Group III and Lanthanide Bis-phenyl-phenoxy Metal-Ligand Complexes

Abstract

Embodiments of the present disclosure are directed to catalyst systems comprising metal-ligand complexes according to formula (I). [Formula 1] JPEG2023512638000112.jpg44128

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 62 / 968,678, filed January 31, 2020, the entire disclosure of which is incorporated herein by reference.

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

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

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

[0005] There is a continuing need to create catalyst systems or metal-ligand complexes that have high selectivity to ethylene during the copolymerization reaction of ethylene and α-olefins. Furthermore, the metal-ligand complexes should have high catalytic efficiency, increased efficiency, and the versatile ability to produce high or low molecular weight polymers at high temperatures (e.g., greater than 140° C. or around 190° C.).

[0006] An embodiment of the present disclosure includes a catalyst system comprising a metal-ligand complex according to formula (I).

[0007] [ka]

[0008] In formula (I), M is scandium, yttrium, a lanthanide metal, or an actinide metal having an oxidation state of +3. (T) n The subscript n is 0, 1, or 2, and X is (C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C, -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C )3, -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C )2, -C(O)NHR C , —C(O)NH2, halogen, or hydrogen; C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl. The subscript Q is 0, 1, 2, or 3, and the subscript W is 0, 1, or 2. T is a Lewis base. (T) n When the subscript n in is 1, X and T are optionally connected. The metal-ligand complex is overall charge neutral.

[0009] In formula (I), R 1 and R 16 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C) 2NC(O)-, a halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

[0010] [ka]

[0011] In formula (II), (III), and formula (IV), R 31-35 , R 41-48 , and R 51-59 Each of is independently -H, (C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) 2NC(O)-, or halogen.

[0012] 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 -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C)3, -Ge(R C )3, -P(R P )2, -N(R N )2-OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) 2NC(O)-, and halogen.

[0013] In formula (I), L is a group selected from the group consisting of (C1-C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, each Z is independently -O-, -S-, -N(R N )- or -P(R P )- is selected from.

[0014] In formulas (I), (II), (III), and (IV), each R C , R P , and R N are independently 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or -H. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Specific embodiments of the catalyst system will now be described. It is understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as being limited to the specific embodiments described in this disclosure.

[0016] Common abbreviations are listed below. R, Z, M, X, and n: as defined above, Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: iso-propyl, t-Bu: tert-butyl, t-Oct: tert-octyl(2,4,4-trimethylpentan-2-yl), Tf: trifluoromethane sulfonate, 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)dichloropalladium(II), Pd(AmPhos): chloro(crotyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II), Pd(dppf) Cl2: [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, ScCl3: scandium(III) chloride, PhMe: triene, THF: tetrahydrofuran, CHCl2: 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, SiO2: silica, CDCl3: chloroform-D, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: mole, min or mins: minutes, h or hrs: hours, d: days, TLC: thin layer chromatography, rpm: revolutions per minute, rt: room temperature.

[0017] The term "independently selected" means 1 , R 2 , R 3 , R 4 , and R 5 The R groups, such as R 1 , R 2 , R 3, R 4 , and R 5 may all be substituted alkyl, or R 1 and R 2 may be substituted alkyl, R 3 R may be aryl, etc. Chemical names associated with R groups are intended to convey chemical structures that are recognized in the art as corresponding to the chemical structure of the chemical name. Thus, the chemical names are intended to supplement and illustrate, not preclude, structural definitions known to those of skill in the art.

[0018] When used to describe certain carbon atom-containing chemical groups, "(C x -C y A parenthetical expression having the form "(C1-C2)" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, inclusive. For example, (C1-C2) 50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S The parenthetical "(C x -C y )" S The substituted chemical group can be any group R S For example, "R S Exactly one group R is phenyl (-C6H5) S (C1-C 50 "(C)alkyl" can contain from 7 to 56 carbon atoms. Thus, in general, the parenthetical "(C x -C y )" is a group defined as one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is determined by the sum of all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0019] The term “substituted” refers to the replacement of at least one hydrogen atom (—H) bonded to a carbon or heteroatom of a corresponding unsubstituted compound or functional group with a substituent (e.g., R S The term "persubstituted" means that all hydrogen atoms (H) attached to carbon or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by a substituent (e.g., R S ) is substituted. The term "polysubstituted" means that at least two, but fewer than all, of the hydrogen atoms bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group are replaced by a substituent. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0020] "(C1-C 50 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical having 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical having from 1 to 50 carbon atoms, each of which may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and may contain one or more R S is or is not replaced by

[0021] In this disclosure, (C1-C 50 ) Hydrocarbyl is unsubstituted or substituted (C1-C 50 )Alkyl, (C3-C 50 )Cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 ) alkylene, such as benzyl (-CH2-C6H5).

[0022] "(C1-C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to a group that is unsubstituted or has one or more R S and saturated linear or branched hydrocarbon radicals of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively, which are substituted by unsubstituted (C1-C 50 Examples of alkyl groups include unsubstituted (C-C 20 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C-C 20 ) Alkyl, Substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" refers to up to 45 carbon atoms in the radical, including the substituents, e.g., one R, each of which is (C-C) alkyl. S Replaced by (C 27 -C 40 )alkyl. Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0023] "(C6-C 50 The term "aryl" refers to an aryl group having 6 to 40 carbon atoms, of which at least 6 to 14 are aromatic ring carbon atoms, unsubstituted or (containing one or more R S(by) substituted monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radicals. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may independently be fused or non-fused and aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl include unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18 )aryl, 2-(C1-C5)alkylphenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indakenyl, hexahydroindenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 40 Examples of aryl include substituted (C1-C 20 )Aryl, Substituted (C6-C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0024] "(C3-C 50 The term "cycloalkyl" means unsubstituted or substituted with one or more R S means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms, substituted by other cycloalkyl groups, such as (C x -C y )Cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3-C 40 Examples of cycloalkyl are unsubstituted (C-C 20 )Cycloalkyl, unsubstituted (C3-C 10) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C-C 20 )Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0025] (C1-C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C6-C 50 )Arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). The diradicals may be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include 1,2-diradicals. α,ω-diradicals are the diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH-), 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (C6-C 50 ) Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0026] "(C1-C 50 The term "alkylene" may be unsubstituted or may contain one or more R Smeans a saturated straight or branched diradical of 1 to 50 carbon atoms (i.e., the radical is not on a ring atom) substituted by 50 Examples of alkylene are unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3 and -(CH2)4C * (H) Unsubstituted (C1-C 20 ) alkylene, where "C * " represents a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 50 Examples of alkylenes are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted 1,20-eicosylene). As mentioned above, the two R S Together, (C1-C 18 ) alkylene, so that the substitution (C1-C 50 Examples of alkylenes include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0027] "(C3-C 50 The term "cycloalkylene" may be unsubstituted or may contain one or more R S "R" means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms substituted by

[0028] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O), Si(R C )2, P(R P ), N(R N ), -N=C(R C)2, -Ge(R C )2-, -Si(R C )-, boron (B), aluminum (Al), gallium (Ga), or indium (In), C and each R P is unsubstituted (C1-C 18 ) hydrocarbyl or -H, and each R N is unsubstituted (C1-C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 50 The term "heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms, and is defined as "(C1-C 50 The term "heterohydrocarbylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 )heterohydrocarbyl or (C1-C 50 The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be on a carbon atom or on a heteroatom. The two radicals of the heterohydrocarbylene may be on a single carbon atom or on a single heteroatom. Furthermore, one of the two radicals of the diradical may be on a carbon atom and the other radical on a different carbon atom, or one of the two radicals may be on a carbon atom and the other radical on a heteroatom, or one of the two radicals may be on a heteroatom and the other radical on a different heteroatom. (C1-C 50 )heterohydrocarbyl and (C1-C 50 Each heterohydrocarbylene is unsubstituted or (one or more R S The aromatic ring may be substituted (by) and may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0029] (C1-C 50) Heterohydrocarbyl may be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heterohydrocarbyls include (C-C 50 )heteroalkyl, (C1-C 50 ) hydrocarbyl-O-, (C1-C 50 ) hydrocarbyl-S-, (C1-C 50 )hydrocarbyl-S(O)-, (C1-C 50 )hydrocarbyl-S(O)2-, (C1-C 50 ) Hydrocarbyl-Si(R C )2-, (C1-C 50 )hydrocarbyl-N(R N )-, (C1-C 50 ) hydrocarbyl-P(R P )-, (C2-C 50 )heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 )heteroalkylene, (C1-C 50 )heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0030] "(C1-C 50 The term "heteroaryl" refers to an unsubstituted or heteroaryl group having a total of 1 to 50 carbon atoms and 1 to 10 heteroatoms, each of which is selected from the group consisting of one or more R S(C1-C3) means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical substituted with (C1-C3). A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C1-C3) 12 )heteroaryl, etc. x -C y ) Heteroaryl (general) has x to y carbon atoms (e.g., 1 to 12 carbon atoms) and is unsubstituted or has one or more R SThe monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as being substituted with. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3, or 4, and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. A 6-membered monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2, and the heteroatom may be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. A bicyclic heteroaromatic hydrocarbon radical may be a fused 5,6 or 6,6 ring system. Examples of a fused 5,6 bicyclic heteroaromatic hydrocarbon radical are indol-1-yl and benzimidazol-1-yl. Examples of a fused 6,6 bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl and isoquinolin-1-yl. A tricyclic heteroaromatic hydrocarbon radical may be a fused 5,6,5, 5,6,6, 6,5,6, or 6,6,6 ring system. An example of a fused 5,6,5 ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6 ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6 ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6 ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6 ring system is acridine-9-yl.

[0031] "(C1-C 50The term "(C1-C2)heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O), each of the heteroalkyl and heteroalkylene groups can be unsubstituted or can have one or more R S has been replaced by

[0032] Unsubstituted (C2-C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 )Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0033] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom, fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I - )

[0034] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double bonds and / or triple bonds may optionally be substituted by a substituent R S The term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, and may be present in the substituent R S (if present), or in an aromatic or heteroaromatic ring (if present).

[0035] The term "lanthanide metals" includes elements 57 through 71 (lanthanum (La) through lutetium (Lu)).

[0036] An embodiment of the present disclosure includes a catalyst system comprising a metal-ligand complex according to formula (I).

[0037] [ka]

[0038] In formula (I), M is scandium, yttrium, a lanthanide metal, or an actinide metal having an oxidation state of +3. (T) n The subscript n is 0, 1, or 2, and X is (C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (ORC ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C )3, -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C )2, -C(O)NHR C , —C(O)NH2, halogen, or hydrogen. C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl. The subscript Q is 0, 1, 2, or 3, and the subscript W is 0, 1, or 2. T is a Lewis base. (T) nWhen the subscript n in is 1, X and T are optionally connected. The metal-ligand complex is overall charge neutral.

[0039] In formula (I), R 1 and R 16 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) 2NC(O)-, a halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

[0040] [ka]

[0041] In some embodiments, in the metal-ligand complex of formula (I), R 1 or R 16 Either of the above or R 1 and R 16 are both selected from radicals having formula (II), formula (III), or formula (IV). Provided that 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.

[0042] When present in a metal-ligand complex of formula (I) as part of a radical having formula (II), formula (III) or formula (IV), the group R 31-35 , R 41-48 , and R 51-59 are each independently (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, Si(R C )3, P(R P )2, N(R N )2, OR C , S.R. C , NO2, CN, CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )NC(O)-, halogen, hydrogen (-H), or combinations thereof. C , R P , and R N is unsubstituted (C1-C 18 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or -H.

[0043] The group R in the metal-ligand complex of formula (I) 1 and R 16 are selected independently of each other. For example, R 1 may be selected from radicals having formula (II), (III), or (IV), R 16 is (C1-C 40 ) hydrocarbyl, or R 1 may be selected from radicals having formula (II), (III), or (IV), R 16 may be selected from radicals having formula (II), (III), or (IV), R 1 Same as or different from that of R 1 and R 16may both be radicals having the formula (II), in which case the group R 31-35 is R 1 and R 16 In another embodiment, R 1 and R 16 may both be radicals having the formula (III), in which case the group R 41-48 is R 1 and R 16 are the same or different in 1 and R 16 may both be radicals having the formula (IV), in which case the group R 51-59 is R 1 and R 16 are the same or different.

[0044] In some embodiments, R 1 and R 16 At least one of R is a radical having the formula (II) 32 and R 34 is tert-butyl. In one or more embodiments, R 32 and R 34 is (C1-C 12 ) hydrocarbyl or -Si[(C1-C 10 ) alkyl]3.

[0045] In some embodiments, R 1 or R 16 is a radical having the formula (III), R 43 and R 46 One or both of R 41-42 , R 44-45 , and R 47-48 is -H. In other embodiments, R 42 and R 47 One or both of R 41 , R 43-46 , and R 48 is -H. In some embodiments, R 42 and R 47and R are -H. 42 and R 47 is (C1-C 20 ) hydrocarbyl or -Si[(C1-C 10 ) alkyl]3. In another embodiment, R 43 and R 46 is (C1-C 20 ) hydrocarbyl or -Si[(C1-C 10 ) alkyl]3. In some embodiments, R 42 and R 43 and are linked to form a ring structure, and R 46 and R 47 are linked to form a ring structure.

[0046] In embodiments, R 1 or R 16 at least one of R is a radical having the formula (IV) 52 , R 53 , R 55 , R 57 , and R 58 is -H, (C1-C 20 ) hydrocarbyl, -Si[(C1-C 20 )hydrocarbyl]3, or -Ge[(C1-C 20 )hydrocarbyl]3. In some embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least one of the (C3-C 10 ) alkyl, -Si[(C3-C 10 ) alkyl]3, or -Ge[(C3-C 10 In one or more embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least two of the 10 ) alkyl, -Si[(C3-C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3. In various embodiments, R52 , R 53 , R 55 , R 57 , and R 58 At least three of the 10 ) alkyl, -Si[(C3-C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3.

[0047] In some embodiments, R 1 or R 16 at least one of R 52 , R 53 , R 55 , R 57 , and R 58 At least two of the 20 ) hydrocarbyl or -C(H)2Si[(C1-C 20 ) hydrocarbyl]3.

[0048] (C3-C 10 Examples of alkyl include, but are not limited to, propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

[0049] In some embodiments of the metal-ligand catalyst according to formula (I), R 1 and R 16are 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 3,5-diisopropylphenyl, carbazolyl, carbazol-9-yl, 1,2,3,4-tetrahydrocarbazolyl, 1,2,3,4,5,6,7,8-octahydrocarbazolyl, 3,6-bis-(3,5-di-tert-butylphenyl)carbazol-9-yl, 3,6-bis-(2,4,6-trimethylphenyl)carbazol-9-yl, 2,7-di(tertiary butyl)-carbazol-9-yl, 2,7-di(tertiary octyl)-carbazol-9-yl, 2,7-diphenylcarbazol-9-yl, 2,7-bis(2,4,6-trimethylphenyl)-carbazol-9-ylanthracenyl, 1,2,3,4-tetrahydroanthracenyl , 1,2,3,4,5,6,7,8-octahydroanthracenyl, phenanthrenyl, 1,2,3,4,5,6,7,8-octahydrophenanthrenyl, 1,2,3,4-tetrahydronaphthyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 3,5-diphenylphenyl, 1-naphthyl, 2-methyl-1-naphthyl, 2-naphthyl, 1,2,3,4-tetrahydronaphth-5-yl, 1,2,3,4-tetrahydronaphthyl It is selected from dronephth-6-yl, anthracen-9-yl, 1,2,3,4-tetrahydroanthracen-9-yl, 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl, 1,2,3,4,5,6,7,8-octahydrophenanthren-9-yl, indolyl, indolinyl, quinolinyl, 1,2,3,4-tetrahydroquinolinyl, isoquinolinyl, or 1,2,3,4-tetrahydroisoquinolinyl.

[0050] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R13 , R 14 , and R 15 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) 2NC(O)-, and halogen.

[0051] In one or more embodiments, R 2 , R 4 , R 5 , R 12 , R 13 , and R 15 is hydrogen and each Z is oxygen.

[0052] In embodiments, the dotted lines are optionally coordinate bonds between the metal center, M, and group Z. In some embodiments, one of the dotted lines connecting Z and M does not form a coordinate bond between Z and M. In various embodiments, both dotted lines form coordinate bonds between groups Z and M.

[0053] In various embodiments, R 3 and R 14 is (C1-C 24 ) alkyl. In one or more embodiments, R 3 and R 14 is (C4-C 24 ) alkyl. In some embodiments, R 3 and R 14is 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. 3 and R 14 -OR C and R C is (C1-C 20 ) a hydrocarbon, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), or 1,1-dimethylethyl.

[0054] In one or more embodiments, R 8 and R 9 In various embodiments, one of R 8 and R 9 At least one of (C1-C 24 ) alkyl. In some embodiments, R 8 and R 9 Both of (C1-C 24 ) alkyl. In some embodiments, R 8 and R 9 is methyl. In other embodiments, R 8 and R 9 is a halogen.

[0055] In some embodiments, R 3 and R 14 is methyl. In one or more embodiments, R 3 and R 14 is (C4-C 24 ) alkyl. In some embodiments, R 8 and R 9are 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

[0056] In various embodiments, in the metal-ligand complex of formula (I), R 6 and R 11 is halogen. In some embodiments, R 6 and R 11 is (C1-C 24 ) alkyl. In various embodiments, R 6 and R 11 is selected from 1-propyl, 2-propyl (also known as iso-propyl), 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. 6 and R 11 is tert-butyl. In embodiments, R 6 and R 11 -OR C and R C is (C1-C 20 ) a hydrocarbon, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), or 1,1-dimethylethyl. 6 and R 11 -SiR C 3, and each R C are independently 20 ) hydrocarbyl, and in some embodiments, R Cis methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), or 1,1-dimethylethyl.

[0057] In some embodiments, the chemical groups (e.g., X and R 1-59 Any or all of the chemical groups X and R of the metal-ligand complex of formula (I) may be unsubstituted. 1-59 Any of the following may contain one or more R S Even if they are not substituted with one or more R S It may be substituted with two or more R S are attached to the same chemical group of the metal-ligand complex of formula (I), the individual R S may be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, the chemical groups X and R 1-59 Any of the following is R S Even if they are not over-substituted with R, any or all of them may be R S It may also be oversubstituted with R. S In chemical groups that are over-substituted with S may all be the same or may be independently selected. In one or more embodiments, R S is (C1-C 20 ) hydrocarbyl, (C1-C 20 ) alkyl, (C1-C 20 ) heterohydrocarbyl, or (C1-C 20 ) heteroalkyl.

[0058] In formula (I), L is a group selected from the group consisting of (C1-C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, each Z is independently -O-, -S-, -N(R N )- or -P(R P )- In one or more embodiments, L contains 1 to 10 atoms.

[0059] In formulas (I), (II), (III), and (IV), each R C , R P , and R N are independently 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or -H.

[0060] In some embodiments of formula (I), L is a (C3-C7) alkyl 1,3-diradical, such as -CH2CH2CH2-, -CH(CH3)CH2C * H(CH3), -CH(CH3)CH(CH3)C * H(CH), -CHC(CH)CH-, cyclopentane-1,3-diyl, or cyclohexane-1,3-diyl, and the like. In some embodiments, L is selected from (C-C 10 ) alkyl 1,4-diradicals, such as, for example, -CH2CH2CH2CH2-, -CH2C(CH3)2C(CH3)2CH2-, cyclohexane-1,2-diyldimethyl, and bicyclo[2.2.2]octane-2,3-diyldimethyl. In some embodiments, L is selected from (C5-C 12 ) alkyl 1,5-diradicals, such as -CH2CH2CH2CH2CH2-, and 1,3-bis(methylene)cyclohexane. In some embodiments, L is selected from (C6-C 14 ) alkyl 1,6-diradicals, such as, for example, —CH2CH2CH2CH2CH2CH2—, or 1,2-bis(ethylene)cyclohexane.

[0061] In one or more embodiments, L is (C-C 40 )heterohydrocarbylene, where at least one of the 2 to 10 atoms includes a heteroatom. In some embodiments, L is -CH2Ge(R C )2CH2-, and each R C is (C1-C 30) hydrocarbyl. In some embodiments, L is -CH2Ge(CH3)2CH2-, -CH2Ge(ethyl)2CH2-, -CH2Ge(2-propyl)2CH2-, -CH2Ge(t-butyl)2CH2-, -CH2Ge(cyclopentyl)2CH2-, or -CH2Ge(cyclohexyl)2CH2-.

[0062] In one or more embodiments, L is -CH-, -CHCH-, -CH(CH) m CH2- (m is 1 to 3), -CH2Si(R C )2CH2-, -CH2Ge(R C )2CH2-, -CH(CH3)CH2CH * (CH3), and -CH2(phen-1,2-diyl)CH2-; each R in L is selected from C is (C1-C 20 ) hydrocarbyl.

[0063] It takes (C1-C 12 ) Examples of alkyl include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl, cyclopentyl or cyclohexyl, butyl, tert-butyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl (2,4,4-trimethylpent-2-yl), nonyl, decyl, undecyl, and dodecyl.

[0064] In some embodiments, in the metal-ligand complex according to formula (I), R 8 and R 9 and R are both methyl. 8 and R 9 one of R 8 and R 9 The other is -H.

[0065] In the metal-ligand complex according to formula (I), X is bonded to M through a covalent or ionic bond. In some embodiments, X can be a monoanionic ligand having a net formal oxidation state of -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) hydrocarbyl carbanion, (C1-C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, carbonates, phosphates, sulfates, HC(O)O - , HC(O)N(H) - , (C1-C 40 ) Hydrocarbyl C(O)O - , (C1-C 40 ) HydrocarbylC(O)N((C1-C 20 )hydrocarbyl) - , (C1-C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L S - Each R may be K , R L , and R M are independently hydrogen, (C1-C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R K and R L Together, (C2-C 40 ) hydrocarbylene or (C1-C 20 ) forms a heterohydrocarbylene, R M is as defined above.

[0066] In some embodiments, X is halogen, unsubstituted (C-C 20 ) Hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O-, or R K R L N- and R K and R L Each of is independently unsubstituted (C-C 20 In some embodiments, each monodentate ligand X is a chlorine atom, (C-C 10 ) hydrocarbyl (e.g., (C 1- C6) alkyl or benzyl), unsubstituted (C1-C 10 ) hydrocarbyl C(O)O-, or R K R L N- and R K and R L Each of is independently unsubstituted (C-C 10 ) hydrocarbyl.

[0067] In some embodiments, n is 1 and X and T are linked and selected from the group consisting of:

[0068] [ka]

[0069] In further embodiments, X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2,-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. X is methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2,-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In one embodiment, n is 2 and at least two X are independently monoanionic monodentate ligands. In a particular embodiment, n is 2 and two X groups together form a bidentate ligand. In a further embodiment, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0070] In one or more embodiments, each X is independently -(CH2)SiR X 3, and each R X are independently 30 ) alkyl or (C1-C 30 ) heteroalkyl, and at least one R X is (C1-C 30 ) alkyl. In some embodiments, R X One of the (C1-C 30 ) heteroalkyl, the heteroatom is a silica or oxygen atom. In some embodiments, R X is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0071] In one or more embodiments, X is -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(CH2CH3), -(CH2)Si(CH3)(CH2CH3)2, -(CH2)Si(CH2CH3)3, -(CH2)Si(CH3)2(n-butyl), -(CH2)Si(CH3)2(n-hexyl), -(CH2)Si(CH3)(n-Oct)R X , -(CH2)Si(n-Oct)R X 2, -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), -CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as -CH2Si(CH3)2CH2TMS). Optionally, in some embodiments, the metal-ligand complex according to Formula (I) has exactly two R X are covalently bonded or exactly three R X is covalently bonded.

[0072] In some embodiments, X is -CHSi(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C )Q , -OSi(R C ) 3-Q (OR C ) Q where the subscript Q is 0, 1, 2, or 3, and each R C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl.

[0073] In some embodiments, X is B(R Y )4, Al(R Y )4, or Ga(R Y ) 4, and each R Y is -H, (C1-C 30 ) a hydrocarbyl, or a halogen atom.

[0074] In the metal-ligand complex according to formula (I), each T is bound to M via a coordinate bond or an ionic bond. In one or more embodiments, T is a Lewis base. A Lewis base can be a compound or ionic species capable of donating an electron pair to an acceptor compound. For purposes of this description, the acceptor compound is M, the metal of the metal-ligand complex of formula (I). A Lewis base can be neutral or anionic. In some embodiments, a Lewis base can be a heterohydrocarbon or a hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. Examples of anionic hydrocarbons include, but are not limited to, cyclopentadiene. Examples of neutral hydrocarbons include, but are not limited to, 1,3-buta-diene.

[0075] In one or more embodiments, the Lewis base may be a monodentate ligand, which may be a neutral ligand. In some embodiments, the neutral ligand may contain a heteroatom. In certain embodiments, the neutral ligand may be R T NR K R L , R K OR L , RK S.R. L , or R T PR K R L Each R T are independently hydrogen, [(C1-C 10 )hydrocarbyl]3Si(C1-C 10 ) hydrocarbyl, (C1-C 40 ) hydrocarbyl, [(C1-C 10 )hydrocarbyl]3Si, or (C1-C 40 ) heterohydrocarbyl, each R K and R L are independently as previously defined.

[0076] In some embodiments, the Lewis base is (C1-C 20 ) hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene or 1,3-buta-di-ene.

[0077] In various embodiments, the Lewis base is (C1-C 20 ) heterohydrocarbon, where the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0078] In the metal-ligand complex of formula (I), each Z is independently O, S, N(C-C 40 ) hydrocarbyl, or P(C1-C 40 ) hydrocarbyl. In some embodiments, each Z is different. For example, one Z is O and the other Z is NCH3. In some embodiments, one Z is O and one Z is S. In other embodiments, one Z is S and one Z is N(C1-C 40 ) hydrocarbyl (e.g., NCH3). In further embodiments, each Z is the same. In yet other embodiments, each Z is O. In other embodiments, each Z is S.

[0079] In formula (I), each Z is connected to M via a dotted line. The dotted lines define an optional coordinate bond. In some embodiments, one of the dotted lines forms a coordinate bond between Z and M, and the second dotted line does not directly connect or bond Z to M. In various embodiments, each Z forms a coordinate bond with M. In other embodiments, each Z is not directly connected or bonded to M. Without intending to be bound by theory, it is believed that the number of ZM coordinate bonds depends on the atomic radius of the metal defined by M.

[0080] In certain embodiments of the catalyst system, the metal-ligand complex according to formula (I) may include, but is not limited to, a complex having the structure of any of the metal-ligand complexes 1-38 of the present invention.

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] Olefin Propagation Although no cocatalyst is required to initiate olefin propagation for the metal-ligand complex of formula (I), it is believed that the metal-ligand catalyst is not efficient when a Lewis base T is coordinated to the metal center M of formula (I). Thus, during olefin propagation, the Lewis base dissociates from the metal center M and the metal-ligand complex has a structure according to formula (Ia).

[0087] [ka]

[0088] In formula (Ia), R 1 ~R 16 , M, Z, and L are as defined in formula (I). P is a hydrocarbyl, the hydrocarbyl having at least 30 carbon atoms and being branched or unbranched. More specifically, X P is the propagating olefin chain.

[0089] Additive Ingredients In some embodiments, the catalyst system does not include an additive. An additive is a chemical agent that is present during the polymerization reaction and does not inhibit olefin propagation. In one or more embodiments, the catalyst system further includes an additive. In some embodiments, the additive functions as a cocatalyst. In other embodiments, the additive functions as a scavenger or scavenger. A cocatalyst is a reagent that cooperates with the catalyst to catalyze a reaction or improve the catalytic activity of the catalyst. Without intending to be bound by theory, it is believed that the Lewis base T of formula (I) dissociates without the presence of a cocatalyst. However, it is also believed that the cocatalyst may facilitate the dissociation of the Lewis base from the metal center of the metal-ligand complex.

[0090] The scavenger is not in the nature of an activator since it sequesters impurities in the reactor before the precatalyst is added. At low loadings of alumoxane it does not act as a cocatalyst but rather as a scavenger.

[0091] Suitable additives may include, but are not limited to, alkylaluminum, polymeric or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds, including the use of such compounds under oxidizing conditions. Combinations of one or more of the foregoing additives and techniques are also contemplated. The term "alkylaluminum" refers to monoalkylaluminum dihydrides or dihalides, dialkylaluminum hydrides or halides, or trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, methylalumoxane modified with triisobutylaluminum, and isobutylalumoxane.

[0092] In some embodiments, the additive is a compound as described herein (C1-C 20 In some embodiments, the additive is a Lewis acid Group 13 metal compound containing a tri((C1-C 20 )hydrocarbyl)-substituted aluminum or tri((C1-C 20 In another embodiment, the additive comprises a tri(hydrocarbyl)-substituted aluminum, tri((C-C 20 )hydrocarbyl)-boron compounds, tri((C1-C 10 ) alkyl) aluminum, tri((C6-C 18 )aryl)boron compounds and their halogenated (including perhalogenated) derivatives.

[0093] In one or more embodiments, the polymerization process further comprises a borate-based additive. In some embodiments, the borate-based additive is selected from tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the cocatalyst is a tri((C 20 )hydrocarbyl)ammonium tetra((C1-C 20As used herein, the term "ammonium" refers to a ((C1-C2) hydrocarbyl) borate (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). 20 ) Hydrocarbyl) 4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 ) HydrocarbylN(H)3 + , or N(H)4 + Each of the nitrogen cations (C1-C 20 When two or more hydrocarbyls are present, they may be the same or different.

[0094] In one or more embodiments, the additive may be selected from polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable additives include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)ammonium, triethylaluminum, butylated hydroxy-toluene diethylaluminum, bis-(butylated hydroxy-toluene) ethylaluminum, tris-(butylated hydroxy-toluene) aluminum, and combinations thereof.

[0095] In some embodiments, one or more cocatalysts can be used in combination with each other. Specific examples of cocatalyst combinations include tri((C1-C8) hydrocarbyl)aluminum, tri((C1-C4) hydrocarbyl)borane, tri((C6-C 18)aryl)borane, or ammonium borate, and an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of the one or more metal-ligand complexes of formula (I) to the total number of moles of one or more of the cocatalysts 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 alumoxane alone is used as the cocatalyst, preferably the ratio of Al of the alumoxane to the metal of the metal-ligand complex of formula (I) (Al / M) is at least 20. When tris(pentafluorophenyl)borane is used alone as the co-catalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of one or more metal-ligand complexes of Formula (I) is from 0.5:1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1.

[0096] Characteristics of the catalytic system Procatalysts comprising a metal-ligand complex of formula (I) and one or more cocatalysts described herein have a reactivity ratio r1, as further defined below, in the range of greater than 100, e.g., greater than 150, greater than 200, greater than 300, or greater than 500.

[0097] For random copolymers, where the properties of the last monomer inserted dictate the rate of insertion of subsequent monomers, the end-copolymerization model is used. In this model, the following types of insertion reactions are considered:

[0098]

number

[0099]

number

[0100] The mole fraction of comonomer (i=2) in the reaction medium is defined by the following equation:

[0101]

number

[0102] As disclosed in George Odian, Principles of Polymerization, Second Edition, John Wiley and Sons, 1970, a simple equation for comonomer composition can be derived as follows:

[0103]

number

[0104] From this equation, the mole fraction of comonomer in a 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:

[0105]

number

[0106] Alternatively, in the penultimate copolymerization model, the properties of the last two monomers inserted into a growing polymer chain dictate the rate of subsequent monomer insertions. The polymerization reaction is of the form:

[0107]

number

[0108]

number

[0109] The comonomer content can be calculated as follows (also disclosed in George Odian, supra):

[0110]

number

[0111]

number

[0112]

number

[0113] In this model, the polymer composition is also a function of only the temperature-dependent reactivity ratios and the comonomer mole fraction in the reactor, even in cases where reversed comonomer or monomer insertions can occur, or in the case of copolymerization of more than two monomers.

[0114] Reactivity ratios for use in the above-mentioned models can be predicted using well-known theoretical methods or empirically derived from actual polymerization data. Suitable theoretical methods are disclosed, for example, in BG Kyle, Chemical and Process Thermodynamics, Third Addition, Prentice-Hall, 1999 and Redlich-Kwong-Soave (RKS) Equation of State, Chemical Engineering Science, 1972, pp1197-1203. Commercially available software programs may be used to assist in the derivation of reactivity ratios from empirically derived data. One example of such software is Aspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, MA 02141-2201 USA.

[0115] Thus, the process for producing ethylene-based polymers according to the present invention selectively provides rich polyethylene (e.g., high density polyethylene) or rich polyethylene segments of poly(ethylene alpha-olefin) copolymers in the presence of alpha-olefins, thereby not being substantially polymerized. The process for producing ethylene-based polymers employs olefin polymerization conditions. In some embodiments, the olefin polymerization conditions independently produce an in situ catalyst formed by reaction of a procatalyst comprising a metal-ligand complex of formula (I) with one or more cocatalysts in the presence of one or more other components. Such other components include, but are not limited to, (i) an olefin monomer, (ii) another metal-ligand complex of formula (I), (iii) one or more of a catalyst system, (iv) one or more chain shuttling agents, (v) one or more catalyst stabilizers, (vi) one or more solvents, and (vii) a mixture of any two or more thereof.

[0116] In particular, the catalyst of the present invention is useful in processes for producing ethylene-based polymers (C3-C 40 ) high selectivity for polymerizing ethylene in the presence of alpha-olefins can be achieved, the high selectivity being characterized by the reactivity ratio r1 described above. 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. As the reactivity ratio r1 of the present invention approaches infinity, the incorporation of alpha-olefins into (or onto) the rich polyethylene produced thereby approaches 0 mole percent (mol%).

[0117] The catalyst compositions of the present invention, comprising a procatalyst and one or more cocatalysts described herein, have catalytic efficiencies in the range of greater than 1,000,000 grams of polymer per gram of active metal center, e.g., greater than 2,000,000 grams of polymer per gram of active metal center, where the catalytic efficiency is measured in terms of the amount of polymer produced compared to the amount of catalyst used in a solution polymerization process, the polymerization temperature is at least 130° C., e.g., in the range of 170-195° C., the ethylene concentration is greater than 5 g / L, e.g., greater than 6 g / L, and the ethylene conversion is greater than 70 percent, e.g., greater than 80 percent, or alternatively, greater than 90 percent.

[0118] Polyolefin The catalyst system described in this disclosure may be utilized for the polymerization of olefins, primarily ethylene, propylene, α-olefins, such as octene, and dienes. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme to produce a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomer typically has 20 or fewer carbon atoms. For example, the α-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, the one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0119] An ethylene-based polymer, e.g., a homopolymer and / or interpolymer (including copolymer) of ethylene, and optionally one or more comonomers, such as an α-olefin, can include at least 50 mole percent (mol %) of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 mole percent" are disclosed herein as separate embodiments, for example, an ethylene-based polymer, a homopolymer and / or interpolymer (including copolymer) of ethylene, and optionally one or more comonomers, such as an α-olefin, can include at least 60 mole percent of monomer units derived from ethylene, at least 70 mole percent of monomer units derived from ethylene, at least 80 mole percent of monomer units derived from ethylene, or from 50 to 100 mole percent of monomer units derived from ethylene, or from 80 to 100 mole percent of monomer units derived from ethylene.

[0120] In some embodiments, the catalyst system can produce an ethylene-based polymer comprising at least 90 mole percent units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer can comprise at least 93 mole percent units derived from ethylene, at least 96 mole percent units derived from ethylene, at least 97 mole percent units derived from ethylene, or alternatively, from 90 to 100 mole percent units derived from ethylene, from 90 to 99.5 mole percent units derived from ethylene, or from 97 to 99.5 mole percent units derived from ethylene.

[0121] In some embodiments, the catalyst system produces an ethylene-based polymer having an amount of the additional α-olefin less than 50 mole percent (mol%), in other embodiments, the amount of the additional α-olefin comprises at least 0.01 mol% to 25 mol%, and in further embodiments, the amount of the additional α-olefin comprises at least 0.1 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0122] Ethylene-based polymers can be produced by other conventional polymerization processes incorporating the catalyst systems according to embodiments of the present disclosure, including, but not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc., in parallel, in series, or any combination thereof.

[0123] In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system described herein and herein and, optionally, one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be used in the first reactor or the second reactor. In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of the catalyst system described herein.

[0124] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system, such as a single loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of a catalyst system described within this disclosure and optionally one or more cocatalysts, as described in the previous paragraph.

[0125] The ethylene-based polymer may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer may contain any amount of additives. The ethylene-based polymer may compromise such additives in a total amount of about 0 to about 10 weight percent based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may contain about 0 to about 20 weight percent of a filler, such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer may be further blended with one or more polymers to form a blend.

[0126] In some embodiments, a polymerization process for producing an ethylene-based polymer comprises polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, where the catalyst system incorporates at least one metal-ligand complex of formula (I). Polymers obtained from such catalyst systems incorporating a metal-ligand complex of formula (I) have a molecular weight of, for example, 0.850 g / cm or less according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.970g / cm 3 , 0.870g / cm 3 ~0.950g / cm 3 , 0.870g / cm 3 ~0.920g / cm 3 , or 0.870 g / cm 3 ~0.900g / cm 3 The density of the sintered body may be 0.01 to 0.01.

[0127] In an embodiment, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a melt flow ratio (I 10 / I2), where the melt index I2 is measured at 190° C. and a load of 2.16 kg in accordance with ASTM D1238, which is incorporated herein by reference in its entirety, and the melt index I 10 is measured at 190° C. and a load of 10 kg according to ASTM D1238. In another embodiment, the melt flow ratio (I 10 / I2) is 5-10, and in other embodiments the melt flow ratio is 5-9.

[0128] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a melt index (I2) of 0.1 to 100, the melt index I2 being measured at 190° C. and a load of 2.16 kg according to ASTM D1238, which is incorporated herein by reference in its entirety.

[0129] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a molecular-weight distribution (MWD) of 1.0 to 25, where MWD is the molecular weight distribution of M w / M n is defined as M w is the weight average molecular weight, M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1.5 to 6. Another embodiment includes an MWD of 1.5 to 3, and another embodiment includes an MWD of 2 to 2.5.

[0130] SymRAD HT-GPC analysis Molecular weight data are determined by analysis on a hybrid robot-assisted dilution high temperature gel permeation chromatography instrument (Sym-RAD-GPC) built by Symyx / Dow. Polymer samples are dissolved by heating at 160° C. for 120 min in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL stabilized with 300 parts per million (ppm) butylated hydroxyl toluene (BHT). Each sample was diluted to 1 mg / mL immediately before injecting a 250 μL aliquot of sample. The GPC is equipped with two Polymer Labs PLgel 10 μm MIXED-B columns (300×10 mm) at a flow rate of 2.0 mL / min at 160° C. Sample detection is performed using a PolyChar IR4 detector in concentration mode. Conventional calibration of narrow polystyrene (PS) standards utilizes apparent units adjusted to homopolyethylene (PE) using the known Mark-Houwink coefficients for PS and PE in the TCB at this temperature.

[0131] 1-Octene Incorporation IR Analysis A sample run for HT-GPC analysis precedes the IR analysis. For IR analysis, a 48-well HT silicon wafer is utilized for sample deposition and analysis of 1-octene incorporation. For analysis, the sample is heated to 160°C for no more than 210 minutes, the sample is reheated to remove the magnetic GPC stir bar, and shaken with a glass rod stir bar on a J-KEM Scientific heated robotic shaker. The sample is deposited with heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene is evaporated from the deposition wells of the wafer at 160°C under a nitrogen purge. Analysis of 1-octene is performed on the HT silicon wafer using a NEXUS 670 ESPFT-IR. EXAMPLES

[0132] Examples 1-22 are synthetic procedures for intermediates of the ligand, the ligand itself, and isolated metal-ligand complexes containing the ligand. Example 24 describes the polymerization results obtained from the metal-ligand complexes prepared according to Examples 1-23. It should be understood that Examples 1-23 are provided to illustrate the embodiments described in this disclosure, and are not intended to limit the scope of this disclosure or its appended claims.

[0133] Example 1 - Synthesis of metal-ligand complex 1 of the present invention (IMLC-1):

[0134] [ka]

[0135] In a nitrogen glovebox, an oven-dried vial was charged with ScCl3 (0.016 g, 0.106 mmol), THF (approximately 50 mL), and a magnetic stir bar. The mixture was cooled at -30°C, then LiCH2TMS (1.0 M in pentane, 0.35 mL, 0.35 mmol) was added dropwise, and the mixture was then stirred at room temperature for 1.5 h. To this mixture was slowly added 1 equivalent of ligand formula i (0.168 g, 0.106 mmol) in THF (approximately 10 mL), and the reaction mixture was stirred at room temperature for 18 h. The solvent was then removed in vacuo to give IMLC-1 as a white solid (0.154 g, 83%).

[0136] 1H NMR(400MHz,ベンゼン-d6)δ 8.18(dd,J=10.3,8.2Hz,2H),8.08(dd,J=11.9,8.3Hz,2H),7.93(d,J=1.7Hz,1H),7.71(dd ,J=7.7,1.7Hz,2H),7.66(d,J=2.8Hz,1H),7.61(d,J=2.7Hz,1H),7.57(dd,J=8.8,1.7Hz,2H ),7.54-7.44(m,3H),7.40-7.29(m,4H),7.21(dd,J=1.8,0.8Hz,1H),7.05(dd,J=1.8,0.8Hz ,1H),4.07(s,1H),3.74-3.61(m,3H),3.61-3.52(m,2H),3.21-3.10(m,2H),1.74(s,3H),1. 70-1.63(m,2H),1.62(s,9H),1.60-1.53(m,2H),1.51(s,9H),1.48(s,3H),1.39-1.23(m,34 H),1.37(s,3H),1.30(s,9H),1.21(s,9H),1.16-1.02(m,5H),0.96-0.84(m,6H),0.90(s,9H) ),0.89(s,9H),0.77(dt,J=9.4,6.9Hz,2H),0.66(d,J=6.8Hz,2H),0.26(s,3H),0.24(s,3H) ,0.15(s,3H),0.12(s,3H),-0.32(s,9H),-0.66(d,J=12.3Hz,1H),-1.37(d,J=12.3Hz,1H).

[0137] International Publication No. 2017 / 058981 (A1) details the modulation of the されている coordination subunit.

[0138] Example 2 - Synthesis of the present metal-ligand complex 2 (IMLC-2):

[0139]

change

[0140] In a glove box, a vial was charged with ScCl3 (0.027 g), THF (approximately 10 mL), and a magnetic stir bar. The mixture was cooled at -30°C, and then LiCH2TMS (approximately 0.55 mL) was added dropwise at room temperature. After stirring for 2 h, 1 equivalent of ligand formula ii (0.226 g) in THF (approximately 5 mL) was added, and the reaction mixture was stirred at room temperature for 18 h. The solvent was then removed in vacuo to give IMLC-2 as a white solid (0.074 mg, 28% yield).

[0141] 1 H NMR (400 MHz, benzene-d6) (selected peaks) δ 8.20 (d, J = 8.2 Hz, 1H), 8.16 (d, J = 8.2 Hz, 1H), 8.14-8.09 (m, 1H), 8.06 (d, J = 8.3 Hz, 2H), 7.81 (d, J = 1.7 Hz, 1H), 7.61 (d, J = 1.6 Hz, 1H), 7.57 (d, J = 2.7 Hz, 1H), 7.51-7.40 (m, 4H), 7.35-7.26 (m, 6H), 7.22-7.17 (m, 1H), 7.03 (dd, J = 9.0, 3.2 Hz, 1H). ,6.43-6.35(m,1H),6.26-6.18(m,1H),3.97-3.85(m,1H),3.58-3.40(m,5H),3.20-3.11(m,2H),1.59(s,9H),1.50(s,9) H),1.27(s,9H),1.19(s,9H),0.85(s,9H),0.83(s,9H),-0.31(s,9H),-0.70(d,J=12.3Hz,1H),-1.42(d,J=12.3Hz,1H).

[0142] 19 F NMR (376 MHz, benzene-d6) δ -115.55, -116.83.

[0143] Preparation of ligands of formula ii as detailed in WO 2014 / 105411(A1).

[0144] Example 3 - Synthesis of metal-ligand complex 3 of the present invention (IMLC-3):

[0145] [ka]

[0146] In a glove box, a 250 mL glass bottle was charged with ScCl3 (0.200 g), THF (approximately 25 mL), and a magnetic stir bar. To this was slowly added LiCH2TMS (1.0 M in hexanes, 4 mL), and the mixture was stirred at room temperature for 4 hours. To this colorless, almost clear mixture was added ligand formula iii (1.62 g), and an immediate darkening of the reaction mixture was observed (transparent dark gray). After stirring the reaction mixture at room temperature for 1 hour, the mixture was filtered, and the filtrate was then dried under vacuum to give IMLC-3 as an off-white solid (1.08 g, 57% yield).

[0147] 1 H NMR (400 MHz, benzene-d6) (selected peaks of major product) δ 8.58 (s, 1H), 8.48 (d, J = 6.9 Hz, 2H), 8.43 (s, 1H), 8.26 (s, 1H), 7.77-6.95 (m, 12H), 6.85 (s, 1H), 6.51 (d, J = 4.9 Hz, 1H), 6.45-6.34 (m, 1H), 5.54 (s, 1H), 5.23 (s, 1H), 4.51 (s, 1H), 3. 63(s,2H),3.44(s,1H),3.36(m,2H),2.86(m,2H),1.51(s,9H),1.499(s,9H),1.497(s,9H ),1.44(s,9H),0.84(m,18H),-0.24(s,9H),-1.39-1.45(m,2H),-2.00(d,J=12.7Hz,1H).

[0148] 19 F NMR (376 MHz, benzene-d6) δ -115.52, -118.51.

[0149] The preparation of ligands of formula iii is detailed in WO 2012 / 027448 A1.

[0150] Example 4 - Synthesis of metal-ligand complex 4 of the present invention (IMLC-4):

[0151] [ka]

[0152] In a glove box, a 250 mL glass bottle was charged with ScCl3 (0.030 g, 0.20 mmol), THF (approximately 50 mL), and a magnetic stir bar. LiCH2TMS (1.0 M in pentane, 0.60 mL, 0.60 mmol) was slowly added, and the mixture was then stirred at room temperature for 2 h. Ligand formula iv (0.249 g, 0.199 mmol) was dissolved in THF and then slowly added to the bottle, and the contents were stirred at room temperature for 18 h. The solvent was then removed in vacuo, and the product was extracted in pentane and passed through a fritted funnel. The filtrate was concentrated under reduced pressure to give IMLC-4 as a white solid (0.213 g, 74% yield).

[0153] 19 F NMR (376 MHz, benzene-d6) δ -115.54, -117.69.

[0154] Preparation of ligands of formula iv as detailed in WO 2016 / 003878 A1.

[0155] Example 5 - Synthesis of metal-ligand complex 5 of the present invention (IMLC-5):

[0156] [ka]

[0157] In a glove box, a 250 mL glass bottle was charged with ScCl3 (0.029 g, 0.19 mmol), THF (approximately 50 mL), and a magnetic stir bar. LiCH2TMS (1.0 M in pentane, 0.58 mL, 0.58 mmol) was slowly added, and the mixture was then stirred at room temperature for 2 h. Ligand Formula v (0.269 g, 0.192 mmol) was dissolved in THF and then slowly added to the bottle, and the contents were stirred at room temperature for 18 h. The solvent was then removed in vacuo, and the product was extracted in pentane and passed through a fritted funnel. The filtrate was concentrated under reduced pressure to give IMLC-5 as a white solid (0.075 g, 24% yield).

[0158] 1 H NMR (400 MHz, benzene-d6) (selected peaks of major product) δ 8.21-8.10 (m, 3H), 8.07 (d, J = 8.3, 1H), 7.69 (d, J = 1.7 Hz, 1H), 7.54 (d, J = 3.0, 1H), 7.51-7.30 (m, 10H), 7.26 (q, J = 3.0 Hz, 1H), 7.04 (d, J = 5.6 Hz, 1H), 6.41-6.34 (m, 1H), 6.26-6.16 (m, 1H), 5.20 (d, J = 12.6 Hz, 1H), 4.76 (d, J = 12.1 Hz, 1H), 4 .03(d,J=12.5Hz,1H),3.78(d,J=12.0Hz,1H),3.62-3.46(m,2H),3.06(m,2H),1.51(s,9H),1.46(s,9H),1.34(s,9H) ,1.28(s,9H),0.72(s,9H),0.68(s,9H),0.34(s,3H),-0.31(s,9H),-0.60(d,J=12.7Hz,1H),-1.17(d,J=12.6Hz,1H).

[0159] 19 F NMR (376 MHz, benzene-d6) δ -116.68, -117.55.

[0160] Example 6 - Synthesis of 2-bromo-4-fluoro-6-methyl-phenol - Preparation of ligand formula (v):

[0161] [ka]

[0162] A 1 liter glass bottle was charged with acetonitrile (ACN) (400 mL), 4-fluoro-6-methyl-phenol (50 g, 396 mmol), and p-toluenesulfonic acid (monohydrate) (PTSA) (75.6 g, 396 mmol) making sure everything was in solution. The solution was cooled to 0° C. in ice for 25 minutes (a precipitate formed). The cooled solution was treated slowly (over approximately 5 minutes) with N-bromosuccinimide (NBS) (70.6 g, 396 mmol) and allowed to reach room temperature with stirring overnight. The volatiles were removed under vacuum and the resulting solid was treated with CHCl (600 mL), cooled in a freezer (0° C.), and filtered through a large plug of silica gel. The silica gel was washed several times with cold CHCl. The volatiles were removed in vacuo to give the product (46 g, 56%).

[0163] 1 H NMR(400MHz,CDCl3)δ 7.05(ddd,J=7.7,3.0,0.7Hz,1H),6.83(ddt,J=8.7,3.0,0.8Hz,1H),5.35(s,1H),2.29(d,J=0.7Hz,3H); 19 F NMR (376MHz, CDCl3)δ-122.84.

[0164] Example 7 - Synthesis of bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermanephenol - Preparation of ligand formula (v):

[0165] [ka]

[0166] In a glove box, in a 250 mL flask equipped with a magnetic stir bar, sodium hydride (NaH) (1.756 g) (Caution: H2 gas is generated) was slowly added to a solution of 2-bromo-4-fluoro-6-methyl-phenol (15 g, 73.16 mmol) in DMF (35 mL) until hydrogen evolution ceased. The mixture was stirred at room temperature for 30 min. After this time, diisopropylgermyl dichloride (6.286 g, 24.4 mmol) was added. The mixture was warmed to 55° C. and held at this temperature for 18 h. The reaction was removed from the glove box and quenched with saturated aqueous NH4Cl (20 mL) and H2O (8 mL). Et2O (30 mL) was added and the phases were transferred to a separatory funnel and separated. The aqueous phase was further extracted with Et2O (20 mL) and the combined organic extracts were washed with brine (10 mL). The organic layer was then dried (MgSO4), filtered, and concentrated to dryness. The crude residue was dry loaded onto silica gel and then purified using flash chromatography (100 mL / min, pure hexanes with ethyl acetate rising to 10% over 20 min) to give a pale yellow oil as the product. All clean fractions (some fractions contained less than 10% of the starting phenol) were combined and the final product was left under vacuum on a Schlenk line overnight (yield: 9 g, 62%).

[0167] 1 H NMR(400MHz,CDCl3)δ 7.10(dd,J=7.7,3.0Hz,2H),6.84(ddd,J=8.8,3.1,0.8Hz,2H),4.14(s,4H),2.33(s,6H),1.74(hept,J=7.4Hz,2H),1.35(d,J=7.4Hz,12H); 19 F NMR (376MHz, CDCl3)δ-118.03.

[0168] Example 8 - Synthesis of ligand formula (v):

[0169] [ka]

[0170] A 500 mL glass bottle equipped with a stir bar was charged with 2,7-di-tert-butyl-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() (29.0 g, 41.9 mmol), bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermane (6.00 g, 8.65 mmol, containing 10% 2-bromo-4-fluoro-2-methyl-phenol), and THF (80 mL). The solution was heated to 55° C. and treated with chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (tBu3P-PdG2) (199 mg, 0.346 mmol, 4 mol%) while stirring. Aqueous NaOH (17.3 mL, 51.9 mmol, 3 M) was purged with nitrogen for 20 min and then added to the THF solution. The reaction was stirred at 55° C. overnight. The aqueous phase was separated and discarded, and the remaining organic phase was diluted with diethyl ether and washed twice with brine. The solution was passed through a short plug of silica gel. The filtrate was dried on a rotary evaporator, dissolved in THF / MeOH (40 mL / 40 mL), treated with HCl (2 mL), and stirred at 70° C. overnight. The solution was dried under vacuum and purified by C18 reverse phase column chromatography (yield: 6.5 g, 54%).

[0171] 1 H NMR(400MHz,CDCl3)δ 8.01(d,J=8.2Hz,4H),7.42(dd,J=25.5,2.4Hz,4H),7.32(dd,J=8.2,1.6Hz,4H),7.17(s,4H),6.87(ddd,J=16.4,8.8,3.0 Hz,4H),6.18(s,2H),3.79(s,4H),2.12(s,6H),1.71(s,6H),1.56(s,4H),1.38(s,12H),1.31(s,36H),0.83-0.73(m,30H); 19 F NMR (376MHz, CDCl3)δ-119.02.

[0172] Example 9 - Synthesis of metal-ligand complex 6 of the present invention (IMLC-6):

[0173] [ka]

[0174] Preparation of ligand formula vi as detailed in WO 2018 / 170138(A1). In a glove box, a 250 mL glass bottle was charged with ScCl3 (0.217 g, 1.44 mmol), THF (approximately 100 mL), and a magnetic stir bar. LiCH2TMS (1.0 M in pentane, 4.4 mL, 4.4 mmol) was slowly added, and the mixture was then stirred at room temperature for 2 hours. Ligand formula vi (1.58 g, 1.44 mmol) was dissolved in THF, then slowly added to the bottle, and the contents were stirred at room temperature for 18 hours. The solvent was then removed in vacuo, and the product was extracted in pentane and passed through a fritted funnel. The filtrate was concentrated under reduced pressure to give IMLC-6 as an off-white solid (1.28 g, 68% yield).

[0175] 1 H NMR (400 MHz, benzene-d6) δ (selected peaks of major product) 8.22 (d, J = 7.6 Hz, 1H), 8.19 (d, J = 7.7 Hz, 1H), 8.09 (d, J = 8.2 Hz, 1H), 8.04 (d, J = 8.2 Hz, 1H), 7.93 (d, J = 7.9 Hz, 1H), 7.63 (d, J = 7.9 Hz, 1H), 7.60-7.02 (overlap, 18H), 6.75 (ddd, J = 9.0, 7.3, 3.2 Hz, 1H), 6. 45-6.38(m,1H),5.59(ddd,J=8.7,4.9,3.7Hz,1H),4.92(dd,J=8.9,5.1Hz,1H),4.85(dd,J=9.1,5.0Hz,1H),4.42(t,J =12.2Hz,1H),3.73-3.61(m,2H),3.30-3.17(m,2H),-0.27(s,10H),-1.72(d,J=12.7Hz,1H),-2.23(d,J=12.6Hz,1H).

[0176] 19F NMR (376 MHz, benzene-d6) δ -116.55, -118.23.

[0177] Example 10 - Preparation of ligand formula (vii) - Synthesis of 4-(octyloxy)phenol (2)

[0178] [ka]

[0179] To a stirred solution of hydroquinone (1) (20 g, 0.181 mol) in DMF (100 mL) was added NaOH (6.67 g, 0.167 mol). 1-Bromooctane (n-Oct-Br) (26.1 mL, 0.150 mol) was then added dropwise to the flask at room temperature, followed by heating the reaction mixture to 60° C. and stirring at this temperature for 12 h. After cooling to room temperature, the reaction mixture was poured into water (300 mL) and the aqueous phase was extracted with EtOAc (300 mL). The organic layer was washed with water (3×100 mL), dried over anhydrous Na2SO4, filtered, and then concentrated to dryness. The residue was purified by SiO2 gel column chromatography. The product was eluted using 10% EtOAc in petroleum (pet) ether, which gave 15.5 g (46%) of 4-(octyloxy)phenol (2): 1 H NMR(400MHz, CDCl3)δ 0.91(t,J=6.92Hz,3H),1.31-1.48(m,10H),1.74-1.81(m,2H),3.92(t,J=6.60Hz,2H),6.76-6.82(m,4H).

[0180] Example 11 - Preparation of ligand formula (vii) - Synthesis of 2-iodo-4-(octyloxy)phenol (3)

[0181] [ka]

[0182] To a solution of 4-(octyloxy)phenol (2) (15.5 g, 0.069 mol) in MeOH (200 mL) was added potassium iodide (KI) (12.6 g, 0.076 mol). The reaction mixture was cooled to 0°C. While maintaining the temperature at 0-3°C, NaOH (3.28 g, 0.082 mol) and 13% aqueous sodium hypochlorite (NaOCl) solution (39.9 mL, 0.069 mol) were added dropwise over 3 h. The resulting mixture was stirred at 0-3°C for 8 h. The mixture was neutralized using 1.5 normal (N) aqueous HCl solution and MeOH was removed under reduced pressure at 35°C. The aqueous layer was extracted with EtOAc (2 x 200 mL) and the combined organic layers were dried over anhydrous Na2SO4, filtered, and then concentrated to dryness. The resulting residue was purified by SiO2 gel column chromatography using 10% EtOAc in petroleum ether to give 5.2 g (22%) of 2-iodo-4-(octyloxy)phenol (3).

[0183] 1 H NMR(400MHz,CDCl3)δ 0.90(t,J=7.20Hz,3H),1.27-1.46(m,10H),1.71-1.77(m,2H),3.88(t,J=6.40Hz,2H),4. 90(s,1H),6.83(dd,J=2.80,8.80Hz,1H),6.91(d,J=8.80Hz,1H),7.19(d,J=2.80Hz,1H); LCMS: 347(M-1).

[0184] Example 12 - Preparation of ligand formula (vii) - Synthesis of 2-(2-iodo-4-(octyloxy)phenoxy)tetrahydro-2H-pyran (4)

[0185] [ka]

[0186] To a solution of 2-iodo-4-(octyloxy)phenol (3) (5.2 g, 0.014 mol) in methylene chloride (CHCl) (50 mL) was added para-toluenesulfonic acid (p-TsOH) (0.026 g, 0.00014 mol). The stirred solution was cooled to 0° C., then 3,4-dihydro-2H-pyran (3.8 mL, 0.042 mol) was added dropwise. The resulting mixture was allowed to warm to room temperature and then stirred for 16 h. The reaction mixture was concentrated to dryness under reduced pressure. The residue was purified by neutral alumina column chromatography eluting with 2-3% EtOAc in petroleum ether to give 5.1 g (84%) of 2-(2-iodo-4-(octyloxy)phenoxy)tetrahydro-2H-pyran (4).

[0187] 1 H NMR(400MHz,CDCl3)δ 0.90(t,J=7.20Hz,3H),1.30-1.63(m,11H),1.68-1.78(m,4H),1.84-1.91(m,1H),1.97-2.01(m,1H),2.13-2.17(m,1H),3.59 -3.64(m,1H),3.87-3.96(m,3H),5.38(s,1H),6.83(dd,J=2.80,8.80Hz,1H),7.00(d,J=8.80Hz,1H),7.32(d,J=2.80Hz,1H); 13 C NMR(100MHz, CDCl3)δ 14.1,18.4,22.7,25.3,26.0,29.2,29.3,30.3,31.8,61.8,68.7,87.8,97.5,115.5,116.3,124.9,149.9,154.2.

[0188] Example 13 - Preparation of ligand formula (vii) - Synthesis of 2,7-di-tert-butyl-9-(5-(octyloxy)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole (6)

[0189] [ka]

[0190] A 100 mL flask was charged with 2-(2-iodo-4-octoxy-phenoxy)tetrahydropyran (4) (2.45 g, 5.67 mmol), 2,7-ditert-butyl-9H-carbazole (5) (2.06 g, 7.37 mmol), copper iodide (CuI) (0.03 g, 0.17 mmol), diamine (0.12 ml, 1.19 mmol), and potassium phosphate tribasic (K3PO4) (3.01 g, 14.17 mmol), followed by the addition of toluene (22 mL). The flask was fitted with a condenser and the solution was stirred at 135° C. for 18 hours (external temperature, reaction should be at reflux). There still appeared to be about 50% starting material remaining. Additional CuI and diamine (same amounts as above) were added and the reaction was continued overnight. The reaction was still proceeding. Additional CuI (32 mg) was added and the reaction was continued overnight. The reaction was still proceeding. Additional CuI (32 mg) was added and the reaction was continued overnight.

[0191] The reaction was cooled to room temperature and then filtered through a SiO2 gel plug. The plug was washed with Et2O (65 mL). The solvent was removed under reduced pressure. The residue was directly purified using SiO2 gel column chromatography (15 g CELITE loaded cartridge, 80 g SiO2, 60 mL / min, 0% hexane to 20% hexane / acetone). The material was not clean so a second column was run. The residue was directly purified using reverse phase column chromatography (15 g CELITE loaded cartridge, 50 g C18, 0% THF to 10% THF / CH3CN, then increased to 95% THF / CH3CN and held for 5 min). The product, 2,7-di-tert-butyl-9-(5-octoxy-2-tetrahydropyran-2-yloxy-phenyl)carbazole (6), was obtained as an off-white solid in 73% yield (2.4 g).

[0192] 1H NMR(400MHz,CDCl3)δ 7.97(ddd,J=8.2,1.6,0.6Hz,2H),7.39(d,J=9.0Hz,1H),7.29(dd,J=8.2,1.7Hz,2H),7.2 4(dd,J=1.7,0.6Hz,1H),7.17(dd,J=1.7,0.6Hz,1H),7.04(d,J=3.0Hz,1H),7.00(dd,J=9 .0,3.1Hz,1H),5.08-4.94(m,1H),3.94(t,J=6.6Hz,2H),3.69(td,J=10.9,2.9Hz,1H),3. 42(dt,J=11.3,3.7Hz,1H),1.79(p,J=6.7Hz,2H),1.54-1.00(m,34H),0.92-0.82(m,3H).

[0193] Example 14 - Preparation of ligand formula (vii) - Synthesis of 2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(octyloxy)-[1,1'-biphenyl]-2-ol) (8) (ligand of formula (vii))

[0194] [ka]

[0195] Preparation of ArZnX solution from 6: 2.4 M n-Butyllithium (n-BuLi) in hexane (0.76 mL, 1.82 mmol) was added to a solution of 2,7-ditert-butyl-9-(5-octoxy-2-tetrahydropyran-2-yloxy-phenyl)carbazole (6) (1.01 g, 1.74 mmol) in THF (7 mL, dried and degassed) in a 40 mL vial in a glove box at −35° C. The solution was stirred for 1.5 h and then recooled to −35° C. A solution of dichlorozinc (ZnCl2) (0.23 g, 1.70 mmol) in THF (3 mL) was then added and the resulting solution was stirred at room temperature for 1 h.

[0196] Cross join: A solution of dibromide 7 (0.34 g, 0.76 mmol) and Pd-Amphos (0.01 g, 0.03 mmol) in THF (3 mL) was added to the above ArZnX solution prepared from 6. The reaction was warmed to 50° C. and maintained at this temperature for 18 h. After this time, the vial was removed from the glove box and MeOH (5 mL) and concentrated HCl (5 drops from a glass pipette) were added to the reaction mixture. The solution was stirred at room temperature for 6 h. The solvent was removed under reduced pressure. The remaining crude residue was evaporated from MeOH (4×5 mL) to give a brown solid. This solid was triturated with MeOH (10 mL) and the insoluble product was collected by filtration. The filter cake was washed with MeOH (2×4 mL). The solid in the filter cake was collected and dried under vacuum to give 2-(2,7-ditert-butylcarbazol-9-yl)-6-[2-[3-[2-[3-(2,7-ditert-butylcarbazol-9-yl)-2-hydroxy-5-octoxy-phenyl]-4-fluoro-6-methyl-phenoxy]propoxy]-5-fluoro-3-methyl-phenyl]-4-octoxy-phenol (8) (0.675 g, yield: 69%) as a tan solid.

[0197] 1 H NMR(400MHz,CDCl3)δ 7.99(d,J=8.2Hz,4H),7.29(dd,J=8.2,1.7Hz,4H),7.08(d,J=1.5Hz,4H),7.04-6.95(m,6H),6.87-6.80(m,2H),6.06(s, 2H),3.88(t,J=6.6Hz,4H),3.65(t,J=6.2Hz,4H),2.03(s,6H),1.83-1.64(m,6H),1.48-1.22(m,56H),0.94-0.79(m,6H); 19 F NMR(376MHz, CDCl3)δ-118.36.

[0198] Example 15 - Synthesis of metal-ligand complex 7 of the present invention (IMLC-7):

[0199] [ka]

[0200] A solution of ScCl3 (0.02 g, 0.16 mmol) in THF (6 mL) was cooled to -35°C. 1M TMSCH2Li in pentane (1M, 0.5 mL, 0.497 mmol) was added to the cold solution, which was then stirred at room temperature for 4 hours, and the slightly cloudy solution was then cooled in a freezer (-35°C) for 5 minutes. Ligand formula vii (0.2 g, 0.16 mmol) in THF (1 mL) was added dropwise. The solution was stirred at room temperature overnight. The solvent was removed by vacuum, and then pentane (4 mL) was added to the residue. The mixture was stirred for 1 minute, and then the solvent was removed by vacuum. Pentane (5 mL) was added to the residue, and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with pentane (5 mL). The combined pentane extracts were dried under vacuum to give (IMLC-7) as an off-white solid (65%, 0.150 g).

[0201] 1H NMR (400 MHz, CD6D6) (selected peaks) δ 8.20 (d, J = 8.2 Hz, 1H), 8.15 (dd, J = 8.2, 5.5 Hz, 2H), 8.07 (d, J = 8.2 Hz, 1H), 7.82 (d, J = 1.6 Hz, 1H), 7.65 (d, J = 1.6 Hz, 1H), 7.60 (d, J = 1.6 Hz, 1H), 7.50-7.40 (m, 3H), 7.35 ( ddd,J=13.0,8.3,1.7Hz,2H),7.14(d,J=3.5Hz,1H),7.10(d,J=3.4Hz,1H),7.02(d, J=3.4Hz,1H),6.99(dd,J=9.3,3.2Hz,1H),6.95(d,J=3.4Hz,1H),6.81(dd,J=9.0,3. 3Hz,1H),6.29(dd,J=8.2,3.1Hz,1H),6.14(dd,J=8.3,3.1Hz,1H),3.91(dd,J=10.7 ,8.2Hz,1H),3.68(dt,J=9.1,6.4Hz,1H),3.55(ddt,J=21.5,9.1,6.3Hz,2H),3.49- 3.33(m,4H),3.31-3.24(m,1H),3.23-3.12(m,3H),1.50(s,9H),1.42(s,9H),1.31( s,9H),1.26(s,9H),-0.30(s,9H),-0.70(d,J=12.2Hz,1H),-1.33(d,J=12.2Hz,1H).

[0202] 19 F NMR(376MHz,C6D6)δ-115.84,-117.09.

[0203] Example 16 - Synthesis of metal-ligand complex 8 of the present invention (IMLC-8):

[0204] [ka]

[0205] Ligand viii prepared according to the procedure cited in WO 2016 / 089935(A1).

[0206] A solution of ScCl3 (0.0356 g, 0.235 mmol) in THF (6 mL) was cooled to -35 °C. TMSCH2Li (1 M, 0.739 mL, 0.739 mmol) in pentane was added to the cold solution, which was stirred at room temperature for 4 h, then the slightly cloudy solution was cooled in a freezer (-35 °C) for 5 min. Ligand formula viii (0.275 g, 0.224 mmol) in THF (1 mL) was added dropwise to the cold solution. The reaction mixture was stirred at room temperature overnight. The solvent was removed by vacuum, then pentane (4 mL) was added to the residue. The mixture was stirred for 1 min, then the solvent was removed by vacuum. Pentane (10 mL) was added to the residue, and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with pentane (2 x 8 mL). The combined pentane extracts were dried under vacuum to give an off-white solid. Pentane (5 mL) was added to the solid and the solution was placed in a freezer (−35° C.). After 72 h, the pentane layer was removed using a pipette. The remaining white solid was dried under vacuum to give (IMLC-8) as a white solid (55%, 0.175 g).

[0207] 1H NMR(400MHz,C6D6)(selected)δ 8.01(d,J=8.2Hz,1H),7.93(dd,J=8.2,4.7Hz,2H),7.86(d,J=8.2Hz,1H),7.73(d,J=1.6Hz,1H),7.47(d,J=2.6Hz,1H),7.40(d,J=2.6Hz, 1H),7.37(dd,J=8.2,1.6Hz,1H),7.32-7.17(m,7H),7.13-7.04(m,3H),6.76(dd,J=8.6,3.1Hz,1H),6.68(dd,J=8.2,3.1Hz,1H),5.37(d,J =2.0Hz,1H),4.60(d,J=2.0Hz,1H),2.64(s,2H),2.48(s,2H),2.28(s,3H),1.86(s,3H),1.59(s,9H),1.34(s,3H),1.29(s,9H),1.23(s,9H ),1.17(s,3H),1.09(d,J=1.2Hz,9H),0.92(s,9H),0.84(s,9H),-0.51(d,J=1.1Hz,9H),-1.17(d,J=12.4Hz,1H),-1.44(d,J=12.4Hz,1H).

[0208] 19 F NMR (376MHz, C6D6) δ-114.87,-117.57.

[0209] Example 17-Synthesis of the present metal-ligand complex 9 (IMLC-9):

[0210]

change

[0211] International Publication No. 2014 / 105411 (A1) details the modulation of the ix coordination formula.

[0212] A solution of ScCl3 (0.0448 g, 0.296 mmol) in THF (8 mL) was cooled to -35 °C. TMSCH2Li (1 M, 0.902 mL, 0.902 mmol) in pentane was added to the cold solution, which was stirred at room temperature for 4 h, then the slightly cloudy solution was cooled in a freezer (-35 °C) for 5 min. Ligand formula ix (0.350 g, 0.282 mmol) in THF (1 mL) was added dropwise to the cold solution. The reaction mixture was stirred at room temperature overnight. The solvent was removed by vacuum, then pentane (10 mL) was added and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with pentane (2 x 4 mL). A new vial was used and the CELITE pad was then extracted with toluene (2 x 8 mL). The combined toluene extracts were dried under vacuum to give an off-white semi-solid. Pentane (6 mL) was added to the semi-solid and the material was triturated to give a white powder. The pentane layer was removed using a pipette. The solid was dried under vacuum to give (IMLC-9) as a white solid (57%, 0.230 g).

[0213] 1H NMR (400 MHz, CD) (selected peaks) δ 8.22 (d, J = 8.2 Hz, 1H), 8.17 (d, J = 8.2 Hz, 1H), 8.13 (d, J = 8.2 Hz, 1H), 8.02 (d, J = 8.2 Hz, 1H), 7.68 (d, J = 1.6 Hz, 1H), 7.59 (d, J = 1.6 Hz, 1H), 7.46-7.29 (m, 10H), 7.21 (dt, J = 9.1, 2.8 Hz, 2H), 6.37 (dd, J = 8.5, 3.1 Hz, 1H), 6.28 (ddd, J = 8.8, 7.3, 3.2 Hz, 1H), 5.80 (dd, J = 8.8, 5.2 Hz, 1H), 4.13 (t, J = 9.6 Hz, 1H ),3.76(ddd,J=9.5,6.4,3.3Hz,1H),3.65(td,J=8.7,3.3Hz,1H),3.60-3. 51(m,1H),3.12(d,J=7.6Hz,2H),3.03(d,J=7.9Hz,2H),1.47(s,9H),1.37 (s,9H),1.26(s,9H),1.25(s,9H),1.16(d,J=5.4Hz,12H),0.84(s,9H),0. 79(s,9H),-0.26(s,9H),-0.64(d,J=12.7Hz,1H),-1.60(d,J=12.7Hz,1H).

[0214] 19 F NMR(376MHz,C6D6)δ-115.93,-116.71.

[0215] Example 18 - Synthesis of metal-ligand complex 10 of the present invention (IMLC-10):

[0216] [ka]

[0217] Ligand formula x prepared according to the procedure cited in US Pat. No. 9,522,855 (B2).

[0218] A solution of ScCl3 (0.0640 g, 0.423 mmol) in THF (8 mL) was cooled to -35 °C. TMSCH2Li (1 M, 1.29 mL, 1.29 mmol) in pentane was added to the cold solution, which was then stirred at room temperature for 4 h, and the slightly cloudy solution was then cooled in a freezer (-35 °C) for 5 min. Ligand formula x (0.350 g, 0.403 mmol) in THF (1 mL) was added dropwise. The solution was stirred at room temperature overnight. The solvent was removed by vacuum, and then pentane (4 mL) was added to the residue. The mixture was stirred for 1 min, and then the solvent was removed by vacuum. Pentane (10 mL) was added to the residue, and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with pentane (2 x 8 mL). A new vial was used, and then the CELITE pad was extracted with toluene (2 x 10 mL). The combined toluene extracts were dried under vacuum to give a slightly yellow oil. Pentane (6 mL) was added and the oil triturated to give a white powder. The pentane layer was removed using a pipette. Again, pentane (6 mL) was added to the white powder and then the pentane layer was removed using a pipette. The solid was dissolved in a minimum amount of toluene (approximately 1.5 mL) which was then layered with pentane (approximately 5 mL). The solution was placed in a freezer (-35°C) for 24 hours. The solvent was removed from the precipitate using a pipette to leave (IMLC-10) (63%, 0.270 g) as a white solid.

[0219] 1H NMR (400 MHz, CD6) (selected peaks of major product) δ 8.39-8.28 (m, 1H), 8.15 (ddt, J = 8.6, 7.7, 1.0 Hz, 2H), 7.93 (dt, J = 7.8, 1.0 Hz, 1H), 7.42 (d, J = 2.6 Hz, 1H), 6.60 (dd, J = 8.4, 2.6 Hz, 1H), 5.90 (d, J = 8.4 Hz, 1H), 5.45 (d, J = 8.5 Hz, 1H), 4.12 (ddd, J = 10.7, 8.9, 3.4 Hz, 1H), 4.04 (ddd, J = 10.7, 9.0 ,3.3Hz,1H),3.01(ddd,J=8.8,3.4,1.7Hz,1H),2.76(ddd,J=9.1,3.4,1.7Hz,1H),2.73-2.56(m,4H),2.27(s,3H),2.1 7(s,3H),1.32(s,9H),1.17(s,9H),0.73-0.62(m,4H),-0.25(s,9H),-1.84(d,J=12.4Hz,1H),-2.36(d,J=12.4Hz,1H).

[0220] Example 19 - Synthesis of metal-ligand complex 11 of the present invention (IMLC-11):

[0221] [ka]

[0222] Preparation of ligands of formula xi as detailed in WO 2018 / 183056(A1).

[0223] In a glove box, a glass bottle was charged with ScCl3 (0.101 g, 0.669 mmol), THF (approximately 100 mL), and a magnetic stir bar. To this LiCH2TMS (1.0 M in pentane, 2.0 mL, 2.0 mmol) was slowly added, and the resulting mixture was then stirred at room temperature for 2 h. Ligand formula xi (0.718 g, 0.669 mmol) was dissolved in THF, then added, and the mixture was continued to stir for 18 h. The solvent was removed in vacuum, and the product was then extracted in hexane and passed through a fritted funnel. The filtrate was dried in vacuum to give IMLC-11 as a white solid (0.682 g, 80%).

[0224] g, 79.9%).

[0225] Example 20 - Synthesis of metal-ligand complex 12 of the present invention (IMLC-12):

[0226] [ka]

[0227] Preparation of ligands of formula xii as detailed in WO 2017 / 058858 A1.

[0228] A 40 mL oven-dried vial was charged with ScCl3 (22 mg, 0.14 mmol), THF (5 mL) and the stir bar was placed in the freezer (-30 °C) for 20 min. With stirring, the solution was treated with LiCH2TMS (460 μL, 0.46 mmol, 1 M) and stirred for 4 h. Upon completion, the reaction was treated (dropwise) with a chilled (-30 °C) solution of ligand formula xii (150 mg, 0.14 mmol) and THF (2 mL) and stirred for 18 h. The volatiles were removed under vacuum, the solution was treated with pentane (10 mL), the solution was filtered through Celite, and the volatiles were removed under vacuum to give IMLC-12 (yield: 100 mg, 59%).

[0229] Example 21 - Synthesis of metal-ligand complex 13 of the present invention (IMLC-13):

[0230] [ka]

[0231] In a glove box, a 250 mL glass bottle was charged with YCl3 (0.069 g, 0.35 mmol) and THF (approximately 50 mL). To this stirred mixture, LiCH2TMS (1.0 M in hexanes, 1.1 mL, 1.1 mmol) was added and the mixture was stirred for 2 h. Ligand formula iii (0.434 g, 0.353 mmol) was dissolved in THF and then slowly added to the mixture to give a yellow mixture. The mixture was stirred at room temperature for 18 h and then the solvent was removed in vacuo to give a yellow solid. The product was extracted in hexanes and then passed through a fritted funnel. The yellow eluate was collected and dried in vacuum to give IMLC-13 as a yellow solid (0.122 g, 23% yield).

[0232] 1 H NMR (400 MHz, benzene-d6) (selected peaks) δ 8.57 (dd, J = 23.0, 1.9 Hz, 2H), 8.48 (m, 1H), 8.24 (d, J = 1.7 Hz, 1H), 7.69 (m, 1H), 7.60 (m, 1H), 7.54-7.49 (m, 2H), 7.33 (d, J = 8.6 Hz, 1H), 7.12 (dd, J = 9.0, 3.1 Hz, 2H), 6.88-6.77 (m, 1H), 6.46-6.42 (m, 1H). ,3.99(ddd,J=10.0,6.5,3.0Hz,1H),3.69-3.65(m,1H),1.52(s,9H),1.485(s,9H),1.479(s,9H),0. 86(s,9H),0.83(s,9H),-0.15(s,9H),-1.88(dd,J=12.1,3.6Hz,1H),-2.32(dd,J=12.1,3.9Hz,1H).

[0233] 19 F NMR (376 MHz, benzene-d6) δ -114.42, -116.71.

[0234] Example 22 - Synthesis of metal-ligand complex 14 of the present invention (IMLC-14):

[0235] [ka]

[0236] In a glove box, a 250 mL glass bottle was charged with YCl3 (0.159 g, 0.814 mmol) and THF (approximately 50 mL). To this stirred mixture, LiCH2TMS (1.0 M in hexanes, 2.5 mL, 2.5 mmol) was added and the mixture was stirred for 2 h. Ligand formula ii (1.02 g, 0.814 mmol) was dissolved in THF and then slowly added to the mixture to give a yellow mixture. The mixture was stirred at room temperature for 18 h and then the solvent was removed in vacuo to give a yellow solid. The product was extracted in hexanes and then passed through a fritted funnel. The yellow eluate was collected and dried in vacuum to give IMLC-14 as a yellow solid (0.877 g, 78% yield).

[0237] 1 H NMR (400 MHz, benzene-d6) (select peak or major product) δ 8.24 (d, J = 8.3 Hz, 1H), 8.18 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 8.8 Hz, 1H), 8.05 (d, J = 8.2 Hz, 1H), 8.03 (d, J = 8.2 Hz, 1H), 7.90 (d, J = 8.2 Hz, 1H), 7.74 (dd, J = 12.1, 1.6 Hz, 1H), 7.71 (d, J = 1.7 Hz, 1H), 7.55-6.98 (m, 8H), 6.94 (dd, J = 8.9, 3.2 Hz, 1H), 6. 68(dd,J=8.7,3.1Hz,1H),6.37(dd,J=8.5,3.1Hz,1H),6.21(dd,J=8.5,3.2Hz,1H),1.57(s,9H),1.54(s,9H),1.25(s,9 H),1.24(s,9H),0.87(s,9H),0.83(s,9H),-0.31(s,9H),-1.47(dd,J=11.4,3.5Hz,1H),-1.72(dd,J=11.3,3.7Hz,1H).

[0238] 19 F NMR (376 MHz, benzene-d6) δ -114.37, -116.13.

[0239] Example 23 - Synthesis of metal-ligand complex 15 of the present invention (IMLC-15):

[0240] [ka]

[0241] In a glove box, a 250 mL glass bottle was charged with GdCl3 (0.428 g, 1.62 mmol) and THF (approximately 100 mL). To this suspension, LiCH2TMS (1.0 M in hexanes, 5.0 mL, 5.0 mmol) was added. The mixture was stirred at room temperature for 2 hours. Ligand formula ii (2.02 g, 1.62 mmol) was then added to give a yellow mixture, which was then stirred at room temperature for 18 hours. The solvent was then removed under reduced pressure, and the resulting solid was then dissolved in hexanes and filtered. The filtrate was dried in vacuum to give IMLC-15 as a yellow solid (0.526 g, 21%). IMLC-15 is a paramagnetic compound, 1 H and 19 The signals in the F NMR spectrum are broad and unresolved.

[0242] Example 24 - Synthesis of metal-ligand complex 16 of the present invention (IMLC-16):

[0243] [ka]

[0244] In a glove box, a 250 mL glass bottle was charged with HoCl3 (0.394 g, 1.45 mmol) and THF (approximately 100 mL). HoCl3 was dissolved in THF to give a light yellow solution. LiCH2TMS (1.0 M in hexane, 4.5 mL, 4.5 mmol) was then added and the mixture was stirred for 2 h, followed by the slow addition of ligand formula i (2.26 g, 1.45 mmol) dissolved in THF. The resulting mixture was stirred at room temperature for 18 h, and then the THF was removed in vacuo. The residue was dissolved in hexane and filtered. The filtrate was collected and dried in vacuum to give IMLC-16 as a yellow solid (1.32 g, 66%). IMLC-16 is a paramagnetic compound, 1 H and 19The signals in the F NMR spectrum are broad and unresolved.

[0245] Example 25 - Synthesis of metal-ligand complex 17 of the present invention (IMLC-17):

[0246] [ka]

[0247] In a glove box, a 40 mL glass vial was charged with ScCl3 (0.17 g, 0.11 mmol) and THF (approximately 10 mL). LiCH2TMS (1.0 M in hexane, 0.34 mL, 0.34 mmol) was then added and the mixture was stirred for 2 h, followed by slow addition of ligand formula xiii (1.38 g, 0.113 mmol) dissolved in THF. The resulting mixture was stirred at room temperature for 18 h, then the THF was removed in vacuo. The residue was dissolved in hexane and filtered. The filtrate was collected and dried in vacuum to give IMLC-17 as a solid (0.100 g, 62%).

[0248] 1H NMR (400 MHz, benzene-d6) δ (major species, selected signals) 8.24-7.98 (m, 8H), 7.65 (d, J = 1.7 Hz, 1H), 7.60 (d, J = 1.8 Hz, 1H), 7.57 (d, J = 2.7 Hz, 1H), 7.54-7.23 (m, 5H), 7.19-7.04 (m, 1H), 6.97-6.93 (m, 1H), 5.03 ( dd,J=8.9,5.1Hz,1H),4.82(dd,J=8.9,5.1Hz,1H),4.37(t,J=9.9Hz,1H),3.89-3.81(m,1H),3.8 0-3.72(m,1H),3.73-3.65(m,1H),3.65-3.54(m,2H),2.85(t,J=6.1Hz,2H),1.35(s,9H),1.30(s, 9H), 1.27(s,9H), 1.20(s,9H), 0.84(s,9H), 0.81(s,9H), -0.27(s,9H), -1.47(d,J=12.9Hz,1H), -2.21(d,J=13.0Hz,1H); (minor species, selected signals) 6.57-6.46(m,2H), 6.29(td,J=8.3,3.2Hz,1H), 6.06 (dd,J=8.9,4.9Hz,1H),5.90(dd,J=9.0,4.7Hz,1H),1.55(s,9H),1.48(s,9H),1.46(s,9H),1.17( s,9H),0.85(s,9H),0.74(s,9H),-0.21(s,6H),-1.11(d,J=11.5Hz,1H),-1.37(d,J=11.5Hz,1H).

[0249] 19 F{ 1 H}NMR (376 MHz, benzene-d6) δ (major species) -115.43(s, 1F), -116.90(s, 1F); (minor species) -116.33(s, 1F), -119.99(s, 1F).

[0250] Example 26 - Preparation of 3'-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-fluoro-2'-((tetrahydro-2H-pyran-2-yl)oxy)-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol (xiii-c):

[0251] [ka]

[0252] A three-neck round bottom flask was charged with 2,7-di-tert-butyl-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 (xiii-a) (3.0612 g, 4.4121 mmol), 2-iodo-4-fluorophenol (xiii-b) (1.0001 g, 4.2021 mmol), sodium carbonate (1.3368 g, 12.6125 mmol), water (4.4 mL), and THF (6.8 mL). The reaction mixture was placed under a nitrogen atmosphere and then a solution of chloro(tri-tert-butylphosphine)(2'-amino-1,1'-biphenyl-2-yl)palladium(II) (tBu3P Pd G2) (0.0470 g, 0.0917 mmol) in THF (2.3 mL) was added via syringe. The reaction was heated at reflux (70 °C) for 1.5 h after which the contents of the flask were cooled and water was added to dissolve the remaining solids. Extraction with ethyl acetate was performed and then the organic phase was washed with brine, dried over magnesium sulfate and filtered. The solvent was removed under reduced pressure to give a brown solid which was dissolved in chloroform and loaded onto an ISCO CombiFlash system using a 300 g Gold RediSep high performance column. The product was eluted using a gradient of 1-5% ethyl acetate in hexanes and the eluent was dried in vacuo to give xiii-c as a white crystalline solid (1.6108 g, 57% yield).

[0253] 1H NMR(400MHz,chloroform-d)δ 8.06(dd,J=8.3,4.3Hz,2H),7.68(d,J=2.4Hz,1H),7.56(d,J=2.4Hz,1H),7.41( ddd,J=7.8,6.2,1.6Hz,3H),7.27(dd,J=9.1,3.0Hz,1H),7.18-7.02(m,2H),7.00 (s,1H),4.44(s,1H),3.32-2.20(b,2H),1.83(d,J=14.8Hz,1H),1.77,(d,J=14.8 Hz, 1H), 1.53 (s, 3H), 1.51 (s, 3H), 1.47 (s, 18H), 1.33-0.95 (m, 6H), 0.91 (s, 9H).

[0254] 19 F NMR (376 MHz, chloroform-d) δ-123.49.

[0255] Example 27- Preparation of 3-((3'-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-fluoro-2'-((tetrahydro-2H-pyran-2-yl)oxy)-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propyl 4-methylbenzenesulfonate (xiii-d) and 1,3-bis((3'-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-fluoro-2'-((tetrahydro-2H-pyran-2-yl)oxy)-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane (xiii-e):

[0256] [ka]

[0257] Glassware was oven dried. In a nitrogen filled glovebox, a three neck round bottom flask equipped with a stir bar and septum was charged with 95% sodium hydride (0.077 g, 3.06 mmol) and anhydrous N,N-dimethylformamide (17.5 mL). The flask was sealed and attached to a hood. The flask was equipped with a nitrogen gas inlet and placed under a nitrogen atmosphere. The stirred white slurry was cooled to 0° C. (ice water bath). 3'-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-fluoro-2'-((tetrahydro-2H-pyran-2-yl)oxy)-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol xiii-c (1.50 g, 2.21 mmol) in anhydrous N,N-dimethylformamide (10 mL) was added slowly via syringe at room temperature. A solution of 1,3-propanediol di-para-tosylate (0.2519 g, 0.3716 mmol) in anhydrous N,N-dimethylformamide (1.75 mL) was added slowly via syringe at 0° C. (ice-water bath). The yellow cloudy solution was stirred at room temperature for 1 h. After 1 h, the reaction was determined to be complete. The reaction was cooled to 0° C. (ice-water bath). Water (23 mL) was added to the reaction causing the solid to precipitate out of solution. Ethyl acetate was added until the solid dissolved. The phases were separated. The aqueous phase was extracted with ethyl acetate (3 x 25 mL portions). The combined organic phase was washed with water (40 mL), brine (40 mL), then 1 M sodium hydroxide (40 mL). The organic phase was dried over magnesium sulfate, filtered, and concentrated by rotary evaporation to give a sticky yellow solid. The solid was purified by column chromatography (silica gel column, 15-70% dichloromethane in hexanes) to give xiii-d as a white crystalline solid and xiii-e as a white crystalline solid. The solid xiii-d was dried under high vacuum to give 0.77 g (39.2%) as white crystals. The white crystalline solid xiii-e was dried under high vacuum to give 0.47 g as white crystals.

[0258] 1H NMR(400MHz,CDCl3)δ 8.02-7.96(m,4H),7.48(d,J=2.5Hz,2H),7.39(t,J=2.3Hz,2H),7.34(s,3H),7.33-7.28(m,5H),7.14(ddd,J=8 .9,3.1,1.3Hz,2H),6.81-6.74(m,2H),6.71(d,J=4.8Hz,1H),6.69(d,J=4.7Hz,1H),4.35(s,2H),4.02(dt,J=9 .8,5.5Hz,4H),2.59(d,J=11.3Hz,2H),2.37(t,J=10.9Hz,2H),2.13-2.02(m,2H),1.81-1.67(m,4H),1.38(s,2 7H),1.37(s,9H),1.36(s,12H),1.04(d,J=9.8Hz,4H),0.83(s,18H),0.79-0.69(m,2H),0.44(d,J=13.3Hz,2H).

[0259] Example 28 - Preparation of 6',6'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol) (ligand formula xiii):

[0260] [ka]

[0261] A three-neck round bottom flask equipped with a stir bar, septum, condenser, and nitrogen gas was charged with 1,3-bis((3'-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-fluoro-2'-((tetrahydro-2H-pyran-2-yl)oxy)-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane (xiii-e) (0.47 g, 0.52 mmol). A mixture of chloroform (2.5 mL) and methanol (2.5 mL) was added and the reaction was placed under a nitrogen atmosphere. The reaction was heated to reflux at 60° C. (heating mantle temperature) and p-toluenesulfonic acid monohydrate was added (0.013 g, 0.066 mmol). Within 10 minutes, a solid precipitated out of solution. After 3 hours the reaction was determined to be complete and was cooled to room temperature. Sodium bicarbonate (2.5 mL) was added to the reaction to quench any remaining acid. The phases were separated. The organic phase was dried over magnesium sulfate, filtered, and concentrated by rotary evaporation to give a crude white solid. The solid was placed under high vacuum to give 0.42 g (64.6%) of the product as a white solid.

[0262] 1 H NMR (400MHz, CDCl3) δ 8.08(d,J=8.2Hz,4H),7.36(dd,J=8.3,1.7Hz,4H),7.33(d,J=2.3Hz,2H),7.26( d,J=2.4Hz,2H),7.03(d,J=1.6Hz,4H),6.95(dd,J=8.7,3.2Hz,2H),6.28(td,J= 8.5,3.2Hz,2H),5.74(dd,J=9.0,4.4Hz,2H),5.15(s,2H),3.71(t,J=5.5Hz,4H) ,1.84(p,J=5.5Hz,2H),1.69(s,4H),1.35(s,12H),1.31(s,36H),0.78(s,18H).

[0263] 13C NMR(101MHz,CDCl3)δ 149.41,148.32,142.63,142.12,129.66,127.55,123.76,121.15,119.71,118.27,118.15,118.04 ,115.43,112.72,112.64,106.21,64.64,57.40,38.31,35.28,32.64,32.02,31.94,31.75,29.03.

[0264] Example 29 - Synthesis of metal-ligand complex 18 of the present invention (IMLC-18):

[0265] [ka]

[0266] In a glove box, a 40 mL glass vial was charged with ScCl3 (0.15 g, 0.099 mmol) and THF (approximately 10 mL). LiCH2TMS (1.0 M in hexane, 0.30 mL, 0.30 mmol) was then added and the mixture was stirred for 2 h, followed by slow addition of ligand formula xiii (1.43 g, 0.0993 mmol) dissolved in THF. The resulting mixture was stirred at room temperature for 18 h, then the THF was removed in vacuo. The residue was dissolved in hexane and filtered. The filtrate was collected and dried in vacuum to give IMLC-18 as a solid (0.106 g, 65%).

[0267] 1H NMR(400MHz,ベンゼン-d6)δ 8.19(dd,J=8.1,1.2Hz,2H),8.09(dd,J=8.2,2.8Hz,2H),8.02(s,1H),7.98(d,J=1.7Hz,1H),7.94(s,1H),7.91(d,J=8.1Hz,2H),7.74(d, J=1.7Hz,1H),7.64-7.20(6H),7.03-6.93(m,3H),6.81(d,J=2.5Hz,1H),4.11(m,1H),3.81-3.74(m,1H),3.74-3.66(m,2H),3.65-3.51(m, 2H),3.14-3.04(2H),2.16(s,3H),1.90(s,2H),1.78-1.06(m,27H)1. 69(s,16H),1.64(s,9H),1.51(s,9H),1.31(s,9H),1.20(s,9H),0.93 (s,9H),0.90(s,6H),0.88(s,6H),0.86(s,9H),0.79(s,9H),0.71(s,9H),-0.32(s,9H),-0.76(d,J=12.4Hz,1H),-1.36(d,J=12.3Hz,1H).

[0268] Example 30-Preparation of 2-メチル-4-(2,4,4-トリメチルペンタン-2-イル)フェノール(xiv-b):

[0269]

change

[0270] Under a N2 atmosphere, 2-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran (xiv-a) (20.00 g) in THF (60 mL) was added in a dropwise fashion to a solution of nBuLi (39.251 mL, 2.5 M) in THF (40 mL). The reaction vessel was then placed in an acetone / dry ice bath and MeI (20.363 mL) was added via syringe. The reactor mixture was then stirred overnight at room temperature after which the mixture was quenched into water and then extracted into methylene chloride. The solvent was removed to give a yellow oil which was then loaded onto the top of a 300 g ISCO column and eluted with a gradient of 0-70 & ethyl acetate in hexanes. The eluent was dried to give a colorless oil which was then dissolved in a mixture of MeOH (50 mL) and THF (50 mL). Concentrated HCl (4-5 drops) was then added until the mixture was acidic (tested with pH paper), then the mixture was heated at 55°C for 6 h, then cooled to room temperature, and the mixture was stirred at this temperature overnight. The solvent was removed under reduced pressure, and the residue was dissolved in methylene chloride, washed with brine (acidified with HCl), and then extracted into methylene chloride. The organic layer was then dried over magnesium sulfate and concentrated under reduced pressure to give XIV-B as a slightly yellow oil (9.22 g, 64% yield).

[0271] 1 H NMR (400 MHz, chloroform-d) δ 7.12 (d, J = 2.5, Hz, 1H), 7.07 (dd, J = 8.2, 2.5 Hz, 1H), 6.70 (d, J = 8.3 Hz, 1H), 5.18 (s, 1H), 2.27 (s, 3H), 1.71 (s, 2H), 1.36 (s, 6H), 0.76 (s, 9H).

[0272] Example 31- Preparation of 2-iodo-6-methyl-4-(2,4,4-trimethylpentan-2-yl)phenol (xiv-c):

[0273] [ka]

[0274] In a glass vessel, 8.760 g of 2-methyl-4-(2,4,4-trimethylpentan-2-yl)phenol (xiv) and 6.805 g of p-toluenesulfonic acid (PTSA) were dissolved in acetonitrile (200 mL) and cooled to 0° C. Once cooled, excess N-iodosuccinimide (NIS) (21 g) was added until all xiv-b was consumed (approximately 4 hours). The mixture was then evaporated to dryness, dissolved in chloroform, washed twice with saturated sodium thiosulfate, then washed twice with water. The organic layer was dried, filtered, and stripped to expose a brown oil, then run through a 330 g ISCO column to give xiv-c as a dark brown oil (7.43 g, 90% yield).

[0275] 1 H NMR (500 MHz, chloroform-d) δ 7.47 (d, J = 2.3 Hz, 1H), 7.11 (m, 1H), 5.17 (s, 1H), 2.34 (s, 3H), 1.71 (s, 2H), 1.35 (s, 6H), 0.79 (s, 9H).

[0276] Example 32-Preparation of 1,3-bis(2-iodo-6-methyl-4-(2,4,4-trimethylpentan-2-yl)phenoxy)propane (xiv-e):

[0277] [ka]

[0278] Under nitrogen atmosphere, a glass round bottom flask was charged with 7.430 g of 2-iodo-6-methyl-4-(2,4,4-trimethylpentan-2-yl)phenol (xiv-c), potassium carbonate (5.338 g), 3.713 g of propane-1,3-diylbis(4-methylbenzenesulfonate) (xiv-d), and DMF (150 mL). After heating the mixture at 120° C. for 60 min, the contents of the flask were cooled and then concentrated to dryness. The residue was dissolved in 50 / 50 methylene chloride / water and extracted into methylene chloride. The organic phases were combined, washed with 2N NaOH (400 mL), brine, then water, then dried over magnesium sulfate, filtered, and concentrated to give a dark brown oil. The residue was dissolved in hexane and loaded onto the top of a 330 g silica (ISCO) column and eluted with 5% ethyl acetate in hexane. The eluate was dried in vacuo to give a dark red oil (5.63 g, 80%).

[0279] 1 H NMR(400MHz,chloroform-d)δ 7.56(d,J=2.3Hz,2H),7.11(d,J=2.3,Hz,2H),4.11(t,J=6.4Hz,4H),2.4 4(p,J=6.4Hz,2H),2.34(s,6H),1.67(s,4H),1.31(s,12H),0.73(s,18H).

[0280] The preparation of propane-1,3-diylbis(4-methylbenzenesulfonate) (xiv-d) is described in detail in WO 2014 / 105411 A1.

[0281] Example 33 - Preparation of 2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5,5'-bis(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol) (ligand formula xiv):

[0282] [ka]

[0283] A three-necked glass round-bottom flask was charged with 1,2-dimethoxyethane (60 mL), followed by 4.00 g of 2,7-di-tert-butyl-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 (xiv-f), 1,3-bis(2-iodo-6-methyl-4-(2,4,4-trimethylpentan-2-yl)phenoxy)propane (xiv-e) (2.032 g), and THF (35 mL). Additional THF was added until all components were completely dissolved, followed by the addition of a NaOH solution (0.6586 g) in water (15 mL). The contents of the flask were then sparged with N2 for 15 minutes, then Pd(PPh3)4 was added, and the contents of the vessel were heated at 85°C for 48 hours. Following this, the contents of the flask were cooled and a precipitate formed which was isolated by vacuum filtration and then dried under high vacuum for 2 hours. The resulting solid was then dissolved in THF (50 mL), MeOH (50 mL), and approximately 100 mg of p-toluenesulfonic acid (PTSA), which was added until the solution was acidic (as tested by pH paper). The solution was heated to 60°C overnight, then the contents were cooled and concentrated. The residue was dissolved in methylene chloride (100 mL), washed with brine (100 mL), dried over magnesium sulfate, filtered through a pad of silica gel, and then dried to give the ligand formula (xiv) as an off-white crystalline solid (1.4 g, 37% yield).

[0284] 1H NMR (400MHz, chloroform-d) δ 8.03(dd,J=8.2,0.6Hz,4H),7.45-7.42(m,4H),7.31(dd,J=8.2,1.7Hz,4H),7. 23(d,J=2.4Hz,2H),7.15(dd,J=1.8,0.7Hz,4H),7.12(dd,J=2.5,0.8Hz,2H),6 .74-5.94(br,2H),3.70(t,J=6.4Hz,4H),2.00(s,6H),1.80-1.74(m,2H),1.76 (s,4H),1.74(s,4H),1.41(s,24H),1.30(s,36H),0.83(s,18H),0.75(s,18H).

[0285] The preparation of 2,7-di-tert-butyl-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 is described in detail in WO 2014 / 105411 A1.

[0286] Example 34 - Synthesis of metal-ligand complex 19 of the present invention (IMLC-19):

[0287] [ka]

[0288] In a glove box, a vial was charged with ScCl3 (0.145 g, 0.96 mmol) and THF (approximately 30 mL). The mixture was stirred at room temperature for 3.5 h and then cooled to -35°C, after which LiMe (1.6 M solution in Et2O, 1.825 mL, 2.88 mmol) was added to the vial and the resulting mixture was stirred for 10 min. Ligand Formula I (1.500 g, 0.96 mmol) was added as a solid and the reaction mixture was then stirred at room temperature overnight. The THF was then removed in vacuum and the resulting residue was dissolved in pentane and filtered. The filtrate was collected and dried in vacuum to give IMLC-19 as a white solid (1.614 g, 99%).

[0289] 1 H NMR(400MHz,ベンゼン-d6)δ 8.26(d,J=8.2Hz,1H),8.19(d,J=8.3Hz,1H),8.17(d,J=1.3Hz,1H),8.09(d,J=8.2Hz,1 H),7.96(d,J=8.2Hz,1H),7.81(d,J=2.5Hz,1H),7.71-7.67(m,2H),7.62-7.57(m,2H),7 .54(dd,J=4.8,2.0Hz,2H),7.49-7.45(m,2H),7.45-7.41(m,2H),7.35(dd,J=8.3,1.6H z,1H),7.23(dd,J=8.2,1.6Hz,1H),7.02(s,1H),4.34-4.15(m,1H),3.88-3.77(m,1H),3 .68-3.57(m,1H),3.48(m,1H),3.21(m,2H),2.84(q,J=6.5,6.0Hz,2H),2.14(s,2H),1. 81-1.72(m,4H),1.68(s,9H),1.58(m,2H),1.50(s,3H),1.49(s,9H),1.40-1.21(m,37H) ,1.183(s,9H),1.180(s,9H),1.02(q,J=6.4,5.9Hz,4H),0.97(s,9H),0.96-0.91(m,6H ),0.90(s,9H),0.71(m,4H),0.19-0.17(m,6H),0.17(s,3H),0.14(s,3H),-1.13(s,3H).

[0290] Example 35 - Synthesis of the present metal-ligand complex 20 (IMLC-20):

[0291]

change

[0292] In a glove box, a 40 mL glass vial was charged with ScCl3 (0.021 g, 0.14 mmol) and THF (approximately 10 mL). The mixture was allowed to stir at room temperature overnight (18 h), after which the contents of the vial were cooled to -30°C for 20 min. LiMe (1.6 M solution in Et2O, 0.27 mL, 0.43 mmol) was then added to the vial, and the resulting mixture was stirred for 5 min. A solution of ligand Formula II (0.175 g, 0.139 mmol) in THF (approximately 10 mL) was added to the vial. The contents of the vial were stirred at room temperature for 18 h, after which the solvent was removed in vacuum. The residue was dissolved in pentane and filtered through a fritted column. The filtrate was collected and dried in vacuum to give IMLC-20 as a white solid in quantitative yield.

[0293] 1H NMR(400MHz,ベンゼン-d6)δ 8.23(dd,J=8.2,1.6Hz,2H),8.13(d,J=8.2Hz,1H),8.04(d,J=1.7Hz,1H),7.94(d,J=8.2Hz ,1H),7.76(d,J=2.6Hz,1H),7.64(d,J=1.6Hz,1H),7.51(d,J=1.2Hz,2H),7.47(dd,J=8.2,1 .7Hz,2H),7.42(dd,J=8.3,1.7Hz,1H),7.39(d,J=1.6Hz,1H),7.33(dd,J=9.0,2.7Hz,2H), 7.21(dd,J=8.2,1.7Hz,1H),7.12-7.07(m,1H),6.93(dd,J=9.0,3.2Hz,1H),6.35(s,1H),6. 22-6.02(m,1H),4.16(d,J=2.2Hz,1H),3.68(s,1H),3.46(d,J=3.0Hz,1H),3.35(s,1H),3. 13(s,2H),2.83(d,J=8.9Hz,2H),2.11(s,2H),1.90(s,3H),1.75-1.65(m,4H),1.63(s,9H), 1.59-1.51(m,3H),1.49(s,9H),1.46-1.43(m,1H),1.31(s,3H),1.25(s,3H),1.22(s,9H),1 .19(s,3H),1.19(s,3H),1.13(s,9H),1.00(s,3H),0.93(s,9H),0.86(s,9H),-1.13(s,3H).

[0294] 19 F NMR (376MHz, ベンゼン-d6) δ-116.50,-116.53.

[0295] Example 36 - Synthesis of the present metal-ligand complex 21 (IMLC-21): International Publication No. 2017 / 004456 (A1) cited in the manual

[0296]

change

[0297] A suspension of scandium trichloride (0.037 g, 0.242 mmol) in THF (8 mL) was cooled to −35° C. Trimethylsilylmethyllithium in pentane (1.00 M, 0.739 mL, 0.739 mmol) was added to the cold suspension, which was stirred at room temperature for 4 h, and then the slightly cloudy solution was cooled in a −35° C. freezer for 5 min. 2-(2,7-ditert-butylcarbazol-9-yl)-6-[4-[3-[5-[3-(2,7-ditert-butylcarbazol-9-yl)-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]-7-methyl-indan-4-yl]oxypropoxy]-7-methyl-indan-5-yl]-4-(1,1,3,3-tetramethylbutyl)phenol (0.300 g, 0.231 mmol) in THF (1 mL) was added dropwise. The reaction mixture was stirred at room temperature overnight. The solvent was removed by vacuum, then pentane (5 mL) was added and the volatiles were removed under vacuum. Pentane (10 mL) was added and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with pentane (10 mL). The combined pentane extracts were dried under vacuum to give a slightly green solid. This material was evaporated from pentane (2×3 mL). Pentane (2 mL) was added and the mixture was placed in a freezer (−35° C.) for 18 h. The pentane layer was removed using a pipette and the remaining solid was dried under vacuum to give IMLC-21 (165 mg, yield: 48%) as a white solid.

[0298] 11H NMR (400 MHz, C6D6 (selected peaks)) δ 8.19 (d, J = 8.2 Hz, 1H), 8.13 (app t, J = 8.4 Hz, 2H), 8.07 (d, J = 8.3 Hz, 1H), 7.95 (d, J = 1.7 Hz, 1H), 7.73 (d, J = 1.7 Hz, 1H), 7.66 (d, J = 1.6 Hz, 1H), 7.58 (dd, J = 3.9, 2.2 Hz, 2H), 7.54 (d, J = 2.8 Hz, 1H), 7.50 - 7.41 (m, 3H), 7.36 (ddd, J = 8.4, 6.8, 1.7 Hz, 2H), 7.27 (d, J = 3.1 Hz, 2H), 7.11 (s, 1H), 4.30 (dd, J = 10.6, 8.3 Hz, 1H), 3.87 (ddd, J = 9.2, 5.6, 3.0 Hz, 1H), 3.81 - 3.61 (m, 3H), 3.48 - 3.22 (m, 3H), 2.07 (s, 3H), 1.93 (s, 3H), 1.60 (s, 9H), 1.51 (s, 9H), 1.32 (s, 9H), 1.26 (s, 9H), 1.20 (s, 6H), 0.88 (d, J = 3.3 Hz, 18H), -0.27 (s, 9H), -0.34 - -0.41 (m, 1H), -1.23 (d, J = 12.3 Hz, 1H).

[0299] Example 37 - Synthesis of the metal - ligand complex 22 (IMLC - 22) of the present invention: A ligand prepared in the same manner as the IMLC - 2 ligand

[0300]

Chemical formula

[0301] A suspension of scandium trichloride (0.042 g, 0.275 mmol) in THF (8 mL) was cooled to −35° C. Trimethylsilylmethyllithium in pentane (1.00 M, 0.838 mL, 0.838 mmol) was added to the cold suspension, which was stirred at room temperature for 4 h, and then the slightly cloudy suspension was cooled in a −35° C. freezer for 5 min. 2-(2,7-ditert-butylcarbazol-9-yl)-6-[2-[2-[2-[3-(2,7-ditert-butylcarbazol-9-yl)-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]-4-fluoro-6-methyl-phenoxy]ethoxy]-5-fluoro-3-methyl-phenyl]-4-(1,1,3,3-tetramethylbutyl)phenol (0.325 g, 0.262 mmol) in THF (1 mL) was added dropwise. The reaction mixture was stirred at room temperature overnight. The solvent was removed by vacuum, then pentane (8 mL) was added and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with pentane (4 mL). The combined pentane extracts were dried under vacuum to give IMLC-22 as an off-white solid (210 mg, 56%).

[0302] 1H NMR(400MHz,C6D6)δ 8.18(d,J=8.2Hz,1H),8.11(dd,J=8.2,5.5Hz,2H),7.98(d,J=8.2Hz,1H), 7.74(d,J=1.6Hz,1H),7.62(d,J=1.6Hz,1H),7.57(d,J=2.6Hz,1H),7.49( d,J=1.6Hz,1H),7.46(q,J=1.2Hz,2H),7.38(t,J=2.7Hz,2H),7.26(d,J=1 .9Hz,2H),6.53(dd,J=8.1,3.1Hz,1H),6.39(dd,J=8.0,3.1Hz,1H),4.29-4 .12(m,2H),3.29(dt,J=7.7,5.8Hz,2H),3.01(dt,J=8.1,6.1Hz,2H),2.88 (dd,J=8.7,2.4Hz,1H),2.78-2.70(m,1H),1.75(s,3H),1.61(s,9H),1.59 (s,2H),1.56(s,9H),1.30(s,9H),1.16(s,9H),0.87(d,J=1.6Hz,12H),0. 84(s,9H),-0.42(s,9H),-0.91(d,J=11.0Hz,1H),-0.99(d,J=11.0Hz,1H); 19 F NMR (376MHz, C6D6) δ-115.26,-116.51.

[0303] Example 38 - Synthesis of the present metal-ligand complex 23 (IMLC-23):

[0304]

change

[0305] A suspension of scandium trichloride (0.020 g, 0.129 mmol) in THF (6 mL) was cooled to -35°C. Trimethylsilylmethyllithium in pentane (1.00 M, 0.404 mL, 0.404 mmol) was added to the cold suspension, which was stirred at room temperature for 4 h, and then the slightly cloudy solution was cooled in a -35°C freezer for 5 min. 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[2-[3-(3,6-ditert-butylcarbazol-9-yl)-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]phenyl]sulfanylpropylsulfanyl]phenyl]-4-(1,1,3,3-tetramethylbutyl)phenol (0.150 g, 0.123 mmol) in THF (1 mL) was added dropwise. The reaction mixture was stirred at room temperature overnight. The solvent was removed by vacuum, then pentane (10 mL) was added and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with pentane (2×4 mL). The combined pentane extracts were dried under vacuum to give IMLC-23 (150 mg, 85%) as a white solid.

[0306] 1 H NMR (400MHz, C6D6 (selected peaks)) δ 8.54(dd,J=1.8,0.8Hz,1H),8.41(d,J=1.8Hz,1H),8.24(d,J=1.7Hz,1H),7.92 (d,J=8.6Hz,1H),6.27(dd,J=6.0,3.3Hz,1H),6.07(dd,J=7.8,1.4Hz,1H),2.6 9(d,J=7.0Hz,2H),2.60(d,J=7.1Hz,2H),1.52(s,9H),1.45(s,9H),0.91(s,9H) ),0.86(s,9H),-0.26(s,9H),-1.35(d,J=12.1Hz,1H),-2.21(d,J=12.1Hz,1H).

[0307] Example 39 - Synthesis of compound 14.

[0308] [ka]

[0309] N,N-Dimethylformamide (DMF) (4 mL) and 2-bromothiophenol (10) (0.245 mL, 2.03 mmol) were added sequentially to a 40 mL vial charged with potassium carbonate (K2CO3) (0.411 g, 2.97 mmol). 1,3-Dibromopropane (13) (0.101 mL, 0.991 mmol) was added and the mixture was stirred at room temperature. After stirring at this temperature for 18 h, the reaction was diluted with diethyl ether (10 mL) and then filtered through a plug of CELITE. The filtrate was washed with water (5 mL), saturated aqueous sodium bicarbonate (5 mL), dried over anhydrous Na2SO4, filtered, and concentrated to dryness. The resulting residue was loaded directly onto a silica gel (SiO2) cartridge and purified using flash column chromatography (40 g SiO2, 40 mL / min, 0% ethyl acetate (EtOAc) to 20% EtOAc / hexanes) to afford 0.35 g (83%) of the desired product 14 as a white solid. 1 H NMR(400MHz,CDCl3)δ 7.59-7.50(m,2H),7.29-7.21(m,4H),7.03(ddd,J=7.9,5.2,3.7Hz,2H),3.11(t,J=7.0Hz,4H),2.05(p,J=7.0Hz,2H); 13 C NMR(101MHz, CDCl3)δ 137.35,133.09,128.33,127.77,126.77,123.85,31.79,27.30.

[0310] Example 40 - Synthesis of Compound 16:

[0311] [ka]

[0312] Degassed toluene (8 mL) and degassed water (2 mL) were added to a 40 mL vial charged with BPin ester 15 (1.27 g, 1.83 mmol), dibromide 14 (0.340 g, 0.813 mmol), and NaOH (0.195 g, 4.88 mmol). The mixture was sparged with nitrogen for 5 min, and then solid tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) (0.047 g, 0.041 mmol) was added. The reaction was then heated to 95° C. (external temperature) and maintained at this temperature for 17 h. After this time, the reaction was cooled to room temperature. The mixture was transferred to a separatory funnel and the toluene layer was isolated and then washed with water (2×8 mL).

[0313] MeOH (10 mL) was added to the above toluene solution followed by concentrated hydrochloric acid (concentrated HCl) (8 drops from a glass pipette). The flask was fitted with a condenser and the mixture was then heated to 75° C. (external temperature) and maintained at this temperature for 3 h. After this time, the reaction was cooled to room temperature and the volatiles were removed under reduced pressure. Water (10 mL) and CHCl (15 mL) were added to the crude residue and the phases were then transferred to a separatory funnel and separated. The aqueous phase was further extracted with CHCl (15 mL) and the combined organic extracts were washed with brine (10 mL), dried (NaSO), and then passed through a silica gel plug. The plug was washed with CHCl (65 mL) to ensure all material was collected (monitored by thin layer chromatography, TLC). The crude residue was directly purified using flash column chromatography (12 g CELITE loaded cartridge, 40 g SiO2, 40 mL / min, 0% EtOAc to 15% EtOAc / hexanes) to give 0.85 g (85%) of ligand 16 as a white powder.

[0314] 1H NMR(400MHz,CDCl3)δ 8.18-8.13(m,4H),7.47(app dd,J=8.6,1.9Hz,4H),7.39-7.26(m,8H),7.23-7.15(m,8H),4.88(s,2H),2.92(app t,J=7.0Hz,4H),1.89(p,J=7.0Hz,2H),1.70(s,4H),1.45(s,36H),1.34(s,12H),0.81(s,18H); 13 C NMR(101MHz,CDCl3)δ 147.05,142.96,142.51,139.46,138.07,136.30,130.89,129.03,128.48,128.45,128.24,126.35,125.80,123 .85,123.63,123.54,116.31,109.59,57.05,38.21,34.75,32.42,32.08,32.04,31.95,27.88;LCMS(ES / APCIMS m / z 1247[(M+Na) + ]).

[0315] Example 41 - Synthesis of metal-ligand complex 24 of the present invention (IMLC-24): Ligands prepared according to the procedures cited in WO 2017 / 004462(A1)

[0316] [ka]

[0317] A suspension of trichloroscandium (0.027 g, 0.181 mmol) in THF (8 mL) was cooled to -35 ° C. Trimethylsilylmethyllithium in pentane (1.00 M, 0.551 mL, 0.551 mmol) was added to the cold suspension, which was stirred at room temperature for 4 h, and then the slightly cloudy suspension was cooled in a -35 ° C freezer for 5 min. 2-[2,7-bis[diisopropyl(octyl)silyl]carbazol-9-yl]-6-[2-[3-[2-[3-[2,7-bis[diisopropyl(octyl)silyl]carbazol-9-yl]-2-hydroxy-5-methyl-phenyl]-4-fluoro-6-methyl-phenoxy]propoxy]-5-fluoro-3-methyl-phenyl]-4-methyl-phenol (0.300 g, 0.172 mmol) in THF (1 mL) was added dropwise. The solution was stirred at room temperature overnight. The solvent was removed by vacuum, then pentane (10 mL) was added and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with pentane (2×4 mL). The combined pentane extracts were dried under vacuum to give an oil. This oil was dissolved in pentane (10 mL) and then filtered through a plug of CELITE. The plug was further extracted with pentane (5 mL). The combined pentane extracts were dried under vacuum to give IMLC-24 (290 mg, yield: 86%) as an off-white solid.

[0318] 1 H NMR (400 MHz, CD) (selected peaks) δ 8.27 (dd, J = 7.6, 2.5 Hz, 2H), 8.18 (t, J = 8.3 Hz, 3H), 7.99 (d, J = 2.1 Hz, 1H), 7.75 (s, 1H), 6.63 (d, J = 2.5 Hz, 1H), 6.39 (dd, J = 8.1, 3.1 Hz, 1H), 6.18 (dd, J = 8.3, 3.2 Hz, 1H), -0.25 (s, 9H), -0.70 (d, J = 12.5 Hz, 1H), -1.38 (d, J = 12.4 Hz, 1H); 19 F NMR(376MHz,C6D6)δ-115.61,-117.20.

[0319] Example 42 - Synthesis of metal-ligand complex 25 of the present invention (IMLC-25): Ligands prepared according to the procedures cited in WO 2017 / 004462(A1)

[0320] [ka]

[0321] A suspension of scandium trichloride (0.038 g, 0.248 mmol) in THF (8 mL) was cooled to −35° C. Trimethylsilylmethyllithium in pentane (1.00 M, 0.757 mL, 0.757 mmol) was added to the cold suspension, which was stirred at room temperature for 4 h, and then the slightly cloudy solution was cooled in a −35° C. freezer for 5 min. 2-[2,7-bis(1,1,3,3-tetramethylbutyl)carbazol-9-yl]-6-[2-[3-[2-[3-[2,7-bis(1,1,3,3-tetramethylbutyl)carbazol-9-yl]-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]-4-fluoro-6-methyl-phenyl]propoxy]-5-fluoro-3-methyl-phenyl]-4-(1,1,3,3-tetramethylbutyl)phenol (0.350 g, 0.236 mmol) in THF (2 mL) was added dropwise. The reaction mixture was stirred at room temperature overnight. The solvent was removed by vacuum, then pentane (5 mL) was added and the volatiles were removed under vacuum (attempting to remove residual THF). Pentane (10 mL) was added and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with pentane (10 mL).

[0322] The combined pentane extracts were dried under vacuum to give a slightly green solid. This material was evaporated from pentane (2×3 mL). Pentane (2 mL) was added and the mixture was placed in a freezer (−35° C.) for 18 hours. The pentane layer was removed using a pipette and the remaining solid was dried under vacuum to give IMLC-25 (325 mg, 82%) as a white solid.

[0323] 1H NMR (400MHz, C6D6 (selected peaks)) δ 8.15(dd,J=10.3,8.2Hz,2H),8.06(dd,J=13.0,8.2Hz,2H),7.76(d,J=1.5Hz, 1H),7.55(dd,J=6.0,2.1Hz,2H),7.50(d,J=1.5Hz,1H),7.44(tt,J=6.8,3.4H z,3H),7.36-7.27(m,5H),7.20(dd,J=9.2,3.2Hz,1H),7.04(dd,J=9.0,3.2Hz ,1H),6.40(dd,J=8.1,3.1Hz,1H),6.21(dd,J=8.2,3.2Hz,1H),3.94(t,J=9.3 Hz,1H),3.63-3.48(m,5H),3.19(d,J=6.9Hz,2H),1.63(s,6H),1.54(s,3H),1 .51(d,J=2.5Hz,6H),1.41(d,J=2.5Hz,6H),1.28(s,6H),1.26(s,6H),1.23(s ,8H),1.16(s,2H),0.96(s,9H),0.92(s,9H),0.85-0.81(m,18H),0.70(s,9H) ,0.66(s,9H),-0.27(s,9H),-0.63(d,J=12.3Hz,1H),-1.34(d,J=12.3Hz,1H); 19 F NMR(376MHz,C6D6)δ-115.40,-116.76.

[0324] Example 43 - Synthesis of metal-ligand complex 26 of the present invention (IMLC-26): Ligands prepared according to the procedures cited in WO 2017 / 004462(A1)

[0325] [ka]

[0326] A suspension of scandium trichloride (0.030 g, 0.200 mmol) in THF (8 mL) was stirred at room temperature for 6 h. The mixture was cooled to −35° C., then methyllithium in EtO (1.60 M, 0.378 mL, 0.604 mmol) was added to the cold suspension, which was stirred at room temperature for 10 min. After this time, the ligand 2-[2,7-bis[diisopropyl(octyl)silyl]carbazol-9-yl]-6-[2-[3-[2-[3-[2,7-bis[diisopropyl(octyl)silyl]carbazol-9-yl]-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]-4-fluoro-6-methyl-phenoxy]propoxy]-5-fluoro-3-methyl-phenyl]-4-(1,1,3,3-tetramethylbutyl)phenol (0.380 g, 0.196 mmol) in THF (2 mL) was added dropwise. The reaction mixture was stirred at room temperature overnight. The solvent was removed by vacuum, then hexane (10 mL) was added and the mixture was filtered through a pad of CELITE. The CELITE pad was further extracted with hexane (2×4 mL). The combined hexane extracts were dried under vacuum to give an oil. The oil was dissolved in hexanes (2 mL) and then removed under vacuum to give IMLC-26 as an off-white solid (395 mg, 94%).

[0327] 1H NMR (400 MHz, CD6) (selected peaks of major product) δ 8.30 (d, J = 7.7 Hz, 1H), 8.25-8.18 (m, 3H), 8.03 (s, 1H), 7.83 (s, 1H), 7.67-7.62 (m, 4H), 7.52 (d, J = 7.8 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 7.37-7.31 (m, 3H), 7.16-7.10 (m, 1H), 6.95 (dd, J = 8.9, 3.2 Hz, 1H), 6.85 (ddd, J = 11 .9,8.6,3.2Hz,1H),6.41(dd,J=8.2,3.2Hz,1H),6.26(dd,J=8.3,3.2Hz,1H),4.28(dt,J=10.2,4.4Hz,1H), 4.04-3.90(m,1H),3.51(q,J=5.7Hz,1H),3.28-3.13(m,3H),3.06-2.87(m,2H),1.93(s,3H),-1.17(s,3H).

[0328] 19 F NMR(376MHz,C6D6)δ-115.88,-116.38.

[0329] Example 44 - Synthesis of metal-ligand complex 27 of the present invention (IMLC-27):

[0330] [ka]

[0331] In a glove box, a 40 mL glass vial was charged with ScCl3 (0.018 g, 0.12 mmol), THF (approximately 5 mL), and a magnetic stir bar. After the mixture was cooled at -30°C, LiCH2TMS (0.371 mL, 0.37 mol, 1.0 M in pentane) was added dropwise at room temperature. After stirring for 3 h, 2 equivalents of ligand formula xxi (0.1 g, 0.335 mmol) in THF (approximately 2 mL) were added, and the reaction mixture was stirred at room temperature overnight. The solvent was then removed in vacuum, and the residue was dissolved in pentane, filtered, and then dried in vacuum to give a yellow solid (120 mg, yield: 64%).

[0332] 1 H NMR(400MHz,ベンゼン-d6)δ 8.73(d,J=1.8Hz,1H),8.66(d,J=1.9Hz,1H),8.37(s,1H),8.25(s,1H),8.19(d,J=9. 3Hz,1H),8.08(dd,J=9.0,7.3Hz,3H),7.96(d,J=1.9Hz,1H),7.90(d,J=9.3Hz,1H),7 .85(d,J=2.0Hz,1H),7.70(d,J=2.7Hz,1H),7.61(ddd,J=8.5,6.0,1.8Hz,2H),7.55- 7.45(m,5H),7.05(dd,J=9.3,2.0Hz,1H),6.37(dd,J=8.2,3.2Hz,1H),6.21(dd,J=8. 3,3.3Hz,1H),5.11(d,J=12.6Hz,1H),4.67(d,J=12.1Hz,1H),3.98(d,J=12.7Hz,1H) ,3.74(d,J=12.1Hz,1H),2.85(q,J=7.2,6.8Hz,3H),2.58-2.44(m,2H),1.48(s,9H), 1.44(s,9H),1.35(s,9H),1.31(s,9H),1.14(d,J=2.6Hz,3H),0.94-0.84(20H),0.79 (s,9H),0.71(s,9H),-0.35(s,9H),-1.66(d,J=12.7Hz,1H),-2.14(d,J=12.6Hz,1H).

[0333] 19 F NMR (376MHz, ベンゼン-d6) δ-117.45,-118.45. (Amount: 120mg, 64%)

[0334] Example 45 - Coordinator formula xxi modulation

[0335]

change

[0336] In a nitrogen filled glove box, a vial equipped with a stir bar was charged with 9-(3-BPin-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2,6-di-tert-butylanthracene (353 mg, 0.54 mmol), bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermane (169 mg, 0.25 mmol), and Pd(PPh3)4 (14 mg, 0.01 mmol). The vial was equipped with a septum cap, removed from the glove box, and nitrogen purged NaOH (0.74 mL, 1.47 mmol, 2 M aqueous solution) was added via syringe. The puncture hole on the septum cap was sealed with vacuum grease. The reaction mixture was stirred at 60 °C overnight. Stirring was stopped and the reaction mixture was cooled to 25 °C. An aliquot was taken, diluted with THF, and analyzed using LC / MS to confirm complete conversion. The aqueous layer of the reaction mixture was removed by pipette, and the organic phase was washed with brine (6 mL). The organic phase was isolated and mixed with 5 mL of methanol, approximately 0.9 mL of concentrated HCl, and 5 mL of THF (to improve solubility), then heated to 60 °C and stirred for 12 h. The reaction mixture was cooled to 25 °C, and the solution was dried under vacuum and purified via reverse phase column chromatography with a 0% to 100% gradient of CH3CN / THF over 10 column volumes. The relevant fractions were combined and dried under vacuum (yield: 270 mg, 78%).

[0337] 1H NMR(400MHz,クロロホルム-d)δ 8.54(s,2H),8.08(s,2H),8.06-8.01(m,2H),7.86(d,J=9.0Hz,2H),7.81-7.68(m,2H),7.64(dd, J=8.9,1.9Hz,2H),7.57(s,2H),7.52(d,J=11.2Hz,2H),7.48(s,2H),7.03(d,J=8.0Hz,2H),6.91 (dd,J=8.7,3.2Hz,2H),4.06(d,J=11.4Hz,2H),4.00(d,J=11.1Hz,2H),2.21(s,6H),2.19(s,4H) ,1.86(m,2H),1.52(m,30H),1.40(d,J=1.4Hz,18H),1.13-1.00(m,12H),0.92(d,J=1.9Hz,18H). 19 F NMR(376MHz,クロロホルム-d)δ-119.69

[0338] Example 46 - Synthesis of the present metal-coordinator complex 28 (IMLC-28): International Publication No. 2020 / 047384 (A1) details the modulation of the されている coordination agent xxii.

[0339]

change

[0340] In a glove box, a 20 mL vial was charged with ScCl3 (44.7 mg, 0.295 mmol, 1.00 equiv) and 4.5 mL of dry THF. The mixture was stirred overnight at ambient temperature. After approximately 16 h, the slurry was placed in a glove box freezer for 1 h. The vial was then removed from the glove box and treated with methyllithium (1.6 M in diethyl ether, 0.554 mL, 0.886 mmol, 3.0 equiv). The mixture became homogenous within a few minutes. Less than 5 minutes after the addition of methyllithium, ligand formula xxii (2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-di-tert-butylanthracen-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)) (377 mg, 0.295 mmol, 1.00 equiv.) was obtained. After stirring for 3 hours, the solvent was removed by vacuum pump and the solid was suspended in 6 mL of hexane. The solution was filtered through a 0.45 um syringe filter and the solvent was removed from the filtrate by vacuum pump. 317 mg of solid was isolated (76%).

[0341] 1H NMR(400MHz,CD2Cl2)δ 8.49(s,1H),8.35(s,1H),8.20(s,1H),8.09-7.98(m,3H),7.93(d,J=8.9Hz,1H),7.74(d,J=8.9Hz,1H),7.63(dd,J=8.9,1.8Hz,1H),7.58(dd,J=8.9,1.9Hz,1H),7.55(s,1H),7.47(s,1H),7.45-7.39(m,2H),7.30(dd,J=8.8,1.9Hz,1H),7.24(d,J=2.7Hz,1H),7.23-7.17(m,2H),6.83(dd,J=9.6,3.2Hz,1H),6.59(dd,J=9.7,3.3Hz,1H),6.42(dt,J=8.7,4.9Hz,1H),6.12(dd,J=8.6,3.1Hz,1H),4.12-4.03(m,1H),3.97(ddd,J=10.2,6.3,3.7Hz,1H),3.78(dtd,J=19.5,9.4,5.0Hz,2H),2.36(td,J=7.0,2.6Hz,2H),2.23(qd,J=6.5,3.0Hz,2H),1.99(p,J=3.0Hz,2H),1.65-1.59(m,3H),1.47(s,9H),1.43(s,3H),1.40-1.37(m,6H),1.35(s,3H),1.31(s,9H),1.27(s,3H),1.07(s,9H),0.93(s,9H),0.85-0.83(m,4H),0.78(s,9H),0.76(s,9H),0.46(s,3H),-2.25(s,3H)。

[0342] 13C NMR(101MHz,CD2Cl2)δ 160.67(d,J=37.6Hz),160.58,158.88,158.26(d,J=36.7Hz),148.73,148.71,148.44,148.42,146 .74,146.19,145.87,145.64,137.96,137.88,137.81,137.78,137.69,137.62,135.85,135.51,13 4.94,134.85,134.41,134.32,132.94,132.64,131.51,130.97,130.82,130.36,130.01,129.93,129.89,129.64,129.29,129.25,128.39,128.30,127.57,127.54,127.22,127.14,126.72,124.98,1 24.31,124.25(2),124.00,123.79,123.48,123.12,122.99,122.13,121.86,117.67(d,J=22.7Hz) ,115.85(d,J=22.4Hz),115.26(d,J=22.7Hz),114.08(d,J=22.5Hz),77.54,73.52,70.64,57.07,5 5.86,37.55,37.51,35.12,34.86,34.62,34.58,33.87,33.31,32.35,32.31,31.71,31.58,31.55,30.88,30.83,30.40,30.21,30.07,29.61,28.64,26.88,25.19,24.16,20.37,18.25,15.43,11.15. 19 F NMR(376MHz, CD2Cl2)δ-118.94(t,J=9.2Hz),-119.05(d,J=8.5Hz).

[0343] Example 47-Synthesis of the present metal-ligand complex 29 (IMLC-29):

[0344]

change

[0345] In a glove box, a 20 mL vial was charged with ScCl3 (20.4 mg, 0.135 mmol, 1.00 equiv) and 4.5 mL of dry THF. The mixture was stirred overnight at ambient temperature. After approximately 16 h, the slurry was placed in the glove box freezer for 1 h. The vial was then removed from the glove box and treated with methyllithium (1.6 M in diethyl ether, 0.253 mL, 0.405 mmol, 3.0 equiv). The mixture became homogenous within 1 min. Less than 2 minutes after the addition of the methyllithium, ligand formula xxiii (2',2''-(propane-1,3-diylbis(oxy))bis(5'-fluoro-3'-methyl-3-(1,1,4,4,8,8,11,11-octamethyl-1,2,3,4,8,9,10,11-octahydropentacene-6-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)) (202 mg, 0.135 mmol, 1.00 equiv.) was added. After stirring for 14 hours, the solvent was removed by vacuum pump and the solid was suspended in 6 mL of hexane. The solution was filtered through a 0.45 um syringe filter and the solvent was removed from the filtrate by vacuum pump. 187 mg of solid was isolated (85%).

[0346] 1H NMR(400MHz,CD2Cl2)δ 8.42(s,1H),8.20(s,1H),8.11(s,1H),8.04(s,1H),8.00(d,J=2.1Hz,2H),7.85(s,1H),7.72(s,1H),7.52(d,J=2.0Hz,2H),7.35(d,J=2.7Hz,1H),7.20(t,J=2.5Hz,2H),7.15(d,J=2.7Hz,1H),6.80(dd,J=9.6,3.2Hz,1H),6.68(dd,J=9.6,3.3Hz,1H),6.35(dd,J=8.6,3.2Hz,1H),6.11(dd,J=8.4,3.2Hz,1H),4.09(dt,J=9.9,4.7Hz,1H),3.99(dt,J=10.4,4.9Hz,1H),3.81(dt,J=10.5,5.4Hz,1H),3.72(dt,J=9.7,4.9Hz,1H),3.53(bs,2H),2.41(dt,J=8.5,6.4Hz,2H),2.22(dt,J=8.9,6.6Hz,2H),1.99-1.20(m,72H),0.99-0.73(m,36H),-2.27(s,3H)。

[0347] 13C NMR(101MHz,CD2Cl2)δ 160.97,160.54,160.41,159.35,158.55,158.00,148.79,148.76,148.49,148.47,143.26,143.00,142.95,142.78,142.60,142.06,141.92,141.76,138.31,138.23,138.15,138.07,136.02,135.90,135.46,135.33,135.24,135.15,134.61,134.52,133.05,132.81,131.29,130.93,130.62,130.25,130.07,129.83,129.50,129.22,129.12,128.83,127.50,127.20,126.90,125.35,125.31,125.21,125.10,124.94,124.53,124.08,123.87,123.79,122.97,122.56,117.05,116.82,116.11,115.88,115.02,114.80,114.00,113.78,77.22,73.84,70.80,56.90,56.64,37.47,35.35,35.23,35.19,35.10,35.04,34.86,34.82,34.67,34.50,34.49,34.45,34.41,34.30,34.21,33.60,33.15,32.93,32.74,32.71,32.61,32.57,32.40,32.36,32.31,32.14,32.11,31.97,31.92,31.89,31.86,31.75,31.73,31.69,31.63,31.54,30.86,30.58,30.09,24.23,22.61,17.80,15.60,13.83。

[0348] 19 F NMR(470MHz,CD2Cl2)δ-118.71(t,J=9.0Hz),-119.21(t,J=9.0Hz)。

[0349] Example 48 - 4,4,5,5-tetramethyl-2-(1,1,4,4,8,8,11,11-octamethyl-1,2,3,4,8,9,10,11-octahydropentacen-6-yl)-1,3,2-dioxaborolane:

[0350] [ka]

[0351] A 50 mL round bottom flask was charged with 6-bromo-1,1,4,4,8,8,11,11-octamethyl-1,2,3,4,8,9,10,11-octahydropentacene (1.30 g, 2.72 mmol, 1.00 equiv) and 14 mL of dry THF. The solution was cooled to -78°C under a nitrogen blanket. N-Butyllithium (1.6 M in hexanes, 1.87 mL, 3.00 mmol, 1.10 equiv) was injected and the mixture was stirred for 30 min. The solution became heterogeneous. Isopropoxy-Bpin (0.666 mL, 3.27 mmol, 1.20 equiv) was injected and the solution was allowed to warm slowly to 0°C over 1 h.

[0352] The solution was quenched with aqueous ammonium chloride. The product was extracted several times with dichloromethane. The combined organic fractions were concentrated, and the residue was purified by chromatography on silica gel (0-20% EtOAc in hexanes). 1.154 g of the boronic ester was isolated as a yellow solid (81% yield).

[0353] 1 H NMR(400MHz, CDCl3)δ 8.42(s,2H),8.24(s,1H),7.83(s,2H),1.78(s,8H),1.58(s,12H),1.42(s,12H),1.40(s,12H).

[0354] 13 C NMR(101MHz, CDCl3)δ 143.56,142.91,134.95,129.97,127.17,125.26,124.88,83.76,35.21,34.89,34.47,32.74,32.48,25.34.

[0355] Example 49 - Preparation of 2',2'''-(propane-1,3-diylbis(oxy))bis(5'-fluoro-3'-methyl-3-(1,1,4,4,8,8,11,11-octamethyl-1,2,3,4,8,9,10,11-octahydropentacen-6-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)-ligand of formula (xxiii):

[0356] [ka]

[0357] A 100 mL round bottom flask was charged with 1,3-bis((5-fluoro-3'-iodo-2'-(methoxymethoxy)-3-methyl-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane (0.951 g, 0.913 mmol, 1.00 equiv.), 4,4,5,5-tetramethyl-2-(1,1,4,4,8,8,11,11-octamethyl-1,2,3,4,8,9,10,11-octahydropentacen-6-yl)-1,3,2-dioxaborolane (1.15 g, 2.19 mmol, 2.20 equiv.), and Pd(Amphos)Cl (65 mg, 0.091 mmol, 10 mol%). A reflux condenser was attached and the unit was placed under a nitrogen atmosphere. Nitrogen-sparged THF (10 mL) was added, followed by nitrogen-sparged K3PO4 (4.57 mL, 9.13 mmol, 10.0 equiv.). The mixture was heated to 70° C. and stirred under a nitrogen blanket for 14 h.

[0358] The solution was cooled and the phases were separated. The organic phase was concentrated and the residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). Three portions were isolated: (1) the protodeborated boronic ester (230 mg), (2) the desired MOM-ether intermediate (772 mg), and (3) unidentified material, possibly a single bond intermediate (405 mg).

[0359] The solid MOM-ether intermediate was dissolved in 10 mL of THF and 10 mL of methanol. Approximately 3 mL of 6M HCl was added and the mixture was refluxed overnight.

[0360] The solution was cooled, diluted with water, and the product was extracted with a portion of dichloromethane. The combined organic fractions were concentrated, and the residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). A second column purification was performed (0-10% dichloromethane in hexanes) to give 529 mg of the final ligand as a yellow solid (39%).

[0361] 1 H NMR(400MHz,CDCl3)δ 8.30(s,2H),7.92(s,4H),7.59(s,4H),7.45(d,J=2.4Hz,2H),7.31(d,J=2. 4Hz,2H),6.95(dd,J=9.1,3.2Hz,2H),6.78(dd,J=8.9,3.1Hz,2H),5.45(s, 2H),3.71(t,J=6.2Hz,4H),1.97(s,6H),1.76-1.62(m,22H),1.43(d,J=2.8 Hz, 12H), 1.39 (d, J=2.3Hz, 24H), 1.15 (s, 12H), 1.09 (s, 12H), 0.78 (s, 18H).

[0362] 13 C NMR(101MHz,CDCl3)δ 159.56,157.15,150.75,150.73,148.78,144.10,143.54,141.50,133.36,133.28,1 33.20,133.11,130.49,130.33,129.05,128.99,128.50,125.46,124.90,124.47,12 4.46, 122.76, 116.54, 116.32, 116.23, 116.01, 70.17, 56.73, 38.12, 35.03, 34.87, 34.66, 34.52, 32.62, 32.50, 32.41, 32.14, 32.02, 31.57, 26.90, 25.26, 20.69, 16.68.

[0363] 19 F NMR (470MHz, CDCl3) δ-119.92 (t,J=8.9Hz).

[0364] Preparation of 1,3-bis((5-fluoro-3'-iodo-2'-(methoxymethoxy)-3-methyl-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane as detailed in WO 2020 / 047384(A1).

[0365] Example 50 - Synthesis of metal-ligand complex 30 of the present invention (IMLC-30):

[0366] [ka]

[0367] In a glove box, a 20 mL vial was charged with ScCl3 (14.9 mg, 0.0985 mmol, 1.00 equiv) and 4.5 mL of dry THF. The mixture was stirred overnight at ambient temperature. After approximately 16 h, the slurry was placed in a glove box freezer for 1 h. The vial was then removed from the glove box and then treated with methyllithium (1.6 M in diethyl ether, 0.191 mL, 0.306 mmol, 3.1 equiv). The mixture became homogenous within 1 min. Less than 2 minutes after the addition of the methyllithium, ligand formula xxiv (2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-bis(trimethylsilyl)-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)) (136 mg, 0.0985 mmol, 1.00 equiv.) was added. After stirring for 14 hours, the solvent was removed by vacuum pump and the solid was suspended in 3 mL of hexane. The solution was filtered through a 0.45 um syringe filter and the solvent was removed from the filtrate by vacuum pump. The solid was dissolved in approximately 1 mL of pentane and then cooled overnight in a glove box freezer. A white solid formed and was then separated by decantation. 57.4 mg of solid was isolated (40%).

[0368] 1 H NMR(500MHz,CD2Cl2)δ 8.20(dd,J=7.6,0.8Hz,1H),8.16(dd,J=7.6,0.8Hz,1H),8.13(dd,J=7.6,0.8Hz,1H),7. 97(dd,J=7.6,0.7Hz,1H),7.95(q,J=1.2Hz,1H),7.60(s,1H),7.54(dd,J=11.3,2.7Hz,1H ),7.51-7.43(m,2H),7.43-7.27(m,3H),7.27-7.18(m,3H),7.14(d,J=0.9Hz,1H),6.92( dd,J=9.3,3.2Hz,1H),6.58(dd,J=9.2,3.2Hz,1H),6.49(dd,J=8.6,3.2Hz,1H),6.28(dd, J=8.7,3.2Hz,1H),4.20-4.05(m,1H),3.96-3.83(m,1H),3.79-3.69(m,1H),3.69-3.59( m,1H),2.87-2.71(m,2H),2.62-2.45(m,2H),1.96(m,1H),1.86(m,1H),1.81-1.74(m,2H) ,1.70-1.55(m,5H),1.41(s,3H),1.39-1.32(m,9H),0.97-0.90(m,4H),0.82(s,9H),0.79 (s,9H),0.66(s,3H),0.42(s,9H),0.28(s,9H),0.11(s,9H),-0.04(s,9H),-1.84(s,3H).

[0369] 19 F NMR(470MHz, CD2Cl2)δ-118.26(t,J=8.8Hz),-118.32(t,J=9.1Hz).

[0370] Example 51-1-(エトキシメトキシ)-4-(2,4,4-トリメチルペンタン-2-イル)ベンゼン:

[0371]

change

[0372] A clear, colorless solution of 4-(2,4,4-trimethylpentan-2-yl)phenol (10.091 g, 48.909 mmol, 1.00 equiv) in THF (300 mL) and HO (3 mL) was sparged under a positive flow of nitrogen for 1 h, at which time aqueous NaOH (7.8 mL, 97.818 mmol, 2.00 equiv, 50% w / w) was added in a fast dropwise fashion via syringe. After stirring (500 rpm) at 23° C. for 20 min, neat chloromethyl ethyl ether (13.6 mL, 146.73 mmol, 3.00 equiv) was added in a fast dropwise fashion via syringe to the clear, colorless solution. After stirring at 23 °C for 2 h, the now white heterogeneous mixture was diluted with aqueous NaOH (150 mL, 1N), the THF was removed by rotary evaporation, and the resulting white biphasic mixture was diluted with CHCl (100 mL), poured into a separatory funnel, partitioned, the organics washed with aqueous NaOH (2 x 50 mL, 1N), the residual organics extracted from the aqueous solution (2 x 25 mL), combined, dried over solid NaSO, decanted, and concentrated. The resulting pale yellow oil was diluted with CHCl (20 mL), suction filtered through a pad of silica gel, rinsed with CHCl (4 x 50 mL), and the filtrate was concentrated to give the phenolic methyl ethyl ether as a clear, colorless oil (12.800 g, 48.420 mmol, 99%).

[0373] 1 H NMR(400MHz,CDCl3)δ 7.29-7.22(m,2H),6.98-6.90(m,2H),5.19(d,J=1.1Hz,2H),3.72(q,J=7 .1Hz,2H),1.69(s,2H),1.33(s,6H),1.21(t,J=7.1Hz,3H),0.71(s,9H).

[0374] 13 C NMR(101MHz, CDCl3)δ 155.01,143.38,127.01,115.44,93.30,64.08,56.99,37.99,32.30,31.75,31.59,15.10.

[0375] Example 5 2-(2-(ethoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)trimethylsilane:

[0376] [ka]

[0377] In a continuously purged nitrogen filled glovebox, a clear, colorless solution of the protected phenol (5.000 g, 18.910 mmol, 1.00 equiv) in deoxygenated anhydrous THF (100 mL) was placed in a freezer cooled to -35°C for 2 h, at which time a solution of n-BuLi (15.4 mL, 24.583 mmol, 1.30 equiv, 2.6 M in hexanes) was added in a rapid dropwise manner via syringe. The now golden yellow solution was placed in the freezer for 45 min, removed and stirred (300 rpm) at 23° C. for 2 h, the now dark golden yellow solution was returned to a −35° C. cooled freezer for 1 h, then neat chlorotrimethylsilane (3.60 mL, 28.365 mmol, 1.50 equiv) was added neat via syringe in a fast dropwise fashion, after 20 min the now white mixture was removed from the freezer and stirred (300 rpm) at 23° C. for 2 h. The resulting clear, colorless solution was removed from the glovebox, neutralized with saturated aqueous NaHCO3 mixture, diluted with CHCl2 (100 mL), poured into a separatory funnel, partitioned, the organics washed with saturated aqueous NaHCO3 mixture (1×50 mL), the remaining organics extracted from the aqueous solution (2×25 mL), combined, dried over solid NaSO4, decanted, and concentrated. The resulting pale yellow oil was diluted with CH2Cl2 (10 mL), suction filtered through a pad of silica gel, rinsed with CH2Cl2 (4 x 25 mL), and the filtrate was concentrated to give the protected phenol as a clear pale yellow oil (5.365 g, 15.939 mmol, 84%).

[0378] 1H NMR(400MHz,CDCl3)δ 7.36(d,J=2.6Hz,1H),7.29-7.24(m,1H),6.96(d,J=8.6Hz,1H),5.20(s,2H),3.71(q,J =7.0Hz,2H),1.69(s,2H),1.35(s,6H),1.22(t,J=7.1Hz,3H),0.71(s,9H),0.27(s,9H).

[0379] 13 C NMR(101MHz, CDCl3)δ 159.89,142.26,132.63,128.10,126.78,111.69,92.67,64.02,57.10,38.03,32.31,31.76,31.53,15.10,-0.77.

[0380] Example 5 3-(2-(ethoxymethoxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)trimethylsilane:

[0381] [ka]

[0382] A 500 mL round bottom flask was charged with (2-(ethoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)trimethylsilane (16.9 g, 50.2 mmol, 1.00 equiv) and 148 mL of dry THF. The solution was cooled to -78°C under a nitrogen blanket. N-butyllithium (2.5 M in hexanes, 22.1 mL, 55.2 mmol, 1.10 equiv) was added dropwise. The mixture was stirred at -78°C and allowed to warm to room temperature over 2 h.

[0383] The flask was returned to the -78°C bath and isopropoxy-Bpin (12.3 mL, 60.3 mmol, 1.20 equiv) was injected. The mixture was allowed to warm gradually to room temperature over 3 h.

[0384] The solution was quenched with saturated aqueous ammonium chloride. The phases were separated and the aqueous phase was extracted several times with dichloromethane. The combined organic fractions were concentrated and the residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 11.434 g of product was isolated as a colorless oil (49%).

[0385] 1 H NMR(500MHz,CDCl3)δ 7.66(d,J=2.7Hz,1H),7.51(d,J=2.8Hz,1H),5.17(s,2H),3.68(q,J=7.1Hz,2H),1. 71(s,2H),1.36(d,J=5.8Hz,18H),1.19(t,J=7.1Hz,3H),0.69(s,9H),0.31(s,9H).

[0386] 13 C NMR(126MHz, CDCl3)δ 165.13,143.13,136.57,135.41,130.36,98.70,83.56,65.55,56.97,38.11,32.33,31.81,31.57,24.82,15.16,-0.13.

[0387] Example 54-1,3-bis((2'-(ethoxymethoxy)-5-fluoro-3-methyl-5'-(2,4,4-trimethylpentan-2-yl)-3'-(trimethylsilyl)-[1,1'-biphenyl]-2-yl)oxy)propane:

[0388] [ka]

[0389] A 500 mL round bottom flask was charged with (2-(ethoxymethoxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)trimethylsilane (11.4 g, 24.6 mmol, 2.20 equiv.), 1,3-bis(2-bromo-4-fluoro-6-methylphenoxy)propane (5.04 g, 11.2 mmol, 1.00 equiv.), sodium hydroxide (4.03 g, 101 mmol, 9.00 equiv.), and Pd(PPh3)4 (1.29 g, 1.12 mmol, 10 mol%). A reflux condenser was attached and the unit was placed under a nitrogen atmosphere. 130 mL of nitrogen sparged 6:1 dioxane:water was added and the mixture was stirred under nitrogen at 85° C.

[0390] After 14 h, the solution was cooled and quenched with brine. The phases were separated and the aqueous phase was extracted twice with dichloromethane. The combined organic fractions were concentrated and the residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 9.33 g of product was isolated as a clear, colorless oil (86%).

[0391] 1 H NMR(400MHz,CDCl3)δ 7.39(d,J=2.5Hz,2H),7.23(d,J=2.5Hz,2H),6.88(dd,J=8.9,3.2Hz,2H),6.82(dd,J=8.9,3.1Hz,2H),4.59(s,4H),3.61-3. 02(m,8H),2.20(s,6H),1.69(s,4H),1.40(t,J=6.5Hz,2H),1.31(s,12H),0.97(t,J=7.1Hz,6H),0.68(s,18H),0.29(s,18H).

[0392] 13C NMR(101MHz,CDCl3)δ 159.32,157.12,156.92,151.31,151.29,144.35,134.86,134.77,133.04,132.96,132.92,131.98,130.61,129.36,129. 35,116.22,116.00,115.74,115.52,97.55,69.38,64.88,56.85,38.16,32.31,31.82,30.91,16.77,16.76,14.86,-0.16.

[0393] 19 F NMR (470MHz, CDCl3) δ-120.59 (t,J=8.8Hz).

[0394] Preparation of 1,3-bis(2-bromo-4-fluoro-6-methylphenoxy)propane as detailed in WO 2020 / 047384(A1).

[0395] Example 55-1,3-bis((2'-(ethoxymethoxy)-5-fluoro-3'-iodo-3-methyl-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane:

[0396] [ka]

[0397] A 500 mL round bottom flask was charged with 1,3-bis((2'-(ethoxymethoxy)-5-fluoro-3-methyl-5'-(2,4,4-trimethylpentan-2-yl)-3'-(trimethylsilyl)-[1,1'-biphenyl]-2-yl)oxy)propane (9.00 g, 9.36 mmol, 1.00 equiv). The solid was dissolved in 130 mL of acetonitrile and 100 mL of dichloromethane. The mixture was protected from light and treated with n-iodosuccinimide (14.7 g, 65.5 mmol, 7.00 equiv). The mixture was stirred for 24 h.

[0398] Only partial conversion was observed by TLC, so an additional 7.00 g of NIS was added. The mixture was stirred for 6 days. TLC showed near completion. A final 5.00 g of NIS was added and the mixture was stirred for an additional 24 hours.

[0399] The reaction was quenched with aqueous sodium thiosulfate. The product was extracted several times with dichloromethane. The combined organic fractions were washed with 5% NaOH. The organic phase was concentrated and the residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 8.314 g of product was isolated as a clear, colorless oil (83%).

[0400] 1 H NMR(400MHz,CDCl3)δ 7.74(d,J=2.3Hz,2H),7.25(d,J=2.4Hz,2H),6.91-6.78(m,4H),4.77(s,4H),3.40(s,4H),3.29(q,J=7.1H z,4H),2.22(s,6H),1.68(s,4H),1.47(p,J=6.6Hz,2H),1.30(s,12H),0.94(t,J=7.1Hz,6H),0.73(s,18H).

[0401] 13 C NMR(101MHz,CDCl3)δ 159.26,156.86,152.18,151.21,151.18,147.89,136.98,133.50,133.41,133.27,133.18,131.66,131.64,129.6 6,116.78,116.56,115.66,115.43,98.00,92.56,69.88,65.32,56.65,38.18,32.39,31.88,30.76,16.82,14.76.

[0402] 19 F NMR(376MHz, CDCl3)δ-120.29(t,J=8.7Hz).

[0403] Example 56 - Preparation of liand formula (xxiv):

[0404] [ka]

[0405] In a glove box, a 50 mL round bottom flask was charged with 1,3-bis((2'-(ethoxymethoxy)-5-fluoro-3'-iodo-3-methyl-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane (0.500 g, 0.468 mmol, 1.00 equiv.), 2,7-bis(trimethylsilyl)-9H-carbazole (0.364 g, 1.17 mmol, 2.50 equiv.), KPO (0.596 g, 2.81 mmol, 6.00 equiv.), CuI (89 mg, 0.47 mmol, 1.0 equiv.), N,N'-dimethylethylenediamine (0.081 mL, 0.75 mmol, 1.6 equiv.), and 6 mL of toluene. A reflux condenser was attached, the unit sealed with a rubber septum, and transferred to a fume hood. The mixture was stirred at 120° C. under a nitrogen blanket for 24 h. The heterogeneous mixture was cooled and diluted with dichloromethane. The slurry was filtered through a plug of silica, and the filtrate was concentrated. The residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 556 mg of a white solid was isolated. Proton / fluorine NMR showed this to be the coupled intermediate with a small amount of residual carbazole. The solid was dissolved in 5 mL of THF. The solution was treated with 1 mL of 6M HCl, and the mixture was stirred overnight at ambient temperature. TLC showed no conversion by morning, so the mixture was stirred at 70° C. for 4 h. TLC showed some product had formed. It was suspected that desilylation may have occurred, and the reaction was stopped. The crude solution was adsorbed onto silica and purified by chromatography (0-10% EtOAc in hexanes). 136 mg of the desired product was isolated as a white solid (22%).

[0406] 1H NMR(500MHz,CDCl3)δ 8.14(d,J=7.7Hz,4H),7.47-7.35(m,8H),7.24(s,4H),6.97(dd,J=8.8,3.1Hz,2H),6.80(dd,J=8.6,3.1Hz,2H),6.40(s ,2H),3.60(t,J=6.4Hz,4H),1.83(s,6H),1.73(s,4H),1.66(q,J=6.3Hz,2H),1.37(s,12H),0.79(s,18H),0.19(s,36H).

[0407] 13 C NMR(126MHz,CDCl3)δ 159.88,157.94,149.93,147.75,142.95,140.99,138.07,133.62,133.55,132.85,132.78,129.19,127.59,126.37,125.01 ,124.43,123.85,119.76,117.37,117.19,116.12,115.94,114.52,70.92,57.06,38.22,32.50,31.94,31.67,16.32,-0.82.

[0408] 19 F NMR (470MHz, CDCl3) δ-118.21 (t,J=8.6Hz).

[0409] Preparation of 2,7-bis(trimethylsilyl)-9H-carbazole as detailed in J. Org. Chem. 2019, 84, 11783.

[0410] Example 57 - Synthesis of metal-ligand complex 31 of the present invention (IMLC-31):

[0411] [ka]

[0412] In a glove box, a 20 mL vial was charged with ScCl3 (18.0 mg, 0.119 mmol, 1.00 equiv) and 4.5 mL of dry THF. The mixture was stirred overnight at ambient temperature. After approximately 16 h, the slurry was placed in a glove box freezer for 1 h. The vial was then removed from the glove box and treated with methyllithium (1.6 M in diethyl ether, 0.231 mL, 0.369 mmol, 3.1 equiv). The mixture became homogenous within 1 min. Less than 2 minutes after the addition of the methyllithium, ligand formula xxv (2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-bis(trimethylgermyl)-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)) (178 mg, 0.119 mmol, 1.00 equiv.) was added. The mixture was stirred for 4 hours and the solvent was removed by vacuum pump. The solid residue was mixed with 5 mL of dry hexane and the slurry was filtered through a 0.45 um syringe filter. The filtrate was concentrated to a white solid. The solid was suspended in approximately 3 mL of pentane. The slurry was filtered and the white solid was collected. 74.9 mg of a white solid was isolated (39%).

[0413] 1H NMR(500MHz,CD2Cl2)δ 8.18(d,J=7.7Hz,1H),8.15(d,J=7.5Hz,1H),8.11(d,J=7.6Hz,1H),7.96(d,J=7.6Hz,1H),7.89(s,1H),7.58-7.50(m,2H),7.46-7.38(m,2H),7.34(d,J=2.6Hz,1H),7.33-7.26(m,2H),7.26-7.21(m,2H),7.17(d,J=7.6Hz,1H),7.09(s,1H),6.91(dd,J=9.3,3.2Hz,1H),6.59(dd,J=9.2,3.2Hz,1H),6.48(dd,J=8.6,3.2Hz,1H),6.29(dd,J=8.5,3.2Hz,1H),4.23-4.10(m,1H),3.95-3.78(m,1H),3.72(dd,J=7.5,4.1Hz,1H),3.68-3.53(m,1H),2.77(q,J=6.7Hz,2H),2.65-2.47(m,2H),2.06-1.92(m,1H),1.86(d,J=16.5Hz,1H),1.77(dd,J=14.4,9.8Hz,2H),1.71-1.55(m,5H),1.41(s,3H),1.38-1.31(m,9H),1.02-0.89(m,4H),0.82(s,9H),0.79(s,9H),0.66(s,3H),0.52(s,9H),0.39(s,9H),0.21(s,9H),0.06(s,9H),-1.84(s,3H)。

[0414] 13C NMR(126MHz,CD2Cl2)δ 160.82,158.88,158.45,155.95,155.35,149.12,148.76,148.74,142.15,14 0.92,139.72,139.66,139.56,139.32,138.90,138.70,137.13,136.91,136. 65,136.45,134.90,134.83,134.14,134.07,129.87,129.17,128.45,127.87,127.62,125.97,124.74,124.56,124.46,123.81,123.54,123.32,123.28,1 23.08,122.88,122.47,119.73,119.41,119.11,118.81,117.54,117.12,116.94,116.26,116.24,116.10,116.03,115.92,115.85,115.08,114.90,114.4 9,78.05,74.23,70.66,57.96,57.04,37.73,33.32,32.37,32.32,32.23,31.67,31.61,30.27,30.22,29.57,24.38,17.30,14.82,-1.67(2),-1.85,-2.35.

[0415] 19 F NMR (470MHz, CD2Cl2)δ-118.22--118.37(m).

[0416] Example 58-2,7-Bis(trimethylgermyl)-9H-carbazole:

[0417] [ka]

[0418] In a glove box, a 50 mL bottle was charged with 2,7-dilithio-9-(tert-butyldimethylsilyl)-9H-carbazole (1.00 g, 3.41 mmol, 1.00 equiv) and 17 mL of dry THF. Chlorotrimethylgermane (1.26 mL, 10.2 mmol, 3.00 equiv) was added and the mixture was stirred for 45 min. The solid organolithium dissolved rapidly as the reaction proceeded. The clear, colorless solution was quenched with aqueous ammonium chloride. The product was extracted several times with dichloromethane. The combined organic fractions were concentrated and the residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 0.995 g of a white solid was isolated. Proton / carbon NMR confirmed this to be the silylated intermediate. The carbazole was dissolved in 10 mL of THF and treated with tetrabutylammonium fluoride trihydrate (0.609 g, 1.93 mmol, 1.00 equiv). The mixture was stirred for 20 min, after which TLC showed complete consumption of the starting material. The solution was quenched with aqueous ammonium chloride. The product was extracted several times with dichloromethane. The combined organic fractions were concentrated, and the residue was purified by chromatography on silica gel (0-20% EtOAc in hexanes). 0.720 g of the product was isolated as a white solid (53% for two steps).

[0419] 1 H NMR(400MHz, CDCl3)δ 8.05(d,J=7.7Hz,2H),7.94(s,1H),7.54(s,2H),7.32(dd,J=7.6,0.8Hz,2H),0.45(s,18H).

[0420] 13 C NMR(101MHz, CDCl3)δ 140.11,139.37,123.64,123.47,119.80,114.94,-1.49.

[0421] Preparation of 2,7-dilithio-9-(tert-butyldimethylsilyl)-9H-carbazole as detailed in WO 2017 / 058981 A1.

[0422] Example 59 - Preparation of ligand formula (xxv):

[0423] [ka]

[0424] In a glove box, a 50 mL round bottom flask was charged with 1,3-bis((2'-(ethoxymethoxy)-5-fluoro-3'-iodo-3-methyl-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane (0.500 g, 0.468 mmol, 1.00 equiv.), 2,7-bis(trimethylsilyl)-9H-carbazole (0.469 g, 1.17 mmol, 2.50 equiv.), KPO (0.595 g, 2.81 mmol, 6.00 equiv.), CuI (89 mg, 0.47 mmol, 1.0 equiv.), N,N'-dimethylethylenediamine (0.081 mL, 0.75 mmol, 1.6 equiv.), and 6 mL of toluene. A reflux condenser was attached, the unit sealed with a rubber septum, and transferred to a fume hood. The mixture was stirred at 120° C. under a nitrogen blanket for 48 h. The heterogeneous mixture was cooled and diluted with dichloromethane. The slurry was filtered through a plug of silica, and the filtrate was concentrated. The residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 552 mg of a white solid was isolated. Proton / fluorine NMR showed this to be the coupled intermediate with a small amount of residual carbazole. The intermediate (420 mg, 0.260 mmol, 1.00 equiv) was dissolved in 4.5 mL of dry DMF. The solution was treated with sodium ethanethiolate (88 mg, 4.0 equiv) and stirred at 100° C. for 2 h. TLC showed complete consumption of starting material. The solution was cooled, quenched with brine, and the product was extracted several times with diethyl ether. The combined organic fractions were concentrated and the residue was purified by chromatography on silica gel (0-20% dichloromethane in hexanes). 347 mg of product was isolated as a white solid (49% over two steps).

[0425] 1 H NMR(400MHz, CDCl3)δ 8.12(d,J=7.7Hz,4H),7.42(s,4H),7.35(d,J=7.6Hz,4H),7.18(s,4H),6.97(dd,J=8.8,3.2Hz,2H),6.79(dd,J=8.7,3.1Hz,2H) ,6.36(s,2H),3.61(t,J=6.2Hz,4H),1.84(s,6H),1.73(s,4H),1.66(p,J=6.0Hz,2H),1.37(s,12H),0.79(s,18H),0.29(s,36H).

[0426] 13 C NMR(101MHz,CDCl3)δ 160.10,157.68,150.01,149.98,147.73,142.96,141.01,140.19,133.61,133.52,132.83,132.75,129.14,127.53,126.38,126.37 ,125.03,124.04,123.52,119.75,117.36,117.14,116.12,115.89,114.03,70.90,57.06,38.22,32.48,31.93,31.66,16.33,-1.50.

[0427] 19 F NMR (376MHz, CDCl3) δ-118.23 (t, J=8.7Hz).

[0428] Example 60 - Synthesis of the present metal-ligand complex 32 (IMLC-32):

[0429]

change

[0430] In a glove box, a 20 mL vial was charged with ScCl3 (28.3 mg, 0.187 mmol, 1.00 equiv) and 4.5 mL of dry THF. The mixture was stirred overnight at ambient temperature. After approximately 16 h, the slurry was placed in the glove box freezer for 1 h. The vial was then removed from the glove box and treated with methyllithium (1.53 M in diethyl ether, 0.379 mL, 3.1 equiv). The mixture became homogenous within a few minutes. Less than 5 minutes after the addition of the methyllithium, ligand formula xxvi (6',6'''-(propane-1,3-diylbis(oxy))bis(3-(2,6-di-tert-butylanthracen-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)) (234 mg, 0.187 mmol, 1.00 equiv.) was added. After stirring for 3 hours, the solvent was removed by vacuum pump and the solid was suspended in 6 mL of 1:1 hexane:toluene. The solution was filtered through a 0.45 um syringe filter and the solvent was removed from the filtrate by vacuum pump. A yellow solid was isolated. The solid was dissolved in 1 mL of dry pentane and cooled in a glove box freezer overnight. A small amount of white solid precipitated and was removed by decantation. The solid was dried (32 mg). The decanted liquid was concentrated to give 182 mg of a yellow solid (71%). Proton / fluorine NMR of each portion indicated that the product was contained primarily in the pentane soluble portion. The complex existed as a mixture of four different rotamers.

[0431] 1 H NMR(400MHz,CD2Cl2)δ 8.47-6.05(m,24H),4.59-3.28(m,6H),2.27-0.72(m,78H),-2.76--3.06(m,3H).

[0432] 19F NMR(470MHz,CD2Cl2)δ-117.10--117.24(m),-117.31--117.43(m),-117.56--117.68(m),-117.79(td,J =8.5,5.1Hz),-119.21(td,J=8.8,5.5Hz),-119.35(td,J=8.9,5.6Hz),-120.05(qd,J=10.8,8.9,6.3Hz).

[0433] Preparation of ligands of formula xxvi as detailed in WO 2020 / 047384(A1).

[0434] Example 61 - Synthesis of metal-ligand complex 33 of the present invention (IMLC-33):

[0435] [ka]

[0436] In a glove box, a 20 mL vial was charged with ScCl3 (27.0 mg, 0.179 mmol, 1.00 equiv) and 4.5 mL of dry THF. The mixture was stirred overnight at ambient temperature. After approximately 16 h, the slurry was placed in the glove box freezer for 1 h. The vial was then removed from the glove box and treated with methyllithium (1.53 M in diethyl ether, 0.362 mL, 0.554 mmol, 3.1 equiv). The mixture became homogenous within 1 min. Less than 2 minutes after the addition of the methyllithium, ligand formula xxvii (2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-bis(dimethyl(phenyl)silyl)-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)) (280 mg, 0.179 mmol, 1.00 equiv.) was added. The mixture was stirred for 4 hours and the solvent was removed by vacuum pump. The solid residue was mixed with 5 mL of dry 1:1 hexane:toluene and the slurry was filtered through a 0.45 um syringe filter. The filtrate was concentrated to a white solid. 266 mg of solid was recovered (87%).

[0437] 1 H NMR(500MHz,CD2Cl2)δ 8.26-8.21(m,1H),8.19-8.15(m,1H),8.12(dd,J=7.7,0.8Hz,1H),7.95(td,J=7.3,0.8Hz,1H),7.93(d,J=1.0Hz,1H),7.65-7.58(m,3H),7.52(dd,J=7.6,0.9Hz,1H),7.51-7.47(m,4H),7.40-7.38(m,3H),7.36-7.32(m,5H),7.32-7.29(m,2H),7.28-7.16(m,13H),6.86-6.82(m,1H),6.54(ddd,J=13.3,8.9,3.3Hz,2H),6.14(dd,J=8.5,3.1Hz,1H),4.01-3.83(m,1H),3.61-3.54(m,1H),3.54-3.39(m,2H),2.72-2.62(m,2H),2.53-2.43(m,2H),1.75(dd,J=14.4,2.1Hz,2H),1.67-1.50(m,4H),1.42(s,3H),1.39(s,3H),1.34-1.26(m,12H),0.78(s,9H),0.76-0.72(m,13H),0.66(s,3H),0.61(s,3H),0.60(s,3H),0.36(s,3H),0.35(s,3H),0.34(s,3H),0.18(s,3H),-1.72(s,3H)。

[0438] 13C NMR(126MHz,CD2Cl2)δ 160.84,160.34,158.90,158.40,155.98,155.42,149.09,149.07,148.64,148.62,142.24,141.24,139 .97,139.94,139.21,139.00,138.99,138.61,136.96,136.90,136.64,136.57,136.47,135.40,134.99, 134.86,134.79,134.35,134.33,134.30,134.27,134.16,134.12,134.09,134.08,134.02,133.98,133.29,129.68,129.25,128.92,128.71,128.66,128.63,128.48,128.11,127.90,127.78,127.77,127.58, 127.57,127.53,127.50,127.43,125.74,125.08,124.92,124.66,124.59,124.41,124.38,123.44,122.99,119.99,119.58,119.29,118.88,118.83,117.72,117.56,117.23,117.05,116.10,115.85,115.67, 115.06, 114.88, 77.80, 74.14, 70.75, 57.74, 56.98, 37.67, 37.66, 33.28, 32.44, 32.30, 32.25, 31.62, 30.14, 30.01, 29.62, 24.18, 24.15, 17.08, 15.05, -2.06, -2.25, -2.38, -2.42, -2.48, -2.53, -2.76, -2.82.

[0439] 19 F NMR (470MHz, CD2Cl2) δ-118.07(t,J=8.9Hz),-118.36(t,J=8.8Hz).

[0440] Example 62-2,7-Bis(dimethyl(phenyl)silyl)-9H-carbazole:

[0441] [ka]

[0442] In a glove box, a 50 mL bottle was charged with 2,7-dilithio-9-(tert-butyldimethylsilyl)-9H-carbazole (1.00 g, 3.41 mmol, 1.00 equiv.) and 17 mL of dry THF. Chlorodimethylphenylsilane (1.72 mL, 10.2 mmol, 3.00 equiv.) was added and the mixture was stirred for 45 min. The solid organolithium dissolved rapidly as the reaction proceeded. The clear, colorless solution was quenched with aqueous ammonium chloride. The product was extracted several times with dichloromethane. The combined organic fractions were concentrated. The solution was dried over Na2SO4, filtered through basic alumina, and concentrated to a white solid. 2.021 g of crude white solid was isolated and used without further purification. The carbazole was dissolved in 10 mL of THF and treated with tetrabutylammonium fluoride trihydrate (2.02 g, 3.41 mmol, 1.00 equiv). The mixture was stirred for 20 min, after which TLC showed complete consumption of the starting material. The solution was quenched with aqueous ammonium chloride. The product was extracted several times with dichloromethane. The combined organic fractions were concentrated, and the residue was purified by chromatography on silica gel (0-20% EtOAc in hexanes). 0.803 g of the product was isolated as a white solid (54% for two steps).

[0443] 1 H NMR (500MHz, CDCl3) δ 8.06(d,J=7.7Hz,2H),7.87(s,1H),7.60-7.49(m,6H),7.44-7.31(m,8H),0.62(s,12H).

[0444] 13 C NMR(126MHz, CDCl3)δ 139.31,138.62,135.79,134.27,129.07,127.81,124.85,123.93,119.93,116.52,-2.07.

[0445] Example 63 - Preparation of ligand formula (xxvii):

[0446] [ka]

[0447] In a glove box, a 50 mL round-bottom flask was charged with 1,3-bis((2'-(ethoxymethoxy)-5-fluoro-3'-iodo-3-methyl-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane (0.500 g, 0.468 mmol, 1.00 equiv.), 2,7-bis(trimethylgermyl)-9H-carbazole (0.500 g, 0.4 The mixture was charged with 1,2,3-tetramethylphenylsilyl (0.68 mmol, 1.00 equiv), 2,7-bis(dimethyl(phenyl)silyl)-9H-carbazole (0.448 g, 1.03 mmol, 2.20 equiv), K3PO4 (0.596 g, 2.81 mmol, 6.00 equiv), CuI (89 mg, 0.47 mmol, 1.0 equiv), N,N'-dimethylethylenediamine (0.081 mL, 0.75 mmol, 1.6 equiv), and 6 mL of toluene. A reflux condenser was attached, the unit was sealed with a rubber septum, and transferred to a fume hood. The mixture was stirred at 120 °C under a nitrogen blanket for 48 h. An additional portion of CuI (89 mg) and DMEDA (0.081 mL) was added. Stirring was continued for an additional 48 h. The solution was cooled, diluted with dichloromethane, and the slurry was filtered through a plug of alumina. The filtrate was concentrated and the residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 177 mg of the desired intermediate was isolated and taken onto the next step. The intermediate was dissolved in 6 mL of 1:1 THF:methanol. This was treated with 20 mg of p-toluenesulfonic acid monohydrate and refluxed for 5 h. TLC showed complete consumption of starting material. The solution was cooled and diluted with dichloromethane and water. The phases were separated and the aqueous phase was extracted several more times with dichloromethane. The combined organic fractions were concentrated and purified by chromatography on silica gel (0-20% EtOAc in hexanes). 129 mg of the product was isolated as a white solid (18% yield over two steps).

[0448] 1H NMR(400MHz, CDCl3)δ 8.13(d,J=7.8Hz,4H),7.46-7.33(m,16H),7.28(s,4H),7.24-7.06(m,12H),6.88(dd,J=8.9,3.2Hz,2H),6.77(dd,J=8.6,3.1Hz,2H ),6.43(s,2H),3.42(t,J=6.3Hz,4H),1.73(s,6H),1.68(s,4H),1.50-1.39(m,2H),1.32(s,12H),0.71(s,18H),0.57-0.36(m,24H).

[0449] 13 C NMR(101MHz,CDCl3)δ 160.13,157.70,149.85,149.82,147.58,142.93,140.99,138.48,135.61,134.15 ,134.09,133.62,133.54,132.81,132.72,128.97,128.87,127.71,127.65,127.6 1,127.40,126.39,125.34,124.92,124.03,119.87,117.31,117.09,116.17,115.94,115.67,70.96,57.02,38.16,32.39,31.83,31.58,30.47,16.19,-2.04,-2.10.

[0450] 19 F NMR (470MHz, CDCl3) δ-118.16 (m).

[0451] Example 64 - Synthesis of the present metal-ligand complex 34 (IMLC-34):

[0452]

change

[0453] In a glove box, a 20 mL vial was charged with ScCl3 (27.0 mg, 0.179 mmol, 1.00 equiv) and 4.5 mL of dry THF. The mixture was stirred overnight at ambient temperature. After approximately 16 h, the slurry was placed in the glove box freezer for 1 h. The vial was then removed from the glove box and treated with methyllithium (1.53 M in diethyl ether, 0.362 mL, 0.554 mmol, 3.1 equiv). The mixture became homogenous within 1 min. Less than 2 minutes after the addition of the methyllithium, 6',6'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-bis(trimethylgermyl)-9H-carbazol-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)) was added (262 mg, 0.179 mmol, 1.00 equiv). The mixture was stirred for 5 h and the solvent was removed by vacuum pump. The solid residue was mixed with 5 mL of dry 2:1 hexane:toluene and the slurry was filtered through a 0.45 um syringe filter. The filtrate was concentrated to a white solid. The solid was suspended in approximately 2 mL of pentane. The mixture was cooled overnight in a glove box freezer. The slurry was filtered and the white solid was dried under vacuum. 199 mg of solid was isolated (69%).

[0454] 1H NMR(500MHz,CD2Cl2)δ 8.32(dd,J=7.7,0.8Hz,1H),8.28(dd,J=7.7,0.8Hz,1H),8.10(dd,J=7.6,0.8Hz,1H),8.05(dd,J=7.6,0.8Hz,1H),7.58(t,J=0.9Hz,1H),7.55(t,J=0.9Hz,1H),7.51-7.44(m,3H),7.37(d,J=2.7Hz,1H),7.27(d,J=2.6Hz,1H),7.25-7.19(m,3H),7.14(d,J=0.9Hz,1H),7.09(t,J=0.8Hz,1H),6.98(ddd,J=9.5,5.2,3.2Hz,2H),6.47(ddd,J=8.9,7.6,3.2Hz,1H),6.11(ddd,J=8.8,7.8,3.2Hz,1H),4.78(dd,J=8.8,5.1Hz,1H),4.48(dd,J=8.9,5.1Hz,1H),4.10(ddd,J=10.7,8.5,2.1Hz,1H),3.60(dddd,J=15.9,10.2,6.6,3.0Hz,2H),3.42(ddd,J=9.4,8.4,3.5Hz,1H),2.45-2.34(m,4H),1.83-1.62(m,5H),1.53(ddt,J=15.7,8.0,4.0Hz,1H),1.45-1.31(m,12H),0.91(ddd,J=7.6,5.0,2.4Hz,4H),0.81(s,9H),0.80(s,9H),0.35(s,9H),0.32(s,9H),0.21(s,9H),0.19(s,9H),-2.51(s,3H)。

[0455] 13C NMR(101MHz,CD2Cl2)δ 161.54,160.60,159.11,158.18,156.96,156.08,151.15,151.13,150.00,149.97 ,141.43,141.30,141.24,141.15,139.99,139.90,139.28,138.89,136.93,136.8 7,136.66,136.57,135.78,135.70,130.01,128.91,128.69,128.19,128.10,127.92,127.55,125.38,125.26,125.18,124.26,123.94,123.40,123.20,123.17,123. 09,123.04,122.73,122.64,122.42,122.28,119.82,119.77,119.19,119.07,117.85,117.61(2),117.36,116.43,115.61,114.85,114.62,113.87,113.80,113.65, 113.46, 78.59, 74.71, 70.21, 57.20, 57.10, 37.81, 37.69, 32.68, 32.40, 32.38, 32.35, 31.70, 31.68, 31.60, 30.64, 30.38, 29.77, 24.50, -1.70, -1.78, -1.99, -2.13.

[0456] 19 F NMR (470MHz, CD2Cl2) δ-116.82--117.34(m), -118.67(td, J=8.2, 5.0Hz).

[0457] Example 65-1,3-bis((5'-fluoro-3'-iodo-2'-methoxy-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane:

[0458] [ka]

[0459] In a glove box, solid 6',6'''-(propane-1,3-diylbis(oxy))bis(3'-fluoro-3-iodo-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol) (5.00 g, 5.41 mmol, 1.00 equiv.) was placed in a 100 mL vial and dissolved in THF (50 mL). The solution was treated with sodium hydride (0.298 g, 2.3 equiv.). After 10 min, the solution was treated with iodomethane (0.81 mL, 2.4 equiv.) and 10 mL of dry DMF. The mixture was stirred for 3 h. TLC indicated complete conversion of the phenol intermediate. The solution was diluted with water and the product was extracted with a portion of dichloromethane. The combined organic fractions were dried over MgSO4 and filtered through a plug of silica gel. The filtrate was concentrated and the residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 4.93 g of a colorless oil was isolated (96%).

[0460] 1 H NMR(400MHz,CDCl3)δ 7.72(d,J=2.4Hz,2H),7.14(d,J=2.4Hz,2H),7.05-6.89(m,4H),6.82(dd,J=8.9,4.5Hz,2H),3.8 7(t,J=5.8Hz,4H),3.27(s,6H),1.86(p,J=5.9Hz,2H),1.69(s,4H),1.31(s,12H),0.73(s,18H).

[0461] 13 C NMR(101MHz,CDCl3)δ 157.78,155.40,154.94,152.18,152.16,147.38,136.50,130.61,130.12,129.12,129.04,117.78,11 7.55,115.07,114.84,113.30,113.21,91.55,65.10,60.52,56.93,38.17,32.41,31.85,31.45,29.16.

[0462] 19 F NMR (470MHz, CDCl3) δ-124.29 (td, J=8.3, 4.5Hz).

[0463] Preparation of 6',6'''-(propane-1,3-diylbis(oxy))bis(3'-fluoro-3-iodo-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol) as detailed in WO 2020 / 047384(A1).

[0464] Example 66 - Preparation of ligand formula (xxviii):

[0465] [ka]

[0466] In a glove box, a 50 mL round bottom flask was charged with 1,3-bis((5-fluoro-3'-iodo-2'-methoxy-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane (0.950 g, 0.997 mmol, 1.00 equiv.), 2,7-bis(trimethylgermyl)-9H-carbazole (0.999 g, 2.49 mmol, 2.50 equiv.), KPO (1.27 g, 5.98 mmol, 6.00 equiv.), CuI (190 mg, 0.997 mmol, 1.0 equiv.), N,N'-dimethylethylenediamine (0.172 mL, 1.60 mmol, 1.60 equiv.), and 10 mL of toluene. A reflux condenser was attached, the unit sealed with a rubber septum, and transferred to a fume hood. The mixture was stirred at 120° C. under a nitrogen blanket for 24 h. The heterogeneous mixture was cooled and diluted with dichloromethane. The slurry was filtered through a plug of silica, and the filtrate was concentrated. The residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 0.970 mg of a white solid was isolated. Proton / fluorine NMR showed this to be the coupled intermediate with a small amount of residual carbazole. The solid was dissolved in 6.5 mL of dry DMF under nitrogen. The solution was treated with sodium ethanethiolate (218 mg, 2.59 mmol, 4.0 equiv) and stirred at 100° C. for 48 h. TLC showed consumption of starting material. The solution was cooled, quenched with brine, and the product was extracted with portions of dichloromethane. The combined organic fractions were purified by chromatography on silica gel (0-40% dichloromethane in hexanes). 510 mg of product was isolated as a white solid (35% over two steps).

[0467] 1H NMR(500MHz,CDCl3)δ 8.21(dd,J=7.7,0.8Hz,4H),7.41(dd,J=7.6,0.8Hz,4H),7.32(d,J=2.4Hz,2H),7.26(s,2H),7.14(d,J=0.9Hz,4H),6.92(dd,J=8.8,3.2Hz,2H), 6.36-6.17(m,2H),5.56(dd,J=9.0,4.4Hz,2H),5.15(s,2H),3.66(t,J=5 .5Hz,4H),1.90-1.77(m,2H),1.35(s,12H),0.77(s,18H),0.34(s,36H).

[0468] 13 C NMR(101MHz,CDCl3)δ 158.06,155.68,151.18,151.16,148.15,142.61,141.36,140.44,129.57,127.67,127.60,127.48,125.88,124.27,123.54,123 .48,119.78,118.11,117.87,115.34,115.12,113.89,112.54,112.45,64.44,57.16,38.13,32.45,31.88,31.58,28.88,-1.45.

[0469] 19 F NMR (470MHz, CDCl3) δ-123.22 (td, J=8.3, 4.3Hz).

[0470] Example 67 - Synthesis of the present metal-ligand complex 35 (IMLC-35):

[0471]

change

[0472] In a glove box, a 20 mL vial was charged with ScCl3 (30.8 mg, 0.204 mmol, 1.00 equiv) and 4.5 mL of dry THF. The mixture was stirred overnight at ambient temperature. After approximately 16 h, the slurry was placed in the glove box freezer for 1 h. The vial was then removed from the glove box and treated with methyllithium (1.53 M in diethyl ether, 0.412 mL, 0.631 mmol, 3.1 equiv). The mixture became homogenous within 1 min. Less than 2 minutes after the addition of the methyllithium, ligand formula xxix (6',6'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-bis(dimethyl(phenyl)silyl)-9H-carbazol-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)) (314 mg, 0.204 mmol, 1.00 equiv.) was added. The mixture was stirred for 5 hours and the solvent was removed by vacuum pump. The solid residue was mixed with 5 mL of dry 2:1 hexane:toluene and the slurry was filtered through a 0.45 um syringe filter. The filtrate was concentrated to a white solid. The solid was dissolved in approximately 2 mL of warm pentane. The mixture was cooled overnight in a glove box freezer to precipitate a white solid. The solvent was removed by decantation and the white solid was dried under vacuum. 0.278 g of solid was isolated (82%).

[0473] 1H NMR(500MHz,CD2Cl2)δ 8.40(dd,J=7.7,0.8Hz,1H),8.29(dd,J=7.7,0.8Hz,1H),8.17(dd,J=7.7,0.8Hz,1H),8.05(dd,J=7.8,0.8Hz,1H),7.65(dd,J=7.7,0.9Hz,1H),7.59(d,J=1.0Hz,1H),7.56(dd,J=7.7,0.9Hz,1H),7.52(d,J=0.9Hz,1H),7.45(d,J=2.6Hz,1H),7.42-7.39(m,2H),7.35-7.29(m,7H),7.25-7.08(m,14H),7.06-6.99(m,4H),6.96-6.90(m,1H),6.88(dd,J=9.4,3.2Hz,1H),6.47(ddd,J=8.9,7.7,3.2Hz,1H),6.10(ddd,J=8.8,7.7,3.2Hz,1H),4.38(dd,J=8.8,5.2Hz,1H),4.23(dd,J=8.9,5.2Hz,1H),3.38(ddd,J=10.6,8.0,2.1Hz,1H),2.92(ddd,J=9.5,5.8,3.5Hz,1H),2.63(dtd,J=13.7,8.5,7.6,2.8Hz,2H),2.26-2.14(m,4H),1.83(d,J=14.5Hz,1H),1.80-1.63(m,4H),1.41(s,3H),1.41(s,3H),1.37(s,3H),1.33(s,3H),1.12-1.02(m,1H),0.84(s,9H),0.80(s,9H),0.61(s,3H),0.60(s,3H),0.54(s,3H),0.52(s,3H),0.43(s,3H),0.36(s,3H),0.35(s,3H),0.31(s,3H),-2.41(s,3H)。

[0474] 13C NMR(101MHz,CD2Cl2)δ 161.58,160.75,159.16,158.33,156.70,155.85,150.92,150.89,149.75,149.72,141.35,141.17,141. 15,140.92,139.04,138.78,138.36,137.47,136.86,136.75,136.68,136.59,136.06,135.98,135.81,1 35.79,135.28,134.19,134.12,134.07,134.04,134.02,133.98,129.58,128.91,128.78,128.68,128.61,128.58,128.30,128.10,127.75,127.57,127.49,127.41,127.38,127.31,127.28,127.09,125.67,125 .58,125.18,125.13,124.66,124.54,124.51,124.30,124.12,123.97,123.70,123.54,123.45,122.88,122.51,119.92,119.88,119.31,119.27,118.08,117.75,117.58,117.52,117.37,117.14,115.11,114.7 6,114.66,114.43,113.78,113.55,77.92,75.13,70.12,57.23,57.17,37.81,37.65,32.92,32.45,32.37,32.34,31.76,31.61,30.71,30.32,29.40,24.25,-1.95,-2.09,-2.47,-2.53,-2.64,-2.78,-2.83(2).

[0475] 19 F NMR(470MHz, CD2Cl2)δ-117.37(td,J=8.2,5.0Hz),-118.41(td,J=8.4,5.2Hz).

[0476] Example 68 - Coordination formula (xxix):

[0477]

change

[0478] In a glove box, a 50 mL round bottom flask was charged with 1,3-bis((5-fluoro-3'-iodo-2'-methoxy-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propane (1.31 g, 1.38 mmol, 1.00 equiv.), 2,7-bis(dimethyl)(phenyl)silyl)-9H-carbazole (1.80 g, 4.13 mmol, 3.00 equiv.), KPO (1.75 g, 8.25 mmol, 6.00 equiv.), CuI (524 mg, 2.75 mmol, 2.00 equiv.), N,N'-dimethylethylenediamine (0.474 mL, 4.40 mmol, 3.2 equiv.), and 13.8 mL of toluene. A reflux condenser was attached, the unit sealed with a rubber septum, and transferred to a fume hood. The mixture was stirred at 120° C. under a nitrogen blanket for 24 h. TLC indicated complete consumption of the diiodide with mostly residual carbazole remaining. The solution was cooled, diluted with dichloromethane, and the slurry was filtered through a plug of alumina. The filtrate was concentrated, and the residue was purified by chromatography on silica gel (0-10% EtOAc in hexanes). 2.028 g of a colorless oil was isolated, containing the desired intermediate with residual carbazole (approximately 1:1.5 molar ratio). The material was dissolved in 13 mL of dry DMF and treated with sodium ethanethiolate (0.434 g, 5.16 mmol). The mixture was stirred at 100° C. for 48 h. The solution was cooled, quenched with brine, and the product was extracted with portions of dichloromethane. The combined organic fractions were purified by chromatography on silica gel (0-40% dichloromethane in hexanes). 1.02 g of product was isolated as a white solid (48% over two steps).

[0479] 1H NMR(400MHz, CDCl3)δ 8.22(dd,J=7.7,0.8Hz,4H),7.47(dd,J=7.7,0.9Hz,4H),7.45-7.38(m,8H ),7.29(d,J=2.4Hz,2H),7.25-7.15(m,18H),6.83(dd,J=8.7,3.2Hz,2H),6 .21(td,J=8.5,3.1Hz,2H),5.62(dd,J=9.1,4.5Hz,2H),5.15(s,2H),3.42 (t,J=5.4Hz,4H),1.30(s,12H),0.71(s,18H),0.50(s,12H),0.48(s,12H).

[0480] 13 C NMR (101MHz,CDCl3)δ ,158.02,155.64,151.10,147.79,142.53,141.24,138.42,135.95,134.10,129.36,128.96,127.68,127.60,127.52,127.15,125.92,125.52,124.04,123.45,119.89,118.10,117.86,115.54,115.27,115.04,112.79,112.70,64.33,57.09,38.08,32.38,31.81,31.53,28.74,-1.99,-2.15.

[0481] 19 F NMR (376MHz, CDCl3) δ-123.09 (td, J=8.3, 4.4Hz).

[0482] Example 69 - Synthesis of the present metal-ligand complex 36 (IMLC-36):

[0483]

change

[0484] In a glove box filled with N2, a 20 mL vial was charged with ScCl3 (17.2 mg, 0.11 mmol, 1 equiv.) in 5 mL of THF. The solution was stirred vigorously at room temperature for 4 h to break up chunks of ScCl3. The solution was cooled to -35°C for 30 min. Recrystallized solid LiCH2TMS (33 mg, 0.35 mmol, 3.1 equiv.) in 5 mL of THF was added to the solution and the reaction mixture was stirred at room temperature for 3 h. The solution was cooled to -35°C for 30 min. A 5 mL THF solution of ligand formula xxx (182 mg, 0.11 mmol, 1 equiv.) was added to the above solution and the final reaction mixture was stirred at room temperature overnight. THF was evaporated under vacuum and the residue was triturated with cold toluene. The residue was dried under vacuum to give a white solid (86 mg, 42%).

[0485] 1 H NMR(400MHz,benzene-d6)δ 8.41-6.94(m,20H),4.17(d,J=9.4Hz,2H),4.05-3.17(m,6H),2.31-0.43( m,142H),-0.24(s,9H),-0.82(d,J=12.5Hz,1H),-1.34(d,J=12.5Hz,1H).

[0486] Preparation of ligands of formula xxx as detailed in WO 2017 / 004462(A1).

[0487] Example 70 - Synthesis of metal-ligand complex 37 of the present invention (IMLC-37):

[0488] [ka]

[0489] In a glove box filled with N2, a 20 mL vial was charged with ScCl3 (16 mg, 0.1 mmol, 1 equiv.) in 5 mL of THF. The solution was stirred vigorously at room temperature for 4 h to break up chunks of ScCl3. The solution was cooled to -35°C for 30 min. Recrystallized solid LiCH2TMS (31 mg, 0.33 mmol, 3.1 equiv.) in 5 mL of THF was added to the solution and the reaction mixture was stirred at room temperature for 3 h. The solution was cooled to -35°C for 30 min. A 5 mL THF solution of ligand formula xxxi (132 mg, 0.1 mmol, 1 equiv.) was added to the above solution and the final reaction mixture was stirred at room temperature overnight. THF was evaporated under vacuum and the residue was triturated with cold toluene. The residue was dried under vacuum to give a white solid (69 mg, 45%).

[0490] 1 H NMR(400MHz,benzene-d6)δ 8.32-6.55(m,24H),5.53(dt,J=9.0,5.5Hz,2H),5.39(ddd,J=8.6,6.8,4.3Hz,2H),5.32(dd,J=8.9,5.0Hz ,2H),3.9-2.9(m,8H),2.9-0.5,(m,76H),-0.39(s,9H),-0.97(d,J=12.9Hz,1H),-1.84(d,J=12.8Hz,1H).

[0491] 19 F NMR (376 MHz, benzene-d6) δ -115.31--115.55 (m), -116.56--116.90 (m).

[0492] Example 71-2,7-Dimesityl-9H-carbazole:

[0493] [ka]

[0494] A 500 mL round bottom flask was charged with 2,7-dibromo-9H-carbazole (4.0 g, 12.0 mmol, 1 equiv), 2,4,6-trimethylphenylboronic acid (6.0 g, 37 mmol, 3 equiv), and cesium carbonate (12.0 g, 37.0 mmol, 3 equiv). Tetrakis(triphenylphosphine)palladium (711 mg, 0.62 mmol, 5 mol%) was then added to the reaction mixture. A RB equipped with a reflux condenser was evacuated and then back-filled with nitrogen, and this evacuation / back-filling process was repeated three times. Freshly prepared deoxygenated toluene (40 mL), ethanol (30 mL), and HO (30 mL) were added to the reaction mixture via syringe, and the yellow mixture was placed in a mantle heated to 100 °C. The reaction mixture was stirred for 24 h and the completion of the reaction was monitored by NMR. The reaction was cooled to room temperature. The organic phase was extracted with dichloromethane (70×3). The combined organic layers were dried over Na2SO4 and the solvent was evaporated under vacuum. The orange solid cake was washed with dichloromethane to give a white solid (4.3 g, 87%).

[0495] 1 H NMR (400MHz, chloroform-d) δ 8.13(d,J=7.9Hz,2H),8.10(s,1H),7.23-7.19(m,2H),7.03(dd,J=7.9,1.3Hz,2H),6.99(s,4H),2.37(s,6H),2.05(s,12H).

[0496] 13 C NMR(101MHz, CDCl3)δ 140.1,139.8,139.1,136.7,136.4,128.2,122.0,121.3,120.3,111.3,21.2,20.92.

[0497] Example 72: 2,7-Dimesityl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole:

[0498] [ka]

[0499] A 100 mL round-bottom flask was charged with 2,7-dimesityl-9H-carbazole (1.2 g, 3.0 mmol, 1 equiv.), 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran (2.2 g, 5.4 mmol, 1.8 equiv.), K3PO4 (3.8 g, 18 mmol, 6 equiv.). The flask was placed in a glove box filled with N2, and Cu2O (851 mg, 6 mmol, 2 equiv.), NN'DMEDA (839 mg, 9.5 mmol, 3.2 equiv.), and dried and degassed xylene (15 mL) were added to it. The heterogeneous reaction mixture was stirred at 145 °C for 24 h with vigorous stirring. Completion of the reaction was monitored by NMR. The orange reaction mixture was removed from the glove box and filtered through Celite. Acetonitrile (50 mL) was added to the filtrate to break up the solid product. The white solid was collected in a disposable fritted funnel and washed with 20 mL of acetonitrile. The white solid was dried under vacuum to give the product (1.3 g, 63%).

[0500] 1 H NMR(400MHz,chloroform-d)δ 8.18(d,J=7.9Hz,2H),7.46(d,J=2.4Hz,1H),7.35(dd,J=8.7,2.5Hz,1H),7.18(d,J=8.7Hz,1H),7.05( dd,J=7.9,1.4Hz,2H),6.97(d,J=1.4Hz,1H),6.95-6.87(m,5H),5.22(t,J=2.9Hz,1H),3.41(td,J=11. 3,2.5Hz,1H),3.27(dt,J=11.5,3.7Hz,1H),2.32(d,J=1.6Hz,6H),2.05-1.97(m,12H),1.56(s,4H),1. 48-1.35(m,1H),1.33(d,J=4.4Hz,5H),1.29-1.2(m,1H),1.15(dq,J=9.8,6.5,5.3Hz,3H),0.67(s,9H).

[0501] 13C NMR(101MHz,CDCl3)δ 151.2,144.7,142.4,142.4,140.0,140.0,138.8,138.7,136.5,136.4,136. 3,136.2,136.2,136.2,128.1,128.1,128.1,128.0,128.0,127.1,126.7,121 .6, 121.6, 121.1, 121.1, 119.9, 117.2, 111.1, 111.0, 97.0, 61.5, 57.2, 38.3, 32.5, 31.8, 31.7, 31.5, 30.1, 25.1, 21.2, 20.9, 20.9, 20.8, 20.8, 20.7, 17.9.

[0502] Example 73 - Preparation of ligand formula (xxxi):

[0503] [ka]

[0504] In a glove box filled with N2, a 40 mL vial was charged with 2,7-dimesityl-9-(5-octoxy-2-tetrahydropyran-2-tetrahydropyran-2-yloxy-phenyl)carbazole (500 mg, 0.72 mmol, 2.3 equiv.) and 3 mL of THF. The solution was cooled to -35°C in a glove box freezer for 20 min and 2.5 M n-butyllithium (0.0.32 mL, 0.78 mmol, 2.4 equiv.) was added to the solution. The solution was stirred at room temperature for 1.5 h and then cooled to -35°C for 30 min. A solution of dichlorozinc (72 mg, 0.53 mmol, 1.7 equiv.) in 3 mL of THF was added and the resulting solution was stirred at room temperature for 1 h. A solution of 1,3-bis(4-fluoro-2-iodophenoxy)propane (160 mg, 0.31 mmol, 1 equiv.) and bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) (11 mg, 0.02 mmol, 0.05 equiv.) in THF (3 mL) was added to the above ArZnX solution. The reaction was heated to 50° C. and the reaction mixture was stirred for 24 h. Completion of the reaction was monitored by NMR. The vial was removed from the glove box and MeOH (5 mL) and concentrated HCl (4 drops from a glass pipette) were added to the reaction mixture. The solution was stirred at room temperature for 18 h. The solvent was removed under reduced pressure. The crude residue was loaded directly onto a column and the product was purified using 50% CHCl in hexanes. Evaporation of the solvent gave a white solid (162 mg, 42%).

[0505] 1 H NMR(400MHz,CDCl3)δ 8.25(d,J=8.0Hz,4H),7.39-7.34(m,2H),7.14-7.05(m,6H),6.94(d,J=1 .8Hz,4H),6.93-6.84(m,10H),6.43(ddd,J=9.0,7.9,3.2Hz,2H),6.01(dd ,J=9.1,4.4Hz,2H),5.64(s,2H),3.40(t,J=5.5Hz,4H),2.27(s,12H),2. 00(d,J=21.6Hz,26H),1.57(d,J=5.8Hz,4H),1.26(s,12H),0.59(s,18H).

[0506] 13 C NMR(101MHz,CDCl3)δ 209.4,207.1,201.7,201.7,199.0,193.9,193.1,190.8,190.0,187.7,187.1,187.1,180.2,179.2,179.1,178.4,177.3,175.3 ,173.0,172.5,171.3,169.5,169.2,166.4,166.2,163.8,163.7,161.7,115.2,108.2,89.1,83.3,82.6,82.4,72.0,71.8,71.8.

[0507] Preparation of 1,3-bis(4-fluoro-2-iodophenoxy)propane as detailed in WO 2012 / 027448.

[0508] Example 74 - Synthesis of metal-ligand complex 38 of the present invention (IMLC-38):

[0509] [ka]

[0510] In a glove box filled with N2, a 20 mL vial was charged with ScCl3 (15 mg, 0.1 mmol, 1 equiv.) in 5 mL of THF. The solution was stirred vigorously at room temperature for 4 h to break up chunks of ScCl3. The solution was cooled to -35°C for 30 min. Recrystallized solid LiCH2TMS (29 mg, 0.31 mmol, 3.1 equiv.) in 5 mL of THF was added to the solution and the reaction mixture was stirred at room temperature for 3 h. The solution was cooled to -35°C for 30 min. A 5 mL THF solution of ligand formula xxxii (127 mg, 0.1 mmol, 1 equiv.) was added to the above solution and the final reaction mixture was stirred at room temperature overnight. THF was evaporated under vacuum and the residue was triturated with cold toluene. The residue was dried under vacuum to give a white solid (81 mg, 55%).

[0511] 1H NMR(400MHz,ベンゼン-d6)δ 8.23-5.9(m,28H),3.99(dt,J=18.3,9.7Hz,2H),3.5-2.7(m,6H),2.5-0.5 (m,78H),-0.53(s,9H),-0.89(d,J=11.9Hz,1H),-1.00(d,J=11.9Hz,1H).

[0512] Example 75 - Modulation of coordination subunit formula (xxxii):

[0513]

change

[0514] In a glove box filled with N2, a 40 mL vial was charged with 2,7-dimesityl-9-(5-octoxy-2-tetrahydropyran-2-tetrahydropyran-2-yloxy-phenyl)carbazole (500 mg, 0.72 mmol, 2.3 equiv.) and 3 mL of THF. The solution was cooled to -35°C in a glove box freezer for 20 min and 2.5 M n-butyllithium (0.0.32 mL, 0.78 mmol, 2.4 equiv.) was added to the solution. The solution was stirred at room temperature for 1.5 h and then cooled to -35°C for 30 min. A solution of dichlorozinc (72 mg, 0.53 mmol, 1.7 equiv.) in 3 mL of THF was added and the resulting solution was stirred at room temperature for 1 h. A solution of 1,3-bis(4-fluoro-2-iodo-6-methylphenoxy)propane (169 mg, 0.31 mmol, 1 equiv.) and bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) (11 mg, 0.02 mmol, 0.05 equiv.) in THF (3 mL) was added to the above ArZnX solution. The reaction was heated to 50° C. and the reaction mixture was stirred for 24 h. Completion of the reaction was monitored by NMR. The vial was removed from the glove box and MeOH (5 mL) and concentrated HCl (4 drops from a glass pipette) were added to the reaction mixture. The solution was stirred at room temperature for 18 h. The solvent was removed under reduced pressure. The crude residue was loaded directly onto a column and the product was purified using 50% CHCl in hexanes. Evaporation of the solvent gave a white solid (161 mg, 41%).

[0515] 1 H NMR(400MHz,CDCl3)δ 8.09(d,J=7.9Hz,4H),7.36(d,J=2.4Hz,2H),7.20(d,J=2.4Hz,2H),6.94(dd,J=7.9,1.4Hz,4H),6.83-6.73(m,11H),6.73-6.60(m, 7H),3.19(t,J=6.7Hz,4H),2.12(s,12H),1.88(s,12H),1.78(s,12H),1.60(s,10H),1.40-1.29(m,2H),1.23(s,10H),0.55(s,18H).

[0516] 13 C NMR(101MHz,CDCl3)δ 160.4,158.0,149.5,149.5,147.9,143.3,142.0,139.9,139.0,136.5,1 36.3,136.1,133.7,133.6,133.2,133.1,129.0,128.5,128.1,128.1,128 .0,126.7,126.7,125.8,122.0,121.4,120.2,117.5,117.3,116.5,116.2,111.0,77.4,71.1,57.4,38.3,32.5,31.8,31.6,21.1,20.9,20.9,16.2.

[0517] Preparation of 1,3-bis(4-fluoro-2-iodo-6-methylphenoxy)propane as detailed in WO 2014 / 105414.

[0518] Each of the comparative metal-ligand complexes C1 and C2 (herein "Comparative C1" and "Comparative C2") was mixed with cocatalyst 1 to form a catalyst system. Metal-ligand complexes 1, 2, and 3 of the present invention have a structure according to the metal-ligand complex of formula (I). The comparative procatalyst had the following structure:

[0519] [ka]

[0520] Example 76 - Continuous process polymerization results Feedstocks (ethylene, 1-octene) and process solvents (high purity narrow boiling range isoparaffinic solvent commercially available under the trademark Isopar E from ExxonMobil Corporation) were purified with molecular sieves prior to introduction into the reaction environment. Hydrogen is supplied in pressurized cylinders as a high purity grade with no further purification. The reactor monomer feed (ethylene) stream is pressurized to a pressure above the reaction pressure of 525 psig via a mechanical compressor. The solvent and comonomer (1-octene) feeds are pressurized to a pressure above the reaction pressure of 525 psig via mechanical positive displacement pumps. Modified methylaluminoxane (MMAO) commercially available from AkzoNobel is used as an impurity scavenger. Individual catalyst components (procatalyst cocatalysts) were manually batch diluted to specific component concentrations with purified solvent (Isopar E) and pressurized above the reaction pressure at 525 psig. The cocatalyst was [HNMe(C 18 H 37 )2][B(C6F5)4] is used in a 1.2 molar ratio relative to the procatalyst. All reaction feed streams are measured using mass flow meters and independently controlled by computer automated valve control systems.

[0521] The continuous solution polymerization is carried out in a 5 L continuously stirred-tank reactor (CSTR). The reactor has independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. The combined solvent, monomer, comonomer, and hydrogen feeds to the reactor are temperature controlled anywhere between 5°C and 50°C, typically 25°C. Fresh comonomer feed to the polymerization reactor is fed along with the solvent feed. Fresh solvent feed is typically controlled with each injector receiving half of the total fresh feed mass flow rate. Cocatalyst is fed to the procatalyst components based on a calculated specific molar ratio (1.2 molar equivalents). Immediately after each fresh injection point, the feed stream is mixed with the contents of the circulating polymerization reactor using a static mixing element. The effluent from the polymerization reactor (including solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the first reactor loop and passes through a control valve (responsible for maintaining the pressure of the first reactor at a specified target). As the stream exits the reactor, it is contacted with water to quench the reaction. Additionally, various additives such as antioxidants can be added at this point. The stream then passes through another set of static mixing elements to uniformly distribute the catalyst kill and additives.

[0522] Following the addition of additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from other low boiling reaction components. The stream then enters a two-stage separation and devolatilization system where the polymer is stripped from the solvent, hydrogen, and unreacted monomer and comonomer. The separated and devolatilized polymer melt is pumped into a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transported to boxes for storage.

[0523] [Table 1] Continuous reactor conditions: solvent feed rate = 17.3 kg / h, ethylene feed rate = 5.3 kg / h, 1-octene feed rate 1.3 kg / h, ethylene outlet = 9 g / L. [A] The % solids is the polymer concentration in the reactor. [B] H2 (mol%) is defined as the mole fraction of hydrogen relative to the ethylene fed to the reactor. [C] Efficiency (Eff.) is 10 6 It is measured as g polymer / g metal. [D] Metal-ligand complex C1 was combined with the additive bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate (1:1.2 ratio of catalyst / additive).

[0524] Procedure for batch reactor polymerization. The feedstocks (ethylene, 1-octene) and process solvent (high purity narrow boiling range isoparaffinic solvent commercially available from ExxonMobil Corporation under the trademark ISOPAR E) were purified with molecular sieves. A 1 gallon (3.79 L) stirred autoclave reactor was charged with ISOPAR E and 1-octene. The reactor was then heated to the desired temperature and charged with ethylene to reach the desired pressure. If necessary, hydrogen was also added at this point. The catalyst composition was prepared in a dry box under an inert atmosphere by mixing the desired procatalyst, and optionally one or more additives as required, with additional solvent to obtain a total volume of about 15-20 mL. The activated catalyst mixture was then rapidly injected into the reactor. The reactor pressure and temperature were kept constant during the polymerization by feeding ethylene and cooling the reactor as needed. After 10 minutes, the ethylene feed was stopped and the solution was transferred to a nitrogen purged resin kettle. The polymer was thoroughly dried in a vacuum oven and the reactor was thoroughly rinsed with hot ISOPAR E between polymerization runs.

[0525] Further polymerizations were carried out in a batch reactor following the procedures previously described in this disclosure. The catalyst solution was prepared under a nitrogen atmosphere. The metal-ligand complex of the present invention was combined with a cocatalyst. Batch polymerization reactions were carried out in the reactor with increasing 1-octene loadings (600 g) to better differentiate the levels of comonomer incorporation between the metal-ligand complex 1 of the present invention and the metal-ligand complex 2 from the comparative metal-ligand complex C1, with the results summarized in Table 2. The batch reactor conditions were as follows: (1) 225 psi of C2, 600 g of 1-octene, and 40 mmol of H2 were reacted in the presence of 750 g of isopar-E at a reaction temperature of 120° C. for a run time of 10 minutes. (2) 320 psi of C2, 600 g of 1-octene, and 40 mmol of H2 were reacted in the presence of 710 g of isopar-E at a reactor temperature of 160° C. and a run time of 10 minutes. or (3) 410 psi of C2, 600 g of 1-octene, 40 mmol of H2, and 50 equivalents of cocatalyst, MMAO, were reacted in the presence of 715 g of isopar-E at a reactor temperature of 190° C. for a run time of 10 minutes. In a comparative example, Comparative C1 was activated using 1.2 molar equivalents of cocatalyst 1 relative to the metal in the procatalyst. The results of the high 1-octene polymerization reactions are shown in Table 2.

[0526] [Table 2-1]

[0527] [Table 2-2] ND = below the detection limit of the instrument

[0528] Reactor conditions in Table 2: (1) 120°C, 225 psi C2, 100 g 1-octene, 1250 g isopar-E, 10 min run time; (2) 160°C, 320 psi C2, 60 g 1-octene, 1250 g isopar-E, 10 min run time; (3) 190°C, 410 psi C2, 65 g 1-octene, 1250 g isopar-E, 10 min run time.

[0529] * The amount of additive was based on equivalents, measured as the ratio of Al / molar M, where M is the metal center of the metal-ligand complex. ** Comparative C2 was activated using 1.2 molar equivalents of bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate (Cocatalyst 1) relative to the metal in the procatalyst.

[0530] [Table 3]

[0531] Reaction conditions in Table 3: (1) 120°C, 225 psi C2, 600 g 1-octene, 750 g isopar-E, 0 mmol H2, 10 min run time; (2) 160°C, 320 psi C2, 600 g 1-octene, 710 g isopar-E, 0 mmol H2, 10 min run time; (3) 190°C, 410 psi C2, 600 g 1-octene, 715 g isopar-E, 0 mmol H2, 10 min run time. Comparative C1 was activated using 50 equivalents of cocatalyst, 1.2 molar equivalents of cocatalyst 1 relative to the metal in the procatalyst. ND = below instrument detection limit. TEA is triethylaluminum.

[0532] In most of the polymerization runs shown in Table 2, the weight percent of units derived from 1-octene was below the detection limit. To get a better understanding of the ethylene selectivity of the metal-ligand complexes of the present invention, the amount of 1-octene in the reactor was increased. The reaction conditions for each polymerization run in Table 3 included 600 grams of 1-octene, which was six times greater than the reaction conditions in Table 2. By increasing the amount of octene in the reactor, the amount of units derived from octene in the produced polymer should increase based on the kinetics of the reaction. At six times the amount of 1-octene in the reactor, the metal-ligand complexes of the present invention were still highly selective for ethylene-produced polymers with less than 3 weight percent of units derived from octene.

[0533] The results in Table 3 showed that IMLC-8 produced polymers with a high weight percent of units derived from octene. However, the polymers produced by IMLC-8 also had very low molecular weights. The low molecular weight combined with the high octene weight percent indicated that the octene acted as a chain terminating reagent. The amount of octene was inversely high because the amount of ethylene polymerized into the polymer chain was excluded. However, based on the results in Table 2, IMLC-8 is ethylene selective.

[0534] [Table 4]

[0535] Reaction conditions in Table 4: (1) 190° C., 410 psi C2, 65 g 1-octene, 1250 g isopar-E, 0 mmol H2, 10 min run time. 20 equivalents of the second additive, TEA, were used in each run.

[0536] Batch Reactor Polymerization Procedure. Batch reactor polymerization reactions are carried out in a 2L Parr™ batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is fitted with a dump valve that transfers the reactor contents to a stainless steel dump pot. The dump pot is pre-charged with catalyst deactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). Both the pot and tank are purged with nitrogen and the dump pot is vented to a 30 gallon blowdown tank. All solvents used for polymerization or catalyst make-up are passed through a solvent purification column to remove any impurities that may affect the polymerization. 1-Octene and IsoparE are passed through two columns, the first containing A2 alumina and the second containing Q5. Ethylene is passed through two columns, the first containing A204 alumina and 4 Å molecular sieves, the second containing Q5. N2 used for transfer is passed through a single column containing A204 alumina, 4 Å molecular sieves and Q5.

[0537] The reactor is initially loaded from a shot tank which may contain IsoparE solvent and / or 1-octene depending on the reactor load. The shot tank is loaded to the load set point using a lab scale equipped with a shot tank. After addition of the liquid feed, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor at the reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored by a micromotion flow meter. For some experiments, the standard conditions at 120°C are 46g ethylene and 303g 1-octene in 611g IsoparE and the standard conditions at 150°C are 43g ethylene and 303g 1-octene in 547g IsoparE.

[0538] The metal-ligand complex and cocatalyst are mixed with an appropriate amount of purified toluene to obtain a molar solution. The metal-ligand complex and cocatalyst are handled in an inert glove box, drawn into a syringe, and pressure transferred into a catalyst shot tank. The syringe is rinsed three times with 5 mL of toluene. Immediately after the catalyst is added, a run timer is started. If ethylene is used, it is added by the Camile to maintain the reaction pressure set point in the reactor. The polymerization reaction is run for 10 minutes, then the agitator is stopped, the bottom dump valve is opened, and the reactor contents are transferred to a dump pot. The dump pot contents are poured into a tray and placed in a lab hood where the solvent is allowed to evaporate overnight. The tray containing the remaining polymer is transferred to a vacuum oven and heated to 140° C. under vacuum to remove any remaining solvent. After the tray is cooled to ambient temperature, the polymer is weighed to determine the yield and polymer testing to measure efficiency.

[0539] [Table 5] ND = below the detection limit of the instrument

[0540] Reactor conditions in Table 5: (1) 190°C, 43 g C2, 28 g 1-octene, 520 g isopar-E, 10 min run time.

[0541] [Table 6] ND = below the detection limit of the instrument

[0542] Reaction conditions in Table 6: (1) 150°C, 43 g C2, 300 g 1-octene, 520 g isopar-E, 0 mmol H2, 10 min run time; (2) 190°C, 43 g C2, 300 g 1-octene, 520 g isopar-E, 0 mmol H2, 10 min run time; ND = below instrument detection limit.

[0543] [Table 7]

[0544] Reaction conditions in Table 7: 190°C, 300g 1-octene, 525g isopar-E, 0mmol H2.

[0545] At low loadings of alumoxane, it does not act as an activator but rather functions as a scavenger. The scavenger is not in the nature of an activator since it sequesters impurities in the reactor before the precatalyst is added. As shown by the results in Table 7, no additives or cocatalysts are required to produce the polymer.

[0546] [Table 8]

[0547] Reaction conditions in Table 8: (1) 160° C., 320 psi C2, 60 g 1-octene, 1250 g isopar-E, 0 mmol H2, 10 min run time; (2) 190° C., 410 psi C2, 65 g 1-octene, 1250 g isopar-E, 0 mmol H2, 10 min run time. 20 equivalents of a second additive, TEA, were used in each run.

[0548] Equipment standards All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether are purified by passage through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments performed in a nitrogen-filled glove box are further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware is dried overnight in an oven before use. NMR spectra are recorded on Varian 400-MR and VNMRS-500 spectrometers. 1 Chemical shifts for H NMR data are reported as ppm downfield from internal tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as the reference. 13 C NMR data is 1Determined with 1 H decoupling and chemical shifts are reported as ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference. The present invention includes the following aspects. Section 1. A metal-ligand complex according to formula (I) [ka] During the ceremony, M is scandium, yttrium, or a lanthanide metal having an oxidation state of +3; X is (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)RC , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C )3, -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C )2, -C(O)NHR C , -C(O)NH2, halogen, B(R Y )4, Al(R Y )4, or Ga(R Y ) 4, or hydrogen; C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl, each Q is 0, 1, 2, or 3, each W is 0, 1, or 2, and each R Y But -H, (C1-C 30 ) a hydrocarbyl or halogen atom; each T is independently a Lewis base; n is 0, 1, or 2, and when n is 1, X and T are optionally linked, and when n is 2, X and one of T are optionally linked; the metal-ligand complex is overall charge neutral; Each Z is independently -O-, -S-, -N(R N )- or -P(R P )-, with the dotted lines optionally defining coordinate bonds; R 1 and R 16 But independently, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P)2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, 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 Independently, -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2-OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, (R C )2P=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) 2NC(O)-, and halogen; 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-C40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene; Each R in formula (I) C , R P , and R N But independently, (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or -H. Section 2. R 1 and R 16 is selected from a radical having formula (II), a radical having formula (III), and a radical having formula (IV), [ka] In the formula, R 31-35 , R 41-48 , and R 51-59 each independently represents -H, (C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) NC(O)-, or halogen, where R 1 and R 16 is formula (II), R 31 ~R 35 Item 10. The metal-ligand complex of item 1, wherein at least one of: Section 3. When M is yttrium or a lanthanide metal, R 5-8At least one of the following is R, not -H: 9-12 Item 3. The metal-ligand complex according to item 1 or 2, wherein at least one of the groups is not -H. Section 4. R 1 and R 16 and are the same. Item 3. The metal-ligand complex according to item 1 or 2. Section 5. R 1 and R 16 At least one of the groups is a radical having the formula (III). Section 6. R 42 and R 47 But, (C1-C 20 ) hydrocarbyl, -Si[(C1-C 20 )hydrocarbyl]3, or -Ge[(C1-C 20 Item 6. The metal-ligand complex according to item 5, wherein the metal-ligand complex is a aryl group, and the ring structure is a aryl group. Section 7. R 43 and R 46 But, (C1-C 20 ) hydrocarbyl, -Si[(C1-C 20 )hydrocarbyl]3, or -Ge[(C1-C 20 Item 6. The metal-ligand complex according to item 5, wherein the metal-ligand complex is a aryl group, and the ring structure is a aryl group. Section 8. Optionally, R 42 and R 43 and are joined together, and optionally, R 46 and R 47 and are bonded together, the metal-ligand complex according to any one of items 5 to 7. Section 9. R 1 and R 16 at least one of R 31 ~R 35 Item 3. The metal-ligand complex according to item 2, wherein at least one of is not -H. Section 10. R 32 and R 34 But, (C1-C 20) hydrocarbyl, -Si[(C1-C 20 )hydrocarbyl]3, or -Ge[(C1-C 20 Item 10. The metal-ligand complex according to item 9, wherein the metal-ligand complex is a aryl group, and the ring structure is a aryl group. Section 11. R 1 and R 16 At least one of the groups is a radical having the formula (IV). Section 12. R 52 , R 53 , R 55 , R 57 , and R 58 At least two of the 20 ) hydrocarbyl, -Si[(C1-C 20 )hydrocarbyl]3, or -Ge[(C1-C 20 Item 12. The metal-ligand complex according to item 11, wherein the metal-ligand complex is a aryl group, and the ring structure is a aryl group. Section 13. Optionally, R 52 and R 53 and are linked to form a cyclic structure, and optionally, R 57 and R 58 and (b) are linked to form a ring structure. Section 14. R 6 , R 7 , and R 8 At least one of is a halogen; R 9 , R 10 , and R 11 Item 14. The metal-ligand complex according to any one of items 1 to 13, wherein at least one of is a halogen. Section 15. R 8 and R 9 Item 13. The metal-ligand complex according to any one of items 1 to 12, wherein at least one of the following is not -H: Section 16. R 3 and R 14 But, (C1-C 1016. The metal-ligand complex according to any one of items 1 to 15, wherein R is an alkyl group. Section 17. R 3 and R 14 is methyl, and R 6 and R 11 Item 17. The metal-ligand complex according to any one of items 1 to 16, wherein is a halogen. Section 18. R 3 and R 14 But -OR C and R C But, (C1-C 30 16. The metal-ligand complex according to any one of items 1 to 15, wherein the metal-ligand complex is a hydrocarbyl. Section 19. R 6 and R 11 Item 16. The metal-ligand complex according to any one of items 1 to 15, wherein is tert-butyl. Section 20. R 3 and R 14 Item 16. The metal-ligand complex according to any one of items 1 to 15, wherein is tert-octyl, n-octyl, or n-octylalkoxy. Section 21. L is -CH2-, -CH2(CH2) m CH2- (m is 0 to 3), -CH2Si(R C )2CH2-, -CH2Ge(R C )2CH2-, -CH(CH3)CH2CH * (CH3), and -CH2(phen-1,2-diyl)CH2-; each R in L is selected from C But, (C1-C 20 ) hydrocarbyl, and "C * 21. The metal-ligand complex according to any one of items 1 to 20, wherein "is a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Section 22. X is -CH2Si[(C1-C 20 ) alkyl]3, (C1-C 12 22. The metal-ligand complex according to any one of items 1 to 21, wherein R is an alkyl or halogen atom. Section 23. n is 1 or 2, and at least one T is (C 20 23. The metal-ligand complex according to any one of items 1 to 22, wherein the heterohydrocarvone is a heterohydrocarvone, and the heteroatom of the heterohydrocarvone is oxygen. Section 24. 24. The metal-ligand complex according to any one of items 1 to 23, wherein n is 1 or 2, and at least one T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE). Section 25. R 2 , R 4 , R 5 , R 12 , R 13 , and R 15 is hydrogen, 25. The metal-ligand complex according to any one of items 1 to 24, wherein each Z is oxygen. Section 26. 1. A polymerization process comprising: 25. A polymerization process comprising polymerizing ethylene and one or more olefins under olefin polymerization conditions in the presence of a catalyst system comprising the metal-ligand complex of any one of claims 1 to 24 to form an ethylene-based polymer. Section 27. 27. The polymerization process of claim 26, wherein the catalyst system further comprises at least one cocatalyst. Section 28. 27. The polymerization process of claim 26, wherein a cocatalyst is not present in the catalyst system. Section 29. Item 29. The polymerization process according to any one of items 26 to 28, wherein the polymerization process is a solution polymerization process. Section 30. 30. The polymerization process according to any one of items 26 to 29, wherein the catalyst system further comprises an additive. Section 31. 31. The polymerization process of claim 30, wherein the additive is a modified methylaluminoxane. Section 32. 31. The polymerization process of claim 30, wherein the additive is an alkyl aluminum. Section 33. 27. The polymerization process of claim 26, wherein the polymerized ethylene occurs in the presence of a borate-based additive. Section 34. An olefin propagating catalyst species according to formula (Ia), [ka] During the ceremony, M is scandium, yttrium, or a lanthanide metal having an oxidation state of +3; X P is a ligand selected from hydrocarbyl, said hydrocarbyl having at least 30 carbon atoms and being branched or unbranched; Each Z is independently -O-, -S-, -N(R N )- or -P(R P )-, with the dotted lines optionally defining coordinate bonds; R 1 and R 16 But independently, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O) 2- , -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, or halogen; R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R10 , R 11 , R 12 , R 13 , R 14 , and R 15 Independently, -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2-OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, (R C )2P=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) 2NC(O)-, and halogen; 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 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene; Each R in formula (I) C , R P , and R N But independently, (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or -H. Section 35. M is yttrium or a lanthanide metal; R 5-8 At least one of the following is R, not -H: 9-12 Item 35. The olefin propagating catalyst species of item 34, wherein at least one of is not -H. Section 36. R 1 and R 16 is selected from a radical having formula (II), a radical having formula (III), and a radical having formula (IV), [ka] In the formula, R 31-35 , R 41-48 , and R 51-59 each independently represents -H, (C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) NC(O)-, or halogen, where R 1 and R 16 is formula (II), R 31 ~R 35 36. The olefin propagating catalyst species according to claim 34 or 35, provided that at least one of: Section 37. R 8 and R 9 36. The olefin propagating catalyst species according to claim 34 or 35, wherein at least one of is not -H. Section 38. R 3 and R 14 But, (C1-C 10 37. The olefin propagating catalyst according to any one of items 34 to 36, wherein the olefin propagating catalyst is an alkyl group. Section 39. R 3and R 14 But -OR C and R C But, (C1-C 30 Item 38. The olefin propagating catalyst species according to any one of items 34 to 37, wherein the olefin propagating catalyst species is a hydrocarbyl. Section 40. R 3 and R 14 Item 38. The olefin propagating catalyst species according to any one of Items 34 to 37, wherein is tert-octyl, n-octyl, or n-octylalkoxy. Section 41. R 6 and R 11 Item 34 to 40, wherein the olefin propagating catalyst species is tert-butyl. Section 42. R 1 and R 16 is selected from radicals having formula (III) and optionally R 42 and R 43 and are linked to form a cyclic structure, and optionally, R 46 and R 47 and are linked to form a cyclic structure. Section 43. L is -CH2-, -CH2(CH2) m CH2- (m is 0 to 3), -CH2Si(R C )2CH2-, -CH2Ge(R C )2CH2-, -CH(CH3)CH2CH * (CH3), and -CH2(phen-1,2-diyl)CH2-; each R in L is selected from C But, (C1-C 20 ) hydrocarbyl, and "C * 43. The olefin propagating catalyst species according to any one of claims 34 to 42, wherein "is a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical." Section 44. A catalytic structure comprising scandium, yttrium, or a lanthanide metal having an oxidation state of +3 coordinated to a bis(phenylphenoxy) ligand.

Claims

1. A metal-ligand complex according to formula (I) 【Chemistry 1】 During the ceremony, M is scandium, yttrium, or a lanthanide metal having an oxidation state of +3; X is (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —CH ２ Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , or -OSi(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ where each Q is 0, 1, 2, or 3; each T is independently a cycloether or an ether; n is 0, 1, or 2, and when n is 1, X and T are optionally linked, and when n is 2, X and one of T are optionally linked; the metal-ligand complex is globally charge neutral; Each Z is independently -O-, -S-, -N(R Ｎ ) - or -P(R Ｐ )-, with the dotted lines optionally defining coordinate bonds; R 1 and R 16 are selected from a radical having the formula (II), a radical having the formula (III), and a radical having the formula (IV); 【Chemistry 2】 wherein each of R 31-35 , R 41-48 , and R 51-59 is independently -H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, -Si(R C ) 3 , -Ge(R C ) 3 , -P(R P ) 2 , -N(R N ) 2 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , R C S(O)-, R C S(O) 2 -, (R C ) 2 C═N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) 2 NC(O)-, or halogen, with the proviso that when R 1 and R 16 are of formula (II), at least one of R 31 to R 35 is not -H, and with the proviso that when R 1 and R 16 are of formula (II), M is not yttrium; R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , and R １５ are independently -H, (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, (R Ｃ ) ２ P=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R C C(O)N(R N )-, (R Ｃ ) ２ NC(O)—, and halogen; L is (C １ -C ４０ ) hydrocarbylene or (C １ -C ４０ ) heterohydrocarbylene; Each R in formula (I) Ｃ , R Ｐ , and R Ｎ But independently, (C １ -C ３０ ) hydrocarbyl, (C １ -C ３０ ) heterohydrocarbyl, or —H.

2. When M is yttrium or a lanthanide metal, R ５－８ At least one of the groups is not —H and is R ９－１２ The metal-ligand complex of claim 1, wherein at least one of:

3. R 1 and R 16 are radicals having the formula (III): R ４２ and R ４７ However, (C １ -C ２０ ) hydrocarbyl, —Si[(C １ -C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ -C ２０ ) hydrocarbyl] ３ or R ４３ and R ４６ However, (C １ -C ２０ ) hydrocarbyl, —Si[(C １ -C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ -C ２０ ) hydrocarbyl] ３ 2. The metal-ligand complex of claim 1, wherein

4. R 1 and R 16 are radicals having the formula (II): R ３２ and R ３４ However, (C １ -C ２０ ) hydrocarbyl, —Si[(C １ -C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ -C ２０ ) hydrocarbyl] ３ and R ３１ ~R ３５ The metal-ligand complex of claim 1, wherein at least one of:

5. R 1 and R 16 are radicals having the formula (IV) and R ５２ , R ５３ , R ５５ , R ５７ , and R ５８ At least two of (C １ -C ２０ ) hydrocarbyl, —Si[(C １ -C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ -C ２０ ) hydrocarbyl] ３ 2. The metal-ligand complex of claim 1, wherein

6. R ８ and R ９ A metal-ligand complex according to any one of claims 1 to 5, wherein at least one of is methyl.

7. R ３ and R １４ However, (C １ -C １０ ) alkyl, methyl, tert-octyl, n-octyl, or n-octylalkoxy, —OR Ｃ and R Ｃ However, (C １ -C ３０ 7. The metal-ligand complex of claim 1, wherein the metal-ligand complex is a aryl group.

8. R ６ and R １１ is tert-butyl, or R ６ and R １１ A metal-ligand complex according to any one of claims 1 to 7, wherein is a halogen.

9. L is -CH ２ --, --CH ２ (CH ２ ) ｍ CH ２ -(m is 0 to 3), -CH ２ Si(R Ｃ ) ２ CH ２ --, --CH ２ Ge(R Ｃ ) ２ CH ２ -, -CH(CH ３ ) CH ２ C*H(CH ３ ), and -CH ２ (phen-1,2-diyl)CH ２ -, and each R in L is selected from Ｃ However, (C １ -C ２０ 9. The metal-ligand complex of claim 1, wherein "C*" is a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical.

10. X is -CH ２ Si[(C １ -C ２０ ) alkyl] ３ , or (C １ -C １２ 10. The metal-ligand complex of claim 1, wherein:

11. 11. The metal-ligand complex of any one of claims 1 to 10, wherein n is 1 or 2 and at least one T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

12. A metal-ligand complex according to any preceding claim, wherein M is scandium.

13. 1. A polymerization process comprising:

13. A polymerization process comprising polymerizing ethylene and one or more olefins under olefin polymerization conditions in the presence of a catalyst system comprising the metal-ligand complex of any one of claims 1 to 12 to form an ethylene-based polymer.

14. 14. The polymerization process of claim 13, wherein the catalyst system further comprises at least one cocatalyst.

15. 14. The polymerization process of claim 13, wherein a cocatalyst is not present in the catalyst system.

16. The polymerization process according to any one of claims 13 to 15, wherein the polymerization process is a solution polymerization process.

17. The polymerization process according to any one of claims 13 to 16, wherein the catalyst system further comprises an additive.

18. 18. The polymerization process of claim 17, wherein the additive is a modified methylaluminoxane or an alkylaluminum.

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