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

Abstract

Embodiments of the present disclosure relate to catalyst systems comprising a metal-ligand complex according to formula (I): # imgabs0 #

Description

[0001] Cross-references to related patent applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 401,915, filed on August 29, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more particularly to bisphenylphenoxy metal-ligand complexes having a Group III or lanthanide metal center. Background Art

[0004] Olefin-based polymers such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers are produced by various catalyst systems. The selection of such catalyst systems used in the polymerization process of olefin-based polymers is an important factor contributing to the characteristics and properties of such olefin-based polymers.

[0005] Ethylene-based polymers and propylene-based polymers are manufactured for various articles. Polyethylene and polypropylene polymerization processes can differ in many aspects to produce various resulting polyethylene resins with different physical properties, which make various resins suitable for different applications. Ethylene monomer and optional one or more comonomers are present in a liquid diluent or solvent, such as an alkane or isoalkane, with specific examples being hexane and isobutane. Hydrogen can also be added to the reactor. Catalyst systems for producing ethylene-based catalysts can generally include chromium-based catalyst systems, Ziegler-Natta catalyst systems and / or molecular (metallocene or non-metallocene (molecule)) catalyst systems. The reactants and diluents in the catalyst system circulate in the reactor at an elevated polymerization temperature to produce homopolymers or copolymers based on ethylene. Periodically or continuously remove a portion of the reaction mixture from the reactor, including the polyethylene product dissolved in the diluent, and unreacted ethylene and one or more optional comonomers. The reaction mixture can be processed after being removed from the reactor to remove the polyethylene product and unreacted reactants in the diluent, wherein the diluent and unreacted reactants are usually recycled back to the reactor. Alternatively, the reaction mixture can be sent to a second reactor connected in series with the first reactor, in which a second polyethylene fraction can be produced. Although research is devoted to developing catalyst systems suitable for olefin polymerizations such as polyethylene polymerization, it is still necessary to improve the efficiency of catalyst systems that can produce polymers with high molecular weight and narrow molecular weight distribution and have high selectivity to ethylene.

[0006] For previously discovered Group III bisphenylphenoxy metal-ligand catalysts, the catalyst does not require a cocatalyst or activator to initiate polymerization. While it may be beneficial not to resort to a catalyst or activator, this also presents problems within the reactor. Due to the reactivity of the Group III bisphenylphenoxy metal-ligand catalyst, the catalyst may react in the feed line or as soon as the Group III catalyst comes into contact with ethylene and thereby contaminate the injection point or feed line. Summary of the invention

[0007] There is a continuing need to produce catalyst systems or metal-ligand complexes that have high selectivity for ethylene during copolymerization of ethylene and α-olefins. In addition, the metal-ligand complex should have high catalyst efficiency and the general ability to produce polymers with high or low molecular weight at high temperatures (such as greater than 140° C. or about 190° C.).

[0008] Embodiments of the present disclosure provide a chloro-scandium-bis(phenylphenoxy) metal-ligand complex that is unreactive until the chlorine atom is replaced with an alkyl group, rendering the metal-ligand complex an active catalyst.

[0009] Embodiments of the present disclosure include catalyst systems comprising a metal-ligand complex according to formula (I):

[0010]

[0011] In formula (I), M is scandium, yttrium, a lanthanide metal or an actinide metal in oxidation state +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 electrically neutral as a whole.

[0012] In formula (I), R 1 and R 16 Independently selected from the group consisting of: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -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)-、RC C(O)N(R)-、(R C )2NC(O)-, halogen, a group having the formula (II), a group having the formula (III) and a group having the formula (IV):

[0013]

[0014] In formulas (II), (III) and (IV), each of R31-35, R41-48 and R51-59 is independently selected from -H, (C1-C40)alkyl, (C1-C40)heteroalkyl, -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.

[0015] In formula (I), R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 and R15 are independently selected from -H, (C1-C40) heteroalkyl, (C1-C40) heteroalkyl, -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)- or halogen.

[0016] In formulas (I), (II), (III) and (IV), each R C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H. DETAILED DESCRIPTION

[0017] Specific embodiments of the catalyst system will now be described.It should be understood that the catalyst system of the present disclosure can be embodied in different forms and should not be construed as limited to the specific embodiments set forth in the present disclosure.

[0018] Common abbreviations are listed below:

[0019] 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 (used in column chromatography); EtOAc: ethyl acetate; TEA: triethylaluminum; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; LiCH2TMS: (trimethylsilyl)methyllithium; TMS: trimethylsilyl; Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II) dichloride; Pd(AmPhos): chloro(crotyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II); Pd(dppf)Cl2: [1,1 '-Bis(diphenylphosphino)ferrocene]palladium(II) chloride; ScCl3: scandium(III) chloride; PhMe: toluene; THF: tetrahydrofuran; CH2Cl2: dichloromethane; DMF: N,N-dimethylformamide; EtOAc: ethyl acetate; Et2O: diethyl ether; MeOH: methanol; NH4Cl: ammonium chloride; MgSO4: magnesium sulfate; Na2SO4: sodium sulfate; NaOH: sodium hydroxide; brine: saturated aqueous sodium chloride solution; SiO2: silicon dioxide; CDCl3: chloroform-D; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimole; mL: milliliter; M: mole; min or mins: minutes; h or hrs: hours; d: day; TLC: thin layer chromatography; rpm: revolutions per minute; rt: room temperature.

[0020] The term "independently selected from" is used herein to indicate that, for example, R 1 , R 2 , R 3 , R 4 and R 5 The R groups may be the same or different (e.g., R 1 , R 2 , R 3 , R 4 and R 5 can be substituted alkyl, or R 1 and R 2 may be a substituted alkyl group, and R 3The chemical names associated with the R groups are intended to convey chemical structures recognized in the art as corresponding to the chemical structures of the chemical names. Therefore, the chemical names are intended to supplement and illustrate rather than exclude structural definitions known to those skilled in the art.

[0021] When used to describe certain chemical groups containing carbon atoms, the form "(C x -C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms (including x and y). For example, (C1-C 50 )alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted with one or more substituents such as RS. The parenthetical phrase "(C x -C y )” defined by R S The substituted chemical group may contain more than y carbon atoms, depending on the number of carbon atoms in any group R. S For example, "exactly one group R S Substituted (C1-C 50 ) alkyl, wherein R S The phenyl group (-C6H5)" may contain from 7 to 56 carbon atoms. Therefore, in general, when the parenthetical phrase "(C x -C y )" is replaced by one or more carbon-containing substituents R S When substituted, both x and y are added to the substituent R from all carbon atoms. S The combined sum of the number of carbon atoms is used to determine the minimum and maximum total number of carbon atoms in a chemical group.

[0022] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "fully substituted" means that each hydrogen atom (H) bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ) replacement. The term "polysubstituted" means that at least two but less than all hydrogen atoms bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen group covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless expressly specified.

[0023] The term "(C1-C 50 )hydrocarbyl" means a hydrocarbon group having 1 to 50 carbon atoms, and the term "(C1-C50 )alkylene group" means a hydrocarbon diradical having 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (having three carbons or more, and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and is substituted by one or more R S Substituted or unsubstituted.

[0024] In the present disclosure, (C1-C 50 The hydrocarbon group may be unsubstituted or substituted (C1-C 50 )alkyl, (C3-C 50 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40 )aryl or (C6-C 20 )aryl-(C1-C 20 ) alkylene (such as benzyl (-CH2-C6H5)).

[0025] The term "(C1-C 50 )alkyl" and "(C1-C 18 )alkyl" refers to unsubstituted or substituted with one or more R S Substituted saturated straight chain or branched hydrocarbon groups having 1 to 50 carbon atoms and saturated straight chain or branched hydrocarbon groups having 1 to 18 carbon atoms. 50 Examples of alkyl groups are unsubstituted (C1-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. Substituted (C1-C5)alkyl 40 Examples of alkyl groups are substituted (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl and [C 45 ] alkyl. The term "[C 45 ] alkyl" means that there are up to 45 carbon atoms in the group (including substituents), and for example, one R is respectively (C1-C5) alkyl S Replaced (C 27 -C 40 Each (C1-C5)alkyl group may be a methyl group, a trifluoromethyl group, an ethyl group, a 1-propyl group, a 1-methylethyl group or a 1,1-dimethylethyl group.

[0026] The term "(C6-C 50 ) aryl" means an unsubstituted or substituted aryl having 6 to 40 carbon atoms (one or more R S ) substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon groups, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. Monocyclic aromatic hydrocarbon groups include one aromatic ring; bicyclic aromatic hydrocarbon groups have two rings; and tricyclic aromatic hydrocarbon groups have three rings. When a bicyclic or tricyclic aromatic hydrocarbon group is present, at least one of the rings of the group is aromatic. The other one or more rings of the aromatic group may independently be fused or non-fused and be aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl groups include: unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 40 Examples of aryl groups include: substituted (C1-C 20 ) aryl; substituted (C6-C 18 )aryl; 2,4-bis([C 20 ] alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-on-1-yl.

[0027] The term "(C3-C 50 "Cycloalkyl" means a saturated cyclic hydrocarbon group having 3 to 50 carbon atoms, which is unsubstituted or substituted by one or more R S Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) is defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C3-C 40 Examples of cycloalkyl groups are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. 40 Examples of cycloalkyl groups are substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 )cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

[0028] (C1-C 50 Examples of the alkylene group include unsubstituted or substituted (C6-C50 ) arylene, (C3-C 50 )cycloalkylene and (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). The diradicals can be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more than two intermediate carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-diradicals, 1,3-diradicals, 1,4-diradicals, or α,ω-diradicals and other 1,2-diradicals. α,ω-diradicals are diradicals with the largest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diyl radicals include ethane-1,2-diyl (ie, -CH2CH2-), propane-1,3-diyl (ie, -CH2CH2CH2-), 2-methylpropane-1,3-diyl (ie, -CH2CH(CH3)CH2-). (C6-C 50 Some examples of arylene α,ω-diyl radicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0029] The term "(C1-C 50 ) Alkylene means a group having 1 to 50 carbon atoms which is unsubstituted or substituted with one or more R S Substituted saturated straight or branched chain diradicals (i.e., the groups are not on ring atoms). Unsubstituted (C1-C 50 Examples of alkylene groups are unsubstituted (C1-C 20 )alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), wherein "C*" represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. Substituted (C1-C 50 Examples of alkylene groups are substituted (C1-C 20 )alkylene, -CF2-, -C(O)- and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosene). As mentioned above, the two R S can form together (C1-C 18 ) alkylene, substituted (C1-C 50Examples of the alkylene group 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.

[0030] The term "(C3-C 50 ) Cycloalkylene means a cycloalkylene having 3 to 50 carbon atoms which is unsubstituted or substituted with one or more R S Substituted cyclic diradicals (ie, the groups are on ring atoms).

[0031] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O)2, Si(R C )2. P(R P )、N(R N )、-N=C(R C )2、-Ge(R C )2-、-Si(R C )-, boron (B), aluminum (Al), gallium (Ga) or indium (In), wherein each R C and each R P is unsubstituted (C1-C 18 )alkyl or -H, and each R N is unsubstituted (C1-C 18 ) hydrocarbon group. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. 50 )heteroalkyl" means a heteroalkyl group having 1 to 50 carbon atoms, and the term "(C1-C 50 "Heteroalkylene" means a heteroalkylene group having 1 to 50 carbon atoms. (C1-C 50 )heteroalkyl or (C1-C 50 ) The heteroalkylene group has one or more heteroatoms. The radicals of the heteroalkylene group can be on carbon atoms or heteroatoms. The two radicals of the heteroalkylene group can be on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of the diradical can be on a carbon atom and the other can be on a different carbon atom; one of the two radicals can be on a carbon atom and the other can be on a heteroatom; or one of the two radicals can be on a heteroatom and the other can be on a different heteroatom. Each (C1-C 50 ) heteroalkyl and (C1-C 50 ) heteroalkylene may be unsubstituted or substituted with (one or more R S) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0032] (C1-C 50 )Heteroalkyl may be unsubstituted or substituted. 50 Non-limiting examples of heteroalkyl groups include (C1-C 50 ) heteroalkyl, (C1-C 50 )alkyl-O-, (C1-C 50 )alkyl-S-, (C1-C 50 )alkyl-S(O)-, (C1-C 50 )alkyl-S(O)2-, (C1-C 50 )alkyl-Si(R C )2-、(C l -C 50 )alkyl-N(R N )-、(C l -C 50 )alkyl-P(R P )-、(C2-C 50 )heterocycloalkyl, (C2-C 19 )heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 )heterocycloalkyl-(C1-C 20 )heteroalkylene, (C1-C 50 )heteroaryl, (C1-C 19 )heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )aryl-(C1-C 19 )heteroalkylene, or (C1-C 19 )heteroaryl-(C1-C 20 ) heteroalkylene.

[0033] The term "(C1-C 50 ) heteroaryl" means an unsubstituted or substituted (one or more R S) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups. Monocyclic heteroaromatic hydrocarbon groups include one heteroaromatic ring; bicyclic heteroaromatic hydrocarbon groups have two rings; and tricyclic heteroaromatic hydrocarbon groups have three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon group is present, at least one of the rings in the group is heteroaromatic. The other one or more rings of the heteroaromatic group may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., typically (C x -C y ) heteroaryl, such as (C1-C 12 ) heteroaryl) is defined in a similar manner as having x to y carbon atoms (such as 1 to 12 carbon atoms) and being unsubstituted or substituted with one or more than one R S substituted. The monocyclic heteroaromatic hydrocarbon group is a 5-membered ring or a 6-membered ring. The 5-membered ring monocyclic heteroaromatic hydrocarbon group has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3 or 4, and each heteroatom can be O, S, N or P. Examples of 5-membered ring heteroaromatic hydrocarbon groups include: pyrrol-1-yl; piperidin-2-yl; furan-3-yl; thien-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring monocyclic heteroaromatic hydrocarbon group has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon groups include: pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon group can be a fused 5,6- or 6,6-ring system. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl; and isoquinolin-1-yl. The bicyclic heteroaromatic hydrocarbon group can be a fused 5,6,5-ring system; a 5,6,6-ring system; a 6,5,6-ring system; or a 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 acridin-9-yl.

[0034] The term "(C1-C 50 ) heteroalkyl" means a saturated straight or branched chain group containing from one to fifty carbon atoms and one or more heteroatoms. The term "(C1-C 50) heteroalkylene" means a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of heteroalkyl or heteroalkylene may include Si(R C )3、Ge(R C )3、Si(R C )2、Ge(R C )2. P(R P )2. P(R P )、N(R N )2、N(R N )、N、O、OR C , S, SR C , S(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or substituted with one or more R S replace.

[0035] Unsubstituted (C2-C 40 Examples of the heterocycloalkyl group include unsubstituted (C2-C 20 )heterocycloalkyl, unsubstituted (C2-C 10 )heterocycloalkyl, aziridine-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxy-2-yl, morpholin-4-yl, 1,4-dioxane-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thioxo-cyclononyl and 2-aza-cyclodecyl.

[0036] 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: a fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) or iodide ion (I - ).

[0037] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. S In the case of substitution, one or more double bonds and / or triple bonds may optionally be present in the substituent R S The term "unsaturated" means containing one or more carbon-carbon double bonds or carbon-carbon triple bonds or (in a group containing heteroatoms) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds or carbon-silicon double bonds, excluding those that may be present in the substituent R S (if any) or double bonds (if any) in an aromatic ring or a heteroaromatic ring.

[0038] The term "lanthanide metal" includes elements 57 to 71 (lanthanum (La) to lutetium (Lu)).

[0039] Embodiments of the present disclosure include catalyst systems comprising a metal-ligand complex according to formula (I):

[0040]

[0041] In formula (I), M is scandium, yttrium, or a lanthanide metal. (T) n The subscript n is 0, 1 or 2; X is a halogen atom, and the subscript k is 1 or 2. Each R C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C 30 ) heteroalkyl. T ​​is a Lewis base. The metal-ligand complex is electrically neutral as a whole.

[0042] In formula (I), R 1 and R 16 Independently selected from the group consisting of: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -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 group having the formula (II), a group having the formula (III) and a group having the formula (IV):

[0043]

[0044] In some embodiments, in the metal-ligand complex of formula (I), R 1 or R 16 Any of, or R 1 and R 16 Both are selected from groups having formula (II), formula (III) or formula (IV). Provided that when M is yttrium or a lanthanide metal, R1 is not -H, phenyl or tert-butyl; and R 16 Not -H, phenyl or tert-butyl.

[0045] When present in the metal-ligand complex of formula (I) as part of a group having formula (II), formula (III) or formula (IV), the group R of the metal-ligand complex of formula (I) 31-35 , R 41-48 and R 51-59 Each independently selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, Si(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 N )2NC(O)-, halogen, hydrogen (-H) or a combination thereof. Each R C , R P and R N are independently unsubstituted (C1-C 18 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

[0046] The group R in the metal-ligand complex of formula (I) 1 and R 16 are chosen independently of each other. For example, R 1 can be selected from a group having formula (II), (III) or (IV), and R 16 It can be (C1-C 40 ) hydrocarbon group; or R 1 can be selected from a group having formula (II), (III) or (IV), and R 16 Can be selected from R 1 The same or different groups having the formula (II), (III) or (IV). 1 and R 16 Both may be groups having formula (II) wherein the group R 31-35 In R 1 and R 16 In other examples, R1 and R 16 Both may be groups having formula (III) wherein the group R 41-48 In R 1 and R 16 the same or different in R 1 and R 16 Both may be groups having the formula (IV) wherein the group R 51-59 In R 1 and R 16 The same or different.

[0047] In some embodiments, R 1 and R 16 At least one of them is a group having formula (II), wherein R 32 and R 34 In one or more embodiments, R 32 and R 34 is (C1-C 12 )alkyl or -Si[(C1-C 10 )alkyl]3.

[0048] In some embodiments, when R 1 or R 16 When at least one of them is a group having formula (III), R 43 and R 46 One or both of them are tert-butyl, and R 41-42 , R 44-45 and R 47-48 In other embodiments, R 42 and R 47 One or both of them are tert-butyl, and R 41 , R 43-46 and R 48 is -H. In some embodiments, R 42 and R 47 Both are -H. In various embodiments, R 42 and R 47 is (C1-C 20 )alkyl or -Si[(C1-C 10 )alkyl]3. In other embodiments, R 43 and R 46 is (C1-C 20 )alkyl or -Si(C1-C 10 )alkyl]3. In some embodiments, R 42 and R 43 connected to form a ring structure, and R 46 and R 47 connected to form a ring structure.

[0049] In an embodiment, when R 1 or R 16 When at least one of them is a group having formula (IV), each R 52 , R 53 , R 55 , R 57 and R 58 -H, (C1-C 20 )alkyl, -Si[(C1-C 20 )alkyl]3 or -Ge[(C1-C 20 )alkyl]3. In some embodiments, R 52 , R 53 , R 55 , R 57 and R 58 At least one of (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 are (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 are (C3-C 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10 )alkyl]3.

[0050] In some embodiments, when R 1 or R 16 When at least one of them is a group having formula (IV), R 52 , R 53 , R 55 , R 57 and R 58 At least two of them are (C1-C 20 )alkyl or -C(H)2Si[(C1-C 20 )hydrocarbon group]3.

[0051] (C3-C10 Examples of alkyl groups include, but are not limited to, propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl.

[0052] In some embodiments of the metal-ligand catalyst according to formula (I), R 1 and R 16 Selected from 3,5-di-tert-butylphenyl; 2,4,6-trimethylphenyl; 2,4,6-triisopropylphenyl; 3,5-diisopropylphenyl; carbazolyl; carbazole-9-yl, 1,2,3,4-tetrahydrocarbazolyl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl; 3,6-bis-(3,5-di-tert-butylphenyl)carbazole-9-yl; 3,6-bis-(2,4 ,6-trimethylphenyl)carbazole-9-yl); 3,6-bis-(2,4,6-triisopropylphenyl)carbazole-9-yl; 2,7-di(tert-butyl)-carbazole-9-yl; 2,7-di(tert-octyl)-carbazole-9-yl; 2,7-diphenylcarbazole-9-yl; 2,7-bis(2,4,6-trimethylphenyl)carbazole-9-ylanthracenyl; 1,2,3,4-tetrakis Hydroanthracenyl; 1,2,3,4,5,6,7,8-octahydroanthracenyl; phenanthrene; 1,2,3,4,5,6,7,8-octahydrophenanthrene; 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-tetrahydronaphthalen-6-yl; anthracene-9-yl; 1,2,3,4-tetrahydroanthracene-9-yl; 1,2,3,4,5,6,7,8-octahydroanthracene-9-yl; 1,2,3,4,5,6,7,8-octahydrophenanthrene-9-yl; indolyl; dihydroindolyl; quinolyl; 1,2,3,4-tetrahydroquinolyl; isoquinolyl; or 1,2,3,4-tetrahydroisoquinolyl.

[0053] 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 , R 13 , R 14 and R 15 are independently selected from -H, (C1-C 40) hydrocarbon group, (C1-C 40 ) heteroalkyl, -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.

[0054] In one or more embodiments, R 2 , R 4 , R 5 , R 12 , R 13 and R 15 For hydrogen.

[0055] In embodiments, the dashed line is optionally a coordinate bond between the metal center M and the oxygen atom. In some embodiments, one of the dashed lines connecting the oxygen atom and M is a coordinate bond, while the other dashed line does not form a coordinate bond between the oxygen atom and M. In various embodiments, two dashed lines form a coordinate bond between the oxygen atom and M.

[0056] In various embodiments, R 3 and R 14 Yes (C1-C 24 ) alkyl. In one or more embodiments, R 3 and R 14 Yes (C4-C 24 In some embodiments, R 3 and R 14 is 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In an embodiment, R 3 and R 14 For-OR C , where R C is (C1-C 20 ) hydrocarbon, and in some embodiments, R CIt is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0057] 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 In some embodiments, R 8 and R 9 Both are (C1-C 24 In some embodiments, R 8 and R 9 In other embodiments, R 8 and R 9 It is a halogen.

[0058] In some embodiments, R 3 and R 14 is methyl; in one or more embodiments, R 3 and R 14 Yes (C4-C 24 In some embodiments, R 8 and R 9 are 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl and decyl.

[0059] In various embodiments, in the metal-ligand complex of formula (I), R 6 and R 11 In some embodiments, R 6 and R 11 is (C1-C 24 ) alkyl. In various embodiments, R 6 and R 11 R is independently selected from methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 In the embodiment, R 6 and R 11 For-OR C, where R C is (C1-C 20 ) alkyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl) or 1,1-dimethylethyl. In other embodiments, R 6 and R 11 -SiR C 3, where each R C Independently (C1-C 20 ) alkyl, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0060] 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 None of them are S or any or all of them may be replaced by one or more than one R S When two or more R S When the same chemical group of the metal-ligand complex of formula (I) is bonded, each R S can be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. 1-59 None of them were R S All of them can be replaced by R S Completely replaced. S In a fully substituted chemical group, each R S Can all be the same or can be independently selected. In one or more embodiments, R S Selected from (C1-C 20 ) hydrocarbon group, (C1-C 20 )alkyl, (C1-C 20 )heteroalkyl or (C1-C 20 ) heteroalkyl.

[0061] In formula (I), L is (C1-C 40 )alkylene or (C1-C 40 ) heteroalkylene; and each Z is independently selected from -O-, -S-, -N(R N )-or-P(R P )-. In one or more embodiments, L comprises 1 to 10 atoms.

[0062] In formulas (I), (II), (III) and (IV), each R C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

[0063] In some embodiments of formula (I), L can be selected from (C3-C7) alkyl 1,3-diyl, such as -CH2CH2CH2-, -CH(CH3)CH2C*H(CH3), -CH(CH3)CH(CH3)C*H(CH3), -CH2C(CH3)2CH2-, cyclopentane-1,3-diyl or cyclohexane-1,3-diyl. In some embodiments, L can be selected from (C4-C 10 )alkyl 1,4-diyl groups, 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 can be selected from (C5-C 12 ) alkyl 1,5-diradicals, such as -CH2CH2CH2CH2CH2- and 1,3-bis(methylene)cyclohexane. In some embodiments, L may be selected from (C6-C 14 )alkyl 1,6-diradicals such as -CH2CH2CH2CH2CH2CH2- or, for example, 1,2-bis(ethylene)cyclohexane.

[0064] In one or more embodiments, L is (C2-C 40 ) heteroalkylene, and at least one of the 2 to 10 atoms includes a heteroatom. In some embodiments, L is -CH2Ge(R C )2CH2-, where each R C is (C1-C 30 In some embodiments, L is -CH2Ge(CH3)2CH2-, -CH2Ge(ethyl)2CH2-, -CH2Ge(2-propyl)2CH2-, -CH2Ge(tert-butyl)2CH2-, -CH2Ge(cyclopentyl)2CH2-, or -CH2Ge(cyclohexyl)2CH2-.

[0065] In one or more embodiments, L is selected from -CH2-; -CH2CH2-; -CH2(CH2) m CH2-, wherein m is 1 to 3; -CH2Si(R C )2CH2-;-CH2Ge(R C)2CH2-; -CH(CH3)CH2CH*(CH3); and -CH2(phenyl-1,2-diyl)CH2-; wherein each R in L C is (C1-C 20 ) hydrocarbon group.

[0066] This type (C1-C 12 Examples of alkyl groups include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl, cyclopentyl, or cyclohexyl, butyl, tert-butyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, decyl, undecyl, and dodecyl.

[0067] In some embodiments, in the metal-ligand complex according to formula (I), R 8 and R 9 In other embodiments, R 8 and R 9 One of them is methyl, and R 8 and R 9 The other one is -H.

[0068] In the metal-ligand complex according to formula (I), X is bonded to M via a covalent bond or an ionic bond. In some embodiments, X is a fluorine, chlorine, bromine or iodine atom.

[0069] In one or more embodiments, M is scandium, yttrium, a lanthanide metal. The lanthanide metal can be lanthanum, cesium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium.

[0070] In the metal-ligand complex according to formula (I), each T is bonded to M by 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 an ionic substance that can donate an electron pair to an acceptor compound. For the purposes of this embodiment, the acceptor compound is M, which is the metal of the metal-ligand complex of formula (I). The Lewis base can be neutral or anionic. In some embodiments, the Lewis base can be a heterohydrocarbon or a hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cyclic ethers, or sulfides. Examples of anionic hydrocarbons include, but are not limited to, cyclopentadiene. Examples of neutral hydrocarbons include, but are not limited to, 1,3-butadiene.

[0071] In one or more embodiments, the Lewis base can be a monodentate ligand, which can be a neutral ligand. In some embodiments, the neutral ligand can contain a heteroatom. In a specific embodiment, the neutral ligand is a neutral group, such as R T NR K R L, R K OR L , R K SR L or R T PR K R L , where each R T are independently hydrogen, [(C1-C 10 )alkyl]3Si(C1-C 10 ) hydrocarbon group, (C1-C 40 )alkyl, [(C1-C 10 )alkyl]3Si or (C1-C 40 ) heteroalkyl, and each R K and R L Independently as defined previously.

[0072] In some embodiments, the Lewis base is (C1-C 20 In some embodiments, the Lewis base is cyclopentadiene or 1,3-butadiene.

[0073] In various embodiments, the Lewis base is (C1-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).

[0074] In a specific embodiment 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 one of the metal-ligand complexes 1-12 of the present invention:

[0075]

[0076]

[0077] Olefin Growth

[0078] When the ligand X is a halogen atom, the metal-ligand complex of the present disclosure cannot initiate olefin growth. It is believed that the halogen atom X is transferred to the co-catalyst, and the alkyl group of the co-catalyst is transferred to the metal center M. Once the alkyl group ligand is present, growth (i.e., polymerization) can begin. In addition and without being bound by theory, it is believed that when the Lewis base T coordinates with the metal center M of formula (I), the metal-ligand catalyst is not effective. Therefore, it is believed that during the olefin growth process, the Lewis base dissociates from the metal center M, and the metal-ligand complex has a structure according to formula (Ia):

[0079]

[0080] In formula (Ia), R 1To R 16 , M and L are as defined in formula (I). P is a hydrocarbon group, wherein the hydrocarbon group is branched or unbranched, and has at least 30 carbon atoms. More specifically, X P It is a growing olefin chain.

[0081] Additive components

[0082] In some embodiments, the catalyst system comprises one or more additives. In some embodiments, the additive acts as a co-catalyst, an alkylating agent, a Lewis acid or a Lewis base. In other embodiments, the additive is used as a scavenger or a scavenger. A co-catalyst is a reagent that cooperates with a 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 co-catalyst. However, it is also believed that a co-catalyst can promote the dissociation of the metal center of a Lewis base and a metal-ligand complex.

[0083] Scavengers clean the reactor of impurities prior to the addition of the precatalyst and therefore do not constitute an activator. Lower loadings of aluminoxanes do not act as cocatalysts, instead, they act as scavengers.

[0084] Without wishing to be bound by theory, it is believed that the metal-ligand complex of formula (I) is not an active species unless the alkylating agent exchanges an alkyl group for the halogen (particularly X) coordinated to the center M. When the metal-ligand complex of formula (I) is alkylated and the Lewis base is dissociated, the complex is active and can polymerize olefin monomers.

[0085] In one or more embodiments, the alkylating agent may be selected from methyl-modified aluminoxanes (MMAO) or alkyl aluminum compounds.

[0086] In some embodiments, additives may include, but are not limited to, alkylaluminums; polymeric or oligomeric aluminoxanes (also referred to as alumoxanes); 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" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or dialkylaluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0087] In some embodiments, the additive is a compound containing (C1-C 20 ) hydrocarbyl substituent Lewis acid Group 13 metal compound. In some embodiments, the additive includes tri((C1-C 20 ) alkyl) substituted aluminum or tri((C1-C20 In other embodiments, the additive is selected from tri(hydrocarbyl)substituted aluminum, tri((C1-C 20 )alkyl)-boron compounds, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 )aryl)boron compounds and their halogenated (including perhalogenated) derivatives.

[0088] In one or more embodiments, the polymerization method further comprises a borane or borate-based additive. In some embodiments, the borane-based additive is selected from tri(fluoro-substituted phenyl)borane, tri(pentafluorophenyl)borane. In some embodiments, the cocatalyst is tri((C1-C 20 )alkyl)ammonium tetra((C1-C 20 )alkyl) borate (e.g., bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to a nitrogen cation, which is ((C1-C 20 )alkyl)4N + 、((C1-C 20 )alkyl)3N(H) + 、((C1-C 20 )alkyl)2N(H)2 + 、(C1-C 20 )Hydrocarbon N(H)3 + or N(H)4 + , where each (C1-C 20 ) The hydrocarbon groups may be the same or different (when there are two or more).

[0089] In one or more embodiments, the additive can be selected from polymeric or oligomeric aluminoxanes, especially methylaluminoxane, and inert, compatible, non-coordinating ion-forming compounds. Exemplary suitable additives include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1-)ammonium, triethylaluminum, butylated hydroxytoluene, diethylaluminum, bis-(butylated hydroxytoluene)ethylaluminum, tri-(butylated hydroxytoluene)aluminum, and combinations thereof.

[0090] In some embodiments, the alkylaluminum material is triisobutylaluminum (TiBAl) or aluminoxane. The alkylaluminoxane can be (C1-C 10 ) alkylaluminoxane or a polymeric form of polymethylaluminoxane (PMAO). PMAO may be polymethylaluminoxane with improved performance (PMAO-IP), which is commercially available from AkzoNobel. (C1-C 10The alkylaluminoxane may be methylaluminoxane (MAO), modified methylaluminoxane (MMAO) (e.g., 3A type (MMAO-3A), 7 type (MMAO-7), or 12 type (MMAO-12) modified methylaluminoxane), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, or 1-methylcyclopentylaluminoxane. The arylaluminoxane may be (C6-C 10 ) Arylaluminoxane, which may be phenylaluminoxane, 2,6-dimethylphenylaluminoxane, or naphthylaluminoxane.

[0091] In some embodiments, one or more co-catalysts may be used in combination with one another. Specific examples of co-catalyst combinations are tri((C1-C8) hydrocarbyl)aluminum, tri((C1-C4) hydrocarbyl)borane, tri((C6 ... 18 ) aryl) borane or ammonium borate and a mixture of oligomeric or polymeric aluminoxane compounds. The ratio of the total moles of one or more metal-ligand complexes of formula (I) to the total moles of one or more co-catalysts in the co-catalyst is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When aluminoxane is used alone as a co-catalyst, preferably, the ratio of Al of aluminoxane to the metal of the metal-ligand complex of formula (I) (Al / M) is at least 20. In some other embodiments, when tris(pentafluorophenyl)borane is used alone as a co-catalyst, the ratio of the moles of tris(pentafluorophenyl)borane used 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.

[0092] Catalyst system components

[0093] 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 comprises a bis-biphenylphenoxy Group IV metal-ligand complex, a procatalyst, which can impart catalytic activity when contacted with an activator of the present disclosure.

[0094] According to some embodiments, the bis-biphenylphenoxy Group IV metal-ligand complex has a structure according to Formula (X):

[0095]

[0096] 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 ligand or a bidentate ligand, and when the subscript n is 2, each X X In formula (X), each Z is independently selected from -O-, -S-, -N(R N )-or-P(R P )-;R 2-4 , R 5-8 , R 9-12 and R 13-15 Independently selected from the group consisting of: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -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)- and halogen. 1 and R 16 is selected from a group having formula (XI), a group having formula (XII) and a group having formula (XIII):

[0097]

[0098] In formulae (XI), (XII) and (XIII), R 31 To R 35 , R 41 To R 48 and R 51 To R 59 Each of which is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(RN )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.

[0099] In one or more embodiments, in Formula (X), each X X It can be a monodentate ligand that is independent of any other ligand X X , is halogen, unsubstituted (C1-C 20 ) alkyl, unsubstituted [(C1-C 20 )alkyl]C(O)O- or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 20 ) hydrocarbon group, (C1-C 20 In some embodiments, X X is a phenyl group, a benzyl group, a chlorine atom, (C1-C 10 )alkyl or -CH2Si(R XV )3, where R XV is (C1-C 20 )alkyl.

[0100] Other bis-biphenylphenoxy Group IV metal-ligand complexes that can be used in combination with the bimetallic activators in the catalyst systems of the present disclosure will be apparent to those skilled in the art.

[0101] In one or more embodiments, the Group IV metal-ligand complex comprises a constrained geometry Group IV complex having a structure according to Formula (XV):

[0102]

[0103] In formula (XV), M 2 is titanium, hafnium or zirconium. (X y ) b The subscript b is 1, 2, or 3. Each X y are independently selected from unsaturated (C2-C 50 ) hydrocarbons, unsaturated (C2-C50 ) heterohydrocarbons, saturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (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 electrically neutral as a whole.

[0104] In one or more embodiments, each X y It can be a monodentate ligand that is independent of any other ligand X y , is halogen, unsubstituted (C1-C 20 ) alkyl, unsubstituted [(C1-C 20 )alkyl]C(O)O- or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 20 ) hydrocarbon group, (C1-C 20 In some embodiments, X y is a phenyl group, a benzyl group, a chlorine atom, (C1-C 10 )alkyl or -CH2Si(R XV )3, where R XV is (C1-C 20 )alkyl.

[0105] In formula (XV), Cp is selected from the group consisting of cyclopentadienyl and R S The group consisting of substituted cyclopentadienyl groups, the Cp is η 5 The bonding mode of M is combined with R S Independently selected from the group consisting of: (C1-C 20 )alkyl, (C1-C 20 ) heteroalkyl, (C1-C 20 ) aryl or R S Substituents (C1-C 20 ) aryl, (C1-C 20 ) heteroaryl or R S Substituents (C1-C 20 ) heteroaryl, wherein two adjacent R S The groups are optionally linked to form a ring.

[0106] In Formula (XV), N is nitrogen; Y is carbon or silicon; wherein Y is covalently bonded to Cp; and R1 and R 2 are independently selected from -H, (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl; and R 3 Independently selected from (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl.

[0107] Other catalysts, especially catalysts comprising one or more other Group IV metal-complexes not specifically listed above, will be apparent to those skilled in the art.

[0108] Catalyst system characteristics

[0109] As described herein, the reactivity ratio r1 (as further defined below) of the main catalyst comprising a metal-ligand complex of formula (I) and one or more co-catalysts is in the range of greater than 100, for example, in the range of greater than 150, greater than 200, greater than 300 or greater than 500.

[0110] A terminal copolymerization model is used for random copolymers in which the properties of the last monomer inserted determine the rate of subsequent monomer insertion. In this model, the type of insertion reaction is

[0111]

[0112] Among them, C * Represents catalyst, M i represents monomer i, and k ij is the rate constant with the following rate equation:

[0113]

[0114] The comonomer mole fraction (i=2) in the reaction medium is defined by the following equation:

[0115]

[0116] A simplified equation for comonomer composition can be derived as disclosed in George Odian, Principles of Polymerization, 2nd Edition, John Wiley and Sons, 1970, as follows:

[0117]

[0118] For 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:

[0119]

[0120] Alternatively, in the penultimate copolymerization model, the properties of the last two monomers inserted into the growing polymer chain determine the rate of subsequent monomer insertion. The polymerization reaction takes the form

[0121]

[0122] And the individual rate equations are:

[0123]

[0124] The comonomer content can be calculated (again as disclosed in George Odian, Supra.) as:

[0125]

[0126] where X is defined as:

[0127]

[0128] And the reactivity ratio is defined as:

[0129]

[0130] Also for this model, the polymer composition is simply a function of the temperature-dependent reactivity ratio and the mole fraction of the comonomer in the reactor. This is also true when reverse comonomer or monomer insertion may occur, or in cases where more than two monomers are copolymerized.

[0131] The reactivity ratios used in the foregoing models can be predicted using well-known theoretical techniques or derived empirically from actual polymerization data. Suitable theoretical techniques are disclosed, for example, in BG Kyle, "Chemical and Process Thermodynamics", 3rd edition, Prentice-Hall, 1999, and in the Redlich-Kwong-Soave (RKS) Equation of State, Chemical Engineering Science, 1972, pp. 1197-1203. Commercially available software programs can be used to assist in deriving the reactivity ratios from experimentally derived data. An example of such software is Aspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, MA 02141-2201, USA.

[0132] Thus, the method for producing ethylene-based polymers according to the present invention selectively produces polyethylene-rich (e.g., high density polyethylene) or polyethylene-rich segments of poly(ethylene alpha-olefin) copolymers in the presence of alpha-olefins, which are therefore substantially unpolymerized. The method for producing ethylene-based polymers employs olefin polymerization conditions. In some embodiments, the olefin polymerization conditions independently produce an in-situ catalyst formed by reacting a primary catalyst comprising a metal-ligand complex of formula (I) with one or more co-catalysts in the presence of one or more other ingredients. Such other ingredients include, but are not limited to, (i) an olefin monomer; (ii) another metal-ligand complex of formula (I); (iii) one or more of the 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.

[0133] In particular, the catalyst of the invention is useful in a process for producing ethylene-based polymers in the presence of (C3-C 40 ) α-olefins, wherein the high selectivity is characterized by the reactivity ratio r1 described previously. Preferably, for 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, even more preferably greater than 200. When the reactivity ratio r1 of the process of the present invention approaches infinity, the incorporation of α-olefins in (or on) the resulting polyethylene-enriched polyethylene approaches 0 mole percent (mol%).

[0134] As described herein, the catalytic efficiency of the catalyst composition of the present invention comprising a procatalyst and one or more cocatalysts is in the range of greater than 1000,000 g polymer / g active metal center; for example, greater than 2000,000 g polymer / g active metal center. The catalytic efficiency is measured based on 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, such as in the range of 170°C to 195°C, and the ethylene concentration is greater than 5 g / L, such as greater than 6 g / L, and wherein the ethylene conversion is greater than 70%, such as greater than 80%, or alternatively, greater than 90%.

[0135] Polyolefins

[0136] The catalytic system described in the present disclosure can be used for polymerizing olefins, mainly ethylene, propylene, α-olefins, such as octene and diene. In some embodiments, there is only a single type of olefin or α-olefin in the polymerization scheme, thereby forming a homopolymer. However, other α-olefins can be incorporated into the polymerization procedure. Other α-olefin comonomers generally have no more than 20 carbon atoms. For example, α-olefin comonomers can 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 can be selected from the group consisting of the following items: propylene, 1-butene, 1 hexene and 1-octene; or in an alternative, selected from the group consisting of the following items: 1-hexene and 1 octene.

[0137] Ethylene-based polymers, e.g., homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers (such as α-olefins), can contain at least 50 mole % (mol%) of monomeric units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 mole %" are disclosed herein as separate embodiments; for example, ethylene-based polymers, i.e., homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, can contain at least 60 mole % (mol %) of monomeric units derived from ethylene; at least 70 mole % of monomeric units derived from ethylene; at least 80 mole % of monomeric units derived from ethylene; or 50 to 100 mole % of monomeric units derived from ethylene; or 80 to 100 mole % of monomeric units derived from ethylene.

[0138] In some embodiments, the catalyst system can produce an ethylene-based polymer comprising at least 90 mol % of units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed as separate embodiments herein. For example, an ethylene-based polymer may include at least 93 mol % of units derived from ethylene; at least 96 mol % of units; at least 97 mol % of units derived from ethylene; or alternatively, 90 mol % to 100 mol % of units derived from ethylene; 90 mol % to 99.5 mol % of units derived from ethylene; or 97 mol % to 99.5 mol % of units derived from ethylene.

[0139] In some embodiments, the amount of additional α-olefins in the ethylene-based polymer produced by the catalyst system is less than 50 mole percent (mol%); in other embodiments, the amount of additional α-olefins comprises at least 0.01 mol% to 25 mol%; and in other embodiments, the amount of additional α-olefins comprises at least 0.1 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0140] Ethylene-based polymers can be produced by other conventional polymerization processes, which include catalyst systems according to embodiments of the present disclosure. Such conventional polymerization processes include, but are not limited to, for example, solution polymerization, gas phase polymerization, slurry phase polymerization, 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 in parallel or in series, or any combination thereof.

[0141] In one embodiment, ethylene-based polymers can be produced by solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more cocatalysts. In another embodiment, ethylene-based polymers can be produced by solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more other catalysts in the present disclosure. The catalyst system as described herein can be optionally used in combination with one or more other catalysts for the first reactor or the second reactor. In one embodiment, ethylene-based polymers can be produced by solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described herein in these two reactors.

[0142] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system (e.g., a single loop reactor system) wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described within the present disclosure and optionally one or more cocatalysts as described in the preceding paragraphs.

[0143] Ethylene-based polymers may also include one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. Ethylene-based polymers may contain any amount of additives. Based on the weight of the polymer of ethylene and one or more additives, the polymer based on ethylene may contain about 0% to about 10% of such additives by combined weight. Ethylene-based polymers may further include fillers, which may include, but are not limited to, organic or inorganic fillers. Based on the combined weight of the polymer of ethylene and all additives or fillers, the polymer based on ethylene may contain about 0% by weight to about 20% by weight of fillers, such as calcium carbonate, talcum powder, or Mg(OH)2. Ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0144] In some embodiments, a polymerization process for producing an ethylene-based polymer may comprise 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). The density of a polymer produced by such a catalyst system incorporating a metal-ligand complex of formula (I) may be, for example, 0.850 g / cm according to ASTM D792 (incorporated herein by reference in its entirety). 3 Up to 0.970g / cm 3 、0.870g / cm 3 Up to 0.950g / cm 3 、0.870g / cm 3 Up to 0.920g / cm 3 or 0.870g / cm 3 Up to 0.900g / cm 3 .

[0145] In an embodiment, the melt flow ratio (I) of the polymer produced by the catalyst system comprising the metal-ligand complex of formula (I) is 10 / I2) is 5 to 15, wherein the melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190°C and a load of 2.16 kg, and the melt index I 10It is measured according to ASTM D1238 at 190°C and 10 kg load. In other embodiments, the melt flow ratio (I 10 / I2) is 5 to 10, and in other embodiments, the melt flow ratio is 5 to 9.

[0146] In some embodiments, the melt index (I2) of the polymer produced by the catalyst system comprising the metal-ligand complex of formula (I) is from 0.1 to 100, wherein the melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190°C and 2.16 kg load.

[0147] In some embodiments, the polymer produced by the catalyst system including the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 1.0 to 25, wherein MWD is defined as M w / M n , where M w is the weight average molecular weight, and M n is the number average molecular weight. In other embodiments, the polymer produced by the catalyst system has an MWD of 1.5 to 6. Another embodiment includes an MWD of 1.5 to 3; and other embodiments include an MWD of 2 to 2.5.

[0148] SymRAD HT-GPC Analysis

[0149] Molecular weight data were determined by analysis on a hybrid robotic-assisted dilution high temperature gel permeation chromatograph (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 by 300 ppm of butylated hydroxytoluene (BHT) by heating at 160°C for 120 minutes. Each sample was diluted to 1 mg / mL immediately before injecting a 250 μL aliquot of the sample. The GPC was equipped with two Polymer Labs PLgel 10 μm MIXED-B columns (300 x 10 mm) with a flow rate of 2.0 mL / min at 160°C. Sample detection was performed using a PolyChar IR4 detector in concentrated mode. Conventional calibration with narrow polystyrene (PS) standards was used, adjusted to apparent units of homopolymer polyethylene (PE) using the known Mark-Houwink coefficients of PS and PE in TCB at this temperature.

[0150] IR Analysis of 1-Octene Incorporation

[0151] Samples for HT-GPC analysis were run prior to IR analysis. For IR analysis, 48-well HT silicon wafers were utilized to deposit and analyze samples for 1-octene incorporation. For this analysis, the samples were heated to 160°C for less than or equal to 210 minutes; the samples were reheated to remove the magnetic GPC stir bar and oscillated with a glass stir bar on a J-KEM Scientific heated mechanical oscillator. The samples were deposited while heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene was evaporated from the deposited wafer holes at 160°C under a nitrogen purge. Analysis of 1-octene was performed on HT silicon wafers using a NEXUS 670E.SPFT-IR.

[0152] Differential Scanning Calorimetry (DSC)

[0153] Differential scanning calorimetry (DSC) is used to measure Tm, Tc, Tg and crystallinity in ethylene (PE) samples and propylene (PP) samples. Each sample (0.5g) is compressed into a film at 5000psi, 190°C for two minutes. About 5mg to 8mg film samples are weighed and placed in a DSC pan. The lid is screwed on the pan to ensure a closed atmosphere. The sample pan is placed in a DSC unit and then heated to a temperature of 180°C for PE (for PP, heated to 230°C) at a rate of about 10°C / min. The sample is kept at this temperature for three minutes. Then, the sample is cooled to -90°C (for PP, cooled to -60°C) at a rate of 10°C / min for PE, and isothermally kept at the temperature for three minutes. The sample is then heated at a rate of 10°C / min until fully melted (second heating). Unless otherwise stated, the melting point (Tm) and glass transition temperature (Tg) of each polymer are determined from the second heating curve, and the crystallization temperature (Tc) is determined from the first cooling curve. The corresponding peak temperatures of Tm and Tc are recorded. The percentage of crystallinity can be calculated by dividing the heat of fusion (Hf) determined from the second heating curve by the theoretical heat of fusion of 292 J / g for PE (165 J / g for PP) and multiplying this number by 100 (e.g., % crystallinity = (Hf / 292 J / g) × 100 (for PE)).

[0154] Example

[0155] Examples 1 to 10 are synthetic procedures for intermediates for the ligands, for the ligands themselves, and for isolated metal-ligand complexes containing these ligands. Example 11 describes the polymerization results obtained from the metal-ligand complexes prepared according to Examples 1 to 10. It should be understood that Examples 1 to 10 are provided to illustrate the embodiments described in the present disclosure and are not intended to limit the scope of the present disclosure or the claims thereto.

[0156] Example 1—Synthesis of Metal-Ligand Complex 1 (MLC-1)

[0157]

[0158] In a nitrogen-filled glove box, ScCl (0.024 g, 0.16 mmol, 1 equivalent) and 6 mL THF were loaded into a vial. The mixture was stirred at 50 ° C for 2 hours, and then the ligand i (0.200 g, 0.16 mmol, 1 equivalent) in solid form was added, followed by Et N (0.22 mL, 1.59 mmol, 10 equivalents). The reaction mixture was heated to 50 ° C and stirred for one hour. The reaction mixture was evaporated under vacuum to dryness, and the residue was extracted with 10 mL hexane. After filtering through diatomite, the filtrate was evaporated under vacuum to obtain a white solid. 1 H NMR showed the desired product and traces of Et3N. The product was redissolved in hexanes (~8 mL) and evaporated to dryness under vacuum. 1 H NMR did not detect amine in the resulting white solid. The yield was quantitative when taking into account the sample taken for NMR.

[0159] 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).

[0160] 19F NMR (376MHz, C6D6) δ-115.56,-116.20.

[0161] The preparation of the ligand of formula i is detailed in WO2014105411 A1.

[0162] Example 2—Synthesis of Metal-Ligand Complex 2 (MLC-2)

[0163]

[0164] In a nitrogen-filled glove box, ScCl (0.111 g, 0.73 mmol, 1.15 eq) and 30 mL THF were loaded into a vial. Ligand ii (1.000 g, 0.64 mmol, 1 eq) was added in solid form, followed by Et N (0.89 mL, 6.38 mmol, 10 eq). The reaction mixture was heated to 50 ° C and stirred for 4 hours. A small sample was taken, evaporated to dryness under vacuum, mixed with C D and purified by 1 H and 19 F NMR inspection.Only about 85% conversion into product was observed.Add more Et3N (0.89mL, 6.38mmol, 10 equivalents), the reaction was heated to 60°C and stirred for 3 hours.The sample did not show changes.The temperature was reduced to 50°C and more ScCl3 (0.014g, 0.10mmol, 0.15 equivalents) was added.After 1.5 hours, the sample showed that ~97% was converted into product.The reaction mixture was cooled to 25°C and evaporated to dryness overnight under vacuum.The solid was ground with pentane (10mL) and evaporated to dryness under vacuum.Then the solid was extracted with pentane (100mL), filtered through a diatomaceous earth pad and the solvent was removed from the filtrate under vacuum to obtain the product (0.260g) as a white solid.The filter cake was washed with toluene (40mL), 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).

[0165] Overall yield adjusted for removed NMR samples: 1.02 g, 93%.

[0166] 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).

[0167] 19 F NMR(376MHz,C6D6)δ-115.63,-116.04.

[0168] The preparation of the ligand of formula i is detailed in WO2014105411 A1.

[0169] Example 3—Synthesis of Metal-Ligand Complex 3 (MLC-3)

[0170]

[0171] In a N2 filled glove box, ScCl3 (9.6 mg, 0.063 mmol, 1.00 equiv) and 3 mL of anhydrous THF were loaded into a 20 mL vial. Add formula (iii) ligand (86 mg, 0.063 mmol, 1.00 equiv) followed by triethylamine (0.090 mL, 10 equiv). The mixture was stirred overnight at 50 ° C. The solution was cooled and filtered through a 0.45 um syringe filter. The filtrate was concentrated to dryness. The solid was suspended in 2 mL of hexane. The white solid was precipitated and separated by filtration (60.6 mg, 64%).

[0172] 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,2H),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)。

[0173] 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 5.36,135.29,134.78,134.50,134.40,134.27,133.96,133.82,133.74,133.57,133.5 0.131.14,131.03,130.55,129.28,129.24,128.90,128.68,128.58,128.56,128.40.1 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

[0174] 19 F NMR(471MHz,C6D6)δ-115.80(t,J68.8Hz),-116.12(t,J9.0Hz).

[0175] Example 3-1—2,7-bis(dimethyl(phenyl)silyl)-9-(5-methyl-2-((tetrahydro-2H-pyran-2- Synthesis of (4-(2-( ...

[0176]

[0177] In a N2-filled glove box, 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 anhydrous toluene and DMEDA (0.877 mL, 8.15 mmol, 71.0 mol%). A coil reflux condenser was connected to the round-bottom flask, and the reaction mixture was stirred at 120°C in the glove box for 24 hours. The solution was cooled, and the reaction mixture was filtered. The filter cake was rinsed with several portions of dichloromethane. The filtrate was concentrated and the residue was purified by silica gel chromatography (0% to 50% dichloromethane / hexanes) to give the desired product (3.06 g, 43%).

[0178] 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).

[0179] 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.

[0180] The preparation of 2,7-bis(dimethyl(phenyl)silyl)-9H-carbazole is described in detail in WO 2021155158.

[0181] Example 3-2—Synthesis of ligand of formula (iii)

[0182]

[0183] 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 anhydrous THF. The solution was placed under nitrogen and cooled to -78 °C. n-Butyl lithium (2.5 M in hexanes, 16.7 mL, 41.8 mmol, 1.10 equiv) was added dropwise. The mixture was slowly warmed to 0 °C and stirred for 90 minutes. A white solid precipitated during this time. 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.

[0184] The solution was quenched with aqueous ammonium chloride and the product was extracted with several portions of 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.

[0185] A 500 mL round bottom flask was charged with borate (2.2 eq), 1,2-bis(2-bromo-4-fluoro-6-methylphenoxy)ethane (7.50 g, 17.2 mmol, 1.00 eq) and Pd(Amphos)Cl2 (609 mg, 0.860 mmol, 5.00 mol%). A reflux condenser was connected and the unit was placed under a nitrogen blanket. 170 mL of anhydrous, degassed THF was added followed by a nitrogen-bubbled aqueous solution of K3PO4 (2.0 M in water, 51.6 mL, 0.103 mol, 6.00 eq). The mixture was stirred at 70 °C overnight.

[0186] The solution is cooled down, and each phase is separated. The aqueous phase is extracted with several parts of dichloromethane. The organic fractions merged are washed with salt water, dried with Na2SO4, and filtered through a silica gel plug. The filtrate is concentrated to obtain a crude oil. The oil is dissolved in 150mLTHF, 50mL MeOH and 25mL 6M HCl. The mixture is refluxed for 3 hours. The solution is cooled down, and diluted with dichloromethane and salt water. Each phase is separated, and the aqueous phase is extracted with several parts of dichloromethane. The organic fractions merged are washed with sodium bicarbonate aqueous solution. The organic phase is dried and concentrated with Na2SO4. The residue is purified by silica gel chromatography (0% to 10% EtOAc / hexane), to obtain 19.73g product (85%).

[0187] 1H 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).

[0188] 13 C 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.

[0189] 19 F NMR (471MHz, CDCl3) δ-117.74 (t, J=7.7Hz).

[0190] Example 4—Synthesis of Metal-Ligand Complex 4 (MLC-4)

[0191]

[0192] In a N2 filled glove box, ScCl3 (35.1mg, 0.232mmol, 1.00 equivalent) and 11mL anhydrous THF were loaded into a 20mL vial. Add formula (iv) ligand (421mg, 0.232mmol, 1.00 equivalent), followed by triethylamine (0.33mL, 10 equivalents). The mixture was stirred overnight at 50°C. Add another 7mg ScCl3 and 0.066mL triethylamine. Continue stirring for 6 hours. At this point, NMR showed that the starting material was consumed. The solution was cooled in a glove box freezer and filtered through a 0.45um syringe filter. The filtrate was concentrated to dryness. The solid was mixed with 3mL anhydrous hexane, and the liquid was removed by decantation. The solid was rinsed with two other portions of hexane. The final white solid was dried to obtain 0.371g material (81%).

[0193] 1 H 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)。

[0194] 13C NMR(126MHz,C6D6)δ161.52,160.99,159.57,159.03,155.78,155.66,149.23,149.21,149.00,148.97,142.80,142.02,141.20,141.02,138.08,137.26,137.11,137.01,136.95,136.89,136.75,136.69,136.43,136.03,135.96,135.79,135.78,135.76,135.71,135.68,135.65,135.55,135.48,135.44,135.42,135.37,135.28,134.75,134.68,133.21,132.39,132.33,129.67,129.53,129.29,129.23,129.07,129.04,129.00,128.84,128.79,128.60,128.47,128.08,128.05,127.19,126.76,126.69,126.58,126.23,126.10,125.46,124.75,124.25,123.28,120.56,120.21,120.10,120.00,119.36,119.23,118.60,117.74,117.63,117.10,116.92,115.99,115.81,115.47,115.30,77.65,75.20,72.25,57.37,56.69,37.53,37.43,34.62,32.73,32.30,32.11,32.09,31.67,31.63,31.60,30.16,30.13,30.05,29.97,24.29,22.68,17.15,16.17,13.97,-2.67,-2.91,-2.95。

[0195] 19 F NMR(471MHz,C6D6)δ-115.59(t,J=8.5Hz),-115.92(t,J=8.1Hz)。

[0196] Example 4-1—Synthesis of 2,7-bis(methyldiphenylsilyl)-9H-carbazole

[0197]

[0198] In a N2-filled glove box, 2,7-dithio-9-(tert-butyldimethylsilyl)-9H-carbazole (2.00 g, 6.82 mmol, 1.00 equiv) and 34 mL of anhydrous THF were charged into a 50 mL wide-mouth bottle. Chloromethyldiphenylsilane (3.01 mL, 14.3 mmol, 2.10 equiv) was added, and the mixture was stirred for 45 minutes. As the reaction proceeded, the solid organolithium dissolved rapidly.

[0199] The colorless transparent solution was quenched with aqueous ammonium chloride. The product was extracted with several portions of dichloromethane. The combined organic fractions were concentrated. The solution was dried over Na2SO4, filtered through basic alumina, and concentrated to a white solid. Crude oil was isolated.

[0200] Carbazole is dissolved in 34mL THF and treated with tetrabutylammonium fluoride trihydrate (2.15g, 6.82mmol, 1.00 equivalent). The mixture is stirred for 20 minutes, and the aqueous solution is quenched with NaHCO3 aqueous solution. The product is extracted with several portions of dichloromethane. The combined organic fractions are concentrated, and the residue is purified by silica gel chromatography (0% to 20% EtOAc / hexane). 2.213g product (58%, by two steps) is isolated as a white solid.

[0201] 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).

[0202] 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.

[0203] Example 4-2—2,7-bis(methyldiphenylsilyl)-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)- Synthesis of 5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole

[0204]

[0205] In a N2-filled glove box, 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 anhydrous toluene DMEDA (8.74 mL, 81.2 mmol, 71.0 mol%) were charged into a 1000 mL round-bottom flask. A coil reflux condenser was connected, and the reaction mixture was stirred at 120°C. After 6.5 hours, partial conversion was observed by TLC. Another batch / lot of CuI and DMEDA (22% and 71% respectively) was added.

[0206] 24 hours after the start of the reaction, another batch of CuI and DMEDA (22% and 71%, respectively) and 10 g of iodide were added. Stirring was continued for 24 hours.

[0207] The solution was cooled and filtered to remove solids. The solid filter cake was rinsed with dichloromethane (3 × 100 mL). The filtrate was concentrated and the residue was purified by silica gel chromatography (0% to 10% EtOAc / hexane). The white solid residue was separated and suspended in 250 mL of cold hexane. The slurry was filtered to remove the block solids, and the solid was rinsed with another hexane portion (3 × 50 mL). The solid was dried under vacuum to obtain 78.369 g of the product (81%) as a clean white solid.

[0208] 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).

[0209] 13C 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.

[0210] Example 4-3—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- Synthesis of Carbazole

[0211]

[0212] 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 anhydrous THF. The solution was placed under nitrogen and cooled to -78 °C. n-Butyl lithium (2.5 M in hexanes, 40.2 mL, 100.5 mmol, 1.10 equiv) was added dropwise. The mixture was slowly warmed to 0 °C and stirred for 90 minutes. During this time a white solid precipitated.

[0213] 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 hour. The solution was quenched with aqueous ammonium chloride and the product was extracted with several portions of dichloromethane. The combined organic fractions were dried with Na2SO4 and concentrated to a white solid (87.92 g). This material was used without further purification.

[0214] 1H NMR(500MHz,CDCl3)δ8.09(dd,J=7.7,2.4Hz,2H),7.74(d,J=2.6Hz,1H),7.60-7.39(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),1.12(dt,J=19.2,10.0Hz,3H),0.94-0.85(m,1H),0.82(d,J=6.5Hz,6H),0.64(s,9H)。

[0215] 13 C NMR(126MHz,CDCl3)δ155.94,145.59,140.96,140.85,136.71,136.67,136.65,136.62,135.28,135.26,135.22,135.19,134.04,133.27,132.96,129.99,129.12,129.08,129.07,128.85,127.79,127.72,127.71,127.69,126.05,125.92,124.09,123.66,119.54,119.47,118.20,117.28,101.22,83.51,60.97,56.84,38.22,32.29,31.75,31.59,31.01,29.89,25.03,24.99,24.77,18.09,-3.09。

[0216] Example 4-4—Synthesis of ligand of formula (iv)

[0217]

[0218] 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)Cl2 (456 mg, 0.644 mmol, 5.00 mol%). A reflux condenser was attached and the unit was placed under a nitrogen blanket. Degassed, anhydrous THF (128 mL) was added, followed by a nitrogen-bubbled aqueous solution of K3PO4 (2.0 M in water, 38.7 mL, 77.3 mmol, 6.00 equiv). The mixture was stirred at 70°C overnight.

[0219] The solution is cooled and diluted with dichloromethane and salt solution. The aqueous phase is extracted with several portions of dichloromethane. The organic fractions combined are concentrated and the residue is purified by silica gel chromatography (0% to 10% EtOAc / hexane) to obtain about 24g of white solid. The white solid is dissolved in 128mL THF, 12.8mL MeOH and 4.3mL 6M HCl. The mixture is stirred at 50 ℃ overnight.

[0220] The solution was cooled and diluted with 100 mL of dichloromethane and saturated sodium bicarbonate aqueous solution. The phases were separated and the aqueous phase was extracted with several additional portions of dichloromethane. The organic phase was separated, concentrated and the residue was purified by silica gel chromatography (0% to 10% EtOAc / hexane). The residue was heated in 200 mL of acetonitrile and then cooled. A clean white solid was isolated by filtration and dried under vacuum. 19.16 g of product (82%) was isolated.

[0221] 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).

[0222] 13C 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.

[0223] 19 F NMR (471MHz, CDCl3) δ-118.20.

[0224] Example 3—Synthesis of Metal-Ligand Complex 3 (MLC-3)

[0225] Synthesis of 2,7-dibromo-9-(tert-butyldimethylsilyl)-9H-carbazole-2,7-dibromo-9H-carbazole:

[0226]

[0227] In a glove box, 2,7-dibromo-9H-carbazole (50.0 g, 154 mmol, 1 equivalent) was loaded into a glass jar with a stirring rod, followed by anhydrous THF (300 mL). Sodium hydride powder (90%) (4.5 g, 169 mmol, 1.1 equivalents) was slowly added to the solution in batches over a 30-minute period. After stirring at room temperature for 60 minutes, tert-butyldimethylsilyl chloride (44.2 g, 231 mmol, 1.5 equivalents) was added to the reaction mixture. The solution was stirred at room temperature for 17 hours. The reaction mixture was taken out of the glove box, and THF was evaporated and filtered through a glass frit funnel. The white solid was then washed with 25 mL of THF, and the white solid was transferred to a 50 mL jar. 40 mL of water was added to the jar 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 glass frit funnel, and acetone was added to wash the filter cake. The white solid was then transferred into 500 mL RB and the solid was dried under vacuum overnight. Yield (62.5 g, 93%).

[0228] 1H NMR (500 MHz, chloroform-d) δ7.85 (dd, J = 8.3, 1.7 Hz, 2H), 7.73 (d, J = 1.8 Hz, 2H), 7.35 (dd, J = 8.2, 2.2 Hz, 2H), 1.05 (d, J = 1.9 Hz, 9H), 0.76 (d, J = 1.8 Hz, 6H).

[0229] 13 C NMR (126MHz, CDCl3) δ146.2, 124.8, 123.4, 121.0, 119.4, 117.3, 26.7, 20.6, -1.1.

[0230] Synthesis of 2,7-Bis(triisobutylsilyl)-9H-carbazole :

[0231]

[0232] 2,7-dibromo-9-(tert-butyldimethylsilyl)-9H-carbazole (24 g, 55 mmol, 1 equivalent) and 250 mL of anhydrous THF were loaded into a 500 mL round-bottom flask. RB was kept under a nitrogen atmosphere and stirred at -78 ° C for 15 minutes. Then a solution of 2.5 M n-BuLi in hexane (46 mL, 114.7 mmol, 2.1 equivalents) was added dropwise to the reaction mixture for 15 minutes. The solution color turned pale yellow and became a heterogeneous white slurry. Since the generated dilithium salt is heterogeneous in nature, the stirring of the reaction is stopped. Therefore, the reaction mixture needs to be manually stirred several times to properly mix 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 equivalents) was added to the heterogeneous slurry at 0 ° C. After adding chlorosilane, the heterogeneous reaction mixture became uniform (colorless) within 15 minutes. The reaction mixture was stirred for another 30 minutes. Then 120mL NaHCO3 solution was added, and the organic layer was extracted with EtOAc (50×3). The combined organic layer was dried with Na2SO4. The solvent was evaporated under reduced pressure. A white solid was precipitated. The white solid was washed twice with 60mL solvent of acetonitrile and EtOH (20:4) mixture. The white solid was filtered through a glass frit funnel and dried under vacuum to obtain 36g of white solid.

[0233] 9-(tert-butyldimethylsilyl)-2,7-bis(triisobutylsilyl)-9H-carbazole (20 g, 29.5 mmol, 1 eq) was placed in 250 mL RB, and anhydrous THF was added under N2 atmosphere. The solution was stirred at 0 ° C for 15 minutes. At 0 ° C, a solution of TBAF.3H2O (9.7 g, 31 mmol, 1.05 eq) in anhydrous THF (15 mL) was added dropwise to the solution. The reaction mixture changed from colorless to light yellow. The progress of the reaction was monitored by TLC. The reaction was carried out within 10 minutes. 100 mL NaHCO3 solution was added to quench the reaction. The organic layer was extracted with (4×70 mL) DCM. The combined organic layers were dried with Na2SO4. The solvent was evaporated under reduced pressure. The light yellow oil was directly loaded onto the ISCO column. A 50% DCM / hexane gradient was used. A white solid product was obtained at 30% DCM / hexane. Yield (96% for the second step 16 g).

[0234] Alternatively, the deprotected crude product was purified by recrystallization from ACN: ethanol (10: 1) mixture. The crude yellow liquid was dissolved in 20mL: 2mL ACN: ethanol mixture. The RB containing the mixture was kept in a refrigerator for 1 day. The solid product precipitated from the solvent. The solid product was then washed twice with acetonitrile: acetone mixture (30mL: 5mL) to obtain a white solid product. Washing the solid product with acetonitrile: acetone mixture helped to remove impurities. Although in this case, the yield was relatively low compared to column purification techniques. Yield (12g, 72%)

[0235] 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(d d, J=7.8, 0.9Hz, 2H), 1.82 (dq, J=13.3, 6.6Hz, 6H), 0.91 (dd, J=13.4, 6.7Hz, 48H).

[0236] 13 C NMR (101MHz, CDCl3) δ139.4,137.0,125.2,123.7,119.6,116.4,26.7,25.1,24.6.

[0237] 9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2,7-bis(tri Synthesis of (Isobutylsilyl)-9H-carbazole :

[0238]

[0239] A 500 mL round-bottom flask was charged with 2,7-bis(triisobutylsilyl)-9H-carbazole (11.5 g, 20.4 mmol, 1 eq.), 2-(2-iodo-4-(2,4,4-trimethylpent-2-yl)phenoxy)tetrahydro-2H-pyran (13.6 g, 32.6 mmol, 1.6 eq.), K3PO4 (19.5 g, 92 mmol, 4.5 eq.). RB was placed in a N2-filled glove box, and CuI (1.6 g, 8.2 mmol, 0.4 eq.), NN'DMEDA (2.2 g, 24.5 mmol, 1.2 eq.) and anhydrous and degassed toluene (50 mL) were added thereto. The heterogeneous reaction mixture was stirred at 125 ° C for 48 hours under vigorous stirring. The initial reaction color was light yellow, but after 1 hour, the reaction color turned green and remained green for a period of time. After 48 hours, the reaction color turned brown. After 48 hours, crude NMR was performed in chloroform, which showed that carbazole and dehalogenated protonated THP-protected phenol were completely consumed. The reaction mixture was cooled in a glove box. Afterwards, the reaction mixture was taken out of the glove box and filtered through the neutral alumina in the glass frit funnel. The solid in the glass frit funnel was washed with 70mL EtOAc. The brown filtrate was then evaporated under vacuum. The viscous orange-brown liquid was dissolved in dichloromethane: hexane (1: 1) mixture, and filtered through a glass frit funnel containing neutral alumina, and the neutral alumina was washed with 30ml DCM: hexane (1: 1) mixture. The filtrate was concentrated under reduced pressure. The method was repeated three times to remove all copper salts and other metal-based impurities. The light yellow oily material was dissolved in 60mL acetonitrile and stirred vigorously (1500rpm) for 20 minutes at 45°C. It was then cooled and kept in a refrigerator for 30 minutes. The solvent was then poured out. The brown oil was washed three times with cold acetonitrile (30 mL) and the solvent was separated out. 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%).

[0240] 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).

[0241] 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.

[0242] 9-(2-((Tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) Synthesis of 2,7-bis(triisobutylsilyl)-9H-carbazole (2,4,4-trimethylpentan-2-yl)phenyl)-5-(2,4,4-trimethylpentan-2-yl)phenyl) :

[0243]

[0244] 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 eq) and 150 mL of anhydrous 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 eq) was added dropwise. The mixture was slowly warmed to 0 °C and stirred for 2 hours. After the addition of n-BuLi, the dark brown color of the solution changed to orange-brown. The reaction mixture was treated with isopropoxy-Bpin (8.5 mL, 41.4 mmol, 2 eq) and stirring was continued at 0 °C for 1 hour. After the 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.

[0245] The solution was quenched with a saturated aqueous sodium bicarbonate solution, and the product was extracted with several portions of dichloromethane. The color of the organic phase was yellow. The combined organic fractions were concentrated and dried over Na2SO4. The solvent was evaporated under reduced pressure. 7mL of dichloromethane was added to the viscous yellow oil and 30mL of acetonitrile was added, and the viscous oil was stirred at 45°C for 30 minutes. The mixture was then kept in a refrigerator for 20 minutes. The supernatant was then precipitated, and 3 portions of acetonitrile were further added to the viscous oil for washing. The viscous oil was dissolved in 30mL of dichloromethane and filtered through a glass frit funnel containing neutral alumina. The alumina was then washed twice with 50mL of dichloromethane: hexane 1:1 mixture. The colorless filtrate / solution was dried under reduced pressure and kept under vacuum for 3 hours. The oil became a white foam. NMR was carried out in chloroform. Yield (18.9g, 92%)

[0246] 1 H NMR (400 MHz, chloroform-d) δ 8.07 (d, J = 7.7 Hz, 2H), 7.87 (d, J = 2.5 Hz, 1H), 7.51 (d, J = 2.6 Hz, 1H), 7.45 (s, 1H), 7.42-7.35 (m, 3H), 5.01 (t, J = 2.9 Hz, 1H), 2.55 (dd, J = 5.8, 2.7 Hz ,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).

[0247] 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.

[0248] Example 5—Synthesis of Metal-Ligand Complex 5 (MLC-5) :

[0249]

[0250] In a N2 filled glove box, ScCl3 (7.6 mg, 0.050 mmol, 1.00 equiv) and 3 mL of anhydrous THF were loaded into a 20 mL vial. 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 hour, an aliquot was taken out, concentrated, and analyzed by proton / fluorine NMR to assess the conversion. There was a mixture of materials, indicating that the reaction was incomplete. The reaction mixture was stirred overnight. The solution was cooled and filtered through a 0.45 um syringe filter. The filtrate was concentrated to dryness. Proton / fluorine NMR showed that the product existed with some triethylamine. The solid was suspended in 2 mL of hexane. The white solid was precipitated and separated by filtration (60.0 mg, 60%).

[0251] 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,1H), 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=6.5Hz, 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).

[0252] 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 .07,135.48,135.42,135.22,135.15,130.09,129.77,129.39,129.34,129.16,129.08,128.06,126.73,126.42,126.38,126.28,126.10,126.00,125.97,125.88,125.78,125.65,125.47,124.70,124.24,123.46,120.36,120.32,120.17,119.74,11 9.58,118.99,118.18,117.98,117.80,117.60,117.42,116.50,116.30,116.20,116.12,115.83,115.65,78.48,75.49,72.57,71.75,57.45,57.06,56.96,38.34,37.97,37.91,34.99,34.88,34.36,33.25,33.13,32.67,32.61,32.28,32.26,32.17, 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.

[0253] 19 F NMR (471 MHz, benzene-d6) δ -115.39, -115.69.

[0254] 2',2"'-(ethane-1,2-diylbis(oxy))bis(3-(2,7-bis(triisobutylsilyl)-9H-carbazole- Synthesis of 9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol :

[0255]

[0256] A 1L three-necked 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 eq), 1,2-bis(2-bromo-4-fluoro-6-methylphenoxy)ethane (3.7 g, 8.5 mmol, 1 eq), 350 mL of anhydrous THF and 2(M)K3PO4 solution (25 mL, 61 mmol, 6 eq). Pd(Amphos)Cl2 (0.30 g, 0.42 mmol, 5 mol%) was added to the solution. The reaction mixture was stirred at 65°C with a reflux condenser overnight. The color of the solution changed to brown-orange. After 16 hours, the proton and 19 FNMR analysis reaction mixture. Take out aliquots from reaction mixture and filter through neutral alumina pipette. Rinse with dichloromethane. Evaporate the solvent and perform NMR. Suzuki double-coupled product, proto-deborylated top 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 / hexane. The product was obtained using 20% ​​dichloromethane / hexane. The product fractions were combined and evaporated under reduced pressure to obtain a white fluffy solid.

[0257] The product is dissolved in 30mL THF: MeOH mixture (2: 1) and 1mL concentrated HCl is added, and refluxed for 40 minutes. Excess acid is quenched with 50mL saturated NaHCO solution, and organic layer is extracted with dichloromethane (60mL × 3). The organic layer is dried over Na2SO4. The organic layer is dried under vacuum. Using ISCO, 20% DCM / hexane is used to purify the product. The product fractions are merged and evaporated under reduced pressure to obtain a white fluffy solid (8.6g, yield 56%, by 2 steps).

[0258] 11H NMR (400 MHz, chloroform-d) δ 8.12 (d, J = 7.7 Hz, 4H), 7.52 - 7.37 (m, 8H), 7.28 (s, 4H), 6.91 (dd, J = 8.7, 3.1 Hz, 2H), 6.73 (dd, J = 8.7, 3.1 Hz, 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).

[0259] 13 13C NMR (101 MHz, CDCl3) δ 160.5, 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, 126.3, 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.

[0260] 19 19F NMR (376 MHz, CDCl3) δ -118.10.

[0261] Example 6—Synthesis of Metal-Ligand Complex 6 (MLC-6) :

[0262]

[0263] In a nitrogen-filled glove box, ScCl (0.286 g, 1.89 mmol, 1.4 equivalents) was loaded into an oven-dried 250 mL flask. Ligand vi (2.447 g, 1.35 mmol, 1 equivalent) was dissolved in THF (60 mL) and added to ScCl, followed by the addition of Et N (1.88 mL, 13.51 mmol, 10 equivalents). The reaction mixture was heated to 50 ° C and stirred for 14 hours. The reaction was found to be incomplete by 1H and 19F NMR spectroscopy. Heating and stirring were continued for 4 more days. Another NMR analysis showed impure product. Additional ScCl (0.122 g, 0.81 mmol, 0.6 equivalent) and Et N (1.0 mL, 7.17 mmol, 5.3 equivalents) were added and the reaction was continued for 16 hours. NMR analysis showed the desired product and unknown impurities. 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 it was found to contain only impurities. The filtrate was evaporated to dryness under vacuum to obtain the pure desired product (1.40 g, 53%) as a white solid.

[0264] 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).

[0265] 19 F NMR (376MHz, C6D6) δ-115.25,-115.65.

[0266] Example 7—Synthesis of Metal-Ligand Complex 7 (MLC-7) :

[0267]

[0268] In a N2-filled glove box, a 20 mL vial was charged with the compound of formula (i) (20 mg, 0.01, 1.0 eq.) and 5 mL of benzene-d6. Ether containing 2(M) HCl (7 μL, 0.01 mmol, 1.0 eq.) was added to the Sc-complex and the reaction mixture was stirred for 5 minutes. An aliquot was then taken from the vial and filtered. 1H NMR spectroscopy analysis showed that some amount of compound of formula (i) remained. An aliquot was transferred to a vial and another 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 the compound of formula (i) and the formation of two new products, identified as the major species of MLC-7.

[0269] 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),2.55 -2.02(m,4H),1.86(s,3H),1.80-1.06(m,142H),1.06-0.54(m,48H).

[0270] 19 F NMR (376 MHz, benzene-d6) δ -115.42 (t, J = 8.6 Hz), -116.31 (t, J = 8.6 Hz), -118.13 (t, J = 8.8 Hz).

[0271] Example 8—Synthesis of Metal-Ligand Complex 8 (MLC-8) :

[0272]

[0273] In N2 filled glove box, YCl3(0.048g, 0.25mmol), THF(about 10mL) and magnetic stirring bar were loaded into a vial. The mixture was heated at 50°C for 15 minutes, then THF solution (about 5mL) containing formula (i) ligand (0.200g, 0.159mmol) was added, followed by excessive Et3N(about 0.30mL, 1.6mmol). The resulting mixture was stirred at 50°C for 3 days, followed by the addition of the second equivalent of YCl3, followed by excessive Et3N(about 0.30mL, 1.6mmol). The mixture was stirred overnight at 50°C, and then the solvent was removed in a vacuum, and the complex was extracted with pentane and passed through a sintered column. The solvent was removed in a vacuum to obtain MLC-8(175mg, 76% yield) as a white solid.

[0274] 1 H NMR (400MHz, benzene-d6) δ8.24(dd,J=8.3,5.9Hz,2H),8.15(d,J=8.2Hz,1H),8.01(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,5H), 7.39(s,1H),7.26(m,2H),7.21(d,J=8.1Hz,1H),7.00(dd,J=9.0,3.1Hz,1H),6.9 0(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(shading,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).

[0275] 19 F NMR (376 MHz, benzene-d6) δ -114.55 (t, J = 8.9 Hz), -115.09 (t, J = 8.9 Hz).

[0276] Example 9—Synthesis of Metal-Ligand Complex 9 (MLC-9) :

[0277]

[0278] In a glove box, LuCl3 (0.045 g, 0.16 mmol), THF (about 10 mL) and a magnetic stirring bar were loaded into a vial. The mixture was heated at 50 ° C for 15 minutes, then a THF solution (about 5 mL) containing a ligand (0.200 g, 0.159 mmol) of formula (i) was added, followed by an excess of Et3N (about 0.30 mL). The resulting mixture was stirred at 50 ° C for 3 days, followed by a second aliquot of LuCl3 (0.50 g, 0.18 mmol), followed by an excess of Et3N (about 0.50 mL). The mixture was stirred overnight at 50 ° C, and then the solvent was removed in a vacuum, and the complex was extracted with pentane and passed through a sintered column. The solvent was removed in a vacuum to obtain MLC-9 as a white solid.

[0279] 11H NMR (400 MHz, benzene-d6) δ 8.23 (t, J = 7.8 Hz, 2H), 8.13 (d, J = 8.2 Hz, 1H), 7.99 (d, J = 1.7 Hz, 1H), 7.93 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 2.6 Hz, 1H), 7.61 (d, J = 1.7 Hz, 1H), 7.53 (m, 2H), 7.50 - 7.39 (m, 3H), 7.36 (d, J = 1.6 Hz, 1H), 7.26 (dd, J = 12.4, 2.6 Hz, 2H), 7.20 (dd, J = 8.3, 1.7 Hz, 1H), 7.00 (dd, J = 8.9, 3.2 Hz, 1H), 6.87 (dd, J = 8.9, 3.2 Hz, 1H), 6.24 (dd, J = 8.2, 3.2 Hz, 1H), 6.05 (dd, J = 8.6, 3.2 Hz, 1H), 3.92 - 3.77 (m, 2H), 3.64 - 3.55 (m, 1H), 3.38 (m, 1H), 3.03 (dt, J = 8.2, 6.1 Hz, 2H), 2.65 (dt, J = 8.0, 6.1 Hz, 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), 1.186 (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).

[0280] 19 19F NMR (376 MHz, benzene-d6) δ -115.01 (t, J = 8.6 Hz), -115.11 (t, J = 8.6 Hz).

[0281] Example 10—Synthesis of Metal-Ligand Complex 10 (MLC-10) :

[0282]

[0283] In N2 filled glove box, TmCl3(0.054g), THF(about 10mL) and magnetic stirring bar were loaded into a vial. The mixture was heated at 50°C for 15 minutes, then a THF solution (about 5mL) containing formula (i) ligand (0.200g, 0.159mmol) was added, followed by an excess of Et3N(about 0.30mL). The resulting mixture was stirred at 50°C for 3 days, followed by a second aliquot of TmCl3(0.77g, 0.16mmol), followed by an excess of Et3N(about 0.50mL). The mixture was stirred overnight at 50°C, and then the solvent was removed in a vacuum, and the complex was extracted with pentane and passed through a sintered column. The solvent was removed in a vacuum to obtain MLC-10(199mg) as a white solid.

[0284] MLC-10 is a paramagnetic compound: 1 H NMR (400 MHz, benzene-d6) signal from δ 350 to -242 ppm.

[0285] 19 F NMR (376 MHz, benzene-d6) δ -42.36 (s), -57.37 (s).

[0286] Example 11—Synthesis of Metal-Ligand Complex 11 (MLC-11) :

[0287]

[0288] In N2 filled glove box, TbCl3 (0.051g, 0.19mmol), THF (about 7mL) and magnetic stirring bar were loaded into a vial. The mixture was heated at 50°C for 15 minutes, then a THF solution (about 5mL) containing a ligand (0.205g, 0.163mmol) of formula (i) was added, followed by an excess of Et3N (about 0.30mL). The resulting mixture was stirred at 50°C for 3 days, then sampled and analyzed by19F NMR spectroscopy, showing the presence of both ligand (i) and metal-ligand complex 11. A second aliquot of TbCl3 (0.079g, 0.30mmol) was added, followed by an excess of Et3N (about 0.50mL). The mixture was stirred at 50°C overnight, and then the solvent was removed in a vacuum, and the complex was extracted with pentane and passed through a sintered column. The solvent was removed in vacuo to give MLC-11 (232 mg, 94% yield) as a white solid.

[0289] MLC-11 is a paramagnetic compound: 1 H NMR (400 MHz, benzene-d6) signal from δ 140 to -375 ppm.

[0290] 19F NMR (376 MHz, benzene-d6) δ -143.67 (s), -175.09 (s).

[0291] Example 12—Synthesis of Metal-Ligand Complex 12 (MLC-12) :

[0292]

[0293] In N2 filled glove box, HoCl3(0.050g, 0.18mmol), THF(about 7mL) and magnetic stirring bar were loaded into a vial. The mixture was heated at 50°C for 15 minutes, then a THF solution (about 5mL) containing formula (i) ligand (0.202g, 0.161mmol) was added, followed by an excess of Et3N(about 0.30mL). The resulting mixture was stirred at 50°C for 3 days, followed by a second aliquot of HoCl3(0.050g, 0.18mmol), followed by an excess of Et3N(about 0.50mL). The mixture was stirred overnight at 50°C, and then the solvent was removed in a vacuum, and the complex was extracted with pentane and passed through a sintered column. The solvent was removed in a vacuum to obtain MLC-12(228mg, 93% yield) as a white solid.

[0294] MLC-12 is a paramagnetic compound: 1 H NMR (400 MHz, benzene-d6) signal from δ 168 to -212 ppm.

[0295] 19 F NMR (376 MHz, benzene-d6) δ -143.36 (s), -175.48 (s).

[0296] Comparative metal-ligand complexes C1 and C2 (hereinafter "Comparative C1" and "Comparative C2") are each mixed with a cocatalyst 1 to form a catalyst system. The metal-ligand complexes 1-12 of the present invention have the structure of a metal-ligand complex according to formula (I). The comparative main catalysts have the following structures and their preparation is reported in WO2021155158 A1.

[0297]

[0298] Example 13 - Batch Reactor Polymerization Results

[0299] Procedure for batch reactor polymerizations. Batch reactor polymerizations were carried out in a 2L Parr TM The reactor is heated by an electric heating mantle and cooled by an internal winding cooling coil containing cooling water. TMThe TG process computer controls and monitors the reactor and heating / cooling system. A dump valve is installed at the bottom of the reactor to discharge the contents of the reactor into a stainless steel dump pot. The dump pot is optionally pre-filled with a catalyst kill solution (usually 5 mL of an Irgafos / Irganox / toluene mixture). The dump pot is drained into a 30-gallon blowdown tank, where both the pot and the tank are purged with nitrogen. All solvents used in the polymerization or catalyst composition are passed through solvent purification columns to remove any impurities that may affect the polymerization. 1-Octene and Isopar E are passed through two columns, the first column containing A2 alumina and the second column containing Q5. Ethylene is passed through two columns, the first column containing A204 alumina and molecular sieves, the second column contains the Q5 reactant. The N2 used for transfer is passed through a column containing A204 alumina, A single column of molecular sieves and Q5.

[0300] The reactor is first loaded from a jet tank which may contain IsoparE solvent and / or 1-octene, depending on the reactor load. The jet tank is filled to the load set point by using a laboratory scale equipped with a jet tank. After the liquid feed is added, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor when it is at the reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored by a micro-motion flow meter. For some experiments, the standard condition at 120°C was 611 g IsoparE containing 46 g ethylene and 303 g 1-octene, and the standard condition at 150°C was 547 g IsoparE containing 43 g ethylene and 303 g 1-octene.

[0301] The metal-ligand complex and the co-catalyst are mixed with an appropriate amount of purified toluene to obtain a molar concentration solution. The metal-ligand complex and the co-catalyst are processed in an inert glove box, extracted into a syringe and transferred to a catalyst injection tank under pressure. The syringe is rinsed three times with 5mL of toluene. After adding the catalyst, the run timer starts immediately. If ethylene is used, it is added by Camile to maintain the reaction pressure set point in the reactor. The polymerization reaction runs for 10 minutes, then the agitator is stopped, and the bottom discharge valve is opened to discharge the reactor contents to the pouring pot. The contents of the pouring pot are poured into a tray and placed in a laboratory fume hood, where the solvent is evaporated overnight. The tray containing the remaining polymer is transferred to a vacuum oven, where it is heated to 140°C under vacuum to remove any residual solvent. After the tray is cooled to ambient temperature, the yield of the polymer is weighed to measure efficiency, and the polymer test is submitted. The results of the high 1-octene polymerization reaction are shown in Table 1.

[0302] Table 1. Summary of batch reactor results for MLC-1 and MLC-2 .

[0303]

[0304] Reactor conditions of Table 1: 190°C, 410 psi C2, 65 g 1-octene, 1250 g isopar-E, 10 min run time. ND = below the detection limit of the instrument. [a] The promoter / additive is mixed with the catalyst before injection. [b] The cocatalyst / additives are added to the polymerization prior to catalyst injection.

[0305] In Example 1, the metal-ligand complex 1 (IMLC-1) of the present invention is mixed with a modified MMAO co-catalyst to activate the pre-catalyst before injection. In Example 2, the MMAO-co-catalyst is fed into the reactor separately and before the pre-catalyst, and then the pre-catalyst is injected into the reactor. Both show the same efficiency and produce the same polymer, indicating that the pre-catalyst is activated quickly. In Example 3, IMLC-1 is pre-mixed with 20 equivalents of MMAO and fed into the reactor, and the efficiency is very low, indicating that MMAO is relied on to activate the catalyst. Low levels of MMAO are selected to show low reactivity rather than not using MMAO, because MMAO also acts as a scavenger and prevents IMLC-1 from being poisoned by impurities (therefore preventing false negative results). Example 4 uses the same conditions as Example 1, but uses a comparative catalyst, which is synthesized as a pre-activated catalyst with an alkyl leaving group. The efficiency of the comparative catalyst is slightly lower than that of the IMLC-1 with a co-catalyst, and the same polymer is prepared.

[0306] Example 14—Continuous Process Polymerization Results

[0307] Raw materials (ethylene, 1-octene) and process solvents (narrow boiling range high purity isoparaffin solvents, commercially available from ExxonMobil Corporation under the trademark Isopar E) are purified with molecular sieves and subsequently introduced into the reaction environment. Hydrogen is supplied in a high purity grade in a pressurized cylinder and is not further purified. The reactor monomer feed (ethylene) stream is pressurized to a reaction pressure higher than 525psig via a mechanical compressor. The solvent and comonomer (1-octene) feed are pressurized to a reaction pressure exceeding 525psig via a mechanical positive displacement pump. Triethylaluminum (TEA) and modified methylaluminoxane (MMAO) (commercially available from AkzoNobel) are used as cocatalysts, and each can be used alternately as an impurity scavenger. Each catalyst component (primary catalyst cocatalyst) is manually diluted in batches to a specified component concentration with a purified solvent (Isopar E) and pressurized to a reaction pressure exceeding 525psig. All reaction feed streams are measured with mass flow meters and independently controlled with a computer automated valve control system.

[0308] Continuous solution polymerization is carried out in a 5L continuous stirred tank reactor (CSTR). The reactor can independently control all fresh solvent, monomer, comonomer, hydrogen and catalyst component feeds. The temperature of the combined solvent, monomer, comonomer and hydrogen fed to the reactor is controlled at any temperature between 5°C and 50°C, and is usually 25°C. The fresh comonomer feed of the polymerization reactor is fed together with the solvent feed. The fresh solvent feed is usually controlled with each injector receiving half of the total fresh feed mass flow rate. 6.0mmol / kg of cocatalyst 1 solution is fed at a rate of 56.6 grams / hour, while 16.0mmol / kg of cocatalyst 2 solution is fed at a rate of 65.44 grams / hour. Close to each fresh injection position, a static mixing element is used to mix the feed stream with the circulating polymerization reactor contents. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst component and molten polymer) leaves the first reactor loop and passes through the control valve (responsible for maintaining the pressure of the first reactor at the specified target). As the stream leaves the reactor, it comes into contact with water to stop the reaction. Additionally, various additives, such as antioxidants, can be added at this time. The stream then passes through another set of static mixing elements to evenly disperse the catalyst deactivator and additives.

[0309] After the addition of additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components and molten polymer) passes through a heat exchanger to increase the temperature of the stream in preparation for separation of the polymer from other lower boiling reaction components. The stream then enters a secondary separation and de-volatilization system where the polymer is removed from the solvent, hydrogen and unreacted monomer and comonomer. The separated and de-volatilized polymer melt is pumped through a die specially designed for underwater granulation, cut into uniform solid beads, dried and transferred to boxes for storage.

[0310] Table 2. Continuous process for ethylene / 1-octene copolymerization using MLC-6 .

[0311]

[0312] Continuous reactor conditions: solvent feed = 21.28 kg / hr, ethylene feed = 4.87 kg / hr, 1-octene feed 2.09 kg / hr, ethylene outlet = 8.53 g / L, and Al concentration = 1 ppm. [A] % Solids is the concentration of polymer in the reactor. [B] H2 (mol%) is defined as the mole fraction of hydrogen fed to the reactor relative to ethylene. [C] Efficiency (Eff.) is measured as 10 6 g polymer / g metal.

[0313] Equipment Standards

[0314] Unless otherwise noted, all solvents and reagents were obtained from commercial sources and used as received. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing through activated alumina and, in some cases, through Q-5 Reactants. Solvents used for experiments performed in a nitrogen-filled glove box were obtained by purifying the solvents in an activated The samples were further dried by storing over 100% 1% zeolite. Glassware used for moisture-sensitive reactions was dried in an oven overnight before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. The residual protons in the deuterated solvent were used as reference and reported downfield from internal tetramethylsilane (TMS, scaled δ). 1 Chemical shifts (in ppm) for H NMR data were calculated using 1 H decoupling method was used to determine 13 C NMR data and chemical shifts are reported in ppm downfield from tetramethylsilane (TMS, scale δ) compared to the reference using the residual protons in the deuterated solvent.

Claims

1. A polymerization method comprising: Ethylene and optionally one or more olefins are polymerized in a reactor system comprising one or more reactors in the presence of a catalyst system comprising one or more olefin polymerization catalysts, an alkylating agent, and optionally a Lewis acid under olefin polymerization conditions to form an ethylene-based polymer. in: M is scandium, yttrium or a lanthanide metal in the oxidation state +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 electrically neutral; R 1 and R 16 Independently selected from the group consisting of: (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -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)- 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 selected from -H, (C 1- -C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -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 )2P=N-、R C C(O)O-、R C OC(O)-、 R C C(O)N(R)-、(R C )2NC(O)- and halogen; The prerequisite is that 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 (C1-C 40 )alkylene or (C1-C 40 )heteroalkylene; and Each R in formula (I) C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

2. The polymerization process according to any one of the preceding claims, wherein the alkylating agent is a modified aluminoxane.

3. The polymerization process according to any one of the preceding claims, wherein the alkylating agent is an aluminum alkyl.

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

5. A polymerization process according to any one of the preceding claims, wherein the Lewis acid cocatalyst is a catalyst having the formula AlR A 3 alkylaluminum, wherein each R A Independently (C1-C 40 ) hydrocarbon group.

6. The polymerization process according to claim 5, wherein each R A Independently (C1-C 40 )alkyl.

7. The polymerization process according to claim 1, wherein the Lewis acid comprises: (A) at least one cocatalyst selected from aluminoxanes or (B) at least one cocatalyst selected from the formula AlR 1 R 2 R 3 or (C) at least one cocatalyst selected from aluminoxanes and at least one selected from the formula AlR 1 R 2 R 3 Activator of alkyl aluminum.

8. The polymerization process of claim 1, wherein the at least one Lewis acid cocatalyst is selected from a mixture of an alkyl aluminum compound and an alkyl zinc compound.

9. The polymerization process of claim 1, wherein the at least one Lewis acid is selected from a mixture of an alkyl aluminum compound and a boron-based Lewis acid.

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

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

14. A polymerization process according to any one of the preceding claims, wherein R 1 and R 16 is selected from a group having formula (II), a group having formula (III) and a group having formula (IV): Where R 31-35 , R 41-48 and R 51-59 Each of the following is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -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; provided that when R 1 and R 16 When it is formula (II), R 31 To R 35 At least one of them is not -H.

15. A polymerization process according to any one of the preceding claims, wherein when M is scandium, yttrium or a lanthanide metal, R 5-8 At least one of is not -H, and R 9-12 At least one of them is not -H.

16. A polymerization process according to any one of the preceding claims, wherein R 1 and R 16 At least one of them is a group having formula (III), wherein: R 42 and R 47 is (C1-C 20 )alkyl, -Si[(C1-C 20 )alkyl]3 or -Ge[(C1-C 20 )alkyl]3; or R 43 and R 46 is (C1-C 20 )alkyl, -Si[(C1-C 20 )alkyl]3 or -Ge[(C1-C 20 )hydrocarbon group]3.

17. The polymerization process according to any one of claims 1 to 15, wherein R 1 and R 16 At least one of them is a group having formula (II), wherein: R 31 To R 35 At least one of is not -H; or R 32 and R 34 is (C1-C 20 )alkyl, -Si[(C1-C 20 )alkyl]3 or -Ge[(C1-C 20 )hydrocarbon group]3.

18. The polymerization process according to any one of claims 1 to 15, wherein R 1 and R 16 At least one of them is a group having formula (IV), wherein: R 52 , R 53 , R 55 , R 57 and R 58 At least two of them are (C1-C 20 )alkyl, -Si[(C1-C 20 )alkyl]3 or -Ge[(C1-C 20 )alkyl]3; and Optional R 52 and R 53 connected to form a ring structure, and optionally R 57 and R 58 connected to form a ring structure.

19. The metal-ligand complex according to any one of the preceding claims, wherein L is selected from -CH2-, -CH2(CH2) m CH2- wherein m is 0 to 3, -CH2Si(R C )2CH2-、-CH2Ge(R C )2CH2-, -CH(CH3)CH2CH*(CH3) and -CH2(phenyl-1,2-diyl)CH2-, wherein each R in L C is (C1-C 20 ) hydrocarbon group, and "C*" is a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group.

20. The metal-ligand complex according to any one of the preceding claims, wherein n is 1 or 2; and at least one T is (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen.

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

22. The metal-ligand complex according to any one of the preceding claims, wherein: R 2 , R 4 , R 5 , R 12 , R 13 and R 15 For hydrogen.

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