Biaryl Phenoxy Group Group 4 Transition Metal Catalysts for Olefin Polymerization

Abstract

A catalytic system comprising a metal-ligand complex according to formula (I).

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 62 / 782,855, filed on December 20, 2018, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure generally relate to olefin polymerization catalyst systems and processes, and more specifically, to the synthesis of biaryl - phenoxy Group IV transition metal catalysts for olefin polymerization and olefin polymerization processes incorporating such catalyst systems.

Background Art

[0003] Olefin - based polymers such as polyethylene and / or polypropylene are produced via various catalyst systems. The selection of such catalyst systems used in the polymerization process of olefin - based polymers is an important factor contributing to the characteristics and properties of such olefin - based polymers.

[0004] Polyethylene and polypropylene are manufactured for a wide variety of products. The polyethylene and polypropylene polymerization processes can be varied in several respects to produce polyethylene resins that result in a wide variety of physical properties suitable for different uses for different resins. Ethylene monomer and optionally one or more comonomers are present in a liquid diluent such as an alkane or isoalkane, such as isobutane. Hydrogen can also be added to the reactor. The catalyst system for producing polyethylene can typically include a chromium-based catalyst system, a Ziegler-Natta catalyst system, or a molecular (either metallocene or non-metallocene) catalyst system. The reactants in the diluent and catalyst system are circulated in the reactor at a high polymerization temperature, thereby producing a polyethylene homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture containing the polyethylene product dissolved in the diluent is removed from the reactor along with unreacted ethylene and one or more optional comonomers. The reaction mixture when removed from the reactor may be processed to remove the polyethylene product from the diluent and unreacted reactants, and the diluent and unreacted reactants are typically recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor, such as a reactor connected in series to the first reactor, where a second polyethylene fraction may be produced.

[0005] Despite research efforts in the development of catalyst systems suitable for olefin polymerization such as polyethylene or polypropylene polymerization, there is still a need for pro-catalysts and catalyst systems that exhibit higher efficiency and higher comonomer incorporation than comparative catalyst systems that produce polymers having a high mole percent (mol%) of α-olefin incorporation that varies depending on the reactor. (For example, for a batch reactor, the high mol% α-olefin incorporation can be 15 - 20%.) Further, the catalyst and catalyst system must be able to produce polymers having a high molecular weight and a narrow molecular weight distribution. SUMMARY OF THE INVENTION

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

Chemical formula

[0007] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, and the metal has an oxidation state in the form of +2, +3, or +4: each X is an unsaturated (C2-C 20 ) hydrocarbon, an unsaturated (C2-C 50 ) heterohydrocarbon, a (C1-C 50 ) hydrocarbyl, a (C6-C 50 ) aryl, a (C6-C 50 ) heteroaryl, a cyclopentadienyl, a substituted cyclopentadienyl, a (C4-C 12 ) diene, a halogen, -OR C , -N(R N )2, and -NCOR C and is 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 is independently -H, a (C1-C 40 ) hydrocarbyl, a (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)Selected from the group consisting of 2NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV):

Chemical formula

[0009] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , and R 51~59 each independently is (C1-C 40 ) hydrocarbyl, (C1-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 , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, halogen, or -H, provided that at least one of R 1 is a radical having formula (II), a radical having formula (III), or a radical having formula (IV).

[0010] In formula (I), Q is (C1-C 12 ) alkylene, (C1-C 12 ) heteroalkylene, (-CH2Si(R C )2CH2-), (-CH2CH2Si(R C )2CH2CH2-), (-CH2Ge(R C )2CH2-), or (-CH2CH2Ge(R C )2CH2CH2-), wherein R Cis a (C1-C 20 ) hydrocarbyl.

[0011] In formula (I), for each individual ring containing groups z1 and z2, each of z1 and z2 is independently selected from the group consisting of sulfur, oxygen, -N(R C )-, and -C(R C )-, provided 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 are independently (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, and 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 7bcan be covalently bonded to form an aromatic or non-aromatic ring.

[0012] In formula (I), each R in formula (I) C , R N , and R P is independently selected from the group consisting of (C1-C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, and -H.

[0013] In formula (I), when Q is -CH2CH2CH2CH2-, each R 1 is 3,6-di-tert-butylcarbazol-9-yl, z2 is sulfur, and when each X is benzyl, R 5a and R 5b are not -OMe, fluorine, or tert-octyl. Further, when Q is -CH2CH2CH2CH2-, at least one of R 4a , R 5a , R 6a , and R 7a is halogen, and at least one of R 4b , R 5b , R 6b , and R 7b is halogen, or when Q is -CH2CH2CH2CH2-, R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b is (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (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 CS(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 selected from the group consisting of halogen.

Brief Description of Drawings

[0014]

Figure 1-1

Figure 1-2

Figure 1-3

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Mode for Carrying Out the Invention

[0015] Here, specific embodiments of the catalyst system will be described. It should be understood that the catalyst system of the present disclosure may be implemented in different forms and should not be construed as limited to the specific embodiments described in the present disclosure. Rather, the embodiments are provided so that the present disclosure will be thorough and complete and will fully convey the scope of the subject matter to those skilled in the art.

[0016] General 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: tert-butyl, t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl), Tf: trifluoromethanesulfonate, THF: tetrahydrofuran, Et2O: diethyl ether, CH2Cl2: dichloromethane, CV: column volume (used in column chromatography), EtOAc: ethyl acetate, C6D6: deuterated benzene or benzene-d6, CDCl3: deuterated chloroform, Na2SO4: sodium sulfate, MgSO4: magnesium sulfate, HCl: hydrogen chloride, n-BuLi: butyllithium, t-BuLi: tert-butyllithium, Cu2O: copper(I) oxide, N,N’-DMEDA: N,N’-dimethylethylenediamine, K3PO4: tripotassium phosphate, Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), Pd(dppf)Cl2: [1,1’-bis(diphenylphosphino)ferrocene]dichloropalladium(II), K2CO3: potassium carbonate, Cs2CO3: cesium carbonate, i-PrOBPin: 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, BrCl2CCCl2Br: 1,2-dibromotetrachloroethane, HfCl4: hafnium(IV) chloride, HfBn4: hafnium(IV) tetrabenzyl, ZrCl4: zirconium(IV) chloride, ZrBn4: zirconium(IV) tetrabenzyl, ZrBn2Cl2(OEt2): zirconium(IV) dibenzyldichloride mono-diethyl etherate, HfBn2Cl2(OEt2): hafnium(IV) dibenzyldichloride mono-diethyl etherate, TiBn4: titanium(IV) tetrabenzyl, N2: nitrogen gas, PhMe: toluene, PPR: parallel polymerization reactor, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: molar, min or mins: minute, h or hrs: hour, d: day, R f: Retention fraction, TLC: Thin layer chromatography, rpm: Revolutions per minute.

[0018] The term "independently selected" is used herein to indicate that variable groups such as R 1 , A, z 1~5 may be the same or different. The chemical names associated with the R groups are intended to convey chemical structures recognized in the art as corresponding to the chemical structures of the chemical names. Thus, the chemical names are intended to supplement and exemplify structural definitions known to those skilled in the art and are not intended to exclude.

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

[0020] When used to describe a particular carbon atom-containing chemical group, the parenthetical expression in the form of "(C x -C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms, including x and y. For example, (C1-C 50 ) alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, a particular chemical group may be substituted by one or more substituents such as R S . The R x -C y )" and defined using the parenthetical expression "(C S substitution version of the chemical group may contain more than y carbon atoms depending on the identity of any group R S . For example, "(C1-C S ) alkyl substituted by exactly one group R S where R 50 is phenyl (-C6H5)" may contain 7 to 56 carbon atoms. Thus, generally, the parenthetical "(Cx -C y )」 is defined by using one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total numbers of carbon atoms of the chemical group are for both x and y, all carbon atom-containing substituents R S Determined by adding the total number of carbon atoms derived from.

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

[0022] The term "(C1-C 50 ) hydrocarbyl" means a hydrocarbon radical having 1 to 50 carbon atoms, and the term "(C1-C 50 ) hydrocarbylene" means a hydrocarbon diradical having 1 to 50 carbon atoms, where each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and is substituted or unsubstituted by one or more R S s.

[0023] In the present disclosure, (C1-C 50 ) hydrocarbyl is unsubstituted or substituted (C1-C50 ) Alkyl, (C3-C 50 ) Cycloalkyl, (C3-C 20 ) Cycloalkyl-(C1-C 20 ) Alkylene, (C6-C 40 ) Aryl, or (C6-C 20 ) Aryl-(C1-C 20 ) Alkylene (such as benzyl (-CH2-C6H5)) can be.

[0024] “(C1-C 50 ) Alkyl” and “(C1-C 18 ) Alkyl” terms mean, respectively, a saturated straight-chain or branched hydrocarbon radical having 1 to 50 carbon atoms and a saturated straight-chain or branched hydrocarbon radical having 1 to 18 carbon atoms, which are unsubstituted or substituted by one or more R S . Examples of unsubstituted (C1-C 50 ) alkyl are unsubstituted (C1-C 20 ) alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Examples of substituted (C1-C 40 ) alkyl are substituted (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 alkyl. The term “[C 45 alkyl” means that there are up to 45 carbon atoms in the radical containing the substituent, for example, (C S -C 27 -C 40 ) alkyl substituted by one R

[0025] “(C6-C 50The term "aryl" means an unsubstituted or (by one or more R S s) substituted monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical having 6 to 40 carbon atoms, at least 6 to 14 of which are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other one or more rings of the aromatic radical can independently be fused or unfused aromatic or non-aromatic. Examples of unsubstituted (C6-C 50 ) aryl include unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 ) aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrenyl. Examples of substituted (C6-C 40 ) aryl include substituted (C1-C 20 ) aryl, substituted (C6-C 18 ) aryl, 2,4-bis([C 20 alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-one-1-yl.

[0026] The term "(C3-C 50 ) cycloalkyl" means a saturated cyclic hydrocarbon radical having 3 to 50 carbon atoms that is either unsubstituted or substituted by one or more R S s. Other cycloalkyl groups (e.g., (C x -C y ) cycloalkyl) having x to y carbon atoms are defined in a similar manner as being either unsubstituted or substituted by one or more R S s. Examples of unsubstituted (C3-C 40 ) cycloalkyl are unsubstituted (C3-C20 )Cycloalkyl, unsubstituted (C3 - C 10 )Cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3 - C 40 )Examples of substituted (C3 - C 20 )Cycloalkyl, substituted (C3 - C 10 )Cycloalkyl, cyclopentanone - 2 - yl, and 1 - fluorocyclohexyl.

[0027] (C1 - C 50 )Examples of (C1 - C 50 )hydrocarbylene include unsubstituted or substituted (C6 - C 50 )arylene, (C3 - C 50 )cycloalkylene, and (C1 - C 20 )alkylene (e.g., (C1 - C 20 )alkylene). The diradical may be on the same carbon atom (e.g., - CH2 -) or on adjacent carbon atoms (i.e., 1,2 - diradical), or separated by one, two, or more intervening carbon atoms (e.g., 1,3 - diradical, 1,4 - diradical, etc.). Some diradicals include 1,2 -, 1,3 -, 1,4 -, or α,ω - diradicals, and others include 1,2 - diradicals. The α,ω - diradical is a diradical having the maximum carbon skeleton spacing between the radical carbons. (C2 - C 50 )Some examples of (C2 - C

[0028] The term “(C1 - C 50 )alkylene” means unsubstituted or one or more RS means a saturated straight-chain or branched-chain diradical having 1 to 50 carbon atoms which is substituted by (i.e., the radicals are not on ring atoms). Examples of unsubstituted (C1-C 50 ) alkylene are 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), where "C*" represents the carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1-C 50 ) alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As described above, since the two Rs S can together form (C1-C 18 ) alkylene, examples of substituted (C1-C 50 ) alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

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

[0030] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms are 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 -Si(R C )- is mentioned, and each R C and each R P is an unsubstituted (C1-C 18 ) hydrocarbyl or -H, and each R N is an unsubstituted (C1-C 18 ) hydrocarbyl. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms. The term "(C1-C 50 ) heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms, and the term "(C1-C 50 ) heterohydrocarbylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. The (C1-C 50 ) heterohydrocarbyl or (C1-C 50 ) heterohydrocarbylene heterohydrocarbons have one or more heteroatoms. The radical of the heterohydrocarbyl can be present on a carbon atom or on a heteroatom. The two groups of the heterohydrocarbylene can be present on a single carbon atom or on a single heteroatom. Further, one of the two radicals of the diradical can be present on a carbon atom, and the other radical can be present on a different carbon atom, one of the two radicals can be present on a carbon atom, and the other can be present on a heteroatom, or one of the two radicals can be present on a heteroatom, and the other radical can be present on a different heteroatom. Each (C1-C 50 ) heterohydrocarbyl and (C1-C 50 ) heterohydrocarbylene can be unsubstituted or substituted (by one or more R S ), aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including monocyclic and polycyclic, fused polycyclic and non-fused polycyclic) or acyclic.

[0031] (C1-C 50 ) heterohydrocarbyl can be unsubstituted or substituted. (C1-C50 ) Non-limiting examples of hetero hydrocarbyl include (C1-C 50 ) heteroalkyl, (C1-C 50 ) hydrocarbyl-O-, (C1-C 50 ) hydrocarbyl-S-, (C1-C 50 ) hydrocarbyl-S(O)-, (C1-C 50 ) hydrocarbyl-S(O)2-, (C1-C 50 ) hydrocarbyl-Si(R C )2-, (C1-C 50 ) hydrocarbyl-N(R N )-, (C1-C 50 ) hydrocarbyl-P(R P )-, (C2-C 50 ) heterocycloalkyl, (C2-C 19 ) heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 ) cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 ) heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 50 ) heteroaryl, (C1-C 19 ) heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 ) aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 ) heteroaryl-(C1-C 20 ) heteroalkylene.

[0032] The term “(C4-C 50 ) heteroaryl” refers to unsubstituted or (one or more R Smeans a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical substituted by). A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other one or more rings of the heteroaromatic radical can independently be fused or unfused and aromatic or non-aromatic. Other heteroaryl groups (e.g., generally (C x -C y ) heteroaryl, (C4-C 12 ) heteroaryl, etc.) have x to y carbon atoms (such as 4 to 12 carbon atoms) and are unsubstituted or substituted with one or more R SIt is defined in a similar manner as that replaced by. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and each heteroatom can be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatom can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radicals include indol-1-yl and benzimidazol-1-yl. Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radicals include quinolin-2-yl and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring system. Examples of the fused 5,6,5-ring system include 1,7-dihydropyrrolo[3,2-f]indol-1-yl. Examples of the fused 5,6,6-ring system include 1H-benzo[f]indol-1-yl. An example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of the fused 6,6,6-ring system is acridin-9-yl.

[0033] “(C1-C 50) The term "heteroalkyl" means a saturated straight-chain or branched-chain radical containing from 1 to 50 carbon atoms, or fewer carbon atoms, and one or more of the heteroatoms. "(C1-C 50 ) The term "heteroalkylene" means a saturated straight-chain or branched-chain diradical containing from 1 to 50 carbon atoms and one or two or more heteroatoms. Examples of heteroatoms for heteroalkyl or heteroalkylene include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P )、N(R N )2, N(R N )、N、O、OR C 、S、SR C 、S(O), and S(O)2, and each of the heteroalkyl and heteroalkylene groups is unsubstituted or substituted by one or more R S .

[0034] Examples of unsubstituted (C2-C 40 ) heterocycloalkyl include unsubstituted (C2-C 20 ) heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thia-cyclononyl, and 2-aza-cyclodecyl.

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

[0036] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group having one or more substituents R S when substituted with, one or more double and / or triple bonds may or may not be present in the substituent R S The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, and not including double bonds that may be present in the substituent R S (if present), or in a (hetero)aromatic ring (if present).

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

[0038] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, and the metal has a formal oxidation state of +2, +3, or +4: each X is an unsaturated (C2-C 20 ) hydrocarbon, an unsaturated (C2-C 50 ) heterohydrocarbon, a (C1-C 50 ) hydrocarbyl, a (C6-C 50 ) aryl, a (C6-C 50 ) heteroaryl, a cyclopentadienyl, a substituted cyclopentadienyl, a (C4-C 12 ) diene, a halogen, -OR C , -N(R N )2, and -NCOR C and is a monodentate or bidentate ligand independently selected from. (X) n The subscript n of is 1 or 2.

[0039] In formula (I), each R 1 is 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 radical having formula (II), a radical having formula (III), and a radical having formula (IV):

Chemical formula

[0040] In formulas (II), (III), and (IV), each of R 31~35 , R 41~48 , and R 51~59 is independently, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -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 OC(O)-, R C C(O)N(R N )-, (R C)Selected from 2NC(O)-, halogen, or -H, provided that at least one of R 1 is a radical having formula (II), a radical having formula (III), or a radical having formula (IV).

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

[0042] In formula (I), for each individual ring containing the groups z1 and z2, each of z1 and z2 is independently selected from the group consisting of sulfur, oxygen, -N(R C )-, and -C(R C )-, provided 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 are independently (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)(RP ) 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, and 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 bonded to form an aromatic or non-aromatic ring.

[0043] In formula (I), each R in formula (I) C , R N , and R P is independently selected from the group consisting of (C1-C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, and -H.

[0044] In formula (I), when Q is -CH2CH2CH2CH2-, each R 1 is 3,6-di-tert-butylcarbazol-9-yl, z2 is sulfur, and when each X is benzyl, R 5a and R 5b are not -OMe, fluorine, or tert-octyl. Further, when Q is -CH2CH2CH2CH2-, R 4a , R 5a , R 6a , and R 7a at least one of is halogen, and R 4b , R 5b , R 6b , and R 7b at least one of is halogen, or when Q is -CH2CH2CH2CH2-, R 4a , R5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b is (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (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, 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 is selected from the group consisting of 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 other embodiments, Y is oxygen and z2 is sulfur.

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

[0048] In one or more embodiments of formula (I), each R 1 is a radical having formula (III), where (1) R 42 and R 47 are selected from the group consisting of (C1-C 20 ) alkyl, -Si(R C )3, -CF3, or halogen, and R 43 and R 46 are -H, or (2) R 43 and R 46 are selected from the group consisting of (C1-C 20 ) alkyl, -Si(R C )3, -CF3, or halogen, and R 42 and R 47 are -H.

[0049] In various embodiments of formula (I), each R 1 is a radical having formula (IV), and R 51~59 is -H. In other embodiments of (I), each R 1 is a radical having formula (IV), and at least one of R 51-59 is selected from the group consisting of (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, or halogen.

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

[0051] In one or more embodiments of formula (I), Q is (C2-C 12 )alkylene, and R 6a and R 6b are fluorine. In other embodiments of formula (I), Q is (C2-C 12 )alkylene, and R 6a and R 6b are chlorine. In various embodiments, Q is (C2-C 12 )alkylene, and R 6a , R 6b R 5a , and R 5b are fluorine. In other embodiments, Q is (C2-C 12 )alkylene, and R 6a , R 6b R 5a , and R 5b are chlorine. In some embodiments, Q is (C2-C 12 )alkylene, and R 6a , R 6b R 5a , R 5b , R 4a , and R 4b are fluorine. In other embodiments, Q is (C2-C 12 )alkylene, and R 6a , R 6b R 5a , R 5b , R 4a , and R 4b are chlorine. In one or more embodiments, Q is (C2-C12 ) is alkylene, R 6a , R 6b R 5a , R 5b , R 7a , and R 7b is fluorine. In some embodiments, Q is (C2-C 12 ) alkylene, 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 1is selected from 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 3,5-di-isopropylphenyl, carbazolyl, carbazol-9-yl, 1,2,3,4-tetrahydrocarbazolyl, 1,2,3,4,5,6,7,8-octahydrocarbazolyl, 3,6-bis-(3,5-di-tert-butylphenyl)carbazol-9-yl, 3,6-bis-(2,4,6-trimethylphenyl)carbazol-9-yl), 3,6-bis-(2,4,6-triisopropylphenyl)carbazol-9-yl, 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-ylanthracenyl, 1,2,3,4-tetrahydroanthracenyl, 1,2,3,4,5,6,7,8-octahydroanthracenyl, phenanthrenyl, 1,2,3,4,5,6,7,8-octahydrophenanthrenyl, 1,2,3,4-tetrahydronaphthyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 3,5-diphenylphenyl, 1-naphthyl, 2-methyl-1-naphthyl, 2-naphthyl, 1,2,3,4-tetra-hydronaphtha-5-yl, 1,2,3,4-tetrahydro-naphtha-6-yl, anthracen-9-yl, 1,2,3,4-tetrahydroanthracen-9-yl, 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl, 1,2,3,4,5,6,7,8-octahydrophenanthren-9-yl, indolyl, indolinyl, quinolinyl, 1,2,3,4-tetrahydroquinolinyl, isoquinolinyl, 1,2,3,4-tetrahydroisoquinolinyl.

[0053] In some embodiments of formula (I), when Q is (C3-C4) alkylene, R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7bOf which at least two 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, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or a halogen. In one or more embodiments, when Q is (C3-C4) alkylene, at least one of R 4a , R 5a , R 6a , R 7a is a halogen, and at least one of R 4b , R 5b , R 6b , R 7b is a halogen. In other embodiments, when Q is (C3-C4) alkylene, at least two of R 4a , R 5a , R 6a , R 7a are halogens, and at least two of R 4b , R 5b , R 6b , R 7bの are halogens. In other embodiments, when Q is (C3-C4) alkylene, at least three of R 4a , R 5a , R 6a , R 7a are halogens, and at least three of R 4b , R 5b , R 6b , R 7b are halogens.

[0054] In one or more embodiments of formula (I), Q is (-CH2Si(R Q )2CH2-), (-CH2CH2Si(R Q )2CH2CH2-), (-CH2Ge(R Q )2CH2-), or (-CH2CH2Ge(R Q )2CH2CH2-), wherein R Q is (C1-C5) alkyl. In other embodiments, Q is benzene-1,2-diyl or cyclohexane-1,2-diyl.

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

[0056] In some embodiments of formula (I), Q is benzen-1,2-diyl dimethyl.

[0057] In some embodiments of the catalyst system, it further comprises a chain transfer agent.

[0058] One or more embodiments of the present disclosure include a process for polymerizing olefins. This process includes contacting ethylene and optionally one or more (C3-C 12 ) α-olefins in the presence of a catalyst system according to any one embodiment disclosed in the present disclosure. In some embodiments, this process further comprises a chain transfer agent.

[0059] In an exemplary embodiment, the catalyst system may comprise a metal-ligand complex according to any of formulas (I) having the structure of any of pro-catalysts 1, 2, 5 to 34.

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

[0060] Cocatalyst component The catalyst system comprising the metal-ligand complex of formula (I) can be catalytically activated by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the precatalyst with the metal-ligand complex of formula (I) can be catalytically activated by contacting the complex with an activating cocatalyst or by combining the complex with an activating cocatalyst. Further, the metal-ligand complex according to formula (I) includes both a neutral precatalyst form and a catalytic form that can be positively charged by the loss of a monoanion ligand such as benzyl or phenyl. Suitable activating cocatalysts for use herein include alkylaluminum, polymeric or oligomeric alumoxane (also known as aluminoxane), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A preferred activating technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means monoalkylaluminum dihydride or monoalkylaluminum dihalide, dialkylaluminum hydride or dialkylaluminum halide, or trialkylaluminum. Examples of polymeric or oligomeric alumoxane include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0061] The Lewis acid activating cocatalyst is (C1-C as described herein 20)It contains a Group 13 metal compound containing a hydrocarbyl substituent. In some embodiments, the Group 13 metal compound is tri((C1-C 20 )hydrocarbyl)-substituted aluminum or tri((C1-C 20 )hydrocarbyl)-boron compound. In other embodiments, the Group 13 metal compound is tri(hydrocarbyl)-substituted aluminum, tri((C1-C 20 )hydrocarbyl)-boron compound, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 )aryl)boron compound, and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluorosubstituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C 20 )hydrocarbyl)borate (e.g., trityl tetrafluoroborate) or tri((C1-C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borate (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to a nitrogen cation that is ((C1-C 20 )hydrocarbyl)4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 )hydrocarbylN(H)3 + , or N(H)4 + , and each (C1-C 20 )hydrocarbyl may be the same or different when two or more are present.

[0062] Examples of combinations of neutral Lewis acid activating cocatalysts include tri((C1-C4)alkyl)aluminum and halogenated tri((C6-C 18)Mixtures comprising an aryl)boron compound, particularly in combination with tris(pentafluorophenyl)borane, are included. Other embodiments are combinations of such neutral Lewis acid mixtures with polymers or oligomeric aluminoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymers or oligomeric aluminoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluoro-phenylborane):(aluminoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluoro-phenylborane):(aluminoxane)]) is from 1:1:1 to 1:10:30, and in other embodiments from 1:1:1.5 to 1:5:10.

[0063] An active catalyst composition can be formed by activating a catalyst system comprising a metal-ligand complex of formula (I) and combining it with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, and combinations thereof, but are not limited thereto.

[0064] In some embodiments, two or more of the aforementioned activating cocatalysts can be used in combination with each other. Specific examples of combinations of cocatalysts are mixtures of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total molar amount of one or more metal-ligand complexes of formula (I) to the total molar amount of one or more activating cocatalysts is from 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000, in some other embodiments at least 1:1000, and 10:1 or less, and in still some other embodiments, 1:1 or less. When an alumoxane is used alone as an activating cocatalyst, the molar amount of the alumoxane used is preferably at least 100 times the molar amount of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane is used alone as an activating cocatalyst, in some other embodiments, the molar amount of tris(pentafluorophenyl)borane used relative to the total molar amount of one or more metal-ligand complexes of formula (I) is from 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of formula (I).

[0065] Chain shuttling agent The term "shuttling agent" refers to a compound or mixture of compounds used in the compositions of the present disclosure that can cause polymeryl exchange between at least two active catalyst sites of a catalyst contained in the composition under polymerization conditions. That is, the movement of polymer fragments occurs both to and from one or more of the active catalyst sites. In contrast to a shuttling agent, a "chain transfer agent" causes termination of polymer chain growth and corresponds to a single transfer of a growing polymer from the catalyst to the transfer agent. In some embodiments, the shuttling agent has an activity ratio RA-B / RB-A of 0.01 to 100, 0.1 to 10, 0.5 to 2.0, or 0.8 to 1.2. The activity ratio RA-B is the rate of polymeryl transfer from the catalyst A active site to the catalyst B active site via the shuttling agent, and RB-A is the reverse polymeryl transfer rate, which is the rate of exchange from the catalyst B activity starting via the shuttling agent to the catalyst A active site. The intermediate formed between the shuttling agent and the polymeryl chain is sufficiently stable such that chain termination is relatively rare. In one or more embodiments, less than 90 percent, less than 75 percent, less than 50 percent, or less than 10 percent of the shuttle-polymeryl product is terminated before three distinguishable polymer segments or blocks are achieved. The rate of chain shuttling (defined by the time required to move a polymer chain from a catalyst site to a chain shuttling agent and then back to a catalyst site) is equal to or faster than the rate of polymer termination, and further up to 10 times, or even 100 times faster than the rate of polymer termination at most. This allows polymer blocks to be formed on the same time scale as polymer propagation.

[0066] Polymer products having different tacticity or regioerror segments, different block lengths, or different numbers of such segments or blocks in each copolymer can be prepared by selecting different combinations of catalysts and various chain shuttling agents. The catalyst can be selected from metal-ligand complexes of formula (I) paired with a mixture of agents having different polymerization capabilities and various chain shuttling agents or combinations of these catalysts. For example, when the activity of the chain shuttling agent is low relative to the catalytic polymer chain propagation rate of one or more catalysts, multi-block copolymers and polymer blends with longer block lengths can be obtained. In contrast, when the chain shuttling is very fast relative to the propagation of the polymer chain, copolymers with more random chain structures and shorter block lengths are obtained. Extremely fast chain shuttling agents can produce multi-block copolymers having substantially random copolymer properties. By appropriately selecting both the catalyst mixture and the chain shuttling agent, relatively pure block copolymers, copolymers containing relatively large polymer segments or blocks, and / or blends of the foregoing with various homopolymers and / or copolymers can be obtained.

[0067] Suitable compositions comprising catalyst A, catalyst B, and a chain shuttling agent can be obtained by the following multi-step procedure specifically adapted for block differentiation based on tacticity or regioerror content.

[0068] I. Polymerize one or more addition-polymerizable C3-30 α-olefin monomers using a mixture comprising a potential catalyst and a potential chain shuttling agent. This polymerization test is carried out using a batch or semi-batch reactor (i.e., without resupplying the catalyst or the chain shuttling agent), preferably at a relatively constant monomer concentration, under solution polymerization conditions, typically using a molar ratio of catalyst to chain shuttling agent of 1:5 to 1:500. After forming a suitable amount of polymer, the reaction is stopped by the addition of a catalyst poison and the properties of the polymer (tacticity and optionally regioerror content) are measured.

[0069] II. Repeat the foregoing polymerization and polymer tests over several different reaction times to provide a series of polymers having a range of yields and PDI values.

[0070] III. A pair of catalyst / shuttling agent that shows significant polymer transfer both to and from the shuttling agent is characterized by a polymer series with a minimum PDI of less than 2.0, more preferably less than 1.5, and most preferably less than 1.3. Moreover, when chain shuttling occurs, the Mn of the polymer increases linearly with increasing conversion. The pair of catalyst and shuttling agent gives the polymer Mn as a function of conversion (or polymer yield) that fits a line having a statistical accuracy (R2) greater than 0.95, preferably greater than 0.99.

[0071] Next, Steps I - III were performed for one or more additional pairings of potential catalysts and / or putative shuttling agents.

[0072] In one or more embodiments, a polymer composition comprising Catalyst A, Catalyst B, and one or more chain shuttling agents according to the present invention is then selected such that each of the two catalysts undergoes chain shuttling by one or more of the chain shuttling agents, and Catalyst A has a higher ability to selectively form stereospecific polymers compared to Catalyst B under the selected reaction conditions. At least one of the chain shuttling agents undergoes polymer transfer in both the forward and reverse directions (as identified in the aforementioned tests) with both Catalyst A and Catalyst B. Further, the chain shuttling agent preferably does not reduce the catalytic efficiency of either catalyst (measured as the weight of the catalyst / weight of polymer produced per unit time) by more than 60% compared to the activity in the absence of the shuttling agent, more preferably does not reduce such catalytic efficiency by more than 20%, and most preferably increases the catalytic efficiency of at least one of the catalysts compared to the catalytic efficiency in the absence of the shuttling agent.

[0073] Alternatively, it is also possible to detect a pair of a catalyst and a shuttling agent by performing a series of polymerizations under standard batch reaction conditions and measuring the resulting polymer properties. Suitable shuttling agents are characterized by reducing the resulting Mn without a significant broadening of the PDI or loss of activity (decrease in yield or rate) with increasing amount of shuttling agent used.

[0074] The aforementioned tests are readily adaptable to high-throughput screening techniques using automated reactors and analytical probes and to the formation of polymer blocks having different discriminative properties (syndiotacticity, isotacticity, and optionally, regioerror content). For example, by combining various organometallic compounds with various proton sources and compounds or reaction products added to the polymerization reaction using an olefin polymerization catalyst composition, a number of potential shuttling agent candidates can be pre-identified or synthesized in situ. Vary the molar ratio of the shuttling agent to the catalyst and conduct several polymerizations. As a minimum requirement, a suitable shuttling agent, as described above, produces a minimum PDI of less than 5.0 in the variable yield experiment while, as described above, not significantly adversely affecting the catalyst activity and catalyst efficiency and preferably improving the catalyst activity and efficiency.

[0075] Regardless of the method for presumptively identifying a shuttling agent, this term is meant to refer to a compound that can currently prepare the identified multiblock copolymer or that can be effectively used under the polymerization conditions disclosed herein. Highly desirably, the average number of blocks or segments per chain (defined as the average number of blocks of different composition divided by the Mn of the polymer) is greater than 3.0, more preferably greater than 3.5, even more preferably greater than 4.0, and less than 25, preferably less than 15, more preferably less than 10.0, and most preferably less than 8.0, formed in accordance with the present invention.

[0076] Suitable chain transfer agents for use herein include metal compounds or complexes of Groups 1, 2, 12, or 13 containing at least one C1-20 hydrocarbyl group, preferably hydrocarbyl-substituted aluminum, gallium, or zinc compounds containing 1 to 12 carbons in each hydrocarbyl group, and reaction products thereof with proton sources. The hydrocarbyl group is an alkyl group, a linear or branched C2-8 alkyl group. In one or more embodiments of the present disclosure, the chain transfer agent may be added to the polymerization process. Chain transfer agents may include trialkylaluminum and dialkylzinc compounds, particularly triethylaluminum, tri(i-propyl)aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium, or diethylzinc. Additional suitable chain transfer agents include the aforementioned organometallic compounds, preferably tri(C1-8)alkylaluminum or di(C1-8)alkylzinc compounds, particularly triethylaluminum, tri(i-propyl)aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, or diethylzinc, combined with a secondary amine or hydroxyl compound in a sub-stoichiometric amount (relative to the number of hydrocarbyl groups), particularly bis(trimethylsilyl)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-azacycloheptaneamine), or 2,6-diphenylphenol, reaction products or mixtures formed thereby. In some embodiments, the chain transfer agent may be selected from amine or hydroxyl reagents such that one hydrocarbyl group remains per metal atom.The main reaction products of the aforementioned combinations for use as chain shuttling agents in the present disclosure are n-octylaluminum di(bis(trimethylsilyl)amide), i-propylaluminum bis(dimethyl(t-butyl)siloxide), and n-octylaluminum di(pyridinyl-2-methoxide), i-butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminum bis(bis(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), i-butylaluminum 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 bis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminum bis(dimethyl(t-butyl)siloxide, ethylzinc(2,6-diphenylphenoxide), and ethylzinc(t-butoxide).

[0077] One of ordinary skill in the art will understand that a chain shuttling agent suitable for a particular catalyst or combination of catalysts may not necessarily be good or even satisfactory for use with different catalysts or combinations of catalysts. Some potential chain shuttling agents may negatively impact the performance of one or more catalysts and may be excluded from use in the polymerization processes of the present disclosure. Thus, in order to achieve a polymer having hard and soft segments, it is necessary to balance the activity of the chain shuttling agent with the catalytic activity of the catalyst.

[0078] However, generally, chain shuttling agents possess the highest polymer transfer rate and the highest transfer efficiency (reduction in the incidence of chain termination). Such chain shuttling agents can still achieve a certain degree of chain shuttling even when used at low concentrations. In addition, such chain shuttling agents result in the generation of the shortest possible polymer block lengths. Due to the fact that the effective molecular weight of the polymer in the reactor decreases, a chain shuttling agent having a single exchange site is used.

[0079] Polyolefin The catalyst systems described in the previous paragraph are utilized for the polymerization of olefins, mainly ethylene and propylene. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme, producing a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomers typically have 20 or fewer carbon atoms. For example, the α-olefin comonomer can have 3 to 10 carbon atoms, or alternatively 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively from the group consisting of 1-hexene and 1-octene.

[0080] In some embodiments, the ethylene-based polymer can comprise at least 50 mole percent of units derived from ethylene. All individual values and subranges from at least 60 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer can comprise at least 63 mole percent of units derived from ethylene, at least 86 mole percent of units, 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, 69 to 85.5 mole percent of units derived from ethylene.

[0081] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50 mol%, other embodiments include at least 1 mole percent (mol%) to 40 mol%, and in further embodiments, the amount of additional α-olefin includes at least 10 mol% to 20 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0082] The ethylene-based polymer may be produced using any conventional polymerization process. Such conventional polymerization processes include solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and any combination thereof that use one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc., in parallel, in series, or any combination thereof, but are not limited thereto.

[0083] In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of the catalyst system described herein and optionally one or more cocatalysts. In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of the catalyst systems disclosed and described herein and optionally one or more other catalysts. The catalyst systems described herein can be used in combination with optionally one or more other catalysts in the first reactor or the second reactor. In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in both reactors in the presence of the catalyst system described herein.

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

[0085] The ethylene-based polymer may further contain one or more additives. Such additives include, but are not limited to, antistatic agents, color intensifiers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer can contain any amount of additives. The ethylene-based polymer can compromise about 0 to about 10 percent of the total weight of such additives, based on the weight of the ethylene-based polymer and one or more additives. The ethylene-based polymer may further contain a filler, and examples of such filler include, but are not limited to, organic or inorganic fillers. The ethylene-based polymer can contain about 0 to about 20 weight percent of a filler, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer can be further blended with one or more polymers to form a blend.

[0086] In some embodiments, the polymerization process for producing the ethylene-based polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, the catalyst system incorporating at least one metal-ligand complex of formula (I). Polymers obtained from such catalyst systems incorporating the metal-ligand complexes of formula (I) can have a density of, for example, 0.850 g / cm 3 ~0.950 g / cm 3 、0.880 g / cm 3 ~0.920 g / cm 3 、0.880 g / cm 3 ~0.910 g / cm 3 、or 0.880 g / cm 3 ~0.900 g / cm 3 in accordance with ASTM D792, which is hereby incorporated by reference in its entirety.

[0087] In another embodiment, the polymer resulting from a catalyst system containing the metal-ligand complex of formula (I) has a melt flow ratio (I 10has an Melt Index I2, where the Melt Index I2 is measured at 190 °C and a load of 2.16 kg in accordance with ASTM D1238 (incorporated herein by reference in its entirety), and the Melt Index I 10 is measured at 190 °C and a load of 10 kg in accordance with ASTM D1238. In other embodiments, the Melt Flow Ratio (I 10 / I2) is from 5 to 10, and in others, the Melt Flow Ratio is from 5 to 9.

[0088] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a polydispersity index (PDI) of from 1 to 25, where the PDI is defined as M w / M n where M w is the weight average molecular weight and M n is the number average molecular weight. In other embodiments, the polymer obtained from the catalyst system has a PDI of from 1 to 6. Another embodiment includes a PDI of from 1 to 3, and other embodiments include a PDI of from 1.5 to 2.5.

[0089] Embodiments of the catalyst systems described in the present disclosure result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0090] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing them through activated alumina and, in some cases, Q-5 reactant. Solvents used in experiments conducted in a nitrogen-filled glove box were further dried by storage over activated 4 Å molecular sieves. Glassware for moisture-sensitive reactions was dried in an oven overnight before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis was performed using a Waters e2695 separation module combined with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation was carried out on an XBridge C18 3.5 μm 2.1×50 mm column using a gradient of acetonitrile and water from 5:95 to 100:0 (containing 0.1% formic acid as the ionizing agent). HRMS analysis was performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1×50 mm column combined with an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 1H NMR data are reported as follows: chemical shift (multiplicity (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet, and m = multiplet), integration value, and assignment). Residual protons in deuterated solvents were used as reference substances, 1 and the chemical shifts of 1H NMR data are reported in ppm (TMS, δ scale) of low magnetic field from the inside of tetramethylsilane. 13 13C NMR data were 1 determined using 1H decoupling, and the chemical shifts are reported as low magnetic field (ppm) from tetramethylsilane (TMS, δ scale) using residual carbon in deuterated solvents as a reference.

[0091] General Procedure for PPR Screening Experiments Polyolefin catalyst screening is performed in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consists of an array of 48 single-cell (6×8 matrix) reactors within an inert atmosphere glove box. Each cell is equipped with a glass insert having an internal working liquid volume of approximately 5 mL. Each cell has independent pressure control and continuously stirs the liquid within the cell at 800 rpm. The catalyst solution is prepared by dissolving an appropriate amount of procatalyst in toluene, unless otherwise stated. All liquids (e.g., solvent, 1-octene, chain shuttling agent solution appropriate for the experiment, and catalyst solution) are added to the single-cell reactor via a robotic syringe. Gaseous reagents (i.e., ethylene, H2) are added to the single-cell reactor via a gas injection port. Prior to each run, the reactor is heated to 80 °C, purged with ethylene, and aerated.

[0092] A portion of Isopar-E is added to the reactor. The reactor is heated to the operating temperature and pressurized with ethylene to the appropriate psig. The toluene solution of the reagents is added in the following order: (1) 1-octene together with 500 nmol of the scavenger MMAO-3A, (2) the activator (cocatalyst-1, cocatalyst-2, etc.), and (3) the catalyst.

[0093] After adding each liquid, a small amount of Isopar-E is added to make the total reaction volume 5 mL after the final addition. When the catalyst is added, the PPR software starts monitoring the pressure of each cell. The pressure (within approximately 2 - 6 psig) is maintained by additional addition of ethylene gas by opening the valve at the setpoint minus 1 psi and closing the valve when the pressure exceeds 2 psi. All pressure drops are cumulatively recorded as "uptake" or "conversion" of ethylene over the course of the run, or at the earliest time during the run that the uptake or conversion request value is reached. Each reaction is quenched by addition of 10% carbon monoxide in argon for 4 minutes at a pressure 40 - 50 psi higher than the reactor pressure. A shorter "quench time" means the catalyst is more active. To prevent the formation of excess polymer in any given cell, the reaction is quenched when a predetermined uptake level (50 psig for a run at 120 °C, 75 psig for a run at 150 °C) is reached. After quenching all reactions, the reactor is cooled to 70 °C. The reactor is vented and purged with nitrogen for 5 minutes to remove carbon monoxide, and the tube is removed. The polymer sample is dried in a centrifugal evaporator at 70 °C for 12 hours, weighed to determine the polymer yield, and subjected to IR (incorporation of 1-octene) and GPC (molecular weight) analysis.

[0094] SymRAD HT - Composition GPC Analysis The molecular weight data of the samples prepared by PPR experiments were determined by analysis with a Robot-Assisted Dilution High-Temperature Gel Permeation Chromatographer (Sym-RAD-GPC) jointly constructed by Symyx / Dow. The polymer samples were dissolved by heating in 1,2,4-trichlorobenzene (TCB) at 160 °C for 120 minutes at a concentration of 10 mg / mL stabilized with 300 parts per million (ppm) of butylated hydroxytoluene (BHT). Immediately prior to injecting 250 μL aliquots of the samples, each sample was diluted to 1 mg / mL. The GPC was equipped with two Polymer Labs PLgel 10 μm Mixed-B columns (300 × 10 mm) at a flow rate of 2.0 mL / min at 160 °C. Detection of the samples was performed using a PolymerChar IR5 detector in the concentration mode. A conventional calibration with narrow polystyrene (PS) standards was utilized with apparent units adjusted to homopolyethylene (PE) using known Mark-Houwink coefficients for PS and PE in TCB at this temperature. The incorporation of octene was determined using a linear calibration developed by analyzing copolymers of known composition using a PolymerChar IR5 detector.

[0095] 1-Octene Incorporation IR Analysis The execution of the sample for HT-GPC analysis precedes the IR analysis. In some cases, the incorporation of octene is determined from the compositional GPC analysis, and in other cases, this individual IR analysis is performed. For the IR analysis, a 48-well HT silicon wafer is utilized for the deposition of the sample and the analysis of 1-octene incorporation. In the analysis, the sample is heated to 160 °C for up to 210 minutes, the sample is reheated to remove the magnetic GPC stir bar, and shaken using a glass rod stir bar in a J-KEM Scientific heated robotic shaker. The sample is deposited while being heated using the 75 deposition stations of a Tecan MiniPrep, and 1,2,4-trichlorobenzene is evaporated from the deposition wells of the wafer at 160 °C under a nitrogen purge. The analysis of 1-octene is performed on the HT silicon wafer using a NEXUS 670 E.S.P. FT-IR.

[0096] Batch Reactor Polymerization Procedure The polymerization reaction in the batch reactor is 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 are controlled and monitored by a Camile™ TG process computer. At the bottom of the reactor, a dump valve is attached to transfer the contents of the reactor to a stainless-steel dump pot. The dump pot is pre-filled with a catalyst deactivation solution (typically, a 5 mL mixture of Irgafos / Irganox / toluene). Both the pot and the tank are purged with nitrogen and the dump pot is vented to a 30-gallon blowdown tank. All solvents used for polymerization or catalyst replenishment are passed through a solvent purification column to remove any impurities that could affect the polymerization. 1-Octene and Isopar E are passed through two columns, a first column containing A2 alumina and a second column containing Q5. Ethylene is passed through two columns, a first column containing a204 alumina and a second column containing Q5. The N2 used for transfer is passed through A204 alumina,

Chemical formula

[0097] The reactor is first charged from a shot tank that may contain IsoparE solvent and / or 1-octene, depending on the reactor load. The shot tank is filled to the load set point using a lab scale attached to the shot tank. After adding the liquid feed, the reactor is heated to the polymerization temperature set point. When using ethylene, ethylene is added to the reactor when the reaction temperature is reached to maintain the reaction pressure set point. The amount of ethylene added is monitored by a Micro Motion flow meter. For some experiments, the standard conditions at 120 °C are 46 g of ethylene and 303 g of 1-octene in 611 g of IsoparE, and the standard conditions at 150 °C are 43 g of ethylene and 303 g of 1-octene in 547 g of IsoparE.

[0098] The procatalyst and activator are mixed with an appropriate amount of purified toluene to obtain a molar concentration solution. The procatalyst and activator are processed inside an inert glove box, drawn into a syringe, and pressure transferred into the catalyst shot tank. The syringe is rinsed three times with 5 mL of toluene. Immediately after the catalyst is added, the run timer starts. When using ethylene, it is added by Camille to maintain the reaction pressure set point inside the reactor. The polymerization reaction is run for 10 minutes, then the stirrer is stopped and the bottom dump valve is opened to transfer the contents of the reactor to the dump pot. The contents of the dump pot are poured into a tray and placed in a fume hood where the solvent is evaporated overnight. The tray containing the remaining polymer is transferred to a vacuum oven and heated to 140 °C under vacuum to remove any remaining solvent. After the tray is cooled to ambient temperature, the polymer yield is measured to determine efficiency and the polymer is subjected to polymer testing.

[0099] PolymerChar HT - Composition GPC Analysis The polymer samples generated by the batch polymerization process were analyzed by high-temperature GPC analysis using a PolymerChar GPC equipped with an infrared detector (IR5) and an Agilent PLgel MIXED-A column. Decane (10 μL) was added to each sample for use as an internal flow marker. First, the sample was diluted to a concentration of 10 mg / mL in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm of butylated hydroxytoluene (BHT) and dissolved by stirring at 160 °C for 120 minutes. Prior to injection, the sample was further diluted to a concentration of 2 mg / mL with TCB stabilized with BHT. The sample (200 μL) was eluted through one PLgel 20 μm (50×7.5 mm) guard column, followed by four PLgel 20 μm (300×7.5 mm) MIXED-A columns, and maintained at 160 °C with TCB stabilized with BHT at a flow rate of 1.0 ml / min. The total run time was 40 minutes. To calibrate the molecular weight (MW), Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 mL of TCB stabilized with BHT and dissolved by stirring at 160 °C for 15 minutes. The PS standards were injected into the system without further dilution to create a tertiary MW calibration curve with apparent units adjusted to homopolyethylene (PE) using the known Mark-Houwink coefficients (α sty = 0.722, logK sty = -3.993, α eth = 0.725, logK eth = -3.391) for PS and PE. The incorporation of octene was determined by the use of a linear calibration developed by analyzing copolymers with known compositions.

[0100] Chain shuttling activity Catalytic efficiency, i.e., the M of the corresponding polymer produced from a specific catalyst w, incorporation of comonomers, and beyond PDI, understanding the chain transfer ability of new catalysts is one of the important aspects in developing new polyolefin catalyst groups at Dow. The chain transfer ability of a catalyst is initially evaluated by performing experiments to vary the level of chain transfer or chain shuttling agent (CSA) in order to observe the expected decrease in molecular weight and narrowing of PDI for a shuttling catalyst. The molecular weight of the polymer produced by a catalyst that has the potential to be a good chain transfer agent is more susceptible to the addition of CSA than the molecular weight of the polymer produced by a shuttling catalyst with inferior functionality. The Mayo equation (Equation 1) represents how the number average chain length

Chem.

Chem.

Math.

[0101] To determine the chain transfer rates of precatalysts 1 - 7 and 9 - 52, semi - batch experiments were conducted using various amounts of the chain transfer agent, Et2Zn (0, 50, and 200 μmol). All reactions were carried out at 120 or 150 °C with 1.2 equivalents of [HNMe(C 18 H 37)2][B(C6F5)4] was used and precatalysts 7, 8, 11, and 12 were premixed for 10 minutes in a 0.005 M solution containing excess MMAO-3A (10.0 equivalents) prior to subjecting them to polymerization experiments. Batch runs were conducted at 120 °C and 150 °C using 11.1 or 12.1 g of ethylene, 56 g or 57 g of 1-octene, and 528 g or 555 g of Isopar E under a pressure of 76 - 136 psi. Catalyst efficiency, as well as the M w , PDI, and comonomer incorporation of the corresponding polymers produced are shown in Table 2. The M n for each run was calculated using Equation 3 with the values of Ca and M n0 fit using Microsoft Excel Solver to minimize the sum of the squared deviations between the fitted molecular weight data and the experimental molecular weight data for all runs using a particular catalyst. Plots of M n versus [CSA] for precatalysts 1 - 52 are shown in Figure 5, including a line showing the expected dependence of M n on [CSA] from the best-fit value of Ca, and the calculated Ca values are shown in Table 3.

Examples

[0102] Examples 1 - 79 are synthetic procedures for ligands, ligands, and isolated precatalyst intermediates, see Figures 1 - 4. One or more features of the present disclosure are illustrated in the context of the following examples.

[0103] Precatalysts 1 - 34 were synthesized from ligands 1 - 17 presented in Figure 1. Ligands 1 - 17 were synthesized by the representative synthetic schemes shown in Figures 2 and 3.

[0104] All solvents and reagents were obtained from commercial suppliers and used as received without further purification unless otherwise specified. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing them through activated alumina and, in some cases, Q-5 reactant. Solvents used in experiments conducted in a nitrogen-filled glove box were further dried by storage over activated 4 Å molecular sieves. Glassware for moisture-sensitive reactions was dried in an oven overnight before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis was performed using a Waters e2695 separation module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation was carried out on a 3.5 μm, 2.1×50 mm XBridge C18 column using a gradient of acetonitrile to water from 5:95 to 100:0 with 0.1% formic acid as the ionizing agent. HRMS analysis was performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm, 2.1×50 mm column coupled to an Agilent 6230 TOF mass spectrometer by electrospray ionization method. 1 1H NMR data are reported as follows: chemical shift (multiplicity (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet, and m = multiplet), integration value, and assignment). Residual protons in deuterated solvents were used as reference substances. 1 The chemical shifts of 1H NMR data are reported in ppm (TMS, δ scale) at lower magnetic field than internal tetramethylsilane. 13 13C NMR data were 1 determined by 1H decoupling and the chemical shifts are reported in ppm (TMS, δ scale) at lower magnetic field than tetramethylsilane using residual carbon in deuterated solvents as reference substances.

[0105] Example 1: Synthesis of Hydroxy-Thiophene Intermediate - Steps 1 and 2 of Figure 2 [Chemical] To a suspension of hydroxythiophene (10.020 grams, 42.267 mmol, 1.00 equivalent) in nitrogen-purged 1,4-dioxane (100 mL) and H2O (450 mL), NaOH (50.000 g, 1.250 mol, 29.6 equivalents) was added all at once. At this point, a reflux condenser was attached to the pale yellow mixture, and it was placed in a mantle heated to 80 °C. After stirring (500 rpm) for 2.5 hours, the TLC of the bright yellow solution at this point showed complete conversion to a lower R spot of the starting thiophene. The mixture was removed from the mantle, cooled gradually to 23 °C, placed in an ice bath for 60 minutes, and concentrated HCl (125 mL, 37%) was added over 10 minutes. At this point, the white heterogeneous mixture was removed from the ice bath, placed in a mantle heated to 60 °C, stirred vigorously (1000 rpm) for 5 hours, and at this point, the pale bright yellow solution was removed from the mantle, cooled gradually to 23 °C, diluted with Et2O (100 mL), stirred vigorously for 2 minutes, poured into a separatory funnel, separated, the organic layer was washed with aqueous HCl (2 × 100 mL, 1 N), the remaining organic matter was extracted from the aqueous layer using Et2O (2 × 50 mL), dried over solid Na2SO4, decanted, and the Et2O was removed by rotary evaporation to obtain crude bromo-hydroxythiophene as a 1,4-dioxane (100 mL) solution. An aliquot was taken out and completely concentrated under reduced pressure, and NMR showed a pure product present as a mixture of tautomers. This material was used in the next experiment without concentration or purification. f

[0106] A clear pale yellow solution of hydroxythiophene in 1,4 - dioxane (100 mL, as above) was diluted with anhydrous, non - deoxygenated THF (400 mL), H2O (6 mL) was added, the solution was placed in an ice - water bath, sparged with nitrogen for 1 hour, placed under a positive flow of nitrogen, and then solid lithium hydroxide monohydrate (3.544 g, 84.453 mmol, 2.00 equivalents) was added. The mixture, which had changed to a dark reddish - brown solution, was stirred vigorously (1000 rpm) for 1 hour, and then undiluted chloroethyl methyl ether (11.8 mL, 126.80 mmol, 3.00 equivalents) was added rapidly via syringe in a drop - wise manner. After stirring at 0 °C for 2 hours, the dark brown solution was diluted with aqueous NaOH solution (200 mL, 1 N), stirred for 2 minutes, THF was removed under reduced pressure, the biphasic mixture was diluted with CH2Cl2 (100 mL), suction - filtered through a Celite pad, rinsed with CH2Cl2 (4×50 mL), the dark brown filtrate mixture was poured into a separatory funnel, separated, the organic matter was washed with aqueous NaOH solution (2×100 mL, 1 N), the remaining organic matter was extracted from the aqueous solution using CH2Cl2 (2×50 mL), mixed, dried over solid Na2SO4, decanted, and carefully concentrated to give an amber oil, which was diluted with CH2Cl2 (25 mL), suction - filtered through a silica gel pad, rinsed with CH2Cl2 (4×50 mL), and the filtrate was concentrated to give thiophene - ether as a bright yellow oil (9.534 g, 40.209 mmol, 95% 2 - step). NMR indicated the product.

[0107] Hydroxythiophene exists as a mixture of tautomers: * indicates the keto tautomer. 1 H NMR (400 MHz, chloroform - d) δ(8.34(s, 1H))*, 7.12(d, J = 3.7 Hz, 1H), 6.43(d, J = 3.7 Hz, 1H), 5.49(s, 1H),(3.72(s, 2H))*. 13 C NMR (101 MHz, chloroform - d) δ(210.23)*, 195.46, 160.19, (149.69)*, 121.43, (111.65)*, 100.24, (37.05)*.

[0108] Characteristics Evaluation of Protected Hydroxythiophene: 1 1H NMR (400 MHz, chloroform-d) δ 7.15 (d, J = 3.6 Hz, 1H), 6.61 (d, J = 3.5 Hz, 1H), 5.19 (s, 2H), 3.73 (q, J = 7.1 Hz, 2H), 1.22 (t, J = 7.1 Hz, 3H). 13 13C NMR (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 Figure 2

Chemical Structure

[0110] 1 1H NMR (500 MHz, chloroform-d) δ 8.12 (d, J = 1.9 Hz, 2H), 7.45 (dd, J = 8.6, 2.0 Hz, 2H), 7.32 (d, J = 3.6 Hz, 1H), 7.20 (d, J = 8.6 Hz, 2H), 6.89 (d, J = 3.6 Hz, 1H), 3.56 (q, J = 7.1 Hz, 2H), 1.47 (s, 18H), 1.16 (t, J = 7.1 Hz, 3H). 13 13C 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 Boropinate Intermediate - Step 4 of Figure 2

Chemical Structure

[0112] 1 H NMR (500 MHz, chloroform-d) δ 8.11 - 8.08 (m, 2H), 7.62 (d, J = 0.9 Hz, 1H), 7.45 (dt, J = 8.6, 1.4 Hz, 2H), 7.23 (dd, J = 8.7, 0.7 Hz, 2H), 4.88 (d, J = 0.8 Hz, 2H), 2.96 - 2.88 (m, 2H), 1.46 (s, 18H), 1.38 (s, 12H), 0.58 (t, J = 7.1 Hz, 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, 98.24, 84.20, 64.53, 34.71, 32.03, 24.80, 14.14.

[0113] Example 4: Synthesis of Linked Iodophenyl Ether Intermediate

Chemical formula

[0114] 1 H NMR (500 MHz, chloroform-d) δ 7.77 (dd, J = 7.8, 1.8 Hz, 2H), 7.34 - 7.22 (m, 2H), 6.83 (d, J = 8.2 Hz, 2H), 6.70 (t, J = 7.6 Hz, 2H), 4.14 (d, J = 5.3 Hz, 4H), 2.17 - 2.06 (m, 4H). 13 C NMR (126 MHz, chloroform-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 Intermediate

Chemical formula

[0116] 1 H NMR (500 MHz, chloroform-d) δ 7.74 (dd, J = 7.7, 1.6 Hz, 2H), 7.30 (ddd, J = 8.6, 7.6, 1.6 Hz, 2H), 6.98 (dd, J = 8.1, 1.3 Hz, 2H), 6.69 (td, J = 7.6, 1.4 Hz, 2H), 3.95 (s, 4H), 1.16 (t, J = 7.8 Hz, 6H), 0.99 (qd, J = 7.8, 1.1 Hz, 4H). 13 C NMR (126 MHz, chloroform-d) δ 159.46, 139.14, 129.41, 122.23, 111.16, 86.44, 57.91, 7.44, 1.74.

[0117] Example 6: Synthesis of 1,2-dibenzyl-bridged iodophenyl ether intermediate

Chemical formula

[0118] 1 H NMR (500 MHz, chloroform - d) δ 7.81 (dd, J = 7.7, 1.6 Hz, 2H), 7.71 - 7.64 (m, 2H), 7.46 - 7.39 (m, 2H), 7.30 (ddd, J = 8.3, 7.4, 1.6 Hz, 2H), 6.97 (dd, J = 8.3, 1.3 Hz, 2H), 6.74 (td, J = 7.6, 1.4 Hz, 2H), 5.31 (s, 4H). 13 C NMR (126 MHz, chloroform - d) δ 156.94, 139.60, 134.42, 129.60, 128.75, 128.45, 112.55, 86.46, 69.21.

[0119] Example 7: Synthesis of trans - methylenecyclohexylbis(iodophenyl)ether cross - linking intermediate

Chemical formula

[0120] 1 1H NMR (500 MHz, chloroform-d) δ 7.76 (dd, J = 7.9, 1.6 Hz, 2H), 7.26 (td, J = 7.8, 1.6 Hz, 2H), 6.82 (dd, J = 8.2, 1.3 Hz, 2H), 6.69 (td, J = 7.6, 1.4 Hz, 2H), 4.10 - 3.98 (m, 4H), 2.01 (ddt, J = 25.4, 13.2, 2.9 Hz, 4H), 1.86 (dq, J = 8.4, 2.9 Hz, 2H), 1.52 (dd, J = 17.3, 7.8 Hz, 2H), 1.41 (ddt, J = 12.0, 8.9, 4.9 Hz, 2H). 13 13C NMR (126 MHz, 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: 11H NMR (500 MHz, chloroform-d) δ 7.76 - 7.71 (m, 3H), 7.28 - 7.23 (m, 3H), 6.69 (td, J = 7.6, 1.3 Hz, 1H), 6.62 (dd, J = 8.3, 1.4 Hz, 1H), 4.09 - 4.03 (m, 2H), 3.81 (dd, J = 9.3, 4.4 Hz, 1H), 3.74 (dd, J = 9.3, 3.6 Hz, 1H), 2.38 (s, 3H), 1.93 - 1.64 (m, 6H), 1.46 (qd, J = 12.1, 3.0 Hz, 1H), 1.28 (dd, J = 11.3, 8.4 Hz, 3H). 13 13C NMR (126 MHz, chloroform-d) δ 157.17, 144.65, 139.25, 132.77, 129.80, 129.40, 127.94, 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: Synthesis of Trans-Methylenecyclohexylbisiodophenyl Ether Crosslinking Intermediate

Chemical Structure

[0123] 1 1H NMR (500 MHz, chloroform-d) δ 7.76 (dd, J = 7.9, 1.6 Hz, 2H), 7.26 (td, J = 7.8, 1.6 Hz, 2H), 6.82 (dd, J = 8.2, 1.3 Hz, 2H), 6.69 (td, J = 7.6, 1.4 Hz, 2H), 4.10 - 3.98 (m, 4H), 2.01 (ddt, J = 25.4, 13.2, 2.9 Hz, 4H), 1.86 (dq, J = 8.4, 2.9 Hz, 2H), 1.52 (dd, J = 17.3, 7.8 Hz, 2H), 1.41 (ddt, J = 12.0, 8.9, 4.9 Hz, 2H). 13 13C NMR (126 MHz, 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 in Figure 2

Chemical Structure

[0125] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupled product in CH2Cl2-1,4-dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1 × 10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 75% CH2Cl2 in hexane to give bisthiophene as a pale yellowish brown solid (0.563 g, 0.5668 mmol, 75%, 66% over 2 steps). NMR indicated a 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, 1.7 Hz, 2H), 7.40 (dd, J = 8.6, 1.9 Hz, 4H), 7.32 (s, 2H), 7.30 - 7.20 (m, 6H), 7.12 (t, J = 7.5 Hz, 2H), 6.90 (d, J = 8.2 Hz, 2H), 4.11 - 4.04 (m, 4H), 1.95 - 1.87 (m, 4H), 1.43 (s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 153.71, 146.43, 142.65, 139.63, 130.50, 128.74, 127.55, 123.42, 123.16, 123.08, 122.96, 120.13, 116.18, 115.28, 114.09, 109.57, 69.98, 34.68, 32.02, 25.86.

[0127] Characterization of the protected coupled product: 11H NMR (500 MHz, chloroform-d) δ 8.13 (h, J = 1.9 Hz, 4H), 7.94 (ddd, J = 7.6, 4.1, 2.3 Hz, 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 = 3.0 Hz, 4H), 4.30 - 4.19 (m, 4H), 2.79 (qt, J = 7.2, 2.7 Hz, 4H), 2.29 - 2.20 (m, 4H), 1.48 (s, 36H), 0.52 (tt, J = 7.1, 2.9 Hz, 6H). 13 13C NMR (126 MHz, chloroform-d) δ 155.83, 147.29, 142.72, 139.49, 131.10, 129.37, 129.13, 124.29, 123.66, 123.07, 121.52, 120.61, 119.19, 115.96, 112.07, 109.85, 96.97, 68.36, 64.61, 34.73, 32.06, 26.37, 14.17.

[0128] Example 10: Synthesis of Pro-catalyst 3

Chemical Structure

[0129] 11H NMR (500 MHz, benzene-d6) δ 8.48 (dd, J = 2.0, 0.6 Hz, 2H), 8.22 (dd, J = 1.9, 0.7 Hz, 2H), 7.50 - 7.46 (m, 4H), 7.31 - 7.24 (m, 6H), 6.98 - 6.96 (m, 4H), 6.86 (s, 2H), 6.83 - 6.75 (m, 4H), 6.70 (td, J = 7.5, 1.2 Hz, 2H), 6.23 - 6.17 (m, 4H), 5.12 (dd, J = 8.2, 1.2 Hz, 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 = 12.4 Hz, 2H), 0.77 - 0.67 (m, 2H), 0.52 - 0.44 (m, 4H). 13 13C NMR (126 MHz, benzene-d6) δ 156.11, 152.23, 147.06, 143.09, 142.73, 139.24, 139.14, 130.95, 129.75, 126.42, 126.17, 125.92, 125.20, 124.55, 123.48, 122.65, 122.35, 120.75, 117.04, 116.94, 116.27, 115.52, 112.51, 108.85, 80.97, 75.18, 34.57, 34.41, 32.01, 31.71, 26.01.

[0130] Example 11: Synthesis of Pro-Catalyst 4 [Chemical formula] The thiophene ligand was azeotropically dried using PhMe (4 × 10 mL) before use. In a nitrogen-filled glove box at 23 °C, a solution of HfBn4 (8.4 mg, 15.50 μmol, 1.10 equiv) in C6D6 (0.33 mL) was added dropwise to a clear colorless solution of thiophene (14.0 mg, 14.09 μmol, 1.00 equiv) in anhydrous C6D6 (2.49 mL). After stirring for 30 min (500 rpm), the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.0025 M solution in C6D6. NMR indicated the product. Using the same procedure with PhMe as the solvent, a precatalyst solution (0.0025 M) used immediately after filtration for the polymerization experiment could be prepared.

[0131] 1 1H NMR (500 MHz, benzene-d6) δ 8.49 (dd, J = 2.0, 0.6 Hz, 2H), 8.23 (dd, J = 2.0, 0.6 Hz, 2H), 7.47 (ddd, J = 8.8, 5.0, 1.9 Hz, 4H), 7.27 (ddd, J = 8.5, 4.4, 1.2 Hz, 4H), 7.17 (dd, J = 8.7, 0.6 Hz, 2H), 6.99 - 6.95 (m, 4H), 6.86 (s, 2H), 6.78 (dddd, J = 8.6, 7.3, 3.6, 1.5 Hz, 4H), 6.71 (td, J = 7.6, 1.2 Hz, 2H), 6.22 - 6.16 (m, 4H), 5.15 (dd, J = 8.2, 1.2 Hz, 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 = 13.3 Hz, 2H), 0.78 - 0.68 (m, 2H), 0.47 - 0.36 (m, 2H), 0.22 (d, J = 13.3 Hz, 2H). 1313C NMR (126 MHz, benzene-d6) δ 155.80, 152.29, 147.74, 143.15, 142.74, 139.23, 139.09, 130.95, 129.74, 128.54, 127.06, 126.75, 126.10, 125.28, 124.59, 123.68, 122.60, 122.28, 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

Chemical formula

[0133] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupled product in CH2Cl2-1,4-dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1×10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2×10 mL), mixed, dried over solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system, with 10% - 75% CH2Cl2 in hexane, to give bisthiophene (0.559 g, 0.5368 mmol, 77%, 62% over 2 steps) as a pale yellowish brown solid. NMR indicated a 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, 1.7 Hz, 2H), 7.41 (dd, J = 5.6, 3.5 Hz, 2H), 7.36 - 7.30 (m, 8H), 7.25 - 7.20 (m, 2H), 7.13 (t, J = 7.5 Hz, 2H), 7.07 (d, J = 8.5 Hz, 4H), 6.95 (d, J = 8.2 Hz, 2H), 6.91 (s, 2H), 5.20 (s, 4H), 1.46 (s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 153.64, 146.41, 142.61, 139.45, 133.72, 130.67, 129.89, 129.34, 128.95, 127.80, 123.54, 123.37, 123.19, 123.18, 119.90, 116.09, 115.35, 114.78, 109.55, 70.58, 34.69, 32.04.

[0135] Characterization of the protected coupled product: 11H NMR (500 MHz, chloroform-d) δ 8.12 (d, J = 1.8 Hz, 4H), 7.84 (dd, J = 7.7, 1.7 Hz, 2H), 7.69 (dd, J = 5.5, 3.4 Hz, 2H), 7.50 (dd, J = 5.6, 3.4 Hz, 2H), 7.41 (dd, J = 8.6, 1.9 Hz, 4H), 7.32 (d, J = 1.2 Hz, 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 = 7.0 Hz, 4H), 1.49 (s, 36H), 0.51 (t, J = 7.0 Hz, 6H). 13 13C NMR (126 MHz, chloroform-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, 119.10, 115.91, 112.86, 109.84, 96.87, 68.89, 64.52, 34.74, 32.07, 14.19.

[0136] Example 13: Synthesis of the precatalyst 1

Chemical formula

[0137] 11H NMR (400 MHz, benzene-d6) δ 8.49 (d, J = 1.9 Hz, 2H), 8.22 (d, J = 1.9 Hz, 2H), 7.53 (dd, J = 8.6, 1.9 Hz, 2H), 7.44 (dd, J = 8.7, 1.9 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H), 7.24 (d, J = 8.7 Hz, 2H), 7.17 (dd, J = 7.7, 1.7 Hz, 2H), 6.98 - 6.94 (m, 4H), 6.79 (td, J = 7.7, 1.8 Hz, 2H), 6.75 (s, 2H), 6.66 (ddd, J = 10.5, 6.6, 2.2 Hz, 2H), 6.58 (t, J = 7.1 Hz, 2H), 6.29 (dd, J = 5.5, 3.4 Hz, 2H), 6.25 - 6.20 (m, 2H), 5.40 (d, J = 13.0 Hz, 2H), 5.35 (dd, J = 8.4, 1.1 Hz, 2H), 4.18 (d, J = 13.0 Hz, 2H), 1.53 (s, 18H), 1.27 (s, 18H), 0.94 (d, J = 12.0 Hz, 2H), 0.46 (d, J = 12.0 Hz, 2H). 13 13C NMR (101 MHz, benzene-d6) δ 155.22, 151.79, 145.67, 142.96, 142.78, 139.33, 139.29, 133.07, 131.03, 129.54, 128.17, 127.00, 125.46, 125.05, 124.45, 122.85, 122.43, 121.17, 117.52, 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 Pro-Catalyst 2

Chem.

[0139] 1 1H NMR (500 MHz, benzene-d6) δ 8.52 (dd, J = 2.0, 0.6 Hz, 2H), 8.24 (dd, J = 2.0, 0.6 Hz, 2H), 7.53 (dd, J = 8.5, 1.9 Hz, 2H), 7.44 (dd, J = 8.7, 1.9 Hz, 2H), 7.36 (dd, J = 8.5, 0.6 Hz, 2H), 7.18 (dd, J = 7.7, 1.7 Hz, 2H), 7.16 (dd, J = 8.7, 0.6 Hz, 2H), 6.99 - 6.95 (m, 4H), 6.82 (ddd, J = 8.2, 7.4, 1.7 Hz, 2H), 6.76 (s, 2H), 6.68 (dd, J = 7.6, 1.1 Hz, 2H), 6.64 (dd, J = 5.6, 3.3 Hz, 2H), 6.29 - 6.23 (m, 4H), 5.37 (d, J = 13.1 Hz, 2H), 5.35 (dd, J = 8.3, 1.2 Hz, 2H), 4.17 (d, J = 13.2 Hz, 2H), 1.54 (s, 18H), 1.29 (s, 18H), 0.90 (d, J = 13.2 Hz, 2H), 0.21 (d, J = 13.2 Hz, 2H). 1313C NMR (126 MHz, benzene-d6) δ 154.89, 151.88, 146.91, 143.06, 142.81, 139.32, 139.30, 132.85, 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, 117.02, 116.31, 115.53, 112.45, 109.11, 80.12, 78.51, 34.63, 34.41, 32.05, 31.73.

[0140] Example 15: Synthesis of Ligand 4 [Chemical formula] A mixture of thiophene boropinicolate ester (1.931 g, 2.476 mmol, 3.00 equivalents, purity 72% by NMR), K3PO4 (1.577 g, 7.428 mmol, 9.00 equivalents), Pd(AmPhos)Cl2 (117.0 mg, 0.1650 mmol, 0.20 equivalents), and bisphenyl iodide (0.456 g, 0.8252 mmol, 1.00 equivalent). The mixture was evacuated and then refilled with nitrogen, and this process was repeated 3 more times. Then, deoxygenated 1,4-dioxane (15.0 mL) and deoxygenated water (1.5 mL) were sequentially added by syringe. The mixture was then placed in a mantle heated to 50 °C. After vigorous stirring (1000 rpm) for 40 hours, the black mixture was removed from the mantle, cooled slowly to 23 °C, suction filtered through a silica gel pad, washed with CH2Cl2 (4 × 20 mL), the clear black filtrate was concentrated, and the residual 1,4-dioxane was removed azeotropically using toluene (2 × 10 mL) by rotary evaporation. Then, the black mixture was suspended in CH2Cl2 (20 mL), suction filtered through a silica gel pad, rinsed with CH2Cl2 (4 × 20 mL), and then the black filtrate was concentrated onto celite and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 50% CH2Cl2 in hexanes to give bisthiophene (0.822 g, 0.7040 mmol, 85%) as a red amorphous oil. NMR indicated a pure product.

[0141] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupling product in CH2Cl2-1,4-dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1×10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2×10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system. With 10% - 75% CH2Cl2 in hexane, bisthiophene (0.541 g, 0.5145 mmol, 73%, 62% over 2 steps) was obtained as a pale yellowish brown solid. NMR indicated a 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, 1.9 Hz, 2H), 7.45 (dd, J = 8.6, 1.9 Hz, 4H), 7.37 (s, 2H), 7.23 (d, J = 8.6 Hz, 4H), 7.04 (dtd, J = 20.2, 7.5, 1.6 Hz, 4H), 6.78 (s, 2H), 6.69 (dd, J = 8.1, 1.4 Hz, 2H), 3.88 (s, 4H), 1.50 (s, 36H), 0.85 (t, J = 7.9 Hz, 6H), 0.67 (q, J = 7.9 Hz, 4H). 13 C NMR (126 MHz, chloroform-d) δ 156.35, 146.38, 142.68, 139.95, 130.38, 129.03, 127.25, 123.52, 123.23, 122.36, 122.20, 120.34, 116.12, 115.34, 113.40, 109.62, 59.41, 34.75, 32.10, 6.95, 1.15.

[0143] Example 16: Synthesis of Procatalyst 7

Chemical formula

[0144] 1 H NMR (500 MHz, benzene-d6) δ 8.51 (dd, J = 1.9, 0.6 Hz, 2H), 8.25 (dd, J = 1.9, 0.6 Hz, 2H), 7.54 - 7.49 (m, 4H), 7.37 (dd, J = 8.5, 0.6 Hz, 2H), 7.31 (dd, J = 8.7, 0.6 Hz, 2H), 7.26 (dd, J = 7.8, 1.7 Hz, 2H), 6.98 - 6.96 (m, 4H), 6.89 (s, 2H), 6.84 - 6.78 (m, 2H), 6.69 (td, J = 7.6, 1.2 Hz, 2H), 6.64 - 6.52 (m, 2H), 6.30 - 6.26 (m, 4H), 5.40 (dd, J = 8.2, 1.1 Hz, 2H), 4.23 (d, J = 14.8 Hz, 2H), 3.15 (d, J = 14.8 Hz, 2H), 1.48 (s, 18H), 1.27 (s, 18H), 1.15 (d, J = 12.5 Hz, 2H), 0.87 (t, J = 7.9 Hz, 2H), 0.52 (d, J = 12.5 Hz, 2H), 0.36 (t, J = 8.0 Hz, 6H), 0.01--0.10 (m, 1H), -0.24 (dq, J = 14.9, 8.0 Hz, 1H). 1313C NMR (126 MHz, benzene-d6) δ 158.69, 152.42, 147.10, 143.14, 142.73, 140.21, 139.56, 139.39, 130.37, 129.00, 128.32, 128.17, 126.35, 125.98, 125.45, 125.19, 124.64, 122.76, 122.43, 120.81, 117.66, 117.18, 116.33, 115.52, 112.52, 108.88, 75.73, 71.46, 34.59, 34.41, 31.99, 31.71, 6.60, 0.73.

[0145] Example 17: Synthesis of Procatalyst 8

Chemical Structure

[0146] 11H NMR (500 MHz, benzene-d6) δ 8.52 (dd, J = 2.0, 0.6 Hz, 2H), 8.26 (dd, J = 1.9, 0.6 Hz, 2H), 7.51 (ddd, J = 8.7, 1.9, 1.3 Hz, 4H), 7.35 (dd, J = 8.5, 0.6 Hz, 2H), 7.26 (dd, J = 7.8, 1.7 Hz, 2H), 7.23 (dd, J = 8.7, 0.6 Hz, 2H), 6.98 - 6.95 (m, 4H), 6.89 (s, 2H), 6.84 (ddd, J = 8.2, 7.4, 1.8 Hz, 2H), 6.79 - 6.73 (m, 2H), 6.70 (td, J = 7.6, 1.1 Hz, 2H), 6.31 - 6.26 (m, 4H), 5.42 (dd, J = 8.2, 1.2 Hz, 2H), 4.28 (d, J = 14.9 Hz, 2H), 3.16 (d, J = 14.9 Hz, 2H), 1.48 (s, 18H), 1.28 (s, 18H), 0.98 (d, J = 13.4 Hz, 2H), 0.35 (t, J = 8.0 Hz, 6H), 0.26 - 0.21 (m, 2H), -0.06 (dq, J = 15.9, 8.0 Hz, 2H), -0.27 (dq, J = 15.0, 8.0 Hz, 2H). 13 13C NMR (126 MHz, benzene-d6) δ 158.36, 152.51, 147.68, 143.20, 142.73, 139.56, 139.36, 130.37, 129.54, 128.73, 127.07, 126.75, 126.16, 125.70, 125.26, 124.68, 122.72, 122.37, 121.72, 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

Chemical Structure

[0148] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupling product in CH2Cl2 - 1,4 - dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1×10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2×10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system. With 10% - 75% CH2Cl2 in hexane, bisthiophene (0.368 g, 0.3513 mmol, 74%, 59% over 2 steps) was obtained as a pale yellowish - brown solid. NMR showed a 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, 1.7 Hz, 2H), 7.43 - 7.35 (m, 6H), 7.28 - 7.21 (m, 2H), 7.16 (d, J = 8.6 Hz, 4H), 7.13 - 7.06 (m, 4H), 6.82 (dd, J = 8.3, 1.1 Hz, 2H), 4.11 (dd, J = 9.8, 3.3 Hz, 2H), 3.93 (dd, J = 9.9, 4.3 Hz, 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, 127.60, 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

Chemical formula

[0151] 1 H NMR (500 MHz, benzene-d6) δ 8.49 (dd, J = 2.0, 0.6 Hz, 2H), 8.24 (dd, J = 1.9, 0.6 Hz, 2H), 7.54 - 7.50 (m, 2H), 7.48 (dd, J = 8.6, 2.0 Hz, 2H), 7.31 (ddd, J = 8.7, 2.0, 0.6 Hz, 2H), 7.28 (d, J = 1.8 Hz, 2H), 6.98 - 6.96 (m, 4H), 6.89 (s, 2H), 6.81 (tt, J = 7.4, 1.2 Hz, 2H), 6.77 (ddd, J = 8.2, 7.4, 1.8 Hz, 2H), 6.67 (td, J = 7.6, 1.1 Hz, 2H), 6.63 - 6.59 (m, 2H), 6.26 - 6.22 (m, 4H), 5.18 (dd, J = 8.3, 1.1 Hz, 2H), 4.17 (dd, J = 12.6, 8.3 Hz, 2H), 3.20 (d, J = 12.6 Hz, 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 = 12.4 Hz, 2H), 0.52 - 0.44 (m, 2H). 1313C NMR (126 MHz, benzene-d6) δ 156.40, 152.24, 147.22, 143.15, 142.86, 139.15, 138.97, 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, 115.50, 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 Pro-Catalyst 6

Chemical formula

[0153] 11H NMR (500 MHz, benzene-d6) δ 8.50 (dd, J = 2.0, 0.6 Hz, 2H), 8.25 (dd, J = 2.0, 0.6 Hz, 2H), 7.48 (ddd, J = 15.6, 8.6, 1.9 Hz, 4H), 7.29 (dd, J = 8.5, 0.6 Hz, 2H), 7.26 (dd, J = 7.7, 1.8 Hz, 2H), 7.22 (dd, J = 8.7, 0.6 Hz, 2H), 6.99 - 6.96 (m, 4H), 6.89 (s, 2H), 6.81 - 6.76 (m, 4H), 6.68 (td, J = 7.6, 1.1 Hz, 2H), 6.25 - 6.18 (m, 4H), 5.21 (dd, J = 8.3, 1.1 Hz, 2H), 4.21 (dd, J = 12.6, 8.4 Hz, 2H), 3.22 (d, J = 12.7 Hz, 2H), 1.51 (s, 18H), 1.30 (s, 18H), 1.14 - 1.04 (m, 4H), 0.91 (d, J = 13.4 Hz, 2H), 0.74 (t, J = 8.5 Hz, 2H), 0.59 (d, J = 12.7 Hz, 2H), 0.46 (t, J = 10.0 Hz, 2H), 0.25 (d, J = 13.3 Hz, 2H). 13 13C NMR (126 MHz, benzene-d6) δ 155.98, 152.30, 147.83, 143.20, 142.86, 139.16, 138.96, 131.06, 129.76, 128.67, 128.57, 128.18, 127.07, 126.75, 126.12, 124.66, 123.30, 122.68, 122.32, 120.76, 116.87, 116.25, 116.21, 115.44, 112.73, 109.23, 86.74, 78.29, 42.23, 34.60, 34.43, 32.01, 31.73, 29.56, 25.30.

[0154] Example 21: Synthesis of Ligand 5 [Chemical formula] A mixture of thiophene boropinicolate ester (1.644 g, 2.108 mmol, 3.00 equivalents, purity 72% by NMR), K3PO4 (1.342 g, 6.323 mmol, 9.00 equivalents), Pd(AmPhos)Cl2 (99.0 mg, 0.1405 mmol, 0.20 equivalents), and bisphenyl iodide (0.433 g, 0.7026 mmol, 1.00 equivalent). The mixture was evacuated and then refilled with nitrogen, and this process was repeated 3 more times. Then, deoxygenated 1,4-dioxane (15.0 mL) and deoxygenated water (1.5 mL) were sequentially added via syringe. The mixture was then placed in a mantle heated to 50 °C. After vigorously stirring (1000 rpm) for 40 hours, the black mixture was removed from the mantle, cooled slowly to 23 °C, suction filtered through a silica gel pad, washed with CH2Cl2 (4 × 20 mL), the clear black filtrate was concentrated, and the residual 1,4-dioxane was removed azeotropically using toluene (2 × 10 mL) by rotary evaporation. Then, the black mixture was suspended in CH2Cl2 (20 mL), suction filtered through a silica gel pad, rinsed with CH2Cl2 (4 × 20 mL), and then the black filtrate was concentrated onto celite and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 55% CH2Cl2 in hexanes to give bisthiophene (0.452 g, 0.3670 mmol, 52%) as a red amorphous oil. NMR indicated a pure product.

[0155] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupled product in CH2Cl2-1,4-dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1 × 10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, dried over solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 75% CH2Cl2 in hexane to give bisthiophene (0.280 g, 0.2510 mmol, 68%, 36% 2 steps) as a clear amorphous foam. NMR indicated a pure product.

[0156] 1 H NMR (400 MHz, chloroform-d) δ 8.18 - 8.12 (m, 4H), 7.41 (dd, J = 8.6, 1.9 Hz, 4H), 7.33 (s, 2H), 7.14 (dd, J = 8.5, 0.6 Hz, 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 = 7.3 Hz, 12H). 19 F NMR (376 MHz, 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 = 2.2 Hz), 146.63, 142.86, 139.79, 127.10, 123.54, 123.20, 122.96 (d, J = 8.5 Hz), 120.74, 116.56 (d, J = 24.4 Hz), 116.07, 115.07 (d, J = 23.2 Hz), 114.22 (d, J = 1.9 Hz), 114.08 (d, J = 8.8 Hz), 109.53, 58.54, 34.72, 32.03, 17.90, 9.71.

[0157] Example 22: Synthesis of Pro-Catalyst 9 [Chemical Formula] The thiophene ligand was azeotropically dried using PhMe (4×10 mL) before use. In a nitrogen-filled glove box at 23 °C, a solution of ZrBn4 (4.1 mg, 9.07 μmol, 1.10 equiv) in C6D6 (0.33 mL) was added dropwise to a clear, colorless solution of thiophene (9.2 mg, 8.25 μmol, 1.00 equiv) in anhydrous 6D6 (2.97 mL). After stirring for 30 minutes (500 rpm), the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex as a 0.0025 M solution in C6D6. NMR indicated the product. Using the same procedure with PhMe as the solvent, a pro-catalyst solution (0.0025 M) used immediately after filtration for the polymerization experiment could be prepared.

[0158] 1 H NMR (500 MHz, benzene-d6) δ 8.45 (dd, J = 1.9, 0.6 Hz, 2H), 8.30 (dd, J = 1.9, 0.6 Hz, 2H), 7.55 (dd, J = 8.7, 1.9 Hz, 2H), 7.50 (dd, J = 8.5, 1.9 Hz, 2H), 7.40 (dd, J = 8.7, 0.7 Hz, 2H), 7.33 (dd, J = 8.5, 0.6 Hz, 2H), 7.06 - 7.02 (m, 2H), 6.99 - 6.92 (m, 4H), 6.84 (s, 2H), 6.80 - 6.74 (m, 2H), 6.62 (ddd, J = 9.0, 7.3, 3.1 Hz, 2H), 6.37 - 6.34 (m, 4H), 5.37 (dd, J = 9.0, 4.8 Hz, 2H), 4.17 (d, J = 14.7 Hz, 2H), 3.15 (d, J = 14.8 Hz, 2H), 1.40 (s, 18H), 1.28 (s, 18H), 1.12 (d, J = 12.5 Hz, 2H), 0.58 (d, J = 12.5 Hz, 2H), 0.52 (d, J = 7.1 Hz, 6H), 0.42 (d, J = 6.5 Hz, 6H), 0.37 (tt, J = 8.0, 6.0 Hz, 2H). 19 F NMR (470 MHz, benzene-d6) δ -115.88 (td, J = 7.8, 4.5 Hz).13 13C NMR (126 MHz, benzene-d6) δ 159.41 (d, J = 245.7 Hz), 154.25, 154.23, 152.87, 146.47, 143.27 (d, J = 52.4 Hz), 139.70 (d, J = 31.6 Hz), 130.56, 128.33, 128.16, 126.41, 125.21, 124.60, 124.12, 122.82, 122.52, 122.29 (d, J = 9.1 Hz), 121.24, 119.11, 116.65, 116.35, 116.19 (d, J = 13.2 Hz), 116.00 (d, J = 13.5 Hz), 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 Pro-Catalyst 10

Chem.

[0160] 11H NMR (500 MHz, benzene-d6) δ 8.46 (dd, J = 1.9, 0.6 Hz, 2H), 8.31 (dd, J = 1.9, 0.6 Hz, 2H), 7.54 (dd, J = 8.7, 1.9 Hz, 2H), 7.49 (dd, J = 8.5, 1.9 Hz, 2H), 7.32 (ddd, J = 10.9, 8.6, 0.6 Hz, 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, 3.1 Hz, 2H), 6.40 - 6.35 (m, 4H), 5.39 (dd, J = 9.0, 4.7 Hz, 2H), 4.20 (d, J = 14.8 Hz, 2H), 3.15 (d, J = 14.8 Hz, 2H), 1.40 (s, 18H), 1.28 (s, 18H), 1.01 (d, J = 13.6 Hz, 2H), 0.50 (d, J = 7.1 Hz, 6H), 0.40 (d, J = 7.1 Hz, 6H), 0.39 - 0.30 (m, 2H), 0.27 (d, J = 13.6 Hz, 2H). 19 19F NMR (470 MHz, benzene-d6) δ -115.48 (td, J = 8.1, 4.8 Hz). 13 13C NMR (126 MHz, benzene-d6) δ 159.61 (d, J = 246.2 Hz), 153.86 (d, J = 2.7 Hz), 152.98, 147.22, 143.32 (d, J = 61.0 Hz), 139.69 (d, J = 36.3 Hz), 138.52, 129.89, 128.61, 127.17, 126.71, 124.65, 124.35, 122.78, 122.71 (d, J = 8.9 Hz), 122.46, 121.25, 119.23, 116.32, 116.17 (d, J = 10.2 Hz), 115.98 (d, J = 9.8 Hz), 115.95, 115.55, 112.30, 108.98, 83.00, 71.02, 34.54, 34.45, 31.89, 31.69, 17.49, 17.45, 9.50.

[0161] Example 24: Synthesis of Ligand 6

Chemical Structure

[0162] At 23 °C under nitrogen, concentrated HCl (3 mL) was added to a solution of the impure coupled product in CH2Cl2 - 1,4 - dioxane (6 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1×10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2×10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 75% CH2Cl2 in hexane to give bisthiophene (0.100 g, 0.08617 mmol, 17% 2 steps) as a transparent amorphous foam. NMR indicated a pure product.

[0163] 1 H NMR (500 MHz, chloroform - d) δ 8.16 (dd, J = 1.9, 0.6 Hz, 4H), 7.42 (dd, J = 8.6, 1.9 Hz, 4H), 7.35 (s, 2H), 7.17 (dd, J = 8.6, 0.7 Hz, 4H), 7.12 (dd, J = 9.2, 3.1 Hz, 2H), 6.71 (s, 2H), 6.56 (ddd, J = 9.0, 7.7, 3.1 Hz, 2H), 6.34 (dd, J = 9.2, 4.6 Hz, 2H), 3.94 (s, 4H), 1.47 (s, 36H), 1.39 - 1.29 (m, 2H), 0.94 (d, J = 7.5 Hz, 12H). 19 F NMR (470 MHz, chloroform - d) δ - 121.59 (td, J = 8.4, 4.6 Hz). 13 C NMR (126 MHz, chloroform - d) δ 157.50 (d, J = 240.5 Hz), 152.50, 146.74, 142.85, 139.78, 127.26, 123.55, 123.25 (d, J = 9.3 Hz), 123.21, 120.73, 116.49 (d, J = 24.6 Hz), 116.08, 115.02 (d, J = 22.9 Hz), 114.50 (d, J = 8.9 Hz), 114.22 (m), 109.59, 60.00, 34.73, 32.04, 19.34, 13.91.

[0164] Example 25: Synthesis of Pro-Catalyst 11 [Chemical formula] The thiophene ligand was azeotropically dried using PhMe (4 × 10 mL) before use. In a nitrogen-filled glove box at 23 °C, a solution of ZrBn4 (2.2 mg, 4.74 μmol, 1.10 equivalents) in C6D6 (0.33 mL) was added dropwise to a clear colorless solution of thiophene (5.0 mg, 4.31 μmol, 1.00 equivalent) in anhydrous C6D6 (1.54 mL). After stirring for 30 minutes (500 rpm), the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex as a 0.0025 M solution in C6D6. NMR indicated the product. Using the same procedure with PhMe as the solvent, a pro-catalyst solution (0.0025 M) used immediately after filtration in the polymerization experiment can be prepared.

[0165] 1 H NMR (500 MHz, benzene-d6) δ 8.45 (dd, J = 1.9, 0.6 Hz, 2H), 8.30 (dd, J = 2.0, 0.6 Hz, 2H), 7.54 (dd, J = 8.7, 1.9 Hz, 2H), 7.49 (dd, J = 8.5, 1.9 Hz, 2H), 7.38 (dd, J = 8.7, 0.6 Hz, 2H), 7.31 (dd, J = 8.5, 0.6 Hz, 2H), 7.07 - 7.02 (m, 2H), 6.99 - 6.95 (m, 4H), 6.83 (s, 2H), 6.77 (tt, J = 7.3, 1.2 Hz, 2H), 6.61 (ddd, J = 9.0, 7.3, 3.2 Hz, 2H), 6.37 - 6.34 (m, 4H), 5.42 (dd, J = 9.0, 4.7 Hz, 2H), 4.32 (d, J = 13.0 Hz, 2H), 3.33 (d, J = 13.0 Hz, 2H), 1.40 (s, 18H), 1.28 (s, 18H), 1.17 (d, J = 12.5 Hz, 2H), 0.71 (dp, J = 14.1, 6.9 Hz, 2H), 0.60 (d, J = 7.2 Hz, 6H), 0.57 (d, J = 12.5 Hz, 2H), 0.51 (d, J = 7.3 Hz, 6H). 1919F NMR (470 MHz, benzene-d6) δ -115.87 (td, J = 8.0, 4.8 Hz). 13 13C NMR (126 MHz, benzene-d6) δ 159.44 (d, J = 245.5 Hz), 154.21, 154.19, 152.80, 146.62, 143.27 (d, J = 53.0 Hz), 139.67 (d, J = 30.0 Hz), 130.56, 128.33, 128.16, 126.33, 125.24, 124.59, 122.81, 122.51, 121.20, 119.01, 116.58 (m), 116.35, 116.19 (d, J = 17.8 Hz), 116.01 (d, J = 16.9 Hz), 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 Pro-Catalyst 12

Chem.

[0167] 11H NMR (500 MHz, benzene-d6) δ 8.46 (dd, J = 2.0, 0.6 Hz, 2H), 8.31 (dd, J = 1.9, 0.6 Hz, 2H), 7.53 (dd, J = 8.7, 1.9 Hz, 2H), 7.48 (dd, J = 8.5, 1.9 Hz, 2H), 7.30 (ddd, J = 11.7, 8.6, 0.6 Hz, 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, 3.1 Hz, 2H), 6.52 - 6.48 (m, 2H), 6.40 - 6.35 (m, 4H), 5.44 (dd, J = 9.0, 4.8 Hz, 2H), 4.36 (d, J = 13.0 Hz, 2H), 3.33 (d, J = 13.1 Hz, 2H), 1.40 (s, 18H), 1.28 (s, 18H), 1.03 (d, J = 13.5 Hz, 2H), 0.68 (dq, J = 14.1, 7.2 Hz, 2H), 0.58 (d, J = 7.3 Hz, 6H), 0.49 (d, J = 7.3 Hz, 6H), 0.28 (d, J = 13.7 Hz, 2H). 19 19F NMR (470 MHz, benzene-d6) δ -114.35--117.32 (m). 13 13C NMR (126 MHz, benzene-d6) δ 159.63 (d, J = 246.1 Hz), 153.86 (d, J = 2.5 Hz), 152.93, 147.26, 143.32 (d, J = 61.1 Hz), 139.67 (d, J = 33.6 Hz), 129.89, 128.58, 128.18, 127.17, 126.70, 125.31, 124.49 (d, J = 34.8 Hz), 123.03 (d, J = 9.2 Hz), 122.78, 122.45, 121.24, 119.15, 116.32, 116.16 (d, J = 13.5 Hz), 115.98 (d, J = 13.4 Hz), 115.90, 115.88, 115.53, 112.32, 108.97, 83.00, 72.10, 34.53, 34.45, 31.88, 31.70, 19.13, 19.07, 13.67.

[0168] Example 27: Synthesis of Ligand 7

Chemical Structure

[0169] At 23 °C under nitrogen, concentrated HCl (4 mL) was added to a solution of the impure coupling product in CH2Cl2 - 1,4 - dioxane (8 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1×10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2×10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 50% CH2Cl2 in hexane to give bisthiophene (80.0 mg, 0.0657 mmol, 33% 2 steps) as a pale yellowish - brown solid. NMR indicated a pure product.

[0170] 1 H NMR (400 MHz, chloroform - d) δ 8.11 (d, J = 1.9 Hz, 4H), 7.57 (d, J = 2.3 Hz, 2H), 7.47 (s, 2H), 7.41 (dd, J = 8.7, 1.9 Hz, 4H), 7.31 (s, 2H), 7.27 - 7.20 (m, 4H), 6.78 (d, J = 8.6 Hz, 2H), 4.07 - 3.97 (m, 4H), 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 (101 MHz, 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, 109.61, 69.95, 56.86, 38.19, 34.69, 32.41, 32.05, 31.91, 31.62, 25.90.

[0171] Example 28: Synthesis of Pro - catalyst 13

Chemical formula

[0172] 1 H NMR (400 MHz, benzene-d6) δ 8.55 (d, J = 1.9 Hz, 2H), 8.15 - 8.11 (m, 2H), 7.57 (d, J = 2.5 Hz, 2H), 7.51 (dd, J = 8.6, 1.9 Hz, 2H), 7.43 (dd, J = 8.7, 1.9 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.21 (dd, J = 8.7, 0.6 Hz, 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 = 8.7 Hz, 2H), 4.08 - 3.98 (m, 2H), 3.42 - 3.34 (m, 2H), 1.68 (d, J = 14.6 Hz, 2H), 1.57 (s, 18H), 1.51 (d, J = 14.6 Hz, 2H), 1.23 (s, 18H), 1.20 (s, 6H), 1.16 (s, 6H), 1.02 (d, J = 12.3 Hz, 2H), 0.89 (q, J = 11.9, 10.7 Hz, 2H), 0.70 (s, 18H), 0.64 - 0.56 (m, 2H), 0.52 (d, J = 12.3 Hz, 2H). 1313C NMR (101 MHz, benzene-d6) δ 153.93, 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, 122.65, 122.26, 120.58, 74.94, 72.00, 56.54, 38.25, 34.66, 34.36, 32.13, 32.10, 31.71, 31.66, 30.04, 25.93.

[0173] Example 29: Synthesis of Procatalyst 14

Chem.

[0174] 11H NMR (500 MHz, benzene-d6) δ 8.57 (dd, J = 1.9, 0.6 Hz, 2H), 8.15 (dd, J = 2.0, 0.7 Hz, 2H), 7.58 (d, J = 2.5 Hz, 2H), 7.52 (dd, J = 8.5, 1.9 Hz, 2H), 7.42 (dd, J = 8.7, 1.9 Hz, 2H), 7.33 (dd, J = 8.5, 0.6 Hz, 2H), 7.14 - 7.07 (m, 6H), 7.05 - 7.02 (m, 2H), 6.85 (s, 2H), 6.82 (tt, J = 7.3, 1.2 Hz, 2H), 6.24 - 6.18 (m, 4H), 5.21 (d, J = 8.7 Hz, 2H), 4.15 - 4.06 (m, 2H), 3.50 - 3.41 (m, 2H), 1.69 (d, J = 14.6 Hz, 2H), 1.59 (s, 18H), 1.53 (d, J = 14.7 Hz, 2H), 1.25 (s, 18H), 1.22 (s, 6H), 1.17 (s, 6H), 0.92 (t, J = 9.5 Hz, 2H), 0.84 (d, J = 13.2 Hz, 2H), 0.72 (s, 18H), 0.59 - 0.51 (m, 2H), 0.27 (d, J = 13.2 Hz, 2H). 13 13C NMR (126 MHz, benzene-d6) δ 153.62, 152.32, 149.13, 147.76, 142.98, 142.63, 139.24, 139.11, 128.73, 128.66, 128.04, 127.05, 126.99, 126.92, 125.36, 124.67, 122.99, 122.61, 122.21, 120.63, 116.95, 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 Bis-t-octyl-iodophenyl Ether Intermediate

Chemical Structure

[0176] 1 1H NMR (500 MHz, chloroform - d) δ 7.73 (d, J = 2.4 Hz, 2H), 7.28 - 7.24 (m, 2H), 6.73 (d, J = 8.6 Hz, 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 13C 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

Chemical formula

[0178] 1 H NMR (500 MHz, chloroform-d) δ 7.60 (d, J = 2.3 Hz, 1H), 7.24 (dd, J = 8.5, 2.3 Hz, 1H), 6.90 (dd, J = 8.6, 0.5 Hz, 1H), 5.11 (s, 1H), 1.68 (s, 2H), 1.32 (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

Chemical Structure

[0180] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupling product in CH2Cl2-1,4-dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1 × 10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system. With 10% - 75% CH2Cl2 in hexane, bisthiophene (0.514 g, 0.4879 mmol, 76%, 57% over 2 steps) was obtained as a pale yellowish brown solid. NMR indicated a 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, 1.9 Hz, 4H), 7.35 (s, 2H), 7.25 (d, J = 8.6 Hz, 4H), 7.14 (d, J = 2.9 Hz, 2H), 6.84 (d, J = 9.0 Hz, 2H), 6.79 (dd, J = 8.9, 2.9 Hz, 2H), 3.99 (q, J = 3.5, 2.1 Hz, 4H), 3.84 (s, 6H), 1.83 (q, J = 2.8 Hz, 4H), 1.46 (s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 155.34, 147.83, 146.76, 142.68, 139.64, 127.76, 124.50, 123.45, 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

Chemical Structure

[0183] 1 H NMR (400 MHz, benzene-d6) δ 8.47 (dd, J = 2.0, 0.6 Hz, 2H), 8.24 (dd, J = 1.9, 0.6 Hz, 2H), 7.49 (td, J = 8.6, 1.9 Hz, 4H), 7.30 (ddd, J = 8.5, 5.3, 0.6 Hz, 4H), 7.08 - 7.03 (m, 2H), 6.96 (dtd, J = 6.9, 1.4, 0.7 Hz, 2H), 6.92 (d, J = 3.1 Hz, 2H), 6.84 (s, 2H), 6.78 (tt, J = 7.3, 1.3 Hz, 2H), 6.45 (dd, J = 9.1, 3.1 Hz, 2H), 6.31 - 6.26 (m, 4H), 5.04 (d, J = 9.1 Hz, 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 = 12.3 Hz, 2H), 0.88 - 0.74 (m, 2H), 0.58 (d, J = 12.3 Hz, 2H), 0.56 - 0.51 (m, 2H). 1313C NMR (101 MHz, benzene-d6) δ 157.39, 152.38, 149.56, 147.35, 143.13, 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, 115.68, 115.54, 114.96, 112.51, 108.91, 81.18, 75.06, 54.73, 34.55, 34.42, 31.99, 31.72, 25.92.

[0184] Example 34: Synthesis of Procatalyst 16

Chem.

[0185] 11H NMR (500 MHz, benzene-d6) δ 8.50 (dd, J = 2.0, 0.6 Hz, 2H), 8.26 (dd, J = 1.9, 0.6 Hz, 2H), 7.50 (dd, J = 2.5, 1.9 Hz, 2H), 7.48 (t, J = 2.1 Hz, 2H), 7.29 (dd, J = 8.5, 0.6 Hz, 2H), 7.23 (dd, J = 8.7, 0.6 Hz, 2H), 6.99 - 6.95 (m, 2H), 6.93 (d, J = 3.1 Hz, 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 = 9.0 Hz, 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 = 13.3 Hz, 2H), 0.85 - 0.77 (m, 2H), 0.55 (m, 2H), 0.31 (d, J = 13.3 Hz, 2H). 13 13C NMR (126 MHz, benzene-d6) δ 157.52, 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, 122.30, 120.69, 117.13, 116.30, 115.70, 115.48, 114.96, 112.58, 108.91, 83.01, 78.24, 54.76, 34.57, 34.43, 32.00, 31.73, 26.04.

[0186] Example 35: Synthesis of Bis-4-methoxy-2-iodophenyl Ether [Chemical formula] A white heterogeneous mixture of 2-iodophenol (1.890 g, 7.559 mmol, 2.00 equiv), K2CO3 (3.134 g, 22.677 mmol, 6.00 equiv), and 1,4-dibromobutane (0.45 mL, 3.779 mmol, 1.00 equiv) in acetone (40 mL) equipped with a reflux condenser was placed in a mantle heated to 60 °C and stirred (500 rpm) for 36 h. Then, the white heterogeneous mixture was removed from the mantle, cooled to 23 °C, diluted with CH2Cl2 (50 mL), stirred for 2 min, suction filtered through a Celite pad, rinsed with CH2Cl2 (4 × 20 mL), and the resulting pale yellow filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatography purification system with 50–100% CH2Cl2 in hexanes to give iodophenyl ether (1.945 g, 3.510 mmol, 93%) as a white solid. NMR indicated a pure product.

[0187] 1 1H NMR (500 MHz, chloroform-d) δ 7.32 (d, J = 2.9 Hz, 2H), 6.84 (dd, J = 8.9, 3.0 Hz, 2H), 6.76 (d, J = 8.9 Hz, 2H), 4.11–3.99 (m, 4H), 3.75 (s, 6H), 2.13–2.01 (m, 4H). 13 13C NMR (126 MHz, 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

Chemical Structure

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

[0190] Example 37: Synthesis of Ligand 9 [Chemical formula] A mixture of thiophene boropinate ester (0.605 g, 0.5387 mmol, 2.70 equivalents, purity 50% by NMR), K3PO4 (0.343 g, 1.616 mmol, 8.10 equivalents), Pd(AmPhos)Cl2 (28.3 mg, 0.0399 mmol, 0.20 equivalents), and bis(phenyl)iodonium (0.106 g, 0.1995 mmol, 1.00 equivalent). The mixture was evacuated and then refilled with nitrogen, and this process was repeated three more times. Then, deoxygenated 1,4-dioxane (4.0 mL) and deoxygenated water (0.4 mL) were sequentially added by syringe. The mixture was then placed in a mantle heated to 50 °C. After vigorous stirring (1000 rpm) for 40 h, the black mixture was removed from the mantle, cooled slowly to 23 °C, suction filtered through a silica gel pad, washed with CH2Cl2 (4 × 20 mL), the clear black filtrate was concentrated, and the residual 1,4-dioxane was removed azeotropically using toluene (2 × 10 mL) by rotary evaporation. Then, the black mixture was suspended in CH2Cl2 (20 mL), suction filtered through a silica gel pad, rinsed with CH2Cl2 (4 × 20 mL), and then the black filtrate was concentrated onto celite and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 50% CH2Cl2 in hexanes to give bisthiophene (0.101 g) as an off-white solid. NMR indicated a product containing a small amount of impurities. This material was used for subsequent deprotection without further purification.

[0191] At 23 °C under nitrogen, concentrated HCl (3 mL) was added to a solution of the impure coupled product in CH2Cl2-1,4-dioxane (6 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1×10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2×10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system, with 10% - 75% CH2Cl2 in hexane to give bisthiophene (52.0 mg, 0.05052 mmol, 25% 2 steps) as a pale yellowish brown solid. NMR indicated a 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 = 10.3 Hz, 2H), 7.19 (d, J = 8.6 Hz, 4H), 6.90 (td, J = 8.2, 7.5, 3.0 Hz, 2H), 6.80 (dd, J = 9.1, 4.6 Hz, 2H), 4.01 (d, J = 4.8 Hz, 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, 4.7 Hz). 13 C NMR (101 MHz, chloroform-d) δ 158.08 (d, J = 241.4 Hz), 149.83 (d, J = 2.3 Hz), 146.99, 142.85, 139.52, 127.55, 124.80 (d, J = 8.6 Hz), 123.50, 123.21, 120.82, 116.56 (d, J = 24.7 Hz), 116.24, 115.69 (d, J = 8.8 Hz), 114.72 (d, J = 23.3 Hz), 114.00 (d, J = 1.8 Hz), 109.47, 70.96, 34.68, 31.99, 25.83.

[0193] Example 38: Synthesis of Procatalyst 17

Chemical formula

[0194] 1 H NMR (500 MHz, benzene-d6) δ 8.42 (dd, J = 2.0, 0.6 Hz, 2H), 8.28 (dd, J = 1.9, 0.7 Hz, 2H), 7.51 (dd, J = 8.7, 1.9 Hz, 2H), 7.44 (dd, J = 8.5, 1.9 Hz, 2H), 7.33 (dd, J = 8.7, 0.6 Hz, 2H), 7.21 (dd, J = 8.5, 0.7 Hz, 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, 3.2 Hz, 4H), 6.36 - 6.32 (m, 2H), 6.27 - 6.23 (m, 4H), 4.99 (dd, J = 9.0, 4.8 Hz, 2H), 3.87 - 3.75 (m, 2H), 3.11 (dd, J = 11.8, 4.6 Hz, 2H), 1.43 (s, 18H), 1.30 (s, 18H), 1.02 (d, J = 12.4 Hz, 2H), 0.98 - 0.82 (m, 2H), 0.75 - 0.63 (m, 2H), 0.52 (d, J = 12.3 Hz, 2H). 19 F NMR (470 MHz, benzene-d6) δ -114.74--117.39 (m). 1313C NMR (126 MHz, benzene-d6) δ 159.84 (d, J = 246.8 Hz), 152.62, 151.81 (d, J = 2.6 Hz), 146.41, 143.19 (d, J = 49.2 Hz), 139.19 (d, J = 20.1 Hz), 130.56, 128.33, 128.06, 126.53, 125.18, 124.92 (d, J = 8.9 Hz), 124.30 (d, J = 47.3 Hz), 122.56 (d, J = 38.4 Hz), 121.16, 118.06, 116.69 (d, J = 47.1 Hz), 116.69, 115.98 (d, J = 91.0 Hz), 115.83 (d, J = 1.9 Hz), 112.30, 108.75, 74.98, 72.01, 34.52, 34.45, 31.94, 31.72, 25.71.

[0195] Example 39: Synthesis of Pro-Catalyst 18

Chemical Structure

[0196] 11H NMR (500 MHz, benzene-d6) δ 8.43 (dd, J = 2.0, 0.6 Hz, 2H), 8.29 (dd, J = 1.9, 0.6 Hz, 2H), 7.49 (dd, J = 8.7, 1.9 Hz, 2H), 7.44 (dd, J = 8.5, 1.9 Hz, 2H), 7.24 (dd, J = 8.7, 0.6 Hz, 2H), 7.19 (dd, J = 8.5, 0.6 Hz, 2H), 7.02 - 6.96 (m, 2H), 6.94 - 6.90 (m, 2H), 6.82 (s, 2H), 6.75 (tt, J = 7.5, 1.3 Hz, 2H), 6.55 - 6.47 (m, 4H), 6.30 - 6.25 (m, 4H), 5.01 (dd, J = 9.0, 4.8 Hz, 2H), 3.89 - 3.78 (m, 2H), 3.15 (dd, J = 12.4, 4.7 Hz, 2H), 1.43 (s, 18H), 1.30 (s, 18H), 0.90 (d, J = 13.4 Hz, 2H), 0.73 - 0.62 (m, 2H), 0.49 - 0.40 (m, 2H), 0.24 (d, J = 14.0 Hz, 2H). 19 19F NMR (470 MHz, benzene-d6) δ -115.11--115.24 (m). 13 13C NMR (126 MHz, benzene-d6) δ 159.97 (d, J = 247.4 Hz), 152.66, 151.46 (d, J = 2.7 Hz), 147.32, 143.24 (d, J = 55.5 Hz), 139.14 (d, J = 26.6 Hz), 138.52, 130.56, 128.38 (d, J = 11.1 Hz), 127.15, 126.72, 124.55, 124.35, 122.64, 122.33, 121.13, 118.09, 116.76 (d, J = 23.4 Hz), 116.46 (d, J = 23.3 Hz), 116.32, 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

Chem.

[0198] At 23 °C under nitrogen, concentrated HCl (3 mL) was added to a solution of the impure coupling product in CH2Cl2-1,4-dioxane (6 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1×10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2×10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatography purification system. With 10% - 75% CH2Cl2 in hexane, bisthiophene (0.105 g, 0.09856 mmol, 49% 2 steps) was obtained as a transparent amorphous foam. NMR indicated a pure product.

[0199] 1 H NMR (400 MHz, chloroform-d) δ 8.12 (dd, J = 1.9, 0.6 Hz, 4H), 7.56 (dd, J = 11.4, 8.8 Hz, 2H), 7.39 (dd, J = 8.6, 1.9 Hz, 4H), 7.30 (s, 2H), 7.17 (dd, J = 8.6, 0.6 Hz, 4H), 6.74 (dd, J = 11.4, 6.8 Hz, 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, 8.8 Hz), -144.91 (ddd, J = 22.2, 11.2, 6.8 Hz). 13 C NMR (101 MHz, chloroform-d) δ 150.19 - 149.71 (m), 149.36 (dd, J = 250.5, 13.9 Hz), 146.75 - 144.02 (m), 146.55, 143.08, 139.43, 127.14, 123.61, 123.29, 120.52, 119.32 - 118.89 (m), 118.15 (d, J = 20.6 Hz), 116.34, 112.97, 109.37, 103.52 (d, J = 20.8 Hz), 70.59, 34.70, 31.97, 25.83.

[0200] Example 41: Synthesis of Pro-Catalyst 19 [Chemical formula] The thiophene ligand was azeotropically dried using PhMe (4 × 10 mL) before use. In a nitrogen-filled glove box at 23 °C, a solution of ZrBn4 (5.3 mg, 11.56 μmol, 1.10 equivalents) in C6D6 (0.42 mL) was added dropwise to a clear colorless solution of thiophene (11.2 mg, 10.51 μmol, 1.00 equivalent) in anhydrous C6D6 (3.78 mL). After stirring for 30 minutes (500 rpm), the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex as a 0.0025 M solution in C6D6. NMR indicated the product. Using the same procedure with PhMe as the solvent, a pro-catalyst solution (0.0025 M or 0.005 M) used immediately after filtration in the polymerization experiment could be prepared. Crystallization of the zirconium complex was obtained by slowly and gradually evaporating the NMR solution, and the crystals were evaluated using X-ray diffraction to clearly confirm the structure.

[0201] 11H NMR (500 MHz, benzene-d6) δ 8.55 (d, J = 1.9 Hz, 1H), 8.46 (d, J = 1.9 Hz, 1H), 8.39 (t, J = 1.3 Hz, 1H), 8.33 (dd, J = 2.0, 0.7 Hz, 1H), 7.58 (d, J = 1.3 Hz, 2H), 7.52 (ddd, J = 8.5, 6.7, 1.9 Hz, 3H), 7.47 (dd, J = 8.7, 0.7 Hz, 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, 6.9 Hz, 1H), 5.00 - 4.91 (m, 1H), 3.80 - 3.71 (m, 1H), 3.04 (dd, J = 12.5, 3.7 Hz, 1H), 2.68 (dd, J = 11.4, 7.2 Hz, 1H), 2.11 (d, J = 10.1 Hz, 1H), 1.53 (s, 9H), 1.27 (d, J = 1.2 Hz, 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 19F NMR (470 MHz, benzene-d6) δ -131.71 (dt, J = 23.0, 9.6 Hz), -134.32 (dt, J = 19.7, 9.7 Hz), -136.51 - -137.09 (m), -138.80 (ddd, J = 22.8, 10.4, 6.9 Hz).

[0202] Example 42: Synthesis of Pro-Catalyst 20

Chemical Structure

[0203] 1 1H NMR (500 MHz, benzene-d6) δ 8.57 (d, J = 1.9 Hz, 2H), 8.33 (dd, J = 2.0, 0.6 Hz, 2H), 7.54 - 7.48 (m, 4H), 7.41 (dd, J = 8.7, 0.6 Hz, 2H), 7.19 (dd, J = 8.4, 0.6 Hz, 2H), 6.99 - 6.95 (m, 2H), 6.82 (s, 2H), 6.79 (dd, J = 10.5, 8.6 Hz, 2H), 6.77 - 6.70 (m, 2H), 6.53 - 6.48 (m, 2H), 6.36 - 6.32 (m, 4H), 4.98 (dd, J = 10.5, 7.0 Hz, 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 = 13.5 Hz, 2H), 0.67 - 0.58 (m, 2H), 0.52 - 0.43 (m, 2H), 0.37 - 0.31 (m, 2H). 19 19F NMR (470 MHz, benzene-d6) δ -131.68 (dt, J = 23.1, 9.5 Hz), -138.29 (ddd, J = 23.0, 10.7, 7.2 Hz).

[0204] Example 43: Synthesis of bis-4,5-difluoro-2-iodophenyl ether

Chemical formula

[0205] 1 1H NMR (500 MHz, chloroform-d) δ 7.57 (t, J = 9.0 Hz, 2H), 6.67 (dd, J = 11.9, 6.7 Hz, 2H), 4.05 (d, J = 5.3 Hz, 4H), 2.10 (q, J = 4.9, 3.7 Hz, 4H). 19 19F NMR (470 MHz, chloroform-d) δ -134.17 (ddd, J = 21.0, 12.1, 8.8 Hz), -145.86 (dt, J = 21.0, 8.2 Hz). 13 13C NMR (126 MHz, chloroform-d) δ 154.03 (dd, J = 7.6, 2.4 Hz), 150.52 (dd, J = 249.2, 13.5 Hz), 144.64 (dd, J = 245.3, 13.1 Hz), 126.87 (d, J = 20.4 Hz), 101.50 (d, J = 21.5 Hz), 77.77 (dd, J = 6.1, 4.0 Hz), 69.55, 25.86.

[0206] Example 44: Synthesis of 4,5-difluoro-2-iodophenol:

Chemical Structure

[0207] 1 H NMR (500 MHz, chloroform - d) δ 7.45 (dd, J = 9.2, 8.4 Hz, 1H), 6.86 (dd, J = 11.3, 7.0 Hz, 1H), 5.16 (s, 1H). 19 F NMR (470 MHz, chloroform - d) δ -133.85 (dp, J = 20.7, 10.3, 9.5 Hz), -145.38 (tq, J = 20.8, 8.2, 7.7 Hz). 1313C NMR (126 MHz, chloroform-d) δ 151.61 (dd, J = 9.9, 2.7 Hz), 151.13 (dd, J = 249.5, 13.6 Hz), 144.79 (dd, J = 245.8, 13.5 Hz), 125.24 (d, J = 20.5 Hz), 103.94 (d, J = 21.1 Hz), 76.65 (dd, J = 6.6, 4.1 Hz).

[0208] Example 45: Synthesis of Ligand 11 [Chemical Structure] A mixture of thiophene boropinicolate ester (0.605 g, 0.5387 mmol, 2.70 equivalents, 50% purity by NMR), K3PO4 (0.343 g, 1.616 mmol, 8.10 equivalents), Pd(AmPhos)Cl2 (28.0 mg, 0.0399 mmol, 0.20 equivalents), and bis(phenyl)iodonium (0.120 g, 0.1995 mmol, 1.00 equivalent). The mixture was evacuated and then refilled with nitrogen, and this process was repeated three more times. Then, degassed 1,4-dioxane (4.0 mL) and degassed water (0.4 mL) were sequentially added by syringe. The mixture was then placed in a mantle heated to 50 °C. After vigorously stirring (1000 rpm) for 40 h, the black mixture was removed from the mantle and cooled slowly to 23 °C, suction filtered through a silica gel pad, washed with CH2Cl2 (4 × 20 mL), the clear black filtrate was concentrated, and the residual 1,4-dioxane was removed azeotropically using toluene (2 × 10 mL) by rotary evaporation. Then, the black mixture was suspended in CH2Cl2 (20 mL), suction filtered through a silica gel pad, rinsed with CH2Cl2 (4 × 20 mL), and then the black filtrate was concentrated onto celite and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 60% CH2Cl2 in hexane to give impure bisthiophene (0.201 g) as a bright yellow foam. NMR indicated a product containing impurities. This impure material was used in the subsequent reaction.

[0209] At 23 °C under nitrogen, concentrated HCl (3 mL) was added to a solution of the impure coupling product in CH2Cl2-1,4-dioxane (6 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1 × 10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 75% CH2Cl2 in hexane to give bisthiophene (0.107 g, 0.09716 mmol, 49% 2 steps) as a transparent amorphous foam. NMR indicated a 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 = 8.6 Hz, 4H), 6.52 (ddd, J = 11.6, 6.1, 1.9 Hz, 2H), 5.57 (s, 2H), 3.93 - 3.88 (m, 4H), 1.84 (q, J = 2.8, 2.3 Hz, 4H), 1.44 (s, 36H). 19 F NMR (470 MHz, chloroform-d) δ -130.70 (dd, J = 22.3, 6.5 Hz), -132.47 (ddd, J = 22.4, 11.5, 6.7 Hz), -167.89 (td, J = 22.0, 6.2 Hz). 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, 5.8 Hz), 147.48, 143.25, 139.32, 138.59 - 137.90 (m), 135.69 (dt, J = 246.1, 16.1 Hz), 126.44, 123.69, 123.35, 121.40, 116.39, 109.27, 107.74 (dd, J = 14.5, 3.8 Hz), 106.21, 97.67 (dd, J = 21.2, 3.2 Hz), 69.89, 34.70, 31.95, 25.62.

[0211] Example 46: Synthesis of Procatalyst 21 [Chemical formula] The thiophene ligand was azeotropically dried using PhMe (4 × 10 mL) before use. In a nitrogen-filled glove box at 23 °C, a solution of ZrBn4 (6.2 mg, 13.58 μmol, 1.10 equivalents) in C6D6 (0.50 mL) was added dropwise to a clear, colorless solution of thiophene (13.6 mg, 12.35 μmol, 1.00 equivalent) in anhydrous C6D6 (4.44 mL). After stirring for 30 minutes (500 rpm), the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex as a 0.0025 M solution in C6D6. NMR indicated the product. Using the same procedure with PhMe as the solvent, a procatalyst solution (0.0025 M or 0.005 M) for use immediately after filtration in the polymerization experiment can be prepared.

[0212] 1 H NMR (500 MHz, benzene-d6) δ 8.53 (d, J = 1.9 Hz, 2H), 8.34 (dd, J = 1.8, 0.7 Hz, 2H), 7.52 - 7.47 (m, 4H), 7.45 (dd, J = 8.7, 0.7 Hz, 2H), 7.20 (dd, J = 8.5, 0.6 Hz, 2H), 6.92 (ddd, J = 8.1, 7.3, 1.6 Hz, 4H), 6.89 (s, 2H), 6.74 - 6.70 (m, 2H), 6.24 - 6.21 (m, 4H), 4.65 (dd, J = 10.6, 6.3 Hz, 2H), 3.71 (dd, J = 12.8, 7.7 Hz, 2H), 3.04 (dd, J = 11.6, 4.6 Hz, 2H), 1.53 (s, 18H), 1.26 (s, 18H), 0.78 (d, J = 11.8 Hz, 2H), 0.67 (dd, J = 16.2, 7.2 Hz, 2H), 0.58 - 0.52 (m, 2H), 0.52 (d, J = 12.0 Hz, 2H). 1919F NMR (470 MHz, benzene-d6) δ -130.11 (ddd, J = 23.0, 10.5, 5.8 Hz), -131.31--131.90 (m), -160.87 (td, J = 23.0, 6.6 Hz).

[0213] Example 47: Synthesis of Procatalyst 24

Chemical formula

[0214] 1 1H NMR (400 MHz, benzene-d6) δ 8.53 (d, J = 1.9 Hz, 2H), 8.33 (dd, J = 1.8, 0.7 Hz, 2H), 7.51-7.42 (m, 6H), 7.16 (dd, J = 8.5, 0.6 Hz, 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, 6.3 Hz, 2H), 3.63-3.53 (m, 2H), 2.98 (dd, J = 11.5, 4.6 Hz, 2H), 1.52 (s, 18H), 1.23 (s, 18H), 0.99 (d, J = 13.5 Hz, 2H), 0.65-0.53 (m, 2H), 0.51-0.44 (m, 2H), 0.31 (d, J = 13.5 Hz, 2H). 1919F NMR (470 MHz, benzene-d6) δ -130.09 (ddd, J = 23.0, 10.6, 6.0 Hz), -131.00--131.79 (m), -160.31 (td, J = 22.8, 6.5 Hz).

[0215] Example 48: Synthesis of bis-3,4,5-trifluoro-2-iodophenyl ether [Chemical formula] A white heterogeneous mixture of iodophenol (5.444 g, 19.870 mmol, 2.00 equivalents), K2CO3 (8.238 g, 59.610 mmol, 6.00 equivalents), and 1,4-dibromobutane (1.10 mL, 9.935 mmol, 1.00 equivalent) in acetone (100 mL) equipped with a reflux condenser under nitrogen was placed in a mantle heated to 60 °C and stirred (500 rpm) for 36 h. The white heterogeneous mixture was then removed from the mantle, cooled to 23 °C, diluted with CH2Cl2 (50 mL), stirred vigorously (1000 rpm) for 5 min, suction filtered through a Celite pad, rinsed with CH2Cl2 (3 × 25 mL), the resulting filtrate solution was concentrated onto Celite, purified by silica gel chromatography with 10% CH2Cl2 in hexanes to 50% CH2Cl2 in hexanes to afford bisiodophenyl ether (5.086 g, mmol, 85%) as a white solid. NMR indicated the product.

[0216] 1 1H NMR (500 MHz, chloroform-d) δ 6.55 (ddd, J = 11.8, 5.9, 2.3 Hz, 2H), 4.07 (h, J = 2.6 Hz, 4H), 2.15-2.07 (m, 4H). 19 19F NMR (470 MHz, chloroform-d) δ -111.26 (dd, J = 23.3, 6.7 Hz), -132.95 (ddd, J = 19.9, 11.8, 6.7 Hz), -166.63--167.33 (m). 1313C NMR (126 MHz, chloroform-d) δ 153.44 (m), 152.96 - 152.33 (m), 150.64 (m), 134.41 (ddd, J = 248.0, 17.9, 15.8 Hz), 96.35 (dd, J = 22.0, 2.8 Hz), 69.51, 25.75.

[0217] Example 49: Synthesis of 3,4,5-Trifluoro-2-iodophenol

Chem.

[0218] 1 1H NMR (400 MHz, chloroform-d) δ 6.80 - 6.63 (m, 1H), 5.33 (s, 1H). 1919F NMR (376 MHz, chloroform-d) δ -112.07 (ddd, J = 22.3, 6.8, 2.6 Hz), -132.68 (ddd, J = 21.1, 11.1, 6.8 Hz), -166.81 (td, J = 21.7, 6.2 Hz). 13 13C NMR (101 MHz, chloroform-d) δ 153.58 - 151.73 (m), 150.78 (dd, J = 10.8, 5.5 Hz), 151.07 - 149.29 (m), 136.06 - 132.30 (m), 98.90 (ddd, J = 21.8, 3.2, 1.3 Hz), 68.51 (d, J = 26.4 Hz).

[0219] Example 50: Synthesis of Ligand 12 [Chemical formula] A mixture of thiophene boropinic acid ester (1.000 g, 1.104 mmol, 2.70 equiv., purity by NMR 62%), K3PO4 (0.703 g, 3.312 mmol, 8.10 equiv.), Pd(AmPhos)Cl2 (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bis(phenyl)iodonium (0.246 g, 0.4089 mmol, 1.00 equiv.). The mixture was evacuated and then refilled with nitrogen, and this process was repeated 3 more times, then deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated water (0.8 mL) were sequentially added by syringe. The mixture was then placed in a mantle heated to 50 °C. After vigorously stirring (1000 rpm) for 40 h, the black mixture was removed from the mantle and cooled slowly to 23 °C, suction filtered through a silica gel pad, washed with CH2Cl2 (4 × 20 mL), the clear black filtrate was concentrated, and the residual 1,4-dioxane was removed azeotropically using toluene (2 × 10 mL) by rotary evaporation. Then, the black mixture was suspended in CH2Cl2 (20 mL), suction filtered through a silica gel pad, rinsed with CH2Cl2 (4 × 20 mL), and then the black filtrate was concentrated onto celite and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 60% CH2Cl2 in hexane to give impure bisthiophene (0.202 g) as a bright yellow foam. NMR indicated a product containing impurities. This impure material was used in the subsequent reaction.

[0220] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupled product in CH2Cl2 - 1,4 - dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1×10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2×10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system, with 10% - 75% CH2Cl2 in hexane to give bisthiophene as a white foam (0.141 g, 0.1280 mmol, 31% 2 steps). NMR indicated a 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, 0.9 Hz, 4H), 7.38 (d, J = 0.9 Hz, 2H), 7.35 (ddd, J = 10.6, 7.9, 2.1 Hz, 2H), 7.20 (d, J = 8.6 Hz, 4H), 6.96 (d, J = 1.5 Hz, 2H), 4.15 - 4.05 (m, 4H), 1.91 (q, J = 3.2, 2.8 Hz, 4H), 1.45 (s, 36H). 19 F NMR (470 MHz, chloroform - d) δ - 137.56 (ddd, J = 21.7, 11.4, 3.9 Hz), - 147.93 (d, J = 19.3 Hz), - 157.70 (td, J = 20.7, 8.1 Hz). 13 C NMR (126 MHz, chloroform - d) δ 148.89 - 146.76 (m), 147.27, 146.77 - 144.58 (m), 143.19, 139.52 (ddd, J = 254.7, 16.3, 14.1 Hz), 139.36, 139.25 (dd, J = 10.1, 3.5 Hz), 127.64, 123.67, 123.38, 123.03 (dd, J = 8.0, 3.0 Hz), 121.41, 116.39, 111.90, 111.46 - 111.11 (m), 109.34, 75.47 (d, J = 3.5 Hz), 34.72, 31.98, 26.07.

[0222] Example 51: Synthesis of Pre-Catalyst 23

Chem.

[0223] 1 H NMR (400 MHz, benzene-d6) δ 8.52 - 8.49 (m, 2H), 8.33 (dd, J = 1.9, 0.7 Hz, 2H), 7.62 (dd, J = 8.6, 1.9 Hz, 2H), 7.54 (dd, J = 8.6, 0.7 Hz, 2H), 7.49 (dd, J = 8.7, 1.9 Hz, 2H), 7.37 (dd, J = 8.6, 0.6 Hz, 2H), 6.91 - 6.86 (m, 2H), 6.83 (s, 2H), 6.70 (t, J = 7.3 Hz, 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 = 11.5 Hz, 2H), 0.90 - 0.73 (m, 2H), 0.65 - 0.58 (m, 2H). 19 F NMR (376 MHz, benzene-d6) δ -135.52 (ddd, J = 22.5, 10.7, 6.3 Hz), -141.09 (d, J = 20.9 Hz), -155.07 (td, J = 21.2, 7.9 Hz).

[0224] Example 52: Synthesis of Procatalyst 24

Chem.

[0225] 1 H NMR (400 MHz, benzene-d6) δ 8.53 (dd, J = 2.0, 0.6 Hz, 2H), 8.32 (t, J = 1.3 Hz, 2H), 7.61 (dd, J = 8.5, 1.9 Hz, 2H), 7.48 - 7.45 (m, 2H), 7.35 (dd, J = 8.5, 0.6 Hz, 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, 6.5 Hz), -140.74 (d, J = 19.9 Hz), -154.84 (td, J = 21.4, 7.9 Hz).

[0226] Example 53: Synthesis of Bis-4,5,6-trifluoro-2-iodophenyl Ether [Chemical formula] A white heterogeneous mixture of iodophenol (1.550 g, 5.657 mmol, 2.00 equivalents), K2CO3 (2.346 g, 16.972 mmol, 6.00 equivalents), and 1,4-dibromobutane (0.34 mL, 2.829 mmol, 1.00 equivalent) in acetone (50 mL) equipped with a reflux condenser under nitrogen was placed in a mantle heated to 60 °C and stirred (500 rpm) for 36 hours. Then, the white heterogeneous mixture was removed from the mantle, cooled to 23 °C, diluted with CH2Cl2 (50 mL), stirred vigorously (1000 rpm) for 5 minutes, suction filtered through a Celite pad, rinsed with CH2Cl2 (3 × 25 mL), the resulting filtrate solution was concentrated onto Celite, purified by silica gel chromatography with 10% CH2Cl2 in hexane to 50% CH2Cl2 in hexane, and bisiodophenyl ether (1.410 g, 2.342 mmol, 83%) was obtained as a white solid. NMR indicated the product.

[0227] 1 H NMR (400 MHz, chloroform-d) δ 7.38 (td, J = 8.5, 2.6 Hz, 2H), 4.20 - 4.09 (m, 4H), 2.09 (h, J = 2.7 Hz, 4H). 19 F NMR (376 MHz, chloroform-d) δ -138.88 (ddd, J = 20.5, 9.0, 3.2 Hz), -146.39 (dt, J = 19.7, 2.8 Hz), -155.64 (td, J = 20.0, 7.9 Hz). 13 C NMR (126 MHz, chloroform-d) δ 147.31 (ddd, J = 250.6, 10.6, 2.7 Hz), 144.51 (dd, J = 10.0, 3.9 Hz), 144.51 (ddd, J = 254.7, 11.0, 4.1 Hz), 140.78 (ddd, J = 254.1, 16.0, 14.1 Hz), 120.35 (dd, J = 20.2, 3.7 Hz), 82.83 (dd, J = 7.7, 4.2 Hz), 74.23 (d, J = 4.5 Hz), 26.72.

[0228] Example 54: Synthesis of 4,5,6-Trifluoro-2-iodophenyl Ether

Chemical formula

[0229] 1 H NMR (400 MHz, chloroform-d) δ 7.33 (tdd, J = 8.8, 2.7, 0.9 Hz, 1H), 5.37 (s, 1H). 19 F NMR (376 MHz, chloroform-d) δ -143.20 (ddd, J = 21.0, 9.5, 3.8 Hz), -152.54 (dt, J = 19.4, 3.4 Hz), -156.04 (td, J = 20.0, 7.6 Hz). 1313C NMR (101 MHz, chloroform-d) δ 145.31 (ddd, J = 247.4, 10.7, 2.4 Hz), 142.06 - 141.31 (m), 139.45 (ddd, J = 249.4, 12.7, 3.8 Hz), 139.64 - 139.11 (m), 119.82 (dd, J = 20.6, 4.1 Hz), 75.21 (dd, J = 8.0, 4.6 Hz).

[0230] Example 55: Synthesis of Ligand 13

Chemical Structure

[0231] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupling product in CH2Cl2-1,4-dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1 × 10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system. With 10% - 75% CH2Cl2 in hexane, bisthiophene (0.143 g, 0.1346 mmol, 33% 2 steps) was obtained as a white foam. NMR indicated a pure product.

[0232] 1 H NMR (500 MHz, chloroform-d) δ 8.15 (dd, J = 1.9, 0.6 Hz, 4H), 7.66 (d, J = 2.6 Hz, 2H), 7.42 (dd, J = 8.6, 1.9 Hz, 4H), 7.35 (s, 2H), 7.24 - 7.20 (m, 4H), 7.18 (dd, J = 8.7, 2.6 Hz, 2H), 7.04 (s, 2H), 6.79 (d, J = 8.8 Hz, 2H), 4.04 (q, J = 3.6, 2.8 Hz, 4H), 1.91 (q, J = 2.8, 2.4 Hz, 4H), 1.47 (s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 152.34, 146.98, 142.94, 139.54, 129.92, 128.19, 127.84, 127.46, 124.63, 123.58, 123.27, 120.85, 116.30, 115.08, 113.72, 109.51, 70.29, 34.74, 32.05, 25.81.

[0233] Example 56: Synthesis of Procatalyst 25

Chemical formula

[0234] 1 H NMR (500 MHz, benzene-d6) δ 8.43 (dd, J = 2.0, 0.6 Hz, 2H), 8.29 (dd, J = 1.9, 0.6 Hz, 2H), 7.53 - 7.48 (m, 4H), 7.45 (dd, J = 8.5, 1.9 Hz, 2H), 7.34 (dd, J = 8.7, 0.6 Hz, 2H), 7.31 (d, J = 2.6 Hz, 2H), 7.22 - 7.19 (m, 2H), 6.91 - 6.86 (m, 2H), 6.83 (dd, J = 8.7, 2.7 Hz, 2H), 6.81 (s, 2H), 6.79 - 6.74 (m, 2H), 6.24 - 6.19 (m, 4H), 4.98 (d, J = 8.7 Hz, 2H), 3.88 - 3.78 (m, 2H), 3.12 (dd, J = 11.9, 4.7 Hz, 2H), 1.44 (s, 18H), 1.29 (s, 18H), 0.98 (d, J = 12.3 Hz, 2H), 0.71 - 0.64 (m, 2H), 0.53 (d, J = 12.3 Hz, 2H), 0.53 - 0.47 (m, 2H). 1313C NMR (126 MHz, benzene-d6) δ 154.32, 152.71, 146.13, 143.43, 143.02, 139.29, 139.12, 131.33, 130.56, 130.43, 129.56, 128.90, 128.33, 126.54, 126.07, 125.16, 124.69, 124.51, 124.12, 122.73, 122.43, 121.25, 118.17, 116.44, 115.69, 115.54, 112.22, 108.73, 74.66, 72.01, 34.54, 34.46, 31.94, 31.71, 25.77.

[0235] Example 57: Synthesis of Procatalyst 26

Chem.

[0236] 11H NMR (400 MHz, benzene-d6) δ 8.43 (d, J = 1.9 Hz, 2H), 8.28 (d, J = 1.8 Hz, 2H), 7.49 (dd, J = 8.7, 1.9 Hz, 2H), 7.43 (dd, J = 8.6, 2.0 Hz, 2H), 7.31 (d, J = 2.6 Hz, 2H), 7.24 (d, J = 8.7 Hz, 2H), 7.17 (d, J = 8.6 Hz, 2H), 6.98 - 6.93 (m, 2H), 6.92 - 6.87 (m, 2H), 6.83 (dd, J = 8.8, 2.7 Hz, 2H), 6.79 (s, 2H), 6.73 (tt, J = 7.3, 1.3 Hz, 2H), 6.27 - 6.22 (m, 4H), 4.96 (d, J = 8.8 Hz, 2H), 3.88 - 3.76 (t, J = 10.8 Hz, 2H), 3.19 - 3.06 (m, 2H), 1.43 (s, 18H), 1.28 (s, 18H), 0.89 (d, J = 13.4 Hz, 2H), 0.70 - 0.57 (m, 2H), 0.47 - 0.36 (m, 2H), 0.27 - 0.20 (m, 2H). 13 13C NMR (101 MHz, benzene-d6) δ 153.93, 152.73, 147.19, 143.50, 143.04, 139.24, 139.01, 138.50, 131.61, 130.40, 129.58, 129.05, 128.32, 126.62, 124.98, 124.56, 124.34, 122.64, 122.33, 121.16, 118.13, 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

Chem.

[0238] 1 1H NMR (500 MHz, chloroform-d) δ 7.73 (d, J = 2.5 Hz, 2H), 7.27 - 7.23 (m, 2H), 6.73 (d, J = 8.8 Hz, 2H), 4.14 - 4.04 (m, 4H), 2.10 (h, J = 2.4 Hz, 4H). 13 13C NMR (126 MHz, chloroform-d) δ 156.29, 138.50, 129.17, 126.28, 112.40, 86.72, 69.01, 25.92.

[0239] Example 59: Synthesis of Ligand 14

Chemical Structure

[0240] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupling product in CH2Cl2-1,4-dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1 × 10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, dried over solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system, with 10% - 75% CH2Cl2 in hexane to give bisthiophene as a white solid (0.121 g, 0.1139 mmol, 24% 2 steps). NMR indicated a pure product.

[0241] 1 H NMR (500 MHz, chloroform-d) δ 8.13 (d, J = 1.9 Hz, 4H), 7.60 (d, J = 8.3 Hz, 2H), 7.39 (dd, J = 8.6, 1.9 Hz, 4H), 7.31 (s, 2H), 7.20 (d, J = 8.6 Hz, 4H), 7.10 (dd, J = 8.4, 2.0 Hz, 2H), 6.94 (d, J = 2.0 Hz, 2H), 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, 121.45, 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

Chemical formula

[0243] 1 H NMR (500 MHz, benzene-d6) δ 8.51 - 8.44 (m, 4H), 8.35 - 8.26 (m, 2H), 7.63 - 7.54 (m, 4H), 7.29 - 7.26 (m, 2H), 7.14 (d, J = 8.3 Hz, 2H), 6.94 (s, 2H), 6.91 (dd, J = 8.3, 2.1 Hz, 2H), 6.85 - 6.77 (m, 4H), 6.51 - 6.48 (m, 4H), 6.40 - 6.32 (m, 2H), 5.86 (d, J = 2.1 Hz, 2H), 3.48 - 3.38 (m, 2H), 3.32 (m, 2H), 1.73 (d, J = 13.1 Hz, 2H), 1.33 (s, 18H), 1.23 (s, 18H), 1.03 - 0.96 (m, 2H), 0.92 - 0.79 (m, 2H), 0.50 (d, J = 13.1 Hz, 2H). 13 C NMR (126 MHz, 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, 134.86, 130.56, 126.63, 126.27, 124.11, 123.99, 123.63, 123.00, 122.36, 121.39, 116.78, 115.97, 75.66, 72.03, 34.54, 34.50, 34.47, 34.41, 31.82, 31.69.

[0244] Example 61: Synthesis of Procatalyst 28

Chem.

[0245] 1 1H NMR (400 MHz, benzene-d6) δ 8.57 (d, J = 1.9 Hz, 2H), 8.43 - 8.38 (m, 2H), 7.60 - 7.43 (m, 4H), 7.18 (d, J = 8.6 Hz, 2H), 6.96 (ddq, J = 7.4, 1.4, 0.7 Hz, 4H), 6.91 - 6.85 (m, 2H), 6.81 (s, 2H), 6.82 - 6.79 (m, 2H), 6.75 (tt, J = 7.3, 1.2 Hz, 2H), 6.66 (dd, J = 8.4, 2.1 Hz, 2H), 6.50 - 6.45 (m, 4H), 5.54 (d, J = 2.1 Hz, 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, 5.9 Hz, 2H), 0.91 - 0.71 (m, 2H), 0.55 - 0.40 (m, 2H), 0.34 (d, J = 13.6 Hz, 2H).

[0246] Example 62: Synthesis of Bis-5-chloro-2-iodophenyl ether

Chem.

[0247] 1 1H NMR (400 MHz, chloroform-d) δ 7.64 (d, J = 8.3 Hz, 2H), 6.79 (d, J = 2.2 Hz, 2H), 6.70 (dd, J = 8.3, 2.2 Hz, 2H), 4.16 - 4.03 (m, 4H), 2.15 - 2.04 (m, 4H). 13 13C NMR (101 MHz, chloroform-d) δ 158.00, 139.68, 135.13, 122.49, 112.66, 83.83, 68.90, 25.86.

[0248] Example 63: Synthesis of Ligand 15

Chemical formula

[0249] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupled product in CH2Cl2 - 1,4 - dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1 × 10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system with 25% - 100% CH2Cl2 in hexane to give bisthiophene as a white solid (0.126 g, 0.1114 mmol, 27% over 2 steps). NMR indicated a 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, 7.4 Hz, 4H), 7.37 (s, 2H), 7.27 (d, J = 9.4 Hz, 2H), 7.22 (d, J = 8.6 Hz, 4H), 6.64 (d, J = 9.0 Hz, 2H), 4.84 (s, 2H), 3.95 - 3.85 (m, 4H), 1.81 - 1.73 (m, 4H), 1.44 (s, 36H). 13 C NMR (126 MHz, 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, 111.71, 109.32, 69.13, 34.74, 32.00, 25.74.

[0251] Example 64: Synthesis of Procatalyst 29

Chemical formula

[0252] The thiophene ligand was co-azeotropically dried using PhMe (4 × 10 mL) before use. In a nitrogen-filled glove box at 23 °C, a solution of ZrBn4 (4.6 mg, 10.02 μmol, 1.10 equiv) in C6D6 (0.18 mL) was added dropwise to a clear colorless solution of thiophene (10.3 mg, 9.11 μmol, 1.00 equiv) in anhydrous C6D6 (1.64 mL). After stirring (500 rpm) for 30 minutes, the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex as a 0.005 M solution in C6D6. NMR indicated the product. Using the same procedure with PhMe as the solvent, a precatalyst solution (0.0025 M or 0.005 M) used immediately after filtration in the polymerization experiment can be prepared.

[0253] 1 H NMR (500 MHz, benzene-d6) δ 8.42 (d, J = 1.9 Hz, 2H), 8.26 (d, J = 1.9 Hz, 2H), 7.47 (ddd, J = 8.5, 6.3, 1.9 Hz, 2H), 7.38 (d, J = 8.7 Hz, 2H), 7.25 (d, J = 8.5 Hz, 2H), 6.99 - 6.95 (m, 6H), 6.94 (s, 2H), 6.86 (d, J = 8.8 Hz, 2H), 6.80 (d, J = 7.4 Hz, 2H), 6.37 - 6.32 (m, 2H), 6.09 (m, 2H), 4.91 (d, J = 8.8 Hz, 2H), 3.79 (t, J = 10.1 Hz, 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 = 11.6 Hz, 2H), 0.63 - 0.55 (m, 2H), 0.35 (d, J = 11.7 Hz, 2H).

[0254] Example 65: Synthesis of Precatalyst 30

Chemical formula

[0255] Example 66: Synthesis of bis-3,4-dichloro-2-iodophenyl ether [Chemical formula] A white heterogeneous mixture of iodophenol (4.112 g, 14.234 mmol, 2.20 equiv), K2CO3 (5.902 g, 42.702 mmol, 6.60 equiv), and 1,4-dibromobutane (0.77 mL, 6.470 mmol, 1.00 equiv) in acetone (65 mL) equipped with a reflux condenser under nitrogen was placed in a mantle heated to 60 °C and stirred (500 rpm) for 36 h. The white heterogeneous mixture was then removed from the mantle, cooled to 23 °C, diluted with aqueous NaOH (100 mL, 1 N), stirred for 2 min, suction filtered, and the filtered white solid was rinsed with aqueous NaOH (2×25 mL, 1 N), then with water (2×25 mL) and cold CH2Cl2 (2×20 mL). The resulting filtered white solid was collected, the biphasic mixture of the filtrate was poured into a separatory funnel, separated, and the organic matter was washed with aqueous NaOH (2×25 mL). The residual organic matter was extracted with CH2Cl2 (2×25 mL), combined, dried over solid Na2SO4, concentrated, and mixed with the filtered solid to obtain iodophenyl ether (3.813 g, 6.034 mmol, 93%) as a white solid. NMR (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 = 8.9 Hz, 2H), 4.11 (q, J = 4.3, 3.2 Hz, 4H), 2.11 (dt, J = 5.4, 3.3 Hz, 4H).

[0257] VT NMR at 100 °C: 1 H NMR (400 MHz, DMSO-d6) δ 7.54 (dd, J = 8.9, 1.5 Hz, 2H), 6.96 (dd, J = 8.9, 1.8 Hz, 2H), 4.16 (ddt, J = 5.9, 3.6, 2.2 Hz, 4H), 1.97 (dq, J = 5.9, 2.6 Hz, 4H). 13 C NMR (101 MHz, 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

Chemical Structure

[0259] The NMR spectrum was realized at 55 °C: 1 1H NMR (500 MHz, chloroform-d) δ 7.80 (s, 2H), 6.88 (s, 2H), 4.12 (qd, J = 5.6, 3.7, 3.3 Hz, 4H), 2.11 (dq, J = 5.7, 2.9 Hz, 4H). 13 13C NMR (126 MHz, chloroform-d) δ 156.81, 139.43, 133.07, 125.07, 113.61, 84.17, 69.50, 25.82.

[0260] Example 68: Synthesis of 4,5-dichloro-2-iodophenol and 3,4-dichloro-2-iodophenol

Chem.

[0261] Characterization of 2 - iodo - 4,5 - dichlorophenol: 1 1H 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 1H NMR (400 MHz, chloroform - d) δ 7.32 (d, J = 8.9 Hz, 1H), 6.86 (d, J = 8.8 Hz, 1H), 5.44 (s, 1H). 1313C NMR (101 MHz, chloroform-d) δ 155.15, 136.20, 130.76, 123.74, 113.74, 91.99.

[0263] Example 69: Synthesis of Ligand 16

Chemical formula

[0264] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupling product in CH2Cl2-1,4-dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1 × 10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system, with 25% - 100% CH2Cl2 in hexane to give bisthiophene as a white solid (0.113 g, 0.0999 mmol, 24% 2 steps). NMR indicated a 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, 1.9 Hz, 4H), 7.32 (s, 2H), 7.18 (d, J = 8.6 Hz, 4H), 7.03 (s, 2H), 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, 122.96, 120.92, 116.36, 115.20, 112.57, 109.39, 70.17, 34.72, 32.00, 25.85.

[0266] Example 70: Synthesis of Pro-Catalyst 31

Chemical Structure

[0267] 1 1H NMR (500 MHz, benzene-d6) δ 8.54 (dd, J = 1.9, 0.7 Hz, 2H), 8.42 (dd, J = 1.8, 0.8 Hz, 2H), 7.62 - 7.56 (m, 4H), 7.47 (dd, J = 8.6, 1.9 Hz, 2H), 7.18 (dd, J = 8.5, 0.7 Hz, 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 precatalyst 32

Chemical formula

[0269] 1 1H NMR (500 MHz, benzene-d6) δ 8.56 (dd, J = 2.0, 0.6 Hz, 2H), 8.44 (dd, J = 1.7, 0.8 Hz, 2H), 7.62 - 7.53 (m, 4H), 7.46 (dd, J = 8.6, 1.9 Hz, 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, 1.3 Hz, 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 = 13.7 Hz, 2H).

[0270] Example 75: Synthesis of Precatalyst 31

Chemical Structure

[0271] At 23 °C under nitrogen, concentrated HCl (5 mL) was added to a solution of the impure coupled product in CH2Cl2-1,4-dioxane (10 mL, 1:1). The amber solution was stirred for 20 h (500 rpm), diluted with 1 N HCl (10 mL) and CH2Cl2 (10 mL), poured into a separatory funnel, separated, the organic matter was washed with 1 N HCl (1 × 10 mL), the residual organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 10 mL), mixed, dehydrated with solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography via an ISCO chromatography purification system with 10% - 75% CH2Cl2 in hexane to give bisthiophene (0.115 g, 0.09583 mmol, 11% 2 steps) as a pale yellowish brown solid. NMR indicated a 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 = 8.6 Hz, 4H), 6.98 (s, 2H), 3.96 - 3.91 (m, 4H), 1.85 - 1.80 (m, 4H), 1.44 (s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 156.24, 146.49, 143.49, 139.20, 136.25, 134.68, 125.81, 124.47, 123.91, 123.49, 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 Pro-Catalyst 33

Chemical Structure

[0274] 1 H NMR (400 MHz, benzene-d6) δ 8.48 (d, J = 1.9 Hz, 2H), 8.36 (d, J = 1.8 Hz, 2H), 7.59 (d, J = 8.7 Hz, 2H), 7.50 (ddd, J = 8.8, 3.8, 1.9 Hz, 4H), 7.23 (d, J = 8.6 Hz, 2H), 6.98 - 6.94 (m, 4H), 6.89 (s, 2H), 6.74 (t, J = 7.3 Hz, 2H), 6.27 - 6.21 (m, 4H), 5.41 (s, 2H), 3.60 - 3.50 (m, 2H), 2.97 - 2.90 (m, 2H), 1.49 (s, 18H), 1.28 (s, 18H), 1.16 (d, J = 13.9 Hz, 2H), 0.90 - 0.80 (m, 2H), 0.68 - 0.60 (m, 2H).

[0275] Example 77: Synthesis of Precatalyst 34

Chemical formula

[0276] 1 1H NMR (400 MHz, benzene-d6) δ 8.51 (d, J = 1.9 Hz, 2H), 8.39 (d, J = 1.8 Hz, 2H), 7.61 (d, J = 9.0 Hz, 2H), 7.50 (ddd, J = 21.9, 8.7, 1.9 Hz, 4H), 7.19 (d, J = 8.6 Hz, 2H), 6.98 - 6.94 (m, 4H), 6.90 (s, 2H), 6.75 (t, J = 7.5 Hz, 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 = 14.1 Hz, 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

Chem.

[0278] The NMR spectrum was realized at 60 °C: 1 1H NMR (500 MHz, chloroform-d) δ 6.87 (s, 2H), 4.21 - 4.08 (m, 4H), 2.13 (dq, J = 5.3, 3.4, 2.7 Hz, 4H). 13 13C 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 [Chemical formula] A clear, colorless solution of starting phenol (3.600 g, 18.233 mmol, 1.00 equiv), KI (5.297 g, 31.909 mmol, 1.75 equiv), and aqueous NaOH solution (55.0 mL, 54.699 mmol, 3.00 equiv, 1 N) in methanol (100 mL) and water (100 mL) was placed in an ice bath and stirred vigorously (1000 rpm) for 1 h. Subsequently, pre-cooled commercial aqueous bleach (46.0 mL, 31.909 mmol, 1.75 equiv, 5.2% w / w) was added dropwise over 10 min. At this point, the opaque, pale yellow mixture was stirred at 0 °C for 2 h, removed from the ice bath, stirred at 23 °C for 4 h, solid NaH2PO4 (10 g) was added, followed by saturated aqueous Na2S2O3 (100 mL) to reduce residual iodine and water (100 mL). The mixture was stirred vigorously for 10 min, diluted with CH2Cl2 (50 mL), the biphasic yellow mixture was poured into a separatory funnel, separated, the organic layer was washed with aqueous Na2S2O3 solution (2 × 50 mL), the residual organic matter was extracted from the aqueous layer using CH2Cl2 (2 × 25 mL), combined, dried over solid Na2SO4, decanted, concentrated onto celite, purified by silica gel chromatography, eluting with 35% CH2Cl2 in hexanes to 100% CH2Cl2 in hexanes to afford o-iodophenol (1.497 g, 4.630 mmol, 25%) as a white solid and starting phenol (2.544 g, 12.885 mmol, 71%) as a white solid. NMR showed pure product.

[0280] 1 1H NMR (500 MHz, chloroform-d) δ 7.11 (s, 1H), 5.52 (s, 1H).

[0281] Example 80: Polymer Obtained from the Procatalyst Using a parallel polymerization reactor (PPR) and a semi-batch reactor, the catalytic efficiency (g polymer yield / g metal) and the resulting polymer properties were evaluated for precatalysts 1 - 34. The polymerization reaction in the batch reactor was carried out in a 2-L semi-batch reactor without initially using diethylzinc (DEZ) and then adding three different amounts of DEZ (0, 50, and 200 μmol). The activator was 1.5 molar equivalents of bis(hydrotalcite alkyl)methylammonium tetrakis(pentafluorophenyl)borate.

[0282] The precatalysts can produce polymers at temperatures up to 150 °C. All precatalysts except precatalysts 1 and 2 are very active as indicated by the short quench time in the PPR, and most show high efficiency (>200,000 g polymer / g metal) in the semi-batch reactor experiments under these reactor conditions. The linking unit (crosslink) directly affects the activity and efficiency of the catalyst, leading to the formation of polymers with higher comonomer incorporation (up to 23 mol%). Precatalysts 3 and 4 linked with a four-carbon alkyl n-butyl chain produce polymers with lower 1-octene incorporation (10 - 12 mol%), while disubstituted silyl and germanyldimethylene, and trans-1,2-methylenedicyclohexyl crosslinks, precatalysts 5 - 12 result in higher catalytic activity, efficiency (up to 29 MMg polymer / g metal), and 1-octene incorporation (up to 23 mol%). Also, the functional groups and substitution positions located in the neutral phenyl ether donors (i.e., precatalysts 13 - 34) directly affect the activity and efficiency of the catalyst (up to 32 MMg polymer / g metal), leading to the formation of polymers with higher comonomer incorporation (up to 21 mol%) and higher molecular weight (up to 774,000 g / mol). Precatalysts 3 and 4 with unsubstituted neutral, non-anionic phenyl ether donors produce polymers with lower 1-octene incorporation (10 - 12 mol%) and, depending on the comparison of the precatalysts under these reactor conditions, can result in lower catalytic efficiency at temperatures up to 150 °C.

Table 1-1

Table 1-2

[0283] *Standard PPR reactor conditions: 120 °C - 150 psi ethylene, 838 uL 1-octene, [C8]:[C2] = 2.24, 10% CO quench, run time = 30 minutes, or until 50 psi conversion at 120 °C. MMAO-3A = 500 nanomoles. Activator = bis(hydrogenated tallow alkyl)methyl-ammonium, tetrakis(pentafluorophenyl)borate (1.50 equivalents)* Mol% octene or C8 / olefin is defined as (moles of 1-octene / (total moles of 1-octene and ethylene)) × 100. N.D. = not determined.

Table 2-1

Table 2-2

[0284] *Standard semi-batch reactor conditions: 46 g of ethylene and 303 g of 1-octene in 611 g of IsoparE at 120 °C, 43 g of ethylene and 303 g of 1-octene in 547 g of IsoparE at 150 °C, and 46 g of ethylene and 292 g of 1-octene in 515 g of IsoparE at 190 °C. * Mol% octene or C8 / olefin is defined as (moles of 1-octene / (total moles of 1-octene and ethylene)) × 100. N.D. = not determined.

Table 3-1

Table 3-2

Table 3-3

[0285] *Standard semi-batch reactor conditions using Et2Zn as CSA: 11 g of ethylene and 59 g of 1-octene in 610 g of IsoparE at 120 °C; 12 g of ethylene and 59 g of 1-octene in 531 g of IsoparE at 150 °C. *Mol% octene or C8 / olefin is defined as (moles of 1-octene / (total moles of 1-octene and ethylene)) × 100. N.D. = not determined.

Table 4

[0286] For precatalysts 3, 4, 13 - 20, 25, and 26 at 150 °C, moderate to high chain transfer constants (Ca ≤ 0.6) indicate that these catalysts have high sensitivity to chain transfer agents and undergo rapid chain transfer with these agents. Overall, as the amount of Et2Zn (DEZ) increases, a decrease or relatively persistent narrow PDI of these precatalysts is observed, evidence that these specific precatalysts undergo reversible chain transfer by CSA rather than irreversible chain transfer. These behaviors are not observed with other precatalysts having much lower Ca and / or a significant increase or broadening in PDI. Precatalysts 12 and 27 have high Ca, but the increase in PDI suggests irreversible chain transfer by DEZ. The present invention includes the following aspects. Item 1. A catalyst system comprising a metal-ligand complex according to formula (I),

Chemical formula

Claims

1. A catalyst system comprising a metal-ligand complex according to formula (I), 【Chemical 1】 wherein, M is a metal selected from zirconium or hafnium, and the metal has a formal oxidation state of +2, +3 or +4, Each X is a monodentate or bidentate ligand independently selected from (C １ -C ５０ ), (C ６ -C ５０ ), heteroaryl, halogen, -OR Ｃ , -N(R Ｎ ), ２ and -NCOR Ｃ ; n is 1 or 2, Y is oxygen or sulfur, Each R １ is independently selected from the group consisting of a radical having the formula (II), a radical having the formula (III), and a radical having the formula (IV), 【Chemical formula 2】 wherein R ３１～３５ , R ４１～４８ , and R ５１～５９ are each independently (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -CN, -CF ３ , halogen, or -H, provided that at least one R １ in formula (I) is a radical having formula (III), Q is -CH ２ CH ２ CH ２ CH ２ -, cyclohexane-1,2-diyl, 1,2-bis(methylene)cyclohexane, (-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 CH ２ -), where R Ｑ is (C １ -C ２０ ) hydrocarbyl, each z １ and z ２ are independently selected from the group consisting of sulfur, oxygen, -N(R Ｃ ), and -C(R Ｃ ), provided that in each individual ring containing the groups z １ and z ２ , at least one of z １ and z ２ is sulfur, R ４ａ 、R ５ａ 、R ６ａ 、R ７ａ 、R ４ｂ 、R ５ｂ 、R ６ｂ 、and R ７ｂ are independently selected from (C １ -C ５０ ) hydrocarbyl, (C １ -C ５０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -OR Ｃ , -CN, -CF ３ , halogen, and -H, and 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 bonded to form an aromatic or non-aromatic ring, Each R in formula (I) Ｃ , and R Ｎ are each independently selected from the group consisting of (C １ -C ２０ ) hydrocarbyl, (C １ -C ２０ ) heterohydrocarbyl, and -H. However, when Q is -CH ２ CH ２ CH ２ CH ２ -, (1) Each R １ is 3,6-di-tert-butylcarbazol-9-yl, z ２ is sulfur, and when each X is benzyl, R ５ａ and R ５ｂ is not -OMe, fluorine, or tert-octyl, or (2) R ４ａ , R ５ａ , R ６ａ , and R ７ａ at least one of which is halogen, R ４ｂ , R ５ｂ , R ６ｂ , and R ７ｂ at least one of which is halogen, or (3) R ４ａ , R ５ａ , R ６ａ , R ７ａ , R ４ｂ , R ５ｂ , R ６ｂ , and R ７ｂ in which at least one is selected from the group consisting of (C １ - C ５０ ) hydrocarbyl, (C １ - C ５０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -OR Ｃ , -CN, and -CF ３ , provided that the catalyst system is selected from the group consisting of.

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

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

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

5. The 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 at least one of the Rs ４１～４８ is selected from (C １ -C ４０ ), hydrocarbyl, (C １ -C ４０ ), heterohydrocarbyl, -Si(R Ｃ ), ３ -CN, -CF ３ or halogen, and the catalyst system according to any one of claims 1 to 5.

7. Each R １ is a radical having the formula (III), (1) R ４２ and R ４７ are independently (C １ -C ２０ ) alkyl, -Si(R Ｃ ) ３ , -CF ３ , or halogen, and R ４３ and R ４６ are -H or (2) R ４３ and R ４６ are independently (C １ -C ２０ ) alkyl, -Si(R Ｃ ) ３ , -CF ３ , or halogen, and R ４２ and R ４７ are -H, the catalyst system according to any one of claims 1 to 6.

8. Q is -CH ２ CH ２ CH ２ CH ２ -, R ４ａ , R ５ａ , R ６ａ , R ７ａ , R ４ｂ , R ５ｂ , R ６ｂ , and R ７ｂ At least two of the groups are -Si(R Ｃ ) ３ , -OR Ｃ , -CN, -CF ３ 8. The catalyst system according to claim 1, wherein the halogen atom is selected from the group consisting of:

9. R ４ａ 、 R ５ａ 、 R ６ａ 、 R ７ａ Among them, at least one is halogen, and R ４ｂ 、 R ５ｂ 、 R ６ｂ 、 and R ７ｂ The catalyst system according to any one of claims 1 to 8, wherein at least one of them is halogen.

10. R ４ａ 、 R ５ａ 、 R ６ａ 、 R ７ａ Among them, at least two are halogen, and R ４ｂ 、 R ５ｂ 、 R ６ｂ 、 and R ７ｂ Among them, at least two are halogen. The catalyst system according to any one of claims 1 to 8.

11. R ４ａ 、R ５ａ 、R ６ａ 、R ７ａ Of these, at least three are halogen, and R ４ｂ 、R ５ｂ 、R ６ｂ 、and R ７ｂ Of these, at least three are halogen, the catalyst system according to any one of claims 1 to 8.

12. Q is (-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 CH ２ -), wherein R Ｑ is (C １ -C ５ ) alkyl, the catalyst system according to any one of claims 1 to 8.

13. The catalyst system according to any one of claims 1 to 8, wherein Q is cyclohexane-1,2-diyl.

14. Q is (-CH ２ Si(R Ｑ )) ２ CH ２ -), where R Ｑ is ethyl or 2-propyl, the catalyst system according to any one of claims 1 to 8.

15. The catalyst system according to any one of claims 1 to 14, further comprising a chain transfer agent.

16. A process for polymerizing an olefin, comprising contacting ethylene with optionally one or more (C ３ -C １２ ) α-olefins in the presence of the catalyst system according to any one of claims 1 to 14.

17. The process according to claim 16, further comprising a chain transfer agent.

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