Group III halide or lanthanide halide bis(phenylphenoxy) metal-ligand complexes

Abstract

Embodiments of the present disclosure are directed to catalyst systems comprising metal-ligand complexes according to formula (I). [Formula 1] JPEG2025531691000050.jpg60170

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 401,915, filed August 29, 2022, which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more specifically to bis-phenylphenoxy metal-ligand complexes having Group III or lanthanide metal centers. [Background technology]

[0003] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, are produced by a variety of 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 and propylene-based polymers are produced for a wide variety of articles. Polyethylene and polypropylene polymerization processes 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. Ethylene monomer, and optionally one or more comonomers, are present in a liquid diluent or solvent, such as an alkane or isoalkane, of which hexane and isobutane are particular examples. Hydrogen may also be added to the reactor. Catalyst systems for producing ethylene typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (either metallocene or non-metallocene) catalyst systems. The reactants in the catalyst system and diluent are circulated within the reactor at elevated polymerization temperatures, thereby producing an ethylene-based homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture, including the polyethylene product dissolved in the diluent, is removed from the reactor along with unreacted ethylene and one or more optional comonomers. After being removed from the reactor, the reaction mixture 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 catalyst systems suitable for olefin polymerization, such as polyethylene polymerization, there remains a need for improved efficiency of catalyst systems capable of producing polymers with high molecular weights and narrow molecular weight distributions, and high selectivity to ethylene.

[0005] Previously discovered Group III bis-phenylphenoxy metal-ligand catalysts did not require a cocatalyst or activator to initiate polymerization. While not requiring a cocatalyst or activator can be beneficial, it also presents problems within the reactor. Due to the reactivity of Group III bis-phenylphenoxy metal-ligand catalysts, the catalyst can react in the feed lines or as soon as the Group III catalyst comes into contact with ethylene, thereby fouling the injection site or feed lines. Summary of the Invention

[0006] There is a continuing need to create catalyst systems or metal-ligand complexes that have high selectivity to ethylene during the copolymerization reaction of ethylene and α-olefins. Furthermore, the metal-ligand complexes should possess high catalytic efficiency and the versatile ability to produce high or low molecular weight polymers at high temperatures (e.g., above 140°C or around 190°C).

[0007] Embodiments of the present disclosure provide chloro-scandium-bis(phenylphenoxyl) metal-ligand complexes that are unreactive until the chlorine atom is replaced with an alkyl group, making the metal-ligand complex an active catalyst.

[0008] Embodiments of the present disclosure include catalyst systems comprising metal-ligand complexes according to formula (I).

[0009] [ka]

[0010] In formula (I), M is scandium, yttrium, a lanthanide metal, or an actinide metal having an oxidation state of +3. (T) n The subscript n is 0, 1, or 2, X is a halogen atom, and the subscript k is 1 or 2. T is a Lewis base. The metal-ligand complex is overall charge neutral.

[0011] In formula (I), R1 and R 16 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

[0012] [ka]

[0013] In formulas (II), (III), and (IV), each of R31-35, R41-48, and R51-59 is independently selected from —H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(RN)—, (RC)2NC(O)—, or halogen.

[0014] In formula (I), R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15 are independently —H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(R C )3, -P(R P)2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, and halogen.

[0015] In formulas (I), (II), (III), and (IV), each R C , R P , and R N are independently (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H. DETAILED DESCRIPTION OF THE INVENTION

[0016] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure.

[0017] Common abbreviations are listed below.

[0018] R, Z, M, X, and n: as defined above, Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: isopropyl, t-Bu: tert-butyl, t-Oct: tert-octyl(2,4,4-trimethylpentan-2-yl), Tf: trifluoromethanesulfonate, CV: column volume (if used in column chromatography), EtOAc: ethyl acetate, TEA: triethylaluminum, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, LiCH2TMS: (trimethylsilyl)methyllithium, TMS: trimethylsilyl, Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), Pd(AmPhos): chloro(crotyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II), Pd(dpp f) Cl2: [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, ScCl3: scandium(III) chloride, PhMe: toluene, THF: tetrahydrofuran, CHCl2: dichloromethane, DMF: N,N-dimethylformamide, EtOAc: ethyl acetate, Et2O: diethyl ether, MeOH: methanol, NHCl: ammonium chloride, MgSO4: magnesium sulfate, NaSO4: sodium sulfate, NaOH: sodium hydroxide, Brine: saturated aqueous sodium chloride solution, SiO2: silica, CDCl3: chloroform-D, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: molar concentration, min or mins: minute, h or hrs: hour, d: day, TLC: thin layer chromatography, rpm: revolutions per minute, rt: room temperature.

[0019] The term "independently selected" refers to 1 , R 2 , R 3 , R 4 , and R 5 and the R groups may be the same or different (e.g., R 1 , R 2 , R3 , R 4 , and R 5 may all be substituted alkyl, or R 1 and R 2 may be substituted alkyl, R 3 The R group is used herein to indicate that the R group may be an aryl group, etc. Chemical names associated with R groups are intended to convey chemical structures recognized in the art as corresponding to the chemical structure of the chemical name. Thus, the chemical names are intended to supplement and illustrate, not preclude, structural definitions known to those of skill in the art.

[0020] When used to describe certain carbon atom-containing chemical groups, x -C y A parenthesized expression having the form "(C1-C2)" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, inclusive. 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 parenthesized "(C x -C y )" S The substituted chemical group can be any group R S For example, "R S exactly one group R is phenyl (-C6H5) S (C1-C 50 A "(C ) alkyl" can contain 7 to 56 carbon atoms. Thus, in general, the parenthesized "(C x -C y )" is a group defined using 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 the sum of all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0021] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "fully substituted" means that all hydrogen atoms (H) bonded to carbon atoms 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 atom or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0022] "(C1-C 50 The term "(C-C)hydrocarbyl" means a hydrocarbon radical of 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 50 carbon atoms, each hydrocarbon radical and each hydrocarbon diradical being 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 containing one or more R S is or is not replaced by

[0023] In this disclosure, (C1-C 50 ) hydrocarbyl is unsubstituted or substituted (C-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).

[0024] "(C1-C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an unsubstituted or alkyl group containing one or more R S and saturated straight-chain or branched-chain hydrocarbon radicals of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively, 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" refers to a group having up to 45 carbon atoms in the radical, including the substituents, e.g., one R that is (C-C) alkyl. S replaced by (C 27 -C 40 Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0025] "(C6-C 50 The term "aryl" refers to an unsubstituted or (one or more R S"Aromatic hydrocarbon radicals" refers to monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radicals substituted (by C6-C), where at least 6 to 14 of the carbon atoms are aromatic ring carbon atoms. 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, and aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl include unsubstituted (C-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 (C-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0026] "(C3-C 50 The term "cycloalkyl" refers to an unsubstituted or substituted group having one or more R S means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms substituted with 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.

[0027] (C1-C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C-C 50 ) arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). Diradicals can be on the same carbon atom (e.g., —CH—) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or three 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 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-), and 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (C-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0028] "(C1-C 50 The term "alkylene" refers to an unsubstituted or substituted group having one or more R Smeans a saturated straight or branched chain diradical of 1 to 50 carbon atoms (i.e., the radical is not on a ring atom) substituted by 50 Examples of alkylene are unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3 and -(CH2)4C * Unsubstituted (C1-C 20 ) alkylene, wherein "C * " denotes 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 (C-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 are combined together, (C1-C 18 ) alkylene, so that substituted (C1-C 50 Examples of )alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0029] "(C3-C 50 The term "cycloalkylene" refers to a group that is unsubstituted or has one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms substituted by

[0030] 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(RC )2, -Ge(R C )2-, -Si(R C )-, boron (B), aluminum (Al), gallium (Ga), or indium (In), and each R C and each R P is unsubstituted (C1-C 18 ) hydrocarbyl or —H, and each R N 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 "(C-C)heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 ) heterohydrocarbyl or (C-C 50 The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The heterohydrocarbyl radical can be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene can be on a single carbon atom or a single heteroatom. Additionally, 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; one of the two radicals can be on a carbon atom and the other on a heteroatom; or one of the two radicals can be on a heteroatom and the other radical on a different heteroatom. Each (C-C 50 ) heterohydrocarbyl and (C-C 50 ) heterohydrocarbylene is unsubstituted or (one or more R S and may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0031] (C1-C 50 ) Heterohydrocarbyl can be unsubstituted or substituted. (C-C50 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)-, (C-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 (C-C 19 )heteroaryl-(C1-C 20 ) heteroalkylene.

[0032] "(C1-C 50 The term "heteroaryl" refers to an unsubstituted or heteroaryl group having a total of 1 to 50 carbon atoms and 1 to 10 heteroatoms (one or more R S(C1-C3) means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical substituted with a cyclic or cyclic heteroaromatic group. 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(s) of the heteroaromatic radical may independently be fused or non-fused, and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C1-C3) 12 ) heteroaryl, etc. x -C y ) heteroaryl (general) has x to y carbon atoms (e.g., 1 to 12 carbon atoms) and is unsubstituted or has one or more R SThe monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as being substituted with . The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms, which may be 1, 2, 3, or 4, and each heteroatom may 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. A 6-membered monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2, and the heteroatom may be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. A bicyclic heteroaromatic hydrocarbon radical may be a fused 5,6- or 6,6-ring system. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. A tricyclic heteroaromatic hydrocarbon radical may be a fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring system. 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 6,6,6-ring system is acridine-9-yl.

[0033] "(C1-C 50The term "(C1-C2) heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms 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)2, each of the heteroalkyl and heteroalkylene groups may be unsubstituted or may contain one or more R S has been replaced by

[0034] 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.

[0035] 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 - ) means

[0036] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be replaced by a substituent R S The term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, and the substituent R S This means that the aromatic ring or heteroaromatic ring does not contain any double bonds that may be present in the ring (if present), or in the aromatic or heteroaromatic ring (if present).

[0037] The term "lanthanide metals" includes elements 57-71 (lanthanum (La)-lutetium (Lu)).

[0038] Embodiments of the present disclosure include catalyst systems comprising metal-ligand complexes according to formula (I).

[0039] [ka]

[0040] In formula (I), M is scandium, yttrium, or a lanthanide metal. (T) n The subscript n in is 0, 1, or 2, X is a halogen atom, and the subscript k is 1 or 2. C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbyl, or substituted or unsubstituted (C-C 30 ) heterohydrocarbyl. T ​​is a Lewis base. The metal-ligand complex is overall charge neutral.

[0041] In formula (I), R 1 and R 16are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

[0042] [ka]

[0043] In some embodiments, in the metal-ligand complex of formula (I), R 1 or R 16 Either of the above or R 1 and R 16 and R are both selected from radicals having formula (II), formula (III), or formula (IV), provided that M is yttrium or a lanthanide metal. 1 is not -H, phenyl, or tert-butyl, and R 16 is not -H, phenyl, or tert-butyl.

[0044] When present in a metal-ligand complex of formula (I) as part of a radical having formula (II), formula (III), or formula (IV), the group R 31-35 , R 41-48 , and R 51-59 are each independently (C1-C 40 ) hydrocarbyl, (C1-C 40) heterohydrocarbyl, Si(R C )3, P(R P )2, N(R N )2, OR C , S.R. C , NO2, CN, CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )NC(O)-, halogen, hydrogen (-H), or a combination thereof. C , R P , and R N is unsubstituted (C1-C 18 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H.

[0045] R in the metal-ligand complex of formula (I) 1 Groups and R 16 The groups are selected independently of each other. For example, R 1 may be selected from radicals having formula (II), (III), or (IV), and R 16 is (C1-C 40 ) hydrocarbyl, or R 1 may be selected from radicals having formula (II), (III), or (IV), and R 16 may be selected from radicals having formula (II), (III), or (IV), and R 1 R 1 and R 16 may both be radicals having formula (II), in which case R 31-35 The group is R 1 and R 16 In another embodiment, R 1 and R 16 may both be radicals having formula (III), in which case R 41-48 The group is R 1 and R16 are the same or different in R 1 and R 16 may both be radicals having formula (IV), in which case R 51-59 The group is R 1 and R 16 are the same or different.

[0046] In some embodiments, R 1 and R 16 at least one of R is a radical having formula (II) 32 and R 34 is tert-butyl. In one or more embodiments, R 32 and R 34 is (C1-C 12 ) hydrocarbyl or -Si[(C-C 10 ) alkyl]3.

[0047] In some embodiments, R 1 or R 16 is a radical having the formula (III), then R 43 and R 46 one or both of R 41-42 , R 44-45 , and R 47-48 is —H. In other embodiments, R 42 and R 47 one or both of R 41 , R 43-46 , and R 48 is —H. In some embodiments, R 42 and R 47 and R are —H. In various embodiments, R 42 and R 47 is (C1-C 20 ) hydrocarbyl or -Si[(C-C 10 ) alkyl]3. In other embodiments, R 43 and R 46 is (C1-C 20 ) hydrocarbyl or -Si[(C-C 10) alkyl]3. In some embodiments, R 42 and R 43 are linked to form a ring structure, and R 46 and R 47 are linked to form a ring structure.

[0048] In some embodiments, R 1 or R 16 When at least one of R is a radical having formula (IV), then each R 52 , R 53 , R 55 , R 57 , and R 58 is -H, (C1-C 20 ) hydrocarbyl, -Si[(C-C 20 )hydrocarbyl]3, or -Ge[(C1-C 20 )hydrocarbyl]3. In some embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least one of the (C3-C 10 ) alkyl, -Si[(C3-C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3. In one or more embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least two of them (C3-C 10 ) alkyl, -Si[(C3-C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3. In various embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least three of them (C3-C 10 ) alkyl, -Si[(C3-C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3.

[0049] In some embodiments, R 1 or R 16 is a radical having the formula (IV), then R 52 , R 53 , R 55 , R 57 , and R 58 At least two of them (C1-C 20 ) hydrocarbyl or —C(H)2Si[(C1-C 20 ) hydrocarbyl]3.

[0050] (C3-C 10 Examples of alkyl include, but are not limited to, propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

[0051] In some embodiments of the metal-ligand catalyst according to Formula (I), R 1 and R 16are 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 3,5-diisopropylphenyl, carbazolyl, carbazol-9-yl, 1,2,3,4-tetrahydrocarbazolyl, 1,2,3,4,5,6,7,8-octahydrocarbazolyl, 3,6-bis-(3,5-di-tert-butylphenyl)carbazol-9-yl, 3,6-bis-(2,4,6-triisopropylphenyl)carbazol-9-yl, 2,7-di(tertiary butyl)-carbazol-9-yl, 2,7-di(tertiary octyl)-carbazol-9-yl, 2,7-diphenylcarbazol-9-yl, 2,7-bis(2,4,6-trimethylphenyl)-carbazol-9-ylanthracenyl, 1,2,3,4-tetrahydroanthracenyl , 1,2,3,4,5,6,7,8-octahydroanthracenyl, phenanthrenyl, 1,2,3,4,5,6,7,8-octahydrophenanthrenyl, 1,2,3,4-tetrahydronaphthyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 3,5-diphenylphenyl, 1-naphthyl, 2-methyl-1-naphthyl, 2-naphthyl, 1,2,3,4-tetrahydronaphth-5-yl, 1,2,3,4-tetrahydronaphthyl It is selected from dronephth-6-yl, anthracen-9-yl, 1,2,3,4-tetrahydroanthracen-9-yl, 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl, 1,2,3,4,5,6,7,8-octahydrophenanthrene-9-yl, indolyl, indolinyl, quinolinyl, 1,2,3,4-tetrahydroquinolinyl, isoquinolinyl, or 1,2,3,4-tetrahydroisoquinolinyl.

[0052] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R13 , R 14 , and R 15 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, and halogen.

[0053] In one or more embodiments, R 2 , R 4 , R 5 , R 12 , R 13 , and R 15 is hydrogen.

[0054] In embodiments, the dotted lines are optional coordinate bonds between the metal center M and the oxygen atom. In some embodiments, one of the dotted lines connecting the oxygen atom and M is coordinate, and the other dotted line does not form a coordinate bond between the oxygen atom and M. In various embodiments, both dotted lines form coordinate bonds between the group oxygen atom and M.

[0055] In various embodiments, R 3 and R 14 is (C1-C 24 ) alkyl. In one or more embodiments, R 3 and R 14 is (C4-C 24 ) alkyl. In some embodiments, R 3 and R 14is 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. 3 and R 14 -OR C and R C is (C1-C 20 ) hydrocarbon, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl.

[0056] In one or more embodiments, R 8 and R 9 In various embodiments, one of R 8 and R 9 At least one of (C1-C 24 ) alkyl. In some embodiments, R 8 and R 9 Both of (C1-C 24 ) alkyl. In some embodiments, R 8 and R 9 is methyl. In another embodiment, R 8 and R 9 is a halogen.

[0057] In some embodiments, R 3 and R 14 is methyl. In one or more embodiments, R 3 and R 14 is (C4-C 24 ) alkyl. In some embodiments, R 8 and R 9are 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

[0058] In various embodiments, in the metal-ligand complex of formula (I), R 6 and R 11 is halogen. In some embodiments, R 6 and R 11 is (C1-C 24 ) alkyl. In various embodiments, R 6 and R 11 is independently selected from 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. 6 and R 11 is tert-butyl. In some embodiments, R 6 and R 11 -OR C and R C is (C1-C 20 ) hydrocarbyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl. 6 and R 11 -SiR C 3, and each R C are independently (C1-C 20 ) hydrocarbyl, and in some embodiments, R Cis methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), or 1,1-dimethylethyl.

[0059] In some embodiments, the chemical group (e.g., R 1-59 ) may be unsubstituted. In other embodiments, the chemical group R of the metal-ligand complex of formula (I) 1-59 Any of the following may contain one or more R S and any or all of them may be substituted with one or more R S It may be substituted with 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. 1-59 Any of the above is R S In some cases, the group is not fully substituted with any of the groups R S It may also be fully substituted with R S In a chemical group that is fully substituted with S may all be the same or may be independently selected. In one or more embodiments, R S is (C1-C 20 ) hydrocarbyl, (C1-C 20 ) alkyl, (C1-C 20 ) heterohydrocarbyl, or (C-C 20 ) heteroalkyl.

[0060] In formula (I), L is (C1-C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, and each Z is independently —O—, —S—, —N(R N )-, or -P(R P )- In one or more embodiments, L contains 1 to 10 atoms.

[0061] In formulas (I), (II), (III), and (IV), each R C , R P , and R N are independently (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H.

[0062] In some embodiments of Formula (I), L is a (C3-C7) alkyl 1,3-diradical, e.g., -CH2CH2CH2-, -CH(CH3)CH2C * H(CH3), -CH(CH3)CH(CH3)C * In some embodiments, L may be selected from (C4-C 10 ) alkyl 1,4-diradicals, such as -CH2CH2CH2CH2-, -CH2C(CH3)2C(CH3)2CH2-, cyclohexane-1,2-diyldimethyl, and bicyclo[2.2.2]octane-2,3-diyldimethyl. In some embodiments, L is selected from (C5-C 12 ) alkyl 1,5-diradicals, such as —CH2CH2CH2CH2CH2—, and 1,3-bis(methylene)cyclohexane. In some embodiments, L is (C6-C 14 ) alkyl 1,6-diradicals, such as -CH2CH2CH2CH2CH2CH2-, or 1,2-bis(ethylene)cyclohexane.

[0063] In one or more embodiments, L is (C-C 40 ) heterohydrocarbylene, where at least one of the 2 to 10 atoms comprises a heteroatom. In some embodiments, L is —CHGe(R C )2CH2-, and each R C is (C1-C 30) hydrocarbyl. In some embodiments, L is —CHGe(CH3)2CH2—, —CH2Ge(ethyl)2CH2—, —CH2Ge(2-propyl)2CH2—, —CH2Ge(t-butyl)2CH2—, —CH2Ge(cyclopentyl)2CH2—, or —CH2Ge(cyclohexyl)2CH2—.

[0064] In one or more embodiments, L is —CH—, —CHCH—, —CH(CH) m CH2- (m is 1 to 3), -CH2Si(R C )2CH2-;-CH2Ge(R C )2CH2-;-CH(CH3)CH2CH * (CH); and —CH(phen-1,2-diyl)CH—, and each R in L is selected from C is (C1-C 20 ) hydrocarbyl.

[0065] It takes (C1-C 12 Examples of alkyl include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl, cyclopentyl or cyclohexyl, butyl, tert-butyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpent-2-yl), nonyl, decyl, undecyl, and dodecyl.

[0066] In some embodiments, in the metal-ligand complex according to formula (I), R 8 and R 9 and R are both methyl. 8 and R 9 one of R 8 and R 9 The other is -H.

[0067] In the metal-ligand complex according to Formula (I), X is bonded to M through a covalent or ionic bond. In some embodiments, X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0068] In one or more embodiments, M is scandium, yttrium, a lanthanide metal, which may be lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium.

[0069] In the metal-ligand complex according to Formula (I), each T is bonded to M via a coordinate bond or an ionic bond. In one or more embodiments, T is a Lewis base. A Lewis base can be a compound or ionic species capable of donating an electron pair to an acceptor compound. For purposes of this description, the acceptor compound is M, the metal of the metal-ligand complex of Formula (I). A Lewis base can be neutral or anionic. In some embodiments, a Lewis base can be a heterohydrocarbon or hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. Examples of anionic hydrocarbons include, but are not limited to, cyclopentadiene. Examples of neutral hydrocarbons include, but are not limited to, 1,3-butadiene.

[0070] In one or more embodiments, the Lewis base may be a monodentate ligand, which may be a neutral ligand. In some embodiments, the neutral ligand may contain a heteroatom. In certain embodiments, the neutral ligand may be R T NR K R L , R K OR L , R K SR L , or R T PR K R L and each R Tare independently hydrogen, [(C1-C 10 )hydrocarbyl]3Si(C1-C 10 ) hydrocarbyl, (C1-C 40 ) hydrocarbyl, [(C1-C 10 )hydrocarbyl]Si, or (C-C 40 ) heterohydrocarbyl, and each R K and R L are independently as previously defined.

[0071] In some embodiments, the Lewis base is (C-C 20 ) hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene or 1,3-buta-diene.

[0072] In various embodiments, the Lewis base is (C-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0073] In certain embodiments of the catalyst system, the metal-ligand complex according to formula (I) may include, but is not limited to, a complex having the structure of any of the metal-ligand complexes 1-12 of the present invention.

[0074] [ka]

[0075] [ka]

[0076] Olefin Propagation The metal-ligand complexes of the present disclosure are unable to initiate olefin propagation when the ligand X is a halogen atom. It is believed that the halogen atom X transfers to the cocatalyst, and the alkyl group of the cocatalyst transfers to the metal center M. The presence of the alkyl group ligand can initiate propagation (i.e., polymerization). Furthermore, without being bound by theory, it is believed that metal-ligand catalysts are inefficient when a Lewis base T is coordinated to the metal center M of formula (I). Thus, during olefin propagation, the Lewis base dissociates from the metal center M, and the metal-ligand complex has a structure according to formula (Ia).

[0077] [ka]

[0078] In formula (Ia), R 1 -R 16 , M, and L are as defined in formula (I). P is a hydrocarbyl, the hydrocarbyl having at least 30 carbon atoms and being branched or unbranched. More specifically, X P is the propagating olefin chain.

[0079] Additive ingredients In some embodiments, the catalyst system includes one or more additives. In some embodiments, the additive functions as a cocatalyst, alkylating agent, Lewis acid, or Lewis base. In other embodiments, the additive functions as a scavenger or scavenger. A cocatalyst is a reagent that cooperates with the catalyst to catalyze a reaction or improve the catalytic activity of the catalyst. Without being bound by theory, it is believed that the Lewis base T of formula (I) dissociates in the absence of a cocatalyst. However, it is also believed that the cocatalyst may facilitate dissociation of the Lewis base from the metal center of the metal-ligand complex.

[0080] The scavenger is not activator in nature, as it sequesters impurities in the reactor before the precatalyst is added. At low alumoxane loadings, it does not act as a cocatalyst, but rather as a scavenger.

[0081] Without wishing to be bound by theory, it is believed that the metal-ligand complex of formula (I) is not an active species unless an alkylating agent exchanges the alkyl group for the halogen (specifically X) coordinated to the metal center M. Upon alkylation of the metal-ligand complex of formula (I) and dissociation of the Lewis base, the complex is active and capable of polymerizing olefin monomers.

[0082] In one or more embodiments, the alkylating agent may be selected from a methyl-modified aluminoxane (MMAO) or an alkylaluminum compound.

[0083] In some embodiments, additives may include, but are not limited to, alkylaluminums, polymeric or oligomeric alumoxanes (also known as aluminoxanes), Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). Combinations of one or more of the foregoing additives and techniques are also contemplated. The term "alkylaluminum" refers to monoalkylaluminum dihydrides or dihalides, dialkylaluminum hydrides or halides, or trialkylaluminums. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0084] In some embodiments, the additive is a compound described herein (C1-C 20 In some embodiments, the additive is a Lewis acid Group 13 metal compound containing a tri((C-C) hydrocarbyl substituent. 20 )hydrocarbyl)-substituted aluminum or tri((C-C 20 In another embodiment, the additive comprises a tri(hydrocarbyl)-substituted aluminum, tri((C-C 20 )hydrocarbyl)-boron compounds, tri((C-C 10) alkyl) aluminum, tri((C6-C 18 )aryl)boron compounds and their halogenated (including perhalogenated) derivatives.

[0085] In one or more embodiments, the polymerization process further comprises a borane or borate based additive. In some embodiments, the borane based additive is selected from tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the co-catalyst is a tri((C-C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borates (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to a ((C-C 20 ) Hydrocarbyl) 4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + means a nitrogen cation, each (C1-C 20 When two or more hydrocarbyls are present, they may be the same or different.

[0086] In one or more embodiments, the additive may be selected from polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable additives include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)ammonium, triethylaluminum, butylated hydroxytoluene diethylaluminum, bis-(butylated hydroxytoluene)ethylaluminum, tris-(butylated hydroxytoluene)aluminum, and combinations thereof.

[0087] In some embodiments, the alkylaluminum species is triisobutylaluminum (TiBAl) or an aluminoxane. The alkylaluminoxane is a (C-C 10 ) alkylaluminoxane or the polymeric form of polymethylaluminoxane (PMAO). The PMAO may be performance-improved polymethylaluminoxane (PMAO-IP) commercially available from AkzoNobel. (C1-C 10 The alkylaluminoxane can be methylaluminoxane (MAO), modified methylaluminoxane (MMAO), such as modified methylaluminoxane, type 3A (MMAO-3A), type 7 (MMAO-7), or type 12 (MMAO-12), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, or 1-methylcyclopentylaluminoxane. The arylaluminoxane can be (C6-C 10 ) arylaluminoxane, which may be phenylaluminoxane, 2,6-dimethylphenylaluminoxane, or naphthylaluminoxane.

[0088] In some embodiments, one or more cocatalysts can be used in combination with each other. Specific examples of cocatalyst combinations include tri((C1-C8)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, tri((C6-C 18 )aryl)borane or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total moles of one or more metal-ligand complexes of Formula (I) to the total moles of one or more 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 cocatalyst, preferably the ratio of Al of the alumoxane to the metal of the metal-ligand complex of Formula (I) (Al / M) is at least 20. When tris(pentafluorophenyl)borane is used alone as the cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total 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.

[0089] Catalyst System Components The catalyst system includes a procatalyst. The procatalyst can be selected from a Group IV metal-ligand complex, such as a titanium (Ti) metal-ligand complex, a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) metal-ligand complex. In one or more embodiments, the Group IV metal-ligand complex includes a bis-biphenylphenoxy Group IV metal-ligand complex, a procatalyst that can become catalytically active upon contact with an activator of the present disclosure.

[0090] According to some embodiments, the bis-biphenylphenoxy Group IV metal-ligand complex has a structure according to formula (X):

[0091] [ka]

[0092] In formula (X), M is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4. (X) n The subscript n is 0, 1, or 2. When the subscript n is 1, X X is a monodentate or bidentate ligand, and when the subscript n is 2, each X X In formula (X), each Z is independently -O-, -S-, -N(R N )-, or -P(R P )-, and R 2-4 , R 5-8 , R 9-12 , and R 13-15 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, and halogen. 1 and R 16 is selected from a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII).

[0093] [ka]

[0094] In formulas (XI), (XII), and (XIII), R 31-35 , R 41-48 , and R 51-59each independently represents -H, (C-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or halogen.

[0095] In one or more embodiments, in formula (X), each X, independently of any other ligand X, is selected from halogen, unsubstituted (C-C 20 ) hydrocarbyl, unsubstituted [(C-C 20 )hydrocarbyl]C(O)O—, or R K R L N-, wherein R K and R L each independently is unsubstituted (C-C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl. In some embodiments, X X is phenyl, benzyl, chlorine atom, (C1-C 10 ) alkyl, or -CH2Si(R XV )3, wherein R XV is (C1-C 20 ) alkyl.

[0096] Other bis-biphenylphenoxy Group IV metal-ligand complexes that can be used in combination with bimetallic activators in the catalyst systems of the present disclosure will be apparent to those skilled in the art.

[0097] In one or more embodiments, the Group IV metal-ligand complexes include constrained geometry Group IV complexes having a structure according to formula (XV).

[0098] [ka]

[0099] In formula (XV), M 2 is titanium, hafnium or zirconium. (X y ) b The subscript p in is 1, 2, or 3. y is unsaturated (C2-C 50 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, saturated (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 metal-ligand complex is generally charge neutral.

[0100] In one or more embodiments, each X y is any other ligand X y Independently, halogen, unsubstituted (C1-C 20 ) hydrocarbyl, unsubstituted [(C-C 20 )hydrocarbyl]C(O)O—, or R K R L N-, wherein R K and R L each independently is unsubstituted (C-C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl. In some embodiments, X y is phenyl, benzyl, chlorine atom, (C1-C 10) alkyl, or -CH2Si(R XV )3, wherein R XV is (C1-C 20 ) alkyl.

[0101] In formula (XV), Cp is cyclopentadienyl and R S substituted cyclopentadienyl, η 5 binds to M in a bonding manner and R S is (C1-C 20 ) alkyl, (C1-C 20 ) heteroalkyl, (C1-C 20 ) aryl, or R S Substituent (C1-C 20 ) aryl, (C1-C 20 ) heteroaryl, or R S Substituent (C1-C 20 ) heteroaryl, wherein two adjacent R S The groups are optionally joined to form a ring.

[0102] In formula (XV), N is nitrogen, Y is carbon or silicon, Y is covalently bonded to Cp, and R 1 and R 2 is -H, (C1-C 40 ) hydrocarbyl, and (C-C 40 ) heterohydrocarbyl; R 3 is (C1-C 40 ) hydrocarbyl, and (C-C 40 ) heterohydrocarbyl.

[0103] Other catalysts, particularly catalysts containing one or more other Group IV metal complexes not specifically listed above, will be apparent to those skilled in the art.

[0104] Catalytic system characteristics Procatalysts comprising the metal-ligand complex of Formula (I) and one or more cocatalysts described herein have a reactivity ratio r1, as further defined below, in the range of greater than 100, e.g., greater than 150, greater than 200, greater than 300, or greater than 500.

[0105] For random copolymers, where the properties of the last monomer inserted determine the rate of insertion of subsequent monomers, the terminal copolymerization model is used. In this model, the following types of insertion reactions occur:

[0106]

number

[0107]

number

[0108] The mole fraction of comonomer (i=2) in the reaction medium is defined by the following equation:

[0109]

number

[0110] As disclosed in George Odian, Principles of Polymerization, Second Edition, John Wiley and Sons, 1970, a simple equation for comonomer composition can be derived as follows:

[0111]

number

[0112] From this equation, the mole fraction of comonomer in the polymer depends only on the mole fraction of comonomer in the reaction medium and two temperature-dependent reactivity ratios defined in terms of the insertion rate constant as follows:

[0113]

number

[0114] Alternatively, in the penultimate copolymerization model, the properties of the last two monomers inserted into a growing polymer chain dictate the rate of subsequent monomer insertions. The polymerization reaction is of the form:

[0115]

number

[0116]

number

[0117] The comonomer content can be calculated as follows (also disclosed in George Odian, supra):

[0118]

number

[0119]

number

[0120]

number

[0121] In this model, the polymer composition is also a function of only the temperature-dependent reactivity ratio and the comonomer mole fraction in the reactor, even if reversed comonomer or monomer insertion can occur, or in the case of copolymerization of more than two monomers.

[0122] Reactivity ratios for use in the above-mentioned models can be predicted using well-known theoretical methods or empirically derived from actual polymerization data. Suitable theoretical methods are disclosed, for example, in BG Kyle, Chemical and Process Thermodynamics, Third Addition, Prentice-Hall, 1999, and Redlich-Kwong-Soave (RKS) Equation of State, Chemical Engineering Science, 1972, pp. 1197-1203. Commercially available software programs may be used to assist in the derivation of reactivity ratios from empirically derived data. One example of such software is Aspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, MA 02141-2201 USA.

[0123] Thus, a process for producing an ethylene-based polymer according to the present invention selectively provides a rich polyethylene (e.g., high-density polyethylene) or rich polyethylene segment of a poly(ethylene alpha-olefin) copolymer in the presence of an alpha-olefin, thereby substantially unpolymerized. The process for producing an ethylene-based polymer employs olefin polymerization conditions. In some embodiments, the olefin polymerization conditions independently generate an in situ catalyst formed by the reaction of a procatalyst comprising a metal-ligand complex of Formula (I) with one or more cocatalysts in the presence of one or more other components. Such other components include, but are not limited to, (i) an olefin monomer, (ii) another metal-ligand complex of Formula (I), (iii) one or more of a catalyst system, (iv) one or more chain shuttling agents, (v) one or more catalyst stabilizers, (vi) one or more solvents, and (vii) a mixture of any two or more thereof.

[0124] In particular, the catalyst of the present invention is useful in processes for producing ethylene-based polymers (C3-C 40 ) high selectivity for polymerizing ethylene in the presence of alpha-olefins can be achieved, the high selectivity being characterized by the aforementioned reactivity ratio r1. Preferably, in the process of the present invention, the reactivity ratio r1 is greater than 50, more preferably greater than 100, even more preferably greater than 150, and even more preferably greater than 200. As the reactivity ratio r1 of the present invention approaches infinity, the incorporation of alpha-olefins into (or onto) the rich polyethylene produced thereby approaches 0 mole percent (mol%).

[0125] The catalyst compositions of the present invention, comprising a procatalyst and one or more cocatalysts described herein, have catalytic efficiencies in the range of greater than 1,000,000 grams of polymer per gram of active metal center, e.g., greater than 2,000,000 grams of polymer per gram of active metal center, as measured in terms of the amount of polymer produced relative to the amount of catalyst used in a solution polymerization process, wherein the polymerization temperature is at least 130°C, e.g., in the range of 170-195°C, the ethylene concentration is greater than 5 g / L, e.g., greater than 6 g / L, and the ethylene conversion is greater than 70 percent, e.g., greater than 80 percent, or alternatively, greater than 90 percent.

[0126] Polyolefin The catalyst systems described in this disclosure can be utilized in the polymerization of olefins, primarily ethylene, propylene, α-olefins such as octene, and dienes. In some embodiments, there is only one type of olefin or α-olefin in the polymerization scheme, resulting in the production of 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, 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.

[0127] An ethylene-based polymer, e.g., a homopolymer and / or an interpolymer (including a copolymer) of ethylene and, optionally, one or more comonomers such as an α-olefin, can comprise at least 50 mole percent (mol %) of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 mole percent" are disclosed herein as separate embodiments; for example, an ethylene-based polymer, a homopolymer and / or an interpolymer (including a copolymer) of ethylene and, optionally, one or more comonomers such as an α-olefin can comprise at least 60 mole percent of monomer units derived from ethylene, at least 70 mole percent of monomer units derived from ethylene, at least 80 mole percent of monomer units derived from ethylene, or from 50 to 100 mole percent of monomer units derived from ethylene, or from 80 to 100 mole percent of monomer units derived from ethylene.

[0128] In some embodiments, the catalyst system can produce an ethylene-based polymer comprising at least 90 mole percent 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 comprise at least 93 mole percent units derived from ethylene, at least 96 mole percent units, at least 97 mole percent units derived from ethylene, or alternatively, 90 to 100 mole percent units derived from ethylene, 90 to 99.5 mole percent units derived from ethylene, or 97 to 99.5 mole percent units derived from ethylene.

[0129] In some embodiments, the catalyst system produces an ethylene-based polymer having an amount of additional α-olefin less than 50 mole percent (mol %), in other embodiments the amount of additional α-olefin comprises at least 0.01 mol % to 25 mol %, and in further embodiments the amount of additional α-olefin comprises at least 0.1 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0130] Ethylene-based polymers can be produced by other conventional polymerization processes incorporating catalyst systems according to embodiments of the present disclosure, including, but not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, and the like, in parallel, series, or any combination thereof.

[0131] In one embodiment, an 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 a catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, an 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 a catalyst system described herein and herein and, optionally, one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be used in the first reactor or the second reactor. In one embodiment, an 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 a catalyst system described herein.

[0132] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system, for example a single loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized as described in the previous paragraph in the presence of a catalyst system described within this disclosure and optionally one or more cocatalysts.

[0133] The ethylene-based polymer may further comprise 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 comprise any amount of additives. The ethylene-based polymer may comprise from about 0 to about 10 percent by weight of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may contain from about 0 to about 20 percent by weight of a filler, such as 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 blended with one or more polymers to form a blend.

[0134] In some embodiments, a polymerization process for producing an ethylene-based polymer comprises polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one metal-ligand complex of Formula (I). Polymers obtained from such catalyst systems incorporating a metal-ligand complex of Formula (I) have a densitometric value of, for example, 0.850 g / cm according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.970g / cm 3 , 0.870g / cm 3 ~0.950g / cm 3 , 0.870g / cm 3 ~0.920g / cm 3 , or 0.870 g / cm 3 ~0.900g / cm 3 The density may be

[0135] In embodiments, the polymers obtained from catalyst systems comprising the metal-ligand complexes of formula (I) have a melt flow ratio (I 10 / I2), where the melt index I2 is measured at 190°C and a load of 2.16 kg in accordance with ASTM D1238 (which is incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 190°C and a 10 kg load. In other embodiments, the melt flow ratio (I 10 / I2) is 5-10, and in another embodiment the melt flow ratio is 5-9.

[0136] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of Formula (I) has a melt index (I2) of 0.1 to 100, wherein the melt index I2 is measured at 190°C and a 2.16 kg load according to ASTM D1238, which is incorporated herein by reference in its entirety.

[0137] 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 1.0 to 25, where MWD is the molecular weight of the polymer. w / M n is defined as M w is the weight average molecular weight, and M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1.5 to 6. Another embodiment has an MWD of 1.5 to 3, and another embodiment has an MWD of 2 to 2.5.

[0138] SymRAD HT-GPC analysis Molecular weight data were determined by analysis on a hybrid robot-assisted dilution-high-temperature gel permeation chromatography system (Sym-RAD-GPC) built by Symyx / Dow. Polymer samples were dissolved in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL, stabilized with 300 parts per million (ppm) butylated hydroxyl toluene (BHT), by heating at 160 °C for 120 min. Each sample was diluted to 1 mg / mL immediately before injection of a 250 μL aliquot. The GPC was equipped with two Polymer Labs PLgel 10 μm MIXED-B columns (300 × 10 mm) at a flow rate of 2.0 mL / min at 160 °C. Sample detection was performed using a PolyChar IR4 detector in concentration mode. Conventional calibration of narrow polystyrene (PS) standards utilizes apparent units adjusted to homopolyethylene (PE) using the known Mark-Houwink coefficients for PS and PE in TCB at this temperature.

[0139] 1-Octene Incorporated IR Analysis Samples run for HT-GPC analysis precede 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 210 min or less, reheated to remove the magnetic GPC stir bar, and shaken with a glass rod stir bar on a J-KEM Scientific heated robotic shaker. Samples are deposited with heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene is evaporated from the wafer's deposition wells at 160 °C under a nitrogen purge. Analysis of 1-octene is performed on the HT silicon wafer using a NEXUS 670 ESP FT-IR.

[0140] Differential Scanning Calorimetry (DSC) Differential scanning calorimetry (DSC) was used to measure the Tm, Tc, Tg, and crystallinity of ethylene-based (PE) and propylene-based (PP) samples. Each sample (0.5 g) was compression molded into a film at 190 °C for 2 min at 5000 psi. Approximately 5–8 mg of film sample was weighed and placed in a DSC pan. A lid was crimped onto the pan to ensure a sealed atmosphere. The sample pan was then placed in the DSC cell and heated at a rate of approximately 10 °C / min to a temperature of 180 °C for PE (230 °C for PP). The sample was held at this temperature for 3 min. The sample was then cooled at a rate of 10 °C / min to -90 °C for PE (-60 °C for PP) and held isothermally at that temperature for 3 min. The sample was then heated at a rate of 10 °C / min until completely melted (second heat). Unless otherwise noted, the melting point (Tm) and glass transition temperature (Tg) of each polymer were determined from the second heat curve, and the crystallization temperature (Tc) was determined from the first cooling curve. The peak temperatures of Tm and Tc were recorded. The percent crystallinity can be calculated by dividing the heat of fusion (Hf) determined from the second heat curve by the theoretical heat of fusion of 292 J / g for PE (165 J / g for PP) and multiplying this amount by 100 (e.g., % crystallinity = (Hf / 292 J / g) × 100 for PE). [Example]

[0141] Examples 1-10 are synthetic procedures for ligand intermediates, the ligands themselves, and isolated metal-ligand complexes containing the ligands. Example 11 describes polymerization results obtained from metal-ligand complexes prepared according to Examples 1-10. It should be understood that Examples 1-10 are provided to illustrate embodiments described in this disclosure and are not intended to limit the scope of this disclosure or the claims appended hereto.

[0142] Example 1: Synthesis of Metal-Ligand Complex 1 (MLC-1)

[0143] [ka]

[0144] In a nitrogen-filled glovebox, a vial was charged with ScCl (0.024 g, 0.16 mmol, 1 equiv.) and 6 mL of THF. The mixture was stirred at 50 °C for 2 h, then ligand i (0.200 g, 0.16 mmol, 1 equiv.) was added as a solid, followed by EtN (0.22 mL, 1.59 mmol, 10 equiv.). The reaction mixture was heated to 50 °C and stirred for 1 h. The reaction mixture was evaporated to dryness under vacuum, and the residue was extracted with 10 mL of hexane. After filtration through Celite, the filtrate was evaporated under vacuum to give a white solid. 1 H NMR showed the desired product and traces of Et3N. The product was redissolved in hexane (approximately 8 mL) and evaporated to dryness under vacuum. 1 No amine was detected in the resulting white solid by H NMR, and the yield was quantitative considering the sample taken for NMR.

[0145] 1H NMR(400MHz,C6D6)δ8.27(dd,J=8.2,0.7Hz,1H),8.22(d,J=8.2Hz,1H),8.12(d,J=8.2Hz,1H),8 .03(d,J=1.6Hz,1H),7.92(d,J=8.2Hz,1H),7.76(d,J=2.6Hz,1H),7.57(d,J=1.6Hz,1H),7.55-7 .42(m,5H),7.37(d,J=1.6Hz,1H),7.33(d,J=2.7Hz,1H),7.28(d,J=2.6Hz,1H),7.23(dd,J=8.2 ,1.7Hz,1H),7.06(dd,J=9.0,3.2Hz,1H),6.85(dd,J=9.0,3.2Hz,1H),6.33(dd,J=8.2,3.1Hz,1H ),6.07(dd,J=8.5,3.2Hz,1H),4.26(dd,J=10.6,8.0Hz,1H),3.68(t,J=9.3Hz,1H),3.52(dt,J= 7.8,3.6Hz,2H),3.19(dt,J=8.2,6.1Hz,2H),2.83(dt,J=8.3,6.2Hz,2H),1.92(s,3H),1.71-1.6 5(m,2H),1.64(s,10H),1.46(s,9H),1.39(d,J=7.7Hz,1H),1.29(s,13H),1.22(d,J=7.1Hz,13H) ,1.16(d,J=9.1Hz,6H),1.03(s,3H),0.96(d,J=6.6Hz,1H),0.90(d,J=9.5Hz,11H),0.84(s,9H). 19F NMR (376MHz, C6D6) δ-115.56,-116.20.

[0146] International Publication No. 2014105411 (A1) details the modulation of the されている coordination formula i.

[0147] Example 2, synthesis of metal-ligand complex 2 (MLC-2)

[0148]

change

[0149] In a nitrogen-filled glovebox, a vial was charged with ScCl3 (0.111 g, 0.73 mmol, 1.15 equiv.) and 30 mL of THF. Ligand ii (1.000 g, 0.64 mmol, 1 equiv.) was added as a solid, followed by Et3N (0.89 mL, 6.38 mmol, 10 equiv.). The reaction mixture was heated to 50 °C and stirred for 4 h. A small sample was removed, evaporated to dryness under vacuum, and combined with C6D6. 1 H and 19 The reaction mixture was checked by F NMR. Only about 85% conversion to the product was observed. Additional EtN (0.89 mL, 6.38 mmol, 10 equiv.) was added, and the reaction was heated to 60 °C and stirred for 3 h. A sample showed no change. The temperature was lowered to 50 °C, and additional ScCl (0.014 g, 0.10 mmol, 0.15 equiv.) was added. After 1.5 h, a sample showed about 97% conversion to the product. The reaction mixture was allowed to cool to 25 °C and evaporated to dryness under vacuum overnight. The solid was triturated with pentane (10 mL) and evaporated to dryness under vacuum. After this time, the solid was extracted with pentane (100 mL), filtered through a pad of Celite, and the solvent was removed from the filtrate under vacuum to give the product as a white solid (0.260 g). The filter cake was washed with toluene (40 mL), filtered, and the solvent was removed under vacuum. This material was dissolved in methylene chloride (8 mL) to give a slightly cloudy solution which was filtered and the solvent removed in vacuo to give a white solid (0.721 g).

[0150] Total yield adjusted for NMR samples taken: 1.02 g, 93%.

[0151] 1H NMR(400MHz,C6D6)δ8.27(dd,J=7.7,2.6Hz,2H),8.22(s,1H),8.16(d,J=7.7Hz, 1H),7.96(d,J=7.7Hz,1H),7.80(d,J=11.7Hz,2H),7.73-7.69(m,2H),7.69-7.56 (m,8H),7.52(ddt,J=8.2,6.4,1.5Hz,4H),7.46(d,J=2.6Hz,1H),7.39(dd,J=7. 7,0.8Hz,1H),7.34-7.24(m,4H),7.09-6.98(m,6H),6.83(dd,J=9.0,3.3Hz,1H), 6.19(ddd,J=11.9,8.3,3.2Hz,2H),4.05-3.94(m,1H),3.49-3.30(m,3H),3.12- 2.98(m,2H),2.91-2.74(m,3H),1.78-1.33(m,10H),1.22(d,J=16.1Hz,7H),1.14 (d,J=5.4Hz,7H),1.02(s,3H),0.82(d,J=6.2Hz,14H),0.77(s,13H),0.74-0.68 (m,1H),0.65(d,J=12.0Hz,6H),0.58(s,3H),0.43(d,J=7.5Hz,6H),0.38(s,3H). 19 F NMR(376MHz,C6D6)δ-115.63,-116.04.

[0152] International Publication No. 2014105411 (A1) details the modulation of the formula i and the coordination position.

[0153] Example 3, synthesis of metal-ligand complex 3 (MLC-3)

[0154]

change

[0155] In a N2-filled glovebox, a 20 mL vial was charged with ScCl3 (9.6 mg, 0.063 mmol, 1.00 equiv.) and 3 mL of dry THF. The ligand of formula (iii) (86 mg, 0.063 mmol, 1.00 equiv.) was added, followed by triethylamine (0.090 mL, 10 equiv.). The mixture was stirred at 50 °C overnight. The solution was cooled and filtered through a 0.45 μm syringe filter. The filtrate was concentrated to dryness. The solid was suspended in approximately 2 mL of hexane. A white solid precipitated and was isolated by filtration (60.6 mg, 64%).

[0156] 1 H NMR(500MHz,C6D6)δ8.34(d,J=7.6Hz,1H),8.23(d,J=7.7Hz,1H),8.13(d,J=7.8Hz,1H),8.02-7.96(m,2H),7.85(s,1H),7.73-7. 61(m,8H),7.59-7.50(m,6H),7.34-7.17(m,6H),7.15-6.99(m,8H),6.93(s,1H),6.87(s,1H),6.77-6.66(m,2H),6.24-6.14(m,2) H),4.21(td,J=9.2,5.3Hz,1H),4.08(t,J=10.0Hz,1H),3.04-2.84(m,3H),2.71-2.51(m,3H),2.12(s,3H),2.08(s,3H),1.73(s, 3H),1.30(s,3H),0.72(s,3H),0.70(s,3H),0.68(s,3H),0.66(s,3H),0.59(s,3H),0.52(s,3H),0.45-0.38(m,7H),0.31(s,3H). 13C NMR(126MHz,C6D6)δ161.31,160.71,159.36,158.76,155.44,155.38,146.81,146.57 ,146.55,142.13,141.84,140.72,139.96,139.45,139.04,138.87,138.52,137.44,13 5.36, 135.29, 134.78, 134.50, 134.40, 134.27, 133.96, 133.82, 133.74, 133.57, 133.50, 131.14, 131.03, 130.55, 129.28, 129.24, 128.90, 128.68, 128.58, 128.56, 128.40, 1 28.19, 127.30, 127.16, 125.96, 125.80, 125.75, 125.65, 125.60, 125.06, 125.04, 124.81, 124.34, 123.25, 120.38, 120.11, 119.83, 119.21, 118.91, 118.00, 117.92, 117.81 ,117.33,116.93,116.75,116.65,116.57,115.53,115.35,72.04,71.14,68.35,23.85,19.99,19.93,17.68,16.59,-1.62,-1.72,-1.78,-1.84,-2.28,-2.36,-2.38,-2.59. 19 F NMR(471MHz,C6D6)δ-115.80(t,J=8.8Hz),-116.12(t,J=9.0Hz).

[0157] Example 3-1: Synthesis of 2,7-bis(dimethyl(phenyl)silyl)-9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole

[0158] [ka]

[0159] In a N2-filled glovebox, a 100 mL round-bottom flask was charged with 2,7-bis(dimethyl(phenyl)silyl)-9H-carbazole (5.00 g, 11.5 mmol, 1.00 equiv.), 2-(2-iodo-4-methylphenoxy)tetrahydro-2H-pyran (5.11 g, 16.1 mmol, 1.40 equiv.), K3PO4 (7.55 g, 35.6 mmol, 3.10 equiv.), CuI (0.481 g, 2.53 mmol, 22.0 mol%), 28 mL of dry toluene, and DMEDA (0.877 mL, 8.15 mmol, 71.0 mol%). The round-bottom flask was equipped with a coiled reflux condenser, and the reaction mixture was stirred at 120 °C for 24 h in the glovebox. The solution was cooled, and the reaction mixture was filtered. The filter cake was rinsed several times with dichloromethane. The filtrate was concentrated and the residue was purified by chromatography on silica gel (0 to 50% dichloromethane in hexanes) to give the desired product (3.06 g, 43%).

[0160] 1 H NMR(400MHz,CDCl3)δ8.10(d,J=7.7Hz,2H),7.54-7.47(m,4H),7.45(s,1H),7.42-7.37(m,2H),7.37-7.26(m,8H),7.26-7.17(m,2H),5.13(d ,J=3.1Hz,1H),3.53(td,J=11.0,2.6Hz,1H),3.35(dt,J=11.2,3.9Hz,1H),2.34(s,3H),1.47-1.21(m,2H),1.19-1.01(m,4H),0.55(s,12H). 13 C NMR(101MHz,CDCl3)δ151.01,141.03,138.91,138.84,135.11,135.04,134.16,131.83,129.75,129.63,128.92,128.90,127.67,126.52, 125.08,124.95,123.88,119.57,119.55,117.26,116.29,116.20,97 .09,61.49,29.98,24.86,20.52,17.79,-1.97,-2.07,-2.09,-2.13.

[0161] Preparation of 2,7-bis(dimethyl(phenyl)silyl)-9H-carbazole as detailed in WO2021155158.

[0162] Example 3-2: Synthesis of the ligand of formula (iii)

[0163] [ka]

[0164] A 500 mL round-bottom flask was charged with 2,7-bis(dimethyl(phenyl)silyl)-9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole (23.8 g, 38.0 mmol, 1.00 equiv.) and 190 mL of dry THF. The solution was placed under nitrogen and cooled to −78° C. N-butyllithium (2.5 M in hexanes, 16.7 mL, 41.8 mmol, 1.10 equiv.) was added dropwise. The reaction mixture was slowly warmed to 0° C. and stirred for 90 minutes, during which time a white solid precipitated. The slurry was treated with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.31 mL, 45.6 mmol, 1.20 equiv.) and stirring was continued for 1 hour.

[0165] The solution was quenched with aqueous ammonium chloride, and the product was extracted several times with dichloromethane. The combined organic fractions were dried over Na2SO4 and concentrated to a pale yellow residue. This material was used in the next step without further purification.

[0166] A 500 mL round-bottom flask was charged with the boronic ester (2.2 equiv.), 1,2-bis(2-bromo-4-fluoro-6-methylphenoxy)ethane (7.50 g, 17.2 mmol, 1.00 equiv.), and Pd(Amphos)Cl (609 mg, 0.860 mmol, 5.00 mol%). A reflux condenser was attached, and the unit was placed under a nitrogen blanket. 170 mL of dry, degassed THF was added, followed by nitrogen-sparged aqueous KPO (2.0 M in water, 51.6 mL, 0.103 mol, 6.00 equiv.). The mixture was stirred at 70 °C overnight.

[0167] The solution was cooled and the phases were separated. The aqueous phase was extracted multiple times with dichloromethane. The combined organic fractions were washed with brine, dried over Na2SO4, and filtered through a plug of silica gel. The filtrate was concentrated to give a crude oil. The oil was dissolved in 150 mL of THF, 50 mL of MeOH, and 25 mL of 6 M HCl. This mixture was refluxed for 3 h. The solution was cooled and diluted with dichloromethane and brine. The phases were separated, and the aqueous phase was extracted several times with dichloromethane. The combined organic fractions were washed with aqueous sodium bicarbonate. The organic phase was dried over Na2SO4 and concentrated. The residue was purified by chromatography on silica gel (0 to 10% EtOAc in hexanes) to give 19.73 g of product (85%).

[0168] 1 H NMR(500MHz,CDCl3)δ8.12(d,J=7.8Hz,4H),7.46-7.35(m,12H),7.28-7.23(m,4H),7.23-7.16(m,14H),7.09(s,2H),6.90(dd,J =8.8,3.1Hz,2H),6.71(dd,J=8.7,3.1Hz,2H),6.35(s,2H),3.42(s,4H),2.26(s,6H),1.68(s,6H),0.44(s,12H),0.39(s,12H). 13C NMR (126MHz, CDCl3) δ159.11(d,J=243.7Hz),149.14(d,J=2.4Hz),147.76,140.9 9,138.51,135.52,134.15,134.02(d,J=9.0Hz),132.34(d,J=8.7Hz),131.63,13 0.58,130.05,128.91,127.60,126.70,125.60,125.33,123.99,119.84,117.28( d,J=22.5Hz),115.89(d,J=23.4Hz),115.61,72.09,20.41,15.61,-2.10,-2.20. 19 F NMR(471MHz, CDCl3)δ-117.74(t,J=7.7Hz).

[0169] Example 4, Synthesis of Metal-Ligand Complex 4 (MLC-4)

[0170] [ka]

[0171] In a N2-filled glovebox, a 20 mL vial was charged with ScCl3 (35.1 mg, 0.232 mmol, 1.00 equiv.) and 11 mL of dry THF. The ligand of formula (iv) (421 mg, 0.232 mmol, 1.00 equiv.) was added, followed by triethylamine (0.33 mL, 10 equiv.). The mixture was stirred at 50 °C overnight. An additional 7 mg of ScCl3 was added along with 0.066 mL of triethylamine. Stirring was continued for 6 h, at which point NMR indicated that the starting material had been consumed. The solution was cooled in a glovebox freezer and filtered through a 0.45 μm syringe filter. The filtrate was concentrated to dryness. The solid was mixed with 3 mL of dry hexane, and the liquid was decanted off. The solid was rinsed with hexane two more times. The final white solid was dried to give 0.371 g of material (81%).

[0172] 1H NMR(500MHz,C6D6)δ8.23(d,J=7.7Hz,1H),8.19-8.14(m,2H),8.11(d,J=7.7Hz,1H),7.94(d,J=7.7Hz,1H),7.89(s,1H),7.80(s,1H),7.78-7.75(m,2H),7.74-7.70(m,2H),7.66(dddd,J=14.9,7.4,4.4,2.1Hz,11H),7.61-7.54(m,5H),7.53(d,J=2.7Hz,1H),7.47(dd,J=7.7,0.9Hz,1H),7.45(d,J=2.6Hz,1H),7.33-7.17(m,14H),7.15-7.01(m,12H),6.97(dd,J=8.8,3.2Hz,1H),6.72(dd,J=8.9,3.2Hz,1H),6.24(dd,J=8.5,3.2Hz,1H),6.16(dd,J=8.3,3.2Hz,1H),3.89(ddd,J=10.9,7.6,1.9Hz,1H),3.48-3.29(m,3H),2.95(qd,J=6.9,2.8Hz,2H),2.74(qd,J=6.6,2.7Hz,2H),1.56-0.64(m,64H)。 13C NMR(126MHz,C6D6)δ161.52,160.99,159.57,159.03,155.78,155.66,149.23,149.21,149.00,148.97,142.8 0,142.02,141.20,141.02,138.08,137.26,137.11,137.01,136.95,136.89,136.75,136.69,136.43,136.03 ,135.96,135.79,135.78,135.76,135.71,135.68,135.65,135.55,135.48,135.44,135.42,135.37,135.28,134.75,134.68,133.21,132.39,132.33,129.67,129.53,129.29,129.23,129.07,129.04,129.00,128.84,12 8.79, 128.60, 128.47, 128.08, 128.05, 127.19, 126.76, 126.69, 126.58, 126.23, 126.10, 125.46, 124.75, 124.25, 123.28, 120.56, 120.21, 120.10, 120.00, 119.36, 119.23, 118.60, 117.74, 117.63, 117.10, 116.92, 115.9 9, 115.81, 115.47, 115.30, 77.65, 75.20, 72.25, 57.37, 56.69, 37.53, 37.43, 34.62, 32.73, 32.30, 32.11, 32.09, 31.67, 31.63, 31.60, 30.16, 30.13, 30.05, 29.97, 24.29, 22.68, 17.15, 16.17, 13.97, -2.67, -2.91, -2.95. 19 F NMR(471MHz,C6D6)δ-115.59(t,J=8.5Hz),-115.92(t,J=8.1Hz).

[0173] Example 4-1: Synthesis of 2,7-bis(methyldiphenylsilyl)-9H-carbazole

[0174] [ka]

[0175] In a N2-filled glovebox, a 50 mL bottle was charged with 2,7-dilithio-9-(tert-butyldimethylsilyl)-9H-carbazole (2.00 g, 6.82 mmol, 1.00 equiv.) and 34 mL of dry THF. Dichloromethylphenylsilane (3.01 mL, 14.3 mmol, 2.10 equiv.) was added, and the mixture was stirred for 45 min. The solid organolithium rapidly dissolved as the reaction proceeded.

[0176] The clear, colorless solution was quenched with aqueous ammonium chloride. The product was extracted several times with dichloromethane. The combined organic fractions were concentrated. The solution was dried over Na2SO4, filtered through basic alumina, and concentrated to a white solid. A crude oil was isolated.

[0177] Carbazole was dissolved in 34 mL of THF and treated with tetrabutylammonium fluoride trihydrate (2.15 g, 6.82 mmol, 1.00 equiv). The mixture was stirred for 20 min, and the solution was quenched with aqueous NaHCO3. The product was extracted several times with dichloromethane. The combined organic fractions were concentrated, and the residue was purified by chromatography on silica gel (0 to 20% EtOAc in hexanes) to give approximately 24 g of a white solid. 2.213 g of product was isolated as a white solid (58% over two steps).

[0178] 1 H NMR (500MHz, CDCl3) δ8.06(dt,J=7.8,0.7Hz,2H),7.71(s,1H),7.57-7.49(m,8H),7.47(t,J=0.9Hz,2H),7.44-7.30(m,14H),0.89(s,6H). 13 C NMR (126MHz, CDCl3) δ139.29,136.44,135.36,133.73,129.37,127.85,125.86,124.02,120.02,117.81,-3.10.

[0179] Example 4-2: Synthesis of 2,7-bis(methyldiphenylsilyl)-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole

[0180] [ka]

[0181] In a N2-filled glovebox, a 1000 mL round-bottom flask was charged with 2,7-bis(methyldiphenylsilyl)-9H-carbazole (64.00 g, 114.3 mmol, 1.00 equiv.), 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran (85.67 g, 205.8 mmol, 1.80 equiv.), K3PO4 (75.22 g, 354.4 mmol, 3.10 equiv.), CuI (4.79 g, 25.1 mmol, 22.0 mol%), 286 mL of dry toluene, and DMEDA (8.74 mL, 81.2 mmol, 71.0 mol%). A coiled reflux condenser was attached, and the reaction mixture was stirred at 120 °C. After 6.5 h, partial conversion was observed by TLC. Further charges / batches of CuI and DMEDA were added (22% and 71%, respectively).

[0182] 24 hours after the start of the reaction, further charges of CuI and DMEDA were added (22% and 71%, respectively) along with 10 g of iodide. Stirring was continued for 24 hours.

[0183] The solution was cooled and filtered to remove solids. The solid cake was rinsed with dichloromethane (3 x 100 mL). The filtrate was concentrated, and the residue was purified by chromatography on silica gel (0 to 10% EtOAc in hexanes). The white solid residue was isolated and suspended in 250 mL of cold hexanes. The slurry was filtered to remove bulk solids, and the solid was rinsed several more times with hexanes (3 x 50 mL). The solid was dried under vacuum to give 78.369 g of product as a clean white solid (81%).

[0184] 1 H NMR(500MHz,CDCl3)δ8.12(d,J=7.7Hz,2H),7.49(d,J=7.6Hz,7H),7.46(s,1H) ,7.43(s,1H),7.39-7.26(m,17H),7.20(d,J=8.6Hz,1H),5.05(d,J=3.4Hz,1H) ,3.45-3.34(m,1H),3.26(dt,J=11.2,3.7Hz,1H),1,64(s,2H),1.27(d,J=7.9H z,8H),1.06(td,J=17.0,16.6,5.2Hz,4H),0.81(d,J=3.9Hz,6H),0.65(s,9H). 13 C NMR(126MHz,CDCl3)δ150.87,143.99,141.35,141.30,136.66,136.61,136.59,135.30 ,135.29,135.26,135.25,133.25,133.08,129.26,129.24,127.76,127.74,127.32,12 6.92, 126.16, 125.97, 125.61, 124.01, 123.96, 119.70, 117.31, 117.14, 116.07, 96.86, 61.47, 56.94, 38.09, 32.32, 31.73, 31.64, 31.52, 30.04, 24.85, 17.88, -3.06, -3.12.

[0185] Example 4-3: Synthesis of 2,7-bis(methyldiphenylsilyl)-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole

[0186] [ka]

[0187] A 1000 mL round-bottom flask was charged with 2,7-bis(methyldiphenylsilyl)-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (77.5 g, 91.4 mmol, 1.00 equiv) and 450 mL of dry THF. The solution was placed under nitrogen and cooled to −78° C. N-butyllithium (2.5 M in hexanes, 40.2 mL, 100.5 mmol, 1.10 equiv) was added dropwise. The reaction mixture was slowly warmed to 0° C. and stirred for 90 minutes, during which time a white solid precipitated.

[0188] The slurry was treated with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (22.4 mL, 110 mmol, 1.20 equiv.) and stirring was continued for 1 h. The solution was quenched with aqueous ammonium chloride, and the product was extracted several times with dichloromethane. The combined organic fractions were dried over Na2SO4 and concentrated to a white solid (87.92 g). This material was used without further purification.

[0189] 1 H NMR(500MHz,CDCl3)δ8.09(dd,J=7.7,2.4Hz,2H),7.74(d,J=2.6Hz,1H),7.60-7.3 9(m,11H),7.33(ddd,J=20.2,13.7,8.0Hz,14H),4.95(d,J=3.2Hz,1H),2.61-2.41 (m,2H),1.63(d,J=9.7Hz,3H),1.35(d,J=4.1Hz,11H),1.27(d,J=24.0Hz,7H),1.1 2(dt,J=19.2,10.0Hz,3H),0.94-0.85(m,1H),0.82(d,J=6.5Hz,6H),0.64(s,9H). 13C NMR(126MHz,CDCl3)δ155.94,145.59,140.96,140.85,136.71,136.67,136.65,136.62,135.28,13 5.26,135.22,135.19,134.04,133.27,132.96,129.99,129.12,129.08,129.07,128.85,127.79,1 27.72, 127.71, 127.69, 126.05, 125.92, 124.09, 123.66, 119.54, 119.47, 118.20, 117.28, 101.22, 83.51, 60.97, 56.84, 38.22, 32.29, 31.75, 31.59, 31.01, 29.89, 25.03, 24.99, 24.77, 18.09, -3.09.

[0190] Example 4-4: Synthesis of the ligand of formula (iv)

[0191] [ka]

[0192] A 1 L round-bottom flask was charged with 2,7-bis(methyldiphenylsilyl)-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (35.15 g, 36.08 mmol, 2.80 equiv.), 1,3-bis(2-bromo-4-fluoro-6-methylphenoxy)propane (5.80 g, 12.9 mmol, 1.00 equiv.), and Pd(Amphos)Cl (456 mg, 0.644 mmol, 5.00 mol%). A reflux condenser was attached, and the unit was placed under a blanket of nitrogen. Degassed dry THF (128 mL) was added, followed by nitrogen-sparged aqueous KPO (2.0 M in water, 38.7 mL, 77.3 mmol, 6.00 equiv.) The mixture was stirred at 70° C. overnight.

[0193] The solution was cooled and diluted with dichloromethane and brine. The aqueous phase was extracted multiple times with dichloromethane. The combined organic fractions were concentrated, and the residue was purified by chromatography on silica gel (0 to 10% EtOAc in hexanes). The white solid was dissolved in 128 mL of THF, 12.8 mL of MeOH, and 4.3 mL of 6 M HCl. The mixture was stirred at 50° C. overnight.

[0194] The solution was cooled and diluted with 100 mL of dichloromethane and saturated aqueous sodium bicarbonate. The phases were separated and the aqueous phase was extracted several times with dichloromethane. The organic phase was separated and concentrated, and the residue was purified by chromatography on silica gel (0 to 10% EtOAc in hexanes). The residue was heated in 200 mL of acetonitrile and then allowed to cool. The clean white solid was isolated by filtration and dried under vacuum. 19.16 g of product was isolated (82%).

[0195] 1 H NMR(500MHz,CDCl3)δ8.13(dd,J=7.6,2.2Hz,4H),7.46-7.35(m,22H),7.31(s,4H),7.26-7.08(m,26H),6.76(t,J=8 .1Hz,4H),6.53(s,2H),3.24(t,J=6.4Hz,4H),1.69-1.57(m,10H),1.35-1.14(m,14H),0.71(s,12H),0.61(s,18H). 13 C NMR(126MHz,CDCl3)δ159.90,157.96,149.74,147.35,142.86,140.94,136.38, 136.25,135.18,133.65,133.58,133.53,132.81,132.75,129.17,129.14,128. 74, 127.66, 127.63, 127.16, 126.39, 124.86, 124.17, 119.91, 117.20, 117.02, 116.20, 116.02, 71.07, 56.99, 38.08, 32.26, 31.70, 31.50, 30.28, 16.04, -3.06. 19F NMR (471MHz, CDCl3)δ-118.20.

[0196] Example 3. Synthesis of Metal-Ligand Complex 3 (MLC-3) Synthesis of 2,7-dibromo-9-(tert-butyldimethylsilyl)-9H-carbazole-2,7-dibromo-9H-carbazole:

[0197] [ka]

[0198] In a glovebox, a glass bottle equipped with a stir bar was charged with 2,7-dibromo-9H-carbazole (50.0 g, 154 mmol, 1 equiv.) followed by dry THF (300 mL). Sodium hydride powder (90%) (4.5 g, 169 mmol, 1.1 equiv.) was slowly added in portions to the solution over 30 minutes. After stirring at room temperature for 60 minutes, t-butyl-dimethylsilyl chloride (44.2 g, 231 mmol, 1.5 equiv.) was added to the reaction mixture. The mixture was stirred at room temperature for 17 hours. The reaction mixture was removed from the glovebox, the THF evaporated, and filtered through a fritted funnel. The white solid was then washed with 25 mL of THF and transferred to a 50 mL bottle. 40 mL of water was added to the bottle to quench the excess NaH. Acetone (3 × 30 mL) was then used to remove the water in the product. The white solid was filtered through a fritted funnel and acetone was added to wash the cake. The white solid was then transferred to 500 mL of RB and the solid was dried under vacuum overnight. Yield (62.5 g, 93%).

[0199] 1 H NMR (500MHz, Chloroform-d) δ7.85(dd,J=8.3,1.7Hz,2H),7.73(d,J=1.8Hz,2H),7.35(dd,J=8.2,2.2Hz,2H),1.05(d,J=1.9Hz,9H),0.76(d,J=1.8Hz,6H). 13C NMR (126MHz, CDCl3) δ146.2,124.8,123.4,121.0,119.4,117.3,26.7,20.6,-1.1.

[0200] Synthesis of 2,7-bis(triisobutylsilyl)-9H-carbazole:

[0201] [ka]

[0202] A 500 mL round-bottom flask was charged with 2,7-dibromo-9-(tert-butyldimethylsilyl)-9H-carbazole (24 g, 55 mmol, 1 equiv.) and 250 mL of dry THF. The RB was maintained under a nitrogen atmosphere and stirred at −78°C for 15 minutes. A 2.5 M solution of n-BuLi in hexanes (46 mL, 114.7 mmol, 2.1 equiv.) was then added dropwise to the reaction mixture over 15 minutes. The solution color changed to a slightly yellow color and became a heterogeneous white slurry. Because the resulting dilithio salt is heterogeneous in nature, stirring of the reaction was stopped. As a result, the reaction mixture required several manual stirring cycles to ensure proper mixing of the reagents. The heterogeneous slurry was stirred at −78°C for 30 minutes. The reaction mixture was then kept in an ice bath for 15 minutes, and then chlorotriisobutylsilane (34 mL, 126 mmol, 2.3 equiv.) was added to the heterogeneous slurry at 0°C. After the addition of the chlorosilane, the heterogeneous reaction mixture became homogeneous (colorless) within 15 minutes. The reaction mixture was stirred for an additional 30 minutes. Then, 120 mL of NaHCO3 solution was added, and the organic layer was extracted with EtOAc (50 × 3). The combined organic layers were dried over Na2SO4. The solvent was evaporated under reduced pressure. A white solid precipitated (crash-out). The white solid was washed twice with a total of 60 mL of a mixture of acetonitrile and EtOH (20:4). The white solid was filtered through a fritted funnel and dried under vacuum to give 36 g of a white solid.

[0203] 9-(tert-Butyldimethylsilyl)-2,7-bis(triisobutylsilyl)-9H-carbazole (20 g, 29.5 mmol, 1 equiv.) was placed in 250 mL of RB and dry THF was added under a N2 atmosphere. The solution was stirred at 0 °C for 15 min. At 0 °C, a solution of TBAF·3H2O (9.7 g, 31 mmol, 1.05 equiv.) in dry THF (15 mL) was added dropwise. The reaction mixture changed from colorless to pale yellow. The progress of the reaction was monitored by TLC. The reaction was completed within 10 min. The reaction was quenched by the addition of 100 mL of NaHCO3 solution. The organic layer was extracted with DCM (4 × 70 mL). The combined organic layers were dried over Na2SO4. The solvent was evaporated under reduced pressure. The pale yellow oil was directly loaded onto an ISCO column. A 50% DCM in hexane gradient was used. A white solid product appeared in 30% DCM in hexane. Yield (16 g, 96% for the second step).

[0204] Alternatively, the crude deprotected product was purified by recrystallization from an ACN:ethanol (10:1) mixture. The crude yellow liquid was dissolved in a 20 mL:2 mL ACN:ethanol mixture. The RB containing the mixture was kept in a freezer for 1 day. The solid product crashed out of the solvent. The solid product was then washed twice with an acetonitrile:acetone mixture (30 mL:5 mL) to obtain a white solid product. Washing the solid product with an acetonitrile:acetone mixture helps remove impurities. However, the yield in this case is relatively low compared to column purification techniques. Yield (12 g, 72%)

[0205] 1 H NMR(400MHz,Chloroform-d)δ8.07-8.01(m,2H),7.95(s,1H),7.59(d,J=0.9Hz,2H),7. 37(dd,J=7.8,0.9Hz,2H),1.82(dq,J=13.3,6.6Hz,6H),0.91(dd,J=13.4,6.7Hz,48H). 13 C NMR (101MHz, CDCl3) δ139.4,137.0,125.2,123.7,119.6,116.4,26.7,25.1,24.6.

[0206] Synthesis of 9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2,7-bis(triisobutylsilyl)-9H-carbazole:

[0207] [ka]

[0208] A 500 mL round-bottom flask was charged with 2,7-bis(triisobutylsilyl)-9H-carbazole (11.5 g, 20.4 mmol, 1 equiv.), 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran (13.6 g, 32.6 mmol, 1.6 equiv.), and KPO (19.5 g, 92 mmol, 4.5 equiv.). The RB was placed in a N2-filled glovebox, and CuI (1.6 g, 8.2 mmol, 0.4 equiv.), NN'DMEDA (2.2 g, 24.5 mmol, 1.2 equiv.), and dry, degassed toluene (50 mL) were added to the RB. The heterogeneous reaction mixture was heated at 125 °C with vigorous stirring for 48 h. Initially, the reaction mixture was slightly yellow in color. After 1 hour, it turned green and remained green for some time. After 48 hours, the reaction mixture turned brown. After 48 hours, NMR analysis of the crude product in chloroform indicated complete consumption of the carbazole and protodehalogenated THP-protected phenol. The reaction mixture was cooled in the glovebox. The reaction mixture was then removed from the glovebox and filtered through neutral alumina in a fritted funnel. The solid in the fritted funnel was washed with 70 mL of EtOAc. The brown filtrate was then evaporated under vacuum. The viscous orange-brown liquid was dissolved in a 1:1 mixture of dichloromethane and hexane and filtered through a fritted funnel containing neutral alumina. The neutral alumina was washed with 30 mL of a 1:1 mixture of DCM and hexane. The filtrate was concentrated under reduced pressure. This process was repeated three times to remove all copper salts and other metallic impurities. The slightly yellow oil was dissolved in 60 mL of acetonitrile and stirred vigorously (1500 rpm) at 45 °C for 20 minutes. It was then cooled and kept in a freezer for 30 minutes. The solvent was then decanted. The brown oil was washed with cold acetonitrile three times (30 mL) and the solvent was decanted. The brown oil was dissolved in ethyl acetate and transferred to another RB, and the solvent was evaporated under reduced pressure. The oil was further dried under vacuum. Yield (17.3 g, >99%).

[0209] 1H NMR(500MHz,Chloroform-d)δ8.10(d,J=7.7Hz,2H),7.52-7.45(m,2H),7.40(ddd,J=7. 7,2.9,0.9Hz,2H),7.36(d,J=8.6Hz,1H),7.33(s,1H),7.24(s,1H),5.22(t,J=2.9Hz,1H ),3.51(td,J=11.1,2.8Hz,1H),3.38-3.31(m,1H),1.82-1.69(m,8H),1.47-1.30(m,9H ),1.20-1.11(m,2H),1.07(dd,J=10.0,4.4Hz,1H),0.85(d,J=6.7Hz,48H),0.79(s,9H). 13 C NMR(126MHz,CDCl3)δ151.5,144.6,141.5,141.5,136.6,136.4,128.2,127.2,126.9,125.1,124.7,123.4,123.4,119.3,1 19.3,117.1,116.0,115.9,97.2,61.6,57.1,38.4,32.6,32.0,32.0,31.8,30.0,26.7,26.7,25.1,25.0,24.5,24.5,17.9.

[0210] Synthesis of 9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2,7-bis(triisobutylsilyl)-9H-carbazole:

[0211] [ka]

[0212] A 250 mL round-bottom flask was charged with 9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2,7-bis(triisobutylsilyl)-9H-carbazole (17.6.0 g, 21.0 mmol, 1.0 equiv) and 150 mL of dry THF. The solution was placed under nitrogen and cooled to -78 °C. n-BuLi (2.5 M in hexanes, 12.4 mL, 31 mmol, 1.5 equiv) was added dropwise. The mixture was slowly warmed to 0 °C and stirred for 2 h. The dark brown color of the solution changed to orange-brown upon addition of n-BuLi. The reaction mixture was treated with isopropoxy-Bpin (8.5 mL, 41.4 mmol, 2 equiv) and stirring was continued at 0 °C for 1 h. Upon addition of isopropoxy-Bpin, the color of the reaction mixture changed from orange-brown to yellow. The reaction mixture was then stirred at room temperature overnight. The color of the reaction turned red.

[0213] The solution was quenched with sodium bicarbonate solution, and the product was extracted several times with dichloromethane. The organic phase was yellow in color. The combined organic fractions were concentrated and dried over Na2SO4. The solvent was evaporated under reduced pressure. To the sticky yellow oil, 7 mL of dichloromethane was added, and 30 mL of acetonitrile was added, and the sticky oil was stirred at 45 °C for 30 minutes. The mixture was then kept in a freezer for 20 minutes. The supernatant was then decanted, and three portions of acetonitrile were added to the sticky oil to wash it. The sticky oil was dissolved in 30 mL of dichloromethane and filtered through a fritted funnel containing neutral alumina. The alumina was then washed twice with 50 mL of a 1:1 mixture of dichloromethane:hexane. The colorless filtrate / solution was dried under reduced pressure, and it was kept under vacuum for 3 hours. The oil turned into a white foam. NMR was measured in chloroform. Yield (18.9 g, 92%)

[0214] 1H NMR(400MHz,Chloroform-d)δ8.07(d,J=7.7Hz,2H),7.87(d,J=2.5Hz,1H),7.51(d,J =2.6Hz,1H),7.45(s,1H),7.42-7.35(m,3H),5.01(t,J=2.9Hz,1H),2.55(dd,J=5.8,2 .7Hz,2H),1.87-1.71(m,8H),1.70-1.60(m,1H),1.45(s,3H),1.41(s,3H),1.38(d,J =3.5Hz,12H),1.30-1.19(m,2H),1.19-0.99(m,3H),0.93-0.81(m,48H),0.76(s,9H). 13 C NMR (126MHz, CDCl3) δ156.6,145.7,140.8,136.7,136.3,134.1,130.4,129.8,125.0,123.6,123.2,119.1,119.1,117.1,11 6.2,101.8,83.7,61.2,57.0,38.5,32.6,32.1,32.0,31.3,30.0,26.8,26.7,26.7,26.7,25.2,25.0,25.0,24.7,24.5,18.3.

[0215] Example 5, synthesis of metal-ligand complex 5 (MLC-5):

[0216]

change

[0217] In a N2-filled glovebox, a 20 mL vial was charged with ScCl3 (7.6 mg, 0.050 mmol, 1.00 equiv.) and 3 mL of dry THF. Ligand (92 mg, 0.050 mmol, 1.00 equiv.) was added, followed by triethylamine (70 μL, 0.50 mmol, 10 equiv.). The mixture was stirred at 50 °C. After 1 h, an aliquot was removed, concentrated, and analyzed by proton / fluorine NMR to assess conversion. A mixture of materials was present, indicating an incomplete reaction. The reaction mixture was stirred overnight. The solution was cooled and filtered through a 0.45 μm syringe filter. The filtrate was concentrated to dryness. Proton / fluorine NMR indicated the product was present along with some triethylamine. The solid was suspended in 2 mL of hexane. A white solid precipitated and was isolated by filtration (60.0 mg, 60%).

[0218] 1 H NMR(500MHz,Benzene-d6)δ8.28(d,J=7.8Hz,1H),8.22(dd,J=7.8,3.0Hz,2H),8.18(s,1H),8.07(d,J=7.7Hz,1H),7.79(s,1H),7.71-7 .56(m,7H),7.52(d,J=7.6Hz,1H),7.38-7.26(m,3H),6.96(dd,J=8.9,3.2Hz,1H),6.43(dd,J=8.1,3.1Hz,1H),6.22(dd,J=8.4,3.1Hz,1 H),4.43(dd,J=9.5,6.0Hz,1H),4.03(t,J=8.1Hz,1H),3.83-3.66(m,2H),3.42-3.33(m,2H),3.15(q,J=6.8Hz,2H),2.07(hept,J=6.5H) z,3H),1.89(tq,J=21.5,6.6Hz,16H),1.63-1.44(m,3H),1.38(s,2H),1.30-1.06(m,37H),1.05-0.84(m,69H),0.80(d,J=13.7Hz,16H). 13C NMR(126MHz,C6D6)δ162.01,161.63,160.06,159.67,156.82,156.15,149.65,149.63,149.58,149.55,148.42,143.54,143.25,142.96,141.70,141.62,141.56,138.58,138.24,137.89,137.85,137.83,137.08,136.59,136.57,136.49,136.41,136.07,135.48,135.42,135.22,135.15,130.09,129.77,129.39,129.34,129.16,129.08,128.06,126.73,126.42,126.38,126.28,126.10,126.00,125.97,125.88,125.78,125.65,125.47,124.70,124.24,123.46,120.36,120.32,120.17,119.74,119.58,118.99,118.18,117.98,117.80,117.60,117.42,116.50,116.30,116.20,116.12,115.83,115.65,78.48,75.49,72.57,71.75,57.45,57.06,56.96,38.34,37.97,37.91,34.99,34.88,34.36,33.25,33.13,32.67,32.61,32.28,32.26,32.17,31.76,30.89,30.50,30.38,30.22,30.17,29.43,27.20,27.08,27.06,27.00,26.97,26.93,26.84,26.81,25.79,25.65,25.52,25.41,25.28,25.21,25.16,25.06,24.84,24.82,24.74,24.69,23.13,21.43,20.89,18.95,18.15,16.53,16.35,11.65。 19 F NMR(471MHz,Benzene-d6)δ-115.39,-115.69。

[0219] Synthesis of 2',2'''-(ethane-1,2-diylbis(oxy))bis(3-(2,7-bis(triisobutylsilyl)-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol):

[0220] [ka]

[0221] A 1 L three-neck flask was charged with 9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2,7-bis(triisobutylsilyl)-9H-carbazole (18.3 g, 18.6 mmol, 2.2 equiv.), 1,2-bis(2-bromo-4-fluoro-6-methylphenoxy)ethane (3.7 g, 8.5 mmol, 1 equiv.), 350 mL of dry THF, and 2 (M) KPO solution (25 mL, 61 mmol, 6 equiv.). Pd(Amphos)Cl (0.30 g, 0.42 mmol, 5 mol%) was added to the solution. The reaction mixture was stirred overnight at 65° C. with a reflux condenser. The color of the solution turned brownish orange. After 16 hours, the reaction mixture was deprotonated and 19 The product was analyzed by FNMR. An aliquot was removed from the reaction mixture and filtered through a neutral alumina pipette. It was rinsed with dichloromethane. The solvent was evaporated and the NMR was measured. The Suzuki double-coupled product, the proto-deboronated upper fragment, and some other substances were observed by NMR. The aqueous layer was separated from the organic layer. The organic layer was dried over Na2SO4. The organic layer was concentrated under reduced pressure and loaded directly onto the column. The product was purified using 30% DCM in hexanes. The product appeared with 20% dichloromethane in hexanes. The product fractions were combined and evaporated under reduced pressure to give a white fluffy solid.

[0222] The product was dissolved in 30 mL of a 2:1 THF:MeOH mixture, 1 mL of concentrated HCl was added, and refluxed for 40 minutes. Excess acid was quenched with 50 mL of saturated NaHCO3 solution, and the organic layer was extracted with dichloromethane (60 mL x 3). The organic layer was dried over Na2SO4. The organic layer was evaporated under vacuum. The product was purified using an ISCO with 20% DCM in hexanes. The product fractions were combined and evaporated under reduced pressure to give a white fluffy solid (8.6 g, 56% yield over two steps).

[0223] 1 H NMR(400MHz,Chloroform-d)δ8.12(d,J=7.7Hz,4H),7.52-7.37(m,8H),7.28(s,4H),6.91(dd,J=8.7,3.1Hz,2H),6.73 (dd,J=8.7,3.1Hz,2H),6.43(s,2H),3.63(s,4H),1.79(s,6H),1.76-1.64(m,12H),1.38(s,12H),0.89-0.66(m,118H). 13 C NMR(101MHz,CDCl3)δ160.5,158.0,149.5,149.5,147.8,142.9,140.9,137.0,134.3,134.2,133.1,133.0,129.0,127.5,126.3,1 26.3,125.6,125.4,123.8,119.6,117.6,117.4,116.2,116.0,115.8,72.3,57.3,38.3,32.7,32.1,31.8,26.7,24.9,24.6,16.1. 19 F NMR (376MHz, CDCl3)δ-118.10.

[0224] Example 6, Synthesis of Metal-Ligand Complex 6 (MLC-6):

[0225] [ka]

[0226] In a nitrogen-filled glovebox, an oven-dried 250 mL flask was charged with ScCl3 (0.286 g, 1.89 mmol, 1.4 equiv.). Ligand vi (2.447 g, 1.35 mmol, 1 equiv.) was dissolved in THF (60 mL) and added to the ScCl3, followed by Et3N (1.88 mL, 13.51 mmol, 10 equiv.). The reaction mixture was heated to 50 °C and stirred for 14 h. The reaction was found to be incomplete by 1H and 19F NMR spectroscopy. Heating and stirring were continued for an additional 4 days. Further NMR analysis indicated impure product. Additional ScCl3 (0.122 g, 0.81 mmol, 0.6 equiv.) and Et3N (1.0 mL, 7.17 mmol, 5.3 equiv.) were added, and the reaction was continued for 16 h. NMR analysis indicated the desired product and an unknown impurity. The reaction mixture was evaporated to dryness under vacuum. The residue was extracted with 200 mL of hexane (stirred overnight) and then filtered. The filter cake was analyzed by NMR spectroscopy and found to contain only impurities. The filtrate was evaporated to dryness under vacuum to give the pure desired product as a white solid (1.40 g, 53%).

[0227] 1H NMR(400MHz,C6D6)δ8.20(dd,J=14.0,7.7Hz,2H),8.16-8.10(m,2H),8.01(d,J=7.7Hz,1H),7.81(s ,1H),7.68(s,1H),7.65-7.58(m,3H),7.56-7.48(m,3H),7.39(dt,J=5.0,2.8Hz,3H),7.21(dd,J=9 .2,3.2Hz,1H),7.03(dd,J=9.1,3.3Hz,1H),6.76(dd,J=8.1,3.1Hz,1H),6.38(dd,J=8.4,3.1Hz,1H ),4.59(td,J=10.2,9.3,3.7Hz,1H),4.47(td,J=10.8,10.1,3.4Hz,1H),3.42-3.31(m,1H),3.32-3. 18(m,2H),3.13-3.02(m,2H),2.82(dd,J=9.4,3.3Hz,1H),2.26(s,3H),2.05(ddq,J=33.2,13.3,6. 7Hz,6H),1.84(qt,J=12.9,6.5Hz,6H),1.72-1.58(m,2H),1.55(s,3H),1.39(d,J=7.9Hz,1H),1.34 -1.17(m,20H),1.13(dd,J=6.5,3.5Hz,18H),1.09(dd,J=6.9,1.7Hz,5H),1.06(d,J=6.6Hz,9H),1. 01(d,J=6.6Hz,9H),0.97(dd,J=6.5,4.7Hz,3H),0.95-0.87(m,37H),0.84(dd,J=12.9,8.0Hz,24H). 19 F NMR (376MHz, C6D6) δ-115.25,-115.65.

[0228] Example 7, synthesis of metal-ligand complex 7 (MLC-7):

[0229]

change

[0230] In a N2-filled glovebox, a 20 mL vial was charged with compound (i) (20 mg, 0.01, 1.0 equiv.) and 5 mL of benzene-d6. 2 M HCl in ether (7 μL, 0.01 mmol, 1.0 equiv.) was added to the Sc complex, and the reaction mixture was stirred for 5 min. An aliquot was then taken from the vial and 1 Analysis by H NMR spectroscopy indicated that some amount of compound of formula (i) remained. An aliquot was transferred to a vial, an additional 0.5 equivalents of 2 (M) HCl was added to the reaction mixture, and the reaction mixture was stirred for 5 minutes. 19 F NMR analysis showed complete consumption of compound formula (i) and the formation of two new products, the major species was identified as MLC-7.

[0231] 1 H NMR(400MHz,Benzene-d6)δ8.65(d,J=1.9Hz,1H),8.47(dd,J=17.3,1.9Hz,2H),8.40(d,J=1.9Hz,2H),8.29-8.22(m,2H),7.88(dd,J=8.6,6 .1Hz,2H),7.83-7.71(m,3H),7.71-7.61(m,1H),7.58-7.30(m,13H),7.27(t,J=3.1Hz,2H),7.07(ddd,J=8.2,5.2,2.6Hz,2H),6.96(dd,J=9. 0,3.3Hz,1H),6.83(dd,J=9.0,3.2Hz,1H),6.63(td,J=8.7,3.0Hz,1H),6.31(dd,J=8.2,3.2Hz,1H),6.08(dd,J=8.3,3.2Hz,1H),4.02-3.89 (m,1H),3.75-3.29(m,12H),3.28-3.11(m,2H),3.11-2.94(m,2H),2.5 5-2.02(m,4H),1.86(s,3H),1.80-1.06(m,142H),1.06-0.54(m,48H). 19 F NMR (376MHz, Benzene-d6) δ -115.42 (t, J = 8.6 Hz), -116.31 (t, J = 8.6 Hz), -118.13 (t, J = 8.8 Hz).

[0232] Example 8, Synthesis of Metal-Ligand Complex 8 (MLC-8):

[0233] [ka]

[0234] In an N2-filled glovebox, a vial was charged with YCl3 (0.048 g, 0.25 mmol), THF (approximately 10 mL), and a magnetic stir bar. The mixture was heated at 50 °C for 15 min, and then the ligand of formula (i) (0.200 g, 0.159 mmol) in THF solution (approximately 5 mL) was added, followed by excess Et3N (approximately 0.30 mL, 1.6 mmol). The resulting mixture was stirred at 50 °C for 3 days, after which a second equivalent of YCl3 was added, followed by excess Et3N (approximately 0.30 mL, 1.6 mmol). The mixture was stirred overnight at 50 °C, and then the solvent was removed in vacuo. The complex was extracted with pentane and passed through a fritted column. The filtrate was removed in vacuo to give MLC-8 as a white solid (175 mg, 76% yield).

[0235] 1H NMR(400MHz,Benzene-d6)δ8.24(dd,J=8.3,5.9Hz,2H),8.15(d,J=8.2Hz,1H),8.0 1(s,1H)7.94(d,J=8.2Hz,1H),7.73(d,J=2.6Hz,1H),7.62(s,1H),7.57-7.41(m,5 H),7.39(s,1H),7.26(m,2H),7.21(d,J=8.1Hz,1H),7.00(dd,J=9.0,3.1Hz,1H),6 .90(dd,J=9.0,3.1Hz,1H),6.24(dd,J=8.0,3.1Hz,1H),6.04(dd,J=8.7,3.1Hz,1H) ,3.82(t,J=9.7Hz,1H),3.77(s,1H),3.59(t,J=9.6Hz,1H),3.36(t,J=8.4Hz,1H), 3.03-2.95(m,2H),2.65-2.57(m,2H),1.92-1.83(m,1H),1.73-1.61(m,3H),1.61( s,9H),1.57(s,3H),1.56-0.99(obscured,9H),1.47(s,9H),1.38(s,3H),1.29(s, 9H),1.25(s,3H),1.19(s,9H),1.17(s,3H),1.06(s,3H),0.89(s,9H),0.86(s,9H). 19 F NMR(376MHz, Benzene-d6)δ-114.55(t,J=8.9Hz),-115.09(t,J=8.9Hz).

[0236] Example 9, synthesis of metal-ligand complex 9 (MLC-9):

[0237]

change

[0238] In a glovebox, a vial was charged with LuCl (0.045 g, 0.16 mmol), THF (approximately 10 mL), and a magnetic stir bar. The mixture was heated at 50 °C for 15 minutes, and then a ligand of formula (i) (0.200 g, 0.159 mmol) in a THF solution (approximately 5 mL) was added, followed by excess EtN (approximately 0.30 mL). The resulting mixture was stirred at 50 °C for 3 days, after which a second aliquot of LuCl (0.50 g, 0.18 mmol) was added, followed by excess EtN (approximately 0.50 mL). The mixture was stirred overnight at 50 °C, and then the solvent was removed in vacuo. The complex was extracted with pentane and passed through a fritted column. The solvent was removed in vacuo to give MLC-9 as a white solid.

[0239] 1H NMR(400MHz,Benzene-d6)δ8.23(t,J=7.8Hz,2H),8.13(d,J=8.2Hz,1H),7.99(d,J=1.7Hz,1H) ,7.93(d,J=8.2Hz,1H),7.75(d,J=2.6Hz,1H),7.61(d,J=1.7Hz,1H),7.53(m,2H),7.50-7.39( m,3H),7.36(d,J=1.6Hz,1H),7.26(dd,J=12.4,2.6Hz,2H),7.20(dd,J=8.3,1.7Hz,1H),7.00( dd,J=8.9,3.2Hz,1H),6.87(dd,J=8.9,3.2Hz,1H),6.24(dd,J=8.2,3.2Hz,1H),6.05(dd,J=8. 6,3.2Hz,1H),3.92-3.77(m,2H),3.64-3.55(m,1H),3.38(m,1H),3.03(dt,J=8.2,6.1Hz,2H), 2.65(dt,J=8.0,6.1Hz,2H),1.91-1.74(m,2H),1.74-1.64(m,2H),1.63(s,3H),1.62(s,9H),1 .60-1.45(m,2H),1.46(s,9H),1.29(s,3H),1.28(s,9H),1.26-1.21(m,2H),1.193(s,3H),1.1 86(s,9H),1.17(s,3H),1.03(s,3H),1.02-0.92(m,2H),0.89(s,9H),0.86(s,9H)-0.78(m,2H). 19 F NMR(376MHz, Benzene-d6)δ-115.01(t,J=8.6Hz),-115.11(t,J=8.6Hz).

[0240] Example 10, synthesis of metal-ligand complex 10 (MLC-10):

[0241]

change

[0242] In an N2-filled glovebox, a vial was charged with TmCl3 (0.054 g), THF (approximately 10 mL), and a magnetic stir bar. The mixture was heated at 50 °C for 15 min, and then the ligand of formula (i) (0.200 g, 0.159 mmol) in a THF solution (approximately 5 mL) was added, followed by excess Et3N (approximately 0.30 mL). The resulting mixture was stirred at 50 °C for 3 days, after which a second aliquot of TmCl3 (0.77 g, 0.16 mmol) was added, followed by excess Et3N (approximately 0.50 mL). The mixture was stirred overnight at 50 °C, and then the solvent was removed in vacuo. The complex was extracted with pentane and passed through a fritted column. The solvent was removed in vacuo to give MLC-10 as a white solid (199 mg).

[0243] MLC-10 is a paramagnetic compound: 1 H NMR (400 MHz, Benzene-d6) signals are δ350 to -242 ppm. 19 F NMR (376MHz, Benzene-d6) δ-42.36(s),-57.37(s).

[0244] Example 11, Synthesis of Metal-Ligand Complex 11 (MLC-11):

[0245] [ka]

[0246] In an N2-filled glovebox, a vial was charged with TbCl3 (0.051 g, 0.19 mmol), THF (approximately 7 mL), and a magnetic stir bar. The mixture was heated at 50 °C for 15 min, and then the ligand of formula (i) (0.205 g, 0.163 mmol) in a THF solution (approximately 5 mL) was added, followed by excess Et3N (approximately 0.30 mL). The resulting mixture was stirred at 50 °C for 3 days, after which a sample was taken and analyzed by F NMR spectroscopy, revealing the presence of both the ligand of formula (i) and the metal-ligand complex 11. A second aliquot of TBCl3 (0.079 g, 0.30 mmol) was added, followed by excess Et3N (approximately 0.50 mL). The mixture was stirred overnight at 50 °C, then the solvent was removed in vacuo, and the complex was extracted with pentane and passed through a fritted column. The solvent was removed in vacuo to give MLC-11 as a white solid (232 mg, 94% yield).

[0247] MLC-11 is a paramagnetic compound: 1 H NMR (400 MHz, Benzene-d6) signals range from δ140 to -375 ppm. 19 F NMR (376MHz, Benzene-d6) δ-143.67(s),-175.09(s).

[0248] Example 12, Synthesis of Metal-Ligand Complex 12 (MLC-12):

[0249] [ka]

[0250] In an N2-filled glovebox, a vial was charged with HoCl3 (0.050 g, 0.18 mmol), THF (approximately 7 mL), and a magnetic stir bar. The mixture was heated at 50 °C for 15 min, and then the ligand of formula (i) (0.202 g, 0.161 mmol) in THF solution (approximately 5 mL) was added, followed by excess Et3N (approximately 0.30 mL). The resulting mixture was stirred at 50 °C for 3 days, after which a second aliquot of HoCl3 (0.050 g, 0.18 mmol) was added, followed by excess Et3N (approximately 0.50 mL). The mixture was stirred overnight at 50 °C, and then the solvent was removed in vacuo. The complex was extracted with pentane and passed through a fritted column. The solvent was removed in vacuo to give MLC-12 as a white solid (228 mg, 93% yield).

[0251] MLC-12 is a paramagnetic compound: 1 H NMR (400 MHz, Benzene-d6) signals are δ 168 to -212 ppm. 19 F NMR (376MHz, Benzene-d6) δ-143.36(s),-175.48(s).

[0252] Each of the comparative metal-ligand complexes C1 and C2 (herein referred to as "Comparative Example C1" and "Comparative Example C2") was mixed with cocatalyst 1 to form a catalyst system. Metal-ligand complexes 1-12 of the present invention have a structure according to the metal-ligand complex of formula (I). The comparative procatalysts have the following structures, the preparation of which was reported in WO 2021155158 A1:

[0253] [ka]

[0254] Example 13, Batch Reactor Polymerization Results Procedure for Batch Reactor Polymerization. Batch reactor polymerization reactions are carried out in a 2 L Parr™ batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal spiral cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a 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 optionally pre-filled with a 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 Isopar E are passed through two columns: the first containing A2 alumina and the second containing Q5. Ethylene is passed through two columns, the first containing A204 alumina and 4 Å molecular sieves, the second containing Q5. N2, used for transport, is passed through a single column containing A204 alumina, 4 Å molecular sieves, and Q5.

[0255] The reactor is initially charged 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 setpoint using a lab scale shot tank implementation. After the addition of the liquid feed, the reactor is heated to the polymerization temperature setpoint. If ethylene is used, it is added to the reactor at the reaction temperature to maintain the reaction pressure setpoint. The amount of ethylene added is monitored by a micromotion flow meter. For some experiments, the standard conditions at 120°C are 46 g ethylene and 303 g 1-octene in 611 g IsoparE, and the standard conditions at 150°C are 43 g ethylene and 303 g 1-octene in 547 g IsoparE.

[0256] The metal-ligand complex and cocatalyst were mixed with an appropriate amount of purified toluene to obtain a molar solution. The metal-ligand complex and cocatalyst were handled in an inert glovebox, drawn into a syringe, and pressure-transferred into a catalyst shot tank. The syringe was rinsed three times with 5 mL of toluene. Immediately after the catalyst was added, a run timer was started. If ethylene was used, it was added by Camile to maintain the reaction pressure set point in the reactor. The polymerization reaction was run for 10 minutes, then the agitator was stopped, the bottom dump valve was opened, and the reactor contents were transferred to a dump pot. The dump pot contents were poured into a tray and placed in a lab hood, where the solvent was allowed to evaporate overnight. The tray containing the remaining polymer was transferred to a vacuum oven and heated to 140 °C under vacuum to remove any remaining solvent. After the tray cooled to ambient temperature, the polymer yield was measured to determine efficiency and the polymer was subjected to polymer testing. The results of the high 1-octene polymerization reaction are shown in Table 1.

[0257] [Table 1]

[0258] Reactor conditions in Table 1: (1) 190°C, 410 psi C2, 65 g 1-octene, 1250 g isopar-E, 10 min run time. ND = below instrument detection limit. [a] The promoter / additive was mixed with the catalyst before injection. [b] The cocatalyst / additive was added for polymerization before catalyst injection.

[0259] In Example 1, the metal-ligand complex 1 (IMLC-1) of the present invention was mixed with the modified MMAO cocatalyst before injection to activate the precatalyst. In Example 2, the MMAO cocatalyst was fed separately to the reactor before the precatalyst, and then the precatalyst was injected into the reactor. Both showed the same efficiency and produced the same polymer, indicating fast activation of the precatalyst. In Example 3, IMLC-1 was premixed with 20 equivalents of MMAO and fed to the reactor. The efficiency was very low, indicating that catalyst activation is dependent on MMAO. Because MMAO also acts as a scavenger, preventing poisoning of IMLC-1 by impurities (thus preventing false negative results), a low level of MMAO was chosen to demonstrate low reactivity rather than no MMAO. Example 4 uses the same conditions as Example 1, but uses a comparative catalyst synthesized as a preactivated catalyst with an alkyl leaving group. The comparative catalyst's efficiency is somewhat lower than that of the cocatalyzed IMLC-1, but produces the same polymer.

[0260] Example 14: Results of continuous process polymerization The feedstocks (ethylene, 1-octene) and process solvent (a high-purity isoparaffinic solvent with a narrow boiling range, commercially available from ExxonMobil Corporation under the trademark Isopar E) were purified with molecular sieves before being introduced into the reaction environment. Hydrogen was supplied as a high-purity grade in a pressurized cylinder without further purification. The reactor monomer feed (ethylene) stream was pressurized via a mechanical compressor to a pressure above the reaction pressure of 525 psig. The solvent and comonomer (1-octene) feed were pressurized via a mechanical positive displacement pump to a pressure above the reaction pressure of 525 psig. Triethylaluminum (TEA) and modified methylaluminoxane (MMAO), commercially available from AkzoNobel, were used as cocatalysts, each of which could alternately function as an impurity scavenger. Individual catalyst components (procatalyst cocatalysts) were manually batch diluted to specific component concentrations with purified solvent (Isopar E) and pressurized above the reaction pressure at 525 psig. All reaction feed streams are metered using mass flow meters and controlled by independent computer-automated valve control systems.

[0261] Continuous solution polymerization is carried out in a 5 L continuously stirred-tank reactor (CSTR). The reactor independently controls all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. The combined solvent, monomer, comonomer, and hydrogen feeds to the reactor are temperature controlled anywhere between 5°C and 50°C, typically at 25°C. Fresh comonomer feed to the polymerization reactor is fed along with the solvent feed. The fresh solvent feed is typically controlled by each injector receiving half of the total fresh feed mass flow rate. A 6.0 mmol / kg solution of Cocatalyst 1 is fed at a rate of 56.6 g / hr, and a 16.0 mmol / kg solution of Cocatalyst 2 is fed at a rate of 65.44 g / hr. Immediately after each fresh injection point, the feed streams are mixed with the contents of the circulating polymerization reactor using static mixing elements. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the first reactor loop and passes through a control valve (responsible for maintaining the pressure of the first reactor at a specified target). As the stream exits the reactor, it is contacted with water to quench the reaction. Additionally, various additives, such as antioxidants, can be added at this point. The stream then passes through another set of static mixing elements to uniformly distribute the catalyst kill and additives.

[0262] Following additive addition, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from other low-boiling reaction components. The stream then enters a two-stage separation and devolatilization system, where the polymer is stripped from the solvent, hydrogen, and unreacted monomer and comonomer. The separated, devolatilized polymer melt is pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transported to boxes for storage.

[0263] [Table 2]

[0264] Continuous reactor conditions: solvent feed rate = 21.28 kg / hr, ethylene feed rate = 4.87 kg / hr, 1-octene feed rate 2.09 kg / hr, ethylene exit = 8.53 g / L, and Al concentration = 1 ppm. [A] The % solids is the polymer concentration in the reactor. [B] H2 (mol%) is defined as the mole fraction of hydrogen relative to the ethylene fed to the reactor. [C] Efficiency (Eff.) is 10 6 It is measured as g polymer / g metal.

[0265] Equipment standards All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passage through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glovebox were further dried by storage over activated 4 Å molecular sieves. Glassware for moisture-sensitive reactions was dried overnight in an oven before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. 1 Chemical shifts for H NMR data are reported in ppm downfield from internal tetramethylsilane (tetramethylsilane, TMS, δ scale) using residual protons in the deuterated solvent as the reference. 13 C NMR data is 1 Determined using H decoupling, chemical shifts are reported in ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

Claims

1. 1. A polymerization process comprising: polymerizing ethylene and optionally one or more olefins in a reactor system comprising one or more reactors under olefin polymerization conditions in the presence of a catalyst system comprising one or more olefin polymerization catalysts, the catalyst comprising at least one derived from a metal-ligand complex of Formula (I), an alkylating agent, and optionally a Lewis acid, to form an ethylene-based polymer; 【Chemical 1】 During the ceremony, M is scandium, yttrium, or a lanthanide metal having an oxidation state of +3; X is a halogen; each T is independently a Lewis base; n is 0, 1, or 2; k is 1 or 2; the metal-ligand complex is overall charge neutral; R １ and R １６ But independently, (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, -N=C(R Ｃ ) ２ , R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)—, or halogen; R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , and R １５ are independently -H, (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, (R Ｃ ) ２ P=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)— and halogen; However, when M is yttrium or a lanthanide metal, R １ is not —H, phenyl, or tert-butyl, and R １６ is not —H, phenyl, or tert-butyl; L is (C １ -C ４０ ) hydrocarbylene or (C １ -C ４０ ) heterohydrocarbylene; Each R in formula (I) Ｃ , R Ｐ , and R Ｎ But independently, (C １ -C ３０ ) hydrocarbyl, (C １ -C ３０ ) heterohydrocarbyl, or —H.

2. 10. The polymerization process of claim 1, wherein the alkylating agent is a modified aluminoxane.

3. 3. The polymerization process of claim 1 or 2, wherein the alkylating agent is an alkylaluminum.

4. The polymerization process of any one of claims 1 to 3, wherein the alkylating agent is a magnesium alkyl.

5. The Lewis acid cocatalyst is a compound of formula AlR Ａ ３ (In the formula, each R Ａ are independently １ -C ４０ 5. The polymerization process of claim 1, wherein the alkyl group is a hydroxyl group, and the alkyl group is a hydroxyl group.

6. Each R Ａ But independently, (C １ -C ４０ 6. The polymerization process of claim 5 wherein:

7. The Lewis acid is (A) at least one cocatalyst selected from aluminoxanes, or (B) a compound of formula AlR １ R ２ R ３ or (C) at least one cocatalyst selected from an aluminoxane and an alkylaluminum of the formula AlR １ R ２ R ３ 10. The polymerization process of claim 1, comprising at least one activator selected from the group consisting of alkyl aluminums of the formula:

8. 10. The polymerization process of claim 1, wherein the at least one Lewis acid cocatalyst is selected from a mixture of alkylaluminum compounds and alkylzinc compounds.

9. 10. The polymerization process of claim 1, wherein the at least one Lewis acid is selected from a mixture of alkylaluminum compounds and boron-based Lewis acids.

10. The polymerization process according to any one of claims 1 to 9, wherein the polymerization process is carried out in a single reactor.

11. 11. The polymerization process of claim 10, wherein the catalyst system further comprises at least one Group IV catalyst.

12. The polymerization process according to any one of claims 1 to 9, wherein the polymerization process is carried out in multiple reactors.

13. 13. The polymerization process of claim 12, wherein the catalyst system further comprises at least one Group IV catalyst.

14. R １ and R １６ is selected from a radical having formula (II), a radical having formula (III), and a radical having formula (IV), 【Chemistry 2】 In the formula, R ３１－３５ , R ４１－４８ and R ５１－５９ each independently represents —H, (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ NC(O)—, or halogen, with the proviso that R １ and R １６ is formula (II), R ３１ ~R ３５ The polymerization process of any one of claims 1 to 13, provided that at least one of

15. When M is scandium, yttrium, or a lanthanide metal, R ５－８ At least one of R is not —H, ９－１２ The polymerization process of any one of claims 1 to 14, wherein at least one of

16. R １ and R １６ is a radical having the formula (III), R ４２ and R ４７ However, (C １ -C ２０ ) hydrocarbyl, —Si[(C １ -C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ -C ２０ ) hydrocarbyl] ３ is, or R ４３ and R ４６ However, (C １ -C ２０ ) hydrocarbyl, —Si[(C １ -C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ -C ２０ ) hydrocarbyl] ３ The polymerization process according to any one of claims 1 to 15, wherein

17. R １ and R １６ is a radical having the formula (II), R ３１ ~R ３５ is not —H, or R ３２ and R ３４ However, (C １ -C ２０ ) hydrocarbyl, —Si[(C １ -C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ -C ２０ ) hydrocarbyl] ３ The polymerization process according to any one of claims 1 to 15, wherein

18. R １ and R １６ is a radical having formula (IV), wherein R ５２ , R ５３ , R ５５ , R ５７ , and R ５８ At least two of (C １ -C ２０ ) hydrocarbyl, —Si[(C １ -C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ -C ２０ ) hydrocarbyl] ３ and Optionally, R ５２ and R ５３ are linked to form a ring structure, and optionally, R ５７ and R ５８ The polymerization process of any one of claims 1 to 15, wherein:

19. L is -CH ２ -, -CH ２ (CH ２ ) ｍ CH ２ -(m is 0 to 3), -CH ２ Si(R Ｃ ) ２ CH ２ -, -CH ２ Ge(R Ｃ ) ２ CH ２ -, -CH(CH ３ ) CH ２ CH ＊ (CH ３ ), and -CH ２ (phen-1,2-diyl)CH ２ -, and each R in L is selected from Ｃ However, (C １ -C ２０ ) hydrocarbyl, and "C ＊ 19. The metal-ligand complex of any one of claims 1 to 18, wherein " is a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical.

20. n is 1 or 2, and at least one T is (C １ -C ２０ 20. The metal-ligand complex of claim 1, wherein the heteroatom of said heterohydrocarbon is oxygen.

21. 21. The metal-ligand complex of any one of claims 1 to 20, wherein n is 1 or 2 and at least one T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

22. R ２ , R ４ , R ５ , R １２ , R １３ , and R １５ 22. The metal-ligand complex of any one of claims 1 to 21, wherein is hydrogen.

Images