Thiazole- or imidazole-containing olefin polymerization catalysts

Abstract

A process for polymerizing olefin monomers using a catalyst system comprising a procatalyst having a structure according to formula (I): [Formula 1] JPEG2022539506000115.jpg98170

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 867,039, filed June 26, 2019, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate broadly to olefin polymerization catalyst systems and processes, and more specifically to olefin polymerization catalyst systems including thiazole or imidazole Group 4 transition metal catalysts, and olefin polymerization processes incorporating the catalyst systems. [Background technology]

[0003] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, are produced by various catalyst systems. The selection of such catalyst system used in the polymerization process of an olefin-based polymer is an important factor that contributes to the characteristics and properties of such an olefin-based polymer.

[0004] Ethylene-based polymers and propylene-based polymers are produced for a wide variety of articles. The polyethylene and polypropylene polymerization process can be varied in several ways to produce a wide variety of resulting polyethylene resins with different physical properties that make the various resins suitable for use in different applications. The ethylene monomer and optionally one or more comonomers are present in a liquid diluent (such as a solvent), such as an alkane or isoalkane, e.g., isobutene. Hydrogen can also be added to the reactor. The catalyst system for producing ethylene-based polymers can typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (either metallocene or nonmetallocene (molecular)) catalyst systems. The diluent and the reactants in the catalyst system are circulated in the reactor at high polymerization temperatures, thereby producing an ethylene-based homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture containing the polyethylene product dissolved in the diluent is removed from the reactor, along with unreacted ethylene and one or more optional comonomers. The reaction mixture when removed from the reactor may be treated to remove the polyethylene product from the diluent and unreacted reactants, which are typically recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, where a second polyethylene fraction may be produced. Despite research efforts to develop suitable catalyst systems for olefin polymerization, such as polyethylene or polypropylene polymerization, there remains a need for improved efficiency of catalyst systems capable of producing polymers with high molecular weight and narrow molecular weight distribution. Summary of the Invention

[0005] Embodiments of the present disclosure include a catalyst system comprising a procatalyst having a structure according to formula (I). [ka]

[0006] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4. m is 1 or 2 and n is 2 or 3, with the proviso that m+n=4. Each X is independently an unsaturated (C2-C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C6-C 50 )Aryl, (C6-C 50 )Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C The ligand of formula (I) is monodentate or bidentate and is selected from the group consisting of:

[0007] In formula (I), each Z is NR N or S and R N is (C1-C 20 ) hydrocarbyl or (C1-C 20 ) heterohydrocarbyl. Each R 1 is (C1-C 40 ) hydrocarbyl, (C1-C 40 )heterohydrocarbyl, (C1-C 40 ) aryl, or (C1-C 40 ) heteroaryl. Each R 2 and R 3 are independently 50 ) hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C5-C 50 )aryl, (CC 50 )heteroaryl, -Si(R C 3), halogen, and -H; R C are independently 20 ) hydrocarbyl, (C1-C 20 )heterohydrocarbyl, (C1-C 20 ) aryl, or (C1-C 20) heteroaryl, and -H, and optionally R 2 and R 3 are covalently bonded to form a ring.

[0008] Embodiments of the present disclosure include polymerization processes, particularly processes for producing ethylene-based polymers. The polymerization process comprises the polymerization of ethylene and optionally one or more (C3-C 12 ) an α-olefin. [Brief description of the drawings]

[0009] [Figure 1] A four-step synthetic scheme for synthesizing ligands 1–4, 6–7, and 9–12 is shown. [Diagram 2] A four-step synthetic scheme for synthesizing ligands 13-20 is shown. [Diagram 3] A four step synthetic scheme for the synthesis of ligand 22 is shown. [Figure 4] A four-step synthetic scheme for synthesizing ligands 23-24 is shown. [Diagram 5] A six-step synthetic scheme for the synthesis of ligands 27-29, 31, and 32 is shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Specific embodiments of the catalyst system are described below. It should be understood that the catalyst system of the present disclosure may be implemented in different forms and should not be construed as being limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0011] Common abbreviations are listed below.

[0012] R, Z, M, X, and n: as defined above, Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: iso-propyl, t-Bu: tert-butyl, t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl), Tf: trifluoromethanesulfonate, THF: tetrahydrofuran, Et2O: diethyl ether, CH2Cl2: dichloromethane, CV: column volume (used in column chromatography), EtOAc: ethyl acetate, C6D6: deuterated benzene or benzene-d6: CDCl3: deuterated chloroform, Na2SO4: sodium sulfate, MgSO4: magnesium sulfate, HCl: hydrogen chloride, n-BuL i: butyl lithium, t-BuLi: tert-butyl lithium, Cu2O: copper oxide (I), N,N'-DMEDA: N,N'-dimethylethylenediamine, K3PO4: tribasic potassium phosphate, Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), Pd(dppf)Cl2: dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II), AgNO3: silver nitrate, K2CO3: potassium carbonate, Cs2CO3: cesium carbonate, i-PrOBPin: 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, BrCl2CCCl2Br: 1,2-Dibromotetrachloroethane, HfCl4: Hafnium(IV) chloride, HfBn4: Hafnium(IV) tetrabenzyl, ZrCl4: Zirconium(IV) chloride, ZrBn4: Zirconium(IV) tetrabenzyl, ZrBn2Cl2(OEt2): Zirconium(IV) dibenzyl dichloride mono-diethyl etherate, HfBn2Cl2(OEt2): Hafnium(IV) dibenzyl dichloride mono-diethyl etherate, TiBn4: Titanium(IV) tetrabenzyl, Zr(CH2SiMe3)4: Zirconium(IV) tetrakis-trimethylsilylmethyl, Hf(CH2SiMe3)4: Hafnium(IV) tetrakis-trimethylmethyl, N2: Nitrogen gas, PhMe: Toluene, PPR: Parallel pressure reactor, MAO: Methylaluminoxane, MMAO: Modified methylaluminoxane, GC: Gas chromatography, LC: Liquid chromatography, NMR: Nuclear magnetic resonance, MS: Mass spectrometry, mmol: Millimole, mL: Milliliter, M: Mole, min or mins: Minute, h or hrs: Hours, d: Days, R, f : retained fraction, TLC: thin layer chromatography, rpm: revolutions per minute.

[0013] The term "independently selected" followed by multiple options is 1 , R 2 , R 3 , R 4 and R 5 etc. are used herein to indicate that the individual R groups appearing before the term may be the same or different and there is no dependency as to the identity of the other groups appearing before the term.

[0014] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst to convert the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0015] When used to describe certain carbon atom-containing chemical groups, "(Cx -C y A bracketed expression having the form "(C1-C2)" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, inclusive of x and y. For example, (C1-C2) 50 ) Alkyl, in its unsubstituted form, is an alkyl group having 1 to 50 carbon atoms. In some embodiments and general structures, certain chemical groups are R S The parenthetical "(C x -C y ) for the chemical group R S The substituted version can be represented by any group R S Depending on the identity of R, R may contain more than y carbon atoms. For example, S Exactly one group R is phenyl (-C6H5) S Replaced by (C1-C 50 "(C)alkyl" can contain from 7 to 56 carbon atoms. Thus, the parenthetical "(C)alkyl" is generally used. x -C y )" is a group defined as one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is determined by the sum of all carbon atom-containing substituents R S The total number of carbon atoms derived from the aryl group is determined by adding the total number of carbon atoms derived from the aryl group.

[0016] The term "substituted" refers to the replacement of at least one hydrogen atom (-H) bonded to a carbon or heteroatom of a corresponding unsubstituted compound or functional group with a substituent (e.g., R S The term "persubstituted" means that all hydrogen atoms (H) attached to carbon or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by a substituent (e.g., R S). The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by a substituent. The term "-H" means a hydrogen or hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0017] "(C1-C 50 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical having 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical having from 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and contains one or more R S or not replaced by

[0018] In the present disclosure, (C1-C 50 ) Hydrocarbyl is unsubstituted or substituted (C1-C 50 )Alkyl, (C3-C 50 )cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 ) alkylene, such as benzyl (-CH2-C6H5).

[0019] "(C1-C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to a group that is unsubstituted or has one or more R Sand saturated linear or branched hydrocarbon radicals having 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively, which are substituted by unsubstituted (C1-C 50 Examples of alkyl are unsubstituted (C-C 20 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C-C 20 ) Alkyl, Substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" means that there are up to 45 carbon atoms in the radical, including the substituents, e.g., one R, each of which is (C-C) alkyl. S is replaced by (C 27 -C 40 )alkyl. Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0020] "(C6-C 50 The term "aryl" refers to an aryl group having 6 to 40 carbon atoms, of which at least 6 to 14 are aromatic ring carbon atoms, unsubstituted or (one or more R S (by C6-C8) means a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical substituted with a cyclic or cyclic aromatic ring. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may independently be fused or non-fused, aromatic or non-aromatic. Unsubstituted (C6-C8) means a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical substituted with a cyclic or cyclic aromatic ring. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may independently be fused or non-fused, aromatic or non-aromatic.50 Examples of aryl include unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18 )aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 40 Examples of aryl include substituted (C1-C 20 )Aryl, Substituted (C6-C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0021] "(C3-C 50 The term "cycloalkyl" refers to an unsubstituted or substituted cycloalkyl group that is substituted with one or more R S means a saturated cyclic hydrocarbon radical having 3 to 50 carbon atoms, substituted by other cycloalkyl groups, such as (C x -C y )Cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3-C 40 Examples of cycloalkyl are unsubstituted (C-C 20 )Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C-C 20 )Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0022] (C1-C 50Examples of hydrocarbylenes include unsubstituted or substituted (C6-C 50 )Arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). The diradicals may be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include 1,2-diradicals. α,ω-diradicals are the diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e. -CHCH-), propane-1,3-diyl (i.e. -CHCHCH-), 2-methylpropane-1,3-diyl (i.e. -CHCH(CH)CH-). (C6-C 50 ) Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0023] "(C1-C 50 The term "alkylene" refers to a group that is unsubstituted or has one or more R S means a saturated straight or branched diradical having 1 to 50 carbon atoms (i.e., the radicals are not on ring atoms) substituted by 50 Examples of alkylene are unsubstituted (C-C 20) alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), where "C*" represents a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 50 Examples of alkylenes are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, the two R S Together, (C1-C 18 ) alkylene, so that the substitution (C1-C 50 Examples of alkylenes 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]octane.

[0024] "(C3-C 50 The term "cycloalkylene" refers to a cycloalkylene having 3 to 50 carbon atoms, unsubstituted or substituted with one or more R S "R" means a cyclic diradical (i.e., the radicals are on ring atoms) substituted by:

[0025] 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), Si(R C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )-, and each R C and each R P is unsubstituted (C1-C 18 ) hydrocarbyl or -H, and each RN is unsubstituted (C1-C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 50 The term "heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms, and is defined as "(C1-C 50 The term "heterohydrocarbylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 )heterohydrocarbyl or (C1-C 50 The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl can be on a carbon atom or on a heteroatom. The two radicals of the heterohydrocarbylene can be on a single carbon atom or on a single heteroatom. Furthermore, one of the two radicals of the diradical can be on a carbon atom and the other radical can be on a different carbon atom, or one of the two radicals can be on a carbon atom and the other radical can be on a heteroatom, or one of the two radicals can be on a heteroatom and the other radical can be on a different heteroatom. Each (C1-C 50 )heterohydrocarbyl and (C1-C 50 ) Heterohydrocarbylene is unsubstituted or (one or more R S The ring structure may be substituted (by), aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused polycyclic and non-fused polycyclic) or acyclic.

[0026] (C1-C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heterohydrocarbyls include (C-C 50 )heteroalkyl, (C1-C 50 ) hydrocarbyl-O-, (C1-C 50) hydrocarbyl-S-, (C1-C 50 )hydrocarbyl-S(O)-, (C1-C 50 )hydrocarbyl-S(O)2-, (C1-C 50 ) Hydrocarbyl-Si(R C )2-, (C1-C 50 )hydrocarbyl-N(R N )-, (C1-C 50 ) hydrocarbyl-P(R P )-, (C2-C 50 )heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 )heteroalkylene, (C1-C 50 )heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0027] "(C4-C 50 The term "heteroaryl" refers to an unsubstituted or heteroaryl group having a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms, each of which is selected from the group consisting of one or more R S(C4-C6) means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical substituted with a heteroaromatic ring. A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical can independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C4-C6) are also included. 12 ) heteroaryl, etc., (C x -C y ) Heteroaryl (general) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or has one or more R SThe monocyclic heteroaromatic hydrocarbon radicals are defined in the same manner as those substituted by. The monocyclic heteroaromatic hydrocarbon radicals are 5- or 6-membered rings. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms, which can be 1, 2 or 3, and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. The six-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms, which can be 1 or 2, and the heteroatoms can be N or P. Examples of six-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radicals can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals include indol-1-yl, and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals include quinolin-2-yl, and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radicals can be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0028] "(C1-C 50The term "(C1-C2)heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms or fewer and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene 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, S.R. C , S(O), and S(O), each of the heteroalkyl and heteroalkylene groups is unsubstituted or has one or more R S has been replaced by

[0029] Unsubstituted (C2-C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 )Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0030] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom: fluoride (F - ), chloride (Cl - ), bromide (Br -), or iodide (I - ).

[0031] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted with, one or more double and / or triple bonds may optionally be replaced by a substituent R S The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds, and may or may not be present in the substituent R S or absent, but does not include double bonds which may be present in (hetero)aromatic rings.

[0032] Embodiments of the present disclosure include a catalyst system comprising a procatalyst having a structure according to formula (I). [ka]

[0033] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4. The subscript m is 1 or 2. (X) n The subscript n is 2 or 3, with the proviso that m+n=4. Each X is independently an unsaturated (C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C6-C 50 )Aryl, (C6-C 50 )Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR CThe ligand of formula (I) is monodentate or bidentate and is selected from the group consisting of:

[0034] In formula (I), each Z is NR N or S and R N is (C1-C 20 ) hydrocarbyl or (C1-C 20 ) heterohydrocarbyl. Each R 1 is (C1-C 40 ) hydrocarbyl or (C1-C 20 ) heterohydrocarbyl. Each R 2 and R 3 are independently 50 ) hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C 3), halogen, and -H; R C are independently 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl and -H, and optionally R 2 and R 3 are covalently bonded to form a ring.

[0035] In one or more embodiments, in formula (I), Z is NR N and R N is (C1-C8) alkyl. In some embodiments, R N is methyl, ethyl, 1-propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl (isobutyl), n-butyl, n-hexyl, cyclohexyl, n-octyl, or tert-octyl.

[0036] In various embodiments, each R 3is 2,4,6-triisopropylphenyl, 2,4,6-trimethylphenyl, 3,5-di-tert-butylphenyl, naphthyl, carbozolyl, or cyclopropyl.

[0037] In one or more embodiments, each R 1 But linear (C1-C 12 ) Alkyl, branched (C1-C 12 ) alkyl, (C1-C 12 ) cycloalkyl, trimethylsilylmethyl, benzyl, and 1-adamantyl.

[0038] In some embodiments, the metal-ligand complex of formula (I) has a structure according to formula (Ia), formula (Ib), formula (Ic), or formula (Id). [ka]

[0039] In formulas (Ia), (Ib), (Ic), and (Id), each R 1 , R 2 , R 3 , R N , X, and M are defined as in formula (I).

[0040] In one or more embodiments, in formula (I), R 2 and R 3 are covalently linked to form an aromatic ring, and the metal-ligand complex has a structure according to formula (II). [ka]

[0041] In formula (II), each R 1 , Z, X, n, m, and M are defined as in formula (I), and each R 4 , R 5 , R 6 , and R 7 are independently 40 ) hydrocarbyl or (C1-C40 ) heterohydrocarbyl.

[0042] In some embodiments of the present disclosure, in formula (II), R 7 is (C6-C 40 )Aryl or (C6-C 40 ) heteroaryl. In various embodiments, R 7 is phenyl, 2,4,6-triisopropylphenyl, 2,4,6-trimethylphenyl, 3,5-di-tert-butylphenyl, naphthyl, carbozolyl, or cyclopropyl.

[0043] In some embodiments of the present disclosure, in formulas (I) and (II), m is 2. In other embodiments, m is 1.

[0044] In various embodiments, in formula (II), the metal-ligand complex has a structure according to formula (IIa), formula (IIb), formula (IIc), or formula (IId). [ka]

[0045] In formulae (IIa), (IIb), (IIc), and (IId), each R 1 , R 4 , R 5 , R 6 , R 7 , R N , X, and M are defined as in formula (II).

[0046] In the metal-ligand complex according to formula (I) or formula (II), each X is bonded to M through a covalent bond, a coordinate bond, or an ionic bond. In some embodiments, each X has an identity. The metal-ligand complex has six or fewer metal-ligand bonds and can be overall charge neutral or have a positive charge associated with the metal center. In some embodiments, the catalyst system comprises a metal-ligand complex according to formula (I), where M is zirconium or hafnium, and each X is independently selected from the group consisting of (C1-C20 ) alkyl, (C1-C 20 )heteroalkyl, (C6-C 20 )Aryl, (C4-C 20 )heteroaryl, (C4-C 12 ) a diene, or a halogen. In one or more embodiments, each X is independently benzyl, phenyl, or chloro.

[0047] In some embodiments, the monodentate ligand can be a monoanionic ligand. A monoanionic ligand has a net formal oxidation state of -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) hydrocarbyl carbanion, (C1-C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, carbonates, phosphates, sulfates, HC(O)O - , HC(O)N(H) - , (C1-C 40 ) Hydrocarbyl C(O)O - , (C1-C 40 ) HydrocarbylC(O)N((C1-C 20 )hydrocarbyl) - , (C1-C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L S - wherein each R K , R L , and R M are independently hydrogen, (C1-C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R Kand R L Together, (C2-C 40 ) hydrocarbylene or (C1-C 20 ) forms a heterohydrocarbylene, R M is as defined above.

[0048] In other embodiments, at least one monodentate ligand X, independently of any other ligand X, may be a neutral ligand. In certain embodiments, a neutral ligand is R Q NR K R L , R K OR L , R K S.R. L , or R Q PR K R L wherein each R Q are independently hydrogen, [(C1-C 10 )hydrocarbyl]3Si(C1-C 10 ) hydrocarbyl, (C1-C 40 ) hydrocarbyl, [(C1-C 10 )hydrocarbyl]3Si, or (C1-C 40 ) heterohydrocarbyl, each R K and R L are independently as previously defined.

[0049] Further, each X may be, independently of any other X, a halogen, an unsubstituted (C 20 ) Hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbylC(O)O-, or R K R L N-, where R K and R L each independently is unsubstituted (C 20 In some embodiments, each monodentate ligand X is a chlorine atom, (C-C 10 ) hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10) hydrocarbylC(O)O-, or R K R L N-, where R K and R L each independently is unsubstituted (C 10 In one or more embodiments of formula (I), (II), and (III), X is benzyl, chloro, —CH2SiMe3, or phenyl.

[0050] In further embodiments, each X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. In some embodiments, each X is the same. In other embodiments, at least two X are different from each other. In embodiments where at least two X are different from at least one X, X is different from one of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0051] In some embodiments, the chemical groups (e.g., X and R 1 ~R 4 In other embodiments, any or all of the chemical groups X and R of the metal-ligand complex of formula (I) may be unsubstituted. 1 ~R 4 are not substituted, or any or all of them are substituted with one or more R S Two or more R S are attached to the same chemical group of the metal-ligand complex of formula (I), the individual R S may be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, the chemical groups X and R 1 ~R 4 However, both are R Sare not over-substituted with, or any or all of them are R S It may be oversubstituted with R S In chemical groups that are over-substituted with S may all be the same or may be independently selected.

[0052] An embodiment of the present disclosure includes a polymerization process comprising 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).

[0053] In an exemplary embodiment, the catalyst system can include a metal-ligand complex according to formula (I) having the structure of any of the procatalysts 1-22 listed below, which are synthesized from the corresponding ligands 1-43. [ka] [ka] [ka] [ka]

[0054] Chain Shuttling and / or Chain Transfer Agents In one or more embodiments, the polymerization process of the present disclosure comprises the polymerization of ethylene and / or one or more (C3-C4) olefins in a reactor in the presence of a catalyst system and a chain transfer or chain shuttling agent. 12 ) contacting an α-olefin with a procatalyst having a structure of formula (I) and, optionally, a cocatalyst, (B) an olefin polymerization catalyst having a different comonomer selectivity than the procatalyst (A), and (C) a chain transfer or chain shuttling agent.

[0055] As an addition to a catalyst system, chain transfer agents and chain shuttling agents are compounds that can transfer polymer chains between two catalyst molecules in a single polymerization reactor. The catalyst molecules can have the same structure or different structures. When the catalyst molecules have different structures, they can have different monomer selectivities. Whether a compound functions as a chain transfer agent or a chain shuttling agent depends on the type of polymerization reactor, even though the aforementioned three components (A)-(C) can be chemically identical in either type of polymerization reactor. For example, in a batch reactor with a single catalyst system or a dual catalyst system, the compound functions as a chain transfer agent. In a continuous reactor with a dual catalyst system, the compound functions as a chain shuttling agent. In general, a compound that functions as a chain transfer agent in a batch reactor can also function as a chain shuttling agent in a continuous reactor, and conversely, a molecule that functions as a chain shuttling agent can also function as a chain transfer agent. Thus, in embodiments of the polymerization process in this disclosure, it should be understood that the disclosure of a compound as a "chain transfer agent" further constitutes the disclosure of the same compound as a "chain shuttling agent." Thus, the terms "chain transfer agent" and "chain shuttling agent" are interchangeable with respect to compounds, but are distinguishable when the process is designated to take place in a particular type of polymerization reactor.

[0056] The chain transfer ability of a catalyst is first evaluated by running trials of varying the level of chain transfer or shuttling agent (CSA) to observe the overall effect on molecular weight drop and PDI expected for a shuttling catalyst. The molecular weight of the polymer produced by a catalyst that has the potential to be a good chain shuttle agent will be more sensitive to the addition of a CSA than the polymer molecular weight produced by a poorer shuttling or slower chain transfer rate. The Mayo equation (Equation 1) states that the chain transfer agent will increase the molecular weight when no chain transfer agent is present.

number

number

number

number

number

[0057] Typically, the chain transfer agent comprises a metal that is Al, B, or Ga in a formal oxidation state of +3, or a metal that is Zn or Mg in a formal oxidation state of +2. Chain transfer agents suitable for the processes of the present disclosure are described in U.S. Patent Application Publication No. 2007 / 0167315, which is incorporated herein by reference in its entirety.

[0058] In one or more embodiments of the polymerization process, the chain transfer agent, when present, is selected from the group consisting of diethyl zinc, di(isobutyl) zinc, di(n-hexyl) zinc, di(n-octyl) zinc, triethylaluminum, trioctylaluminum, triethylgallium, isobutylaluminum bis(dimethyl(t-butyl)siloxane), isobutylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), bis(n-octadecyl)isobutylaluminum, isobutylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide, n-octylaluminum bis(2,6-di-t-butylphenoxide), ... The ethylaluminum di(ethyl(l-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis(dimethyl(t-butyl)siloxide, ethylzinc(2,6-diphenylphenoxide), ethylzinc(t-butoxide), dimethylmagnesium, dibutylmagnesium, and n-butyl-sec-butylmagnesium.

[0059] cocatalyst component The catalyst system comprising the metal-ligand complex of formula (I) can be made catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the procatalyst according to the metal-ligand complex of formula (I) can be made catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Furthermore, the metal-ligand complex according to formula (I) includes both a procatalyst form that is neutral and a catalyst form that can be positively charged by loss of a monoanionic ligand such as benzyl or phenyl. Activating cocatalysts suitable for use in the present invention include alkylaluminum, polymeric or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum modified methylalumoxane, and isobutylalumoxane.

[0060] The Lewis acid activating cocatalyst may be any of the Lewis acid activating cocatalysts described herein (C1-C 20 In some embodiments, the Group 13 metal compound includes a tri((C1-C2) hydrocarbyl substituent. 20 )hydrocarbyl)-substituted aluminum or tri((C1-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C-C 20 )hydrocarbyl)-boron compounds, tri((C1-C 10 ) alkyl) aluminum, tri((C6-C 18)aryl)boron compounds, and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C 20 ) hydrocarbyl borates (e.g., trityl tetrafluoroborate) or tri((C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)boranes (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to any of the ((C 20 ) Hydrocarbyl) 4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 ) HydrocarbylN(H)3 + , or N(H)4 + Each of the nitrogen cations (C1-C 20 ) Hydrocarbyls, when present in two or more occurrences, may be the same or different.

[0061] The neutral Lewis acid activating cocatalyst combination is tri((C1-C4) alkyl)aluminum and tri((C6-C 18)aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments are combinations of such neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The ratio of the number of moles of (metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane)] is 1:1:1 to 1:10:30, and in other embodiments is 1:1:1.5 to 1:5:10.

[0062] The catalyst system comprising the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxanes, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, and combinations thereof.

[0063] In some embodiments, two or more of the aforementioned activating cocatalysts can be used in combination with each other. Specific examples of cocatalyst combinations are mixtures of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with oligomeric or polymeric alumoxane compounds. The ratio of the total number of moles of the one or more metal-ligand complexes of formula (I) to the total number of moles of the one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, this 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 alumoxane is used alone as the activating cocatalyst, it is preferred that the number of moles of alumoxane used is at least 100 times the number of moles of the metal-ligand complexes of formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of one or more metal-ligand complexes of formula (I) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activating cocatalysts are generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of formula (I).

[0064] Polyolefin The catalyst system described in the previous paragraph is utilized for the polymerization of olefins, primarily ethylene and propylene. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme to produce a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomer typically has 20 or fewer carbon atoms. For example, the α-olefin comonomer 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, the 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.

[0065] An ethylene-based polymer, e.g., a homopolymer and / or interpolymer (including copolymer) of ethylene, and optionally one or more comonomers, such as an α-olefin, can include at least 50 weight percent or more of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 weight percent" are disclosed herein as separate embodiments, for example, an ethylene-based polymer, a homopolymer and / or interpolymer (including copolymer) of ethylene, and optionally one or more comonomers, such as an α-olefin, can include at least 60 weight percent of monomer units derived from ethylene, at least 70 weight percent of monomer units derived from ethylene, at least 80 weight percent of monomer units derived from ethylene, or from 50 to 100 weight percent of monomer units derived from ethylene, or from 80 to 100 weight percent of monomer units derived from ethylene.

[0066] In some embodiments, the ethylene-based polymer can include at least 90 mole percent of units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer can include at least 93 mole percent units derived from ethylene, at least 96 mole percent units derived from ethylene, at least 97 mole percent units derived from ethylene, or alternatively, from 90 to 100 mole percent units derived from ethylene, from 90 to 99.5 mole percent units derived from ethylene, or from 97 to 99.5 mole percent units derived from ethylene.

[0067] In some embodiments of the ethylene-based polymer, the amount of the additional α-olefin is less than 50%, other embodiments include at least 0.5 mole percent (mol%) to 25 mol%, and in further embodiments the amount of the additional α-olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0068] Any conventional polymerization process may be used to produce the ethylene-based polymers, including, but not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and any combination thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc., in parallel, in series, or in any combination thereof.

[0069] In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system described herein and herein and, optionally, one or more other catalysts. The catalyst system described herein can be used in the first reactor or the second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of the catalyst system described herein.

[0070] In another embodiment, the ethylene-based polymer can be produced in a solution polymerization in a single reactor system, such as a single loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of a catalyst system described within this disclosure and optionally one or more cocatalysts, as described in the previous paragraph.

[0071] The ethylene-based polymer 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. The ethylene-based polymer may include any amount of additives. The ethylene-based polymer may include from about 0 to about 10 weight percent of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further include a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may include from about 0 to about 20 weight percent of a filler, such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer may be further compounded with one or more polymers to form a blend.

[0072] In some embodiments, a polymerization process for producing an ethylene-based polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, the catalyst system incorporating at least one metal-ligand complex of formula (I). Polymers obtained from such catalyst systems incorporating a metal-ligand complex of formula (I) can have a molecular weight of, for example, 0.850 g / cm or less according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.950g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm 3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density of the sintered body may be 0.01 to 0.01.

[0073] In another embodiment, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a melt flow ratio (I 10 / I2), where melt index I2 is measured at 190° C. and a load of 2.16 kg according to ASTM D1238, which is incorporated herein by reference in its entirety, and melt index I 10 is measured at 190° C. and a load of 10 kg according to ASTM D1238. In another embodiment, the melt flow ratio (I 10 / I2) is 5-10, and in others, the melt flow ratio is 5-9.

[0074] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 1 to 25, the MWD being w / M n is defined as M w is the weight average molecular weight, M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1 to 6. Another embodiment includes an MWD of 1 to 3, and another embodiment includes an MWD of 1.5 to 2.5.

[0075] Embodiments of the catalyst systems described in this disclosure result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0076] All solvents and reagents are obtained from commercial sources and used as received unless otherwise stated. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether are purified by passing through activated alumina, and in some cases Q-5 reactants. Solvents used in experiments performed in a nitrogen-filled glove box are further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware is dried overnight in an oven before use. NMR spectra are recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis is performed using a Waters e2695 separation module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a 5:95 to 100:0 gradient of acetonitrile and water (with 0.1% formic acid as the ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 H NMR data are reported as follows: chemical shifts, multiplicities (br=broadline, s=singlet, d=doublet, t=triplet, q=quartet, p=quintet, sex=sexet, sept=septet, and m=multiplet), integrals, and assignments. 1 Chemical shifts for H NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, δ scale). 13 C NMR data is 1 Determined with 1 H decoupling and chemical shifts are reported as ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

[0077] General procedure for PPR screening experiments Polyolefin catalyst screening is performed in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consists of an array of 48 single-cell (6 × 8 matrix) reactors in an inert atmosphere glovebox. Each cell is equipped with a glass insert with an internal working liquid volume of approximately 5 mL. Each cell has independent pressure control, and the liquids in the cells are continuously stirred at 800 rpm. Unless otherwise noted, catalyst solutions are prepared by dissolving the appropriate amount of ligand in toluene and mixing it with a solution of hafnium tetrabenzyl or zirconium tetrabenzyl in toluene to form the procatalyst in situ. All liquids (e.g., solvent, 1-octene, chain shuttling agent solution appropriate for the experiment, and catalyst solution) are added to the single-cell reactor via robotic syringes. Gaseous reagents (i.e., ethylene, H2) are added to the single-cell reactor via a gas injection port. Before each run, the reactor is heated to 80 °C, purged with ethylene, and vented.

[0078] A portion of Isopar-E is added to the reactor. The reactor is heated to the run temperature and pressurized with ethylene to the appropriate psig. A toluene solution of the reagents is added in the following order: (1) 1-octene with 500 nmol of scavenger MMAO-3A, ​​(2) activator (cocatalyst-1, cocatalyst-2, etc.), and (3) catalyst.

[0079] A small amount of Isopar-E is added after each liquid addition so that the total reaction volume is 5 mL after the final addition. Once the catalyst is added, the PPR software begins monitoring the pressure in each cell. The pressure (within approximately 2-6 psig) is maintained by additional addition of ethylene gas by opening the valve at set point minus 1 psi and closing the valve when the pressure rises above 2 psi. All pressure drops are recorded cumulatively as ethylene "uptake" or "conversion" over the duration of the run or until the uptake or conversion requirement is reached, whichever comes first. Each reaction is quenched by the addition of 10% carbon monoxide in argon for 4 minutes at a pressure of 40-50 psi above the reactor pressure. A shorter "quench time" means a more active catalyst. To prevent excess polymer formation in any given cell, the reactions are quenched when a predetermined uptake level (50 psig for the 120°C run, 75 psig for the 150°C run) is reached. After all reactions are quenched, the reactor is cooled to 70° C. The reactor is vented and purged with nitrogen for 5 minutes to remove carbon monoxide, and the tube is removed. The polymer sample was dried in a centrifugal evaporator for 12 hours at 70° C., weighed to determine the polymer yield, and submitted for IR (1-octene incorporation) and GPC (molecular weight) analysis.

[0080] SymRAD HT-GPC analysis Molecular weight data are determined by analysis on a hybrid Symyx / Dow built robot-assisted dilution high temperature gel permeation chromatography instrument (Sym-RAD-GPC). Polymer samples are dissolved by heating at 160°C for 120 minutes in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL stabilized by 300 parts per million (ppm) butylated hydroxyl toluene (BHT). Each sample was diluted to 1 mg / mL immediately prior to injection of a 250 μL aliquot of sample. The GPC is 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. Sample detection is performed using a PolyChar IR4 detector in concentration mode. Conventional calibration of narrow polystyrene (PS) standards is utilized in apparent units adjusted to homopolyethylene (PE) using the known Mark-Houwink coefficients of PS and PE in TCB at this temperature.

[0081] 1-Octene Incorporation IR Analysis A sample run for HT-GPC analysis precedes the IR analysis. For IR analysis, a 48-well HT silicon wafer is utilized for sample deposition and analysis of 1-octene incorporation. For analysis, the sample is heated to 160°C for up to 210 minutes, the sample is reheated to remove the magnetic GPC stir bar, and shaken with a glass rod stir bar in a J-KEM Scientific heated robotic shaker. The sample is deposited with heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene is evaporated from the deposition wells of the wafer at 160°C under a nitrogen purge. Analysis of 1-octene is performed on the HT silicon wafer using a NEXUS 670 ESPFT-IR.

[0082] Batch Reactor Polymerization Procedure The batch reactor polymerization reaction is carried out in a 2L Parr™ batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by the Camile™ TG process computer. The bottom of the reactor is fitted with a dump valve that transfers the reactor contents to a stainless steel dump pot. The dump pot is pre-filled with catalyst deactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). Both the pot and the tank are purged with nitrogen and the dump pot is vented to a 30 gallon blowdown tank. All solvents used for polymerization or catalyst make-up are passed through a solvent purification column to remove any impurities that may affect the polymerization. 1-Octene and IsoparE are passed through two columns, the first containing A2 alumina, the second containing Q5. Ethylene is passed through two columns, the first containing A204 alumina and

number

number

[0083] The reactor is first loaded from a shot tank which may contain IsoparE solvent and / or 1-octene depending on the reactor load. The shot tank is filled to the load set point using a lab scale attached to the shot tank. After the liquid feed is added, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor at the reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored by a micromotion flow meter. In some experiments, standard conditions at 120°C are 88g ethylene and 568g 1-octene in 1155g IsoparE, and standard conditions at 150°C are 81g ethylene and 570g 1-octene in 1043g IsoparE.

[0084] The procatalyst and activator are mixed with an appropriate amount of purified toluene to obtain a molar solution. The procatalyst and activator are handled in an inert glove box, drawn into a syringe, and pressure transferred into the catalyst shot tank. The syringe is rinsed three times with 5 mL of toluene. Immediately after the catalyst is added, a run timer is started. If ethylene is used, it is added by Camille to maintain the reaction pressure set point in the reactor. The polymerization reaction is run for 10 minutes, then the agitator is stopped and the bottom dump valve is opened to transfer the reactor contents to a dump pot. The dump pot contents are poured into a tray and placed in a lab hood where the solvent is allowed to evaporate overnight. The tray with the remaining polymer is transferred to a vacuum oven and heated to 140°C under vacuum to remove any remaining solvent. After the tray is cooled to ambient temperature, the polymer yield is measured to measure efficiency and subjected to polymer testing. EXAMPLES

[0085] Examples 1-75 provide synthetic procedures for ligand intermediates, ligands, and isolated procatalyst structures of ligands 1-34. Procatalysts 1-22 were synthesized from ligands 1-8. In Example 76, the results of polymerization reactions of procatalysts 1-22 are tabulated and discussed. One or more features of the present disclosure are illustrated with reference to the following examples.

[0086] Example 1: 2-Bromo-6-methythyranine [ka] Under N2 atmosphere, 2,6-dibromoaniline (1.50 g, 5.98 mmol, 1.0 equiv), mesitylboronic acid (7.17 mmol, 1.18 g, 1.2 equiv), K2CO3 (3.31 g, 23.9 mmol, 4.0 equiv), and Pd(PPh3)4 (0.690 g, 0.60 mmol, 0.1 equiv) were added to a round-bottom flask. Toluene (36 mL), 24 mL of H2O, and 12 mL of EtOH were added, and the resulting mixture was heated to 95 °C for 48 h. After cooling, the biphasic solution was diluted with saturated aqueous NH4Cl (100 mL) and CHCl (100 mL) and separated. The organic phase was washed with water (1 × 100 mL) and saturated aqueous NaHCO3 (1 × 100 mL). The organic phase was dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo to give a brown oil. The crude product was purified by ISCO column chromatography on silica gel using ethyl acetate in hexanes as the solvent system. The product was not separated from residual starting material or bis-coupled material as determined by UPLC and was therefore resubmitted to reverse-phase ISCO column chromatography using a water in acetonitrile solvent system. The purified material was collected as 708.6 mg (41%) of a pale yellow oil. 1 H NMR(400MHz,CDCl3)δ7.41(ddd,J=8.0,1.5,0.6Hz,1H),6.97(s,2H),6.86(ddd,J=7.4,1 .5,0.5Hz,1H),6.67(ddd,J=7.9,7.3,0.6Hz,1H),3.84(s,2H),2.33(s,3H),2.00(s,6H). 13 C NMR (101MHz, CDCl3) δ141.67,137.62,137.07,134.50,131.45,129.25,128.72,127.30,119.02,109.36,21.22,20.17.

[0087] Example 2: 3-Bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl: [ka] To a solution of 2-bromo-6-methythyranilline (846 mg, 2.91 mmol, 1 equiv) in dichloromethane (4 mL) was added a solution of saturated aqueous NaHCO3 (4 mL). The reaction mixture was cooled to 0 °C and thiophosgene (0.581 mL, 7.58 mmol, 2.6 equiv) was added dropwise. The reaction was allowed to warm to room temperature and stirred for 48 h. The mixture was then diluted with methylene chloride (20 mL), washed with brine (20 mL), and the organic layer was dried over Na2SO4 and concentrated in vacuo to give an orange oil. The crude product was purified by ISCO column chromatography on silica gel using ethyl acetate in hexanes as the solvent system. The purified material was collected as pale yellow crystals, yielding 914.3 mg (94% yield). 1 H NMR (400MHz, CDCl3) δ7.57(dd,J=8.0,1.5Hz,1H),7.18(t,J=7.8Hz,1H),7.12(dd,J=7.6,1.6Hz,1H),6.96(s,2H),2.35(s,3H),1.98(s,6H). 13 C NMR (101MHz, CDCl3) δ140.98,138.33,136.28,134.29,132.01,129.79,128.43(2C),128.04,119.90,21.28,20.32.

[0088] Example 3: Ligand 1-N-butyl-4-mesitylbenzothiazol-2-amine [ka] In a glove box, a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and n-butylamine (0.060 mL, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. The next day, copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the glove box. The reaction was diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 75 mg (77% yield). 1 H NMR(400MHz,CDCl3)δ7.62(d,J=7.8Hz,1H),7.13(t,J=7.6Hz,1H),7.05(d,J=7.4Hz,1H),6.97(s,2H),5.36(t,J=5.4Hz,1H) ),3.27(q,J=6.9Hz,2H),2.35(s,3H),2.01(s,6H),1.70-1.56(m,2H),1.42(dq,J=14.5,7.3Hz,2H),0.96(t,J=7.3Hz,3H). 13 C NMR(101MHz,CDCl3)δ167.27,151.08,136.81,136.57,136.29,131.44,130.8 2,128.05,127.24,120.99,119.50,45.71,31.62,21.19,20.64,19.96,13.69.

[0089] Example 4: 1-(3-bromo-2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)-3-((trimethylsilyl)methyl)thiourea: [ka] To a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl (227 mg, 0.68 mmol, 1 equiv.) in dichloromethane (4 mL) was added (trimethylsilyl)methylamine (0.183 mL, 1.37 mmol, 2 equiv.). The reaction was stirred at room temperature overnight. After 16 h, the reaction was complete as determined by UPLC MS. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 286 mg (96%). 1 H NMR(400MHz,CDCl3)δ7.71(d,J=8.0Hz,1H),7.30(t,J=7.8Hz,1H),7.19(d,J=7.6Hz,1H),6 .92(s,2H),6.82(s,1H),5.46(s,1H),3.04(s,2H),2.30(s,3H),1.91(s,6H),0.02(s,9H). 13 C NMR (101MHz, CDCl3) δ181.49,141.87,137.85,135.10,133.64,132.96,130.84,129.68,128.76(2C),123.61,21.10,20.41,-2.55.

[0090] Example 5: Ligand 3-4-mesityl-N-((trimethylsilyl)methyl)benzothiazol-2-amine [ka] To a mixture of thiourea (94.7 mg, 0.22 mmol, 1 equiv.), Cs2CO3 (141.7 mg, 0.43 mmol, 2 equiv.), CuI (2.1 mg, 0.01 mmol, 5 mol%) and 1,10-phenanthroline (3.9 mg, 0.02 mmol, 10 mol%) was added dimethoxyethane (2 mL). The reaction mixture was heated at 70 °C under nitrogen for 16 h, at which point the cyclization was complete as determined by UPLCMS. The reaction was then diluted with ethyl acetate (25 mL) and then washed twice with 25 mL of water, followed by a wash with saturated aqueous NaCl solution (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The reaction yielded 51.3 mg in 67% yield. 1 H NMR(500MHz,CDCl3)δ7.62(dd,J=7.8,1.4Hz,1H),7.10(t,J=7.6Hz,1H),7.03(dd,J=7.4,1.4H z,1H),6.95(s,2H),5.24(s,1H),2.66(d,J=4.8Hz,2H),2.32(s,3H),1.99(s,6H),0.11(s,9H). 13 C NMR(101MHz, CDCl3)δ170.56,151.51,136.97,136.76,136.45,131.38,130.95,128.18,127.30,120.91,119.68,36.53,21.33,20.75,-2.57.

[0091] Example 6: 1-(3-bromo-2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)-3-isopropylthiourea [ka] To a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl (81.1 mg, 0.24 mmol, 1 equiv.) in dichloromethane (2 mL) was added isopropylamine (0.042 mL, 0.49 mmol, 2 equiv.). The reaction was stirred at room temperature overnight. After 16 h, the reaction was complete as determined by UPLC MS and concentrated to 95 mg of a pale yellow oil (99%). The oil was carried on to the next step without further purification. 1 H NMR(400MHz,CDCl3)δ7.70(dd,J=8.0,1.5Hz,1H),7.30(t,J=7.8Hz,1H),7.19(dd,J=7.6,1.5Hz,1H),6 .93(s,2H),5.29(s,2H),4.49(dq,J=13.0,6.3Hz,1H),2.30(s,3H),1.93(s,6H),1.14(d,J=6.6Hz,6H). 13 C NMR(101MHz, CDCl3)δ178.89,141.81,138.07,135.20,133.61,133.26,131.01,129.80,128.94(2C),123.52,47.69,22.30,21.17,20.59.

[0092] Example 7: Ligand 4-N-isopropyl-4-mesitylbenzothiazol-2-amine [ka] To a mixture of thiourea (95.0 mg, 0.24 mmol, 1 equiv.), Cs2CO3 (158.2 mg, 0.49 mmol, 2 equiv.), CuI (2.3 mg, 0.01 mmol, 5 mol%) and 1,10-phenanthroline (4.4 mg, 0.02 mmol, 10 mol%) was added dimethoxyethane (2 mL). The reaction mixture was heated at 70 °C under nitrogen for 4 h, at which point the cyclization was complete as determined by UPLCMS. The reaction was then diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. Product 58.3 mg (77%). 1 H NMR(500MHz,CDCl3)δ7.60(dt,J=7.8,1.1Hz,1H),7.12(td,J=7.6,0.9Hz,1H),7.04(dt,J=7.5,1.1Hz,1H), 6.96(s,2H),5.23(d,J=7.9Hz,1H),3.66(h,J=6.5Hz,1H),2.34(s,3H),2.01(s,6H),1.27(d,J=6.4Hz,6H). 13 C NMR (126MHz, CDCl3) δ166.14,151.05,136.94,136.64,136.40,131.58,130.99,128.16,127.33,121.16,119.59,48.14,23.19,21.32,20.79.

[0093] Example 8: Ligand 5-N-cyclohexyl-4-mesitylbenzothiazol-2-amine [ka] To a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl (99.0 mg, 0.30 mmol, 1 equiv.) in dichloromethane (3 mL) was added cyclohexylamine (0.068 mL, 0.60 mmol, 2 equiv.). The reaction was stirred at room temperature overnight. After 16 h, the reaction was concentrated to a colorless translucent oil and carried on to the next step without further purification. To a mixture of thiourea (128.0 mg, 0.3 mmol, 1 equiv.), Cs2CO3 (193.3 mg, 0.59 mmol, 2 equiv.), CuI (2.8 mg, 0.01 mmol, 5 mol%) and 1,10-phenanthroline (5.3 mg, 0.03 mmol, 10 mol%) was added dimethoxyethane (2 mL). The reaction mixture was heated at 70° C. under nitrogen for 4 hours, at which point the cyclization was complete as determined by UPLCMS. The reaction was then diluted with ethyl acetate (25 mL) and then washed with H2O (2×25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 79.5 mg (77%). 1 H NMR(400MHz,CDCl3)δ7.62(dd,J=7.7,1.4Hz,1H),7.13(t,J=7.6Hz,1H),7.07(dd,J=7.4,1.4Hz,1H),6.99(s,2H),5.42(d,J=8.3Hz,1H),3.31(dddd,J =13.5,9.7,8.1,3.8Hz,1H),2.36(s,3H),2.16-2.06(m,2H),2.04(s,6H),1 .84-1.73(m,2H),1.70-1.59(m,1H),1.50-1.34(m,2H),1.34-1.22(m,3H). 13 C NMR(101MHz,CDCl3)δ166.22,151.05,136.92,136.61,136.35,131.43,130.8 8,128.15,127.27,121.04,119.55,55.09,33.29,25.50,24.68,21.29,20.77.

[0094] Example 9: Ligand 6-N-(tert-butyl)-4-mesitylbenzothiazol-2-amine [ka] To a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl (128.0 mg, 0.39 mmol, 1 equiv.) in dichloromethane (3 mL) was added t-butylamine (0.081 mL, 0.77 mmol, 2 equiv.). The reaction was stirred at room temperature overnight. After 16 h, the reaction was concentrated to a colorless translucent oil, 150 mg (96%). The oil was carried on to the next step without further purification. To a mixture of thiourea (150 mg, 0.37 mmol, 1 equiv.), Cs2CO3 (241.1 mg, 0.74 mmol, 2 equiv.), CuI (3.5 mg, 0.02 mmol, 5 mol%) and 1,10-phenanthroline (6.7 mg, 0.04 mmol, 10 mol%) was added dimethoxyethane (2 mL). The reaction mixture was heated at 70° C. under nitrogen for 16 hours, at which point the cyclization was complete as determined by UPLCMS. The reaction was then diluted with ethyl acetate (25 mL) and then washed with H2O (2×25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 101.2 mg (84%). 1 H NMR(400MHz,CDCl3)7.62(dd,J=7.7,1.4Hz,1H),7.15(t,J=7.6Hz,1H),7.08(dd,J =7.4,1.4Hz,1H),6.99(s,2H),5.40(s,1H),2.38(s,3H),2.05(s,6H),1.42(s,9H). 13C NMR (101MHz, CDCl3) δ163.99,150.50,137.04,136.43,136.40,131.68,131.38,127.99,127.15,121.30,119.25,52.77,29.15,21.29,20.76.

[0095] Example 10: Ligand 7-N-(adamantan-1-yl)-4-mesitylbenzothiazol-2-amine: [ka] To a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl (101.0 mg, 0.30 mmol, 1 equiv.) in dichloromethane (3 mL) was added 1-adamantylamine (0.069 mg, 0.46 mmol, 1.5 equiv.). The reaction was stirred at room temperature overnight. After 16 h, the reaction had concentrated to an off-white solid. The resulting solid was carried on to the next step without further purification. To a mixture of thiourea (147.0 mg, 0.30 mmol, 1 equiv.), Cs2CO3 (198.1 mg, 0.52 mmol, 2 equiv.), CuI (2.9 mg, 0.02 mmol, 5 mol%) and 1,10-phenanthroline (5.5 mg, 0.03 mmol, 10 mol%) was added dimethoxyethane (2 mL). The reaction mixture was heated at 70° C. under nitrogen for 6 hours, at which point the cyclization was complete as determined by UPLCMS. The reaction was then diluted with ethyl acetate (25 mL) and then washed with H2O (2×25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 108 mg (88%). 1H NMR(400MHz,CDCl3)δ7.60(dd,J=7.7,1.3Hz,1H),7.13(t,J=7.6Hz,1H),7.06(dd,J=7.4,1.4Hz,1H),6.98(s,2H) ),5.46(s,1H),2.36(s,3H),2.18-2.11(m,3H),2.03(s,6H),2.01(d,J=2.9Hz,6H),1.70(qd,J=12.2,5.9Hz,6H). 13 C NMR(101MHz,CDCl3)δ163.45,150.04,136.99,136.53,136.41,131.56,131.4 8,128.04,127.09,121.19,119.20,52.86,42.00,36.29,29.60,21.27,20.77.

[0096] Example 11: Ligand 8-N-benzyl-4-mesitylbenzothiazol-2-amine: [ka] In a glove box, a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and benzylamine (0.066 mL, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. The next day, copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the CM-3 glovebox. The reaction was diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 100 mg (93%). 1 H NMR(400MHz,CDCl3)δ7.61(d,J=7.8Hz,1H),7.39-7.30(m,5H),7.15(t,J=7.6Hz,1H),7.07( d,J=6.1Hz,1H),6.97(s,2H),5.67(s,1H),4.49(d,J=5.8Hz,2H),2.35(s,3H),2.01(s,6H). 13 C NMR (101MHz, CDCl3) δ136.83,136.32,129.56,128.09,127.42,124.02,122.38,119.61,119.46,41.00,21.20,20.65.

[0097] Example 12: 1-(3-bromo-2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)-3-phenylthiourea: [ka] To a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl (107.5 mg, 0.32 mmol, 1 equiv.) in dichloromethane (2.5 mL) was added aniline (0.059 mL, 0.65 mmol, 2 equiv.). The reaction was stirred at room temperature overnight. After 16 h, the reaction had concentrated to a pale yellow oil. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 138 mg (87%). 1 H NMR(400MHz,CDCl3)δ7.69(ddd,J=8.0,1.5,0.5Hz,1H),7.50(s,1H),7.35-7.26(m,4H),7.17(ddd, J=7.6,1.5,0.6Hz,1H),6.96(s,2H),6.89(s,1H),6.85(d,J=7.4Hz,2H),2.36(s,3H),1.95(s,6H). 13 C NMR(101MHz,CDCl3)δ180.26,141.87,137.72,136.54,135.03,134.57,132.67 ,130.17,129.87,129.65,128.77,127.58,125.70(2C),125.12,21.26,20.75.

[0098] Example 13: Ligand 9-4-mesityl-N-phenylbenzothiazol-2-amine [ka] To a mixture of thiourea (111.4 mg, 0.26 mmol, 1 equiv.), Cs2CO3 (170.6 mg, 0.52 mmol, 2 equiv.), CuI (2.5 mg, 0.01 mmol, 5 mol%) and 1,10-phenanthroline (4.7 mg, 0.03 mmol, 10 mol%) was added dimethoxyethane (2 mL). The reaction mixture was heated at 70 °C under nitrogen for 18 h, at which point the cyclization was complete as determined by UPLCMS. The reaction was then diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 75.1 mg (83%). 1 H NMR(400MHz,CDCl3)δ7.63(dd,J=7.8,1.3Hz,1H),7.42(s,1H),7.39-7.32(m,2H),7.30(dt,J=8 .3,0.9Hz,2H),7.21(t,J=7.6Hz,1H),7.15-7.09(m,2H),6.98(s,2H),2.35(s,3H),2.02(s,6H). 13 C NMR(101MHz,CDCl3)δ162.99,149.66,140.05,136.86,136.46,136.38,132.23, 130.48,129.51,128.20,127.58,123.94,122.46,119.70,119.47,21.29,20.80.

[0099] Example 14: Ligand 10-N-(3,5-di-tert-butylphenyl)-4-mesitylbenzothiazol-2-amine: [ka] In a glove box, a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and 3,5-di-tert-butylaniline (124 mg, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. The next day, copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the CM-3 glovebox. The reaction was diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 117 mg (85%). 1 H NMR(400MHz,CDCl3)δ7.66(dd,J=7.9,1.3Hz,1H),7.29-7.26(d,2H),7.23(t,J=7.6Hz,1H),7.17( t,J=1.7Hz,1H),7.14(dd,J=7.4,1.3Hz,1H),6.99(s,2H),2.38(s,3H),2.05(s,6H),1.31(s,18H). 13 C NMR(101MHz,CDCl3)δ152.18,136.59,136.27,129.06,128.25,128.09,127 .26,125.32,122.28,119.45,117.80,113.76,34.98,31.35,21.21,20.69.

[0100] Example 15: Ligand 11-N-(2,6-dimethylphenyl)-4-mesitylbenzothiazol-2-amine [ka] In a glove box, a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and 2,6-dimethylaniline (74 uL, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. The next day, copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the CM-3 glovebox. The reaction was diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 80.7 mg (72%). 1 H NMR(400MHz,CDCl3)δ7.52(dd,J=7.7,1.4Hz,1H),7.27-7.20(m,1H),7.19(d,J=7.9Hz,2H),7.15(t,J=7 .6Hz,1H),7.09(dd,J=7.5,1.4Hz,1H),7.07(s,1H),7.00(s,2H),2.39(s,3H),2.30(s,6H),2.07(s,6H). 13 C NMR(101MHz,CDCl3)δ167.79,150.92,137.52,137.18,136.80,136.62,136.40,131 .61,131.10,128.98,128.38,128.29,127.37,121.54,119.66,21.33,20.77,18.23.

[0101] Example 16: Ligand 12-N-(2,6-diisopropylphenyl)-4-mesitylbenzothiazol-2-amine [ka] To a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl (94.2 mg, 0.28 mmol, 1 equiv.) in dichloromethane (3 mL) was added 2,6-diisopropylaniline (0.107 mL, 0.57 mmol, 2 equiv.). The reaction was stirred at room temperature overnight. After 16 h, the reaction had concentrated to a colorless translucent oil. The yield was deemed quantitative and the oil was carried on to the next step without further purification. To a mixture of thiourea (144 mg, 0.28 mmol, 1 equiv.), Cs2CO3 (170.6 mg, 0.57 mmol, 2 equiv.), CuI (2.7 mg, 0.01 mmol, 5 mol%) and 1,10-phenanthroline (5.1 mg, 0.03 mmol, 10 mol%) was added dimethoxyethane (2 mL). The reaction mixture was heated at 70° C. under nitrogen for 16 hours, at which point the cyclization was complete as determined by UPLCMS. The reaction was then diluted with ethyl acetate (25 mL) and then washed with H2O (2×25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography with a silica gel column and a solvent system of ethyl acetate in hexanes. The product that co-eluted with 2,6-diisopropylaniline was collected. The 2,6-diisopropylaniline was further purified using reverse-phase ISCO flash column chromatography with a solvent system of water in acetonitrile. The product was collected to give 57.6 mg (48%). 1H NMR(400MHz,CDCl3)δ7.53(dd,J=7.6,1.5Hz,1H),7.41(t,J=7.7Hz,1H),7.28(d,J=7.7Hz,2H),7.15(t,J=7.5Hz,1H),7.10( dd,J=7.5,1.5Hz,1H),7.03(s,2H),6.73(s,1H),3.29(hept,J=6.8Hz,2H),2.38(s,3H),2.10(s,6H),1.21(d,J=6.9Hz,12H). 13 C NMR(101MHz,CDCl3)δ168.90,151.30,148.16,136.96,136.78,136.46,133.96,131.84 ,131.40,129.44,128.34,127.31,124.42,121.53,119.76,28.51,25.41,21.35,20.84.

[0102] Example 17: 2',4',6'-trimethyl-[1,1'-biphenyl]-2-amine [ka] In a nitrogen-filled glovebox, a reaction vial was charged with SPhos G3 precatalyst (0.552 g, 0.707 mmol, 4 mol%), SPhos (0.290 g, 0.707 mmol, 4 mol%), K3PO4 (7.50 g, 35.3 mmol, 2 equiv), and mesitylboronic acid (4.35 g, 26.5 mmol, 1.5 equiv). The vessel was sealed with a septum, removed from the glovebox, and attached to a nitrogen-filled Schlenk tube. 2-Bromoaniline (2.0 mL, 17.7 mmol, 1 equiv) and anhydrous n-butanol (40 mL) were added via syringe. The reaction was stirred at 100 °C for 20 h, giving a black solution containing a significant amount of precipitate. The material was filtered through a short plug of silica gel, which was eluted with ethyl acetate (3 x 50 mL) to give a light brown solution. The filtrate was concentrated in vacuo, adsorbed onto silica gel, and purified by flash column chromatography (220 g silica gel, 0.5-3% EtOAc in hexanes) to give a white solid (1.48 g, 40% yield). 1H NMR(400MHz,chloroform-d)δ7.15(ddt,J=7.9,7.3,1.6Hz,1H),6.96(s,2H),6.90(dt,J=7.5, 1.5Hz,1H),6.84-6.74(m,2H),3.38(s,2H),2.32(d,J=0.7Hz,3H),2.01(d,J=0.8Hz,6H). 13 C NMR (101 MHz, chloroform-d) δ 143.53, 137.02, 136.95, 134.85, 129.95, 128.37, 128.01, 126.16, 118.46, 114.93, 21.03, 20.07. 15 H 17 HRMS (ESI) calculated for N[M+H]+: 212.1434, found: 212.1431.

[0103] Example 18: 1-(2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)thiourea: [ka] A reaction vial was charged with 2',4',6'-trimethyl-[1,1'-biphenyl]-2-amine (0.973 g, 4.61 mmol, 1 equiv) and acetone (12 mL). Benzoyl isothiocyanate (0.668 mL, 5.07 mmol, 1.1 equiv) was added to give a yellow solution. The reaction was stirred at room temperature for 50 min. All volatiles were removed in vacuo to give a yellow solid. The solid was washed with hexanes (3 x 5 mL). The material was dried in vacuum. The solid was dissolved in THF (20 mL). NaOH (0.921 g, 23.0 mmol, 5 equiv) and water (8 mL) were added and the reaction was stirred at reflux at 85 °C for 2.5 h followed by stirring at room temperature for 2 h. Most of the THF was removed in vacuo. The solution was poured into deionized water (100 mL). The aqueous phase was washed with EtOAc (3 x 50 mL). The combined organic phases were dried over MgSO4, filtered and concentrated in vacuo. The material was adsorbed onto silica gel and purified by flash column chromatography (80 g silica gel, 20-40% EtOAc in hexanes) to provide the product as a green solid (0.921 g, 74% yield). H NMR (400 MHz, chloroform-d) δ 7.45 (dd, J = 8.0, 1.5 Hz, 1H), 7.40 (ddd, J = 8.2, 7.4, 1.6 Hz, 1H), 7.30 (td, J = 7.4, 1.5 Hz, 1H), 7.19-7.15 (m, 1H), 7.13 (s, 1H), 6.43 (s, 2H), 2.29 (s, 3H), 1.90 (s, 6H). 13 C NMR (101 MHz, chloroform-d) δ 181.24, 138.05, 136.18, 135.55, 134.91, 133.03, 131.93, 128.90, 128.74, 127.23, 123.93, 21.22, 20.40.

[0104] Example 19: 4-Mesitylbenzothiazol-2-amine [ka] A 100 mL round bottom flask was charged with 1-(2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)thiourea (0.899 mg, 3.32 mmol, 1 equiv). The vessel was evacuated and backfilled with nitrogen three times. Dichloromethane (19 mL) was added via syringe. Bromine (0.17 mL, 3.32 mmol, 1 equiv) was added dropwise via syringe. In the first half of the addition, the color disappeared immediately after the addition of each drop. After that, some color remained and finally a slightly orange homogeneous solution was obtained. The reaction was stirred at room temperature for 3 h. On top of that, 40% aqueous NH4OH (5 mL) was added via syringe to neutralize the acid. The material was poured into deionized water (100 mL). The aqueous phase was extracted with dichloromethane (3 x 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The residue was adsorbed onto silica gel and purified by flash column chromatography (40 g silica gel, 15-30% EtOAc in hexanes) to give an off-white solid (0.7543 g). NMR analysis indicated the material was an 85:15 mixture of the desired product and the mesityl bromination product 4-(3-bromo-2,4,6-trimethylphenyl)benzothiazol-2-amine. From the molar ratios and crude yield, the actual yield was calculated to be 0.665 g (75%). 1 H NMR (400 MHz, chloroform-d) δ 7.54 (dd, J = 7.8, 1.3 Hz, 1H), 7.15-7.10 (m, 1H), 7.05-7.00 (m, 3H), 6.11 (s, 2H), 2.46 (s, 3H), 1.99 (s, 6H). 13 C NMR (101 MHz, chloroform-d) δ 167.28, 150.70, 137.58, 137.36, 136.45, 130.90, 130.49, 127.72, 126.67, 121.60, 119.64, 21.07, 20.55.

[0105] Example 20: N-(4-mesitylbenzothiazol-2-yl)pivalamide [ka] A 100 mL round bottom flask was charged with 4-mesitylbenzo[d]thiazol-2-amine (0.754 g of crude mixture, corresponding to 0.665 g of pure starting material, 2.48 mmol, 1 equiv.) and N,N-dimethyl-4-aminopyridine (60.5 mg, 0.496 mmol, 20 mol%). The vessel was sealed with a septum. The vessel was evacuated and backfilled with nitrogen (this process was repeated a total of three times). Acetonitrile (25 mL), N,N-diisopropylethylamine (0.86 mL, 4.96 mmol, 2 equiv.), and trimethylacetyl chloride (0.40 mL, 3.22 mmol, 1.3 equiv.) were added via syringe and the reaction was stirred at room temperature for 18 h. Initially, the starting material was not very soluble in acetonitrile. However, the addition of the acyl chloride and short stirring gave a pale yellow clear solution. The mixture was poured into saturated aqueous NH4Cl (100 mL) and washed with ETOAc (3 x 50 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated in vacuo. The mixture was purified by flash column chromatography (40 g silica gel, 1-10% EtOAc in hexanes) to give a white solid (0.7543 g). NMR analysis showed the material contained approximately 15% of the brominated impurity N-(4-(3-bromo-2,4,6-trimethylphenyl)benzo[d]thiazol-2-yl)pivalamide. The yield of pure product is 0.620 g (71% yield). 1 H NMR (400MHz, chloroform-d) δ 8.95(s,1H), 7.81(dd,J=7.9,1.2Hz,1H), 7.34(dd,J=7.9,7.4Hz,1H), 7.17(dd,J=7.4,1.2Hz,1H), 7.00(s,2H), 2.36(s,3H), 1.96(s,6H), 1.31(s,9H) 13 C NMR (101 MHz, chloroform-d) δ 176.59, 157.16, 147.00, 137.17, 136.45, 136.15, 133.61, 132.57, 128.09, 127.21, 123.82, 120.14, 39.32, 27.22, 21.26, 20.56. 21 H 24 N2OS[M+H] +Calculated HRMS (ESI): 353.1682, Measured: 353.1694.

[0106] Example 21: Ligand 2-4-mesityl-N-neopentylbenzo[d]thiazol-2-amine [ka] A 250 mL round bottom flask was charged with N-(4-mesitylbenzo[d]thiazol-2-yl)pivalamide (0.7556 g of crude mixture, corresponding to 0.621 g of pure starting material, 1.76 mmol, 1 equiv.) and THF (15 mL). A suspension of LiAlH4 (0.134 g, 3.52 mmol, 2 equiv.) in THF (2 mL) was added dropwise to the stirring amide solution. Immediately upon addition of LiAlH4, gas evolution was observed. The vial of LiAlH4 was rinsed with THF (3×1 mL) and the reaction was heated to reflux (80° C.) and stirred for 2.5 h. The reaction was diluted with diethyl ether (40 mL), sealed with a septum, and removed from the glove box. The solution was hazy with some precipitate. The solution was cooled in an ice bath. Water (0.13 mL), 15% aqueous NaOH (0.13 mL), and water (0.39 mL) were added sequentially, resulting in the evolution of gas and the precipitation of a white solid. The ice bath was removed and the reaction was stirred for 15 min. MgSO4 was added and the reaction was stirred for an additional 15 min. The reaction was filtered, the filter cake was washed with diethyl ether (2 x 20 mL), and the filtrate was concentrated in vacuo to give a white solid (0.672 g). This material contained 15% of the brominated impurity 4-(3-bromo-2,4,6-trimethylphenyl)-N-neopentylbenzothiazol-2-amine. From the ratios of the NMR spectra, the yield of pure material was calculated to be 0.552 g (93%). The crude mixture containing 4-(3-bromo-2,4,6-trimethylphenyl)-N-neopentylbenzothiazol-2-amine and 4-mesityl-N-neopentylbenzothiazol-2-amine was converted to pure 4-mesityl-N-neopentylbenzothiazol-2-amine by lithium halogen exchange followed by protonolysis. In a nitrogen filled glovebox, a reaction vial was charged with the mixture (0.604 g, 85% pure material) and THF (20 mL). The vessel was sealed with a screw cap septum, removed from the glovebox, installed in a nitrogen filled glovebox, and cooled in an acetone / dry ice bath. A 1.6 M solution of nBuLi in hexanes (2.2 mL, 3.57 mmol, ca. 2 equiv.) was added and the reaction was stirred at -78 °C for 45 min.Saturated aqueous NH4Cl (5 mL) was added dropwise and the solution was removed from the cooling bath and stirred at room temperature for 5 min. The material was poured into 100 mL of water. The aqueous phase was extracted with diethyl ether (3 x 50 mL). The combined organic layers were dried over MgSO4, filtered and concentrated in vacuo to give the product as a white solid (0.575 g). 1 H NMR (400 MHz, chloroform-d) δ 7.58 (dd, J = 7.8, 1.4 Hz, 1H), 7.09 (t, J = 7.6 Hz, 1H), 7.02 (dd, J = 7.4, 1.4 Hz, 1H), 6.94 (t, J = 0.6 Hz, 2H), 5.74 (s, 1H), 2.93 (d, J = 5.7 Hz, 2H), 2.32 (s, 3H), 1.99 (s, 6H), 0.93 (s, 9H). 13 C NMR(101MHz,cdcl3)δ168.23,151.00,136.79,136.58,136.33,131.16,13 0.50,128.05,127.26,120.89,119.41,58.40,32.42,27.20,21.16,20.63. C 21 H 26 N2S[M+H] + Calculated HRMS(ESI): 339.1889, Measured: 339.1890.

[0107] Example 22: 9-(3-bromo-2-nitrophenyl)-carbazole: [ka] Carbazole (0.380 g, 2.27 mmol) and 1-bromo-3-fluoro-2-nitrobenzene (0.5 g, 2.27 mmol) were dissolved in DMSO (7 mL). Cesium carbonate (0.888 g, 2.73 mmol) was added to the solution with stirring. The suspension was stirred at room temperature for 48 h and then diluted with water (10 mL). The mixture was extracted with dichloromethane (3×20 mL). The combined organic layers were washed with water (3×20 mL), dried over MgSO4, and concentrated under reduced pressure. The residue was purified by ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 494.2 mg (59%). 1 H NMR(400MHz,CDCl3)δ8.10(ddd,J=7.7,1.3,0.7Hz,2H),7.88(dd,J=8.1,1.3Hz,1H),7.56(t,J=8.1Hz,1H),7.45( td,J=8.2,8.1,1.3Hz,2H),7.40(dd,J=7.1,1.2Hz,1H),7.32(td,J=7.7,1.0Hz,2H),7.14(dt,J=8.1,0.9Hz,2H). 13 C NMR (101MHz, CDCl3) δ141.56,134.34,132.30,132.02,130.61,126.52,123.96,121.09,120.56,114.62,109.88(2C).

[0108] Example 23: 2-Bromo-6-(carbazol-9-yl)aniline: [ka] A mixture of 9-(3-bromo-2-nitrophenyl)carbazole (0.10 g, 0.27 mmol), iron powder (0.076 g, 1.36 mmol), and ammonium chloride (0.022 g, 0.41 mmol) in a solvent mixture of ethanol (1.5 mL), THF (1.5 mL), and water (0.5 mL) was heated at 95 °C with vigorous stirring for 24 h. The reaction mixture was cooled and filtered through a plug of Celite, and the Celite pad was washed repeatedly with ethanol and THF. The filtrate was concentrated, and the residue was dissolved in ethyl acetate, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude reaction mixture was purified by ISCO column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 91 mg (99% yield). 1 H NMR(400MHz,CDCl3)δ8.18(dt,J=7.7,1.0Hz,2H),7.62(dd,J=8.1,1.4Hz,1H),7.44(ddd,J=8.3,7.2,1.2Hz,2H),7.33(d dd,J=8.1,7.3,1.0Hz,2H),7.26(dd,J=7.8,1.4Hz,1H),7.19(dt,J=8.1,0.8Hz,2H),6.80(t,J=7.9Hz,1H),4.04(s,2H). 13 C NMR (101MHz, CDCl3) δ142.50,140.47,132.97,129.04,126.30,123.60,123.01,120.53,120.34,118.77,110.24,110.16.

[0109] Example 24: 9-(3-Bromo-2-isothiocyanatophenyl)-carbazole [ka] A vial was charged with 2-bromo-6-carbazoleaniline (1.38 g, 4.07 mmol, 1 equiv) and NaHCO3 (1.35 g, 16.28 mmol, 4 equiv) and diluted with acetone (25 mL). The reaction was then cooled to 0° C. and thiophosgene (0.94 mL, 12.21 mmol, 3 equiv) was added. The reaction was then allowed to warm to room temperature and stirred for 24 hours. The reaction was then filtered through Celite with dichloromethane (100 mL) and concentrated under vacuum. The crude mixture was purified by ISCO chromatography using a gradient of methylene chloride and hexanes. The product was isolated in quantity (1.32 g, 85% yield). 1 H NMR(400MHz,CDCl3)δ8.18(d,J=7.8Hz,2H),7.78(dd,J=8.1,1.3Hz,1H),7.53(d,J=9 .2Hz,1H),7.46(t,J=7.7Hz,2H),7.36(td,J=7.9,2.4Hz,3H),7.16(d,J=8.1Hz,2H). 13 C NMR (101MHz, CDCl3) δ140.62,135.41,133.01,128.95,128.09,126.32,123.73,121.20,120.66,120.62,109.65.

[0110] Example 25: Ligand 18-N-(adamantan-1-yl)-4-(9H-carbazol-9-yl)benzothiazol-2-amine [ka] In a nitrogen-filled, continuously purged glovebox, a solution of 9-(3-bromo-2-isothiocyanatophenyl)-carbazole in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and 1-adamantylamine (91 mg, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. Copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were then added to the vial. The vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the glovebox. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel and the organics washed with H2O (2 x 25 mL) followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected, yield 108.9 mg (81%). 1 H NMR(400MHz,CDCl3)δ8.18(dt,J=7.7,1.0Hz,2H),7.69(dd,J=7.9,1.2Hz,1H),7.51(dd,J=7.8,1.2Hz,1H),7.40(ddd,J=8.2,6.9,1.3Hz,2H),7.33 -7.27(m,4H),7.27-7.23(m,1H),5.13(s,1H),2.01-1.91(m,3H),1.84(d, J=2.9Hz,6H), 1.57(dt,J=12.2,3.0Hz,3H),1.43(dq,J=12.5,2.0Hz,3H). 13 C NMR(101MHz,CDCl3)δ163.44,149.26,141.47,133.21,127.58,125.45,125.02 ,123.54,121.59,120.05,119.98,119.50,111.27,53.96,41.43,36.12,29.47.

[0111] Example 26: Ligand 19-N-benzyl-4-(carbazol-9-yl)benzothiazol-2-amine: [ka] In a nitrogen filled, continuously purged glovebox, a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) in dimethoxyethane was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and benzylamine (0.066 mL, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. Copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were then added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the glovebox. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel, partitioned, and the organics washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 116 mg (95%). 1 H NMR(400MHz,CDCl3)δ8.17(d,J=7.5Hz,2H),7.73(dd,J=7.9,1.2Hz,1H),7.47(dd,J=7.8,1.1Hz,1H),7.38(dd d,J=8.3,7.2,1.2Hz,2H),7.28-7.32(m,5H),7.27-7.22(m,5H),5.67(t,J=5.6Hz,1H),4.39(d,J=5.8Hz,2H). 13C NMR(101MHz,CDCl3)δ167.71,149.24,141.26,137.21,132.79,128.58,127.60,1 27.47,125.54,125.37,123.45,121.68,120.46,120.05,119.63,110.98,49.09.

[0112] Example 27: Ligand 13-N-butyl-4-(carbazol-9-yl)benzothiazol-2-amine: [ka] In a nitrogen filled, continuously purged glovebox, a solution of 9-(3-bromo-2-isothiocyanatophenyl)-carbazole in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and n-butylamine (0.059 mL, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. Copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were then added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the glove box. The reaction was diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 106 mg (95%). 1H NMR (400MHz, CDCl3) δ8.17(d,J=7.6Hz,2H),7.74(dd,J=7.8,1.1Hz,1H),7.48-7.44(m,1H),7.41-7.36(m,2H),7.32-7.26( m,4H),5.79(t,J=5.4Hz,1H),3.16-2.89(q,2H),1.42(p,J=7.3Hz,2H),1.23(dq,J=14.4,7.3Hz,2H),0.83(t,J=7.3Hz,3H). 13 C NMR (101MHz, CDCl3) δ168.01,149.53,141.26,132.71,127.27,125.49,125.35 ,123.46,121.34,120.40,120.04,119.56,110.95,45.51,31.30,19.81,13.59.

[0113] Example 28: Coordinator 14-4-(カルバゾール-9-イル)-N-ネオペンチルベンゾチアゾール-2-アミン

change

[0114] Example 29: Ligand 15-4-(carbazol-9-yl)-N-((trimethylsilyl)methyl)benzothiazol-2-amine [ka] In a nitrogen filled, continuously purged glovebox, a solution of 9-(3-bromo-2-isothiocyanatophenyl)-carbazole in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and (trimethylsilyl)methylamine (0.080 mL, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. Copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were then added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the glove box. The reaction was diluted with ethyl acetate (25 mL) and poured into a separatory funnel, then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 107 mg (88%). 1 H NMR(400MHz,CDCl3)δ8.18(d,J=7.7Hz,2H),7.76(d,J=8.4Hz,1H),7.44(d,J=7.7Hz,1H),7.39(t,J=7. 6Hz,2H), 7.29(d,J=7.3Hz,2H),7.23(d,J=7.7Hz,2H),5.67(s,1H),2.50(d,J=5.4Hz,2H),0.01(s,9H). 13 C NMR(101MHz, CDCl3)δ171.00,150.09,141.34,132.72,127.06,125.55,125.52,123.46,121.09,120.55,120.10,119.56,110.88,36.52,-2.84.

[0115] Example 30: Ligand 16-4-(carbazol-9-yl)-N-isopropylbenzothiazol-2-amine [ka] In a nitrogen-filled, continuously purged glovebox, a solution of 9-(3-bromo-2-isothiocyanatophenyl)-carbazole in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and isopropylamine (0.052 mL, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. Copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were then added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the glovebox. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel, then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 101 mg (94%). 1 H NMR(400MHz,CDCl3)δ8.18(d,J=7.7Hz,2H),7.75(d,J=7.8Hz,1H),7.46(d,J=8.7Hz,1H),7.40(t,J=7.6Hz,2H), 7.36-7.28(m,2H),7.27-7.23(m,2H),5.18(d,J=7.9Hz,1H),3.68(dq,J=12.9,6.7Hz,1H),1.22(d,J=6.4Hz,6H). 13 C NMR(101MHz, CDCl3)δ166.39,149.69,141.37,132.88,127.48,125.51,125.42,123.47,121.54,120.43,120.09,119.51,110.93,47.92,22.79.

[0116] Example 31: Ligand 17-N-(tert-butyl)-4-(carbazol-9-yl)benzothiazol-2-amine [ka] In a nitrogen filled, continuously purged glovebox, a solution of 9-(3-bromo-2-isothiocyanatophenyl)-carbazole in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and tert-butylamine (63 uL, 0.6 mmol, 2 equiv) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. Copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv) were then added to the vial. Once all additions were complete, the vial was heated to 70° C. and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the glovebox. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel, then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected, yield 90.7 mg (81%). 1 H NMR(400MHz,CDCl3)δ8.22-8.14(m,2H),7.70(dd,J=7.8,1.2Hz,1H),7.47(dd,J= 7.8,1.2Hz,1H),7.41-7.35(m,2H),7.31-7.23(m,5H),5.16(s,1H),1.26(s,9H). 13C NMR (101MHz, CDCl3) δ164.27,149.47,141.48,133.20,127.77,125.54,125.19,123.54,121.76,120.09,119.53,111.18,53.59,28.88.

[0117] Example 32: Ligand 20-4-(carbazol-9-yl)-N-(3,5-di-tert-butylphenyl)benzothiazol-2-amine: [ka] In a nitrogen filled, continuously purged glovebox, a solution of 9-(3-bromo-2-isothiocyanatophenyl)-carbazole in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv.) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and 3,5-di-tert-butylaniline (123 mg, 0.6 mmol, 2 equiv.) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. Copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv.) were then added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the glove box. The reaction was diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. An attempt at purification using ISCO flash column chromatography with a silica gel column and a solvent system of ethyl acetate in hexanes resulted in a mixture of starting amine and product. The mixture was then successfully purified by reverse-phase ISCO flash column chromatography with a gradient of water and acetonitrile. The product was collected, yield 116 mg (77%). 1H NMR(400MHz,CDCl3)δ8.19(d,J=7.7Hz,2H),7.80(dd,J=7.9,1.0Hz,1H),7.51(dd,J=7.7,1.0Hz,1H), 7.40(t,J=8.2Hz,2H),7.35(t,J=7.8Hz,1H),7.31-7.23(m,4H),7.16(m,J=2.5Hz,3H),1.23(s,18H). 13 C NMR(101MHz, CDCl3)δ163.85,152.32,149.27,141.42,138.66,132.44,129.05,128.06,125. 82,125.65,123.48,122.69,120.55,120.19,119.60,118.40,114.11,110.64,34.90,31.26.

[0118] Example 33: Ligand 21-4-(carbazol-9-yl)-N-(2,6-dimethylphenyl)benzothiazol-2-amine [ka] In a nitrogen filled continuous glove box, a solution of 9-(3-bromo-2-isothiocyanatophenyl)-carbazole in dimethoxyethane (0.3 M, 1.0 mL, 0.3 mmol, 1 equiv) was added to a vial equipped with a stir bar. To the same vial, dimethoxyethane (1.0 mL) and 2,6-dimethylaniline (74 uL, 0.6 mmol, 2 equiv) were added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. Copper(I) iodide (6 mg, 0.03 mmol, 10 mol%), 1,10-phenanthroline (10 mg, 0.03 mmol, 10 mol%), and cesium carbonate (196 mg, 0.6 mmol, 2 equiv) were then added to the vial. Once all additions were complete, the vial was heated to 70 °C and stirred for 2.5 h. The reaction was then cooled to room temperature and removed from the glove box. The reaction was diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 92.5 mg (73%). 1 H NMR(400MHz,CDCl3)δ8.14(dd,J=7.7,1.2Hz,2H),7.90(s,1H),7.59(dd,J=7.8,1.2Hz,1H),7.42(ddd,J=8.3,7.1,1.3Hz,2H),7.38(dd,J=7.8,1.2 Hz,1H),7.32(td,J=7.5,1.1Hz,2H),7.28(d,J=8.3Hz,2H),7.20(t,J=7. 8Hz, 1H), 7.09 (dd, J=8.3, 6.8Hz, 1H), 7.00 (d, J=7.5Hz, 2H), 2.14 (s, 6H). 13 C NMR(101MHz, CDCl3)δ169.43,149.37,141.44,137.01,136.39,132.96,128.78,128. 45,127.99,125.68,125.21,123.83,121.83,120.33,120.22,119.76,111.12,18.01.

[0119] Example 34: 2-(2,6-di-tert-butylanthracen-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ka] In a continuously purged glovebox filled with nitrogen, 9-bromo-2,6-di-tert-butylanthracene (2.0 g, 5.41 mmol, 1 equiv) was charged to an oven dried flask and diluted in dry THF (12.0 mL). The reaction was then pumped out of the glovebox and cooled to -78 C. n-BuLi in hexanes (2.5 M, 2.768 mL, 5.96 mmol, 1.1 equiv) was then added dropwise over 5 min. The reaction was then warmed to 0 C for 4 h. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.77 mL, 13.54 mmol) was then added and the reaction was allowed to warm to room temperature overnight. The reaction was quenched with water (70 mL) and poured into a separatory funnel. The solution was then extracted with dichloromethane (3 x 50 mL) and the combined organic layers were washed with brine (70 mL). The organics were then dried over sodium sulfate and concentrated under vacuum. The reaction mixture was then purified by ISCO chromatography with a gradient of 0-10% dichloromethane and hexanes. The desired product was collected to give 980 mg (44%). 1 H NMR(400MHz,CDCl3)δ8.39-8.30(m,3H),7.90(d,J=8.9Hz,1H),7.83(d,J=1.4Hz,1H),7.57 (dd,J=9.2,2.1Hz,1H),7.51(dd,J=8.8,1.5Hz,1H),1.58(s,12H),1.44(d,J=7.3Hz,18H). 13 C NMR(101MHz,CDCl3)δ147.35,146.63,135.82,134.74,131.01,129.89,128.65,128.2 7,127.87,125.29,124.31,122.87,122.74,84.14,35.29,34.76,31.02,30.95,25.27.

[0120] Example 35: 2-Bromo-6-(2,6-di-tert-butylanthracen-9-yl)aniline [ka] A round bottom flask equipped with a reflux condenser was charged with 2,6-dibromoaniline (360 mg, 1.44 mmol, 2 equiv), 2-bromo-6-(2,6-di-tert-butylanthracen-9-yl)aniline (300 mg, 0.72 mmol, 1 equiv), Pd(PPh3)4 (83 mg, 0.0.72 mmol, 0.1 equiv), and K3PO4 (459 mg, 2.16 mmol, 3 equiv). The flask was then placed under vacuum and refilled with N2 four times. Toluene, water, ethanol (vol?) were then added and the reaction was stirred at 100 °C for 18 h. The reaction was then cooled to room temperature and passed through a pad of silica with ethyl acetate (50 mL) and poured into water. It was extracted with ethyl acetate (3 x 40 mL) and washed with brine. The organics were then dried over sodium sulfate and concentrated in vacuo. The reaction was then purified by ISCO chromatography in a gradient of 0-75% dichloromethane in hexanes to give the aniline (151 mg, 46%). 1 H NMR(400MHz,CDCl3)δ8.42(s,1H),7.97(d,J=8.9Hz,1H),7.90(d,J=1.8Hz,1H),7.63-7.53(m,3H),7.50(s,1H),7.4 7(dd,J=9.2,2.0Hz,1H),7.10(dd,J=7.4,1.4Hz,1H),6.80(t,J=7.7Hz,1H),3.78(s,2H),1.42(s,9H),1.30(s,9H). 13 C NMR(101MHz,CDCl3)δ148.09,147.38,142.83,132.11,131.50,131.47,131.33,130.42,129.76,128.78,128 .13,126.68,125.75,125.57,124.80,124.75,122.74,120.10,118.70,109.56,35.06,34.85,30.94,30.87.

[0121] Example 36: 9-(3-bromo-2-isothiocyanatophenyl)-2,6-di-tert-butylanthracene [ka] A vial was charged with 2-bromo-6-(2,6-di-tert-butylanthracen-9-yl)aniline (151 mg, 0.33 mmol, 1 equiv) and NaHCO3 (110 mg, 1.31 mmol, 4 equiv) and diluted with acetone (2 mL). The reaction was then cooled to 0 °C and thiophosgene (0.08 mL, 0.98 mmol, 3 equiv) was added. The reaction was then allowed to warm to room temperature and stirred for 24 hours. The reaction was then filtered through Celite containing dichloromethane (100 mL) and concentrated under vacuum. The crude material was 1 1 H NMR showed the desired product (162 mg, 98% yield) which was used in the next reaction without further purification. 1 H NMR(400MHz,CDCl3)8.48(s,1H),8.00(d,J=8.9Hz,1H),7.93(s,1H),7.78(dd,J=8.0,1.4Hz,1H),7.57(dd,J= 8.9,1.7Hz,1H),7.49(dd,J=9.2,1.9Hz,1H),7.44-7.39(m,2H),7.36-7.30(m,2H),1.44(s,9H),1.32(s,9H). 13 C NMR(101MHz,CDCl3)δ148.43,147.22,139.20,138.53,132.78,132.56,131.73,131.05,129.96,128.35,127 .51,127.45,125.80,125.01,124.81,124.71,123.16,122.93,122.76,119.32,35.09,34.82,31.36,30.89.

[0122] Example 37: Ligand 22-N-(adamantan-1-yl)-4-(2,6-di-tert-butylanthracen-9-yl)benzothiazol-2-amine: [ka] A solution of 9-(3-bromo-2-isothiocyanatophenyl)-2,6-di-tert-butylanthracene (81 mg, 0.16 mmol, 1 equiv.) in dimethoxyethane (3.0 mL) was added to a vial equipped with a stir bar. To the same vial, adamantylamine (49 mg, 0.32 mmol, 2 equiv.) was added. The reaction was stirred overnight at room temperature to allow for the formation of the thiourea intermediate. Copper(I) iodide (3.1 mg, 0.016 mmol, 10 mol%), 1,10-phenanthroline (4.4 mg, 0.024 mmol, 15 mol%), and cesium carbonate (105 mg, 0.32 mmol, 2 equiv.) were then added to the vial. Once all additions were complete, the vial was heated to 70° C. and stirred again overnight. The reaction was then allowed to cool to room temperature. The reaction was diluted with ethyl acetate (25 mL) and then washed with H2O (2 x 25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over Na2SO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The product was collected to give 114 mg (67%). 1 H NMR(400MHz,CDCl3)δ8.37(s,1H),7.94(m,1H),7.88(d,J=1.9Hz,1H),7.72( dd,J=7.7,1.3Hz,1H),7.53-7.45(m,2H),7.36(dd,J=9.3,2.0Hz,1H),7.31(d d,J=7.4,1.3Hz,1H),7.23(t,J=7.6Hz,1H),5.00(s,1H),2.29(d,J=2.2Hz,1H ),1.91(s,3H),1.78(s,6H),1.52(d,J=9.6Hz,5H),1.41(s,9H),1.23(s,9H). 13C NMR(101MHz, CDCl3)δ162.84,151.81,146.49,146.39,134.44,131.41,131. 30,130.28,129.90,129.25,129.17,128.94,127.78,127.05,127.00,125.7 1,124.24,124.12,122.43,121.59,120.92,119.78,53.29,41.61,36.08,34.88,34.71,31.58,31.12,30.97,30.92,30.81,29.74,29.35,22.64,14.11.

[0123] Example 38: 2-Bromo-1-mesityltan-1-one: [ka] To a solution of 2-acetyl-mesitylene (CAS 1667-01-2, 1.18 g, 7.27 mmol, 1.0 equiv) in ethyl acetate (50 ml) under nitrogen was added copper(II) bromide (3.25 g, 14.6 mmol, 2.0 equiv). The reaction was heated to reflux (85° C.) and stirred for 2 hours. The reaction was cooled and stirred at room temperature overnight. The solids were filtered off and the filtrate was concentrated. The residue was taken up in dichloromethane and the solids were filtered off. The filtrate was concentrated and pumped. The product was isolated as an orange solid (68% yield). The product was a mixture of 40% 2-acetyl-mesitylene starting material and 60% desired product. The crude mixture was carried on to the next step without further purification. 1 H NMR (400 MHz, chloroform-d) δ 6.89-6.85 (m, 2H), 4.26 (d, J=0.5 Hz, 2H), 2.30 (s, 3H), 2.23 (s, 6H).

[0124] Example 39: 4-Mesitylthiazol-2-amine: [ka] Under nitrogen, a water condenser was equipped, and nitrogen was purged through a base bath of sodium hydroxide. 2-Bromo-1-mesityltan-1-one (1.500 g, 1 To a solution of 1H NMR-ca. 56% pure, 4.07 mmol, 1.00 equiv. was added thiourea (0.402 g, 5.29 mmol, 1.30 equiv.). The reaction was stirred and refluxed (98° C.) for 3 h, then cooled and stirred at room temperature overnight. The solvent was removed in vacuo and the residue was recrystallized twice from isopropanol. The product was isolated as 0.356 g of a pale yellow solid (40% yield). 1 H NMR (400MHz, DMSO-d6) δ9.15 (s, 2H), 7.00 (s, 2H), 6.79 (s, 1H), 2.28 (s, 3H), 2.13 (s, 6H).

[0125] Example 40: N-(4-mesitylthiazol-2-yl)pivalamide: [ka] To a solution of 4-mesitylthiazol-2-amine (0.521 g, 2.39 mmol, 1.00 equiv) dissolved in dichloromethane (20 mL) and THF (5 mL) under nitrogen was added DMAP (0.010 g, 8.1140.0811 mmol, 0.034 equiv) and pyridine (2.15 mL, 26.7 mmol, 11.2 equiv). Trimethylacetyl chloride (0.88 mL, 7.79 mmol, 3.00 equiv) was added dropwise and the reaction was stirred at 18 °C for 5.5 h. The reaction was quenched with methanol (3 ml) and stirred for 15 min. The reaction was concentrated and the remaining material was taken up in ethyl acetate (30 mL). The organics were extracted with saturated ammonium chloride solution (30 mL x 1). The aqueous layer was re-extracted with ethyl acetate (30 mL x 1). The combined organics were washed with saturated ammonium chloride solution (20 mL x 2) and brine (25 mL x 1). The organics were dried over magnesium sulfate, filtered, and concentrated. The crude product was purified by ISCO column chromatography on silica gel using ethyl acetate in hexanes as the solvent system. The product was isolated as 0.474 g of a white solid (65%). 1 H NMR (400 MHz, chloroform-d) δ 9.19 (s, 1H), 6.91 (s, 2H), 6.71 (d, J = 0.7 Hz, 1H), 2.30 (s, 3H), 2.08 (s, 6H), 1.32 (d, J = 0.9 Hz, 9H). 13 C NMR(101MHz,cdcl3)δ176.28,157.58,148.81,137.86,137.36,132.13,128.30,111.30,39.27,27.34,21.22,20.42.

[0126] Example 41: Ligand 23-4-mesityl-N-neopentylthiazol-2-amine: [ka] To a solution of N-(4-mesitylthiazol-2-yl)pivalamide (0.363 g, 1.20 mmol, 1.0 equiv) in THF (30 mL) cooled in an ice bath under nitrogen, lithium aluminum hydride solution (1.0 M in THF, 3.60 mL, 3.60 mmol, 3.0 equiv) is added dropwise. The reaction was stirred cold for 5 h and then at room temperature overnight. The reaction was heated to 40° C. for 1 h and then allowed to cool to room temperature. The reaction was worked up using a Fieser and Fieser workup by sequentially adding 0.15 mL of water, 0.15 mL of 15% aqueous sodium hydroxide, and 0.45 mL of water. The organics were diluted with ether and dried over magnesium sulfate. The crude product was purified by ISCO column chromatography on silica gel using ethyl acetate in hexanes as the solvent system. The product was isolated as a white solid (0.180 g) (52%). 1 H NMR (400MHz, chloroform-d) δ6.87(s,2H),6.18(d,J=0.9Hz,1H),5.29(s,1H),3.04(d,J=5.2Hz,2H),2.28(s,3H),2.14(s,6H),0.98(d,J=0.9Hz,9H). 13 C NMR(101MHz,cdcl3)δ170.20,150.47,137.44,137.36,133.10,128.12,103.18,58.30,32.43,27.45,21.20,20.37.

[0127] Example 42: N-(4-mesitylthiazol-2-yl)heptanamide: [ka] To a solution of 4-mesitylthiazol-2-amine (0.500 g, 2.29 mmol, 1.00 equiv) dissolved in dichloromethane (20 mL) under nitrogen was added pyridine (2.00 mL, 24.7 mmol, 10.8 equiv). Heptanoyl chloride (1.06 mL, 6.87 mmol, 3.00 equiv) was added dropwise and the reaction was stirred at 18° C. overnight. The reaction was concentrated and the remaining material was taken up in ethyl acetate (60 mL). The organics were washed with saturated ammonium chloride solution (40 mL) and brine (30 mL×1). The organic layer was dried over magnesium sulfate, filtered and concentrated in vacuo. The crude product was purified by column chromatography on silica gel using ethyl acetate in hexanes as the solvent system. The product was isolated as 0.320 g of a white solid (42%). 1 H NMR (400MHz, chloroform-d) δ11.61(s,1H),6.90(s,2H),6.72(d,J=0.6Hz,1H),2.30(s,3H),2.08( s, 6H), 1.69 (t, J = 7.5Hz, 2H), 1.43 (p, J = 7.6Hz, 2H), 1.35-1.09 (m, 7H), 0.88 (t, J = 7.0Hz, 3H). 13 C NMR (101 MHz, chloroform-d) δ 171.79, 158.90, 147.70, 137.91, 137.24, 131.82, 128.57, 111.07, 34.71, 31.56, 28.64, 24.49, 22.50, 21.04, 20.37, 14.03.

[0128] Example 43: Ligand 24-N-heptyl-4-mesitylthiazol-2-amine: [ka] To a solution of N-(4-mesitylthiazol-2-yl)heptanamide (0.258 g, 0.781 mmol, 1.0 equiv) in THF (35 mL) cooled in an ice bath under nitrogen, lithium aluminum hydride solution (1.0 M in THF, 2.73 mL, 2.73 mmol, 3.5 equiv) is added dropwise. The reaction is stirred at 0° C. for 1 h and then at room temperature overnight. The reaction is quenched by Fieser workup by sequential addition of 0.11 mL of water, 0.11 mL of 15% aqueous sodium hydroxide, and 0.33 mL of water. The organics were diluted with ether and dried over magnesium sulfate. The crude product was purified by column chromatography on silica gel using ethyl acetate in hexane as the solvent system. The product was isolated as 0.191 g of a white solid (77%). 1 H NMR (400MHz, chloroform-d) δ6.87(s,2H),6.17(s,1H),6.10(s,1H),3.09(td,J=7.2,5.2Hz,2H) ,2.28(s,3H),2.14(s,6H),1.50(p,J=7.2Hz,2H),1.34-1.21(m,8H),0.89(t,J=6.8Hz,3H). 13 C NMR (101 MHz, chloroform-d) δ 169.73, 150.29, 137.32, 137.18, 133.04, 127.96, 102.82, 46.24, 31.76, 29.27, 28.96, 26.88, 22.59, 21.05, 20.24, 14.07.

[0129] Example 44 Methyl-(Z)-N'-(3-bromo-2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)-N-isopropylcarbamidothioate: [ka] To a solution of 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl (69.0 mg, 0.21 mmol, 1 equiv.) in dichloromethane (2 mL) was added isopropylamine (0.036 mL, 0.42 mmol, 2 equiv.). The reaction was stirred at room temperature overnight. After 16 h, the reaction was concentrated to a colorless translucent oil and carried on to the next step without further purification. To a mixture of thiourea (0.21 mmol) in ethanol and dichloromethane (4 mL, 1:1) was added iodomethane (0.028 mL, 0.45 mmol, 2.15 equiv). The mixture was then stirred at room temperature overnight. The clear, colorless solution was then neutralized with a saturated aqueous mixture of NaHCO3 (6 mL), diluted with dichloromethane (2 mL) and stirred vigorously (1000 rpm) for 2 min. An aqueous solution of NaOH (1 mL, 1N) was then added, the biphasic mixture was poured into a separatory funnel, partitioned and the organic layer was washed with a saturated aqueous mixture of NaHCO3 (3 x 5 mL). The residual organics were back-extracted from the aqueous layer using dichloromethane (2 x 5 mL) and all organic layers were combined, washed with brine (1 x 5 mL), dried over solid Na2SO4, filtered and concentrated to give the product (83.2 mg, 99%) as a yellow oil. This product was carried over to the next reaction without further purification. 1 H NMR(400MHz,CDCl3)δ7.55(dd,J=8.0,1.5Hz,1H),7.04(dd,J=7.5,1.5Hz,1H),6.92(t,J=7.7Hz,1H),6.88-6 .82(m,2H),3.93(s,1H),3.84(q,J=6.4Hz,1H),2.29(s,3H),2.17(s,3H),2.09(s,6H),1.04(d,J=6.2Hz,6H). 13 C NMR (101MHz, CDCl3) δ146.54,136.58,136.37,136.16,135.56,131.53,129.89,127.86,123.37,117.37,44.76,23.15,21.15,20.72,14.31.

[0130] Example 45: N-(3-bromo-2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)-N-isopropylmethanediimine: [ka] A solution of methylisothiourea (83.2 mg, 0.21 mmol, 1.00 equiv) and Et3N (57.2 μL, 0.41 mmol, 2.0 equiv) in MeCN-dichloromethane (3.0 mL, 1:1) in an oven-dried, light-shielded brown bottle was placed in an ice-water cooling bath and stirred (300 rpm) for 30 min. Solid AgNO3 (69.7 mg, 0.41 mmol, 2.0 equiv) was added all at once. After 1 h, the yellow heterogeneous mixture was diluted with hexanes (4 mL), stirred vigorously (1000 rpm) for 5 min, suction filtered cold over a Celite pad with hexanes, and concentrated to approximately 1 mL. The mixture was diluted with hexanes (4 mL) and concentrated to approximately 1 mL. This process was repeated two more times, then the hexane mixture was suction filtered over a Celite pad with hexanes and concentrated in vacuo to give the carbodiimide (67.6 mg, 0.21 mmol, 92%). The oil was carried on to the next step without further purification. 1 H NMR (400MHz, CDCl3) δ7.55(dd,J=7.5,2.1Hz,1H),7.03-6.95(m,4H),3.24(hept,J=6.5Hz,1H),2.34(s,3H),2.01(s,6H),1.00(d,J=6.4Hz,6H). 13 C NMR (101MHz, CDCl3) δ137.86,137.59,137.45,136.67,135.39,132.01,129.71,128.33,125.32,118.93,49.33,24.08,21.19,20.48.

[0131] Example 46: 2-(3-bromo-2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)-1,3-diisopropylguanidine: [ka] To a solution of N-(3-bromo-2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)-N-isopropylmethandiimine (67.6 mg, 0.19 mmol, 1 equiv.) in dichloromethane (1.5 mL) was added isopropylamine (32.5 μL, 0.38 mmol, 2 equiv.). The reaction was stirred at room temperature overnight. After 16 h, the reaction was concentrated to give a pale yellow oil (78.7 mg, 99%). The oil was carried on to the next step without further purification. 1 H NMR(400MHz,CDCl3)δ7.55(dd,J=7.9,1.5Hz,1H),7.02(dd,J=7.4,1.5Hz,1H),6.90-6.82(m,3H) ,3.61(q,J=6.7Hz,2H),3.20(d,J=8.2Hz,2H),2.28(s,3H),2.07(s,6H),1.00(d,J=6.4Hz,12H). 13 C NMR (101MHz, CDCl3) δ147.57,146.58,137.36,137.14,136.22,135.83,131.71,129.97,127.74,122.44,119.40,43.10,23.35,21.09,20.79.

[0132] Example 47: Ligand 27-N,1-diisopropyl-4-mesitylbenzimidazol-2-amine: [ka] A reaction vial was charged with 2-(3-bromo-2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)-1,3-diisopropylguanidine (78.7 mg, 0.19 mmol, 1 equiv), K3PO4 (160.5 mg, 0.76 mmol, 4 equiv), and CuI (3.6 mg, 0.02 mmol, 0.1 equiv). N,N'-DMEDA (12.2 μL, 0.11 mmol, 0.6 equiv) and anhydrous DMAc (2 mL) were added via syringe and the reaction was stirred at 140 °C for 18 h. The reaction was then cooled to room temperature. A small aliquot was dissolved in acetonitrile and analyzed by UPLC-MS, which showed complete conversion to the desired product. The material was poured into water (50 mL). The aqueous phase was washed with diethyl ether (3 × 25 mL). The combined organic layers were dried over MgSO4, filtered and concentrated in vacuo. The crude product was purified by ISCO column chromatography on silica gel using ethyl acetate in hexanes as the solvent system. The purified material was collected as 51.9 mg (82%) of a pale yellow solid. 1 H NMR(400MHz,CDCl3)δ7.22(dd,J=7.9,1.1Hz,1H),7.03(t,J=7.7Hz,1H),6.96(s,2H),6.85(dd,J=7.5,1.1Hz,1H),4.39(hept,J=7.0H) z,1H),4.06(hept,J=13.0,6.5Hz,1H),3.70(d,J=8.0Hz,1H),2.35(s,3H),2.05(s,6H),1.62(d,J=6.9Hz,6H),1.21(d,J=6.3Hz,6H). 13 C NMR(101MHz,CDCl3)δ152.89,141.22,137.10,136.54,136.21,133.29,129.3 1,128.02,122.32,118.72,107.91,46.37,45.54,23.38,21.26,21.21,20.92.

[0133] Example 48: 3-Fluoro-2',4',6'-trimethyl-2-nitro-1,1'-biphenyl: [ka] A vial was charged with 1-bromo-3-fluoro-2-nitrobenzene (200 mg, 0.91 mmol, 1 equiv), mesitylboronic acid (220 mg, 1.36 mmol, 1.5 equiv), Pd(PPh3)4 (110 mg, 0.09 mmol, 0.1 equiv), and K3PO4 (580 mg, 2.73 mmol, 3 equiv). The vial was then placed under vacuum and refilled with N2 four times. Toluene (5.0 mL) and water (0.20 mL) were then added and the reaction was stirred at 100 °C for 18 h. The reaction was then cooled to room temperature and passed through a pad of silica with ethyl acetate (20 mL) and concentrated under vacuum. The reaction was then purified by ISCO chromatography using a solvent system of EtOAc in hexanes and the desired product was collected (156 mg, 66% yield). 1 H NMR(500MHz,CDCl3)δ7.55(td,J=8.0,5.3Hz,1H),7.28(ddd,J=9.6,8.4,1.3 Hz, 1H), 7.05 (dt, J=7.7, 1.1Hz, 1H), 6.92 (s, 2H), 2.32 (s, 3H), 2.02 (s, 6H). 13 C NMR(126MHz, CDCl3) δ153.85(d,J=257.9Hz),138.53,136.40,133.85(d,J=19.5Hz),131.97(d,J=8.2 Hz),128.74(d,J=24.2Hz),128.58,128.36,126.67(d,J=3.7Hz),115.93(d,J=19.0Hz),21.20,20.31.

[0134] Example 49: N-isopropyl-2',4',6'-trimethyl-2-nitro-[1,1'-biphenyl]-3-amine: [ka] 3-Fluoro-2',4',6'-trimethyl-2-nitro-1,1'-biphenyl (150 mg, 0.58 mmol) was diluted with DMSO (3.0 mL). Potassium carbonate (240 mg, 1.74 mmol) and isopropylamine (0.342 mL, 4.05 mmol) were then added and the reaction was warmed to 70° C. and stirred overnight. The reaction was then poured into water and extracted with ethyl acetate (3×10 mL). It was then dried over sodium sulfate and concentrated under vacuum. A bright orange-red oil was obtained. 1 1 H NMR showed the desired product which was used without further purification (158 mg, 92% yield). 1 H NMR(400MHz,CDCl3)δ7.35(dd,J=8.4,7.4Hz,1H),6.88(s,2H),6.82(dt,J=8.6,0.9Hz,1H),6.38(dd,J=7.3,1 .2Hz,1H),6.13(d,J=7.1Hz,1H),3.86-3.68(m,J=6.4Hz,1H),2.30(s,3H),2.01(s,6H),1.30(d,J=6.3Hz,6H).

[0135] Example 50: 1-Isopropyl-4-mesityl benzimidazole: [ka] N-isopropyl-2',4',6'-trimethyl-2-nitro-[1,1'-biphenyl]-3-amine (690 mg, 2.31 mmol) was diluted with ethanol and water. Iron powder (646 mg, 11.56 mmol) and NH4Cl (186 mg, 3.47 mmol) were then added and THF was used to rinse into the flask. The reaction was then fitted with a reflux condenser and heated to 95°C. After 3 hours, the reaction was suction filtered through Celite with ethyl acetate (50 mL) and poured into saturated aqueous NH4Cl. The biphasic mixture was poured into a separatory funnel, partitioned, and the organics were extracted with ethyl acetate (3 x 50 mL), washed with brine, dried over sodium sulfate, and concentrated in vacuo. The mixture was then refluxed in the appropriate triethyl orthoformate (30 mL) for 2 hours to complete the desired cyclization. The reaction was then concentrated in vacuo and purified by ISCO chromatography using an ethyl acetate and hexanes gradient to afford the desired product (554 mg, 86%). 1 H NMR(400MHz,CDCl3)δ7.92(s,1H),7.41(d,J=7.5Hz,1H),7.33(t,J=7.7Hz,1H),7.06(d,J=6.5H) z,1H),6.97(s,2H),4.66(hept,J=6.8Hz,1H),2.33(s,3H),1.98(s,6H),1.66(d,J=6.7Hz,6H).

[0136] Example 51: 2-Bromo-1-isopropyl-4-mesitylbenzimidazole: [ka] 1-Isopropyl-4-mesitylbenzimidazole (550 mg, 1.98 mmol) was diluted with THF (20 mL). N-bromosuccinimide (387 mg, 2.17 mmol) was then added and the reaction was heated to reflux for 4 h. The solvent was then evaporated in vacuo and the reaction was purified by ISCO chromatography using an ethyl acetate and hexane gradient to give the bromide product (356 mg, 50.4%). 1H NMR(400MHz,CDCl3)δ7.51(dd,J=8.3,1.1Hz,1H),7.26(t,J=7.8Hz,1H),7.00(dd,J=7.4,1.0H z,1H),6.94(s,2H),4.97(hept,J=6.9Hz,1H),2.32(s,3H),1.97(s,6H),1.70(d,J=7.0Hz,6H). 13 C NMR(101MHz,CDCl3)δ142.60,136.96,136.56,134.98,134.14,132.86,129 .44,128.31,123.49,122.50,109.83,109.83,50.57,21.27,21.27,20.83.

[0137] Example 52: Ligand 31-N-benzyl-1-isopropyl-4-mesitylbenzimidazol-2-amine: [ka] 2-Bromo-1-isopropyl-4-mesitylbenzimidazole (30 mg, 0.084 mmol, 1 equiv) was diluted with 1-butanol (0.80 mL). Benzylamine (0.092 mL, 0.84 mmol, 10 equiv) was then added all at once and the reaction was sealed, heated to 120° C., and stirred overnight. The reaction was then cooled to room temperature and purified by ISCO chromatography using a gradient of ethyl acetate and hexanes to give the product as a yellow oil (24.5 mg, 76%). 1 H NMR(400MHz,CDCl3)δ7.38-7.27(m,5H),7.23(dd,J=7.9,1.1Hz,1H),7.06(t,J=7.7Hz,1H),6.97(s,2H),6.88(dd,J= 7.5,1.0Hz,1H),4.60(s,2H),4.41(hept,J=7.0Hz,1H),4.19(s,1H),2.35(s,3H),2.06(s,6H),1.62(d,J=6.9Hz,6H). 13C NMR(101MHz,CDCl3)δ153.35,141.07,139.53,137.03,136.42,136.22,133.61,129.63 ,128.67,128.19,128.04,127.51,122.48,118.97,107.93,48.32,46.47,21.28,20.98.

[0138] Example 53: Ligand 32-N-(2,6-dimethylphenyl)-1-isopropyl-4-mesitylbenzimidazol-2-amine: [ka] In a continuously purged glovebox filled with nitrogen, 2-bromo-1-isopropyl-4-mesitylbenzimidazole (50 mg, 0.14 mmol) was charged into a vial and diluted with toluene (1.0 mL). Pd2(dba)3 (13 mg, 0.012 mmol), BINAP (9 mg, 0.012 mmol), and sodium tert-butoxide (30 mg, 0.31 mmol) were then added, followed by 2,6-dimethylaniline (0.029 mL, 0.24 mmol). The reaction was then sealed and heated to 100 °C for 2 h, at which point UPLC indicated complete conversion of the starting bromide. The reaction was then filtered through silica with ethyl acetate (30 mL) and purified by ISCO chromatography in an ethyl acetate and hexane gradient to give the product as a tan oil (46 mg, 83% yield). 1 H NMR(500MHz,DMSO-d6)δ7.80(s,1H),7.42-7.36(m,1H),7.06-6.92(m,4H),6.79(s,2H),6.62(dd,J=7. 4,1.2Hz,1H),4.91(hept,J=6.8Hz,1H),2.19(s,3H),2.11(s,6H),1.84(s,6H),1.62(d,J=6.8Hz,6H). 13C NMR(126MHz,DMSO-d6)δ151.60,141.01,137.53,136.59,135.72,135.17,135.01,132.90,128.88,1 28.18,127.96,127.91,127.57,125.40,121.30,118.48,108.54,45.77,20.59,20.53,20.39,18.08.

[0139] Example 54: Ligand 28-N-cyclohexyl-1-isopropyl-4-mesityl benzimidazol-2-amine: [ka] In a nitrogen-filled, continuously purged glovebox, sodium tert-butoxide (45 mg, 0.47 mmol) and a solution of 2-bromo-1-isopropyl-4-mesitylbenzimidazole in toluene (0.3 M, 0.69 mL, 0.21 mmol, 1 equiv.) were added to a vial equipped with a stir bar. To the same vial were added cyclohexylamine (0.041 mL, 0.36 mmol, 1.7 equiv.), a solution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene in toluene (0.31 M, 0.068 mL, 0.02 mmol, 10 mol%), a solution of tris(dibenzylideneacetone)dipalladium(0) in toluene (0.31 M, 0.067 mL, 0.02 mmol, 10 mol%), and toluene (2 mL). Once all additions were complete, the vial was heated to 100° C. and stirred for 3 h. The reaction was then cooled to room temperature and removed from the glovebox. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel, then washed with H2O (25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes to give the product (54 mg, 69%). 1H NMR(400MHz,CDCl3)δ7.22(d,J=8.0Hz,1H),7.04(t,J=7.7Hz,1H),6.97(s,2H),6.86(d,J=7.4Hz,1H),4.53-4.33(m,1H),3.7 8(m,2H),2.36(s,3H),2.06(s,6H),1.77-1.67(m,4H),1.64(d,J=6.9Hz,6H),1.40(q,J=14.5,13.3Hz,2H),1.24-1.14(m,2H). 13 C NMR(101MHz,CDCl3)δ152.73,141.13,136.98,136.41,136.04,133.24,129.11,128.22,127.93, 122.28,118.50,107.67,60.40,51.91,46.25,33.66,25.83,24.72,21.13,21.10,20.82,14.21.

[0140] Example 55: Ligand 25-1-isopropyl-4-mesityl-N-pentylbenzimidazol-2-amine: [ka] In a nitrogen-filled, continuously purged glovebox, sodium tert-butoxide (45 mg, 0.47 mmol) and a solution of 2-bromo-1-isopropyl-4-mesitylbenzimidazole in toluene (0.3 M, 0.69 mL, 0.21 mmol, 1 equiv.) were added to a vial equipped with a stir bar. To the same vial were added amylamine (0.041 mL, 0.36 mmol, 1.7 equiv.), a solution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene in toluene (0.31 M, 0.068 mL, 0.02 mmol, 10 mol%), a solution of tris(dibenzylideneacetone)dipalladium(0) in toluene (0.31 M, 0.067 mL, 0.02 mmol, 10 mol%), and toluene (2 mL). Once all additions were complete, the vial was heated to 100° C. and stirred for 3 h. The reaction was then cooled to room temperature and removed from the glovebox. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel, then washed with H2O (25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes to give the product (48 mg, 63%). 1 H NMR(400MHz,CDCl3)δ7.22(dd,J=7.9,1.1Hz,1H),7.05(t,J=7.7Hz,1H),6.97(s,2H),6.86(dd,J=7.5,1.1Hz,1H),4.42(p,J=7.0Hz,1H) ,3.86(t,J=5.7Hz,1H),3.41(q,J=6.6Hz,2H),2.36(s,3H),2.07(d,J=1.4Hz,6H),1.64(m,8H),1.35(q,J=3.7Hz,4H),0.95-0.86(m,3H). 13C NMR(101MHz,CDCl3)δ153.51,141.10,136.96,136.41,136.05,133.39,129.22,127.89,122.22,11 8.56,107.62,60.40,46.23,44.08,29.66,29.10,22.48,21.14,21.10,21.06,20.82,14.21,14.00.

[0141] Example 56: Ligand 30-N-(adamantan-1-yl)-1-isopropyl-4-mesitylbenzimidazol-2-amine: [ka] In a nitrogen-filled, continuously purged glovebox, sodium tert-butoxide (45 mg, 0.47 mmol) and a solution of 2-bromo-1-isopropyl-4-mesitylbenzimidazole in toluene (0.3 M, 0.69 mL, 0.21 mmol, 1 equiv.) were added to a vial equipped with a stir bar. To the same vial was added a solution of 1-adamantylamine in toluene (1.55 M, 0.231 mL, 0.36 mmol, 1.7 equiv.), a solution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene in toluene (0.31 M, 0.068 mL, 0.02 mmol, 10 mol%), a solution of tris(dibenzylideneacetone)dipalladium(0) in toluene (0.31 M, 0.067 mL, 0.02 mmol, 10 mol%), and toluene (2 mL). Once all additions were complete, the vial was heated to 100° C. and stirred for 3 h. The reaction was then cooled to room temperature and removed from the glovebox. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel, then washed with H2O (25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes, followed by supercritical fluid chromatography to give the desired product (13.3 mg, 15%). 1H NMR(400MHz,CDCl3)δ7.26(dd,J=7.9,1.1Hz,1H),7.05(t,J=7.7Hz,1H),6.95(s,2H),6.88(dd,J=7.5,1.1Hz,1 H),4.55(hept,J=7.0Hz,1H),3.60(s,1H),2.35(s,3H),2.07(s,9H),2.00(d,J=2.9Hz,6H),1.68-1.59(m,12H). 13 C NMR(101MHz, CDCl3)δ151.36,141.23,136.98,136.48,135.97,132.79,129.92,127. 96,122.49,118.96,108.17,53.46,46.56,42.91,36.59,29.90,21.30,21.25,21.01.

[0142] Example 57: Ligand 29-1-isopropyl-4-mesityl-N-(2,4,4-trimethylpentan-2-yl)-benzimidazol-2-amine: [ka] In a nitrogen-filled, continuously purged glovebox, sodium tert-butoxide (45 mg, 0.47 mmol) and a solution of 2-bromo-1-isopropyl-4-mesitylbenzimidazole in toluene (0.3 M, 0.69 mL, 0.21 mmol, 1 equiv.) were added to a vial equipped with a stir bar. To the same vial were added tert-octylamine (57 μL, 0.36 mmol, 1.7 equiv.), a solution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene in toluene (0.31 M, 0.068 mL, 0.02 mmol, 10 mol%), a solution of tris(dibenzylideneacetone)dipalladium(0) in toluene (0.31 M, 0.067 mL, 0.02 mmol, 10 mol%), and toluene (2 mL). Once all additions were complete, the vial was heated to 100° C. and stirred for 3 h. The reaction was then cooled to room temperature and removed from the glovebox. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel, then washed with H2O (25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes to give the desired product (45.7 mg, 54%). 1 H NMR(400MHz,CDCl3)δ7.21(dd,J=7.9,1.1Hz,1H),7.02(t,J=7.7Hz,1H),6.96(s,2H),6.85(dd,J=7.4,1.1Hz,1H),4.37( hept,J=7.0Hz,1H),3.80(s,1H),2.37(s,3H),2.08(s,6H),1.89(s,2H),1.63(d,J=6.9Hz,6H),1.48(s,6H),0.98(s,9H). 13 C NMR(101MHz,CDCl3)δ151.43,141.65,136.98,136.88,135.73,132.70,129.51,127.74, 122.07,118.29,107.58,56.29,51.29,46.23,31.85,31.66,30.06,21.29,21.27,20.97.

[0143] Example 58: Ligand 26-1-isopropyl-4-mesityl-N-neopentylbenzimidazol-2-amine: [ka] In a nitrogen-filled, continuously purged glovebox, sodium tert-butoxide (45 mg, 0.47 mmol) and a solution of 2-bromo-1-isopropyl-4-mesitylbenzimidazole in toluene (0.3 M, 0.69 mL, 0.21 mmol, 1 equiv.) were added to a vial equipped with a stir bar. To the same vial were added neopentylamine (42 μL, 0.36 mmol, 1.7 equiv.), a solution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene in toluene (0.31 M, 0.068 mL, 0.02 mmol, 10 mol%), a solution of tris(dibenzylideneacetone)dipalladium(0) in toluene (0.31 M, 0.067 mL, 0.02 mmol, 10 mol%), and toluene (2 mL). Once all additions were complete, the vial was heated to 100° C. and stirred for 3 h. The reaction was then cooled to room temperature and removed from the glovebox. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel, then washed with H2O (25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes to give the desired product (30.9 mg, 40%). 1 H NMR(400MHz,CDCl3)δ7.18(d,J=7.8Hz,1H),7.07-6.99(m,1H),6.96(s,2H),6.84(d,J=7.5Hz,1H),4.45(p,J =7.0Hz,1H),3.98(s,1H),3.27(s,2H),2.35(s,3H),2.09-1.99(m,6H),1.73-1.59(m,6H),1.00-0.89(m,9H). 13C NMR(101MHz,CDCl3)δ154.17,141.08,137.11,136.57,136.16,133.71,129.2 1,128.03,122.41,118.63,107.43,55.17,46.28,32.21,27.45,21.27,20.92.

[0144] Example 59: 9-(3-fluoro-2-nitrophenyl)-carbazole: [ka] Carbazole (1.05 g, 6.29 mmol) and 1,3-difluoro-2-nitrobenzene (1.0 g, 6.29 mmol) were dissolved in DMSO (14 mL). Potassium carbonate (1.04 g, 7.54 mmol) was added to the solution with stirring. The suspension was stirred at room temperature for 18 h before being cooled and diluted with water (20 mL). The mixture was extracted with dichloromethane (3×40 mL). The combined organic layers were washed with water (3×40 mL), dried over MgSO4, and concentrated under reduced pressure. The residue was purified by ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes (1.3 g, 75%). 1 H NMR(400MHz,CDCl3)δ8.16-8.06(m,2H),7.80-7.68(m,1H),7.48(td,J=8.7,1.2Hz,1 H),7.44-7.37(m,3H),7.32(ddd,J=8.2,7.3,1.0Hz,2H),7.17(dt,J=8.2,0.9Hz,2H). 13 C NMR (101MHz, CDCl3) δ141.08,133.01,132.92,132.43,126.60,126.55,124.07,121.19,120.70,117.64,117.45,109.52.

[0145] Example 60: 3-(carbazol-9-yl)-N-isopropyl-2-nitroaniline: [ka] 9-(3-Fluoro-2-nitrophenyl)-carbazole (1.3 g, 4.25 mmol) was diluted with DMSO (30 mL). Potassium carbonate (1.759 g, 12.75 mmol) and isopropylamine (2.507 mL, 29.74 mmol) were then added and the reaction was warmed to 70° C. and stirred overnight. The reaction was then poured into water, extracted with ethyl acetate (3×50 mL) and washed with brine. The combined organic layers were then dried over sodium sulfate and concentrated under vacuum. The bright orange-red solid was carried on to the next step without further purification (1.21 g, 82.5%). 1 H NMR(400MHz,CDCl3)δ8.11(dt,J=7.7,1.1Hz,2H),7.52(ddd,J=8.4,7.6,0.6Hz,1H),7.38(ddd,J=8.3,7.2,1.3Hz,2H),7.30- 7.22(m,4H),7.04-6.95(m,1H),6.81(dd,J=7.6,1.2Hz,1H),6.39(d,J=7.1Hz,1H),3.89-3.78(m,1H),1.35(d,J=6.3Hz,6H).

[0146] Example 61: 9-(1-isopropylbenzimidazol-4-yl)-carbazole: [ka] 3-(Carbazol-9-yl)-N-isopropyl-2-nitroaniline (962 mg, 2.79 mmol) was diluted with THF (15 mL). Iron powder (780 mg, 13.93 mmol) and NH4Cl (447 mg, 8.36 mmol) were then added, followed by water (5 mL) and ethanol (15 mL). The reaction was then fitted with a reflux condenser, heated to 95 °C and monitored by TLC for reduction of the nitro group. After stirring for 4 h, TLC indicated nearly complete reduction. The reaction was then filtered through Celite with ethyl acetate (50 mL) and poured into saturated aqueous NH4Cl extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated under vacuum. The mixture was then refluxed in the appropriate triethyl orthoformate (30 mL) for 2 h to complete the desired cyclization. The reaction was then concentrated in vacuo and purified by ISCO chromatography using an ethyl acetate and hexanes gradient to afford the benzimidazole (803 mg yield, 78%). 1 H NMR(400MHz,CDCl3)δ8.15(dd,J=7.9,1.3Hz,2H),7.99(s,1H),7.56(q,J=4.2Hz,1H),7.50-7.45(m,2H) ,7.36(ddd,J=8.2,6.9,1.3Hz,2H),7.31-7.22(m,4H),4.74(hept,J=6.8Hz,1H),1.71(d,J=6.8Hz,6H).

[0147] Example 62: 9-(2-Bromo-1-isopropylbenzimidazol-4-yl)-carbazole: [ka] To a solution of 9-(1-isopropylbenzimidazol-4-yl)-carbazole (415 mg, 1.28 mmol) in DMF (6.4 mL) was added carbon tetrabromide (845.8 mg, 2.55 mmol) and sodium t-butoxide (980.4 mg, 10.2 mmol). The mixture was stirred at room temperature for 25 min. The solution was poured into water and then extracted with Et2O (3 x 30 mL). The combined organic phase was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure. The reaction mixture was purified using ISCO flash column chromatography with a silica gel column and a solvent system of ethyl acetate in hexane to give the bromide (44.5 mg, 9%). 1 H NMR(400MHz,CDCl3)δ8.15(dd,J=8.1,1.4Hz,2H),7.66(p,J=4.0Hz,1H),7.45-7 .33(m,4H),7.32-7.24(m,4H),5.03(hept,J=7.1Hz,1H),1.75(d,J=7.0Hz,6H). 13 C NMR (101MHz, CDCl3) δ141.49,140.57,135.96,130.26,128.84,125.75,123.94,123.19,121.38,120.22,119.90,110.85,110.80,50.93,21.24.

[0148] Example 63: Ligand 34-N-(adamantan-1-yl)-4-(carbazol-9-yl)-1-isopropylbenzimidazol-2-amine: [ka] In a continuously purged glovebox filled with nitrogen, sodium tert-butoxide (42 mg, 0.44 mmol) and a solution of 9-(2-bromo-1-isopropylbenzimidazol-4-yl)-9H-carbazole in toluene (0.3 M, 0.651 mL, 0.2 mmol, 1 equiv) were added to a vial equipped with a stir bar. To the same vial was added a solution of 1-adamantylamine in toluene (1.55 M, 0.218 mL, 0.34 mmol, 1.7 equiv), a solution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene in toluene (0.31 M, 0.065 mL, 0.02 mmol, 10 mol%), a solution of tris(dibenzylideneacetone)dipalladium(0) in toluene (0.31 M, 0.064 mL, 0.02 mmol, 10 mol%), and toluene (1.5 mL). Once all additions were complete, the vial was heated to 100 °C and stirred for 3 h. The reaction was then cooled to room temperature and removed from the glove box. The reaction was diluted with ethyl acetate (25 mL), poured into a separatory funnel, then washed with HO (25 mL), followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography with a silica gel column and a solvent system of ethyl acetate in hexanes to give the product (54.8 mg, 58%). 1 H NMR(400MHz,CDCl3)δ8.17(d,J=7.7Hz,2H),7.51(d,J=8.2Hz,2H),7.36(ddd,J=8.4,7.1,1.5Hz,3H),7.34-7.22(m,3H),7 .15(t,J=7.9Hz,1H),4.42(hept,J=7.0Hz,1H),3.80(s,1H),2.04-1.96(m,9H),1.65(d,J=6.9Hz,6H),1.62-1.43(m,6H). 13C NMR(101MHz,CDCl3)δ151.28,141.23,138.79,134.73,126.07,125.06,123.61,119.7 6,119.28,118.91,118.77,112.20,108.07,53.12,46.52,42.21,36.43,29.77,21.22.

[0149] Example 64: Ligand 33-4-(carbazol-9-yl)-1-isopropyl-N-(2,4,4-trimethylpentan-2-yl)-benzimidazol-2-amine: [ka] In a nitrogen-filled, continuously purged glovebox, sodium tert-butoxide (42 mg, 0.44 mmol) and a solution of 9-(2-bromo-1-isopropylbenzimidazol-4-yl)-9H-carbazole in toluene (0.3 M, 0.651 mL, 0.2 mmol, 1 equiv.) were added to a vial equipped with a stir bar. To the same vial were added tert-octylamine (54 μL, 0.34 mmol, 1.7 equiv.), a solution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene in toluene (0.31 M, 0.065 mL, 0.02 mmol, 10 mol%), a solution of tris(dibenzylideneacetone)dipalladium(0) in toluene (0.31 M, 0.064 mL, 0.02 mmol, 10 mol%), and toluene (1.5 mL). Once all additions were complete, the vial was heated to 100 °C and stirred for 3 h. The reaction was then cooled to room temperature and removed from the glove box. The reaction was diluted with ethyl acetate (25 mL) and poured into a separatory funnel, then washed with H2O (25 mL) followed by saturated aqueous NaCl (25 mL). The organic layer was dried over MgSO4 and concentrated in vacuo. The crude reaction mixture was purified using ISCO flash column chromatography using a silica gel column and a solvent system of ethyl acetate in hexanes. The desired product was collected to give 40.1 mg, a 45% yield. 1H NMR(400MHz,CDCl3)δ8.17(dd,J=7.8,1.3Hz,2H),7.46(dd,J=8.3,1.1Hz,2H),7.37(ddd,J=8.3,7.1,1.3Hz,2H),7.31(dd,J=8.0,1.0Hz,1H),7.27(dd d,J=8.3,6.9,1.2Hz,3H),7.13(t,J=7.8Hz,1H),4.36(hept,J=7.0Hz,1H), 3.95(s,1H),1.78(s,2H),1.66(d,J=6.9Hz,6H),1.38(s,6H),0.96(s,9H). 13 C NMR(101MHz,CDCl3)δ151.60,141.50,139.40,134.74,125.92,125.32,123.53,119.81,1 19.21,119.08,118.76,111.89,108.14,56.40,51.09,46.45,31.83,31.70,29.83,21.25.

[0150] Example 65: Procatalyst 2 [ka] 4-Mesityl-N-neopentylbenzothiazol-2-amine (10 mg, 0.03 mmol) was dissolved in deuterated benzene (2 mL) and then added to tetrabenzylzirconium (13.5 mg, 0.03 mmol). The reaction mixture was stirred for 10 min, 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex as a yellow film (20 mg, 96%). 1 H NMR(500MHz,C6D6)δ7.15(dd,J=6.1,3.0Hz,1H),7.03(t,J=7.7Hz,6H),6.87-6.81(m,5H),6.77 (s,2H),6.46(d,J=7.6Hz,6H),2.92(s,2H),2.08(s,6H),2.05(s,3H),2.04(s,6H),0.77(s,9H). 13C NMR(126MHz,C6D6)δ179.24,148.38,143.15,138.11,137.10,136.74,129.88,129.60,129.51 ,129.31,128.74,127.67,123.12,122.17,120.44,79.68,65.96,34.70,28.09,21.19,21.09.

[0151] Example 66: Procatalyst 3 [ka] 4-Mesityl-N-neopentylbenzothiazol-2-amine (10 mg, 0.03 mmol) was dissolved in deuterated benzene (2 mL) and added to tetrabenzylhafnium (15.8 mg, 0.03 mmol). The reaction mixture was stirred for 10 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the hafnium complex as a yellow film (22 mg, 94%). 1 H NMR(500MHz,C6D6)δ7.19-7.17(m,1H),7.13(t,J=7.8Hz,6H),6.90-6.85(m,5H),6.82(s, 2H), 6.81-6.75 (m, 6H), 2.88 (s, 2H), 2.13 (s, 3H), 2.10 (s, 6H), 1.99 (s, 6H), 0.66 (s, 9H). 13 C NMR(126MHz,C6D6)δ179.00,148.25,143.18,138.24,136.96,136.37,129.60,129.42,129.34 ,129.26,129.04,128.57,123.05,122.47,120.36,89.87,65.59,34.35,27.87,21.35,21.12.

[0152] Example 67: Procatalyst 4 [ka] To a solution of tetrabenzylzirconium (12.9 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added a solution of 4-mesityl-N-((trimethylsilyl)methyl)benzothiazol-2-amine in deuterated benzene (10 mg, 0.03 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex as a yellow film (19 mg, 94%). 1 H NMR(400MHz,C6D6)δ7.21(ddd,J=5.6,3.6,0.5Hz,1H),7.11-7.06(m,6H),6.91-6.86(m,3H),6.84(dd,J=2.0,0.4Hz,1H),6.83(d,J=0 .4Hz,1H),6.79(dt,J=1.2,0.6Hz,2H),6.47-6.40(m,6H),2.82(s,2H),2.07(s,6H),2.07(s,6H),2.07(s,3H),0.04(d,J=0.4Hz,9H). 13 C NMR(101MHz,C6D6)δ177.68,148.88,142.87,137.05,136.99,130.97,129.95,129.70,12 9.29,128.93,128.74,128.54,123.14,121.55,120.50,78.24,45.59,21.43,21.06,-1.5.

[0153] Example 68: Procatalyst 5 [ka] To a solution of tetrabenzylhafnium (15.1 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added a solution of 4-mesityl-N-((trimethylsilyl)methyl)benzothiazol-2-amine in deuterated benzene (10 mg, 0.03 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5 min. 1H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the hafnium complex as a yellow film (21 mg, 92%). 1 H NMR(400MHz,C6D6)δ7.19(ddd,J=4.8,4.3,0.5Hz,1H),7.16-7.10(m,6H),6.90-6.84(m,5H),6.82(dt,J=1.2,0.6 Hz,2H),6.76-6.71(m,6H),2.69(s,2H),2.11(s,3H),2.09(d,J=0.6Hz,6H),1.96(s,6H),-0.10(d,J=0.5Hz,9H). 13 C NMR(101MHz,C6D6)δ177.51,148.68,143.13,138.27,136.99,136.55,129.49,129.23,129 .10,129.08,128.37,127.91,123.05,121.96,120.46,88.92,44.99,21.44,21.26,-1.89.

[0154] Example 69: Procatalyst 6 [ka] To a solution of tetrabenzylzirconium (14.7 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added a solution of N-isopropyl-4-mesitylbenzothiazol-2-amine in deuterated benzene (10 mg, 0.03 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex as a yellow film (21 mg, 97%). 1H NMR(500MHz,C6D6)δ7.21(dd,J=7.6,1.5Hz,1H),7.11-7.04(m,6H),6.92-6.85(m,3H),6.86(t,J=7.5Hz,1H),6.82(dd,J=7.5,1. 5Hz,1H),6.79(s,2H),6.58-6.52(m,6H),3.46(hept,J=6.8Hz,1H),2.20(s,6H),2.12(s,3H),2.07(s,7H),0.91(d,J=6.7Hz,6H). 13 C NMR(126MHz,C6D6)δ177.12,148.21,142.75,138.13,137.12,137.09,129.72,129.53,129 .19,129.14,128.60,128.01,123.11,121.88,120.24,79.67,55.17,21.53,21.44,21.23.

[0155] Example 70: Procatalyst 7 [ka] N-isopropyl-4-mesitylbenzothiazol-2-amine (10 mg, 0.03 mmol) was dissolved in deuterated benzene (2 mL) and added to tetrabenzylhafnium (17.2 mg, 0.03 mmol). The reaction mixture was stirred for 10 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the hafnium complex as a yellow film (23 mg, 94%). 1 H NMR(500MHz,C6D6)δ7.19(dd,J=7.2,1.9Hz,1H),7.11(dd,J=8.2,7.3Hz,6H),6.90-6.80(m,7H),6.7 9-6.73(m,6H),3.39(p,J=6.7Hz,1H),2.15(s,3H),2.08(s,6H),2.04(s,6H),0.77(d,J=6.7Hz,6H). 13C NMR(126MHz,C6D6)δ176.67,148.18,142.74,138.23,136.99,136.60,129.46,129.34,129 .18,128.97,128.57,128.13,123.00,122.22,120.22,89.49,55.23,21.57,21.31,21.19.

[0156] Example 71: Procatalyst 8 [ka] To a solution of tetrabenzylzirconium (13.0 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added a solution of N-cyclohexyl-4-mesitylbenzothiazol-2-amine in deuterated benzene (10 mg, 0.03 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex as a yellow film (19 mg, 93%). 1 H NMR(400MHz,C6D6)δ7.23(dd,J=7.6,1.7Hz,1H),7.11-7.06(m,6H),6.88(tdd,J=7.5,3.6,2.3Hz,4H),6.83(dd,J=7.5,1.7Hz,1H),6 .81-6.79(m,2H),6.61-6.53(m,6H),3.16-3.00(m,1H),2.23(s,6H),2.13(s,3H),2.07(s,6H),1.67-1.30(m,7H),1.11-0.82(m,3H). 13 C NMR(101MHz,C6D6)δ177.28,148.13,142.98,138.15,137.14,137.13,129.71,129.53,129.21,12 9.14,128.57,128.00,123.10,121.93,120.20,79.99,63.50,31.63,26.08,25.70,21.45,21.24.

[0157] Example 72: Procatalyst 9 [ka] To a solution of tetrabenzylhafnium (15.2 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added a solution of N-cyclohexyl-4-mesitylbenzothiazol-2-amine in deuterated benzene (10 mg, 0.03 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the hafnium complex as a yellow film (22 mg, 96%). 1 H NMR(400MHz,C6D6)δ7.21(dd,J=7.1,2.0Hz,1H),7.12(t,J=6.8Hz,6H),6.90-6.81(m,7H),6.80-6.75(m,6H),3.03(tt ,J=10.6,5.3Hz,1H),2.16(s,3H),2.09(s,6H),2.07(s,6H),1.57-1.46(m,2H),1.42-1.19(m,5H),1.04-0.80(m,3H). 13 C NMR(101MHz,C6D6)δ176.87,148.12,143.06,138.24,137.02,136.65,129.48,129.34,129.21,12 8.97,128.57,128.10,122.97,122.27,120.18,89.81,63.36,31.72,25.91,25.53,21.45,21.31.

[0158] Example 73: Procatalyst 10 [ka] To a solution of tetrabenzylzirconium (14.0 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added a solution of N-(tert-butyl)-4-mesitylbenzothiazol-2-amine in deuterated benzene (10 mg, 0.03 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5-10 min.1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex as a yellow film (20 mg, 94%). 1 H NMR(400MHz,C6D6)δ7.21(dd,J=7.2,1.9Hz,1H),7.09(dd,J=8.2,7.3Hz,6H),6.94-6.86(m,5 H),6.85-6.82(m,2H),6.71-6.67(m,6H),2.33(s,6H),2.21(s,3H),2.10(s,6H),0.99(s,9H). 13 C NMR(101MHz,C6D6)δ172.98,147.24,143.33,137.67,137.22,137.09,130.39,129.83,129 .80,129.51,129.40,127.97,123.15,122.01,120.02,82.17,56.06,28.73,21.45,21.35.

[0159] Example 74: Procatalyst 11 [ka] To a solution of tetrabenzylhafnium (16.5 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added a solution of N-(tert-butyl)-4-mesitylbenzothiazol-2-amine in deuterated benzene (10 mg, 0.03 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the hafnium complex as a yellow film (21 mg, 88%). 1 H NMR(400MHz,C6D6)δ7.18(ddd,J=6.3,2.9,0.6Hz,1H),7.15-7.09(m,6H),6.92-6.87(m,3H) ,6.87-6.81(m,10H),2.19(s,3H),2.13(s,6H),2.10(d,J=0.6Hz,6H),0.92(d,J=0.5Hz,9H). 13C NMR(101MHz,C6D6)δ173.50,147.13,143.38,136.89,136.76,130.30,130.13,129.78,129.67 ,129.37,128.98,128.90,128.16,122.97,122.26,119.79,91.22,55.88,28.83,21.45,21.41.

[0160] Example 75: Procatalyst 13 [ka] To a solution of tetrabenzylhafnium in deuterated benzene (0.10 M, 273 μL) was added a solution of N-(adamantan-1-yl)-4-mesitylbenzothiazol-2-amine in deuterated benzene (11.0 mg, 0.03 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 × 0.25 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the hafnium complex as a yellow film (23 mg, 98%). 1 H NMR(400MHz,C6D6)δ7.22(dd,J=6.7,2.4Hz,1H),7.13(t,J=7.7Hz,7H),6.95-6.89(m,2H),6.89-6.80(m,10 H),2.23(s,3H),2.17(s,6H),2.12(s,6H),1.91-1.83(m,3H),1.55(d,J=2.9Hz,6H),1.45(d,J=3.1Hz,6H). 13 C NMR(101MHz,C6D6)δ172.77,146.83,143.98,137.87,136.92,130.51,129.86,129.74,129.4 3,128.86,128.18,122.92,122.32,119.73,91.75,56.50,40.70,36.25,29.98,21.43,21.38.

[0161] Example 76: Procatalyst 14 [ka] To a solution of tetrabenzylhafnium (14.9 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added a solution of N-benzyl-4-mesitylbenzothiazol-2-amine (10.0 mg, 0.03 mmol) in deuterated benzene (0.5 mL) and rinsed with deuterated benzene (2 x 0.25 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the hafnium complex as a yellow film (20 mg, 89%). 1 H NMR(400MHz,C6D6)δ7.10(t,J=7.2Hz,8H),7.08-7.05(m,1H),6.87(dt,J=7.5,1.3Hz,4H), 6.85-6.79(m,5H),6.69-6.64(m,6H),4.11(s,2H),2.16(s,3H),2.05(s,6H),2.00(s,6H). 13 C NMR(101MHz,C6D6)δ179.91,147.99,142.97,138.32,138.04,137.02,136.59,129.46,129.43,129 .23,129.08,128.95,128.73,127.76,127.42,123.10,122.35,120.39,89.06,55.31,21.44,21.24.

[0162] Example 77: Procatalyst 15 [ka] To a solution of tetrabenzylhafnium (14.3 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added dropwise a solution of N-(2,6-dimethylphenyl)-4-mesitylbenzothiazol-2-amine in deuterated benzene (10 mg, 0.03 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the hafnium complex as a yellow film (21 mg, 95%). 1 H NMR(400MHz,C6D6)δδ7.07-7.01(m,6H),6.99(dd,J=6.9,2.3Hz,1H),6.89(s,3H),6.87(s,2H) ),6.85-6.78(m,5H),6.57-6.51(m,6H),2.22(s,3H),2.10(s,6H),2.06(s,6H),1.84(s,6H). 13 C NMR(101MHz,C6D6)δ179.93,148.46,145.20,143.05,138.42,137.21,136.53,133.98,130.29,129.74, 129.46,129.31,128.96,128.86,128.69,127.06,122.94,122.79,120.60,91.64,21.44,21.30,18.15.

[0163] Example 78: Procatalyst 17 [ka] To a solution of tetrabenzylzirconium (13.2 mg, 0.03 mmol) in deuterated benzene (0.5 mL) was added a solution of 4-mesityl-N-((trimethylsilyl)methyl)benzothiazol-2-amine in deuterated benzene (20 mg, 0.06 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5-10 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex (26 mg, 93%). 1 H NMR(500MHz,C6D6)δ7.21(s,2H),7.12(t,J=7.3Hz,3H),7.09-6.99(m,8H),6.95-6. 84(m,7H),6.79(s,3H),6.70(s,4H),6.42(s,3H),2.13(s,6H),2.08-1.96(m,16H).

[0164] Example 79: Procatalyst 18 [ka] To a solution of tetrabenzylhafnium (11.9 mg, 0.02 mmol) in deuterated benzene (0.5 mL) was added a solution of N-(adamantan-1-yl)-4-(carbazol-9-yl)benzothiazol-2-amine (10.0 mg, 0.02 mmol) in deuterated benzene (0.5 mL) and rinsed with deuterated benzene (2 x 0.25 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex as a yellow film (19 mg, 95%). 1 H NMR(400MHz,C6D6)δ8.04(dt,J=7.6,1.0Hz,2H),7.20(ddd,J=7.9,6.1,1.3Hz,3H),7.16-7.10(m,5H),7.07-6.99(m,5H), 6.97(dd,J=7.8,1.3Hz,1H),6.84-6.74(m,4H),6.64(d,J=7.3Hz,6H),1.90-1.81(m,3H),1.73(s,6H),1.49-1.39(m,12H). 13 C NMR(101MHz,C6D6)δ171.86,145.96,143.38,141.59,132.32,128.69,128.15,126.70,125.99 ,124.28,122.88,122.63,121.03,120.89,120.58,111.01,91.75,56.32,40.29,36.20,29.95.

[0165] Example 80: Procatalyst 19 [ka] To a solution of tetrabenzylhafnium (13.2 mg, 0.02 mmol) in deuterated benzene (0.5 mL) was added a solution of N-benzyl-4-(carbazol-9-yl)benzothiazol-2-amine (20.0 mg, 0.05 mmol) in deuterated benzene (0.5 mL) and rinsed with deuterated benzene (2 x 0.25 mL). The reaction mixture was stirred for 5 min. 1H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex as a yellow film (27 mg, 89%). 1 H NMR(400MHz,C6D6)δ8.05(d,J=7.6Hz,4H),7.23-7.15(m,4H),7.15-7.10(m,6H),7 .13-7.04(m,4H),6.96(t,J=7.7Hz,4H),6.86(dd,J=7.8,1.3Hz,4H),6.86-6.74(m, 2H),6.77-6.69(m,6H),6.58-6.47(m,6H),6.41(dd,J=7.8,1.3Hz,2H),3.80(d,J=1 5.5Hz,2H), 3.15(d,J=15.6Hz,2H),1.88(d,J=12.4Hz,2H),1.54(d,J=11.0Hz,2H). 13 C NMR(101MHz,C6D6)δ181.57,147.99,147.07,143.68,137.41,130.60,128.93,128.85,1 28.39,127.47,127.45,126.78,125.54,121.84,121.49,121.32,110.77,84.64,54.18.

[0166] Example 81: Procatalyst 20 [ka] In a nitrogen-filled, continuously purged glovebox, a 3 M solution of MeMgBr (0.19 mL, 0.580 mmol, 4.4 equiv) in diethyl ether was added dropwise to a rapidly stirring suspension of HfCl4 (42.2 mg, 0.132 mmol, 1 equiv) in cold (-30 °C) dichloromethane (5 mL). The reaction was stirred for 2 min, then a cold (-30 °C) solution of 4-mesityl-N-neopentylthiazol-2-amine (76.0 mg, 0.264 mmol, 2 equiv) in anhydrous deoxygenated dichloromethane (2.5 mL) was added dropwise. The vial of 4-mesityl-N-neopentylthiazol-2-amine was rinsed with dichloromethane (2.5 mL) and this was added to the reaction. The clear solution containing a white precipitate was stirred for 3 h and allowed to warm to room temperature. Over time, the color of the solution darkened slightly. The suspension was filtered through a 0.45 μm syringe filter and rinsed with dichloromethane (2×1 mL). The resulting pale yellow filtrate solution was concentrated in vacuo to give a pale brown solid (approximately 160 mg). The solid was suspended, triturated with hexanes (10 mL), filtered through a 0.45 μm syringe filter lined with a 0.2 μm syringe filter, and the filtrate solution was concentrated to give the hafnium complex as a pale yellow / brown solid (97.6 mg, 95% yield). 1 H NMR(400MHz,C6D6)δ6.71(s,4H),5.23(s,2H),2.87(s,4H),2.09(s,12H),2.08(s,6H),0.86(s,18H),0.42(s,6H). 13 C NMR (101 MHz, benzene-d6) δ 182.79, 147.35, 137.34, 137.19, 131.06, 127.94, 98.43, 65.70, 54.24, 33.95, 27.70, 20.71, 20.05.

[0167] Example 82: Procatalyst 22 [ka] To a solution of tetrabenzylzirconium (9.2 mg, 0.02 mmol) in deuterated benzene (0.5 mL) was added a solution of N,1-diisopropyl-4-mesitylbenzimidazol-2-amine in deuterated benzene (6.8 mg, 0.02 mmol in 0.5 mL of C6D6) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5 min. 1 H NMR showed conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex as a yellow film (14 mg, 99%). 1 H NMR(400MHz,C6D6)δ7.09(t,J=7.7Hz,6H),7.00(d,J=1.5Hz,1H),6.97(t,J=7.6Hz,1H),6.93-6.87(m,4H),6.85(s,2H),6.66-6.60(m,6H) ,4.44(hept,J=7.0Hz,1H),3.80(hept,J=6.5Hz,1H),2.24(s,6H),2.19(s,3H),2.15(s,6H),1.20(d,J=6.9Hz,6H),1.02(d,J=6.4Hz,6H). 13 C NMR(101MHz,C6D6)δ160.41,144.28,139.72,137.60,137.22,136.48,133.05,129.61,129.1 5,128.01,125.20,122.59,120.34,110.27,77.28,49.64,48.10,25.01,21.44,21.20,20.43.

[0168] Example 83: Procatalyst 21 [ka] To a solution of tetrabenzylhafnium (11.2 mg, 0.02 mmol) in deuterated benzene (0.5 mL) was added a solution of N,1-diisopropyl-4-mesitylbenzimidazol-2-amine in deuterated benzene (0.1 M, 0.209 mL, 0.02 mmol) and rinsed with deuterated benzene (2 x 0.5 mL). The reaction mixture was stirred for 5 min. 1H NMR showed the conversion of the starting ligand to the desired complex. The solution was concentrated to give the zirconium complex as a yellow film (16 mg, 97%). 1 H NMR(400MHz,C6D6)δ7.13(dd,J=8.0,7.2Hz,6H),6.99-6.96(m,2H),6.90(dd,J=5.8,3.2Hz,1H),6.89-6.84(m,5H),6.82-6.78(m,6H),4 .33(hept,J=7.0Hz,1H),3.87(hept,J=6.5Hz,1H),2.20(s,3H),2.18(s,6H),2.11(s,6H),1.13(d,J=7.0Hz,6H),0.89(d,J=6.5Hz,6H). 13 C NMR(101MHz,C6D6)δ159.26,144.48,139.42,137.80,137.07,136.03,132.81,129.11,128.8 3,128.12,125.11,122.47,120.52,110.27,87.84,48.91,48.11,24.76,21.44,21.27,20.31.

[0169] Example 84 - Polymerization Reaction The catalytic activity (in terms of quench time and polymer yield) as well as the resulting polymer properties were evaluated for procatalysts 1 to 22. The polymerization reactions were carried out in a semi-batch reactor and a parallel pressure reactor (PPR).

[0170] The reaction conditions for the results reported in Tables 1 and 2 were as follows: Polymerization reactions were carried out in a 2 L semi-batch reactor, first without diethylzinc (DEZ) and then with the addition of three different DEZ loadings (0, 50, and 200 μmol). The activator was 1.2 molar equivalents of [HNMe(C 18 H 37)2][B(C6F5)4], with each analysis performed for 10 minutes. Standard semi-batch reactor conditions in Table 1 results for polymerization reaction at 120°C include 46g ethylene and 303g 1-octene in 611g IsoparE. Standard semi-batch reactor conditions in Table 1 results for polymerization reaction at 150°C include 43g ethylene and 303g 1-octene in 547g IsoparE. Mol% octene or C8 / olefin is defined as (moles 1-octene / (total moles 1-octene and ethylene)) x 100. [Table 1] [Table 2] [Table 3]

[0171] PPR polymerization experiments were performed using [HNMe(C 18 H 37 )2][B(C6F5)4] was used as the activator in an amount of 1.5 molar equivalents relative to the procatalyst and was carried out at both 120 and 150 °C, with MMAO-3 (500 nmol at 120 °C or 750 nmol at 150 °C) as the scavenger. [Table 4-1] [Table 4-2] [Table 4-3] [Table 5]

[0172] The high chain transfer constants Ca of 0.6 or more for the procatalysts recorded in Table 5 indicate that these procatalysts have high sensitivity to chain transfer agents and undergo rapid chain transfer when combined with these agents. Overall, a decrease or a relatively persistent narrow PDI for these procatalysts was observed as the amount of Et2Zn(DEZ) was increased, which is evidence that these particular procatalysts can undergo reversible chain transfer rather than irreversible chain transfer when combined with CSA.

[0173] Computational studies were performed to determine whether the nitrogen or sulfur atoms of the ligands of procatalyst 2, procatalyst 3, and procatalyst 11 were complexed with the metal. The geometries of procatalyst 2, procatalyst 3, and procatalyst 11 in two different configurations (N atom bound to metal (configuration 1) or S atom bound to metal (configuration 2)) were optimized using constrained (closed shell) hybrid density functional theory (DFT), Becke, three-parameter, Lee-Yang-Parr (B3LYP) (see Becke, ADJ Chem. Phys. 1993, 98, 5648; Lee, C. et al., Phys. Rev B 1988, 37, 785; and Miehlich, B. et al. Chem. Phys. Lett. 1989, 157, 200) and the 6-31G* basis set. For metal atoms (Zr / Hf), Lanl2dz was used as the effective inner core potential. The minimum of the ground state potential energy surface (PES) is verified by the absence of imaginary frequencies in the optimized ground state conformations. The energies of the optimized configurations were further evaluated using higher basis sets (6~311+g**) for all atoms except metal atoms. All the above calculations were performed using the G16 program suite and the results were recorded in Table 6. [Table 6]

[0174] Based on the above methodology, configuration 1 (N-bonded to metal) showed higher stability compared to configuration 2 (S-bonded to metal), regardless of the selected procatalyst and metal. The present invention includes the following aspects. Section 1. A catalyst system comprising a procatalyst having a structure according to formula (I): [ka] During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, said metal having a formal oxidation state of +2, +3, or +4; Each X is independently an unsaturated (C2-C 50 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C6-C 50 )Aryl, (C6-C 50 )Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C is a monodentate or bidentate ligand selected from m is 1 or 2; n is 2 or 3 with the proviso that m+n=4; Each Z is NR N or S and R N But, (C1-C 40 ) hydrocarbyl or (C1-C 40 ) heterohydrocarbyl; Each R 1 But, (C1-C 40 ) hydrocarbyl or (C1-C 40 ) heterohydrocarbyl; Each R 2 and R 3 But independently, (C1-C 50 ) hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C 50)heteroaryl, -Si(R C 3), halogen, and -H; R C But independently, (C1-C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, and -H; Optionally, R 2 and R 3 are covalently bonded to form a ring, a catalytic system. Section 2. R 3 Item 2. The catalyst system according to item 1, wherein is (2,4,6-triisopropyl)phenyl, 2,4,6-trimethylphenyl, 3,5-di-tertbutylphenyl, naphthyl, carbozolyl, or cyclopropyl. Section 3. R 2 and R 3 are covalently linked to form an aromatic ring, and the metal-ligand complex has a structure according to formula (II): [ka] In the formula, each R 1 , Z, X, n, m, and M are defined as in formula (I); Each R 4 , R 5 , R 6 , and R 7 But independently, (C1-C 40 ) hydrocarbyl or (C1-C 40 Item 2. The catalyst system according to item 1, wherein the heterohydrocarbyl is a heterohydrocarbyl. Section 4. Each R 7 However, (C6-C 40 )Aryl or (C6-C 40 Item 4. The catalyst system according to item 3, wherein the heteroaryl is a heteroaryl. Section 5. Each R 7 Item 4. The catalyst system according to item 3, wherein is phenyl, (2,4,6-triisopropyl)phenyl, 2,4,6-trimethylphenyl, 3,5-di-tert-butylphenyl, naphthyl, carbozolyl, or cyclopropyl. Section 6. Each Z is NR N and R N 6. The catalyst system according to any one of items 1 to 5, wherein is (C1-C8) alkyl. Section 7. 6. The catalyst system according to any one of items 1 to 5, wherein each Z is S. Section 8. 8. The catalyst system according to any one of items 1 to 7, wherein m is 2. Section 9. 8. The catalyst system according to any one of items 1 to 7, wherein m is 1. Section 10. the metal-ligand complex has a structure according to formula (Ia), (Ib), (Ic), or (Id); [ka] In the formula, each R 1 , R 2 , R 3 , R N 6. The catalyst system according to any one of items 1 to 5, wherein X and M are as defined in formula (I). Section 11. the metal-ligand complex has a structure according to formula (IIa), (IIb), (IIc), or (IId); [ka] In the formula, each R 1 , R 4 , R 5 , R 6 , R 7 , R N 6. The catalyst system according to any one of items 3 to 5, wherein X and M are as defined in formula (II). Section 12. Each R 1 But linear (C1-C 12 ) Alkyl, branched (C1-C 12 ) alkyl, (C1-C 12 12. The catalyst system according to any one of items 1 to 11, wherein the aryl group is selected from the group consisting of cycloalkyl, trimethylsilylmethyl, benzyl, and 1-adamantyl. Section 13. 13. The catalyst system of any one of paragraphs 1 to 12, wherein each X is independently benzyl, phenyl, or chloro. Section 14. 14. The catalyst system of any one of the preceding claims, further comprising a chain transfer agent and an activator mixed in solution with one or more metal-ligand complexes of any one of claims 1 to 13. Section 15. 1. A polymerization process comprising: polymerizing ethylene and one or more olefins under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based polymer, said catalyst system comprising a metal-ligand complex according to formula (I): [ka] During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, said metal having a formal oxidation state of +2, +3, or +4; Each X is independently an unsaturated (C2-C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C6-C 50 )Aryl, (C6-C 50 )Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C is a monodentate or bidentate ligand selected from m is 1 or 2; n is 2 or 3 with the proviso that m+n=4; Each Z is NR N or S and R N But, (C1-C 20 ) hydrocarbyl or (C1-C 20 ) heterohydrocarbyl; Each R 1 But, (C1-C 40 ) hydrocarbyl or (C1-C 20 ) heterohydrocarbyl; Each R 2 and R 3 But independently, (C1-C 50 ) hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C 3), halogen, and -H; R C But independently, (C1-C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, and -H; Optionally, R 2 and R 3 A polymerization process in which the monomers are covalently bonded to form a ring. Section 16. Z is NR N and R N Item 16. The catalyst system according to item 15, wherein is (C1-C8) alkyl. Section 17. Item 16. The catalyst system according to item 15, wherein Z is S. Section 18. 16. The polymerization process of claim 15, wherein the catalyst system is the catalyst system of claim 14, and the process further comprises mixing the chain transfer agent and the activator with the one or more metal-ligand complexes in solution.

Claims

1. A catalyst system comprising a procatalyst having a structure according to formula (I): 【Chemistry 1】 During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, said metal having a formal oxidation state of +2, +3, or +4; Each X is independently an unsaturated (C ２ -C ５０ ) Hydrocarbon, unsaturated (C ２ -C ５０ ) heterohydrocarbons, (C １ -C ５０ ) hydrocarbyl, (C ６ -C ５０ ) aryl, (C ６ -C ５０ ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C ４ -C １２ ) diene, halogen, -N(R Ｎ ) ２ and -NHCOR Ｃ is a monodentate or bidentate ligand selected from m is 1 or 2; n is 2 or 3 with the proviso that m+n=4; Each Z is NR Ｎ or S, R Ｎ However, (C １ -C ４０ ) hydrocarbyl or (C １ -C ４０ ) heterohydrocarbyl; Each R １ However, (C １ -C ４０ ) hydrocarbyl or (C １ -C ４０ ) heterohydrocarbyl; Each R ２ and R ３ But independently, (C １ -C ５０ ) hydrocarbyl, (C １ -C ５０ ) heterohydrocarbyl, (C ６ -C ５０ ) aryl, (C ４ -C ５０ ) heteroaryl, —Si(R Ｃ ) ３ , halogen, and —H; R Ｃ But independently, (C １ -C ２０ ) hydrocarbyl, (C １ -C ２０ ) heterohydrocarbyl, and —H; Optionally, R ２ and R ３ are covalently bonded to form a ring, a catalytic system.

2. R ３ 2. The catalyst system of claim 1, wherein is (2,4,6-triisopropyl)phenyl, 2,4,6-trimethylphenyl, 3,5-di-tertbutylphenyl, naphthyl, carbazolyl, or cyclopropyl.

3. R ２ and R ３ are covalently linked to form an aromatic ring, and the procatalyst has a structure according to formula (II): 【Chemistry 2】 In the formula, each R １ , Z, X, n, m, and M are defined as in formula (I); Each R ４ , R ５ , R ６ , and R ７ But independently, (C １ -C ４０ ) hydrocarbyl or (C １ -C ４０ 2. The catalyst system of claim 1, wherein said heterohydrocarbyl is aryl.

4. Each R ７ However, (C ６ -C ４０ ) aryl or (C ６ -C ４０ 4. The catalyst system of claim 3, wherein:

5. Each R ７ 4. The catalyst system of claim 3, wherein is phenyl, (2,4,6-triisopropyl)phenyl, 2,4,6-trimethylphenyl, 3,5-di-tert-butylphenyl, naphthyl, carbazolyl, or cyclopropyl.

6. Each Z is NR Ｎ and R Ｎ However, (C １ -C ８ 6. The catalyst system according to claim 1, wherein the aryl group is aryl, ...

7. 6. The catalyst system of claim 1, wherein each Z is S.

8. 8. The catalyst system according to claim 1, wherein m is 2.

9. 8. The catalyst system according to claim 1, wherein m is 1.

10. the procatalyst has a structure according to formula (Ia), (Ib), (Ic), or (Id); 【Chemistry 3】 In the formula, each R １ , R ２ , R ３ , R Ｎ 2. The catalyst system of claim 1, wherein X and M are as defined in formula (I).

11. the procatalyst has a structure according to formula (IIa), (IIb), (IIc), or (IId); 【Chemistry 4】 In the formula, each R １ , R ４ , R ５ , R ６ , R ７ , R Ｎ 4. The catalyst system of claim 3, wherein X and M are as defined in formula (II).

12. Each R １ But linear (C １ -C １２ ) alkyl, branched (C ３ -C １２ ) alkyl, (C ３ -C １２ 12. The catalytic system according to claim 1, wherein the aryl group is selected from the group consisting of cycloalkyl, trimethylsilylmethyl, benzyl, and 1-adamantyl.

13. 13. The catalyst system of any one of claims 1 to 12, wherein each X is independently benzyl, phenyl, or chloro.

14. 14. The catalyst system of any one of claims 1 to 13, further comprising a chain transfer agent and an activator mixed in solution with one or more procatalysts of any one of claims 1 to 13.

15. 1. A polymerization process comprising: A polymerization process comprising polymerizing ethylene and one or more olefins in the presence of the catalyst system of any one of claims 1 to 14 under olefin polymerization conditions to form an ethylene-based polymer.

16. 16. The polymerization process of claim 15, wherein the catalyst system is the catalyst system of claim 14, and the process further comprises mixing the chain transfer agent and the activator with the one or more procatalysts in solution.

Images