Biaryl phenoxy group iv transition metal catalysts for olefin polymerization

Abstract

To provide, as a catalyst system suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, a procatalyst and a catalyst system which exhibit higher efficiency and high comonomer incorporation and produce polymers with high mole percent α-olefin incorporation varying depending on reactors.SOLUTION: Catalyst systems are provided which include a metal-ligand complex according to formula (I).SELECTED DRAWING: Figure 1-1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. Provisional Patent Application No. 62 / 782,8 filed on December 20, 2018. No. 55, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more specifically to Specifically, we will study the synthesis of biarylphenoxy Group IV transition metal catalysts for olefin polymerization, and and an olefin polymerization process incorporating the catalyst system. [Background technology]

[0003] Olefin-based polymers such as polyethylene and / or polypropylene are used in a variety of applications. It is produced through a catalytic system and is used in the polymerization process of olefin polymers. The selection of such catalyst systems contributes to the characteristics and properties of such olefin-based polymers. This is an important factor.

[0004] Polyethylene and polypropylene are manufactured for a wide variety of products. The polyethylene and polypropylene polymerization processes produce a variety of resins suitable for use in different applications. Produce a wide variety of resulting polyethylene resins with different physical properties The monomers may be varied in several ways to achieve the above-mentioned properties. in a liquid diluent such as an alkane or isoalkane, e.g., isobutane. Hydrogen can also be added to the reactor. Catalytic systems for producing polyethylene Typically, chromium-based catalysts, Ziegler-Natta catalysts, or molecular (metallocene or The reactants in the diluent and catalyst system may include a catalyst system (either metallocene or non-metallocene). The reactor is circulated at high polymerization temperatures, thereby producing polyethylene homopolymer or copolymer. Periodically or continuously, the polyethylene product dissolved in the diluent is a portion of the reaction mixture comprising, together with unreacted ethylene and one or more optional comonomers, The reaction mixture when removed from the reactor is free of diluent and unreacted The reaction may be treated to remove the polyethylene product, diluent and unreacted The reactants are typically recycled into the reactor. Alternatively, the reaction mixture can be recycled to a second reactor, For example, it may be fed to a reactor connected in series with the first reactor, where a second polyethylene A fraction can be produced.

[0005] Development of catalytic systems suitable for olefin polymerization such as polyethylene or polypropylene polymerization Despite research efforts in the field, the high mole percentage (mol % α-olefin incorporation There remains a need for procatalysts and catalyst systems that exhibit high comonomer incorporation. (For example, high mole percent α-olefin incorporation for a batch reactor is 15-20%. In addition, the catalyst and catalyst system may have a high molecular weight and a narrow molecular weight distribution. It must be possible to produce a polymer. Summary of the Invention

[0006] According to some embodiments, the catalyst system comprises a metal-ligand complex according to formula (I). [ka]

[0007] In formula (I), M is selected from titanium, zirconium, or hafnium. metal, which has a formal oxidation state of +2, +3, or +4; each X is an unsaturated (C 2-C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 )Hido Locarbyl, (C6-C 50 )Aryl, (C6-C 50 ) Heteroaryl, cyclopentane cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )Diene, halogen, -OR C , -N(R N )2, and -NCOR C A monodentate or bidentate ligand independently selected from (X) n The subscript n is 1 or 2. Y is oxygen, sulfur, or -N (R N )-.

[0008] In formula (I), each R 1 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)-, halogen, a lanthanide having the formula (II) the group consisting of dicarbal, a radical having the formula (III), and a radical having the formula (IV) Select from: [ka]

[0009] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , and R 51~59 Each of the groups independently represents (C1-C 40 ) hydrocarbyl, (C1-C4 0) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2,- N(R N )2, -N=CHR C , -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 O.C. O)-, R C C(O)N(R N )-, (R C )2NC(O)-, halogen, or -H are selected from the following, where R 1 at least one of the radicals having the formula (II), III) or a radical having the formula (IV) .

[0010] In formula (I), Q is (C1-C 12 ) alkylene, (C1-C 12 ) Heteroa alkylene, (-CH2Si(R C)2CH2-), (-CH2CH2Si(R C )2CH 2CH2-), (-CH2Ge(R C )2CH2-), or (-CH2CH2Ge(R C )2CH2CH2-), where R C But, (C1-C 20 ) hydrocarbyl .

[0011] In formula (I), for each individual ring containing groups z1 and z2, each independently represents sulfur, oxygen, -N(R C )-, and -C(R C )- with the proviso that at least one of z1 and z2 is sulfur. .R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b is independent , (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C 6- C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -C F3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N- , R C C(O)O-, R C OC(O)-, RC C(O)N(R)-, (R C )2NC(O )-, halogen, and -H, optionally R 4a and R 5a , or R 5a and R 6 a , or R 6a and R 7a , or R 4b and R 5b , or R 5b and R 6b , or R 6 b and R 7b may be covalently linked to form an aromatic or non-aromatic ring.

[0012] In formula (I), each R C , R N , and R P are independent, (C1 -C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, and -H The compound is selected from the group consisting of:

[0013] In formula (I), when Q is -CH2CH2CH2CH2-, each R 1 is 3, 6-di-tert-butylcarbazol-9-yl, z2 is sulfur, and each X is phenyl. When it is Njil, R 5a and R 5b -OMe, fluorine, or tert-octyl Furthermore, when Q is -CH2CH2CH2CH2-, R 4a , R 5a , R 6a , and R 7a At least one of R is halogen. 4b , R 5b , R 6 b , and R7b At least one of is halogen or Q is -CHCH 2CH2CH2-, R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6 b , and R 7b is (C1-C 50 ) hydrocarbyl, (C1-C 50 ) Heterohydro Carbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -N O2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, 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. [Brief description of the drawings]

[0014] [Figure 1-1] Various ligands which form metal-ligand complexes of formula (I) are shown. [Figure 1-2] Various ligands which form metal-ligand complexes of formula (I) are shown. [Figure 1-3] Various ligands which form metal-ligand complexes of formula (I) are shown. [Diagram 2]A four-step synthetic scheme for synthesizing ligand 2 (L-2) is shown. [Diagram 3] A two-step synthetic scheme for synthesizing ligands 1–6 (L-2–L-3) is shown, where the reagents in the first step are changed depending on the ligand. [Figure 4] Three images generated by X-ray diffraction of procatalyst 19. [Diagram 5] 3 shows three images generated by X-ray diffraction of Procatalyst 20. [Figure 6] 1 is a graph of the change in polymer molecular weight as a function of the amount of chain shuttling agent for procatalysts 3-8. [Figure 7] 1 is a graph of the change in polymer molecular weight as a function of the amount of chain shuttling agent for procatalysts 9-14. [Figure 8] 1 is a graph of the change in polymer molecular weight as a function of the amount of chain shuttling agent for procatalysts 15-21 and 25. [Figure 9] 1 is a graph of the change in polymer molecular weight as a function of the amount of chain shuttling agent for procatalysts 26, 27, 29, 31, and 33. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Specific embodiments of the catalyst system will now be described. The catalyst system of the present disclosure can be implemented in different forms. and should not be construed as being limited to the specific embodiments described in this disclosure. It should be understood that the embodiments are not intended to be limiting, and are not to be construed as limiting, unless otherwise specified. These are provided so that this will fully convey the scope of the subject matter to those skilled in the art.

[0016] Common abbreviations are listed below.

[0017] R, Z, M, X, and n are as defined above. Me: methyl, Et: Ethyl, Ph: Phenyl, Bn: Benzyl, i-Pr: Iso-propyl, t-Bu: Te rt-Butyl, t-Oct: tert-octyl (2,4,4-trimethylpentane-2 -yl), Tf: trifluoromethanesulfonate, THF: tetrahydrofuran, Et 2O: diethyl ether, CH2Cl2: dichloromethane, CV: column volume (column volume) (used in chromatography), EtOAc: ethyl acetate, C6D6: deuterated benzene or Benzene-d6: CDCl3: deuterated chloroform, Na2SO4: sodium sulfate , MgSO4: magnesium sulfate, HCl: hydrogen chloride, n-BuLi: butyl lithium, t-BuLi: tert-butyl lithium, Cu2O: copper oxide(I), N,N'-DME DA: N,N'-dimethylethylenediamine, K3PO4: potassium phosphate tribasic, P d(AmPhos)Cl2: Bis(di-tert-butyl(4-dimethylaminophenyl) )Phosphine)dichloropalladium(II), Pd(dppf)Cl2:[1,1'-Bi (diphenylphosphino)ferrocene]palladium(II) dichloride, K2CO3:carbonate Potassium, Cs2CO3: Cesium carbonate, i-PrOBPin: 2-isopropoxy-4 ,4,5,5-Tetramethyl-1,3,2-dioxaborolane, BrCl2CCCl2B r: 1,2-dibromotetrachloroethane, HfCl4: Hafnium(IV) chloride, Hf Bn4: Hafnium(IV) tetrabenzyl, ZrCl4: Zirconium(IV) chloride, ZrBn4: Zirconium(IV) tetrabenzyl, ZrBn2Cl2(OEt2): Di Ru(IV) dibenzyl dichloride mono-diethyl etherate, HfBn2Cl 2(OEt2): Hafnium(IV) dibenzyl dichloride mono-diethyl etherate , TiBn4: titanium (IV) tetrabenzyl, N2: nitrogen gas, PhMe: toluene, PPR: Parallel polymerization reactor, MAO: Methylaluminoxane, MMAO: Modified methylaluminum Noxan, GC: Gas Chromatography, LC: Liquid Chromatography, NMR: Nuclear Magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: mole, mi n or mins: minutes, h or hrs: hours, d: days, R f : Retention fraction, TLC: Thin layer Chromatography, rpm: revolutions per minute.

[0018] The term "independently selected" is used herein to refer to 1 , A, z 1~5 etc. possible It is used to indicate that the variables can be the same or different. The chemical name associated with the R group is Conveying a chemical structure that is recognized in the art as corresponding to the chemical structure in the scientific name Thus, the chemical names are intended to supplement and illustrate the structural definitions known to those of skill in the art. The provisions of the IFRS 10 are intended to include, not exclude.

[0019] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a procatalyst that converts a procatalyst into a catalytically active catalyst. As used herein, "cocatalyst" refers to a compound that chemically reacts with the catalyst. The terms "activator" and "activator" are interchangeable terms.

[0020] When used to describe certain carbon atom-containing chemical groups, "(C x -C y ) " means that the unsubstituted form of the chemical group has x carbon atoms, inclusive of x and y. It means that the cation has y carbon atoms. For example, (C1-C 50 ) Al In its unsubstituted form, alkyl is an alkyl group having 1 to 50 carbon atoms. In the embodiments and general structures of the present invention, certain chemical groups are S One or more substituents such as may be replaced by the parenthesized "(C x -C y )" R in the group S The substituted version can be represented by any group R S may contain more than y carbon atoms depending on the identity of For example, "R S Exactly one group R is phenyl (-C6H5) S Replaced by (C1-C 50 )Alkyl" can contain 7 to 56 carbon atoms. Thus, In general, parenthesized "(C x -C y ) is a chemical group defined using one or more carbon atoms. child-containing substituent R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group , both x and y are any carbon atom-containing substituent R S Add the total number of carbon atoms from It is determined by.

[0021] The term "substituted" refers to a carbon atom or hetero atom of a corresponding unsubstituted compound or functional group. At least one hydrogen atom (-H) attached to an atom is replaced by a substituent (e.g., R S ) by The term "oversubstituted" means that the corresponding unsubstituted compound or functional group All hydrogen atoms (H) attached to carbon atoms or heteroatoms of the group are replaced by substituents (e.g., R S The term "polysubstituted" means replaced by the corresponding unsubstituted at least two, but not all, of the aryl groups bonded to carbon or heteroatoms of the compound or functional group; "-H" means that fewer than all hydrogen atoms are replaced by a substituent. The term "hydrogen" means a hydrogen or hydrogen radical that is covalently bonded to another atom. " and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0022] "(C1-C 50 The term "hydrocarbyl" refers to a group having 1 to 50 carbon atoms. It means a hydrocarbon radical, "(C1-C 50 The term "hydrocarbylene" refers to a compound having 1 to 1 means a hydrocarbon diradical having 50 carbon atoms, where each hydrocarbon radical and and each hydrocarbon diradical may be aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched. Branched, cyclic (having 3 or more carbons, monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and one or more R S Is it replaced by , or has not been replaced.

[0023] In the present disclosure, (C1-C 50 ) Hydrocarbyl is unsubstituted or substituted (C1-C 50 )Alkyl, (C3-C 50 )cycloalkyl, (C3-C 20 )Cycloalkyl- (C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C 20 ) Ant Rule-(C1-C 20 ) alkylene (such as benzyl (-CH2-C6H5)) .

[0024] "(C1-C 50 ) alkyl" and "(C1-C 18 The term "alkyl" means Unsubstituted or one or more R S each of 1 to 50 carbon atoms substituted by and saturated linear or branched hydrocarbon radicals having 1 to 18 carbon atoms. Means a straight-chain or branched hydrocarbon radical. Unsubstituted (C1-C 50 ) Examples of alkyl are: Unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) Alkyl, unsubstituted (C1-C 5) Alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl , 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-hexyl butyl, 1-nonyl, and 1-decyl. 40 ) Examples of alkyl are: Substitution (C1-C 20 ) Alkyl, Substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" includes substituents. This means that there are up to 45 carbon atoms in the radical, e.g., (C1 -C5) one R that is alkyl S is replaced by (C 27 -C 40 ) Alkyl Each (C1-C5) alkyl is methyl, trifluoromethyl, ethyl, 1-propyl, It may be pyryl, 1-methylethyl, or 1,1-dimethylethyl.

[0025] "(C6-C 50 The term "aryl" refers to a group having 6 to 40 carbon atoms, At least 6 to 14 of the carbon atoms are aromatic ring carbon atoms, unsubstituted or (one or more R S means a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical substituted by Monocyclic aromatic hydrocarbon radicals contain one aromatic ring, whereas bicyclic aromatic hydrocarbon radicals Aromatic hydrocarbon radicals have two rings, whereas tricyclic aromatic hydrocarbon radicals have three rings. or when a tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical At least one of the rings in the aromatic radical may be aromatic. The other ring or rings in the aromatic radical may be independently fused or unfused. It can be aromatic or non-aromatic, fused or unfused. 50 ) Examples of aryl As for unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18 )aryl, 2-(C 1-C5) alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, Indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl , tetrahydronaphthyl, and phenanthrenyl. 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.

[0026] "(C3-C 50 The term "cycloalkyl" means unsubstituted or one or more R S A saturated cyclic hydrocarbon radical having 3 to 50 carbon atoms, substituted by Other cycloalkyl groups, such as (C x -C y )Cycloalkyl) is x~ It has y carbon atoms and is unsubstituted or has one or more R S has been replaced by Unsubstituted (C3-C 40 ) Cycloal Examples of kills are non-substitutions (C3-C 20 )Cycloalkyl, unsubstituted (C3-C 10 ) Cycloa alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 )Cycloalkyl, substituted (C3-C 10 ) Cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl. do.

[0027] (C1-C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C6-C 50 )Arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) Alkylene (For example, (C1-C 20 ) alkylene). Diradicals are those that have two alkoxy groups on the same carbon atom. (e.g. -CH2-) or on adjacent carbon atoms (i.e. 1,2-diradicals). or separated by 1, 2, or 3 or more intervening carbon atoms. (e.g. 1,3-diradical, 1,4-diradical, etc.) Examples include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, and others Examples of diradicals include 1,2-diradicals. α,ω-diradicals have a maximum of 1,2-diradicals between the radical carbons. It is a diradical with a carbon skeleton spacing of 1.5 mm. (C2-C 20 ) Alkylene α,ω-diyl Some examples of dialkyls are ethane-1,2-diyl (i.e. -CH2CH2-) , propane-1,3-diyl (i.e. -CH2CH2CH2-), 2-methylpropane -1,3-diyl (i.e., -CH2CH(CH3)CH2-). C 50 Some examples of arylene α,ω-diradicals are phenyl-1,4-di naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0028] "(C1-C 50 The term "alkylene" refers to an unsubstituted or substituted alkylene with one or more R S By Saturated linear or branched diradicals having 1 to 50 carbon atoms substituted with (i.e., the radical is not on a ring atom). 50 ) Examples of alkylene is unsubstituted (C1-C 20 ) alkylene, unsubstituted -CH2CH2-, -(CH2) 3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, - (CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3) wherein "C*" is a hydrogen atom forming a secondary or tertiary alkyl radical. Substitution (C1-C 50 Examples of alkylenes are substituted (C 1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH 3) 2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosyl As mentioned above, the two R S Together, (C1-C 18 ) Alkylene Since it is possible to form a substitution (C1-C 50 Examples of alkylene 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 is also included.

[0029] "(C3-C 50 The term "cycloalkylene" refers to a cycloalkylene having 3 to 50 carbon atoms. unsubstituted or one or more R S A cyclic diradical (i.e., The radical is on a ring atom.

[0030] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing the above heteroatoms include O, S, S(O), S(O)2, Si(R C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -S i(R C )-, and each R C and each R P is unsubstituted (C1-C 18 ) Hydrocarbohydrates R is -H or -H. N is unsubstituted (C1-C 18 ) hydrocarbyl. The term "hydrocarbon" refers to a hydrocarbon in which one or more carbon atoms have been replaced by a heteroatom. "(C1-C 50 ) Heterohydrocarbyl means a heterohydrocarbon radical having 1 to 50 carbon atoms, and "(C1-C 50 The term "heterohydrocarbylene" refers to a heterohydrocarbylene having 1 to 50 carbon atoms. It means an atomic diradical. (C1-C 50 )heterohydrocarbyl or (C1-C 50 The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The hydrocarbyl radical can be present on a carbon atom or a heteroatom. The two groups of a heterohydrocarbylene are located on a single carbon atom or a single heteroatom. Furthermore, one of the two radicals of the diradical can be present on a carbon atom. The other radical can be on a different carbon atom, and the two One of the radicals can be on a carbon atom and the other on a heteroatom. or one of the two radicals can be on a heteroatom. The other radical can be on a different heteroatom. 50 ) Heterohydrocarbyl and (C1-C 50 ) Heterohydrocarbylene is unsubstituted or (One or more R S substituted, aromatic or non-aromatic, saturated or unsaturated, linear or is branched, cyclic (including monocyclic and polycyclic, fused polycyclic and non-fused polycyclic) or non- It may be cyclic.

[0031] (C1-C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1 -C 50Non-limiting examples of heterohydrocarbyls include (C-C 50 ) Heteroar Kill, (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 ) H Dorocarbyl-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 ) Heteroalkyl N, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C 1-C 50 )heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) Al Kiren, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1 -C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0032] "(C4-C 50 The term "heteroaryl" refers to any group having a total of 4 to 50 carbon atoms and and 1 to 10 heteroatoms, unsubstituted or (one or more R S (by means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical having a ring structure Heteroaromatic hydrocarbon radicals contain one heteroaromatic ring and are bicyclic heteroaromatic hydrocarbons. A hydrogen radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When bicyclic or tricyclic heteroaromatic hydrocarbon radicals are present, the radicals have At least one of the rings in the heteroaromatic radical is heteroaromatic. The ring or rings may be independently fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., generally (C x -C y ) heteroaryl, ( C4-C 12 ) Heteroaryl, etc.) is a group consisting of x to y carbon atoms (e.g., 4 to 12 carbon atoms). etc.) and is unsubstituted or has one or more R S Replaced by A monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as A five-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms. and may be 1, 2, or 3, and each heteroatom may be O, S, N, or P. Examples of five-membered heteroaromatic hydrocarbon radicals are pyrrol-1-yl, pyrrole- 2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxa 2-azolyl, isothiazol-5-yl, imidazol-2-yl, oxazole -4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4 -Oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazole tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. The ring has 6 minus h carbon atoms, where h is the number of heteroatoms, and may contain 1 to The heteroatom may be N or P. Examples of dialkyls include pyridin-2-yl, pyrimidin-2-yl, and pyrazine-2-yl. Bicyclic heteroaromatic hydrocarbon radicals include fused 5,6- or 6, It can be a 6-ring system. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are: Condensation 6 includes indol-1-yl and benzimidazol-1-yl. Examples of 6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon radicals are fused It can be a 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring system. An example of a 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1 An example of a fused 5,6,6-ring system is 1H-benzo[f]indole. 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 ,6,6-ring system is acridine-9-yl.

[0033] "(C1-C 50 The term "heteroalkyl" refers to a heteroalkyl group having 1 to 50 carbon atoms, or Saturated straight-chain or means a branched chain radical. (C1-C 50 The term "heteroalkylene" refers to 1 Saturated straight or branched chain containing up to 50 carbon atoms and one or more heteroatoms means a branched diradical. As a heteroatom in a heteroalkyl or heteroalkylene is 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), O and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is a non-substituted alkyl group. or one or more R S has been replaced by

[0034] Unsubstituted (C2-C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 )Heterocycloalkyl, unsubstituted (C2-C 10 ) Heterocycloalkyl, Aziridine- 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-cyclo octyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0035] The term "halogen atom" or "halogen" refers to a fluorine atom (F), a chlorine atom ( "Halogen" refers to the radical of an iodine atom (I), a bromine atom (Br), or an iodine atom (I). The term "fluoride" refers to fluoride (F - ), chloride (Cl - ), bromide (Br - ),or Iodide (I -) means the anionic form of a halogen atom.

[0036] The term "saturated" refers to carbon-carbon double bonds, carbon-carbon triple bonds, and (hetero)- (b) In the atom-containing group, carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds are lacking. It means that saturated chemical groups are one or more substituents R S If replaced with one or more The double and / or triple bonds may optionally be substituted with a substituent R S It may or may not be present in the The term "saturated" refers to a compound that has one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (hetero)heterocyclic groups. one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or Contains a carbon-silicon double bond and has a substituent R S (if present), or (hetero)aromatic ring This is meant to exclude double bonds that may be present in (if present).

[0037] According to some embodiments, the catalyst system comprises a metal-ligand complex according to formula (I). [ka]

[0038] In formula (I), M is selected from titanium, zirconium, or hafnium. metal, which has a formal oxidation state of +2, +3, or +4; each X is an unsaturated (C 2-C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 )Hido Locarbyl, (C6-C 50 )Aryl, (C6-C 50 ) Heteroaryl, cyclopentane cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )Diene, halogen, -ORC , -N(R N )2, and -NCOR C A monodentate or bidentate ligand independently selected from (X) n The subscript n is either 1 or 2.

[0039] In formula (I), each R 1 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)-, halogen, a lanthanide having the formula (II) the group consisting of dicarbal, a radical having the formula (III), and a radical having the formula (IV) Select from: [ka]

[0040] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , and R 51~59 Each of the groups independently represents (C1-C 40 ) hydrocarbyl, (C1-C4 0) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(RP )2,- N(R N )2, -N=CHR C , -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 O.C. O)-, R C C(O)N(R N )-, (R C )2NC(O)-, halogen, or -H are selected from the following, where R 1 at least one of the radicals having the formula (II), III) or a radical having the formula (IV) .

[0041] In formula (I), Q is (C1-C 12 ) alkylene, (C1-C 12 ) Heteroa alkylene, (-CH2Si(R C )2CH2-), (-CH2CH2Si(R C )2CH 2CH2-), (-CH2Ge(R C )2CH2-), or (-CH2CH2Ge(R C )2CH2CH2-), where R C But, (C1-C 20 ) hydrocarbyl .

[0042] In formula (I), for each individual ring containing groups z1 and z2, z1 and z Each of 2 is independently sulfur, oxygen, -N(R C )-, and -C(R C )- with the proviso that at least one of z1 and z2 is sulfur. R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b is independent Then, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C 6- C 50 )Aryl, (C4-C 50 )heteroaryl, -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)-, -P(O)(R P )2, 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)-, halogen, and -H, optionally R 4a and R 5a , or R 5a and R 6a , or R 6a and R 7a , or R 4b and R 5b , or R 5b and R 6b ,or R 6b and R 7b may be covalently linked to form an aromatic or non-aromatic ring.

[0043] In formula (I), each R C , R N, and R P are independent, (C1 -C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, and -H The compound is selected from the group consisting of:

[0044] In formula (I), when Q is -CH2CH2CH2CH2-, each R 1 is 3, 6-di-tert-butylcarbazol-9-yl, z2 is sulfur, and each X is phenyl. When it is Njil, R 5a and R 5b -OMe, fluorine, or tert-octyl Furthermore, when Q is -CH2CH2CH2CH2-, R 4a , R 5a , R 6a , and R 7a At least one of R is halogen. 4b , R 5b , R 6 b , and R 7b At least one of is halogen or Q is -CHCH 2CH2CH2-, R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6 b , and R 7b is (C1-C 50 ) hydrocarbyl, (C1-C 50 ) Heterohydro Carbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -ORC , -SR C , -N O2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, 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.

[0045] In some embodiments, Y is oxygen, sulfur, or -N(R N )-, wherein R N is -H or (C1-C 20 ) hydrocarbyl.

[0046] In various embodiments of formula (I), Y is oxygen and z1 is sulfur. In the formula, Y is oxygen and z2 is sulfur.

[0047] In some embodiments of Formula (I), each R 1 is a radical having the formula (III) R 41-48 At least one of (C1-C 40 ) hydrocarbyl, (C1 -C 40 ) heterohydrocarbyl, -Si(R C )3, -OR C , -SR C , -NO2, is selected from -CN, -CF3, or halogen.

[0048] In one or more embodiments of formula (I), each R 1 is a radical having the formula (III) (1) R 42 and R 47 is (C1-C 20) alkyl, -Si(R C )3, -C F3, or halogen; R 43 and R 46 is -H or or (2) R 43 and R 46 is (C1-C 20 ) alkyl, -Si(R C )3, -C F3, or halogen; R 42 and R 47 is -H.

[0049] In various embodiments of formula (I), each R 1 is a radical having the formula (IV) 51~59 is -H. In another embodiment of (I), each R 1 is a compound having the formula (IV) It is a logical and R 51-59 At least one of (C1-C 40 ) Hydrocarbohydrates le, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -OR C , -SR C , Selected from the group consisting of -NO2, -CN, -CF3, or halogen.

[0050] In some embodiments of Formula (I), each R 1 is a radical having the formula (II) , R 31 , R 33 , and R 35 is (C1-C 20 ) hydrocarbyl. In one or more embodiments, each R 31 , R 33 , and R 35 are independent, (C1-C5) Alkyl, (C6-C 24 In another embodiment of formula (I), each R 1 is a radical having the formula (II) 32 and R 34 is (C1-C 20 ) In one or more embodiments, each R 32 and R 34 is independent and (C1-C5) alkyl or (C6-C 24 ) aryl.

[0051] In one or more embodiments of formula (I), Q is (C-C 12 ) alkylene, and R 6a and R 6b In another embodiment of formula (I), Q is (C2-C1 2) alkylene, R 6a and R 6b is chlorine. In various embodiments, Q is , (C2-C 12 ) alkylene, and R 6a , R 6b R 5a , and R 5b Ha, huh In other embodiments, Q is (C-C 12 ) alkylene, and R 6a , R 6 b R 5a , and R 5b In some embodiments, Q is chlorine. 12 ) alkylene, and R 6a , R 6b R 5a , R 5b , R 4a , and R 4b teeth, In another embodiment, Q is (C2-C 12 ) alkylene, and R 6a , R 6b R 5a , R5b , R 4a , and R 4b is chlorine. In one or more embodiments , Q is (C2-C 12 ) alkylene, and R 6a , R 6b R 5a , R 5b , R 7a , and R 7b In some embodiments, Q is fluorine. 12 ) Al Kiren and R 6a , R 6b R 5a , R 5b , R 7a , and R 7b is chlorine.

[0052] In some embodiments of the metal-ligand catalyst according to formula (I), R 1 is 3,5-di- tert-Butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropyl propylphenyl, 3,5-diisopropylphenyl, carbazolyl, carbazole-9 -yl, 1,2,3,4-tetrahydrocarbazolyl, 1,2,3,4,5,6,7,8 -Octahydrocarbazolyl, 3,6-bis-(3,5-di-tert-butylphenyl ) Carbazol-9-yl, 3,6-bis-(2,4,6-trimethylphenyl)carbazol 3,6-bis-(2,4,6-triisopropylphenyl)carba 2,7-di(tert-butyl)-carbazol-9-yl, 2,7- Di(tert-octyl)-carbazol-9-yl, 2,7-diphenylcarbazol- 9-yl, 2,7-bis(2,4,6-trimethylphenyl)-carbazol-9-yl Anthracenyl, 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-tetrahydrofuran -Hydronaphth-5-yl, 1,2,3,4-tetrahydronaphth-6-yl, anthrahydronaphth-5-yl 1,2,3,4-tetrahydroanthracen-9-yl, 1,2,3, 4,5,6,7,8-Octahydroanthracen-9-yl, 1,2,3,4,5,6, 7,8-Octahydrophenanthrene-9-yl, indolyl, indolinyl, quinolinyl 1,2,3,4-Tetrahydroquinolinyl, Isoquinolinyl, 1,2,3,4-Tetrahydroquinolinyl is selected from hydroisoquinolinyl.

[0053] In some embodiments of Formula (I), when Q is (C-C)alkylene, R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b At least one of Both are (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -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)-, -P(O)(R P )2, RC 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. When Q is (C-C) alkylene, R 4a , R 5a , R 6a , R 7a Of At least one is a halogen, and R 4b , R 5b , R 6b , R 7b At least one of Another embodiment is halogen. In another embodiment, Q is (C3-C4) alkylene. K, R 4a , R 5a , R 6a , R 7a At least two of R are halogen. 4 b , R 5b , R 6b , R 7bの At least two of which are halogen; in other embodiments So, when Q is (C3-C4) alkylene, R 4a , R 5a , R 6a , R 7a brain At least three of them are halogens, and R 4b , R 5b , R 6b , R 7b A small number of At least three are halogens.

[0054] In one or more embodiments of formula (I), Q is (-CHSi(R Q )2CH2-), (-CH2CH2Si(R Q)2CH2CH2-), (-CH2Ge(R Q )2CH2- ), or (-CH2CH2Ge(R Q )2CH2CH2-), where R Q teeth,( In other embodiments, Q is benzene-1,2-diyl or is cyclohexane-1,2-diyl.

[0055] In various embodiments of formula (I), Q is (-CHSi(R Q )2CH2-) or (-CH2Si(R Q )2CH2-), where R Q is ethyl or 2-propyl It is.

[0056] In some embodiments of Formula (I), Q is benzene-1,2-diyldimethyl. do.

[0057] Some embodiments of the catalyst system further comprise a chain transfer agent.

[0058] One or more embodiments of the present disclosure include a process for polymerizing olefins. The process comprises reacting ethylene and and optionally one or more (C3-C 12 ) α-olefin. In some embodiments, the process further includes a chain transfer agent.

[0059] In an exemplary embodiment, the catalyst system has the structure of any of procatalysts 1, 2, 5-34. The metal-ligand complex may comprise any of the metal-ligand complexes according to formula (I). [ka] [ka] [ka] [ka] [ka] [ka]

[0060] Cocatalyst Component The catalyst system comprising the metal-ligand complex of formula (I) is useful for catalyzing the metal-based polymerization of olefins. The catalyst may be made catalytically active by any technique known in the art for activating the catalyst. For example, a procatalyst based on a metal-ligand complex of formula (I) can be prepared by contacting the complex with an activating cocatalyst. Alternatively, the complexes can be made catalytically active by combining them with an activating cocatalyst. Additionally, the metal-ligand complexes according to formula (I) are available in neutral, procatalyst form, and in benzyl or Both catalytic forms can be positively charged by loss of monoanionic ligands such as phenyl or phenyl. Suitable activating cocatalysts for use herein include aluminum alkyls, Polymeric or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (such compounds under oxidizing conditions) The preferred activation technique is bulk electrolysis. Combinations of one or more of the alkylaluminum catalysts and techniques are also contemplated. The term "monoalkylaluminum dihydride" refers to a monoalkylaluminum dihydride or monoalkylaluminum dihydride. Aluminum dihalide, dialkylaluminum hydride or dialkylaluminum Aluminum halides, or trialkylaluminums. Polymeric or oligomeric aluminum Examples of alumoxanes include methylalumoxane, triisobutylaluminum modified methylalumoxane, lumoxane, and isobutylalumoxane.

[0061] The Lewis acid activating cocatalyst may be any of the Lewis acid activating cocatalysts described herein (C1-C 20 ) Hydrocarbyl Substituent In some embodiments, the Group 13 metal compound comprises , Tri((C1-C 20 )hydrocarbyl)-substituted aluminum or tri((C1-C 20 In another embodiment, the Group 13 metal compound is a is tri(hydrocarbyl)-substituted aluminum, tri((C1-C 20 ) Hydrocarbohydrates Tri((C1-C 10 ) alkyl) aluminum, tri((C6- C 18 )aryl)boron compounds and their halogenated (including perhalogenated) derivatives In a further embodiment, the Group 13 metal compound is a tris(fluoro-substituted phenanthroline). In some embodiments, the borane is selected from the group consisting of tris(pentafluorophenyl)borane and tris(pentafluorophenyl)borane. The activating cocatalyst is tris((C1-C 20 ) hydrocarbyl borates (e.g., tri ethyl tetrafluoroborate) or tri((C1-C 20 ) Hydrocarbyl) Ammonium Umtetra ((C1-C 20 )hydrocarbyl)borates (e.g., bis(octadecyl) )methylammonium tetrakis(pentafluorophenyl)borate. As used in the literature, the term "ammonium" means ((C1-C 20) Hydrocarbohydrates 4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 ) H Dorocarbil)2N(H)2 + , (C1-C 20 ) HydrocarbylN(H)3 + ,or N(H)4 + Each of the nitrogen cations (C1-C 20 ) Hydrocarbyl has two When more than one is present, they may be the same or different.

[0062] The combination of neutral Lewis acid activating cocatalysts includes tri((C1-C4) alkyl) Aluminum and trihalide ((C6-C 18 )aryl)boron compounds, especially tris Mixtures containing combinations with (pentafluorophenyl)borane are also included. The form is a combination of such a neutral Lewis acid mixture with a polymeric or oligomeric alumoxane. In combination with a single neutral Lewis acid, especially tris(pentafluorophenyl)borane, In combination with polymeric or oligomeric alumoxanes. (Metal-ligand complexes): (Tris(pentafluorophenylborane): (alumoxane) [e.g. (Group 4 metal -ligand complex):(tris(pentafluorophenylborane):(alumoxane)] The ratio of the number of moles is 1:1:1 to 1:10:30, and in another embodiment, 1:1:1.5 ~1:5:10.

[0063] The catalyst system comprising the metal-ligand complex of formula (I) may be activated by the addition of one or more cocatalysts, e.g. cation forming cocatalyst, strong Lewis acid, or a combination thereof. Suitable activating cocatalysts include polymers, or oligomeric aluminoxanes, especially methylaluminoxane, as well as inert, compatible Exemplary suitable cocatalysts include modified metal ions. Thioaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis( pentafluorophenyl)borate(1-)amine, and combinations thereof. These include, but are not limited to:

[0064] In some embodiments, two or more of the aforementioned activating cocatalysts are used in combination with each other. A specific example of a combination of cocatalysts is tri((C1-C4)hydrocarbonyl) tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium The compound is a mixture of aluminoxane compounds having the formula (I) and an oligomeric or polymeric alumoxane compound. the ratio of the total number of moles of one or more metal-ligand complexes to the total number of moles of one or more activating cocatalysts In some embodiments, the ratio is at least 1:10,000 to 100:1. in some other embodiments at least 1:1000, and In some other embodiments, the ratio is 1:1 or less. When alumoxane is used alone as an activating cocatalyst, the number of moles of alumoxane used is determined by the formula It is preferably at least 100 times the number of moles of the metal-ligand complex of (I). When tris(pentafluorophenyl)borane is used alone as an activating cocatalyst, In some other embodiments, based on the total moles of one or more metal-ligand complexes of formula (I), The molar ratio of tris(pentafluorophenyl)borane used is 0.5:1 to 10:1. , 1:1 to 6:1, or 1:1 to 5:1. The remaining activating cocatalyst is generally a compound represented by the formula (I ) is used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of

[0065] Chain Shuttling Agent The term "shuttle agent" refers to at least one shuttling agent that, under polymerization conditions, inhibits the release of at least one of the catalysts contained in the composition. The compositions of the present disclosure are capable of inducing polymeric exchange between two active catalytic sites. This refers to a compound or mixture of compounds used to Shuttling occurs both to and from one or more of the catalytic sites. In contrast, "chain transfer agents" cause the termination of growing polymer chains and transfer them away from the catalyst. In some embodiments, the chattering agent is a single transfer of the growing polymer to the agent. The blocking agent has an activity of 0.01-100, 0.1-10, 0.5-2.0, or 0.8-1.2. The activity ratio RA-B / RB-A is the ratio of the catalytic activity of A via the shuttling agent. is the rate of polymeryl transfer from the catalytic B active site to the catalytic B active site, and RB-A is the rate of reverse polymeryl transfer. is the rate of transfer from catalyst B to catalyst A via a shuttling agent. The intermediate formed between the shuttling agent and the polymeryl chain is the chain-terminating In one or more embodiments, the three Before achieving distinct polymer segments or blocks, the shuttle-polymerization step is Less than 90 percent, 75 percent, 50 percent, or 10 percent of the composition The rate of chain shuttling (the rate at which polymer chains are pulled away from the catalytic site) is The time required to transfer the amine to the shuttle agent and then back to the catalytic site is determined. (defined as the rate of polymer termination) is equal to or faster than the rate of polymer termination and can even exceed the rate of polymer termination. This is 10 or even 100 times faster than the termination rate of the mer. The polymer blocks are then formed on the same time scale as seeding.

[0066] Segments of different tacticity or regioerror, different block lengths, or Polymers having different numbers of such segments or blocks in each copolymer can be produced. The composition is prepared by selecting different combinations of catalysts and various shuttling agents. The catalysts have different polymerization capabilities and can be prepared using various shuttling agents or The metal-ligand complexes of formula (I) are combined with a mixture of agents having the following catalytic combinations: For example, the activity of the shuttling agent may be selected from the group consisting of the catalytic polymer chain transfer of one or more catalysts. At low seeding rates, longer block length multiblock copolymers and polymers In contrast, the shuttling is non-linear to the propagation of the polymer chains. If it is always faster, copolymers with more random chain structures and shorter block lengths will be obtained. The extremely fast shuttling agent produces a copolymer having a substantially random copolymer character. Both the catalyst mixture and the shuttling agent can produce multiblock copolymers. By appropriately selecting the method, relatively pure block copolymers, relatively large polymers, - Copolymers containing segments or blocks, and / or similar to the above. Blends with various homopolymers and / or copolymers can be obtained.

[0067] A preferred composition comprising Catalyst A, Catalyst B, and a chain shuttling agent is tactically The following multi-step procedure was specifically adapted for block differentiation based on error content or region-error content: It can be obtained by

[0068] I. Using a mixture containing a potential catalyst and a potential chain shuttling agent, The above addition-polymerizable C3-30 α-olefin monomers are polymerized. Using a batch or semi-batch reactor (i.e., without refeeding catalyst or shuttling agent) ), preferably operated under solution polymerization conditions at a relatively constant monomer concentration, typically at 1 The molar ratio of catalyst to chain shuttling agent is 1:5 to 1:500. After the polymer is formed, the reaction is stopped by adding a catalyst poison, and the polymer properties (tacticity) are The error (and optionally the regioerror content) is measured.

[0069] II. The above polymerization and polymer testing were repeated for several different reaction times. The method provides a series of polymers having a range of yields and PDI values.

[0070] III. Catalysts / Catalysts that Show Significant Polymer Transfer Both to and from the Shuttling Agent The shuttling agent pair should have a minimum PDI of less than 2.0, more preferably less than 1.5; and Most preferably, the polymer is characterized by a chain shuttling ratio of less than 1.3. When this occurs, the Mn of the polymer increases linearly with increasing conversion. Pairing with a chattering agent should have a statistical significance greater than 0.95, preferably greater than 0.99. Fit the line with a reasonable accuracy (R2) to the polymer Mn as a function of conversion (or polymer yield). This gives the following:

[0071] Steps I-III are then combined with potential catalysts and / or potential shuttling One or more additional pairings of agents were performed.

[0072] In one or more embodiments, catalyst A, catalyst B, and one or more catalysts according to the present invention are then The polymer composition containing the chain shuttling agent is subjected to a chain shuttling reaction in which each of the two catalysts is a chain shuttling agent. to undergo chain shuttling by one or more of the catalysts, is capable of selectively forming stereospecific polymers compared to catalyst B under selected reaction conditions. At least one of the chain shuttling agents is highly effective against both Catalyst A and Catalyst B. On the other hand, it is subject to polymer migration (as determined by the tests described above) in both the forward and reverse directions. In addition, chain shuttling agents may be used to inhibit the activity of the enzyme (compared to the activity in the absence of the agent). The catalytic efficiency of either catalyst (weight of catalyst / weight of polymer produced per unit time) Preferably, the amount of oxidative stress (measured as the amount of oxidative stress) is not reduced by more than 60 percent, more preferably Preferably, such catalyst efficiency is not reduced by more than 20 percent, and most preferably, The catalytic efficiency of at least one of the catalysts is compared to the catalytic efficiency in the absence of the shuttling agent. Increase.

[0073] Alternatively, a series of polymerizations were carried out under standard batch reaction conditions and the resulting polymer properties were analyzed. By measuring, it is also possible to detect pairs of catalysts and shuttling agents. Shuttling agents are used in a variety of applications, including: By lowering the available Mn without loss of activity (yield or rate reduction), To be designated.

[0074] The aforementioned studies were carried out using automated reactors and analytical probes for rapid throughput screening. screening techniques and the different distinguishing characteristics (syndiotactic, isotactic, and In particular, it is easily adapted to the formation of polymer blocks having regioerror content. , combinations of various organometallic compounds with various proton sources, and olefin polymerization catalysts Depending on the compound or reaction product added to the polymerization reaction using the composition, a large number of potential Candidate shuttling agents can be identified in advance or synthesized in situ. Several polymerizations are carried out with varying molar ratios of the catalyst to the catalyst. While the glycerol produced a minimum PDI of less than 5.0 in variable yield experiments, as described above, As described above, the catalyst activity and efficiency are not significantly adversely affected, and preferably the catalyst activity and efficiency are The aim is to improve the efficiency of

[0075] Regardless of the method for presumptively identifying the shuttling agent, the term is used to refer to the currently identified Multiblock copolymers as described herein can be prepared or can be prepared by the methods disclosed herein. It is intended to refer to compounds which are effectively used under the polymerization conditions described above. The average number of blocks or segments per average chain (the average number of blocks of different compositions) The Mn of the polymer is preferably greater than 3.0. is greater than 3.5, even more preferably greater than 4.0 and less than 25, preferably is less than 15, more preferably less than 10.0, and most preferably less than 8.0 according to the present invention. It is formed.

[0076] Shuttling agents suitable for use herein include at least one C1-20 hi Group 1, 2, 12, or 13 metal compounds or complexes containing hydrocarbyl groups, preferably or hydrocarbyl-substituted aluminum containing 1 to 12 carbons in each hydrocarbyl group. and their reaction products with a proton source. The hydrocarbyl group is an alkyl group, a linear or branched C2-8 alkyl group. In one or more embodiments of the disclosure, a shuttling agent may be added to the polymerization process. Chain transfer agents include trialkylaluminum and dialkylzinc compounds, especially Triethylaluminum, tri(i-propyl)aluminum, tri(i-butyl)aluminum aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, Additional suitable shuttling agents include triethylgallium, diethylzinc, and diethylzinc. The organometallic compounds mentioned above are preferably tri(C1-8)alkylaluminum compounds. Di(C1-8)alkylzinc compounds, especially triethylaluminum, tri(i-pro (pyl)aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum ammonium, tri(n-octyl)aluminum, or diethylzinc in less than stoichiometric amounts ( (relative to the number of dihydrocarbyl groups) secondary amines or hydroxyl compounds, especially bis(trimethylsilyl) Methylsilyl)amine, t-butyl(dimethyl)siloxane, 2-hydroxymethylpyridine di(n-pentyl)amine, 2,6-di(t-butyl)phenol, ethyl(1- naphthyl)amine, bis(2,3,6,7-dibenzo-1-azacycloheptanamine) or the reaction product formed by combining with 2,6-diphenylphenol In some embodiments, the shuttling agent is a metal atom or mixture. Choose from amine or hydroxyl reagents so that one hydrocarbyl group remains per molecule. The main reaction products of the aforementioned combinations for use in the present disclosure as shuttling agents are The composition is n-octylaluminum di(bis(trimethylsilyl)amide), i-propionate. Bis(dimethyl(t-butyl)siloxide), and n-octyl aluminium Aluminum di(pyridinyl-2-methoxide), i-butylaluminum bis(dimethoxide) (t-butyl)siloxane), i-butylaluminum bis(di(trimethylsilyl) (amino)amide), n-octylaluminum di(pyridine-2-methoxide), i-butyl Aluminum bis(di(n-pentyl)amide), n-octylaluminum bis (2,6-di-t-butylphenoxide), n-octylaluminum di(ethyl(1 -naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), Ethylaluminum di(bis(trimethylsilyl)amide), Ethylaluminum bi (2,3,6,7-dibenzo-1-azacycloheptanamide), n-octylaluminum Nium bis(2,3,6,7-dibenzo-1-azacycloheptanamide), n-octyl ethylaluminum bis(dimethyl(t-butyl)siloxide), ethylzinc(2,6-di phenylphenoxide), and ethylzinc(t-butoxide).

[0077] A suitable shuttling agent for a given catalyst or combination of catalysts may be a shuttling agent for a different catalyst or combination of catalysts. may not necessarily be good or even satisfactory for use in combination with Those skilled in the art will appreciate that some potential shuttling agents may be one or more of: may adversely affect the performance of the above catalysts and are excluded from use in the polymerization processes of the present disclosure. Thus, a polymer having hard and soft segments can be achieved. To achieve this, it is necessary to balance the activity of the chain shuttling agent with the catalytic activity of the catalyst. There is.

[0078] In general, however, the shuttling agent is selected to provide the highest polymer transfer rate and the highest transfer rate. Such shuttling agents possess high efficiency (reduced incidence of chain termination). Even when using a suction pump, some degree of shuttling can still be achieved. The stringing agent results in the production of the shortest possible polymer block length. Due to the fact that the effective molecular weight of the polymer in A shuttling agent is used.

[0079] Polyolefin The catalyst system described in the previous paragraph is useful for the polymerization of olefins, primarily ethylene and propylene. In some embodiments, a single olefin or Only α-olefins are present, forming homopolymers. However, additional α-olefins The additional α-olefin comonomer may be incorporated into the polymerization procedure. , 20 or less carbon atoms. For example, the α-olefin comonomer has 3 to 10 Exemplary α-olefin comonomers include: The following are examples of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene: Examples of ethylenediaminetetraacetone, 1-pentene, 1-nonene, 1-decene, and 4-methyl-1-pentene are For example, the one or more α-olefin comonomers may be propylene, 1 1-butene, 1-hexene, and 1-octene, or alternatively 1-hexene. The alkylene may be selected from the group consisting of 1-octene and 1-octene.

[0080] In some embodiments, the ethylene-based polymer comprises at least one unit derived from ethylene. 50 mole percent. At least 60 mole percent of all the individual components. Each value and subrange is included herein and is disclosed herein as a separate embodiment. For example, the ethylene-based polymer may contain at least 63 mole percent units derived from ethylene. , at least 86 mole percent of units derived from ethylene, at least 90 mole percent of units derived from ethylene or alternatively, 70 to 100 mole percent of units derived from ethylene, 70 to 89.5 mole percent of units derived from ethylene, and 69 to 85.5 mole percent of units derived from ethylene It may include percent.

[0081] In some embodiments of the ethylene-based polymer, the amount of the additional α-olefin is %. In other embodiments, the mol% is from at least 1 mole percent (mol%) to 40 In a further embodiment, the amount of additional α-olefin is at least 10 In some embodiments, the additional α-olefin comprises 1-octyl olefin. It's a ten.

[0082] Any conventional polymerization process may be used to produce the ethylene-based polymer. Conventional polymerization processes include one or more conventional reactors, e.g., loop reactors, isothermal reactors, Reactors such as fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc., can be used in parallel, in series, or in any combination thereof. A solution polymerization process, a gas phase polymerization process, a slurry phase polymerization process, using any combination of processes, and any combination thereof.

[0083] In one embodiment, the ethylene-based polymer is produced in a dual reactor system, e.g., a dual loop reactor. In the system, the copolymer may be produced by solution polymerization, in which ethylene and, optionally, one or more The 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 is produced in a dual reactor system, e.g., a dual loop. It can be produced by solution polymerization in a reactor system, where ethylene and any Optionally, the one or more α-olefins can be produced using the catalyst system and optionally one or more of the catalyst systems disclosed herein. The catalyst systems described herein are optionally polymerized in the presence of one or more other catalysts. It can be used in combination with other catalysts in the first reactor or in the second reactor. In one embodiment, the ethylene-based polymer is produced in a dual reactor system, e.g., a dual loop reactor system. In the present invention, ethylene and optionally one The above α-olefins are polymerized in both reactors in the presence of the catalyst system described herein. will be done.

[0084] In another embodiment, the ethylene-based polymer is produced in a single reactor system, e.g., a single loop reactor. In the system, ethylene and optionally 1 can be produced by solution polymerization. One or more α-olefins can be produced in the presence of a catalyst system as described within this disclosure and, optionally, one or more cocatalysts. In the presence of the solvent, the mixture is polymerized as described in the previous paragraph.

[0085] The ethylene-based polymer may further comprise one or more additives. Such additives include These include 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. Based on the weight of the ethylene-based polymer and one or more additives, the sum of such additives The ethylene-based polymer may further comprise a filler, the filler being about 0 to about 10 percent by weight. The filler may include, but is not limited to, organic or inorganic fillers. Ethylene-based polymers are not intended to be polymers that are made from ethylene-based polymers and any additives or fillers. Based on the total weight, about 0.01% of calcium carbonate, talc, or Mg(OH)2, etc. The ethylene-based polymer may include up to about 20 weight percent of a filler. The composition may be further combined with a polyether ether ester to form a blend.

[0086] In some embodiments, the polymerization process for producing an ethylene-based polymer comprises The process comprises polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst. and the catalyst system incorporates at least one metal-ligand complex of formula (I): The polymers obtained from such catalyst systems incorporating the metal-ligand complexes of formula (I) are For example, according to STM D792 (which is incorporated herein by reference in its entirety), , 0.850g / cm 3 ~0.950g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density of the sintered body may be 0.01 to 0.01.

[0087] In another embodiment, the catalyst system resulting from the metal-ligand complex of formula (I) The polymers used have melt flow ratios (I 10 / I2), where Dex I2 was prepared according to ASTM D1238, which is incorporated herein by reference in its entirety. ) at 190°C and a load of 2.16 kg, and has a melt index of I 10 is measured at 190°C and 10 kg load according to ASTM D1238. In an embodiment, the melt flow ratio (I 10 / I2) is 5 to 10, and in others, the melt flow The ratio is 5 to 9.

[0088] In some embodiments, the poly(ethylene glycol) derivative obtained from a catalyst system comprising a metal-ligand complex of formula (I) The polymers have a polydispersity index (PDI) of 1 to 25, and the PDI is w / M n Defined as R, M w is the weight average molecular weight, M n is the number average molecular weight. In another embodiment, The polymers obtained from the catalyst system have a PDI of 1 to 6. Another embodiment has a PDI of 1 to 3. and other embodiments include a PDI of 1.5 to 2.5.

[0089] The embodiments of the catalyst system described in this disclosure provide high molecular weight and high molecular weight polymers formed. The amount of comonomer incorporated into a mer results in unique polymer properties.

[0090] All solvents and reagents were obtained from commercial sources and were used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were used. The ether was passed through activated alumina and, optionally, Q-5 reactant. The solvents used in the experiments, which were carried out in a nitrogen-filled glove box, were purified using activated 4 Further drying is performed by storage over molecular sieves. Moisture sensitive glassware is The mixture was dried overnight in an oven before use. NMR spectra were recorded on a Varian 400-M R and VNMRS-500 spectrometers. LC-MS analyses were performed using a Waters 24 24 ELS detector, Waters 2998 PDA detector, and Waters 3 A Waters e2695 separation module coupled with a 100 ESI mass detector was used. LC-MS separation was performed using an XBridge C18 3.5μm 2.1×50m column. m column with a gradient of 5:95 to 100:0 acetonitrile and water (as ionization agent). HRMS analysis was performed using electrospray ionization (ESI) with 0.1% formic acid. The Zorbax E was coupled to an Agilent 6230 TOF mass spectrometer equipped with Agi equipped with a clipse Plus C18 1.8 μm 2.1 × 50 mm column The analysis was performed using a Lent 1290 Infinity LC. 1 H NMR data is Report the chemical shifts as follows: = triplet, q=quartet, p=quintet, sex=sexet, sept=septet, and m=multiplet. The residual protons in the deuterated solvent were used as the standard. hand, 1Chemical shifts of H NMR data are expressed as ppm ( The results are reported using the TMS, δ scale. 13 C NMR data is 1 Using H decoupling Chemical shifts were determined using the residual carbon in the deuterated solvent as the reference. Reported as parts per million downfield from ruthenium dioxide (TMS, δ scale).

[0091] General procedure for PPR screening experiments Polyolefin Catalyst Screening Using High-Throughput Parallel Polymerization Reactors (PPR) The PPR system consists of 48 single cells in an inert atmosphere glove box. The reactor is composed of an array of 6 × 8 matrix reactors. Each cell contains an internal volume of approximately 5 mL. Each cell has an independent pressure control, and the cells are fitted with a glass insert that contains a working liquid volume. The liquid in the flask is continuously stirred at 800 rpm. The catalyst solution is The catalyst is prepared by dissolving a suitable amount of the procatalyst in toluene. solvent, 1-octene, a chain shuttling agent solution appropriate for the experiment, and a catalyst solution) Add gaseous reagents (i.e., ethylene) to the single-cell reactor via a robotic syringe. , H2) is added to the single cell reactor through the gas inlet port. Before each run, the reactor Heat to 80°C, purge with ethylene and vent.

[0092] Add a portion of Isopar-E to the reactor. Heat the reactor to operating temperature and add ethyl acetate. Pressurize with a gas turbine to the appropriate psig. Add the toluene solutions of the reagents in the following order: (1 ) 1-octene with 500 nmol of scavenger MMAO-3A, ​​(2) activator (catalyst (catalyst-1, cocatalyst-2, etc.), and (3) catalyst.

[0093] A small amount of Isopar-E was added after each liquid addition, so that the total reaction volume was 5 mL after the final addition. mL of catalyst. As catalyst is added, the PPR software begins monitoring the pressure in each cell. Start by opening the valve at a pressure (within approximately 2-6 psig) below the set point by 1 psi. Add ethylene gas by closing the valve when the pressure rises above 2 psi. All pressure drops are maintained over the duration of the run or the uptake or change. The ethylene intake is then increased over a period of time until the conversion requirement is reached, whichever comes first. Each reaction is recorded cumulatively as "conversion" or "addition." Quench by addition of 10% carbon monoxide in argon at low pressure for 4 minutes. The shorter the "ch time", the more active the catalyst. To prevent excess polymer formation, the reaction was run at a given incorporation level (120°C). The quench was performed when the pressure reached 50 psig for the run and 75 psig for the 150°C run. After quenching the entire reaction, the reactor is cooled to 70° C. The reactor is vented and filled with nitrogen for 5 min. The polymer sample is purged for 7 min to remove carbon monoxide and the tube is removed. The polymer was dried at 0°C for 12 hours and weighed to determine the polymer yield and IR (1-octene The mixture was subjected to incorporation) and GPC (molecular weight) analysis.

[0094] SymRAD HT-Composition GPC Analysis The molecular weight data of the samples produced by the PPR experiment was compiled jointly by Symyx and Dow. Robot-Assisted Dilution High-Temperature re Gel Permeation Chromatographer(Sym-RA The polymer samples were analyzed by D-GPC to determine the solubility of 300 parts per million (ppm ) stabilized with butylated hydroxyl toluene (BHT) at a concentration of 10 mg / mL Heating in 1,2,4-trichlorobenzene (TCB) at 160°C for 120 minutes Immediately prior to injection of a 250 μL aliquot of sample, each sample was dissolved at 1 mg / mL. GPC was performed using two polymers at 160 °C and a flow rate of 2.0 mL / min. The column is equipped with a 10 μm Mixed-B column (300 x 10 mm) from Labs PLgel. Detection is performed using a PolymerChar IR5 detector in enrichment mode. The conventional calibration of polystyrene (PS) standard was performed for PS and PE in TCB at this temperature. Adjusted to homopolyethylene (PE) using the known Mark-Houwink coefficients of The incorporation of octene is done by PolymerChar I. Linear calibration developed by analyzing copolymers of known composition with the R5 detector was determined using

[0095] 1-Octene Incorporation IR Analysis Running the sample for HT-GPC analysis precedes the IR analysis. The incorporation of is determined from the compositional GPC analysis; in other cases, this separate IR analysis was performed. For IR analysis, a 48-well plate was used for sample deposition and analysis of 1-octene incorporation. The HT silicon wafers were used. For the analysis, the samples were heated to 160°C for up to 210 minutes. The sample was then reheated, the magnetic GPC stir bar was removed, and the mixture was then cooled using a J-KEM Scientific The samples are shaken using a glass rod stirrer in a thermal robotic shaker. Deposition was performed with heating using the MiniPrep 75 deposition station. 4-Trichlorobenzene is evaporated from the deposition wells of the wafer at 160 °C under a nitrogen purge. Analysis of 1-octene was performed using a NEXUS 670 ESP FT-IR spectrometer. This is carried out on a silicon wafer.

[0096] Batch Reactor Polymerization Procedure The batch reactor polymerization reaction was carried out in a 2 L Parr™ batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal coiled cooling coil containing cooling water. Both the reactor and the heating / cooling system were equipped with Camile™ TG Pro. The reactor is controlled and monitored by a process computer. At the bottom of the reactor, a It is fitted with a dump valve that transfers the contents to a stainless steel dump pot. Catalyst deactivation solution (typically 5 mL of Irgafos / Irganox / toluene mixture) Both the pot and the tank are purged with nitrogen and the dump pot is The mixture is vented to a 30 gallon blowdown tank. All solvents were passed through a solvent purification column to remove any impurities that may affect the polymerization. The 1-octene and Isopar E are separated by a first column containing A2 alumina, The ethylene is passed through two columns, the second column containing Q5. The first column contains Q1 and the second column contains Q5. N2, A204 alumina, [ka] Pass through a single column containing molecular sieves, and Q5.

[0097] The reactor was filled with IsoparE solvent and / or 1-octene depending on the reactor loading. The shot tank, which may contain ethanol, is loaded first. Use the attached lab scale to fill to the load set point. After adding the liquid feed, Heat the reactor to the polymerization temperature set point. If ethylene is used, the reactor is heated to the polymerization temperature set point. Ethylene is added to the reactor to maintain the reaction pressure set point. The amount of ethylene added is The flow rate is monitored by a micromotion flowmeter. For some experiments, the flow rate is measured at 120 °C. The standard conditions were 46 g of ethylene and 303 g of 1-octyl in 611 g of IsoparE. The standard conditions at 150°C are 43 g of ethylene in 547 g of IsoparE. and 303g of 1-octene.

[0098] The procatalyst and activator were mixed with an appropriate amount of purified toluene to obtain a molar solution. The procatalyst and activator are handled in an inert glove box and drawn into a syringe. The syringe is filled with 5 mL of toluene three times and then pressure-transferred into the catalyst shot tank. Rinse. Immediately after the catalyst is added, the run timer begins. If ethylene is used, It is added by Camille to maintain the reaction pressure set point in the reactor. The reaction was carried out for 10 minutes, then the agitator was stopped and the bottom dump valve was opened to allow the reactor to cool. Transfer contents to a dump pot. Pour contents of dump pot into tray and place in lab hood. The tray containing the remaining polymer is placed in a vacuum oven where the solvent is allowed to evaporate overnight. The mixture is transferred to a flask and heated to 140° C. under vacuum to remove any remaining solvent. After the trays were cooled to ambient temperature, the polymer yield was measured to determine efficiency. It was subjected to the Remar test.

[0099] PolymerChar HT-composition GPC analysis Polymer samples produced by batch polymerization process were analyzed using infrared detector (IR5) and PolymerChar with Agilent PLgel MIXED-A column Analyzed by high temperature GPC analysis using GPC as an internal flow marker To determine the concentration of decane, 10 μL was added to each sample. 1,2,4-Trichlorobenzene stabilized with butylated hydroxytoluene (BHT) The solution was diluted to a concentration of 10 mg / mL in TCB and stirred at 160°C for 120 min. Prior to injection, samples were diluted to a concentration of 2 mg / mL in BHT-stabilized TCB. The sample (200 μL) was then placed on one PLgel 20 μm (50 × 7.5 mm) guard column, followed by four PLgel 20 μm (300 × 7.5 mm) MIX The BHT-stabilized TCB was eluted through an ED-A column at a flow rate of 1.0 ml / min. The temperature was maintained at 160°C by a pressure of 1000 K. The total run time was 40 min. The molecular weight (MW) was calibrated. To determine the solubility of the Agilent EasiCal polystyrene standards (PS-1 and PS-2 ) was diluted with 1.5 mL of BHT-stabilized TCB and stirred at 160°C for 15 minutes. The PS standards were dissolved according to the known Mark-Houwi method for PS and PE. nk coefficient (α sty = 0.722, log K sty =-3.993, alpha eth =0.72 5. logK eth =-3.391) was used to adjust the PE to homopolyethylene. To generate a third-order MW calibration curve with apparent units, the system was diluted without further dilution. Octene incorporation was determined by analyzing copolymers with known compositions. This was determined by use of a linear calibration method developed using the

[0100] Chain Shuttling Activity Catalytic efficiency, i.e., the M w , comonomer Beyond incorporation and PDI, understanding the chain transfer capabilities of new catalysts is key to Dow’s This is one of the important aspects for developing new polyolefin catalyst families. The kinetics was observed to be consistent with the expected molecular weight reduction and narrowing of the PDI for the shuttling catalyst. Varying the levels of chain transfer or chain shuttling agents (CSAs) to observe the The catalysts that are likely to be good chain transfer agents are first evaluated by running The molecular weight of the polymer produced by The molecular weight of the polymer is more sensitive to the addition of CSA than the molecular weight of the polymer. is the number average chain length that a chain transfer agent would naturally produce in the absence of the chain transfer agent. [ka] Number average chain length [ka] Equation 2 represents the chain transfer constant or chain shuttling constant. The constant Ca is defined as the ratio of the chain transfer constant and the propagation rate constant. The majority of chain propagation occurs at , by assuming that this occurs via ethylene insertion rather than comonomer incorporation. Equation 3 represents the expected M n Represents M no in the absence of chain shuttling agents. is the original molecular weight of the catalyst, M n is the observed molecular weight of the chain shuttling agent (M n = No chain shuttling agent M no ).

number

[0101] To determine the chain transfer rates of procatalysts 1–7 and 9–52, we used a mixture of procatalysts with varying amounts of chain transfer. Semi-batch trials were performed using the inducing agent, Et2Zn (0, 50, and 200 μM). All reactions were carried out at 120 or 150 °C using 1.2 equivalents of [HNMe (C 18 H 37 )2][B(C6F5)4] was used to synthesize procatalysts 7, 8, 11, and 1 2 was treated with excess MMAO-3A (10.0 equiv.) for 10 min prior to polymerization. The batch trials were carried out at pressures ranging from 76 to 136 psi. 11.1 or 12.1 g of ethylene, 56 or 57 g of 1-octene, and 5 The experiments were carried out at 120°C and 150°C using 28g or 555g of IsoparE. Efficiency, as well as the M of the corresponding produced polymer w , PDI, and comonomer incorporation The M for each run is shown in Table 2. n is the percentage for all runs with a particular catalyst. To minimize the squared deviation between the fitted and experimental molecular weight data, Ca and M using osoft Excel Solver n0 The value of fit in Eq. 3 The M for procatalysts 1-52 was calculated using the n Plots of Ca vs [CSA] are From the best fit value of [CSA], M n Figure 5 shows the expected dependence of The calculated Ca values ​​are shown in Table 3. EXAMPLES

[0102] Examples 1-79 provide synthetic procedures for ligands, ligand intermediates, and isolated procatalyst intermediates. 1-4. One or more features of the present disclosure will now be illustrated with reference to the following examples. do.

[0103] Procatalysts 1-34 were synthesized from ligands 1-17 shown in Figure 1. 7 was synthesized according to the representative synthetic schemes shown in FIGS.

[0104] All solvents and reagents were obtained from commercial suppliers and were used as received unless otherwise stated. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were used. The ter was purified by passing it through activated alumina and optionally Q-5 reactant. The solvents used in the experiments, which were carried out in a nitrogen-filled glove box, were activated 4 Å molar. The moisture-sensitive glassware was dried further by storage over microsieves. The NMR spectra were obtained using a Varian 400-MR and NMR spectra were recorded on a VNMRS-500 spectrometer. LC-MS analyses were performed using a Waters 2424 ELS detector, Waters 2998 PDA detector, and Waters 3100 The experiments were performed using a Waters e2695 separation module coupled to an ESI mass detector. LC-MS separation was performed using 0.1% formic acid as the ionization agent at a dilution ratio of 5:95–100: 2.1 μm of XBridge C18 3.5 μm using a gradient of acetonitrile to water of 0.0 HRMS analysis was performed using an Agilent 6230TOF mass spectrometer. Zorbax Eclipse Plus C18 1.8μm 2.1× coupled with a An Agilent 1290Infinity LC equipped with a 50 mm column was used. The analysis was carried out using electrospray ionization. 1 H NMR data is reported as follows: Chemical shifts (multiplicities (br=broadline, s=singlet, d=doublet, t=triplet, q=quartet) , p=quintet, sex=septet, sept=septet, and m=multiplet), integrals, and Using residual protons in deuterated solvents as standards, 1 H NMR data Chemical shifts of the data are in ppm downfield from the tetramethylsilane interior (TMS, δ scale). Report. 13 C NMR data is 1 Determined with H decoupling. Chemical shifts are relative to The carbon residue in a deuterated solvent was used as the material. Reported in parts per million downfield (TMS, δ scale).

[0105] Example 1: Synthesis of Hydroxy-Thiophene Intermediate - Steps 1 and 2 of FIG. 2 [ka] Hydrogenated in 1,4-dioxane (100 mL) and HO (450 mL) under nitrogen to a suspension of thiophene (10.020 g, 42.267 mmol, 1.00 equiv.) , NaOH (50.000 g, 1.250 mol, 29.6 equiv.) was added all at once. At this point, the pale yellow mixture was fitted with a reflux condenser and placed in a heating mantle at 80°C. After stirring (500 rpm) for 2.5 hours, at which point the TLC of the bright yellow solution showed Lower R of thiophene f The mixture was removed from the mantle and the complete conversion to the spot was observed. The solution was then slowly cooled to 23 °C, placed in an ice-water bath for 60 min, and concentrated HCl (125 mL, 37 %) was added over a 10 minute period, at which point the white heterogeneous mixture was removed from the ice-water bath. The mixture was then placed in a mantle heated to 60° C. and stirred vigorously (1000 rpm) for 5 hours, at which point the mixture was stirred at 60° C. for 5 hours. The pale yellow solution was removed from the mantle and slowly cooled to 23 °C and diluted with EtO (100 1 mL), stir vigorously for 2 min, pour into a separatory funnel, separate the layers, and dilute the organics with aqueous HCl. (2 × 100 mL, 1N) and the remaining organics were washed with EtO (2 × 50 mL). The aqueous layer was extracted, dried over solid Na2SO4, decanted, and the Et2O was removed by rotary evaporation. The crude bromo-hydroxythiophene was removed and collected as a solution in 1,4-dioxane (100 mL). An aliquot was removed and concentrated completely under reduced pressure, and NMR showed that it was a mixture of tautomers. This material was used in subsequent experiments without concentration or purification. do.

[0106] A clear, pale yellow solution of hydroxythiophene in 1,4-dioxane (100 mL, top The mixture was diluted with non-anhydrous, non-deoxygenated THF (400 mL) and H2O (6 mL) was added. The solution was then placed in an ice-water bath, sparged with nitrogen for 1 hour, and placed under a positive flow of nitrogen. Then, solid lithium hydroxide monohydrate (3.544 g, 84.453 mmol, 2.00 The mixture, which turned into a dark reddish brown solution, was stirred vigorously (1000 rp) for 1 hour. m), followed by neat chloromethyl ethyl ether (11.8 mL, 126.80 m mol, 3.00 equiv.) was added dropwise via syringe quickly. The mixture was stirred at 0° C. for 2 hours. The dark brown solution was then diluted with aqueous NaOH (200 mL, 1N), stirred for 2 min, and then cooled to 37° C. F was removed under reduced pressure, and the biphasic mixture was diluted with CH2Cl2 (100 mL) and padded with Celite. Filter the mixture over a suction filter, rinse with CH2Cl2 (4 x 50 mL), and separate the dark brown filtrate mixture. Pour into funnel, separate layers, wash organics with aqueous NaOH (2 x 100 mL, 1N), and The organics were extracted from the aqueous solution using CH2Cl2 (2 × 50 mL), combined, and washed with solid Na Drying over 2SO4, decanting, and carefully concentrating gave an amber oil which was dissolved in CH2Cl Dilute with 2 (25 mL), suction filter over a pad of silica gel, and eluate with CH2Cl2 (4 × 50 mL). L) and the filtrate was concentrated to give the thiophene-ether (9.534 g) as a bright yellow oil. , 40.209 mmol, 95% 2 steps) was obtained. NMR showed the product.

[0107] Hydroxythiophene exists as a mixture of tautomers: * denotes the keto tautomer Shows. 1 H NMR (400MHz, chloroform-d) δ(8.34(s, 1H))* , 7.12(d, J=3.7Hz, 1H), 6.43(d, J=3.7Hz, 1H), 5 .49(s, 1H),(3.72(s, 2H))*. 13 C NMR (101MHz, Fluoroform-d) δ(210.23)*, 195.46, 160.19, (149.6 9)*, 121.43, (111.65)*, 100.24, (37.05)*.

[0108] Characterization of protected hydroxythiophenes: 1 H NMR (400 MHz, chloroform-d) δ 7.15 (d, J = 3.6 Hz, 1H), 6.61(d, J=3.5Hz, 1H), 5.19(s, 2H), 3.7 3(q, J=7.1Hz, 2H), 1.22(t, J=7.1Hz, 3H). 13 CN MR (101 MHz, chloroform-d) δ 151.51, 121.50, 103. 84, 101.55, 95.07, 64.53, 15.05.

[0109] Example 2: Synthesis of Hydroxythiophene Carbazole Intermediate - Step 3 of FIG. 2 [ka] Bromothiophene (5.883 g) was placed in a nitrogen-filled, continuously purged glove box. , 24.811 mmol, 1.00 equiv.), 3,6-di-t-butylcarbazole (15 .252g, 54.585mmol, 2.20eq), Cu2O(7.100g, 49. 622 mmol, 2.00 equiv.), and K2CO3 (34.290 g, 248.11 m mol, 10.00 equiv.) was suspended in deoxygenated anhydrous xylene (200 mL), N,N'-DMEDA (21.5 mL, 199.84 mmol, 4.00 equiv.) was added. Fit the mixture with a reflux condenser and a rubber septum and remove it from the glove box. , placed under nitrogen, placed in a heated mantle at 140°C, and stirred vigorously (1000 r pm), remove from the mantle, and at this point the deep red-black mixture is gradually cooled to 23°C. Then, CH2Cl2 (100 mL) was added and the mixture was stirred for 5 min and then loaded onto a silica gel pad. The amber filtrate was concentrated onto Celite by suction filtering with 100 mL of ethyl acetate, rinsing with CH2Cl2 (4 x 75 mL). and purified by silica gel chromatography using an ISCO chromatographic purification system. The compound was purified several times by filtration and extracted with 15% CH2Cl2 in hexane as a white amorphous foam. The olefin-carbazole product (7.699 g, 17.673 mmol, 71%) was obtained. NMR showed a pure product.

[0110] 1 H NMR (500 MHz, chloroform-d) δ 8.12 (d, J = 1.9 Hz, 2H), 7.45(dd, J=8.6, 2.0Hz, 2H), 7.32(d, J= 3.6Hz, 1H), 7.20(d, J=8.6Hz, 2H), 6.89(d, J=3. 6Hz, 1H), 3.56(q, J=7.1Hz, 2H), 1.47(s, 18H), 1 .16(t, J=7.1Hz, 3H). 13 C NMR (126 MHz, chloroform- d) δ 150.87, 142.60, 139.70, 127.62, 123.44, 123.08, 120.21, 116.07, 109.57, 102.36, 94.78 , 64.37, 34.70, 32.03, 15.01.

[0111] Example 3: Synthesis of Hydroxythiophene Boropinacolate Intermediate - Step 4 of FIG. 2 [ka] Anhydrous, deoxygenated EtO (75 mL) in a nitrogen-filled, continuously purged glovebox A bright yellow solution of thiophene (3.000 g, 6.887 mmol, 1.00 equiv) in Place in a freezer (-35°C) and pre-cool for 14 hours. Then add n-BuLi (3.50 mL, 8 .608 mmol, 1.25 equiv., titrated dropwise rapidly with a pre-cooled solution of 2.5 M in hexane The pale orange solution was left in the freezer for 4 hours, after which the isopropoxyboron was added. Naphthalene ester (2.81 mL, 13.774 mmol, 2.00 equiv) was added neat. At this point the bright yellow solution was stirred at 23° C. for 2 hours, at which point a white heterogeneous solution was formed. The mixture was diluted with aqueous phosphate buffer (20 mL, pH = 8, 0.05 M) and rotary evaporated. The mixture was diluted with CH2Cl2 (25 mL) and water (25 mL) and poured into a separatory funnel. Pour into a tub, separate the layers, wash the organics with water (1 × 25 mL), and dilute the remaining organics with CH2Cl2 (2 × 25 mL), mixed, dried over solid Na2SO4, decanted, concentrated, and the resulting The resulting bright yellow foam was dissolved in CH2Cl2 (10 mL) and mixed with a short pad of silica gel. Filter through a suction filter, rinse with CH2Cl2 (4 x 20 mL), and concentrate the bright yellow filtrate solution. Thiophene-boropinacolate ester (2.581 g, The yield was 4.596 mmol, 67%, approximately 72% purity by NMR. , used in subsequent reactions without further purification.

[0112] 1 H NMR (500 MHz, chloroform-d) δ 8.11-8.08 (m, 2H), 7.62(d, J=0.9Hz, 1H), 7.45(dt, J=8.6, 1.4 Hz, 2H), 7.23(dd, J=8.7, 0.7Hz, 2H), 4.88(d, J= 0.8Hz, 2H), 2.96-2.88(m, 2H), 1.46(s, 18H), 1. 38(s, 12H), 0.58(t, J=7.1Hz, 3H).13 C NMR(126 MHz, chloroform-d) δ 158.93, 142.70, 139.53, 130 .88, 127.58, 123.65, 123.00, 115.86, 109.77, 9 8.24, 84.20, 64.53, 34.71, 32.03, 24.80, 14.14 .

[0113] Example 4: Synthesis of linked iodophenyl ether intermediates [ka] 2-Iodophenol (2. 000g, 9.091mmol, 2.00eq), K2CO3(2.513g, 18.1 80 mmol, 4.00 equiv.), and 1,4-dibromobutane (0.54 mL, 4.5 A white heterogeneous mixture of 45 mmol, 1.00 equiv. was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 36 hours, the white heterogeneous mixture was removed from the mantle. Cool to 23 °C, dilute with CH2Cl2 (50 mL), stir for 2 min, and pad with Celite. The pale yellow filtrate was filtered over a filter paper and rinsed with CH2Cl2 (4 x 20 mL). The mixture was concentrated onto a light source and then purified by silica gel chromatography using an ISCO chromatographic purification system. The compound was purified by chromatography and extracted with 25% CH2Cl2 in hexane as a white solid. The resulting product was 2.024 g (4.096 mmol, 90%) of diphenyl ether. Showed pure product.

[0114] 1 H NMR (500 MHz, chloroform-d) δ 7.77 (dd, J=7. 8, 1.8Hz, 2H), 7.34-7.22(m, 2H), 6.83(d, J=8.2 Hz, 2H), 6.70(t, J=7.6Hz, 2H), 4.14(d, J=5.3Hz , 4H), 2.17-2.06(m, 4H). 13 C NMR (126 MHz, chloroform lm-d) δ 157.42, 139.39, 129.44, 129.43, 122. 42, 112.11, 112.09, 86.68, 68.61, 26.04.

[0115] Example 5: Synthesis of linked diethylsilyl-bridged iodophenyl ether intermediates [ka] 2-Iodophenol (3. 671g, 16.686mmol, 2.50 eq), K2CO3 (6.918g, 50. 055 mmol, 7.50 equiv.), and bischloromethyldiethylsilane (1.236 g, 6.674 mmol, 1.00 equiv.) was heated to 60 °C. After stirring (500 rpm) for 72 hours, a white heterogeneous mixture was Remove from the oven, cool to 23 °C, dilute with CH2Cl2 (50 mL), stir for 2 min, and Filter the resulting pale yellow eluate over a light pad and rinse with CH2Cl2 (4 x 20 mL). The filtrate was diluted with aqueous NaOH (50 mL, 1N) and the biphasic mixture was poured into a separatory funnel and separated. The organics were then washed with aqueous NaOH (2 × 30 mL, 1N) to remove any remaining starting phenol. The remaining organics were extracted with CH2Cl2 (2 x 20 mL), mixed and diluted with solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography using a 5–15% CH in hexane system. The desired bis-alkylated phenol was obtained as a clear, colorless, viscous oil (3.551 g, The yield was 6.430 mmol, 96%). NMR showed pure product.

[0116] 1 H NMR (500 MHz, chloroform-d) δ 7.74 (dd, J=7. 7, 1.6Hz, 2H), 7.30(ddd, J=8.6, 7.6, 1.6Hz, 2H) , 6.98(dd, J=8.1, 1.3Hz, 2H), 6.69(td, J=7.6, 1 .4Hz, 2H), 3.95(s, 4H), 1.16(t, J=7.8Hz, 6H), 0 .99(qd, J=7.8, 1.1Hz, 4H). 13 C NMR (126MHz, Chrom Roform-d) δ 159.46, 139.14, 129.41, 122.23, 11 1.16, 86.44, 57.91, 7.44, 1.74.

[0117] Example 6: Synthesis of 1,2-dibenzyl-bridged iodophenyl ether intermediates [ka] Iodophenol (2.5 mL) in acetone (100 mL) with a reflux condenser under nitrogen. 80g, 11.727mmol, 2.00 eq), K2CO3 (4.862g, 35.1 78 mmol, 6.00 equiv.), and dibumid (1.548 g, 5.863 mmol, A white heterogeneous mixture of 1.00 equiv. (1.00 equiv.) was placed in a heating mantle at 60°C and stirred for 36 h. After stirring (500 rpm), the white heterogeneous mixture was removed from the mantle and cooled to 23°C. The mixture was cooled, diluted with CH2Cl2 (50 mL), stirred vigorously (1000 rpm) for 5 min, and centrifuged. Filter the solution over a light pad and rinse with CH2Cl2 (3 x 25 mL). The liquid was concentrated onto Celite and purified by silica gel chromatography, followed by 10% in hexane. 50% CH2Cl2 in CH2Cl2-hexane gave bis-iodofuran as a white solid. The product was purified by NMR spectroscopy (NMR spectroscopy) and the product was purified by NMR spectroscopy (NMR spectroscopy) ... showed.

[0118] 1 H NMR (500 MHz, chloroform-d) δ 7.81 (dd, J=7. 7, 1.6Hz, 2H), 7.71-7.64(m, 2H), 7.46-7.39(m, 2H), 7.30(ddd, J=8.3, 7.4, 1.6Hz, 2H), 6.97(dd , J=8.3, 1.3Hz, 2H), 6.74(td, J=7.6, 1.4Hz, 2H) , 5.31(s,4H). 13 C NMR (126MHz, chloroform-d) δ 1 56.94, 139.60, 134.42, 129.60, 128.75, 128.45 , 112.55, 86.46, 69.21.

[0119] Example 7: trans-methylenecyclohexyl bisiodophenyl ether bridged intermediate Body composition [ka] Iodophenol (2.19 mL) in acetone (50 mL) with a reflux condenser under nitrogen 4g, 9.972mmol, 2.00 eq), K2CO3 (2.257g, 29.916 mmol, 6.00 equiv.), and bistosylate (2.257 g, 4.986 mmol A white heterogeneous mixture of 1.00 equiv. (1.00 equiv.) was placed in a heating mantle at 60° C. for 40 h. After stirring (500 rpm), the white heterogeneous mixture was removed from the mantle and cooled to 23°C. Cool, dilute with CH2Cl2 (50 mL), stir vigorously (1000 rpm) for 5 min, Filter the resulting filtrate through a pad of Celite and rinse with CH2Cl2 (3 x 25 mL). The solution was concentrated onto Celite and purified by silica gel chromatography, and eluted with 10 50% CH2Cl2 in hexane to give bis-iodo as a white solid Phenyl ether (1.420 g, 2.590 mmol, 52%) and mixed mono- Silyl monoiodophenyl ether (0.992 g, 1.982 mmol, 40%) NMR of each showed pure product.

[0120] 1 H NMR (500 MHz, chloroform-d) δ 7.76 (dd, J=7. 9, 1.6Hz, 2H), 7.26(td, J=7.8, 1.6Hz, 2H), 6.82 (dd, J=8.2, 1.3Hz, 2H), 6.69(td, J=7.6, 1.4Hz, 2H), 4.10-3.98(m, 4H), 2.01(ddt, J=25.4, 13.2 , 2.9Hz, 4H), 1.86(dq, J=8.4, 2.9Hz, 2H), 1.52( dd, J=17.3, 7.8Hz, 2H), 1.41(ddt, J=12.0, 8.9, 4.9Hz, 2H). 13 C NMR (126MHz, chloroform-d) δ 157 .47, 139.27, 129.46, 122.24, 111.89, 86.52, 72 .02, 39.71, 30.29, 26.16.

[0121] NMR characterization of monotosylate-monoiodophenyl ether: 1H NMR (500 MHz, chloroform-d) δ 7.76-7.71 (m, 3H), 7.28-7.23(m, 3H), 6.69(td, J=7.6, 1.3Hz, 1H), 6.62(dd, J=8.3, 1.4Hz, 1H), 4.09-4.03(m, 2H), 3.81(dd, J=9.3, 4.4Hz, 1H), 3.74(dd, J=9. 3, 3.6Hz, 1H), 2.38(s, 3H), 1.93-1.64(m, 6H), 1 .46(qd, J=12.1, 3.0Hz, 1H), 1.28(dd, J=11.3, 8 .4Hz, 3H). 13 C NMR (126 MHz, chloroform-d) δ 157. 17, 144.65, 139.25, 132.77, 129.80, 129.40, 12 7.94, 122.43, 111.72, 86.52, 73.15, 71.16, 38. 97, 38.61, 30.02, 29.41, 25.81, 25.64, 21.62.

[0122] Example 8: trans-methylenecyclohexyl bisiodophenyl ether bridged intermediate Body composition [ka] Iodophenol (0.45 mL) in acetone (25 mL) with a reflux condenser under nitrogen. 8g, 2.082mmol, 1.05eq), K2CO3 (0.863g, 6.246m mol, 3.15 equiv.), and monotosylate (0.992 g, 1.982 mmol, A white heterogeneous mixture of 1.00 equiv. (1.00 eq.) was placed in a heating mantle at 60°C and stirred for 48 h. After stirring (500 rpm), the white heterogeneous mixture was removed from the mantle and cooled to 23°C. The mixture was cooled, diluted with CH2Cl2 (50 mL), stirred vigorously (1000 rpm) for 5 min, and centrifuged. Filter the solution over a light pad and rinse with CH2Cl2 (3 x 25 mL). The liquid was concentrated onto Celite and purified by silica gel chromatography, followed by 10% in hexane. Bisiodine was obtained as a white solid by 75% CH2Cl2 in CH2Cl2-hexane. The phenyl ether (0.677 g, 1.235 mmol, 62%) was obtained. Showed pure product.

[0123] 1 H NMR (500 MHz, chloroform-d) δ 7.76 (dd, J=7. 9, 1.6Hz, 2H), 7.26(td, J=7.8, 1.6Hz, 2H), 6.82 (dd, J=8.2, 1.3Hz, 2H), 6.69(td, J=7.6, 1.4Hz, 2H), 4.10-3.98(m, 4H), 2.01(ddt, J=25.4, 13.2 , 2.9Hz, 4H), 1.86(dq, J=8.4, 2.9Hz, 2H), 1.52( dd, J=17.3, 7.8Hz, 2H), 1.41(ddt, J=12.0, 8.9, 4.9Hz, 2H). 13 C NMR (126MHz, chloroform-d) δ 157 .47, 139.27, 129.46, 122.24, 111.89, 86.52, 72 .02, 39.71, 30.29, 26.16.

[0124] Example 9: Synthesis of Ligand 2 - Steps 5 and 6 of FIG. 2 [ka] Thiophene boropinacolate ester (2.017 g, 2.586 mmol, 3.0 0 equiv., 72% purity by NMR), K3PO4 (1.647 g, 7.758 mmol, 9.00 equivalents), Pd(AmPhos)Cl2 (122.0mg, 0.1724mmol , 0.20 equiv.), and bisphenyl iodide (0.426 g, 0.8620 mmol The mixture was evacuated and then backfilled with nitrogen to complete the process. This was repeated three more times, followed by deoxygenated 1,4-dioxane (17.0 mL) and deoxygenated Oxygenated water (1.7 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. Remove from the torch, slowly cool to 23°C, suction filter over a pad of silica gel, and dilute with CH2 Wash with Cl2 (4 x 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. The was azeotropically removed using toluene (2×10 mL) by rotary evaporation, and then the black The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and The black filtrate was then concentrated onto Celite and washed with ISC Purify the mixture by silica gel chromatography using a HeO chromatography purification system. Bisthiophene ( The yield was 0.837 g, 0.7544 mmol, 88%). NMR showed a pure product. .

[0125] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to give bisthiophene (0.563 g, 0.5668 m mol, 75%, 66% 2 steps) was obtained. NMR showed pure product.

[0126] 1 H NMR (500 MHz, chloroform-d) δ 8.11 (d, J = 2.0 Hz, 4H), 7.61(dd, J=7.7, 1.7Hz, 2H), 7.40(dd, J =8.6, 1.9Hz, 4H), 7.32(s, 2H), 7.30-7.20(m, 6H) ), 7.12(t, J=7.5Hz, 2H), 6.90(d, J=8.2Hz, 2H), 4.11-4.04(m, 4H), 1.95-1.87(m, 4H), 1.43(s, 3 6H). 13 C NMR (126 MHz, chloroform-d) δ 153.71, 14 6.43, 142.65, 139.63, 130.50, 128.74, 127.55, 123.42, 123.16, 123.08, 122.96, 120.13, 116.1 8, 115.28, 114.09, 109.57, 69.98, 34.68, 32.02 , 25.86.

[0127] Characterization of the protected conjugation product: 1 H NMR (500 MHz, chloroform-d) δ 8.13 (h, J = 1.9 Hz, 4H), 7.94(ddd, J=7.6, 4.1, 2.3Hz, 2H), 7.49 -7.44(m, 4H), 7.38-7.34(m, 6H), 7.34-7.28(m, 2H), 7.08-7.01(m, 4H), 4.46(t, J=3.0Hz, 4H), 4 .30-4.19(m, 4H), 2.79(qt, J=7.2, 2.7Hz, 4H), 2 .29-2.20(m, 4H), 1.48(s, 36H), 0.52(tt, J=7.1 , 2.9Hz, 6H). 13 C NMR (126MHz, chloroform-d) δ 15 5.83, 147.29, 142.72, 139.49, 131.10, 129.37, 129.13, 124.29, 123.66, 123.07, 121.52, 120.6 1, 119.19, 115.96, 112.07, 109.85, 96.97, 68.3 6, 64.61, 34.73, 32.06, 26.37, 14.17.

[0128] Example 10: Synthesis of Procatalyst 3 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (7.4 mg, 7.45 μmol, 1.00 equiv.) was added to C6D of ZrBn4 (3.8 mg, 8.20 μmol, 1.10 equiv.) in 6 (0.15 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The zirconium complex was obtained as a 0.5M solution. NMR showed the product was. Using the same procedure with e, the procatalyst solution (0. 0.0025M or 0.005M) can be prepared.

[0129] 1 H NMR (500 MHz, benzene-d6) δ 8.48 (dd, J = 2.0 , 0.6Hz, 2H), 8.22(dd, J=1.9, 0.7Hz, 2H), 7.50- 7.46(m, 4H), 7.31-7.24(m, 6H), 6.98-6.96(m, 4 H), 6.86(s, 2H), 6.83-6.75(m, 4H), 6.70(td, J= 7.5, 1.2Hz, 2H), 6.23-6.17(m, 4H), 5.12(dd, J= 8.2, 1.2Hz, 2H), 3.97-3.88(m, 2H), 3.28-3.21( m, 2H), 1.49(s, 18H), 1.28(s, 18H), 1.06(d, J=1 2.4Hz, 2H), 0.77-0.67(m, 2H), 0.52-0.44(m, 4H) ). 13 C NMR (126 MHz, benzene-d6) δ 156.11, 152.2 3, 147.06, 143.09, 142.73, 139.24, 139.14, 130 .95, 129.75, 126.42, 126.17, 125.92, 125.20, 1 24.55, 123.48, 122.65, 122.35, 120.75, 117.04 , 116.94, 116.27, 115.52, 112.51, 108.85, 80.9 7, 75.18, 34.57, 34.41, 32.01, 31.71, 26.01.

[0130] Example 11: Synthesis of Procatalyst 4 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (14.0 mg, 14.09 μmol, 1.00 equiv.) was added to C HfBn4 (8.4 mg, 15.50 μmol, 1.10 equiv.) in 6D6 (0.33 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. The solution was filtered using a 0.20 μm PTFE submicron filter to obtain C6D6 The hafnium complex was obtained as a 0.0025M solution. NMR showed the product was Use the same procedure with PhMe, and filter the procatalyst solution immediately after polymerization experiments. (0.0025M) can be prepared.

[0131] 1 H NMR (500 MHz, benzene-d6) δ 8.49 (dd, J = 2.0 , 0.6Hz, 2H), 8.23(dd, J=2.0, 0.6Hz, 2H), 7.47( ddd, J=8.8, 5.0, 1.9Hz, 4H), 7.27(ddd, J=8.5, 4 .4, 1.2Hz, 4H), 7.17(dd, J=8.7, 0.6Hz, 2H), 6.9 9-6.95(m, 4H), 6.86(s, 2H), 6.78(dddd, J=8.6, 7.3, 3.6, 1.5Hz, 4H), 6.71(td, J=7.6, 1.2Hz, 2H) ), 6.22-6.16(m, 4H), 5.15(dd, J=8.2, 1.2Hz, 2H ), 4.02-3.93(m, 2H), 3.35-3.26(m, 2H), 1.50(s , 18H), 1.28(s, 18H), 0.89(d, J=13.3Hz, 2H), 0. 78-0.68(m, 2H), 0.47-0.36(m, 2H), 0.22(d, J=1 3.3Hz, 2H). 13C NMR (126 MHz, benzene-d6) δ 155. 80, 152.29, 147.74, 143.15, 142.74, 139.23, 13 9.09, 130.95, 129.74, 128.54, 127.06, 126.75, 126.10, 125.28, 124.59, 123.68, 122.60, 122.2 8, 120.78, 117.11, 116.38, 116.26, 115.45, 112 .56, 108.84, 81.81, 78.35, 34.57, 34.42, 32.01 , 31.72, 26.11.

[0132] Example 12: Synthesis of Ligand 1 [ka] Thiophene boropinacolate ester (2.017 g, 2.586 mmol, 3.0 0 equiv., 72% purity by NMR), K3PO4 (1.647 g, 7.758 mmol, 9.00 equivalents), Pd(AmPhos)Cl2 (122.0mg, 0.1724mmol , 0.20 equiv.), and bisphenyl iodide (0.467 g, 0.8620 mmol The mixture was evacuated and then backfilled with nitrogen to complete the process. This was repeated three more times, followed by deoxygenated 1,4-dioxane (17.0 mL) and deoxygenated Oxygenated water (1.7 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. Remove from the torch, slowly cool to 23°C, suction filter over a pad of silica gel, and dilute with CH2 Wash with Cl2 (4 x 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. The was azeotropically removed using toluene (2×10 mL) by rotary evaporation, and then the black The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and The black filtrate was then concentrated onto Celite and washed with ISC Purify the mixture by silica gel chromatography using a HeO chromatography purification system. Bisthiophene ( The yield was 0.810 g, 0.6997 mmol, 81%). NMR showed a pure product. .

[0133] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to give bisthiophene (0.559 g, 0.5368 m mol, 77%, 62% 2 steps) was obtained. NMR showed pure product.

[0134] 1 H NMR (500 MHz, chloroform-d) δ 8.08 (d, J = 1.9 Hz, 4H), 7.60(dd, J=7.6, 1.7Hz, 2H), 7.41(dd, J =5.6, 3.5Hz, 2H), 7.36-7.30 (m, 8H), 7.25-7.20 (m, 2H), 7.13 (t, J=7.5Hz, 2H), 7.07 (d, J=8.5Hz , 4H), 6.95(d, J=8.2Hz, 2H), 6.91(s, 2H), 5.20( s, 4H), 1.46 (s, 36H). 13 C NMR (126MHz, クロロホルム- d) δ 153.64, 146.41, 142.61, 139.45, 133.72, 130.67, 129.89, 129.34, 128.95, 127.80, 123.5 4, 123.37, 123.19, 123.18, 119.90, 116.09, 115 .35, 114.78, 109.55, 70.58, 34.69, 32.04.

[0135] Evaluation of the characteristics of the protective bonded product: 1 H NMR (500MHz, クロロホルム-d) δ 8.12 (d, J=1.8 Hz, 4H), 7.84 (dd, J=7.7, 1.7Hz, 2H), 7.69 (dd, J =5.5, 3.4Hz, 2H), 7.50 (dd, J=5.6, 3.4Hz, 2H), 7 .41(dd, J=8.6, 1.9Hz, 4H), 7.32(d, J=1.2Hz, 2H ), 7.27-7.22(m, 6H), 7.09-7.02(m, 4H), 5.33(s , 4H), 4.42(s, 4H), 2.76(q, J=7.0Hz, 4H), 1.49( s, 36H), 0.51 (t, J=7.0Hz, 6H). 13 C NMR (126MHz , クロロホルム-d) δ 155.75, 147.38, 142.71, 139.42 , 135.12, 131.45, 129.50, 129.40, 129.28, 128. 45, 124.21, 123.75, 123.07, 121.89, 121.06, 11 9.10, 115.91, 112.86, 109.84, 96.87, 68.89, 64 .52, 34.74, 32.07, 14.19.

[0136] Example 13: Synthesis of Procatalyst 1 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (13.0 mg, 12.48 μmol, 1.00 equiv.) was added to C ZrBn4 (6.3 mg, 13.73 μmol, 1.10 equiv.) in 6D6 (0.26 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. The solution was filtered using a 0.20 μm PTFE submicron filter to obtain C6D6 The zirconium complex was obtained as a 0.005M solution. NMR showed the product was Use the same procedure with PhMe, and filter the procatalyst solution immediately after polymerization experiments. (0.0025M or 0.005M) can be prepared.

[0137] 1 H NMR (400MHz, benzene-d6) δ 8.49 (d, J=1.9H z, 2H), 8.22(d, J=1.9Hz, 2H), 7.53(dd, J=8.6, 1 .9Hz, 2H), 7.44(dd, J=8.7, 1.9Hz, 2H), 7.36(d, J=8.5Hz, 2H), 7.24(d, J=8.7Hz, 2H), 7.17(dd, J =7.7, 1.7Hz, 2H), 6.98-6.94(m, 4H), 6.79(td, J =7.7, 1.8Hz, 2H), 6.75(s, 2H), 6.66(ddd, J=10. 5, 6.6, 2.2Hz, 2H), 6.58(t, J=7.1Hz, 2H), 6.29( dd, J=5.5, 3.4Hz, 2H), 6.25-6.20(m, 2H), 5.40( d, J=13.0Hz, 2H), 5.35(dd, J=8.4, 1.1Hz, 2H), 4 .18(d, J=13.0Hz, 2H), 1.53(s, 18H), 1.27(s, 18 H), 0.94(d, J=12.0Hz, 2H), 0.46(d, J=12.0Hz, 2 H). 13 C NMR (101 MHz, benzene-d6) δ 155.22, 151. 79, 145.67, 142.96, 142.78, 139.33, 139.29, 13 3.07, 131.03, 129.54, 128.17, 127.00, 125.46, 125.05, 124.45, 122.85, 122.43, 121.17, 117.5 2, 117.10, 116.33, 115.63, 112.32, 109.12, 79. 48, 73.48, 34.62, 34.39, 32.04, 31.72.

[0138] Example 14: Synthesis of Procatalyst 2 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (15.8 mg, 15.17 μmol, 1.00 equiv.) was added to C HfBn4 (9.1 mg, 16.69 μmol, 1.10 equiv.) in 6D6 (0.37 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. The solution was filtered using a 0.20 μm PTFE submicron filter to obtain C6D6 The hafnium complex was obtained as a 0.005M solution. NMR showed the product was Using the same procedure with hMe, the procatalyst solution used immediately after the filtration of the polymerization experiment ( 0.005M) can be prepared.

[0139] 1 H NMR (500 MHz, benzene-d6) δ 8.52 (dd, J = 2.0 , 0.6Hz, 2H), 8.24(dd, J=2.0, 0.6Hz, 2H), 7.53( dd, J=8.5, 1.9Hz, 2H), 7.44(dd, J=8.7, 1.9Hz, 2 H), 7.36(dd, J=8.5, 0.6Hz, 2H), 7.18(dd, J=7.7 , 1.7Hz, 2H), 7.16(dd, J=8.7, 0.6Hz, 2H), 6.99- 6.95(m, 4H), 6.82(ddd, J=8.2, 7.4, 1.7Hz, 2H), 6.76(s, 2H), 6.68(dd, J=7.6, 1.1Hz, 2H), 6.64( dd, J=5.6, 3.3Hz, 2H), 6.29-6.23(m, 4H), 5.37( d, J=13.1Hz, 2H), 5.35(dd, J=8.3, 1.2Hz, 2H), 4 .17(d, J=13.2Hz, 2H), 1.54(s, 18H), 1.29(s, 18 H), 0.90(d, J=13.2Hz, 2H), 0.21(d, J=13.2Hz, 2 H). 13 C NMR (126MHz, benzene-d6) δ 154.89, 151 .88, 146.91, 143.06, 142.81, 139.32, 139.30, 1 32.85, 131.02, 129.53, 129.21, 128.24, 128.18 , 127.20, 127.17, 126.97, 125.88, 125.21, 124. 54, 122.81, 122.35, 121.90, 121.04, 117.18, 11 7.02, 116.31, 115.53, 112.45, 109.11, 80.12, 7 8.51, 34.63, 34.41, 32.05, 31.73.

[0140] Example 15: Synthesis of Ligand 4 [ka] Thiophene boropinacolate ester (1.931 g, 2.476 mmol, 3.0 0 equiv., 72% purity by NMR), K3PO4 (1.577 g, 7.428 mmol, 9.00 equivalents), Pd(AmPhos)Cl2 (117.0 mg, 0.1650 mmol , 0.20 equiv.), and bisphenyl iodide (0.456 g, 0.8252 mmol The mixture was evacuated and then backfilled with nitrogen to complete the process. This was repeated three more times, followed by deoxygenated 1,4-dioxane (15.0 mL) and deoxygenated Oxygenated water (1.5 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. Remove from the torch, slowly cool to 23°C, suction filter over a pad of silica gel, and dilute with CH2 Wash with Cl2 (4 x 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. The was azeotropically removed using toluene (2×10 mL) by rotary evaporation, and then the black The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and The black filtrate was then concentrated onto Celite and washed with ISC Purify the mixture by silica gel chromatography using a HeO chromatography purification system. Bisthiophene ( The yield was 0.822 g, 0.7040 mmol, 85%). NMR showed a pure product. .

[0141] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to give bisthiophene (0.541 g, 0.5145 m mol, 73%, 62% 2 steps) was obtained. NMR showed pure product.

[0142] 1 H NMR (500 MHz, chloroform-d) δ 8.18 (d, J = 1.9 Hz, 4H), 7.51(dd, J=7.5, 1.9Hz, 2H), 7.45(dd, J =8.6, 1.9Hz, 4H), 7.37(s, 2H), 7.23(d, J=8.6Hz , 4H), 7.04(dtd, J=20.2, 7.5, 1.6Hz, 4H), 6.78( s, 2H), 6.69(dd, J=8.1, 1.4Hz, 2H), 3.88(s, 4H) , 1.50(s, 36H), 0.85(t, J=7.9Hz, 6H), 0.67(q, J =7.9Hz, 4H). 13 C NMR (126MHz, chloroform-d) δ 15 6.35, 146.38, 142.68, 139.95, 130.38, 129.03, 127.25, 123.52, 123.23, 122.36, 122.20, 120.3 4, 116.12, 115.34, 113.40, 109.62, 59.41, 34.7 5, 32.10, 6.95, 1.15.

[0143] Example 16: Synthesis of Procatalyst 7 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (16.5 mg, 15.69 μmol, 1.00 equiv.) was added to C ZrBn4 (7.9 mg, 17.26 μmol, 1.10 equiv.) in 6D6 (0.32 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. The solution was filtered using a 0.20 μm PTFE submicron filter to obtain C6D6 The zirconium complex was obtained as a 0.005M solution. NMR showed the product was Use the same procedure with PhMe, and filter the procatalyst solution immediately after polymerization experiments. (0.0025M or 0.005M) can be prepared.

[0144] 1<h2 style=";text-align:left;direction:ltr">H NMR(500MHz、ベンゼン-d6) δ 8.51(dd、J=1.9<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 0.6Hz, 2H), 8.25(dd, J=1.9, 0.6Hz, 2H), 7.54-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7.49(m、4H)、7.37(dd、J=8.5、0.6Hz、2H)、7.31(<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> dd, J=8.7, 0.6 Hz, 2 H), 7.26(dd, J=7.8, 1.7 Hz, 2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> H)、6.98-6.96(m、4H)、6.89(s、2H)、6.84-6.78(<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> m、2H)、6.69(td、J=7.6、1.2Hz、2H)、6.64-6.52(<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> m、2H)、6.30-6.26(m、4H)、5.40(dd、J=8.2、1.1H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> z, 2H) 4.23(d, J=14.8Hz, 2H) 3.15(d, J=14.8H)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> z, 2H)、1.48(s, 18H)、1.27(s, 18H)、1.15(d, J=1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2.5Hz, 2H)、0.87(t、J=7.9Hz、2H)、0.52(d、J=12<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> .5Hz、2H)、0.36(t、J=8.0Hz、6H)、0.01--0.10(m)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 、1H)、-0.24(dq、J=14.9、8.0Hz、1H)。<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> C NMR(1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 26MHz、ベンゼン-d6) δ 158.69、152.42、147.10、14<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 3.14, 142.73, 140.21, 139.56, 139.39, 130.37<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 129.00, 128.32, 128.17, 126.35, 125.98, 125.4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 5, 125.19, 124.64, 122.76, 122.43, 120.81, 117<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> .66, 117.18, 116.33, 115.52, 112.52, 108.88, 7<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 5.73, 71.46, 34.59, 34.41, 31.99, 31.71, 6.60<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 0.73.<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0145] Example 17: Synthesis of Procatalyst 8 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (13.0 mg, 12.36 μmol, 1.00 equiv.) was added to C HfBn4 (7.4 mg, 13.60 μmol, 1.10 equiv.) in 6D6 (0.30 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. The solution was filtered using a 0.20 μm PTFE submicron filter to obtain C6D6 The hafnium complex was obtained as a 0.005M solution. NMR showed the product was Using the same procedure with hMe, the procatalyst solution used immediately after the filtration of the polymerization experiment ( 0.005M) can be prepared.

[0146] 1 H NMR (500 MHz, benzene-d6) δ 8.52 (dd, J = 2.0 , 0.6Hz, 2H), 8.26(dd, J=1.9, 0.6Hz, 2H), 7.51( ddd, J=8.7, 1.9, 1.3Hz, 4H), 7.35(dd, J=8.5, 0. 6Hz, 2H), 7.26(dd, J=7.8, 1.7Hz, 2H), 7.23(dd, J=8.7, 0.6Hz, 2H), 6.98-6.95(m, 4H), 6.89(s, 2 H), 6.84(ddd, J=8.2, 7.4, 1.8Hz, 2H), 6.79-6.7 3(m, 2H), 6.70(td, J=7.6, 1.1Hz, 2H), 6.31-6.2 6(m, 4H), 5.42(dd, J=8.2, 1.2Hz, 2H), 4.28(d, J =14.9Hz, 2H), 3.16(d, J=14.9Hz, 2H), 1.48(s, 1 8H), 1.28(s, 18H), 0.98(d, J=13.4Hz, 2H), 0.35 (t, J=8.0Hz, 6H), 0.26-0.21(m, 2H), -0.06(dq, J=15.9, 8.0Hz, 2H), -0.27(dq, J=15.0, 8.0Hz, 2 H). 13 C NMR (126 MHz, benzene-d6) δ 158.36, 152. 51, 147.68, 143.20, 142.73, 139.56, 139.36, 13 0.37, 129.54, 128.73, 127.07, 126.75, 126.16, 125.70, 125.26, 124.68, 122.72, 122.37, 121.7 2, 120.87, 117.78, 116.49, 116.32, 115.45, 112 .55, 108.84, 78.79, 71.96, 34.59, 34.41, 32.00 , 31.71, 6.55, 0.77.

[0147] Example 18: Synthesis of Ligand 3 [ka] Thiophene boropinacolate ester (1.352 g, 1.806 mmol, 3.0 0 equiv., 72% purity by NMR), K3PO4 (1.150 g, 5.418 mmol, 9.00 equivalents), Pd(AmPhos)Cl2 (85.0mg, 0.1204mmol, 0.20 equiv.), and bisphenyl iodide (0.330 g, 0.6020 mmol, The mixture was evacuated and then backfilled with nitrogen and the process was Repeat three more times, then add deoxygenated 1,4-dioxane (15.0 mL) and deoxygenated Hydrogenated water (1.5 mL) was then added via syringe. The mixture was then heated to 50°C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was The mixture was removed from the flask, slowly cooled to 23°C, and suction filtered over a pad of silica gel. Wash with L2 (4 × 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by rotary evaporation, and then a black mixture was obtained. The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and then extracted with CH2 Rinsing with Cl2 (4 x 20 mL) and then concentrating the black filtrate onto Celite and column chromatography on an ISCO Purify the hexane by silica gel chromatography using a chromatographic purification system. Bisthiophene (0.0100) was extracted as a red amorphous oil from 10% to 50% CH2Cl2 in water. Yield: 0.550 g, 0.4727 mmol, 79%). NMR showed pure product.

[0148] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to give bisthiophene (0.368 g, 0.3513 m mol, 74%, 59% 2 steps) was obtained. NMR showed pure product.

[0149] 1 H NMR (400 MHz, chloroform-d) δ 8.10 (d, J = 1.9 Hz, 4H), 7.59(dd, J=7.7, 1.7Hz, 2H), 7.43-7.35 (m, 6H), 7.28-7.21(m, 2H), 7.16(d, J=8.6Hz, 4H ), 7.13-7.06(m, 4H), 6.82(dd, J=8.3, 1.1Hz, 2H ), 4.11(dd, J=9.8, 3.3Hz, 2H), 3.93(dd, J=9.9, 4.3Hz, 2H), 1.83-1.77(m, 2H), 1.72-1.65(m, 2H) ), 1.63-1.54(m, 2H), 1.43(s, 36H), 1.15-1.00( m, 4H). 13 C NMR (101 MHz, chloroform-d) δ 153.90; 146.54, 142.61, 139.83, 130.67, 128.93, 127.6 0, 123.51, 123.12, 122.70, 122.60, 120.56, 116 .14, 115.34, 113.45, 109.42, 73.64, 40.37, 34. 68, 32.01, 29.91, 25.43.

[0150] Example 19: Synthesis of Procatalyst 5 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (9.0 mg, 8.59 μmol, 1.00 equiv.) was added to C6D of ZrBn4 (4.3 mg, 9.45 μmol, 1.10 equiv.) in 6 (0.17 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The zirconium complex was obtained as a 0.5M solution. NMR showed the product was. Using the same procedure with e, the procatalyst solution (0. 0.0025M or 0.005M) can be prepared.

[0151] 1 H NMR (500 MHz, benzene-d6) δ 8.49 (dd, J = 2.0 , 0.6Hz, 2H), 8.24(dd, J=1.9, 0.6Hz, 2H), 7.54- 7.50(m, 2H), 7.48(dd, J=8.6, 2.0Hz, 2H), 7.31( ddd, J=8.7, 2.0, 0.6Hz, 2H), 7.28(d, J=1.8Hz, 2 H), 6.98-6.96(m, 4H), 6.89(s, 2H), 6.81(tt, J= 7.4, 1.2Hz, 2H), 6.77(ddd, J=8.2, 7.4, 1.8Hz, 2 H), 6.67(td, J=7.6, 1.1Hz, 2H), 6.63-6.59(m, 2 H), 6.26-6.22(m, 4H), 5.18(dd, J=8.3, 1.1Hz, 2 H), 4.17(dd, J=12.6, 8.3Hz, 2H), 3.20(d, J=12. 6Hz, 2H), 1.51(s, 18H), 1.42-1.35(m, 2H) 1.30( s, 18H), 1.13-1.06(m, 4H), 0.76-0.69(m, 2H), 0 .65-0.58(m, 2H), 0.54(d, J=12.4Hz, 2H), 0.52- 0.44(m, 2H). 13C NMR (126MHz, benzene-d6) δ 156 .40, 152.24, 147.22, 143.15, 142.86, 139.15, 1 38.97, 131.05, 129.79, 128.30, 128.17, 127.36 , 126.40, 125.92, 125.23, 124.64, 123.12, 122. 71, 122.38, 120.71, 116.84, 116.72, 116.23, 11 5.50, 112.72, 109.26, 86.21, 75.13, 42.35, 34. 59, 34.43, 32.00, 31.80, 31.72, 29.67, 25.35.

[0152] Example 20: Synthesis of Procatalyst 6 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (9.3 mg, 8.88 μmol, 1.00 equiv.) was added to C6D of HfBn4 (5.3 mg, 9.77 μmol, 1.10 equiv.) in 6 (0.22 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.5M solution. NMR showed the product was in PhMe as the solvent. The procatalyst solution (0.0 05M) can be prepared.

[0153] 1 H NMR (500 MHz, benzene-d6) δ 8.50 (dd, J = 2.0 ,0.6Hz,2H),8.25(dd,J=2.0,0.6Hz,2H),7.48( ddd, J=15.6, 8.6, 1.9Hz, 4H), 7.29 (dd, J=8.5, 0 .6Hz, 2H), 7.26(dd, J=7.7, 1.8Hz, 2H), 7.22(dd , J=8.7, 0.6Hz, 2H), 6.99-6.96(m, 4H), 6.89(s, 2H), 6.81-6.76(m, 4H), 6.68(td, J=7.6, 1.1Hz, 2H), 6.25-6.18(m, 4H), 5.21(dd, J=8.3, 1.1Hz, 2H), 4.21(dd, J=12.6, 8.4Hz, 2H), 3.22(d, J=12 .7Hz, 2H), 1.51(s, 18H), 1.30(s, 18H), 1.14-1. 04(m, 4H), 0.91(d, J=13.4Hz, 2H), 0.74(t, J=8. 5Hz, 2H), 0.59 (d, J=12.7Hz, 2H), 0.46 (t, J=10. 0Hz, 2H), 0.25 (d, J=13.3Hz, 2H). 13 C NMR (126M Hz, ベンゼン-d6) δ 155.98, 152.30, 147.83, 143.2 0, 142.86, 139.16, 138.96, 131.06, 129.76, 128 .67, 128.57, 128.18, 127.07, 126.75, 126.12, 1 24.66, 123.30, 122.68, 122.32, 120.76, 116.87 , 116.25, 116.21, 115.44, 112.73, 109.23, 86.7 4, 78.29, 42.23, 34.60, 34.43, 32.01, 31.73, 29 .56, 25.30.

[0154] Example 21: Synthesis of Coordinator 5 [ka] Thiophene boropinacolate ester (1.644 g, 2.108 mmol, 3.0 0 equiv., 72% purity by NMR), K3PO4 (1.342 g, 6.323 mmol, 9.00 equivalents), Pd(AmPhos)Cl2 (99.0mg, 0.1405mmol, 0.20 equiv.), and bisphenyl iodide (0.433 g, 0.7026 mmol, The mixture was evacuated and then backfilled with nitrogen and the process was Repeat three more times, then add deoxygenated 1,4-dioxane (15.0 mL) and deoxygenated Hydrogenated water (1.5 mL) was then added via syringe. The mixture was then heated to 50°C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was The mixture was removed from the flask, slowly cooled to 23°C, and suction filtered over a pad of silica gel. Wash with L2 (4 × 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by rotary evaporation, and then a black mixture was obtained. The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and then extracted with CH2 Rinsing with Cl2 (4 x 20 mL) and then concentrating the black filtrate onto Celite and column chromatography on an ISCO Purify the hexane by silica gel chromatography using a chromatographic purification system. Bisthiophene (0.0100) was extracted as a red amorphous oil from 10% to 55% CH2Cl2 in water. Yield: 0.452 g, 0.3670 mmol, 52%). NMR showed pure product.

[0155] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to prepare bisthiophene (0.280 g, 0.251 g) as a transparent amorphous foam. 0 mmol, 68%, 36% 2 steps) was obtained. NMR showed pure product.

[0156] 1 H NMR (400 MHz, chloroform-d) δ 8.18-8.12 (m, 4H), 7.41(dd, J=8.6, 1.9Hz, 4H), 7.33(s, 2H), 7 .14(dd, J=8.5, 0.6Hz, 4H), 7.07(dd, J=9.2, 3.1 Hz, 2H), 6.55-6.45(m, 4H), 6.21(dd, J=9.2, 4.6 Hz, 2H), 3.72(s, 4H), 1.46(s, 36H), 1.08-0.95( m, 2H), 0.88(d, J=7.3Hz, 12H). 19 F NMR (376MHz , chloroform-d) δ -121.90 (td, J = 8.5, 4.7 Hz). 13 C NMR (101 MHz, chloroform-d) δ 157.34 (d, J = 240.5 Hz), 152.56(d, J=2.2Hz), 146.63, 142.86, 139. 79, 127.10, 123.54, 123.20, 122.96(d, J=8.5Hz ), 120.74, 116.56 (d, J=24.4Hz), 116.07, 115.0 7(d, J=23.2Hz), 114.22(d, J=1.9Hz), 114.08(d , J=8.8Hz), 109.53, 58.54, 34.72, 32.03, 17.90 , 9.71.

[0157] Example 22: Synthesis of Procatalyst 9 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, thio A clear, colorless solution of phene (9.2 mg, 8.25 μmol, 1.00 equiv.) was added to C6D6 Dissolution of ZrBn4 (4.1 mg, 9.07 μmol, 1.10 equiv.) in 100 mL of 1000 sulphuric acid (0.33 mL) The solution was added dropwise. After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained with a concentration of 0. Filter using a 20 μm PTFE submicron filter to obtain 0.00 in C6D6 The zirconium complex was obtained as a 25M solution. NMR showed the product was. Using the same procedure with e, the procatalyst solution (0. 0025M) can be prepared.

[0158] 1 H NMR (500 MHz, benzene-d6) δ 8.45 (dd, J=1.9 , 0.6Hz, 2H), 8.30(dd, J=1.9, 0.6Hz, 2H), 7.55( dd, J=8.7, 1.9Hz, 2H), 7.50(dd, J=8.5, 1.9Hz, 2 H), 7.40(dd, J=8.7, 0.7Hz, 2H), 7.33(dd, J=8.5 ,0.6Hz,2H),7.06-7.02(m,2H),6.99-6.92(m,4 H), 6.84 (s, 2H), 6.80-6.74 (m, 2H), 6.62 (ddd, J =9.0, 7.3, 3.1Hz, 2H), 6.37-6.34(m, 4H), 5.37( dd, J=9.0, 4.8Hz, 2H), 4.17 (d, J=14.7Hz, 2H), 3 .15(d, J=14.8Hz, 2H), 1.40(s, 18H), 1.28(s, 18 H), 1.12(d, J=12.5Hz, 2H), 0.58(d, J=12.5Hz, 2 H), 0.52(d, J=7.1Hz, 6H), 0.42(d, J=6.5Hz, 6H) , 0.37 (tt, J=8.0, 6.0Hz, 2H). 19 F NMR (470MHz, ベンゼン-d6) δ -115.88 (td, J=7.8, 4.5Hz). 13 CN MR (126MHz, ベンゼン-d6) δ 159.41 (d, J=245.7Hz) ,154.25,154.23,152.87,146.47,143.27(d,J= 52.4Hz), 139.70 (d, J=31.6Hz), 130.56, 128.33 , 128.16, 126.41, 125.21, 124.60, 124.12, 122. 82, 122.52, 122.29 (d, J=9.1Hz), 121.24, 119.1 1. 116.65, 116.35, 116.19 (d, J=13.2Hz), 116.0 0(d, J=13.5Hz), 115.64, 112.22, 108.99, 75.76 ,70.55,34.54,34.45,31.89,31.69,17.55,17. 51,9.44.

[0159] Example 23: Synthesis of プロcatalyst 10 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (8.9 mg, 7.98 μmol, 1.00 equiv.) was added to C6D of HfBn4 (4.8 mg, 8.78 μmol, 1.10 equiv.) in 6 (0.39 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.25M solution. NMR showed the product was Using the same procedure with e, the procatalyst solution (0. 0025M) can be prepared.

[0160] 1 H NMR (500 MHz, benzene-d6) δ 8.46 (dd, J=1.9 , 0.6Hz, 2H), 8.31(dd, J=1.9, 0.6Hz, 2H), 7.54( dd, J=8.7, 1.9Hz, 2H), 7.49(dd, J=8.5, 1.9Hz, 2 H), 7.32(ddd, J=10.9, 8.6, 0.6Hz, 4H), 6.99-6. 89(m, 6H), 6.84(s, 2H), 6.78-6.71(m, 2H), 6.65 (ddd, J=9.0, 7.3, 3.1Hz, 2H), 6.40-6.35(m, 4H) , 5.39(dd, J=9.0, 4.7Hz, 2H), 4.20(d, J=14.8Hz , 2H), 3.15(d, J=14.8Hz, 2H), 1.40(s, 18H), 1.2 8(s, 18H), 1.01(d, J=13.6Hz, 2H), 0.50(d, J=7. 1Hz, 6H), 0.40(d, J=7.1Hz, 6H), 0.39-0.30(m, 2 H), 0.27(d, J=13.6Hz, 2H). 19 F NMR (470MHz, Ben Zen-d6) δ -115.48(td, J=8.1, 4.8Hz). 13 C NMR (126MHz, benzene-d6) δ 159.61(d, J=246.2Hz), 1 53.86(d, J=2.7Hz), 152.98, 147.22, 143.32(d, J=61.0Hz), 139.69(d, J=36.3Hz), 138.52, 129. 89, 128.61, 127.17, 126.71, 124.65, 124.35, 12 2.78, 122.71 (d, J=8.9Hz), 122.46, 121.25, 119 .23, 116.32, 116.17(d, J=10.2Hz), 115.98(d, J =9.8Hz), 115.95, 115.55, 112.30, 108.98, 83.0 0, 71.02, 34.54, 34.45, 31.89, 31.69, 17.49, 17 .45, 9.50.

[0161] Example 24: Synthesis of Ligand 6 [ka] Thiophene boropinacolate ester (1.602 g, 2.077 mmol, 4.0 0 equiv., 72% purity by NMR), K3PO4 (1.323 g, 6.230 mmol, 12.0 equivalent), Pd(AmPhos)Cl2 (74.0 mg, 0.1038 mmol, 0.20 equiv.), and bisphenyl iodide (0.294 g, 0.5192 mmol, The mixture was evacuated and then backfilled with nitrogen and the process was Repeat three more times, then add deoxygenated 1,4-dioxane (10.0 mL) and deoxygenated Hydrogenated water (1.0 mL) was then added via syringe. The mixture was then heated to 50°C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was The mixture was removed from the flask, slowly cooled to 23°C, and suction filtered over a pad of silica gel. Wash with L2 (4 × 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by rotary evaporation, and then a black mixture was obtained. The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and then extracted with CH2 Rinsing with Cl2 (4 x 20 mL) and then concentrating the black filtrate onto Celite and column chromatography on an ISCO Purify the hexane by silica gel chromatography using a chromatographic purification system. Impure bismuth was obtained as a pale yellow amorphous foam with 10% to 55% CH2Cl2 in hexane. NMR showed the product to be impure. The correct material was used in the subsequent reaction.

[0162] Impure HCl in CH2Cl2-1,4-dioxane (6 mL, 1:1) at 23 °C under nitrogen To the solution of the coupled product was added concentrated HCl (3 mL). The amber solution was stirred for 20 h (5 00 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. Extract from the aqueous solution using CH2Cl2 (2 × 10 mL), mix, and add solid Na2SO The mixture was dried at 4°C, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. Purify by silica gel chromatography through a gel column and eluate in 10% to 75% CH2 in hexane. Cl2 produced bisthiophene (0.100 g, 0.0861 g) as a transparent amorphous foam. 7 mmol, 17% 2 steps) was obtained. NMR showed pure product.

[0163] 1 H NMR (500 MHz, chloroform-d) δ 8.16 (dd, J=1. 9, 0.6Hz, 4H), 7.42(dd, J=8.6, 1.9Hz, 4H), 7.35 (s, 2H), 7.17(dd, J=8.6, 0.7Hz, 4H), 7.12(dd, J =9.2, 3.1Hz, 2H), 6.71(s, 2H), 6.56(ddd, J=9.0 , 7.7, 3.1Hz, 2H), 6.34(dd, J=9.2, 4.6Hz, 2H), 3 .94(s, 4H), 1.47(s, 36H), 1.39-1.29(m, 2H), 0. 94(d, J=7.5Hz, 12H). 19 F NMR (470MHz, chloroform- d) δ -121.59(td, J=8.4, 4.6Hz). 13 C NMR(126 MHz, chloroform-d) δ 157.50(d, J=240.5Hz), 152. 50, 146.74, 142.85, 139.78, 127.26, 123.55, 12 3.25(d, J=9.3Hz), 123.21, 120.73, 116.49(d, J =24.6Hz), 116.08, 115.02(d, J=22.9Hz), 114.5 0(d, J=8.9Hz), 114.22(m), 109.59, 60.00, 34.7 3, 32.04, 19.34, 13.91.

[0164] Example 25: Synthesis of procatalyst 11 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (5.0 mg, 4.31 μmol, 1.00 equiv.) was added to C6 ZrBn4 (2.2 mg, 4.74 μmol, 1.10 equiv) in D6 (0.33 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. Filter using a 0.20 μm PTFE submicron filter to obtain 0. The zirconium complex was obtained as a 0.25M solution. NMR showed the product was P Using the same procedure with hMe, the procatalyst solution used immediately after the filtration of the polymerization experiment ( 0.0025M) can be prepared.

[0165] 1 H NMR (500 MHz, benzene-d6) δ 8.45 (dd, J=1.9 , 0.6Hz, 2H), 8.30(dd, J=2.0, 0.6Hz, 2H), 7.54( dd, J=8.7, 1.9Hz, 2H), 7.49(dd, J=8.5, 1.9Hz, 2 H), 7.38(dd, J=8.7, 0.6Hz, 2H), 7.31(dd, J=8.5 , 0.6Hz, 2H), 7.07-7.02(m, 2H), 6.99-6.95(m, 4 H), 6.83(s, 2H), 6.77(tt, J=7.3, 1.2Hz, 2H), 6. 61(ddd, J=9.0, 7.3, 3.2Hz, 2H), 6.37-6.34(m, 4 H), 5.42(dd, J=9.0, 4.7Hz, 2H), 4.32(d, J=13.0 Hz, 2H), 3.33(d, J=13.0Hz, 2H), 1.40(s, 18H), 1 .28(s, 18H), 1.17(d, J=12.5Hz, 2H), 0.71(dp, J =14.1, 6.9Hz, 2H), 0.60(d, J=7.2Hz, 6H), 0.57( d, J=12.5Hz, 2H), 0.51(d, J=7.3Hz, 6H). 19 F.N.M. R(470MHz, benzene-d6) δ -115.87(td, J=8.0, 4.8 Hz). 13 C NMR (126 MHz, benzene-d6) δ 159.44 (d, J =245.5Hz), 154.21, 154.19, 152.80, 146.62, 14 3.27(d, J=53.0Hz), 139.67(d, J=30.0Hz), 130. 56, 128.33, 128.16, 126.33, 125.24, 124.59, 12 2.81, 122.51, 121.20, 119.01, 116.58(m), 116. 35, 116.19(d, J=17.8Hz), 116.01(d, J=16.9Hz) , 115.62, 112.27, 108.98, 76.05, 71.65, 34.53, 34.45, 31.89, 31.70, 19.18, 19.13, 13.59.

[0166] Example 26: Synthesis of procatalyst 12 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (5.2 mg, 4.48 μmol, 1.00 equiv.) was added to C6D of HfBn4 (2.7 mg, 4.93 μmol, 1.10 equiv.) in 6 (0.22 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.25M solution. NMR showed the product was Using the same procedure with e, the procatalyst solution (0. 0025M) can be prepared.

[0167] 1 H NMR (500 MHz, benzene-d6) δ 8.46 (dd, J = 2.0 , 0.6Hz, 2H), 8.31(dd, J=1.9, 0.6Hz, 2H), 7.53( dd, J=8.7, 1.9Hz, 2H), 7.48(dd, J=8.5, 1.9Hz, 2 H), 7.30(ddd, J=11.7, 8.6, 0.6Hz, 4H), 6.99-6. 94(m, 4H), 6.82(s, 2H), 6.78-6.73(m, 2H), 6.65 (ddd, J=9.0, 7.2, 3.1Hz, 2H), 6.52-6.48(m, 2H) , 6.40-6.35(m, 4H), 5.44(dd, J=9.0, 4.8Hz, 2H) , 4.36(d, J=13.0Hz, 2H), 3.33(d, J=13.1Hz, 2H) , 1.40(s, 18H), 1.28(s, 18H), 1.03(d, J=13.5Hz , 2H), 0.68(dq, J=14.1, 7.2Hz, 2H), 0.58(d, J=7 .3Hz, 6H), 0.49(d, J=7.3Hz, 6H), 0.28(d, J=13. 7Hz, 2H). 19 F NMR (470MHz, benzene-d6) δ -114.3 5--117.32(m).13 C NMR (126MHz, benzene-d6) δ 1 59.63(d, J=246.1Hz), 153.86(d, J=2.5Hz), 152 .93, 147.26, 143.32(d, J=61.1Hz), 139.67(d, J =33.6Hz), 129.89, 128.58, 128.18, 127.17, 126 .70, 125.31, 124.49(d, J=34.8Hz), 123.03(d, J =9.2Hz), 122.78, 122.45, 121.24, 119.15, 116. 32, 116.16(d, J=13.5Hz), 115.98(d, J=13.4Hz) , 115.90, 115.88, 115.53, 112.32, 108.97, 83.0 0, 72.10, 34.53, 34.45, 31.88, 31.70, 19.13, 19 .07, 13.67.

[0168] Example 27: Synthesis of Ligand 7 [ka] Thiophene boropinacolate ester (0.605 g, 0.5387 mmol, 2. 70 equiv., 50% purity by NMR, K3PO4 (0.343 g, 1.616 mmol , 8.10 eq.), Pd(AmPhos)Cl2 (28.3 mg, 0.0399 mmol , 0.20 equiv.), and bisphenyl iodide (0.143 g, 0.2000 mmol The mixture was evacuated and then backfilled with nitrogen to complete the process. was repeated three more times, followed by deoxygenated 1,4-dioxane (4.0 mL) and deoxygenated Hydrogenated water (0.4 mL) was then added via syringe. The mixture was then heated to 50°C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was The mixture was removed from the flask, slowly cooled to 23°C, and suction filtered over a pad of silica gel. Wash with L2 (4 × 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by rotary evaporation, and then a black mixture was obtained. The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and then extracted with CH2 Rinsing with Cl2 (4 x 20 mL) and then concentrating the black filtrate onto Celite and column chromatography on an ISCO Purify the hexane by silica gel chromatography using a chromatographic purification system. Bisthiophene was prepared as an off-white solid by 10% to 50% CH2Cl2 in water. (0.168 g). NMR showed the product to contain a small amount of impurity. and used for subsequent deprotection without further purification.

[0169] Impure HCl in CH2Cl2-1,4-dioxane (8 mL, 1:1) at 23 °C under nitrogen To the solution of the coupled product was added concentrated HCl (4 mL). The amber solution was stirred for 20 h (5 00 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. Extract from the aqueous solution using CH2Cl2 (2 × 10 mL), mix, and add solid Na2SO The mixture was dried at 4°C, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. Purify by silica gel chromatography through a gel column and eluate in 10%-50% CH2 in hexane. The bisthiophene (80.0 mg, 0.0657 mmHg) was obtained as a light tan solid by Cl2. ol, 33% 2 steps) was obtained. NMR showed pure product.

[0170] 1 H NMR (400 MHz, chloroform-d) δ 8.11 (d, J = 1.9 Hz, 4H), 7.57(d, J=2.3Hz, 2H), 7.47(s, 2H), 7.4 1(dd, J=8.7, 1.9Hz, 4H), 7.31(s, 2H), 7.27-7.2 0(m, 4H), 6.78(d, J=8.6Hz, 2H), 4.07-3.97(m, 4 H), 1.93-1.85(m, 4H), 1.77(s, 4H), 1.44(s, 36H) ), 1.40(s, 12H), 0.77(s, 18H). 13 C NMR (101MHz , chloroform-d) δ 151.42, 146.28, 144.75, 142.58 , 139.67, 128.29, 127.66, 126.52, 123.39, 123. 14, 121.99, 119.81, 116.16, 116.04, 113.38, 10 9.61, 69.95, 56.86, 38.19, 34.69, 32.41, 32.05 , 31.91, 31.62, 25.90.

[0171] Example 28: Synthesis of procatalyst 13 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (7.4 mg, 6.08 μmol, 1.00 equiv.) was added to C6D of ZrBn4 (3.0 mg, 6.69 μmol, 1.10 equiv.) in 6 (0.13 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The zirconium complex was obtained as a 0.5M solution. NMR showed the product was. Using the same procedure with e, the procatalyst solution (0. 005M) can be prepared.

[0172] 1 H NMR (400 MHz, benzene-d6) δ 8.55 (d, J = 1.9H z, 2H), 8.15-8.11(m, 2H), 7.57(d, J=2.5Hz, 2H) , 7.51(dd, J=8.6, 1.9Hz, 2H), 7.43(dd, J=8.7, 1 .9Hz, 2H), 7.34(d, J=8.4Hz, 2H), 7.21(dd, J=8. 7, 0.6Hz, 2H), 7.09-7.04(m, 2H), 7.03-6.97(m, 2H), 6.98-6.94(m, 2H), 6.84(s, 2H), 6.86-6.81 (m, 2H), 6.24-6.17(m, 4H), 5.17(d, J=8.7Hz, 2H ), 4.08-3.98(m, 2H), 3.42-3.34(m, 2H), 1.68(d , J=14.6Hz, 2H), 1.57(s, 18H), 1.51(d, J=14.6H z, 2H), 1.23(s, 18H), 1.20(s, 6H), 1.16(s, 6H), 1.02(d, J=12.3Hz, 2H), 0.89(q, J=11.9, 10.7Hz , 2H), 0.70(s, 18H), 0.64-0.56(m, 2H), 0.52(d, J = 12.3 Hz, 2H). 13 C NMR (101MHz, benzene-d6) δ 1 53.93, 152.24, 148.83, 147.09, 142.92, 142.61 , 139.23, 139.15, 130.55, 128.65, 128.35, 128. 32, 126.79, 126.61, 124.62, 124.10, 122.79, 12 2.65, 122.26, 120.58, 74.94, 72.00, 56.54, 38. 25, 34.66, 34.36, 32.13, 32.10, 31.71, 31.66, 3 0.04, 25.93.

[0173] Example 29: Synthesis of procatalyst 14 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (8.3 mg, 6.82 μmol, 1.00 equiv.) was added to C6D of HfBn4 (4.1 mg, 7.50 μmol, 1.10 equiv) in 6 (0.17 mL) The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.5M solution. NMR showed the product was in PhMe as the solvent. The procatalyst solution (0.0 05M) can be prepared.

[0174] 1 H NMR (500 MHz, benzene-d6) δ 8.57 (dd, J=1.9 , 0.6Hz, 2H), 8.15(dd, J=2.0, 0.7Hz, 2H), 7.58( d, J=2.5Hz, 2H), 7.52(dd, J=8.5, 1.9Hz, 2H), 7. 42(dd, J=8.7, 1.9Hz, 2H), 7.33(dd, J=8.5, 0.6H z, 2H), 7.14-7.07(m, 6H), 7.05-7.02(m, 2H), 6. 85(s, 2H), 6.82(tt, J=7.3, 1.2Hz, 2H), 6.24-6. 18(m, 4H), 5.21(d, J=8.7Hz, 2H), 4.15-4.06(m, 2H), 3.50-3.41(m, 2H), 1.69(d, J=14.6Hz, 2H), 1.59(s, 18H), 1.53(d, J=14.7Hz, 2H), 1.25(s, 1 8H), 1.22(s, 6H), 1.17(s, 6H), 0.92(t, J=9.5Hz ,2H),0.84(d,J=13.2Hz,2H),0.72(s,18H),0.5 9-0.51 (m, 2H), 0.27 (d, J=13.2Hz, 2H). 13 C NMR (126MHz, ベンゼン-d6) δ 153.62, 152.32, 149.13, 147.76, 142.98, 142.63, 139.24, 139.11, 128.7 3. 128.66, 128.04, 127.05, 126.99, 126.92, 125 .36, 124.67, 122.99, 122.61, 122.21, 120.63, 1 16.95, 116.79, 116.28, 115.61, 112.50, 108.93 , 81.86, 77.99, 56.54, 38.31, 34.68, 34.37, 32. 15, 32.12, 31.68, 31.65, 30.04, 26.03.

[0175] Example 30: Synthesis of ビス-t-オクチル-ヨードフェニルエーテル intermediate

change

[0176] 1 H NMR (500 MHz, chloroform-d) δ 7.73 (d, J = 2.4 Hz, 2H), 7.28-7.24(m, 2H), 6.73(d, J=8.6Hz, 2H ), 4.14-4.06(m, 4H), 2.14-2.06(m, 4H), 1.68(s , 4H), 1.32(s, 12H), 0.73(s, 18H). 13 C NMR(126 MHz, chloroform-d) δ 155.12, 144.49, 137.18, 127 .03, 111.29, 86.27, 68.68, 56.87, 37.89, 32.35 , 31.83, 31.57, 26.11.

[0177] Example 31: Synthesis of 4-t-octyl-2-iodophenol [ka] Dissolve the starting phenol (3. 324g, 16.110mmol, 1.00 eq), KI (3.477g, 20.943 mmol, 1.30 equiv.), and aqueous NaOH (21 mL, 20.943 mmol, A clear, colorless solution of 1.30 equiv., 1N) was placed in an ice bath and stirred vigorously for 1 h, after which it was cooled to room temperature. Chilled commercial aqueous bleach (26 mL, 20.943 mmol, 1.30 equiv., 5.2% w / w) was added dropwise over a period of 10 minutes, at which point a pale opaque yellow mixture was formed. The mixture was stirred at 0 °C for 2 h, removed from the ice-water bath and stirred at 23 °C for 3 h. Solid N aH2PO4 (20 g) was added, followed by a saturated aqueous mixture of Na2S2O3 (100 mL). was added to reduce residual iodine and water (100 mL) was added, and the mixture was stirred vigorously for 10 min. Stir, dilute with CH2Cl2 (50 mL), pour the biphasic yellow mixture into a separatory funnel, and separate. The organic matter was washed with aqueous NaSO (2 x 50 mL) and the remaining organic matter was dissolved in CH The aqueous layer was extracted with I2 (2 x 50 mL), mixed, and dried over solid Na2SO4. Decant, concentrate onto Celite, and purify by silica gel chromatography using hexane- o-Iodophenol (3.25%) was extracted with 25% CH2Cl2 as a clear, colorless, amorphous foam. Yield: 240 g, 9.340 mmol, 58%). NMR showed pure product.

[0178] 1 H NMR (500 MHz, chloroform-d) δ 7.60 (d, J = 2.3 Hz, 1H), 7.24(dd, J=8.5, 2.3Hz, 1H), 6.90(dd, J =8.6, 0.5Hz, 1H), 5.11(s, 1H), 1.68(s, 2H), 1.3 2(s,6H), 0.73(s,9H). 13 C NMR (126 MHz, chloroform -d) δ 152.34, 144.65, 135.66, 128.14, 114.23 , 85.38, 56.87, 37.93, 32.35, 31.81, 31.55.

[0179] Example 32: Synthesis of Ligand 8 [ka] Thiophene boropinacolate ester (2.017 g, 2.586 mmol, 3.0 0 equiv., 72% purity by NMR), K3PO4 (1.647 g, 7.758 mmol, 9.00 equivalents), Pd(AmPhos)Cl2 (122.0mg, 0.1724mmol , 0.20 equiv.), and bisphenyl iodide (0.478 g, 0.8620 mmol The mixture was evacuated and then backfilled with nitrogen to complete the process. This was repeated three more times, followed by deoxygenated 1,4-dioxane (17.0 mL) and deoxygenated Oxygenated water (1.7 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. Remove from the torch, slowly cool to 23°C, suction filter over a pad of silica gel, and dilute with CH2 Wash with Cl2 (4 x 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. The was azeotropically removed using toluene (2×10 mL) by rotary evaporation, and then the black The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and The black filtrate was then concentrated onto Celite and washed with ISC Purify the mixture by silica gel chromatography using a HeO chromatography purification system. Bisthiophene ( 0.747g, 0.6387mmol, 74%) was obtained. NMR showed pure product. .

[0180] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to give bisthiophene (0.514 g, 0.4879 m mol, 76%, 57% 2 steps) was obtained. NMR showed pure product.

[0181] 1 H NMR (500 MHz, chloroform-d) δ 8.14 (d, J = 1.9 Hz, 4H), 7.68(s, 2H), 7.42(dd, J=8.6, 1.9Hz, 4H ), 7.35(s, 2H), 7.25(d, J=8.6Hz, 4H), 7.14(d, J =2.9Hz, 2H), 6.84(d, J=9.0Hz, 2H), 6.79(dd, J= 8.9, 2.9Hz, 2H), 3.99(q, J=3.5, 2.1Hz, 4H), 3.8 4(s, 6H), 1.83(q, J=2.8Hz, 4H), 1.46(s, 36H). 1 3 C NMR (126 MHz, chloroform-d) δ 155.34, 147.83, 146.76, 142.68, 139.64, 127.76, 124.50, 123.4 5, 123.19, 120.26, 120.23, 116.56, 116.20, 115 .24, 115.18, 113.95, 109.61, 71.38, 55.77, 34. 71, 32.05, 25.85.

[0182] Example 33: Synthesis of procatalyst 15 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (7.4 mg, 7.02 μmol, 1.00 equiv.) was added to C6D of ZrBn4 (3.7 mg, 7.72 μmol, 1.10 equiv.) in 6 (0.16 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The zirconium complex was obtained as a 0.5M solution. NMR showed the product was. Using the same procedure with e, the procatalyst solution (0. 0.0025M or 0.005M) can be prepared.

[0183] 1H NMR (400MHz, ベンゼン-d6) δ 8.47 (dd, J=2.0 ,0.6Hz,2H),8.24(dd,J=1.9,0.6Hz,2H),7.49( td, J=8.6, 1.9Hz, 4H), 7.30 (ddd, J=8.5, 5.3, 0. 6Hz, 4H), 7.08-7.03 (m, 2H), 6.96 (dtd, J=6.9, 1 .4, 0.7Hz, 2H), 6.92 (d, J=3.1Hz, 2H), 6.84 (s, 2 H), 6.78(tt, J=7.3, 1.3Hz, 2H), 6.45(dd, J=9.1 ,3.1Hz,2H),6.31-6.26(m,4H),5.04(d,J=9.1H z, 2H), 3.95-3.85 (m, 2H), 3.28-3.19 (m, 2H), 3. 16(s, 6H), 1.47(s, 18H), 1.27(s, 18H), 1.08(d, J=12.3Hz, 2H), 0.88-0.74 (m, 2H), 0.58 (d, J=12 .3Hz, 2H), 0.56-0.51(m, 2H). 13 C NMR (101MHz, ベンゼン-d6) δ 157.39, 152.38, 149.56, 147.35, 1 43.13, 142.70, 139.32, 139.16, 128.21, 128.19 , 128.15, 126.46, 125.20, 124.57, 124.45, 122. 63, 122.35, 120.62, 117.06, 116.85, 116.29, 11 5.68, 115.54, 114.96, 112.51, 108.91, 81.18, 7 5.06, 54.73, 34.55, 34.42, 31.99, 31.72, 25.92 .

[0184] Example 34: Synthesis of プロcatalyst 16

change

[0185] 1 H NMR (500 MHz, benzene-d6) δ 8.50 (dd, J = 2.0 , 0.6Hz, 2H), 8.26(dd, J=1.9, 0.6Hz, 2H), 7.50( dd, J=2.5, 1.9Hz, 2H), 7.48(t, J=2.1Hz, 2H), 7. 29(dd, J=8.5, 0.6Hz, 2H), 7.23(dd, J=8.7, 0.6H z, 2H), 6.99-6.95(m, 2H), 6.93(d, J=3.1Hz, 2H) , 6.85(s, 2H), 6.79-6.74(m, 2H), 6.52-6.44(m, 4H), 6.32-6.28(m, 4H), 5.09(d, J=9.0Hz, 2H), 4 .02-3.92(m, 2H), 3.33-3.25(m, 2H), 3.17(s, 6H) ), 1.48(s, 18H), 1.29(s, 18H), 0.92(d, J=13.3H z, 2H), 0.85-0.77(m, 2H), 0.55(m, 2H), 0.31(d, J = 13.3 Hz, 2H). 13 C NMR (126MHz, benzene-d6) δ 1 57.52, 152.44, 149.28, 148.02, 143.20, 142.73 , 139.32, 139.12, 129.89, 128.60, 128.57, 128. 03, 127.04, 126.83, 124.63, 124.35, 122.58, 12 2.30, 120.69, 117.13, 116.30, 115.70, 115.48, 114.96, 112.58, 108.91, 83.01, 78.24, 54.76, 3 4.57, 34.43, 32.00, 31.73, 26.04.

[0186] Example 35: Synthesis of bis-4-methoxy-2-iodophenyl ether [ka] 2-Iodophenol (1. 890g, 7.559mmol, 2.00 eq), K2CO3 (3.134g, 22.6 77 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.45 mL, 3.7 A white heterogeneous mixture of 1.00 eq. (79 mmol) was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 36 hours, the white heterogeneous mixture was removed from the mantle. Cool to 23 °C, dilute with CH2Cl2 (50 mL), stir for 2 min, and pad with Celite. The pale yellow filtrate was filtered over a filter paper and rinsed with CH2Cl2 (4 x 20 mL). The mixture was concentrated onto a light source and then purified by silica gel chromatography using an ISCO chromatographic purification system. The product was purified by chromatography using 50-100% CH2Cl2 in hexane to give a white solid. As a result, 1.945 g (3.510 mmol, 93%) of iodophenyl ether was obtained. NMR showed a pure product.

[0187] 1 H NMR (500 MHz, chloroform-d) δ 7.32 (d, J = 2.9 Hz, 2H), 6.84(dd, J=8.9, 3.0Hz, 2H), 6.76(d, J= 8.9Hz, 2H), 4.11-3.99(m, 4H), 3.75(s, 6H), 2.1 3-2.01(m, 4H). 13 C NMR (126MHz, chloroform-d) δ 154.26, 152.05, 124.61, 114.78, 113.06, 86.94 , 69.58, 55.92, 26.15.

[0188] Example 36: Synthesis of 4-methoxy-2-iodophenol [ka] The starting phenol (5 mL) was dissolved in methanol (300 mL) and water (200 mL) under nitrogen. .000g, 40.277mmol, 1.00eq), KI(7.020g, 42.29 1 mmol, 1.05 equiv.), and aqueous NaOH (201 mL, 201.39 mmol). A clear, colorless solution of 1.00 g of 1N (1, 5.00 equiv., 1N) was placed in an ice bath and stirred vigorously for 1 h, after which , pre-chilled commercial aqueous bleach (61 mL, 42.291 mmol, 1.05 equiv., 5.2 % w / w) was added dropwise over a period of 30 minutes, at which point the dark orange mixture was cooled to 0°C. The mixture was stirred at RT for 30 min, removed from the ice-water bath, and solid NaH2PO4 (30 g) was added. Addition of Na2S2O3 (200 mL) followed by addition of aqueous Na2S2O3 (200 mL) removed residual iodine and water (2 The mixture was stirred vigorously for 10 min and diluted with CH2Cl2 (50 mL). The biphasic dark red-orange mixture was poured into a separatory funnel, the layers were separated, and the organics were diluted with Na2S2O3 aqueous solution. solution (2 × 50 mL) and the remaining organics were washed with CH2Cl2 (2 × 50 mL). The aqueous layers were extracted, combined, dried over solid Na2SO4, decanted, and concentrated to give a red-brown A viscous oil was obtained. NMR showed the starting phenol and observable products in small amounts. It shows a SM:product mixture of about 70:30, with other decomposition adducts present. Crude mixture was dissolved in CH2Cl2, concentrated onto Celite, and purified by silica gel chromatography. 25% CH2Cl2-100% CH2Cl2 in hexane produces a pale purple amorphous foam O-Iodophenol (0.877 g, 3.508 mmol, 9%) as a cation, and recovered The starting phenol (1.277 g, 10.287 mmol, 26%) was obtained. Showed pure product.

[0189] 1 H NMR (500 MHz, chloroform-d) δ 7.18 (d, J = 2.9 Hz, 1H), 6.90(d, J=8.9Hz, 1H), 6.83(dd, J=8.9, 2.9Hz, 1H), 5.00(s, 1H), 3.74(s, 3H). 13 C NMR( 126MHz, chloroform-d) δ 153.93, 149.17, 122.66, 116.37, 115.13, 85.07, 55.99.

[0190] Example 37: Synthesis of ligand 9 [ka] Thiophene boropinacolate ester (0.605 g, 0.5387 mmol, 2. 70 equiv., 50% purity by NMR, K3PO4 (0.343 g, 1.616 mmol , 8.10 eq.), Pd(AmPhos)Cl2 (28.3 mg, 0.0399 mmol , 0.20 equiv.), and bisphenyl iodide (0.106 g, 0.1995 mmol The mixture was evacuated and then backfilled with nitrogen to complete the process. was repeated three more times, followed by deoxygenated 1,4-dioxane (4.0 mL) and deoxygenated Hydrogenated water (0.4 mL) was then added via syringe. The mixture was then heated to 50°C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was The mixture was removed from the flask, slowly cooled to 23°C, and suction filtered over a pad of silica gel. Wash with L2 (4 × 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by rotary evaporation, and then a black mixture was obtained. The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and then extracted with CH2 Rinsing with Cl2 (4 x 20 mL) and then concentrating the black filtrate onto Celite and column chromatography on an ISCO Purify the hexane by silica gel chromatography using a chromatographic purification system. Bisthiophene was prepared as an off-white solid by 10% to 50% CH2Cl2 in water. (0.101 g). NMR showed the product to contain a small amount of impurity. and used for subsequent deprotection without further purification.

[0191] Impure HCl in CH2Cl2-1,4-dioxane (6 mL, 1:1) at 23 °C under nitrogen To the solution of the coupled product was added concentrated HCl (3 mL). The amber solution was stirred for 20 h (5 00 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. Extract from the aqueous solution using CH2Cl2 (2 × 10 mL), mix, and add solid Na2SO The mixture was dried at 4°C, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. Purify by silica gel chromatography through a gel column and eluate in 10% to 75% CH2 in hexane. Cl2 produced bisthiophene (52.0 mg, 0.05052 m mol, 25% 2 steps) was obtained. NMR showed pure product.

[0192] 1 H NMR (400 MHz, chloroform-d) δ 8.10 (d, J = 1.9 Hz, 4H), 7.43-7.29(m, 8H), 7.25(d, J=10.3Hz, 2 H), 7.19(d, J=8.6Hz, 4H), 6.90(td, J=8.2, 7.5, 3.0Hz, 2H), 6.80(dd, J=9.1, 4.6Hz, 2H), 4.01(d , J=4.8Hz, 4H), 1.92-1.81(m, 4H), 1.42(s, 36H) . 19 F NMR (376 MHz, chloroform-d) δ -120.34 (td, J =8.5, 4.7Hz). 13 C NMR (101MHz, chloroform-d) δ 1 58.08(d, J=241.4Hz), 149.83(d, J=2.3Hz), 146 .99, 142.85, 139.52, 127.55, 124.80(d, J=8.6H z), 123.50, 123.21, 120.82, 116.56(d, J=24.7H z), 116.24, 115.69(d, J=8.8Hz), 114.72(d, J=2 3.3Hz), 114.00(d, J=1.8Hz), 109.47, 70.96, 34 .68, 31.99, 25.83.

[0193] Example 38: Synthesis of procatalyst 17 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, thiocyanate was dissolved in 1.61 mL of anhydrous C6D6. A clear, colorless solution of thiophene (9.2 mg, 8.94 μmol, 1.00 equiv.) was added to C6D of ZrBn4 (4.5 mg, 9.83 μmol, 1.10 equiv.) in 6 (0.18 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The zirconium complex was obtained as a 0.5M solution. NMR showed the product was. Using the same procedure with e, the procatalyst solution (0. 005M) can be prepared.

[0194] 1 H NMR (500 MHz, benzene-d6) δ 8.42 (dd, J = 2.0 , 0.6Hz, 2H), 8.28(dd, J=1.9, 0.7Hz, 2H), 7.51( dd, J=8.7, 1.9Hz, 2H), 7.44(dd, J=8.5, 1.9Hz, 2 H), 7.33(dd, J=8.7, 0.6Hz, 2H), 7.21(dd, J=8.5 , 0.7Hz, 2H), 7.01-6.95(m, 2H), 6.83(s, 2H), 6. 79-6.74(m,2H),6.50(ddd,J=9.0,7.4,3.2Hz,4 H), 6.36-6.32(m, 2H), 6.27-6.23(m, 4H), 4.99( dd, J=9.0, 4.8Hz, 2H), 3.87-3.75(m, 2H), 3.11( dd, J=11.8, 4.6Hz, 2H), 1.43(s, 18H), 1.30(s, 1 8H), 1.02(d, J=12.4Hz, 2H), 0.98-0.82(m, 2H), 0.75-0.63 (m, 2H), 0.52 (d, J=12.3Hz, 2H). 19 F NMR (470MHz, ベンゼン-d6) δ -114.74--117.39(m) . 13 C NMR (126MHz, ベンゼン-d6) δ 159.84 (d, J=24 6.8Hz), 152.62, 151.81 (d, J=2.6Hz), 146.41, 1 43.19(d, J=49.2Hz), 139.19(d, J=20.1Hz), 130 .56, 128.33, 128.06, 126.53, 125.18, 124.92(d , J=8.9Hz), 124.30(d, J=47.3Hz), 122.56(d, J= 38.4Hz), 121.16, 118.06, 116.69 (d, J=47.1Hz) , 116.69, 115.98 (d, J=91.0Hz), 115.83 (d, J=1. 9Hz), 112.30, 108.75, 74.98, 72.01, 34.52, 34. 45, 31.94, 31.72, 25.71.

[0195] Example 39: Synthesis of プロcatalyst 18

change

[0196] 1 H NMR (500 MHz, benzene-d6) δ 8.43 (dd, J = 2.0 , 0.6Hz, 2H), 8.29(dd, J=1.9, 0.6Hz, 2H), 7.49( dd, J=8.7, 1.9Hz, 2H), 7.44(dd, J=8.5, 1.9Hz, 2 H), 7.24(dd, J=8.7, 0.6Hz, 2H), 7.19(dd, J=8.5 , 0.6Hz, 2H), 7.02-6.96(m, 2H), 6.94-6.90(m, 2 H), 6.82(s, 2H), 6.75(tt, J=7.5, 1.3Hz, 2H), 6. 55-6.47(m, 4H), 6.30-6.25(m, 4H), 5.01(dd, J= 9.0, 4.8Hz, 2H), 3.89-3.78(m, 2H), 3.15(dd, J= 12.4, 4.7Hz, 2H), 1.43(s, 18H), 1.30(s, 18H), 0 .90(d, J=13.4Hz, 2H), 0.73-0.62(m, 2H), 0.49- 0.40(m, 2H), 0.24(d, J=14.0Hz, 2H). 19 F NMR(4 70MHz, benzene-d6) δ -115.11--115.24(m). 13 C NMR (126MHz, benzene-d6) δ 159.97 (d, J = 247.4Hz ), 152.66, 151.46(d, J=2.7Hz), 147.32, 143.24 (d, J=55.5Hz), 139.14(d, J=26.6Hz), 138.52, 1 30.56, 128.38 (d, J=11.1Hz), 127.15, 126.72, 1 24.55, 124.35, 122.64, 122.33, 121.13, 118.09 , 116.76(d, J=23.4Hz), 116.46(d, J=23.3Hz), 1 16.32, 115.52, 115.27, 112.43, 108.74, 82.00, 78.84, 34.52, 34.46, 31.94, 31.72, 25.86.

[0197] Example 40: Synthesis of ligand 10 [ka] Thiophene boropinacolate ester (0.605 g, 0.5387 mmol, 2. 70 equiv., 50% purity by NMR, K3PO4 (0.343 g, 1.616 mmol , 8.10 eq.), Pd(AmPhos)Cl2 (28.3 mg, 0.0399 mmol , 0.20 equiv.), and bisphenyl iodide (0.113 g, 0.1995 mmol The mixture was evacuated and then backfilled with nitrogen to complete the process. This was repeated three more times, followed by deoxygenated 1,4-dioxane (10.0 mL) and deoxygenated Oxygenated water (1.0 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. Remove from the torch, slowly cool to 23°C, suction filter over a pad of silica gel, and dilute with CH2 Wash with Cl2 (4 x 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. The was azeotropically removed using toluene (2×10 mL) by rotary evaporation, and then the black The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and The black filtrate was then concentrated onto Celite and washed with ISC Purify the mixture by silica gel chromatography using a HeO chromatography purification system. Impure bisthiophene was obtained as a pale red foam from 10% to 60% CH2Cl2 in xanthene. The resulting product was 0.154 g of phenylene. NMR showed the product to be impure. The material was used in subsequent reactions.

[0198] Impure HCl in CH2Cl2-1,4-dioxane (6 mL, 1:1) at 23 °C under nitrogen To the solution of the coupled product was added concentrated HCl (3 mL). The amber solution was stirred for 20 h (5 00 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. Extract from the aqueous solution using CH2Cl2 (2 × 10 mL), mix, and add solid Na2SO The mixture was dried at 4°C, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. Purify by silica gel chromatography through a gel column and eluate in 10% to 75% CH2 in hexane. Cl2 produced bisthiophene (0.105 g, 0.0985 g) as a transparent amorphous foam. 6 mmol, 49% 2 steps) was obtained. NMR showed pure product.

[0199] 1 H NMR (400 MHz, chloroform-d) δ 8.12 (dd, J=1. 9, 0.6Hz, 4H), 7.56(dd, J=11.4, 8.8Hz, 2H), 7.3 9(dd, J=8.6, 1.9Hz, 4H), 7.30(s, 2H), 7.17(dd, J=8.6, 0.6Hz, 4H), 6.74(dd, J=11.4, 6.8Hz, 2H) , 6.54(s, 2H), 4.06-3.97(m, 4H), 1.95(p, J=2.5 Hz, 4H), 1.42(s, 36H). 19 F NMR (376 MHz, chloroform -d) δ -135.22(ddd, J=22.5, 11.5, 8.8Hz), -14 4.91(ddd, J=22.2, 11.2, 6.8Hz). 13 C NMR (101M Hz, chloroform-d) δ 150.19-149.71(m), 149.36(d d, J=250.5, 13.9Hz), 146.75-144.02(m), 146.5 5, 143.08, 139.43, 127.14, 123.61, 123.29, 120 .52, 119.32-118.89(m), 118.15(d, J=20.6Hz), 116.34, 112.97, 109.37, 103.52 (d, J=20.8Hz), 70.59, 34.70, 31.97, 25.83.

[0200] Example 41: Synthesis of procatalyst 19 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (11.2 mg, 10.51 μmol, 1.00 equiv.) was added to C ZrBn4 (5.3 mg, 11.56 μmol, 1.10 equiv.) in 6D6 (0.42 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. The solution was filtered using a 0.20 μm PTFE submicron filter to obtain C6D6 The zirconium complex was obtained as a 0.0025M solution. NMR showed the product. The procatalyst solution used immediately after the polymerization experiment was filtered using the same procedure with PhMe. A 0.0025M or 0.005M solution can be prepared. By slowly evaporating the solution, the zirconium complex crystallizes, and the crystals are analyzed by X-ray diffraction. Diffraction was used to evaluate and clearly confirm the structure.

[0201] 1 H NMR (500 MHz, benzene-d6) δ 8.55 (d, J = 1.9H z, 1H), 8.46(d, J=1.9Hz, 1H), 8.39(t, J=1.3Hz, 1H), 8.33(dd, J=2.0, 0.7Hz, 1H), 7.58(d, J=1.3 Hz, 2H), 7.52(ddd, J=8.5, 6.7, 1.9Hz, 3H), 7.47 (dd, J=8.7, 0.7Hz, 1H), 7.23-7.20(m, 2H), 7.08 -7.02(m, 3H), 6.96-6.94(m, 2H), 6.93(s, 1H), 6 .82(s, 1H), 6.80-6.72(m, 3H), 6.54-6.48(m, 2H ), 6.29-6.24(m, 2H), 5.67(dd, J=10.8, 6.9Hz, 1 H), 5.00-4.91(m, 1H), 3.80-3.71(m, 1H), 3.04( dd, J=12.5, 3.7Hz, 1H), 2.68(dd, J=11.4, 7.2Hz , 1H), 2.11(d, J=10.1Hz, 1H), 1.53(s, 9H), 1.27 (d, J=1.2Hz, 18H), 1.25(s, 9H), 0.96(d, J=12.0 Hz, 2H), 0.93-0.83(m, 1H), 0.71-0.63(m, 1H), 0 .63-0.58(m, 2H), 0.57-0.52(m, 1H), 0.38-0.27 (m, 1H). 19 F NMR (470MHz, benzene-d6) δ -131.71 (dt, J=23.0, 9.6Hz), -134.32(dt, J=19.7, 9.7H z), -136.51--137.09(m), -138.80(ddd, J=22.8 , 10.4, 6.9Hz).

[0202] Example 42: Synthesis of procatalyst 20 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (8.6 mg, 8.07 μmol, 1.00 equiv.) was added to C6D of HfBn4 (4.8 mg, 8.88 μmol, 1.10 equiv.) in 6 (0.38 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.25M solution. NMR showed the product was Using the same procedure with e, the procatalyst solution (0. 0025M) can be prepared.

[0203] 1 H NMR (500 MHz, benzene-d6) δ 8.57 (d, J = 1.9H z, 2H), 8.33(dd, J=2.0, 0.6Hz, 2H), 7.54-7.48( m, 4H), 7.41(dd, J=8.7, 0.6Hz, 2H), 7.19(dd, J= 8.4, 0.6Hz, 2H), 6.99-6.95(m, 2H), 6.82(s, 2H) , 6.79(dd, J=10.5, 8.6Hz, 2H), 6.77-6.70(m, 2H ), 6.53-6.48(m, 2H), 6.36-6.32(m, 4H), 4.98(d d, J=10.5, 7.0Hz, 2H), 3.76-3.65(m, 2H), 3.07- 2.99(m, 2H), 1.53(s, 18H), 1.26(s, 18H), 1.00( d, J=13.5Hz, 2H), 0.67-0.58(m, 2H), 0.52-0.43 (m, 2H), 0.37-0.31(m, 2H). 19 F NMR (470MHz, Ben Zen-d6) δ -131.68(dt, J=23.1, 9.5Hz), -138.2 9(ddd, J=23.0, 10.7, 7.2Hz).

[0204] Example 43: Synthesis of bis-4,5-difluoro-2-iodophenyl ether [ka] Iodophenol (5.7 mL) in acetone (100 mL) with a reflux condenser under nitrogen. 00g, 22.266mmol, 2.00eq), K2CO3(9.232g, 66.7 99 mmol, 6.00 equiv.), and 1,4-dibromobutane (1.33 mL, 11. A white heterogeneous mixture of 133 mmol, 1.00 equiv. was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 36 hours, the white heterogeneous mixture was removed from the mantle. The mixture was then cooled to 23 °C, diluted with CH2Cl2 (50 mL), and stirred vigorously (100 0 rpm), suction filter through a pad of Celite, and rinse with CH2Cl2 (3 × 25 mL). The resulting filtrate solution was concentrated onto Celite and purified by silica gel chromatography. 10% CH2Cl2 in hexane-50% CH2Cl2 in hexane gave a white solid to obtain bis-iodophenyl ether (5.798 g, 10.243 mmol, 92%). NMR showed the product.

[0205] 1 H NMR (500 MHz, chloroform-d) δ 7.57 (t, J = 9.0 Hz, 2H), 6.67(dd, J=11.9, 6.7Hz, 2H), 4.05(d, J =5.3Hz, 4H), 2.10(q, J=4.9, 3.7Hz, 4H). 19 F.N.M. R(470MHz, chloroform-d) δ -134.17(ddd, J=21.0, 12.1, 8.8Hz), -145.86(dt, J=21.0, 8.2Hz). 13 C NMR (126 MHz, chloroform-d) δ 154.03 (dd, J = 7.6, 2.4Hz), 150.52(dd, J=249.2, 13.5Hz), 144.64( dd, J=245.3, 13.1Hz), 126.87(d, J=20.4Hz), 10 1.50(d, J=21.5Hz), 77.77(dd, J=6.1, 4.0Hz), 6 9.55, 25.86.

[0206] Example 44: Synthesis of 4,5-difluoro-2-iodophenol: [ka] Dissolve the starting phenol (5. 000g, 38.434mmol, 1.00 equivalent), KI (10.846g, 65.33 7 mmol, 1.70 equiv.), and aqueous NaOH (65 mL, 65.337 mmol A clear, colorless solution of 1.70 equiv., 1N) was placed in an ice bath and stirred vigorously (1000 rpm) for 1 h. pm) and then pre-chilled commercial aqueous bleach (84 mL, 65.337 mmol, 1. 70 equivalents, 5.2% w / w) was added dropwise over a period of 10 minutes. The colored solution was stirred at 0 °C for 2 h, the mixture was removed from the ice-water bath and stirred at 23 °C for 4 h, Solid KH2PO4 (25 g) was added, followed by water (100 mL) to reduce the residual iodine. To dissolve the mixture, saturated aqueous Na2S2O3 (100 mL) was added and the mixture was stirred for 10 min. Stir gently, dilute with CH2Cl2 (50 mL), and pour the biphasic yellow mixture into a separatory funnel. The organic matter was washed with an aqueous solution of Na2S2O3 (2 x 50 mL) and the remaining organic matter was separated. The aqueous layer was extracted with H2Cl2 (2 x 25 mL), combined and dehydrated with solid Na2SO4. The mixture was washed with water, decanted, concentrated onto Celite, and purified by silica gel chromatography to give hexane. o-Iodofluorescence was obtained from 50% CH2Cl2 in hexane as a clear light brown viscous oil. The phenol (5.742 g, 22.431 mmol, 58%) was obtained. NMR showed a pure product. Showed the thing.

[0207] 1 H NMR (500 MHz, chloroform-d) δ 7.45 (dd, J=9. 2, 8.4Hz, 1H), 6.86(dd, J=11.3, 7.0Hz, 1H), 5.1 6(s, 1H). 19 F NMR (470 MHz, chloroform-d) δ -133. 85(dp, J=20.7, 10.3, 9.5Hz), -145.38(tq, J=20 .8, 8.2, 7.7Hz). 13 C NMR (126MHz, chloroform-d) δ 151.61(dd, J=9.9, 2.7Hz), 151.13(dd, J=249. 5, 13.6Hz), 144.79(dd, J=245.8, 13.5Hz), 125. 24(d, J=20.5Hz), 103.94(d, J=21.1Hz), 76.65( dd, J = 6.6, 4.1 Hz).

[0208] Example 45: Synthesis of Ligand 11 [ka] Thiophene boropinacolate ester (0.605 g, 0.5387 mmol, 2. 70 equiv., 50% purity by NMR, K3PO4 (0.343 g, 1.616 mmol , 8.10 eq.), Pd(AmPhos)Cl2 (28.0 mg, 0.0399 mmol , 0.20 equiv.), and bisphenyl iodide (0.120 g, 0.1995 mmol The mixture was evacuated and then backfilled with nitrogen to complete the process. was repeated three more times, followed by deoxygenated 1,4-dioxane (4.0 mL) and deoxygenated Hydrogenated water (0.4 mL) was then added via syringe. The mixture was then heated to 50°C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was The mixture was removed from the flask, slowly cooled to 23°C, and suction filtered over a pad of silica gel. Wash with L2 (4 × 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by rotary evaporation, and then a black mixture was obtained. The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and then extracted with CH2 Rinsing with Cl2 (4 x 20 mL) and then concentrating the black filtrate onto Celite and column chromatography on an ISCO Purify the hexane by silica gel chromatography using a chromatographic purification system. Impure bisthiophene was obtained as a bright yellow foam in 10% to 60% CH2Cl2 in ethanol. NMR showed the product to be impure. was used in the subsequent reaction.

[0209] Impure HCl in CH2Cl2-1,4-dioxane (6 mL, 1:1) at 23 °C under nitrogen To the solution of the coupled product was added concentrated HCl (3 mL). The amber solution was stirred for 20 h (5 00 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. Extract from the aqueous solution using CH2Cl2 (2 × 10 mL), mix, and add solid Na2SO The mixture was dried at 4°C, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. Purify by silica gel chromatography through a gel column and eluate in 10% to 75% CH2 in hexane. Cl2 produced bisthiophene (0.107 g, 0.0971 g) as a transparent amorphous foam. 6 mmol, 49% 2 steps) was obtained. NMR showed pure product.

[0210] 1 H NMR (500 MHz, chloroform-d) δ 8.13 (d, J = 1.9 Hz, 4H), 7.44-7.36(m, 6H), 7.18(d, J=8.6Hz, 4H ), 6.52(ddd, J=11.6, 6.1, 1.9Hz, 2H), 5.57(s, 2 H), 3.93-3.88(m, 4H), 1.84(q, J=2.8, 2.3Hz, 4H ), 1.44(s, 36H). 19 F NMR (470MHz, chloroform-d) δ -130.70(dd, J=22.3, 6.5Hz), -132.47(ddd, J= 22.4, 11.5, 6.7Hz), -167.89(td, J=22.0, 6.2Hz ). 13 C NMR (101 MHz, chloroform-d) δ 152.20-150. 50(m), 151.18-150.88(m), 148.81(ddd, J=133. 2, 10.8, 5.8Hz), 147.48, 143.25, 139.32, 138.5 9-137.90(m), 135.69(dt, J=246.1, 16.1Hz), 12 6.44, 123.69, 123.35, 121.40, 116.39, 109.27, 107.74(dd, J=14.5, 3.8Hz), 106.21, 97.67(dd, J=21.2, 3.2Hz), 69.89, 34.70, 31.95, 25.62.

[0211] Example 46: Synthesis of procatalyst 21 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (13.6 mg, 12.35 μmol, 1.00 equiv.) was added to C ZrBn4 (6.2 mg, 13.58 μmol, 1.10 equiv.) in 6D6 (0.50 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. The solution was filtered using a 0.20 μm PTFE submicron filter to obtain C6D6 The zirconium complex was obtained as a 0.0025M solution. NMR showed the product. The procatalyst solution used immediately after the polymerization experiment was filtered using the same procedure with PhMe. A solution (0.0025M or 0.005M) can be prepared.

[0212] 1 H NMR (500 MHz, benzene-d6) δ 8.53 (d, J = 1.9H z, 2H), 8.34(dd, J=1.8, 0.7Hz, 2H), 7.52-7.47( m, 4H), 7.45(dd, J=8.7, 0.7Hz, 2H), 7.20(dd, J= 8.5, 0.6Hz, 2H), 6.92(ddd, J=8.1, 7.3, 1.6Hz, 4 H), 6.89(s, 2H), 6.74-6.70(m, 2H), 6.24-6.21( m, 4H), 4.65(dd, J=10.6, 6.3Hz, 2H), 3.71(dd, J =12.8, 7.7Hz, 2H), 3.04(dd, J=11.6, 4.6Hz, 2H) , 1.53(s, 18H), 1.26(s, 18H), 0.78(d, J=11.8Hz , 2H), 0.67(dd, J=16.2, 7.2Hz, 2H), 0.58-0.52( m, 2H), 0.52(d, J=12.0Hz, 2H). 19 F NMR (470MHz , benzene-d6) δ -130.11(ddd, J=23.0, 10.5, 5.8H z), -131.31--131.90(m), -160.87(td, J=23.0, 6.6Hz).

[0213] Example 47: Synthesis of procatalyst 24 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (9.6 mg, 8.72 μmol, 1.00 equiv.) was added to C6D of HfBn4 (5.2 mg, 9.59 μmol, 1.10 equiv.) in 6 (0.42 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.25M solution. NMR showed the product was Using the same procedure with e, the procatalyst solution (0. 0025M) can be prepared.

[0214] 1 H NMR (400 MHz, benzene-d6) δ 8.53 (d, J = 1.9H z, 2H), 8.33(dd, J=1.8, 0.7Hz, 2H), 7.51-7.42( m, 6H), 7.16(dd, J=8.5, 0.6Hz, 2H), 7.02-6.94( m, 6H), 6.87(s, 2H), 6.73-6.65(m, 2H), 6.36-6. 30(m, 4H), 4.63(dd, J=10.6, 6.3Hz, 2H), 3.63-3 .53(m, 2H), 2.98(dd, J=11.5, 4.6Hz, 2H), 1.52( s, 18H), 1.23(s, 18H), 0.99(d, J=13.5Hz, 2H), 0 .65-0.53(m, 2H), 0.51-0.44(m, 2H), 0.31(d, J= 13.5Hz, 2H). 19 F NMR (470MHz, benzene-d6) δ -13 0.09(ddd, J=23.0, 10.6, 6.0Hz), -131.00--131 .79(m), -160.31(td, J=22.8, 6.5Hz).

[0215] Example 48: Synthesis of bis-3,4,5-trifluoro-2-iodophenyl ether [ka] Iodophenol (5.4 mL) in acetone (100 mL) with a reflux condenser under nitrogen. 44g, 19.870mmol, 2.00 eq), K2CO3 (8.238g, 59.6 10 mmol, 6.00 equiv.), and 1,4-dibromobutane (1.10 mL, 9.9 A white heterogeneous mixture of 35 mmol, 1.00 equiv. (1.0 mmol, 1.0 equiv.) was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 36 hours, the white heterogeneous mixture was removed from the mantle. Cool to 23 °C, dilute with CH2Cl2 (50 mL), and stir vigorously (1000 rpm), suction filter through a pad of Celite, rinse with CH2Cl2 (3 x 25 mL), and The resulting filtrate solution was concentrated onto Celite and purified by silica gel chromatography to give hexane. 10% CH2Cl2 in hexane - 50% CH2Cl2 in water to give a white solid. The bisilodophenyl ether was obtained (5.086 g, mmol, 85%). The product was shown.

[0216] 1H NMR (500 MHz, chloroform-d) δ 6.55 (ddd, J=1 1.8, 5.9, 2.3Hz, 2H), 4.07(h, J=2.6Hz, 4H), 2.1 5-2.07(m, 4H). 19 F NMR (470MHz, chloroform-d) δ -111.26(dd, J=23.3, 6.7Hz), -132.95(ddd, J=1 9.9, 11.8, 6.7Hz), -166.63--167.33(m). 13 CN MR(126MHz, chloroform-d) δ 153.44(m), 152.96-1 52.33(m), 150.64(m), 134.41(ddd, J=248.0, 17 .9, 15.8Hz), 96.35(dd, J=22.0, 2.8Hz), 69.51, 25.75.

[0217] Example 49: Synthesis of 3,4,5-trifluoro-2-iodophenol [ka] The starting phenol (4) was dissolved in methanol (150 mL) and water (200 mL) under nitrogen. .950g, 33.428mmol, 1.00 eq), KI(9.710g, 58.50 0 mmol, 1.75 equiv.), and aqueous NaOH (100 mL, 100.30 mmol). A clear, colorless solution of 1000 ml of 1.00 eq. of 1N was placed in an ice bath and stirred vigorously for 1 h (1000 rpm) and then added pre-chilled commercial aqueous bleach (84.0 mL, 58.500 mmol , 1.75 eq., 5.2% w / w) was added dropwise over a period of 10 minutes. The bright yellow solution was stirred at 0 °C for 2 h, and the mixture was then removed from the ice-water bath and stirred at 23 °C for 4 h. Stir and add solid NaH2PO4 (50 g), followed by residual iodine, water (100 mL). A saturated aqueous mixture of Na2S2O3 (200 mL) was added to reduce the Stir vigorously for 10 min, dilute with CH2Cl2 (50 mL), and separate the biphasic yellow mixture. Pour into a funnel, separate the layers, wash the organics with aqueous Na2S2O3 (2 x 100 mL), and The organics were extracted from the aqueous layer using CH2Cl2 (2 × 25 mL), combined, and washed with solid Na2 It was dried over SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography. o-Iodine was prepared from hexane-hexane with 50% CH2Cl2 as a clear, colorless oil. The resulting product was dophenol (5.444 g, 19.870 mmol, 60%). NMR showed that the product was pure. The product was shown.

[0218] 1 H NMR (400 MHz, chloroform-d) δ 6.80-6.63 (m, 1H), 5.33(s, 1H). 19 F NMR (376 MHz, chloroform-d) δ -112.07(ddd, J=22.3, 6.8, 2.6Hz), -132.68( ddd, J=21.1, 11.1, 6.8Hz), -166.81(td, J=21.7 , 6.2Hz). 13 C NMR (101 MHz, chloroform-d) δ 153.5 8-151.73(m), 150.78(dd, J=10.8, 5.5Hz), 151. 07-149.29(m), 136.06-132.30(m), 98.90(ddd, J=21.8, 3.2, 1.3Hz), 68.51(d, J=26.4Hz).

[0219] Example 50: Synthesis of Ligand 12 [ka] Thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.7 0 equiv., 62% purity by NMR), K3PO4 (0.703 g, 3.312 mmol, 8.10 equivalents), Pd(AmPhos)Cl2 (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.246 g, 0.4089 mmol, The mixture was evacuated and then backfilled with nitrogen and the process was Repeat three more times, then add deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated Hydrochloric acid (0.8 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. The mixture was removed from the oven, slowly cooled to 23 °C, suction filtered over a pad of silica gel, and then extracted with CHCl. 2 (4 × 20 mL) and concentrated the clear black filtrate to recover residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by evaporating, followed by the formation of a black mixture. The material was suspended in CH2Cl2 (20 mL), suction filtered over a silica gel pad, and The black filtrate was then concentrated onto Celite and purified by ISCO chromatography. The mixture was purified by silica gel chromatography using a hexafluoroethylene chromatography system. Impure bisthiophene was synthesized as a bright yellow foam with 10% to 60% CH2Cl2 in ethanol. (0.202 g). NMR showed the product to be impure. and used in the subsequent reaction.

[0220] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to produce bisthiophene (0.141 g, 0.1280 mm ol, 31% 2 steps) was obtained. NMR showed pure product.

[0221] 1 H NMR (500 MHz, chloroform-d) δ 8.16-8.12 (m, 4H), 7.43(ddd, J=8.7, 1.9, 0.9Hz, 4H), 7.38(d, J=0.9Hz, 2H), 7.35(ddd, J=10.6, 7.9, 2.1Hz, 2H ), 7.20(d, J=8.6Hz, 4H), 6.96(d, J=1.5Hz, 2H), 4.15-4.05(m, 4H), 1.91(q, J=3.2, 2.8Hz, 4H), 1 .45(s, 36H). 19 F NMR (470MHz, chloroform-d) δ -1 37.56(ddd, J=21.7, 11.4, 3.9Hz), -147.93(d, J =19.3Hz), -157.70(td, J=20.7, 8.1Hz). 13 CNM R(126MHz, chloroform-d) δ 148.89-146.76(m), 14 7.27, 146.77-144.58(m), 143.19, 139.52(ddd, J=254.7, 16.3, 14.1Hz), 139.36, 139.25(dd, J= 10.1, 3.5Hz), 127.64, 123.67, 123.38, 123.03( dd, J=8.0, 3.0Hz), 121.41, 116.39, 111.90, 111 .46-111.11(m), 109.34, 75.47(d, J=3.5Hz), 34 .72, 31.98, 26.07.

[0222] Example 51: Synthesis of procatalyst 23 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (7.4 mg, 6.72 μmol, 1.00 equiv.) was added to C6D of ZrBn4 (3.4 mg, 7.39 μmol, 1.10 equiv.) in 6 (0.27 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The zirconium complex was obtained as a 0.25M solution. NMR showed the product. Using the same procedure with Me, the procatalyst solution (0.01 mL) used immediately after filtration for the polymerization experiments was 0.0025M or 0.005M) can be prepared.

[0223] 1 H NMR (400 MHz, benzene-d6) δ 8.52-8.49 (m, 2 H), 8.33(dd, J=1.9, 0.7Hz, 2H), 7.62(dd, J=8.6 , 1.9Hz, 2H), 7.54(dd, J=8.6, 0.7Hz, 2H), 7.49( dd, J=8.7, 1.9Hz, 2H), 7.37(dd, J=8.6, 0.6Hz, 2 H), 6.91-6.86(m, 2H), 6.83(s, 2H), 6.70(t, J=7 .3Hz, 2H), 6.57-6.47(m, 2H), 6.17-6.13(m, 4H) , 5.60-5.55(m, 2H), 4.02-3.91(m, 2H), 3.23-3. 12(m, 2H), 1.58(s, 18H), 1.29(s, 18H), 1.06(d, J=11.5Hz, 2H), 0.90-0.73(m, 2H), 0.65-0.58(m , 2H). 19 F NMR (376MHz, benzene-d6) δ -135.52(d dd, J=22.5, 10.7, 6.3Hz), -141.09(d, J=20.9Hz ), -155.07(td, J=21.2, 7.9Hz).

[0224] Example 52: Synthesis of procatalyst 24 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (8.8 mg, 7.99 μmol, 1.00 equiv.) was added to C6D of HfBn4 (4.8 mg, 8.79 μmol, 1.10 equiv.) in 6 (0.38 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.25M solution. NMR showed the product was Using the same procedure with e, the procatalyst solution (0. 0025M) can be prepared.

[0225] 1 H NMR (400 MHz, benzene-d6) δ 8.53 (dd, J = 2.0 , 0.6Hz, 2H), 8.32(t, J=1.3Hz, 2H), 7.61(dd, J= 8.5, 1.9Hz, 2H), 7.48-7.45(m, 2H), 7.35(dd, J= 8.5, 0.6Hz, 2H), 6.98-6.93(m, 6H), 6.83(s, 2H) , 6.74-6.66(m, 2H), 6.57-6.49(m, 2H), 6.25-6. 19(m, 4H), 6.08-5.98(m, 2H), 4.00-3.91(m, 2H) , 3.20-3.11(m, 2H), 1.58(s, 18H), 1.32-1.27(m , 2H), 1.28(s, 18H), 0.83-0.76(m, 2H), 0.76-0. 68(m, 2H), 0.58-0.46(m, 2H). 19 F NMR (376 MHz, Benzene-d6) δ -134.93(ddd, J=22.5, 10.5, 6.5Hz ), -140.74(d, J=19.9Hz), -154.84(td, J=21.4, 7.9Hz).

[0226] Example 53: Synthesis of bis-4,5,6-trifluoro-2-iodophenyl ether [ka] Iodophenol (1.55 mL) in acetone (50 mL) with a reflux condenser under nitrogen 0g, 5.657mmol, 2.00 eq), K2CO3 (2.346g, 16.972 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.34 mL, 2.829 A white heterogeneous mixture of 1.0 mmol, 1.00 equiv. was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 36 hours, the white heterogeneous mixture was removed from the mantle and Cool to 23 °C, dilute with CH2Cl2 (50 mL), and stir vigorously (1000 rp) for 5 min. The mixture was then suction filtered over a Celite pad and rinsed with CH2Cl2 (3 x 25 mL). The filtrate solution was concentrated onto Celite, purified by silica gel chromatography, and 10% CH2Cl2 in hexane-50% CH2Cl2 in hexane gave biphenyl as a white solid. The obtained iodophenyl ether (1.410 g, 2.342 mmol, 83%) was R indicated the product.

[0227] 1 H NMR (400 MHz, chloroform-d) δ 7.38 (td, J = 8. 5, 2.6Hz, 2H), 4.20-4.09(m, 4H), 2.09(h, J=2.7 Hz, 4H). 19 F NMR (376MHz, chloroform-d) δ -138.8 8(ddd, J=20.5, 9.0, 3.2Hz), -146.39(dt, J=19. 7, 2.8Hz), -155.64(td, J=20.0, 7.9Hz). 13 CNM R(126MHz, chloroform-d) δ 147.31(ddd, J=250.6, 10.6, 2.7Hz), 144.51(dd, J=10.0, 3.9Hz), 144. 51(ddd, J=254.7, 11.0, 4.1Hz), 140.78(ddd, J= 254.1, 16.0, 14.1Hz), 120.35(dd, J=20.2, 3.7H z), 82.83(dd, J=7.7, 4.2Hz), 74.23(d, J=4.5Hz ), 26.72.

[0228] Example 54: Synthesis of 4,5,6-trifluoro-2-iodophenyl ether [ka] The starting phenol (4) was dissolved in methanol (200 mL) and water (100 mL) under nitrogen. .700g, 31.740mmol, 1.00 eq), KI(9.221g, 55.54 4 mmol, 1.75 equiv.), and aqueous NaOH (95.2 mL, 95.208 mm A clear, colorless solution of 100 ml of 1.00 mol (1.00 eq., 1N) was placed in an ice bath and stirred vigorously for 1 h (100 0 rpm) and then cooled with pre-chilled commercial aqueous bleach (80.0 mL, 55.544 mmo 1, 1.75 equivalents, 5.2% w / w) was added dropwise over a period of 10 minutes. The bright yellow solution was stirred at 0 °C for 2 h, the mixture was then removed from the ice-water bath and incubated at 23 °C for 4 h. Stir and add solid KH2PO4 (25 g) followed by residual iodine and water (100 mL). A saturated aqueous mixture of Na2S2O3 (100 mL) was added to reduce the Stir vigorously for 10 min, dilute with CH2Cl2 (50 mL), and separate the biphasic yellow mixture. Pour into a separatory funnel, separate the layers, wash the organics with aqueous Na2S2O3 (2 x 50 mL), and remove any remaining The product was extracted from the aqueous layer using CH2Cl2 (2 x 25 mL), mixed, and added to solid Na2S Dry with O4, decant, concentrate onto Celite, and purify by silica gel chromatography. o-Iodide was obtained as a clear, pale yellow oil by hexane-hexane 50% CH2Cl2. The resulting product was dophenol (4.202 g, 15.337 mmol, 48%). NMR showed that the product was pure. The product was shown.

[0229] 1H NMR (400 MHz, chloroform-d) δ 7.33 (tdd, J=8 .8, 2.7, 0.9Hz, 1H), 5.37(s, 1H). 19 F NMR (376M Hz, chloroform-d) δ -143.20(ddd, J=21.0, 9.5, 3. 8Hz), -152.54(dt, J=19.4, 3.4Hz), -156.04(td , J=20.0, 7.6Hz). 13 C NMR (101 MHz, chloroform-d) δ 145.31(ddd, J=247.4, 10.7, 2.4Hz), 142.06- 141.31(m), 139.45(ddd, J=249.4, 12.7, 3.8Hz) , 139.64-139.11(m), 119.82(dd, J=20.6, 4.1Hz ), 75.21(dd, J=8.0, 4.6Hz).

[0230] Example 55: Synthesis of Ligand 13 [ka] Thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.7 0 equiv., 62% purity by NMR), K3PO4 (0.703 g, 3.312 mmol, 8.10 equivalents), Pd(AmPhos)Cl2 (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.230 g, 0.4089 mmol, The mixture was evacuated and then backfilled with nitrogen and the process was Repeat three more times, then add deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated Hydrochloric acid (0.8 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. The mixture was removed from the oven, slowly cooled to 23 °C, suction filtered over a pad of silica gel, and then extracted with CHCl. 2 (4 × 20 mL) and concentrated the clear black filtrate to recover residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by evaporating, followed by the formation of a black mixture. The material was suspended in CH2Cl2 (20 mL), suction filtered over a silica gel pad, and The black filtrate was then concentrated onto Celite and purified by ISCO chromatography. The mixture was purified by silica gel chromatography using a hexafluoroethylene chromatography system. Impure bisthiophene was obtained as a pale red amorphous foam with 10% to 75% CH2Cl2 in toluene. NMR showed the product to be impure. The material was used in the subsequent reaction.

[0231] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to obtain bisthiophene (0.143 g, 0.1346 mm ol, 33% 2 steps) was obtained. NMR showed pure product.

[0232] 1H NMR (500 MHz, chloroform-d) δ 8.15 (dd, J=1. 9, 0.6Hz, 4H), 7.66(d, J=2.6Hz, 2H), 7.42(dd, J =8.6, 1.9Hz, 4H), 7.35(s, 2H), 7.24-7.20(m, 4H) ), 7.18(dd, J=8.7, 2.6Hz, 2H), 7.04(s, 2H), 6.7 9(d, J=8.8Hz, 2H), 4.04(q, J=3.6, 2.8Hz, 4H), 1 .91(q, J=2.8, 2.4Hz, 4H), 1.47(s, 36H). 13 CNM R(126MHz, chloroform-d) δ 152.34, 146.98, 142.9 4, 139.54, 129.92, 128.19, 127.84, 127.46, 124 .63, 123.58, 123.27, 120.85, 116.30, 115.08, 1 13.72, 109.51, 70.29, 34.74, 32.05, 25.81.

[0233] Example 56: Synthesis of procatalyst 25 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (9.2 mg, 8.66 μmol, 1.00 equiv.) was added to C6D of ZrBn4 (4.3 mg, 9.53 μmol, 1.10 equiv.) in 6 (0.18 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The zirconium complex was obtained as a 0.5M solution. NMR showed the product was. Using the same procedure with e, the procatalyst solution (0. 0.0025M or 0.005M) can be prepared.

[0234] 1 H NMR (500MHz, benzene-d6) δ 8.43 (dd, J=2. 0, 0.6Hz, 2H), 8.29(dd, J=1.9, 0.6Hz, 2H), 7.53 -7.48(m, 4H), 7.45(dd, J=8.5, 1.9Hz, 2H), 7.34 (dd, J=8.7, 0.6Hz, 2H), 7.31(d, J=2.6Hz, 2H), 7 .22-7.19(m, 2H), 6.91-6.86(m, 2H), 6.83(dd, J =8.7, 2.7Hz, 2H), 6.81(s, 2H), 6.79-6.74(m, 2H) ), 6.24-6.19(m, 4H), 4.98(d, J=8.7Hz, 2H), 3.8 8-3.78(m, 2H), 3.12(dd, J=11.9, 4.7Hz, 2H), 1. 44(s, 18H), 1.29(s, 18H), 0.98(d, J=12.3Hz, 2H ), 0.71-0.64(m, 2H), 0.53(d, J=12.3Hz, 2H), 0. 53-0.47(m, 2H). 13 C NMR (126MHz, benzene-d6) δ 154.32, 152.71, 146.13, 143.43, 143.02, 139.2 9, 139.12, 131.33, 130.56, 130.43, 129.56, 128 .90, 128.33, 126.54, 126.07, 125.16, 124.69, 1 24.51, 124.12, 122.73, 122.43, 121.25, 118.17 , 116.44, 115.69, 115.54, 112.22, 108.73, 74.6 6, 72.01, 34.54, 34.46, 31.94, 31.71, 25.77.

[0235] Example 57: Synthesis of procatalyst 26 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (6.8 mg, 6.40 μmol, 1.00 equiv.) was added to C6D of HfBn4 (3.8 mg, 7.04 μmol, 1.10 equiv.) in 6 (0.16 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.5M solution. NMR showed the product was in PhMe as the solvent. The procatalyst solution (0.0 05M) can be prepared.

[0236] 1 H NMR (400 MHz, benzene-d6) δ 8.43 (d, J = 1.9H z, 2H), 8.28(d, J=1.8Hz, 2H), 7.49(dd, J=8.7, 1 .9Hz, 2H), 7.43(dd, J=8.6, 2.0Hz, 2H), 7.31(d, J=2.6Hz, 2H), 7.24(d, J=8.7Hz, 2H), 7.17(d, J= 8.6Hz, 2H), 6.98-6.93(m, 2H), 6.92-6.87(m, 2H) ), 6.83(dd, J=8.8, 2.7Hz, 2H), 6.79(s, 2H), 6.7 3(tt, J=7.3, 1.3Hz, 2H), 6.27-6.22(m, 4H), 4.9 6(d, J=8.8Hz, 2H), 3.88-3.76(t, J=10.8Hz, 2H) , 3.19-3.06(m, 2H), 1.43(s, 18H), 1.28(s, 18H) , 0.89(d, J=13.4Hz, 2H), 0.70-0.57(m, 2H), 0.4 7-0.36(m, 2H), 0.27-0.20(m, 2H). 13 C NMR(101 MHz, benzene-d6) δ 153.93, 152.73, 147.19, 143. 50, 143.04, 139.24, 139.01, 138.50, 131.61, 13 0.40, 129.58, 129.05, 128.32, 126.62, 124.98, 124.56, 124.34, 122.64, 122.33, 121.16, 118.1 3, 116.39, 115.56, 114.96, 112.37, 108.72, 82. 98, 78.97, 34.53, 34.45, 31.93, 31.70, 25.93.

[0237] Example 58: Synthesis of bis-4-chloro-2-iodophenyl ether [ka] Iodophenol (1.60 mL) in acetone (60 mL) with a reflux condenser under nitrogen. 4g, 6.303mmol, 2.00 eq), K2CO3 (2.613g, 18.909 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.38 mL, 3.151 A white heterogeneous mixture of 1.0 mmol, 1.00 equiv. was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 48 hours, the white heterogeneous mixture was removed from the mantle and Cool to 23 °C, dilute with CH2Cl2 (50 mL), and stir vigorously (1000 rp) for 5 min. The mixture was then suction filtered over a Celite pad and rinsed with CH2Cl2 (3 x 25 mL). The filtrate solution was concentrated onto Celite, purified by silica gel chromatography, and 10% CH2Cl2 in hexane-50% CH2Cl2 in hexane gave biphenyl as a white solid. The obtained iodophenyl ether (1.712 g, 3.041 mmol, 97%) was R indicated the product.

[0238] 1 H NMR (500 MHz, chloroform-d) δ 7.73 (d, J = 2.5 Hz, 2H), 7.27-7.23(m, 2H), 6.73(d, J=8.8Hz, 2H ), 4.14-4.04(m, 4H), 2.10(h, J=2.4Hz, 4H). 13 C NMR (126MHz, chloroform-d) δ 156.29, 138.50, 12 9.17, 126.28, 112.40, 86.72, 69.01, 25.92.

[0239] Example 59: Synthesis of ligand 14 [ka] Thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.7 0 equiv., 62% purity by NMR), K3PO4 (0.703 g, 3.312 mmol, 8.10 equivalents), Pd(AmPhos)Cl2 (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.230 g, 0.4089 mmol, The mixture was evacuated and then backfilled with nitrogen and the process was Repeat three more times, then add deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated Hydrochloric acid (0.8 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. The mixture was removed from the oven, slowly cooled to 23 °C, suction filtered over a pad of silica gel, and then extracted with CHCl. 2 (4 × 20 mL) and concentrated the clear black filtrate to recover residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by evaporating, followed by the formation of a black mixture. The material was suspended in CH2Cl2 (20 mL), suction filtered over a silica gel pad, and The black filtrate was then concentrated onto Celite and purified by ISCO chromatography. The mixture was purified by silica gel chromatography using a hexafluoroethylene chromatography system. Impure bisthiophene was obtained as a pale red amorphous foam with 10% to 75% CH2Cl2 in toluene. NMR showed the product to be impure. The material was used in the subsequent reaction.

[0240] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to give bisthiophene (0.121 g, 0.1139 mmol) as a white solid. l, 24% 2 steps) was obtained. NMR showed pure product.

[0241] 1 H NMR (500 MHz, chloroform-d) δ 8.13 (d, J = 1.9 Hz, 4H), 7.60(d, J=8.3Hz, 2H), 7.39(dd, J=8.6, 1.9Hz, 4H), 7.31(s, 2H), 7.20(d, J=8.6Hz, 4H), 7.10(dd, J=8.4, 2.0Hz, 2H), 6.94(d, J=2.0Hz, 2 H), 6.70(s, 2H), 4.09-4.02(m, 4H), 1.99-1.90( m, 4H), 1.44(s, 36H). 13 C NMR (126 MHz, chloroform- d) δ 154.27, 146.45, 142.91, 139.52, 133.98, 131.08, 127.26, 123.54, 123.24, 122.78, 121.4 5, 120.37, 116.29, 114.09, 114.02, 109.48, 69. 93, 34.70, 32.01, 25.84.

[0242] Example 60: Synthesis of procatalyst 27 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (10.7 mg, 10.10 μmol, 1.00 equiv.) was added to C ZrBn4 (5.0 mg, 11.10 μmol, 1.10 equiv) in 6D6 (0.20 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. The solution was filtered using a 0.20 μm PTFE submicron filter to obtain C6D6 The zirconium complex was obtained as a 0.005M solution. NMR showed the product was Use the same procedure with PhMe, and filter the procatalyst solution immediately after polymerization experiments. (0.0025M or 0.005M) can be prepared.

[0243] 1 H NMR (500 MHz, benzene-d6) δ 8.51-8.44 (m, 4 H), 8.35-8.26(m, 2H), 7.63-7.54(m, 4H), 7.29- 7.26(m, 2H), 7.14(d, J=8.3Hz, 2H), 6.94(s, 2H) , 6.91(dd, J=8.3, 2.1Hz, 2H), 6.85-6.77(m, 4H) , 6.51-6.48(m, 4H), 6.40-6.32(m, 2H), 5.86(d, J=2.1Hz, 2H), 3.48-3.38(m, 2H), 3.32(m, 2H), 1 .73(d, J=13.1Hz, 2H), 1.33(s, 18H), 1.23(s, 18 H), 1.03-0.96(m, 2H), 0.92-0.79(m, 2H), 0.50( d, J = 13.1 Hz, 2H). 13 C NMR (126MHz, benzene-d6) δ 152.92, 151.61, 146.86, 146.45, 143.89, 143. 60, 143.13, 142.96, 140.01, 138.84, 138.68, 13 4.86, 130.56, 126.63, 126.27, 124.11, 123.99, 123.63, 123.00, 122.36, 121.39, 116.78, 115.9 7, 75.66, 72.03, 34.54, 34.50, 34.47, 34.41, 31 .82, 31.69.

[0244] Example 61: Synthesis of procatalyst 28 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (12.0 mg, 11.30 μmol, 1.00 equiv.) was added to C HfBn4 (6.8 mg, 12.43 μmol, 1.10 equiv.) in 6D6 (0.27 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. The solution was filtered using a 0.20 μm PTFE submicron filter to obtain C6D6 The hafnium complex was obtained as a 0.005M solution. NMR showed the product was Using the same procedure with hMe, the procatalyst solution used immediately after the filtration of the polymerization experiment ( 0.005M) can be prepared.

[0245] 1 H NMR (400 MHz, benzene-d6) δ 8.57 (d, J = 1.9H z, 2H), 8.43-8.38(m, 2H), 7.60-7.43(m, 4H), 7. 18(d, J=8.6Hz, 2H), 6.96(ddq, J=7.4, 1.4, 0.7H z, 4H), 6.91-6.85(m, 2H), 6.81(s, 2H), 6.82-6. 79(m, 2H), 6.75(tt, J=7.3, 1.2Hz, 2H), 6.66(dd , J=8.4, 2.1Hz, 2H), 6.50-6.45(m, 4H), 5.54(d, J=2.1Hz, 2H), 3.66-3.53(m, 2H), 2.90-2.83(m, 2H), 1.33(s, 18H), 1.22(s, 18H), 1.05(dd, J=13 .4, 5.9Hz, 2H), 0.91-0.71(m, 2H), 0.55-0.40(m , 2H), 0.34(d, J=13.6Hz, 2H).

[0246] Example 62: Synthesis of bis-5-chloro-2-iodophenyl ether [ka] Iodophenol (2.4 mL) in acetone (100 mL) with a reflux condenser under nitrogen. 75g, 9.727mmol, 2.00 eq), K2CO3 (4.033g, 29.18 0 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.58 mL, 4.86 A white heterogeneous mixture of 4 mmol, 1.00 equiv.) was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 36 hours, the white heterogeneous mixture was removed from the mantle. The mixture was cooled to 23 °C, diluted with CH2Cl2 (50 mL), and stirred vigorously (1000 rpm) for 5 min. The mixture was then filtered through a pad of Celite and rinsed with CH2Cl2 (3 x 25 mL) to obtain The filtrate solution was concentrated onto Celite and purified by silica gel chromatography to give hexafluorophenyl 10% CH2Cl2 in hexane-50% CH2Cl2 in hexane as a white solid Bis-iodophenyl ether (2.456 g, 4.362 mmol, 90%) was obtained. MR indicated the product.

[0247] 1 H NMR (400 MHz, chloroform-d) δ 7.64 (d, J = 8.3 Hz, 2H), 6.79(d, J=2.2Hz, 2H), 6.70(dd, J=8.3, 2.2Hz, 2H), 4.16-4.03(m, 4H), 2.15-2.04(m, 4H) ). 13 C NMR (101 MHz, chloroform-d) δ 158.00, 139. 68, 135.13, 122.49, 112.66, 83.83, 68.90, 25.8 6.

[0248] Example 63: Synthesis of Ligand 15 [ka] Thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.7 0 equiv., 62% purity by NMR), K3PO4 (0.703 g, 3.312 mmol, 8.10 equivalents), Pd(AmPhos)Cl2 (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.258 g, 0.4089 mmol, The mixture was evacuated and then backfilled with nitrogen and the process was Repeat three more times, then add deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated Hydrochloric acid (0.8 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. The mixture was removed from the oven, slowly cooled to 23 °C, suction filtered over a pad of silica gel, and then extracted with CHCl. 2 (4 × 20 mL) and concentrated the clear black filtrate to recover residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by evaporating, followed by the formation of a black mixture. The material was suspended in CH2Cl2 (20 mL), suction filtered over a silica gel pad, and The black filtrate was then concentrated onto Celite and purified by ISCO chromatography. The mixture was purified by silica gel chromatography using a hexafluoroethylene chromatography system. Impure bismuth was obtained as a pale red amorphous foam with 10% to 100% CH2Cl2 in ethanol. 0.271 g of thiophene was obtained. NMR showed the product to be impure. The correct material was used in the subsequent reaction.

[0249] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. Purify by silica gel chromatography through a column and dilute with 25% to 100% C in hexane. Bisthiophene (0.126 g, 0.1114 mmH2Cl2) was obtained as a white solid. ol, 27% 2 steps) was obtained. NMR showed pure product.

[0250] 1 H NMR (500 MHz, chloroform-d) δ 8.13 (d, J = 1.9 Hz, 4H), 7.41(h, J=8.6, 7.4Hz, 4H), 7.37(s, 2H) , 7.27(d, J=9.4Hz, 2H), 7.22(d, J=8.6Hz, 4H), 6 .64(d, J=9.0Hz, 2H), 4.84(s, 2H), 3.95-3.85(m , 4H), 1.81-1.73(m, 4H), 1.44(s, 36H). 13 C NMR (126MHz, chloroform-d) δ 156.55, 146.38, 143.30 , 139.26, 134.56, 130.70, 125.87, 125.62, 123. 84, 123.40, 122.00, 120.38, 116.38, 111.87, 11 1.71, 109.32, 69.13, 34.74, 32.00, 25.74.

[0251] Example 64: Synthesis of procatalyst 29 [ka]

[0252] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (10.3 mg, 9.11 μmol, 1.00 equiv.) was added to C6 ZrBn4 (4.6 mg, 10.02 μmol, 1.10 equiv.) in D6 (0.18 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. was filtered using a 0.20 μm PTFE submicron filter to obtain 0.1% by weight of C6D6. The zirconium complex was obtained as a .005M solution. NMR showed the product was P Using the same procedure with hMe, the procatalyst solution used immediately after the filtration of the polymerization experiment ( 0.0025M or 0.005M) can be prepared.

[0253] 1 H NMR (500MHz, benzene-d6) δ 8.42 (d, J=1.9H z, 2H), 8.26(d, J=1.9Hz, 2H), 7.47(ddd, J=8.5, 6.3, 1.9Hz, 2H), 7.38(d, J=8.7Hz, 2H), 7.25(d, J=8.5Hz, 2H), 6.99-6.95(m, 6H), 6.94(s, 2H), 6 .86(d, J=8.8Hz, 2H), 6.80(d, J=7.4Hz, 2H), 6.3 7-6.32(m, 2H), 6.09(m, 2H), 4.91(d, J=8.8Hz, 2 H), 3.79(t, J=10.1Hz, 2H), 3.20-3.13(m, 2H), 1 .47(s, 18H), 1.27(s, 18H), 0.95-0.78(m, 2H), 0 .73(d, J=11.6Hz, 2H), 0.63-0.55(m, 2H), 0.35( d, J = 11.7 Hz, 2H).

[0254] Example 65: Synthesis of Procatalyst 30 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (7.6 mg, 6.72 μmol, 1.00 equiv.) was added to C6D of HfBn4 (4.0 mg, 7.40 μmol, 1.10 equiv) in 6 (0.16 mL) The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.5M solution. NMR showed that it existed as a complex mixture of rotamers. The same procedure was used with PhMe as the solvent to obtain the filtration product of the polymerization experiment. A procatalyst solution (0.005 M) can be prepared for immediate use.

[0255] Example 66: Synthesis of bis-3,4-dichloro-2-iodophenyl ether [ka] Iodophenol (4.11) in acetone (65 mL) with a reflux condenser under nitrogen 2g, 14.234mmol, 2.20 eq), K2CO3 (5.902g, 42.70 2 mmol, 6.60 equiv.), and 1,4-dibromobutane (0.77 mL, 6.47 A white heterogeneous mixture of 1.0 mmol, 1.00 equiv. was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 36 hours, the white heterogeneous mixture was removed from the mantle. Cool to 23° C., dilute with aqueous NaOH (100 mL, 1N), stir for 2 min, and aspirate. Filter and rinse the filtered white solid with aqueous NaOH (2×25 mL, 1N) and then with water. (2 × 25 mL) and cold CH2Cl2 (2 × 20 mL), and the resulting filtered solution was rinsed with The white solid was collected, and the biphasic mixture was poured into a separatory funnel, separated, and the organic was washed with NaOH. solution (2×25 mL) and the remaining organics were extracted with CH2Cl2 (2×25 mL). The mixture was dried over solid Na2SO4, concentrated, and combined with the filtered solid to give a white solid. The iodophenyl ether (3.813 g, 6.034 mmol, 93%) was obtained. R (at 60°C and 100°C) indicated the product.

[0256] VT NMR at 60°C: 1 H NMR (400 MHz, chloroform-d) δ 7.38 (d, J = 8.8 Hz, 2H), 6.65(d, J=8.9Hz, 2H), 4.11(q, J=4.3, 3 .2Hz, 4H), 2.11(dt, J=5.4, 3.3Hz, 4H).

[0257] VT NMR at 100°C: 1 H NMR (400MHz, DMSO-d6) δ 7.54(dd, J=8.9 , 1.5Hz, 2H), 6.96(dd, J=8.9, 1.8Hz, 2H), 4.16( ddt, J=5.9, 3.6, 2.2Hz, 4H), 1.97(dq, J=5.9, 2. 6Hz, 4H). 13 C NMR (101MHz, DMSO-d6) δ 158.69 , 136.57, 130.92, 130.75, 123.17, 93.97, 70.20 , 25.87.

[0258] Example 67: Synthesis of bis-4,5-dichloro-2-iodophenyl ether [ka] Iodophenol (2.45 mL) in acetone (50 mL) with a reflux condenser under nitrogen 4g, 8.494mmol, 2.00 eq), K2CO3 (3.522g, 25.483 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.50 mL, 4.247 A white heterogeneous mixture of 1.0 mmol, 1.00 equiv. was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 36 hours, the white heterogeneous mixture was removed from the mantle and Cool to 23° C., dilute with aqueous NaOH (100 mL, 1N), stir for 2 minutes, and filter with suction. The filtered white solid was rinsed with aqueous NaOH (2×25 mL, 1N) and then with water ( (2×25 mL) and cold CH2Cl2 (2×20 mL), and the resulting filtered The white solid was collected and the biphasic mixture of the filtrate was poured into a separatory funnel, the layers were separated, and the organics were washed with aqueous NaOH. The remaining organic matter was extracted with CH2Cl2 (2 x 25 mL) and mixed. The mixture was combined, dried over solid Na2SO4, concentrated, and mixed with the filtered solid to give a white solid. The iodophenyl ether was obtained (2.272 g, 3.596 mmol, 85%). NMR (at 55° C.) indicated the product.

[0259] NMR spectra were obtained at 55°C: 1 H NMR (500 MHz, chloroform-d) δ 7.80 (s, 2H), 6 .88(s, 2H), 4.12(qd, J=5.6, 3.7, 3.3Hz, 4H), 2. 11(dq, J=5.7, 2.9Hz, 4H). 13 C NMR (126 MHz, chloro Holm-d) δ 156.81, 139.43, 133.07, 125.07, 113 .61, 84.17, 69.50, 25.82.

[0260] Example 68: 4,5-Dichloro-2-iodophenol and 3,4-dichloro-2 -Synthesis of iodophenol [ka] The starting phenol (5 mL) was dissolved in methanol (250 mL) and water (125 mL) under nitrogen. .020g, 30.798mmol, 1.00 eq), KI(8.947g, 53.89 6 mmol, 1.75 equiv.), and aqueous NaOH (92 mL, 92.394 mmol A clear, colorless solution of 1.00 equiv. (1N) was placed in an ice bath and stirred vigorously (1000 rpm) for 1 h. pm) and then pre-chilled commercial aqueous bleach (77 mL, 53.896 mmol, 1. 75 equivalents, 5.2% w / w) was added dropwise over a period of 10 minutes. The colored solution was stirred at 0 °C for 2 h, the mixture was removed from the ice-water bath and stirred at 23 °C for 4 h, Solid KH2PO4 (25 g) was added, followed by water (100 mL) to reduce the residual iodine. To dissolve the mixture, saturated aqueous Na2S2O3 (100 mL) was added and the mixture was stirred for 10 min. Stir gently, dilute with CH2Cl2 (50 mL), and pour the biphasic yellow mixture into a separatory funnel. The organic matter was washed with an aqueous solution of Na2S2O3 (2 x 50 mL) and the remaining organic matter was separated. The aqueous layer was extracted with H2Cl2 (2 x 25 mL), combined and dehydrated with solid Na2SO4. The mixture was washed with water, decanted, concentrated onto Celite, and purified by silica gel chromatography to give hexane. 2-Isopropyl alcohol was synthesized by 50% CH2Cl2 in hexane as a clear, pale yellow amorphous foam. 4,5-dichlorophenol (2.738 g, 9.478 mmol, 31%), and 2-iodo-3,4-dichlorophenol (3.325) as a clear light yellow foam. g, 11.509 mmol, 37%). NMR showed pure product.

[0261] Characterization of 2-iodo-4,5-dichlorophenol: 1 H NMR (500 MHz, chloroform-d) δ 7.71 (s, 1H), 7 .10(s, 1H), 5.27(s, 1H).

[0262] Characterization of 2-iodo-3,4-dichlorophenol: 1 H NMR (400 MHz, chloroform-d) δ 7.32 (d, J = 8.9 Hz, 1H), 6.86(d, J=8.8Hz, 1H), 5.44(s, 1H). 13 C NMR (101MHz, chloroform-d) δ 155.15, 136.20, 13 0.76, 123.74, 113.74, 91.99.

[0263] Example 69: Synthesis of Ligand 16 [ka] Thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.7 0 equiv., 62% purity by NMR), K3PO4 (0.703 g, 3.312 mmol, 8.10 equivalents), Pd(AmPhos)Cl2 (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.258 g, 0.4089 mmol, The mixture was evacuated and then backfilled with nitrogen and the process was Repeat three more times, then add deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated Hydrochloric acid (0.8 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. The mixture was removed from the oven, slowly cooled to 23 °C, suction filtered over a pad of silica gel, and then extracted with CHCl. 2 (4 × 20 mL) and concentrated the clear black filtrate to recover residual 1,4-dioxane. Toluene (2 x 10 mL) was removed azeotropically by evaporating, followed by the formation of a black mixture. The material was suspended in CH2Cl2 (20 mL), suction filtered over a silica gel pad, and The black filtrate was then concentrated onto Celite and purified by ISCO chromatography. The mixture was purified by silica gel chromatography using a hexafluoroethylene chromatography system. Impure bismuth was obtained as a pale red amorphous foam with 10% to 100% CH2Cl2 in ethanol. NMR showed the product to be impure. The correct material was used in the subsequent reaction.

[0264] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. Purify by silica gel chromatography through a column and dilute with 25% to 100% C in hexane. Bisthiophene (0.113 g, 0.0999 mmHg) was obtained as a white solid from H2Cl2. ol, 24% 2 steps) was obtained. NMR showed pure product.

[0265] 1 H NMR (500 MHz, chloroform-d) δ 8.13 (d, J = 1.9 Hz, 4H), 7.85(s, 2H), 7.40(dd, J=8.6, 1.9Hz, 4H ), 7.32(s, 2H), 7.18(d, J=8.6Hz, 4H), 7.03(s, 2 H), 6.46(s, 2H), 4.11-4.05(m, 4H), 2.04-1.96( m, 4H), 1.44(s, 36H). 13 C NMR (126 MHz, chloroform- d) δ 152.71, 146.95, 143.16, 139.40, 131.51, 130.92, 127.07, 125.84, 123.68, 123.34, 122.9 6, 120.92, 116.36, 115.20, 112.57, 109.39, 70. 17, 34.72, 32.00, 25.85.

[0266] Example 70: Synthesis of procatalyst 31 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (8.8 mg, 7.78 μmol, 1.00 equiv.) was added to C6D of ZrBn4 (3.9 mg, 8.56 μmol, 1.10 equiv.) in 6 (0.16 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The zirconium complex was obtained as a 0.5M solution. NMR showed that the product exists as a mixture of rotamers. The product was obtained immediately after filtration of the polymerization experiment using the same procedure with PhMe as the solvent. You can prepare the procatalyst solution (0.0025M or 0.005M) to be used in do.

[0267] 1 H NMR (500 MHz, benzene-d6) δ 8.54 (dd, J=1.9 , 0.7Hz, 2H), 8.42(dd, J=1.8, 0.8Hz, 2H), 7.62- 7.56(m, 4H), 7.47(dd, J=8.6, 1.9Hz, 2H), 7.18( dd, J=8.5, 0.7Hz, 2H), 6.99-6.96(m, 6H), 6.94- 6.90(m, 2H), 6.77(s, 2H), 6.38-6.32(m, 4H), 5. 58(s, 2H), 3.58-3.50(m, 2H), 2.85-2.79(m, 2H) , 1.48(s, 18H), 1.30(s, 18H), 0.92-0.83(m, 2H) , 0.72(d, 2H), 0.59-0.54(m, 4H).

[0268] Example 71: Synthesis of procatalyst 32 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, thiocyanate was dissolved in 1.24 mL of anhydrous C6D6. A clear, colorless solution of thiophene (8.0 mg, 7.07 μmol, 1.00 equiv.) was added to C6D of HfBn4 (4.2 mg, 7.78 μmol, 1.10 equiv.) in 6 (0.17 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.5M solution. NMR showed that the product existed as a mixture of rotamers. Immediately after filtration of the polymerization experiment, using the same procedure with PhMe as the solvent, The procatalyst solution (0.005M) used can be prepared.

[0269] 1 H NMR (500 MHz, benzene-d6) δ 8.56 (dd, J = 2.0 , 0.6Hz, 2H), 8.44(dd, J=1.7, 0.8Hz, 2H), 7.62- 7.53(m, 4H), 7.46(dd, J=8.6, 1.9Hz, 2H), 7.16- 7.13(m, 2H), 6.99-6.84(m, 4H), 6.77(s, 2H), 6. 52-6.47(m, 6H), 6.42(dd, J=8.1, 1.3Hz, 2H), 5. 60(s, 2H), 3.55-3.45(m, 2H), 2.83-2.77(m, 2H) , 1.48(s, 18H), 1.30(s, 18H), 1.06-0.98(m, 2H) , 0.55-0.48(m, 4H), 0.45(d, J=13.7Hz, 2H).

[0270] Example 75: Synthesis of procatalyst 31 [ka] Thiophene boropinacolate ester (2.017 g, 2.586 mmol, 3.0 0 equiv., 72% purity by NMR), K3PO4 (1.647 g, 7.758 mmol, 9.00 equivalents), Pd(AmPhos)Cl2 (122.0mg, 0.1724mmol , 0.20 equiv.), and bisphenyl iodide (0.604 g, 0.8620 mmol The mixture was evacuated and then backfilled with nitrogen to complete the process. This was repeated three more times, followed by deoxygenated 1,4-dioxane (17.0 mL) and deoxygenated Oxygenated water (1.7 mL) was then added via syringe. The mixture was then heated to 50° C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was placed in the mantle. Remove from the torch, slowly cool to 23°C, suction filter over a pad of silica gel, and dilute with CH2 Wash with Cl2 (4 x 20 mL) and concentrate the clear black filtrate to remove residual 1,4-dioxane. The was azeotropically removed using toluene (2×10 mL) by rotary evaporation, and then the black The mixture was suspended in CH2Cl2 (20 mL), suction filtered over a pad of silica gel, and The black filtrate was then concentrated onto Celite and washed with ISC Purify the mixture by silica gel chromatography using a HeO chromatography purification system. Bisthiophene ( NMR showed that the product was a mixture of rotamers and contained a small amount of impurity. This material was used in the next reaction without further purification.

[0271] Impure HCl in CH2Cl2-1,4-dioxane (10 mL, 1:1) at 23 °C under nitrogen To the solution of the purified coupled product was added concentrated HCl (5 mL). The amber solution was stirred for 20 h ( 500 rpm) and diluted with 1N HCl (10 mL) and CH2Cl2 (10 mL). Pour into a separatory funnel, separate the layers, wash the organics with 1N HCl (1 x 10 mL), and remove the remaining organics. The material was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, and solid Na2S The mixture was dried over O4, decanted, concentrated onto Celite, and purified using an ISCO chromatographic purification system. The mixture was purified by silica gel chromatography through a 10% to 75% CH in hexane. 2Cl2 to give bisthiophene (0.115 g, 0.09583 g) as a light tan solid. NMR showed pure product.

[0272] 1 H NMR (500 MHz, chloroform-d) δ 8.13 (d, J = 1.9 Hz, 4H), 7.44-7.38(m, 4H), 7.39(s, 2H), 7.21(d , J=8.6Hz, 4H), 6.98(s, 2H), 3.96-3.91(m, 4H), 1.85-1.80(m, 4H), 1.44(s, 36H). 13 C NMR (126M Hz, chloroform-d) δ 156.24, 146.49, 143.49, 139. 20, 136.25, 134.68, 125.81, 124.47, 123.91, 12 3.49, 120.80, 120.64, 116.49, 112.77, 110.93, 109.20, 69.04, 34.75, 31.98, 25.60.

[0273] Example 76: Synthesis of procatalyst 33 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, A clear, colorless solution of thiophene (10.2 mg, 8.50 μmol, 1.00 equiv.) was added to C6 ZrBn4 (4.3 mg, 9.35 μmol, 1.10 equiv) in D6 (0.17 mL) After stirring (500 rpm) for 30 minutes, a pale bright yellow solution was obtained. Filter using a 0.20 μm PTFE submicron filter to obtain 0. The zirconium complex was obtained as a 0.05M solution. NMR showed that it exists as a mixture of rotamers. The product was obtained by filtration directly after the polymerization experiment using the same procedure with PhMe as the solvent. It is possible to prepare the procatalyst solution (0.0025M or 0.005M) to be used later. Cut.

[0274] 1 H NMR (400 MHz, benzene-d6) δ 8.48 (d, J = 1.9H z, 2H), 8.36(d, J=1.8Hz, 2H), 7.59(d, J=8.7Hz, 2H), 7.50(ddd, J=8.8, 3.8, 1.9Hz, 4H), 7.23(d, J=8.6Hz, 2H), 6.98-6.94(m, 4H), 6.89(s, 2H), 6 .74(t, J=7.3Hz, 2H), 6.27-6.21(m, 4H), 5.41(s , 2H), 3.60-3.50(m, 2H), 2.97-2.90(m, 2H), 1.4 9(s, 18H), 1.28(s, 18H), 1.16(d, J=13.9Hz, 2H) , 0.90-0.80(m, 2H), 0.68-0.60(m, 2H).

[0275] Example 77: Synthesis of procatalyst 34 [ka] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) prior to use. In a nitrogen-filled glove box at 23 °C, thiocyanate was dissolved in 1.17 mL of anhydrous C6D6. A clear, colorless solution of thiophene (8.0 mg, 6.67 μmol, 1.00 equiv.) was added to C6D of HfBn4 (4.0 mg, 7.33 μmol, 1.10 equiv.) in 6 (0.16 mL). The solution was added dropwise. After stirring (500 rpm) for 30 minutes, the pale yellow solution was Filter using a 0.20 μm PTFE submicron filter to obtain 0.0 in C6D6. The hafnium complex was obtained as a 0.5M solution. NMR showed that the product existed as a mixture of rotamers. Immediately after filtration of the polymerization experiment, using the same procedure with PhMe as the solvent, The procatalyst solution (0.005M) used can be prepared.

[0276] 1 H NMR (400 MHz, benzene-d6) δ 8.51 (d, J = 1.9H z, 2H), 8.39(d, J=1.8Hz, 2H), 7.61(d, J=9.0Hz, 2H), 7.50(ddd, J=21.9, 8.7, 1.9Hz, 4H), 7.19(d , J=8.6Hz, 2H), 6.98-6.94(m, 4H), 6.90(s, 2H), 6.75(t, J=7.5Hz, 2H), 6.41-6.36(m, 4H), 5.31( s, 2H), 3.43-3.35(m, 2H), 2.87-2.79(m, 2H), 1. 49(s, 18H), 1.29(s, 18H), 1.06(d, J=14.1Hz, 2H ), 0.95-0.82(m, 2H), 0.59-0.48(m, 2H), 0.41(d , J = 14.0 Hz, 2H).

[0277] Example 78: Synthesis of bis-3,4,5-trichloro-2-iodophenyl ether [ka] Iodophenol (1.31 mL) in acetone (50 mL) with a reflux condenser under nitrogen 5g, 4.067mmol, 2.00 eq), K2CO3 (1.686g, 12.201 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.24 mL, 2.034 A white heterogeneous mixture of 1.0 mmol, 1.00 equiv. was placed in a heating mantle at 60 °C. After stirring (500 rpm) for 36 hours, the white heterogeneous mixture was removed from the mantle and Cool to 23° C., dilute with aqueous NaOH (100 mL, 1N), stir for 2 minutes, and filter with suction. The filtered white solid was rinsed with aqueous NaOH (2×25 mL, 1N) and then with water ( (2×25 mL) and cold CH2Cl2 (2×20 mL), and the resulting filtered The white solid was collected and the biphasic mixture of the filtrate was poured into a separatory funnel, the layers were separated, and the organics were washed with aqueous NaOH. The remaining organic matter was extracted with CH2Cl2 (2 x 25 mL) and mixed. The mixture was combined, dried over solid Na2SO4, concentrated, and mixed with the filtered solid to give a white solid. The iodophenyl ether was obtained (1.300 g, 1.855 mmol, 91%). NMR (at 60° C.) indicated the product.

[0278] NMR spectra were obtained at 60°C: 1 H NMR (500 MHz, chloroform-d) δ 6.87 (s, 2H), 4 .21-4.08(m, 4H), 2.13(dq, J=5.3, 3.4, 2.7Hz, 4 H). 13 C NMR (126 MHz, chloroform-d) δ 157.26, 139 .11, 134.26, 123.39, 111.64, 91.01, 69.80, 25. 82.

[0279] Example 79: Synthesis of 3,4,5-trichlorophenol-2-iodophenol [ka] The starting phenol (3 .600g, 18.233mmol, 1.00 eq), KI(5.297g, 31.90 9 mmol, 1.75 equiv.), and aqueous NaOH (55.0 mL, 54.699 mm A clear, colorless solution of 100 ml of 1.00 mol (1.00 eq., 1N) was placed in an ice bath and stirred vigorously for 1 h (100 0 rpm) and then added pre-chilled commercial aqueous bleach (46.0 mL, 31.909 mmol / L). 1, 1.75 equivalents, 5.2% w / w) was added dropwise over a period of 10 minutes. The pale yellow mixture, which was opaque at the time of the analysis, was stirred at 0° C. for 2 h. The mixture was then removed from the ice-water bath and 23 The mixture was stirred at 37 °C for 4 h, and solid NaH2PO4 (10 g) was added, followed by the addition of residual iodine, water ( A saturated aqueous mixture of Na2S2O3 (100 mL) was added to reduce the The mixture was stirred vigorously for 10 min, diluted with CH2Cl2 (50 mL), and a biphasic yellow solution was obtained. The mixture was poured into a separatory funnel, the layers were separated, and the organics were washed with aqueous Na2S2O3 (2 x 50 mL). The remaining organics were extracted from the aqueous layer using CH2Cl2 (2 × 25 mL), mixed, and Dry over solid Na2SO4, decant, concentrate onto Celite, and chromatograph on silica gel. Purified by filtration, 35% CH2Cl2 in hexane - 100% CH2Cl2 in hexane to give o-iodophenol (1.497 g, 4.630 mmol) as a white solid. 25%), and starting phenol (2.544 g, 12.885 mmol) as a white solid. l, 71%). NMR showed pure product.

[0280] 1 H NMR (500 MHz, chloroform-d) δ 7.11 (s, 1H), 5 .52(s,1H).

[0281] Example 80: Polymers obtained from procatalysts Catalyst efficiency (g poly) was measured using parallel polymerization reactors (PPR) as well as semi-batch reactors. The polymer yield (p / g metal) and the resulting polymer properties were evaluated for procatalysts 1-34. The polymerization reaction in the batch reactor was carried out first without diethylzinc (DEZ), then in three batches. Different DEZ dosages (0, 50, and 200 μmol) were added to 2-L semi-batch The reaction was carried out in a reactor. The activator was 1.5 molar equivalents of bis(hydrogenated tallow alkyl)methyl It was ammonium tetrakis(pentafluorophenyl)borate.

[0282] The procatalysts are capable of producing polymers at temperatures up to 150° C. All procatalysts except for 1 and 2 exhibited short quench times in the PPR. The reaction was highly active, with most of the It shows high efficiency (>200,000 g polymer / g metal) in the synthesis of catalysts. Directly impacts the activity and efficiency of the This leads to the formation of a polymer with four carbon alkyl n-butyl chains linked together. Catalysts 3 and 4 produced poly(1-octene) with lower 1-octene incorporation (10–12 mol%). mers, but disubstituted silyl and germanyl dimethylenes, as well as trans-1, 2-Methylenedicyclohexyl bridged, procatalysts 5-12 have higher catalytic activity, efficiency (maximum Large (29 mm g polymer / g metal), and 1-octene incorporation (up to 23 mol%) In addition, the neutral phenyl ether donor (i.e., procatalysts 13-34) was used as a catalyst. The functional groups and substitution positions affect the activity and efficiency of the catalyst (up to 32 MMg polymer / g metal). ) directly impacting the polymers with higher comonomer incorporation (up to 21 mol%). and higher molecular weights (up to 774,000 g / mol), resulting in the formation of Procatalysts 3 and 4, which possess anionic, non-anionic phenyl ether donors, exhibited lower 1 -Octene incorporation (10-12 mol%) was observed in these reactors to produce polymers. Depending on the conditions, the procatalysts have lower catalytic efficiencies at temperatures up to 150 °C. It is possible. [Table 1-1] [Table 1-2]

[0283] *Standard PPR reactor conditions: 120℃-150psi ethylene, 838uL1-octane , [C8]:[C2]=2.24, 10% CO quench, run time=30 min, or 1 Up to 50 psi conversion at 20°C. MMAO-3A = 500 nmol. Activator = Bis(hydrogen Tetrakis(pentafluorophenyl)borane (1.50 equivalents)*Mol% octene or C8 / olefin is (1-octene It is defined as the number of moles / (total number of moles of 1-octene and ethylene) × 100. .D.=Not Measured. [Table 2-1] [Table 2-2]

[0284] *Standard semi-batch reactor conditions: 120°C - 46g ethyl acetate in 611g IsoparE 150°C - 43g of 1-octene in 547g of IsoparE Ethylene and 303g of 1-octene, and 190°C - 515g of IsoparE 46g ethylene and 292g 1-octene. *Mol% octene or C8 / octene The olefin is (moles of 1-octene / (total moles of 1-octene and ethylene)) × 100. ND = not determined. [Table 3-1] [Table 3-2] [Table 3-3]

[0285] *Standard semi-batch reactor conditions using Et2Zn as CSA: 120℃-610℃ g of IsoparE, 11 g of ethylene and 59 g of 1-octene, 150°C-53 12g ethylene and 59g 1-octene in 1g IsoparE. C8 / olefin is (moles of 1-octene / (moles of 1-octene and ethylene) The total number of moles of toluene (total moles of toluene) × 100. ND = not determined. [Table 4]

[0286] Moderate continuation for procatalysts 3, 4, 13–20, 25, and 26 at 150 °C The high chain transfer constant (Ca≦0.6) indicates that these catalysts are effective against chain transfer agents. It has high sensitivity to these agents and shows rapid chain transfer with these agents. As the amount of n(DEZ) increases, the decrease or relatively persistent narrowing of these procatalysts A low PDI was observed, indicating that these particular procatalysts promote CSA rather than irreversible chain transfer. These behaviors are consistent with the much lower Ca and and / or a significant increase or spread in PDI observed with other procatalysts. Although procatalysts 12 and 27 have high Ca, the increase in PDI is not observed. This suggests irreversible chain transfer via EZ.

Claims

1. A catalytic system comprising a metal-ligand complex according to formula (I), 【Chemistry 1】 During the ceremony, M is a metal selected from titanium, zirconium, or hafnium; the metal has a formal oxidation state of +2, +3, or +4; Each X is an unsaturated (C ２ -C ２０ ) Hydrocarbon, unsaturated (C ２ -C ５０ ) Heterocarbonization Hydrogen, (C １ -C ５０ ) hydrocarbyl, (C ６ -C ５０ ) aryl, (C ６ -C ５０ ) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C ４ -C １２ ) Diene, halogen, -OR Ｃ , -N(R Ｎ ) ２ , and -NCOR Ｃ Selected independently from is a monodentate or bidentate ligand which is n is 1 or 2; Y is oxygen, sulfur, or -N(R Ｎ ) - and Each R １ 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 C(O)O-、R Ｃ OC(O)-、R Ｃ C(O) N(R)-, (R Ｃ ) ２ NC(O)-, halogen, radicals having the formula (II), II) and a radical having the formula (IV), 【Chemistry 2】 In the formula, R ３１～３５ , R ４１～４８ , and R ５１～５９ Each of the following is independent: (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 、-N=CHR Ｃ 、-OR Ｃ 、-SR Ｃ 、-NO ２ 、-CN、-CF ３ 、R Ｃ 2000(1000) 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)-, halogen, or -H, provided that in formula (I), At least one R １ is a radical having the formula (II), a radical having the formula (III) or a radical having the formula (IV): Q is (C １ -C １２ ) alkylene, (C １ -C １２ ) heteroalkylene, (- CH ２ Si(R Ｑ ) ２ CH ２ -)、(-CH ２ CH ２ Si(R Ｑ ) ２ CH ２ CH ２ -)、 (-CH ２ Ge(R Ｑ ) ２ CH ２ -), or (-CH ２ CH ２ Ge(R Ｑ ) ２ CH ２ C H ２ -), wherein R Ｑ However, (C １ -C ２０ ) hydrocarbyl, each z １ and z ２ are independently sulfur, oxygen, -N(R Ｃ )-, and -C(R Ｃ )-, provided that the group z １ and z ２ In each individual ring containing , z １ and z ２ is sulfur; R ４ａ , R ５ａ , R ６ａ , R ７ａ , R ４ｂ , R ５ｂ , R ６ｂ , and R ７ｂ is Stand up, (C １ -C ５０ ) hydrocarbyl, (C １ -C ５０ ) heterohydrocarbyl, ( C ６－ C ５０ ) aryl, (C ４ -C ５０ ) heteroaryl, —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)-、-P(O)(R Ｐ ) ２ 、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)-、(R Ｃ ) ２ N C(O)—, halogen, and —H, optionally R ４ａ and R ５ａ , or R ５ａ and R ６ａ , or R ６ａ and R ７ａ , or R ４ｂ and R ５ｂ , or R ５ｂ and R ６ｂ ,Also is R ６ｂ and R ７ｂ may be covalently linked to form an aromatic or non-aromatic ring; Each R in formula (I) Ｃ , R Ｎ , and R Ｐ is independent, (C １ -C ２０ ) Hide Locarville, (C １ -C ２０ ) heterohydrocarbyl, and —H R, However, Q is -CH ２ CH ２ CH ２ CH ２ -When (1) Each R １ is 3,6-di-tert-butylcarbazol-9-yl , z ２ is sulfur and each X is benzyl; ５ａ and R ５ｂ Ha, -OMe, Fu fluorine or tert-octyl, or (2) R ４ａ , R ５ａ , R ６ａ , and R ７ａ At least one of the Rogen, R ４ｂ , R ５ｂ , R ６ｂ , and R ７ｂ At least one of the Gen or (3) R ４ａ , R ５ａ , R ６ａ , R ７ａ , R ４ｂ , R ５ｂ , R ６ｂ , and R ７ｂ At least one of (C １ -C ５０ ) hydrocarbyl, (C １ -C ５０ ) Tetrahydrocarbyl, (C ６ -C ５０ ) aryl, (C ４ -C ５０ ) heteroaryl, - Si(R Ｃ ) ３ 、-Ge(R Ｃ ) ３ 、-P(R Ｐ ) ２ 、-N(R Ｎ ) ２ 、-OR Ｃ 、-S R Ｃ 、-NO ２ 、-CNN、-CF ３ ,R Ｃ S(O)-、-@(O)(R). Ｐ ) ２ ,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)- and (R Ｃ ) ２ NC(O)—, provided that the aryl group is selected from the group consisting of: Catalyst system.

2. each z １ 2. The catalyst system of claim 1, wherein is sulfur.

3. each z ２ 2. The catalyst system of claim 1, wherein is sulfur.

4. 4. The catalyst system according to any one of claims 1 to 3, wherein each Y is oxygen.

5. Catalyst system according to any one of claims 1 to 4, further comprising one or more cocatalysts.

6. Each R １ is a radical having the formula (III) and R ４１～４８ At least one of One is (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, - Si(R Ｃ ) ３ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , or halogen The catalyst system according to any one of claims 1 to 5, which is selected from

7. Each R １ is a radical having the formula (III) (1) R ４２ and R ４７ is independent, (C １ -C ２０ ) alkyl, —Si(R Ｃ ) ３ , -CF ３ or halogen; R ４３ and R ４６ is -H or Or (2) R ４３ and R ４６ is independent, (C １ -C ２０ ) alkyl, —Si(R Ｃ ) ３ , -CF ３ or halogen; R ４２ and R ４７ is -H, Item 7. The catalyst system according to any one of items 1 to 6.

8. Each R １ is a radical having the formula (IV) and R ５１～５９ At least one of However, (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, Si (R Ｃ ) ３ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ or halogen The catalyst system according to any one of claims 1 to 6, wherein

9. Each R １ is a radical having the formula (IV) and R ５１～５９ is -H, Item 7. The catalyst system according to any one of items 1 to 6.

10. Q is (C ３ -C ４ ) alkylene, R ４ａ , R ５ａ , R ６ａ , R ７ａ , R ４ ｂ , R ５ｂ , R ６ｂ , and R ７ｂ At least two of (C ６ -C ５０ ) Ally Ru, (C ４ -C ５０ ) heteroaryl, —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)-、-P(O)(R Ｐ ) ２ 、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)-, and 10. The catalytic system according to any one of claims 1 to 9, wherein the halogen is selected from the group consisting of halogens.

11. R ４ａ , R ５ａ , R ６ａ , R ７ａ At least one of R is halogen; ４ ｂ , R ５ｂ , R ６ｂ , and R ７ｂ At least one of is a halogen.

11. A catalyst system according to any one of claims 1 to 10.

12. R ４ａ , R ５ａ , R ６ａ , R ７ａ At least two of R are halogen; ４ ｂ , R ５ｂ , R ６ｂ , and R ７ｂ At least two of are halogen.

11. A catalyst system according to any one of claims 1 to 10.

13. R ４ａ , R ５ａ , R ６ａ , R ７ａ At least three of R are halogen; ４ ｂ , R ５ｂ , R ６ｂ , and R ７ｂ At least three of are halogen.

11. A catalyst system according to any one of claims 1 to 10.

14. Qが、(-CH ２ () Ｑ ) ２ CH ２ -)、(-CH ２ CH ２ () Ｑ ) ２ CH ２ CH ２ -), (-CH ２ Ge(R Ｑ ) ２ CH ２ -), or (-CH ２ CH ２ Ge(R Ｑ ) ２ CH ２ CH ２ -), wherein R Ｑ (C １ -C ５ ) alkyl, 11. A catalyst system according to any one of claims 1 to 10.

15. Q is benzene-1,2-diyl or cyclohexane-1,2-diyl; 11. The catalyst system according to any one of claims 1 to 10.

16. Q is (-CH ２ Si(R Ｑ ) ２ CH ２ -) or (-CH ２ Si(R Ｑ ) ２ CH ２ -), wherein R Ｑ Any of claims 1 to 10, wherein is ethyl or 2-propyl. Catalyst system according to any one of claims 1 to 5.

17. Q is benzene-1,2-diyldimethyl. The catalyst system described.

18. The catalyst system according to any one of claims 1 to 17, further comprising a chain transfer agent. Medium system.

19. A process for polymerizing olefins, comprising the steps of: In the presence of the above-described catalytic system, ethylene and optionally one or more (C ３ -C １２ ) α-olefin and The process comprising contacting

20. 20. The process of claim 18, wherein the process further comprises a chain transfer agent.

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