150.55,147.60,140.27,139.36,138.21,134.95,133.25,132.10,130.54,129.02,128.43,128.22,127 .33,124.49,123.72,123.24,118.73,104.25,99.54,44.31,35.15,31.28,30.99,29.52,26.54,22.43,21.34,19.94,13.97.

[0170] Example 12 – Synthesis of 1-hexyl-N-(2-isopropylphenyl)-2-trimethylmethyl-1H-benzo[d]imidazol-4-amine become

[0171]

[0172] Inside the glove box, add 1-bromo-2-isopropylbenzene (0.065 g, 0.33 mmol), 1-hexyl-2-trimethyl-1H-benzo[d]imidazol-4-amine (0.100 g, 0.30 mmol), Pd(BINAP) (0.030 g, 0.03 mmol), and NaO to a 20 mL vial.t Bu (0.072 g, 0.75 mmol) and toluene (8 mL). The vials were heated to 100 °C for 6 hours and examined by LC-MS. The product was confirmed by LC-MS. Water and EtOAc were added, the organic layer was collected, and all volatiles were removed. The crude product was purified by column chromatography (hexane:EtOAc 80:20). 1 ¹H NMR revealed some residual impurities. The sample was purified by supercritical CO₂ column chromatography to obtain the pure product. Yield: 0.112 g, 83%.

[0173] 1 H NMR (400MHz, CDCl3) δ7.60 (dd, J=7.8, 1.5Hz, 1H), 7.43 (dd, J=7.6, 1.7Hz, 1H), 7.27 (td, J=7.5, 1.9Hz,1H),7.20(td,J=7.5,1.5Hz,1H),7.17(d,J=7.9Hz,1H),7.06(s,2H),6.92(dd,J=8.0,0.9 Hz,1H),6.81(s,1H),6.78(dd,J=7.9,0.9Hz,1H),3.98-3.84(m,2H),3.46(G,J=6.8Hz,1H),2.4 3(s,3H),2.19(s,6H),1.84-1.68(m,2H),1.32(d,J=6.9Hz,6H),1.29(m,4H),0.96-0.86(m,3H).

[0174] 13 C NMR (101MHz, CDCl3) δ150.58,142.73,139.39,138.88,138.20,138.12,135.17,132.75,128.49,127.30,126.31,126 .22,124.28,124.08,123.20,103.40,100.08,44.29,31.29,29.54,27.66,26.55,23.47,22.47,21.34,20.03,14.03.

[0175] Example 1: Synthesis of 3–4-bromo-1-butyl-2-(naphth-1-yl)-1H-benzo[d]imidazole

[0176]

[0177] 3-Bromo-N-methyl ... 11,2-Butylphenyl-1,2-diamine (1.62 g, 6.66 mmol), 1-naphthaldehyde (0.91 mL, 6.66 mmol), and EtOH (50 mL, anhydrous) were added. The mixture was heated to 70 °C for 15 hours. All volatiles were removed, and then CH₂Cl₂ (50 mL), K₂CO₃ (2.03 g, 14.66 mmol), and I₂ (1.69 g, 6.66 mmol) were added, and the mixture was stirred for 3 hours. Water was added to the mixture, and the organic layer was collected. The crude product was purified by column chromatography (60:40 hexane:EtOAc, second product). Yield: 1.84 g, 73%.

[0178] 1 H NMR (400MHz, CDCl3) δ8.03 (dt, J=8.3, 1.2Hz, 1H), 7.96-7.91 (m, 1H), 7.70 (dt, J=7. 0,1.2Hz,1H),7.60(dtd,J=7.1,4.4,3.5,2.3Hz,2H),7.57-7.50(m,2H),7.47(dq,J= 8.3,1.8,1.4Hz,1H),7.44(dd,J=8.0,1.0Hz,1H),7.23(tt,J=7.9,1.5Hz,1H),3.98 (t,J=7.4Hz,2H),1.69-1.49(m,2H),1.19-0.99(m,2H),0.67(tt,J=7.4,1.5Hz,3H).

[0179] 13 C NMR (101MHz, CDCl3) δ153.27,142.13,135.53,133.47,132.29,130.46,128.97,128.40,127.76 ,127.20,126.45,125.34,124.98,123.58,113.60,109.51,109.49,44.76,31.63,19.70,13.37.

[0180] Example 14 – Synthesis of 4-bromo-1-butyl-2-isopropyl-1H-benzo[d]imidazole

[0181]

[0182] 3-Bromo-N-methyl ... 11,2-Butylphenyl-1,2-diamine (1.50 g, 6.17 mmol), isobutyraldehyde (0.56 mL, 6.17 mmol), and EtOH (50 mL, anhydrous) were added. The mixture was heated to 70 °C for 15 hours. All volatiles were removed, and then CH₂Cl₂ (50 mL), K₂CO₃ (1.88 g, 13.57 mmol), and I₂ (1.57 g, 6.17 mmol) were added, and the mixture was stirred for 3 hours. Water was added to the mixture, and the organic layer was collected. The crude product was purified by column chromatography (60:40 hexane:EtOAc, second product). Yield: 1.55 g, 89%.

[0183] 1 H NMR (400MHz, CDCl3) δ7.39(dd,J=7.7,0.9Hz,1H),7.24(dd,J=8.0,1.0Hz,1H),7.06(t,J=7.9Hz,1H),4.13-4.05(m,2H),3. 20 (G, J=6.9Hz, 1H), 1.76 (tt, J=9.2, 6.8Hz, 2H), 1.47 (d, J=6.9Hz, 6H), 1.39 (dt, J=14.8, 7.4Hz, 4H), 0.97 (t, J=7.4Hz, 3H).

[0184] 13 C NMR (101MHz, CDCl3) δ160.44,141.54,135.61,124.64,122.64,112.85,108.68,43.68,32.15,26.74,21.71,20.19,13.76.

[0185] Example 15 – Synthesis of 4-bromo-1-butyl-1,3-dihydro-2H-benzo[d]imidazol-2-one

[0186]

[0187] Add 3-bromo-N to a 20 mL vial 1 1,2-Butylbenzene-1,2-diamine (0.589 g, 2.42 mmol) and THF (10 mL, non-anhydrous). 1,1'-Carbonyldiimidazole (0.393 g, 2.42 mmol) was added, and the mixture was heated to 55 °C for 15 hours. All volatiles were removed, and the crude product was purified by column chromatography (hexane:EtOAc 60:40) to obtain the pure product. Yield: 0.493 g, 76%.

[0188] 1H NMR (400MHz, CDCl3) δ9.45(s,1H),7.20(dd,J=7.9,1.2Hz,1H),6.99(t,J=7.9Hz,1H),6.94(dt,J=7 .9,1.0Hz,1H),3.90(t,J=7.2Hz,2H),1.89-1.68(m,2H),1.60-1.28(m,2H),0.98(t,J=7.4Hz,3H).

[0189] 13 C NMR (101MHz, CDCl3) δ154.61,131.17,127.63,123.95,122.34,106.76,102.29,41.02,30.37,20.05,13.72.

[0190] Example 16 – Synthesis of 4-bromo-1-butyl-2-chloro-1H-benzo[d]imidazole

[0191]

[0192] 4-Bromo-1-butyl-1,3-dihydro-2H-benzo[d]imidazol-2-one (0.493 g, 1.83 mmol) and POCl3 (2.05 mL, 21.98 mmol) were added to a 20 mL vial. The purified mixture was heated overnight at 100 °C under nitrogen. The reaction was cooled, and CH2Cl2 (8 mL) was added, followed by the slow addition of water (quenching was initially slow but became very rapid over time). The organic layer was collected and dried over Na2SO4. The solid was filtered off, and all volatiles were removed. NMR showed a good crude product. No further purification was required. Yield: 0.498 g, 95%.

[0193] 1 H NMR (400MHz, CDCl3) δ7.34 (dd, J=7.8, 0.9Hz, 1H), 7.18 (dd, J=8.1, 0.9Hz, 1H), 7.06 (t, J=8.0Hz, 1H), 4.08 (t, J = 7.3Hz, 2H), 1.69 (dq, J = 9.2, 7.3Hz, 2H), 1.37-1.19 (m, 2H), 0.86 (t, J = 7.4Hz, 3H).

[0194] 13 C NMR (101MHz, CDCl3) δ141.07,139.59,135.04,125.90,124.23,112.02,109.06,44.91,31.18,19.82,13.55.

[0195] Example 17 – Synthesis of 9-(4-bromo-1-butyl-1H-benzo[d]imidazol-2-yl)-3,6-di-tert-butyl-9H-carbazole become

[0196]

[0197] In a glove box, add NaH (0.031 g, 1.31 mmol) to a 20 mL vial. Remove the vial from the glove box and add a 6 mL solution of DMF containing 3,6-di-tert-butyl-9H-carbazole (Cbz, 0.365 g, 1.31 mmol) and 4-bromo-1-butyl-2-chloro-1H-benzo[d]imidazole (0.365 g, 0.65 mmol). Heat the vial to 120 °C over the weekend. Add hexane and water and collect the organic layer. Remove all volatiles and purify the crude product by column chromatography (hexane:EtOAc, 90:10). The product and the starting material Cbz were almost co-eluted. Yield: 0.064 g, 18%.

[0198] 1 H NMR (400MHz, CDCl3) δ8.12(dd,J=2.0,0.7Hz,2H),7.59(dd,J=7.8,0.9Hz,1H),7.52-7.44(m,3H),7.28(t,J=8.0Hz,1H),7.2 6(dd,J=8.5,J=0.6Hz,2H),4.08(t,J=7.1Hz,2H),1.45(s,18H),1.37-1.25(m,2H),1.06-0.95(m,2H),0.61(t,J=7.4Hz,3H).

[0199] 13 C NMR (101MHz, CDCl3) δ145.48,144.43,140.93,138.96,134.79,125.79,124.34,124.2 2,123.88,116.40,113.82,110.25,109.61,44.63,34.81,31.95,31.12,19.56,13.20.

[0200] Example 18 – 1-Butyl-2-(3,6-di-tert-butyl-9H-carbazole-9-yl)-N-(o-tolyl)-1H-benzo[d] Synthesis of imidazole-4-amine

[0201]

[0202] Inside a glove box, o-toluidine (0.014 g, 0.13 mmol), 9-(4-bromo-1-butyl-1H-benzo[d]imidazol-2-yl)-3,6-di-tert-butyl-9H-carbazole (0.064 g, 0.12 mmol), Pd(BINAP) (0.006 g, 0.01 mmol), NaOtBu (0.029 g, 0.30 mmol), and toluene (8 mL) were added to a 20 mL vial. The vial was heated to 100 °C for 6 hours and examined by LC-MS. The product was confirmed by LC-MS. Water and EtOAc were added, the organic layer was collected, and all volatiles were removed. The crude product was purified by column chromatography (hexane:EtOAc 90:10). Some residual impurities were found by 1H NMR, but the product was tested in PPR anyway. Yield: 0.050 g, 74%.

[0203] 1 H NMR (400MHz, CDCl3) δ8.20 (d, J=1.9Hz, 2H), 7.63-7.57 (m, 1H), 7.54 (dd, J=8.6, 1. 9Hz,2H),7.32-7.25(m,5H),7.07(td,J=7.4,1.2Hz,1H),6.99(dd,J=8.1,0.8Hz,1 H),6.95(dd,J=7.9,0.8Hz,1H),6.69(s,1H),4.07(t,J=7.2Hz,2H),2.39(s,3H),1 .71-1.59(m,3H),1.53(s,18H),1.11(dq,J=9.5,7.4Hz,2H),0.67(t,J=7.4Hz,3H).

[0204] 13 C NMR (101MHz, CDCl3) δ144.24,142.63,140.03,139.37,137.06,134.96,131.57,131.05,130.71,126.63,124.35,1 24.10,124.07,123.15,121.42,116.48,110.08,104.48,100.70,44.25,34.86,32.03,31.33,19.72,18.08,13.30.

[0205] High-throughput synthesis using the CM3 liquid processor - General procedures of Examples 15 to 30

[0206] High-throughput sequences starting from CM3 operations are used to provide bromides and amines for Buchwald-Hartwig cross-coupling reactions.

[0207] The bromination starting material was provided and reacted with excess amine (2:1). All reactants / reagents were delivered in solution (toluene), except for sodium tert-butoxide and the catalyst (each weighed as a solid). The reaction was diluted to 10 mL with a separate reaction solvent and then allowed to proceed overnight. The reaction conversion was examined by UPLC the following day. After reacting at 95 °C for 16 hours, the conversion was high enough for purification.

[0208] Purification consists of three steps: liquid / liquid extraction, stoppered filtration, and supercritical fluid chromatography (SFC). After removing the vial from the glove box, add 5 mL of chloroform and 5 mL of saturated sodium chloride solution to the reaction vial. Cap the vial, shake to expel gas quickly, and then pour in 25 mL of Biotage. In a phase separation column, add another 5 mL of chloroform and collect the organic phase after gravity filtration. Pour the collected material into a GL Sciences 20 mL InertSep PS-SL filter and filter again by gravity. Similarly, wash once with 5 mL of chloroform to rinse the phase separation column and the InertSep filter. Perform a final wash of the silica pad with 5 mL of ethyl acetate and concentrate the collected sample at 80 °C under vacuum on a Savant SpeedVac for more than 10 hours, with the Savant SpeedVac changing at a rate of 5 Torr / min. Purify the solid on an SFC.

[0209] Use 1-AA A 5 μm OBD 30 mm × 150 mm column was used with CO2 as the mobile phase A and 75% acetonitrile:25% isopropanol as the mobile phase B. Purification was performed using a preparative SFC. The gradient used was 5% B to 50% B over 10 minutes, with a total flow rate of 100 mL / min. The collection replenishment solvent used was ethyl acetate, the BPR pressure was 100 bar, the oven temperature was 40 °C, the sample concentration was 50 mg / mL, and the injection volume was 960 μL. The desired compounds were identified by mass spectrometry.

[0210] Example 19 – 1-Butyl-2-isopropyl-N-(2-isopropylphenyl)-1H-benzo[d]imidazol-4-amine

[0211]

[0212] Using the "CM3 Synthesis General Procedure". Yield: 0.096 g, 54%.

[0213] 1H NMR (400MHz, CDCl3) δ7.57 (dd, J=7.9, 1.4Hz, 1H), 7.44 (dd, J=7.6, 1.7Hz, 1H), 7.26 (td, J=7.6, 1.8Hz ,1H),7.19(td,J=7.4,1.5Hz,1H),7.12(t,J=7.9Hz,1H),6.83(dd,J=8.0,0.9Hz,1H),6.79(s,2H),6.7 6(dd,J=7.9,0.9Hz,2H),4.22-4.08(m,2H),3.46(G,J=6.8Hz,1H),3.28(G,J=6.9Hz,1H),1.89(tt,J=9 .1,6.8Hz,2H),1.55(d,J=6.8Hz,6H),1.55-1.45(m,4H),1.37(d,J=6.8Hz,6H),1.07(t,J=7.4Hz,3H).

[0214] 13 C NMR (101MHz, CDCl3) δ157.48,142.02,139.19,137.40,135.50,132.21,126.33,126.12,123. 81,123.22,122.73,103.73,99.81,43.53,32.34,27.75,26.59,23.37,22.01,20.35,13.89.

[0215] Example 20 – 1-Butyl-2-isopropyl-N-(trimethylsilylmethyl)-1H-benzo[d]imidazol-4-amine synthesis

[0216]

[0217] Using the "CM3 Synthesis General Procedure". Yield: 0.061 g, 34%.

[0218] 1 H NMR (400MHz, CDCl3) δ7.15(t,J=7.9Hz,1H),6.66(dd,J=8.1,0.9Hz,1H),6.48(dd,J=7.8,0.8Hz,1H),4.88(s,1H),4.14-4.02(m,2H ), 3.29-3.08(m,1H),2.72(s,2H),1.90-1.72(m,2H),1.47(d,J=6.8Hz,6H),1.46-1.38(m,4H),1.01(t,J=7.4Hz,3H),0.25(s,9H).

[0219] 13¹³C NMR (101 MHz, CDCl₃) δ 156.52, 142.47, 134.77, 123.32, 100.57, 97.70, 43.41, 33.25, 32.26, 26.48, 21.92, 20.26, 13.82, -2.37.

[0220] Example 21 – Synthesis of 1-Butyl-2-(naphth-1-yl)-N-(o-tolyl)-1H-benzo[d]imidazol-4-amine

[0221]

[0222] The "General Procedure for CM3 Synthesis" was used. Yield: 0.110 g, 51%.

[0223] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.05 (dt, J=8.2, 1.1 Hz, 1H), 8.00-7.94 (m, 1H), 7.76-7.70 (m, 2H), 7.64 (dd, J=8.2, 7.0 Hz, 1H), 7.57 (ddd, J=8.1, 6.7, 1.4 Hz, 2H), 7.51 (ddd, J=8.2, 6.8, 1.4 Hz, 1H), 7.28-7.24 (m, 1H), 7.24-7.17 (m, 2H), 7.04 (td, J=7.4, 1.3 Hz, 1H), 6.95 (dd, J=8.1, 0.9 Hz, 1H), 6.89 (dd, J=7.9, 0.9 Hz, 1H), 6.73 (s, 1H), 3.99 (t, J=7.4 Hz, 2H), 2.37 (s, 3H), 1.66 (tt, J=9.0, 6.8 Hz, 2H), 1.13 (sept, J=7.7 Hz, 2H), 0.71 (t, J=7.4 Hz, 3H).

[0224] 13 ¹³C NMR (101 MHz, CDCl₃) δ 150.41, 140.23, 136.89, 135.61, 133.64, 132.99, 132.52, 130.98, 130.69, 130.23, 128.82, 128.38, 127.13, 126.55, 126.45, 125.54, 125.08, 123.64, 122.97, 121.45, 104.31, 100.55, 44.51, 31.73, 19.78, 18.08, 13.41.

[0225] Example 22 – Synthesis of 1-butyl-N-(3,5-di-tert-butylphenyl)-2-isopropyl-1H-benzo[d]imidazol-4-amine become

[0226]

[0227] Using the "CM3 Synthesis General Procedure". Yield: 0.112 g, 62%.

[0228] 1 H NMR (400MHz, CDCl3) δ7.31 (d, J = 1.7Hz, 2H), 7.22-7.18 (m, 2H), 7.16 (q, J = 2.3, 1.7Hz, 1H), 7.13 (s, 1H), 6.88 (h, J = 4.0Hz, 1H), 4.23-4.10 (m, 2 H), 3.28 (G, J=6.9Hz, 1H), 1.89 (tt, J=9.1, 6.8Hz, 2H), 1.55 (d, J=6.9Hz, 6H), 1.50 (dd, J=8.6, 6.5Hz, 4H), 1.45 (s, 18H), 1.07 (t, J=7.4Hz, 3H).

[0229] 13 C NMR (101MHz, CDCl3) δ157.54,151.64,141.55,135.82,135.56,132.40,122.78,115. 71,114.21,103.80,100.14,43.51,35.00,32.35,31.61,26.55,22.06,20.33,13.89.

[0230] Example 23 – Synthesis of N-(adamantane-1-yl)-1-butyl-2-isopropyl-1H-benzo[d]imidazol-4-amine

[0231]

[0232] Using the "CM3 Synthesis General Procedure". Yield: 0.012 g, 7%.

[0233] 1 ¹H NMR (400MHz, CDCl₃) δ 7.11–6.94 (m, 1H), 6.69 (d, J = 7.9 Hz, 1H), 6.61 (d, J = 7.9 Hz, 1H), 4.93 (br s, 1H), 4.10–4.00 (m, 2H), 3.16 (heptane, J = 6.7 Hz, 1H), 2.21–2.11 (m, 9H), 1.84–1.71 (m, 8H), 1.44 (d, J = 6.9 Hz, 6H), 1.42–1.36 (m, 2H), 0.98 (t, J = 7.3 Hz, 3H). Due to the small sample size, no further information was obtained. 13 C NMR data.

[0234] Example 24 – Synthesis of 1-Butyl-N-cyclohexyl-2-isopropyl-1H-benzo[d]imidazol-4-amine

[0235]

[0236] Using the "CM3 Synthesis General Procedure". Yield: 0.085 g, 47%.

[0237] 1 H NMR (400MHz, CDCl3) δ7.12(t,J=7.9Hz,1H),6.65(dd,J=8.0,0.9Hz,1H),6.48-6.36(m,1H),4.89(s,1H),4.15-4.02(m,2H),3.48(t,J=9 .2Hz, 1H), 3.21 (G, J = 6.9Hz, 1H), 2.29-2.16 (m, 2H), 1.94-1.68 (m, 5H), 1.48 (d, J = 6.9Hz, 6H), 1.47-1.28 (m, 6H), 1.02 (t, J = 7.4Hz, 3H).

[0238] 13 C NMR (101MHz, CDCl3) δ156.57,139.40,135.18,131.04,123.15,100.72,97. 44,51.62,43.38,33.53,32.28,26.50,26.12,25.39,21.98,20.29,13.84.

[0239] Example 25 – Synthesis of 1-butyl-2-isopropyl-N-(2,3,5,6-tetrafluorophenyl)-1H-benzo[d]imidazol-4-amine become

[0240]

[0241] Using the "CM3 Synthesis General Procedure". Yield: 0.056 g, 31%.

[0242] 1 H NMR (400MHz, CDCl3) δ7.13(t,J=7.9Hz,1H),6.95(dd,J=8.1,0.8Hz,1H),6.87-6.75(m,2H),6.55(dt,J=7.0,3.2Hz,1H),4.20-4.0 6(m,2H),3.31-3.17(m,J=6.8Hz,1H),1.83(tt,J=9.2,6.8Hz,2H),1.49(d,J=6.9Hz,6H),1.48-1.39(m,2H),1.02(t,J=7.4Hz,3H).

[0243] 13C NMR (101MHz, CDCl3) δ158.46,145.17-147.83(m),139.46-142.06(m),135.45,133.13,132. 90,122.27,105.53,102.60,98.79(t,J=23.2Hz),43.55,32.25,26.53,21.90,20.25,13.76.

[0244] Example 26 – Synthesis of 1-Butyl-2-(naphth-1-yl)-N-neopentyl-1H-benzo[d]imidazol-4-amine

[0245]

[0246] Using the "CM3 Synthesis General Procedure". Yield: 0.091 g, 45%.

[0247] 1 H NMR(400MHz, CDCl3)δ8.05(dt,J=8.2,1.1Hz,1H),8.01-7.94(m,1H),7.76-7.69(m,2H),7.64(dd,J=8 .2,7.0Hz,1H),7.57(ddd,J=8.2,6.8,1.4Hz,1H),7.50(ddd,J=8.3,6.8,1.4Hz,1H),7.27(t,J=8.0Hz, 1H),6.82(dd,J=8.1,0.9Hz,1H),6.56(dd,J=7.9,0.8Hz,1H),5.19(t,J=6.1Hz,1H),3.97(t,J=7.4Hz ,2H),3.19(d,J=5.0Hz,2H),1.79-1.53(m,2H),1.19-1.12(m,2H),1.11(s,9H),0.71(t,J=7.4Hz,3H).

[0248] 13 C NMR (101MHz, CDCl3) δ149.54,141.80,135.15,133.67,132.68,131.89,130.10,128.86,128.67,128.36,1 27.06,126.41,125.65,125.12,124.22,100.78,98.06,55.69,44.39,32.46,31.76,27.84,19.79,13.45.

[0249] Example 27 – 1-Butyl-2-(naphth-1-yl)-N-(trimethylsilylmethyl)-1H-benzo[d]imidazol-4- Amine Synthesis

[0250]

[0251] Using the "CM3 Synthesis General Procedure". Yield: 0.074 g, 37%.

[0252] 1 H NMR(400MHz, CDCl3)δ8.04(dt,J=8.2,1.1Hz,1H),8.00-7.94(m,1H),7.74-7.68(m,2H),7.64(d d,J=8.2,7.0Hz,1H),7.56(ddd,J=8.2,6.8,1.3Hz,1H),7.49(ddd,J=8.2,6.8,1.4Hz,1H),7.31( t,J=8.0Hz,1H),6.84(dd,J=8.2,0.9Hz,1H),6.62(dd,J=7.9,0.9Hz,1H),5.02(s,1H),4.03-3.8 7(m,2H),2.78(s,2H),1.77-1.48(m,2H),1.18-1.06(m,2H),0.71(t,J=7.3Hz,3H),0.23(s,9H).

[0253] 13 C NMR (101MHz, CDCl3) δ149.49,143.01,135.03,133.67,132.67,131.87,130.10,128.89,128.66,128.3 5,127.03,126.40,125.65,125.12,124.28,100.84,98.27,44.38,33.43,31.74,19.77,13.45,-2.37.

[0254] Example 28 – Synthesis of 1-butyl-N-(2-isopropylphenyl)-2-(naphth-1-yl)-1H-benzo[d]imidazol-4-amine become

[0255]

[0256] Using the "CM3 Synthesis General Procedure". Yield: 0.084 g, 42%.

[0257] 1H NMR(400MHz, CDCl3)δ8.08(dt,J=8.2,1.1Hz,1H),8.04-7.97(m,1H),7.84-7.74(m,2H),7.68(dd, J=8.3,7.0Hz,1H),7.64-7.51(m,3H),7.44(dd,J=7.6,1.7Hz,1H),7.33-7.18(m,3H),6.96(dd,J= 8.1,0.8Hz,1H),6.83(s,1H),6.79(dd,J=7.9,0.9Hz,1H),4.03(t,J=7.4Hz,2H),3.47(G,J=6.8Hz ,1H),1.78-1.62(m,2H),1.31(d,J=6.9Hz,6H),1.17(dd,J=6.9,4.5Hz,2H),0.75(t,J=7.4Hz,3H).

[0258] 13 C NMR (101MHz, CDCl3) δ150.32,143.10,138.71,138.40,135.60,133.69,132.76,132.59,130.25,128.88,128.50,128.45,127.1 7,126.50,126.39,126.27,125.63,125.14,124.54,124.41,123.80,103.64,100.07,44.55,31.79,27.68,23.51,19.84,13.48.

[0259] Example 29 – Synthesis of N-(adamantane-1-yl)-1-butyl-2-(naphthyl-1-yl)-1H-benzo[d]imidazol-4-amine

[0260]

[0261] Using the "CM3 Synthesis General Procedure". Yield: 0.063 g, 31%.

[0262] 1H NMR (400MHz, CDCl3) δ8.03 (dt, J=8.2, 1.1Hz, 1H), 7.98-7.93 (m, 1H), 7.72-7.66 (m, 2H), 7.62 (dd, J= 8.2,7.0Hz,1H),7.55(ddd,J=8.2,6.8,1.3Hz,1H),7.48(ddd,J=8.3,6.8,1.4Hz,1H),7.19(t,J=8.0 Hz,1H),6.84(dd,J=8.0,0.8Hz,1H),6.79(dd,J=8.1,0.8Hz,1H),5.10(s,1H),3.93(t,J=7.4Hz,2H) ,2.19(s,9H),1.77(t,J=2.6Hz,6H),1.68-1.55(m,2H),1.11(h,J=7.4Hz,2H),0.69(t,J=7.4Hz,3H).

[0263] 13 C NMR (101MHz, CDCl3) δ149.37,138.94,135.11,133.64,133.14,132.66,130.06,128.86,128.62,128.30,127. 00,126.38,125.67,125.08,123.60,104.93,98.23,51.80,44.34,42.78,36.68,31.72,29.83,19.77,13.42.

[0264] Example 30 – Synthesis of 1-Butyl-N-cyclohexyl-2-(naphth-1-yl)-1H-benzo[d]imidazol-4-amine

[0265]

[0266] Using the "CM3 Synthesis General Procedure". Yield: 0.054 g, 27%.

[0267] 1H NMR(400MHz, CDCl3)δ8.03(dt,J=8.2,1.1Hz,1H),7.99-7.94(m,1H),7.73-7.67(m,2H),7.62(dd,J=8.2,7.0Hz,1 H),7.55(ddd,J=8.2,6.8,1.4Hz,1H),7.48(ddd,J=8.3,6.8,1.4Hz,1H),7.24(t,J=8.0Hz,1H),6.79(dd,J=8.1,0. 8Hz,1H),6.56-6.47(m,1H),5.03(s,1H),3.97(q,J=7.8,7.4Hz,2H),3.61-3.42(m,1H),2.24(dd,J=12.5,4.0Hz, 2H),1.85(dp,J=10.9,3.6Hz,2H),1.76-1.56(m,3H),1.54-1.22(m,5H),1.16-1.05(m,2H),0.70(t,J=7.3Hz,3H).

[0268] 13 C NMR (101MHz, CDCl3) δ149.53,139.85,135.28,133.63,132.64,131.88,130.06,128.82,128.63,128.33,127. 05,126.38,125.63,125.07,124.20,101.04,97.92,51.64,44.38,33.50,31.74,26.03,25.32,19.77,13.43.

[0269] Example 31 – Synthesis of 1-Butyl-2-(naphth-1-yl)-N-(o-tolyl)-1H-benzo[d]imidazol-4-amine

[0270]

[0271] Using the "CM3 Synthesis General Procedure". Yield: 0.070 g, 35%.

[0272] 1H NMR(400MHz, CDCl3)δ8.08(dt,J=8.3,1.1Hz,1H),8.03-7.97(m,1H),7.78(td ,J=7.2,1.3Hz,2H),7.70-7.51(m,4H),7.34-7.23(m,3H),7.08(td,J=7.4,1. 3Hz,1H),6.99(ddd,J=11.0,8.0,0.9Hz,2H),6.83(s,1H),4.04(t,J=7.4Hz,2 H), 2.43 (s, 3H), 1.76-1.63 (m, 2H), 1.24-1.10 (m, 2H), 0.75 (t, J = 7.4Hz, 3H).

[0273] 13 C NMR (101MHz, CDCl3) δ150.46,140.32,136.92,135.69,133.69,133.10,132.57,131.06,130.65,130.29,128.88,128.46,12 8.44,127.20,126.62,126.51,125.59,125.14,123.72,123.00,121.39,104.41,100.66,44.55,31.78,19.83,18.16,13.48.

[0274] Example 32 – 1-Butyl-2-(naphth-1-yl)-N-(2,3,5,6-tetrafluorophenyl)-1H-benzo[d]imidazol-4-amine Synthesis

[0275]

[0276] Using the "CM3 Synthesis General Procedure". Yield: 0.045 g, 22%.

[0277] 1H NMR (400MHz, CDCl3) δ8.06 (dt, J=8.2, 1.1Hz, 1H), 7.98 (dd, J=8.1, 1.4Hz, 1H), 7.76-7.69 (m, 2H), 7 .65(dd,J=8.2,7.0Hz,1H),7.55(dddd,J=22.7,8.2,6.8,1.4Hz,2H),7.31-7.25(m,1H),7.11(dd,J =8.2,0.8Hz,1H),6.94(s,1H),6.84(tt,J=9.9,7.0Hz,1H),6.65(dt,J=7.2,3.3Hz,1H),4.02(t,J= 7.4Hz, 2H), 1.66 (tdd, J=10.3, 8.0, 4.4Hz, 2H), 1.12 (dd, J=14.9, 7.5Hz, 2H), 0.71 (t, J=7.4Hz, 3H).

[0278] 13 C NMR (101MHz, CDCl3) δ151.19,135.51,133.84,133.63,133.39,132.40,130.39,128.78,128.44,128.04,1 27.27, 126.53, 125.39, 125.05, 123.35, 105.67, 103.04, 99.28 (t, J = 23.1Hz), 44.61, 31.73, 19.77, 13.39.

[0279] Example 33 – 1-Butyl-N-(3,5-di-tert-butylphenyl)-2-(naphth-1-yl)-1H-benzo[d]imidazol-4-amine Synthesis

[0280]

[0281] Using the "CM3 Synthesis General Procedure". Yield: 0.114 g, 57%.

[0282] 1H NMR(400MHz, CDCl3)δ8.08(dt,J=8.3,1.2Hz,1H),8.02-7.97(m,1H),7.80-7.72(m,2 H),7.67(dd,J=8.2,7.0Hz,1H),7.56(dddd,J=21.9,8.3,6.8,1.4Hz,2H),7.37-7.33 (m,2H),7.32(d,J=1.8Hz,3H),7.16(t,J=1.7Hz,1H),7.01(p,J=4.3Hz,1H),4.08-4. 03(m,2H),1.78-1.63(m,2H),1.43(s,18H),1.24-1.11(m,2H),0.75(t,J=7.4Hz,3H).

[0283] 13 C NMR (101MHz, CDCl3) δ151.77,150.31,141.37,136.31,135.58,133.69,132.96,132.57,130.30,128.77,128.45,128.3 4,127.24,126.53,125.53,125.10,123.91,115.88,113.99,103.90,100.61,44.53,35.00,31.79,31.57,19.81,13.48.

[0284] Example 34 – Synthesis of 1-Butyl-N,2-Di(naphthyl-1-yl)-1H-benzo[d]imidazol-4-amine

[0285]

[0286] Using the "CM3 Synthesis General Procedure". Yield: 0.071 g, 31%.

[0287] 1 H NMR (400MHz, CDCl3) δ8.32 (dq, J=7.9, 0.8Hz, 1H), 8.08 (dt, J=8.3, 1.1Hz, 1H ),8.02-7.98(m,1H),7.94-7.90(m,1H),7.83-7.76(m,3H),7.71-7.65(m,2H ),7.63-7.45(m,6H),7.24(t,J=8.0Hz,1H),7.04-6.98(m,2H),4.09-4.02(m ,2H),1.71(tt,J=9.0,6.9Hz,2H),1.23-1.12(m,2H),0.75(t,J=7.4Hz,3H).

[0288] 13C NMR (101MHz, CDCl3) δ150.58,137.93,137.43,135.69,134.82,133.69,133.14,132.56,130.33,128.87,128.70,128.47,128.37,128.35 ,127.25,126.54,126.15,125.97,125.63,125.55,125.14,123.77,1 23.56,122.81,117.69,104.89,100.83,44.58,31.78,19.83,13.48.

[0289] Example 35 – Synthesis of 1-Butyl-2-isopropyl-N-(o-tolyl)-1H-benzo[d]imidazol-4-amine

[0290]

[0291] Using the "CM3 Synthesis General Procedure". Yield: 0.105 g, 58%.

[0292] 1 H NMR (400MHz, CDCl3) δ7.61 (dd, J=8.0, 1.3Hz, 1H), 7.33 (dd, J=7.6, 1.6Hz, 1H), 7.27 (td, J=7.7 ,1.6Hz,1H),7.16(t,J=7.9Hz,1H),7.07(td,J=7.4,1.3Hz,1H),6.92(dd,J=7.9,0.9Hz,1H),6 .87(dd,J=8.1,0.9Hz,1H),6.79(s,1H),4.21-4.09(m,2H),3.27(G,J=6.9Hz,1H),2.47(s,3H) ,1.96-1.81(m,2H),1.55(d,J=6.9Hz,6H),1.50(dt,J=14.8,7.2Hz,2H),1.07(t,J=7.4Hz,3H).

[0293] 13 C NMR (101MHz, CDCl3) δ157.66,140.69,136.08,135.60,132.53,130.95,129.89,126.60,1 22.67,122.41,120.46,104.41,100.34,43.53,32.34,26.59,22.02,20.34,18.17,13.90.

[0294] Example 36 – 1-Butyl-N-(2,6-diisopropylphenyl)-2-(naphth-1-yl)-1H-benzo[d]imidazol-4-amine Synthesis

[0295]

[0296] Inside the glove box, add 2,6-diisopropylaniline (0.105 g, 0.59 mmol), 4-bromo-1-butyl-2-(naphth-1-yl)-1H-benzo[d]imidazole (0.204 g, 0.54 mmol), Pd2dba3 (0.025 g, 0.03 mmol), PCy3 (0.054 mL, 0.05 mmol), and NaO to a 20 mL vial. t Bu (0.129 g, 1.34 mmol) and toluene (8 mL). The vials were heated to 100 °C for 6 hours and examined by LC-MS. The product was confirmed by LC-MS. Water and EtOAc were added, the organic layer was collected, and all volatiles were removed. The crude product was purified by column chromatography (hexane:EtOAc 90:10). Yield: 0.140 g, 55%.

[0297] 1 H NMR (400MHz, CDCl3) δ8.09 (dt, J=8.2, 1.1Hz, 1H), 8.03-7.99 (m, 1H), 7.87 (dq, J=7.4, 0.9Hz, 1H), 7.83 (dd, J=7.0,1.3Hz,1H),7.69(dd,J=8.3,7.0Hz,1H),7.64-7.53(m,2H),7.45-7.39(m,1H),7.39-7.33(m,2H),7.1 6(t,J=7.9Hz,1H),6.90(dd,J=8.1,0.9Hz,1H),6.57(s,1H),6.11(dd,J=7.9,0.9Hz,1H),4.10-4.01(m,2H) ,3.49(G, J=6.9Hz,2H),1.81-1.69(m,2H),1.27(d,J=6.9Hz,12H),1.24-1.16(m,2H),0.77(t,J=7.4Hz,3H).

[0298] 13 C NMR (101MHz, CDCl3) δ149.94,148.21,140.57,135.43,135.03,133.74,132.67,131.58,130.22,128.93,128.63,128.4 8,127.42,127.17,126.49,125.69,125.17,124.02,123.85,102.44,98.90,44.59,31.88,28.29,24.81,19.92,13.50.

[0299] Example 37 – Synthesis of 1-butyl-N-(2,6-diisopropylphenyl)-2-isopropyl-1H-benzo[d]imidazol-4-amine become

[0300]

[0301] In a glove box, a 20 mL vial was charged with 2,6-diisopropylaniline (0.071 g, 0.40 mmol), 1-butyl-N-(2,6-diisopropylphenyl)-2-isopropyl-1H-benzo[d]imidazol-4-amine (0.108 g, 0.37 mmol), Pd₂dba₃ (0.017 g, 0.02 mmol), PCy₃ (0.037 mL, 0.04 mmol), NaO t Bu (0.088 g, 0.91 mmol) and toluene (8 mL). The vial was heated to 100 °C for 6 hours and checked by LC-MS. The product was confirmed by LC-MS. Water and EtOAc were added, the organic layer was collected, and all volatiles were removed. The crude product was purified by column chromatography (hexane:EtOAc 90:10). Yield: 0.109 g, 76%.

[0302] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.40 (dd, J=8.8, 6.4 Hz, 1H), 7.34 (d, J=6.8 Hz, 2H), 7.01 (t, J=7.9 Hz, 1H), 6.74 (d, J=8.0 Hz, 1H), 6.49 (s, 1H), 5.99 (d, J=7.8 Hz, 1H), 4.22-4.10 (m, 2H), 3.42 (h, J=6.9 Hz, 2H), 3.31 (hept, J=7.0 Hz, 1H), 1.92 (tt, J=9.3, 6.8 Hz, 2H), 1.58 (d, J=6.9 Hz, 6H), 1.57-1.49 (m, 2H), 1.25 (d, J=6.9 Hz, 12H), 1.09 (t, J=7.3 Hz, 3H).

[0303] 13 ¹³C NMR (101 MHz, CDCl₃) δ 156.94, 148.01, 140.04, 135.39, 135.28, 130.78, 127.14, 123.76, 122.91, 102.32, 98.43, 43.58, 32.42, 28.17, 26.62, 24.25, 22.09, 20.42, 13.90.

[0304] General procedure for the synthesis of metal complexes

[0305] Inside a glove box, at room temperature, add the ligand solution (0.5 mL, C6D6) (approximately 15 mg, 1 equivalent for mono[2,1] complexes and 2 equivalents for bis[2,1] metal complexes) to solid M(Bn)4 (M = Zr or Hf, approximately 15 mg) over 3 minutes. Rotate the vial after each addition to ensure mixing. After addition, transfer the solution to an NMR tube and pass through... 1 H and 13 C10 NMR analysis. Return the sample to the glove box and remove all volatiles. Allow the ligand and MBn4 to contact each other for approximately 0.5 hours. Remove all volatiles; the crude product is ready for batch reactor testing without further purification. Confirm the 1- or 2-equivalent toluene by NMR based on the ligand:metal ratio.

[0306] Example 38 – Metal-ligand complex 1 (IMLC) of the present invention 1) Synthesis

[0307]

[0308] The general procedure for synthesis using metal complexes.

[0309] 1 H NMR (400MHz, C6D6) δ7.41-7.31(m,1H),7.19-7.07(m,6H),7.07-7.01(m,6H),7.00(d,J=1.5Hz,1H),6.88-6.80(m, 3H),6.75(d,J=1.6Hz,1H),6.62(d,J=1.7Hz,1H),6.56-6.49(m,6H),6.45-6.39(m,1H),6.04(d,J=7.8Hz,1H),3.55 (G, J=6.8Hz,1H),3.40(tt,J=9.2,7.0Hz,2H),2.31-2.13(m,6H),2.11(s,3H),2.03(s,3H),1.85(s,3H),1.45-1.2 9(m,2H),1.21(d,J=6.9Hz,3H),1.15(d,J=6.8Hz,3H),1.06-0.95(m,2H),0.94-0.80(m,4H),0.75(t,J=7.2Hz,3H).

[0310] 13C NMR (101MHz, C6D6) δ151.99,147.04,147.02,145.52,144.85,141.00,138.57,138.40,138. 01,137.52,132.11,131.97,129.92,129.27,129.07,128.97,128.88,128.60,128.31,128.2 0,127.64,126.92,126.88,126.44,126.23,125.33,124.76,124.38,121.90,105.75,98.39,84.92,44.65,30.96,29.11,27.82,26.22,24.94,23.67,22.20,20.78,20.19,19.94,13.72.

[0311] Example 39 – Synthesis of the metal-ligand complex 2 (IMLC 2) of the present invention

[0312]

[0313] The general procedure for synthesis using metal complexes.

[0314] 1 H NMR (400MHz, C6D6) δ7.70(t,J=1.8Hz,1H),7.48(d,J=1.8Hz,2H),7.30(d,J=1.9Hz,3H),7.15-6.90( m,14H),6.79(tt,J=7.3,1.3Hz,3H),6.68-6.59(m,6H),6.53(dd,J=8.1,1.5Hz,1H),6.39(dd,J=8.1 ,0.7Hz,1H),5.97(dd,J=7.9,0.7Hz,1H),3.44(t,J=7.4Hz,2H),3.39(q,J=6.8Hz,1H),2.34(s,6H), 1.36-1.23(m,2H),1.20(s,18H),1.10(d,J=6.7Hz,6H),0.82(h,J=7.4Hz,2H),0.51(t,J=7.3Hz,3H).

[0315] 13C NMR (101MHz, C6D6) δ153.32,152.16,146.94,145.28,145.20,131.81,131.45,129.92,128.96,128.60,128.26,128.19,127.34,126. 54,126.22,125.33,124.65,124.44,124.38,121.73,106.66,98.33,44.48,34.85,31.42,30.95,28.86,25.83,23.89,19.48,13.13.

[0316] Example 40 – Metal-ligand complex 3 (IMLC) of the present invention 3) Synthesis

[0317]

[0318] The general procedure for synthesis using metal complexes.

[0319] 1 H NMR (400MHz, C6D6) δ8.68-8.62(m,2H),8.20(s,1H),7.94(d,J=9.0Hz,2H),7.51(dd,J=8.9,1.9Hz,2H),7.14 -7.05(m,7H),7.05-6.99(m,3H),6.98-6.92(m,3H),6.89(t,J=7.7Hz,6H),6.84(t,J=8.0Hz,2H),6.79(s,2H) ,6.76-6.68(m,3H),6.57-6.49(m,4H),6.44(d,J=8.0Hz,1H),6.26-6.16(m,6H),5.92(d,J=7.7Hz,1H),3.50 -3.36(m,2H),2.23(s,6H),2.10(s,3H),2.06(s,6H),1.33(s,18H),1.02(q,J=7.5Hz,4H),0.78-0.71(m,3H).

[0320] 13C NMR(101MHz,C6D6)δ152.56,148.03,146.32,145.81,141.90,141.09,138.56,138 .38,132.52,131.97,131.25,129.92,129.04,129.02,128.96,128.61,128.20,127 .87,127.53,126.74,125.33,124.44,124.38,124.06,121.67,118.26,106.79,99.14,88.88,83.07,44.68,34.91,30.94,29.06,26.21,22.21,20.82,19.91,13.69.

[0321] Example 41 – Metal-ligand complex 4 (IMLC) of the present invention 4) Synthesis

[0322]

[0323] The general procedure for synthesis using metal complexes.

[0324] 1 H NMR (400MHz, C6D6) δ7.46 (t, J=1.8Hz, 1H), 7.23 (d, J=1.8Hz, 2H), 7.15-7.04 (m, 12H), 7.01 (ddq, J=7. 4,1.4,0.8Hz,2H),6.97-6.92(m,1H),6.87-6.80(m,3H),6.68(dd,J=8.3,1.3Hz,8H),6.55-6.51(m,2 H),6.49(dd,J=8.1,0.7Hz,1H),6.45(dd,J=7.8,0.7Hz,1H),3.37(dd,J=9.0,6.5Hz,2H),2.29(s,6H) ,1.99(s,3H),1.87(s,6H),1.36(s,18H),1.06-0.96(m,2H),0.94-0.79(m,4H),0.74(t,J=7.2Hz,3H).

[0325] 13C NMR(101MHz,C6D6)δ152.46,152.18,148.67,147.16,144.83,140.90,138.56,1 38.06,137.52,133.07,131.80,129.92,128.96,128.82,128.61,128.27,128.19 ,127.79,126.65,125.33,124.81,124.38,122.68,121.86,118.48,105.01,98.11,85.50,44.49,34.81,31.44,30.95,29.01,26.17,22.21,20.74,19.88,13.70.

[0326] Example 42 – Metal-ligand complex 5 (IMLC) of the present invention 5) Synthesis

[0327]

[0328] The general procedure for synthesis using metal complexes.

[0329] 1 H NMR(400MHz,C6D6)δ7.24-6.98(m,21H),6.98-6.86(m,4H),6.82-6.74(m,9H),6.63- 6.57(m,1H),6.56-6.50(m,5H),6.26(d,J=8.1Hz,1H),5.82(d,J=7.8Hz,1H),3.44(d d,J=9.4,7.0Hz,2H),3.11(G,J=7.3Hz,1H),2.45(d,J=2.3Hz,6H),1.95(s,3H),1.42 (p, J=7.9Hz, 2H), 1.06 (d, J=7.3Hz, 6H), 0.98 (h, J=7.4Hz, 2H), 0.69 (t, J=7.4Hz, 3H).

[0330] 13C NMR (101MHz, C6D6) δ157.14,147.47,144.90,144.78,138.57,137.53,135. 46,132.65,131.04,130.60,130.57,129.93,128.97,128.77,128.60,128. 35,128.20,127.36,127.11,125.87,125.76,125.33,124.38,121.74,104.47,98.00,86.14,44.56,31.56,29.17,21.08,20.15,19.81,17.42,13.30.

[0331] Example 43 – Metal-ligand complex 9 (IMLC) of the present invention Synthesis of 9)

[0332]

[0333] The general procedure for synthesis using metal complexes.

[0334] 1 H NMR is too complex to specify. Restricted rotation requires variable-temperature NMR. Due to the low signal-to-noise ratio, it is not possible to... 13 CNMR.

[0335] Example 44 – Metal-ligand complex 6 (IMLC) of the present invention 6) Synthesis

[0336]

[0337] The general procedure for synthesis using metal complexes.

[0338] 1 H NMR (400MHz, C6D6) δ8.38-8.27(m,2H),7.41-6.98(m,16H),6.94(q,J=7.6Hz,8H),6.7 5(t,J=7.3Hz,3H),6.63(dd,J=7.7,1.3Hz,1H),6.56-6.48(m,4H),6.49-6.43(m,6H),6 .03(d,J=7.9Hz,1H),3.24(t,J=7.4Hz,2H),2.17(s,6H),2.13(s,3H),1.30(s,9H),1. 25(s,9H),1.17(dq,J=13.4,6.7,5.8Hz,2H),0.70-0.55(m,2H),0.31(t,J=7.3Hz,3H).

[0339] 13C NMR(101MHz,C6D6)δ147.61,146.45,145.45,144.12,142.01,139.48,139.28,138.54 ,137.48,135.35,131.82,131.24,131.03,130.56,129.87,128.92,128.90,128.56,12 8.29,128.15,125.88,125.28,124.95,124.33,121.93,116.95,110.02,105.28,98.25,85.10,44.10,34.44,31.83,31.76,31.59,31.48,31.43,30.98,19.27,17.61,12.72.

[0340] Example 45 – Synthesis of the metal-ligand complex 8 (IMLC 8) of the present invention

[0341]

[0342] The general procedure for synthesis using metal complexes.

[0343] 1 H NMR (400MHz, C6D6) δ7.20-6.98(m,13H),6.97-6.75(m,11H),6.25(dd,J=8.1,0.7Hz,1H),5.86(dd ,J=7.9,0.7Hz,1H),3.50-3.40(m,2H),3.29(p,J=6.8Hz,2H),3.04(p,J=7.3Hz,1H),2.95-2.13(br s, 6H), 1.40-1.28 (m, 2H), 1.21 (d, J = 6.9Hz, 6H), 1.04 (d, J = 6.7Hz, 6H), 0.96 (d, J = 7.3Hz, 6H), 0.95-0.87 (m, 2H), 0.65 (t, J = 7.3Hz, 3H).

[0344] 13 C NMR (101MHz, C6D6) δ157.54,145.99,145.46,144.40,138.56,137.53,132.85,130.59,130.25,129.92,128.96,128.60,128.46,128. 19,127.27,126.64,125.51,125.32,124.44,121.84,106.26,98.31,44.82,31.40,29.32,28.64,25.88,24.07,20.04,19.81,13.26.

[0345] Example 46 – Metal-ligand complex 7 (IMLC) of the present invention 7) Synthesis

[0346]

[0347] The general procedure for synthesis using metal complexes.

[0348] 1 H NMR(400MHz,C6D6)δ7.60(d,J=8.2Hz,1H),7.53-7.44(m,2H),7.34-7.25(m,3H),7.14-6.99(m,10H),6.95(t,J=7.6Hz,6H ),6.81-6.72(m,3H),6.55(d,J=7.6Hz,6H),6.46(d,J=8.1Hz,1H),6.03(d,J=7.8Hz,1H),3.65(G,J=6.9Hz,1H),3.38(ddd ,J=13.8,8.0,5.5Hz,1H),3.27(p,J=6.7Hz,1H),3.19(dt,J=14.1,7.7Hz,1H),2.26(s,6H),1.34-1.28(m,2H),1.26(d,J= 6.9Hz, 3H), 1.16 (d, J = 6.7Hz, 3H), 1.11 (d, J = 6.8Hz, 3H), 1.08 (d, J = 6.7Hz, 3H), 0.78-0.53 (m, 2H), 0.37 (t, J = 7.3Hz, 3H).

[0349] 13 C NMR(101MHz,C6D6)δ151.32,146.97,145.57,145.19,144.89,137.53,133.41,132.0 7,131.88,131.33,129.94,128.96,128.71,128.60,128.37,128.22,128.20,127.36, 126.92,126.62,126.52,125.41,125.33,125.17,124.62,124.41,124.32,121.74,106.76,98.45,44.68,31.17,28.88,28.72,26.03,25.91,24.03,23.82,19.24,12.97.

[0350] Example 47 – Metal-ligand complex 10 (IMLC) of the present invention Synthesis of 10)

[0351]

[0352] The general procedure for synthesis using metal complexes.

[0353] 1 H NMR (400MHz, C6D6) δ8.31-8.18(m,1H),7.78-7.69(m,2H),7.69-7.18(m,20H),7.13-6.82(m,32H),6.79(t, J=7.2Hz,6H),6.51(d,J=8.1Hz,2H),6.43-6.33(m,8H),6.29(d,J=7.6Hz,5H),5.93(dd,J=12.0,7.7Hz,2H), 3.44(tt,J=14.7,6.7Hz,2H),3.26(q,J=7.0Hz,4H),2.25(d,J=5.2Hz,4H),2.21(s,2H),2.19(s,2H),2.13(s ,2H),1.37(dddd,J=13.6,9.1,7.7,6.0Hz,2H),1.29-1.13(m,2H),0.90-0.60(m,4H),0.46(t,J=7.0Hz,6H).

[0354] 13 C NMR (101MHz, C6D6) δ147.57,144.24,137.53,131.92,131.26,130.56,130.22,128.35,128.20,126.89,126.73,126.26,126.11,125.95,125. 33,124.97,124.79,124.46,124.10,122.10,121.94,105.26,104.77, 97.78,76.18,75.43,72.13,44.49,31.55,31.29,21.07,19.32,13.08.

[0355] Example 48 – Metal-ligand complex 11 (IMLC) of the present invention Synthesis of 11)

[0356]

[0357] The general procedure for synthesis using metal complexes.

[0358] 1H NMR(400MHz,C6D6)δ7.91(d,J=8.3Hz,1H),7.73(dd,J=8.6,4.4Hz,2H),7.69-7.17(m,19 H),7.13-7.08(m,6H),7.08-6.85(m,19H),6.83-6.71(m,5H),5.87(t,J=8.4Hz,1H),3.43 (ddd,J=13.9,7.9,5.8Hz,2H),3.27(dtd,J=14.0,6.9,3.8Hz,2H),2.19-2.12(m,8H),1.2 9(dddt,J=60.0,22.7,15.6,7.2Hz,4H),0.91-0.58(m,4H),0.46(dd,J=20.0,7.3Hz,6H).

[0359] 13 C NMR(101MHz,C6D6)δ151.11,145.82,144.57,137.53,135.26,135.17,133.51,13 1.88,131.48,131.41,128.97,128.23,128.20,128.18,127.56,127.09,126.95,1 26.44,126.12,125.82,125.71,125.33,125.19,125.04,124.87,124.39,121.69,121.61,106.01,105.74,98.22,85.89,44.72,44.57,31.53,31.21,19.36,13.09.

[0360] Example 49 – Metal-ligand complex 12 (IMLC) of the present invention Synthesis of 12)

[0361]

[0362] The general procedure for synthesis using metal complexes.

[0363] 1 H NMR is too complex to be specified. Restricted rotation requires variable temperature NMR.

[0364] 1H NMR(400MHz,C6D6)δ7.75-7.25(m,8H),7.14-6.90(m,13H),6.75(td,J=7.3,1.3Hz,2H),6.60-6.42(m,5H),6.33-6.18(m,2H),3.32-3.2 2(m,2H),3.22-3.01(m,2H),2.25-2.12(m,2H),2.10(s,6H),1.31-1.15(m,1H),1.09-0.91(m,2H),0.72-0.46(m,3H),0.46-0.23(m,6H).

[0365] 13 C NMR (101MHz, C6D6) δ137.53,131.97,131.53,129.82,128.96,126.95,125.32,122. 14,109.17,104.97,99.64,88.42,65.54,44.63,31.16,21.05,19.27,15.22,12.98.

[0366] 19 F NMR(376MHz,C6D6)δ-139.81,-139.84,-139.87,-139.88,-139.91,-139.93,-14 0.21,-141.01,-142.05,-143.40,-145.81,-147.07,-147.13,-148.89,-151.69.

[0367] Example 50 – Metal-ligand complex 13 (IMLC) of the present invention 13) Synthesis

[0368]

[0369] The general procedure for synthesis using metal complexes.

[0370] 1 H NMR is too complex to specify. Restricted rotation requires variable temperature NMR. The signal-to-noise ratio is too low to obtain good results. 13 C NMR.

[0371] 1 H NMR(400MHz,C6D6)δ7.72-7.20(m,10H),7.13-6.86(m,16H),6.83

[0372] -6.32(m,12H),6.31-5.59(m,5H),3.66-3.05(m,4H),2.79-2.43(m,2H),2.40

[0373] -2.14(m,5H),2.11(s,6H),1.81-0.87(m,7H),0.84-0.52(m,4H),0.52-0.16(m,6H).

[0374] Example 51 – Synthesis of 7-bromo-3,3-dimethyl-2-phenyl-3H-indole

[0375]

[0376] Step 1: Add (2-bromophenyl)hydrazine-HCl (6.86 g, 33.7 mmol), toluene (100 mL), NEt3 (4.70 mL, 30.7 mmol), 2,4-dimethylpentan-3-one (5.00 g, 3.7 mmol), and pTSA (20 mg, catalyst) to a 20 mL vial. Heat the reaction to 100 °C for 15 hours. Add aqueous K₂CO₃ and EtOAc, collect the organic layer, and dry it over Na₂SO₄. Filter the solid and remove all volatiles to obtain a yellow oil. Crude NMR shows the desired product and some starting materials. This mixture can be used without further purification.

[0377] Step 2: After washing with water, glacial acetic acid was added to the crude mixture from the previous step and the mixture was heated to 120°C for 3 hours. Crude LC-MS of the product showed a clean Fisher-indole product formation. The reaction was cooled to room temperature, then diethyl ether and water were added, and the organic layer was collected. All volatiles were removed, and the crude product was purified by column chromatography (80:20 hexane:EtOAc). Yield: 0.45 g, 23%.

[0378] 1H NMR (400MHz, CDCl3) δ 8.24–8.18 (m, 2H), 7.59–7.48 (m, 4H), 7.31–7.26 (m, 1H), 7.15 (dd, J = 8.0, 7.3Hz, 1H), 1.62 (s, 6H).

[0379] 13 C NMR (101MHz, CDCl3) δ184.24,151.47,149.30,132.94,131.19,130.93,128.64,128.61,127.16,119.96,115.03,55.33,24.73.

[0380] Example 52 – Synthesis of 3-bromo-N-butyl-2-nitroaniline

[0381]

[0382] 1-Bromo-3-fluoro-2-nitrobenzene (10.00 g, 45.45 mmol), K₂CO₃ (7.54 g, 54.55 mmol), and acetonitrile (100 mL) were added to a 250 mL round-bottom flask. n-BuNH₂ (4.5 mL, 45.45 mmol) was added, and the reaction was stirred at room temperature for 2 days. All volatiles were removed, and the crude product was absorbed in EtOAc and water. The organic layer was collected and dried over Na₂SO₄. The solid was filtered off, and all volatiles were removed to give the product as an orange solid / oil. NMR showed a product-to-starting material ratio of 75:25. This material was ready for the next step without further purification. Yield: 12.20 g, 98%.

[0383] 1 H NMR (400MHz, CDCl3) δ7.15(dd,J=8.5,7.8Hz,1H),6.94(dd,J=7.8,1.1Hz,1H),6.76(dd,J=8.6,1.1Hz,1H),5. 73(s,1H),3.20(td,J=7.1,5.1Hz,2H),1.66(tt,J=8.6,6.8Hz,2H),1.52-1.39(m,2H),0.98(t,J=7.3Hz,3H).

[0384] 13 C NMR (101MHz, CDCl3) δ143.83,132.99,121.39,116.29,112.38,43.23,31.00,20.14,13.76.

[0385] Example 53 – 3-Bromo-N 1 Synthesis of 1,2-butylphenyl-1,2-diamine

[0386]

[0387] 3-Bromo-N-butyl-2-nitroaniline (2.64 g, 9.67 mmol), ethanol (30 mL), and saturated NH4Cl aqueous solution (10 mL) were added to a 100 mL round-bottom flask. The mixture was stirred at room temperature under nitrogen, and then Zn powder (5.06 g, 77.33 mmol) was added in portions. The reaction was monitored by LC-MS. After stirring for 2 hours, EtOAc was added, and the mixture was filtered through diatomaceous earth. The organic layer was collected and purified by column chromatography (80:20 hexane:EtOAc). Yield: 1.72 g, 73%.

[0388] 1H NMR (400MHz, CDCl3) δ6.95(dd,J=8.1,1.3Hz,1H),6.70(t,J=8.0Hz,1H),6.65-6.58(m,1H),3.76(s,2H),3.35( s,1H),3.12(td,J=7.0,3.6Hz,2H),1.68(dtd,J=8.6,7.3,5.9Hz,2H),1.56-1.42(m,2H),1.00(t,J=7.3Hz,3H).

[0389] 13 C NMR (101MHz, CDCl3) δ138.89,132.35,121.60,120.82,111.23,110.41,44.14,31.71,20.41,13.95.

[0390] Example 54 – Synthesis of 4-bromo-1-butyl-2-(2-methylphenyl)-1H-benzo[d]imidazole

[0391]

[0392] 3-Bromo-N-methyl ... 1 1,2-Butylbenzene-1,2-diamine (2.08 g, 8.55 mmol), 2-methylbenzaldehyde (0.99 mL, 8.55 mmol), and EtOH (100 mL, anhydrous) were added. The mixture was heated to 70 °C for 15 hours. All volatiles were removed, and then CH₂Cl₂ (100 mL), K₂CO₃ (2.60 g, 18.8 mmol), and I₂ (2.17 g, 8.55 mmol) were added, and the mixture was stirred for 3 hours. Water was added to the mixture, and the organic layer was collected. The crude product was purified by column chromatography (60:40 hexane:EtOAc, second product). Yield: 2.21 g, 75%.

[0393] 1 H NMR (400MHz, CDCl3): δ7.50(dd,J=7.7,0.9Hz,1H),7.44–7.35(m,3H),7.35–7.29(m,2H),7.18(t,J=7.9 Hz, 1H), 4.04–3.93 (m, 2H), 2.24 (s, 3H), 1.72–1.58 (m, 2H), 1.18 (h, J = 7.4Hz, 2H), 0.79 (t, J = 7.3Hz, 3H).

[0394] 13C NMR (101MHz, CDCl3) δ154.06,141.89,138.03,135.15,130.40,130.25,129.99,12 9.86,125.69,125.18,123.33,113.45,109.35,44.35,31.54,19.77,19.76,13.46.

[0395] Example 55 – Synthesis of 4-bromo-1-butyl-2-(4-tert-butylphenyl)-1H-benzo[d]imidazole

[0396]

[0397] 3-Bromo-N-methyl ... 1 1,2-Butylbenzene-1,2-diamine (1.00 g, 4.11 mmol), 4-tert-butylbenzaldehyde (0.69 mL, 4.11 mmol), and EtOH (100 mL, anhydrous) were added. The mixture was heated to 70 °C for 15 hours. All volatiles were removed, and then CH₂Cl₂ (100 mL), K₂CO₃ (1.25 g, 9.05 mmol), and I₂ (1.04 g, 4.11 mmol) were added, and the mixture was stirred for 3 hours. Water was added to the mixture, and the organic layer was collected. The crude product was purified by column chromatography (60:40 hexane:EtOAc, second product). Yield: 1.11 g, 70%.

[0398] 1 H NMR (400MHz, CDCl3) δ7.59–7.52(m,2H),7.47–7.41(m,2H),7.37(dd,J=7.8,0.9Hz,1H),7.24(dd,J=8.1,0.9Hz,1H) ,7.03(t,J=7.9Hz,1H),4.13–4.07(m,2H),1.74–1.59(m,2H),1.30(s,9H),1.24–1.10(m,2H),0.77(t,J=7.4Hz,3H).

[0399] 13 C NMR (101MHz, CDCl3) δ154.45,153.06,141.84,136.05,129.20,127.20,125.5 7,125.08,123.24,113.16,109.46,44.78,34.79,31.72,31.21,19.82,13.51.

[0400] Example 56 – Synthesis of 4-bromo-1-butyl-1,3-dihydro-2H-benzo[d]imidazol-2-one

[0401]

[0402] Add 3-bromo-N to a 20 mL vial 1 1,2-Butylbenzene-1,2-diamine (0.589 g, 2.42 mmol) and THF (10 mL, non-anhydrous). 1,1'-Carbonyldiimidazole (0.393 g, 2.42 mmol) was added, and the mixture was heated to 55 °C for 15 hours. All volatiles were removed, and the crude product was purified by column chromatography (hexane:EtOAc 60:40) to obtain the pure product. Yield: 0.493 g, 76%.

[0403] 1 H NMR (400MHz, CDCl3) δ9.45(s,1H),7.20(dd,J=7.9,1.2Hz,1H),6.99(t,J=7.9Hz,1H),6.94(dt,J=7 .9,1.0Hz,1H),3.90(t,J=7.2Hz,2H),1.89-1.68(m,2H),1.60-1.28(m,2H),0.98(t,J=7.4Hz,3H).

[0404] 13 C NMR (101MHz, CDCl3) δ154.61,131.17,127.63,123.95,122.34,106.76,102.29,41.02,30.37,20.05,13.72.

[0405] Example 57 – Synthesis of 4-bromo-1-butyl-2-chloro-1H-benzo[d]imidazole

[0406]

[0407] 4-Bromo-1-butyl-1,3-dihydro-2H-benzo[d]imidazol-2-one (0.493 g, 1.83 mmol) and POCl3 (2.05 mL, 21.98 mmol) were added to a 20 mL vial. The purified mixture was heated overnight at 100 °C under nitrogen. The reaction was cooled, and CH2Cl2 (8 mL) was added, followed by the slow addition of water (quenching was initially slow but became very rapid over time). The organic layer was collected and dried over Na2SO4. The solid was filtered off, and all volatiles were removed. NMR showed a good crude product. No further purification was required. Yield: 0.498 g, 95%.

[0408] 1H NMR (400MHz, CDCl3) δ7.34 (dd, J=7.8, 0.9Hz, 1H), 7.18 (dd, J=8.1, 0.9Hz, 1H), 7.06 (t, J=8.0Hz, 1H), 4.08 (t, J = 7.3Hz, 2H), 1.69 (dq, J = 9.2, 7.3Hz, 2H), 1.37-1.19 (m, 2H), 0.86 (t, J = 7.4Hz, 3H).

[0409] 13 C NMR (101MHz, CDCl3) δ141.07,139.59,135.04,125.90,124.23,112.02,109.06,44.91,31.18,19.82,13.55.

[0410] Example 58 – Synthesis of 9-(4-bromo-1-butyl-1H-benzo[d]imidazol-2-yl)-3,6-di-tert-butyl-9H-carbazole become

[0411]

[0412] In a glove box, add NaH (0.031 g, 1.31 mmol) to a 20 mL vial. Remove the vial from the glove box and add a 6 mL solution of DMF containing 3,6-di-tert-butyl-9H-carbazole (Cbz, 0.365 g, 1.31 mmol) and 4-bromo-1-butyl-2-chloro-1H-benzo[d]imidazole (0.365 g, 0.65 mmol). Heat the vial to 120 °C over the weekend. Add hexane and water and collect the organic layer. Remove all volatiles and purify the crude product by column chromatography (hexane:EtOAc, 90:10). The product and the starting material Cbz were almost co-eluted. Yield: 0.064 g, 18%.

[0413] 1 H NMR (400MHz, CDCl3) δ8.12(dd,J=2.0,0.7Hz,2H),7.59(dd,J=7.8,0.9Hz,1H),7.52-7.44(m,3H),7.28(t,J=8.0Hz,1H),7.2 6(dd,J=8.5,J=0.6Hz,2H),4.08(t,J=7.1Hz,2H),1.45(s,18H),1.37-1.25(m,2H),1.06-0.95(m,2H),0.61(t,J=7.4Hz,3H).

[0414] 13C NMR (101MHz, CDCl3) δ145.48,144.43,140.93,138.96,134.79,125.79,124.34,124.2 2,123.88,116.40,113.82,110.25,109.61,44.63,34.81,31.95,31.12,19.56,13.20.

[0415]

[0416] Buckwald- of 9-(4-bromo-1-butyl-1H-benzo[d]imidazol-2-yl)-3,6-di-tert-butyl-9H-carbazole Hartwig's Couplets :

[0417] The Buchwald-Hartwig cross-coupling reaction in high-throughput sequences is initiated with a CM3 operation (Library 75278).

[0418] The bromination starting material was provided and reacted with excess amine (2:1). All reactants / reagents were delivered in solution (toluene), except for sodium tert-butoxide and the catalyst (weighed as solids). The reaction was diluted to 10 mL with a separate reaction solvent and then allowed to proceed overnight. The reaction conversion was checked by UPLC the following day. After reacting at 95 °C for 16 hours, the conversion was high enough for purification.

[0419] Purification consisted of three stages: liquid / liquid extraction, stoppered filtration, and supercritical fluid chromatography (SFC). After removing the vial from the glove box, 5 mL of chloroform and 5 mL of saturated sodium chloride solution were added to the reaction vial. The vial was capped, shaken to expel gas quickly, and then 25 mL of Biotage was added. In a phase separation column, add another 5 mL of chloroform and collect the organic phase after gravity filtration. Pour the collected material into a GL Sciences 20 mL InertSep PS-SL filter and filter again by gravity. Similarly, wash once with 5 mL of chloroform to rinse the phase separation column and then rinse the InertSep filter. Perform a final wash of the silica pad with 5 mL of ethyl acetate and concentrate the collected sample at 80 °C under vacuum on a SavantSpeedVac for more than 10 hours, with the SavantSpeedVac changing at a rate of 5 Torr / min. Deliver the solid back to T. Paine for purification on an SFC.

[0420] Use 1-AA A 5 μm OBD 30 mm × 150 mm column was used with CO2 as the mobile phase A and 75% acetonitrile:25% isopropanol as the mobile phase B. Purification was performed using a preparative SFC. The gradient used was 5% B to 50% B over 10 minutes, with a total flow rate of 100 mL / min. The collection replenishment solvent used was ethyl acetate, the BPR pressure was 100 bar, the oven temperature was 40 °C, the sample concentration was 50 mg / mL, and the injection volume was 960 μL. The desired compounds were collected by mass spectrometry.

[0421] Example 59 – Compound 1

[0422] Yield = 0.114g, 57%.

[0423] 1 H NMR (400MHz, CDCl3) δ8.16 (d, J=1.9Hz, 2H), 7.60–7.55 (m, 1H), 7.51 (dd, J=8.6, 1.9Hz,2H),7.31–7.19(m,5H),7.05(td,J=7.4,1.3Hz,1H),6.96(dd,J=8.2,0.9 Hz,1H),6.92(dd,J=7.9,0.8Hz,1H),6.65(s,1H),4.04(t,J=7.2Hz,2H),2.36(s ,3H),1.68–1.58(m,2H),1.50(s,18H),1.15–0.99(m,2H),0.65(t,J=7.3Hz,3H).

[0424] 13 C NMR (101MHz, CDCl3) δ144.16,142.23,139.42,138.72,137.77,136.67,134.76,130.41,128.43,126.06,1 24.33,124.26,124.03,116.43,110.05,102.57,99.38,44.21,34.83,31.99,31.36,19.76,18.42,13.29.

[0425] Example 60 – Compound 2

[0426] Yield = 0.092g, 46%.

[0427] 1¹H NMR (400 MHz, CDCl₃) δ 8.20–8.10 (m, 2H), 7.57–7.49 (m, 2H), 7.40–7.22 (m, 6H), 7.11 (t, J=8.0 Hz, 1H), 6.84 (dd, J=8.1, 0.9 Hz, 1H), 6.35 (s, 1H), 6.03 (dd, J=8.0, 0.9 Hz, 1H), 4.04 (t, J=7.3 Hz, 2H), 3.36 (hept, J=6.8 Hz, 2H), 1.50 (s, 18H), 1.19 (d, J=6.9 Hz, 12H), 1.10 (dt, J=14.4, 7.2 Hz, 2H), 0.66 (t, J=7.3 Hz, 3H).

[0428] 13 ¹³C NMR (101 MHz, CDCl₃) δ 148.12, 144.14, 142.10, 140.58, 139.40, 134.71, 134.64, 130.01, 127.40, 124.33, 124.29, 124.01, 123.78, 116.44, 110.06, 102.58, 98.91, 44.22, 34.83, 32.00, 31.49, 31.37, 28.19, 19.77, 13.29.

[0429] Example 61 – Compound 4

[0430] Yield = 0.059 g, 29%.

[0431] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.16 (d, J=1.9 Hz, 2H), 7.57–7.49 (m, 2H), 7.33–7.26 (m, 3H), 7.20–7.11 (m, 4H), 6.87 (dd, J=8.1, 0.9 Hz, 1H), 6.40 (s, 1H), 6.06 (dd, J=7.9, 0.9 Hz, 1H), 4.04 (t, J=7.3 Hz, 2H), 2.33 (s, 6H), 1.70–1.59 (m, 2H), 1.50 (s, 18H), 1.17–1.03 (m, 2H), 0.66 (t, J=7.3 Hz, 3H).

[0432] 13C NMR (101MHz, CDCl3) δ144.16,142.23,139.42,138.72,137.77,136.67,134.76,130.40,128.43,126.05,1 24.33,124.26,124.03,116.43,110.05,102.57,99.38,44.21,34.83,31.99,31.35,19.75,18.42,13.29.

[0433] Example 62 – Compound 5

[0434] Yield = 0.099g, 49%.

[0435] 1 H NMR (400MHz, CDCl3) δ8.14(d,J=1.9Hz,2H),7.49(dd,J=8.6,1.9Hz,2H),7.33–7.14(m,4H),6.79(dd,J=8.2,0.8Hz,1H),6.54(d,J=7 .9Hz,1H),5.05(s,1H),3.97(t,J=7.2Hz,2H),3.14(s,2H),1.65–1.51(m,2H),1.49(s,18H),1.07(s+m,9+2H),0.62(t,J=7.3Hz,3H).

[0436] 13 C NMR (101MHz, CDCl3) δ144.04,141.82,141.65,139.39,134.49,130.34,124.57,124.23,123.92, 116.37,110.00,100.94,98.13,55.54,44.05,34.81,32.42,31.99,31.28,27.76,19.67,13.25.

[0437] Example 63 – Compound 6

[0438] Yield = 0.081g, 40%.

[0439] 1¹H NMR (400 MHz, CDCl₃) δ 8.14 (d, J = 1.8 Hz, 2H), 7.49 (dd, J = 8.6, 1.9 Hz, 2H), 7.31 (d, J = 8.0 Hz, 1H), 7.24–7.16 (m, 2H), 6.81 (dd, J = 8.1, 0.9 Hz, 1H), 6.59 (dd, J = 8.0, 0.8 Hz, 1H), 4.84 (s, 1H), 3.95 (t, J = 7.2 Hz, 2H), 2.73 (s, 2H), 1.61–1.51 (m, 2H), 1.49 (s, 18H), 1.09–0.96 (m, 2H), 0.61 (t, J = 7.4 Hz, 3H), 0.19 (s, 9H).

[0440] 13 ¹³C NMR (101 MHz, CDCl₃) δ 144.01, 143.03, 141.57, 139.39, 134.38, 130.35, 124.64, 124.21, 123.89, 116.36, 110.00, 100.97, 98.33, 44.02, 34.81, 33.27, 31.99, 31.27, 19.65, 13.24, -2.45.

[0441] Example 64 – Compound 7

[0442] Yield = 0.109 g, 55%.

[0443] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.16 (d, J = 1.9 Hz, 2H), 7.53 (ddd, J = 8.6, 4.9, 1.7 Hz, 3H), 7.39 (dd, J = 7.6, 1.8 Hz, 1H), 7.31–7.26 (m, 3H), 7.26–7.16 (m, 3H), 6.93 (dd, J = 8.1, 0.9 Hz, 1H), 6.78–6.72 (m, 1H), 6.65 (s, 1H), 4.04 (t, J = 7.2 Hz, 2H), 3.36 (hept, J = 6.9 Hz, 1H), 1.68–1.58 (m, 2H), 1.50 (s, 18H), 1.26 (d, J = 6.8 Hz, 6H), 1.14–1.02 (m, 2H), 0.65 (t, J = 7.3 Hz, 3H).

[0444] 13C NMR (101MHz, CDCl3) δ144.18,143.05,142.46,139.37,138.44,138.42,134.84,131.22,126.36,126.25,124.60,124. 30,124.29,124.13,124.02,116.44,110.06,103.72,100.12,44.21,34.83,31.99,31.32,27.68,23.40,19.71,13.28.

[0445] Example 65 – Compound 8

[0446] Yield = 0.027g, 14%.

[0447] 1 H NMR (400MHz, CDCl3) δ8.17–8.10 (m, 2H), 7.76 (dd, J = 8.6, 1.2Hz, 1H), 7.50 (ddd, J=8.6,5.6,1.7Hz,4H),7.42–7.34(m,4H),7.33–7.19(m,6H),7.15(td,J=7.5,1 .2Hz,1H),6.99(dd,J=7.7,1.2Hz,1H),6.80(s,1H),4.03(t,J=7.2Hz,2H),1.60 (dq,J=9.4,7.4Hz,2H),1.50(s,18H),1.10–0.96(m,2H),0.63(t,J=7.4Hz,3H).

[0448] 13 C NMR (101MHz, CDCl3) δ144.18,142.73,139.12,139.03,138.98,136.62,135.01,133.90,132.02,131.13,129.26,128.74,128.0 3,127.33,124.23,124.02,123.92,122.55,120.96,116.39,110.13,104.81,101.23,44.29,34.82,31.99,31.20,19.66,13.25.

[0449] Example 66 – Compound 9

[0450] Yield = 0.125g, 62%.

[0451] 11H NMR (400 MHz, CDCl3) δ 8.16 (d, J=1.9 Hz, 2H), 7.51 (dd, J=8.6, 1.9 Hz, 2H), 7.36–7.22 (m, 4H), 7.11 (dd, J=8.2, 0.8 Hz, 1H), 6.85 (tt, J=9.9, 7.0 Hz, 1H), 6.77 (s, 1H), 6.65 (dt, J=7.2, 3.1 Hz, 1H), 4.09 (t, J=7.2 Hz, 2H), 1.69–1.56 (m, 2H), 1.13–1.01 (m, 2H), 0.65 (t, J=7.4 Hz, 3H).

[0452] 13 13C NMR (101 MHz, CDCl3) δ 144.39, 143.47, 139.19, 134.78, 134.01, 131.98, 124.41, 124.14, 123.73, 116.51, 110.00, 105.91, 103.16, 99.52, 44.39, 34.83, 31.96, 31.27, 19.66, 13.25.

[0453] Example 67 – Compound 10

[0454] Yield = 0.021 g, 11%.

[0455] 1 1H NMR (400 MHz, CDCl3) δ 8.24–8.19 (m, 1H), 8.17 (d, J=1.9 Hz, 2H), 7.94–7.87 (m, 1H), 7.72 (d, J=7.4 Hz, 1H), 7.67 (d, J=8.2 Hz, 1H), 7.57–7.43 (m, 5H), 7.35–7.19 (m, 5H), 6.99 (dd, J=8.1, 0.9 Hz, 1H), 6.93 (dd, J=7.9, 0.8 Hz, 1H), 4.08 (t, J=7.2 Hz, 2H), 1.70–1.61 (m, 2H), 1.50 (s, 18H), 1.18–1.03 (m, 2H), 0.67 (t, J=7.3 Hz, 3H).

[0456] 13C NMR (101MHz, CDCl3) δ144.28,142.78,139.35,137.63,137.56,134.93,134.75,131.59,128.75,128.35,126.14,125.90,125.7 2,124.37,124.11,124.09,123.82,122.62,118.07,116.50,110.04,104.88,100.84,44.28,34.84,31.99,31.33,19.71,13.30.

[0457]

[0458] Buckwald-Hartwig coupling of 7-bromo-3,3-dimethyl-2-phenyl-3H-indole :

[0459] High-throughput sequences starting from CM3 operations are used to provide bromides and amines for Buchwald-Hartwig cross-coupling reactions.

[0460] The bromination starting material was provided and reacted with excess amine (2:1). All reactants / reagents were delivered in solution (toluene), except for sodium tert-butoxide and the catalyst (weighed as solids). The reaction was diluted to 10 mL with a separate reaction solvent and then allowed to proceed overnight. The reaction conversion was checked by UPLC the following day. After reacting at 95 °C for 16 hours, the conversion was high enough for purification.

[0461] Purification consisted of three stages: liquid / liquid extraction, stoppered filtration, and supercritical fluid chromatography (SFC). After removing the vial from the glove box, 5 mL of chloroform and 5 mL of saturated sodium chloride solution were added to the reaction vial. The vial was capped, shaken to expel gas quickly, and then 25 mL of Biotage was added. In a phase separation column, add another 5 mL of chloroform and collect the organic phase after gravity filtration. Pour the collected material into a GL Sciences 20 mL InertSep PS-SL filter and filter again by gravity. Similarly, wash once with 5 mL of chloroform to rinse the phase separation column and then rinse the InertSep filter. Perform a final wash of the silica pad with 5 mL of ethyl acetate and concentrate the collected sample at 80 °C under vacuum on a SavantSpeedVac for more than 10 hours, with the SavantSpeedVac changing at a rate of 5 Torr / min. Deliver the solid back to T. Paine for purification on an SFC.

[0462] Use 1-AA A 5 μm OBD 30 mm × 150 mm column was used, with CO₂ as mobile phase A and 75% acetonitrile: 25% isopropanol as mobile phase B, and purification was performed by preparative SFC. The gradient used was 5% B to 50% B over 10 minutes, with a total flow rate of 100 mL / min. The collection make-up solvent used was ethyl acetate, the BPR pressure was 100 bar, the oven temperature was 40°C, the sample concentration was 50 mg / mL, and the injection volume was 960 μL. The desired compound was collected by mass spectrometry.

[0463] Example 68 – Compound 11

[0464] Yield = 0.115 g, 81%.

[0465] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.31–8.18 (m, 2H), 7.54 (qd, J = 7.8, 6.8, 3.8 Hz, 3H), 7.44–7.26 (m, 3H), 7.03 (t, J = 7.7 Hz, 1H), 6.73 (d, J = 7.4 Hz, 1H), 6.50 (s, 1H), 6.17 (d, J = 8.1 Hz, 1H), 3.40 (hept, J = 6.8 Hz, 2H), 1.68 (s, 6H), 1.24 (d, J = 6.9 Hz, 12H).

[0466] 13 ¹³C NMR (101 MHz, CDCl₃) δ 179.68, 148.31, 147.93, 141.05, 138.69, 135.21, 133.93, 129.99, 128.61, 128.07, 127.31, 127.07, 123.82, 110.10, 109.43, 54.32, 28.29, 25.00, 24.02.

[0467] Example 69 – Compound 12

[0468] Yield = 0.071 g, 59%.

[0469] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.25 (dt, J = 7.3, 1.5 Hz, 2H), 7.85 (dd, J = 10.1, 8.1 Hz, 2H), 7.81–7.73 (m, 2H), 7.61–7.44 (m, 6H), 7.44–7.37 (m, 2H), 7.36–7.32 (m, 1H), 7.31–7.25 (m, 1H), 6.94 (dd, J = 7.3, 1.0 Hz, 1H), 1.69 (d, J = 1.4 Hz, 6H).

[0470] 13 C NMR (101MHz, CDCl3) δ180.79,148.84,141.11,139.92,136.05,134.66,133.58,130.34,129.55,129.17,128. 69,128.66,128.20,127.73,127.06,126.77,126.46,123.76,121.07,113.06,112.71,112.19,54.58,24.87.

[0471] Example 70 – Compound 13

[0472] Yield = 0.095g, 46%.

[0473] 1 H NMR (400MHz, CDCl3) δ8.26–8.14(m,2H),7.57–7.47(m,4H),7.30(d,J=6.4Hz,1H),7.23(td,J=7.7,1.6Hz ,1H),7.16(t,J=7.7Hz,1H),7.10–6.98(m,2H),6.88–6.82(m,1H),6.80(s,1H),2.43(s,3H),1.65(s,6H).

[0474] 13 C NMR (101MHz, CDCl3) δ180.28,148.69,140.67,140.42,137.08,133.56,130.98,130.20,129 .74,128.60,128.13,126.92,126.67,122.55,119.87,112.39,111.33,54.45,24.88,18.11.

[0475] Example 71 – Compound 14

[0476] Yield = 0.086g, 43%.

[0477] 11H NMR (400 MHz, CDCl3) δ 8.22–8.13 (m, 2H), 7.57–7.46 (m, 3H), 7.30–7.24 (m, 1H), 7.20 (d, J = 1.6 Hz, 2H), 7.19–7.15 (m, 1H), 7.12 (t, J = 1.7 Hz, 1H), 7.08 (s, 1H), 6.83 (dd, J = 7.3, 1.0 Hz, 1H), 1.64 (s, 6H), 1.38 (s, 18H).

[0478] 13 13C NMR (101 MHz, CDCl3) δ 180.27, 151.84, 148.65, 141.09, 140.38, 136.98, 133.69, 130.12, 128.60, 128.09, 127.01, 116.20, 114.31, 111.55, 111.04, 54.46, 34.96, 31.50, 24.82.

[0479] 1 1H NMR (400 MHz, CDCl3) δ 8.22–8.13 (m, 2H), 7.57–7.46 (m, 3H), 7.30–7.24 (m, 1H), 7.20 (d, J = 1.6 Hz, 2H), 7.19–7.15 (m, 1H), 7.12 (t, J = 1.7 Hz, 1H), 7.08 (s, 1H), 6.83 (dd, J = 7.3, 1.0 Hz, 1H), 1.64 (s, 6H), 1.38 (s, 18H).

[0480] 13 13C NMR (101 MHz, CDCl3) δ 180.27, 151.84, 148.65, 141.09, 140.38, 136.98, 133.69, 130.12, 128.60, 128.09, 127.01, 116.20, 114.31, 111.55, 111.04, 54.46, 34.96, 31.50, 24.82.

[0481] Example 72 – Compound 15

[0482] Yield: 0.075 g, 38%.

[0483] 1¹H NMR (400 MHz, CDCl₃) δ 8.21 (dt, J = 7.8, 2.0 Hz, 2H), 7.52 (tdd, J = 7.0, 4.8, 1.9 Hz, 3H), 7.17 (q, J = 5.8 Hz, 3H), 7.03 (t, J = 7.7 Hz, 1H), 6.73 (dt, J = 7.4, 1.3 Hz, 1H), 6.48 (s, 1H), 6.16 (dd, J = 8.1, 1.1 Hz, 1H), 2.33 (d, J = 2.1 Hz, 6H), 1.65 (s, 6H).

[0484] 13 ¹³C NMR (101 MHz, CDCl₃) δ 179.84, 148.45, 139.22, 139.06, 138.05, 136.54, 133.81, 130.00, 128.57, 128.46, 128.07, 127.06, 125.95, 110.05, 109.76, 54.27, 24.94, 18.54.

[0485] Example 73 – Compound 16

[0486] Yield = 0.054 g, 27%.

[0487] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.21 (dtd, J = 8.5, 4.3, 2.5 Hz, 2H), 7.57–7.47 (m, 4H), 7.39 (dt, J = 7.7, 2.0 Hz, 1H), 7.23 (tt, J = 7.7, 2.3 Hz, 1H), 7.14 (tdd, J = 8.1, 5.5, 2.0 Hz, 2H), 6.94 (dt, J = 8.2, 1.4 Hz, 1H), 6.84 (s, 1H), 6.81 (ddd, J = 7.3, 2.1, 1.0 Hz, 1H), 3.39 (pd, J = 6.9, 6.5, 1.6 Hz, 1H), 1.66 (d, J = 1.8 Hz, 6H), 1.35 (dd, J = 6.8, 2.0 Hz, 6H).

[0488] 13 ¹³C NMR (101 MHz, CDCl₃) δ 180.07, 148.61, 141.55, 140.37, 138.97, 138.15, 133.58, 130.15, 128.60, 128.08, 126.95, 126.36, 126.15, 123.76, 122.30, 111.81, 110.85, 54.43, 27.81, 24.90, 23.18.

[0489] Example 74 – Compound 17

[0490] Yield = 0.055g, 27%.

[0491] 1 H NMR (400MHz, CDCl3) δ8.31–8.18(m,3H),7.98–7.86(m,1H),7.66(d,J=7.8Hz,2H),7.60–7.45(m,6H),7.36 (s, 1H), 7.14 (dd, J = 8.2, 7.2Hz, 1H), 7.06 (dd, J = 8.1, 1.1Hz, 1H), 6.86 (dd, J = 7.2, 1.1Hz, 1H), 1.68 (s, 6H).

[0492] 13 C NMR (101MHz, CDCl3) δ180.45,148.69,140.74,137.92,137.70,134.78,133.57,130.24,128.63,128.52, 128.47,128.16,126.94,126.16,125.97,125.75,123.38,122.34,116.85,112.65,111.47,54.52,24.90.

[0493] Example 75 – Compound 18

[0494] Yield = 0.095g, 47%.

[0495] 1 H NMR(400MHz, CDCl3)δ8.22–8.13(m,2H),7.51(qq,J=4.4,2.7,1.7Hz,3H),7.42–7.36(m,2H),7.31–7.25(m ,3H),7.17(t,J=7.7Hz,1H),7.03(s,1H),6.83(dd,J=7.3,1.1Hz,1H),1.63(s,6H),1.37(d,J=1.4Hz,9H).

[0496] 13 C NMR (101MHz, CDCl3) δ180.34,148.64,144.69,140.44,139.45,136.80,133.64,130.16 ,128.61,128.08,126.95,126.10,119.30,111.84,111.26,54.45,34.27,31.52,24.82.

[0497] Example 76 – Compound 19

[0498] Yield = 0.015 g, 8%.

[0499] 1 1H NMR (400 MHz, CDCl3) δ 8.26–8.17 (m, 2H), 7.55–7.47 (m, 3H), 7.45 (d, J = 8.1 Hz, 2H), 7.12 (dt, J = 11.2, 7.9 Hz, 2H), 6.95 (s, 1H), 6.87 (dd, J = 7.4, 1.0 Hz, 1H), 6.45–6.36 (m, 1H), 1.65 (s, 6H).

[0500] 13 13C NMR (101 MHz, CDCl3) δ 180.58, 148.49, 140.37, 136.40, 136.14, 133.58, 132.43, 130.19, 128.82, 128.54, 128.24, 126.40, 125.90, 112.20, 112.11, 54.35, 24.87.

[0501] Example 77 – Compound 20

[0502] Yield = 0.094 g, 47%.

[0503] 1 1H NMR (400 MHz, CDCl3) δ 8.26–8.16 (m, 2H), 7.86–7.70 (m, 4H), 7.57–7.50 (m, 3H), 7.50–7.43 (m, 3H), 7.37 (ddd, J = 8.1, 6.8, 1.2 Hz, 1H), 7.27–7.22 (m, 2H), 6.91 (dd, J = 7.3, 0.9 Hz, 1H), 1.66 (s, 6H).

[0504] 13 13C NMR (101 MHz, CDCl3) δ 180.79, 148.79, 141.04, 139.87, 135.99, 134.61, 133.53, 130.31, 129.50, 129.13, 128.66, 128.16, 127.69, 127.01, 126.73, 126.42, 123.71, 121.04, 113.00, 112.66, 112.15, 54.56, 24.83.

[0505] Example 78 – Compound 21

[0506] Yield = 0.025g, 13%.

[0507] 1 H NMR (400MHz, CDCl3) δ8.23–8.09(m,2H),7.56–7.45(m,3H),7.30(d,J=8.4Hz,1H),7.27–7.22(m,2H),7.20–7.0 9(m,2H),7.01(s,1H),6.81(dd,J=7.2,1.0Hz,1H),1.73(d,J=14.3Hz,4H),1.63(s,6H),1.33(d,J=2.2Hz,12H).

[0508] 13 C NMR (101MHz, CDCl3) δ180.23,148.62,145.90,140.30,139.23,138.65,137.01,133.69,130.11,128.60,1 28.08,127.31,126.98,117.69,117.63,111.58,110.98,54.45,35.23,34.41,33.86,31.96,31.90,24.82.

[0509]

[0510] Buckwald-Hartwig coupling of 4-bromo-1-butyl-2-(o-tolyl)-1H-benzo[d]imidazole :

[0511] High-throughput sequences starting from CM3 operations are used to provide bromides and amines for Buchwald-Hartwig cross-coupling reactions.

[0512] The bromination starting material was provided and reacted with excess amine (2:1). All reactants / reagents were delivered in solution (toluene), except for sodium tert-butoxide and the catalyst (weighed as solids). The reaction was diluted to 10 mL with a separate reaction solvent and then allowed to proceed overnight. The reaction conversion was checked by UPLC the following day. After reacting at 95 °C for 16 hours, the conversion was high enough for purification.

[0513] Purification consisted of three stages: liquid / liquid extraction, stoppered filtration, and supercritical fluid chromatography (SFC). After removing the vial from the glove box, 5 mL of chloroform and 5 mL of saturated sodium chloride solution were added to the reaction vial. The vial was capped, shaken to expel gas quickly, and then 25 mL of Biotage was added. In a phase separation column, add another 5 mL of chloroform and collect the organic phase after gravity filtration. Pour the collected material into a GL Sciences 20 mL InertSep PS-SL filter and filter again by gravity. Similarly, wash once with 5 mL of chloroform to rinse the phase separation column and then rinse the InertSep filter. Perform a final wash of the silica pad with 5 mL of ethyl acetate and concentrate the collected sample at 80 °C under vacuum on a SavantSpeedVac for more than 10 hours, with the SavantSpeedVac changing at a rate of 5 Torr / min. Deliver the solid back to T. Paine for purification on an SFC.

[0514] Use 1-AA A 5 μm OBD 30 mm × 150 mm column was used with CO2 as the mobile phase A and 75% acetonitrile:25% isopropanol as the mobile phase B. Purification was performed using a preparative SFC. The gradient used was 5% B to 50% B over 10 minutes, with a total flow rate of 100 mL / min. The collection replenishment solvent used was ethyl acetate, the BPR pressure was 100 bar, the oven temperature was 40 °C, the sample concentration was 50 mg / mL, and the injection volume was 960 μL. The desired compounds were collected by mass spectrometry.

[0515] Example 79 – Compound 22

[0516] Yield = 0.072g, 38%.

[0517] 1 H NMR (400MHz, CDCl3) δ7.49–7.31(m,4H),7.26–7.17(m,4H),7.09(dd,J=4.0,2.2Hz,2H),6.91(dd,J=7.2,1.7Hz,1 H), 4.00 (t, J = 7.4Hz, 2H), 2.29 (s, 3H), 1.79–1.65 (m, 2H), 1.36 (s, 18H), 1.29–1.17 (m, 2H), 0.83 (t, J = 7.3Hz, 3H).

[0518] 13 C NMR (101MHz, CDCl3) δ151.72,151.21,141.23,138.15,136.08,135.14,132.72,130.52,130.42,130.31,1 29.82,125.85,123.52,115.83,113.89,103.63,100.51,44.13,34.94,31.66,31.49,19.85,19.76,13.52.

[0519] Example 80 – Compound 23

[0520] Yield = 0.012 g, 6%.

[0521] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.84–7.71 (m, 4H), 7.50–7.42 (m, 4H), 7.42–7.24 (m, 7H), 7.00 (dd, J = 8.0, 0.9 Hz, 1H), 4.02 (t, J = 7.4 Hz, 2H), 2.30 (s, 3H), 1.80–1.65 (m, 2H), 1.32–1.17 (m, 2H), 0.84 (t, J = 7.4 Hz, 3H).

[0522] 13 ¹³C NMR (101 MHz, CDCl₃) δ 151.51, 139.93, 138.14, 135.25, 135.19, 134.61, 130.59, 130.29, 129.95, 129.40, 129.02, 127.65, 126.72, 126.34, 125.91, 123.59, 123.48, 121.01, 112.78, 105.00, 101.60, 44.19, 31.64, 19.85, 19.78, 13.52.

[0523] Example 81 – Compound 24

[0524] Yield = 0.095 g, 50%.

[0525] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.49–7.32 (m, 4H), 7.32–7.25 (m, 3H), 7.24–7.12 (m, 3H), 7.03 (s, 1H), 6.90 (dd, J = 7.7, 1.2 Hz, 1H), 3.99 (t, J = 7.4 Hz, 2H), 2.28 (s, 3H), 1.78–1.63 (m, 2+4H), 1.32 (d, J = 1.7 Hz, 12H), 1.28–1.18 (m, 2H), 0.83 (t, J = 7.4 Hz, 3H).

[0526] 13C NMR (101MHz, CDCl3) δ151.17,145.78,139.35,138.26,138.15,136.13,135.13,132.60,130.52,130.39,130.31,129.83,127.23 ,125.85,123.50,117.42,117.15,103.63,100.43,44.12,35.25,35.21,34.38,33.82,31.95,31.89,31.65,19.86,19.77,13.52.

[0527] Example 82 – Compound 25

[0528] Yield = 0.036g, 19%.

[0529] 1 H NMR (400MHz, CDCl3) δ7.53–7.29(m,6H),7.25–7.10(m,3H),7.07(t,J=7.9Hz,1H),6.82(d,J=8.0Hz,1H),6.45(s,1H),6.0 1(d,J=7.8Hz,1H),3.99(t,J=7.4Hz,2H),2.32(s,3+6H),1.82–1.66(m,2H),1.25(h,J=7.5Hz,2H),0.84(t,J=7.4Hz,3H).

[0530] 13 C NMR (101MHz, CDCl3) δ150.91,138.43,138.20,138.08,136.58,135.07,131.68,130.59,130.50,130.4 2,129.74,128.40,125.88,125.80,123.54,102.25,99.29,44.14,31.69,19.91,19.83,18.42,13.53.

[0531] Example 83 – Compound 26

[0532] Yield = 0.101g, 53%.

[0533] 1¹H NMR (400 MHz, CDCl₃) δ 7.52 (dd, J=7.8, 1.5 Hz, 1H), 7.48–7.31 (m, 5H), 7.26–7.09 (m, 3H), 6.87 (dd, J=8.1, 0.9 Hz, 1H), 6.73–6.64 (m, 2H), 4.00 (t, J=7.4 Hz, 2H), 3.39 (hept, J=6.9 Hz, 1H), 2.31 (s, 3H), 1.77–1.64 (m, 2H), 1.27 (d, J=6.9 Hz, 6H), 1.25–1.17 (m, 2H), 0.83 (t, J=7.4 Hz, 3H).

[0534] 13 ¹³C NMR (101 MHz, CDCl₃) δ 151.16, 142.86, 138.68, 138.22, 138.15, 135.16, 132.51, 130.55, 130.51, 130.37, 129.77, 126.30, 126.19, 125.82, 124.35, 124.17, 123.42, 103.44, 100.01, 44.14, 31.65, 27.63, 23.42, 19.87, 19.85, 13.51.

[0535] Example 84 – Compound 27

[0536] Yield = 0.099 g, 52%.

[0537] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.76–7.69 (m, 1H), 7.53–7.48 (m, 2H), 7.44–7.26 (m, 10H), 7.25–7.17 (m, 2H), 7.12 (td, J=7.5, 1.2 Hz, 1H), 6.93 (dd, J=6.3, 2.6 Hz, 1H), 6.75 (s, 1H), 3.98 (t, J=7.4 Hz, 2H), 2.21 (s, 3H), 1.77–1.62 (m, 2H), 1.29–1.16 (m, 2H), 0.82 (t, J=7.4 Hz, 3H).

[0538] 13C NMR (101MHz, CDCl3) δ151.23,139.20,139.11,138.25,136.35,135.36,133.67,133.30,131.12,130.55,130.28,130.19,12 9.69,129.32,128.67,127.95,127.28,125.70,123.25,122.34,120.95,104.51,101.09,44.11,31.65,19.86,19.79,13.51.

[0539] Example 85 – Compound 28

[0540] Yield = 0.056g, 30%.

[0541] 1 H NMR (400MHz, CDCl3) δ7.49–7.31(m,6H),7.31–7.26(m,3H),7.19(dd,J=8.1,3.7Hz,2H),7.05(s,1H),6.91(dd,J=6.4,2.6Hz ,1H),3.99(t,J=7.4Hz,2H),2.28(s,3H),1.77–1.63(m,2H),1.36(s,9H),1.23(dd,J=6.6,1.8Hz,2H),0.82(t,J=7.3Hz,3H).

[0542] 13 C NMR (101MHz, CDCl3) δ151.22,144.38,139.49,138.15,136.00,135.15,130.53,130.34,130.30,129.8 5,126.03,125.85,123.45,119.09,103.86,100.66,44.13,34.23,31.64,31.50,19.85,19.77,13.51.

[0543] Example 86 – Compound 29

[0544] Yield = 0.018g, 9%.

[0545] 1H NMR (400MHz, CDCl3) δ7.44(dd,J=7.8,6.4Hz,4H),7.41–7.31(m,2H),7.13(td,J=8.0,5.2Hz,2H),6.96(d,J=8.0Hz,1H),6.92( s,1H),6.27(d,J=7.8Hz,1H),4.00(t,J=7.4Hz,2H),2.31(s,3H),1.78–1.65(m,2H),1.30–1.16(m,2H),0.83(t,J=7.3Hz,3H).

[0546] 13 C NMR (101MHz, CDCl3) δ151.54,138.22,136.48,135.45,135.19,132.61,132.60,130.51,130.41,13 0.39,129.78,128.81,125.92,125.77,122.87,104.73,101.65,44.17,31.66,19.88,19.85,13.51.

[0547]

[0548] Buckwald-Hartwig coupling of 4-bromo-1-butyl-2-(4-(tert-butyl)phenyl)-1H-benzo[d]imidazole :

[0549] High-throughput sequences starting from CM3 operations are used to provide bromides and amines for Buchwald-Hartwig cross-coupling reactions.

[0550] The bromination starting material was provided and reacted with excess amine (2:1). All reactants / reagents were delivered in solution (toluene), except for sodium tert-butoxide and the catalyst (weighed as solids). The reaction was diluted to 10 mL with a separate reaction solvent and then allowed to proceed overnight. The reaction conversion was checked by UPLC the following day. After reacting at 95 °C for 16 hours, the conversion was high enough for purification.

[0551] Purification consisted of three stages: liquid / liquid extraction, stoppered filtration, and supercritical fluid chromatography (SFC). After removing the vial from the glove box, 5 mL of chloroform and 5 mL of saturated sodium chloride solution were added to the reaction vial. The vial was capped, shaken to expel gas quickly, and then 25 mL of Biotage was added. In a phase separation column, add another 5 mL of chloroform and collect the organic phase after gravity filtration. Pour the collected material into a GL Sciences 20 mL InertSep PS-SL filter and filter again by gravity. Similarly, wash once with 5 mL of chloroform to rinse the phase separation column and then rinse the InertSep filter. Perform a final wash of the silica pad with 5 mL of ethyl acetate and concentrate the collected sample at 80 °C under vacuum on a SavantSpeedVac for more than 10 hours, with the SavantSpeedVac changing at a rate of 5 Torr / min. Deliver the solid back to T. Paine for purification on an SFC.

[0552] Use 1-AA A 5 μm OBD 30 mm × 150 mm column was used with CO2 as the mobile phase A and 75% acetonitrile:25% isopropanol as the mobile phase B. Purification was performed using a preparative SFC. The gradient used was 5% B to 50% B over 10 minutes, with a total flow rate of 100 mL / min. The collection replenishment solvent used was ethyl acetate, the BPR pressure was 100 bar, the oven temperature was 40 °C, the sample concentration was 50 mg / mL, and the injection volume was 960 μL. The desired compounds were collected by mass spectrometry.

[0553] Example 87 – Compound 30

[0554] Yield = 0.066g, 55%.

[0555] 1 H NMR (400MHz, CDCl3) δ7.69–7.52(m,4H),7.25–7.14(m,4H),7.14–7.06(m,2H),6.90(dd,J=7.4,1.5Hz,1H), 4.29–4.18(m,2H),1.94–1.79(m,2H),1.41(s,9H),1.37(s,18H),1.33–1.29(m,2H),0.92(t,J=7.3Hz,3H).

[0556] 13 C NMR (101MHz, CDCl3) δ152.77,151.85,151.68,141.30,136.10,136.02,132.84,129.01,127.95,125. 78,123.56,115.81,113.99,103.71,100.53,44.65,34.94,34.87,31.98,31.50,31.27,20.00,13.62.

[0557] Example 88 – Compound 31

[0558] Yield = 0.073 g, 61%.

[0559] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.71–7.53 (m, 4H), 7.21–7.10 (m, 3H), 7.04 (t, J=7.9 Hz, 1H), 6.80 (dd, J=8.1, 0.9 Hz, 1H), 6.46 (s, 1H), 5.98 (dd, J=7.7, 0.8 Hz, 1H), 4.28–4.15 (m, 2H), 2.31 (s, 6H), 1.96–1.82 (m, 2H), 1.41 (s, 9H), 1.35 (dd, J=14.9, 7.4 Hz, 2H), 0.93 (t, J=7.4 Hz, 3H).

[0560] 13 ¹³C NMR (101 MHz, CDCl₃) δ 152.65, 151.54, 138.36, 138.08, 136.61, 135.99, 131.74, 129.09, 128.39, 128.08, 125.87, 125.72, 123.62, 102.27, 99.30, 44.69, 34.85, 32.04, 31.28, 20.07, 18.43, 13.64.

[0561] Example 89 – Compound 32

[0562] Yield = 0.076 g, 63%.

[0563] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.63 (ddd, J=44.8, 8.4, 1.5 Hz, 4H), 7.51 (dd, J=7.8, 1.6 Hz, 1H), 7.39 (dt, J=7.6, 1.6 Hz, 1H), 7.27–7.08 (m, 3H), 6.89–6.83 (m, 1H), 6.72 (s, 1H), 6.68 (d, J=7.8 Hz, 1H), 4.23 (t, J=7.7 Hz, 2H), 3.39 (sept, J=6.8 Hz, 1H), 1.97–1.80 (m, 2H), 1.41 (s, 9H), 1.35 (p, J=7.5 Hz, 2H), 1.27 (dd, J=6.8, 1.3 Hz, 6H), 0.93 (td, J=7.4, 1.4 Hz, 3H).

[0564] 13C NMR (101MHz, CDCl3) δ152.73,151.79,142.71,138.74,138.02,136.10,132.62,129.07,127.99,126.30,126. 16,125.74,124.25,123.98,123.49,103.59,100.05,44.70,34.86,32.00,31.28,27.64,23.40,20.04,13.63.

[0565] Example 90 – Compound 33

[0566] Yield = 0.069g, 58%.

[0567] 1H NMR (400MHz, CDCl3) δ7.72–7.65(m,2H),7.60–7.51(m,3H),7.27–7.12(m,3H),7.02(td,J=7.4,1.3Hz,1H),6.93–6.88(m,1H),6.86(d ,J=7.8Hz,1H),6.70(s,1H),4.28–4.17(m,2H),2.38(s,3H),1.95–1.80(m,2H),1.41(s,9H),1.40–1.29(m,2H),0.92(t,J=7.4Hz,3H).

[0568] 13 C NMR (101MHz, CDCl3) δ152.78,151.94,140.35,136.58,136.17,132.96,130.94,130.34,129.07,127.93,126.5 6,125.77,125.76,123.40,122.74,121.00,104.38,100.63,44.70,34.87,31.98,31.28,20.02,18.10,13.62.

[0569] Example 91 – Compound 34

[0570] Yield = 0.069g, 57%.

[0571] 1¹H NMR (400 MHz, CDCl₃) δ 7.74–7.52 (m, 4H), 7.39–7.21 (m, 4H), 7.02 (t, J = 7.9 Hz, 1H), 6.77 (dd, J = 8.1, 0.9 Hz, 1H), 6.38 (s, 1H), 5.94 (dd, J = 7.8, 0.9 Hz, 1H), 4.27–4.16 (m, 2H), 3.36 (septet, J = 6.9 Hz, 2H), 1.97–1.84 (m, 2H), 1.42 (s, 9H), 1.37 (d, J = 7.4 Hz, 2H), 1.17 (d, J = 6.9 Hz, 12H), 0.94 (t, J = 7.4 Hz, 3H).

[0572] 13 ¹³C NMR (101 MHz, CDCl₃) δ 152.62, 151.41, 148.15, 140.31, 135.86, 134.94, 131.33, 129.11, 128.16, 127.26, 125.73, 123.74, 123.66, 102.26, 98.77, 44.70, 34.86, 32.10, 31.29, 28.15, 23.94, 20.11, 13.66.

[0573] Example 92 – Compound 35

[0574] Yield = 0.039 g, 33%.

[0575] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.70–7.54 (m, 4H), 7.21 (t, J = 8.0 Hz, 1H), 7.04 (d, J = 8.1 Hz, 1H), 6.89–6.78 (m, 2H), 6.58 (dt, J = 7.2, 3.2 Hz, 1H), 4.29–4.19 (m, 2H), 1.86 (ddt, J = 9.2, 7.7, 3.6 Hz, 2H), 1.41 (s, 9H), 1.35 (q, J = 7.5 Hz, 2H), 0.92 (t, J = 7.4 Hz, 3H).

[0576] 13 ¹³C NMR (101 MHz, CDCl₃) δ 153.02, 152.68, 136.04, 133.61, 133.31, 129.03, 127.64, 125.82, 123.08, 105.60, 103.04, 99.39, 99.16, 98.93, 44.77, 34.89, 31.96, 31.25, 20.00, 13.59.

[0577] Example 93 – Compound 36

[0578] Yield = 0.054 g, 45%.

[0579] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.24 (d, J = 8.1 Hz, 1H), 7.90 (dd, J = 7.6, 1.9 Hz, 1H), 7.75–7.43 (m, 10H), 7.30 (d, J = 10.9 Hz, 2H), 7.14 (td, J = 7.9, 2.7 Hz, 1H), 6.90 (ddd, J = 16.9, 7.8, 2.7 Hz, 2H), 4.26 (t, J = 7.6 Hz, 2H), 1.98–1.80 (m, 2H), 1.42 (s, 9H), 1.37 (q, J = 8.0, 7.5 Hz, 2H), 0.94 (td, J = 7.3, 2.7 Hz, 3H).

[0580] 13 ¹³C NMR (101 MHz, CDCl₃) δ 152.83, 152.08, 137.92, 137.17, 136.17, 134.75, 133.04, 129.07, 128.62, 128.34, 127.93, 126.08, 125.95, 125.80, 125.59, 123.44, 122.67, 117.56, 104.77, 100.80, 44.73, 34.88, 32.00, 31.28, 20.03, 13.64.

[0581] Example 94 – Compound 37

[0582] Yield = 0.067 g, 56%.

[0583] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.86–7.65 (m, 6H), 7.59 (d, J = 8.4 Hz, 2H), 7.50–7.42 (m, 3H), 7.40–7.22 (m, 5H), 6.98 (d, J = 8.0 Hz, 1H), 4.26 (t, J = 7.7 Hz, 2H), 1.88 (p, J = 7.6 Hz, 2H), 1.42 (s, 9H), 1.38–1.28 (m, 2H), 0.93 (t, J = 7.4 Hz, 3H).

[0584] 13C NMR (101MHz, CDCl3) δ153.13,151.98,139.94,136.04,135.09,134.61,129.41,129.04,129.01,127.65,126.7 3,126.32,125.89,123.66,123.58,121.05,112.82,105.23,101.59,44.77,34.91,31.94,31.26,20.00,13.61.

[0585] Example 95 – Compound 38

[0586] Yield = 0.076g, 63%.

[0587] 1 H NMR (400MHz, CDCl3) δ7.73–7.68(m,1H),7.62–7.48(m,6H),7.44–7.29(m,5H),7.23–7.08(m,3H),6.92(dd,J=7.1,1 .8Hz,1H),6.76(s,1H),4.25–4.15(m,2H),1.92–1.81(m,2H),1.38(s,9H),1.36–1.31(m,2H),0.92(t,J=7.3Hz,3H).

[0588] 13 C NMR (101MHz, CDCl3) δ152.68,151.92,139.35,139.22,136.32,136.26,133.65,133.55,131.13,129.32,128.99,128.7 2,127.97,127.82,127.28,125.67,123.28,122.22,120.72,105.05,101.17,44.67,34.83,31.99,31.25,20.03,13.62.

[0589]

[0590] Buckwald-Hartwig conjugate of 4-bromo-1-butyl-2-(2,3,5,6-tetrafluorophenyl)-1H-benzo[d]imidazolium Alliance :

[0591] High-throughput sequences starting from CM3 operations are used to provide bromides and amines for Buchwald-Hartwig cross-coupling reactions.

[0592] The bromination starting material was provided and reacted with excess amine (2:1). All reactants / reagents were delivered in solution (toluene), except for sodium tert-butoxide and the catalyst (weighed as solids). The reaction was diluted to 10 mL with a separate reaction solvent and then allowed to proceed overnight. The reaction conversion was checked by UPLC the following day. After reacting at 95 °C for 16 hours, the conversion was high enough for purification.

[0593] Purification consisted of three stages: liquid / liquid extraction, stoppered filtration, and supercritical fluid chromatography (SFC). After removing the vial from the glove box, 5 mL of chloroform and 5 mL of saturated sodium chloride solution were added to the reaction vial. The vial was capped, shaken to expel gas quickly, and then 25 mL of Biotage was added. In a phase separation column, add another 5 mL of chloroform and collect the organic phase after gravity filtration. Pour the collected material into a GL Sciences 20 mL InertSep PS-SL filter and filter again by gravity. Similarly, wash once with 5 mL of chloroform to rinse the phase separation column and then rinse the InertSep filter. Perform a final wash of the silica pad with 5 mL of ethyl acetate and concentrate the collected sample at 80 °C under vacuum on a SavantSpeedVac for more than 10 hours, with the SavantSpeedVac changing at a rate of 5 Torr / min. Deliver the solid back to T. Paine for purification on an SFC.

[0594] Use 1-AA A 5 μm OBD 30 mm × 150 mm column was used with CO2 as the mobile phase A and 75% acetonitrile:25% isopropanol as the mobile phase B. Purification was performed using a preparative SFC. The gradient used was 5% B to 50% B over 10 minutes, with a total flow rate of 100 mL / min. The collection replenishment solvent used was ethyl acetate, the BPR pressure was 100 bar, the oven temperature was 40 °C, the sample concentration was 50 mg / mL, and the injection volume was 960 μL. The desired compounds were collected by mass spectrometry.

[0595] Example 96 – Compound 39

[0596] Yield = 0.013g, 11%.

[0597] 1¹H NMR (400 MHz, CDCl₃) δ 7.49 (dd, J = 7.7, 1.7 Hz, 1H), 7.38 (ddd, J = 8.8, 6.2, 2.7 Hz, 1H), 7.32 (ddd, J = 9.5, 7.3, 2.2 Hz, 1H), 7.26–7.15 (m, 3H), 6.88 (dd, J = 8.1, 0.9 Hz, 1H), 6.67 (dd, J = 7.9, 0.9 Hz, 1H), 6.64 (s, 1H), 4.08 (t, J = 7.4 Hz, 2H), 3.36 (p, J = 6.9 Hz, 1H), 1.87–1.71 (m, 2H), 1.26 (d, J = 6.9, 6+2H), 0.88 (t, J = 7.3 Hz, 3H).

[0598] 13 ¹³C NMR (101 MHz, CDCl₃) δ 143.16, 138.66, 138.22, 135.61, 133.18, 126.40, 126.31, 126.27, 124.78, 124.76, 124.50, 108.34, 108.12, 103.59, 99.99, 99.93, 44.71, 31.51, 27.70, 23.39, 19.77, 13.47.

[0599] Example 97 – Compound 40

[0600] Yield = 0.019 g, 17%.

[0601] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.39–7.23 (m, 5H), 7.12–7.04 (m, 1H), 6.80 (dd, J = 8.0, 3.2 Hz, 1H), 6.34 (s, 1H), 5.98 (dd, J = 7.8, 3.3 Hz, 1H), 4.08 (t, J = 7.4 Hz, 2H), 3.32 (hept, J = 6.8 Hz, 2H), 1.87–1.74 (m, 2H), 1.30 (m, 2H), 1.18 (d, J = 6.8 Hz, 12H), 0.90 (t, J = 7.4 Hz, 3H).

[0602] 13 ¹³C NMR (101 MHz, CDCl₃) δ 148.06, 140.65, 135.48, 134.53, 132.07, 127.46, 124.94, 123.81, 102.54, 98.82, 44.75, 31.55, 28.56, 28.18, 24.19, 23.35, 19.85, 13.49.

[0603] Example 98 – PPR Screening

[0604]

[0605] Table 1. PPR results for tricresyl or 3,5-di-tert-butylphenyl substituted amino-benzimidazole ligands. It is the average of two runs. .

[0606]

[0607]

[0608] Table 2. PPR results of naphthyl-substituted amino-benzimidazole ligands .

[0609]

[0610]

[0611] Table 3. PPR results of isopropyl-substituted amino-benzimidazole ligands .

[0612]

[0613]

[0614] Table 4. PPR results for alkyl-substituted amino-benzimidazole ligands .

[0615]

[0616] Example 99 – Screening of Batch Reactors

[0617]

[0618] Table 5. Results of batch reactor for aryl-substituted amino-benzylimidazole ligands

[0619]

[0620] Semi-batch reactor conditions at 120°C (for a series of data on ethylene-octene copolymerization using amino-benzimidazole catalysts): 46.3 g ethylene, 302 g 1-octene, 612 g Isopar E, 1.2 equivalents of RIBS-2 activator relative to the catalyst, 10 μmol MMAO-3A, ​​290 psi reactor pressure. Semi-batch reactor conditions at 150°C (for a series of data on ethylene-octene copolymerization using amino-benzimidazole catalysts): 43 g ethylene, 301 g 1-octene, 548 g Isopar E, 1.2 equivalents of RIBS-2 activator relative to the catalyst, 10 μmol MMAO-3A, ​​327 psi reactor pressure.

[0621]

[0622] Table 6 presents the polymerization and polymerization results generated by the metal-ligand complexes IMLC-9, IMLC-10, IMLC-11, IMLC-12, and IMLC-13. Comparative catalyst C1 (Comp.Cat.C1) was run under the same conditions, and the polymerization results of Comp.Cat.C1 are recorded in Table 6.

[0623] Comparison of catalyst C1 (Comp.Cat.C1)

[0624] Table 6. Data for a series of amino-benzimidazole catalysts in a semi-batch reactor

[0625]

[0626] Semi-batch reactor conditions at 120°C (ethylene-octene copolymerization data): 46.3 g ethylene, 302 g 1-octene, 612 g Isopar E, 1.2 equivalents of RIBS-2 activator relative to the catalyst, 10 μmol MMAO-3A, ​​290 psi reactor pressure. Semi-batch reactor conditions at 150°C (ethylene-octene copolymerization data for a series of amino-benzimidazoles): 43 g ethylene, 301 g 1-octene, 548 g Isopar E, 1.2 equivalents of RIBS-2 activator relative to the catalyst, 10 μmol MMAO-3A, ​​327 psi reactor pressure.

[0627] Example 100 – Chain Shuttle Capability

[0628]

[0629]

[0630] Table 7: Ethylene-octene copolymerization data under chain transfer conditions for a series of amino-benzimidazole catalysts.

[0631]

[0632] Semi-batch reactor conditions at 120°C: 11.3 g ethylene, 57 g 1-octene, 557 g Isopar E, 1.2 equivalents of RIBS-2 activator relative to the catalyst, 10 μmol MMAO-3A, ​​reactor pressure 138 psi.

[0633]

[0634] Table 8. Ethylene-octene copolymerization data under chain transfer conditions for a series of amino-benzimidazole catalysts.

[0635]

[0636] Semi-batch reactor conditions at 120°C: 11.3 g ethylene, 57 g 1-octene, 557 g Isopar E, 1.2 equivalents of RIBS-2 activator relative to the catalyst, 10 μmol MMAO-3A, ​​reactor pressure 138 psi.

[0637] Table 9. Chain transfer constant (Ca), average PDI over three runs, and standard deviation of PDI .

[0638] IMLC-1 2.3 0.1 4.7 IMLC-2 2.1 0.2 0.5 IMLC-3 2.4 0.5 1.0 IMLC-4 2.9 0.7 5.0 IMLC-9 6.0 0.8 1.2 IMLC-2 3.6 1.0 2.2 IMLC-7 2.2 0.1 4.2 IMLC-8 1.9 0.2 0.8 IMLC-10 16.8 8.6 5.2 IMLC-11 7.2 2.6 1.7 IMLC-12 3.5 0.5 2.6 IMLC-13 6.0 0.4 0.2

[0639]

[0640] Table 10. PPR results of carbazole-based amino-benzimidazole catalysts .

[0641]

[0642]

[0643] A negative value for 1% octene indicates that the signal is too low and can be considered essentially 0.

[0644]

[0645] Table 11. PPR results of amino-benzimidazole catalysts based on gem-dimethylamine .

[0646]

[0647]

[0648]

[0649] Table 12. PPR results of amino-benzimidazole catalysts based on o-tolyl groups

[0650]

[0651]

[0652]

[0653] Table 13. PPR results of carbazole-based amino-benzimidazole catalysts .

[0654]

[0655]

[0656] general material

[0657] All commercially available chemicals can be used without further purification. Hexane, Isopar E, and toluene used in the glove box were purified using a solvent purification system and then dried over molecular sieves.

Claims

1. A catalyst system comprising a metal-ligand complex according to formula (I): in M is a metal selected from titanium, zirconium, or hafnium, wherein the metal has an oxidation state of +2, +3, or +4. Each X is a monodentate or bidentate ligand, wherein the monodentate or bidentate ligand is independently selected from (C6−C6). 50 aryl; n is 2 or 3; m is 1 or 2; The metal-ligand complex has six or fewer metal-ligand bonds; Each R 1 Independently selected from unsubstituted (C6−C) 50 ) aryl or substituted (C6−C 50 aryl; Each R 2 R 3 and R 4 Independently selected from –H; Each R 5 Selected from -NR N , where each R N For (C1-C 20 ) hydrocarbon group; and Each R 6 Independently selected from (C1−C 50 ) hydrocarbon group, (C6−C 50 ) aryl and (C4−C 50 ) Mixed aromatic compounds.

2. The catalyst system according to claim 1, wherein: M represents zirconium or hafnium; Each X is independently selected from (C6−C 20 ) aryl; and Each R 1 Independently selected from unsubstituted (C6−C) 50 ) aryl or substituted (C6−C 50 Aryl.

3. The catalyst system according to claim 1, wherein each R 1 It can be an unsubstituted phenyl, a substituted phenyl, an unsubstituted anthraquinone, a substituted anthraquinone, an unsubstituted naphthyl or a substituted naphthyl.

4. The catalyst system according to claim 3, wherein the substituted phenyl group is selected from 2-methylphenyl, 2-(isopropyl)phenyl, 2,4,6-trimethylphenyl, 2,6-di(isopropyl)phenyl, 2,4,6-tri(isopropyl)phenyl, 3,5-di-tert-butylphenyl, 3,5-diphenylphenyl, and 2,3,5,6-tetrafluorophenyl.

5. The catalyst system according to claim 1, wherein m is 2, and the metal-ligand complex has a structure according to formula (II): Each R 1 R 2 R 3 R 4 R 5 R 6 X is as defined in equation (I); and n is 1 or 2.

6. The catalyst system according to claim 5, wherein: M represents zirconium or hafnium; Each X is independently selected from (C6−C 50 aryl; Each R 1 Independently selected from (C6−C) 50 Aryl.

7. The catalyst system according to claim 1, wherein each X is benzyl.

8. The catalyst system according to claim 1, wherein each R 6 It can be a substituted carbazolyl, an unsubstituted carbazolyl, an unsubstituted phenyl, a substituted phenyl, an unsubstituted anthraquinone, a substituted anthraquinone, an unsubstituted naphthyl, or a substituted naphthyl.

9. The catalyst system according to claim 1, wherein each R 6 It is naphthyl, 2-propyl, 2-methylphenyl, 2-(isopropyl)phenyl, 2,4,6-trimethylphenyl, 2,6-di(isopropyl)phenyl, 2,4,6-tri(isopropyl)phenyl, 3,5-di-tert-butylphenyl, 3,5-diphenylphenyl or 2,7-di-tert-butylcarbazole.

10. The catalyst system according to claim 8, wherein the substituted phenyl group is selected from 2-methylphenyl, 2-(isopropyl)phenyl, 2,4,6-trimethylphenyl, 2,6-di(isopropyl)phenyl, 2,4,6-tri(isopropyl)phenyl, 3,5-di-tert-butylphenyl, 3,5-diphenylphenyl, and 2,3,5,6-tetrafluorophenyl.

11. A method for polymerizing a polymer, the method comprising: In the reactor, ethylene and optionally one or more (C3−C) are contacted in the presence of the catalyst system according to claim 1. 12 α-olefins, wherein the catalyst system further comprises an activator.

12. A metal-ligand complex, said metal-ligand complex being selected from: 。 13. A ligand, said ligand being selected from: 。

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